Document jndV07qrzNVmoN8Ldx7RaNyZ

CCHHAAPPTTEER4R4 IInndduussttrriiaall aanndd UUttiilliittaarriiaann AAspsecptsooeffFFclluuotorriisnnee CChheenmisistteryy BY 1. G. BRYCE Mimsts Miing and MBomYfoHc.tuGi.ngBRCYomCpEas, St. Pas, Mimcta f~Iinnesota ~Vlining and Manufacturing Company, St. Paul, Minnesota 1 tdci. eevee sestrsses BT I. Introduction ....................................................... 297 H. Hits sd Ecorse cos. sescresesees B98 II. Historical and Economic Factors ..................................... 298 HL Chace Propeorflsrorbons. an III. Characteristic Properties of Fluorocarbons .............................. 302 "A" Bond EnaendBorndDiigsan... a A. Bond Energies and Bond Distances ............................... 302 5. Boing Poise sndMtnsPei Cm B. Boiling Points and Melting Points ................................ 303 Sure Foe everest am C. Surface Energy ................................................ 304 B.Suing -- 00 D. Stability ...................................................... 309 fa ------ m E. Electrical Properties ............................................ 312 F. Polity of Oude os ide a Beof Sesto nm F. Polarity of Oxides or Nitrides and Effect of Structure ............... 312 & Soi. 8 III G. Solubility ..................................................... 314 IV. Regand e Proprels eon a6 IV. Refrigerants and Propellants ......................................... 316 A proper LL aw A. Properties ..................................................... 317 a --- B. Refrigeration Characteristics ..................................... 320 . ApfporSpi ecieCaompon inis IIe C. Applications for Specific Compounds ............................. 323 V.HostTamates Medi... i = V. Heat Transfer Media ................................................ 323 HowTomer Pcs. Clam A. Heat Transfer Processes ........................................ 323 B. Miirinion - ry 4 B. Miniaturization ................................................ 324 Chenin of Foch, Fist Hest Titer Proles.-. 328 C. Application of FIuorocarbon Fluids to Heat Transfer Problems ....... 325 >. PepofeFirsorioason his Dm D. Properties of Fluorocarbon Fluids ................................ 331 VL. GaseousDik. er U8 VI. Gaseous Dielectrics .................................................. 346 N Factors ating Dei Singh re so A. Factors affecting Dielectric Strength .............................. 347 5. ApnbasSiuloenHsofous nd... 550 B. Applications for Sulfur Hexafluoride .............................. 350 & FhirocuonGoes sd Thee Appin. Te C. Fluorocarbon Gases and Their Application ........................ 351 VI. Fie Extingisting Ags I sss VII. Fire Extinguishing Agems ............................................ 354 Pi ------------ A. Physical Extinguishment ........................................ 354 . Chemie Exige Da B. Chemical Extinguishment ....................................... 354 & etmofSpeCompours 355 C. Action of Specific Compounds ................................... 355 ChanidCoty. ees D. CF=Brz and CFsBr ............................................. 357 VIL Lube oon _ VIII. Lubricants ......................................................... 358 N Fron. is A. Friction ...................................................... 358 ow Types of Lnbricaion. IIIs B. Two Types of Lubrication ...................................... 358 9s295 33002222..00000011 Exhibit 3022 I3MM_MMNNO044885555111100 2% 1. mvee 296 H. Go BRYCE C. HilofOir,Waexecs,audGoren. 3 C. Halofluorocarbon Oils, Waxes, and Greases ........................ 359 D. Other Fluorine-containing Fluids ................................. 366 E. Flscrocrbon Moola +++ 111-111 360 E. Fluorocarbon Monolayers ....................................... 367 IX. FlonobonSusur. - eee TO IX. Fluorocarbon Surfactants ............................................ 370 A SuneActive Natureof FlossCompound... 31 A. Surface Active Nature of Fluorocarbon Compounds ................. 371 5 SureAchy in Woke. m B. Surface Activity in Water ....................................... 373 C. Sura Acti in StrongAcssnd Bose. 374 C. Surface Activity in Strong Acids and Bases ........................ 374 D. Theemai Sabie Ho D. Thermal Stability .............................................. 380 E Sure Acivty inOrr Ndi. EE E. Surface Activity in Organic Media ............................... 380 E. AduorpioSnaon a IIIs F. Adsorption on Solids ........................................... 388 . MicopiocatAchy... i. Claw G. Microbiocidal Activity .......................................... 389 HE Trial Tesomn. 111-11 eee389 H. Interracial Tensions ............................................ 389 1 Commercial pers. Bo I. Commercial Aspects ............................................ 390 X. Tele " wo X. Textiles ........................................................... 396 N Suri mens fo Fibs. A. Surface Treatment for Fibers .................................... 396 1B. InducttoFiionbers... LLL B, Introduction to Fibers .......................................... 397 Chm NuofPatsrcrson ie 0 C. Chemical Nature of Fluorocarbon Finishes ........................ 399 A SO D. Methods for Measuring Repellency ............................... 401 E. Fern Affting DhofFo oorcw sbon Dine 00 Fabric 105 E. 'Factors Affecting Behavior of Fluorocarbon Derivatives on Fabrics... 405 E. Corman Prodan orev vores oreo 48 F. Commercial Products .......................................... 408 SunRename ofFarocarbon Trewed Fibre 1-. 413 G. Stain Resistance of Fluorocarbon Treated Fabrics .................. 413 i Durtbo Cliinyg Proce. i H. Durability to Cleaning Processes ................................. 413 3. CoTmrim n Proecedurres 1-1-1111: 45 I. Commerical Treating Procedures ................................ 415 XE Later 418 XI. Leather ........................................................... 418 A Lear Frocesing. a A. Leather Processing ............................................ 418 1. FroopfFisroroiarbeon reved Lester. 111+... 20 B. Properties of Fluorocarbon Treated Leather ....................... 420 . CommindlAppin +e 428 C. Commercial Applications ....................................... 425 XU Papers EO XII. Paper ............................................................. 426 inioa opner essssimmesstersens A. Introduction to Paper .......................................... 426 5 Fhiocuapbe Sohns & B. Fluorocarbon Paper Sizes ....................................... 427 C. Commreesrincriocarls. & C. Commercial Treating Procedures ................................. 432 1D. Proper of Tested apr III D. Properties of Treated Paper ..................................... 433 E. Appcsion for True Popes sd PaperBod. 11111111 438 E. Applications for Treated Paper and Paper Board ................... 436 Xl.FlonrPoclymserston Plastics... SY XIII. Fluorocarbon Polymers--Plastics ...................................... 440 Xtfo Bc almer... HO A. Introduction to Polymers ....................................... 440 B. Fuytarssometiien. IE B. Polytetrafluoroethylene ......................................... 442 Jou rio Se -- pl C. Chlosotrifluoroethylene Polymers ................................. 449 D. FlyinFh. 459 D. Polyvinylidene Fluoride ......................................... 459 E Pipi!Floste Ee] E. Polyvinyl Fluoride ............................................. 461 F, Copterof TewsihwsdrHomotuessiopoipsoisn. $81 F. Copolymer of Tetrafluoroethylene and Hcxafluoropmpylene .......... 461 G. Conaimerssetuid Crier oer reo 462 G, Copolymers containing Chlorotrifluoroethylene ..................... 462 LA NAAN. H. Summation ................................................... 463 Ropleiom. PEE I. Applications .................................................. 463 33002222..00000022 33MM_MMNNo04488s5s5111111 INDUSTRIAL ASPECTS OF FLUORINS CHEMISTRY. El INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 297 XIV. FitX BC1E...inFCCFFtlooi.orpcoproooirlaT nnyinymnccmceiooroenoominsgnffinoti iiRCEsinnhaunggtibSAbuoBrtscsbaoreineesoe.reirnoR.ep.Eaaib.belenrlsaennadnrVdeViern.dd.eeF.oF-rrdied. AG"i4-7De628 XIV. Fluorine-containing Elastomers ....................................... 466 A. Introduction to Rubbers ........................................ 466 B. Fluorine-containing Elastomers .................................. 467 C. Copolymers of Chlorotrifluoroethylene and Vinylidene Fluoride ...... 468 D. Copolymers of Hexafiuoropropylene and Vinylidene Fluoride ........ 472 E. Fluorine-containing Silicone Rubber ............................. 476 F. Fluorine-containing Acrylate Elastomer ........................... 477 XV. Mises ad Rots Pa XV. Missiles and Rockets ................................................ 479 X FinoplesGovesning Jo Engine. 1-11-11 AT A. Principles Governing Jet Engines ................................ 479 5. Ligod Poplin. a B. Liquid Propellants ............................................. 482 C. Solid Propellants .............................................. 482 . Bement Forze 5 D. Elemental Fluorine ............................................ 483 . Compounodt Fine iss E. Compounds of Fluorine ........................................ 485 . Sod ropelats comeing Florin. CII F. Solid Propellants containing Fluorine ............................. 486 XVI Cais... ecmssstsissssssssn I XVI. Catalysis .......................................................... 488 "A pres Fide ws A. Hydrogen Fluoride ............................................ 488 B aroscec Ack and Abide ol 0 B. Trifluoroacetic Acid and Anhydride .............................. 490 Coron Tabor 1 C. Boron Trifiuoride ............................................. 491 bagrrny esses wn Bibliography ....................................................... 492 1 lntroduction natuArAess. a a Trrtaawcwommmpaartetiersrieiaasll affpoorprriionnxddiIuu.mssattItrrnieiatlalryouu0dsse.eu,,0c6fAtli5uvo%onorrionfne tiihserreeellaaartttiivhv'eesllyycaarbbuuusnnd)daancnttoiimnn nppinaaartrureearddeth.toe00rI0t.c.00co5o5m5m5p%l%perixffsooerrsincchoahlrplogoprarirninoniexec.i.mcM Maootomsesptltyoofou0tfn.htd0his6is5s%afftlluuroooerrfliiannttheei,,evehhleooyawwreltevhove'wesrr,,lcerisvusceslcots(om1m)abnbicdinonemeiddn- icAcnouoonnrrssaseetqpqhauuereernn(cccReeoumowwrpioleue,oxldCbibnaeueoFdrdi)gifafliwfnichicuciulcdltcthotooomcrprceeuoccruoosvnvedeqrsur..itaTTethhwreeiedlmmealotoiysv.stet liTiymmhpilpoosowrirtstaalntenthvteemmlispirnniaeenrnrcadaillpaiiinlss fsasloroueuuorrrvccsieeplaoolrfafu(ffnflluliuuotooerrriiinn(teeeN,aaaFtCt)app,Frree2sss)eeewltna.th.iitcOOehtthh(oeeMcrrgcuFssirismsm)p,pqllueeyittfuetloruworociirdeiddieeetlsyse.oo(TccCcchauuisrsrCrreiiisnanVggtehaa)esFepmm,riiinnnaecelrlirapaloalssfl awwrhheii"ccvThhihlelaairraeemumsrraatirteee..im(NpoarFt)a,ntseollfartithee (MgF2), complex yttrocerite (Ca3Ce~Y~)F6, all vorides occurring nawrally of is cemrriyynooTollrihtteeeam((mNoNauoas3nsAtAtIs1iFmFya)6pr.)oe. rOOtuatotnhrhteoecrroifrmmibthinoneeneraractaloelssms,piinnlefxuwwohrhfioilcucsuhholrfiffdalltueuesoosrr,ioinncefecuuoiirsrrioaanallgrssosoennppaartrueetrsseaee,lnnltytaniiidnns mfApluuionorroroorpephahaomorsssepopshucuhanfatfttesaiescs.ia. terenTItnnftluotthohmeeroackccaaaerssbeetohnooeaffmtettashh,nee filnnmuaapottoruuorrrsaaaullnlftppahthfeooussts,puphrfhaleuatstoeersso,,oarttstuh~oeeenfarfaatuemmosoe,rouiuannenntetd,ss pppararertstTiieeccnsuutlilaadarrerllesyystasuhsfsefaicnbbiaeyytn--utpprratrooollddmyuucacotktcecoouffthrttrehhimeengmmaanmaninuinmufefarpacacotltr,uutrareeCntaoofFffu,sstuuurptpeheeerrsoppmuhhoroocsssetpphohaifatmftepelsuos.or. rtiannet, fABlusuoorwBriiienlnsleeidbeccesoosmmthhppoeoowuunnnnaddtluarootanenllyiaannnotchiicinnsuddruucrshistnatrrpgiitaaellmr,issnccteaahrlliaeesl,ciissoCmahhpFyy~odd,urroontgghdeeennhmasffollusu4otorrniiiudmdemepbo((eHHrrtEaF)no).f.t vtvAheeserryywprssiloiilggdnnubiciefftiiiccsaoahnnnottwofuunmssoeelssasttieittorssefeillntffhddteihiericescoctmtcllmyhye.a.rpIcItnenira,aalddltdhdyiiitstaiivoocannol,,ambiittpicoiissucntthhdoee hmssattsaparttaiionnnogguufmpcpnooabiiredanbrttosioinnnf tlaahunnebddrpiffcrluoauotdoriurniicgnnteeioaiinnnndccollfuuhmddeiioanntsggt oggtafarsstaeehnssesfuucessoreemddfmiaaesdsrecrr,eieafflrrliiyAggueeaorrvraaaonnictltaassbraablennonddc-otdamyeeprrpooeos.souolnlpdlppsarrsoootppifecelcsllalaarnbantnotssdn,, lubricating and heat transfer fluids, fluorocarbon-type plastics and 33002222..00000033 I3MM_MMNNo04488s5s5111122 208 298 H.G6.. owxcr BRYCE eSelelaanssittlooemm,eerrossi,l, rsseuusrirffsatacacneet aapccattpiiveveer saaiggzeeen,ntsat, ns2ad,ss spwweecelillal l 3atssressatttaamiinennrrteesssifissottraannetstthffeiinrn.iisshheess for for pterxotdiIIltutecsiie,ss onntioholtetrettvshhaieesrtiaooonbubtjsjeepcccattopiimvvemeeresoroifcfziehtsahi,lissanpccrdhhoadaspuppctetteecsrri.alttootArserreaevttvmihieeewewncthttshhaeepfotmermreleetttahhitoohledder.iuumsspeelddiettsoo, acpeanmrmdopp,dhhuawacshseieissrtehwwieiilllmlvpabbareeriotppaulnlsaatcc,ceeododmnppmrsriieommrmacaeriraiiolllyfyptroohonneduasacpetrrscee.ivvfiiiAeecwswtteoohcffehniirocntdlhduoausgpstytrtreiiaarasllotipcatillpeaiptcliieamcdtapitwilooiientnsshs, tfathhnoeedrssm,eeawnuuhcsseeeesrs.e.chiAAamrnnapcoaaterttttrteaiemnsmttpip,tctosnwwaiisnlloldmaalelasslooosofbbteethoemmeasapmddepeechiafttiosocizptpeeoociihnntntthoeoolouuutgtlytttihhameesastuouencniiieaqqctueuodeenowppmeeiitrrch- aCfaoddorvvvmaeanrnatentaadcggeeeasrscehiinnanorattthchteeneercppiesaastrristtcaiiscrciuulallyaanrrdheaeannnldddsloeuusdsteoe..oneTTmhhtpheeehavvbsaaiarrziiseoosuutssohfettoorppueiillcctaisstmivwwaehtheiciccohehmcmowweinrilolcllmiabbilcee mdmceoeervvrieeittrleooodprrmuauesrsneaagtgene.ho.atsTTnhhoeneeclreeyessohhacaarcvviuleeyrrbbheeedaeennnidnaaletnndhueummopnbabeestrhr ieoovffebrtaareoseiasatsseonwwfhyhreererlesea.tittvhhSeeeocccmoooemmmmommeftreehcrreiccsiiaaaelll araadrereeeavaasesslwowoipfillmllwbbeaenegttetrrh,eaaatsnteeaoddmnielilnynyaao,cmmgculuuaccrsrhhsemdmaoniorndreetcchcoeeomrmpapmlapieslctetstf,eifvfhseaahstsihooiaontle.nrn.eOaOyndeyneaerbosoe.ffetStnhhoeermeiievmmipopeofworterthtdaeansnitent Varoelasumoef 1usoafgeth, isnasmaemley,segrlaisessa.nd ceramics, has already been reviewed in Volume I of this same series(2). IILI.. HHiissttoorriiccaall aanndd EEccoonnoommiicc FFaaccttoorrss. FroT"mThheecarwwlooyrrddh,,isfftlouurooyr,riinnmee,a, niiss hddaeesrriivuvseeedddffrtrohomem mttihhneeerLLaalat,tiinnflwwuooorrrdsd,p,afl,luuteroree,,Acttcooeleffllrooawwt.e. tctFhhoreemopmmmleeeteltneainrglsgyepppharriorosactctoeeisrsoysn,oofofmfmmaatanhnneyyh"assesiillliiauccgsaasett"eed mmftirhinoneemerrmaatllihsn,e,ettmrhaheetel,arrelef,bblyuyoFpporseleprlmaorrwi,timtntioinggtttahthchteceeeminlmeotnreoraogrte-ee dcdcuooucmnctstipiuoolmennptetooiffsoettnphhaeeorfaootppifoeeunnno-r-ohshfepeaaathrrrtethin"ppcsrrrloaoecgacesses"essdfffrroooarrmpissdttlteehyee,ell msmmtaaaennttuaifulnaf.agcFcttauoutrlrleoea,,wboUiUunntngiittSteeh0dde00SSintttaatorttoneess-s consumption of fluorspar increased rapidly, pienr1y9e5a3r6i,n p1.88154).and reachinag maximm of per year in 1888 and reaching a maximum of approximately 645,000 starting at about 5000 approximately 645,000 tonstons tons i5n01%FF9ooo5fr3r mmt(h3ooe,rrepet.ottth1ha4ala)nnf. 66l00uyyoeeararsscttohhneesusstmceeeedl.iinnTddtuusissttrriyyntaaeccrccesootuuinnnttgeedtdoffonorropaeprtporhxoaixtmihmaetauetselelyy: ooo8fff0s%fftluueooolrfrssitpnhpaear19tiio2nnt7ta1thlheefloluopeospersesntnp-h-ahahrneecaa4orr.ntt0hs1uppmrroopeccedeer.sstssIothhniaasissnindd1teee9cc5rrr7eee.saatssineegdd from 7.4 Ib to note that from 7.4 Ib perthe per tonuse ton of in ss"AtteAesseeFllFiiminnnaggn1eeu9rrf2at7ecatttlaou.lr.leepp,soisicnntohttuaoopnulutet4d.((033,w,libppt..hpa11e55r)),t,torttnheheemienllnaag1dg9oii5unn7scc. ooinnncssruuemmapspettiiioonnnhooyffdrofolrufolsurpsopraiarcr aiaFncicigisdd.tepp1e,rrloocmdodvuuaeccnrttuiiionfoangncttiiuhnnererrse,epcccaeeonnnuttfpeyrleaeodarmrssw,1,9ihh4tha1assatbbotrrr1oeo9muu5gg9ehh,nttdaaobbuoosuutitnctthrheeeacscehhaainnnggehesys dssrhhooofwlwunnoriiincn Fexigce."WpW1thh,iifclloeeovsseatctreieelnrlgtccatoohinnenssuusapmmmapopntutiifnoortonnomoofff1fyf9leu4uao1orrrststoppoaa1yrr9e5hha9aar.sscrryecemlmiaaniginn,eetddherreehllaayttdiirvvoeeflllyyuoccrooinnscsttaaacnnittd,, eii1nnx9ddc4uue9spstt1trryfyo3rhh0aa0ass,c0uve0isr0eetaddtioniinnnsaccmrrieenoaauss1ini9n5ntg9g.ofqquTuyahaenneatrtriitettiioeeassryceooaffsreffvlcueuyorocrarllssinpprgaaee,ratsffhroroenomsmhfy11odr00r00ot,,f0i0lu00s0o0grttirocoonnwasstchiiid,nn oaaf1m9m4auo9onnrggtoowwc3hah0iri0ccb,hh0o0naa0rreedetottrhihnveesatiiininnvccerr1see,9aa5ssa9iinn.ngdgTptphhrreeoorddepuurcacotrtdeiiuoocnsnteivooofefnroaaallfluuurmermaiainsnnouuinmmus,m,f.otthrhCeetohnppisrrsoougddmruupocctwttiiitooohnnn, ofFciiafggrufublrruoeeonssrffotoocyrrapr11eb99og55an77seaadrsreeeraisssvhahaoteiworvonewssioin,nnlaTTnpardaobbptllheeelelI1(ap84nr.)to. sdTTuahhcneetdiorraraneppfiiorddfigrruieirssraeeanniiitnnustmthhis.eeusCushsooenowosfnuf mffbluuypootritroooh-ne- aan carbon Ttyapbelega1sefsoarsthaeerpoesroilodprforpoemlla1n9t5s1 atn0d19re6f1ri(g5e,rpa.nt9s1).is shown by the data in Table II for the period from 1951 to 1961 (5, p. 91). 33002222..00000044 I3MM_MMNNO044885555111133 sain, wots on von cry 29 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY --_ HYOROFLUOI[|C J4!D = = m CERAMI~ & GLASS 299 wl R| nI ENilD RnfHo A tl i fl PACER Cdn z =U = wo 0H Hn Him HAH i | HH Ji HIN 0TH RT | i HoHBOLLE oH HolLgle I i tiH on 100 CLL 8 I JA IE) VIE) IE IF 1942 !944 ~946 194~ 195G ~95'2 1954 1956 195| PatoFro. 1. Consumption of fluorspar in the United States. T_T: The growtl~ in this area is largely due to the usage as aerosol propellants fo pac, Pgs he ce in fe mobs oF oo Bn pr for specialty packaging; the increase in the number of unit packages per `yyeeaarriisssshhoowwnn iinnFFiigg.. 22 ((55,,pp.. 9966).). ee ast iy fpzlofes ie frie While the commercial usage of fluorine chemicals at this time is largely py accounted for on the basis of uses listed in Table I, it may be anticipated Tt hee wil be iene er i some of he nn pes that there will be significant increases in some of the newer products hh oeben iced peea which have been introduced in the past five to ten years. pits No analysis of the industrial situation would be complete without some erent os one a te maple nd wt of reference to costs associated with the manufacture and use of these i products. As has been pointed out earlier, fluorine is not a rare element an. Preen podcton of yrs nee om repo es in nature. Present production of hydrogen fluoride from fluorspar results 33002222..00000055 aw_nossss114 3M MN04855114 30 WG. wwvee 300 H.G. BRYCE TABLE 1 TABLE I Hyomorsuonc Act vas i 1s Unie Seams HYDROFLUORIC ACID USAGE IN THE UNITED STATES(4} AA(Smmhooouruntntttwounissee)dd % used % used (Short tons) Alain Production seo wa Aluminum Production Fliorocarbon Dervis 00 25 Fluorocarbon Derivatives rani Production 1600 ns Uranium Production Convenion of als is 6 Conversion of Salts Suivi Sie Picking 00 s2 Stainless Steel Pickling Petrol, Aly ion wn a Petroleum Alkylation Eiching and Frosing Gass 200 15 Etching and Frosting Glass Others 200 is Others TOTAL [Ex wo TOTAL 53,000 38,500 16,000 7500 7000 6000 2000 2000 135,000 39.2 28.5 11.8 5.6 5.2 4.5 1.5 1,5 100.0 TABLE 11 TABLE II Phopucion or Fuuonocamsax GASES ron Faorrcaxt Axo Rirmaematios Uior-- PRODUCTION OF FLUOROCARBON GASES FOR PROPELLANT AND REFRIGERATION USAGE-- Charen Sears UNITED STATES or Milions of pounds Year Millions of pounds 1955 wo 1955 140 1956 bi 1956 170 1957 EY 1957 200 1938 20 1958 220 he a0 1959 240 1960 300 1961 320 Voreate vs Sra Pics ron Counmacin. Fuvomtsr Croacars ron 1560 1 7in TABLE III VOLUME VS SELLING PRICE FOR COMMERCIAL FLUORINE CHEMICALS FOR 1960 IN THE UNITED STATES Commi Commodity Volume wage Volume usage oivaed estimated Mito of (Millions of per) lb per yr) Selig price Selling price (pert) (:~ per lb) Flaoropar Fluorospar Hydrogen fuori Hydrogen fluoride Flooroccbon efigerants snd propels Fluorocarbon refrigerants and propellants Polyctnfornehytere Polytetrafluoroethylene 12000 1200(6) 00300 w300 10 0o0.0a02r2s5 030.2220.0-51-067070.7000 3.25-6.00 33002222..00000066 I3MM_MMNNO044885555111155 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. 30011 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY ioinfntt1hh5ee0pprroo1dd8uucccettnbbteeiipnneggroopffoffeeurrneeddd.ccoTomtmmhemarsceirbcaeilaellnlyyefsfrtroiommmsaetseevvdeertrahalaltrssooeuucrroccveeessriiynnptrthhoeecreraasnnsggeees oaarssofssc1ook5ccsiitaacottoeeu1ddl8dwwciieittnnhhctsrttehhpaeeeserpprprmeeoappunaaynrr-daaft.tioioIoltnndohoaftfhsessbuuevppeoeenlrruppemhhseotoissmoppfhahatahettydeedtrffheeoarrgttteiilrlnieizzcefeorruvssoerffriryrodomepmraoaatcppeaeastvtsiieettnese Troocwkesr ccoosutlsd tihnacnretahsoesemaatnypr-efsoelrds.the volume of hydrogen fluoride at even lower costs than those at present. 80O 70O 6GO iow i 400 200 100 1~51 53 55 57 59 61 Fio, 2 Growth in production of ses! propels in he Unied Sis 1950 1952 1954 1956 1958 1960 1962 1964 1966 1968 FIG. 2. Growth in production of aerosol propellants in the United States. |970 andIIennstTTiaambabltleeedTIsIIaIlettshheevorrleeullaamtteiioofnnossrhhiifppluioissrissnhehoocwwhnnembbieecttawlwseeeewnnhippcrrheesseeenxntctesseeedlllli2in,ng0g0pp0rr,ii0cc0ee0ss al1bbndpp`eeeBrresstyyiieemdaaerarstfeftoodhrresttahahlebeeosyyveeveaaorrllua11mr99g66ee00.f.voorlfulmueoriinteemcsh,emthiecraelsiswuhnicehveerxcienecdre2a,s0i0n0g,0l0is0t oogffronnwBeeiewwnsgidppesrrasooleddtsuhu.cecttAssasbbboaamvssieeegddlhatroognnbeeffvluoeuoxloruprimeinnceeet,e,idtss,eoommmtshee,e tooshffeelrwwleihhniiigscchhparniaacrreeeevsessrghheooinnwwccirirannelggalsyirrnaargppaiinddligllsyeyt g`nuuerppowwuweeaarircnddpgssrosffdarruoleocmsmt.sttAhihnosocssremeeiallgiissshettetseddtbeiiwnnoettuxhhlpeedecttaatapebbpdlleee,a..rthHHtheoowwseeevtlvelhierenr,sg,elaaplssirinttchghepeesrvvigoocellenuusemamraneeldlooyffmrtatahhnneeugss-eee ifnfanaecdcwittucuerarritinpengrdgoccidonousscttTtsssabooilfnfecmmrIoeoIsaTs.sttesffl,luuiootrrwiinnoeeulccdhheeammpipicceaaallrssthsshhaoot uuthlldde fall in selling fall in the general range prices and manu- the generai range tinhderi`CceCaootimesmdppraeailrnraeetddTivaettbololyettshhIpeeIeIa.ggkeeinnneegrraall vffeiireeyllddssmeooaffgeiinrnooarrggmaaonnuiincctaaonnfddbaoosrriggcaannkiicncoccwhhleeemmdigsiesttrroyyn,, there is relatively speaking a very meager amount of basic knowledge on 33002222..00000077 I3MM_MMNN0044885555111166 02 meyer 302 H.G. BRYCE ffsliuunoocrreiinnWeeoraalnnddd iiWttssarccoomm1p1,opvoawunhndedsr.se. M Mthueuccnhheeoodff ttfhhoiirss lkkunnboor~wivclaleenddtggseeahbnaadss sbbeeealeeannntaasccqqwuuhiiirrecedhd wswtihonoeucruleeldfdoWrbbeeeo,rsslttdaabbmWlleaeakttroeo IuurIrra,atanhwneiihuruemlmraerhhgeteehxxeaiafnflnvuoeeoresridtiddmeeefonwartsalsuibtthrhireeceasiimnematppsreectathuunssad.ndIIstteadiilsenavnnceetelsceoeswpsasmhraeiryncy,ht, etiinhnnteiroorerrefddloeyerrern,etttwooo tmddyeepavvekeseellooorfppacthhnneeeemrwwilcaarpplgrreoopddriuuoncccvettessssstemwwsiaeitrtnhhetsinninenevwworlevsaaeeppdpaplrilicincchaatthtaiieonoindnsss.md.aenvGGueefenlanoecerptramualrlleleyyn,,,t aaearnnnetddirreooeflfyqtteuenninertwtehhdeetytuuposseeesesssotaafarrbecelhissesoomh uuitcnnhaiielqqupuneereoetcthdheaaststfeosssrppeaetcrcheiieaaisllnevmmoaualrnvrkikeeqedtutiiiennnggtphraaeonnidddrumcssteeasllnlliiunbnfeggafcocetrfouferroerta,t profitable commercial market are required to establish the profitable commercial market can be need can be realized for these realized. unique products before a ILIII. CChhaararcatcetreirsisttiicc PPrrooppeerrttiieess ooff FFlluuoorrooccaarrbboonnss partFFlltuuooorrtiihnneeeiuisniooqnnueeeoofpfottshhieetommnoosisttt orrecemcmuaaprrikkeaasbbllieen eltlehememeneptnesrt.si.odTTihhciisstabiissledd,uuebeeiiinnngllaartrghgeee fpfKiinarssrotttwmmnto,eemmtebhxbeecererueoondfftiiqnthuhgeeeihhpnaaollhsooiigtgiseeonnnreffiasatmmpieoliclcyty.c.uipIIttstieiisnssetatihnrheeestmmhtoeoscsotptmelpereelieotccidtttrircooornnsteae,gbgalacsethi,ilvvobeereiceinlnleeegmmaetenhnndtet ogokxixnyvyogegwenennn.a,.seQQ2xu.uac8nae5tenidttivitana0tgt.iivvieen"llTyyhthottsihhseeeorppefosotpcteeehnncltottiiraaiilltnseoofnfaenttahdhreeeosnntxooycrrgommemanallpaefurtlieurtooirrrensisn,epeeccheetlllioeevcrceittlnrryoeodd1eea3nii6dss aagannnivdddeni11t..s22a2n2s.e. i2gTT.8hhh5beeossrveeit7nl)lga.arregTgleeheomddiesiffenfiteesorrefeennmcccpehehssloaiirsnniinzleeeelecacttnthrrdeoodduoeenxupypsogoutetaeenlnnattaiitaraeulslrrbbeeeesottpwfwetecehteeiinnvseefflllyouerom1irei.nn3ne6te caaalnnnedddmiemmtnosotsnstteokiongffohiwitbtsnso,rccinoocgmmopmpeobloeuiumnnndiedsnns.gt.sTIeennnmeccrpgohoenatsnisecisqzaeuleletynqhcewueiouetofnhftnuhtmschiuosisaes,lt, niiottafitissutrhtteheheeootfmmhtehosrisstcerreelemeacemcinteivtvneset tAetoouleomffroioernrnmemt akeelnxxsoottrrwefemnomr,eemllcsyyocmssottbamaibbpnllioeenugccnoodemmsnpepworoguiuenhntdidcstsa.h.lelyRRreaewcrceeietnnhgttamsrreeoessssetcsaauorrcfcchhthhaehhsaaosxstehnsseohrhnoo(eww1le%nnm0,etthnhAaatstst wffwiloulilrolltrbbisenedeudisiaseslccsiuounssrsfsooeecrddmkeltsatetecfruro,e,mlthshpe,eoweuehnnnieedlrrseggetewthtiiieccthennxatachtteeuuprrteerioaoorfnefacelgllesaetmsmaeebesnintlstaiautllcyfhfallunuaoosdrriinxnnoeeenno-iisnr(ett1hah9eec0ibb)v.aaisAstiiysss of many compoundsof fluorine for its use in rocket fuels, while of many compounds of fluorine have resulted in many other the exceptional stability and have resulted in many other uses,non-reactivity uses. A. Boo Exancrrs xp Bown Distaxess umbIInen rT"TaoafbbllseepecIIViVfAic.tthbheBoeOneeNdnnDseerrEgg9iNiee.EssRGaannIEddS interatomic distances AND BOND DISTANCES interatomic distances are are given given for for a a wnhuimlFFebooterrhreccoCoofmm~sppFpaearicriisisfsiooc1nn.,b,3o6onoAdnn,seea(Snnn,9oodt)t.Ceess--Ctthhlaaittstthh1ee76CCA---.-H HIsbbooannlddosddeiissettaantnhccaeet tiihsse11C..0099CA4,, tbwbhoohennilddoentddlhiiyessttaChanan-clc-eeoFgiiesisns 111w...553h446icAAA.h., ahIInttasdiissCaoo-bbb-vvCoiinIooduuisssr1tta.hhd7aai6ttuAsffl.uuloeIosrtrsiiisnnteeahlasiisons usutennheiianqqtuutoheefaiitnntthhttehehaaCCt ---tit-CCiiss sdtdhtiirsseuttacaontnncuclerey,e,shhhwaeeilnnotcchgeeoeuniitttwdccihaasinntcohrrrteehippnallgsaaccoaeer sbhhtoyyrnddadrironoiggrnaeegdnninuoiisnnrmleeeassslssseecntnathtisiaaabnllollynythtaaaolltllcaohhrfyybddtohrrnoeoccbaaCorrn-bbd-ooCsnn bsIIyntnrtuhaacddetduvdirietetirisooynnw,,hiitoohgffohucchtooeuduartrissseteo,o,frtttfihonheregmssaeeotribbosoont.nnraddisAsnginaaarigreenn,eeotxxrhmtterreaeumlmneceilalqyyrubeossttpnaaobbtsollieetcosaansrbooeefvvnfiidbudeoeonrnniccdneesedd. i illustrated by by the very high is illustrated by the fat heat of the fact that the heat of formation of C--F is about 20 formation. Again, the unique position of fluorine that the heat of formation of C--F is about 20 33002222..00000088 I3MM_MMNNo04488S555111177 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 303 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 303 TABLE IV TABLE IV Bono Disancrs vo oxo Exenas BOND DISTANCES AND BOND ENERGIES(s) Bond Compound DistW ancealEnpeerrgmyote Bond Compound Distance (A) Energy (kcal per moIe) on C--H oF C--I~ ca C--C1 SF S--F H--F Hct H--CI Ho H--O cc C--C oc C--C ccrCHHe4 CF4 caSleCCh SF6 HF HetHCI HoH~O cate C~I I6 ckC~F6 199 98s 1.09 136 1160 1.36 170 5 1.76 158 0 1.58 98.8 116.0 78.5 68.0 0.92 128 102 1.28 036 1105 0.96 154 1 1.54 is 50 1.52 147.5 103.2 110,6 83.1 83.0 klheecsaasll tgghrraeenaattteehrrattthhoaafnnCtt--hhHaat.t ooff CC----HH,, wwhheerreeaass tthhaatt ffoorr CC----CCl1 iiss aabboouutt 2200 kkecaall hleasvseBBtehesosaitinddheeetsrshpapoutosnssoisefqesusCsseii-nn-pggHreoe.pxxettrrretemimeees ssdttauabbeiilliitttoyy taahnneddiriinnleeorrttwnneeesssns,e, rffglluyuoorrsiitnnaeetecc.oomFmrppoooumunndadsns ehlaevcetroontihcersturnuicqtuuree pprooipnetrtioefs videuwe, tmoosthteifrluloorwineenceormgpyoustnadtes. eFxrhoimbitana `evleercytrnoenuitcrasltrourctnuornepoplaorincthaorfacvtieewr ,whmicohstsfhlouwosrinsecclominptohuenfdosremxohfibvietrya vTeorwyinnteeurtrmaolleocrulnaornpfoorlcaers.character which shows itself in the form of very low intermolecular forces. B. Botixg Pons axp MELTING Pots Figure 3 shoBw.sBaOsILtrINikGinPgOsIiNmTilSarAiNtDy bNe~tIEwLeTeINnGtPheOIiNnTerSt or noble gases aoarnnddmFossilaagettucuururrelaaatt3ereddswheffoillugwuhoostsrsoo.accaasrFrtbbrooiorknnsiens,x,gawwmsphihmleeenni,lacckrioortmymyppptbaaorerntiiwnnhggeaesnbbooaitinhlliienantggionmppeioorcitinnowttsser inaagonhnbtddleoaafttgoo$amm3s.iei7ccs oawanerniddmgaahotbbleoooiciflluiiln8nagg8rppowhoiaeinsingtthaootfsfb.o11iF22lo00irnKgKe;;xpawowmihhnepetrlreeeoa,afssk1rcc4yaa5prrbtbKooo.nnn tthBeeayttsrracaafoflnnuutooarrrtaoiisddmtee,iwcwhiiwettxhheaiaangemhm,otoloCleefeccHu8uul3laa.a7,rr wwheiigchht hoafs a88 mhoalsecaulbaorilwinegigphtoinoft o86f,1h4a5sKa. bBoiylicnogntproaisntt, ohfex3a4n2e',KC.6HIt14is, cowolbbhovvsiiiceoohuutsosh,,tahsttahhteaerroecmfffootorhrleeee,c,iunttlehharaartttwgttahehsieeegsh;mmtaoololsefeacctu8uul6lra,aarrtheappdsoolhlaaayrrdibirttoyyoicliooanfrfgbaaopnffo,lluiunooontrroootcchfaaer3rbo4btoo2hnneKriis.shaIvvtneedrriyy,s chhulaarossasneaaitmmouumutchchhhaetxmmaoofoflrrtueehoerppiooidnlleaae.rrriit`zzTgaahabbisllseeescss;ttoarrmuuscpcattotuuururerne.a.dteAAdhnnaohsotythadherebrorocissatltrrribiinkokgiinnnp,ggooieennxxtaathmmoepfplolSeet6ihiesCr,tthhheaaatvtnedoonf,f uttchhrhoaaornuuaiggcuthhmeriiitthshhteaaixscsafaaallusvvooeerrrisyydhehho.iiwgTgshhhuimmspoolcileoenccmutulhplaeaorrulnwwoedweiighgmhahetslt,,tainnnaabgmmoeipelloilniyyngt33s55p22oo..ifnTTtmhhaioisnsf y5llo6oiwwnCoee,rnngeeeavrrngegiynyc fcfuluhsuoaaorgrraieincnoteeefcrcfioosltmumiocpproioanuluesnnocddossshmaaopnnwoddushhnueedpnnsccieeansaatcfchccueoosuuilnonntwgtssamffgooeerrnlppttiesenrrgihhnaappmpoessitnttahthlseeluooorfllgddimeecssaattlnccypoorimmonmcomeersregscraicinniagialc.l usage of fluorine compounds as fluxing agents in metallurgical processing. 33002222..00000099 I3MM_MMNNO044885555111188 304 200 H.G. BRYCE Hydrocarbons ~i 0 > ofInert Gases Saturated Fluorocarbons I I 1 I 200 300 400 S00 MOLECULAR WEIGHT FiG. 3. Comparison of inert gases ~vith fluorocarbon on a molecular weight vs boiling point basis. C. SURFACE E~;ERG Another consequence of these low intermolecular forces is the very low surface energies of the fluorocarbons. While hydrocarbons have surface tensions of 20 to 35 dynes per cm, fluorocarbons have surface tensions of 9 to 18 dynes!era. Typical values are given in Table V. As can be seen in the table, the compound n-CsFls has a surface tension of 13.7 dynes per Ws cm; whereas the value for the hydrocarbon analog, n-CsH~8 is 21.8 dynes per cm. Figure 4 shows surface tension vs concentration for a homologous series of fluorocarbon carboxylic acids(~3). Of particular note are the minimum 33002222..00001100 3M MN04855119 ST. 8 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 305 I I I 2 | i :{ i; .2 : i ii i 3 i g "iHiH i i i : I il i 3 RE i : ! i 3 ii t i : i % I 3 I RSI rh T 38 = 33002222..00001111 _oisss120 3M MN04855120 = on 306 H.G. BRYCE Ss To on tn Pm ors TABLE V SURFACE TENSION FOR TYPICAL FLUOROCARBON COMPOUND~ Compound Surface tension nesperem) (dynes per cm) Reference n-C5FI~ 9.87 (20C) (10) n-CTF16 12.69 (20C) (10) n-CsFzs 13.7 (25C) (11) cyclo-CsFz60 15.1 (25C) (12) (CaFg)3N 16.1 (25C) (45) FO -- surface tensions between 15 and 18 dynes per cm. For comparison, ams rp: typical surface active hydrocarbon compounds are capable of reducing the en ner surface tension of water to only 28 32 dynes per cm. a hay of oe W. A. Zisman and co-workers have pioneered in the study of low a eg fo pe energy surfaces. Their work has emphasized the unique surface properties i of fluorocarbon derivatives. Zisman has studied the spreading or wetting characteristics of liquid materials on a variety of low energy surfaces(14,17). In preparing the low energy surfaces he used clean, smooth glass or Ee om on platinum, on which he adsorbed close-packed condensed films of various BE rent os long-chain hydrocarbon and fluorocarbon type surface active compounds. om oc In such a case the condensed films have the terminal group of the molecule ra oriented so as to form the new surface covering the glass or platinum. EZ . [ JN = _= \ AN \ A ANNM ANT \ Se osha toms fruition Fro. 5. Definition of contact angle for a drop of liquid on a solid surface. 33002222..00001122 sen 3M MN04855121 A ---- INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 307 mn dc ores350 hvmur he oc ars or 3 Zisman and co-workers(l~,16,18) have measured the contact angles for a Loiogons ses of ral sate ti whee os rms re homologous series of normal alkane liquids, whose surface tensions are ee he psd pence Fs known, when these liquids are placed on the "treated" surface. Figure 5 rier pad ro oh i is snd coms ae illustrates a liquid drop on such a solid surface and the contact angle, 0. pig i Sama det he sovbin or enaonn. of Without going into theoretical details, the condition for equilibrium of Ye a drop of liquid on a surface is: Jor y= rm : where 7SV -- SL~/SL = =yvLV COS0 [(10]) where Te = verti sy fo ld ad sed sp 7sv = interfacial energy for solid and saturated vapor a py fo nd po 7sT, = interracial energy for solid and liquid Te a oon td a sed spr 7LV = surface tension for liquid and saturated vapor. he onion fpr of the i an fc, rly The condition for spreading of the liquid on the surface, namely anon a 0 = 0 degrees, is such that cos 0 = 1. Foes hows te mel ene the wn ae cris Figure 6 shows the relationship between the known surface tensions oo ots wt cof net srs for a series of n-alkane liquids and the cosine of the measured contact nh is eeddt ste re piherbed angle, when the liquids are placed on that surface. Three typical adsorbed So ashe ht Ted om, sdeyomine wih 3 surfaces are shown, namely, that formed from octadecylamine with a CH tm pono sh Chr terminal CH3 group, that from polytetrafluoroethylene witk a ee Fe CO wis cml groups, and the surface resulting from C12Fz6COOH with a terminal En pasoif otnat Isso lo of 1 --CF3 group. Extrapolation of the straight lines to the value of cos 0 -- 1, mn to edi. ht So ed ih the condition for spreading, gives what Zisman has defined as the critical a. Vs Fo te ohio surface tension value of that surface. Values for these critical surface 1.0 af0.8 on0.6 iPr a0.4 Rh\ NN\ \ "Octodecylarnine monoloyer "-- | , Polytetrafluoroethylene 0.2 "Perfluorolouric acid "0 rae we x ww 20 24 28 52 56 40 Surface tension (20C) dynes/cm T le Ee peN e ie tR id Er ret FIG. 6. Contact angles for a series of liquid normal alkancs on various types of soiid surfaces. The critical surface tension ~,~, is defined as the intercept of the extrapolation of straight line with the horizontal line corresponding to cos 0 = 1. 33002222..00001133 aw _mosss2s2 3M MN04855122 08 WG mvs 308 H, G. BRYCE tsteeunnrssfiiaoocnness,t,e77nes,,ioaanrreevaiilnnuccellsuuddiseeddreaiindnilTTyaabubnlldeeerVVsIt.I.ooTTdh.heeFssioigrgnni2iffliicicaqaunniccdee toooff wttehhteessaeesuccrerifitiaeccaaell clsciouoqnrnusfsaiiicdsstetimintnueggsontosfifcholcnloosvasaeae-l-usppveuaaseccfkkieaseecddreehhatyydedndilsrryioooccunaanrrodbbfeoorlnnsetsggosrrootodhuu.appFnsswo2wir2tiathhdlyaianqtetueesirrdmmpietiornnaacwllme---.t-CCTaHoHsu3,wr,feattthchee3e stlsieuuqnrrusffaiiadcocneemssmuuuusccsthhthaaabssveeppoloaleltysseutctrttrfhraaaacfnfeiluu1tooe8rrnoodseeyitotnhhneyyslloeefnpneleeerswwsciimttt.hhha-n--O-n-2CC2tFFhd2ey.-n-oetggshrrepoorueuprphsasc,,nmdtt.,hheTetoossuuwwrreffeatatcceeaa tension s--urCfaFce surface gmccrooouum mspptpso,obsseetehdldeessoolfiftqhuccaillndoossm1ee8u--pspdatayccknhkeeaedsvdepffselluururoocfrramoocc.ceaaOtrrbebnnoosnntihoenggrrovooatuuhlppuessersw hwoaiifntthdhle,stttseoertrmhwmaiiennntaa6lal --CF3 groups, the liquid must have surface tension values of less than 6 TABLE VI Curias. Suwanee TenToArBsLE) VoIr LawExomor Scaoncs CRITICAL SURFACE TENSIONS (Te) OF Low-ENERGY SUm'ACES Sua cmsitaion dyesperm 20C) Surface constitution To(dynes per cm at 20C) --cr, . --CFz 6 om 5 --CF~H 15 "or 5" - CFz~ 18 Zan 2 --CHz 22 "ci 5 --CH~-- 31 on wenn 35 --CH-- (benzene 35 in de) ring edge) can --CC12 43 dedyynnneeess oppreefrgrtcchyme..--TTChhFiissyeetmmeprphmhaiasnsiaizzteeessdvvfeelrruyyorssottcrroaonrnbgglolyyngtrthhoeeupeesxx.cceepIptttiihoonneaalslllyyuloorwwfsssauusrrcfufaucecchee ttethhenaanetstrigottyhnheeovfa---lt-hCuCeeFF-iy2-sCHH15F3ttdeeytrrnemmreimisnnaiapnlelartggecrrdomouu,flppuwohiirsisoccoohannribttohthneewogssruuaorrnuffdaapccsoee.n,,Ieft-thhhtheaelefccsrrmuiittreiifccasaaclleassisusurrlsffauaurcccgheee actaeshsnlostthirhoaiantntevffoaoalrrtuoetthmhieess---1i-5sCCdFiyFlznluessssuutrrrpaffeatareccdeec..mbTT,yhhweethhihheciihggdhihasteteswnneeofrroggaryynodpoofoflnyaavsei-ushnuryarfllfafiacdctieeemnecceoosnncathtsaalioilnnariiringndggee i"icnnThhlwweohrhuiinincceihhquattehthoneemevsvseseorryyifsthhhiiilgegluhhs--t77Cr~atvvFeaadlluuseeburyooffaftch44e3e3isdddcyylannetaeaersslyfppsoeerhrropcwcomnml,yhhvaaainntsydbblieededennynaemmeesecaahpssleuuorrrreeicdddme. iTisshttehhAeelutmnmhoioqossuuttgehnnnoeomsntswwheeoetfttttataehbbrellmeei-n-ssaCuulrrFffaagzccreesouueerpvvfseaercredrreoeisppmoiocrnlrettaeaetddrel..y shown, and the effet 6 dynes on the per cm surface seeernnieeerrAsggolyythfooofffuugoaahrssouuctrhrafferaaccbeeot,e,nrmttchhaieernbaddolixatytgaalriociinunapcFFsiiidgged,uuorrtmeehie77neasstiehhsooawtwshsisegntthiehffaafitteccafftnootrrodnaaechhtrhooeemmaooslsluooirnggfooatucuhsees gescerrrirotiiieuccspaaloifssnuufclrrruffeaoasccrsoeeecstta;eernnbCssoiiynooFnnc,A,aCy7rbeOe,,oOxvvIyaaLllliuuceehsisasc8aids,stt,hhtveehaelccruhheeaaiiisonfalleseaninpgggpnttrhihfoixoocifafmnttathhtedeeelfucylrouero1a0ors,osecaCiantribbtoooh--nne geFFxr2i,o1sutCCspOOevOOineHHcnreaaiansvveacaslll;uuoeesCeoo-3ffpFa8Tc,,kCewwOdhhiOsillHteeruCChcita1us2srFFe~zse'c~iCsvCOaiOlOmuOpeHHorohhtfaaassanpy~t'epe rf==ooxi662.m.saTTwthiehlalalyttbtet1hh0iio,ssbveefifffoeecucts:t ffperaxropiomsemtrs,lleaaovttreeerrnlessiattnutuhddceiilereosssfeiww-bipeitrtashhc,kvvteeehdrreyysetrfrrofuoeuuccgtgtuohhrfeaasnncddihsaiiiirmrnrreplegeogunurlgtlaatarnhtss;iuusrrfffvoaaerccreeaysss pwssruuiocclnlhhobuaaensscoeccbdoov.toitoonIun,ns, tthpphraeeopcpcelelroo,rssoaeerl--piplagaecncakmktheeedednrtoorfrfiobccreoormnnsdda, eextnnhissemeedduefmfffiiellmcomrt istoetafantttecea,h,tiattohihnnee.mmloOelnonelgscetuuchlucelihesssavsaueerrreyffraicprlemrsoylnayhoheutlenhdlcedeiifdnni.bttehIhrnese proper alignment for maximum orientation. On such surfaces as the fibers 33002222..00001144 I3MM_MMNNo044885555112233 ER -- INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 309 ntl A A STL mentioned above, there is no real opportunity for close packing, and the Tr uy proper orientation of the fluorocarbon group is entirely dependent on its nl} ability to move freely. This free movement is, of course, much more readily er Fh il Ch rs saced rg hoo ath achieved if the terminal ---CFa group is attached to the surface through a ----{(CCFF~a),)~---- ggrroouupp wwhheerree n iiss aatt lleeaasstt 66.. 1.0 . os0.8 \ \, \ \ \ | afrr Sm y 0.2 A. Perfluoro butyric acid ~ C B. Perfluoro caprylic acid (3. Perfluoro ]auric acid 0 P4EE TIIIEE] 8 12 16 20 24 28 32 36 Sever Surface tension (20=C) dynes/cm Fag Asien FIo. 7. The dependence ofyc, critical surface tension, on chain length for a homologous wn aeries of fluorocarbon carboxylic acids absorbed on a solid surface. soup ef tac pone gun vary Some idea of the degree of packing obtained on fiber surfaces may be hd pmo ewer gathered from the fact that a textile fabric treated with a --CsFlv group will HAA SR pe usually be wet by hydrocarbon liquids, whose surface tensions are less ors Sn dg Sm a than 22 dynes per cm. It would appear that where close packing is not me in worn achieved, then the nature of the absorbing substrate will affect the critical fi surface tension of the surface. Ln afin, ve tase i As we shall see from later considerations, these characteristics are a the basis for some unusual surface behavior of fluorocarbon type materials, Ag np A including surface active effects in various liquid media and as surface ee ee a org treatments on solid surfaces including fibers such as paper, textiles, and a leather. J D. STABILITY hs uly fn pag fo Spon wi Sg It has already been pointed out that fluorine combines with many Etca o ge 0a elements, and that in most cases, the combinations are very stable. The mt oe Tce Sn i os various compounds of carbon and fluorine illustrate this stability effect ai very well. With hydrocarbon compounds many of the reactions are due to 33002222..00001155 aw_osss1s24 3M MN04855124 310 nc. ave 310 H.G. BRYCE rareecaatcdityioononsxsidiinantvviooollnvviininngg ttthhheee pccraaecrsbbeoonnncettooofhhyy3ddrroooggreenonxybbgooennndd,,, seeuxxbaasmmtipptllueetssiobbneeiirIneaaggctttihhoeenisirr. birinenovavndoodlylvvbiionenxghgiadhhvaaaetllioooiggnneennaisnsn,, cteeahtttcce.i.rpTeTlrwweysoodeinfffcaafeccrtteooonrrfsts,,afiaaarttsholleieroaasnsot.t,x, yImmgnaaektknehe,estthiuheenbtscctaaiptrrulbbatoocionen,nttotorheffeallucuCotoirr--oiidnFdese abbbooornnnedddduibicsseehadalalsrrveaeeaatddienyy Taiinnhneaaennnsetioocrxxoeiinlddydiizzdfeeaiddfcftessorttreaantiteet,,tfhwaweshhheveireorreenyaa.sshIittnhghheethhCCea1tfir1Hosftfobbproloamnncaddet, irrteeohppnerroeeCfsseet-nnh-ttFess aaCClr-reF-edFaudycbbeoobdennesddtnaaatresse.fccTeoorhmmrepepdasaretreceooddinntdtooTfaattbhchlteeoerCCIiVs.HthHIe bbviosoenrnndydo..thiTaTgthhheaehlssleeeastubbpooorfnnifddsoireenmnnge,earrtgitgoihineecrsseofhhfoaatrhvveeee, atoUolnredffaieindnrdyd obtthrhedeeeinnCCarr-eFy-fFercrobbendoodnnittddoioiiinnnnseeTrrtttahbtteoloeoeeInssVlssyee.nntIstitiiaagillsnlliyynfioaactllalnattttyyaprpleeelasscstuoioroffpnrscci.hshieeinmmngiv,icocaltahlvleearaecctftthoiiooorsnene., wwnUieintsthdhieumrmmooolalttrtdeeinrnneaaaarsllykkoanalalciibolnmmydeeitettaliaoelssnvasootrertdhwweitiettomhhnpelssyruuacctshhuigrenmmseif.etitacalalInssnt ar5eaacltiuonisnuinmvoalvned tmhaogs:e atsheasleumcaisneusmtheanrdeamctaiogn- vwwnheehisiniccuhhmhioogccahccteuurrrreessanseiionrnngvviaooelblsvvlyeeossfettflhehoeveramtffaeootdrrimmotaneattmtiiohopnanenrooatffthuettrhheCees. mmIeFnettaatllhecAfsoluuemoopicrodiaudesneesdss,,s.twwhhehiiccrehhachhtaaiovvnee pervoecn"TeTshhhsiiiesgssh;ccehhrteehemmenireicecraagallireesssttnaoaobbfiiflkloiinttryyomwaaanlltsisooobnioeeltxxhottgaeeinnncdadstlhs.eoiirt-ssg-elaClnffi-st-toomFsaacltllolhmatttyypapporeeuessnadoobsffl.ebbtiiooollaootggtiiacccaakll ttphhreeocTccehaasrersbbeoos;nnpr--tifThlnueucoroierpriaiannlreeerbbneoooanncdkdtinoiionnnwa3nwffhlbuiuiocoohrlr.ooocgcsifarclrbabuoloononr,r.ogcaanribsomns that are able undergo at to attack elevated ttcelememapTpveaehrgreaeat.tuuprrTreehissnecsiiinnepattchlhreearceppkarriceentssgieeonnnrcceeeawcoothffiiocaanhswwaaalfrllllucoiisrsvoettcrhhayaartbtsooionmff~iclcaaaurrrbnbtodoonenrtgtohooscceaaarrtbobocoencnleuvbbraooitnnnedddg twcwelieimttahphvearhhgayyetdd.urrrooTecchsaaesrfsbbreooonnmcssra6aac0nnk0ddi,n,tgoddee1repp0aee0cnntddCioi.innngsgAoaorcnneomccvhhpeaaoriiyunnnsdllieemnnsgigulttachhrh,, tammosaaytCyhottFsaaekkeewoicpplclhauccsreerhionaagwtt tstseoeommmmpepeeerccraaaattsruubbrrooeennss ttfaoropopmccraaorr6bab0coo0hnnitnbbogoonn11dd00000bb0rrCeeaaC.kkAiibnneggcfooaarmttep66oC00u00--nCCdC,,swwubhcohehnerrdeaesaacssClesCCaF2av1Fa8Fg6ewrrieelolqqcuucsuihirrroseew.dd IstIetttambssiphhleooirtuuaylltddusruebbcseeh abbapoosprrnngroieevaeciinnhninammbgioivnn1edd.00tt0hMhaaaCttnooybnnellfcyyoormeppmuuerCrreec-i-ffCaluuloorbrfooolccunaaodrrrbboococlnanesrsabvowwanigillellproeeoxcxdhchuiucibbrtisist.t saa(tcrFaeeybeliielssisstsyrssetapsaboublrcletehdedduautseeogtbtooievttcehhnoeempapplbrreeoestsveeeenn.lccyeeM stoofaaflnbllyeeessasctossttmtaaebmbmllpeeeerriicmamiptapuulrusifertlisuitieoeisrns.o.ecTTahrhxbeeocncocoofmmpe1pr0poos0oduuunnsCcddt.,s, tCoFn4sII,nniosttfrhheeuepooaarbrbotsseceedanncrctoeebboooenffcacaoomrrmeepapalccoetttuiievvnleeydsesetnnapvvbirilrroeoodannutmmcteeeenmntpt,rp,iemttrhahareetiultrtyheheseorrimtnmhaaeellxrcccefrrsuaasoccokrkfioinnc1gga2r0rrb0eeoaarCccs.-. ostoitffoabniggslrrieetoayaf.tteefrrlTuhoooerrrsoellc,eeassrossbefeorrncmmouocorloslemeecc,puuloalauaerrndwwfseoeirpiggmrhohetdtdubbcbuueytt proorefifcmoeemaqqrbuuiilaaynllatoooitrrhoenggrrroeeffsaluttteeohrrreottcvhhaaeerrrbrimomoanualssl fftsrthraaeabgrgimmmliaetelynn.tdtsseTssguuhrccaedhhsaaeat,ssi--oonfCCicFFoca,au,rrsrei--C,eCd~saoFFruses,t, f~-ioCnrCamnrnFFeead~nn+bt~ysv,-reiCcCoFrFm~ obwihn-,ni,a--cti(m(hoCCcnFFoean~loty)nfu--aitthnesc,eiectvc.sa.IcrIiffiottvhuheees ssptihcpe.ecericgmeilesaasslsssduueccoghhrraaacssdera-at-imCoCinc-Hs-i,sH,ct,ahCr-er-niCCead-l-voCau,r1ti,eiontoryarinoinnfernrreeevaaaicccrtottiiinooomnnnvsevenswetisslswelelhlsosiccccchooummcrpopbonoestsateeiwdndesooerffneasstiiclhltiieiccvsaaee,, irrp.eereaao.,ccdttugiivclvateessssspspoeuerccccihieeesraasaamnnHiddcEstt,hhtaeehnehhdniiggSahhilflvyyya.reeinneOeetrynrggeoettfthiirecceafofcltluthuioeoorrrnooschcaaawrrnbibdlolo,nnomcrrecaatuddairicclbaaslel--sstewxlleeeeaeaedndpiitntnhggtehsttoeeo a`aplulrkknoaaddleliiurcooctrrsrasaacullkkkciaahnllgiinanceseonHeedaaiFrrtttihhaossnn-sd-.aaSrrTeieFh4eie.ssssOieesnnnttdiitauahllelleyytooiitnhnteeehrrrett hpttaroonotdeff,lcuutmooirrveooetecasaslsrrc-bbt-ooeonnxncrroeaafpddtiivccetaahrlleyss tituhhnniidntnheefrfiilplcmmrrssaecsookeffnincttgehheeocfommnefedtutaioatlirioofunclosua.rorirbTdiodehnesiss,r,aidwwsihchidaiclcushhe,,, tabboeeesstiihaddleeesssopribboemetipiennecggrtimvcceeooammbaplpcletle;ietoteenblluyyotfsssttvaaoebbmrlleyee in the presence of fluorocarbon radicals, are also impermeable; but some 33002222..00001166 I3MM_MMNNO044885555112255 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 3s1n1 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY oorfeftathchteeivmmityaaorrfe kklnnaooswwsnnorttoocbebreeaccmaaittcaallsyyussrttssfaffcooerr,fflolufuoocrrooouccraasrrebboiosnn drreueaaecctt1ii0otonnhsse.. TTfahhceet utunnhuutssutuhaaell rfaflelnuaudoocrrttiiihdvdeeiertssyefoooofffrssegiillolaificsfcoseonrnornaanoncddeprrahhomyytddiercrcooisggvueeernnf,aa,cctSSeiisioF,Fn.4sofaacnnoddurH HseFFisrreedssuppeeecctttoiivvetehllyye,, arfact are gascous that tile gaseous maensdcFFitllhauuleoolrryreoofaoccvaarierrlbboaoofbnnflesser aapnrrroeeopdqqruuoucittiteteecktnissvotteaawbbanllceetaisottoonF.Crr-aa7ddi5iaa,ttiiaoonnnd.. coFFnoosrriseetxxinaagmmpopllefe,3, maaixcctooummree- of Cog and .CuF140, has mercially available product kbneoewnnsuabsjFecCt-e7d5,toanvadricoounssidsotisnaggeosf oaf gamma mixture of CsFIs and c-CsF160, has been subjected to various dosages of gamma Tam VI "FABLE VII Exrosces 0 FC-75 0 Gaus ap Beseraon Raoaton EXPOSURE OF FC-75 TO GAMMA AND ELECTRON RADIATION Devs repre Dosage represents Vioity | Dent Hydeolrbie Viscosity (nO) QF Chootdaefart) (cs at 25C) Density Hydrolyzable fluoride (25oC) (o/; of total fluoride) Smras Starting materials Tne 1 x 10s (gamma) Slleemmn 5 x 10++ (gamma) 0k Irene 0.75 10~ (electron) inn 3 I0~ (electron) Sie 5 x 10~ (electron) oo0.800 0.974 2052.115 08%0.855 11.420 202.850 170 000 1.770 moo 1.783 Lom os 1.979 Ian om 1.804 -- om --- om -- 0.00 0.07 0.35 0.07 0.23 0.53 TABLE VOT TABLE VIII Compa Seaman or Faomocamons wi Hrosocimns 10 Rapin COMP.~RATIVE STABILITY OF FLUOROCARBONS AND HYDROCARBONS TO t~ADIATION Compound Zon Go eGno Compound - GM G (Gas) G (Poly) us eran - om - n-butyl benzene isopropyl benzene fr Ss = n-C~Ill4 ni 2 is z n-CsHls Cricin 32 o3s = C~F~C~FI~ cr asus z CsFI~ cro [I = CsF~O Gor B C+F+ + Cans oom om C~Ho Cr bos zo C~F~ --9.9 ->2.2 2.75 3.25 2-3 0.33 0.18 3.8 4.48 0.75 0.5 1.0 0.088 0.045 -------- 0.93 2.01 erraalddeiicaatttiirooonnnswu,isinngTghbbeootthhFC2a.7ss5ppeenwntat sffuuseeellacleelledemmeiennnttspsseoocuuirraccleelyaannpddrepaaallrsoeod.hhiiagghlhueemnnieenrruggmyy cCecalaienntcsest..rroAAntsshs(e~ssLhhgooawwTmnnhmeaiinn FrTTaCayab-sb7ll5eoerVVwItIaLhIs,e, stthhehiaeeglehrrdeeessunuinleltrssgsayaprreeeeclieeaescslstlsyerenontntpisia.ralelllpyyWairtttehhdhee ssaiaalnummcmreeeisnwwiiunittmghh. either the gamma rays or the high energy electrons. With increasing 33002222..00001177 I3MM_MMNNO044885555112266 an uc. sees 312 H, G. BRYCE sddouosmsaaaggbeelytthhdeeureee iitsso4athssieiggnnfiioffriicmcaaannttit oiinnnccorrfeeaahssieeghiinnerbboomtothhlevcviuisslccaoorssiitwtyyeiaagnnhddt density, predpreondsuitcyt,s,prbey- scfcuraamarrbgbaomobennlnyttto0sdccuoaarerrbbftooolnnutobbhrooeonncddaforccbrllmoeenaaavvtriaaaoggdneiecaaaolnnfsdd.hssiugubbhsseeerqqmuueeonnltet crrueelccaoormmbwbieinniagathtiitoonnproofofsderuescsutulslt,tiibnnygg fnruamgIIbmnneerTnTatasbbolfoleer hfVVlyIudIIoIrIrIooccddaaaarrttbbaaoonniiss raggaiindvvidecenanlAsccu.ooormmoppcaaarrriibnnoggn,tthhece orrmaaddpiioaattuiiononndsssttaaabLbiiEllii.ttyy oToffheaa neeusmulbtsearr oefxphryesdsroedcairnbotenrmsanofdthe fluG foarocctaorrb,onGbecionmgpoduenfdisn(e2da,zsl,2th/)e. mTurh.e rbbeeenesrerurlogotfysf sammrboeeololeeerxccbupuelrldeeesssbsyeoodffthittnehhtemeeartssmeuurbisbassoltt,faanntThccheeeeGiinnsfuabqqcsuutceoersrsit,tpiiGtooinnsbeppuisrrnoeogddduudtcceofeeiiddnnedbbdiyycaast11et00ht00ehenetevvuympooe-ff. ogoefanfsemmergaoatyuteseraripbiaraslolodrppubrcreootdddsubuacycreeedtdh.p.eromFFdooaurrtceeriiindnasslttp.aienTnrcchee1e,,00sGGucgbvuaossc=fsr=ipent33eisriignunyddsiieaccdbaatstteeoossribn33eddiimmconaoltleeaecctsuhualelmeeptssylepoo.eff gSSdieaimmssietilorlaoauryrslleyypdr---poGedGruyuc1it0isnn0ddaixricceoaatpfteerssoendtthehueercgennyduampbeubsroerr1ob0omef0fdmmeobvlobyeloeacfcuueclenloeeesmsropgoforyftuthahnbeeds.ooorrriibggeiinndaalilnccooammspapmoouupnnledd. tdheesGt"TrTohhyeeveadddlaaputteaaesriin1nfc0oclr0luudeAdveueddoorfiionnecnTaTeraarbbgbolylneeasVVbIasIIroIeIrIbissesidgrrnabaittyfhhieeacrracnssotkklmeeyttpcclohhouyyw,n,edrbb.uuttthdadnoocessthssehhoonwworttmhhaaaltt oatahlfliieppthhhGaaettiivccaarhhlouyymedadsrtrooifcccoaarrrhbbyfolodunrnsoos,rc,oaacarannbroddbnosii.nnnsffAaaaccrttesaausrrrieevgensayittfieolcefaaanssttttlhyeaappllpopirwrtooeeaarrccathhtuihirnnaeggnottnhthheeerssatntdaaiobbaritimlliiiotatynyl rmroeefassniitssyhttaeanwnccaoeerrokoomeffrasftfillcuwuoeohrrroyeocdcanarroorbbctooancnrabrmmoeanfatsute.elrriAioaallsssduellrefeviaaenddeyss tptoooufrccitoothnnyeffuuolsfsiiitntenghrgaetccuosorntneaccrlltuouissnniigoonrnmasssd,,tisasriitininoaccnlee oocmrararnbttoooynaaswvv,oooiriidtkdemusrsuseeswtooeffrbeerreenaaeoccmtttpiivvcheeaarssseiuufzrurfeflaadcctoeeassgdasseiuufniccnhheth3aapsstuggrltiltahaysesss..opfrIIenntshetetnhhceesetaccraaotssfieenlgooesffmsffalsluttueoaorbrrioloae--l icmaprburointsi,esitwimllugsitvebeveermy pehrraosinzeeodusargeasiunlttshat the presence of less stable impurities will give very erroneous resuits. E. Eurcraiea, Proves carbOOottnhheecrroppmrrpoooppeuernrttdiieesss awwrhehiiEcct.hhheEaaiLrreeECriineTnfdRridIacCciaAtticiLvvaeePotRiofOinftdPvthiEhceReeTsllIooEawwSndppooltalhreaizrrabidiilzeiltayecbootfrififflcluuiocorotronoy-.- ssctaaarnnbtTossan.blceom1Xpoguinvdess are their values of refractive indices and their those properties which are dielectric associated con- with tpthaheretTinncaooubnlnlpaperoollInaaXorrtenngaiavattreuuesrreetvhaooelfuf4evaservvoyaarfriilteeohttwyoysedooiffeplllreiioqcqtpuureiiidrdctiefcflsolunuowsortrohaocinccatahrsrbboaoarnnnedccaoostmmshopepocoiulaunotndewsdd.sd.wisiOOsthF-f spppaoaattmriiteoioocnnuflfftaaarhccettnoooerrlssteecwwtarhhrieciiacclhthha-e-p--apslsviecwwrayeteiolssonhhswa.alllldTihsseeeleeecetllraaixtcteertcr-o---rppnllsealatayyonmwtaavsennaalliinummdeyppsotorhfrteotarannlrottewfrrrooadllceeitsisiioinnn- index are also shown some of the electrical index are also shown in the tbe applications. in the table. The extremely low values for refraction F. Pouanrry or Oxipss ox Niratoes ax Esrecr of Staveruas ThF.e data giivn Teabnle POLARITY OF OXIDESIXORemphasize NITRIDES AgNaDinEFtFhEeCsbTilOitFy oSTfRUanCTcUnRvEiron- `mmCeeonnTmttphooeouffndffdalltsuauoosgrruiiinvcneeehnaaaisttnootmTmhsseab(ttloeoCaIFnnXyee)uweatamrNlapiloihzzraees(iCztthehieeFa)gppzaoo0ilnl,aarrthbennyaaattabuunirraleeiltoyoogfoyffwaaaintmmheoonlhleveycicdruuorllonee--. cpcCoaaolrrmabbroopnncohuttaenerrrdattcsiiaearrsry.yucaaThmmhiiainnsseeatsshseosorur(mChep3ttehFireTors)ns3Nimmsiieoggnrhthtit(rCebb4leeyF9aaw)ssr2ssou0nu,mgm,ebeddyssttaoomnaapplyooobgssseyeesswsseict4ah ddhfeefyrfiiodnnmriiotteae- survey of not only the electrical polar character. This assumption survey of not only the electrical properties but also is entirely wrong, as properties but also themay the boiling be seen boiling points. from a points. 33002222..00001188 I3MM_MMNNo04488s555112277 sn EAT INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 313 $i12 [fevesan3 <k 07 233322, HELENE g|||8HJ.ue;pEamsaR zznaesRsne H3| HFPig VVVVVVV samnnens : Ree 3: i pasmsan H14Nc5e, ssagact Fi aananast iis snrssses 3Ioaziasd2d3 33002222..00001199 ses 3M MN04855128 sue wo. mer 314 n.G. BRYCE For al nents nd puspscs the presence of the ivugen or the oxygen For all intents and purposes the presence of the nitrogen or the oxygen tom in th shove Artes doc na contribute any pla chris to atom in the above structures does not contribute any polar character to hemoles, Hen, moe rope 0 eer sah aorothon om. the molecules. Hence, it is more proper to refer to such fluorocarbon compounds 5 Rarucirhon side or oxide, Ther ha to sce hen pounds as fluorocarbon nitride or oxides, rather than to associate them i oil rapes of hydocsbon miso chr. with typical properties of hydrocarbon amines or ethers. TABLE X ProorCotma 12: Comos Pcs Courses PROPERTIESOFCERTAIN12-CARBON FLUOROCARBON COMPOUNDS Compt (C0 Cat CRON Compound (C6F13)~O C~2F26 (C~Fg)3N Bem ws Boiling point, C 172 175 Posmc ea Pour point, C -90 42 VEiremo aw -- (ASTM D-97) om177 owam -50 Viscosity, cs (25 C) 2.11 -- 2.96 TabXlthee fc of structurei show fo sic of weve carbon In Table X the effect of structure is shown for a series of twelve carbon uorcarbon compounds, i il be abs that all compounds bal fluorocarbon compounds(24). It will be observed that all compounds boil a bout the same temperature. On the tbe hand, + maced dere at about the same temperature. On the other hand, a marked difference Shows uy in the esing pots. CaF 3 31 3 oom empersune; shows up in the freezing points. C~2F26 is a solid at room temperature; hres the othe wo compos 3 kd, With ecio pots of whereas the other two compounds are liquids, with freezing points of 50nd 90C. rspectivly. The presen ofthe oxygen nd icogen -50 and -90C., respectively. The presence of the oxygen and nitrogen toma pls an important uk in oneting mal SRY to he atoms plays an important role in contributing internal flexibility to the molecules hee vermin the normal seni ec of a Busrocarbon molecule, hence overcoming the normal stiffening effect of a fluorocarbon ainchain. 6. Sowomuiny G. ,.~OLUBILITY "The slit eaionsips of lrocahon compounds ae sho quite The solubility relationships of fluorocarbon compounds are also quite unig, Hhdcband and Soh have show ha th Shemodyoami unique. Hildebrand and Scott(~) have shown that the thermodynamic properis of sluonsinvling wo components depend upon the sae properties of solutions involving two components depend upon the square Fhe ene beni the vloh of 3 quay 8 fo che of the tn of the difference between the values of a quantity ~ for each of the two Componente. These b value have brn tnd sob paseo components. These ~ values have been termed "solubility parameters" cd have been emi wil he square sts ofthe nena pres or and have been identified with the square roots of the internal pressure or Cohesive ena deitiesof he pu substances The scab pramter cohesive energy densities of the pure substances. The solubility parameter foe a peste subse my be Sends for a specific substance may be defined: J [Ca @ where E cnofcsaporriseion ofthe ure component and Ve moll where E = energy of vaporization of the pure component and V its molal lume lt the ame tempers 7. he tern, SEV] is de iene volume all at the same temperature T. The term, AEv/V is the "internal presse or esheive nergy deny." pressure" or "cohesive energy density." 3300222..00002200 W_NodBssi20 3M MN04855129 INDUSTRINL ASPECTS OF FLUOKINE CHEMISTRY 331s5 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY theW Wrhhieserrneeotthhheeeastsoololuufbbimilliiixttyiynppgaarraaanmmdeethteeerrnssceffoortrhttewwtoowlloiiqqluuiiiqddussi,,ds5~,iaraaennddmi3~s2ciaabrrlececeiqqnuuaaalll,i, ptrphrreeooaprpoe,orrtitsiciooonnmnsops.l.heW Wetaehhteemonnifscttmihhbeieixliddinitigfyffeearirnesndncncehoeebbnleeocttnewgweteehreeennpto5~ws1soiaabnnlliddeq;ub$is2adnsbbdeeaccroteomwmmoeessispchssuiuabffsflfeeiicsciiienemnnattallylyyl goccoorfeeetxaxhitise,stt.ctowAAmossplttlihehqeteueiaadmsbbssidooselclcuiurbteteialsivvteayasll,uuieesunoontffiol5$lfIo-o-nr~gl2evriignnepccorrdeesiaasfsisfbeeeslsre,,e;ntthchaeeensdmmtuhtutwetuyuoaahllpahsvsooeallsubeubbseiicllmiotiimaeeeyss aoallfmmtoWhoshesttitliiwnneoffiitnnlhiiiteqteeusssiioidmlmsuaablldileaaicnntryddeaadaslleemmsp,oeosnusttdns"t"icclpoorfmmoipmrplalleraeicrtlegey""e oidinnnisfsofotellharueebbindilcliiiettfsyyftriihseenrryceeeaahccaihhvneeded5..bveacloumcse, iiVttiiissW =aallhssViooaleaafmtfhVuuen,ncstotciohluetnbomiiofltfihottytehhnceedoemnmpdooeillntaaidllosvvnopoflroluirmmtcsaeors,mi,lpylVVe,,otnaaenntmddhisettchhideebiifttlfeeiemmtrypepeniercsraeattuuirnreesSs,.vW Walhuheeesnn, V1 = V~ = V, then the condition for complete miscibility is Vie, - 3 < 2RT) molaCClaallvceoulllsuatmtieoo,nn ooVffrt,thheeanssdoolluutbhbieVill(iihStyyeIaptp-aaorr~afa2m)mv2eaetpt<eeorr,,2izR,Sa~Tt.,iorrnee,qquAuirliefss"kk,nnooawwtlletehddeggeedeoosffirtt(heh3ede) mteomlpaelravtoulruem.e,TaVb~l.e, XIand itnhceluhdeeast doaftavaopnortizhaetitohne, rAmHod:yrvn,amaitcthperodpeerstirieeds temperature. Table XI includes data on the thermodynamic properties TnL Xi TABLE XI Tuemvoonsue Porm or Su oF Crcic AD NoRSAL ALKOAANES THERMODYNAMIC PROPERTIES OF A SERIES OF CYCLIC AND NORMAL ALKFORANES FormanTTT Name hp[aCuRm (aopner aa Gamb)e (momner Formula Name Boiling point (C) V~SSK (cma per mole) AH2~sK (kcal per mole, estimated) ~sK (cal per cm~) t Cite toe n-Butforane Ci retone n-Pentforane Cr atom n-Hexforane Cit tiesto n-Heptforanc Cin Otome n-Octforane Cin onto n-Nonforane Cn ane cyclohexforane Chie mdonl adsbetonne methforyl cyclohexforane 2 ws os --2 163 ws wm ae Ss 29.5 183 saw 21 se 58 205 Be owo m5 82.4 227 mE ow 8 104 253 mm a 5 123 279 whe 6% ab sublimes 170 TIS BS 7 60 77.5 195 5.0 5.2 6.0 5.5 7.1 5.6 8.1 5.7 8.9 5.7 9.7 5.7 6.8 6.0 7.7 6.0 ocoaffrabonnnuusmmibbneegrrenooeffraffllourohoarcovacerarvbbaoolnunses.s. oAAfss"ccsoaalnnubbbieelissteyeenpnafrfraromomemtetthhrii"ss bddeaatttaw,,eethhneeffallunuoodrroo6-scuabrsb"TtoTaaannbbcslleeiesn.XXgIIeA1Inseggrwiiavvoleeushsladssvooelbluuevbbiaipllluiritteeyydsippocaaftrre"aadsmmoefletruteobermrilivvttayahlleuupeeasssorlaffumoobrrielta2ietrynn"uurbmmeeblbtaewetrrieoeoonnfsfh5ssiecpallsenecddctiees6dd-. csscuuuabsssssleteauddnbcaaeibbsool.ovvfetAet,,ishtctewhheoemruaeeltdeiirssbiaerrleespaarsiseonodnnTiaacabbtblellyyde ggfXroo1ooo1mddwtcichooterhrrreteslohlaaelttuiifboolinnuliotbbyreoecttrwaewrleeabeetoinnnosnttshahhneeidptastcuhdtoauissale-l vAsvoaualllouuurbeeossicliatpprierrbseeodndoisifccttehehddeavmeooannatertutihhnaeeilsqduidnieifffTiepearorebsnnlieccieeoXssnIIiiinnnwi"t"thsshaootltluhubtebihilfeliliyuttyyohraoppvcaaearrraabemmoxentetrseteerarmssn"e"d.l.ythTTlohhosewee f"lsuoolroucbairibyonpsarhaamveeteea"uvnailqiuces position in that they have extremely low "solubility parameter" values. 3300222..00002211 I3MM_MMNNO04488S555113300 316 WG. mrves 316 H.C. BRYCE Lp ------ TABLE XII ~OLUBILITY I~ARAME'I'ERS FOR SELECTED ~UBSTANCES Phosphorus Tome 5 ho Iodine er 3% 3 Sulfur Pyne wt 107 Pyridine Clr indie a io1 Carbon disulfide Corben 0 oe Chlorobenzene Chloroform Sone o 3 Benzene Ei ote " i Ethyl acetate Coton echoes 3 i Carbon tetrachloride Creermne 0 x2 Cyclohexane Nel cbse 128 a Methyl cyclohexane pray 1 io n-Octane Em ee 105 is Ethyl ether icpne w is n-IIeptane ican 2 5 n-Hexane rene i 7 n-Pentane 70 59 136 81 61 102 81 89 99 97 109 128 164 105 147 132 I 16 14.6 14.1 11.7 10.7 10.1 9.5 9.3 9.2 9.1 8.6 8.2 7.8 7.6 7.5 7.5 7.3 7.0 manFHyiaaovvfiinniggsrreecvvoiimeewpwoeeuddnssdoosmm,eeitooffwitthhleelbccehhaarorafacctitenertrieisrstetisicct pp1r0roopcpeoernrtstiiieedsseroofftffhlleuuooirrniidnnuees,,traainnaddl maauppnapiplnqliyiucceaaottpfiioroinontpsssefrfcootorrimettshphiiowssuhrrineecdllhaast,tiitvvihteeellyywy ipnnloleeswvsbeescclsloaa.sfsssoinoftfeccrhheesemtmitciocaalclsso,,nbbsieedaierrinnggthiienn immnidinnuddstrttihhaeel unique properties which they possess. IV. Refrigerants and Propellant of mIIennth11a99n33e00 aM MnididdggltlIeheVyay.neaaR,nneddfirnHHigeewenhrnniaecnn(h2tess)aalddnilissdocctooPvveearrrloeempddoesltttlhhaaanatttlsvvlaaorrfiioouutssheddeehrryiidvvaratotiigvveeenss oaaprttfooompmmessretthiwweaeesnrreeefoarrrneeppdpllraaaecccteehtddiacnabbelyy,lyiffnlliuudoowerrahilinniceerheaafnnaedgdl.el-r-ccaohnhrtlloso,rraiilnmneTeohsaaetttyooammlswlse,-,r-eohh.faaddtnhoettnhhteeohxyidddceerssoii3grrneeenddd properties for practically ideal refrigerants. They were nontoxic and TABLE X11 FonocTannRAswtomasnt AoTAPBrLoEsXANITIIS or Mon Counpocis.ce FLUOROCARBON TYPE REFRIGERANT AND PROPELLANTS OF MAJOR COMMERCIAL IMPORTANCE Cote Compound Methane series Code Compound ri cor F-11 Fn Con F-t2 Fn co F-13 Fon F-14 Ea Gior F-21 ER Gin F-22 CCIaF CCI2F2 CCIFa CF4 CHCI=F CHC1F= Code Compound Ethane series Code Con~p~und Fan coco F-112 Fil Couredr F-113 Ells Canear F-114 Fas Cake F-115 CCI2FCCI2F CCI2FCC1F2 CCIF=CC1F2 CCIFuCFa 33002222..00002222 33MM_MMNNo044885555113311 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 317 nonflammable. They were first offered for sale in 1931 under the trade- mmaarrkk,, ""FFrreeoonn"" hhaallooggeennaatteedd lhlyyddrrooccaarrbboonnss bbyy tthhee KKiinneettiiccss CChheemmicicaall Division of the E. I. duPont de Nemours and Company. Other companies in the United States llave since introduced the same products using their ite LdSe ns cme pb ge own trade-names, i.e., "Genetron" (General Chemical Company), e co oe te B5i, Gcaor ne(,Co nCedm"Conr" Ceoy "Isotron" (Pennsalt Manufacturing Company), and "Ucon" (Union Carbide Company). All the above companies have adopted the same code numbers for the same compounds. Those having the greatest commercial usage are listed in Table XlII. J A. PROPERTIES There are many factors that must be taken into account when selecting Seft n maben nn cin a chemical for use as a refrigerant or an aerosol propellant. Besides boiling point, pressure, stability, toxicity, and flammability, such factors as molecular weight, density, compression ratio, heat value, temperature of a4] 1[dA Tl ETN Lt1Aa TNFoz eTTE] Ye E Enna . CH, FIG. 8. Properties of chlorofluoro derivatives of methane. cx, 33002222..00002233 3M MN04855132 3s WG. mrvee 318 ~. G. BRYEE ecctoocmmpprmereusssssitiooann,l, occbooemmpcprorenessssisodoerrredddii.ssppllaacceemmeenntt,, design design or or type type of of compressor, compressor, Hetce.,AAnmnuggeesrtaappahhlsiiioccs bqppeurriecetsoseeennnuststiaadetfteiiuroolenndi.nwwghhiiivccihhng wwaaabssettddeeervveeullnoodppeeerddstabbnyydinM Mgiidodgfgllteehyye paarnnodd- ptpHeheerorntstniieeec(sswZhSooi,ff2c9haa) hinnsauuvmmqeubbbieetererenuoofsfseoftthuhweleissdieenelffgyluiuvoaoiicrncnigneeep-a-tcceobodnentftttaoierinrniuiunnsneggdacecroosrmmtepafpnoroduiugninnedrdgsasn,,otsfsepstahpenecedicapiaalrllolslyy-o atahsso""siaseneerwrtoohhsseiaocllhg""rhppaarrpovohpepeelsbllhelaaonentnwstns,s.oinwiFdiegl.yactcheeptreudlefsorofusseuassbiretfurtigoenrawniltsl and also apply to tstyyeppriiiIccenaasllt1hggerrioolgnulrppassbpehhhnaasovvhtiionenwgdg ntoohnnaienet wFcchaaigrreb.bnoo8nnthtehaattefoolmrmuuolreppiseenrerocfmmoonsolutleeescncbututliletenu,,ctrioooernssttwehhsieellfmmraeopetmpthhlytaahnnateoet osoiefnfcrirCCeesHHa.s2FeIFst:,2wR((iFlaFl-m-3b3m22ea))bniottolotetdCCyHHtdhFFea,catrew((aFFhs--ee22sn33,))t,,haentthdhfeelutbbooxoroiiinicliienntgygcodppneootcieirnnnetttasiddeneescccrrreaeeasaassseieesnssd,,fircssoattmaatbbeiditllhiitatiyynt ttiChnhceeFreggar(rsaaFep-psh1h,.4.)f,lLLaiimtkkheemewwiaispbsreieo,l,ipteywwrhthdeieeenncsrttechhaheesaensfRl,guueooatnritidnoneeetovccxeooinnnctitetelynnotwtdeieirnncccrbreroeeaiasslsseieesnssgassspitiolliillnndtff,uiucrrattghthreeeedarrttetionor ssCttaFabb4iHilloii(ttwFyye-,,1vaae4nnr),dd, tllhieefesssstphttoreooxxpiifccelurnnotaiaretitusunrereec.h.caonntgeen to even lower boiling point, t remains constant and subst greater itution ipissoimmnHatadodiweenecffvrooeerrar,shheyyi,fddrrstoothaggebeeinnlfilutbbyoyyrainanaenndootctthhooexenirrtceitnhtiaytalloroieggnmecernnaeiasnssuusecchhcsloi3angssshttacclhnyhl,tloorbraiiunnntdee,,Fslttuhhabeemstmbbitooauiibtlliiilonnengg odpdceeocccirunreretaaswsienehscs.e.rnBeBaytsyheaesag,gcahaslitinoarbrriieenlfifeteeyrcrrroiainnnntggedntttotoixFFiiigicg.ni.tcyr,8e,iaanassciesrdmiemiaflsrileaoarmrslcCcihhgHaahnntlFggyee, (iibFnnu-p5prt2orf)oplepatrmeotrCmitieHeassCbwIiwilFiiltl:yll (o(FcF-c-2uI22rn))waTahannebddnlssethteiellXl cIffhuVulrrottarhhireenerre t0scohoonCCwtCenLnlztFsFios2(miF(neF-c1-ro12ef)2a,s)te.hde from CH.~F~ important (F-32) to members CHC1F2 of fully sesatathtuauIrnnraeiteeTsddearbieffl.leuuooTrXrihiInneVee-g-cecaonorncentrtaaasilihnnoriiuwnnleggns osccfooommmsueppboosoutufinntddtuhssteioiininnmaspttohehreevtianemmtweeettmldhaeaafmnnoeerbtehssreeserrmiioeeefssthfuaaalnnnlddey dtedheteherraiivcnaahtetaiisnvvegeeressiweswsi.ilinllTl hpaarppeopppglleeyycnataeillrseaooslttrwoouimltmehseehmomafblsboeugrbseeosnotfriftctutohhstneietoeenenttthahsaahnnraeeevvsesieeerrawiileeesssdo;;cfbcuoeurrersvtnheeseds rmsshaheoowtwwhniainnn.gge taIIhntneottmhchsehecapcaneasgrseeeosmoofiflnefflclpuuuroloorerpi,iennreeAt--iucecooosrnnwtntaseiiitnhnsiiunnhbggasltccoioogtmmueptnpioooncnuiosnnnddctessannhhtaabhvveaiivnnmeggaadttwlesroofooborrreemmhnoyorddrzereaowccgnaae(rrnZbbSoooLnnr acCshthsolylmoomrrmsiienntpeeceiroocnnamleoeirliettrhhcaeeunrrlego,oeffmfeluttnhhoteer.inttewwoosuccbaasrrtbibtouonntiosanttsoommcsasnppbrroeoddmuuccaiidnnegg fsosyyrmmhmmyetderrtoiricgcaealnl oror or acsoymmFFprromootmeamtrdiscaaailccnooammrtrmhameenregmcreecimtiaahlelannvvte.iieeawwnppadoiinenttt,h, anpperriimsmeaarirreyys.iinInttneerrteehssett UiinssitcceoodnnccSeetrrannteeedds Fww-ii1tth2h caFacco1ccm1oopu3unontmutssankdffisoornrignaaluhthmpnoeostsmthteehhtbaahullalffnketthohfeaentdpphreroeodrtdhueuacmcntatieiioonnsni,e,nrgiwweispi.trthohIdnuFFc-tt-h11ie1o1n,,.UFFn--i22te22,d, F114, and States F-12 F-114, and Fpr-e1s1TTs3hhieoemnsseeaktcycinpoogemmspupopoouuftnnhddersesfbruaaisslgkerrroeaeftffrirtioihgngeeerrrsaaeynnmsttsstaeimaansrri.eengaaTddphaarepopudtuapubbhclylteesioicnffaoo.lrr, uucssheeemiiinncaaalllll,ccoaomnmd- mtptherheetershrmsamioonondedyyanntnyaadpmmeieisccthaoppnrfroeopprceeeorfrtmrtiiipgeeasesnruaoontffidosqqnuuhiiattseevyes8atebmenneuusn.mmbcbTaeerirerrefuoolffplhytthyhaeesnicdffaluulfo,oarrlicilenh-eesc-mtocunoidctniaatelia,dniniaainnnngddg. dmdbeaaetaatrhpeapuvnuibebelwliiaessndhh.deedde~t18h8as.nLe However, compounds However, a fo of their outstanding properties have been carefully and fully studied few of their outstanding properties willand will obdeorrTTleehvhsieese,wffewllduiu.otohrriinbneoe-i-clcoionnntgtaaipnioinniingntgs_cchvhallororyroiohnhgyyddrorovocecararrbbaoonnwssidesaereetemccpooellororarlteeusssr,,e aarllammnogosest.t odorless, with boiling points varying over a ~vide temperature range. 33002222..00002244 I3MM_MMNNO044885555113333 Ecose | ov scrs oF vos cupasTRy 319 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 319 F [[eIEaRRE| 3 i ; [EEEFEERIE E1 RERRRTAR FEE i 4 || : :i: {t_ ae : |BEEEEs| . BErEfEaEbEeReEEyET] | EgRESiRsss zali 3 i TP- E blgoepeegy Hz IE210 i3| d| TM 383s 1 | FEl |gFpepsoptoiTizEoifReoReoEsd I || EsEuasEssuRszmangmsess || 1 53sr8eg, emdsdes. 1|588g0e,s Siiiifidiic 2888885558: | 1 bition 33002222..00002255 W_nodsstss 3M MN04855134 2 Wo. mavee 320 H.G. BRYCE Ta"sThhoposrseoepttehhlaaltatnaatrrsee aoorffepperrsiimsmeaanrtryiyaliilmmypponorortntaatnnoxccieec,iinnnttohhneecoefrilerloddsioosffe,rreeffnrroiinggieerrrraaitttiiaootnninaags,s wwaenelldll nnpasrooennppffarllaorampemdemmlalababbynllteesreauuprnnleaddceeeirrsnsgennnooctrhrimlamolalarlylinneccooononndrtdioitxthiiiyoocdnn,rssongoooenffncouusrswaraioggteseh.i.vefTTl,uhhonereoiyynnei,raarrrieeCtahtggeinemenginec,eraraaalllnllldyyy tdtphihrteeeiyypoanaarsrreeedfoiiunbnneeysdrttrieaanpnnladdacctttiuhnhaeeglrrmmucashalelllolyayrsinssretteaafbborllireegehuuryppandttrtsooogottereenmmpprpweoepciretaahlttluuafrrnleeutssso.rffiaanrre.bbeeCyyhooennmddicccaoolnlny- ditions found in actual use as refrigerants or propellants. B. Resmcerariox CimcriaisTics of tPPhrereesssssyuusrrteeessm;rreerqqefuuriii]rr~gee.eddrRattEtooiFnRllgIiiGqqeuEfufeReeffAcyytTIttaOhhnNeedCrrsHeefpfArreRiigcAgeieCrreTaaEunvtRtoISvlvTauaIppmCooeSrroafaffffteehccett rtthehfeeriddgeeesrsiaigngtnn tvvoiaafopptnohoreranddsdeyettseseteprrmemmciii;nnfieerceftthrvhieeogleccurooammmteipnprgoreefsessfslfooierqrcutddidiaissnpprdlelafacsrcpeieegmmecereinfanitnctt;; vafaonneldducmttthheeteohhhefeeqatahuttaeonotffrievtvfyaraippgoooerfrriiazzrnaae.t-drtfireioivggniecereraa.annntdTt a0tsbopleebbceeiXficccViirrvcccouuolllvuaaettmreesded bttoohhifrrloiloiunuqggguhhpidottihhnreetefp1pritrrgeeaessnrssaueunrrateetamrrfeoefggseuupclhltaaetttrihinene,ggqfvvuraaeallevnvzeteiitnooygrropooofttihhnreeter,-r device. Table XV covers boiling point at one atmosphere, freezing point, Tame xv TABLE XV [ep -- COMPARISON OF ~ARIOUS REFRIGERANTS(s0) Reg Refrigerant Boliog Freeing Boiling ay ee point oo (C) Freezing point (C) Crtial Criticai Tee temperature (C) Crval Critical aTie) pressure (psi, absolute) Ere CF4 (F-14) cir gets) CC1Fa (F-13) corCOa cur ra) CHCIF= (F-22) ityNHa cer CCI=F= (F-12) S60$O= Celcom ris) CC1F~CC1F2 (F-114) cnet 30) CHClzF (F-21) cer in) CCIaF (F-11) cocony CC12FCC1F= (F-113) Cm om es a -- 128 no Sm wm Ed -81 ET wi --78 ao iTp)ew 16 -41 Ey noms -33 Do amos sm -30 Tus Tn as ie -10.5 Gow de pl 4.7 5 Bows ow 9 wom ie 24 8% ne be 48 -191 --182 -54.7 (triple) --160 -77 --157 -73 --94 -135 --111 --35 --45 29 31 96 132.7 111.5 157 146 167.5 198 214 542 579 1071 716 1651 582 1142 474 750 635 495 ctcrariiittniiiccnaagll mtteeemtmphpeaernraeattuuarnreed,, eaatnnhdadneccrrdiiettiircciaavllatppirrveeessss,suubrrueetss oootffhennrootctooomnnmllyoynttlhhyee uffsllueuodoriiennfeei--gcceoornn--ataannittnssT,i.nhgemcehtlhoarnoefiavnordoetdhearniveatdievreivsaotifvemse, tbhuatnoethaenrdcoemthmaonenlyhauvseedrrleafirivgeelrylmooewwreThlehyeseatmt cevvhaaallnlouusereoss.tf.lhuaTTothhrioaissgdssrehherooaitvuuelalrddtivvnneoooslttuobbmfeeemccoooefnntshlsiiiaddqneueeirrdeeaddmnudaasddteiitsshbaaaeddnvvepaanunhttmaaapgvgeeeedssrieintlnhcaeertiovttuehhgliiyhss tmheerselyystmemeapnesrtuhnaitt atngreeattoerprvoodluucmetehoef rlieqquuiidremd uasmtobuentpoufmrpeefrdigtehrartoiuong.h the system per unit time to produce the required amount of refrigeration. 33002222..00002266 I3MM_MMNNO044885555113355 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY E32l1 eFFsrrpoeomcmiaaalnnlyeenfognrinsgemearliilngntpoponoeininantegt oeofrfuvnviiiiteesww,n,, sttihhgniicssettuumrronnrsseoouautcttctuoorbbateeeadaedncedciidrdeeelddiaaabdldevvaacnontntaatggreoe,l, ovoefasflplluieiqecqsuiuaiildfdloyfrfllfooobwwrotsiihssmppaloolilssqsiutioibbdnllneeaawwnghdeheeuvnnanplliatoasrrr,gg,eesrir3nsffclleowowewmlsslooorfafesllaiqrceuciliuadrtaaiqavtrreeeeiuarinnnevfdvoirolirvlegvedeledirad.ab.tliTTenhghceeoenfhhfteereaoactttl ofa number of common refrigerant, values for both liquid and vapor, as of a number of common refrigerants, is shown in Table XVI. well as relative refrigerating is shown in Table XVI. effect TABLE XE Hour Vases son Liguso axTAVaBsLoEn SXtVaIrs son Vasios Resins HEAT VALUES FOR LIQUID AND VAPOR STATES FOR VARIOUS REFRIGERANTS Retigent Refrigerant [Tr Heat value (BTU per Ib) Vapor Lid Vapor CFG wo (-isc) Liquid (3ooc) -- Refrigerating efteffect co, Te CO~ 102 Hem 2) 105 CHC1F~ (F-22) 106 i, a NH3 613 cer raz) CCI~F~ (F-12) 79 So. - SOa 183 cer cara 7 CCIF~ CCIF2 (F-114) 72 cau Ein 5 CCI~F (F-11) 93 ws s61 45 56.7 So 1 36 69.3 wos 139 474.5 = i 28 51.1 2 wi 42 141.4 5 ai 29 43.1 x @s 25 67.5 TABLE XVII Opening FrisiTaABsoLnEVaXnVtoIIrs Resonant OPERATING PRESSURES FOR VARIOUS REFRIGERANTS(81 [rm Refrigerant aPnraezoUeR)S Pressure (psigauge) At 30~C At -15C cor ws wer CO~ cure, a2) ws ws CHC1F~ (F-22) oy Ws we NH3 Ser ey na ws CCI~F~ (F-12) So fs in SO~ clncan@eng mo en CC1F~CCIF~ (F-114) cau rn) Se ae CChF (F-11) 1024.3 159.8 15t-.5 93.2 51.8 22.0 3.6 319,7 28.3 19.6 11.8 5.9~ 16.1~ 24.0~ Csee nso mebre ronysphere Units are inches of rnercut3T below one atmosphere. refrIIinngeTTraaabnbtllsee bXXaVVsIeI1dI aaorrnee'ggisivvteeannndttahhreedooppteeorrnaattiicnongngdipptrrieeossnsssuu.rreessCffaoorrrbaaossneerrideiisoeoxofsifdssettaanhnaddsaarrd3d rmmheoufurrccsihgheeprhhoaiiwnggehthrseerrrbeappqsrureeeidssrsseuumorerneent,ttshhtaaannndatthrhdee others, with a consequent much ton conditions. Carbon dioxide others, with a consequent much higher has a higher ahnotrssIaIennspoTTswaatbbealrlbeelrieXXsqVhVuIeidIIrIeIIbmyddeaanttthtaa.e iisUsnggdiievvreewnnriootnnertthsheeLeaexxbppollrooasstiivvoeerippersor.poeArltpieetsohorfefrtfreleofifuririgegienerser--- containing refrigeranatrse ants as established by the containing refrigerants are ponflammable. Underwriters Laboratories(at). nonflammable. All the flourine- 33002222..00002277 I3MM_MMNNO044885555113366 2 WG. mvc 322 H.G. BRYCE efr"TiTgaaebblrleeaXnXtIIsXX.ccoontnataininss ddaattaaoonntthhee ccoommpparrtaitivvee ttooxxiicc pprorpoertpieesoofcfvvtaarriiiooususs trehferTirTghmte~eoreadssnyeetnsff(alu3umo1oir)r.ciinnepe-r-ccooopnenrtttaaiiinensiinngwghhhiaacllhooceamsrrabbkooennssthhhaaevvmee ccrhheaaardraiaclctyteeraridisstatipicctappbhhlyyessiicfcoaarll aaunnsdde ithnerremcoidpryoncaamtiincg prrootpareyr,tieasndwhceicnlt~rimfuagkale cthomepmresrseoardsil,y wahdiacphtavbalreyfoirn suiszee in reciprocating, rotary, and centrifugal compressors, which vary in size Fuasmiiny ap Bross Proms or Vacs Resco TABLE XVIII FLAMMABILITY AND t~XPLOSIVE PROPERTIES OF VARIOUS REFRIGERANTS(30) Refrigerant -- Explosive range (Concemstion in sie (Concentration in air by one) % by volume) Ni,NH3 ana CH3C1 50SO2 peroCO2 FaF-11 FRF-22 Fal F-114 FRF-12 1s 16--25 sion 8.1--17.2 pentru nonflammable wierd nonflammable ontammble nonflammable montane nonflam~nable onammable nonflammable ontementic nonflammable Tans xix TABLE XIX Toxires or Vases Rerniesawirs? TOXICITY OF VARIOUS ]~EFRIGERANTS(3) Retigens Dursianofexposes Co350ncaseoruwtxlhasomi)resit Refrigerant Duration of exposure Concentration in air to kill or injure seriously (~}~ by voIume) souSO2 itNH~ coircar an CC12FCC1Fz (F-113) co!CO~ Cir an) CCI~F (F-~1) CHOIR (22) CHC1F~ (F-22) CARCAR, (Fi) CC1F~CCIF~ (F-114) Cait CCI~F~ (F-12) min 5 rain Somin 30 min ome 30 min 500mm 30-60 min nr2 hr in2 hr ane2 hr he2 hr or0.7 oso 0.5 0.6 peas 4.8-5.2 20300 29.0-30.0 wo10 pa9.5-11.7 wins 20.1-21.5 Reis 28.5-30.5 Tffrrhooemmy ffprrraaocctdtiiuoocnneaallwriredefefriiggreearrnagatetiosonnofttootnnennmaapggeeeratt1o0urseseesvveefrrraalolmtthhfooouuossmaanntddemttopoennrssacctaauppraaeccistityty.o. tTTloyohwpweeyssouufpbbriszoneesdrrtouoacltteaeetmmwipopeinderearaatnutrdurarenaesgs.oe.sTTtohhhfeeetdeppsmaairrpettiieeccrduualltcauaorrroelccsihhnoofgiriocccaeempaddcreeiotppyoee.mnnddssteuumpppooennrasstiiuzzreeesaanntodd type of installation and also the desired cooling capacity. 33002222..00002288 I3MM_MMNNO044885555113377 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY an INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 323 C. Arrvicarions ron Sriciric Compousos. 93.2FF-p-11o22i ((aCCtCL8162FFC)F2.,,),AihhPaaPvvuLisiInCneggAdTaaeIOxbbtNaoeSinillsiiFinnOvggRelppySooPii2EnnsCttIaFoonIffCa-~Cc22rO11oMs..6oP6lOFUFpNraoaDpnnSeddllaaanpptrreefssossruurrseeucoohff 9it3e.2mspsaisg ihtoesmtosfaost hiinaenstrsee8pccrt6tioicdcFiuid,cdetesis,s,. iuinFnsss-eee2dcc2tt e(rrxCeetHpepCenelIlslliFava:nen)tltsy,,,b eaddsseeiooadddoneorsbiraizeezerierornsss,go, luhhsaapeirirdopdd2rer5eel2lssasslniionntwggsfsto,,ermaspsnnueddcrh-aa hpaaottoulusyrrtteeoetfrrreoeafftfrrhliieuggoreerrrpoaarcnnottthd,,yuliicesstnseaa..lkFsFoo-2-2uu1ss1(eeC3ddH(CaaCss1CFlaa.i~nn-),FiibnCneCtteseIirrFdmm:eee)sddbiiiaeatitneeugseiiundnsettidhhneeahsppeararoolvodydwuuccdttetaiimtooynnpeaoorif-rf mCpcoooennlddydiitieatttiierooannifiilnnunggothruuoenneiptithtrssoydlaaeunnncddet.iiisosFnsa-lh1osofo13puuoss(leeCyffCcuulhlllzaao-sFroaCauCissfpp1leeFucczoii)araloltitesyythussysoolellevdvneeenni.tnt and as heavy and as an inter duty air an inter- imnetdrRRioeaedctcueeecnneitntdllyyt3hetth5hepenrooccndootummocpxptoiiouocunnnmdado,t,ferpci--oaCCllyi4FcFfehosr,l,ourooosccetttraia5fflfluuuaooonrrorocoaeycctchytlycoollbesounbtepau.rntoepa(eanl~el),a, nhhtaaissn bbfeeoeeonnd Taianpphtpiprlsoliidccmaauattctiieoeodnrnissaaslssuuabccohhniloaasnsstaowwtxhhi--icippmppCeeaddtearccnirradeelaamhfmoa,,rsssuaaasleavaaddapsdodrrareensspsiraienensgrgosssus,,orelppoaapfnnrcoc4aap0kkeepellsamminiitsaxebiesnss,o,floecuiottccde.. aTanttohnit22so11xmiCCc.a.,tehrAAielaltltihhbooouuusiglgeshhhaatttshh-een6octcChhlblooearreniinndneep--heccaroosmnnitattaatiivnenaiidpnnoggirn pccfroooemomsdpspuooarupuepnnldodifssca4t0aairreoep.nssirrseeaillbaansttcoiiv,vlueellatyeys nththhoieegnhtddoalaxtetiaavce,,iilnn.thTTTeahaibriblslueesueXXseIIhXeXamspssnhhhaoooswwt issbz,,eeettshnheayygpaeiddrnoomhthaithavtveefedsacsoitonmmtehfaeotott&odoxxcaiiccoppmeeflpfiffcoeeacuctttnissodanattcsorrsneeiltlnaaacttiieinv,vieenallygsy oCohhnnigllloyyhrilccenaaverrebbloosor.nnTha2hynndiddsrouffglslueeuoonerrmiinanpetehoiiamssssieezssiessnseennatttghiiaeaallilnlmyyotlhnneeoocnnfutatloocexxtiitccih;;nattwwrahohedcersorceemeaasssposttuhohneemdeppcrrdeoeessnegetnraneiccneeeinooogfff scohlluobriilnietyoirnhbyoddryogfelnuidastowmhsicihn atchee bmotohleacuqlueeoiunstroodruocregsansiocmien dnaetgurreee. of solubility in body fluids which are both aqueous or organic in nature. VV.. HHeeaatt TTrraannssffeerr MMeeddiiaa tivesIInnoftthheemepptrrheeaccneeeddiinnaggndsseecectttiihooannnetthhieen aarddevvfaarnnitgtaaegrgaeetssioiinnn suuysssiintngegmffsluuoworeroorccehhlleoomrrpoohdadeserriiizvveaad- ctwWiohvhneeedsrrieetoittfohhneemopepfrtrhohoaiccegneshsesesraiissntoedonmnpeeeeotrhoafaftnurfereeem.minoovvI riiennftggrhiighhseearsataetctitfforironoonmm,sya3asttleleoonmwwteiseror wntteeewmrimelppleeerbrmaeattpguuhirraveeseitntzoetdoa3 cttihoheen3pdprirotociocelensosswsooeforffhtirrgeeehmmmpeooervrvtaiietnnmuggrpehhe.eeraaattTtufhfrrrioeosm.miIsaannnateheplliersevovsacaetetceestddsiottnwee,hmmiappcteethreranaatttfuuiforreneectaawsnnitddllhdedbiieesscfcghihicaavirreeggnniincntoygg oaiaftnntddaht epparrwaalcocotrtwiilccedaarlltiiotttyedyamyoo.pffemmTraahatneunyryeav.ooeffTratthhghieees isisnscctiieaeeznnntptiairflfoiicccceoaasmnnsbdduwseehinniogcginhinneeeaneefgrfreiiincnntgegs uddtsheeeevvdeeelltofoofppicpmmioeeewnnnecttyrss oac0nfhataahmuebtueowrmstoorbliodinlettmmomhdueaosuysct.tybblTbieehincdecoeoloraolvleeebedldr,oa,cgggke.eennienOertrFaealrllclnyyoabulbyrycscoc,miricibnuulsmraiatoinnncygelulnioigqqpiueulnriiedadtawuwiasoatenttedser,rtitotshhuprntcooohuwgggaiehsrs ceeillhree.accmttIrrbiniccermmsonotiutonomrrsbts,he, ersaoiicrrfccyrrlcsailnffettdceeetnrniggcibiannlloeescsC,k,o.ttmhhOpeeocfncoceooolnoiutlnirsngs,gei,sissiunaacchmccoa4mcn5 yptolroiasmpnheseprfdaobtlrbiymoyecinricssri,s,rccsuhuu4llacaenthtiiondnanggs vavpoirorlol.savttIiiinlldeeeahhtnyyhdeudrmrrooecbcqaeaucrribbcoooefnnd--etdtlyeyipcpcteeercicootiaiilllciicsspormuuospspeeeroddt,n,iecnnnso.otstt, onlysuch only asas as & a coolant, but transformers, coolant, but 410 0 a non- also to provide the required dielectric properties. A. Hear Tansren Processes ofaT"TuhhieedpprrooovcceeerssssthbbeyyswwurhhfAiiacc.chheH,hhEbeeAaeaTtttiiTssRrrAegeNmamSsooFvsvEeuRecddPhfRfrarOosoCmamEiSaaSEobbSrooddhyyydbbryyogttehhnee occriirrccauulllaiagttiuioiondn osufcahfalusidwatoevre,r otihles, tc, s surface,rbeefeirt eadgtaos assuccohnvasetaiivreocroohlyidnrgo.gTehneorefafilciiqeuncidy such as water, oils, etc., is referred to as convective cooling. The efficiency 33002222..00002299 I3MM_MMNNO044885555113388 2 a. maven oooftfhttehhriissfpaprcrotooccreessssss issupparscriimrmahaatreriilloyyf aaflffouuwnncactntiidoonnvioosfcfottshhieetyhh.eeTaatht eccaamppoaacscitittyyefooffifcitthehneet fmflleuuaiiddnsaannoddf sorreote-mhmceooarvlvlfiiaenncdggtoehhrveesaaastptuocffrrhroaomtamsearacaothhoeooltiotnfgss.fuulrroffwIaanccaeetnhidiinnsvvvcooiasllscvveoee,sssitttyhhr.eeeTleeahtvveiaavppmeoolryoraasltttiiooeowfnnfibcoooifiefl3naitnffmglluueliidadi,n,dstthhoieesf ppspoouui-ttncitainn.lleccTdoohnnetetavacacetptvoawwrpiaiotttrhihvatetthhieecoonhhooolpittnrgossuu.crreIffsnaa,ccteekoiaafstt ttcceeaomruserap,speeea,rraratetualubarrestiesovreiibnlsyeexxlhocceweaetss,ssbooofnitflaithnmheegelyfbbl,oouiiildtinnhgiges shphueeocaaiftntaotoc.fef vTvawahphpoeeorrireeizzvaaattthipieooonnr,ta, tewwiomhnpihcehpriraiosistclleeiisbbcseei,srraahotmteefaddicnaaotggauaairiisnnnee,uudppaboobernsloccoroowbnnsdtdehehnenesasabttao,iotinninoaoogmnnepaalonynio,onttthhtheoerefr the uid. surface where the temperature is maintained below the boiling point of the fluid. B. Mivuaromzario of mSSaiinnncyceepiW WeocorerlslddofeW WqauarripI1mI,,etntB hhte.e w~ceh/nn~eggIN riinneIA tceeTherUreRhhfIaaZassAcTibbIleeOieeNnns fffaoarcceecddoowwliiittnhhg atthrheee operation eoxpterreamteiolny lJioitifmmbmiietteaeiddnn..y EEtphssiepepececfeciosiaraollmllfyyeoifqisuhittiphhgmiihssettsnrrputeuewedoohffearmmieracantrnh'a'efsst,fceaffclfoioorlrnitttgssiesrotoafnoccgrooenncqqomuuoielesirrsnlgsseppa,iarcceeoe,r,exwwvtherheheeimtcthhleeeelysrr ffiftoaocrrbteoooruusitnteewrrtuhcssehppaafaoccseermsttirrzaaoevvfeelak.ln.idgTIhnnwespitthhgeeehetdoopapaeriererrcaartntaiioofottnn, nloeoofafnrgleeyqqruuaaiinsppgmmeiemenmpntotirstsaaiattlneggts,rro3oosuurnntvddheehllyeiecvvaleerelles,, wwofarhhceetsonnprasttchheseeuscsshahaimmpa.ees ttFsyyoippzreee eooaxffnadeemqqpwuuliieepp,imgmheaetnntptaireiiescsettnoooobtbfeencoeolpapeererlrryiaacttaaeesldd iciimnnqpuaaoinnprtasmaiienrenctcrtraaffstst,,utchmmheiisys2ss8lialere3,e, orpraoardwdeaasrrpr.attcubeAbleeslhrrioeepfqq.uutiFihrireosesr grreaeaxtrtahh,meerrpinlsseiciz,zleeuaaadbbilplneeigeaactueuhxieiollfitaaureybylee,gcgetergaaiercrnaettloroaepptqreruooivvcpiiomddneeseinttdhtheeersaucebelclechecrtirhaicescaaatlal wtpwhhoheiwicceuhhnr.itmmAuwuslilstltlobbfceeothnrrtieesimmngouoeevvaeertdd,o ibbonpeecellloruowadwtienssgoofmomtreheeprcrrtioiulttbioccenaa,glegtdteeemnmpeepprreaeirtroaeadttsuucrrooeenfsiitinndiemoorearrbddweleierrthhttohheuaaatttt ftpfhaaliieillsuuhurreeen.d.itqITunwnitigglelrrroeocauuodnnniddtliynlluebevveyeelltosiipnnaossctptiaaelnlrllgaaatttteiiohoennfsosv,,rarttphihroiiossulsoccncoogooolemliidpnnoggpnececraaninnotdsuusfssauuoaafllalltpyyiamrbbteeeawaancicdtchcoaoolmusmo-t epbbfyylfiisppchrireeoodnvvtiilqddyuiinibntygeg aarueuusxaxeidillioiilaayfrryyabycccooosoaoplllaaiicnnnigtgngttlhhitrhqroueouiudgvgahharnittohdhueesaccnciiorraccmpuuplplraioottnipioroenninoatofstfefsaaihirrreaaootprraeerextvvceeahnnnadnmmgaoeolrrsreoe. ieIInnfnfiacaadiiidersinbbttoiolyorrnnn,beeyeeevuqqesuureiyippoemmfxetenarntatc,,opowwoleuaeinniggtdhhlttciqaaarunrnididdedassnppndaaocctaeenonaalarrypeepreereoxxqtpturrreiierammeteeedllyyhaedialdimtemidetixteefcdudhe;;la,naagnbnedudr,t,. aacincoctntuuasadaildldlleyiyrtiaorrteneipp,ollnaeascvceee3ssrsyfftuueheexelltsretathhhaaptatovummeniidglghehcdttartbbrheeieedbbeaannddgolliytyneonneneerleeyddtoeereddqlouffoooikrrredfpporrraoopdprudualedlssidiicooanfln.ul.eylS,Spuubeccuwhht ftcteoeocrcnhhstnnihdiieqequursaeeatsstioiffsnoofrsracccatoosooorliytihnnoeggpseetthrhaeehtahhiveeoeaanttlogegfdeennmetehorraedatteiiernnnngggccianooiemmrepbrpooorntnnoeeennltootssrokwwshphfiaoicccrhhe raaadrideericennaccetlccleyeedssssnaiaeirrrwyy- cfcorrarafBt,t,hesemmiidisssesassitililseetfssha,,ecaatonsnrpddyacoooeuuptteeearrrnadsstpipoaawncceeeiogccfhrrtaamffttlo.idmeitrnatiaoinrsb,ortnheeroerisspaascoe directed the wide air- ex- ttbreeemmoBepeeesssrioaodfbfelstteeemtmghpepeenerersraapattaluuclrryeeefuuarnnnodddmeerwr--$wewih0ghihiccFthhtlittomhhseeietvavvetaarirroaiilnoosuuh,ssuntpphdiieerrcceeesds idooseffgaerlesqeqoeuusiitpphFmmeaehewnrnetitdnhemmeueuisxtst-t aAbAnenlyyo'opwcceoortuaoelblmaalpnene,t,,rgattethhnueeeerrreeeafflooslryrueec,f,hrommmauussst-t8nn80oo0ttFFbbeetocictoosmecmvaeeenrnssaooolltliihddubenoodrpreeeuvvdmeepnndees1gdo0revvweiiissstccFhooauurhsserletathnthiaahvtteeilaatyt.t alalonowylwowhghoaoritresnsmeeppipnaoewwrewaeretr.iu.grheIItfstotuhhrceehvfAolauulsiuddm-e8vvi0issbccyoFosstiithittyye caauattsnellnoooowwtf tbtseeeummcpphpeuermaraatptcuueorrodeelssawniitissthwhhoiirgguehhll,a,dtittvhiheeenlnny meditely be lost by having to provide very any gain in weight or volume by the use of mediately be lost by having to provide very large sucti large sart-up horsepower. a coolant would im- start-up horsepower. 33002222..00003300 I3MM_MMNNO044885555113399 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. 322s5 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY the MMaabaonnvyey. oocTthhheeerryrreemqquuusiitrreembmeeenngttossommduulssuttbraailcssaoontbbse,e mmmeuetsttbbbyyessuunccohhnfccooaoomllmaanantbtsslbb,eessniioddnee-ss tceehxlxpecpltloroasibsiciovvavele,e,e. qnnTuooihnnptetmoyoexxinmictc,,,ussatahnnbodduelgndnooohnonacdcvooerlrurrgoboossrioivvcdeea,,netlsaea,cnntddmricueeasslstpppeebrcceoiipaaenllrllotyyinefsliifa.fmusmseeaddbleaa,rroonuuonnndd- electrical equipment, should have good electrical properties. C. Avpnicarion or Fuuomocrsox FuuivsTo Hear Tastes Prowuesss iCn,teAT"rTePhshPteeLiICnhheAetaaThtteIOtptNrraaasOnntsFsfffeeFerLrwUppOyrerRaooOrppsCe.erArtRtIiiBneesOs1N9oo8ffF4L,iUinOnIeeDlrrySttpThMfOaluunoHotrrEooaAccnTaadcrTbbBRooAnnrssNiScFhheEaaRvveerPeRcbbOoeegBeenLnniEzMeoodSff ittmnhhotaadetteresffoostrtr hinnneaaattttuhuretraralpanaccssooftnnevfrveeewcactdtiviyooaennnatrllsaii.gqqeuIuniidodv1cec9oor5oo4ltl,iirnnaOggn,,lsyf4apohrfflmlaueunorotrroaoofcncl.adarrbObBoonrnnicetll(ihi'q~eqsuu)oiidcdrehhhceoraadgdhnaooiznnnedlld,yy tmithnheoessdeeebsowwtioolhrirekknaegetrrsfstlraffuonoourusofnnecddrarbbabyydovnuuassnliiitnnaqggugiedaa,nnovteehellareetcctttrtrraiiecncnaasllftlloiyyrmmehhseeeaar3tt5eeoddiml.cuchhOcoohnkkeethheccesootiiollwthiiamemsrmmetherrarassnneesddd-, fiifneenrrrtraereddabnoffsioolfirronrgaameggfrliiuvvooeeirnnowctteahemrembrppoeeenrroaalntitluquyrureeinda,rrtiisutsehraa3alt8sctewwonnhhveeetnnicmtttiehhoseenasscsaaommmuleeudccchooociicl!huewrw.aaatsswiimamsmmetrerasrsneedsd.- in transformer oil where only naturaI convection could occur. 1. Transformers AhePPartroonmmoppftteetddheaattRallyeetaahsstteoiinnniittCiiaaollrll1yy.poTbbryryaantmmsiifilooliirnttmaarerwyyresrnneeeeetddhsse,, fKKiirisllthha1am0m,,stUUurdrsyscchth,h,e aaunnsdde "oAoffThhfeAlaueuoronrwriionnoreefk--ctchioonennitttiaaRaiilannlyiiyntnhwggeaosccnoodmmiCprpoeoocruuptnoneddrdasstaitoaansst(hzded4ii1eepllreewocctbetrrlriieeccmtcchoooefoollmfaaiinnrnstttsisatiiuonnristtztrruaiandnnsygsffoaothrrtmemaeenurrssss-.e. fftToolhrrommemeierre,rr.wsoTrTokhhfeeinyyCitFiinanililttyiClawllFlyyaCs,ssdccirrreedoeicenctneheedlddoartaaoothcwwteiiaddpfeeuroorbvvoalaebrrmiuieetttayoynfe,omoffinprillaioiqtqduuuuriiciddztsssingiinrneccaslltuuurdldaiiinnnnsgggftcferarolroombmmontethhrseediddeoilifrreeecctcCtrtiFfcfl2lu=AoouCrriiiFdnnsCaa,tt1iooa, nnnddooiffcfhklklueeororroorossooeecncnaetrea,b,folccunooonnlrvvoieqebnunutititdiaoosnnneaca,lolsnisptilalriioiccndooiunnnecegatsanandndreohshxuyyylddtgrirneoong-coo"raTrhrbennoyiiattnlrrosogdogeieeennlxeaacatmttoroiimcmn,e,fdlssuiiginnadccsseee, odaduenesssdipiggrnfnoladuatutoeecdrdt.osc,ccaoorsmbmumocmenhrecalrisicqaiSuallilFldyysaa2ncssodnFFCtyCaCFi-7ny7,i55nagaannpaddnerFmoFCaxC-ny-4eg43ne3.nt. TdtdhiihaetecleyctchttareliiscocosnelttxooyabbmAeeiinduuesssdeedwdghaiiinsncecohcoounssnjsjptuuinrnosccidtteiiudoocnntaslww, istituthhhechttehhsaeessellnSiitqFqiuu6ailiddasrsn.e.dKqKiuCliiallrhFaeasmm,meaenstetpst eaawlrl.em. rffaeoonuutennhnddet ltlihiqqauutBiiddethssf,,eorFFoeCCn-lt-yh77e55fsleuaainndfddlsuiwFFdCCsh-i-o5c4r3h3,,gsaaaastnneisddsfitwtehhedeeraegglalapssterehsose,,veeSSnsFFs,6seantaatiinnasddflarCCceto3qoFFru8yi(,rae15hm).o. weenvtserw,eirte wthase nneevececeenBsssestafarorrayryceetttoohaemppsuoeururifinflfutyyisdttshhoeoefmrmcgottaomospeaasonnuwneedexxrsett.rrepemcrmooeevnllyteynihnhsiiiaggnthhgisfddaheecyggtdrorreeryoee,gtethoonowfforreereveeecrtth,hlheoietmrmiwneooa.fsf eTm"Tvuhheciinsshpptooroaifincntetthcceaaamncannorotultyntbbwseeorossttkfrreecsossonsemeddspotto-oocuooanlsdslttserrdoonncfgogllnlyuy.toa.rionITcttinaiirgssboiihnnndydedmeeaerotddegruueinnnaffloosoirrtrtuunncsaahtttlreeoornttihnghlaaeyt.t sEsmuususpcpeHhecctot---f-dodturhueeeCettoCaorlffyLaaiilwluuorrFeerkssrottoomonrraeseompmr-oocovvacleeelsesiidmmspfptulauurniroditrtpioioeecissanrtssb,uioccnphhurmiaafsaitctterarrataiicacoeelsn aapimmsrooosucutnernodttnussrgeoloysff o-aaf-creCctooh-fe-fttHeefnnlounnrooort-to-cttCoaoro-o-bCoddini1ffff.miiccaFuutlreltotrmittoaolaccataprorrrroyysccooetusutos.tn.sGGtoaefennnedvrepearroalyillnlyyts,,,trptthohuneergyyificiicnhnavevtmoiooillvnceeaplsssruuobbcsjjeueedccchuttiiroeo3nn5s offtuiufossneteshdd,e ssefoolxdudpioiuorumomsceahhryybtddoorrnooexxmliieddaveetaetrooeirdralccttooeonmncpcaeeecnrnttaitrotraaunttreeeoddsf,ppvoogetertaynasessrssiatiurluomlmyngppieencrrhmmteahmaneniggcapaanrlnaesasttseeeunccssehooluoalsfmtieotnasl,s esxupcohsuares ctooppeelerv,atseedc]t,emnipcekrealt,ureetcs., gUenndeerarllysucinh tchoendiptrieosnesn,ceanoy.f metals such as copper, steel, nickel, etc. Under such conditions, any 33002222..00003311 I3MM_MMNNO044885555114400 " ome 326 u. ~. BRYCE oss lec sous ibe end ih i. hydrogen or chlorine-containing products will be destroyed with no sig- nificant effect on the saturated fluorocarbons. Using two commercially available fluorocarbon fluids, FC-75 and --_ i i" = El ra : [8Eae a y mn B i) a by St es wi a _: be FIc. 9. (Courtesy of Raytheon Corporation.) Comparison between standard transformer and specially designed transformer of same power rating but cooled with fluorocarbon coolant. 33002222..00003322 3M MN04855141 si, wos of sous cos INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 327 FAS, nd SF, Kila eal. designed tsformers which bd sc FC-43, and SF6, Kilham et al. designed transformers which had a reduct of fut tne by slic amg on by wc: he soon duction of four to one by volume and two to one by weight. The cooling mgd sig ee Bt lg wi ed cretion was accomplished using these fluids by boiling without forced circulation Tod Tt me cect han ee soto vin het and was 1.5 to 3 times more effective than natural convection using either ne So ems To ge deb opto pr transformer oil or a silicone oil. To give a desired operating pressure, eres F353 070 md FE oe 75190) a id a mixture of FC-75 (b.p. 99-107C) and FC-43 (b.p. 170-180C) was used. comple of hs dwg 1 1.9 oli magnon Ram An example of this is shown in Fig. 9 involving a magnetron filament aoe The ns on th gh or nnd orc ied transformer. The core on the right is from a standard transformer cooled it tito of te pie ae comp with air ; while the u~it on the left of the picture is the completely assemed rors whi ho bh edna vo 2 0 a eure bled transformer which has been designed so as to use the evaporative Cong clef te roc Hae cooling effect of the fluorocarbon liquids. nweeN L ENE e T) 2 | i.Liquid e= nd Le y hIee.oe CUeY li fe e.N| | REI aAN en Fe. 0. Cot of Ran Corp) Cty iw offs id FIC. 10. (Courtesy of Raytheon Corporation.) Cutaway view of fluorocarbon cooled transformer. Fes of his desig show hs he it copieof peng in ded Tests of this design show that the unit is capable of operating in deadair ambien of 10C with 8 hot spr roof 35C. Rapoed ile air ambients of 140C with a hot spot rise of 35C. Repeated dielectric esliones oor 0% son ct vt lags do mons he che breakdowns of over 50% above rated test voltages do not lower the breakGone of he ut crit promanes ccl, eluding down strength of the liquid. Electrical performance is excellent, including CE hacion i cro The mamas apron mt considerable reduction in corona. The maximum operating internal ee los 35C en eam 13 pressure at full load, 125C ambient, is less than 12 psig. Fire 10 thoes + utowar view of + apt orosrbon-lled Figure 10 shows a cut-away view of a typical fluorocarbon-filled andr, OF por mth eve of te Rd a transformer. Of particular note is the level of the liquid in the unit and a iio enc he cpp wi mh ct the wicks of woven glass insulation between the copper wire in the coil. 33002222..00003333 aw_ossssa2 3M MN04855142 aKeswill be red ha nly he oewoe.s parvoesn ofthe cil smc nthe It will be noted that only the lower portion of the coil is immersed in the Td and hh er of he Sone i ld wi vor epi ht liquid and that the rest of the container is filled with vapor excepting that Whi dem up pt hs by ho king sto of 5 Ft which is drawn up into the coil by the wicking action of the glass fabric. Th fc thn th Tamora per tome nophrs he alec The fact that the fluorocarbon vapors at one atmosphere have dielectric engi cena saul to. ht of te Tid iow this paral il strengths essentially equal to that of the liquid allows this partial fill emcee Ent ngs of decie rakdoun.A eprsrs technique to be used without danger of electric breakdown. At temperatures iow thi ling oc thape rere 1 0 ow 10 fv gh below their boiling points, the vapor pressures are too low to give enough Ecc woeng fo il a ens ho Spat on 1h Hh dielectric strength for initial start-up; hence, the space above the liquid a Fe to sho ome. Bf msgs rears wh SFe. was filled to about one-half atmosphere pressure with SF6. iCT ian - . ` ogos he Fr. 1 . Couto of Weighs ie Capon Lr od pve Fro. 11. (Courtesy of Westinghouse Electric Corporation.)Large-sized power transCo A former using fluorocarbon dielectric coolant. The Westinghouse Hlcsic Cogporsion has manicured large The Westinghouse Electric Corporation has manufactured large owe suormr i hich he Gc sth an he nln power transformers in which the dielectric strength and the cooling are risa by a combination 1 3 Sagrosrion Hui ECT, nd ges provided by a combination of a fluorocarbon liquid, FC-75, and gases oa Sh Tr wamlomrs av ings of 700 0d 03 kx (such as SF~). These transformers have ratings of 7500 kva and 34.5 kv kp: Fite 11 shows pictur, th a bung nice by the and up. Figure 11 shows a typical unit, the size being indicated by the ran Seng. Tn ths sn he orcs coh snd vind sr man alongside. In these units, the transformer coils and windings are 33002222..00003344 owosessian 3M MN04855143 acer, srs or son coer 309 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 329 continues prayed ith the Sunsocabon liquid, which by saporsion continuously sprayed with the fluorocarbon liquid, which by evaporation {io he hotsate uric way th eatand Jeers 0hcn wher from the hot surfaces carries away the heat and delivers it to the case where tthhee lliiqquuiidd ccoonnddeennsseess aannddrreettuurrnnssttoo aareresseerrvvooirir..TThheelliiquqidiusistithhedenn ppuummppeedd vinheohe puythhes ed rptrerae In is cose ny again through thq spray heads and repeats the cycle. In this case, a relatively Eo Exons ofRunonhon ak a atnlcoe i Sonfarnc and re few gallons of fluorocarbon fluid is able to cool the transformer and proie in smelt ile edi. Unlike elas nis fll ith vide an excellent dielectric medium. Unlike equivalent units filled with Somemion i, all fe hoard 3 died Thee farorion: conventional oils, all fire hazards are eliminated. These fluorocarbonFldvaporgmtrirormers an thst beaicly ald ndorown filled vapor-gas transformers can, therefore, be safely installed in downtown oorr rreessiiddeennttiiaall aarreeaass,, iinnddoooorrss oorr oouuttddoooorrss,, wwiitthhoouutt nneeeedd ffoorr ffiirree--ffiigghhttiinngg Cope, rt wal o diva pe. Botde he gre aes pon equipment, fire walls, or drainage pits. Besides the greater safety factor, alan nd maitenance eats 6 roduc 20 sv 1h une installation and maintenance costs are reduced; and since the unit is SF cog. operation ue with no extern ons repune. self-cooling, operation is quieter with no exterior fans required. 2. Pacer Tubes 2. Power Tubes Fre of the RCA. Laboratori ha studied freed ciation Etter of the R.C.A. I,aboratories(a7) has studied forced circulation cling Tor + High paver Comming. tue. The Tutgocarbon td cooling for a high power transmitting tube. The fluorocarbon fluid, FET was sled he cont for ste on he as of ht FC-75, was selected as the coolant for this system on the basis of heat HE H H alE il HE ARE Ee dT Hi mE -- i JE iH --FO -- -------- -- Fie. 12. (Courtesy of Radio Corporation of America.) High power radar tube cooled with fluorocarbon coolant. 33002222..00003355 awuNossss1as 3M MN04855144 30 no. mes H.G. BRYC~ 330 Tttrrhaainnsssffceearrlcccouoelefafftfiiiccoiineennittssnwwhdhi.iicchh,cawwaeetrrwteeocfecaoalldlcudulalaadttveeaddnbtbyaygtethhoeevDDeirittttuuhses--nBBeooxcetlltbtererseeqqluuiaaqtutiiiodonsn;. bnTnoaahimmilesielnlcygya,,lFcCtturr-alaa7nnt3sisoffonworirmitmnheedrrifcooaoriticleleddaannacdditrwcssuoiilllfiaoictcloidononneeadocoviflia.lt.nhtEEeaxgxlpepieqerouriviimmederanettnhat3eal.ll5lnyyet,,xetEEtbrttteseesrret cluuiotqtviiulleiiizdrzeesdda; Shhbqeoeiaialntit.ree~ddg(wwF1i7iCer0,e-,.7050IIn0nwBttihhtihiTssfccUoaarssc/eees,,dhqtthhc)reeir.cmmualOaaxttiihmioenurmmoffahhtcheetaeaotrtlsiffqlluwuuxhxidioocbbahtttaa3iiwn.ne5eerddfewt wpaieasmsrpso33er55ct00aowwpnvteepreirnar thsthqhiiessirnaamp.pappll(1iliac7can1atd,ti0ioo0cnn0h,,eBmasissTcffaUalor/aharstsraittbshhiqelefitctc)yhh.ooiiinOcceecthooonefftrafflclfuutaiicddwtioiisstrshccoos~nnuvccrheefirracnncheeedsdw,,weiihnrnieccclluhiumddweepeddorreeetxxamttnrraetemiminnee rtttaheiiesnnriemddaanaalcttea3n300dt0o0cCChX,ee,mrssaeeiycllffsa--lhhrseeetaaasllubiinlintlggiitnyuugnniddnfeerrcroomeenllteeatccchttretriicwcoaaiplltehddriiassstuccihrhof.aaanrrcggeoeesf;; waatnhnhiddischaahllswioogehttr-hehveeomlggtaooaioongddetreubsei.staFnicgeurteo 1X2 -srhayoswsrethsuelttiunbge dfreosmigntehdetoopoepreartaitoen woifththFiCs-7h5ighco-ovloilntga.ge tube. Figure 12 shows the tube designed to operate with FC-75 cooling. 3. Electronic Assembles sieRRaeennndaauuwddeigddheestsccrrrieibbdeeussctiaaonnn3uu.wmmaEbsbleeeecrrftfrooeocnffticeaadssAssiseesmmehbmbillbigileheisesvsoiinnlawwghehiipccohhweaarccsoounnspsipiddleeirraaebbsll.ee sTsTiuezepcecphhlannyniidqqwuuweeerseseiagarrhpeetlddareecedesscducrciitbbiineeoddnaiiwancaowwslhlhesiifpcfscheicahbatleekkdyysidsnitterrholoenincgthttruuibvbcoeelctppaollgnuutessaiptitnossewraaeuuroxifislluiapapropyylliyepptsooe(3wwi8eaeLr-r usfHlnuuuipootrproloywcetethhswyylelaerebennleeepwwltahohcieiccddhhisiswwniaapssaatettchhoeealnnblaopfufisitlillbee2ldde2wwdi0iitte0hhlecFFotCCfr-i-c7p75o5.c.woenIIrntnaitttnhhheirirsouocegxxfhaammpepopbllulyeel,t,leittterhhaneet- CCucaoontooiiltlaiilnnswggabspperrtooawvvbeilieeddneeddttohbbeyydcisttsohhieepmapFtFeCCa--a7n7b55o,,suuwtwrifit2athc2h.e0rr0aeellnwaadttiivotvehfelelyypbolluowolwwkerltteietmqhmu.prpioedeurrgatahtet,muuprreeeerbauddtiliulffirfeeeern.r--t eAw`Anhnnetiraaaelccsattsuubaael5ltwgccaooeemmsnp-palatrehriidessoocSnnoFmooffpuoppnniootewwnewetrersiuuugnnrhfiieattdsceoo1ffa2n1eed5qquutaahanlledKKbhuVValdAAk alrriaqavttuoiinilndgugmtsseehhmooofpwweee1rdd0at2utt1hhr5aea,t.t wtthhheeeRrFFeeCCan.s-a77ua55dglliaaiqlsquc-ufoiiidldlp--efofdiillllneSetddFed~uunnouiuintttiwwttewehiaieggtihhgseehtddeadnS5d1l1abb2rdaalbnnIddawnhhdaacddaharaabdvvooonalluvruemomslieeusomtofofer5s5o44fcoii1nun03l.2.dinb~e, srsaaeffleeilRlyyaebnaolpaypeu.erdraattaeelsddo st $ w in boiling pointed out that at 5 w in boiling FC-75 20 standard FC-75 at 100C with 1-w carbon 100C with excellent life and resistors could be excellent life and ireglhiatDDbrripeelaixxtceyekl.lagrrieenvvgiieeawwnssd tthhhieeghpprrhooebbatlleemdmissooiffpacctooiosonllinnpggerueenlleeicctttvrrooonnliiuccmeeeaqquuriieppmmseeennntttwiwhal~elerr.ee otHHivgeehrsst hhcpoooawwncvskseanttghhtiaiantotgn3aaalfnfludufoohrdrioogscchaarrahbbn.eoodannt idfunliiusfdisadi,c,ptasstupuiooccshnhspcaassseerFFsuCC-nm-7i7ot5s5v,t,ohhlouaafmss temmhaeaanrneeyysessaeasnddetvvniaatainlnatlt(aapaggrseoe~s-s. eovretriscotnovemneteitonsaulcfhlurideqsuainrdemeinntfsacat: possesses most of the essential pro- perties to meet such requirements as: (((121))) BFBoroleilieinniggngppoopiionnittntooffbbaeboloouwutt--11S00000CCC tttooo pppeerremmiiitt rroaamrwm-etaieicrmpcceoorooaliitnnuggr.e operation. prov(((233i)))deFLLgrooeowweozdivvnifigssucciopodsosiiitctnyyot,,nvbehheciiltgogihwhon.dd-een5ns0siittCyy,, toaannpddermhhiiiggthhlowvvooltleuummmepetterrriiacctueerxxeppoaanpnsesirioaotnnionttoo. rperaodv((i44i)ld)LyeLopgorowwooddusscuufilrrunffaiagdcceescmoattnelevnlneessicriootinbnounbss.boolevvsaappaoonrrdbbtuuhbbubbslleepssrobbmaooiitllinoofgfff nttuhhceelehhaototet bssouuirrlffiaanccgee readily producing smaller bubbles sbao(r5ptiHoing.h thermal conductivity (5) High th.ermal conductivity andand and highthus h.igh specific heat for good hext promoting nucleate boiling. specific kent for good heat absorption. 33002222..00003366 I3MM_MMNNO044885555114455 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY st INDUSTRIAI. ASPECTS OF FLUORINE CHEMISTRY 331 amo(u(66n))tSSsoeelflf-d-hheeecaaollmiinpngogsppirrtooippeoernrttiipeersso:; dbbuoocttthh laliiqqsuuiriddeasaunnlddtoggfaaassnwwiiellllleppctrrrooiddcuusccreec. mmiinniimmuumm aamndo((g7u0a))nstNNswooionntfcchdooierrncroohossmeiivepteo,e,sminnptooienonrtnatootxpxuirirccoe,,drauaanncntddsgennaoosofnnafftllrhaeaemsmuemmqlataubboillfpeemaeppnrnrooetlppeeeetrttiriicecss affroocrr. tthheelliiqquuiidd and gas within the temperature range of the equipment. Tame x00 TABLE XX [I ---- t)ROPERTIES OF SOME DIELECTRIC COOLANTS Compound Compound seeS F~ ernCaI:8 cor CClaF Career CCI~FCC1Fz Corer CCI2FCC12F Fon FC-75 rea FC-43 Smee Silicate ester Bollng Fring Boiling mm point to (C) Freezing point (C) cw ow -- 64 (iim) (sublimes) WY ce -38 noon 24 a 3 47 a * 93 oot 101 nol 178 ws <om >315 -- 51 --160 -- 111 -35 26 < --75 --66 <--65 Dielectric wenn strength GICre (at 25C relative ew to air) 22.2 22.2 i3.1 %2.6 x-=7.5 08.0 "5.4 CCForomompmapratarhatetiivveeexappmrrpoolppeeesrttiicesisteaadrreeallbiiosstvteeedd, iiinnt TTwaaabbslleeapXXpXXa.r.ent that the principal aaToddvvtaaFrnnarttonaasmggfeeeortohfhfeettahheteexabfumlyourpobolroeocisclaiarncrgbib.tooendnThllaiiibqqsouuviiadded,avasaitnat~ahhvgeeaesaatt-ca-taprrnapananbsrsefefenrrotbffttlluhauiiaiddnt ewwtdhasesbiyiaptbsrniiaanlbtcuiiilrptiatayyll cctcoiiirrrccctuuuralllaaantttsiiifoooennnr lpphoooecooaaltl bbbbloyoiiillbniinongggil,,ians4agsw. iiiTtnnhhRiRRsaayCyaitdhAhvceaoonnn'ta'tssgreattrnrascanmanisnstffotboirremnmgeeotrrbutbooaerir.nebbdyy the forced by natural the forced cViirqcuA"uiAdlttastthihiowishnsipplcooohciianaalt,,rbeiiottitwwlihonoeugullbaddassbbiwseeitwwfholerllRl t.tChoe.iArrree.vv'osiieuetwtrwsatttnhahseenmdppiirtrntoogipnpegeprrtettiriueefbssoeoro.fmfaffnllucuoeorrooscscaarrhbbeooannt tlirqaunsidfesr wmehdiciha,asrpeectihaellbyasiis tfhoer ctlheeriircaolutpstlaincdaitnigonpserrfoevrmieawnecdesbaosveheat transfer media, especially in the electrical applications reviewed above. In Table XXDDI.. Proveriss are given a PROPERTIES or Fuuonacamton Fins nub of properties of 1 OF FLUOROCARBON FLUIDS typical fuoror chcyaaerrbrbIoooncnnaTthhbaeeobaanltt.e ttrXtraarXnnassnIffseefarrorreffmluuegiiridv,,eoinlFF.CCa--O77nF55u,,mpaa3bretttriyycppouiilfccaaarpllrpossoipcltieecorotninieeses tufohliufediad,l,otywaapnniddpcoaua3ltfttylyupppooiiicrcnoaatl-l aphooffyidttnhhrtoeec2FFa3CCr.b-7o75hn5.e.attITrttatniarssafnsaoslfsromeorttehhfrleeuoiooidnln,.llyyiOnfffclauepiddahrwwethihcisiuccilhlhairciisosnnaaeocctttaeuunaadillsllyyhtyhvudessrefofluouclwlaraabttpo1iontsuorbbaloplioliiainnrngget spenesoosntientnbitteaiaalslullsyyachdnnoeonsanvatovfloetarlltaayintlisdelfe.ue.er LLftoloouwwitdh,bbeoiosiriilnliicennexggttrhhheeyymddesrrioolficccaaaomrrnbmbeoaonnbainooidrrttysslyiill3diicnrcoodoncneaetrhfbfellouuneiiddxssopliclcosoosuuialorldden 7hhnaao5zzt6aa8brrddeatiuinns~eecd6aa5ssseeafCooefflytoad2llueeaeavkk.at.louT`Tthhhoeeefir0ee.xxe6ttxr5retermametemellreyyoofsslmmmaamaltllmel maccpbhheiaarlnniatggtyeueraeiinnndmvvetiihasseccnoossesiixtttpyhyalotffsrrotioohmnme 7.8 cs at -65C to a value of 0.65 at room temperature means that the 3300222..00003377 I3MM_MMNNO0A4B8S555114466 = oma 332 H.G. BRYCE Swfliuutoohrroooucctaarrebbxoocnenssffliuiviedd hccoaarnnsebbpeeoweeaeassriillryyeqppuuuimmrpepmeeeddntoosvveerr a a wide wide temperature temperature range range awnith"iToTmhhpueeotrecetxuxactnterrtesemsmifveealeclyythorollorowsiwnepsswouuewrrtffetaariccneergetqteseununirssrfiieoaomcnneesnoo,ftfsh.ttehhneeceff,lluuioonrrococecacarurbibonongn ftflhuedidtriisasmaaafllsesoro oioanfnf thhiheemeatpt.f.oorrIItnmnaantcctiaasosfeenacoootffofrebbxooitinirlleiinwmngegelthhytieensaagttattslrruaarnnsfsasnffcdeeerrs,d,,istthhchereenetclleoeow,bwuissbnuubcrrlrffeeaaac,cseeiwntthgeeinnctsshhiieooinnmtrprraeernssosuuvflleettssrs hineatthetrfaonrsmfeartifornomoftehxtrheomt esluyrfsamcea.ll and discrete bubbles, which improves heat transfer from the hot surface. Tam xt TABLE XXI Tomas Prormn or Haar Tessas Lioios tao x Essences. TYPICAL PROPERTIES OF HEAT TRANSFER LIQUIDS USED IN ELECTRICAL sem ase Specific gravity (25C) Pop Pour point (C) Boing rg () Boiling range (C) Nisam pean temperate () Maximum operating temperature (C) Vice ay Viscosity (cs) ae -65C asc25C Sse 37.5C wc 100C Reimesve nde Refractive index Sore enon G5) Surface tension (25C) Shin hm 35-0, cape cm pe) Specific heat (25C, cal per cm per C) Toi Liquid Sched vapor Saturated vapor Etc seen (ks, ASTAL D477) Electricai strength (kv, ASTM D-877) Dit omar 136 Dielectric constant at 1 kc Diipion ar a 11 Dissipation factor at 1 kc Rests Gh perm) Resistivity (ohm pcr ml) Theral conductors (FTU pF be) Thermal conductivity (BTU per F hr ft) Tiaud Liquid Site vor st 1 11m Saturated vapor at 1 atm FCs Shrasne FC-75 Silicone oil am om 1.77 Je Sa - 130 0 Demons 99-107 wD 400 roe7.84 sw 0.65 0.97 -62 Decomposes 200 100 ox " 0.33 EY 1.277 ww 15.1 ozs on 0.248 om 2 0.236 Ps 3s 35 Ge a 1.86 Coos <ooms 0.0005 axe Te 6 x 1014 wos oom 0.081 wo0.008 60 1.403 20.9 0.33 -- 35 2.74 <0.0005 1 x 10~4 0.090 -- Ariss APPLICATIONS ydrmeaion Hydrocarbon ot wd oil transil se--56 Dero Decomposes 148 soc 56 sec ais (Saybolt) x25 Ba2.2 <oons -<0.0005 ime 1.25 x 1014 SuidPPeearrrhheaapptssheoonneseeseoonfftittahhleelymmeooqssuttaluunnvuuassluuuaealsl cfcohhraarrtaahccetteesrriipssetticciisceooffhetthahee offflluutoohrreoocclaairqrbuboiondn,, aSfaltnnuaddinddttahahbreeleesstaahwtteuuhrreaeanttsesededonnvtvieaaappllcooyorrnesaaqittdueoaorlnnseevataalhtutemmesoovssefpprohyhreertrhheeiegoohsffpmepprcoreeilfssiesscucururheel.e.eatTTwhoheifiissgthhiitses uuloinnfqddueteirhdr.-e, Assflutauaomonterdoocabcabaarlireblboionwnn.gh. epFFnoooirnrotneeex3xsaammcFpopClnle-se,7i,d5ewwriwastiteettrrhhewwaiitvtmhheorlyaaecmmhuoilolgaleherccuuwmlelaaiorrglehwwcteueiloigagfhrhtatwboooeffuitg11h884t2hh5oaa.sfs thethe the same boiling point as FC-75 with a molecular weight of about 425. 3300222..00003388 I3MM_MMNNO0A4B8S555114477 INDUSTRIAL ASPECTS OF FLUOWINE CHEMISTRY INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 3333 andTTihhneeorgccahhneeimmciiccmaaaltleiirnniecarrltisnneicsssssalaasnnodda tvthheeerylloiowmwpossrooltlvvaeennntttfppacootwwoererrinffootrrhemmouosssettofoorrggtahanenisicce aflnuiddsi.noIrnga`nTiacblme aXtXerIiaIlsarise allsstoead vteherysoimlubpiolrittayntreflaacttioornsihniptshefoursetwoof cthoems-e fpmmloeueirirncdctisisa.allIlolynyf Taa1vv0aaa1biillleaaCbbXllaeenXdffIlluIu1oo7arr7rooeccCaal,irrsbbtroeoednnspteffhclluetuiiiddvssseo,,llyu.FFbCCiTl-i-ht77ye55rseaaolnnladdutiboiFFnlCCst-hi-4ci4ps33s,,afrwowcirititthhnwgobbeoonicileolirimnnaggl.- tqpquhouieiitnteFetsCll7ooo5wwf,;;1tt0hh1oossCee of the higher boiling, FC-43, and 177C, respectively. The of the higher boiling, FC-43, being lowe than those of solubilities are in general being lower than those of the FC-75. Sotumuis Reavononcrs SOLUBILITIES RELATIONSHIPS Accone Acetone Beene Benzene Benmore Benzot~'ifluoride Berayl schol Benzyl alcohol Carbon temchloride Carbon tetrachloride Chlorbeniene Chlorobenzene Chlortorm. Chloroform Cresrenme Cyclohexane Dione Dioxane Edy aber Ethyl ether Eby wee Ethyl acetate Hiprne Heptane Isopropyl shel Isopropyl alcohol Mey lchol Methyl alcohol Ole pics Oleum spirits Petri ee ow Petroleum ether (low Stodnd sort Stoddard solvent Towne Toluene Turpenine Turpentine iene Xylene boing) boiling) Water TABLE XX1 sonTAFrBcLoEnceXaXmaIIon Fuono, FC75 and FCA! FOR FLUOROCARBON FLUIDS, FC-75 and FC-43(4> Solubility gm per 100ml 020C) Solubility (gin per 100 ml at 20C) FCtin FC-43 in Sort Solvent 090.9 030.3 mice miscible imate insoluble 22.4 =-21.2 is1.8 OF0.1 pts4.9 222.2 ot6.4 fouls insoluble imoitle insoluble 030,8 $3233.2 ih1.4 os0.4 030.9 =-- Savew Solvent FCA in FC-43 Mm0.6 020.2 mocible miscible imolabie insoluble To15.0 os0.4 5a5.4 222.2 mabe insoluble 05.0 22.4 ni3.4 iliie insoluble mob insoluble hile insoluble 707.0 -- ---mabe insoluble to1,0 FCS Sohn FC-75 in Sow in POTS Solvent ws 2 4.8 20 35 2.6 mite miscible miscible 02 04 0.2 mas 20,2 is Hd 1.8 7 is 7.7 73 5 7.7 09 24 0.9 whale male miscible 7s 5 7.5 as ie 25.5 41 13 4.1 10 oi 1.0 54 23 5,4 mie miae miscible 5 So 5.9 25 0 2.9 5 io 5.3 50 30 3.0 Solvent in FC-75 1.2 3.8 miscible 0.4 36.5 3.2 4.5 8.4 2.4 miscible 6.5 11.6 1.3 0.1 2.3 miscible 4. 1.0 3.0 insoluble insoluble insoluble insoluble liquIIinnd TFTaCab-bl7leeS XXarXXeIIsIIhIottwhhnee. ssEooxllucubebipliltiittiifeeossr ffcoohrlrovvraianrreiio,ouumssoggsaatsseegssasiiennsttahhpeepefRlauuroortroooccfaaorrlbblooonnw lttithiqeeuEieedvxxeppFneeCccut-teen7ddd5essaraorlebluurbsbiehilaloiikwttydyno.aawccEnccxoocrcroddeniipdnntiggtfiottooroncsbbhowolihoilleriiinrnnggee,pphmoioigionnhtstttaeagnmnapddseersmmaoaotlplueeprcceeuuallaraarrrctoswweofeiocgilcghluohtrw.t,. amaanntyyeErccvitha~ealnanngugpeenrssoddeiinurncbttehrhdeeeakiffsllduuoieidwdxsstnraaecrrmeoeenloodyffitssisouumnccaskhllw;aahnneaaranettduuhrreiehgehttnhhctaaeett,mtttpthaeheeeraraatemmuoroieusunanetrtscssooeffnotciiiocoannulilirccy, material produced is extremely small; and hence, there is essentially 33002222..00003399 I3MM_MMNN0044885555114488 33344 6. saves II. G. BRYCE TABLE X11 TABLE XXIII Soca or Vasiots Gus 1 FC7S SOLUBILITY OF VARIOUS GASES IN FC-75 Gs "Temtpeorstre SMolabtileey Gas Temperature (C) Solubility Mot ,'oa Ammonia Chine Chlorine Nissen Nitrogen pyAir Fluorine Fluorine Ason Argon~ Niger Nitrogen& Ouran Oxygen~ Carbon divided Carbon dioxidev Suuhestuordes Sulfur hexafluorideo 25 Fl25 =25 o0 225 080 by25 is4.5 ie11.6 ws19.4 2025.0 is31.8 10610.6 "014.0 0a20.4 x025.0 os30.4 so5.6 "114.3 =025.0 ais31.5 04.0 559.5 50!8.0 24.9 x025.0 3231.2 33-- 35 =+25 0.44 ao ca. 10 Gin0.39 03s0.48 os0.46 os0.42 ois0.14 os 0.532 asa0.521 050s 0.508 osm 0.500 oat0.491 03st0.354 fed 0.352 03s 0.350 03 0.349 or 0.347 oss 0.554 pres O.540 os 0.520 oso 0.510 20052.606 a 2.363 2m 2.179 2.000 1996 1.996 Tso 1.850 1315.5 a7.3 "Comte 1 tm paral presse of the on. aCorrected to 1 atrn partial pressure of the gas. ppeiv(41) cnnoooveccrhheaadnnggieen iinna ttphhreeeveeilleoeccuttsrriiccsaaelcltppiroronoppeeorrtntiieecsshaoorffacttthheereisfftlluuiicidd..prTTohhpieisrstippeoosii.nntt `hhTahaess bbheieeegnnh eocenfonevercergargireieebdssonaainvvtaaoiiallcaaabbplrlreebeovddniuuorrubiiosnnnggdsesaacnntfiooeenlrleemccitotnrrniigcc fcaalhrruaccorrarroececstsaeuulrrltibtsotppnicrriirmmapadarirorciipalllyeysr,tiiinnewshtt.hiheecThhccllereeeaaavvhdaaiiggglehey. tuouhfnnoddcueeagrrrhggbooondirrfteefocceoorcmimanbbrgibirnoi~annattibisootonnrnudcttstooufroffeoromrrommringmnnofeellwuwecourffolluucaoarorrrobowcoceaanirrgbhbrtooa,nndicpammolossols,leeewcscusuhllieeccsashserwwnethhaiiadicclihhlly,y, though differing in structure or molecular weight, possess essentially 33002222..00004400 I3MM_MMNN0044885555114499 INDUSTRIAL Mss oF FLOWN cHsTEY 5 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 335 htthhoeewessvaaemrm,ee occnhhleeymmiiiccnaallthiienneearrbttnsneeenssssceoororfeelileemccptturrriicicaatlileppsrrocooppnetreatriien.si.ngTThhhiiyssdrwwoiiglllelnbb,eesttcrrueue,,, however, only in the absence or oEtvhernluondgeer.conditions of or other halogens. of impurities containing leated temperatures in hydrogen, excess of silica, 00C ffmooxreEppsrrvooelln2oonnuggsneeedddle,ppr eescrrioioinodddnsitoosifof ntfissrmeeole,f,, ttehhcleeeovpffpaletuueridd,dsstbehhrmaaavvpeesernniaooet.uocroerrIsrnocisntihsveeexacacacecstsioesonnooffooFnn3C0.ss0u7uc5cCh,h ilmeenisesstatttlhshhaaranns coosonntpeeepeelpp,roessrotarccieensnnltteisddnseekggsrtsreaaeddlsaa,tetiiclooonnpcphohenaartss,aibbbneeerraeessnn.s,nnEoeevttceed.dnIaaenffxttpetrhorse22u44rc00easfhheoeroaaf6ttF044C0h0-t075aCCt, 7i4n755eIiCCtnhaeiinrnacahosrsptipagneirnlralepeoshsrsiscsassttaleeienldlleevmvseoessnssssseettlelrearrlteeiscouosnlnts,staiiinnnpelrlIase.tsesiEnttuvhhneaannnwie1r1x3e57p,%ohssutddereeedcccfoolommerpcp6too0rssiiihctiirloolnnayt. 1oto0r 6d6I0c0n00oa--m66rp5a5a0t0hseiCCrigowwrnhahipilolhefeictiiamhmlmmdfeeearmrsdsoeenddsTiithnrnaetFFipoCChn-7o,7t55aogpssrhlhaaootpwiwhnsssumnnioonwnnFiooirtgetsii.cche1eeaaa3bbtlleeeadnbbedrrleecca1atkrddisocohwawolalw,ny or decomposition of the fluid. The photographs in Figs. 13 and 14 show | | 1| |8 | I | |4 {EN "1 Fc. 1. Hs re sm bt wis mec fn FC75 shonin condition for Fie,. 13. tleat transfer from hot wire immersed in FC-75 showing condition for nucleate boiling. W'ire temperature is approximateIy 105C. 33002222..00004411 3M_MNOABSS150 3M MN04855150 3% WG. awe 336 H.G. BRYCE | |[| ; i Fi.Fro. 14.14. enHeat ste transfer forfrom hothot wiewire imesed immersed inin FG75, FC-75, showing showing codon condition forfor film boiling. Wire temperature is approximately 550C. ssstuuaccbhhilitaaynnofeexxtphpeeerruiimmieden,nttaasllucaharrrraaamnnggeeexmmpeenertni.tm.enBBteesasiliddseeossshiiolllwluusssttrtrahaettiinneggxcettphhteeiontthahleerrhmmeaaaltl tsrtrtaeaannmbAAssiplsfsfeieteryrttshhppoteerrfoouptpttheeeteermomrttpipfiteeleeuhrssriaadootbt,ffuuosrirttuehelhiceenhoogffffllaupunttoohohirreeeonoxtccpwwaaoerriifbrrbeioeomhnneeiislHsnilqtogiguaqurriulaads.iddo.duu,asalhalllpoyypwrsiionnxtccihrrmeeeaaatesseexeldcdyepffr1trio0oom1nmaCl,rrohotoeohmamet thrhcbeeeeaemgaacaicthtnpheseei.idssrd,a,TrtruehttehmhrimeeesootFvvFioseeCCdd-lt-h77leff5SsrrrobbobamoeemtiggleiiittdnnnhhssgeeittnpowowoiFibbirironoeegitli,lb,ob1yyf3anntdbhccdyooennttvtlhvheiheqeecetcuitcaciiodooponn,pnn.ded.aiaipttrAAiipaososrnnnocxttehoohiomefeffannbbtauueoeclcicilyllieoennaa1uggtt0dee1oppbobofCioai,nnlivlttietinhnrisygegs sbffiihenngoee,iv,nsbbs.uuttThiddhsiiisssccchriresaetnteilglebbuuustibbrnbbatllweeeidsrooeifnf tvvFeaaimppgpoo.errr1ar3iitssbuiinyrngegthfffrerooromampipntthhecreaeraawwsniiircrneeegssouhuferrfaafatscce,lfo.uuFFediiggoiuunfrrveeteh11riy55s Asnnhuuuocxclwleeisaastteteihnicbbsrooeiicallhisinaengndggccmeooannindndiytitiwiotoininr.me.estI1,etmtwwhpiileelllrrabbtiueesreannoorftteoeelrdadtiinttvhchelaaryettaeesmivvineengnnorhtthehCaoohtuuaggnflhhguextthhiienen whhtieheraaiestt flux is increased many times, there is a relatively minor cl~ange in wire 3300222..00004422 3MM_MMNN0O4485E5S1155S11 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY Ee INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 337 ttbeeemmpspeeercaratnut--urderse..peAAnbbdoosvveeupaaoncceertrthtaaeiinndeccgrrriitetiieccaaollfhhfeaoatrtceffldluux,c,onhhvooewcwteeivvoeenrr,,, twwhhehiricechitw-i---laslssbcceaann3 sbsrueuoddmsddeeeetnnnhrre-a-adppceiioddpnedrsniiisdteeosiinnnuopwwfoiirnneeutcttheleememapptdeeereargabtrtueoureiree.no.gfTTfhthoiorisscoectndreatncoiosfintovifoenincmtiifsobnddo,iuenethg0te.ortethhTweehiciclshlhaabcnnoeggne-ea ion is from the schoonwdnitiionnFoifg 15. When lm nucleate boiling btoaloinneg oocfcfuilrm, tbhoe iwliinrge. Tsiufrffsacceoni-s dition is shown in Fig. 15. When fiIm boiling occurs, the wire surface is 240 tPT 1o60 pEo tyes) i EX f-- :. 5 or i IIoS vans BnEcSe, ~~L CIRCULATION 4O 200 400 600 800 1000 1200 1400 1600 1800 Fi. 1. Typical bln bes ser cure for 8 chon id, WIRE TEMP, F FIC. 15. Typical boiling heat transfer curves for a fluorocarbon liquid. n0oFillomonnggoeferrvaiinpnordd.iirreeTcchtteccoohnnetataatcctmt uwwsiittthhbetthhereellmiiqoquvueiiddd ppfhhraaossmee,,thbbeuuttwiiirssessuubrryrrocouounnnvddeeecddtibbvyye a film Twhreene forces tiiohnnfe tvtwhhaiipiseovvr.aatppeTomohrpreefErihlalmtemuatraaennmddxuctsrteaanbndsefterre8erm7ed0dovCtte,ood ttthfhhreeroemssuuirrtsrhronoeuuonwnddniiironentggibcylgaiuqbciluodeind,vc. ehEEcatvvineevgnne wiiannheesanpptpptechaaoerrrawannscierceeveootreffamliepihteeohurrearrstu.ttrhheFeeuerlTxitgqchueueeiirdddmsooor8rre7,0tthhieCe ,issstuuhrrreflfarcaeceteissoolfnfyotthchneeostppiclltaeaotatibnimlanueiumnmcthawwaiininrrgeee,, at least for several hours. Furthermore, it is relatively uCotns"tauntewioruteomfpetrhaetpulraetainndumheRnacen,t.steady state of constant wire temperature and hence, a steady state of eateasy heat trate wih to maintain a transfer with- sooumt"Te"Thbheoeufrrrneteshoaueullttss"umooosfffnittthhaheele p""chhlahootatitnawuwcimeirrseeif""islaeeimxxsppeeenorrtfi.immAeeunontroddceeassrccbrroiibnbeesdd aaa3bboohvveeeat iiltllrusastntsraafieteer sfHbloyuumdidtsesh..eoTTffhhateehcettthhhueearnrtmmuastaluhleaasltbpailcblahiitlaitirtayyncutmooeffriwsttihthireceesffcloouarfonorfocmlcuiaaoeirnrbbotaocannainrbmmoo3olnlesercceuuablsleieshiilessyaditllucutosrsnartsnrwatsatefeneddtr esbtehymmopvtpheeeesrBatftCuaucr.eet iitnnhDtahehtceeotmpphprereossepeinlstaciteeioonnonfufcmtttohheefwoqliirqurmeuiicddcaaraanbnnoddmnooraorifvvnaoataptpiohonrersrseanevovrneevnloaalattiatvttteieellmmyeppepcerroraoantdtsuuturarceentsst n"awwbdooouuvllhedden8erc0ee0ssu"Ctlbt.uiiDrnnnecddaoeeumpptoo"pssoitotssfsittiffohooenrrmwmtioiirnnef.ggormooTnnhcettahFrheabcotwwntiirohrertowwttihhitteehhrfppnmoooonnbrveeoorrliahhntieeglaestcpot(rnroadadirntussifceoetsnsr and hence "burn out" of the wire. The fact that the film boiling condition 33002222..00004433 IM_MNodsss152 3M MN04855152 3 no. sree 338 H. G, BRYCE FccaaCnn-7bb5ee vmmaaapioinnrttsaa,iinnweehddicssooh rrheeaaasddiiallyyvaiissluaaellssaoot dd2uu5eeCttooattnhhdee hh1 iiaggthhmssppoeefcci0iff2iicc3hhceeaalaptt eooffgmtthh,ee cFoCm-p7a5revdaptoors,thwehv{aclhuehafsora lviaqluuied aotf 205.2C6 caanldper1 gamrm (osfee0.T2a3bclael pXeXr).gm, AcouomrITpnonacrmmaeradabnnoytyno ooltffhiqettuhhievedasccluootemmommfecoroercnrcidliiauqalclutiuudssheeeossaftdd0eef.s2srcc6orriimcbbaeelsddupreeefraaarcrgllemiiseerr,a(tsttehhetiishsTeaasabebbiilllvieitteyyrXyooXffi).ttghhhee fluorocarbon liquids to conduct heat from surfaces at these very high TALE XNIV TABLE XXIV Eascr op FCS ox Moras, Pasms, xo Eustonsss EI,'I:ECT OF FC-75 ON METALS, PLASTICS, AND ELASTOMERS wTiwme TemOpher Reni Time (days) Temperature (F) Result A. ~Vletals Seis te 15.8 Stainless Steel 18-8 Cd rod es Cold rolled steel riot $35 Aluminiam 52S Staten eran lk~agnesium extrusion CHoppierghtmidpeseG57rSt50u9e) Silver solder on cold rolled steel Hightemperaturesolder(95.,~Sn-5%Sb) Copper B. Mais B. Plastics fr -- "KEL-F" brand plastics "oar" "Formvar" Jo -- "Teflon" coated wire Teton ee "Teflon" sheet "eliminate (GAF) "Melamine" laminate (GAF) Nyon lsc sheet Nylon plastic sheet Hatem Elagtomers Scns D957 conon ctoppdse Silicone DC 997 coated on copper 3" ere 1610) (25 cure, 16 hr) Sitcoms urd GES Silicone cured GE76 Siem Bes Silicone I3C 80 Scone D181 Sillcone DC 7181 Sione rabbertype HTC Silicone rubber-type HTC oo me 10 230 Bo he 10 230 oo mo 10 230 wow 10 230 10 230 10 250 10 230 wooom 10 230 vow 10 230 ood 10 230 wom 10 230 oom t0 230 ow 10 230 wow 10 230 3 30 356 oo a 30 356 oo30 356 os 30 356 wom 10 230 Cured "Viton" brand elastomer Cord "FLUOREL brand cores Cured "FLUOREL" brand elastomer Curl monroe 6 (ompaicied Cured neoprene W (unplasticized) Crd kel FA (snpienicend Cured thiokol FA (unplasticized) Core a 150 (plained) Cured butyl 150 (unplasticized) Curd hea 100) (spianicied Cured hycar 100I (unplasticized) Cord pain (arte Cured hypalon (unplasticized) L555 L Bonrentivoe) LS-53 (a fluorosilicone) 3 194 3 194 3 194 310% 3 194 FI3 194 3m 3 194 FE3 194 FI3 194 HE 3 77 No change No change Ro chirse No change No hangs .No change No cham _No change No change No change No change No hanes No change No charge No change No hance No change Nochuree No change No change No change No change No change No change No change Sige che Slight curled edge No nse No change No hanes No change No danee No change No change No change Volume scl %Volume swell 7 77 No change No change Nourse -No change No change No change No chanee No change No hunse -No change 33 33002222..00004444 I3MM_MMNNO044885555115533 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 3 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 339 ttfeaemimlpupereerroaatftuumrraeessnyggiipvvieeesscestthoheef eddqeeussiiiggpnnmeneentng,giinwneheeeerrthaaerbbauuniilletil-eiicnntrisscaaafflee,ttyy nffaaucccttoolrr..eaoTTfrhh,3ee sfswaiihmimilpupclrhleee lottefhhaeedmrsrmamtnaaoylldpeddiseeevtvciriecucsece,t,oifoiissenqddouuuifspemcttoreointttith,chaeewl heaaeplptpephemeeaearrnraataonnnccfeeelteoohcffetriasacyasllltoo,eccmaaa.llnu""chhlooettar$s,ppooortt""a wswheilDDclhuuoeelreattdodoesctthtohoemeiprdroellssaaetccrkukacnootiyffosnstooylolpvvfeeeannottfcrppoiotoriwwgceaaernlr,i,eclttehhmmeeassteeeenrtAfilaouulofortrthoohcecaatasrrybbmsooitnnegmhfAtl.iubiddess uddsooednnoott sssaewetaauellrslsel iintonoriinnwdssheuuicllcoaathmtiioopsnnoucsccehooaatamtinainntygge,r,tiyeeaptclces.., aoaarftteollesraatgsasatbtlneuui.cpp1Tmt0ohaittthsheeerilammalcaaktxxhoiiamfmt suumommlivguuehsnsattabbbplleeeowttueeesmrmepdpaeesraro-s- aeeetxxtuhtteryeenlneddtnssoe wttaoohndi.ctthhhepeosulttycyychpphiilccmoaarlalotetffrililluauuolosorrrooaoccreaeatrrhbsbytooalnnbenleepp..llaaTsstthTiiicycspssilcassacuulkcchhodfaaassso-lpavproeoelnlytyitetnpcteorlrwauafdeleuurdoo.arrloosi-on- Table XXIV. ethylene and Table XXIV. polychlorotrifluoroethylene. Typical data are included in 1. Heat Transfer Characteristics the MMhaeraacrtceeltlllruuassn,,sfSeSrpphhipileltirl1aaf.uuosHrs,,meaaaantnncddeTrTToafrnroosFfeeeCllrt.zzC7ssc5chhharaahhncaadtvveeermiasmmtdiacaesddeecommmpeeaaarssiuusrroeenmmseennwtitssthoonn3 sswthihlleieicracheteeeattheesestttreeharrenasaatfnneedddr spaauerssrffiialolciicrecmootnnaeeenmcpoaeeil9roa~.ftLuFrRRCeee-is7ssau52llt0ssa5naadCrr.eemiianndccelluudcdoeedmd piinanriTTsoaabnblsleewXXitXXh VVa where the heated surface temperature is 205C. TabLE XV TABLE XXV Macasas Haas Fux Vers von Disscome Fuvion MAXIMUM HEAT FLUX VALUES FOR DIELECTRIC FLUIDS Lida 0 Liquid at 120F Moma be x Maximum heat flux wien (watts/in2) 20mm Shon 250 rpm 450 rpm Remar Remarks FT Fluorocarbon FC-75 Sion at Silicate oil Silicone oil WD 338 420 212 277 118 232 Nee Boils Nonvolatile Nonvolatile heatM Mafarlcrucxeelwllliuutssheestuaarllf..achheaavvteeemaapllessoroaddteuetrteeerrmfmoiirnneeFddC-ee7xx5ppeeririnimmceeonnnttvaaellclltyyivttheheeavnvaadrriinaauttciioloennatooeff hbbaooeniaidlltiinanflglgsuoxheaeswtattivtahttrrraiasnonuussrsfffeaeprrcreewwsitiesttumhhrpettshehreeaantppudeeraaetkkefmohhpreeeaarFttaCtff-ull7urux5xe,aaitntTvvhcaaoerrnyiivooeuwucesstrilvleiieqqauubaiilnddedvv1eneluloooccbclitiettaaiiieetness aahaenmmdpaaeaxrxlsii<momquau)mtmvahahrteeiaaotatusfufllupiuxrxdeswwstiuiettrmhhepseFFraCCan.-td77u55rteemooffopf5Se11r5a88tuww,reppvseee.rlroTsschqqkteiiyynn..owf((e22r755ef55t,,a0p0b00el0e0 sBBtoeTTeo,UUbtappaneiednrr h2215raa,uprmaemnr dpsprqree1sfs9sts)uurfreaoe.tr. auTTihfhledueiiiedrteddtmeaaptmteaarpaaeatrrrueaertuerresreepprorefeossfee5nn5t,teeFd4d.,5vggFrer,aalopphc1hii2itcc0yaalFloll,yyf a7iinnnfdtFFpii1gegs7rs.0.seF11c.66,,,Ta11hn77ed,, eff1f8ref,oecmctatncoodhnnan1tt9ghheeefsowwriinirrfeeltuhittedeemfmtlpepuemierdrapavteteuurlraroeetcuirtrreyee,sssuualolttnfiidnn5ggf,rffro4rom5ommtFh,iienncc1crr2hee0aaasnsFeeg,ssesaiinnni dtthhte1eh7e0hhepeFara"tet.sffsTlluuuhrxxe,e, farpopmliecdhaanegesshoinwnthei ftluheidsevfeilgoucrietsy., and from the changes in the pressure applied are shown in these figures. 33002222..00004455 I3MM_MMNNO044885555115544 sa fp J) ~ 600 Fluid temp 500 en Increasing pressur~ I--"'r-., 400 300 of 2 8OO ~00 o i1 0 200 300 400 500 600 Wire femp F F~G. 16. Heat flux vs wire temperature at varying fluid velocities and LR ee i is Fluorocarbon fluid (FC-75) at 5F. 7 re pr 600 Fluid letup 45F pressures. +5OO TE Increasing pressure | ni o400 500 Fa-r v20o0r | 44 ook -- ;00 SL rir I00 200 500 4 0 500 600 RE ke i sn wire letup in F FIG. 17. Heat flux vs wire temperature at varying fluid velocities and Fluorocarbon fluid (FC-75) at 45F. pr pressures. 33002222..00004466 ausissies 3M MN04855155 ------ INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 341 rt ve Fluid letup 120F 600 , , , el TERE 5010 t ,ncreos oq pres,ure am] 3: an; {3300 f~owoh iMJY IO0 we Fluid velocity ft/sec > G2 i 0 I00 200 300 400 500 6O0 Wire temp F SA dr ai gore sg i ih ob F]c. 18. Heat flux vs wire temperature at varying fluid velocities and RR Fluorocarbon fluid (FC-75) at 120F. pressures. p600 Fluid temp 170F ] ~ 5OO 400 b : wf 300 ier200 smerge n Increasing pressure ;)468 arm 0111 ~ 1| ~ }/ {" I I I I I I 1 NET Fluid velocity / ft/sec OTe he wo wo 0 0 I00 200 .300 400 Wire temp F rgd 14 spe ot ere 58 Fro. 19. Heat flux vs wire temperature at varying fluid LE Fluorocarbon fluid (FC-75) at 170F. wo500 6OO i velocities and mn. pressures. 33002222..00004477 awosss1ss 3M MN04855156 w 0. ser 342 ~. G. BRYCE Marclo ef, have suid the het ener fom a wie of dis Marcellus et al. have studied the heat transfer from a wire of dia- mt D028 ie, of spe, only a i ed. Never, meter 0.028 in., which, of course, is only a fine rod. Nevertheless, it is i hn the rior il in onal spl to ay geomet she. felt that the relationships will in general apply to any geometric shape. Thc colon with othe eo ses sth a bored of vert The correlation with other geometric shapes, such ppllaanneess,, sshhoouulldd bbee ssiimmiillaarr ttoo tthhoossee eessttaabblliisshheedd ffoorr affslluuhiidodssrizssuouccnhhtalaassorwwavateteretrricooarrl Lo i. organic liquids. TABLE XXVI men. Concer ar FC sm FCS bs Laas so Vivo Stns "I'HERMAL CONDUCTIVITY OF FC-75 AND FC-43 iN LIQUID AND VAPOR STATES -- i sun -- Tene -- Wp iF Fluid State Temperature Thermal conductivity BTU per hr ft~F ren we FC-75 liquid fewFC-43 ram vapor (1 atm) weliquid vapor (1 arm) owe- 70 F Eh --62.5F --35.5F Die +76.75F 212F hee214F WE250F 300F EF- 65F --50F Hr +77C'F Say250F 348F EH380F aomm0.0890 0.0876 0.0836 ows0.0813 0.0705 oi0.0080 fod0.01t2 0.0251 fe]0.0520 0.0515 Som0.0490 Soe0.0435 0.01350 Sit 0.01300 `he thermal conductivity of the flrocrbon lids, FCTS and The thermal conductivity of the fluorocarbon liquids, FC-75 and C43, ha en eased by Ht, The dr sr given in Tale XXVT FC-43, has been measured by Hsu(4a). The data are given in Table XXVI fo he gd ad pa vos emperor, for both the liquid and vapor at various temperatures. re -- 2. Thermodynamic Properties Yariogton ant Kay have determined th shormdymands. properties Yarrington and Kay have determined the thermodynamic properties of c-CHFO. The lus wire salted by soln Wh goers of c-CsF160(44). The values were calculated by applying the rigorous hermolynais squaions. to th da hey crac nd ETT thermodynamic equations to the data on heat capacities and P-V-T eon of this compound. Th dts preted Fig. 20 shfo relations of this compound. The data is presented in Fig. 20 in the form Fa lg voi nga wah cores of sons emperor of a log P vs enthalpy diagram with curves of constant temperature, Cont sso, ad santa aha constant entropy, and constant volume. Figure 2 and 22 sho he he expcity dts of Varington and Kay Figures 21 and 22 show the heat capacity data of Yarrington and Kay for Ah mar boing rage cu of ECTS (005-10150) Fur 31 for the narrow boiling range cut of FC-75 (100.5-101.5C). Figure 21 33002222..00004488 W_nodsssts 3M MN04855157 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 343 a en 50 seEEEeunseeE 43B 00 H EET 25 Fe NSN 20 16 SE mT 12 ROR pe ee 8 19C ~ P a ee a d E 2.5 eEE SHHiH po2.0 rt AAR ETT | J 1,5 | 1.0 ! ! II I II " ~/ 180=1 200Ol ~lo~l 240' 260 2 i0 12 14 16 18 20 A A FiG. 20. Pressure-Enthalpy chart for FC-75 fraction boiling 213-215F. Pressure-- arm; enthalpy--kcal per mole; temperature--C; entropy--kcal per mole, K; volume-ml per gin. Source: private communication with R. M. Yarrington and W. B. Kay, Chemical Engineering Dept., Ohio State University. .300 a A . TI .280 i|1 fe a ~ .260 .2,~|o ~ - -1 EEE. .2~0 1 IB ---- tt a WTR i T| | | 200 I 20 30 40 50 60 70 80 90 Temperature, Fzo. 2l. Heat capacity of fluorocarbon FC-75 in liquid state. 33002222..00004499 3M MN04855158 w p-- PH ATT I SJ TH A H I] : ol LL t fel [ere TTT [TB o TTl TT e 11 t= TTT PeEH HEH, FI Ce HH Patho --T TEMPERATURE -- C Fie. 22. Heat capacity of fluorocarbon FC-75 in vapor state. iy he a apt of hot, Wher Fig 28 hs bt aay of is the l~eat capacity of the liquid, whereas Fig. 22 is tke heat capacity of pasa dh i wat om te the vapor, both over their normal useful temperature ranges. Dr huguatyn The vapor pressures of the two commercially available fluorocarbon id PCTS I FAS ws Fncton of persone 5 so In fluids, FC-75 and FC-43, as a function of temperature are shown in Fis snd 2h, Figs. 23 and 24(40,46). 33002222..00005500 awosss1ss 3M MN04855159 otsranL rs on rows cuss 345 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 345 mi sft re LFoEF HEe H T BE EEE EA HEA A AReeeg4a] wpsPS EbErEH bEL EEEPETEE EEE tre f ebro neh EE EE E TTreR nt ffeeelaode rEEE en Ee A e wFeE brbEEbPEEHEH HEE EFeoAEeE reer } EEEEEEREERhre rA E A AH E PR E mEEE SEEREEEEEEEFe E RE EH E ErA eA AbA eE AETE E EHR T ETR h HERE E Ra EBH E E ph a e C s afE e Ee rT plE H EeE EEy R mE Er Fi 23. Vp a ecionotTepmepsersos ron Wd FC35 Fro. 23. Vapor pressure as a function of temperature for fluorocarbon liquid FC-75. 33002222..00005511 W3M_MNMONA0E4S85S5116600 46 wo. mer sh He | a Cel GHEe E CEPRCaape wWEeEFE EhR re E bote hH pef Ee neh nH EEe rieA bf e Fyne eelA oH : ~EE REERETT AT H wEAEER TEeHre WEES EREEbrEEhT rEeE HrEE ei E Ee ET Hr EfEr f r aHeEe or WEEE h S EEEE E EEE Et HEEeEEe aE EE E aE e pEHAREA EErEE eErrER e WECEEEHEhR ErEr E E E EEe EF E Ef HA EA E A E e Er HERE WOE BEBE hEtiErE ei b pE e e i e A cE Eh hHE E al ChE TH HORE oe, 2OO 4. Voporre econ res rcao UFC. 24. Vapor pressure as a function of temperature for fluorocarbon liquid FC-43. plicGGauatssiceooonuusss bffluueconrcooccasorebfVboVItonI.hns. iGGaaarrgaeeseseenossoipuunepsscliDiyfDiiclmeaileelllelyneccthootrfrfiaiccifsnsctteeerresstatndiinn.Hihhgiihgghhdvveooleltaasggee aapstporrpelIiTniniscgoaltTThtnfia.aobrbnllseehbeXXexXcXaaVfVuIusIIreIioaadfr,rethsliielstitreoodfgeaawnhenmiruuasmmlhlbybreeirerneooarfftsffclsuuhroaaorrtoacccirtareorrbbooomannnedccmoohmmpigppehooruudnonieddrlssecasstnrnnidddc Poses acl proper also sulfur hexafluortde, pcos deci. all of which are gases at room temperature and possess useful properties as gaseous dielectrics. 33002222..00005522 W3M_MMNNO04A85B5S1166S11 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. 7 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 347 TABLE Xx TABLE XXVII J a -- PHYSICAL ~DIIOPERTIES OF FLUOROCARBON GASES AND SULFUR HEXAFLUORIDE Compan Compound lnegl Molecular ,~eight DoliCogOpoe Boiling point (C) pFirnieng() dsRecineenh Freezing Relative point (C) dielectric strength cre 5 CF4 88 ce 55 CzF~ 138 cm is CaFs 188 cir on C~F10 238 dsc, 20 cyclo-C~F8 200 Qasciro a cyclo-C4FaO 216 pr C~F5OC.aF5 254 Sk fa SF~ 146 cove - 128C San -78.3 "a - 37.0 S28--2.5 en- 6.0 W+ 1 o0 ogy - 63.(subI.) ows Io - 198 1.1 Zin it -101 1.8 Sean - 160 2.2 Iw i < --80 2.8 a i - 41 2.8 <meoo < 130 2.8 is i -- 125 2.8 ss 22 --50.8 2.2 Factors of importance in choosing an insulating gas for cletresl Factors of importance in choosing an insulating gas for electrical use (((a121r)))e :HLHioiggwhh tddeiimeelpleeeccrttarrtiicucrssettrroeefnnggcttohhndensation ((((3283)))) CGCLhooheowemmditicehcamealalptiienncreeaorrntttudnnrueeecsstssoi,,fvninctoooynnnttdooexsniitstya,,tiaaonnndd nnoonnffllaammmmaabbiilliityy (5)(4) (5) Availability and cost. Good heat conductivity Availability and cost. AA.. Facrons FACTORS Arrrcrive AFFECTING Dieser DIELECTRIC Sasson STRENGTH enceC(CatammhielillldiiiaacnnkddctPPilculmsuptmr(4ep6n)gthhhaavvoeef rraeevgaives.iwveTdehadaeynnuupmmobibneetrrooofuftffaatcchtteoorrissmwwphohirictchahniicnnefflluouf-- eeeellnleeeccccetttrreiotochddaeele dfssiihheeaalledppiceetriaacunnnddsitfrsseoppnriagmcctiihonnrggofnwwoianittuhhgnaisppf.aoarrTritmihc.ceuuyllTaaarprboleeinemmtppXhohaXuasVstiIisstIhIeoonniimlwwlphuhsoetertrtthahateneercrsettthhhoeeef pevvlalaerarciniataerttiiicodoainnlskttfoieellbbedeectiorosobbdusseenesrri,fvvoeetrddhmewwoioitttrhhhenrttowwanoou0ns.si5eeftotsirnmoo.ff.spceThlleacectrbteelreoodtdeoXess4,X, pVoolnnIaeeInIesseeidlttilsubkbs.eetirinanItggnes33b-o-titihnnhe,., lccpaaaltassteneesser ttghdhiieesvskspepaes&aclceinicnnotggrnouwwdnaeaisssf,o00tr.5h5meiifnoni.e.tl;hd.etthhreTeahffoe0or.r5mdmeaeirnra.ggsisivvpeeghssievraeenuutnnofiioffraoorarpmimlefaifnaeieenlldddd,,iswswuhklhe.freuIerrneaahssbexotthahthe-e Alfaluutotore"irrTiddhegee.i.vdeiselaecntroincusntirfeonrgmthfioeldfa. The data is given for gasis generally raised air by and sulfur increasing hexa- pres- snsuuorrneeuT;;nhtitehhfiiosdsriiiemsslemfmcioteorslisdtcts,rtsrtpiuraeeerntiiginntchuttlhhoaeerfeycasaswgeehaoseofnfisuuagnneiipfnfooesorirrmatmillvyfeeillerydladsicss..headSSrppgbeeeyccdiiaianpllcaccireaansasteessseinleegcxxtiprsertoediisnen- niissouunssIueennddi,g,feoiinrnnmerwwahfhliiieccltdhhhse,ccraaepssaeeirstttihnhceoeulddfaiirfeclcylketecwttrorhificecntstetmaerpeepennorgtastithhtuivrmmeealayyoyncddheteachcrrergeeedaaidsseeelpewwocitiitrnthihtcpepsrlrteeerscssetsurnuorgredte.eh. ooffaaCIgngoatagsstceeooonnuuelsrsailddn,iiceatlhlneeedccrttedrriuiccisstppnrrhoooavvveiiefddfeebecddetettnohhfeestheddoemenwnspnsieitttryyaootloufofrwtetehhoreentgghtaahessebiirsdseikkeaeelkeppdcttotrcwciooncnnssssttttraraenenntnt.g.gtthh ooff gaseous Cotton gaseous dicectics. lint and dust dielectrics. have been shown to lower the breakdown strength 33002222..00005533 33MM_MMNN0o48458511s66s22 334s8 Wn. 6. purer H.G. BRYCE Conran or DisDacirsaecnSteEausresneoanr ACommaavtnmSneiroenns Hesaronos worn TABLE XXVIII COMPARISON OF DIELECTRIC STRENGTHS OF AIR AND SULFUR HEXAFLUORIDE V~IITH DIFFERENT ELECTRODE CONFIGURATIONS Contin Condition PromPressure Gam(atm) IV. Spree IV. Sparkover eye" Ra SEsic 60 cycle Ratio SFdair 3 in. plane discs Ta a n Air 1 23 SR ' 2 a SF6 1 52 08. ober 0 psne 0.5 in. sphere to plane Ne ' 1 Air SF6 Ne Open abot 3 Air sre Whi 6 28 SF~ he Uhh 8 Air i Shine 0 20 SF~ 1 16 1 42 30 lb per in2 absolute 24 30 lb per in2 absolute 60 45 lb per in2 absolute 45 45 lb per in2 absolute 90 2.25 2.6 2.5 2.0 geneAArlalttlhhooiuunggcrhheaffsooerr aiannnyydiggeiilvveeecnntrihhcoommsotolrleoongggootuuhss wssieetrriihecssmoooflf ecccooummlppeoouuwnnedidsgs,h,t,tthheeirrteediiossesaa nwgneoeoitntgehnnrtaeeclceweisislnsslacarrrhieillavyyseehhtooihlnledd sdttaihhemaaletetcdtttirwweiclooecsdtdtirirfifeffcneesgrrteetrnnhettngwggtahai,stsheess mwwoiilttehhcuttlhhaeer same molecular weight, it does same molecular nweeg"iaAgAthsisttvthehweeidvlaldalahutaaeasvi,iennatTThlaseaobbsllapeemoXXsesXXedIsIiXseXlsehshichogtorhwiwcses,sl,ttetrhcheteenehgohantalhlo.aogfgfeiennniatatiteoosmmsasndhhaavhveiehghihigghihoenelilezecactttrirooo-n- `nppeoogtteaEentlnitteviicaeatllsrsv,oanwwleuiigtetahsht, tithahieletsyovvaailplsuuoeeassssetffseooserr mfhflliuguwoohhrriiincenelehebcbrteeeriifonnengrgspapafoafrrittniiticchtuuieellsaaarrballiyynlidhhtiiygghhhio.g.fhanionsitzoamtiotno attrEacltecetlreocntergoanstivfirtyomisotahetreramtowmshiwcihthrefwehrisctho itthheasabfiolirtymeodf 4anmoalteocmulet.o attract electrons from other atoms with which it has formed a molecule. TABLE XXIX TABLE XXlX ]~LECTRONIC CHARACTER OF SELECTED ELEMENTS Heri duncaiis Electronic characteristics BH We FG CN H He F C1 C N O S Rasve decronegsivin Relative electronegativity(s) 21 -- 40 30 25 30 35 28 2.1 -- 4.0 3.0 2.5 3.0 3.5 2.5 Flr sini) Electron affinity(471 en vo (electron volts) ST X + e- ~'-X- 70s aese3s 1s 06 11 1s 0.74 --0.53 3.6518i 3.8 1.5 --0.6 2.3 1.5 "{deegryi Ionization potential(s) (electron volts) X--~X+ + e- Be Me mS BO HI 16 Be 104 13.6 24.6 17.5 13.0 11.3 14.6 13.6 10.4 33002222..00005544 I3MM_MMNNo044885555116633 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. 39 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 349 ToTfhhuutshs,e, iihnnaalaosgseeerrniieeasstoooffmlhaaialnliciddreeessa,,seHHslI,f, rHHoBBmrr,t,hHHatCCo1,f, aainnodddinHHe,EFwtthhhieeceehllecbctytrrootnneseggagtaeitniveviritatyyl tcochhhfaeetnmmhiehiccyaahdllarloppogrrgoeoepnpne,ertrtatoiiteoefssmluiiosirnirrcneerecce,ooaggtsnnheieiszzmeefodrdosmtttooetbblheeeacttoornnoollnfyyeigaaoadtlfiiitntvtleeloee, fwmmaohlorlirceecheeemblleeeyccntttirrtosso.nngeeggeanatteiirvvaeel tthriacnaG(lGhaabyssreedsesroawwkgidiettonhhw, hhntioi;ggfhhilunddoiifreeaillcneetec,c,ttrratiihncceyssmttgrraeoesnsntggwttehhhlieccccatahrnnodnppoerregoosdaditunisvoccetee onfnfeeoggaralamlttiievnvleeeegmiaooetnninssvtseoo. nniocenllseecci--s tuurnnilcliia"kklTeehllbeyyrettlaooekchhdtaaorvvwoeennee;axxfcicfneiepnpitfttaiiycootnn,iaalaltnddhyieieelgeleeanccsettrrrwiigccyhssiccttrhhreeanndngggotteehhs.innvootlvfoerdmwhneegnaatinvestioonms is or mmreoopllreTeecchsuueellneeteefflodeo:crrmtmroasnaa negative ion by lectron attachment; the process ty affinity is the energy change involved when an atom negative ion by electron attachment; the process may beor be represented: Xieox @ aIItttommmaasyywbibteehcchooinngcchlluueddleeedcdtrtthohnaattafggiaanssieetssiXsww.+iittehh-.hh+iiggxhh-ddiieelleeccttrriicc ssttrreennggtthh wwiillll conta(i4n) contain iantodmeTTxshheeowfiiitoiohtnnsiihzzdiaaigttehiilooeenncltepprcoiottcrteeonsnncrtieiaanalfglf,,tinhaai.nntiooetsIthht. eeirrs ppdrreoosppiegernrttayytoeofdf aaasggtaahss,e, ssehhnooeuurlglddy aacllhsooanbbgeee aainnn. the process: index of its the process: dielectric strength. It is designated Xoxete as the energy change in PpProratacectntiticciaaalllllyyvaaalrlllymmianatgttteefrrrocaamnnsppurrboosddtuuaccnXeece~ppootsXsoiittiisv+vueebesii-tooannnssceaa.nnddHeeolleewccettvrroeonnrss,,, ttthhheee iiofoannciitzzaatttihio(ao5ntn) hhspereolletieinunugmtmtiahwwolhhfiviacacnrhhyyihhnagagasst,tfhrhoweemohhuiilggsdhhueebisssntttdaifinocoacnnteiiezraatsttotiiorosnonungppbloosyttteaetnnnthctiiteaa.lliohHhnaaoisszwatthethiveeoenloro,pwwotetehessenttddifiaiaeeclllteeaclcttothrnraiiecc.t saistrnneoonFttgrtaaohnnmoiitnfnhddaeeensxxybooogffvadsedi,icdewillseeocccuuttlrsdriscciionssnttd,rrieceinntaggtwettohhs.u.tlrodnsglpy tehatthiaotnnizoatsiionnglpeoftaecnttoiralcaanlobnee eeannnttdiiFrreeerllloyyemctrrreteihsscpepaoloannbsspoiirbbvollepeeedrfifstoocrirusdsdsiiiielonlenec,sctairrtyiicwsossutturbrlesedntnggaatntphhcp,,eeattuhrhneetdhocacuoot bmmntbobeiindsnialnatygtiilooiennnffaloocuffteonpprchhecyysassniitccbhaaelel aaacncttduuBaaelelslvvieadacleltuurseie.c.dailelpecrtorpiecrsttiersengitnh,atnhyerseuabrsetaontcheerufnadctoourbstwehdilychinarfleueinmpcoerstathnte ipinnoinccBtoo,nensssmiiiedddleeetsrriiidnnnigggelp4aeociggtnraatissc,eeosvotuuarsspeonddrgiietephllree,ecctstthrsrieuiccrr,,ee,mmaortoeosxstoitctsishtiiegygr,nniifcffaihicccetaamonnirttcsaoowlffhiwwinchhchiircctahhnreeaasrir,meetpbbhoooeirirltlmaiinannglgt spstaoabibnCiitll,iatyymi,,elaaltnniddnhagppsrrpiipoccoei.sn.ttu, lvaatpeodrtphartesstuhree,motolexcicuiltye, CcFhe,moicnaladindeirntgneasns,clthecetrrmona,l wwtiooounuClslddasmuppcirrlholoiddauuhccaeetsh3eapofCCsoytFlu.4lloawt.eiTTdnghhetewhnnoa,,utilitfdhsseouufcmffcfiiuoccrliie:eecnnuttleeennCeerrFgg4yy, is presen, on adding is present, other reac. an electron, other reac- tions such as the Cher +E following would occur: Creche CFa- --~ CFa ++ FF- n (6) CreaCr AE CFa- ~ CF3+ + F- + e- (7) o`ofmfuttchhheesseeh,,igtthhheeerffieersnstetrttgwwyoo raaerraeectmmiCuouFsn~c.c-hhT--mmh~oeCorsFreee~llpi+irkkoelFdlyyuct+totoseoo-cclcickuuerrwisssiinenccceattnhheeinllaststutroonnneeeniitss(ea8ra.) ieminfnftutoeocchtffuuuhrrttnihgheehbrreereeolleeenncceettrrroogofnyncrroreeenaaatcccitttniiioouoinnnns.s;g;Taaehnnneeddsregbbyyyparccoboosdnnouttrciipnnttsuuiiiolnninkgg.ettwooisaaettttacacacknk clectron, the in turn enter electrons, the effect can be one of continuing energy absorption. 33002222..00005555 I3MM_MMNNo04488s555116644 30 wer tran"TsTfhheeer umusseeedioofufama iggsaaossfeetooeuunss dddiiiceetllaeetccetdtrr.iiccbyaassusaaenns eeillneecvctotrrliivcciaanllgiinnlssiuumlilaattteiidoonnspaaancnded.. hhFeeoaartt ssdtroioasmmnseisepfeaaaptrppiplomlinicceaoadtftiiiuoohmnnessa,,tisssgoooleliinfddteessrnacctaadennidnncotobatttyebbdeethbuuessyeceddquusbbieeepsccmaaeinuunvstsee.oltvthhIienenygymbblalilmonoccyikktetctdhahesesepsnnaeecocceree.gssassFnaaoirrycyr ldTliaiiqcsqugsueiiidpdpssartieooosrrnsuooiorillefss shaauerrreaegteaasgerroenenaaellrsafiotirelrcedagaabennyddbrteehexxaepkpldleoooqsswuiinoio.pnnmhheaanzztaa.rrddIn5a6smwwaenelylll 2s producing cases organic as producing lwahrgeAeAeiiprrriwewtsasasssuprttrehhoeepseuoorrrtrgiiieggeisisnnaoalanlrggevaaossslutauufgfssieeecddibenrffteoo,rarkeedTlloehecwcettrrnii.cccaaarllliiynnsswuuollaarttkiioonno,,faaCnnhddiairs hssttoiinlll uuassneeddd wCuCooohroeoporeecprate4irtsrsb)opahnnrdgodapsPePeroostllilleaoosnccdkkasraaeunnlddfsuurCCffoohioceopixeeapnrf(te4u. 9or)rTihdddeeeemmoweoneansrrtsleytrradaitwtseetoddirnkttchthaloaytf sccueCeprrhettaaariiirnlnotroecnhthlolooairrnrood.-- TfTulshuhaeoegreocccdhhaullrooebrrooponffrluugiooarrsmooecacsaartarrbnboiodotlnnhsssyuelhhffaauavvcrteehtennhxoaoatttfulaaupccoohhriniiedevveveeowddlaeagreeggdrrbeeirsaaetttiankddcdeetoalaylwlnsoo,uffptehccerooiymmomrbmeetreorcraicatiaiarel.l cuhslaogreiddeueiopnriwmhiacrihlyhtaosthveeryfasctcithoautsuepffoenctvsoolntageleecbtrreiackaldoswysn,teth,ey liberate chloride ion which has very serious effects on electrical systems. B. Avpuications so Suet HexasLvonioe absoAArssptrrieeovvniieoewfweee~ddlBe. eecaAtarrrPloliPineeLsrr,I,,CtASShTFuFIs6O:NccSaannFOffRoorrSmmULrrFeeUllaRattiiHvveEellXyyAFsstLtaaUbbOlleeBIDnnEeeggaattiivvee fons ions by by absorption of electrons, thus: Sees consi SF6 + e- -+ SF6- {9) fTTrhheeeesseeeleeecllteerccottrnrosonnweehggiaatctiihvveecoggmaamsseeessinhhtaaosveecobbneetaeecnnt lliwikiketennheeddthtteoon.a sponge sponge which which sosks soaks up up dfrieceeSScueutlllefifcuuctrrroshnthreesexswnaaglfhtlvuihocorhoriifddceoe2m2iiess rippenhlhtyaoystsiicivoooellnoogttgaoiiccctanalilwlltyyritohiignnetcenhrrtet(,,mfoi.irss 6nn0oonncffyllacamlmemmacabublrleree,,nthhaaassndaa cuduonineniilfvfeoeocrcrtmtrmiicoffiineeslltoddr)fe),,nphhgauatshmsgpgooioofnodgd2.hh2ceeiaarrtetcluccaloottinnveddseuuctctthotiiennngggiatppsr.rrooogppIeteenrrittsi(iefssostrauubnn6ldd0eeeirrcncycocotnlhnededictiptiuiroorenrnsessennwwtchheeaenrordeef amcmooionsostvtremmecatmaitaoteienrnriisoaarl4lsopgouaffscmocupnonisnndtsgertrruucccmitrtoicisooutnnlautuuesppse tttcohooenttdeegimmatpspie.oernrIasatttuduisrroeeswsstnatoobffleaabbiinosouubttthael11i55pn00rgeCCsp,,eonaiacnnnetddooiifftt "65C. also remains a gas under most use conditions down to its boiling point of - 63.8C. 1. Transformers formSSeFrF6s hwhaiastshbbreeaeetnninuugss4etdd20aas0s 02a kgg1Aaa.ss,eeToo6ruu9assnkdsdfyiioecr)lmeeccetrrrsiic in in a a serie series of of power power trans. trans- gfoersmKKaieibrllshohvaawmemi,t,MhUUurrorassrtccionhhc,g,raaabnntodd2n0AA0blh0ieeqakaurvrinnAds,hhaa6svv9ueeckhppvo(oaiai5nnLtteeFddCt.too7t5thheeanuudssee ooFffCSS4FF362a5isn:apspamaaddlddleeerrr lgaescatbioovne "flutoeraoncsafrboornmelriqsuids such as FC-75 and FC-43 in smaller "electronic" transformers(34L 2. Interupter Switches kv, HH1e,en0nr0ry0y,,,00FF0rriikeeeddrAriiccrhha,,tiaangnn,dd2w.RRheieIcnecsstheeerhrhhuaaavpvveteeerbddeeeSesswnccirrtfiicblbheeeeddsd ccwiiirrtccuhuiittSbbFrree.aakkeerrssooff aa 111155 kv, 1,000,000 kvA rating, xvhich have been filled with SF6~L 33002222..00005566 I3MM_MMNNo044885555116655 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY ES INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 351 3. Radar and Microscave Frequency Poser Transmission cxbleSSsuu.llffTuutrr3i.shheeRrxxeaaapdfoflalruurtooerardiindddteehMahhtaaicasstrobb0wee3eea7nnv5euumFsseree,eddqtueehexexnttceepynnosswPiievvoreewllyecyrariinTrnyria""nnllogsonmncggiaspsllaiiiocnnineet""y cocoofaaSxxiFiaaall twhcwaaeabsspleo77s.5w..5eItrttiiimcsmaeerrsserpyttoihhnraatgttecdffaooptrrhacaasititri(ay5rt2o.9)f.3S7AAF5nnomwottahch,esertrh10eww.5ooptrroikkwemerreersrrecetppahoroarrrtyttissfnogttrhhacaatatipea3at.tci33ty0000o00f me,SF6 mc, tehqeuiSSpupuolmwlffeuuenrrrtchhaieernxxrcaaylffiullnudugoiornrciigaddpeeXa-chhriaaatsysy aoalmlfssaoSocFhff6ioonuuwcnnsadd,s uu1cs0saee.t5hiitonnidmea3eswrwaitiyhddeeaatcvvcfaaoerrlriieeerttayytooorffs,eellVeeccattnrriiccdaaell Graaf machines, and equipment including Graaff machines, and television flterplxers. X-ray machines, cathode television filterplexers. ray accelerators, Van de C. Fruorocarson Gases axp Tae AppuicaTios promSSieesvveeerraaalsl C g33a.saaeFnnLoddU usO44RdccOiaaeClrrAbebRcootBnnrOiNffcl.luuGoIoArnroSoEcctSaahrrebAboNpoannDstgT gaaHtssEweesoIsRyhhA eaaavvPreePsLssIoChhnA ooewTwIonnOfNcctoohnensssiei,ddeeCrraaabbFll,ee hnphaoarosrsmmabbileseleeeynnasuiisnngettardrsoeodfodouuurccseiedndddiueccslooetrmcmitmrameilcrescpr.iclaaiIanlnltllyytohreiinnopfaf3aiscte11t00wb00uo00ilykdkeievanAArg,s, uos11ne55(eskk)ovv.f Tttthrhreaiasnnsess,fufoCnorirmatmFeesirrs, fpnfrrroeeereesmeffnarrtloloymamnuyddsaeatndnoggsefieorcrrssiyioonhffdausffasiirrrteredi.aoolrrOpteelhxaxepnplrtloocsosioiroomnnop,,ffoiaaucennndddbsuiininwldhcciinaacssghee uhoosafef(v5ea4)rll.eeeacTkkehiivddseoodcuessnsiotnnmooietst apattrtteeesn"neAttsniiotosnneaenaanyreeftdordexoeccimcaaiffttllyhuueoohrdraoaoztbbaauurttdiaa.nnnOeeTat((hCbCley4reFFi1cXo0o))XmaaVpnnIdodLu,oonccdttthasaefflwluduihooeirrlcooehcccytyhrccaillvcooebbsuutrttreaaecnnneeegiev((heccd--oCCf1s4FoSFem6F).)ee. aaennldedcAtCCsraaisFefcsensaaerrfeeernogeemiqqhuutsahal,e,ofdeeaaatthccaehhiRnbbueeToiirnnaoggbclea22r..2X2boXggnrrVeecaaIotItm,eerprtohttuehhnaaddnnise,lthehacCattitrFicooiffostnnraieinttnrrdogoggtcehe-nnC.o..fFTTSyhhFiee6s daaSbbieFooluuetctit22nrci55cr%e%satsggrererseenaagtwtteeihrrtshtthhoaaifnnntchrttheehaaatfstliuffnooogrrroCCgcaaaaFFpr8bodoorinrstSScaFFon6mc..epTToihhuneenndpposee,nrruccCnee4ninFtft1aao0ggreemaininfdncicerelead-assCs,ee4Fwoo8ivvteeihrsr (CSCFaaF6"FsTiaahnlelcsooreflabbcseeeoiinsrnoggcwbbaireetbhtttoeenrirnttcghhraaeasnanessSiSnFhgF~avguueannpddseeedrvreisttrhthaaeelnssceeaedccovoinanndndittniatioigoonnensuss.n.oifvoerrm s fields, ulfur with hexa- AfulupuoporTeirirdhdeee.l.imfAiAlutmmooorofonnc1gga5r0tbthhoeeCnsseeisgaaarrsreeeocsommmhuumaccvehhendggsererdeev.aaettreeWarrlhettahhndeevrrpmamrnaoatlpalegrssettlsaaybbioipllvuiirtetyiyrf..iseFFudoo,lfrruarSSfFlbFu~_oerxaaoann-- cucfaauprropbbreooornnclsdidcmiibeciolltenecoctfrgriiu1ccs5ess0succCahhriea3s1sarCClescaFooFsm8esmmmsaeeanyyntdibbaeeeldl.uuyssWeenddohreaanttt ottpeecmrm.opppeeeFrrroaaltrytuurepreexussarimoofpiffel44de35,,00aCCCf.Fl.usToTrhho2ee-5 uaful1ssueeo7ddr0oii%cnnarbppbyooowwnveeorrglauttsmrreaeasnnsesafvfroeoernrmmaewelsrhrossenwweisiltslllheennntmiooaitlclkkyeiillrlnoemmniietccoxeexpiowcws.hheeedFnnofrommrieixx1x6eeahddm.pwwlieEitt,vhheConoaxxFwyy8hggeeeannns asaSubtulbb7yjj0eetc,c/oottreeidbdcy,ttooavlovvtolohullomttauageggeehebbvirfreeentaahkwkeddhaooerwwncnni,tn,tg~ttehhpeemroddiceceegegerradaarsddeaaitteniixootpnnhoeppserrpdoorddefuusocecrtntssc1e6aasrhoeefr.nnmoEoottvisaeatnppupwrrpeehceroinr- ahbyldyrotocxaricb,oanltvba.opuorgsh,iftrtahcee aqrucainntgitpieroscoefedasciidnicthoer portehseerncneoxoifoumsopisrtoudruectosr hmmyaadyy"rTorrhceeessauurlCbtl,.to. nflvuaoproocrsa,rbtorancgeasqeusaanltlitbieosi of acidic within a or other noxious products few degroef0eCs, conse- qAquuulelenTndtthillcyeyleaaCcrrt4eerifllcliiumsmotiirrttoeeecddnagriitnbnhtoohtnhefiegrtiahrsesseeesmrrvevaiildclcieebuottmoioltitweesmmittpohpeibernearatamtuuafrerieewnsshaidihnegiegghdhree.ererstthohafann000C,CCcioiffnttshheee- AfuulolrBBdoaaicssehalhaerarcbartCorain)ca)t)sythfpreaeanssggarrtsheeespp.ooofrrTtttehyedpedimcooanneldttidhuhemeaddiisiisectllioeencccbttleriiuccmdeassdittnrrietenannigFgntitehhgd..ooff25aaannnuudmm2b6be.err of of fluo"rTohcearcbsosnentyipseegqaseus.iTvypoaicfla(l CedaanFtagc}isOe,incl-uCdaeFdyOi,n sFnigds.Ca2F5iagnadre26n.oted. The essential equivalence of (C~Fa)~O, c-C4F80, and C4F10 are noted. 33002222..00005577 I3MM_MMNNo044885555116666 352 H.O. BRYCE TTA LZ 5O iTAiBE 3O JT 2O I0 60 90 120 150 ABSOLUTE PRESSURE--CM MERCURY Key A. (C~Fs)=O B. c-C4F~O C. C~F~o D. C~F, E. CF4 F. CF]Br G. Nitrogen H. SF~ Fro, 25. Dielectric strength of fluorocarbon gases with 1-in. diameter spherical electrodes at 0.2-in. gap. 3022.0058 3M MN04855167 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 353 60 LLL 5O 2B& 4O 10274 3O i724 2O oA 10 eA 0 30 60 90 120 150 ABSOLUTE PRESSURE--CM MERCURY Key A. (C~Fs)~O B. c-C,FsO C. C4F~o D. C=F, E. CF, F. CF=Br G. Nitrogen H. SF~ F~. 26. Dielectric strengtb of fluorocarbon gases with 0.3-in. gap between electrodes, one of which is a 1-in. diameter sphere, the other being a 0.1-in. diameter rod of 0.05-in. radius. Tim equivaience of CaF8 and SF6 in a relatively uniform field is seen from Fig. 25; on the other hand, in the nonuniform field, the CaFs has considerably higher breakdown voltage tEan the SF6. 3022.0059 3M MN04855168 354 HG. mvs 354 H.G. BRYCE VIL Fire Extinguishing Agents HoweFFsiierreerss,wmmhaaiyylebbdeeieefxxiVtrtiieInnIngg.tuuiFeissxihhtreeieddngEubbiyyxstheieiniinttghghueecrrisfhppchhitynyssgsiciccaaAanllgbooeerrnstcceshhpeeammriaictcaealdl mmineecpcrhhiaanncniiipsslmme.,. titHhnhoeetwhaaeeccvttiieroorn,enwaoohffaiolaefggdoiiinvvffeeeennroeeernxxtattiinennoxggttuiuhniiesgsrhhuiiionsnfghgitnaahgggeeeennmfttefecddchootascenssciasnnnmoostbt.ehhsaaIevvnpeeagrtteoaonteeffaradlallllin,eexxptccrhllieuunrssceiiivvpeaellrelyye, tditnhihfrreftehueetseeytyrptepeoaeslsmothofefoffAcloaaommmnbeeeusss:o:tria#badldnieioffftfghusaseisiroonnfoofrffltlahaimtemsee,m,coieinmncbhwwuahsnhitiiscicmhohnstt;.hheeI3noopxxgryyeeggnmeeeinnrxaeolod,rr taafhiiaerrmemmeuuasirstent wodwnhihfeifiucctshhyepaaetiiocrofitishsmeosslterceceocaamummlbieiunnisggstiibtthnhlevroootlugivaggeshhdfattohnhreeditffisuuteeclld;o;emcaaonnbmddupsota3sioimmntoi;ononoanoffuprueeresellumliitinnsxeiwwdnhhsifiucclfahhfmicooeinnelilnnyyt heatto suse a flame. one type of molecule is involved heat to sustain a flame. and its decomposition results in sufficient A. Pussieas Bxoausinient froAAm tddhiieffffuusssuiiopopnnlyffllaoammfeeoAcxc.iaadnnaPnHbtbY.eeSIeeCTxxhAttiLiinsngEguuXisiiTssIhghNeeeGnddeUriIiafSfltllttMhyheeEkNccnTooommwbnbuustsatisibbblleleaniisskeistsioonllgaeteoddr `sffrsmaommmootethhteezhrroeiinnneggsuittpshhpeecloyffnlllaoaemmfde,e.o.xhAAiednsnaotontptth.hreoeTrrduhppcihshiyynsisgisiccargaleleancmmeterieaaoalnnnlsyss akiirnnnevvoooswlllvvnoeewsseasdcc,oobooalllaininnndggk..emtaiITnffygttbhoheeer fccrleaaaarsmcritieieeoddnz.ot(on0Tetthhhiesee cfppioooroieinnletitds,wwthhhheeeernareet-epiixnrntossiuudnfgfuffuiciiccisiniheegenndtt.rehhaeeOcaattttihioeinsrsppprrahooryeddsuuisccclaoeelddwemttdooe,ammnaasnaidinnottfmaaiieannyxttthbhneee guishiment involve reaction. The fire guishment involve 2n aerodynamic disturbance is then extinguished. Other an aerodynamic disturbance of the flame zone. physical means of of the flame zone. extin- BB.. Cumviens. Exmivcuisinext invoIIlttiveisrwwaedelillclaeelsssttaaanbbldliissahhreeddcChiiInanIiEmmnMaarInenCayyAcLtcciaao]nss~seeX.ssTIttThhNoaaGtbtUIeppSrreeHefffMlleEaaNcmmTteeivaanniddn cfflhaaemmmeiecrraeelaaccettixiootnnsns. igunuivisos"hhlTvmmoeecenrontantd,s,iicttdhaheleers eetaxxhnttediinnaaggcrutueiiisoschnhhiianonifggnfaarlggeaeeamncnetttiiommnnuhusis.bstitTtssioeeorrnbvv,eeeitettofosfebbcnrrteeeicvaaekekssittnhahreecyhccfehhiamraisitinncssta..ol extin- define tthhee TBccrrroiiottaecedrroiilnaaysffiodsorpreerccalltkahaissenssgiiaf,fycytiiinanogngnaoisnsfhuufibblbassimtttaaoennrccineeihs3aissbaiaatnsniouinibnns,hhtiiiatbbniiicstteoonrr.e.wcheiscsahrymfaikrsetstoitdmefoirnee ddbieiffficiBccouurnloslttaifdfdooleyrrretthsdhpeee1ffsalaakfmmilneeagm,tteooaibbnnuuhrrininnb..ihtMM iobariastnnoydyrossiuustbhbisasst.taasnnTucchbeeusssstwa,whnhicteichcehhwawwhdodoicuiuhltliddomnnnaoookttfeoosnrriddititirnnmoaagrroeiinllrye,y aaabrrenggdoocnnol,,nasomoirrdeeaasrnnepyydeeiiandnseerarfttlnadggmaaceso1niton0thraaaibcpptirtrsoeermtmshiiesxdeeofddltahffmlilmasaa.mmbeTeilhlliouotwswy,eerrrtsshanettghhaeeedudffnllitataimimoleenatttoeefsmmonppmeietrerraoactgtouuenrrn-ee, acoefnenndtftaurfeatllatiimooannendsoopffaeiraae.dddddiTaitthniieoodsnnsecs,,oenttfhthfreeeaccftftlslasamamtrheeeewwrifielllalllamtnnimoovttealbppyirrloowitppeylaalggraaautntneegdefefoorurrsntaatonniolyydacctaoosnmmobdmbiincenaaatnctioiobonnen- eaoexxfmppefllu.aaeiinlneTeadndndiignnenatteeirrr.amelTs,orhoftefhmsheheesesaeaettfcfccefaceaptcspatcsaairtcsieeeiseroteofplifahtettyhihsvseeieclaaayddlddwiiitteniilvvlneeassutnaaudrnneedd,rstththaoeenoddddiilaluaucnttciiodoornndciooanfntfglthbhyeee, ffflaaiimrlrTyen.llgaaIerrngngeeergaaaelmmn,oeorucuanhln,ettmsstihoocefafsletthhieeenfhaafieddbcddititsittoiirvavsreeeasaeepreeheynnfseefieeeccddateleiddvienffioonnrraeaetxxumttroieiun,nnggtauusniisdshmhmuamcececnnhott.rsdmianlglleyr, ttihnhhaainnIbnittthoghrooesssn:eeeroarrnele,eqquucihgirrreeemodduipcffaoolrirsiniimnlnaaeeirdrbttietoggaruassspeesas.r.oefTTehifhfneeeorcrretegivaanearireiecn ttsawawmlootos;uttyyntppthseeessmoooutffchheccrhhseemgmmriaoiclcluaealprl iipinnnhchcollisubupddihteeoossrrsutt:shh,eeosnuhhelaaflulgiirdrd,oeeaussnpdooffinsinntmoroonnagmmdeenete.atlauTllplaiibccolfeeclliXenemXomreeXgnnattsns ihcssouuwsccahhsaltsca3;osmthpccaeaarrrbbiooostnhon,ne,or sfsiigdlliriacoctoousnnp,,, phosphorus, sulfur, and nitrogen. Table XXX shows a comparison of data, 33002222..00006600 I3MM_MMNNo044885555116699 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 355 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 355 PR COMPARISON OF THE TABLE xx TABLE XXX -- A VE EXTINGUISHING POWER OF METHYL ------ ]~ROMIDE~ NYI'ROGEN~ AND CARBON DIOXIDE(55,56) Gun Combustible (in air) dn Hydrogen Connmonoits Carbon monoxide Eien Ethylene Methane wrin-Hexane Benzene New MethyI bromide m713.7 836.2 BH11.7 4.7 i7.1 7.8 News Peak percentage Nitrogen 75 68 050 38 a42 44 Cin Carbon dioxide a61 52 i41 25 29 31 o`ombbetttashiiynnleeddbrbboyymiBBdueurrggfoooryynnveearaainnoudds WWfiuicllllliiasmmyssst--eLLmeesiirwfifootrrh ttthhheee pppeeesaakkk pppeeerrrccceeennntttaaagggeeesss ooofff tbtmhhyeeetChiionynwelerattbrrggdoaasmsaeensisd,d, ennJiifttoorrornoggveeeannsriaa.onnudds carbon dioxide, as fuel systems with carbon dioxide, as taken from the tabulation the peak percentages of taken from the tabulation bthyaFCnFoootrwhraoaalsrlledl fssaoyynrssdttteehmJmeossn,n,esemm{re5e~ttg,hh5ey~yel)ls. bb.rrBooommtiihddeeniiitssrceofgffeeentcitaivvneed iicnnaraabmmooonuundnttssimmouucacxhrheispsmmuadralellleleeyrr tphhaynsitchaolseexftoirntghueisihneerrst;gawsheesr. eBaosthmnetithroylgenbraonmdidcaerbiosn4diochxeidmeicaarle pxutrienlye usher. physical guisher. extinguishers; whereas methyl bromide is a chemical extin- . Action or Seeciric Courousos. 56 cAAomggprroooruuippndaastt aPPuurfrCddi.ruueeAeCxUUtTniIniOnivgvNeuerirOsssiFhittiySynPgEhhCaaagssIeFnImtmCsa.aCddOeeTMhaaPeOssUcyyNsosttDmeepSmmoaauttiniccdseevviaanllcuulaauttidioeondn ooinff Tc5Taa6arbbblclooeenmsXX,pXXobXuuXnTtIdhsaaarraleesidmmfeiasroesosttfellxyy3timmnfogeonuwnoioshohhatialhnleogorggeaenngnoseanintmeetsedd.taTaalnnhsddewppceooolelmyyhhpaaaolllsuooonggdeeinsnncaalittnueedcddeldu.hhdyyedddTsrhooie-n- cfwalaeamrrmbeeoenesssvyy,asslbtteuuematmthuueassdlec.idddewwsaaossfnna--hhfeeeppwttaaonnteehemirn air, nd. the peak percentage values nonmetals were also included. The air, and the peak percentage values wpeerrcC`eeConeotmvmaappglauearasritienondfgg(51tt71hh.)ee5.,cc2oo6mm,pp1oo2u.un5n,dd,a,nCCdCC6lI.~,, rCCesFFp4e,,ctCCivFFealCCy,,1,itaaannpddpeCCarFFsaBBtrhawwiibttrhhomppeieanakke. percentages of 11.5, 26, mSoorrine. ffctive than is more effective than chlorine: 12.3, and chlorine; while chlorine 6.1 respectively, while chlorine isit is more effective than appears that bromine more effective than ffliueo`MrcMinxooeltle.eiccnuuglluaairrhiwwneegiiggahhgttenaatnnddobbeooxiitlliiinnngggupipsooihinntftidrdeeeffiianntiittlelelayystaafpffheyccsticttahlhleey.aabbCiilhiletyyrmioocffalaa itfinihnrheeiibbceiioxctitmooinpnn,go,uuooinnsndhhtihnteego odoatitghhseeoenrcrtihhataatonendde,ax,ttaaicnppegppreuetaiaasrirhsns ttcfooirrietbbsieecaasaltsstsslooeeccamisipaatetirepeaddhtyuwwsriiietcthshalltityhnh.eetCahabebhiiellfimiattyymiceooa,ffl tppBharreosotddciuuooccnmiinnppggroouffcrnreeedsees trraoaanddddiiccistaaslelo,sr.cmiiaTTnthaeheteesasteehcerreaarcddtaihiccianaaillnsscrrpipetarricceetassiuloumnmtsea.ambblFplyyreroeaemnntuttteerherresiidninantootathttihhenee fTlccaaoobmmmle.e-, XXX, bustion XXXI, it s apparent that compounds such as CFB and CFSBr process and terminate the chain reactions. From the data it is apparent that compounds such as CFaBr2 and CFaBr are very in Table are very 3300222..00006611 I3MM_MMNNO0A4B8S555117700 33566 Hn.oG.o wBwRrYCcEr (RFEoIoRTmE (Room TABLE X01 TABLE XXXI -------- EXTINGUISHING AaENTS FOR n-HEPTANE--AIR temperate, 300-500 rm ig boise pressure) temperature, 300-500 mm Hg absolute pressure) Compound Compound CrCFaBra CFBr~ crGmon CFnCHBrCHa eens CBrFCBrFz cracCF~ICFsI Chie CHsBr~ cri CFaCFsI cramcm CFaCHzCH~Br crcEe CFsCF~Br crm CFaBr cubcricn CH~BrCF~CH~ pete CHIlr~F CFC CBrF~CH~Br crc CF~CHzBr ptC~FnC~F~ [rookie 1, 3-C6F~o(CF~)~ CFsI Carin CCIFzCH~Br Cine C~FnCF~ Cre C~FIs cite, CHBrF~ rere CC1F~CC12F Gncik, CBrCIF~ CH~Br Cramp CF~=CHBr Poin Peak in famratity flammability CUrVe Golam 2) (volume %) iz4.2 4.3 494.9 "4.9 505.0 55.2 =5~3 45.4 pH6.1 a6.1 036.3 a"6.4 a6.8 is6.8 os6.8 6.8 6.8 27.2 57.5 is7.5 i8.4 509.0 i9.3 9.7 59.7 C4FIo CBrF2CBrC1F Cenc, 103 CC1F~CC1F~ ca is CCI4 9.8 10.8 10.8 11.5 CF~CI IC1CH~ chal 123 CF.~C1 pee 4 CF~CF~ cra i CF~CI~ CF~H aa, kn CHCIF~ an jo C4F8 Sk ns SF6 BF~ cr a CF4 co. Bs CO~ 12.0 12.3 13.4 14.9 17.8 17.9 18.1 20.5 20.5 26 29.5 33002222..00006622 33MM_MMNNo044885555117711 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 37 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 357 e--efCffFfeesccatntiidvvee.. II--tt CmmaFayygbrbaeedippcrraeelsssuaummseewdd tthheaaasttbttrlhhoeemccilllneeaeavvaaagtgoeemoosf.f ttThhheeeCCf---c-BtBrrthbbatoonncddhsosryyiiineeelld-d as-s-uruCbebssFnttoi2itttuauattnesedddr-e-ccaCoodmimFlppysoorbuuarndnodidkcssealnaasrrdeeausennwoottetollaatsaheseefbfiffreeogccmtrtiieivvneaeetssauuetggonggmeeersssgt.tyssTttohhhfeaaftfoattrhchmteeattChCi--ao-tn-CC.clh1Olobbnrooinnntddhesesoaobtrutehhteenhrroatvhheaaansnaddr,pe,uarccdeooillmmyyppbpoorhuuoynsnkdidecsnsaldssuueueccfhhetocaatssihneCCieFrFxyt4g,i,rneg$SautFFie6sr,,heinaanrregeertghynneooottffreaaf.occttriimvveeaticcohhnee.mmiOcicanallltlhyye,, but have a purely physical effect in extinguishing the fire. D. CFabrs avo CF3Br atteTTnthhieeonwtwiono rffelcuueoonrrtiinnyeee--accroosnnDtahai.ainnvCieinnFggb2eBeccrnoo2mmACppNoFoDuuBnnC,ddFssabBwwrrohhmiiaccthhcihhlaauvvoeerorrmeeeccteeihivvaeendde.,mmtoonssdtt attention C25E8BC,a CF~Br2, ndiddniibb2rrr5eoocmmeConodtdrieifyfsllpeuieaoocrrtrsioovmmheealetvyth,ehaahnbneaee.ve.en bTTCehheFeenassBeserh, occbwoornmommptpoooouutbrnneidfdlhssuiogrhwwolhmyhiieccetfhhhiacinbbeeaoni,itll afniaardtet ete-xhx5tat8iinnnggCtuuhiiesashnhiidtnnyggp2ia5cgaageClenntrtnsseo~s5napSfe9l,cautg.io)v.reilBBnyaeo,t-thhhcaovnaaterreeabicnceonoengnnssisiaddhgeoeerrwnaatbnbsll,yytosmmbuoceorhrheeiagttshhhleeycrrammerafabflliollcnyyiensstttaeabtfbilrrleeea c(tchh"hlaCloonBrr"ii)ddthe,e,e, CCCHtCyiClpC1sii4c,b,aelmm.enettohhnyyflllubborrroionmmei-iddceoenCtCaHiHn3ianB,gr, and methylene agents, such as and methylene chlorobromide carbon tetra- chlorobromide b("oCthTTBhh"ine)ei,tiCCCalHFul3yB~BCrarInBdeerss.appefececiriaallellyyxpioisssummrueuccthho llceoesmssbuttsootxxiiioccn.tthhaaTnnheccoonanvpvepenrntotisiooinnmaaallteaaggleeentnthtsas,l, a`bcscoo.ontnhcrceeeinsnntutirtleaitaatitlooloynnfaoon1ffdSmCCaFiFfataneBBerr,x,epxotthpshoeuersuecco,orennwccaeteosnnfttrcraoatomtiioobnnuutsnnoteiebnoccneees.sds8sTaa.rr3hyyextt1oaop0kkp8iirllollpxpmmimmiiccaee(teSoo0rrl7e0rtrhaaxtatssl ca11sa008arabmmrogengpsuapelgetrernommtfi'~a)"),,C15wBwh"hmiicciCnhhHLeiisxCIpceBoqqursuiu,ivrveaaol,lneewnnttathstteoof8oo8tu33hn%e%dr tbbhoyyabnvvedoo,8llu.iu3msmteeoxiini1nc0aa6iairrtp..p3TTm0hh0ee(05hh00yy7pdd0rropo-- e(c(11xa66prb00oosxuxnrea11gs00e0a1nmmt vgg"aCpppoBeerrr"smmoCdfa)H)C2ooFCrra13l3B9%rr.,atbboyyncovvtnhoocelleunuomtmtreehaetiirinnoahniaaesirn..odf,IInn2i3scc,hht0orr0xoo0nincipiccaptttoo3xs(0ii1c,c04iit00yy0xttpeessp1ttm0ss,, ermmaxtggsp.oppseeNurroremmsiea)vt)oiffdovoerranpcceoeiigrgshwhttaoeesfeenCnfFoswuaeenBekdrkssafotddrciidodeintnnchooeettnrtssrphahuotoilwowmnoaasnnnoayyfrtty2oo3xse,ii0cdc0e0eemfffpfaeepccomttrss (oop1nnu4l0mmmioixccneea1roo0yrar n`rnaeCectHcsrr,.ooCssNiIisBso..reOaOvpninpdeeantthrhcesee twooottahhbseeerrfosbuhhoanaunndtdd,f,o10rtth0he0eeitphmmeparamxxpii(um5ml.umu3mmoxnapp1rrr0yoollmoeopdnneggemeeddra ottomorflleep)rruaaflttomiirooonnfnoauffroroy-rr tetCeeHenn2TwCtw1eieBseekrrsake(~pplsop,6re.~tae)r.ds to be about 1000 that when a half ppm (5.3 x 10~ mg per ma) for four- poundofgusaline was poured into a 011.3 iinnII..tb ohhisfiiggCrhhe,F,pso11Br22teessdxqit-tinihnn.ag,tuippwsaahhnneedniintnhae3ahfa22il00rf pmminodau15nttsedessctto;fccwghhhaaaesmmrobeblaeiensrre 1waa3nnasddIbp.iiooggunnfiriCtteeedHdd:,,iCnootIonnBlleyya 0ww.e3erreAelbrlretoeqhqfuouCiuircFgeehaddB(6br90oe.)tx.htinCgFuyiBsrheda the nd fire in 15 CFabry h sec; ave whereas 1.3 been used lb. in of mil CHzCIBr itary and cccooonmmfmAimenlsteehcrdocisiuapalglahaaciierrb,ccorrCtaahffFtt CiiBnnFtathhBhaeesr apparrconothdteeiccCtetiiFovoatnneBohdoref2fagairhisearcacvtrreeaasffttbt eueesennangggiiennu.eesBenndaaecceienlllsleemsst,i,islgaaitenndanddreyerooattalhhsnleedyrr cfoloiowrwneesferiranteoodrlrddoseewprratcooeeffsm,ttpooCexxrFiicacaiiBtttuyyr,r,heiaitsts iiassc(hcc6oio5ennvsFse)iidddteethrrhaaaenbblglCyyreFmamtoBeorsr.eteueesffaffgeeecc.ttiiBvveeesiiindn eeesxxitttsiinngggeuuniiessrhhaiilnnlygg ffiirreessT"Tahfhtreesosloeemwclctiooeqmmmuipppdooeuurrnaonctdduksserethshfaa(uvv-eeel6s5aasllsusFooc)hbbt3hee5eeannnwhCfifotFoueu2nnBfddru2m.eeiffffneegccttinivvieetiiicnnaceeixxdttiinannggduuiissJhhPii-nn3gg. f`iTraebslefroXmXXlIiqIuicdormopcakreetsfuseevlsersaulcfhireasexwthinitgeuifsuhmininggagneitnrtics)a.cid and JP-3. Table XXXII compares several fire extinguishing agents(~a). 33002222..00006633 I3MM_MMNNo044885555117722 335588 Hwc.G.. BsReYvCeE Excess or Wan Fosse Nomi Aco wo 3 Liquo Fis TABLE XXXII EXTINGUISHMENT OF V~rHITE FUMING NITRIC ACID .AND JP-3 LIQUID FUELS Fonds Pounds of Agent cine CH~Br perCH~BrC1 Chie CF2Brz agent used Remarks 90 Gmetad 9.0 fire not affected a] 5.5 fire not affected 55 foe ined exingibed 1.5 fire immediately extinguished CF~Br 0.7 fire immediately extinguished ireWWeixitttihhngffuuuirrstthhhieenrrg rfreeiddcuiucectntiicooynn, iiitnnspccoposeststraasnnoddbvggirroeeuaastteetrrhateemmtphpheharaessiiwssiloonnbemmiaanxrxeiimamsueudmm. ufisreageexotifnfgiuxeisehxitnigngeuffiischieinncgya,gietnatpspseuacrhs oasbvCiFoauBs rthaantdthCerFeBw.ill be increased usage of fire extinguishing agents such as CF3Br and CF~Br2. VILL Lubricants "ThoIIsnne ttthhhiiasstssaeercctetiioloninqtutwiodos ttiyynppceehssVaroIoaIffcI.tffleluLruo,ourrobsocurcaciacrhrbaboanonsntsolliuulbbs,rriicgcaraennattsssesww;iillal nbbdee trrheeovvsiieeewwetedhda:t: Tarhcosuesetdha1t arseurlfiaqcueidscoaintincghsa.racTthere, sluocwh caoseofiilcs,engtreaofsesf;riacntidonthoofsepothlya-t attfereoteruraanuffdlsuueocodroronoseaeitstdhheysyrullaeerbfnnaleeecewwuisilclelloaabbsteeinarrgneesvv.oiiielTew-whleeeedds iilbnonewaaarillcnaaogttee,efrrfoirssceeieticnintiototnnh.oe.f TTffhohririicsmstiooppfonolltyyhommifneerprfoihhllyaamss-s foonun8 dmectoanlssiduebrsatbrlaeteuse, as an oil-less bearing, or in the form of thin films on a metal substrate(~4). A. Puerox hesiSSollniiddbiinenggtwfferreiicncttiiotohnnosiises aapllammrtoosssttofccAeetr.rhtteaaFiinsRnullIyryCfTsddIcuueOeesN ttwoohitthchehe eecxxoccmeeeeeddiiinnntggollyyressattlrroocnnoggntaaacddt-- awhwtieitsthhihoigncehaabccsehhptweooetetdhheseenrr,i,thwwoehsvheieednnpenattcrwwtesootoshsfoaotlltiihddtehbbesooudpdriofiiaeenssctettso0ouuwcchhph.io.cihnTTthchaocatmotnetffrariicicncttttsioioobnnreetiaisslweppcerorneenssteetanhnctett wtarwteosohulisstguushrriffsnaapccteeehsseedaaslrrieeibseffroeoarvrtmiimdoeeenddnocvvefee2rrtyyhlaarrrtaagppteihiddeallmyyp.o.ouIIintntttiissotofaallhpssoeooaiwwn,etelwllclhoikKncnnthaoocwwmtnsnaybtt,hehaatowttf effcerroiinuccrttitsioheone,n rbbeeesuccLlaautllsbccruuiinllcaaatttheendedtslffirrbsooeemprmaatrtt{hahoteene wwotofohrreakkslraroeerlgqqieuduiiarrsemeuddrofutatoocnetssslloiisfddoeehetttahhhteea,twffaathccheieecsshsoolmvvieegarhryt,lecyaaoccfchhlceooovtutahhretsereer,d., pap5oorrwttLiihouoennbnssritcwwhahheniyitccshhwesccreopeomamcreelaetaeiinnn.tttoohWehccooisnlnotetlaaidccatt scccuoaanrnfnsanincodoeettsrasssbeeoliizzeeethdwweaigtitrthhteheetthohfeesllissguaabhmrmtlieeycaiitennilttoeeenvnnassctiiaettydny abmlsoeelwooebbchttueaalniiennteehtddheiywwcikiw,tthhetrffheiiellmcmelssenagoonfif.nvveWaaerrrihiooiulsueissmaoosrrcggowaahnnneisiccnideooevrrreariibn.nlooerprgogdsaaesnngiiirbccelesseuuobbafststtlasaunenbpccraeeicrssaaoottinniolnlnyyg ooctnanhenee: mmtmhoooevlvoieiicnnlugglienssuutbrrhuffilaackcck.ee,ss thbbyey 4 Alm of engineer a film of ail thick enough to have aims whenever possible oil thick enough to have the propertics of at separating the the properties of the oil in bulk. B. Two Trees or Lusmieation bouTTndw waooryssttlaauttbeerssicoosftfiollnuu.Bbbr.rTiicncTaawtttiihoooennThYccyaaPdnnErSobbdeOeyFnddaLiimUssittBiicnRngIglCuuuAiibssTrhhiIOeceaddNt::iohhn,yyddtrrhooeddryyenniaasmm4iicccoaamnn-dd bpaoruantidvaerlyy lduhbircikcaltaiyoenr. oIfnitlheevheyrdyrwohdeyrneabmeitcweluebnritchaetiofanc,est;hewrheeriseaascwoimth- paratively thick layer of oil everywhere between the faces; whereas with 33002222..00006644 I3MM_MMNNO044885555117733 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 35 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 359 fbbioouumnndwdahariryychlluumbbrariiyccaaottfiiotoennn,, ttbhheee mssouurnrffoaamcceeossleccocomumele.iinnttooccoonnttaacctt except except for for an an invisible invisible sfiqlmueIIenwnzhehhidyychddorrumootddayyaynnnoaadmfmtiaeiiccndsbllueudbbrmrraiicogcaganttioiinomognnotlaaehcehhuioilgiaglhrh. ivvni.issccAoosssiitttyyhehhioinnnddleyerrssfrittchhteeionooiillisbbAeeuiiningdg sfftrqrhiieuccetctieoiozonmenp,dlttehhoteeuetvvuiiassinccoddossiiiattyimyd,ssshhdwooiruuatllghddgainnnoetgst stbbhoeeenahhobiigilglheheeinmrr.attrhAhgaasinnnthiiossefnnsoeeanccfeleeystssysafasrrrhiyyctettitrooonpmmraoiasivininftdtlaiuainiindng stffihooteirronaac,nnoeyymtepll.iilkekTeetellhyyeflllauoobiwwideleirfrtiiilynnmogg,foowaffiltvvhiiussaccoobrsseiirattysyoittnohhacrlrboolatueuoggtmlhhuaibhhrregeinaiacntatgiitnoneggfoasnoafdfftetphthyeeeaoofitirlel,,rafddpeenrooccuovommrimdbppiemonor-g- ocsofhifitaitirotsasnc,sateseirstgicigs.nntTeiecdhdseffuuaonnbfccitltitiitohoyennossfoiifasllllaaurarbgrgreeeilclyyadmtdaeinietngteelrorymmiliiitnnomeepldduobbrbytryiaciniatttsstevviiaisnsnccodoseispntieysty.ru.froTTirnhmhgeecacchnhheueemmmmiicicbcaaeallrl scsttthoaaoabbriihalliiicgtttyhye.raaisnnAtddichsa2igffoaahfvvodotrerhaagebbrlleeeoeoittlefemmaapdrpeehereraamsttiuuaorirnneelyccbooeeeitmifwfciepiceoieenrnnttattonhofetf vaviiinilssccaoeosnnsidisttuyyt,r,hinwewghhmiiecccthhhaeliimsssinnucoroat-tl ftfoaaccoeeTsshhiiigesshdd.ceeosAsinirdraahibbtilgileeoh..nsdeagtreteheofsuardfhaecseiobneibnegtwluebernictahteedoialreanadlstoheimmpeotarltasun--rt- tothihlee 1Tss0ooh--wecceaatlcllloetenddhdetrieetsigguoiirnoofsnnaocoaeftfi""tshbbceooauussninulddyraafarricyyneflIulubebbenrriicinccegaadttilboounynb""r.ai.cbTTashtohereedbaaeabbdirilelmiittoayynlsoooolffaaaiymlleuurpbb.orriircctCaaaltnteiitnan-gng- momceailtetatitalonllgliiwocclessstuu,trrhftfaeahcceesescus,o,rnfffatooacrrceteeixxsaaanemmgaplspleileleyb,,eiiaannrrfeeglugugeesennunceaeerlrdalalyllblyyfyesqqasuubtiisthotearnbeeeaa5sds0illmyy owwneetottltaeeydderbbsyy. lube Clean lubri- cdaimt"iiAAnngimsmohoiolensnso,omtmhotheloeelcecocufnurlitlaacartcritoffaniilnmmgvleeoorffybeaaignrllgeooanntulggsy--u.ccahhlalaLyiiannlnesgssusumbbutshsittaeaannncct5eer0anoo.snnfeaarrsseoodlliidda ssmuuorrffnaaocc-ee dmtmhoiomellreeiecncbuiusyllhaaelrrsowffieiltmrhmienoogfffrtioochlleteiioiccenoeaafccvfiiieddcriyeffrnrotgomrmoefattthflhyreei.csstuLuiorranffnaacfgceremouoomffirawwbatoartutaeetnrrsuft1eno0irrtaaeydggtlloaaass0ssm.pp1ohla3antt0oee,-, AtAthshseeryfferibrrceytiailocllonytiwitsiedordouiunucenghe,tttoohaesspeecriizziouunercrfeeif,ip,cattioleonttrthheeeoasfaaoddfnrhhiecefstsoiiirooonnntshsferbboeelmttuwwbreeaieebcnnoatuttihthneegumnmeoioetlylceectctuoulloee0fss.1lww3a(hyh6ee5ern)ns. toovhnniellsyyy acorennoaeemllemmyooiltnleoetcuocuculrhlede,alttahhciiopccnkrktinaisscctittp.hhaaaTltthrttehehaeessyytorncceoonvvfgoeetrrrh tttohhhfeeetrrlheeueggbiiarooidnnchssaetswwiinhhvgieiccehhffofwrwecocoetuusllobddfeootlattwhyheeeeerrrns- wttthhhieeesetmtwwcuooocmhsseooslliimidndasstlolcceaarrennaslntnrooceonllnogotntnahggceetor.rfTbbaeehdehtthehsseetirssoettnnrregebntnehggtttwohhefeootnffhettthhhaeeedssmhoooelllsiiieddvcsseuttlhfheoeesrmmcswesehselilvbvceeehsts,w,haebbveuuent.t tbheeenmaubcshorsbmeda.ller strength of adhesion between the molecules which have been absorbed. C. HavorLuoocaRso Oits, Waxes, ao Greases of sW `oWlhhveeennnttthoChre.e ppoHootAlhlyyLemmOreFeraLrigiUzezaOnatRttiisOooCnnWAohoRfifBcCCOhNFF2cOaI==nLSfCC,uEFnW CCcltA1iiXoissEncSca,a1rA srirNieceDdhdaGiouRnutEtA tiirSnnaEnttSshhfeerpprraeegsseeennntccsee,. ttTohhhfeeisnnsoltaaveelssnoeetmrreiioeressrizoaootftfhioellonrowwraegammecontolitlesoecncuwulmlhaaairrychwwbeeeciaiggrnhehtptfruooeniiscllesstinotaannendddasggrrceehaaassieenss are formed. transfer agents, are formed(66). This telomerization reaction may be represented : Pandey a Peroxideh_.e.~ R" (10) Re + CFs = CFC RICHLCFCI, an R + n(CFz = CFCI)-.'- R(CFz-CFCI)~., (11) RCFLCECI, + CHClRICF=CFONH + CCl ay R(CF~-CFC1)n " + CHCIa..->- R(CF~-CFC1)nH + CC13. (12) CCl + MCF CECI COUR CFC a CCla + n(CF2 = CFCI)~ CCIa(CF2-CFCI)n (13) 33002222..00006655 I3MM_MMNNO044885555117744 " wo mer 360 H, G. BRYCE ls ge2l 1Ei] von 2 in 8an ls | SB ERiVgIhEo Rrn aPrey oC | co :tlHe| IE3 en i gt Fe agg Zl j,E gle 3 il 2 . Frys HEA Br iiti - iIis HgIp. pub, ' sas0 H3Haol(l.E E.F.3sEtusaet a1m3 v | yy 4 3 i i fe. $F o Sl| aLpf idipi: LsiEeSnheE etn ifedE ilElR0lREy 33002222..00006666 aw_oass1s7s 3M MN04855175 TTC HD INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 361 JT wr Em ty3 ig28 an 3og a el Et d saTMr olSFEg aan i woe Ea : i: LEHHE iy iE So fred 38: 3 4H obiieF pee]efRelogl5iiidfy|| lidl BRoepRpgpEiotohrnf;aagisRiflizEaTf|f| lCty 33002222..00006677 awoss176 3M MN04855176 In the above n can be controlled so that distribution of telomer products ranges from n = 2 to n = 20 are readily obtained with a number averaging 12 carbon atoms. As might be expected, it is difficult to control the reaction Fm erie so as to obtain narrow boiling range products. ee Te ret A second procedure has also been used to prepare chlorofluorocarbon oils. This involves the thermal cracking of the high molecular weight aFo lr ST wn polychlorotrifluoroethylene resins. When carried out under proper con- ditions of temperature and pressure, high yield of products boiling in the Be Foe SL same range as the telomer products are produced. The crude product resulting from either the telomerization or the thermal cracking processes must generally be stabilized by reaction with chlorine or various fluorinating agents such as F2 or CoF~. Vacuum distillation of this product leads to a series of products ranging from light oils to heavy greases and waxes. Such products are available from several sources and are known as "Kel-F" Brand halofluorocarbon oils and greases (Minnesota Mining and Manufacturing 1,000 . J 100 < : IN 10 -32 DEGREES CENTIGRADE F~c. 27. Kinematic viscosity of chlorofluorocarbon oils, 33002222..00006688 3M MN04855177 ors cr cn sos omy 8 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 363 Comtep rCona s Co.on sd Hesston Company), Fluorolubes (Hooker Chemical Corporation), and Halocarbon rate Coin Oils (Fluorochem Corporation). Typical properties for such a commercial series of products is in- cluded in Table XXXIII. It will be seen that the products range from light oils to hard waxes at room temperature. The kinematic viscosity of the chlorofluorocarbon oils as a function1 of temperature is shown in Fig. 27. Figures 28 and 29 show the variation in 2.03 .! .99 .95 fFom S 1.91 1,87 Se F RS s 1.83 1.79 1.75 0 10 20 30 40 50 60 70 80 90 100 DEGREES CENTIGRADE 1.5 te ts tases Fie. 28. Specific gravity of chIorofluorocarbon oils and waxes. ET -- specific gravities and vapor pressures respectively for representative memnr bers of these chlorofluorocarbon products. po r Hod e I, procs whe As can be seen from the data in Table XXXIII, all the products when properly prepared, are colorless and odorless. Siace these products are substantially free of hydrogen, they are transparent in the 2 to 4/~ infrared region, where most organic liquids are strongly absorbing. Bt co os Because of their high fluorine content, these oils are very resistant to Sc es comin ht mit all types of oxidation whether by combustion by air or chemical action of liquid oxygen, hydrogen peroxide, or fuming nitric or sulfuric acids. BE Pht sn They are also not attacked by CIFa at 150C or concentrated I-I2SO4 at Ey dn vk asd kr i 200C. They do not attack metals used in normal construction such as 33002222..00006699 awmsessie 3M MN04855178 364 H.G. BRYCE steels, copper, nickel, or alloys of these metals. Under conditions of high heat, they can react vigorously with light metals such as aluminum and magnesium. Under normal service conditions, the oils are stable up to temperatures of 260C. _ rE T1777 /? ! / 5 .. ~ lO.O o/ Xr LE 1.0 TANT JA wl TTTTTTTT] 0.1 150 200 250 30035040045050 DEGREES CENTIGRADE 29. Vapor pressure of CTFE oils and waxes. rvs feria eal praia dnt tat The oils and waxes are soluble in aromatic, aliphatic, and chlorinated hydrocarbons, alcohols, ketones, esters, and fluorocarbons. They are es sey eoncsi ,nd rorsT,hy20 insoluble in water. The degree of solubility, of course, varies widely with molecular weight, the high molecular weight waxes being less soluble than the oils. It should be noted that the relatively high solubilities of these oils are due to the presence of the chlorine atom. Comparison with the fluorocarbon liquids, such as FC-75 and FC-43 containing no chlorine, as discussed earlier under Coolants, will emphasize this difference. The oils are excellent lubricants. Under certain conditions they exhibit the properties of a pure extreme pressure additive. The mean Hertz load as measured by 10-sec run in the Shell 4-ball E. P. Tester(6s) is 120 kg, 33002222..00007700 3M MN04855179 mca, esc o moon cums 365 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 365 + vile yh comps aval ith ype vale of 70-30 bg. or accoovmmammleureecrciwiaalhlihchhyyddrcroooccmaaprrbabrooenns ttfyyappveeorggaeebaalrryulubwbrkircihcaantntystps.i.cal values of 70-80 kg for "Ti chlrarscabon obs hav found exenive we ss ibsicans ffoorr Thhihiggehhllcyyhlccooorrrorrfoolssuiiovvreeocssaeerrrbvvioiccnee..oTTilhsheehyyavwweeerrfeeouoonrrdiiggiiennxaatllellnyysiddveeevveeullsooeppeeadds ffloourrbruuiscseeaniitnsn h`anhdlaingntthhdeeslseeppaiarranattiigoonnoofftthheehheexxaaflfuolriudoesorofiftdthhee iisotsopoesootffuuroraannpiiuumme((6ss8$).. Toes he sh ing cd iy to fits. pro, ie They are also being used extensively to lubricate compressors, valves, we a, Hy and ws oF WO seals, etc., in handling liquid oxygen, and a varicty of highly oxidizing rin mal and oa and corrosive missile and rocket propellants. ee oe av oh ep at. 2 Tato Ads i yr These oils have also found extensive use as flotation fluids in gyroci doin We ig dn he OT gay scopic devices. While high density is the primary property in this use, a me Se Sw we chemical inertness, as well as the ability to attain specific density values ain the ifn ol, es ak porn. Sil ore by blending the different oils, are also important. A typical gyroscopic Tm device is shown in Fig. 30. ( hl EHH oo 3 Rn HEHEHBLEHEHRIENE HI if Hy fHRese: bo HH HEHEHE f( i HiLEnRH n nH n HE E --FHnL8 F~G. 30. Gyroscope utilizing clorofluorocarbon oils as flotation fluids. 33002222..00007711 awnosso 3M MN04855180 336666 6.H.G. mmc BRYCE a vW Wahherennoifttgehhriiectcakkseeyennseedmdawwyiitbthhe mvvaaadrriieoouufssroiimnnotohrrgegaacnnhiilccorttohhfiicuckkoeernnoeecrrassr,,bossnuuccohhisaass ssiilliiccaa,, a variety of greases may be made from the chlorofluorocarbon oils. D. Oren Fuvonix-Coxaiivg Fiums `wetAiAnllgtt,hhoosueugvgehhrattlhheefyyluohhOraaiTvvnH eeeE-nnRcoootnFttLaaaUiccO nhhiiiReneIvgvNeeEfddl-C uaiaOdnnN syyThA eeaxxvItNteeeInnNbssGeiivevenFeLiuuUnssItaaDrggSoeeduaatctettdhheaesttsiimpmeeeciaoolff lmwluuarbbtirretiiidnccaagnna,tstsss.e.FvIISenn-rcac1lll2uu6fdld5uee,oddriaaFnrrSeee--a1cas2oes5nre0tir,aieienssiFnooSgff-1flf2lluuu8ooi1rdr,oosssiihFllaSiicv.coeo1nn2ebe9e0fAe,lniuiddaisnsntdraaonndddFuScgg-rer1eed2aa9ssae1essssddp(eeeDsscoiiigawg-l mCnCoeaorrtmensdiibnnaggasseCCdoForoSrppno-o1rfar2aut6tio5ioor,nno))sF..lSTcT-ho1hne2ees8see0d,epprrriFeevSsasut-u1immv2aea8bsb1oll,yyf atFahrSree-1tlloy2opw9we0.mm, oolalenecdcuullaFarrS-ww1e2eii9gg1hhtt poly- (Dow poly- mers based on fluorosilicone Pp derivatives of the type Cl Ramon!N-1%}cis RtCH~CH2Si -- CHa wwarhheeersreehoRRwfinissian ffTlluauoborrlooeccaaXrrbXboXonnIggVrr.oouupp such such as as CFs,C1 CFa, CF, C3F7, et. etc. Typical Typical properties properties are shown in Table XXXIV. -- TABLE XXXIV men. Pores TYPICAL PROPERTIES Fuvosoenaon Fuums FS 1266 FLUOROCARBON FLUIDS FS 1265 Baa Nitcwoagrade 250 cs Viscosity grade 1000 cs water white to straw 00a 10,000 cs Color aa, cr 25C Viscosity, cs at 25C Veet om Viscosity, cs at Te -18C Te37~C 0c 100C asC 205C Specie gravy 125C Specific gravity at 25C Fre pon Freeze point [---- Flash point, open cup Fie pane Fire point Vola (v1 Volatility (wt %) 4 hr at 200C shee 0c 48 hr at 200C 120k 20C 120 hr at 200C 20h 0C 240 hr at 200C Ge, hem 20C Gel time, hr at 200C Aid mbar Acid number Suc eon Gyms perc) Surface tension (dynes per cm) 0250 wo3900 To140 n24 s5 tas1.24 sie -51C msc 225C TEC 275C 4.1 ns13.5 2020.0 io25.0 550350 Eetrace 325.7 wo1000 mow 22,000 So510 i74 ins11.5 Tas1.28 owe --40C mse 275C sas >325C 1.5 53.1 `05.0 so8.0 350350 --trace PY26.1 00m 10,000 wom 440,000 Shao5400 e690 [80 Tao1.30 we -32C msc 275C suse >325C 1.5 303.0 Ps4.9 506.0 550350 eetrace El28.7 33002222..00007722 33MM_MMNNo04488s5s5118811 sees rs pee come 30 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 367 J E. FLUOROCARBON ~IONOLAYERS pgp on ini Zisman has studied a series of hydrocarbon and fluorocarbon derivatives i pp adsorbed on clear glass surfaces(7). He measured the contact angles, O, ay anny es exhibited by methylene iodide (surface tension 50.8 at 20C) on the i min My UL adsorbed surfaces. IIe also measured the coefficient of friction for a stainless sSiinlobSenppe iS00)c pe he ry g steel ball sliding at the speed of 0.01 cm per sec while pressing against TT the coated glass plate. Typical data are plotted in Fig. 31 comparing the iL] e Lo tii fe 40 i |Tog 0.25 TT [o=n o 6 0.05 22 FIG. 31. Frictional and wetting properties of condensed monolayers. crt mer org of CHAT COON, HERE contact angle for homologues of CH3(CH2)nCOOH, HCF2(CF2)~toi COOH, and CF~(CF2)nCOOH. I retaining Whereas the plots of 0max vs number of carbon atoms differ quite rn fe o,f sn om markedly, the plots of /~K, the coefficient of friction, vs the number of oS carbon atoms lie quite closely together. It is particularly noteworthy that A the HCF2- and CF3- terminal groups cause major differences in the wettaa Br thom laptop yt bility of these condensed monolayers, but these groups cause no essential difference in frictional behavior. As might also be expected, the hydro- iy mi ty yet re carbon compounds show much lower contact angles, 0~ax, to methylene S R p ok y de Sr iodide. The coefficient of friction, lzn, however, does fall to a value lower than that for the fluorocarbon derivatives. 33002222..00007733 Pp 3M MN04855182 8 noon 368 m G. BRYCE [A ---- It is concluded from this work that while wettability of the surface is A he opoews determined by the substituents on the terminal group, these substituents es or cr play a very insignificant part in boundary lubrication. The coefficient of BE oe ett Seot tr friction of either a fluorocarbon or hydrocarbon derivative is most influee btpkhh enced by the ability of the molecules in the monolayer to close pack through resesem o the strong adlineating effects of intermolecular cohesive forces. Ee osoe he hy It is noted that the t~; vs number of carbon atoms curve for the hydroa oe re Hato cps carbon fatty acids crosses the curve for the fluorocarbon compounds at mi between 12 and 13 carbon atoms and thus has a lower asymptotic value. a to nh rg 5 emt mesh This means that for chain length greater than 12, the mechanical strength i. es so of the condensed monolayer of the fatty acids is greater than that of the em in corresponding fluorocarbon derivatives. Ce g / K4 RE 5 .50 i .40 i= 4 idan .30 sre .20 . eZ .10 i 0 LL | ! S I0 15 20 25 3O Number of Traverses TE -- FIG. 32. Comparative durabilities of straight chain fluorocarbon and hydrocarbon aS i carboxylic acids when adsorbed on solid surface. an os ho sti se ditof ded So, by mong Zisman has also studied the durability of adsorbed films, by making a ecmraieTe oFf oee esdtaSom 3 monn series of successive unidirectional traverses of the steel ball over a 2 mm path on the film-coated glass plates. The ball was held firmly in one 33002222..00007744 Swnoses6s3 3M MN04855183 soo sr ow orn 50 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 369 position in its holder so that the same area of the bali was always in contact en with the glass plate. Using this procedure Zisman has shown that for a homologous series of fatty acid, there was no change in the coefficient of friction even after 35 traverses for CI~H,~TCOOH and higher homologues. Lower homologues showed coefficient of friction increases at progressively fewer traverses. In Fig. 32 data is plotted showing the changes in coefficient of friction for straight chain hydrocarbon and fluorocarbon carboxylic acids of equal chain length. It will be noted that a monolayer of CHa(CH2)~0COOH under a load RE of 1000 gm will break down after only 3 or 4 traverses, whereas a monole layer of CF~(CF2)10COOH has essentially tke same coefficient of friction even after 30 traverses. This means that a condensed monolayer of the fluorocarbon acid is a solid, whereas lauric acid is a liquid. Similarly, a nan condensed monolayer of CF3(CF~)6COOH is so much less durable than a ssoolliidd mmoonnoollaayyeerr ooff CCHHya((CCHHz2))1i0oCCOOOOHH ttkhaatt iitt mmuusstt bbee ccllaassssiiffiieeddaass a2 lliiqquuiidd monolayer. On the other hand, the eight-carbon fluorocarbon acid is more durable than a liquid monolayer of its hydrocarbon analog. Presumably this greater durability is associated with the stronger bond to the glass because of the much greater acidity of CF3(CF2)loCOOH. 0.7 W JLT T Ei 1 g | 0.4 0.3 ~ 30, Ector o | go.2 3 REG | O. I Cl (CF~CFCl)~ CFaCOOH ( W = lO00J ) 5 IO 15 20 25 30 35 Number of troverses FI(~. 33. Effect of halogen substituent on the durability of a condensed monolayer. 33002222..00007755 3M MN04855184 33700 wo muvee ~. G. BRYCE for"ToTchhaeerbddaaottnaaaiicnnidFFiiisgg.s.o33m22ewaahllsasoot smshhooorwwessduttrhhaaabttletthhetehaCCnFFs3thtteeerr--mmCiiFnneaatlteeldd t11e22r-m-cciaanrrabbtooennd fI1l33u--occFraaiorrgcbbuaoorrnneboaanc3ci3idad.c.isdhoiswssomtheewhcaotmmpaorriesdounrabbeletwteheann the the --CF2H terminated fuorocarbon acid, C`CCEFFY3F(C(CiOCgFuOF2rH)e).6oCC3OO3ItOOHsHihs,,oawpaaspnnaddrthettenhhteectcochhamhltlpooratriihrninesereoe--nssuuisbbbss4etttiiwtiuurettgeeeendd aaatnhnndaealloobfggel,,unocCCrhoIIi(c(aCaClrFFb2.foCCfnFFcCCta1Tc))io3d.n-, afBCitilFmomgmCsssOttrfrOeoernnHggA.ttuhhoIrticcnaaiesuu.ssaeepdTdphabbsryye,ntttwhhtheehearssteuusbtbshsstetitirttehuuettiiisofonlnauoloorafforgccceaoorvbvaaonalnldeenncbttiednbbeoaffnniocddrieeamddls eccffhhelolcoirtqriuionnin-d- Tammtohoonemnoolsglaaryfeyeoaerrtr,e,frluttmhhoeeercinhcceahh.nlliooTcrrhaiinluneess-,.ctcorwoennhnttgaeitirnnehiiannsoggfthtaaehnneaaflllcoouhggo.lororffocionarrmarmbtsseodnaalappcmlildiaassttfiioccarmtmmtsoroinbnaouoltlalieayqdyeuertird.o. tTthhheeeIlltaagrrrrggaeeeayrrtbeeerenneemrrcggoeyynchcoolaffundiiicnenatdtelerfrsmmrtorooelmlneecgcZuutilhlsaamrroafccnoot'hhheeeswsioiocornhnk.l.otrhiantatAeudorfiolcmaribsonattdreirbiuvtaetdivetos ctchaaenn Ispsthrhmooopwwaeyreebxxceccheecalloilleennnnctltluelldnuugebbtdrrhiicfcr5aao0nnm.tt35ppZrroiotspopmeerhartatniivee'sess,,wgbboouurokttdttthhahadattlt ifiilnttueoiiassrtoonncneeaccreoebsfsossnaatrhrdyyeert1ooi0rviasseteenillvteeeeccsdtt mmmthoaoelxelecpicurmuloelupesms.e.rbTIctothniiasdinaaillssnlooetgoniigmmttphhpoeorssrtotuaabnnsatttsrttatoootessheetlaloeevccbetteaaglouffbouurdnniccctataiidtooelnnidnaa.lel aggtirrooonuuppotfthhtaahttewwioillrliessnhhtooewdw maximum bonding to the substrate to be lubricated. IIXX.. FFlluuoorrooccaarrbboonn SSuurrffaaccttaannttss AuorIIonncttahhreebsoseenccsttiihooannvooenntCChheharalaroacwtceetesrtirisststiiuccefPPrcrooeppeetrerttniiseeissoinitswwaoasfs saseeneeynn ktthnaaottwa5ns:amactlleaarssissalttshh,ee cfW Wlouhhomeernpnocoaaaurffbnuuodnnniccssttiifoohonnarsav]mleeggdtrrhooweuuhppliociiwssheaaasttrttteaascecuhxhretefdradecetteosoetaaleynfflssvuiuooorrnrfoosacccaeoarrfabbcaootninnvyett.aakillSn,,uor8awfnnnaeecwewmaaccctltleaairsvsisisatloyos,f.f omcofoef mdccooipuuuorrmsuse,en,,tdiisossdmidesiefgffioirnnraeemtddeeaatdssotwthahheeniacadbhbiilaoliirrtteiyyeeonoxtfftcaroecnmoometmIhypepossuouunrrufdfa,anwccweehd,heaec,ntnthivedderii.sessbsSoylulvvrreefaeddcidieunncaiaclnltigiivqquiuttihiydde, sismsuuerrdffdeaaifcucieemnnee,ndeetroarggsmyyai((goomrrroalstseeuucrrffutoaalcceaee,nttdoenneoesniroiesennn)idtooofofotnnfthh)etwehhelliiiqcqsuuhuiiddr.if.sacAA4e,Afsluotuholourerboroiecclbaaiyrrzbbinoorgenndfssuuuucnrricffntaagiccottnatahannlett ggmisrrioonduueippf,m,inuwwemdhhioilaefs ttfahhoeeumrooottclhhaeeecrrruboleeennn,ddaotccnoooemnnssseiinsastdtnssodooftffewaarmhfRiliuuncoaohrtrooeicsdcaabrarybbsoo3onnlu--ggbrrCiooliuuFzppingcgcrooonnfutuptaan.iicnntiiiTnonhgngeayal have the general formula minimum of four carbon have the general formula atoms and terminated crac =X by a --CF8 group. They CF3(CF~)n -- X FABLE XV TABLE XXXV Moss Seance Testo Vase 1 Warrso Serres Fwomocmmn MINIMUM SURFACE TENSION ~ALUES IN WVATEII FOR SUBSTI~fUTED FLUOROCARBON [-- SU~FACTANTS Compound Compound Concent. Mim race ersion Concentration Minimum surface tension (emper 100m) (ms permet 570) (gm per 100 mI) (dynes per cm at 25 C) Rete Reference Crycrycoon 03s I an CF~(CF~)~COOH HCH(CECO0N os as @ HCFz(CF~)~COOH ick CRabCRcoon 050 0 an CI(CF~ CFC1)~CFzCOOH 0.35 0.50 0.50 15.3 21.8 24.0 (13) (72) (71) 33002222..00007766 I3MM_MMNNo044885555118855 INDUSTRIAL ASPECTS OF FLUONINE CHEMISTRY an INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 371 When eiathyhdreogren atom or another halogen C1,o Bir are substituted W f2fosorrhaaaennnsyyuebooistffhitttehhureetaeffdhliuuyofodlrrriiuonnogeereoaancttaooarmmtbososmniinngorttrhohaeeunpffo.liutuhFooerrrrooochcmaaarlrtbobhogoenenndggarCrtooaIuu,ppio,n,rttTBhhaiirbss, lawweriielllXlsbbuXeebXsddtVeeiftfuiiintnteeeiddds assiseseeeaann sttvhuheaabrtytswtwihsthiuegetnnenidfttihhfceelausnsuotubrbsoitscnitacitrrtuubetaotiisnooenntgiatrnaokkuetepshs.eppFllmaariocceenmiiinnthmtehttuhemeedrtsaemutrairmfniainnacealTlCtaCebFFnlseagigorXrnooXuulXppo,Vw, etthshiiteenrrigees if`pspuooossassriiobbvlcleeea.r.yrbTToshhingeencissfiuuocrraffnaamctceeinpaacccirttesioiavvaisiptteupyyriooonnxffitttmhhdhaeeetemshhlyyiynddirrtmooheggueemsnnamsaaeunnarddfsatccchehhallototerroininfnseeicoossnnuuvbblesosntwttiiitteuourttineneadgdl fhhcloyyuuddorrrrsoooecc,caaairrrbbbcoooonnnnscissosuutmrreffnpaatccowttuiaantnndthtsss titthseeerarmpZmpiiinnsroaamtxtaeeinmddcarbbtiyyetliycaaaltshtteueerrrmsmfaiaimnncaeaeltleanCCssHHtihoaaantggorvrfoaoulucpuop.en.svTTrehehniptisois,ro,tneooadffl ecaorulriseer,wisheconntshisetesnatmweigthrothuepsZaisrmcadansocrribteicdaol nsursfoalciedtseunrsfaiocens.values reported earlier when the same groups are adsorbed on solid surfaces. A. Susrace Acrive NATURE OF FLUOROCARRON COMPOUNDS SchoAl.be~rUgR,FGAuCeEntAhCnTeIrV,E aNnAdTCUoRoEnOrFepFoLrUtOeRdOoCnAtRhBeOsNurCfO acMePaO ctUiNvDe Sproper CitieeFss,SCoocfOfhOoaalHb,ehhroogmmC,oaoGllFoousggeCoonuuOthssOnHess,cre,rriiaeCcnssydFooC:ffoCfofOlunuOoorHrer,oopccoaaCrrrtsbebFodoynno;nCccaatOhrrObbeHoosx,xuyylrlfiCiaccicfeaa3accsiciddtCissvO,,eOnHnpaa,rmmoepealelynyr,d-, C`CCpogFoFFau11Cn9dsOsCCOOaOrHOOeHH,aU(bCIlMse2),.FtAAsoCssrOewwdOaaussHcess,hhtoCohwewanFnsvuiirCnnfOaFFcOiieggtH..e,+n4sCooiffosanFaollppfCrreeOavvOiiwooaHuutss,esrsCeetccTottiFioo1Inn~6,1,C0ttOhheOe1ss8Heed,ccyoanomnemds`ipppneeocrrurcencamdmse.s.s.aTTrhehFeeaobrcclooepnnrctcoaeecntnrtietrcrdaaautltciioeopnnutrhrrpeeeoqqssuucuisirrr,feeaddcoenddleetyeccnrrteeshaiaoossnseeessosscfhhoaaamrrwppplaolyytuenraassdtsotthh1ewe6icctthhhoaaiia1nn8clladeerynnbnggoetthnsh hicnhacairi"nenToahsofeefssfs.ilixxuFoooorrrrocmmpaorroarbrcoeetniccccaaaannlrbbbpoeeuxryccploooinnscsseiiasddc,eeidrroesenddalyraaesstaheelfofsffsoeeeccittmiicvpvoeeomrsstpuuarornffuatanccdaeessaacccwhtteiiivtmvheeicaaaaggleecnniatntrsstb.eorn`medTiahteesfliunordoecrairvbionng caarvbaostxyalricraayciodfs oatrheearlsfoluimorpoocartrabnotnassucrfhaecmtainctasl. The intercccmaaherrebdbmooiiawxctyyaelllsiiccirneaaaccdciiteddiroinvggsirr.nooguEupxpaavmmmapaaslyyteasbbrreeoafyaatllohtteifesrreoedatdhreeiirnnsfhlmmouaowannrnoyycianwwrabaFyoyigsns. sbb3uyy4r.faccIcoontnnavvnteethnsint.stiiToocnnahasaelel chemical reactions. Examples of this are shown in Fig. 34. In this case F,,co0m (1) C,F~ ~COOH (1) ' C,TF,~,sCcO0O0MM ((22)) EL F C,FLCOF-- - CCrTFFL~.CCOOOORR(8(3))=-C-yCF,F,,CsCHHzMOH ((44)) C.F CONHC, N(CH, 1X (6) Cv F, sC ONHC~ I-I~N(CH~)~- HX (6) C.FCONHC HN(CH,H\CCO. (6) - C~F~ sCONHCaI~N(C I-I~)~ (5) ?[C~F~sCONHCaH~N(CHa)~R]+X- (7) [- C, Ft sC ONHC .I~(CH .)~C ,H.COO- (8) Fie. 34. Surface ative composnds baseodn funrocarhon carbonyl cid. Ftc,. 34. Surface active compounds based on fluorocarbon carboxylic acid. ttchhheeemcciocoammlppocoeululnn.dd,,FrCCoFvmiF:tsshCCisOOFcF,o,mmmpaoayuynbbdeeappwrrieedppeaarrveeaddriuucstsyiionnggfsttuhhreefaSSciiemmooancntssivceelleeccctotrrmoo--`cphoeumndicsaml aceyll.beFrpormoduthciesd,coamllpoofuwnhdicahwcidonetvaianrietthye osfamsuerfCarcFeisa-ctgivreoucopm.pfuoourBBnrodricisccaeermbaaaoynnnddbseTTurlproforototnttdyulrrceeefppldoou,rrottraeeildddleostt,fhheewwhhppiirrcceehpphaacrrboaaynttitioahoinynndrootofhfleyaassiahhsmoommemooalClyoovgFgb~ooe5uu-sscgossroneeruvriipeee(rss7t4eoo}df.f fluorocarbon sulfonyl fluorides, which by hydrolysis may be converted 33002222..00007777 33MM_MMNN0044885555118866 wn" rr 372 H.G. BRYCE othe coresponding luorocarbon sufi aids. Besides showing he to the corresponding fluorocarbon sulfonic acids(172). Besides showing the pica propofeaRrroiccbosn aractan, he avon compounds well typical properties of a fluorocarbon surfactant, the above compounds are all expand stron acids, heving acid Sent gress ch he song exceptionally strong acids, having acid strength greater than the strong mince acids, HCL HNO, and 1:50, mineral acids, HC1, HNO3, and II2SO4. Fliorocibon sulfonic cde sec sso important 8a sorting materia Fluorocarbon sulfonic acids are also important as a starting material forth synthe of many 20ditional suse sei compounds coining for the synthesis of many additional surface active compounds containing he same fluorocarbon a but with rey varying ncion rope the same fluorocarbon tail, but with greatly varying functional groups. Gucnthnce and Victor have reported om humic of (hes Compoari, Guenthner and Victor have reported on a number of these compounds, example oaGfarwrhssiocohnna@e) included in Fig. 350. Tn she Sar the writ examples of which are included in Fig. 35(75). In the figure the starting ans c.e,0ckcoon 4) R ~C.FnSO,NCH, COOH (4) crasol of somone Learrvslolsliceaimnsn -CaF,~SO~NH (3) R CsF~vSO~NC.tI, OH C~FnSO~N(C~I~O)nH (5') R Cs FnSO~/WC.I~OP (OH)~ (9) Larso0lnoson uo (5) ~C,Fx~SO~C~H~OsH (I0) feRCaHNCrHIIs RIX (6) H cursofemaicn), ofsroonierence o Curso emacs), x @) H [-"[CsF,vSO.NC.H,N(C.Hs),R]+X- (6) - C,F~vSO, NC~H~N(CH~)~ (3) + C,F,~So~NHc~H,I~(C~H~)~C2H,COO- (7) ~- Ce FnSO,~qC. I~N(CH.)." I-[X (8) io 3. Sr civ compounadn arco sili ie FIG. 35. Surface active compounds based on fluorocarbon sulfonic acids. matali the compound, RSOSF, which is a product of the Simons material is the compound, R~SO2F, ~vhich is a product of the Simons ectrchemical procs. 1h the Rui the xamp. chosen bs ConSORF electrochemical process. In the figure the example chosen is CsFnSOzF Which, 2 wes shown ric, ha 3 Saorouubon sil of he ight chain which, as was shown earlier, has a fluorocarbon tail of the right chain Tengh show goo uae Scinty. Dirck hydrops of the CLE ASOR length to show good surface activity. Direct hydrolysis of the CsFITSOzF cud to the acid, CuSO or ssh. The two wlfnamd pes rc leads to the acid, CsFnSO~H, or its salts. The two sulfonamido types are dived by dint eso wih a pemry oc acondry amine Thos derived by direct reaction with a primary or secondary amine. These mines canth be comer 0 sulfonate ac nd sls o amines can then be converted to a sulfonamido aliphatic acid and its salts or he sich. Reaction ofhe skohal vith then axe give a poor the alcohols. Reaction of the alcohol with. ethylene oxide gives a nonionic ype. Quatemizstion of te. ery amino sulfonamide ves the quer type. Quaternization of the tertiary amino sulfonamide gives the quaterry xan The ection wih. lke la tan aphore beiie, nary cationic. The reaction with a lactone leads to an anaphoteric betaine. From tho alcohol, on th other hand, normal suf o phosphate cer From the alcohol, on the other hand, normal sulfate or phosphate esters canbe prepared. can be prepared. "Thin, 3 very ore number of compaunds can be made in which the Thus, a very large number of compounds can be made in which the 33002222..00007788 W_MNOABS18S7 3M MN04855187 rfehtee,PR heft a 3, sasd INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 373 fluorocarbon group, Rt, and the functional group, X, are varied. For a given fluorocarbon group, i.e., CsF~7 the solubility of the whole molecule can be varied by changing the character of the functional group X. The sulfonic group, the carboxyl group, the quaternary nitrogen group, etc., all impart a degree of solubility in aqueous solutions. On the other hand, the introduction of hydrocarbon groups will give solubility in a variety of organic liquids. SA -- B. SURFACE ACTIVITY IN WATER ie i Sn et sn The data in Fig. 36 shows the effect of changing of the solubilizing r ER Sfe b pn ae thtn ieeg group for a series of fluorocarbon sulfonic acid derivatives containing the CsFIv group. Of particular note are the extremely surface active compounds, [[CCssFFI~1S3OS2ONNIHICCasHH6gNN((CCHH~s)~)]Ia+I]=- aanndd CCasFF~1T3SSOO~aNN((CC2aHH5)s(HCC2HoHaOi)OI)4HH 7TOOT fio wo: 5 /CuRaSONCHICHOPOIOH), Gensou EY @ . i 2O tt p-- y 0.0001 I 0.001 FSONICH) {ensomCyNCH" Fig. 36. Surface activity of various fluorocarbon sulfonlc acid derivatives in water. Lip On the other hand, the free acid and its salt are much less effective. It is interesting to note that the lithium salt is much more surface active than the potassium salt. pnTe En m A similar relationship exists for a variety of derivatives of CTF15COOH ; again the properties are very greatly dependent on the nature of the functional group. Fig. 37 shows the relationship between surface tension and concentration for a number of specific compounds. 33002222..00007799 3M MN04855188 a wo. wee H.G. BRYCE ciscoE+no H,,CO0- T5 wo7 [CHF ACONNCHONICHy)ST fa ciracomns fo aracoon $J3 wwo 1 oon com oa or 10 wo 0.0001 0.001 0.01 0.I I I 1.0 I0.0 is Wt % solids Fo 37 Sc tofyos Ron oie evs ne FIo. 37. Surface activity of various fluorocarbon carboxylic acid derivatives in water, C. Suamace Acriviry i Staavo Acts wo Bes C. SURFACE ACTIVITY IN STRONG ACIDS AND BASES "Thelonger hanfsuolfonirccdoslsctratrthbe groaphicnally The longer chain fluorocarbon sulfonic acids illustrate rather graphically come of he ariguIs dus of the FuomenT bon sudan, TPIS. some of the unique qualities of the fluorocarbon surfactants. Typical 7O . fI!e C| o HE [ Lo i ON FE al TR 4 - ~ so i. Ao . ore | come riersom Concentration of FC-95, Wt Fi 38 Ste ety ofGu aBot bcc FIo. 38. Surface activity of CsF:TSO~K in aqueous hydrochloric acid. 33002222..00008800 W3M_MNMONA0B4S85S5116809 ocean, rss of rns core INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY { um i : | ile] I| boVO ii : \| 1) i3 i Li{ti3i%tf t i A Vi [IR i3 evI xI +! a1 % i 33002222..00008811 aw_nossss1so 3M MN04855190 337%6 iHo.G.. sBRRYcCeE ``eecxxoaanmmvpeplrlteeessdaarirenetCCotahsFeFii~rySSsOaOl3stHsH. oorTrChCae2FFf5(lCuCo6erFFo1cS0aSOrObso3HnH,,abbooctthharooicffwawhdmhioiccnshhgmmatahyyebbseetrrroeenaagddeiisllyty tacachcoioinddsvsseekkartnneboodwwonin.n.htoaIIvtttehmmeuaainryyussnnauooltattsl.bbseeTuhttroofeosocfssleuuuroprpprrrooripicsseaiirrnntbggioenttsooaifnfciiinsdndodslttauhhtraaeittoanccmsoooomfmnppsgootuturhnonedndgssstmsrsiouunncceghhreaaaslsst aotahllnsooeo.s.eoIfTannbtohFFiveiggesas.h.iad33v5s8e,, mu33en99n,u,ts44iu00oa,,nleaasdnnuddrafab44co11veettph,hreeoCpddaaeaFtrtiaatiressSshhOoioInwwKs,ssottlihhuseetivoppenroosyttaaosssfusiirsufotmramocenssgaaallcmttooiifnvfeettrhhiaeenl one of the acids mentioned above, CsFI~$O3K, is very surface active in Fi. 40, Sutfc sci of CHFsSOAK in aque hoshorc acid. Fro. 40. Surface activity of CsF~vSOaK in aqueous phosphoric acid. hhTyyiddirrnooecchrhlelosortriiiccngaacctiiodd,n,otsseuulltffuhurraiiccwhaaeccriidde,,s ptphhheoosasppbhohovorericiccomaapccioiddu,,ndaannidds nnnoitittvrreiiccrysaacucidri(f7dc6.)e. aatIchtctetiiisvvcieenontiiencnreenppstuutrirraneetgiwwtoaonatteneroor,f,tettththhheeearreetmiwiisnsheeaarraemmlaaasrartkkiheededdaibiinnoncccrvrreeeaeasacessoseem,iipnnaotttuhhlneeedasstiuusrrnuffaoapccteevtoe3arc6y3tti7svvu%iirtyyfafc3oae5rs ctHHhoOCemI1p,,coo55nn00nc,/%de'onstffrosoarurtciH Hoh2n2S1S5o0Of5C4,t,,haaeFnnSddmOi22nS55eK/r%/oaliffnooarrctihHHdeNsNieOnOcss3r.te.raoTTsnehhgsee,miassnutuerrlrffeaaaacclseetaaacucciptdtiisvvteoeisnn3daa7utt%uuerreetfoooo3frf `ccpclooeommtmebbpliyionnuaasntttiidaoobsnnloeso;uffcshsseeecvvaoesenrrdaCalllsyFff,aaIccTtttShooerOrsss..vKeIIrnnyinttshhtteehreoffiisnrregssttssppturllloaafccnoeeng,,icmtthhaieenceccdrooammgl prpaoocouuiudpnnsddesisnsaaadbrrlueeeeccsoototmmh-e-a cScpoaolemmmteepployotuuisnnmtdedabmttlooeab;ibensetseuicsfuonffnifadiccliyireee,nnltattllhtyyievssevoolyelluurhybbillgeeshtriionnlnettvghehleesusoslfctfrrootonhnnieggc fmmaoicnininidezerergsda]rlofaauoccrpiimdd.enasInantbddwleisalsttlttthhbheeee nesnaoommtteeaeddt ticiinmnonaaeclllelmncctaaarssiaenetsstiatotihnhnaastatittnrhheetelahssteiuuvrrreffaalanyccgeeehottiegefnnhss0ii.loeo0vnn0ess1tlaaoorreef0.trrhe0ede1duuicwcoeenddiz%bb,eeedllofowowrm2200.ddyItynnweesislplpeberer cm at concentrations in the range of 0.001 to 0.01 wt %. 33002222..00008822 33MM_MMNNo04488s555119911 susso uscm 57 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 377 l ~ I i A - seerTEE ar FIo. 41. Surface activity of CsF17SOaK in aqueous nitric acid. I KEY TEMP. - 25 C 7O __ CONCENTRATION n-C~F~7$O~K- 10-;M/L {HEvBeerEiorR @ - HNO; SOLUTIONS - HC! SOLUTIONS ~)- H=SO, SOLUTIONS -- = ACETIC ACID SOLUTIONS Q = ACETIC ACID SOLS. (CONC. OF DISSOCIATED [H] GIVEN IN MOLES/LITER) x = PRECIPITATE PRESENT aEH Ss -~ 40 3o 2o tO0 Concentration (moles/liter) Fzc. 42. The concentration effect of various acid media on the surface tension of CsF17SO~K solutions. 33002222..00008833 3M MN04855192 ws WG. mmce 378 H.G. BRYCE sulfTTonaailbclobat(co7iatd) phhoaatssassmmieeuaamssuusrareeldtd, ttChheeeFrssuuSrrOffaSaccKee, ttCeennRssiAiooCnnssoFooffSOtthhKee affnluudoorrCoooccFaairrbCboeonrn sFsFuhIuloofSSwoOOsnisatcKKhaatciinintdhddeipillcouuotttameespsoaairunnidmdndccssooanhnltccosee,wnnsiCtresataFthee1edd7sSaaaOccm3iiedKd ,issnooClcluuFrtet3iiaCoonsn6ssF.f.nIoTsTSuhhOreef~aKddcaeattaaeanctdiiinnvCiFFt2iyiFgg,ws.Ci44t6h22oasahcvcieoddrwshsstretrheeannctgognitthchheenffctooorrramtttpihhooeenunrssdatornosgnhnegogowfmmsi1tin0hne-eer2rasatlalomaa1ecc0iiiddnMssNc,,.reHHaOsNNneOOitsnha,e,suoHHrtfCCahc1,ee, haaaacnnntdiddv,itHHyCio2wFSSiOOirt,hSfoSveOOecartKKsthiiaessrmmcocuuonccnchhseinllsettersesasnttissouuwnrrifftaraachcneetghaaeccttoviivefver1yiin0ns-taaartowwoneega1al0kky aaM accciii.dddOssnuauntccuhthhsreeassoocfatcchtteehtireicchfaaalccuniiodddr,..oCcTTahshrFeebIsso?eensesuufflleff"cooTtnnshiiecacruaaeccoicirddosos.n.csaisrtbenotnwsiutlhfotnhiecvaecriydsstarolnogslyhoawcidprnoantuourencoefdthseurffluicoeroaccatirvbiotny in sTtrhoengfbluaosroecsaolrbutoinonssu.lfoTnhiceadcaidtas ailnsoFisgh.aw43psrohnoowusntcheed ssuurffsaccee atcetnisviiotyn in strong base solutions. The data in Fig. 43 shows the surface tension 80 ElN ~N~e[ ws T] T] 60 L~XS present i| 50 IN [1 Sd40 ~~ 7 T 1 g 30 r 1 1 2O 10 0.001 0.01 0.1 Fis. 42. Stace eof CoFSORK 1 25% NOH. Contendration of L-1159, Wt % FIG. 43. Surface tension of CsF17SOaK in 25/, NaOH. ddeepprrTeenssssFiiioognn, oof#f CCsutFhtSeTOSnOosnaKiKoniinincas22u55i%a%cissaoonddtii,uummCohhFyyddsrrSooOxxiSiddNee(ssCooIlluuHttRiiooYnnC..LHLO)H is ssAhllohwItnhnetotFoosibugbwre.efva4vecn4ereryytthessenuusrrifnfaoocncneeimoaaecncattiicsivvueesruieinnrmfevaancavttraasrinicetw,tyeyrCooefsfFmca1cai7idSd,e,ObbgsiaNssfe(e,Cc, aaaHtnnhddTe)ss(sCaolllatuHsts4ooil0oluun)tnstiiHoohnnsas.ids. etAbheelelensntuhaarelflaoscwuleretfdaetcntloeossistotetnoaanonnsfddioftwfnohoerm22ceel4eahchsotuodurruorelrsmystaaeetnsrrtosooloouwmmtieorttneee;mmmtppheaeerdraseashtuuaaerfdet.ee.drTTathhhreeeabbstaaohtrleurreteiedpopurnecrssteebinsoatsdns tiihnnessuusEurrxffraafamaccpceeeltteeteesnnnssosiiofioonnnthwwoehhfivitccahrhheiewwetalayessctommrfeoealmaysesuteudrerisedaod.l.uintiownh;itchhe shaded area the sls of the reduction fluorocarbon ssisuulliffnEoodnnxiiiacccmataapeccldiieddsbssyosaefrteehthecceoormmevpdaplureliectetteetylilyyonossftaiambnblleseeduirasaerfeeiincsshhtwooewwhnsnincihoiinnnth3FF5eiiggs,s. ha44la3t5sw,. noSSufubrryffflaautccoheeeroaasccchattairivbvdiioettnydy is indicated by the reductions in surface tension as shown by the shaded 3300222..00008844 I3MM_MMNNO044885S5511933 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 379 SSuurrffaaccee tteennssiioonn ooff pelaeci trolyte ssoolluuttiioonnss. Joo oconnationinnigng 00.0011%% CCgaFF,i-t7SSO0zzNN(C(aCHo,H~4OO),l~HH I00 80) - 6O - 4 3a0 3 20 o 1 1100%% HHz2SSO0,4~ 1100%% NNaaOOHH mm | 4400%% NNaeOOHH 2200%% CCaaCCll2 Fro. 44. Surface activity of nonionic surfactant in various media. THT } 8O NY ANNINN Te NN 2O [1 [1 20% NaCI 20% CaCl:~ 50% NaOH 10% ACETIC ANHYDRIDE WHITE FUMING HNOa 30% H20= 95% HYDRAZINE cos epee sta oso wi on bie. Thesuid erent be Fro. 45. Surface activity of CsF17SO3t{ in various chemical media. The tops of the columns represent surface tension without surfactant added. The shaded areas indicate the surface tension reductions obtained with CsF~TSO3K. 33002222..00008855 3M MN04855194 30 no. saves 380 H.G. BRYCE aairrneedaai..caMMtaeadxxiibmmyuuCmmaFddieepzprSreeOss5ssKiio.onn`isTshoneottcaaollmwwpaaoyyussnoodbb,ttaaCiinnFeeCddwOwiOtithLhtLhthe,ettoyyrppeeiotosffsssattrrluusccttauuxrreee, ifnordiecxaatemdplbe,y mCosrFeITsSuOrf3aKc.e Tachteivecoamndpoeuqunadl,lyCsTaFbIlaCe OinOhHy,droorgietsn spaelrtos,siadree., for example, more surface active and equally stable in hydrogen peroxide. D. Tus, Sramwry TheTThhteeheffrllmuuaoolrrooscctaaarbrbiblooinntyggroroofDuuapp. giiTssiHvssEettanRabbMllfeeAuLottoroSoTttceAeammBrphIpLeoerInTraaYttsuuurrreefssacitinnanetexxcwcieelsslss, oohffo44w00e0v0eCrC.,. b"TbeTehhdeedeefptpleheuneonrdrdmeoencanatltrbsuuotppanoobsnniluilttthyfhoeenoattfhtheeeasrrammgraiaevlleessnxtacaefbblpiiutlloiitroyyonacoolafflrbytthhoseenabaalsttteuta,arcfcshahceetddhanffutuonnwncctiiwoilool,ndnaieahlcloogwgnrrremoovupgupeop.r-., ossTiitththiieoeornnflhubbaoeenrlldooo,wcwadr33be55oc00nomCCspu..olfsTToehhneeabtyeffslleuualoorirermooieccnxaaacrrtbebipoootnnniooccnfaaacrrlbbalyoorsxbsyytolalinbiccledaa,icoisixhddiossdweaainnnatddg tnsseaoalmlttdpssee,,croooatnnmupetthoeheseoofth1e7r5ha1n0d3, 5de0comCpose by elimination of carbon dioxide at temperatures of 175 to 250C(77). E. Sumrace Acriviry ix Organic Mein iofW Wshuhecehnn atthhneeatffuuurnE necc.tttiihSooaUnntRaaiFlltAwggCirrlEooluAusppoClTuwwIbhWhiiliTcciYzhheiiitNs haaOttrRttaeaGsccA uhhlN eetddIiCntgto~ocEttoDhhmeeIApffolluuuonordroocc1aa0rr.bboodnnefttiaanil-l iriistteeeco,,ufltthssh,uoocuuhggAhhbalnssbmmaraetaulcllrhietdd,teehggaBrrlteeaeeikteiiw,nnilaalannnsodoolrruggPbaarinnlyiiiczcceemmtewhedeediriareae,,stuaahletuuinnnriigqqsuucteeomtccollpaaossrssueopnofodfsrustturofrofaanaccdttseaafunnictnthssusfrleeousiroucorlsotcsca.oafrrAbbsoohunnblbsrtsseiuuctrrhuffttaa,eccdeeBalaaamcckitteiidv,veeesanaaogdgfeenCBtns7r(tyTFcsSie,);. wC"TOeThrhOeeeHyythawweneedrrfeeiCrsyaatbbFltlyoeeyttrCooeOpOssohhrHotowcwoonutthlhsadauttcbhe8a `sTmmeohordieidefiscfiieoeodmdfpttsooouussbhnhsodotiwwstsusstteuuudrdfraiacemfed ciaaadcrieetvcisvsiieohtyyfowiiCnnnTaaiFnnn~uuCmTmabObbelOererHooXffXahhXnyyVdddIrroo.Ccc~aaFFrribIbg~.ooCnn4Oty6yOppgeHievmmeacstaoettuerylripdiaiacllbassel.. raTresehsspuellstcos.to.tme"TdpThhoaeeulnorrndiigggshhstttthueeednnbiddeossdttooaofrfemtthshoheefobtbwhaanerrssicnhiiannTrddtaii.cbcaalTetteheXettXhhseetXrnVnipooIerr.dmmFaaailrgle.ssa4uus6rrrffageaccpiveereesttseeetnnynsstpiiiotocnhnasesl amsagpnliotttueddesaloofngthtehelobwoetrtoimngsofobtthaeincehda.rt.ItTchaen sbtreipseedenartehaastredepcrreesaesnetsthien magnitudes of the lowerings obtained. It can be seen that decreases in TABLE Jo0v1 TABLE XXXVI Tome. Fusonocusson Soscrasns TYPICAL FLUOROCARBON SURFACTANTS Chere formuie Cote Chemical formula Code arson vt CsF~vSOaH CIFLCONHCHN(CHL ra CTFisCONHC~H6N(CHs)~I CIRMCONHCHNCHCalle 3 C~F~sCONHC~H6N(CH~)zC~ol l~IIr CIEACONHCHANCHCIL 4 C~F~CONHCzH~N(CHa)~C~HaI CIrLCONHCHANGH Fs C~F~CONHCaH6N(CH~)~I corucontCaNd 5 cl I CTF~sCONHC~H4N<~' C1 CIRCONHCINCTonc 2 CTFI~CONHC~H6N(C~H~)~CH~I CRCONICHNG CH a CTFI~CONI IC~HaN(C~Hs)zCH~I CIRACONHCN(CTi I C7FI~CONHCaHaN(CHa)~ CRaCONHEMNCI, Fo CrF~sCONHC~H4N(CzH~)~ F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8 F-9 F-10 33002222..00008866 I3MM_MMNNO044885555119955 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 381 surface tension range from about 5 dynes per cm in Stoddard solvent to 14 or 15 dynes per cm in molten microcrystalline wax, linseed oil, and lubricating oil. TOLUENE I PERCHLORO- ee ETHYLENE 57 STODDARD SOLVENT a aT" | KEROSENE CY LUBE OIL TT NUJOL LINSEED OIL MICRO WAX owe 100~C TT 20 30 SURFACE TENSIONS (DYNES) CM Fro. 46. Surface tension depression for a fluorocarbon surfactant in a variety of organic liquids. Several fluorocarbon surfactants are quite effective in lowering the surface tensions of melted petroleum waxes. Data is shown in Fig. 47 for a fully refined paraffin wax with a melting range of 52-55C. The normal surface tension of tEis wax at 100C is 24.3 as measured using a DuNuoy Tensiometer. Tt~e minimum effective concentrations are at the knees of the curves and occur at between 0.006 and 0.03%. The compound F-2, CTF15CONHCaH~N(CH3)aI, is rite most effective of the compounds containing the CTFta- group, giving a surface tension of 15 dynes per cm at 00..0011%%..OOnn ttth~eeootthheerr hl~aanndd,, tthhee ccoommppoouunndd FF--55,, CCsgFF~1gsCCOONNHHCCs~HHgNaN(C(CHHa)a)a~TI will reduce the surface tension to 12 dynes per cm at 0.01% concentration. Fig. 48 shows rite effect of temperature ; as would be expected, the surface tension vs temperature curve for 100C is displaced downward from the curve at 75~C. 33002222..00008877 3M MN04855196 m2 6. me th AAassbssihhtoowwtnno irinnedFFuiicgg.e. 44t9h,e, ttshhueerfccaoocmempptooeumunindodsnssFE-o-33f,,3FF-m-44i,n,eF7r.-a99l,,iaannddbyFF--111000 osaelllmhhoaarvveee dutdhyysenndeeassbfiopplieetrtyrhecctomme.x.rpeeTIdnrnuicmtteehhniittsshse,ccaassuAeelrlfaaahceebbaatcsseeeonmsssipotoooncucskknodIlfsuuabbarrpmiicpciaaenttsieinrnag1gl boooiieil,l, fbSSeycAAt1EEi0vo2e20r0,n,mvwotiharsees 0021.0008%, by weigh concnaton ane. used for the experiments. All the compounds appear to be effective in tt~e 0.002 to 0.008/{) by weight concentration range. pot25 24.3 PARAFFIN WAX AT 100~C We 2O iii 15 11 0.0001 0.001 0.01 conammaron wi x CONCENTRATION, WT % Fi 1. Stier of parti a coming vis ocemtooffnarse FI~. 47. Surface tension of paraffin wax containing various concentrations of fluoromeni, carbon surfactant. SOSGGHuueeannlttohhanpeerrrodaaunncdde VViicmettaoorrrkehadavvereedssuhhcootwwinonnttihhnaattsuvvraafrraiicooeuussteddnesecirivovanatotiifvvee3ss ovofafrCCitslyFzio?footShrrOggaaanpnHiriccoapllqiesqoruuiipsdordslo(Vaudb5TMui)cl.ieI0zstianiasgmpagapprrakporeauderpennrtietdffourfoocmtmpioathnrhaeeimneeoxxusuaanmmrtfpapliclemeespsotcertinttaeseniddocenhth.aatoitfntthahdeeevccvahheroolieioicctpyeeinooogfff stmmhuaetaxapicmireoumpmteernssssuuoirrolffuanacbceeidleiazcpciirntveigvsisiygtiy.ro.onusZZpiisimminsaaonsnfcaaepnnnaddrtasccmooo-wswuounrcothkrkeiemr3rs3spohharatahavevnexcsrpeedopiernoctradteenedd,veoolohnnpettihnhhege cscccuaahhrrrllfbobrSaoroocoonnbembucucetaattaearrdnbvdbieosoicerxixonynyyenleli,i,iccndaataaenneccpddriirdsdestttssr,ri,isinciiicgohnnhnlccloesllourfuorcddiodcniidntinpisggpshhoeChCelnaoavnvyFeyFelTn,,:tCsCbbbOyeyOOseOuaanCCc~nnhArHuueHmmp~a,ob,sCbreCetrrnreTF-dFohos1fef5xCeCeaxOsOdtwteOeOherciCCrsac4noHohHeff,TaClf(l7urhu.9oaeo)rx.riooan--- Some very interesting effects have been reported in whictt certain 33002222..00008888 M_MNosss19T 3M MN04855197 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 3 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 383 `Aflwuuhooirrcoohcctaaerrbnbdoosnn tssouurprffraaeccvtteaannntttssthpperroomddiuugccraeetaaiossnuurrofffaaccteheebboaarrgrsaienericaattma0atnerooirargglaatnnihiccrossuuugrrhffaatccheee,, wsiinnuthtreeifrcraffhcaatcctaeee.n.ntsdAAsbhiltnlobbhrirpebeicrctekhivt,n,egneefttthtaahlel.e. ehhmvaaavvipgeeorrarrateeitvoviinioeenwoweefoddfthttvehhoeleoarteegiffalffneeeccictthyoomdffrassotueucrccaihharlbfAotluhnuosrororoosucucgaachrrhbbtohosnnes sggaaufasrslofoulaliecinnntecae,en, tshhoefeippntothaarinngbeaei,nt,iinceegttcca..tc(h7t8ei1v.eevGsGauupureofenarndacthtthianonnenetrrsofaainnnvddodleaVVctiirileeeetawosrhriyndghhraaovvtcheeaerbrremoevivnigiserewawsteeuiddcohntthhoaeesf pipvnillafnlsyautliescnpitcozeleiyrcsmooeiofrrrzosoot,erthgrhaeaessnrrhicmmailigag,ecrataaitvtdooherreyyssicucvoorefmmsa,pcpoetotanenae.etns7ntt.ssinffrroodmmescsurueccahhsinssygsytethm.essaamstspiplgalerasastttiimioccniizzseeoddf vinyl polymers, aspl~Lalt, adhesives, etc.(7~). PARAFFIN WAX 28 25 15 14 concomaron or rawr 5, 0.0001 0.001 0.0! 0.1 CONCENTRATION OF F-2, WT ~o Fic 45, Bile: of tempers on sca tension deprevin of 8 freon Fro. 48. Effect of temperature on surface tension depression of a fluorocarbon surfactant. cet IInnalmmcaoahnnoyyl haaarriivdde rrbeeeggeiinoonnussseoodff tttohheerewwdouorcrlelddthhheyydedevraoopccoaarrrabbtooinnonssuuorfrffwaaacctttaaennrttfssrssouumcchoh.uaatss cdopeoootouyrrnl dppafoolocnnorddhsmso..slIihnnaavtt"lheasiikssbieccnaea"ssneeoufiisttmeaaodpplppteeoecaaurrrlessadrttuhhcdaaeittmtttehhhneeesiennovoonnanvspvoooloralnaatttiiitlolheenessouulfrirfqfwauacicadeetaecsartucifrtvrifeovaemccecooosmumn.td-pthoeurnedbyfoirnmtesrfaer"eskwiint"hotfhemeosleccaupelaorfdtimheenvoslioatnisleownattheer lmioqlueicdulseusr.face and ttlereby interferes with the escape of the volatile water molecules. 33002222..00008899 I3MM_MMNNO044885555119988 384 H.G. BRYCE Ahlbrecht, Blake, and Bryce were able to produce very marked reductions in the evaporation of gasoline, through the use of the fluorocarbon ssuurrffaaccttaanntt,, CCyTFFi1;5CCOONNHCHsCH3eHN(6CNH(aC)Hs3*)I3-+(I-F(-F2-2)).. FFiigg.. 5500 sshhoowwss tthhee eeffffeecctt 31 FATT] MINERAL OIL AT 25C ! \\ | A = 2O 17 0,001 0.01 0.1 CONCENTRATION, WT % FIO. 49. Surface activity of fluorocarbon surfactants in mineral oil. of 0.003/; by weight of this compound in inhibiting the evaporation of gasoline. In the example shown, the beakers were placed in an open hood with a constant air flow. When the per cent of liquid remaining is plotted against time, results such as those in Fig. 50 were obtained. It will be noted that the rate of evaporation is quite rapid initially in both cases; however, there is an abrupt decrease in evaporation rate for the F-2 treated gasoline. The initial rapid evaporation in this case is probably due to the time 33002222..00009900 3M MN04855199 oues sofs, ons Gury 385 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 385 pT -- | 1] 75 : PH ! \ 5O TH 25 - TIME, DAYS Bat -------- FIG. 50. Inhibition of rote of evaporation of gasoline by a fluorocarbon surfactant. FEE ER CHE gg iH ie = H Lill 2i 1 Beitofpug Sion FIG. 51. Decrease in flammability of gasoline containing 0.003 wt o~ of a fluorocarbon surfactant. 33002222..00009911 awosss200 3M MN04855200 386 H.G. BRYCE required to form the barrier film on the surface ~vhich requires migration eT rir of the F-2 molecules to the surface and then orientation to form a closeRR re me packed fiIm. When the treated gasoline is stirred, there is a sudden increase in evaporation rate, which appears in the case of F-2 to require 10-15 EE TR Sr EI min to return to the inhibited condition. It has been found that F-2 ES, hE mn EY forms a condensed or solid film on the surface of the gasoline, which S haH g Te EtEt EoL l el me accounts for the length of time required to form initially and to restore BAC TE hut flit itself when stirred~80L From a practical point of view, compounds which would form liquid films would be much more rapid in forming at the surface. The much lower rate of evaporation is graphically illustrated in | | | Lenseosars ousoueson | GASOLINE--3 DAYS STODDARD SOLV.--9 DAYS ifr | AN / | o LL 0.001 0.01 0.1 FIG. 52. Effect of concentration of surfactant F-2 on inhibiting action of rate of evaporation. Fig. 51, where untreated gasoline is shown to ignite rapidly when a match ER a LS is placed over the beaker, while a treated gasoline cannot be ignited. [rt As might be expected, any given compound has a rather specific a oe 7 Td i effect on a given hydrocarbon solvent. Through the proper choice of potable CAN ok solubilizing group, however, compounds can be made which will have a A ATSTE pronounced effect on a wide variety of organic solvents. i boy melAEE te ote The relationskip between concentration of F-2 in the gasoline and effectiveness in inhibiting evaporation is shown in Fig. 52. It is interesting to note that there is an optimum concentration of about 0.003 ~ by weight. 33002222..00009922 suamossszon 3M MN04855201 INDUSTRIAL ASPECTS OF FLUORINE CHINISTRY 37 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 387 TtThhheiisssuprpfrraeecsseuummlaaaybbellryy; ihissigtthhheeer cccooonnnccceeennnttterraaatttiiiooonnns rrieenqquutihirreeeddgasttoooliccnooemmtppellneedetell1yy pssraatotuudrruaactteee ataahddsessoousrrubsbreefddaacnlleadayylceearrryasseckraa;st. the surface that are 00 thick higher concentrations in the the surface that are too thick and which contain many gasoline tend to produce and which contain many friesgsuuSSrmlmeaaslallgal-s-nssodcclaaicllnereaecefkisleshld.dowtteeedssttssa uursseiidnnuggctttihhoeen FFin--22evccaoopmmorppaootuuinonndd lasottssaaebsbooouftt a00b..o00u00t55%3%0ii%nn sirnnue'rgafaualcasstriiammngtuuaslls,aaotteleeisdndpeecrreiseahffilionlnweyerreyoydnessattogorirreavadgiguenecgtttiaaaonnnklk.i.qinuW Widieitvsthhauprfotthahrcaeeetiddofeenilvvmeleollasoonsppedmms eheonanftvt iaoonbfgfoussatpplee3coci0wiff%eiircc aCscpuooprsslftta,icciiatttatinisotasann,nstteiwiscchpiiepepraacettieaedlvdloylttahhotaanittleetthhgoeeirvssgeeiannfgfiloucsarooorlliocqvcaeuarnirdtbbsoosnnuarssefuuarcriffenaavccfotitlalamnnetdtssa.nssdhhoohuuallvddinffgiinndda many lower many tahpep"rAAlmicoapssteleicaocsoontnnsiddcwtthysyeppyreeestvooeofflma""stbbi.alaerrrroiiAreegsrrap""nhiaeecflfff,seeocclttfvoehhrnaastssexbbaaeermeeepnnilneoov,bboslsveecerrovdvns.eeiddstiisnn oa4fvvaa3rriieerttayytheoorff tbbthorreooraanmoddmovrrpoaallnnaaggstteeiilcooeffsrcycesoostimmenmpsp.oso(uu7nIantd)d.sshaArrsaasnnpbggheiianenlgngt, ffrrfreooopmromretrrxeeedlalaamttitipvhvleaeetll,yy wcllohoowenwsnibbsootaisilliiunonogfgrlloaiicggahhrttartboohoiiellnsrs ststouuhrerffnaamoccinttgavirnnoattltaiiitsosilneddiiossrfsseoostllivhnveeesdd. giiIhnntttthhhaoeeislhhsbootteteaantsshppherheaaslpultotr,,rftattehchdeeerreotehfiaisstthaawemmahaseaprnrhkkaeleatdd. frrleeuTddeouusrcoctttcsiiaoorhnnbaoviinnen tssahhnhegoolwwemnntiogtthrhHaaayttti,,dorwnwohhicoillfaeerthttbhheoeenlasimgsipphnhtlearolaatillastassatloii,nnitiothtinieaallslsltyuyarnppfdaooicuunerrgeeoddffoddtoroahceessfeannwsoopththoassulhhtr.osowwTtheaaestcscsouonrnhtftaaaavcccteet ababnpeepgcceoloeammrteeostsoaqqbhuuieyittdeesrooooliciulabrrrleebeppoeienlnlllemetnhntie,tn.eiIrIgannhltttohhoiiilss,f,occanawseeshtiatthcnhehediffanllugtuoohfrroeooryccamaarirfbbgeoowennnhtssueoururftfraaoscctttthhaaeennttssuuwwrrooffuaaulcclddee aooCfpafrpttbhehoaeenraatssotppahibhlaeaslltts,o,orccliuaearbnrrrtleyy tittnhhheeetmhssseueurlrlffvigaaecchstttaaonnatintlsssd,wwwieitvthhheincttthhhueeaammls.l.tyhAAefytottmrhhmeeigssrauuaertceffaoactcnoeedettthhnheseeesffduluurofofraricoome-- cwwocaiicrttubhhrosntt,hheettahCCielEsFlsaiogrhttieteerrnmomtfiilnntahaclleamnggsrrnoeooluuvppelsssoneegaxxenttredennmddieiigvnnregganttooeuuuatotlwwlayartdrhdf,eo.rsmWW urhfhaeaecnen.cotthnNhiidossetnccsoooennndlddiyitftiiiaolormnne ottthohceecwyyuertbbs,lltoohtcchekkeeledodlwigbbheyynt ettohrhiegelsyhhc--eeaaaCnvvFyynsoffllsuuluoorofnrraogoccecea.arrrbmbooinngrmmaotoelleectcouullteehsse,, but they are surface. Not but they are not able only are not able tuontwrSSeeeeatvvteteehrrdeaalllaoggswrpraaheppanhhleiitcrcgaeeyrxxe-aa-mmCfpopFlrleaemssesduoofrffiattnhhctiieoss. shhhaaevveeetsb,beeaeennndsshhtoohwewsnne.. sW Whheheeetnsn pttrlreaeaactteeeddd iaannndda Cwuwaeneratabrtteohhaneetrresodoumrmfeaeatstcepetrh,a,aniitltttsrhheaaasssiresbbtseefoeetrnhnmennewoodettaeetiddnhtettohrhiaastnthgetthaehcteest,iaaossanppnhhodafalltttthheeccsooewnnatttsaaheiirneneiiantnsnggdpttlhuhaleecterffdaluvuiooiornrlooe-at- clTiiaggrhhbt`toAmmnnuoustccuhhhreframmcoeotxraraenemteepfrfleffeeesccisttiitivsnvveetollhyylevttehwhsaaennathttthehheeeruisuunenngttroraeefcaattaitoesendpdhaoaaslsfptpthhhaiaelnlttw.partoedruacnidngulptarapveirolteot aaasstppahhAacalnolttnollctaahemmneitrinrnaaeattxeteisaso.m.npIIofflfeaa ff1ilnu0uv0ooorr1loo0vccea3aser0bb0tohonnpepssumuusr,reffaaacconttfdaannatttshphhiahsassaablbsteepehiennanltpaaddrioddsdeeuuddscettioodntgtohheppaaarpssepepphrhaaarltloett aaaatnlldaaammwciioinncnaakcttieeenngwtwriaoitttfhhiotnhaaeowwifhhgi1ihtt0tee0opptioaalpp3eeb0rry,0 iitptthpehhmaaw,sshiabhtneeedeennpthaaopisbebsrsacesrripsvvheeraddeltdttuhihscaaetutdsttehthdoee temmosisigpegenrrtesaipttaiialoorlneny aazZseenprrdhooawleetivv,ceekonninngwwthhhoeeefnnothttethhheeelrighlThaaatmnmdoii,ninlaasstteehboyiiwssrsithheseeeaawvtteeehrddie.t.ewAiApcakpccieoonnrngttirrsoooflrletduuhsuesiicnlnegigdghaattonnieluussnnstetbrrneeytaiaatttleehldyde awwBshohpiuihtrteeasltppa,atapopreneorrothssmooe tttoehhmtaahptteeiirrttahiitssauncrcdehh.,aannsggheeoddws1to0sea2vyyeeerellllowowwiciiskshihn--bgbrrooowfwnnthcceoolllooigrrhiitnn oly 3 oils by only a fewthe few hinoculOOrustdthheaeetprrlroaeesoxxtamaimmciptpzleelmeedsspovoeifnfrayttlthhuiiprsseoss.lecyccmooennrdds ttayynppdeeopoflfasbbtaairrcrriiizeeerrd wwahdhhiieccshhivhheaasvv.ee been been studied. studied include plasticized vinyl polymers and plasticized adhesives. 33002222..00009933 I3MM_MMNNo044885555220022 as x. c. wwe 388 H, G. BRYCE . Avsonerion ox Sous F. ADSORPTION ON SOLIDS Surface active fluorocarbon compounds can be either physically or Surface active fluorocarbon compounds can be either physically or chemically adsorbed on a sod sufi. In sithe cas the resuling lms chemically adsorbed on a solid surface. In either case the resulting films exhibic both oil and wate sepeleny, lower coefcints of Fiction, ow exhibit both oil and water repellency, lower coefficients of friction, low Sdhesive qualities, and other eects asocared with low energy lms. adhesive qualities, and other effects associated with low energy films(Tin. Figure 53 shows the contact angleosf vater, methylene iodide and hess. !~'igure 53 shows the contact aagles of water, methylene iodide, and hexadecane on lm of CFSO:NHCH.COOH hich has been chemisarbed decane on a film of CsFI?SO2NHCHuCOOH which has been chemisorbed i war [r-- ae Waler o> Tr Meigeas 160 Hexodecane I10o Methylene iodide 160o Fi. 55. Adscingconnc angefor vos uso skinsafc i FIG. 53. Advancing contact angIes for various liquids on an aluminum surface coated with a fluorocarbon surfactant. oothnnesahhliuugmmhieinnstuumme.v.erTThmheeeassseeurcceoodnn.ttaacTctthaaenngdgleleeosliinnbtrthhoemirrdaanenggqeeuaootffer11n11a00ry--11o6600tfhsarrecsauammlolonan,:g the highest ever measured. The decyl bromide quaternary of the sulfona- smhiodwes satmrionneg,a(dsCoorpPtSioOn ,onNgHa(sCanHdAsNli(cCsrHfc)eCs.ioBHr]y for. example, mide amine, [CsFlvSOp,NH(C3Ha)N(CHa)2C10H2z]+Br-, for example, cshuobw"UosnsUisnstdgreortnthihgveeaatSSdhihsavoelerlllpat44id-o-sRBnoaalrollblneW Wdgelaeaosanrs,r aTTmneeedtsstas(liStlil,c)s,auiristfuarhhcfaeaasscebbssee.heeonnwsshhiomowpwrnnovtthheaamttenffltuusoorrooi-n- brsCbceoaoooptrmptbohhpoorartpnpretooadeiibdnnlettttehrhiBaaBvtttao(t(ftfilvloohaueeaodosdbrrooeavvcctdssaasrawowbbraooedbnraner)id)eexxeaaottnnrnreddkernmmnsaeeollestwoopparnrlwewesssesessua5auurrrrfraeevvcsseaasddttdidimsiimhtieeiovvweevvsasalliuussmehehspos.o.rwwoIIvttefefimhhfciaaicessienentnbbscceeiieeeiennnss ocnoma"AlpAggiaaarmiiainnb,r,luewwmhth,oeenntthhtteehirecbeeccisoostmmaapndpodo8uiut0nnivd%desCCsaskeFfnd~ouSwcvOtSniO{No7~n~CN,isHCn2L~Ct,HhIe~HCaLd~hHOe4sPOio(Pn(OOoHHf f)o)2isisscaaoddmsspooarrrbbeeeddd on to u"nTtheestceodmbhinuedmpmro.petis aluminum, there is an 80% untreated aluminum(7al. reduction in of adsorption the adhesion and stability of the foro- of ice compared cCcoaarrrrbbToooshnnieossnuucroriffnmaahccibtbtiaainnntetotdrsssmmpiarnaokkapeeeswsritiiidtteesppvoooassfrssiiiaebbtdllyeesooTfforsopyrtisottthnheeemmamsndttaoonsdfftauucbnnoicclnttiitidoyoinntoieefofflfntehcscce.ttiivfvTeleulhlyoyerso3ae3s- ccccoooermmrpoposoiuuonann.ddissnFhcaciaarbnnietffxouuarnnsrccpittnilioo,annwtbbhoioedttehhcovaamasprssioeoltualyunttidoioofCnnsaybiFsnithebimSblisOteoaNrsnsd(aaCnenodLdnaHadsCsitHipPorIrnooOstt(eeP7cc(~ttii.OvvFTee)hsseeuusr,re- faaSaddtcsaseoocrrkfbibleemoddfs.oo3nnF%oaarlhueylmxdrainiomcuphmnlleo,ar.sithcaepapccrriooodt.mteecpcWttoiihvuveenednfliChitnsh,F,eIccvsooSammOpmlpe~eleNtcte(eolClmyy~pHiionn~uhh)niiCbdbi2itHst5atthOhweePess(duuOrrHff3aa8)cc28ee, attack of 3% hydrochloric acid. When the same compound is used as a 33002222..00009944 IM_MNO4855203 3M MN04855203 vn. rsa ve pny 59 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 389 hon ii 10 hee sr 5 dscns hte solution inhibitor at 200 ppm, there is over a 75% reduction in the rate En eh phn ee of reaction with dilute sodium hydroxide. Copper, brass, steel, etc., can re also be protected by the use of specific fluorocarbon derivatives. The Bs IR rm ee ee Te surface active compounds can also modify the reaction of metals with Ss Toe on et on of ml brightening or etching compositions. As an example, the addition of Bi fo rT, mm i, ee 25-50 ppm of C8FzTSO3K to a conventional aluminum bright dip solution eS LA improves the brightening action of the solution as well as increasing the rate. 6 tena Acs G. MICROBIOCIDAL ACTIVITY Fito compart oe ems tig mii Fluorocarbon compounds have shown some interesting mierobiocidals Th Re activity. As might be expected, the fluorocarbon portion of tke molecule is i ST i Pes he ies physiologically inert; but by varying the functional group, some compounds SR re mn have been shown to have unusually high activity as bactericides and algaeSalm a ml ha bee nd de tides. Therefore, the application of such compounds in insecticide, de a I BB herbicides, or fungicides can be viewed from either of two desirable rn AE on henSe approaches. Those which are inert may be used as wetting agents or disA persants in microbiocides where biological activity of the surfactant would E Tn LT ye be an undesirable side effect; or those with activity can serve in a dual role as a surfactant-biocide. tr sos H. INTERFACIAL TENSIONS lion sutton he nic Fluorocarbon surfactants are also effective in reducing the interracial ob ee ee tensions between aqueous and organic media(76). For example, the interSE facial tension between concentrated hydrochloric acid and an organic Sa ee ester, tributyl aconitate, was lowered from 12.6 to 1.8 dynes per cm by the EROR LE FeES addition of 0.5% CsF17SOaK to the acid phase. Figure 54 shows the effect of ---------- u 50 i mL] ~40 WT 3%| =; P r C T N --10 O.O000I 0.0001 0.001 0.01 O. I 1.0 oe omens. Molar Concentration of H~SO~ F[o. 54. Effect of CsF17SOaK on the interracial tension between n-decane and dilute wizsulfuric acid. 33002222..00009955 suosszca 3M MN04855204 330900 Wo. never H.G. BRYCE ofCCassFul~lyTfsuSrSOiO3cKKaciinnidttohhfeeviiannrtteierocrfuaasciiasalrlteteennngsstiihoosnn.ssbTbehetitwwseeaeecnnt,nn-cdoe-mcbaindneaeadnneddwdiidtclihuluttetaehsioseolnulcutithioeoennsms. iiroccefaaalslcutsslittfoaaunbbriiililciinttayyac,, ihdeeennotaaefbbrvlloeeagssreiontthuchoseeusssesetrsemmyanastgettterehrimsiaa.lwlTsshhetoiorsebbfaeeacthuu, ysscdeeodrdmocttbooainriibenndoccnrrweeataitsysheepettthhhseeeuirrrrfaacattheceetssamonotf-f wrwreeooafuucllutliddxoinnbbgeeiniddneaessthctrroeoontyeycereedodn.gt.ernIIanneteottduhhseehsyccydaasrsstoeeecmhoolffowrtthhiheceerehhaycyadiddrrh,oolylytdyshsrieoisscaeoortffbeoeertnthhwyytlaylspmmeacalostooumnpnraflaatetceteteabblnyyyt hThreyyhfddelrurooxcllioynynzzgteerddioni,inncottohnhnrrceeteeehnehhtrooaouuttrehrsdserwwhhhhyeaednnnrdo,CCcoh2wlFFao~CsrCi,c6FiFn1azccoooiSSdmOp,Ol5aetHhHteeoorreasfiittttessrrssaacwllittagssshwwtecerhoroeemurapasddl.eddteeeIddlny. iaTannmhaoeetthhbeceroyrneeotxxrnoaaemlm-,ptphlolieenr,,d ttthhihneee taaohddetdhdiseitturiiloofhnnoaroonaffdti,CCoo2wnFFao.hsfCCobi6FneFycnlooozSmSeOnOpeS3leHHwteitoohrarifisttteusrlssuaeatlilitgtscshtrr3eedhdduoucuc,eersdd. theIn the time by one-third in the sulfonation of benzene with sulfuric acid(75). I. Comniemern. Asvicrs COMMERCIAL ASPECTS 1. Chromium Plating suppHtrtaaemmssaai,,onFFrorefeddceehrririccokkm,,icMMiailcllil1aadg.gemeC,i,shtaarnnoaddmnidBuBmrsropoewPwalnnyathfihnaragvvoeme crrehepprooorrmtteieddumrreepssluualltttissngoonnbattthhhsee stpthulharpaotpoiuurngeggshhisiotthihnneeowufuossrceelhdroo-offwmiaidcfeflaluuucosoiderroofmccoiarisrsdbtbeooacnnnodrssauustrpriffvraaaeccyeeafnraadoccmtteiivnvgeceihnaarcgogeemrneitin(unStgm3.)p.purCClaphhtoirrsnooegsmm,biiuaudtmmuh.es- ptttooalamtttiihhnseeghssiauuspnpiedenrrllwaaatttoimivrvoleesdp-ppwhrreioordppieeecrruttsicieeeossrfroooorsffidoccenhhcrroororemamstiiiisvuutemamnacpnpeld,laatteieetnsgffriornouoemtmesrtittanhhngeedipssnuttgaranpnrdodeppssoeoiisis,nntttadnuoocefef tttooarhhn"eeiTasahhtteaaannbnddadtwwheaseatamrrf,,oaorasnnpdtdhhieetirtsiscellooccwwtoerccorooodeeesffipfofoiinccsiiieetrnneittsooionfsftaoffnrfiiccctecti,ihoonrin.to.smoiuutrstacnondsiinsgt resistance of rather `Ccco0onn4Tcc)eehnneattrnraadbttaecetddohnssstooaflilouuntrtiiioontanhndssedoiofetflieccochhntrrrdoooemdfmieiinpcciotaaseccitiisiddoln((alsbobofpouetcrthc1e1ro5n500tmaitgtuooems44o00fs00cuolggnfmsmaitstepp,eeorrffllluiroetaerrtirhdeeoo,frf cooCrurrrOffrluaeuo)nortaroonsdsdleiilncicscoaiantitteeeasiaannnaiirioonennsas.rd.edqIIuinntiissroooenllduudbbfellofeerinleteiathaeeddsdmooerrpaolllleseaipadtdeiraaocllnellonoyytfaagacnnehosorddooeefmsssiuaaulrrmfeea,tuuesas,eebdfdol.u.uo:HHrii1idgg4ehh0, t1tcoh0ue.r2r2re8e5f00notraaemmd,eppn4sppileetarirregssseqqarvffetto..lrTTuehqmheueeirccoeaafdtthhhfooyodddreertoheegfefeffiindcceiieiepsnnoccsliieieitssbioevvrnaaartroyyefdffcrrhdoourmomrmin11igu00tmtpool,2a2at00ib%%nog;u;;t saa1nnn4ddd0 ssthiinneccrTeeehfoeiinrnsesseo,olluaguabbllslaeeersgaaennaoorvddeoeelsseuvmaaorrleeevuueosdsfeddhd,,yuoordxxiroynyggggeeennncliieisssceerovvliloobyllesvvrieeasddte1aidnt ttdhthuheeeraainnnfogooddreepmssl.a. otifngm; ualntd octufuddtiiThnnehooeucusossenbbcuuegbnbabtsblreleasestseaoodrfefhchiheigrgvhohoemelrvirecssduuarrcffdiaaudccreesitnoteelgnnustsieiiolooennncbtaburnroudslrysttstiiihnnsrggovivwnioiiolntlehgenentotlulfyytor2aamtttftihhnoeeefsmsumuirsrfuftaaltccoieef- cbocuhhfrrrtsoohtmmeiinicccgoinaascccioieddfncotrddnarrstooeippddlleeecsrths.a.rbolTTmehhievceoaslscppuirdrmaaeysyoalaanunndtddiornemmqiuaissinttrderrsteehslsruaaorllwgtiieninngvggofflorruouommtmeaattfhnhiniidsseemfbbfuuiibscbibtbelolneetf Tlbloohucceraassllteieenxexghxhahaiusaususotstftcvvseoeynnntsstitiilldeaamettsirioaoanbnrleessiievnnxoccpeeleunmccshhierrvooaemnnaidinccdreaahqccaiuiddvireeiishssibblgaoohrttgmhheacivcoonorrtlrrueoomnssaiievnveecaenaadcnnoddesftfttsioocxdxiieuiccn.e.t 0tTochoceaos"taeTithnieengxglhaoaansundsdotfccsoycorshrrtroeromdonidsniicgaornaoefgcfiettdxhhpeetehhnhroosooiouvddgessh,,andmddiuuscchtttas,a,vneaadnntfddsigpffhraaannmyss.aaimnoteunnatnscetocaopsptsrodxuie- mpmoaaltlteeuTlltyyihoe33n,00lo%t%shsoeofocffththchrheeroottmoomttaaisclleicacdhchmirrdoiosmmtthiirccmouuaasccgtiihddbmeuussrieeseddtm..aonIIvndnedsooprrbddryaeeyrrexatpo0menvaosvouioinvitddes sootiouurtt-addwpooapsoohrrroinxaagiii.e-r equipment. pollution, the equipment. chromic acid mist must be removed by expensive air-washing 33002222..00009966 I3MM_MMNNO044885555220055 or re or mone coy 98 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 391 Vaio stmt ov bec mde fr "Bankes" on the fic Various attempts have been made to form "blankets" on the surface ooff tthhee bbaatthh ttoo ttrraapp tthhee mmiisstt aanndd sspprraayy,, iinncclluuddiinngg llaayyeerrss ooff vvaarriioouuss hhyyddrroo-- med carbon oils, organics, foaming agents, such as cresylic acid, etc.; but because they are rather rapidly oxidized, requiring frequent or continuous additions, and because tl~ey also contaminate the battt as well as tl~e plated ppaarrtt,, ssuucchhmmataetreiriaallss hhaavveenneevveerrbbeeeennuusseeddexetxetnesnisviveleyly..FFllooaattiinngg oobbjjeecctsts,,ssuucchh. "7O 1 Ge65 C1 E l [1] 50 i JA45 1E ..H f F hN P] e | e e LL 25 [TV| 2O Cr rene fen CONC. OF ZEROMIST (LBS/100 GAL ) 2.5 etn titsdm ec Fro. 55. Variation of surface tension of a chromium plating solution with concentra- brpipvee d coea, psri bois,etc. have sh ben ipi : bat tion of a commercial product "zeromist", which contains a fluorocarbon surfactant. as paraffin-dipped corks, piastic bubbles, etc. have also been tried; but although they help to reduce the mist losses, they are confined to "hard" chromium plating, where thick deposits of plate are formed and the parts to E ac ems be plated are left in the bath for several hours. However, in decorative or bright chromium plating, the plating time is usually around 5 min or less, and it is too difficult to keep the bead layer properly distributed over the surface with the very frequent entry and removal of plating racks. 33002222..00009977 swnosssszos 3M MN04855206 392 H.G. BRYCE Tp -------- Even though plastic bubbles or beads have proved useful in "hard" Crm pata no dese emi reomanded fo suth chromium plating, no decrease in ventilation is recommended for such systems. "SiSlilvveerrmmaann aanndd TThhoommppssoonn rreeppoorrtteedd oonn tthhee uussee ooff cceerrttaaiinn hhyyddrrooccaarrbboonn sutciane 0 ior the safc fens of the Shr acd son and surfactants to lower the surface tension of the chromic acid solution and Ren orm s foun blanket 0 the sree of th pig bah: bowen, hence form a foam blanket on the surface of the plating bath; however, ht Sufi at wed re ot cy bl th power the surface active agents used were not sufficiently stable to the powerful red cdi dig Ping vobof rch eon, anodic oxidation during plating to be of practical value(84). %:,|~L<L v\ ] Eg A L 8 TTINN 70 60 SO 40 30 20 J SURFACE TENSION (DYNES/CM } Fc. 50. Es of mh es ive acs cso o the scion FIG. 56, Effect of fluorocarbon surface active agent concentration on the reduction rH TET mae of chromic acid mist in a discharge duct. (a) Plating bath at 55C ; (b) plating bath at 38C. was found tha 3 uae ace agent with o oro "ai" It was found that a surface active agent with a fluorocarbon "tail" we ok aly sable to big soncmined trois ud end he Hight was not only stable to boiling concentrated chromic acid and the highest iliing ondiions t he aod dri chromium png, but hat shy oxidizing conditions at the anodes during chromium plating, but that they er ves ete i eon tes ee of he lA were very effective in reducing the surface tension of the plating solution Vi he mano arin sable bone, Fre hom the with the formation of arelatively stablefoamblanket(Sa). Figure 55 shows the rin sfc io of hori lang oom wih omen variation in surface tension of a chromium plating solution with concenraion of proper product, Tarameabt i ich the furocabon tration of a proprietary product, "Zeromist"(85) in which the fluorocarbon icant anih-tpos iticacd al. FiSgosuhorwse thereon: surfactant is an eight-carbon sulfonic acid salt. Figure 56 shows the relationHi beeen sce scion of the ath nd she micropems of Co ship between surface tension of the bath and the micrograms of CrO3 in the cat te fom 4 plating bach. Figas 37 shows sh elec of in the exhaust gases from a plating bath. Figure 57 shows the effect of 33002222..00009988 aw_uNosssszo7 3M MN04855207 INOUSTIAL ACTS 0 peORI CHEMISTY INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 393 tSteeumpmseperaeterunraseotoonnuntrthchoeeendimmtiiiccorrnoosg,grrnaaammmsselooyff, CC3r/OO3dyiinnnestthhpeeereexxehbmaa.uus3st5 ggdaayssneessesffooprretthherrmee.ee nd 25 surface does pe om tension conditions, namely, 50 dynes per cm, 35 dynes per cm, and 25 dynes per cm. i, LT i --| 110 120 1~0 140 150 TEMP. OF CHROMIUM BATH ~F Fo 57, et fb sempaen rhe cpcnnionofdri cid i fn FIG. 57. Effect of hath temperature on the concentration of chromic acid mist in the big Sot To $s en discharge duct. (a) Surface tension of bath is 50 dynes per cm; (b) 35 dynes per cm; Em. (c) 25 dynes per cm. Figure 59 shows th foam blanket present ona chromium plain tank, Figure 58 shows the foam blanket present on a chromium plating tank, Just avr sh plated wor as een remove just after the plated work has been removed. "The Rustoerban stfu acios agent Lost from the bach ody by The fluorocarbon surface active agent is lost from the bath only by "rag" Gn she Fin of solution on plied acc witha fom th "drag-out" (in the film of solution on plated articles withdrawn from the ahys hes nly infrequent addion ar needed t mata he desired bath) ; hence, only infrequent additions are needed to maintain the desired conctteation o ht sonian Joss of roms 30d ocr trough concentration so that essentially no loss of chromic acid occurs through ing of spaying, In an chal Patin plant va where the tank van misting or spraying. In an actual plating plant test where the tank ventiToon was turned of, maxim cone tatons of Cr of 01-002 mg lation was turned off, maximum concentrations of CrOa of 0.0l-0.02 mg et of tr wre ereeds wherns toe mania allowable lvls per ma of air were observed; whereas the maximum allowable levels are 0 mg Cpe of sie. 0.1 mg CrOa per ma of air. rummy, ie a ofhe foroerbon fac tiv gent hs saved In summary, the use of the fluorocarbon surface active agent has solved several robles avocared with chrom lating: amy, (1) reduced several problems associated with chromium plating; namely, (1)reduced Sony hands to personnel (2) siminted expenuine specl estan toxicity hazards to personnel; (2) eliminated expensive special ventilation Frits; reduced oss of chromic ac sheng <hmination of moe facilities; (3) reduced losses of chromic acid through elimination of mist 33002222..00009999 W_MNOABSS208 3M MN04855208 = p-- 394 H. c, BRYCE 3 y 1 in ne ~ ( Gh -r "~ 4& FIG. 58. A chromium plating bath showing the foam blanket produced by a fluorocarbon surfactant immediately after removal of plated objects. (Courtesy Udylite Corp.) and spe and ts reducions even in "dragon" due to betterrun of and spray and atso reductions even in "drag-out" due to better run-off pangs iom he ied prt: nd (eduction hese fom of plating solution from the plated part; and (4) reduction in heat losses from nsdu to re of serid o rio re plant area due to reduction of ventilation requirement. 2. cling of Lipid Po Wass 2. Levelling of Liquid Floor Waxes(S~) "The foo bing th nega pan of the rior of biding which The floor being the integral part of the interior of a building which it wien efhe ear ot ee pec must withstand most of the wear, it is logical that it should receive special rein and re. Thapiatofon west wen Toor oth rpt: attention and care. The application of waxes to wooden floors for the puroe of precovon dtc ack mans Seti ry Bors re orc pose of preservation dates back many centuries. Many floors are covered hpi mate, shss Eten ibe se cole, and with a soft pliable material, such as linoleum, rubber tile, congoleum, and i par hh aecredo ober Fed oh rp To vinyl plastics, which are cemented or otherwise fixed to the original flooring. Qui pe of fo i bowen the droid the Toe Quite often a layer of felt is laid between the underflooring and the floor nein tose ion The acto of we toh Boring covering to act as a cushion. The application of wax to such flooring materials retards the penetration of air and moisture, thereby increasing on eof the corto revert we on preven roo of the life of the cushioning material, as well as preventing deterioration of esiby sion Fm pe. the surface by abrasion from grit. 33002222..00110000 aw uNossssz0s 3M MN04855209 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 395 Thee see vo min types of for vases, slid or pase waves and There are two main types of floor waxes, solid or paste waxes and au wanes, Cams vets rom the em of he cabs aim liquid waxes. Carnauba wax, from the leaves of the carnauba palm, has Bien he minty of vi repraion, nd rts wins te be ot been the mainstay of wax preparation, and remains today the base for the Bete wa Fl Pte waoneoend ot wood Too best paste wax formulas. Paste waxes are used for wood floors. ction or warped ves, ah coed poling. The emulsion or water-type liquid waxes, also called "self-polishing," cioth rc volume he or wen Fed and rc ed ene en~oy the largest sales volume in the floor wax field and are used extensively ot plsin such fon Cocrngs a phe tie vn poi, onions for polishing such floor coverings as asphalt tile, vinyl plastic, linoleum, Ce Nin of he orl pros coined amass wi of hs ner. etc. Many of the original products contained carnauba wax or other lusterring ardwin ons, sd om dele roporionof producing hard waxes, emulsifiers, and a considerable proportion of shellac, pit forts be: a typical formula being: Sodium soap 13prs Sodium soap Corman $78 prs Carnauba wax Shae is hre Shellac Sod bore 1.08 pa Sodium borate We 48 bre Water 1.3 parts 8.75 parts 2.45 parts 1.05 parts 86.45 parts C 4 Bg RS pr da HEH FiG. 59. Effect of fluorocarbon surfactant on leveling of a liquid emulsion type floor wax. The sample on the right contained no fluorocarbon surfactant; whereas the one on the left contained 0.01 /5 of a fluorocarbon surfactant. 33002222..00110011 aw_osgss210 3M MN04855210 39% no. mevee 396 H.G. BRYCE prSSohhpeeelrllatacieiisss ollfeestsssheeexxpppelennissi,ivveegtthhiaaannqvucciaaecrrknnaauuusbbeaaraa,nnaddndiiss iuunsseecddrettoosaapiidd rttehhseeislleetvvaeenlllciienn,gg pmreonpIItnenrotrrieefaeccseeconnotftntyysheeieaadrrpessorsslaieebsvvhiee,rrpagaolilrvtddeieeaovvneqelluooofipcpbkmmaeletnunhtsttsstehrHhe,aaavvcneeadrbbnirranooucuubrggeahahatstenaadsbblooitpuuhtetrettsshhihseetlalrrneaeccppell(baaaycc6ee)-a-. tvmvhaeerainetptryooolfoyfifsastsyycyenrontentthnhsecietsdyti,ieccratrrbeheslseeiinnpsspooiilnrnytaieeocmmrnuyullolsasfitioeobsnno,tfohorarm~tnh.nd.eIItcnnhaccerllnuuaddpuoeeblddyaasariraenenydttlhahecteheppteoaoltslyeyheseei.tlhhlyaylcTleehnbnecyesss,ea, sqtshuyyanenlttihhpteeyottilivyccasrtrriyeearsnseicninenes,s,aaarrnet,dh, eiffnoorprmoalttnyhhyaeeccrmsyausloaeeststetsm,ppoaararretnt,drellseetisshsssetaeenxxptppoetelnoynsvsyiiievnvleyel,,loawcllieeensstssgatsesssunu.bdbjjeTaecgchtitensgttoe,o `qessuppaeeTlcciihtiayaelllvlyyuasriiiennanocccfooemmt,hpapeansaredriisssioonynnnmttthoaoentssyihcheclrealesaesecis.nsm,ohroewreevseirs,tanitnttoroydeulcleodwinnegwanprdobalgeinmsg., irinnesggiTeesttthtaiiennncggeu.sseeelTl-ofhp-fopetlohilfeisslshhueioinnrsggyo,c,nahhtrhiibgegothhincggllsroouessrsssfinappscrr,tooaphpneoertrwtstiieeehvssa,e,vraae, nniddnsotyyrleoevttdedmmuacaiteihndnittsaaniipennwrohhbiipgglrhhoembwwilaeantmteearsr ruuseunnsriiifqqsutuucaeetnacnffeata.ssshhiTiioonnhn.e.prTTfolhhudeeouyycroicnaaargrerebgommonaoanndsyyu"rttlfiiaemmvceeetalssnintmmsgoo"rhreeoavfeeefftffhsecoectltivievvemeedultthtshhaiainonsnphhryywodadbrxrloo,eccmaabrrebibinoonnnga fsefuffefrccefttcatiicivvvtaeeenntaassttsccinooantncpcterenhontedtrrsuaactteiiionxotngnrssegmoooeffold00y..0l0"0o0l5ew5v-c0e0o.l0.ni1n0c0ge1%n0"t%roabbftyyiothnwwseee,iigegthmhhtte.u.ylsBBdieoeoccnaanuuowssteeaxioon, ftfebttrehfhieenerigire ewwfiifttehhFcitttighvhaeeerndedeese5vs9evalsotehptolhmweoessneptthoemoexffeitgrgoenmomootpddelrwwyaoalttoevewrerrceeirossnniilnsscetteaveannenltcncrieeanottogfioftonthrhsle,eotwwhsaeax)xy ffdoiilomfmn. cootmimneterrcfiearle aaAqquuuoereFoooigucuasusrrebeemom5nuu9lslssusiihroofonnawctsttyaytnpphteee, iFffmllCoop-oorrr1o3wvwe4eamx7x.ettnhhItrrnoionauudglgdehhivteittlhoihnnee,gaat(ddhodedrieigtftiilfoooesnncst)ooooffffc00ao..n0c0c1o1e%mn%tmrooaefftrcittihohaneel ofolffuttohhAreeotsycsupaucirrbfcfoaaanlcctasafnunotrrtfmaiisuclataaallssnooits,2ssFhhsCoowwf-1non3.l.4l(o7w~sk7ian.a:ddition, the effect of concentration A tyPPWpooaillcsyyasslettymyfourrelremsnnieeuonleea.mmuiusllsasiisoofnnol((lo44w00%s%(STssooal,lbiid)d:ss)) 5885510ppaarprttassrts PlAAWalslkaktaxaillciieimsszooeullruulsbbiloleenrreessiinn 5255---p111a000rtpppsaaacrrtttsss PFllausotricoiczaerrbonsurfactant (FC-125)(1% solution) 21 ppaarrtts Fluorocarbon surfactant (FC-128) (1% solution) 1 part 3. Elion Polymerization ofAvAisnsyclemmutlyusplseiiffpiceoerlssyttmhheeeriffllzu3ua.ootrrEiooomccanaursrlbsb.oio9onn.nssPuurorfflaayccmtteaarnnittzssathhiaaovvnee been been used used in in a a variety variety of vinyl type polymerizations(SS,sgL XX.. TTeexxttiilleess A. Suace ThATHrEonNFiTvekSs surfAAascsehhaaisssbboeneeeennorrfeevvAtiihe.eewwSeeuUddnRiFecqAaaurrCellEieeraTr,,tRttuEhhAreeTeM llsooEwwoNfTssuuStrrhFffiaOasccReeclFeeaInnsBseeErrRoggSfyy coooffm2apfoflluuunoodrrosoc.caarrTbbohonen, iowsuroorrfknkaecooewff iiZZstiisosh8mnmecaalnnoosaafenntpddhaecccooku--enwwd{ooqrarukkeererrsfrsehhaaataussnressgshhoooeofwwfonmnrthittehihesaanntttcetttlhadhseefsllleueoaaofssrttoccowwaemerrtbpttoaaonbbullnteedissssuu.rrwffTiaahtccheee httishhaeesoiinrrdeeCCtwEeFirtsshm-iaggnrrecoodluoustppehssapteeaxxacttkeelenniddqdueeaiddrdraoownuuigtttwehwamraader(sn1dut8r.~of.facoTTerooiteenwwnteseetitdossnfuuluoccfohhr6oaadcysasnuurbcreffosainccpeeteariZZlisoisswmmmiaaothnnr has determined that a liquid with a surface tension of 6 dynes per cm or 33002222..00110022 33MM_MMNNo04488s5s5221111 PE -- INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 397 les wuld be reir. On he ther band, 2 highly ried ly less would be required. On the other hand, a highly oriented closelyed dec os ott ew by As ig soit packed hydrocarbon surface would be wet by liquids having surface noms To Tn 33 rs oren, man ppd shed pcs tensions less than 23 dynes per cm. Zisman prepared the close packed ies ih he doer dh conn ing. he Laban structures which he studied under ideal conditions using the Langtnuir Si ne rs von and pach he mle pes The ce film balance to first orient and pack the molecules together. The close Phd Ho wer en re oe Seopi. packed films were then transferred to scrupulously clean glass or platinum Foss surfaces. nop Tie It will be the purpose of the foIlowing sections to review the applicaof Barn oe op ets rd 20 tion of fluorocarbon materials to textiles, paper, and leather fibers and to ho he moe ase sc popes of nie i, show how these modified surfaces affect the properties of textile fabrics, et eer. paper, and leather. [-- B, INTRODUCTION TO FIBERS gener, any mtr cape of xing in 3 er fom may be In general, any material capable of existing in a fiber form may be eis; used to prepare a woven fabric. These materials range quite broadly To Shem nd phot me Fa SOON ae 3 in origin and in chemical and physical nature. Table XXXVII lists a Ef hee cig hs wh oem staal and sho which number of these including those which occur naturally and those which a, are man-made(9,~.~sL TABLE XXXVII Crea CLASSIFICATION OF TEXTILE oe Natural fibers TE a ten Vegetable : cotton, jutc, linen TFois Animal: wool, silk, hair Mineral: asbestos - Man-made UR tir Regenerated cellulosics: rayon, acetate Steric Et Synthetic organic: sou Ie . e fi Mineral: P[etE: E Cih st Metallic: /polyvinyls--"Saran" ~polyamides--"Nylon" |polyesters--"Dacron" kpolyacrylics--"Orlon' ' "Acrilan" "Dyne1" glass fine wire filaments Fluorocarbon: polytetrafluoroethylene meFIBERS Aiough mento sides hae ben made in inducing sn Although tremendous strides have been made in introducing mana wey sc von sw os bh made fibers in the past twenty years, cotton and wool continue to be the Fos ted hbo ond ped helt vn The mics fibers most used for clothing and general household uses. The modified 33002222..00110033 awossss212 3M MN04855212 305 398 wc H.G. BsRaYvCesE coceefltllleuunlloocssoiicmcsp,,etssiuutccihhveaaswirrtaahyyoocnnotaatnonndd iaancceepttraaittceee, rkhaaanvvgeeeaa2ta5taiiwnneeeldld 8llaarreggneeduuusssaaegg.ee aanndd aarree oinftetT"nhTohhsceeeomsscyyopnnuettnthhiteteirtvtiiieccs wooofirrtgghtaahnnceiioccwttooffriinblbeedirrnsswpihhtriaahcvveeewreabblneegccdoeeomvmaeeeslow2apeelvvdleearrcysyheeiimnmmidpcpoauorlsrtetiaa.nnndttusfftaaicccttsoo.rr imnertiW hWcoiisttiehhn cttcohhhueeanreetarxxcicceteeespp,totiifaoonntnhdeoofhfwammvoeeertltdaapllrsw,e, diaatolhlmlliwbfnieeablrnel-trd-plpeyrrvooleddiluonucepcaieirnndggsctmmhraueatcmetteruirciriaaeallslssiwnarhdrieuecshpptrooilaelyyrs.e-. omoFrireibiererinoncutteseiddnmiiancnthettarhhrieeaacllltsooennrd,ggiiifattuenurdddiinnwhaaialldveddeliirrypeerccaettndiiodoonnmiooinfnf attchnhoetenlysffeiibblqeieunrr.ee. naTTcrhheseetarrppuercrotupuorseeeprstdieewsfroohortfifcihtmthhaeeeanssrsyeee fpptieuubnrrrtpposoousasseenssmd aiaitnnweccnrlliiuaunlddgsiisnn,dggifSfhwweeerearawrrciiilnndoggetlhysaa,ppapprnaeardireenlilf,n,orccffieuo~drnrnsnipeitltqauusurrteeei,,nc,ceuusppohahodroellsms"ttaueesrnreyyyd,, lfbobaermediddmndiaiantn~gegy,d, tcceoonnnts"ssttTrrhauuenccdtftiiiorasontwns,m,naieenntcgc-.sm, afdileterfibcelorsthtso, reinforced plastic, achieve commercial and many laminated significance were the mvmoeodldioTifpfhieieeedddfdiurccsreetlilllmnuugllaoontssh-iecmessa1odo9r3er0'frrsiaab,yyeoorannssns.dt.otNNahyceylhlooirennav,p,eidttchhoaeemccffmieirrpesstttracttnirarculueeesoigfssnyytninfhttiihhcseaetnftiiicccbe,,erwwwaeaarrsseouddthneode- va11e99ll44o00ptewwdaavssdarubbiraaaissbneelgedd tsoohinnlek ii1ftts9se3uur0ss'seei,niiannwnodfAmilletaahnmme'eesnrntathpoffisodoirremamrcyc.ttoeoprrtaeenpplchaeiceeoftthhtheeiscexxfppibeeennrssiiavvreeouaannnddd dquiaflIIinntyqmmuviaaatrnneiyaybmlaaaersskpspeieeldckctltssyfibtfethhrreeoissnmee wthssoeyyminnrttehhnneea'tsttiiucchroaslooilreryggryaao.nnciicccurrffiiibbneegrrss,c,oussnuutccekhrpaaarssts,nnyyslluoocnnh,, 5wadesiflfccleoorttdtteqoofunniintaaeenndddmcwwraoorooskoslel-.d.sleTTychthfieeroonssmsyy,nntwtthhhheeeettiriircceanffsaiibbtu2eerrrssaflihhlbyaaervvoeescurrcacautthrhhreei3nrrsgsscmmcootoootuotontnhhtesosruurprraffwraitoccsoe,elsssasuhnncadhds aewanngeelleeaxxdbttelrrfeeeimnmoeeerdllyyacnrrriooomsuuasgl-gshheocrsstiiuugorirnffnaascc,oeer.w.thhUUeenrnlemliaiokskdeeiafittfhehieebdecrnneaalsttluuuucrlrakaolsllliayycs, ooctcochcctetuuorsrnryriinnontgghretwbfiieobcoerflrsisbheaoorssff vhhtheaaegvveeeatavrrbeeerllleaaattgioievvreellmayyoniillmsootwawulraaoebbrsirsgooerirgnppattoniivrveevthappelooumewwseeoorrdfifffooiverradrwwicaoaetutleselurrlfovvisabaipepcorsors,,r.tihs eAAsshccyooonwmmtnhppeaaitrinricissTofoainnbbelooresff XXXVIIL While high moisture absorption i desirable from the comfort the average moisture regain values of various fibers is shown in Table XXXVIII. W'hile high moisture absorption is desirable from the comfort TABLE Xoo TABLE XXXVIII Avian Morons Recaro Vaocs Fiero. 254 AVERAGE ~IOISTURE REGAIN OF VARIOUS FIBERS(90, 9.965} FibsFiber Appia vcs ein a 65% ob. Approximate average regain at 65,~ r.h. and wi room temperature Woot ~ 6 Vise yon i ~Vdscose rayon 13 Stecrid con i Mercerized cotton 11 Coton sd s Cotton and linen 8 Se i Acetate 6 Nyon ` Nylon 4 Oren acric 12 Orlon acrylic 1-2 Dacron polyester 0.4 33002222..00110044 I3MM_MMNNo044885555221133 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 39 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 399 ssdettafainnnddipptoeoiinnttet nwwdhehenecnny iinntoccoownrntitaancckttlewwiaittnhhdtthhaeelsbobootddoyy,,lottshheiissdeppsrrioorppeeedrrttycyreaaalsssooesrreepssuuutlktssiniinnbyaa ppbdrlreeeefssinsnsdiiinsntegg.w.tieTtTnhhhdeeecnosstcyytynontntth,hoeetrtiwiaccyroiffnnii,bkbeleeorrsrsahhwnaaodvvoleea,lffsooobuuencntodadulmsmoesuehtchhdeeyffsaaivvaroeroredr,, rceeeriilettahahtseeievrrselaayllpoournneteesiioonsrrtabiinnynt bttoolewwn`rdrDiisunnrkkwillniiingtnhggthcbbeoopottatthhosntww,thhereenannyyoddnerr,yy oaoorrarnrwwweuoetsomt..l,b,beocfautsreeatthmeeyntasreharveelabtieveenlyderveeslisotpaendt w`TwhhheiiDcschehurhhitaanrvvgeeeatthmmmeaearnprtkkasesedtdltileyynnvioiynlnecvcarereresaar,sseeaeaddcntuttihmhveeebaaerbbreiisloliiifnttytyresooayfftsmtcceooemttnttsotosnnshutatcoovh.erreebsaseisiessttnswwudrberisvintnekiklltoliuipnntgeeg.dd. memfTolheraelmasmameilindnteerehe-fyafoodtrmremmeaonarlltddsveeihhniynyydlvdeoes,l,uvlefttroiinraaeezz.aiicnnteeiveddeerrrieivvsaianttiivvseeyss,,steoomrrs specifically catalyzed suck as substituted specifically catalyzed sftoerumIIcttaulwwrdeieisllhl,ybbbdoeeetohoobbrfvvrvioiioomnuuysslcttshhuheaalmfttiocntteeaexxsltt.iaisllewesselaalnnddssttepehxxtytisillieecaffliibbpeerrss oaaorrfeevinrraeatwth.heerrEsccpooemmcpiplaellexlx.y siissstmrutothhcaiittssuhrttertrsuou,eebbeoooifftnhgtthfhereeoxmtffriibbeaeemcrrehlsseyuumrrrffioacaucacgeelhssa.swwwThhheiielcclshhaesmmspauahryyyfsarriccaaeannslgmgpeeaofyfirnrotolmomefobvbbeieeeiiwnnggm. Eorrsdeeplliaeafttciiiivvaeeeilllldnyyy snnomruummotehoerrtrhooouuutgosshbwwteaahiynyessgapebbpxyyltirccechhameteeimmoliyinccaraololfuaagcchtvti.iaoosTnnt,h, aersssruueaccyhhsuoraaff5sadcmymeeesesrrctmceuerafrisyiz,zaaarlttsieiooosnnibneoo,rrmaonbbldldeeiafaticecexhhdtiiinnilngge oaauurwxitiAhllairaroniruieuesgms.h.bethre application of a vast of hydrocarbon-type array of dyestuffs, resins, and materials have been used for textile many yybereaiarcrAsss.nttoouBmaiimmlbpeeparrarrtoftfowwrhamaytutdelearrroticrroaeenrppbseeollclneol-nnnttcycayypientfeoomd ass2utuevccrhhiaaliisttreehmomaifssveaeaanssbitemtteaeeynlnn,ttuvsaaeenngdeddtfaorrbalraiein,mnwwaaeennaaydrr fmamainbinnrueiermcrasbal.leErwwoaaarxfxleiesessyrnaaftnnohddremtaaiullculuampmtriiioonndnuuusmcmtcsossnoohtaaaappvissneeoobdffseteasetnveaadarreriiivcceetylaacociopiddfe..daTIninninmcmmlaoulor,drieevnegrrgeepeccyteearnnbittldeyyi,eenaaairnrussdm,, dpadreneoruidrvmuacitbtivevsreasgooitfofvfseisystnvteeetaxheacrreeisitlccilceaanpcctiirddo,,wdaaautnnceddtrs ahravvevaapererilbeieteeyneotnoffdtessriivellaeiictlcoomoenpnneeetdsrr,eeinssiicbnnlusustdaa-in--nngddgspoolyimlsrsi,i.gdhTTinhtheieusbsemee. epexxroppedeDccuuttcreetidsdn----gog-ofivtfffeheeerrepnxnaocosetrlsleeepfpnieetvlelleiwnnyaecctayyerrstt,ooretoopeifxellstlilealaennntddfitggnrrireseeahaatessmseessebnooatffss,eaadnnbyyountoo-rr-iifagguisionn.r.mocigahrtbobnse hpheaalvvieeDenucbbryeei,eennngthdtdehseeeevveenllpooeappwseetddffiinvaaiennsddhyeseiiannirttsrmr,opodadtrueutxcceteaiddlehccifoogimnmhmismedhreeecgrsircaeibalellalysyoe..fdaBBoleesnsiirddefeelpusseolrwwcoanactctaeeyrrrbaorrnneeds-- cGonosemquaently increase the resistance to mast staining and soiling cone pellency, these new finishes impart a high degree of oil repellcncy and consequently increase the resistance to most staining and soiling con- ditions(91). . Cumsucas, Naruse oF Fivonocamoos Fists prodPPurrecevveiiooauunssCo.icclooCnnasHsniEidddMeerIwrCaaatAttiieLoornnNssrAehhTpaaUevlvRleeEeneeOtssFttsaaFubbLrllfUiisaOshchReeeOddoCnAtthhRaeeBObppNeooiriFnn,IttNiItttShhHaiasEttSniiennceoosrrsddaeerrry tttooo hhpoaarroivvedeenutttchehedee a5ss0nuu.rr3ffoa5aiclcetea0cncohodvavevewreraeetddtehraaettrieleepataeesslrttlmeiiinnnntapplsaaurrCrttfabbcFyye fuloougnrororoaocucafpairsbrbbeeoro,xnnpioggtsrrieoosduu.pnpssecwwehshisiaccrhhy areto are oflr"iueToTnrhhtoiecidssahrhsaboaossnabbsceetoeeonnmphaaoaccvucceoonmmdtphplewliiiissrthhhteeeddramiinnfisnuesanevclvete-ri-raoaCnllaFlwwaaaygygsrs.ro.ouOOupnpnseewheaaixppcppphorrsooeaawdicc.lhhl iisbseto cuuissteehear faawlddiustsooohrrrobtbcheeaeddrbfssoittbrnseoornncggsolulmyyrfpttaoooceutt.hnheedExssuuwarrmifftpaahlcceeeasoorrfoufwwnhltc~iiticicsohhntwwayilpilllelguuroonfudnbpeorndgwdoihe3aniccgchrhhewemwogmiuicillcoladalblberreeeaaecccihtttrhiiooeon-nr wmmAiiituthymmptihccceaolmfoispbtleremruxcostoupfufrvrfvaealarcroieifo.oeuutEsshxiaasaccmiitddpysspleeccsoomnnoaatfaiyitnnhibiinsneggtiylllopolneunsggtorccfahhtbaaeiodin,nndfvNliiuunzoog,rroowccoaarurbbldoonnbggerrocouuhpprsos.-. A typical structure of this type may be illustrated, viz., 33002222..00110055 I3MM_MMNNo04488s555221144 0 WG. merce on[=CF3 CF~ psCF2 dicer,CF~ pyC F~ CF~ C~O O Cr / \ abONe"cOa \ o / aSSuuccihhsoccphrhorropoymmliiuaumlmhcacoolmm.pplTleehxxeeessaaalrrceohecoaalssilslyyolsusotoliluounbbslleemaaannydd bssettaabbdllieeluiitnnedssoowllvivetennhttsswasstuueccrh,h oabbsufuttitstthohhepeercoaahpqlqyouulreeiooanuulecssoashssooolHlluu.CtItTii.oohnneIrreaetalahccicotshssrolleoloawwcsltloyyilounaattitoorrncooseouommrmsattyoeenmmbptepeehrdraaistltuuuurrtrefeedactteoowoihhtyyhfd1drwroboalleytyrezzr,ee, ssohuuyfcfdchrhtho3xae5yslccc,hoolttoottroroinnna,,emwwiaoonsooaHl,lgCoor,r1ro.unnpIyysfll,ootnhnt,i,hsttuhhrseeeaacccnhhtcirrohoonommroiiiuncumgcmutrwwshieillollnfccsotoohmrmeoppcslleauexrrfbwawoicnitethhtoiccflaaarrtbbfoooixbxyteylhrl,e,, ufhfiniybbsdeetrrraobssxuulyrerffla,aacceone,rd. AAahmssemnimincgoieghhgattrbeobeuepnexosxp,tpetgcehectunteseeddr,aa,lnsslcuuyhccohhdrui""ncccagoobmlmtheppellteoefxl""unololirrnomkicaaalgrnbesolkaanaurrneatadrrieeelgrllaaittotneiigvvteeshollyery dudynrycsctl`aleAebnaalonentiihnnaeggnrdppsrrohpocpeenrcsocseeeassc(eah9rs2e,hg3aans,)o. tbegeennertaollyattdaucrhabtlheetofunoorormcaarlbolanungdreoruinpsg or to ccbooeninvnAvegennntcotihitoohonnreaearllna5hhp0ypydrd2orraooctcchoaa,rrpbbrhoooannvsidbppeooeelglynyommoedteorradasshtttetrausrcichoutuncrthte,,ethttfhelhueeosruoppbcosotallyrrybammtoeeenrrangbbdraaoccaulkkpsbbsooonnbteeoe oolbfafeuinssnuugdffrficyihcceiosensyntestlnltyyesmohhsiiaggsahhntdommopdolrrleoeycvccuuilldelaaearrngiwwoneogeidiggshahotdltvhetteonostisobb,nee Ttiiohnnusstshoo,lleuubbs1lul,eebsIiitn-nraditbbebooytatdhhnrdoaaoqqacluutseeooooruybus!es alaaallcccuyoonhlhdooarllyt,, CCsmyooTsnFFtoe1ymm5CCesHrHs,a2OnOHwdHh,,idcrmmhyacaywlyehabebneneingrrpeeoaaslccoyttlmeevedderniwwtzsie.itdthh,Thsfaueocsrrry,ymlisic1c,thaa1ecc-iidddpiahlttyoyodarcfforoooyrrlcmmttfeo,ttrhhyeel acrylate monomer, which when polymerized, forms the polyacrylate, GR Gs GF an an om doo deo m0 co eenAeNenw aeanMeen"s CH~ 3300222..00110066 I3MM_MMNNO0A4B8S555221155 INDUSTRINL ASPECTS OF FLUGRINE CHEMISTRY 01 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 401 pDDoeelppyeemnnedrdi,innggit oomnnaytthheeeithmmeorolleebcceuulldaarirsowwleeviieggdhhttinaann3dd suootithhseebrrlecchshaoarlravacectnteterriisostrtiiccdssisoopffertsthheeed 2p5olaynmaeqr,ueiotums aeymuelistihoenr wbiethdiistsohlevrednoninionaics,uictaatbiloenisco,lvo enstnioornidcisspgeernstesd. as an aqueous emulsion with either nonionic, cationic, or anionic agents. D. Meriovs ror Messunus Revsuizex whicAAhtttthhhaiivsseppoobieinnettnDiittu. swwMeooduEulTtlddHoObdbDeeetSwweeFrelOmllliRttnooM eccoEtonAhnseSsiUidddReeeIgrNrrsGesooemtm~eoEefoPEoofiLflLttahEhnNedCssYttwaaanntddeaarrrdrdemmpeeelttlhheoonddcsys oowennehtintchhheetrhtteraeeavstaetetedebddewefifanatbbhruriiscace..drAeAtpoefflaladrlt,ee,ntccetllreemmaaannitnesseruuictrahfflaaeccmeedaessgyuurccebhheeazosacflggaollsiaalsssiassfniooedrdr wmmaecaetcttaeoalrrldrwwiehnphigeiccllthheonhhicsatysss dbddereeggoernpreeoeetfreoooiaffteooodfill wwooairrtthewwraaaottnreeertpherreelelppseeuenlrltlfleaemncnecca,yyteOrbbinyyaitmmhmeeeaaatysshuuebrretiinnhcggalanttsdhhs,eeifiaecccdooonnmaatpcacclctoterxdaannisnggtlglreeutcoootfufirteaas sdurochp aof 2oiwl oovrewnatteerviolnetfhaebrsiucrfparcees.enOtns athneenottihreerlyhadnidfe,raenctomtyppleexofssturrufcatcuer.e such as a woven textile fabric presents an entirely different type of surface. 11.. WWaatteerr RReeppeellleennycy, `watSSeeevvreeerrsaaillstmmaneecttehhooofddssa aatrrreeeaaatvevadaiillfaaabbbrllieec.ffooTrrhmmeeeapasrsuourcriienndggurttehheemowwsaattteecrromrreemppoeenllllleeynnccuyyseoodfr AwiinnmaetttrehhrieecraeUUsnninsiAtitsatseenoddcceiSSaotttfaaittoaeensstorfeiisasTteettxdhhteeiflaessbttrCaaihncned.draanTrridhdsetsssppparrrnoaadyyceCdtoteuelssrotteriasmsssto,sddtneevvcdeeollmdooeppmeesoddinglbbynyyautsttehe1hsddee TTTAheemsesterpiM MicceacentethhAooofsfddsaob22cr2i2ia--ct1i19oi69n16(ot19f40eT,4pee1.Ixt5at2,ihtl.e oTTCvhhheereem2ppisdrrtoaoseccaneeniddnudugrrCeehooiilssooprililslwltuush,ssitracrsanhttdeeidsddetiishnniegnFFniiapggtl,.eadc66ea00ds. o2oT5nnh0emaannipioeiicnfneccwlloiainftneeefddrabtprrpillcaanntiseehesanattrtestpaacrha44ey55dedoaaovnnneggrltleehaesdttouaorrnftthiahnecegehhhtooorriohizzpoonrwntathaloa.ilsc. htuAAaipnspgpdptrahrhoroevdxniinmmpoalazattzcelleleydy 2o`AA5nff0ttetemrhrelttasaouppfrppfwiiannacggteerttahhaeedreefftataehbbrrerimincci,,nspetthrdhaeeybyeaadmmvooiousnuunnattlht eooobsffsuewwrrfaaavtcateeetrritohccnrllioinunusgggiiinnhngggaattsoostatonoarrdndarrareedrmmdnaacoiihnznaziirnlntegg.. oiCCfonomrrtr0rheeeessappstoouennrrfdidaiiscnnerggeitswwadiaenetereterdr,mrreeaipprneeeellaldledenibnnccygyyovrrfiasauttii1ann0lgg0oss,bwsashrreeeervrggaeiitavivsoeennnwiuootsnnhintitghhniciassresbbstaaassinsniidsg;a; randnmaaocmmuheenalltryyts,., iootfffhnwwaoetaewtmeroarostoentnr cittsohhnereveesstnauuriirnffeaaenccdtee,,f,aovvauarledluulaeeidszsienddgaeecncordrfeegaa1ss0ee0i,990a0w,v,sh8i8e00mer,,peal77ss0e0,r,w55ei00t,xh, apainnnrddc0ere0.sa. ssTToihnfihigitosshanemmmeaeotctuthhnuooatddsl isssuurtrhffAaeaccmeeseorrceseoptpneecdll.ollenenmvncceeyytn.hieondt,towuhtiilcizhe and gives is used p a simpler expression of the actual aricalrly in the evaluation of rrTaniintAwhmiesesaerccaffsoaaenbb,rdriiwccasmst,,eeiitrsihttoshhdeef,oRRrawaciihenndicTThteeshsitrtso((TuTuesegsesahtdt M Mnpeoaeztrtzhhtlioocedudalta33ar55l--y11g99ii66vn11e,,nstshcheeyeed99re4o4v,s,atlppauaataggiteecio1h1n44e33ao))d..f 5bsIo0nlo4atth3seirtts,oo cwiiahmmsieppc,iihnnwiggaseetreoornneisa8wfppoeiireecicceeeadgfoottfhfehrffeoaatbbuhdrrgeiihcc.t.easTTtnh0hoeezzdflfeeaacbbarertiimccaiiinsgseibbvtaaehccnekkheeadyddmbbryyoos3ataowuwtifecewiingaghbthe_teeaerddd bwwhlhoi`itccAtheht,rh,hhiwarasdshmillceeehatakkhieseoddrdeittwhshrertoiohgueuhggeBhhdunttahhdfeeteesrssmppthaeeecnciinmtmeTseeetnnsttodduudrrewiitnhnegigrmctthhihneeiesttuteehssste.te.dapmroeduonmt ionfawntalteyr iiinn aEEApuuprrtlohoippieered.d.tmIIhnnertothtluhaogiidsshiccsaaatsssheep,e,rBttahhyueennffdoaaezbbzsrrmliieccaniiasstnpp2Tlleaacsccotee(n9dds5i)idinnwerhaasibhhclohoelliddsheeeurris;;gehdaatnnpddarenwwddhohipmillreeeinswwasaunatrtteeleyr,r ttTishhheeaepffpawabblairretiidcce itirshsersrroiuuusbbgtbbahneecddae ffsvrpraolromaumyesttnhhaoeerzezrreleeevvxeeparrrtsseeeassssceiiodddneeisnibbdyyterea3ambssslemmooohfooetwtihhgahtrrteooattanattddiinsnopggrreboosbebsjdjueecrcbetty,. thTehefawbraitcerardesiasltasonctehevaalmuoeusnatreofexwaptreesrseacdtuianllteyrtmrasnosmfiwttaetderbaydtshoerbfeadbribcy the fabric and also the amount of water actually transmitted by the fabric. 33002222..00110077 I3MM_MMNNO044885555221166 10 wo. mre & Goss obo fo fosusavcoirng .... ' ony 1s was 6" Glass laoororory runnel ~ N/E "X /Rubber covering for /ring support / / ,Laboratory ring support ~" inside diameter) H Jr\W,C R Nt/ri[1.p E.v..e.n ve -~- Rubber tubinq a so out 19 rts Spray nozzle (19 holes 1 I anes- 035") drill It65 -.0~5") . p= wo wenn 1026) -Metal embroidery hoop a A SeFabric sample (7" x 7"} f[ rs son we ss support and stond Ear L oF. Le Fo. 0 tnd es ps fo menting sry i of reed Bs. 60. Standard test apparatus for measuring spray rating of a treated fabric. 2. Oi Replleny carbOOolinl zrFeenppieesllhlleeesnn,tt etTrahetaetmmeseninmtptsslew2ws.eterrOeeainluudnRnkebmnpoooeslrwltennnrcppyarebioolrrettoomttehhteehuossdeeodofefctthhleeopffleuodorrotoo- carbon finishes. The simplest and most Srratiingthsateewihlaasincg nmisdepvuirseedof20w3hit0e date is that utilizing mixtures of white reliable method developed to egirvearlepalllenacnyd vRaleupestfaongaoley mineral oil and laeptane(96,97). AAmmaAatrteaTertriiCinaalgClss.swwchahilSieccphhrhaaaaysreebTecceeootnmmppddaaeerrvcaairbsbilelebedeoodsonnaabaasorvrteeeop.peegTllilhevninecscyyretepbbseaatlssliecssntcwwhyiiottvhhdailttuhheosssbeeafsoooerffdottihohlnyee ahtAhe.ewAhdd.iTiitff.efCeermr.eCeinnn.tterSppapeelrnnaeiyctreaTiateinnnsdggt ndpperroosocpmpreeiaerbtieicehdsespaotobaffontwvew,eo.oMTmmiihsisistsccuiirtbbeellseset hhomyyfddetrrthhooeoccsadaerrbbitsoownnboalHiisiqeuuddiiddosss,n, Smaarocewummhniiittsseciimoblfleienneii-nrnhaelaaplltlolailppnrreaoonpnpdoorrttntiihoooernnmmssaiaalsnnthddueepeetxxaihhsniiebibi.nittcMrggcriruxeeeatadutt.eerrersAwwsoeefmtttiitignhnhgegtsebppooetwwweeeorxrpleaaicqstuehtidhd,ees amount of n-heptane in the mixture is increased. As might be expected, shpeecst utoftihetecnosmipoonsivtailouens for the miiuee are eliely near wih Te the surface tension values for the mixtures are relatively linear with re- espleevc"TetTnaatbbotlleetshXXeXoXicXXlo,ImIXXpwohggisiiictvvhieeossnT.ttahhneegeoofililnrreecppoeemlllpeeonnscckyyiorrnaattiinfngrgosamassspiigugnrneeeddmttioneecraaacclhh woolff ttbhhyee eleven test oils, which range in composition from pure mineral oil by 33002222..00110088 M_uNosesS217 3M MN04855217 ouSTIAL Asecrs oF FuRIE CUENETAY INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 403 mast xxix TABLE XXXIX Conve or La Missa ron ue Suva Taran Tar COIVlPO$ITION OF LIQUID I~IIX'rURES FOR THE STANDARD OIL REPELLENCY W~sT on T TrwoC ebe Sptoetn Vici, Scie Oil Nowe Sot lot mages) yoy Rating Per cent by volume at 20C MineralOil~ n-Heptane~ Surface tension (dynes per cm) Viscosity (cs) Specific gravity 150 0 100 20.0 oon wm um 140 10 90 20.5 ob moon om 130 20 80 21.2 moon oR nooowe om 120 30 70 21.9 ook Boom am 110 40 60 22.8 wos 0s nom ow 100 50 50 23.8 kw noosa im 90 60 40 24.9 FR 1 nom ow 80 70 30 26.3 oon ow moa ho 70 80 20 28.1 mb nom +] 60 90 10 30.4 FI ono FH 50 100 0 32.8 " (roe mie 0 (no holdout tomineral oil) 0.534 0.668 0.862 1.15 1.60 3.31 3.63 6.16 11.7 26.6 78.6 0.679 0.701 0.722 0.741 0.761 0.780 0.799 0.817 0.840 0.860 0.880 At Ci Shel cy 00 00 Spc iy 03801900 a"Nujol" (Plough, Inc.) Saybolt viscosity 360/390 at 100F; Specific gravity 0.880].900 ewee (isn, Con 1 5 597 at 60F. ~Heptane (Matheson, Coleman & Bell) b.p. 98-99C. 3M OIL RERELLENCY TEST 50.60 70.80. 90. 00 Nof: Fc 1. 0 any Sing ic ih ml in 61. Oil repellency test, showing fabric with an oil rating of 80. en pr cnt increments to pure heptane. T will be noted that on reading ten per cent increments to pure heptane. It will be noted that on reading 1 th tbl rom oil tings of 01 150, th te os sabi gradual up the table from oil ratings of 50 to 150, the test oils exhibit a gradual Feet of suas emo ecrrsg specs Goins amd dees lowering of surface tensions, decreasing specific gravities, and decreasing 33002222..00110099 W3M_NMONA0B4S8S55221188 a0 1. mvs 404 H.G. BRYCE vvcihissaccroaoscisttkieieresis.s.tiITcttsiisofbbetelhliieeesvv,eeddantthhdaattottthhheeer cclooinqnuttirrdoosll,liinangrgevvsaaurrriiafabbalcleeesstiiennnsttihhoeen ww4enetdtttaabvbiaillpiiottyry ppcrhreeassrTssauuocrrteeemr.eiastsiucrseoifltheepseel, laenndcyoothfaer liquids, treated are surface fabric using tension and vapor the above test ois, dudnrrodoippTsssotooumfrfbettehahdseeusseerfeoooroiilillssthraarerrepeeeelgglemeennnitctnllyyuysopp,fllaaaccteerTddehaeootenndnttuhfhameebbrffeiaacrbbrruiiscccionaargnneddsthpaeaollnlalodbowiwoneevgdde tttteooos.tsstoatahinnlasddt, ummpeininxdxetittusurtrraueetrebcceooodnnttawafieionntriinntggthherttehfheaeebrhhmiiicgignhhiueesstsetctso.pnpseeTirrcdcheeeennrtetaadnggueetmheoobffielrhheerppcetotpaarlnnrelee,es,pnwcowyhnhidircicnahhtgiddngootoceossftnnhtohoatett fFfpaaiebbbnrrreieict..r.aFFtIeiingogutrruheewr66ee1ctasssthheheooiwwflsaslubttsrhhtieerca,btbeieesdhhacatvovhinieoosrrifdooaefbfarreaidscseetwrrhioieeueslooodiflf ttrbheehpeegtfleileesvttneconoyiilsasornaontni8n0agtterroaestfaitntteegh.dde uTfTashhbueesrilcldd.yiissItqtniiunnicctthtteiieoosnnhcaabbsreeepttwwialeelnueednnstrpffaraateiieslldueurrneetthseoornr foarrebepssrriiiscosttbaawlnnecocmeeuldoionff bsdseuuectcgcceieervssmessiniinvvieeanngmmi8tisx0htteuurrrabeetrsisenagiiks.s upsouinatlly quite sharp and presents no problem in determining the break point. 33.. SSttaaiinn RRe~si#sttaannccee to cT"oTrhhreeeloaoitille rrweeippteehlllleepnnrccayyctivvcaaallluueerssesddiesettteaenrrcmmeiinnteeoddcbboyymmtthohiinss ttaeenssittmahhlaa,vveevebbgeeeetenan,blffeoo,uunnoddr tmamoinindnecerosraraulrlbeslooaeiitqleussettwnaaitiinntlslsy.~. W Wpblrhaohetcettnneicdattyyloppfiri,cceaasltilshotoialislneycesfsttaaatbiiornnissccoaarrmweeimtddhroroonappnppaeenoddiimooarnnle,pttrerveleeaeagttneeecdtdyabffalraebab,trriiiconcsgsr and subsequently blotted off, those fabrics with an oil repelleney rating = 62. Oil repellency and its relation to stain resistance. 33002222..00111100 33MM_MMNN40S48S555221199 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 05 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 405 Of oGifl 55r00e-p77e00lewwniilcllly eerxxahhtiiibnbigt ooofnnll5yy0ff-au9ir0r rrieelssliissttsaanhncoceew ttgooossottdaaiinrnieinsniggs;;tatthnhcooesseetoffaasbbtrraiiiccnssiwnwgii;tthhanaadnn 6tothhi2loossrteeehpewweiclitlotehhrnraoceyilllatrrraiaaotttiininnngggbsseotoofwffe811e000n-009i0aalnnwddrieluulpppeslhwwloieilwnlllcygggiiovrvoaeedteienxrxgceceseloilslflteeanntnthtceerreefsstaioissbttrsaaitnna,cciene.a,inniIdgnn;sFFtaaiinig.dn. 6rmree2issniietsshrttaeaanlncccieoelrriiessilsacctldlieeoraanorrpllyybpeeddtdweemmeooenonnsnttsohrtierlaattfreeaeddbpreiwwlclhehsneeacnnmypoolrnnaeeetinaccnguudbboiibfccitochcteeetnnetdftiiamombferfei.ttcee,rr anoofdf dyed stain dyed mineral oil is dropped on the fabric sample and blotted off. E. E. Facrors FACTORS Arseciin AFFECTING BBEEHHAAVVIIOOFRRanoOmpiFcsFFLLUUOGRROOCCAARRBSOONN DEUVATIVES DERIVATIVES OX ON 1. ChemFiAcBaRlICSStructure in dTTehhteeermccihhnaaiiinnng lletehnneggttrhhepooefflltteh1hne.ecyCffllhpuueroomorrpoioeccrcaatalrirbSebostornnuicmggtpeuraoorreuutppediiss0aanna siiummrpfpocorert.taannIttn fcfalacocsttoco-rr tpiphnaaeccdkkCeeeFtdde,rssmtttrreiuunrccmitntiuugnrraeeltssh,,gesrsuuoreccuphhpe8lialsssetntthhcheoyosspeeprrissomttpueuedrfidteaiicdetsobbr,yiymOZZpiniassrmmtteahadenn toaaotnnhdadersccuoohr--afwwancooderr,k.keoeIrnrns(s1r(c6ol5o,4u1s9sge),h-, ataehnnendd CgiiFrsr3eeogfgtueulrtlnahaarerinAbfaiulbeoegrrrroocssuuuuprrrbffiaaosccnteehsscehwwaphirheniemrrgeeeovfccaellcrootnssoeesr.tppOhaaeccnkkdiitenhngggereoiiessthoeonfrottohraaaincccdhhni,iaeeotvvineeoddnr,,ouattgnhhdhee lheenngctehtohef tehfectfvlueonreoscsarboofnthechsauirnfagcoevterrneastmtheentdegree of orientation and hence the effectiveness of the surface treatment. TAME XL 'FAILLE XL RurmuincyPoresor Coron Po Clr Wi 3 Heke wa Sats or I~EPELLENCY PROPERTIES OF A COTTON PRINT CLOTH V~HICH IS TREATED WITH A SERIES OF Sin gros Olrepllney_ Weeseplency SUBSTITUTED POLYACRYLATES Substituent group Oil repellency "~Vater repellency cree o CFa-- 0 50 aR Fl n C~F5 -- 60 70 Gr n C2F7 -- 90 70 C~F~ ~-- 100 70 Cra 0 TM CTFxa-- 120 70 Cr w o CsFI~-- 130 80 HRC) o HCF~(CF2) 7-- 50 80 ackcranR- 0 = Ct(CF~CFCI)aCFz-- 0 80 80 xIInn8TT0aabcblolteetoXXnIL.praairrneetsschhlooowwthnn fddoasrttaa ffsooerrrittehhsee oioflii paaonnlddyacwwrayatlteearrterrseeppweeilltllehennccdyyifoofennri3an0ng. gc8cehh0naaeiixnrna8lllee0nsntggcrttouhhctssttouoonrffe,ttphhreReinyfftClluHocor1lrooo:tcch0aa0rrfCbboCoornHna=gg=rrsooCeuuHrpipye,,s,tthhoeTefnmmpocooannlcoyohmamcecrearysrssleafftteoohsrewwwmhahiititccehhhridhahliaafsvvfeeewretitnhrhgeee cSgaepeppnpieelliereiaddelnaascttyraauinncnctaaurdderdedas,--eooRsnn~pooCrffoIg11tr2~%eOossObbiyyvCewwCleyeHiifg~grhChot Hmttoo.0)tt.h1hIeenff1aae3bba0rrciihacc.s. ActAashssee ccftaahlnnuebobmreeosacsetaeeerernbni,ao,lnstthchwheeaeooiriinell virineanpclcruereelelasaessnevecsayrffyrironomcomrnel-Cay-sCFefsFsr3pormttooog0r-e8sCCs0yi9,vFFye~alT9y.h. iOfOsrnonmrttehhl0eeattooiotvtehh1eei3rr0nhhsaaaesnnnddts,h,iettvhhifeelyuawwoasratofteceararrrerbepoapesnelllwcleeahnntacceinyye values vary only from 50-80. This relative insensitivity as far as water 33002222.0.10111 I3MM_MMNNO044885555222200 "0s p-- H.G. BRYCE weeny is concerned is bleed t bedue to she nuofethe ser repellency is concerned is believed to be due to the influence of the ester eis prymes syst The da sho nF. 65 hrs oe linkage in this polymer system. The data shown in Fig. 63 shows a similar rreellaattiioonnsshhiippffoorr aa hhoommoollooggoouuss sseerriieess bbaasseedd oonn aa mmooddiiffiieedd aaccrryyllaattee ppoollyymmeerr.. ie the he ne i epeny wih ce h In this case there is a marked increase in oil repellency with chain length rE vo Cr whl de we pny avs we recy from --C4F9 to --C8F1~, while tke water repellency values are relatively froIniOo iHfHe fg iHjs Io0o 5Ool ooos ao1t35%t,apeer 9) Oil repellency rolim Soran D Spray rating -C4F9 -C6F~3 ruses co tan Fluorocarbon chain length rn. Wovens if soeimet ong rst Fro. 63. Water and oil repellency ratings as a function of chain length for a homologous series. conan, hough ise in the 90-10 rage. The difcion s of constant, tkough this time in the 90-100 range. The modification is of a Bok cnt fe on an enc ht such a nature as to block the influence of the ester linkage, and hence the ier aes epelne e octode i XL efor ro. higher water repellency values, included in Table XL are data for fluoroon vats whch ano ht ermal Rn or bo pn re carbon groups in which one of the terminal fluorine atoms has been re- ppllaacceedd bbyy aa hhyyddrrooggeenn oorr aa cchhlloorriinnee aattoomm.. TThheerree iiss aa mmaarrkkeedd ddeeccrreeaassee iinn Tl ine Icing comer ae safe cacy Fes the oil repellency indicating a considerably higher surface energy. These i oto of Fen a wo results are in line with the observation of Zisman and co-workers as refreebie iy viewed in the section on Characteristic Properties. Fon prs pio of ven, perl se st important aco in From a practical point of view, perhaps the most important factor in drm Bei of + Beaton Bro on Fo tt determining the behavior of a fluorocarbon group on a fiber surface is Ch hemi opin by wh te Tororo groups stated the chemical grouping by which the fluorocarbon group is attached to he on Amn heparin ere on as et i fore the fiber. Among the properties desired on fabrics treated with fluorooe he a TH pln, wie pec duty of carbon-type finishes are oil repellency, water repellency, durability of endo ho nclcing ond ss nc these properties to both drycleaning and laundering, dry soil resistance, ten sree. Dapeng on the enw sm of sho and abrasion resistance. Depending on the end use, some of the above pais wil be ne pn hn ore 1 apen, dheet, properties will be more important than others. It is apparent, therefore, Et vein of varying te pp ors that the most versatile means of varying these properties is to incorporate 33002222..00111122 aw_ossss2z1 3M MN04855221 DUSTIN ASCs OF PORE CTY "or INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 407 the fluorocarbon groups into specific molecules which, when applied f0 5 the fluorocarbon groups into specific molecules which, when applied to a fic, wil ive the balance of propcties dsicd. fabric, will give the balance of properties desired. From care rel, ha Bch shown hat a prime requis or god From earlier results, it has been shown that a prime requisite for good il epllency 3 Auoroctbon group of a Jet fur bon sons, oil repellency is a fluorocarbon group of at least four carbon atoms, xm by a Co group. If such fuorocarbon group is comple terminated by a CFa-- group. If such a fluorocarbon group is complexed ith chromo compound, ae set of properis wil etson the ter with a chromium compound, one set of properties will result; on the other Hand, when tis same fuorocarhon group i atsched 03 povscyite hand, when this same fluorocarbon group is attached to a polyacrylate sicture, diferent lol of prforence wil eu. It 3 deed tre structure, different levels of performance will result. It is indeed true hat possible with many ypeof fncrionsl gross to fave very low that it is possible with many types of functional groups to have very low al snd wer repllenic and por curity chen hough long chain oii and water repellencies and poor durability even though long chain Auorocaon groups se stached fo the ber fluorocarbon groups are attached to the fiber. wo . goI10 I2i r% o= s 3fo "cn -C,~F9 05O 5 es en 0.5 1.0 t.5 2.0 +e roymer tis on tor % Polymer solids on fabric Tio. 64. 1 meen. eld on ric fc 3 sic of pol cnaising FIG. 64. Oil repeIlency vs solids on fabric for a series of polymers containing in Sno up of rr hm og varying fluorocarbon groups of different chain lengths. "The orion ofthe molecule 0 which the Suorocarhon group i svcd, The portion of the molecule to which the fluorocarbon group is affixed, ancy, the bonding group, rides the physical or chemical boning namely, the bonding group, provides the physical or chemical bonding ewe thse grou nd he. subsrte, As ndised shove, the ype nd between these groups and the substrate. As indicated above, the type and atureof thi bonding group ca nfcnes moto th propane soci nature of this bonding group can influence most of the properties associated ih the fanrocarbon group. In paren, however, it determines the with the fluorocarbon group. In particular, however, it determines the Guraiiny of he avacimens to cleaning proces, brave action, 1nd durability of the attachment to cleaning processes, abrasive action, and xponrs to hetor sunlight. In addition, this bonding group vill ao exposure to heat or sunlight. In addition, this bonding group will also Teel determin th cs of and degreof orientation snd he densi of largely determine the ease of and degree of orientation and the density of atingof the fuonocaoon group an he suis. The prope orientation packing of the fluorocarbon group on the surface. The proper orientation EB earocatbon group on the race most import in waning of the fluorocarbon groups on the surface is most important in attaining 33002222..00111133 WM_MNOABSS222 3M MN04855222 - mes 408 H. G, BRYCE th maim spel la with he mir amor of orb the maximum repellency values with the minimum number of fluorocarbon -- ' groups per unit area. ing op ici ypc ca off he nn wae A bonding group which is hydrophilic can offset the inherent water ln ropes of he Hee Borocmbon su we soting repellent properties of the oriented fluorocarbon group with resulting Hover a epee vets paler in, Siy boning song lower than expected water repeliency ratings. Similarly, a bonding group VR dey ily re echoy en hy which has either a dry or tacky surface will very strongly affect the abilky Sh eed te ese of i. of the treated surface to resist the adhesion of dry soil particles. oor cor ~ IO0+- L ,oo [| = 90 Pbrald ~ 8O - CsFI-t Po=l I 50 rama sim ane 0 0 o0.s5 11.00 i1,s5 zo % Polymer solids on fgbric Fo 5 ts ce ie tr is fies onion FIO. 65. Water repellency vs solids on fabric for a series of polymers containing eT i varying fluorocarbon groups of different chain lengths. In Fig. 64 ad 65 te cil and tr repeney for homologs In Figs. 64 and 65 the oil and water repellency for a homologous si of Baron ro wh et he se mid series of fluorocarbon groups which are attached to the same modified Soy pymer boing go rs hor. To mire nd ws acrylate polymer bonding group are shown. The maximum oil and water lend einer eed ppt Hof lon repellency ratings are reached at approximately 1.0-1.5% of solids on the Ee ei ns tk no at how sh, re sl oh fabric. It is apparent that no matter how much material is applied to the ist pale Saad wh + Ce gro ev surface, the oil repellency obtained with a CaFsl group will never ho Co, reach that of a CsFn-- group. . Comms. Proven F. COMMERCIAL PRODUCTS The cts shows i Fi, 6 a 7 re tose or 3 comm The results shown in Figs. 66 and 67 are those for a commercially asl Troorhon i nh dened somal Foul available fluorocarbon textile finish designated commercially as Textile Chenin FEAR ha moh, ho sly andr ins Chemical FC-208<gs). As noted, both oil repellency and spray ratings el the soca is Fo 03 05 wg rise steeply as the concentration increases from 0.2 to 1.0% by weight 33002222..00111144 awmosesszza 3M MN04855223 evra, es on mse mer 48 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 409 FE Tu solids on tke fabric. Above the 1.0% level, the curves flatten out and A give essentially constant repelleney vaiues. hE Sr Eiehd 0fom S aes oE r rie Fluorocarbon type finishes can be applied from aqueous or organic solvent systems. They may be in tke form of true solutions or may be 120 110 100 90 80 70 3 Coon fobs A 60 Cotton fabric r X Cotton fabric 50 | [] Cotton fabric 0 0 0.5 1.0 ! .5 2.0 % F'~20g SOLIDS ON F~g~Rl~ FzG. 66. Oil repeIlency vs FC-208 solids for different cotton fabrics. - reer lOO el / 90 ii i . / Rom, Cotton fabric A Ew x Com cs 50 X Cotton fabric B 5 3[] CCaortteonn fbi fabric C 0 0.5 1.0 1.5 2.0 % r-c20g $01.1D$ ON FABRIC 67. Water repellency vs FC-208 solids for different cotton fabrics, 33002222..00111155 p-- 3M MN04855224 PY wc. mca 410 ~. G. BRYCE cous or ped in fly divided st in isd media. Tn emulsified or dispersed in a finely divided state in a liquid medium. In Fe he se of an ane slens i preen fes problemisn general, the use of an organic solvent will present fewer problems in Siig mma prormane hor geen spose. The tent ies obtaining maximum performance from a given species. The solvent gives or to shin medium 30d sh pr ein wEking 4nd a more uniform treating medium and also permits better wetting and pension of 1h Ber arcs wah xd Smalling of te Fer penetration of the fiber surface without excessive swe!ling of the fiber Er Rene, dcapio of he ot rie: Suh solvent spghstons ae and hence, disruption of the fiber surface. Such solvent applications are acid nds med cremate ut or the Tot pi Power practical under limited circumstances but for the most part, however, Eo omic is anand ele. mil prac, mere are not consistent with standard textile mill practices. A commercial rods of ths ty is alle and i own 3s Textile Chem product of this type is available and is known as Textile Chemical F-31000, 1 ed rime in th sing of ih rade uphotny FC-310(9s). It is used primarily in the finishing of high grade upholstery nd dcorin fai and decorator fabrics. ao . 120 ,A IIO fo = IOO fo 7 90 fol 80 A. Air dried Sn oA ir sama 70 B. Air dried plus 5rain @rsone coe @ 150C cure " Co mao a @ oe 60 C. Dry ond cure 5rain @150c Py5O oe we ww mw 0 0.5 1.O 1.5 2.0 2.5 rczon ses on tec % FC208 solids on fobric Fi, 8 Ecctvain din dco coon0 oloseved FZG. 68. Effect of varying drying and curing conditions on oii repellcncy of a treated hac cotton fabric. Aqueous syste, such ss Texilc Chemical FC20, ae wed in Aqueous systems, such as Textile Chemical FC-208, are used in ens a appa 3 wis vn of pear wrote, general textile mill applications to a wide variety of apparel, upholstery, Eoomote, 3nd indus bro. Such, Aquos mon, of Sos automotive, and industrial fabrics. Such aqueous emulsions, of course Shi ably va vain of sling gene: Depending on she owe their stability to a variety of emulsifying agents. Depending oa the hic of coli hy ay bo iris, onion, a Cont, 1 wll be choice of emulsifier, they may be anionic, nonionic, or cationic. It will be Tek son hat Ts imate pone abe on ghen Abr readily seen that the ultimate performance attainable on a given fabric i tpn vey ray o he sire of ht Sharps of th fave, will depend very greatly on the relationship of the charges on the fluoroion a sion enh shar ocd wih te Fe, wel carbon finish emulsion and the charges associated with the fiber, as well 33002222..00111166 W_nodsssz2s 3M MN04855225 Fp -------- INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 411 a ier clcrolyts presen. For example, arini acs perform bes on as other electrolytes present. For example, anionic latices perform best on ol Hori pH ves shan he ete piofwnok = 4 wool fabrics at pH values less than the isoelectric point of wool (pH = 4.2), rcs coo and moo i are mot Bl or espn Hors whereas cationic and nonionic latices are most suitable for cotton fabrics Seely anfo vol abi tp vs shove Sh sont pn. generally and for wool fabrics at pH values above their isoelectric point. ncn oroonben ih ppd to 3 ois some ing or When a fluorocarbon finish is applied to a fabric, some drying or urn of he ned i ena. trl sprees i 3 curing of the treated fabric is required. In general, this procedure has a LS es oh degre of seein sine. Tn Fp: 68 and 69 marked effect on the degree of repellency obtained. In Figs. 68 and 69 100 i wl 9O B -- 8O | Jo ; 7O :Poo5O poring A Air dried B Air dried plus 5 rain ya @ 150C Cure eu C-Dry & cure 5 rain @ 150C 0 .5 1.0 ~ .5 2.0 2.5 3.0 % r-c208 SOLIDS ON FABRIC Fs. 0. Ei of vi it ed ci srs nes be of 3 Fro. 69. Effect of varying drying and curing conditions on water repel[ency of a ---- treated cotton fabric. ical datas shown when samples of an 80 x 8 coon prin clos typical data are shown when samples of an 80 x 80 cotton prim cloth edi FCA. Th hs of epelenty sins all conc: are treated with FC-208. The higher oil repellency ratings at all concentraoer when de ae a dr, Gave The owes of tions occur when the fabric is air dried, i.e., Curve A. The lowest oil elon iy soul whe te ori ily did or 8 tes repellency ratings result when the fabric is rapidly dried for five minutes STIS Teco sae rol hn he hie 5 51 dri 3nd at 150C. Intermediate values result when the fabric is air dried and ently ove cre. Ths sels re bot undistod in sims of subsequently oven cured. These results are best understood in terms of non oeaion of he Brg rou on Tt ne, shoe maximum orientation of the fluorocarbon groups on the surface. A slow pene lows sh os fot raion of he Aaron drying process allows the most time for migration of the fluorocarbon Ee st hot ope oem a hs fog hom groups to the surface and their proper orientation on the surface; hence, Ee Tove ft rey md omen Wh. See of a1 re the lowest surface energy and consequently highest degree of oil recn pellet~cy. ota be sen from Fi. 3, hover the mama ats spl As can be seen from Fig. 69, however, the maximum water repellency is tind whensh dyin procs ont sept, a dn ht is attained when the drying process is most complete, i.e., air drying plus Sine 50. Tos wel do 4h no sen 5c 5 min at 150C. This is undoubtedly due to the need to remove as comSi pil rom con be the abodes sed pletely as possible from the cotton fiber the absorbed water associated Di he ving mom. with the treating medium. 33002222..00111177 awuNossssozs 3M MN04855226 a 6 mvc 412 H.G. BRYCE Fy ------ Some interesting effects have been observed through the use of cnscbon fps cle mses fn bination wi + nabs of fluorocarbon type textile treatments in combination with a number of aig fae oi ee 1 8 profs Soh crosslinking textile treating resins and other products suck as water reln. For exami, he a Fp. 70 Shoes so rt 4 dere pellents. For example, the data in Fig. 70 shows that there is a definite wl120 110 lOC 4sl712 5~ r* eR t re ae r-c 208 triazine re$i9 +Selected water repellent 1.0 1.5 2.0 2.5 3.0 m ie Te ats ed stdcot iyelsty % K201 SOtlDS ON FABR~ FIc. 70. The effect of a triazine resin and a hydrocarbon water repellent on oil repeIlency of a cotton fabric treated with a commercial fluorocarbon resin FC-208. 1 100 HE 'He70 S EIE iT 50 Fc 1. Th csAot. hos a1 bRonnws tos voc .5 1.0 1.5 2.0 2.5 3,0 % F~2Q~ SOLIDS ON FABRI~ 71. The effect of a triazine resin and a hydrocarbon water repellent on water repellency of a cotton fabric treated with a commercial fluorocarbon resin FC-208. 33002222..00111188 aw_nosess227 3M MN04855227 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY a INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 413 icimommppbrrioonvvaeetmmieoennnttwiiinnthtthhbeeotrrheeppeelltlireienanczciyynerraartteiisnniggnffoaonrdooaiiliswowhhaeecnnomtthmheeerFFciCCa--l2200h88ydiirssouuessseerddboiinnn tcatyyolpptmeehbouwiwngaaahttteeitroronrrewaeppileetelhlsllseebennorttthdaaessagrtaaerieatt,rzreietanahtetmemrreeeeinnstitnffaaoolnrrsdoccoao4tltsnttooonni.a.mcporFFmoiigvgmuueermrreeecni77at11l hissnyhhdotorhwwoescsastrtphbhraaoattny,, araaaltnttidhinnogghuygffdohorrrotwwocaaatrateebrrloenrrseesppeweeralltlldeeeernngccrryyeeepii,ennllttthehhneeetrsepp.rrieesTssteeannlwsccooeeouolaffndsseieslmlpeepcpcetrteaoedrdverrfmeeraaeoccntmtiitvvteeinhtteyystphepeeerrreseespssuriilanntysss tcathhnaaardttbotthhhnyeedgpprrorroeecussapeersnbnccooeen oomfwif gssaruutaeectrlhaetraaeouupsaxeiinllllideaanrryytosr.mmiaeaItntteterrwioiaanollusstlhmdmeaakaskueperspsfeaiiatcreeeaaofssrfiioeetmrrhffeootrhcr oetttshhteeeonffrleuuBsooubrrlo.ot-s- `wcAAiasstrbhssotaaantteevgeddrroyceuaaplrraslirlegtro,e, migrate to and orient on the surface of the cotton fiber. stuhrefaccoettaroan.fiber possesses an extremely rough surface the cotton fiber possesses an extremely rough surface iwniftlhFFureraonocvmmeertyaahelpparrraaagbccietltiiiscctuaayrllfoapfpcooeaiinnaAttrueoooafr.fovvciiaeerwwb,,ontthhteeerreestaaerreefimmniaasnnhyytoffaapccrttooodrrssucwwehhoiipcchhtimmmauaymy Coionioillfrlrouerelnawwtcaaeetdteetrrhweirretepahpbeelltilllheietenynccayobyifrrlaaiatttiiyfnnlguogsosfroootnhcneaaarbmfbaaortbneriritc.ie.aIxlItnin1le0ggeefmninineegrirsraahallt,tetotthheepssreeotdhffaeaucccstteouorrrossfpammctiaeamyyaunbbmdee sgscuurobborrsuseeeplqqsauutoeeednnntttlwlhyyeithosoruritirheefnenattcae5sbo0iIlnit4aycsootntoofsetgghqiiuevveeemncmmaetaaeoxxrftiiiahmlmiusutom,memxeeitxxgrppreoaomstseeuurrcteeoarootehffmeufAlssuuuotorrrfbooaecccaeatrrababkonoendnn buginresobiuecpnionsgngtossanuumirtchentaethnhstaausttr.ttfhhaceeTteff.aisIbnaraikccibooissnipsrpmreproqooipupreetercnalrlcnyyet ppotrhefeaptpthraiorsete,hddeesrxsotomreaaatmsetterooibcabealerseffwrrmeheeeiuocosfhtf bdadreleeleteeautrkesrieei-nd- ioiinnnutscceorocfnnoejjrnuuetnnaccwmtitiiitonohnnantwwthsiei.tthhIptrtthohispeeeafrlllsuuoooorririomoeccnaptaeoarbbtrotioraon,nntffotiinhfniiaststhhhoebbtheefeloorsffomrssoauuctcceahhrribaaaolnsnnawagttrhuuoirruceephs3a.assroennnoouttstehttodeo surface. interfere with surfacer97). the proper orientation of the fluorocarbon groups on the FabrGGi.c.sSSwtThaAinINcshRReEhsSaIstSseTrAabNxeCceEenoOprFroFFpLieUurOolRsyOotCcrAseRsaBsteOodNs wTTiRrtEehAatTaEefDdluFFoAarBosRciaIcCrsSbon type tsteeixxnttsiFill.aeebTffriihincisssshh,wwwfhioiilrlcllhtsshhhheooavfwveresggtoobtooeieddmnessttpiatarinnoisprrpeeerrssaliiycsstttiatacrnnaecclaeettettodoohabbwvooiettthhhrewwasaiaftstleteuraronracaoenncdd0aroobiaiolllnbbcaatysospeerdde jsm mutoiaocinnness,.ssttcTaaoihifnnufiiensn,,ggfsoommrfatattthederreriiinaafkillrssss,t iiatnninm ccdllueuaddkiiitnoniggsapw3ariqqaduucecetioocvuuaasrslittossyyyohsstatfeevm mgesrs.ereassssiyuusocctahrhncoaaeissltyoiinmnakkal,t,lecrffoirram uuliis-tt jooauffnicdceeiisttah,ihleecrrorfvvfeeeepegge,eletsltaaoebbnfltcleeyd,,riaarnannktiisimm,nagalasl,n, dooofrralsm m9oi0innaeoewrrraaildlmeooorvrriiagegiriinne.g.tiyvGGeoeefnneegxerrcraeaelallslllyyyenosstrppeeoraaeiklksyiiinnsmggt,a,antwwecearaitate(elrsr aawahqnqiuduleeeooouuirlssatoroiernrpgaoesilillloe--fbnbocoryr0nneeorrasstttilaaneiisgnnssss..hoaRRvfaaett9ii0npnoggossorroofofmr77o00nroettoorge88is00viseggtaiienvvcxeeec,ffeailiWlcrehnssettaaniirnneastrriseettssaaiicsnshttcaeaendnccte0eo,, wtwthihhleelilsseiuumrrrpffaaaaticcrneetgosoaffosaafig5ffnaa0ibbfriroiicrccanltttehhsrsrroeohusuiaggsvhhteatntphchoeeeotpprorroootrppheenerroalldirinhenkeskiasasggiteaeo,n,nc2aeof.ffllW uduorohyrroeoscncaoarairbtbtopoannacrhggierrdcooluutspop PowPafairlrtltfiiucicmuoulrlpaaorarcllrayytrabnnooosnttiegewcwnaoiofrrirbcttohahnnyyytlaairrrceeesicssstuduaccnshhc0e2mmat9aotte.ertrhiiaaellssapd3aih5seecsttehihoeeonfccohhffrarobodrmrmiyciiuusm wmohielccnoopm maptrptrlileecealxxteeeesssd. wsowoifiittlhhfilnussgouirccbohhycaaaarbmmosaynatnettecrhraieiraatblliocxaattysol%aiicl lleemavviceexildltosuOofrf20e,09.~.s55)u.%c%hAbbayypiwwdeeecesieicggrhohitftobeoffdafsbosrblioyciliddSwssa,,hleswwnbiilullrltryerreaeasstnieidssd.tt Convorkers), soiling by a synthetic soil mixture such as described by Salsbury and co-workers(99). Fabrics may bHHe..cDDulUrRaeAnBbiaILyLiIsnTreYyveeTTrOodalCCLLperEoaAcnNeiIdNvuGreesPPR.rOoTcCheEesSsSysEmsS ay be laundered in wFaatberriccsomntaayinbiengcleaanveadribetyyseovfersaolapprsocaenddurdeest.eTrgheenytsmaaty tbeemlpaeurnadtuerreeds in water containing a variety of soaps and detergents at temperatures 33002222..00111199 I3MM_MMNNo044885555222288 #4 no. wer 414 ~. G. BRYCE suuopplvtteoontstthheseucbbhooiillaiinnggpepproocihinnltto..roTTchthheeyyylemmneaayyorbbee& h""ydddrrryyoccclleeaaarnnbecoddn""frbbayyctiiimomnmmekernrssoiiwoonnn iiann5 us""osSSlettvooeaddnddt3sia%rr,sdducdssheootllevvarseegnnetptn""et..rchTcThloooaddrraoagyeyetk"w"ydidlrteryyhnccellteehoaaenrniiananbgg'ho""vyedpprrrosoooccclaeveressbnsstoeesnss. afarTllamhmcoeotsirsottenuuaknnrinievvoeewarrsisnaaolllalyys3 vsvuaoasrlerivieeeattnyyt3soo,f/of;rssdppseeehctceaiiramagllpeonccoltleieaancnnhgiiannrwgggietmmhewetftihhtohooaddmtssheedssuuadccbehhtoev3aressgesssnopptloovttseonlcctullsete.iaaonnTniishnn.gegrewwiiattrhhe special also a special scoelpveTTelhnheetensrrteeofraairrnseeihshaaa,mnnpwuuohmmoebitbnehegrerrwoofifhthyffdaarfccoottooacrrmassrebdwwohhnidicceohhterraagfRfefunecocttrtoscttohahleuerbtioaaobnbni,isll.iitttyyo oofrfetaaaiggniivvieetnns rrrneeeopppteeellblllleeeennnsctcoyylfuiaabnfflittseeehrr,inllawatuuhhnneeddteehcrreliiernnaggnhiynoodgrrromddcreryaydcrcilbleueoaamnnn;iinnogigr.t. rfNNuluasatottururoraacallalsllroyyb,,obnett,hhceetiotffhiiennrriiessthbhaoinnmmduuesitsdtst accnthhoteetammcibhcieceaadlslllotyylhuattbtooleittthhiewenilffltiihbbneeeorrtcoolrberaeeenllrissneeegmbbomeeveessuddufiffufdiiumccrii;eiennnittgtllyytmhiiuennssseotoxlluapulobbsslloeeurbaaeenntddeoibbttheehee3sro0cbltteoiiagngnhhditntellgdyy. csasoootltnlauustctiihidooeenn.dr.abthITlttaetiiassibtraawallsssioiollveoonbbosvvtciitoobiuueossnrettwmhhhaaiottcvheiindnthdnneuoorrrfimminangaillsthhccellmeeuaaesnnxtiipnnoggwsiutpprhrresootcctoaeenssdstsh.eeess Actthlheceeaorrnteetinoiignss affciisobbneemsrruidwwceihilrlallbasSslweweSela0llbl%riiannswiihhvtooehtt awawcatacitotoeenrrrrewsssoohpioa2csnshdttiotonhgeiinniccfnirrcneeriaasesshaeesemiittsisunscctrsroouwsrssfsi-ta-hssceesectcattainiroodenn..aallAaarrcecoaattobbnyy as is nmoITtttuchshhiaagssnaibsbfeei5ccc0aoon%mtmleeywggrieeetnhnmeeorarvaalecllldoyyrfraaerccsoccpmeeoppnttthdeeeiddnigttbhhiaaenttcsraaeura""fsddieuucreirnaaabbtsllueelre""faasffctiienntiihsasrhrheoauiiss.ghoonnseeevtethrhaaaltt Cleanings. is not significantly removed from the fiber surface at least through several cleanings. Connie Drveueaane Rasarascs or Vasows Wares Rersaasrs TABLE XI,1 COMMERCIAL DRYCLEANING RESISTANCE OF VARIOUS ~VATER REPELLENTS Wats repellent ail daetyAeetrntirenpglercdyy--Ascpmhreaiysntg?igdoy AGdoemsis ~,Vater repellent Initial Water repellency--spray rating After 1 dry cleaning After 5 dry cleanings~ After 5 dry cleamngs x woo o o A 100 0 0 0 a ws B 100 50-- 0 0 wo sl 3 o C 100 50-- 0 0 Flsoochamiod Fluorochemical wean ww " (FC-208) 100 90 80 80 S"vPiedrelredrascvheynne2--%3%ssuopp 2isneecontin < 05% snp. aPerchlorocthylene--3 ~/o soap; rinse contains ~, 0.3/~ soap. ~Stoddard solvent--2}~ soap; no rinse. to h"TaThvheee adduusrrtaarbbollneeg hhafyyfddirnriootccyaarrfbobroonnthooerr sssoiiallpiicscoonaneendttyydppeeeterwwgaaettneetrrs rrueesppeeedlllleeinnnttssstaaappnpdpeaearardr tddtohyreychclwaleeavataeneniriannrggsetpppreorrloonlccgeeenddcauyufrfrieoensfsi.t.tyhBBefeeoccfraaaubutsrhsieeecoosdffoisatthaphipissspea""anpprdoosiiasdsoloemnnteoiinrsngtgge""cnotaasmccpttuiliosoeenntdebblyyiynttehhvseeteanssnooadaafapptrssd,r, onccleaning. Typical the water repellency one cleaning. Typical data is included in Table XL, of the fabric disappears almost data is included in Table XLI, which emphasizes the completely even after which emphasizes the 33002222..00112200 I3MM_MMNNO044885555222209 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. as INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 415 srrauabppsiidtditffuaatlell-dloofmffeliiannmiwwnaaetteetrryperssee,ppaeelllelwnenlcclyyasoonna cttohhmeemehhryycddirraoolccaasrziblbioocnnanpep.yytrryiipddeiinrnieiupumemllaesnnntdd esBBuvyyebnscctooiantntfutretraearsdsttf,,mivtteehhlecaemoffmlilmunueoeorrrtocyocicpaaaerrlsbb,oyoannps ewttyyedppleeelyrarceselttaaeaiacinnnosismangamswwearatcteiearrl rrseeilppieecllollneenenc-etyyyprreaattriiennpggeoollffen88t00. even after five commercial type drycleanings. TABLE XLII TABLE XLII DURABILITY OF WATER t~EPELLENTS Tr ing Ar ne Initial After 5 drycleaningsa After 5 Iauno Werrepllas 01 Spray Bund 01_Spry Bund 03 Spry Water repellent Flaonaberiol (FC-209 Fluorocbemical (FC-208) OT dron thee) 10 100 Tee WT Me 0% (0.3-0.5% solids on fabrics) deringsV Oil Spray Bund.c Oil Spray Bund.* Oil Spray 100 100 7 cc 70 70 14 cc 50 90 Bytespent Pyridinium water repellent "a3on ai 0 Wo se 0 0 me 0 wo (2-3% on fabric) 0 100 5 cc 0 0 210 cc 0 100 Flurocaetd eyrrdisl Fluorochemical and pyridinium omni or) T0100 ee 0 0 Nese 010 (concentration as above) 70 100 24 cc 50 0 314cc 50 100 "Quart" (25% Suorsbemicl "Quarpel" (2}/~ fluorochemical Li, 25 pres ss solids, 2}zo pyridinium solids ne 00 i 2 00 W se 0 on fabric) 100 100 2 cc 100 90 3 cc 90 100 Commit drying. Perrone, 47 oa cha< 0r33g,o,p re. Commercial drycleaning. Perchloroethylene, 4,/, soap charge, < 0.5 ~/~ soap in rinse. iors whereas sesings "Tie np Home automatic washer--moderate settings; "Tide" soap. [ra ---- Bundesmann test--cc penetration through fabric. The U.S. Army Quartermaster Corps have develaowpaetsd repellent The U.S. Army Quartermaster Corps have developed a water repellent finish which has been shown to. possess outstanding. durability. finish which has been shown to possess outstanding durability(~L This finish, known a "Quarpel", is based on a combination of cersin This finish, known as "Quarpel", is based on a combination of certain Suorocarbon type resins, suchas FC-205,with the standard commercially fluorocarbon type resins, such as FC-208, with the standard commercially available pyridinium durable water repellents. In actual practice the available pyridinium durable water repellents. In actual practice the trating bth ismade upso that 2% onsolids basisofboth the Ruoroeasbon treating batl~ is made up so that 2% on solids basis of both the fluorocarbon resin and the pyridinium compound arc put on the fabric. As the data resin and the pyridinium compound are put on the fabric. As the data in Table XLII shows, not only are initial properties excelent; but even in Table XLII shows, not only are initial properties excellent; but even using the extremely rigorous Bundesmann test, both ofl and water re- using the extremely rigorous Bundesmann test, both oil and water repellicies are retained 1t essentialtlh y initial levels ater both laundering pellencies are retained at essentially the initial levels after both laundering Zod drycleaning. and drycleaning. 1. Cownemernt. TrexixgProcepuses is spAAetctittfhhiiicsstppoo&inncttomiittmwewirCilcllOliMbbaMeelliEiynRnCaooIvraAdiLedlrbtTtlRoeeErrfAeevoTvirrIieeoNwwscGassIro~bmRooOenComEoffDfitUntheRhiesEehtS,etewcchhhinncoohlloohggayyswwfhohiuiccnhhd iwsisdpeescpirfiecadto uascaogme mienrctiraellaytmaevnatilaobfle mfla~nmyroctaerbxotne fifnaibsrhi,csw.hiTchhehapsrfooduuncdt widespread usage in treatment of many textile fabrics. The product 33002222..00112211 I3MM_MMNNO044885555223300 416 416 H.G6.. mBReYCrE ccahhqoousseeeonnusbhdaaissspbbeeereesinnonddeeosfsiig4gnnraaettseeiddnsa.ss Textile Textile Chemical Chemical FC-208 FC-208 which which is is an an araqyuo"FenFoCsCu,--s22a00dn88idspiissearyrrsoeeincoc-onosmmyomnmfteeahnnerddteeesiiddcn(ffb9oolsrr)e.nttrdreesaattiiinnngg"ccWooattsttoohnn.ssa,,nccdoo-ttWttoeonna--rsy"ynntrthheesetitiniccsbbyllseetnneddmsss,., rtatoaonydpporrndoorsdd,yuucalccneeeadnooiiirlnlagyaa.onnnddF-Csww-ya2antt0teeh8rretirziseecpapelebslltloeeennnudccsyyesd,wiwnhhiini"ccWchhoaniisssjhuddn-uuacrrntaaidbbo-llnWeewettioatrhbb"oostrethelseillcnaatueusdnnyddrseeetrresiiminnnggss aaannnddd`Sdaapnrieyxclciisfllrieiaciarneiefisnso,,grm.oounnFlCamms-o2osf0sto8truuitpsprhheaooallstlsoistnteeugrrsyyetydpaa,innciddnalddcrorfaaanpbpjreueirrncyycstiffooaafbbnrrtiiwchcsesi.t.htyspeelsecmteendtireosniends taaebbnooivvSleepeevvcaaaiurrfvyiycilwwifiaoidrdrieemellsyyulrddaeeseqpupfeioenrrdnedidtnriegtoanootnginngigrrveeeaatyccttptiihivvceeealdrreeefsssaiiibnnrreiuudcssseefoddafbaartinnhcdde fttthihyneepisevvhsa.arrmiiAooeuunssttyiooopttinhhceeaedlrr eati textilenaufoxrilmiaurliaesforrequitryepdicatlo agppivaerelthecotdteosnirefadbrfiacbmriicghfitnibshe.asAfotyllpoiwcsa:l treating formula for a typical apparel cotton fabric might be as follows: Component Component Racine costing resin Reactive cross-linking rcsin [oes Catalyst Auxiliary V~Tater RepeIIent Sori wenger Nonionic wetting agent PCE harbor ih FC-208 fluorocarbon finish woe Wt ~ * 10010.0 202.0 1-5 9050.05 252.5 "For al tei, ei pe cnt *For all materials, weights per cent ae ad om sh crmmoiy oi are based on the commodity basis. noniAAossni3ac accqooummemomeurescrcieiaxalmlucclooimmonmmowdoiidttihtyy&,, mFFiCCn--i22m00u88miiossfss2uu5pp7pp,lliiaeecddtivaaess soaalnnidsee.ssssAeensntstiuiaamllnliyy. ianincnogtgnuiattohlhnaaitftcliiuannoqruttorerceoeaaaurttsbiinonegngmtrtuhehlseesiinoccnoosttowttlooiinndthsffaadabbemrrpiioccisn,,iimttthehuedemwwweooetutfl2ppd8iicc,b/koke--uau0cppt.iv5iisse%77s0ob0l,y%/i'do,,sw.ettihAhgeehsnntsu.ttmhhTee-t SasAhhcuotoouuuralollddcfablbcueeboornnnooocttgaeerrddbouottpnhhsaa,trtetsbbiheeneccaasfuuolsslueeidorsoooffcdattehrhpebeoosnhhitiieggpdhhrollypwyeorsstuuuilrredffsaa,cbceeei.aa0ecc..t5tii%ovvieel bannaynattduuwrrweeeaitgooehffrt.ttrhheIee.t fpptleheulelollerefnonocccryya,m,rbuaalorranee ddggeiervvvoeeeulnlpoosppa,eebddothvoeoe.nnfttlhuFheooerrssouucorrapffratabccioeemnueemvvp.eernnorpiieennsrutaalietccs,oo,mmtipr.pelel.aee,txxionmmigl,iixaxtndtuurdryrieewnsasgutu,eccrhharneatdes- ctc`huumerriiignnfrggoarmtcciooutnonldonadiitatgiinoiodvnnessonrssihhaeoonbutoualvltddei.obbnFeeoonssruutccohhheptsi4aumssrfuattmocoe results, treating, drying, ,masimize the opportunity maximize the opportunity forand for minicglRRrueaedataeicocttnaiivvtveeoacrcarirnoeotdssysso-lorliiifnneknktitiynanpgtgeiosrrneeissoniicnnnlsstuhdooeirrnsgccuhhrueefrmameiciecac.a-alflssorwwmhlhidiccehhhyaadrreee,ccsouombmsmmtoionunltlyyeduuassneeddd iuiunnnscsstluuuobbdsnsetetiiattruuettvseeiadndrsie, tmmyaeenllodaafmmsitiypnnepeeceisaddleilenryricivvcluaaatdttiiaivvnleeygsszeudpprlelufuaoss-fromffraomolrrmdamclaadhlleyddhdeeyehhdyyesdd,ene,ds, ubvttirsrintiayiaztlzuiintnseeeudlfaaaonnnnddde tspsrooeilalluuzlttoieiootnnnsess..creaAAsnisnssb,4aeagginenedncneoesrrrpapaolelrcairratuulellldyee.., cippanrtraoolptpyrrrzieieaeedtttiaanrrfgyyormfhhoyyardldmdrrueoolhccayaasdrrbbeaoonnnadndttyiynppveeisnyowwlmaaetsteuerrlcfaosrrneeees-- aVpaaccerttliulueaaantlliltyysonseceanninhhnaarnnbecceseeinisntt,hcheeocartpddaoeleyrvvsaeettllseo,odppsmmioenefnnetnttrcerooasfft,inoowigillatfaaeonrnrddmreuwwplaeaaltstleeerrnatnsrrd,eeppweeienllltletnnsicocnymyg..eagM Mceanaatnsnesyy,s variations in resins, catalysts, softeners, water repellents, wetting agents, 33002222..00112222 33MM_MMNNo044885555223311 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY a INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 417 ettecht.ca.taarcreaecpphoosscisobimblbleei;;nabbtuuittoffnoorrbooepptttieimsmtueumdm urrneedssuuellrttsssoopenncaisafpisecpcecicofinfidiccitffiaoabnbsrri.ci,cii,tt iiss essential essential wthiatthOOonenuatcwwhroeooscoliolenemsnnsbsa,,inndwwaotwoiriorslsntlteedbddesesv,,etelaasonntpded.dilwwuoonnoodldl-e-srswyyasnnpttteehhrceeitifriiccecpbceblolleenennndddcistsy,i,ownFFhsCCi. -c-22h00w88ithiissstuuassneeddds rwreeippteheIaaonttueemtddardednrsryyiyncelaslcpeaapanlnniidiconagwgt,i.ilolnsd,evtehleorpe oil is and water repellency wt~icla withstands a definite reduction in the retention of shaaiirvbbeoIonrrmnnmeeadaddnerryyyaaihhproopuulpisesceerahmhtieoooallnbddis,lttiytythppyeeeremssoeoiiailslsss.a.urdDDeeemefMieMnanirattercscoro,ew,dhuMM iccccthQiQounsuahadidoneew,,theaeasnnsrddeentteKKineaetlnnilonynneeddnoyyof hccfohharvaacneneggdeemiiiannndtoetthhteeahierppoofrpraooebsrsriimictt.yyeaooObffiiltt-ihhtbyeeor(fmanbbeerriaicssOctua00riO)ensm),,, ehhwneehtnnsiccecew,h, hssnittcoaahriinmniiasnnlhggloywmmaaatreeteersrsiipeaaalnlrsstiiammclaluayayyrnlbboyee fttlroeroaroucvuebibndllegtesishonometmoeet,,tyhpccieaacnnaflabbbseeriacrrl.eeaaeOddniiillly"y-brrrioeenrmnmg"oeovvsseeitddnacinewwsiti,tthhhwaahsoihhclyyvhdednrnrtoooccrwamairlrablbloonlynnotssaoorwellivvceepknnattartlwwiociniuttglhhaootruhulytet lffeiibabeevrFrissnC..g-2th0e8 typical i also solvent "ring" used in many since the solvent will not wick along the applications to provide functional pro- ppadeedrrittFitieCisso-n2tt0oot8offaaiosbbfrlriaiclcasss.on.duFFswooearrdteeeirnxxaarmmmeppaplenleley,e, nacoopynnp,liaaciuutatttoiomommanokostetisitvvoeepporuusosppvihhboiodllelesstttfeeuhrreynycrtffieaaobmbnroriaivcclassl,p, rooiinfn- aiunndse-epdpdliltaaioonntnnt ssgtttolaaaiisnonsssil fwwaaibinttrdhhioocswuuttaatllneeedraavvrfiieninplggeamlaaleenssntoocllyvvk,neeinnitttt rnrmiiynnalggk.o.ensFFfooparrobsrttlshi~ieecblsseuaasmtmehdeee rrireeneaamsstoohonnev,,aaliiutt toiiosfs uiainnsdddesuudsostrrtoryyn.c.ogTTnlvhaheseenstffifllaouubnooarrrilococschaayrarbdnborodnoncfttaieelraxxbtmtioilleneentfdfiienkntiienssrhihtgeeessnntyaasrlr.oeenuFunnrfiaioqbqmuurieecasiinnpurtstahehcaadttitcittanhhleetyyphoeddioonatunntooootft vavbiudieetswwo,,rtbotthhaciisoqsnummeveoeeaunanstnissosnottahlhlauattthiyttohhndeesrssoeeccoaffnriibtnnaioisisnhnheeidssnegaaterraeergwrreeeinssdtiisess.ttaavFnnatrtroimnmeoottytaooonnfpllryyawcetttotiociappnluugtrpeeaogiwwneantattteseo.rrf AbAclussetaaantioccnoognnasqsieenuqqeutuoeheunensccpeesr,,oelsrrueeetnttiecoenennttsioiofocnnosnooofatfapibbnoaoitnnthhdg wwdaaeatttweeerrridgaeaennntddvsaooriiiileltmyrreueppcoeefhltllweebnneeccttyyteinraagfftteeharragneddnrrftyyos.r-. chhlyyeddarIrnoonincctaaghrrebbinoonnnothrooemrraploorlleeefsooienppnihhsciihebbiiinoccgfttpysyroppoaeecpewswasaanttfdeeorrrdrrteeeetpxepetrielgllleeenlnftetsasn(b9rti6sis.c).sm,utchhe better than for best procedure iipnnavvsoosIllanvvgeeetsshtetthhheneeoouriigmmmhmamelserqfrusisneiiicoosznnheinoorgffolpttlhhsroeewchfefaaesbbsrrrefiiocc3r iictnneoxntttthhirleeoelttlfrraeeebdaarttiaicinmnsgog, utbbhnaaettthhbo,,efsffttoohllpelloroowtwcreeaeddtdiunbbrgyye. oSpsoovallesuusntatiigwooehnnitrrcheehrmmocauaieginnmhssovsiieqnnsuttethheheezeeffwaarbaboririlieclcs.s. waTTnhhhdeeeraelwwseaeottcpffoeaarnbbmtrririoticlsliiestdhttehahemrenenoacuiintnnitttrvroeooddfrueutcschieeenddstiir(nne0ttaocotuinaargnne `oaanvndednIttnhh'weeghffeilnocuehrororarolce,camarroabbtvooentnsghgterhrooetuuewpxptssaitltteeoormmmiaingilgrdlraaatttleehseotopuaaesnnerdmdooioftrrsiiaeetqnnhtuteeooronneuattsichlteeitveffeicibbareeterrisnssigunursbfaratcotfeh(cs9)u8r.i)es. FpprbreeeffrIeesnrrrriegenddecnlffeuoordrrailnaa,gllmamctoooststtttt~oeaannn,tyyerxtattyyiylpopenee,moosffiyllnffatabthbirelriteicci.c.ussT,Tehhaiionssfdwwaowqoouuuolellddo.uiisnFnocctlrlruueddaaeeptipanlalgillcabtttyyaipptoheensss oooinsff 0mfmiabanaenucrusfhfaiaiecncvtcteuulurreedexddcineglietlemecmnsots,tt,roessnsuuu,lcctrhhasyauaossniff,nuugsrrynnsiniottltuuhvrreeeentitcoossrr,olwwauenetaadirroiinwnnsggooofaal.ppfppuFaaororererlol,,caapiirttpbliiiosscnapptdooioesscsnsiiivbboallneee tsttioiyvvseeastsc..el~mSSieuuavccnehhdettxrrreceemeaaolttlmvemaneeltnnotrtfesssemmuxakcaesyysubsbseesinoeelgffuffetescicototliinvvv,eeenoeertiisttbhohyeelurrdtibbiroyyencsiitmmopmmfpelferilrsucsioaiootronnicoiiannnrobttfohhnae dssdeooesllrvivivreeenandt-t qsqyusuat`neAmtalittynahonoofudtfsgrsohieoltmluhuttoetiivoysoannleobbofyfyeafxlcssuepposrrsraaosyycoiianlnruggbtoipponrrnoot,ccyoeeprddeubueryrexe.i.dlireecftinaipspheliscaistinonewofanaddemsuircehd pnprreoogwgArredletseshsvsoehhulaagosshpbbmeteeheenenntmusmasewadidoleelfiifnbnlueaaroefrrleooalrcattatihrivvbceeoollnmyyitsnsyhhgpooerirttnteittixmehteie,le,niitfetisianirsiasanhfntuettisiuccriiisepp.aantteeewdd thatand that many. much many new developments will be forthcoming in the near future. 33002222..00112233 I3MM_MMNNo04488s555223322 "3 wo mes 418 ~. G. BRYCE Leathe is animal bide orXXskLIi.nLLceeoaatnthhveeerrr by chemical treatment and popbrrjooecsLcectessiasivitnenhgsge,,rofkkisnenonaownnwiinmnnagaslsahttraieadnnetnnoiinonrgre,,nsdkttoeionr4aciossdtnaeabvbsleleeratneaaddnnddsbkyinnnoocsnnhppFeuemusttiirrcitifaaialnabtbtlrleteeoastsemtiaceete.un.mt pTTaohnh-ede objectives of tanning are to render hides and skins resistant to decompo- Sphiyosinca0l prboapcerttriels einctah,e cparnnceudlahrildye Worhesnkinw,es;uc10ssactheinesvee ssepeenct, sition or bacterial decay, particularly when wet; to achieve specified ecpflhhexeyxmbsibiiiccilaayiltly,p,prrorroeeppsseeilrlriitteeiiennecscsee,is,ncsatbhbhrreaaassstiiaoornnnonserrodeelssiihassibttdaiaennlsccyeeo;;irnaasnnvkddiant,tteoosuaiictmmhprpaaarsrlettet1nlo0silttehhheeisgtrhlleeenaatgtthhtmheerr, Sppcpeherperaramtetuuisrcrieaemslsa:.prcrUUolnnpytteaar1nnt4inneeesFdd,suhhcwiihdhdeieaslseoonrrmoassnknisioynnlusstbuu3ibpblisesttstyaannoinccfeewlbbeaseettcecoer romamterrossemolaaalibutinblvleeeslyaiibnnhliewwghaaattetrertmhaae1-t baabpootpiilreinongxgvimapppoaooitnreitlypooeffr1mww4ea0aatbteFei.rl,.iwtAAyhIl,Iilswelehtamitehcaehrnryippsotoyaspsiseeisesbsesuosaf balleccaeootmhmteommrohornneemppiahhniyytnsseiircsnctaaasllbpplcerraoopapptleearrttyrhy.ye, water vapor permeability, which is attributable to the internal capillary tona the fives comping leh and to surface vaporation, The action of the fibers composing leather artd to surface evaporation. The ialninp, giotdanordesihsdiennw,edctehpeanmdanausfkacitnur,oifgtih,e narde c4aveariitdyso,f principal hides or skins used in the manufacture of leather are cattle hides, amocnaethehlsfae"rtstrTkhcciaaneoonn,nniuimsgsmeuuoaasmalmlptfpsstaoktiirniionodnen.nst.k..hiTTdeshhrkeeisansese,hhqsiildd~ueeeisespaawraeienddooebblntataamdiinbnveesadkdriina3essd,.mmpToaighjorsekripnTrrasiaw,ncamminapdaattleaercriviaoaallnrssiseffturyromomopmf ttlieioaontnTheiihsrsseii,nnusshsheahosnodefesbooarofglfsaeal,altlhaytenyrpdpaeersberaaqinnuedditvcveaaawsrriseii,dtcieeelsasa.ngOOdatgtvhheaee,rrrieummdp.oahTjoorhlretvurscpessrs,ininnchiacaplrduanldeesecsoggenasas,rrummmaeennpndt-t saddles, andfo cera indus ves su3cblhs, seal. leathers, handbags, and brief cases, luggage, upholstery, harnesses, and saddles, and for certain A. Luma Procisine industrial uses such as belts, seals. in rEEexcxceceneltlllyeennett arreevrviieseww,ss ooff her and cathe prcesing A. LEATHER PROCESSING leather and leather processing have have been been wien written in recent years(~01,t02). 3. Preparationof Hider neceUUspspaoornny rrteeommopovrveaaslleorofvfetthhieet ssf1kk.riionnPmrfferodrpemaocroattmthhipoeeonasaninoitifmmiHaoalnildeaatsthttrhhoeeugsshlhasutgghehhtiaecrpphhioocuustseie,o, niittoiifss necessary to preserve it from decomposition through the application of aShre shi Sl.areIhmeopstinca8sewsetwhcoenrditdihoen.trWahpeorreatoivoenrsoeassssahriopmtents1 arignh-, coarse salt. In most cases where the transportation costs are not too high, rSvthooellvvcseekddi,nsiivctt ahiirsetenakecnecnepeestsrsyiran,ryytahttowoiedddtireyycsottnrhhdeeeitwsisokkaniisnn.heW 1tod0harreenermdems ooovvveeereeso xxectaceseossrsshed mmimpioomsrisetetunatrt.shee.aeUrUxepcpeoionsnn-s "asaaarplrltetivrnaainlddoantotstthhheieernrtvaffoonolrrnveieiignrgnygn,crcotehonmentoathvamimadilneinsaoanfantretsesx..wcTeTashshsheeeyAydhsaar,cnedthdhseeeonnaakisseuuidbbgjtj,oeeccrttaeeenmdddotovlei3amtvvhiaanerrgiieeexttTcyyheoosefsf operations involving removal of excess flesh, dehairing, and liming. The ATifmirngthopleimriongn, tehesasi in tshcralpoesoifnandoftthheehxaicin.iemhesshariemcovesd.by liming operation results in the loosening of the hair in the hair follicles. wamAsafohtseinhrniengthg.e.thTTliemhhedeienggllere,aaattdthhhaeeetrrihoaiinssirsspiuursbbojsdjeceucrccatttepesddedottfoooftfcehnnaaznyydcmmpatihatdteieiccremxsaacceletisiossnnw,l,iimcmceaa.llillseedTdrehbbmeraoitilvnneeggd,h, eb0troy mrmheaeamyyostvtthoehceekntnthoebbe.edssecuuognbbrdajjiedctcacittoteinoddnottfoopcraaoqdppuuiicicckktlsllibinnouggfrppthrrioenocceeespsbsa,i,dtehwwrhlmoaificacshlhulsccfyoousnrntsiesicmisstat.ssiTdoofhfsebbnrrdliiennoaggbtiihennerggr aithe stock to a condition of equilibrium in a bath of sulfuric acid and other salts. 33002222.00112244 W_MNO4858233 3M MN04855233 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. a INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 4"19 2. Tanning nowFFoorlelllaoodwwyiinfnoggr ttthhheee cpphrreeemppiaarcraaatltiiocononnssv2err.erevsvTiiieaoewnnwneetiddnoglaaebbaootvvheee,r,,ttwihlheeihchihiddeepssroacaennsdds ssikskiiknnnssowaanrre.e 2ean5xsorwttaaicnrtnnesaignd.gcyo. nfTotTarhhieetnhiooenllgddceehstsettamnssniyycissanttleemcomoronofvtfaettnraansnniioncnniinnatggcodrrl,eeellaiibetehuddetroo,nnmwotthhhdeieecarhcanctptiirtoooennccehoosnffsovvliseeogggkeeynttoaahbbwallnese eddxeevtvreeVallecoogtppseeetddcaobalnlletaaarrtiggnaeeinnnrrgainnggtaaeinosonfnfsictncihlhelgeomsmrieciectdaaalnlfnagoirgecencnteatscstiaiadnnn,ddsbpppuretorccmieoesoscdteyeseprotneosspptroersfooecddhaeuuntcscoheeleorllge,ayatthptelhaerrar..s. tvtiieccguueVlltaaaerrblglylyeetttahthboaolensseentiauunnssgneepdidnrogiincneisssshhsseootsieellissunoovslleeeossldvaafeonnsrddocauuekpprithtnalogoilnlssttsthpeeerreylyceifallietecahatetthhryeeprfresos.sr. loIInonfnlgggepeaenetnherereiraraol,ld,,psttaohhrfee- ivttiniemcmgleeeutdaiiinbnnlegssootelalxuuntttnriioaioncnntgsssopoofrffoQcaaeusevvsabaerrrsiiaeeicttnyhyvoo,oolffvoevvakees,oggaeeaktunaibbndllgeectohoomerrmelsseryyacnntithtahheleertltiyficcorstytlanaontnnnhngeiinsnpiggezreaaidoggedepnsnrttosos.,f, idfdnouucrcclmttusasdlibbdnaeagshseyeedddxet,oorannctppshhoeenfnooQllssueaabnnrddachnnoaa,pphhottahhkaa,lleaennnedes in various combinations commercially synthesized in various combinations withpro- with ftohromsAAealllttbdhaheoshoueyugddhgaehoa.nvvaaralieutrmyoioinffumemminitneceroryamalpl ottaaunnnnndaasggeeassnhdh.aavvzeeibbreeceeonnniddueemvveeclloooppmeepddo,,uininndccsll,uuddtiinhngeg mntmhisoonsstgtepiirmbmoapcpsoeoersdrtstaapnonrtntossdayyulsscuttemeesmminstshueaamrreergcbboeaasmssetepddvooooulnnnudccmshherroaoonfmmdiliueuamzmt.ihr.ceoIIrnnntiouffdaamaccyt,., cttThohhemeepcchohardurovonmamdneset,attagtahennes.- tonohfifentttghihceeprtccoahhcnerrnosiosmnmgpee,rottaadraneunncnteeehdsdatpphrtreohoeclcaeerlddgeuuaertrseeht,e,vro1asmlsuamccyooenntbtorrefaasslmettaeaeddtdheettorobtyttohhdeteahyeev.gecTgehtehrtaeaobbmalldeeevooparrnrotasscygyensne.ss- mitihnnuecmmtiahcatttgtteaerrnerssantiooenffrs,hhpooraueurrcerisssthiaaonnandtditdsdhaaeayyfssfleoiiarnntdshsettedeeraatddmheooaffytawwbneeeneeekkmrssaibbndyyecovvbneeytggreetotitllaaelbbillnceeghttrtaoahnnmennieinnnagpgt.r.uorAAcelelssosoosf ihhmieissus,coohuuhtitpgpgurhute.ta.tteeCCnrhshirprlooeremmsceteisriettoananngntnnhiees,ddaafllnfeodartdhereeesdrhishsatthasasenetcexteaxcenchtpenotpeictreoihoneinnamlaticllclyoyanlggtrooaogooleddlnitnwwsge,eaatarhrniienndggnwappitrlruloorppeaeelrsor-o-f ties, high tensile strength, and fsteatnd. high temperatures in 3 stand high temperatures in a wet or dey condition, resistance to chemical wet or dry condition without detrimental agents, and will also without detrimental teoffgeeT"ctTthh.heeer cuuqssuuuaaalll ppparrroosccoeeddfuusrroeediiinun mpprbreeippcaahrrriionnmggit2ae accnhhdrroocmmoeencettnaatnnralltiiqeqduuoosrruliifssucttcoo ammciiidxx, aaatogfftegtenerrtt,hddesiirssussceoohqllvuvaiiannglgglputtachhroetessebbo,iifccithshorrhodoemimunaamttaeedhdiiiencndh2arroessmsmmuaalalttlellinaqqgnuuidaannnctttiohittenyycfeooonfrftmrwwaaattatieetodern.r.soufAAlftuhrrreeeidcdbuuracciciiginnhdggt, geag2greleeanenrntgc,echshurrrcooohtmmtiaiicscnggfioloudnnc.r.ouTTsmelh~,,iisisttthataehnnennsnioinnlagugdtsdsioooelndluutbrtiieeoosinnunlgiitstinathgdhedeinenndtrrheegeaarccafttdoeeurddmalwwalityiittohhunntteohh!feetllhceaoeatmtbhhpreleirergthiinent Denctration of the leather has been a large rotating drum, the solution penetration of the leather has been efeced. being added effected. gradually until complete 3. Dyeing andFat Liguori. shadFFeoollallonowdwiinntgghetnthh"eefattatan-nnin3qiin.ungogDroeyopedpei"enrrgatathtaiiroononndu,,gFhttahhteet-Lhellieqeaaaudttohhdreeiirtrnigoiissn ddoyyfeeeddmuttloositthohenesddoeefssiiorrieeldds scaahnnhaddrdottemaaellallontowdwassntnht0oeednpplrr"oeofaddatuuth-ecclreei,qttuithloheeerennddeeyc"cceestishssnaargoeryyuagnlluhdubbrftrihaiccteiittlyyaidqaadunnoiddtriiossnnoogfftotannfreeesesssma..luIIolnnsicottahhnreesriccoeaadfsseeooiuooltfsf icinnhrttohAhmfeeteettaratnnaznnneiinnmneoggdvddalrlreuuamfmthr..oerm, the the dyeing and fat liquoring drum, the leather a then are also carried out prepared for drying eithAerftebryr"epmaosvtianlgf"rotmo 2themedtarulmp,anthele oleratbhyer"tisogtghleinngp"reoprarsetdreftocrhidnrgyitnhge either by "pasting" to a metal panel or by "toggling" or stretching the 33002222..00112255 I3MM_MMNNo044885555223344 42200 ~. 6G.. mBRcYCrE alTeieraattohhveeerrnoonantafarftaramemem.ep.eIIrnnaeteiiuttohhreeferr scchaassoeettth6he5ddCrr.yyiinngg pprroocceesss iinnvvoollvveessaa cciirrccuuliattiinngg air oven at a temperature of about 65C. 4. Finishing to r"TeThmheoevlleeaitehmpeerarisfstetthchteeinnhofnfrsiiensfisohhlerelddo.w.4e.FFdooFrbriynssiiisdtdhheeienltegshaptephlreirscssttthhoiinss mmoaafy&y iivnnavvrooilelvvteey ssoaafnndrdieisnniggn. fitfoiinnnviiroseslhhmveeessosvttbeooufigmgfiiivpvneeegrfltleuoucssrtttierroesentosaarnnefoddnllaaoapbbw.rreaadssiiobonny resistance. For the application resistance. For suede leathers this of a variety of resin suede leatkers this involves buffing to restore nap. 5. ApplicationofFiusnocorbon Derivaties leatT"hTeihrleearmmeoostshtte sscut5hi.atrabAoblmpleeipuliffmclluaucotoiorrooomnccpaalorrefbbxoFoenln.suopoprfrorooctddahuruebccofttnlssuDottoroeorcddiavaarattbeetiovnffeooscrraraabppoppxllyiilcciaacttiicooinndstt,oo lii`nenTahwwtehhsheeiirccchhaoremtthhpteeohuefflnlucudohosrrroooacmcraaeirrubbsmoionmniclggoarrmroouputplopextiissehsoaasttoeflleertaahessevttif66elwucceoaadrrrobbccooaannrrbatroto,onmmcAssaribm"cnooxmllemyenelinrgectghaitca(1hil0d!3l's)y,. aMaTvvihaaneiinlslaeebbslloceeotampprrMpooioddnuuuicnctndtgsoofafarnttedhhiissMsimattnyyiulppafeeracistsocuLLtreheiaoantstghheCeeorrrerCvCmhikpeeewrimnneiydicca9ael9la.rFFlCiCeI--r11.c44o6A6n,s,icpspotrrmsooddomuufecc8reecdd3ia0blb%lyy,y Minnesota Mining and Manufacturing Company(104). It consists of a 30% siosloipdrsopsyolluatlicoonhoolf. the fluorocarbon type chromium complex dissolved in solids solution of the fluorocarbon type chromium complex dissolved in jisuonpcFFtroCCiop--ny11l44w66iatlchiisosthhaaoepplnpp.loliireedmdaiilnn "ttfhhaeet ttlaainnqnnuioinrngsg"ddarrfuutmem tcehiiethhdeeyrreiiinnngppallaanccdeecooofflooorrriniignnoccpoeornn-jaabutytiinoocnonstrsi.o.enW Wxhhwaheuietsnnhtetaadhdd.eddieennddoorwwmitiaththlhe "wwlfeaaaatttteehlrieqrt1uowothtrhihse"elewawfetettheterhhitdihddeeeesus,d,ryttehihiseenrgFFotCCaa-nt-ed11d44.c66olSiiosurbiaansbbgessqaoourrpbbeeeenrddthbhtyyyhddrorloorellayyetttxhiiheccrarrueeesfaateccetctdiitooinnnassotopfoefttrhhtmheaeenleeccnahhttrrhooemlrmiiinwukumahmgieleccoootfmmheptphlleedexrfuwwumioittrhhioscttahrhoseetbappotrrneoodttg.eeriiSonnuupmmbsasaetttqttoeuerethniinent tlilehenaeatttehhrleeefrarerthffeiinebbcreeerrses.wf.fietITchnnt taoohrrepddeeeprrrrmottpaooenreaaccnohhrtiiieleeivvnnetekaaotogippeottnioimofmfuuttmhmheeppffrrluolouoppoereorrrotcticaiearssrbboaaonnnnddggrttroooouupmmpissinntaiiotmmittihzzheeee scsinuuhrtereffmariifccceeeareloonsffcuetttsh~eweedillteiehanattcthhhleeuerrdipfbnriegborepdr,ey,ersiiottturiifissefnsnn,teeacacteietosssnlaairroqyyufott1rhose,eecvfvilacau.llouuraaIottnecegaettrnhhbeeeornaoolttg,hhreeotrrhuepaausupxxriaoiltlciieatahsrryesy liicssehaeqqtmuhuieiirttceeailssssdiiumrmsippeellddeeainaancnndlddufdieeinasnissgsyyhedttdyooeisncctooutnnfhtfertsro,osl.lfa.amtAeAlfifmqtteeaurronrnrrseee,mrmeootdcvve.asalcIlnrffirgbroeeomdnmcertatahhlle,ecthdderr9uu0pmm,r,o, cttehhsees leather is dried and finished in the same manner described earlier(~04). B. Proessrioesr Fruonocamson Teatso Lexi B. 1. Durable LubraindcSoifttneyss PROPERTIES OF FLUOROCARBON TREATED LEATHER KnoTTwhnh.ee Tlleheaiattshheeirrs ffeiisbbpeeerrc1ii.issaDlooyunnreetarbooulfefettoLhhfueebtmmrhioecosisctttyhdrdauuonrrmdaaibbSulloemeftnaatnenasddnsnccehhdeemmlieictcahalelllryy frrieebsserii.ssttaaInnntt lokournrbddoreewirrcnatt.tooeTppthrrhioeossddeiuusccfeeeisbpeaarescss;ooiaffotltltyhaaentnrrdduwiesppleoliifaatbbthlhleeeey ppcfiiheocrccroeemmooaifuf mhllaeeraatdatthhneecnrroe,,mdpiittaleci3astthnnmeeearccseefsssibssaaerUrryyn. tIittonlo gvrlrvueeeeengbccgeeeerertinnatcatatlbablltylyyeee'ee,,aatghororisrservsaaeettnnnhhiieefmmtibahaooleelnnrttslltyy;yyepproeeaamtv,vhoofaaeifliir"sslawfaaababinlntsleeddelggtllorhurureeebbaasyrrssii"eeccf.ssaaonniirntmtnssMaaammwenoreohydrdeaeiirofdiffeaaidctohvvoomeararrruupiisneenahttcomyoytdroimtoodffcfiafoesimmsmed.idiinnnUseagetrtanraeattloeli,,f,,l generally given the term, "fat liquors". Many of the shortcomings of 33002222..00112266 I3MM_MMNNO044885555223355 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY a1 421 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY alleeraaettgkheeenrrearararleelddyudeerttuoomttmhheeedssee nooitilloss aatnnheddlgegaereteahaesserss.i. ItInnhtethhfeeofriimrrssotpfplalaqaccueeeotthhueessseeem""ufflaasttilloiiqnqusuooarrnss"d" aaaprrreeeengennteoornttaetiirnianolaalnynnydyarnwwudmayybmecctehhtdeeemrmiinibctcoasaloltllhryyperblbeiooaonntdnhdeeedbrd.y.inFFttuuhhreretthhfloeeerrrammtmhooeorrrfee,a,fqiiibunneerooos,rnudsdmeeeramtn1o0uyglgsteiootfnbbsteehattetnesedrer pgF"rfelaonatueptllsrii.aqqtuiuSooounrrscs""hansagdcrreeobuempmstoto,dedirifofifaieebcddsoouccrrhhpseetemim,oinciacaraleblllyywyatttthooeeriilnnerttearcctoheodpdeuturcicveefiebsseauurnllsfdf,oonnmmaaaatteyenyoocrraoufsssuuetlhlffetaishtteeee glwleieralaolttuhhcpeeasrru. ttsooSe uaatcbbhhsseooorgrbibrosaautnnpodds,brreeoettfdaaiiicnsnopuwwlaraastceeteer,d.r.afrMMreeoecwmchhaattanheniericcwaraeelltctwewepoodtrrikvkaieirnneggaao;nofdafnttmdhheeahyewwnecectateu,llseeeuaattphthoheenerr wpydrriiyolnldingucgca,,utssttehhbeeathseelJedsoattiohlhsneertrcohwwbirileolllmdihhisauaprmrlddaceecnneodaamfnnrddopmcclrroatahcecfkeks.x.tweeIIaenrnttisecrrdeeaccaneerdnnettam;yyyareenaairrdsssihcccesooncmmcimedme, reaucrnpicdoiaanlal lVvpauarrborirideeiuttcyyacttsioooffbnasssfiileolirdiccooolnneneeatchddehererr.roiimvvTaaihttuiiemvvseeesscophhmraaovvpdeeluecxbbteeesseennoafluussssteeepdadrriottcovoiadppnerrdoorvvmeiisdydieersitsmmationcocrreaeectiddoduurwaraanabtbdleleera alaubbsbsoroFrircplprautitoioioronon.nc. afrobrolneadtehreirv.atTivheess,espucrohdausctsFCa-l1s4o6,proavreidebeirensgisutasnecdeqtuoitwe aetxe-r t`teeunnmssFbiivlveueerollyoyrofiicnvnaerrblleyeoaandttehhsedeirrerraippbvrrlaoeotcicevpseresossi,npsgeis(run1tcgih3s.).0asTTthFhheCee -f1ffilu4uno6sor,hrooecadcaraerlrbebbaootnehn.ienr.gggrrWuoosuhueppedniiqmmpuprpiaotareprtetsrselxy-aa Tanauttutbtamracicbhiheeterdydowttfohoviettchrhhyeegdilleevesaaeittsrhhaleeberrlaetifhipbberereor,4p, esttorhhftteeie,sRfelututooorstrohpocreciaafnrrigbnbyooisnnfhce""dlwta--ilielola""rthippenrrroo.evvaWitiddhheeeessrnalapatrtnyoygpppaeeegreloo,yff glgFueoobeoonrdditci""iotrrnyoo.uuwnnhSddiincndeheesssgs.il.v""eeastTThhlheeiriasssthqqceuuoranalatliiasttiyoynfiiti,ssnygiimemtp4psooprurrtotiaanrnngottyciiafnnecebsshlho-oon-eoes,ry, ipeenessplpeeeatcctriihaeaelallrtyymlaeiinnnngtssuhhaaaaglppseeeo, ereienxxthhetiinhbebtiiitogtnraa.ffiiinnSneeiwdh""ebebrnrleeetaaahkkth"e",el.ras""tBBhrcreoeeranaktkai""sindrrieeonffugeebrrlssaettdooflouttvhoheeerromncoaaantrtubuirorteenseoolftfftywthphieeetchtcrrrteeehaaaestsmeegssreniffotnorrmsamileesddode iicinnnossnitivdhdeeeer..sgAegArlaoygi,nooaodwdphboberorneeraatbkkhreiiessaliikenandsthihdceoariwtesicsdbudabpyoytufifbeininnleedte,dh, eyyoeefvttoennrroomottnoddfeeitceslppae,r,lgfppewe,ennibetehtutrtrtaahntteiionntgggrpccalreienensatssiseifesdus;el; conversely, a poor break shows up in the form of large, but not plentiful creases. 2. Chemical Resistance treaPPteemrrehhnaatppsstoootnnheee oolffattthhheeer mmf2oi.osbsetCtrihssettmreiitkikhciieannlgggRrceceosoaintnstttaririnimbbcpuuerttoiioovnnessmeoonffttthhieen frflelusuoiosrrtooaccnaacrrebbootnno tcccrhoheeneamcmtiemcincatealrnlssst,t. etTTodhhithihssyedccraaloenncahbbtlheeoerrmmiocfosisbtatecrggirdriaasppohhtnihicceatalhlglleyryesarrueetrppfirrmaeecsspeeernnoottvfeeeddtmhbbieyynntppsllitanaiccpirnsiegnsaoigasftaddtnrrrocoeepaptetooodff Tacaeonnadndtchuueennrnttttrreaehsteaettsdeetddihpssyiiddodreleodcllseehaaluttohhpreeircsr..s aTTichnhididiisscoaiinsts eiidtllhlluueusnsttslrruaatrtiefeadddcoeiinunboFFlfieiggst.h. bi77na22c..kstW Wroiinpittshheoluuflnnsttrrweeeiaaattttheeeddd sulcehuarrotlhwaaennregsgtslhleeeentoosifftarlggilrpryeeafantoteoeldrrscttuhuhrapalnnaa99ns0g0li"ne,,.dLiLceSeaiaatmtetihhdleearurrlnppytrr,ioloppbietoerirdllloyiyungttbrrleeceaaastutesebdtdaiccwwkiiwttoihhnllFFitCbCsu-e-rl11fn44w66ciotwwhimil-llal sprphllaeeotttweeellydyeslttsheeharnrottohuiueagrglllh~yilaanloppriiececsuccireesltoaohfnfguaulentn.tttcraSeeciaakmtteoeidfldartlllheyeeaa,tthhhboeeotrri,,lcianwwughshetceriarceeuaasBssteicsttihhwdeeeislffllltubuhouoerrroooncbcavacrirobobmouonsnCatardadevrvaabatneontdntaagglteeerasestahootfeferdmm~alavkekialiiltnnhrggeersllsieesaatattrthhheeeerrmmamotrutuaeccchhkremmosoifosrtrteheaenrrteehsstoiiosstttpacaeannrtutssttptooiicrcc.ahhtBeeimmoeinsciicadtalehlsssa,,tnhtthueheenotffbllauvutoioorrcuood-stclleeoaaanrttb,hhoeewnrrhss.i.trceSShahhtocoeeedollleeenasattthhtheeerrrvass,a, riaffirooterrnymiinnoossfttraeaanncccrieeed,s,iicsbbtmeeaaccntootemmrtioeealpiismemrpspsrurpeceighgrnanaatsaitoteelnddcttwwhiicaittnahh.nudppneebtrrrussetppayiitrrreisadc-- tion, which contains a variety of acidic materials such as lactic and butyric 33002222..00112277 I3MM_MMNNO044885555223366 @ we on er 422 H.G. BRYCE ac Thos acidic materials imately caus the estes arden and acids. These acidic materials ultimately cause the leather to harden and Joncrack. Ng = SN4090-1040 If % s 2 o-- E --aa El aR | i roth i aster, F]c. 72. Acid curl test for leather. 5. Fuge Retone 3. Fungus Resistance The somal ers sed orcas eftersr desroped The normal fat liquors used as lubricants in the leather are destroyed by many bara 2nd fon bene mins ft heer. When by many bacteria and fungi, being nutrients for these organisms. Wken i apps er Lis rd and rc srt sah Shs this happens, regular leather hardens and cracks in service such as shoes. ha en mone caer te ura fete re omlely As has been mentioned earlier, the fluorocarbon derivatives are completely ort 10 such lel acon an hee rman a abc n inert to such biological action and, hence, remain as lubricants in the er kn leather indefinitely. 4. Water ad Ot Resome 4. Water and Oil Resistance I -- The commercially available fluorocarbon derivative, FC-146, imparts High doe oF renee 10 he Srp snd pencnion of wer a high degree of resistance to the absorption and penetration of water dh Fh dep of cine toe ron of i. Te NLS and also a high degree of resistance to the absorption of oils. Table XLIII she pebr o pfin swede hs snd 2 pel cone shows the properties of both a pigskin suede leather and a typical cowhide 33002222..00112288 oM_otssszs? 3M MN04855237 ITT AR EE INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 423 i s : 25g| 5 gl B32 15% ii FT) Sil eHiee i 18:8 eig] i af 1a cd 330 g Bilis & i 73a 2 Bs sel i1 s 3i | HaEse] e]|e HORRY t TE 2 ! fz le al Ig 33002222..00112299 aw_ossss2ss 3M MN04855238 424 ~. G. BRYCE side leather which have been treated with FC-146. Included for comparison orSunS00rS SSe s pmru 1 pt is a typical regular cowhide. 5. Rate of Drying Leather treated with a fluorocarbon treatment such as FC-146 resists wetting by water to a high degree. However, if immersed in water and flexed, it can be wet. As the data in Fig. 73 shows, the fluorocarbon IOO SEI 9o HN 80 70 PFINEI NIS 60 FINS ~ ,Untn ~ote( 50 PITTINTIIR] 40 SCS 2,0 TIT NS 20 TTT Tl eve IO HER o 0 I0 2O 30 40 50 60 70 80 90 I00 I10 120 Time (min) Fla. 73. Drying rate of brushed pigskin at room temperature; one sample has been treated with a fluorocarbon chromium complex, FC-146, and the other is untreated. me a se treated leather dries much more rapidly than the untreated leather. Not S LSm only does the treated leather dry faster, but it also remains soft and pliable even after repeated wetting and drying. 6. Soil Resistance i ee Particularly in the case of suede leathers, which have a rough surface tT ssp and are normally rather absorbent to all types of wet or dry soils, the prem fluorocarbon treatments impart a high degree of resistance to soiling. Er They also permit the easy release of any soil which may be attached to the E b ER p E leather, and in addition, facilitate cleaning by normal soap and water treatment without injury to the leather, either in effect on the softness or a appearance. 33002222..00113300 3M MN04855239 FR ---- INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 425 [I -- C. COMMERCIAL APPLICATIONS 1. ign Sues 1. Pigskin Suedes sting xml of istype splined bye rs A striking example of this type of application is afforded by the recently introduced sede pi lento cnt, Ppt ae hs vel introduced sueded pigskin leather casual shoes. Pigskin leather has excelHen wearing aul nd produ so, brearale leh vi $004 lent wearing quality and produces a soft, breathable leather with good vaiores ws, nh comerionly needs 4 eset abrasion resistance; however, in the conventionally tanned state this leather highly sorwebeseandtal. Afrbec raedwit tr is highly absorbent to water and oils. After it becomes saturated with water, in on dying wd esos ths ard: Teenman of hi eater it shrinks on drying and becomes rather hard. Treatment of this leather ith FC-146 routs i an exelent hethr for col shos wih food with FC-146 results in an excellent leather for casual shoes with good ening ie, ice rmion of wns. snd Shapes 2nd wearing qualities, excellent retention of softness and shape, and easy Sma cleanability. 2. Coie Sie Lathrs 2. Cowhide Side Leathers "The llsiraiinoFing, 74 shows the High epee ofserves wich The illustration in Fig. 74 shows the high degree of serviceability which ha been mpd 0 outa Se th, wd sho whch Rave has been imparted to cowhide side leathers, as used in shoes, which have tHHiti) ng HH | iti od SfE ei Ban ~ Ni HFHr, H1. pofeinBse,aoemde i 5 TC, Fro. 74. A pair of matched shoes, one shoe made from leather treated with FC-146, other regular leather, after having been worn by a chemical plant operator. 33002222..00113311 ov_osgss240 3M MN04855240 422%6 HH.o~.. wBReYCrE bobpeeeeernnstttorrereaaittenedda wwcihittehhmiaacaffllluupooraroorcc,aarrbwbohonenrpperrooodcducucatcs.ti.onBBaooltthhspssihhooleeassgowwefeserreeacwwidoosrrnnorbboyythaaennr Cocihnhpeeetmmrhiaeictcoaaslrlhssotinteoooaookkncphpltelaahmcceeei,cl.aeI1fltw,piwlwlailhlnlitbb,ceehwnnhsooettremeeddaodtthchecaaattfsttrihohoeenmacclchhoesenpmmviileiclcnaaatglliessoshnhaoaalvvfeealcbbaiutudhrrsennroee,drd wohhhtoohillleeeessr twtihnhieelthooaettlhhoseehbrroeseshhsoooeeneenmmthataedhdaeeltefffttr,hroeowmmshhilloceeehaattmhhisaeerrdmettarredfeaearttoeefmddrotwwmrieittachhtoendFFvCCle-e-n1a1tt44iho66enrahhlahaasslsenanrtooehtehharooi,lnleweesd.h. iilITtestt swhiallpealscoonbsiedesereabnlythabtetthtee tshhoane tmheaodtehefrrosmhotereated leather has retained its shape considerably better than the other shoe. XXIlIL. PPaappeerr AA.. InTaopuerios To Pari cemWW enootooeddd,,toiinngeggtehenenererrabalyl,, aiigssummmIaNamddTeyeROuusDppuUbCsooTtffaIOlnloN conenggTcOaffliiPlbbA eeedrPrssElRioogffnicnc.eellIiluunllotossheee p((CrCe6apHba1ur0aOOtsisho)enx ocotfeyfmpppeaaeppnoeteferrdpppatuupolpegpr,e,thbtthheeiiirssnbgllyiiggpannriiognnduimmmcaeamdyy.yoosrrTumhmbesaatyyamnnnacooiettncbbapeellrerrodeecmmleioogsvvnseeidnd,u.,sIddenedeppthefeeonnrddpiiprnnerggpoadoorunnactiittohnhngee tppFyuugpllreppouoaanfrrdeepwaoaaposedrff"oo;blllleo(oibwnw)gss::opo((rkaao))idnummgceeecwcdhih.atanhTniichccaaeaullsmtggiarrciiinnsndodpiidnnragogcuenoosfdfseettrshheepursewwesdoosooufdrdoertttooproppprrdroooudddcuuuincccgeee sws"oagiddtraoahueppnxuudcllweppss;oso((ccsd))u"lc;cfoou(orobkk)diinincogogxoiwikdtiienthhgtoccwaapilltcrchioiuudcmmua,c,uesmmtaiscaguglnsfneoietsdseiaiuupummun,l,dpoo;efrr(apa&)mrmemmcssooouonnrkieiiuuntmgom opbbfirissowuudloluffioicttdeee wcpchhriioitpphdssueciixnencesaasuppslppfrirsootuexxlfiioummrraatKtdeerillaoyyfxtieedqqpeuuulaatplol. pppaKarrrrottadssfu,oocffesucclsaafuuuilstsfetit,itieccansspodouddlsaapo;aadnan(dddp) suscoopoddsoiikuauimrnmegssruuoelllfffaiitwddieevoeolttdoyo rpflrireegoendiunffcrrioeonmmtsuhlellfiigargtnnieiignnio,,arawwlKhwhreoearrfoeetdaap.ssulggIpnrr.oaoluKunnrdcadawfwsto,oesoosddutlhfeppituuewl,lapptaenccrdooinnstotaeadiimannssvpeueelssdpssesenfnatrtirioeaamllllryeytlhaaaeltllilpvutethlhlypee slsiuugssnppIieennnsispniiaooptnnhe,,errroemesrasiuukglilittnniinagnl,ggwitinhoneaoadprr.ueeIlllanapttiiaivvsleledllcyiyasttspheheiisrccstkkheedfeelwblttyaootfefmreddcrirshiieearddneimppcuuoallvlppe..mdefaronms stuhcehpaulsap """hTbeheaeIatnteberepr"a"a,t,peeaarrnnpddmuoloafpkfttieneinnsg,vvctaoahrnreiivooeupurssutlesspdiizziiistnnogdgpiasaagpgpeeeenrnrtstses,od, nppbiiyg4gmmmpeeanenptcteshsr,,acncomoilaclocaorhlrsis,mn,eetee.ctac.n.Osaarrrsdeeuincaaahddrddiaeelsdyd.,a. tTtIhhnl~eerreceeibtaaherreaeerttetwcrwaoospeummlatpachcehhisiinpnceueoslnpuuvssseeeldrdut,,erdrtthyheetoiFFopobuaurrprdoderurriginhnoitineerrianaannpcddaotpnththeaeercyctmylailwicninhtddhieenrrea.mmwaOaiccrrhdehininiesa(cn1rrieel~ey.)n,. ttIehnhlrtro,oeuuiwtgghhhheerrwwehchaimisccoehhrettthhhweeeatp~weuavltaipteerrsrlppueaarmssrsosyeevsse,i,sdttbhbhreeyowsuwqegeuthteteffziiibinbenerrgcss.onaaFrrtreaeocpptmiicwctkkhieetehddfeooalfftfwsbbieryycetaasocnwwroetooeholnel fppieaaelpptd,ee.rwr hwwIienecrbhemappmnaaossysrseeecssawsooeavvste,eerrrwoiohsnneerereemoorr3ommvloerodrgreeebyhhneeusaaqmttubeeedederzrrooionllfllgss."ohoFrorrto""mhhcoaotntthscc"eaannfsesrsle""t uswwsehehcedteri,roeenthiitttehriieess hidissriiaeasdss.seevIppnaearrmaapttraiieonosnyniciinansuetstshhe,eedwddfhroreyryretssheeaecctltaaiidorogdnnie,,tniwwouhnhmeeorrbfeeeoraatohfe""rss"iihzizoneegtrppcerradeeinssesssn"""tsasirs0e iiunntstthererodod,pduatuhpcceeeerdrd.e. sTohri"TsbThhsbieezocectoohpmmrwmemasotsoennrisppauaanpspceeedrorilfifyiobbremerathtiieessrbbiaoaodlttdshhitvhiheoyyrnddyrrooorpfephaohidtilihlliieycc.r aaiInnntddgsrooellcdeoioopehmpnihmtlsioilictnco,, htheencpe,apaebr-. phreanccteic, eabto- a`saopCpprtpblblsyyonb1to0odtethtrhhieewvaatppitaaevppreesea,rrnedssiuutocchihehlrywwimanatatteethrererirr"aeeblssseiiassvttteaaernnrytt" rssoeiirzagidi5nntiglgytssh. aeaIstsrriiososesciinonp,m,reoomsrrso"oontthhpeerrrachhtiyycdderrooto-- cpaarpbeW `orWniittwhdhheittrchhivheeatiddisveebvevosee,tlloheopipthmmhyeeednrnrttionpoohftfhafefblliu"ucoboreraooancctdaearrrob"blooconnarpsshaiiotzzbeteihssce.iitt"siAiisszseppwoopessrsieihbsbalsl"see.e1to0sepperrnoodfduruocceme paper which is both hydrophobic and oleophobic. As we have seen from 33002222..00113322 33MM_MMNNo044885555224411 INDUSTRIAL ASPECTS OF FLUGRINE CHEMISTRY Ie INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 427 ttchhaeerbpporrneevvciiooomuusspodduiissnccduussbssieioononnooenncttoeenxxtttiaillieenssi,,naagllllattfhhlaautoirissocsraeerqqbuuoiinrveetddalii,ss ttphhraaettfetthahebelffyluuoiortrooh-cbbbaieerittbwzwoeeedneennocro66maadnnipdsdopue11nr00dscceaadbrrebibnooonnn4esatstcouooimmtnssat,,baliwwnehihnisigcecdhhiascc.ofolmumWopphroooiuclrnaendrbsiioosscnlcavaetpapnaitalbs,bllepecraooenfffbeebbrieeaibnnulggysesswdoolilutiih-n be`exximlpepizedeerirdiiummmeoenrntthtdaaalilnspwwweooarrrsktke,e,d,iinnineasapaeppcaasipupaeieltrrlaybmmlieiilflllmtiihteediisistarii.memsW pptrrmahaecictnletisiccsaaiolsllvot0oenccatoopsnnpsclsiaiyddneetrorbeaatnhnueyyspeooadttphheeeinrrr wcmwhaheiridlbleeiounoomnnmatttthhheeearnippaaalwppeeabrtreecmmr,oaacmecheshipineneeicet,i.haetIlrltyiicshiefffumutirrhtctheahelertlrrmyemaoobtrromeenedddneetesdirissatobitloheaeat0obphsphaullravyfveaetcoehth,teheoerfflupuuoaoprproooen-recervevaaaradbppiooolrnyraatrmtiieooamnntoervooieffadltthbhbeeeycwoweaimatttheeeerrr,e, istsshouueflfrfieiccesihne,entmtlclyyihceamiilninlscysoaollblusuob,bnioidliiezzdeeaddbtrosasoosthivttehehasaatucrtiifittaocwwne.ii,lllorrnoouttpobbnee readily removed by either solvents, chemicals, or abrasive action. B. Fuuosocsso Papen Sass B. 1. Chemical Nature FLUOROCARBON PAPER SIZES acid"TsThhheeav.cechhrbroeomemniiuumumsedccoocmmoppmllmee1exx.reecssCiahoolefflmyiccceeatrrlottaaNtiinarnetauftfrlleuupooarropocecaarrrCbbBooAnn%Itty0ypp%ee, ccAaarrbbtoyoxpsiyycllaiccl apspcrreiooddddsuuccchottamvoomefferttbhcheiiiessanlttylyupypseeefdoiisrs ckksoennmvooewwmrannelraacyssieaPPlalaayprpeestrro,CCthrhTeeeharmetiscicpeaaalplcehFFrOrCCo-0-m6$8.i001u550m7ww4ohchsioi)cmc. hhpAlhheaaxtsseyspbbieeaceeranncl us3so5os.lelu2udbb3llcee0om%iinnmsovvelaarircrdiiiosaouluslssyolhhufoytyirddorrsnooeccviaanerrribabslooonnyperaaaorllpscc~yoo1lhh0o~aoll)l.cssoThaaohnnl,eddseTaarrhceeehrssocuuomppnppicluleiimneetddrcaccotoomemmdpmmelseroexclreuicstaiialaollnrlyye, wwdaeshshaiicrh3eii0di%sccadonarshcorkkelindggtsrrreeaseetoninlouiintnniowccinootllihoonrrwiddasutuoeeeprrt1ootpottyhhgleeiavcclechhotrrohheomolmp.iuriTmouph,mieeri,ssctrroreenaaacddteiiinllnyytgrddalitieellvuduettlee.sddolt0uotiaaonnnyy, desired concentration with water to give the proper treating level. TABLE XLIV TYPICAL FC-805 TREATING SOLUTION 147mi FCA Commodity 1.67 ml FC-805~ Commodity 167 mune 1.67 gm urea Dilute to 100 ml with water G0 Commodi coi 30%. ~ FC-805 Commodity contains 30% ate ss in pope] sone active solids in isopropyl alcohol. olutAAiontty,yppiiaccaasllhetereaettatioifnnggKrssaooflltuuttipiooannpeiirss wddoeesuscclrrdiibbbeeedd tiinnraTTtaeabdblleeinXXtLhLIeIVVl..abUUorssaiitnnoggrytthhbiiyss sGrdooiilplpluppstiiin0ongng,2iin5na tttsohhheeeoebssttooallouiuftntiioKoannr,,waeftttthheeppnnaipcppkeuu-rttuttpwiinnoogguflttd6hh0eeb%ess,hheetareeenttadtttehhtdrrhooeuiunngghhdtrhyaaeinsslgeat.tboooTfrfhassteoqqurudyeereeizbzeeyed. parpoaalppldseerrsdowwoofao-usuFllCtddoo-3ttohh0nbee5tnnaisnhhoaalvavideesw.3aeAtttsrrpeeihacaitktms-mubeepnentetonllfeemvv6eee0nll%taai,mmoonaouenunddntctiaitnhnliggecnr1t,o0dd0r0uy..r3i3ni0n0g%g%. Thbbyhyyderwwoedleiyriggisehihdtst ooaoffdftdtchh-ooeeunrccshoher,frooFmwmCoii-uuu8lmm0d5cchoosaommvlpipeldlese4.xxeeApssrsotthhnhaeoesrurenbciieseednlliibbmteeerreaannttdtiiioeoonrnnieoondffghheyayerddflsfrieooertcc,hhdollounorrriitcinhgaaecchiicyddedllwwruohlhlioyicscsihhic,s,: of course, would have a pronounced tenderizing effect on the cellulosic 33002222..00113333 I3MM_MMNNo044885555224422 a Ho. meyer H.G. BRYCE 428 fefiivbbeeelrrssioondffictthahteeedpp.aappeer.r. In In order order to to counteract counteract this this acid, acid, ure urea is is added added at at the the lleivmei"DltDeuiudnecdiuttcosoaetttfehhudeel. hhsyyhdedrlrofollyyTssifiss pparrfooteccreessssmaiiknnew-wuaaptte.er,,TttahhbeelecchhrrXooLmmViiuummgiccvooemsmppmlleeixxnihhcaassumaa SlsFihhametelhilfteferlfdifmeeauddrsaakettefaaudlffooirrnschttrheheeleafscceoloimmfiemnmetraehcfretcieiarraalltmepprroaoofkddeuhu-cyuctdtp,r,.oFFlCyCTs--ai88sb00o5le5.. XcIItoLinissVessqeeeugenenivnttethshadttemctthrihneeeirrameesieuissmi1an Srhaethlferlimfaraksetdheinctreemapseeraintutrhee irsatiencorfehayseddroflyrsoims o2r1cContsoeq5u5enC.t dTehcreeraesearine shelf life as the temperature Tan XY is increased from 21C to 55C. There are Sraowry or FC:05 SovTuAioBsLsE1XL4VFenerion or Tesrirint STABILITY OF FC-805 SOLUTIONS AS A FUNCTION OF TEMPERATURE -- wr Temperature Sowion ile Solution life mionn)im minimum (C) (hr) iE H21 38 Tw485 8 55 4 ooTththheeesrrolffaauccttitooorrnssawwnhdhiictchhheaahffafferccdttnetthshsee ossfoolltuuhtteiioownnatssetarab.bliilTitthyye,, aarmmaotoonnfgg whwyhhdiirccohhlyaasrriees ppoHfHthooeff tpCchrhhaerrcotosmiomcliiauulutmimousncceooammanptdpllpeetHhxxeiivnnhaccalrrrueedeaanssseeeisssnsmmeaoaxrfcrkketehesdesdllyyowfawwt4ie.it5tr.hh. Bperalcotwic2al00uspepamt ipsHnovatlureosubilneseoxmcee,sstohfee4.i5. pTpWHHhh;ie;liirenanthffeaaactort,df,nhitetysiidssr0tooofl0oystrrihaseapoiwpdfattffheooerrr aWgehnileerahladrdenecssiofinthsetawbialtietry obofeftltohh`weAeq2ccu0ooe0momupppsllpeesmxxolwwuiistititnhohonsiitnntcocrrfroeeuaaFbssCliien-nsg8go0mhhSaaerrh,ddanntevheseessrs.le. oiws a general decrease in stability surface tensions, generally in ttthheeendAnneeqeniiucggeyhhobb1uo0osrrfhhsoooouolonudd,tioooefnsfps22e00coifaddlyFylnnCyee-sws8h0ppe5eenrrhaecamgmv.ie.talIItonnewdccooosrunnsrspfeeauqqcmuueepenntececdene,s,aiostthnhiesen,rreetgheiiessnceaaarassselttlrryooonnif3gng tttpeyhinpediacuealsnlecppyoaafptpoceeerrfrotmmaaimiillnll, sssepiisezzpceeiefppcirriceaeslsalssyn..twTTihfhhioeiassnmffiaoongagaimmtaaiitgnneggdenttoeetrnnsdpdeu.ennmccpyyeccdaannasbbieencctoohnnettrocooallsleeeddofbbyya the use of certain specific antifoaming agentsa09). 2. InfluofeCnhacien Length rhreeisssiisFFscttrraaoaonnmscmceettthahahsseeotftddhlhaaeertteaaccphheppalalllioionent2tnt.eecllddeyeInnnfogosgflntntmuhheeFFnaooicsifgfgeu..rttoheh77feed5,C,bAfhlttuyauhhoisoeenrtrrrooaeeLcnceaadiinsrsragbbr3atoodhnnmmeasaaatrcrckkiwddeehddiiissciihnniicncnmrrccaererkaeaeasesaseesseeduiid.nns.eaoIIoiinnlfl totthhfhlieesrppeceeiannssceteiattrrnhaacetteiioo1on6inl,ppreooTpwwheeeelrlrreeonosfcfuylttutuisrsrppsmeehnneotatiwisnnuete.rh.eadTTthhwbiiyhssesttteerassntetdiaihassrseadacvhvteeersrrotyymwssiheeuvvicmeehrrceemommmaepkealeasessuxuurerseseeooooffff 6CCo0a.ib.HTl55rFFr9%ueI,Wps~bitCCbsytOydOawneOwOeccHierHe,(egi1,gah1shtCCet))F)s.iFisrTnelrevhspCiCieesOtOntrOeettOIthshruLHeeal,tt,ppsieeaaosnnnnnheeddotrtrwreaaCCstttiogihisoFoFatnn1at1n9woo,cCffehCOtteOauurOtOerrpHapHcseehnnat((htitwwiiennhnhceeeelhnenffrnooograarmtpph33pipsulmlrimialieceindndsc,s,ottttmtoohhhpeepaprrlanaeeeppxeeieieisrsrsgaaohaannttft CCacaeabrnrrbbtuoorpnnast.st.doenFFcooorrrefaee2sxxe.aa0mmi%npplplteeoe,,nttteehhtaeercachctioooammnp3pl-rleeemsxxiinsootfafrneCCcsie6FsFtasa~tnCCcceOhO;aOOiwnHhHelerrrnceegsqqtsuuhiitsrrheeelssesCaasssstFoahlluaiddnCssOeccOiogoHnhn.-t centration of 2.0% to reach a 3-min resistance ; whereas the CaFnCOOH 33002222..00113344 I3MM_MMNNO044885555224433 ovsTN, arts of scone cosy 429 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 429 iL +d 3z i i 2 it i iHE, PAPER CREASED 2-3 MIN. RESISTANCE C~ C7 C, C9 CHAIN LENGTH OF NORMAL ACIDS Fr. 75,1 se input ve ee by roms compen of dion FIG. 75. Oil resistance imparted to paper by chromium complexes of fluorocarbon inbrrtt peta carboxylic acids of differing chain lengths. complex has 0-nin rssnce ven a 3.0% on the paper. In fn with complex has 0-min resistance even at 3.0% on the paper. In line with roses Sonu (ee Tone is necesary fo aon Aotvsabon previous conclusion (see Textiles), it is necessary to utilize fluorocarbon Fut which hav iho more chon shes sins aro of groups which have eight or more carbons to effect efficient orientation of Be Rarosrbon va on th vr ou an oro woe of paps the fluorocarbon tails on tile very rougil and porous surface of a paper Boe.fiber. 33002222..00113355 awuNossssass 3M MN04855244 0 Ww. 6. wes H.G. BRYCE 5. Pafornances Ameonntthe Paper on IaInnKFFaiifgg.e. 77p6apiiessr3pp.laloPtoetierdndfcorrttemhhaeeasniddncegeeggvrerseeveeAsmooffoouaofinilltFrroCeen-ssi5itsh0steaa5nnPccaeeAppewwprrihoiccxhhimiaissteaaltatyaiinn0ab.bl6l%ee obobtnyyhewwareeiKiHggarhhrattdft,iisspsrraeecpqqeeuuriirraaeetmddoittunoonctrrreeseassisipssirnttogctvhhileedeevhheiirlggsehhslloiyysftppaFeneCncnee-et8torr0aa5tt.piinenAgngcpttrpuusrrrtoppixeeonninmttiiannbteeye..lymOOin0nne.6rtth%ahele ooitlh,earsphhaalntd,, olresmsearliamn owauxn.tsTphreosveidreesruelstissthavncee mtoucphenperatrcattiicoanl sbiygnimfiincaenrcael oil, asphalt, or molten wax. These resu!ts have much practical significance i3i win i wax h~,ldout t I I I ~ 0 0.2 0.4 0.6 0.8 ! .0 coFn1t7r5i.t0e ofsarnaemvn ccootnecoef n+ tfoooKiSpapeer staetdFwEi1th .fst Fro. 76. Oil resistance vs concentration for a Kraft paper treated with different concentrations of a chromium complex of a fluorocarbon carboxylic acid FC-805. ssmieinnnctcesiotfeeannabnylegsaitvhheeebnddaeeplggplrrieeeceaootiffsoonli.l reIenpeglpelenenrcaeylt,toobhibeeevvalnarorwiieeedrdcttohmmeyeeesetutrtthhfeesrreetqqeunusiirireoe-n oo2mffetgtnhhiteevseooinliflocaohnrayrigngreeisvalsseeen,n,gattthphhpeeliggtchrraaeettaaitoteenwrri.lttlIhhneebgcceeoonnnerccereeaqnlnu,tiirrtaahettideoonnltoowooffeprrufletouhvooeerconsacueartrfbhbaeoocennoilttteaanifllsssrioooonmff a given eiltlinbge wetting ttmhhcoeehraeppinaappaeelcrertnffgiiibtvhveer.. that a1t i2It is wgaailivsloloenobobebcvvoinirooceuueqsnsutittrrhhaeaatdttioatnollotophnnarggeneevrrefRnlutusohortorhrooetccesarorrbiblooonnnferoataimiilnl pFwprreielerlvvesbenueirtifnnmaggcoewwrehietanteifgnfbge,ec, tnaaivtdeeleuaascst teauudppgbtiovlethnhoeectppohoonaiticnnoettfnhwwtrhehaeteriroseeunrtthhftaehcassenuutrrffaeaaccnseehseeonorifneterorgtchnyeoooniffedhthi.ene fiber surface has been reduced below that of the surface tension of the fluid. 3300222..00113366 IM_MNod8s5245 3M MN04855245 INoUSTRIAL Asecrs op FivonI CHEMSTRY a INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 431 4. Pafornance < Drsing Conditions usiOOnngnaastlbraebostoirrnagotosnroyl4uss.tciaPaollneerafiiottrgismsiavccenooncmmeippnvaasrTraDaitbirvvlyeeilnlyyXgLaeCIaossVyn,dttiofotiootrlnrleesoaawttinaagssthhheeeetpoorffocppeaadppueerrr,e, ouopusutitrnlliigneneeaddctreceicaautrtlliainseehgr.lo.suTTyolhlhueetbieodddnrroyyaniisnneggg3ivmmeaa0nyyitnbbo3eeTaddavsboionlede XciinonLcaaIkVnniyyn, gfccooaolnlnomvdweenwinrineignntktthliffeanagssp.hhriioooDcnnre,,idnbbuguurse.t pCcnorotennhfddeeiritaioorbnenlsysstiacetadnsnphahaoapuvvelede.aabFeimmgadaurorrkkneeee7dd7ssofehfafoetscwttsoooatnnvhtteohihednfddcleeoigcgcrnrkceeleeeinooogfffadoonrlidlyirewenppgreeitlnlleekenlmnicnpcygye.ratDatattariyiunnireneonegdd on the treated paper. Figure 77 shows the influence of drying temperature on Ho 3 & -t.= o0o8 s5ttoo- or , ~ 0.7 =HEL 05B = wo =) TM 7O 120 170 220 270 Fi, 7. Bc of dri Ong Drying tems ternp, F cmp on de pec of pp eed wih FosFIG. 77. Effect of drying temperature on the oil repellency of paper treated with FC-805. nhthiene.fefFfiiocriecenxciaymooepfflFenF,CC-c-a8800y05. iinwntggi%ivviinongfg FtthChee-3pp0aa5ppeeornrtrehesesisitpsaatnpaceenrtctaoentdtuudrrprpyeeinnnttiignnaeetf2fo0orr C33,00 mth"hhaieennd.pp,aFapwpoeehrsreexwnwiailmrllliprreleeeds,siasatttt hiansde,quwinheedn tdoriegdiveat 0pp1.e35en0wenCttrt,a%toaioponpnfrFoooxfCfi-ttm8uua0rrtpp5eeelnonyttniitntnhweeiecffepooarr4ps30e0rmaummnicindhn..dFrOOCyn-inn$gtt0hha5eet 2sooo0tblhieCedrsr, t1h3e0sCam,ea.pppreonxetimraattieolny trweiicseanacse.muTchhesFeC-r8e0su5ltssolaidrse Cicesomonpnrseediqrseautentinrusetsdewwsitistothhagnttihhdveeeoffftaahcccetot usttrhahsaamet,tettthhhpeeeenmrreaotttrereaetooirfofanpddirrdryyeliisynnigsgtthaeiinscdeger.rayeitaTnetgherreoscaaectturrttsehh,seeutlhhteisiggehhaeerserr thofeoefirremficicecipnbtieeeteananrtttattiwotworuinnelirlelalooslbbnn;oestatthhtnahheeedee,masmsiuoutgrfirafrgcaiaarocnat.eutei.irdoosTIennbnn,ootgpffhseettenhcheereemrmafAaolllaiureopponrorrraaocactccpathtaiiirercdcbbeelboyouiinnltttkhtahhaeiaoaillsfsdsstrbbaahyeenneienddnnwgattheethosseeecttiricaraubbassrlltuuisisbt,bsheshsteheemeddqpqeeuuhtlreheeasnnsat-tstt the best results are attained atermepseraatouwresa. possible, ss tures as low as possible, less than 100C, by removing than 100C, allowed the bulk followed byof by nal drying the water at final drying at higher tempera- at higher temperatures. 3300222..00113377 IM_MNod8ss246 3M MN04855246 +a3w2 a. mcs H.G. BRYCE 5. Peformance ss TypeofPulp prioDDreetppoeenncddoininnvgegrosoinnontthhete5o.pp4aaPrrtestiirhccfeouuerlltmaarroafnppcrrpoeoaccpveeesssrss,TuyutpssheeeeddroettfooPmaupprlyrpeeppbaaerreevatthrhieeouppsaappneearrtuffriibableelrryss oCpoaccrrcicobuurorrnrrt.iionnggTcaioinbnnglgvrereeerddXsiiiLeeonnnVttssItowwghhaiiivcceshhhsewwaieiltlllgoebbfneeepmrmaaoolprreeecrl,ooarrstlshleieefssrissecccatomoimoamnyppaobtfiaebcltveowaiwmriimibtotohultsnthhenetayfftpluuuercosarrlooloy.-f carbon. Table XLVI gives a general classification of common types of TAME iNT TABLE XLNTI TYPE OF PULP A. Sulfate BT Sule B. 1. Sulfite 3 Scher 2. Semi-chemical 5 Soa 3. Soda Gramimood C. Groundwood Boi Jwe D. 1. Jute 2 Newobonet 2. Newsboard 5 Chisbeud 3. Chipboard oppfaalppieesrrtippnuugllipp bfbarasoseemddsouonlnfattthheeekpprarrfootcceeastsssteehssebb0yypwwhthioictchhhetthrheeoyy uaarene dpprrweeppoaaaroreneddd..jTTuhhteeeosorrddateethrre obibnofogttlrtitoseotm dmiin,,egnaatinnssddftrhoaaalm lsnsootshucceloofrrcarreteeelsslpkuporloanonfsddtessabttteoothrttsehh.eteoIpoonorrttddoheerrtehrooeffwgoiirnnroccdurrsnee,daassswiiunonlggoftdcceooanknnrtdtaeefnjntutpttueoolsffpaoosttthahthereerer irnelgarteidvieelnytfsrtheaonf natural rosin and the cellulosic fibers. lIingiontsh,erwwheorredsss, the other pulps con sulfate kraft pulps are rtataeyiilpnanetisiivnneJccliyrrseetaaferssdeiinenuggnodfaaem mnroaoutuDunn,rtatsslJurootoffes,ioonttsNhheeearwrnsdccboootninagttrnaadim mn,isinn,aaawnnntdhtsseCrieihnnaisptthbhtheeoeaoororrddtdheeoerrfrtllpeiisnsuttelepcddso.. ncTtToahhnieen- trryaaptthheAeessrr lllaiaasrrtggegeedeneaaurmanlomduernruoltseDo,ou,ffitrJrnueeisctcelltpa,oiim smNsseeieddbwlensnbeetowwoassrpapdrcr,hiininaet,,nvedettchc.Ci. ghhieprbopaerrdfoorfmteanncecolnetvaeilns fofrrnoomtAmhseaaapggugiirveveenernnesraucclloofnnrauctceleeenn,tttryriapattetiiisoopnnuplooopsffssibtaalheafflnltuouooornraoocccthaahirerebvbooelennshsissgipizzhuiiernnregg,,pvaessrruuifeccothhrim esaa.assncTFFteCCw-l-oe88vu00el55ld,s, aoamppnuppetmehaaerrorpttihhueatrntetratththsieeuolnnnfaaaotttfuuerrtaatyhllllepyyefoolpccuuccoulurprorsrrciiantnrhggbaonccnooonnttnatiaalm mtshiieonnanalnentsttssshepinnufetirreeefrfreevrraseeruirewwftiaiitecthehss. .tthIhteFerwm moaoamxuxilid-a- m ppdreruaagcm crtteiieccooaalrfliepponoiolitiannrtttieoosofnifsvtoaivfeniwectwehtetiihsleefrleauaqbbouooriovvrceeeadssrttbfaaoottrenemamteaepinanlrtsttmmiocanauyyltoahornenlalypyfbpiblbeieecsrasitisggiunonrnifif.aifccieasnc.FtaliionFffwtraloehimvigeglhhas dooCfoef gnrrtreeeassemiisisotntafaanonnccitleesrettsosorieswwtnaeoentttctieiann5iggshrooaerrqrussmipprr.reeedaaddfoiinrngga are sufficient, the puriies and particular application. If low levels are sufficient, the impurities and contaminants are not as harmful. . Counmamen. TaawminG Procepuss imOg OFnCn-ac8o0c5mommsemtrecruicsCaiea.lal CsppOiaapzMpeepMrrrEmm eRasIacC.chAhFiLinnTeeRittEhhAe7eT8gmmIosNoshGstoutwPccRsooOannrCvvteEyenDpniieUieceRannElttSmsmieeetthhpoorddoeofsfaasappuppsyley-d- idiinnnrgyppiFaanCppgee-sr8re0cm m5taiaonisnnu.utfoafacuctstueurraiinsniggz,,e which press. which is usually installed part Figure 78 shows a typical is usually installed part waysize way through the press as used through the drying section. 33002222..00113388 I3MM_MMNNO044885555224477 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. EE INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 4"33 %; | Son T Fie. 75. Ske shonin a ypc se prs wed an pape saci FIo. 78. Sketch showing a typical size press as used on a paper machine. D. Provssmes or Treats Parise the T`cTohhneeveaarpptppellrii,ccaaattinioodnntooDhffe.fRleuIu~nooRdrrO-ooPuccEsaaRerrTbbdIooEennSsissOgiiFznizenTrigRnsE3gAttnsooTeEppwDaappPteeoArrooPlfoEffiRefnresrmstathhkeeinppgaapppeearrpemmraakkaeenrrd,, `mtphapataepepreecirroapplnsrrv.ooeddruGtuecrcrtet,ssaaswwnehhdiirccethhhsieaasrteeeannrrtdee-sspuiiasssptteaeannrdttsettsohoigappnveeenerebntaereanenteiowtanvoteaoofifolaoilbillltiyyen((aitamsosowawtkehneienlllgpa1sasppaaaepqqrueucretoorauaunsdsd)e) fmfhooyrardtrellarooitnaneglgds.pppeGeurrlriiepooaddswssehooirfefcshttiisimttmaheene;;tn phhfoaowpweeeovrvseearhrc,r,aovnttehthmeiebssneeeuesonppuaasappveoearrfisslanaaborrleeneptoffoororortmhumseeedfdpialbbpmyy.erhhTitihrggaehhdslleyey hppaaaynppdeeyrrarsstecadaasrreeepsukkiltpnnoioswwwanhnliscoaahsspotpphsaaseirrncbclhhfeommretemnhntrst,o,augggcrrhoeenaattsshieeenppurruooosouoefsof,,foaargnnrnddeosnggsplelaaossrrsseoiisunnisseetfapipnlatamppe.AerlrsTsm.h.seIsItneno mpptorraootnddhyuuecccepeaesanaecslltaarimmtsitiininsaoaatntleoesddfogssprttroreusuacscsittbuyulrreemeatwwthherhrioiiccuahhglshaaffdtfhfeoeporderusndsdsaeinccoeegfrrttogaanriiennatshddeeeeggrgrrereeseeeiasstooaeffnrrrteeessfsiiiilsssmtttaaasnnncccteeoe.. tooeoffwttthhheeeapffppiilrelmmon.a.ecTtTrhha,hteeisouiunsnsceeoefootfgfthirthesheaeissyfftliuhmooeraroiotecscraatirarblbtsooinnmdeesspiitzzehiinanntdgg,i,gnrhhgeooawwoseneevvertehrers,e,isoogtffrfafeeenarrcssseeaairnnepseeoinnsscttsiaiirrnbeeclllyeey nwpwoieintwt-hhoooaiuuplttplarlonoossdasscnhooo,ffns-ppiownoracrotoesesitirhttyyiwseiitninstaththbheeleessfshhirueesreetfttaticssmiiennecceethttahhteegppraaeppaeseerr fiber is given a truly resistance is possible fiber is given a truly nthoen"T-aTohhmileeouaffnnaadtccttnottofhhnaaf-ttlwuttaohhtriieossrcdadwereegbgtorrtneeaeebmleooaftfseurrrerefissaaiicsstetaa.andndcceeedmmtaaoyytbbheee pvvaaaprreiiered,d bobfyy cccooounnrtstrreoo,llllhiinangsg tmmhhiueugcchhahmleppovrreuaalcncttttiihccoaaatfll ftsslhiiuggeonnyriioffpiiccrcaaaernnvbceceone.nt. mFFthooaerrtepeereixxanaalemmtaprpdlaledte,ie,odttnrrteoeoafatttmshmueeecnnhtptssafpltteuhhiraad,ttsoaaafrrseectoaauuttrrpssseeuun,ccthhhian8esa hoohrerigsvvhiooolnllaaetotviifelleleinthhhkyysaddtroroothccseaauyrrcbbhpoornnceovlalieitqnqiuuntiigddtsshs,,easwwpiwielallnlxeaeatllsrssaooatiniiondnntteelorarffcfeqesurreeuercsssh.eerrfiiOloounuuissdlltsyyheawwsoiitttuhhhreptthehheenatniaanddde,-- hesion of inks or such coatings as waxes and lacquers. Or~ the other hand, 33002222..00113399 I3MM_MMNNO044885555224488 a4 no. oavee aamoddleetggerrneeeweaooxfforreesstiihssettaalnnecceae,d, iwwnhghiioccfhhtihisse ssouuiflfsffiifcciireeonnmtt attsoophpparlrete,vveewnnitltlttnhheetppieenntneeertftrearrtaeiotwniiootofhnf gmgooooolTddtehppnerrrwiiennattaxiinrnoeggrtccthhhhraaeerraeabcctpleetrereo.rdp.einrgtioefs the oils from imparted toa asphalt, will not sheet of paper interfere with by the se of ptthhheoesbsTeeihc,fMelurueaoonrradoorcceaaaltrrhsbborooennsehpttorrrweoeaspatmeuarmeted~ienetfsstsi..nimitT"epThahrereetesssidhhsetetcoaetntcaebbseehtcceooemmttheeoessf ppooiallcpeekoeorupphhpbaoyobbifictchd,,eyhhuyyssddoerirlooos-.-f ApAlethtaosnntnoocerrq,mmuaaailnladlttrereenaaaltsttiointnoggshcllooeewnvvveeslelssnatttihdhoeeenfawiwnlaaittrteeeorsrriernres,eisssiiwstsaattaxnan,cncecoeertiiomsmyptpnhatarehrteteeptddiicckttoso-iuzttpteh~.eeofTppaahdppereyerrresisiossiilsaastt.t laaiennnadccsieetcaet0toqeusttihvahegaealeiaannddthhtetehosseiiocolnononwoovffeennddterirroyygnyasslaociihrllaorsppaiaacnrtr,tteiirwccillaseextssi,ciiosssroaafsysstniihgtgehnnieiffftliiicccoaarsnnoittzceappsrr.rbooToppnheerersttuyyrerfsaaiansnctdde- wiwnhhdiiiScccihhanteiicsssercatergehaaaetitneeadditlhooeonnrlttohhgweereppaeasaneppeeergrrreyffsiiibcbsehetrraa..nracecteirmipstairctseodf btyheaflfulouroorcoacrabrobnonsusrifzaicneg totoro wppSiaacpipnkeeicrrnegiis,sthtttehhiaasottoiclofofonccrcooesgaptrttieinnamggsuestththreeebsiiiensntdadaipinvvpciireddeuucaiaimllatpfbeiaebdrertiresnsdasscoobtyuttahhlaatteflnttuhdhoeeuryyoscrereeasasripibsspottlniwwceasettititztoiiinnnn.ggg A`loArmsxwsssitacartkteeeisnddigst,ceataphrerliniseeer,ct,roancctoocinenovpvnetennbmttyiiuoosnfntaoalbrlemggiarrnepgeapasrasee-cecpio-arnpotteroidofonoiuonrforuagsgclltauafsisaslilimnneeenofdppaabuppsaeeerrraesspsooprltichpparlltaoaissuottgniichc. fwawiphlhpmiliccishherde.ttshhiHeesot woopieilelvneooerrrt,raggitrrineeoaantssheeebycecaaafrnsomenroomottfinpptgihasessas,,flceeuovvoneretonnincuawwrohhbueoesnnnfsiisslzmiigegsnn,oiiffrdiiccubaaeannrtttr0ippertrreehtssehssurruorreeeutgeiihss ttatiiphoorpnnoloiouefgfdhtt.hhHteehpopeoworsrehooveuueesstr,,mnaiaenttvuuetrrhneeetoochffaottshuhegeeohssfhhteteheheetet,,bfiiletturiiosssrppoooctssahssreiibmbboslleneelttsvooiezffseoosri,ccleedlutthehneeottooaiilbltheooerrsggirregreenteaiansfseie- tbcchaaurnntottllubyygeihwwneegtthtttepeeodds.r.hoIueTnsen,t,ootwtehhiveelerrnwwntoohotrroddhussa,g,vhsseuitchcsuhhefissfchihbieeeeeenrttstss tmmphraeaemyysssrrueeerslseviissetrtsewwswiiisiccltkklaiinnnncgogetoo(brr0ewwpesretiegtttviniennifnggit,-, thebut the Illbiniqequiuaniidgdsiffmprrioolomramorubbsmee,aiinnnwnggielffrloo,nrrccoteethddehttadhhvirsoeotuuisggnuchhftfiittcohhineeenmpptuaapspperteerrs.assuoreberesmisatdaencewittoh prevent regards tctohoettmhhIineecappalalssasyimastgireleoasaorftfvemavadaapgpsnohorneersees.rt.,,OOtbhtbvhevieiodoruiuasststleliyynocddftuiuoetenrttaoomnsttumhhiseetssppaioolorsrnooouuobssfennvamaattpauuodrrreeesoowftfhittthrhhoeeurffegllghuuaoortrrdohose-- oecevhxxetetrremeemitmcheeaallltyylyottfhhtriiuennnatfftleruudeooarrtsooheccdehheeeftmim,bieticrhcasae.ll rllIaaanytyeeecrroonoofsnnterqecauaancecshhnmcffeiiis,bbseeiarronisisshnoenoefotttvmoamafptaoettrrerseiriaaattlhIellrdyyouaaangfffdeheccutttheended tteorrqveeueaairttleetiddhbaappttaaipopnefegrruusnsnhhtdrooeewwarsstegd&aivssfeiiimnbmieilhrlasau.rrmiImmdnoioitcissyottnuucsrroeeenqdrruieetegginaaocniiensn,.rra~aSttsieehmeiaaleffatteerrorlyfd,dtrrryuyeinianndtgegedraaannvnddadrttyhuhieennnng- hsehiquugmumniiilidfidiibictrtaayyntticcnooginnmddiupitnrtiiodoovennerss,m,gettihnvhetenfflilunhuoourdrmooiccmihdheeeintmmsyiiicoccanaollalnllyydittstrriteoeaaabntitsele.didptSypaiapmopevierelradrrdolyoeu,esnstnurnoneotdatteessrdhhvoopawwarypaaeinnnrgyy. `isWtiWghhinisililfeeictvtahheniirtssy immmiamapypyroorbbvteeeam4nateddniiasstsaapipenppooidiinninmtttmhmeeeennnsatitpopinilnnailcttahhsteetiaoccbniaissloieetfyootffhoemmvseaearnnsyyuanmuutessreeessmataffeootdrrepppraaaipppeeertrr,o,. acictrooettisttoroanenlvwaweeeerdayarrtiiionnmggtphaaoepprptpraaeanraretedllyaswwmshoheeitersriteenussrtuuehccevhhaapffpaoapccrlttiooacrrhassitioa5orsnpcctoooifmomnftfhooaerrnsttedaatsnnarddamnceseaamssimeessaooitfoefnrdd.iarrlyysiinntogg dareepe"TrTnehhdleaeitneccgdoonnudtdopiitottiihnooenntssrheerraeedmppyarreenmssneeeonnrittseetiddunriiwennhviFFacgipgh.o. tr77h99aebipisnnoddriiapcctaaiittopeetnrsseoeaoamnmtdeeerdtii.rnnattTneeshrrmeeessittusiisnpnigpgoeneer.ffmffeoccstttss fssdhhreeeopeemettnthhdhaaienssgtbboeeupeep;nnowntthrreeteharateeteeaddms ffatrnrohnommebrbbtioontttohwhmhssiiisdcdheheesse;t;htthehhepeasammpbieidedrdedilnsleettrssrehheaeaetteeeetdtd.hhfTaarsshoebbmeeueetpnhnpetterrrueemnaadttoeeesddrt stfsriihdodeemen. IItofFhbtetvhhieetodoudepses;lsiywirreehtddehreooebbajtjseewcctotht-iievvseeibdiioesstdtttooomsmmaitisnunhriiaemmteiiitzzoeehnawwsteeytbtptteeiiennnggtorotfrefeattathhtmeeeednpptaafprpoe(emrEr xbbatyyhmtetphhleeueoniodliAlses),r, then obviously the two-sided saturation type treatment (Example A) 33002222..00114400 I3MM_MMNNO044885555224499 INDUSTRIAL ASPECTS oF ORIN CHBMISTRY 5 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 435 tiisshrbbeoesust.gt.hOOonrnpttehhneectoorttahhteeirronhhaoafnndad,, tiihfettrhhmeeopaolbbasjeetccittciivhveydiissrottcooarmmbiionnniimmoiirzzeeoiaaccttthuuraaollussgthrtikteheesstshihhtreeeoeeuttt,gotthhhteehoannrtEEpwxexhnaaimemctprphlalieteisoCCn,i,noiinnfcowawnhhttihaiccechhtrmthwhoeieptlhtearessttaihttcemnhheyyntddtrriiosoccaaaapprrbppbolloiinencdofmtrooaotttihehl erethiisr,idodeueisgpohpbpoptosho,-esT"oinTthehitishtoewwisitllhlalambbteeewseehixxidpcplhioafinnitseehddienbbpeceallooopnwwet.a.cwItIhnniwceeihtxxhaahmmtaphplelebeehBBeyndwwrtohhrceeeaanntrebaado,nnniootmiilwaiddltelrroroeippasl,iistisplplabaecceneesdted. otrnattihoen sianmdeefisniidteeloyfutnhleespsafpoerrcwehiicnhtohtahsebseheenett.reHatoewde, vitew,ililf rtehseisdt rpoepnei-s tration indefinitely unless forced into the sheet. However, if the drop is em kTREATED FROM BOTH SIDES TREATED FROM ONE SIDE C------------ Fi. 9. OR sce of pues tid with F308 3 cof ch of FIG. 79. Oil resistance of paper treated with FC-805 as a function of method of treatment, i.e., one-side vs two-side treatment. fiftoiorrccieenddaiinnnttooenttvhhieerossnhhmeeceetnt,,tiitinwwiwillhllicccoohnnttthiinenurueee ittoo wwgiriccakdkieiittnsst wwaayythetthhrrrooauugmghhebbneecceaavuuesslee oBoit.nnitstOhhineenppataanhppeeeerronfvtbiihbereeorrnshmwwahenihdnci,thchiwnddheewecnreheitactshehestahioisnenfrtetehhisseispddaliiargrecreceatcdditoioiennnootfnftihttnhheeethuaaenrrirrtozroewcwattiiemnndEEeonxxratammloepnpvllleeyel ssmBllm.iigegOhhdttnillyyttetthrrleeayato;teethddbeossrtidehieanosonftfde,ttahhdeweoshsfhhepeneeeetntt,e,hteEErxaxoataiimmlnppiglsleeapgCCla,i,cneiit:drmhoaaenyy tww"hweeeettttutthhanbetirssleuiatrttfyeadugcreoaaadrhiioennnnostlsky"t foirrmereppcmrreeeedssdeeintnattoteeetdldhye;bbyybsutthhteheeirn,aasrrtrrehoeoawwd,f,loiifttipmlmeelenrroeeeftltlryyatssiwnppirgrceeakaabddgssaaicaanlklsootngntgghaetthh"neewtsseuuhtrrtfafaabcdcieleii.tyErEvvgceertannodiwwfiehtohnheentenn" fh""owwerecetcettaodabnbiicnielltionttytytehggserirsaaohddnieieeeontnft,"ttf".h.oerTToohhilecewssaeeiblloceonfffcetgecsrntsowuaapivrcseek,, sbooafhfcikccgoohauuegrsrasstieen,,oinndduutthceheetfodosiurthrehfeceatcieoffaancoctftofthththahaatett tsdshiieddeceeecttaooosnewwchehiinnictcrchhaotnttihocheeenntttorrrefaaaftttliiiunnooggnrossocoofallruuRbtutoiiooonrnnogcwwraoasrusbpaaosppnppilsgliirheeodidug;;phsnaensdotdnottnhthheeterrheeefissbsur3arcfcosaouncrnesfseaoeqcqfueustehen3nat5tt dtheecrseoalsuetiionn cpoennctenattreatdioin toftfhleuovroeciarnbonofgsrhoeuppsapoenr the fiber surfaces as the solution penetrated into the interior of the paper. 33002222..00114411 IM_MNO4E55250 3M MN04855250 "5 wo. vce 436 H.G. BRYCE E. ArricaTions ror TaueTeo Pav ano Pare Boxes ]~. APPLICATIONS FOR TREATED PAPER AND PAPER ]~OARD Av inden care, he use of a Auorocarbon sing agen offers the As indicated earlier, the use of a fluorocarbon sizing agent offers the paper manufacturer ew nl by hich o stain resitance to penceaion paper manufacturer a new tool by which to attain resistance to penetration of many hydrocarbon bused materi incading ol, grec, wise, 0d of many hydrocarbon based materials including oils, greases, waxes, and phasic used aque. Noxon posible 0 produce ly oilepee plastic-based lacquers. Not only is it possible to produce truly oil-repellent papers, but sso to control the degree of of epellency, which may be ex papers, but also to control the degree of oi! repellency, which may be reied for 8 given application quired for a given application. 1. plate Lavisates 1. Asphalt Laminates When tno shectsof Kafe paperare bonded ogc by ayofsephr When two sheets of Kraft paper are bonded together by a layer of asphalt, packaging barr i produced which has condense srcngth and a0 a packaging barrier is produced which has considerable strength and also excellent resistance 10 both moisture and moire vapor. Asplal, hove excellent resistance to both moisture and moisture vapor. Asphalt, tlowesr, a complex mia of Fighter ail and heavy waxes and insolble ever, is a complex mixture of lighter oils and heavy waxes and insoluble sins. Under normal ue i paper mits, thre 2 radial migration resins. Under normal use in paper laminates, there is a gradual migration aF the ail content a th asphalt cough he paps the ose of the oily constituents of the asphalt through the paper to the outside. Thi ra nly cnc considerable discoloration nd ugly ppcirince, This not only causes a considerable discoloration and unsightly appearance, but may contaminate on atile ext fi. As shown in Fig. 8, FC-805 but may contaminate an article next to it. As shown in Fig. 80, FC-805 Sn E amR ie i iCC Sa M rai iEells of eT eH gii3 niiirfHenR IF' :ii h CEhRe ORbf l E| oo rTeenneee CE on TERE FCSFi b3i Aipbaridesedd cr bo. Tog an ht ba ste ly wd wih ST oh Eine ii] FIG. 80. Asphalt laminated seed corn bag. Bag on right has outer ply treated with FC-805 ; bag on left has untreated kraft. 33002222..00114422 M_NoABS5251 3M MN04855251 INDUSTRINL ASPECTS OF FLUGRINE CHEMISTRY 7 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 437 iiIssnuutssheeidds cccaoosmmemmetrehcreicaifallllulyyorffooocrraraabssoppnhhaasliltztellaaimsmiiannpaapttleeissedttootopprroeenvveeensntidttehheeofaasstpphhheaalplttapbbellreeeed3d5. 5iiInnn0ddiit3cchtaa8iotsteeaddcpacepsalearytltiteheherre. afIIlsnnupthotahhrleoetcmmaatraonbnuotufhnfaeacscutitnzuuterrreeeisoaotffaepttdhhpeesliidleleaad.mmitAinonsaawtoteeen,,etthhhsaeeivdeppesaaeppoeeefnrrthiifsserlloaapmmmaipcinnaearartlteeeaddrs sctcoooonntassshiiedtdoeeraraaasptptipihoolanynlsstt,,hteathhnaiidssspooyhnneaeetl--tssptiiroddeeetvhddeenttrtueeisnantttgrmmeeatenhtnetetdiimsssiiecgdfrefcae.cttAtiiosvvnewieoinnfhggatvivhvieeinnsggoeieglgnsoooofarddgoamaaiddnhsheteaesrslitiioohenner to tile asphalt and yet preventing the ~nigration of the oils against the Fic 1. Sho estan of FC-A05 tested paper 1 spl led. Sample on FIG. 81. Shows resistance of FC-805 treated paper to asphalt bleed. Sample on left sidwih FC $5 00.w2t500 on lh aed. Bh wee expose 0 135C. is treated with FC-805 at 0.25 wt % ; one on left is untreated. Both were exposed to ~25C for 1 hr. "wettability gradient." a"twertotaobmilitteympgerraadtieunret.," bSSuuutcchhslsaaosspphmhaaaliltnt tllaaaimmniinnfaartteeeessdaaorrmee fnnrooottmoonsnltlyayinmmionorgreeevuuessneeffuualtl eaealltneeevrvoaaottxeemddattteemmemofpmppteeprrrleaaeattutuererredeassoa,otrnribduinunutrtnthhtsaerelesoapptrrmeeedssaeelinnnaccmteeaiinoonafftfooeriisellyeywdhmmoaimtacethreifrhariaolaslvms.e. bsFFetiiacgginuunrrieneexgp88o11esvsesehhdnoowfwsoas.rt `one he at 125C. an example of treated one hr at 125C. and untreated laminates which have been exposed for 2. Wased PapandeBorarsds coatLLapararggpeeer qqtuuoaanpntrtiiottviieiesdseoof42f .mppoaaWicrsaaatffxfuieirnnde PaavnnaaddppeormmrsiicbacranrorodcrcriBreyyrsostaataranldlldlsiinnaeelsowwaoaxxeegssivaaerreereuusissseetddancttoeo tbtcooroeallatiiqdqpuuawiirpddaepwwrsaat,toteefrrpr,.orozSSevuuniccdfhheooccadoomsapttaoeecdidksatppugrrreooesdd,vuubcacatptkssoerrffiiybnnaddbroreeaixxerttrdeesnan,snsaiidvvneedaltuushosseeetloiiinkneg.ssivuueIccnhhraeifdstdieesimrttasisnocanaes,s bitreiasdcwormampso,nfropzreanctfiocoedipnacaknagyes,pbaackkeargye bcooanrsdtsr,ucatnidontsh,e lwikhee.rIen amdodisittiuorne, it is common practice in many package constructions, where moisture 33002222..00114433 33MM_MMNNo0448s5s5225522 a438 no. ores H.G. BRYCE pvvaaapppeoorrrabbnaadrrrraiieesrrheiissetroreefqqpuuiairrpeeedd,r, bttoooallraadmmitinnoagateteethettwrwooussshheeeieattsslnaooyfgferppaaopfpeemrricoorrrocaaryssshhteaeeletltionoeff wepwaxaaxtpx.ee.nrsFFialvlneuudlooyrraooisccnhaaerrcbebotoonnonjfuttpnrrcaeetpaaitetomrmneebnnowttaiss,tr,dhsstutuohccgehhestehaaessmroFFulCCst-i-en88ng0055aw,,alaxhhyaaevvcreeooaftbbimeeneegincnsrouu1c0ssreeyddpsrtaeqqlvuuleiiinntteete useuxnmnntoneeoencctseehisvsssefaaliyrrlyymiwwnwaaixxctohppneegjnnuoeenottcdrztaiaatoiinnoocnnhwoaarinnathddgeyy.tehetteGseppeneeerrrmmmaiolittlltytteh,hneeiwwtwaaahsxxasttocobofefaoeotrinrnmmgfsaaoucctnooodnntptiairnndeuuvvooeuaunsns.t sttwamaaggxoeeoooiuuthssgefttoinolemuruassleweliyaathaoopnngpeeol--oissediidddeaetdndoctthtrroheeeraaatttgmrmeeee.anntGttedeffnoosreridrmema.lalayxxB,iiemsimtiuudhmmeassootppbhaaeecceirintteyyd..fuocTTuthnhiedeonmmaiodnolvliatteenhnne- swapobbasisxsooirribppslttegiiooe1nnneoorreffattltalhhyieenammtpohpolelltitoeeednnptwwoaaaxxthocfiientntthtoireettashththeeeedeypptaa.sppideeFerr. aaBinneddsighh2deeennshucceoteh,,werasrsseoaaedvvwiuinncggtt,i,hoeiinttopaiisnalcaitslhtsooye soopaoffms#aseibbballlseeeadatchcoheheerueddntawkkiarnraasfftethtdettrsroehaepaettateec.ddityOwwnoiitfthhtthheFeFCCost-h-h85ee0e0rt55.hFaaainnngdddur@wweini8tto2hhrsmnhnaooolwlfwsialllhveeoerwdrreetshmrhneeaseoiitnnpseamcuttishhtytee osbbafeemtffeihillelaleesdodrtiwwhgieiittnhhuanlaawottaipitxaaaecndniitiusyumh;meewppthii.igglOmmeneentnththteettoouonttthhiheeelreeehdxxattenesnnhdteteaootfnfro5$er%ms%ianttlosowrroaeenxttlaaeyiidnn4seeh5vve%eeennt om66f99u%is%tts original opacity. of the original opacity; original opacity. while the unfilled sheet retains only 45% of its 33.. CCaarrbboonniizziinngg TTiissssuueess pIIannitnthhtpeerammnosoemddieetrrtrnninbbguussiiinnnfeeossrssmawwtooirrollndd,,siinnexaftacrctet,m,eiilnny eevvvietearrly.yddaaNyyotlliiovviinnggd,n, otthhteelhrreoocllyleeecoo-ff wtptrrhaooipnnceiihrcc icmcnooutmsmrptapunubtstemeerricsstitriggncrrugiilnnaidtndefdooo,urumttbuaeettnnioootnhrrmemisoomuueosxsdtervveroomnllueusmlmyeeecsrsveittooaafflr.yddNaaittoaat,,roemmqnaulayinnryydeodcctotohpopeiicemessalekoocef-f swmmeahansincyyhfoccrmoopppuiaiseeptssebrooeffhaciisinnrfcfbouoerrlemamntaaetotdiin,ooennb-utffitoomrrtehggeceeannmcrerboraoadlnlerccpniiarrpccsueuelrlcaasrtteiiwotoanhn.ri.ycOOhisnnaereeeqooufufsirttehehddeetgtgoorrrooemwwpiarinnkogg-e. idudsusueccmseeafdocceoro.pppiiTaeepssoeroomffhaaxttshihembiezooerenriiggotiihnnneaeal-lntiuiimmmmepbprerceearssrssboiioofonnncpoaapattipeettshrhseewwhssihaacmimcheehcattairinmemeeubesetthhdmeeatdoooerrr,iieggpitirnnhoaial-sl ippssaaippmeterardpmmeeu.nuscsTtttorbbaeeimoaaanssxibttmhyhiiizntneheaatsshhepptoosnssmsuiiambblllebei,e,nryyeceottafrrrbceeoollanapttiiidevvsoeepllywyehsswitthcrrohioncngghc..aniTTs hhbceeoeyaytmemmdaudusoestn,t aatahllnssieoso Asrseiiudsdoeierstossciipnaneccrneebeotttnrhhaeestiiozoointtnhhgbee,ryrsussthiicddeheeahsmmoutFusCmst-to8bb0ltee5e,nfftrrceoeeaesrbuoofocfhntthshdhiiossepeddteosopp~peeve.rh. imcTTihhtheises tacahpopepaplatleipicdcpalatiotiicnooanntoinoooenff ofoelflfuaotttkhrieoevceddaloyorbpppoeeonrwwosiiiutztshhi,nooguut,tthsussusttcrrihekkfeeaf--esttchFhtrirCono-guu8ggs0hhu5,,p,eeetrovvieeosnnrucwwphehhrseefhnnoeretthtmhsaeenpsscehhereemeeatitttsiiosstwhvveeeerrrayypcpttohhlsiiitcnnattsahinnoaddnn rietlaytivceolnyenptoiroonuasl, thhiugshleyffbeecattinegn saunpderriaotrhepreerfxopremnsainvceecaatrbloonwiezrincgogstratdheasn. with conventional highly beaten and rather expensive carbonizing grades. 4. Pulyethylene Laminates AuorPPoeecrrahhraabppossnoosnniezeedoofpfaptthehere4s.mmioPoshostetlyieiintnuhttsyeelrreieensnsettiitnLnhggaemcddoieenmvvabeetiellnosoapptmmieoennnttwssitiihnnvvpooolllvvyiienntgghyltthehneeess.ee pfLLlaauacrrokggraeeogciqqanuuragbanontpnitrittsoiiieebzssleodeofmfpspapopowleylhryeesetrtihehsyytlhlteeehnneiree usccstooezaaeittnneegddtthhppeaaacppnoeedmrrssbfiaaonrrraeemtaiuuobssnieelddwifyifotohrrcph3aaorlsyvvceaattrrehiireyittlsyyecnioocefs.f opobfafarcttrhkhieaeegrppinaacgppheaerrrpaorcoortrbepprlaeiapsmpteeisrrcswbbooohsfaeerrddte,h, eccthoopemmoblbsiyitennrteeehnddyglwwtehinitethh,anttodhhfeeffemmororoimasinsattbuuerirxleeicteyvvlaalppeconohtrraraapannaccddtekalrliiigqsqituuniicigdds. bmaatrerriiearl.chIanrgaecnteerriaslt,ictsheosfectohmebipnoaltyieothnyslehnaev,eobfefeenr raenstreixccteeldleontuspeascwkhageirneg material. In general, these combinations have been restricted to uses where 33002222..00114444 I3MM_MMNNO044885555225533 prs arma emen s INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY H HIi I iit2k "KH it nn aa s eo lHY BH a HHiEE 1 Hi 33002222..00114455 3M MN04855254 "4400 Hn.oG.. bBaRyYeCrE ttphhoeelyyyeaatrrheeyflfrreeeneeeffrcroooammtieenxxgcceeissssiiavvpeepleeixexpdopstuoorespotauopeirorli,elyyooonrr ggtrrheeeaassuyyntmmartaeetaretireaidalsls.s.idW Weh,heeannndtthheea wpfHlhouuioloyrcreoohtcchaahyrralbebsononenexsscciieozzlaiinetnigngntgisrieaassppipapslpltiipaeenlddiceettdoototttohhpeeepnooaeppptpeproroas,stiiicotoeennsstoiihdfd3eee,, uaanwcictroodenenasstttevrraduurccitsetiiitdooyenn,orrfaeenssoudulllltt,as gwrheaicsehs,haese.exTcheellednattareisnisTtaabnlcee XtoLpVeIneitrlalutisotrnatoesf tahiswpidoeintvaqruieitye colfeaoeillsy, greases, etc. The data in Table XLVII illustrates this point quite clearly; Ot Resemwes c Pouvemuvians-- Farin Lowsarss TABLE XLVII OIL RESISTANCE OF I~OLYETHYLENE--PAPER LAMINATES Comucion Construction Wer Wt % F908 ld) FC-805 (solids) pir on paper Lado ebne Lard oil resistance Ha Cromed Flat Creased 05 wipers 0.5 mil polyethylene on 50 ib kraft 10m pobeaviese " . 1.0 mil polyethylene 0 at 0 wan on 50 Ib kraft 0.5 mil polyethylene a on 45 lb kraft dn FCSS 025 Widm sdm treated with FC-805 0 0 0.25 10 days 18 days 11 hr 30+ days 6 days owfwhheverreeeaans2s nnmeeiitlthhsieersr cttfhhfeectFFiCCv-e-88f00o55 attnrryeeaalttmomneegnnptteraaillooonndeeo,,fnntooiermetthhiee rppeooslilyyseteitthnhgyyllteehnneeepeffniilcmnwtotirrfatatethivio0oe.nnn25oo2ffmwtththilees%ooisiilsess,,offlettihchdetesivoccefoofmmFobrCbi-inanSanat0yti5ilooonnancgohoiffpee1v1re//i22sodmamioivllferootiyffmphpeoiolgilnyyheertltehehsvyyielslleteinnnoeefg ccrtheoosemmibspbiteiannnneeecddewtitho0a.2ni5dgwlreta%sses,soleivdesnowfhFeCn-f8o0l5dedaochriecveesssaedv.ery high level of resistance to oils and greases, even when folded or creased. 55.. CCoorrrmuggaatteedd CCaarrttoonnss cartTTorrneeaahtatmsmeebnnettenoofffoceuiitnthdeetrrogtthhreeeaiinlnssyiiddieencoorrreattsheheethooeuuttssseiirddveeicelliainbneierlritooyff oa8f cccooorrrrrruuugggaaattteeeddd cctcahaarerrtttooopnnnass.c.hkaaIIsgnnibnppegaaerrntotiifcfcouumlulaaanrrnd,,ystsouugccrghheraesccayaatrlryttiootninenssmcsrhheaasavvuseeechggthiiavevseesnnbeireenvxxdiccceeeerllallbeetninwlttiitnyppeee,orrffsfopocraromrmreraaunnpgccaaeerteesiidn,n tsshwweeeeIeppptaiiscnnkggaangcctioioncmmgipppoaootufuenndmdd,ta,hnaeeytttec.b.gerseiadseys items such the present as binder twine, spare parts, commercial usages described abovIet,isthaenrteicwiiplaltebde tmhaant ybemsiodrees uthseespfroerstehnetsecofmlumoreorccaiarlbounsasgizeisngdse.scribed above, there will be many more uses for these fluorocarbon sizings. XII XIII. FFlluuoorrooccaarrbboonn PPoollyymmeerrss---P-lPalsatstiiccss A. Imuopucrios 10 Porvsns in wAAhccicccoohrrddmiinanggny1tosmaaacclccleeApp.tmteeodIdlNeTddceReufOfliienDnisiUttiiCcooTonnIm,,ObN3ainppTeooOlltyPyomOmLefeYrorM riimssERttahSheeverrreeyssuullltatroogeffaamorrleeeaacccuttliioeon.n Tinhewhriecahctimoansnybysmwahlilcmh otlheecsueleusnictommoblienceulteosfcoormmbianveertyo flaorrgme tmheolehcrugleer. The reactions by which these unit molecules combine to form the larger 33002222..00114466 I3MM_MMNNO044885555225555 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 4"41 INDUSTRIAL ASPECTS OF FLUORINE CIIEMISTRY mamanoldlcecccuuolnleedssenmmsaaayytittoaankkeereppsllacactceoeniisnn. ttwTwhooeggeeanndeedrriaatlliowwnaayyrses:a:cnntaaiommneesllyyi,,navadoddldviiettiioocnnomrrepeaaoccuttinioodnnsss appinonovsdsossleecvssoesssniinndtggehneuusnnamsstoaiaotntuunorrmaarteteeearddcteicctohhhnaayrsrl.aaeccnTtteeeh,rretsshuuaeccdhhmdoiaatlisseocddnuooluurebebsallceeotfibbooownnnhsdid.c.inhAAvorttelyvyapcpetiicccataololmgaeepxtmoahpemurnlpdtleeso finovromlvpeoslythetehymleonneomwheircehthmyalyeneb,e trheeprmesoelnetceudleassoffolwlhowics:h react together to form polyethylene CH CH (CH which may be represented CH as follows: an On the other hand, connd(eCnHs~at=ioCnHr2e)a--c~ti--o(nCsHi2n-CvoHl2v)e,,-linkoafgerist mol(1e4-) cpOcuounllleeytssmheccerooinonztttaaahtiieninroiinnnhggarrnereedaaacc,cttcitiioovvnneedgigernrnvooosuulappvtsiesowswnhtihhrceiechahlcaotaisrorseenpospfoolisnyloyfvfmuounelnvcctestiiilomoinpnnalkalealagmaneonsdldeoiicfnnuulwwnehihisticucmhchhottlhehae-e5 acwputoaleletyer.mr,,Feohhrryyizddaerrtxooiaoggmenepnnrl,,eeacc,chhltliooorprniioddleieyn,,evsaaotmmlevmrmeosrnoetinhsaiuea,l, lseoettsfcscr..,ootfmthhseetorrhmeeebberyyesaiffmocotrpirmlomeinnimgonfogaalaemmcdauaiclcberaroossiucmmcohcolaleaer-s- bgbclouoyxlxecyyo.llliiFccwohaariccicieddxh,,mamsasuupycclbhhe,e2aa5srepaapoddrilieyppseiieccsntetaareccdiirdde(saaHunnOltddOsaCafdr(odiCmihHhyy)dtdh(rreiCiccOreaaOlal(cccoCotihhHooon:l)oss:uuf0ccahh0dCaaiss(baCeesttHihhczyyl)lceeeannr-ee- gCClOyOc`OOoAls((CwmCHhiiHg2chh)0t2m~0b-a)e-y-.)be.xepreecptreedseinntetdhe(HcOaOseCo(Cf Ht2he)4(cConOdOen(sCaHti,,o)2nOpOolCy(mCeHrs2,)4- ccthooemmAbebsisisnneiminnntigiggahlllitincnkhbkaaaerggaeeecxtssepuureccichhstteaaidsss ttiohnhfeettehehissestteectrallsieinynokkofaafgpgbeetohniieennd,ttchhoaeenndaadebbneooxsvvaceeteipeoetxxnaafmmoprpoplltlyeehmerreeiertnsacf,ilsnu.as- teechnnhececeemeissoostffernyiitninfaccolrrreecaathsshaiiinrnsaggtcytmmeporeoilsoleteficccaruslelaaaocrrftitwwhoeniesi.iggthhystps,e, follow most of bond, and follow most of the except of the conventional for the influ- conventional cfohrem"AmuAlliltsathtshro,youugsfgouhhrchttthhhesiessccttyhhhepeamemtioisgsftitrvemmeanaacyytfioodrdnee.pssoccrlriyibbceeihytthlheeessneee ppabooollyvyemm,eertrhsseppseeeccsiieiesmpiilnnesssiimtmrppullcee ttftuiouarrrlemess"upaalarroeesla,yamstuebbcreeh"ssttacooshnnatllrhyyaactaatepprgppiirsrvtooeixxnciismm.faoatrtSiiopounnocsslhytteooftahuucyntnlodedrenesrerss3tta5aabnnoeddvniiednn.,ggtghssroeoomsmuepeesso,oimff ittphmhlpeeeueersisstrstsueienecns-- twp`iwoahhiliincct"hhsplloeoelafayddmdtteooevribb"arrtaaicnnohccnahh.riiannIcggtteaairnnsisddtwoiocetlsthh.leeerSdsiudtsciasthbtulurifrsbabhacaetnnodccreestsshaaiintntshe stdehtenefrdesucttrgcusrtcouituunrpreset,haaeirxmeaoopsbbusvvruiiimtooieuuedsss Ssppttoorrluiunycctmttsueurrroeesf saadufeffcvehcciatatsiossiidngge.nnpiiIafftiilccyaiamsnnettllwryyiezlttlahhteeeosntppartrbooolpipsemehrortetnidioeessmtheooarfft, mmdooeowsfsettctteshhmyypiddnerrrooatcchtaaeurrrbbaeoosnnosfuttmylyopepwdee CpeihnoteethyrrggemyyecraccsshheasaiuionncfhAccuiaisasssrtidoaoecnnpaoraalbnnyoddmn eaatlrlysiszpooeatcciprorooonlssysstmlo-leiinrnmkskio,innngtgo.h.meseAAerss,delwwofiewilclllttsebbmeheapssseeeereeaennt,v,uerhhneoogwworereevavletoerewr,r, eienffffeetchc`ttAelooctnnahsoppeurrgooohpfpetefrhlrtuetiioresers,o.acraerbnounmteyrpoeusporleyfmereernsc,etsheisne tdhefelcittserhaatvureee(v0enflguorreiantee:r mccoonnctAtaaailitnnhiionsniuggggncchioofnntihdcdaeeennrncesesaaatatriiteoontnnhueppmooplleryyremmoseueernsrsts,,reinnfmeooenrn.eee.ncTooehffsisttihhnaeepsstehpeeehhaaralissstesiarnattttaaluiiarnnreeegeddtopaaafnnrlyyutotccroioonmmbe-e-- dcmduoueemerpcaittaootlnaasdinnsg,niiinfnaiccncooadmmnptcpleileestateetprthuueennsddupeemrrreessdsttaeatnnnhdtdaiittninmtggheeoo. ffnTetsthhthieesdeacccphhaepedmemeiasirwssttirriylynsooleaffergfmAeluauopnoraryoorctcbaatrsorebbaoobknne cttchhaorrrmoobupuoggonhhuussnndiiinsnt,ddeaietnntedesrrummictihiinnsifinpnagrgseiwwsouaanmyysasesdaatnntoddhpammrtoetdhaueencsoenoefhafxcitcogodhmmnebmcbioailndnseieicnnuwggliatlthleheesweesseimmgamahllaltlneepeyrrfRobluduroeuoracrokot-s-- icwatirthbh`oSeeenvxxecucreenapplitttisifoolinnunaaolslruosscctaaahbrbifbialloistnthyyitoayanpnneddaspccohtholeeymmpmiriecocradaslluocrreefessithisshittegaahnnaccdemed..iotlieocnultayrpwe ehiagvhet products obtsined pccooonlnsysSiimeddeveerrersaarabblllfeefolurccmoooermmodmcmearfrercbroicomian.alltytiiphmmeepppotoorertalrayannmfccieeeo.r.rsoFFoeootfrhrthyltetheheenaed,mdmoitocsisohttlnopptrayasoprtite,,uohttrhahoveeeesseetohbiiyntnlavveioonnlleevvd,ee polymers formed from the tetrafluoroethylene, chlorotrifluoroethylene, 33002222..00114477 I3MM_MMNNO044885555225566 w no. mcs H.G. BRYCE vviniinnyyvlaliirddieeonnuees ffclluoumoorbriiiddneea,,taiaonnnddshh4eesxxaacffoilpusooolrryoompperrroospp.yylleeTnnheee,,sceeiitthmheeorrnoaassmehhroosmmooapproeollyypmmreeeprrassroeordr aiffnrnrodomvmaertvvihoaaarurniiseoo,uucsssoomccmhbhelilnooorarfiitninwoeehnissacnnahdds hcfAalotvuopeororialinylnerme-e-seasurdusbyb.sstbTtieithteuuenttseeerddemvddieoeerrnwiieovvdamattiieivvnresessthaerooeffsepmmcrteeeitptohhanaar0ennd3ee aefnrdigeethraannte,nsdomaecroosfowl hpircohpehllaavnetsa.lready been reviewed in the section on refrigerant and aerosol propellants. BB.. PPOOLLYYTTEETTRRAAFFLLUUOORROOEETTHHYYLLEENNE.E in 1TT9ee3tt3rraaffflruuooomrrooteehttehhyypllreenoneed,,uCCca2oFFf4,,dwweacaossmffipirorssstiitissiooollnaatteoedfd bcbyayrRRbuoufnffftaaenntddafBBlrureoetrtssiccdhhennieenitiddheeerr eeyinlleecc1ntt9rr3iicc3taafrorrhcofc(mnhAeiuL,tohrseCCo-2poFFilr4eofdiccsunaascnntuaaosllssifoondgbbeetechoeppmrrceepoppomaasprriteeoiddounnbbdyyo,fttChchFeeaarggbCeeIonnCneeFrrtSaaeClltIramm.feletuTthhohooreidddmeffoooidrnretttrihhlneee scpcyyoornmmotmlhmeyersesicriscsiiaoaollff fClppuHrroooFrddo.uu-CcocItlteiiofoiinnnnsaooufsfsiilnttvegeetrtrtrahoaferlfutcpooolrrmoaotecpittohnhuyyunllmedenn,teeuCbFeiis2sCatbbICyyteFm2ttphCheeeIr.aTntnouhonrencecamsattoaaabydioytevtireincc. 6p5y0roCly.siTshoef rCeHacFt2ioCn1s iinnvoalsvieldvearreorrepplraetsinenutmedtbuybethaetftoelmlopweirnagtuerqeusataibonosv:e 650C. The reactions Hen involved crcl are represented by the following w equations: CHCla -+ CHF~C1 (15) HRCI CFam CR + HCH ao eTTthhheeyleyyinieeelldds. affrrocomomlorttlhheiissss,rr2eeoCaadHccottrFiilo2oeCnnsIsii~ssgaCrrseFepp~wooi=rtrttheCeddaFll~byyo+i99l002iHngCttoo1po99i55n%t%111o1f9')',). 7TT6ee6ttrraaCflluuaoonr(rd1oo6-a-) arferbteehsceyezilnienncneggoe fppisoooiainxntcytogooleoffnrl---ae11sns00d,22wo..5id5tohCCrl,e,vsawwsrhihgoiiauccsshhwstcciaatabhnnilaibbzeebeorsssitltoisonrurgeecddhpouuaisnnnddpteieornrfeppn-rre7ee6ssss.6uurreeCiiannnttdhheea taebtsreTTaneefctlterroaarofuoflueootorxboryyoelgeteethnhnyeylalene(nndTeeEw_Epip)othollyvwymahmeriirecoirhuizzseeisssstaabvvieelwirrzhyyeitrserr,eseauadddcieihllnyysaes,pttooiahiegnppherrlo.oydduucccreeystapploolillynye- tllieinintnreetaaahfrreluppopoorrlloeyyesmmteehrney.crl.eenOOoenfn w(2aTacctFoeoErmm)mmweirwetcrhhciiiacaflhlicssciiesaealnleat,, ttwmhhiheexitippenoo,gllyydammeennerdsrieizzt,aaettmhiipoiogennrhalissytuccrcaaerrryrriisceteoaddnltloorinuoutelt ianndthweitphreisneitnicaetorosfswucahteraswpiotthasesfifiucmi,enstomdiiuxmin,goranadmmteomnpieurmatuperersuclofnttcrso,l ooafxinxsydytggewesnniu,,tchchheiyynsddiftrruiooaltggoeerpnnsolsppyuemecrerhoorxixaizisddaeetp,,iootnaaansnsdwdiausmppee,rrrosoeoxpxodyyriutooemrrdgg,aaonbnriyiccaPmcclmouonmomknpeptiouotumnuidnnpsdtenrs1as9.uL4lf1aTT0t3ehh)see, sfIIiunnrpsetttrhhsaiiusstcmcccoaeasssspeesh,,feurltthihceepocpployoonmlldyyiemmtreiierzorianiztzsiaaottwniihooinnwleaoosffthrtteeeepttrmoraoarfftlneuioduomorroeboeryetthhwyPyalllesuennneebkeeooitcntccgcuuinrsrrroeer1dd9e4d1uu(nn1idd~ne4erLar sscCuyyylspliitennedrdaemert.rmu. soiBBsnprgruhubebcaraaitkkcaeelrrycsotrrnseedppoiootnirrottanssscttowhhmeehmielffreiicrrssittthaelaaqqsmuuceoeaoonuuolssmee.eermmuPwuloallsssyiitoobennterinppfogoilvlyyosmmrtoeoerrceritidzhzayatlitnieioonnnea s(yFstEem) (aTs FhEig)h uhh3asa5issn9grr,ee0lcl0aaa0tttii,avv0leey0ll0syy.ts hhToiinghghhea mmchoeoolamletecmcuouelflraacrfrioawrwlemesiacigtgahilhetot(ssnl,Z, ~orr)fa.annPpggaoiilnlnyvggctetfftrrrraaooffmlmvuoor44ro00oc00et,,t0hh0y00yl00leennttoceo aff"rTsrohoimhmsigftthahhceetammssoho9onn,uo0olm0mde0,reb0r,e0, 0caa.apprppTeeefhauarelrslsyhtteoboaotbbreenoefiinnifnotthrhmmeeinarratdainongignnee ocooofffn2p2s0i0odlttyeoortei33tnr55gafkktlehcuaaeollrpoppreeeortrphemmyroltoelinlceees. oorTfefhqttiuhshieerfaeppdcootlltsyoyhmmboeerurreldsookffbaetteeccttriaarrrffeblofuournolo-rlcytotoehb-thycolyarenrlenbeneoei.nn. bmIIottinniwddillilinnbbaeecofrrnleeusccioaadrlleollerceidadnrgttbhhotaanhtteittsphhareeobopeeunneteretrrig8gey3ys ereaqluipreerd ekcaall ppeerr mmmtoooloellb.eereaaIantnkdds.tatthhcheaaatntrobnoofofnttt-shthoueer-cpccaraarirrbbsboioonnnng--fbftluohuoanotrdriitnnihneee pabboofnnluoddoriiosslocaaafpprptpbycrrotoonaxxfiimilmsmuaoaatrtbeeeoollcyuytthr11y181-636=. kecnael perlemsso.lset.aIbtleisttohehnignhottesmupreprraistiunrgesthoart thhiegphoelynmeregryorfatdeitaratiflounosrooeurthcyes- lene is less stable to high temperatures or high energy radiation sources 33002222..00114488 I3MM_MMNNo044885555225577 INDUSTRINL ASPECTS OF FLUORINE CHEMISTRY ww INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 443 ttthhhaeannpaosalisyimmmpeprlleefrffollumuoortrohoeccaamrrobbononnomsseuuccrhhi aassmuCCcysFFhylsly,owiseinnrcceethttahhneeteehnanteeorrgfgyyeiootffhffeororrmtmhaaettiiCoonn--ooCff tooohrfretCChpe---o-lpFFyrmobbpeooernrndftdsriso.e.msTTohthfheeeAssueemopproooonicionnamttrssbewworiniillslpmbboeelucyccomhonensrlsoisiwddeieerrrneeatddhtaffeunurrtthrhsaeettrcithoininfoettneh.eriethleiiggrhhtthtoeoffsCsoo-m-mCee coafrthbOOeoffnpccrpoooouuplrreyssremet,e,ierttsshhaoeesssfeefclussoaoammrmpoeeacraeeernnbdeeorrn1gg0yyptoerrlueyeellmaatyteiiodrosnrnsosinhhciiapaprsslbaaatoelinsroosmeoeeclxxteiiiscsotutnl.aaemsm,oonnatgg lhheayysddtrroos-o- dcffaaairrrsb2aostontthhtpeheorermlmypaamrlleesoorerrsnrrcaaaesddiiocaafottimitoohnpneaddrheeeidggghrratloadydatrtraeiuoatecnitahaoirrvyneedccrCooonnccacereHrbrnnoeendd,,mbbboouunltetdacaru3re5eleooscf,ofttneaetntnralmmseataasesskdtkeesdtdo.o thedue the very inert --C--F to the presence of very inert --C--F bond. the highly bond. reactive --C--H bond as contrasted to Tans xiv TABLE XL~,'II I Wen Los or TFE ar Varions Trstmaarnssi WEIGHT Loss OF TFE AT VARIOUS TEMPERATURES(I16) Tampere Weights Temperature Et) (C) "Weight loss wo ooo 204 0.0002~ To ooo 260 0.0002~ I316 0.0002~ Mo door 360 0.001~ eo owe 390 0.006~ wm ow 420 0.09v Tot conducted on gree melding por Test conducted on granular molding powder. Te combed on etded sect Test conducted on molded sheet. thoTu"Tghhhee sddmaaatltaal,iinnch"TaTanabgblelees XXocLLcVuVIrLIrIiIIngiillliulnsstttrhraestecpssoltthyhteeetffaarccattfittohhraaottettthhheeyrrleeenaaerreemoddleeefficinnuilitteee,s, theehvveoeesunnegsahwttesittmgeehmamtlpple,lerorcasahtstaeuunsrrgeeaessrse5aoassscslcloooucwwriraiaatnssegd22iw0n0i00tthChe(C1t1hpUe6o,)le.yvtIIoettlturhhataafilssounobbroeeofeeenngthaddsyeeeletoteneurresmmdmiinenoeeclddeocmtuthhpleaaostt tsSihittteriiusoocenntu:ppwrrraeooligddhuudtcectfltossescsaatesnnsddaiaarnetttrelaoessdasuseotcceiaaadtttettddeeummrwpipeinetgrhr.aattthuupreoreelesysvmoebbreleuillotzoiwaowtni44oo00nf00gwCCaistemmhoaauyyesndbbeereegcioddemuuseepoottofopfsfortorirrumnmccaaittuptiiarooalnnl prdllooeowdfweueeccrrtts ttfhihonaartnnrmoedcdeuiittcihhseeedrrthedt~uhmheroienn--g-o--mC epCro---,l-yCC mC--ae-Fr-i,oozcartw-i--io-tnCCh ---wt-riFFathce bbeaoonmnneoddrsugs.n.ietssTThhooeeff pprriondcuicptasl spurcohduacstCfFoyr,mCeadFeis, CeFs. the monomer, C~F4, with trace amounts of products such as CF4, CaF~, C4F8. 1. Mechanical Propertis XLITTXy.yppiicTcahalle mmleoecwcheharannieicncaealrlgppy1.rrcooMhppaeerecractichiteeaessnriicffsoaotrrilcPsTTroEFofpEEetrhtppieellsaapssotiilccymaaerrree aggriievveeennxhiiinnbitTTeaadbblileen XttthhhLeaetIoXeefxx.tttrrTheeemhmeeaelnlylyaolwolloegowrowuesnccehooreyegffdfycriicociecehnanatrtrssbaoconoteffrpilffsarrtsiiitcccitsitcoionofn~nth69e),, spproximatcly one-ith polymer are exhibited in approximately one-fifth tehxattrT"eToamafbbetlllheeyeLLawnissadhlheooogwwtosseumsptthhehaaryttadtrTTuorFcFeaErbraorrenengssiiepnn,lssasfrrtrieecomm.maaiinn20tto0ouuggChh aatnnodd ossvtterrroonn2gg50oovvCee.rr 2Aan0t extremely wide temperature range, from -200C to over 250C. At 33002222..00114499 I3MM_MMNNO044885555225588 " nc. mvc 444 H.C. BRYCE 196C, for example, TF polymers deform at approximately the same -196C, for example, TFE polymers deform at approximately the same yield stess 353 dete meta, sucha annealed coppe9r. yield stress as a ductile metal, such as annealed copper(US). `While the clongation value of 6% at ~ 196C is substantially ower While the elongation value of 6% at -196C is substantially lower than the value at room temperature, namely 40%, it is adequate for most than the value at room temperature, namely 40%, it is adequate for most low temperature applications. low temperature applications. Tame xx TABLE XLIX ---- TYPICAL MECHANICAL PROPERTIES OF POLYTETRAFLUOROETHYLENE AT 25C(I16) Proers AST met Property ASTM method Specie sy Specific gravity Tot wong 5) Tensile strength (psi) Modulus of elasticity in tension Eitan Elongation (%) Ficora sevngth (os) Elexural strength (psi) Fiona madi (a) Flexurai modulus (psi) Compromise 1 15 off 0) Cornpressive strength at 1% offset (psi) Domain ne od, 1500p SC, 20H 5) Deformation under load, 1200 psi, 50C, 24 hr (%) npc name (20D) pin Impact strength (IZOD) ft lb per in. Frdris, Rodel D Hardness, Rockweli D Coron of oi ss pth sesh Coefficient of friction against polished steel nam | 2.13-2.20 Wooo 1500-3000 58,000 psi oss 100-350 Dime Did not break Honsoon 50,000-90,000 wo600 A4-8 So3.0 ois50-65 or0.04 pms D-792-50 Dwar D-638-52T I)-747 pest D-638-52T DoT D-790-49T Dory D-747-50 fori D-695-52T Dar D-621-51 Dia D-256-47T Dear D-676-49T Tame TABLE L EFFECT Foe Property Come Compressive dois yield strength ke(psi) BomimGo Elongation (%) OF TEMPERATURE ON PROPERTIES OF TFE -WGC_-we we BC -- 196C - 80C - 40C 23 C GT Ww (1) (1) (1) (2) now aw mo we 11,000 4200 2800 1600 S68 ow 0 5-6 8 30 40 RESh~S(lt8) 10C WC 100C @@ (2) ww 700 = = -- 260C (2) 220 -- C5 mow m0 -- wwe mw ew Flexural modulus (psi) 850,000 277,000 -- 80,700 28,700 6500 polyUUmnnellriiskkeedmmoanannoyyt hhbyyeddcrroooccmaaerrbbboornnilooerr ooarrtggaalnnoiiwcc tddeeemrriipvveeerddatmmuarateetee.riiaaAllsts,, tffellumuoporerorocacatarurbrboeonsn {bpthehorhcloyaouvmugigeohhrroosuuutdtpottthhoneeoitirthessbeeeerrlcvvaoiisccmteeiec rrlabainmrniiggttt.eol-e--W-bbhaootettnhhlowthhhiigegthhelmiaampinnteddrialltouorwrewea---sc-.ththheAdee,ytyptslseahhmsootpwiwecrdeeaelltaufasosrtreii-csc bmeahtaivoinotraukpestpolatchee, elastic limit. When the limit is reached, plastic defor- mation takes place. 2. Chemical Resitance the ITpttliissaioobbnvviiaoomuuisslytth.haatBteppsooilldyyet2tsee.tbtreCraifahlnfeugumoarcircohoaeeelmtthiRhyceyalsellinnslteeyiansiiscaneacnne oo0uuttasslttlaantnddyiipnnegg ommfeeommrbdbieenrrarooyff the plastics family. Besides being chemically inert to all types of ordinary 3300222..00115500 I3MM_MMNNO0A4B8S555225509 INDUSTRIAL ASPECTS OF FLUGRINE CHEMISTRY ws INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 445 tccohheewmmaiticceaarll,ss nwwoiinttfhhiattmhhmeeabeelxxecc,eepptatiinoodnn hooaffs mmeoxolclteteepnntioaanllkallalli,r,esiittisiitssanaacllessootonnoodnentaaebbrsisooorrrapptttiiinvvgee. effects of to water, effects of weatheting nonflammable, weathering. and has exceptional resistance to deteriorating 3. Buctical Properties triccAAossnisistsassnhhtooswwannndiinndTTiasabbilpleeaLiL3Io.In,,fETTalceFFtcEoEtrrpiscopaloelvlyyPemmnreooervprseesprrptovioseesssrseeysswssiuudnneuusfsuruaealqllluyyenllocoywwraddniieglleeescc.-tTrhicecyonasltsaonthsaavned hdiisgshipdaiteiolenctfraicctosrstreevnegntho,vevrovleurmyewrideseisftrievqituieens,cyarnadngaersc. Ttley also have high dielectric strength, volume resistivities, and arc resistance. TALE 11 TABLE LI Eten Boreas or Potrerascsormiriene xt 35C ELECTRICAL PROPERTIES OF POLYTETRAFLUOROETHYLENE AT 25aC Dic omtnrt 80 1i00xcls 22 Dielectric constant 60 .10~ cycles Dintor 1a -100cnae. < D002 Dissipation factor 60-106 cycles Dire sng (vis per mi) 40-600 Dielectric strength (voIts per mil) Vara ssi ohn po er) 10% Volume resistivity (ohms per cm) areine (0) EY Arc resistance (sec) 2.2 < 0.0002 400-600 > 1016 > 300 4.Radiation Resistance on T"TphhoeelyddtaaettatariisnnuToTraaobbellteehLLylIIeI4n.ssehhiRoDoaw.wdssiattthhIitoeeneeifRsffeecsiotfosbtofavefniXXco-ceu-rsratayytaahnnatdd ggwaimatmhra rrraaadddiiiaatttiiiooonnn dodroeonssseuelsspteieoxnxlcgyceteieeentdrdraiiafnnltgguhoe00rr..o11pemrmtheoeygnglaoearunranead(cd1ses1dtt7hh)cee.hrraeenIiigtseaasirrsiaantthhboeeobrrtvshsiteeovhvueeesrreeelaatehccctattiirtooinncoawolnniatththnhdemrppeaoocdllhyiyaammtneieoirrn.,, rceceaolslmuppplrtarioornppegeedrritntwiieierstsahtohoftef hrttohphseerorppneoooplluoyynrmmcteeeerddr.. fcIIhffaatntokhhgeenesoddrwioonsnsaabggoAeeutsshoriitnohncccelalueurdldbeeeocddntrisiicntnarlTuTcaaatnbbudlrleeem,sLLeuIcITchI haaan3rri5ee- compared with those reported for a known fluorocarbon structure, such as TABLE Lit Eire or Rasarion or ProTrAaBruLsE oLsIIPosxcauvonoemusssat' EFFECT OF RADIATION OF PROPERTIES OF POLYTETRAFLUOROETI-IYLENE(117) 50 kv X-radiation in 10 s mm Hg Tin Radiation Gompe Diccriccomsan dosage (nde) aps The (megarads) Dielectric constant 60 cps 1 kc Divpstonfactor Dissipation factor 0a Lhe 60 cps 1 kc To as 0 os Tm 0.5 Si im 2.1 4G 4.3 35 In 9.9 56 im 17.6 2.08 2.08 2.12 2.23 2,33 2.20 am2.08 am2.08 dm2.08 IR2.12 an2.12 Im2.08 <om <2 0.001 Com0.024 ow0.144 am0.239 awe0.408 oe0.168 <om < 0.001 Comm0.003 oom0.017 ame0.036 oom0.048 ow0.019 - vacuum Sues Volume Surface soir ressvony resistivity (ohmperan) (om percm) (ohms per cma) Volume resistivity (ohm per cm) sxior 5 x 10~7 dexox 4.8 x 10vt dexim 1.9 x ~0la oxi 2.0 x 10~a kim 4.1 x 10is sya 5.3 x 10la on10xs aici 1.1 x 1017 dixie 3.1 x 10i~ esa 6.9 x 10~ 33 xioe 2.3 x 1016 17aioe 1.7 x 101~ Comotr eillneneeds) (Continued on following page) 33002222..00115511 33MM_MMNNO044885555226600 " - hgahin[TTm oaoa lE aWwS o1tT mCoiosinm =s-- mn iwme 446 H.G. BRYCE TABLE LII (Continued) Gamma radiation--Co 60 Isotope Source(ng~ Radiation dosage ]In air at 1 atm Tensile Elongation strength In 10-6 mm Hg vacuum Tensile strength Elongation (megarads) Tm wm ww 0 LgowZ 4 =C== 0.1 (psi) 3000 1882 (~/o) 165 152 (psi) 3000 -- (}/o) 165 -- 0.5 1539 37 -- -- 1.0 1388 21 2481 92 5.0 1322 -- 1972 73 51.0 1462 38 Cui obvi tt he omer of kyon i ch lo C8Fls, it is obvious that the polymer of tetrafluoroethylene is much less rs stable to degradation by radiation than would be expected for a simple Rn BL ne ore ena 0p nh --CF2--CF2--CF2--CF2-- structure. For example, even at 100 megarads anos there is less tkan 20% change produced in the C8F18 molecule. It is reto tn nb ee dp ported that polytetrafluoroethylene is considerably more stable to degradet ere as ation by radiation in the absence of oxygen or in a vacuum(t20). 5. Comat 5. Crystallinity aprose sommes placc it i e ply As produced commercially, polytetrafluoroethylene exists in a partially an se nL crystalline state. Depending on previous heating or cooling history, the prasad degree of crystallinity ranges generally from 40 to 60%. mig of an at vo spc sity of The relationship of per cent crystallinity to true specific gravity of TEE i ns os ot pedo TFE-fluorocarbon resins is shown in Fig. 83. It should be pointed out ee pr es that many of the true properties of polytetrafluoroethylene polymers are a ito os ot ie et ow hyre. somewhat difficult to attain. This is due to the inherent low energy propera sea rm amr ties of fluorocarbon molecules, which~as has been shown earlier--results eer in very low intermolecular forces. In consequence, it is difficult to force tke A SE very large polymer molecules to stick to each other; hence, polytetraEe vt ns ey fluoroethylene, unless handled very carefully, may contain a relatively ei large percentage of microvoids ranging down in size to molecular dimenae ety bovine sy sions. Therefore, although the relationship between true specific gravity a nh and per cent crystallinity is very direct, in actual practice the measured py rin, 3 Ova re fw specific gravity may not correlate at all. Obviously, the presence of voids md espso ro orm of may very seriously affect many of the properties of any shape or form of pa the TFE polymer(~a~). 33002222..00115522 sw_vosssszot 3M MN04855261 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY wr INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 447 pd ie 2O o 2.00 ! 2AO 2.20 2~30 Fi. 8. Toe pci gaiofpolytetareacyulncnosn ofcpl. True Specific G~'~vity FI~. 83. True specific gravity of potytetrafluoroethylene as a function of crystallinity. TanLE Ln TABLE LIII Commameni Avniancs Foros os Povrrwssomormenist COMMERCIALLY AVAILABLE FORMS OF POLYTETRAFLUOROETHYLENE Type Description tener: pups ing power I General purpose molding powder. percged or god 5 Molding powder specifically granulated for molding cylinders of skive type. Poder or esin xin of till bua ond nd. 6 Powder for use in extrusion of thin-wall tubular goods and tapes. 7 Spe pope ane mingponds onein mong 7 SpeciaI purpose ultrafine molding powder for use in molding pes a ing onde or done pe. shapes and molding cylinders for skieve tapes. 0 Adueos diaper for wt in cing, imprgrin, 3nd 30 Aqueous dispersion for use in coating, impregnation, and casting processes. 33002222..00115533 I3MM_MMNNo0d4s8s5s5226622 ws no. mer 448 ~. G, BRYCE the "TlTehhneegtddheeoggfrreeteeimooeffdccurrryyissnttagallllfiiannbiirttyiycaiistsicocononntthtrraootllllteehdde mbbayytemmroiolalelecciusullmaaarrinwwteeaiiiggnhhettdsawnniddthbbiyyn tttahhhveeeeteleemmdnpigpsetcehruraasotstfueutrdieemarretaanlndegguneergifftnoohgsr trrfahaaepbpiirdidiccncrafyrltysiuotseantnlacllteilhoizzaafatttitidohoenengrm((e33ea00ot00e-f-r33ica22r7l7ysiCstC)am.)l.laSiSiennevitvateeyirrnaaaellwndwodwrovkriokethierdirsnss oohnnavttePhhoeedliyppstrcreooutppsresearefrtdtiiiveeoassrtooolfeeftnffhgaaybbtlhreriinctcehaaetteeidsidnTTfmlFuFaEeEdn-e-cffeluuaooovrfarioodlcceaagabrlrrbeeboenncoorrfemescmsirnieysnr(ssctt2(ia?1al1,l1l1i2l%n~2yi-.t)y. uannddervotihdes tatrrnaadddPeeCommolamyarprtkeka,t,nrya""f.TTleuefofItllrooosnen"t"ahvyFFallileulunaooberrlooeccisaainrrbbmsooeavnnedrRReaeelssaiifnvno,a,rimbblaayyb,lttehthheeecEEo.m.moI1s..mtddeiurmcPpuioaolnrlttyPdadeneutoNnNoedfemenmwrohouitturhcrshes arc indicated in Table LIT, and Company. It is available are indicated in Table I,III. in several forms, the most important of which 6. Fabrication Techniques a. Compression Molding 6. Fabrication Techniques aw.itCh"ToIhthmeeepcmrmheonsolislqdidouiinennsgg~VoosIiffomlppidoolinlalgyryttetetocraatffhlluooosreroocuetstkheyydlleeinnnee p(('oFI'FwFEEe)r) ppmllaesstttaiilcslsuiirssgaayccccaoonmmdpplilinisshhteehdde wpriothcestescihngnioqfuceesrasmimicisla.rGrtoantuhloasre puoswedderinispcoowmpdreersmseedtalalturrgoyomantdemipnertkaebttpuuarrrokeeceeduusnnsodidrneegsrrionaatfeppcrrreeeerdssassmiuunrirceeason.ooffGv22er00an00no00urltatoorup1i1o00d,,w00b0d0a00etrphsisismi;;acioaanmnntddapirttenhhseeesderrdaeetssauuatllttrtiionenomggmpepprrrteaeeftmfouoprrrmeemraoiif-ss 3nb3o77atk00e1thd0oavo33e9r955saiCnCttreuuurnneettidimlleihtlnheteainenengntotiipvrroeeeinnpptoierbcfeuilhtuhaiaddssorcbrceeasaatchcehhhaemevddeaittn8hhteeatirggnaelenlsdssitttaaaittteoe.na. TtTteehhmmiipsspeerrreerasastiitnuunrrddeeooeeaotssf p3n32o2o7l7tyhCCma,e,vreaatttaowwthtrhhiuiecechhammtteoeelrmmtpipnphegeorrauaptstouuirroneert eiibttulctchhfdaaoonnregmgse.esshFaffovrrroeommtahitaanrnnanseeesscsitsstieeiononntntisiaatellwllmyhyipcccerrhryyasstdttuoaarllellniinonateet prrmeeooqqllyuudimirraeeenrdaacctpoccluuartrhcaaeettedeanccmoonaontnrtrprooohllvoeouonffs wddohiirmmeergeneenslsifiiofoobnnrsasm,,k.ttehhFdeeofprprrreteeehfwfiooinrrtmmsheoiicussttirroeenpmmsrooewvvseehuddicehffraropdopmomlienttdhho.eet HmHthoooewwledpeviavceneererd,, pwwlhathecreearrndeesifaaneccrccarunuerrdoaatvtdeeierncceoocwntnthltryreoorflelrooiotffmisssthhbhaaaeppkeeoevdaaennfnrddeteddoiiwmmiecetnhonslosdiuiootcnnpossirenaaiscrsneeugiirmdemipapcoporwptrhtlaaienenrtdt,e., tptphhrreeeessppssiuiuecrrcceeee,-ooiifssf ctttorhhaoeelnisonofgrre.ddreerWrerdhooefdfri22ree00cv00te00lryyppfsscriioommiissplaatheppepxpllsoiiehvedadepntteootsoccaoaonncttrorreolodqlluicddroiiemimdne,eirnnstgshiieoodnnipessrwewwfhhhoieirlrlemee tmmahaaecyyopblbideeecdrerieecimmscoocavvoveieotddlyinffgarro.nomdW m oofhvvoereercennedvwwhehuiriynlledecessorttmillplprliieennsxtsthhuseehrgeageple1el0ssstt1aaar0tte,ee0raa0en0nqddutioqqrueu2idi0cc,,kk0tllhy0ye0ppppllaraceaiefcodienrimitdnno Sasrhheacapsopetle.d.edFtFihoeoarrncahh3vee/iaabtyvviyyna. nsstdeehccetftioipoorrnncsees,,fdossruuumnccdkhiesr3[aespftrrreioosnddsusstrheeaanntmoddoltt1udu0bb,ed0esu0s,r,0ihhntaaogvvit2innh0gge,0b0ttahh0kiicicpknksnngieesssinssteeetossp gacarnrneaddcakttteshhreeatnhppdarreneoffot3orh/rm4emrinppi.rrmeetpshsesseruufrrpeeecretiiifssoonrmmmsa.aiininAsttaaleiifnfniteendsdinhewwtdhhh,ieillmeemococloolddoleliddinnuggprainttcootg aatmvvhaooeiyiddbabsskehhirrnriignenakksdaatiegglpeey cmraacchkisneanddtootghievre ismecpuerrafteectdioinmes.nsAionfisn.ished, molded part may be readily machined to give accurate dimensions. bb.. RRaamm EExxttrruussiioonn indiBBceaestsieidddeessabttohhveee,uussveearioooffusccoofmmopprrremesasssiciooannn mbmoeollmddiainndgge ppurrsooiccneegdduurrrcaesms,, essxuutccrhhusi3aossntthphoroosse-e iccrneeeddcduiiurcprearestos.ec.datTTihahnbiigossvrppearr,oomccveeaossrrssioiaiunnsvvsoocfllorvvereemwsssccaooncmmdapnpatachbcteetininnmggfoattrdhhceeeinuccgoosliltnddhgeppoorcawwomdmdeperearxcwwttirieuttdhshioeepniiotthwhpeedrrreor1artehcriopurgohcaatinhgeatraemd diocr wahesrcerewit iasnsdinttehreend. foArcvinagritthy.eofcosmhappaecsteadndpofwordmesr through a heated die where it is sintered. A variety of shapes and forms 33002222..00115544 I3MM_MMNNo044885555226633 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 449 ctcoaannvibbveee ppserrohoiddcuuhccheeaddvebbyythttihhciikssnemmsesetethshoooddf;0; .ffoo0rr6etex0xoaamm0p.pl3le0e,,fn.ccoooaattiinrnegglssatmmiavaeyylybbteehiaacpkppplrlioieeddds otor wtuibreeswmhaicyhlhiakveweistheicbkenseastsiessfaocfto0r.i0l6y0fotorm0ed.3.0 in. or relatively thick rods or tubes may likewise be satisfactorily formed. ce.. AAqquueoouss DDiissppeerrssiioonnss as 2T"Tmhhieelkaayqq-uuweheoiotuuess lddiiiqssuppieedrrssciiooonnnsiffsotorirmnmg ooofff vppeoorllyyyttseemtrraaalfflllupooarrrootceitcthhleyyslleeonnfeetihisse sspuuopplppyllmiieeedrd carreosessaiaitnnimnssgiuultkssopype-etwnhndedheeistdduerfiilnainqcuewwiadoatfetercr.o.nsusTTbihshsittiissrnagtiisesofsaauvcccehoornynavvsesenmmineeiatenltaln.ltpaommreeteitccthehleroosaddmoioofcfftghaaleappspppsllooyyliiynnmgagneya3r `cmoaatteirnigaltowhthicehsucrafnacteeorf abseubsusbtrjaetcetesductho 3as bmakeitanlgotrecmeprearmaticurgelas3s50orCantyo m3S6wa0teSeCir.in.aclewthhiechpalcyatnetlartaeiruobreocstuhbyjleecnteeddoteosanbotakhianvgeteatmrpueeramtuelreti3ng50poCintto, iiattvacciaaSlnnainnbnolcoetet ftbboheere eempxxeotltrrleuyudtdpeeertddoracfooelrsrusoiiirnnbojjieeectchrttieiyosolnniesnmm.eooldldodeeesdd using conventional techniques not have a true melting point, using conventional techniques available for melt processible resins. C. CioromurLonoETvLENE Pov ~25CChhlClooraroonttderiffillsuupooCrrreo.opceaCtthrhHeyyLdllOeeRinnnOeeTaRliissmIFoLasaUtOccqoRoullOaooErnrltTleeiHsstsYsa,,tLiEovoNeddEooyrrPillOeeelLssdssYsMfggEraaRsosSmwwthhhieiccfhhlubbooroiiilnlssateaadtt p-r2o8ducCt,anCdF:iCsIpCrFeCplasre.dTihnealrmeaocsttiqonuarnatiytatbiveeryepierledssenftroedmatshefofllluoowrsinated product, CF2CICFC12. CTRheICK ZEONCF reaction may be m CFL represented as follows: an CaChnhldloiorsrootrteeriaiffdlliuulooyrroopecottlhhyyymlleeernnisezCeFmm~d2aaCbyy1yCIbb,p-CeeeIr~ossZxttnaia-bdbEieTillOiiczHzae,etdCdalFy2ddsuut=rsriiCtnnoFggCt1hssettooprroaalggyeemebbryy. iiAnnhhviiabbriiitt(oeo1trr7sys) aooofrnf dimmneiestatqhhreuooaedddossiulysaarrpeeemouaalyvvlmasaiiielloarbnbilzlesee,,dyiibsnnyctcllpeuueddmr9iiosnn.xggidppeoollcyyammtaeerlyriiszztasatttiiooonnthiienn mass, in polymer. mass, in solution, A variety solution, foorrei,PPnooalclqyylucacsehhiollfoouirrseoodterrmii3fil8uuuloso3riroooncemtetshhlyyytsllteeepnmnreeos(chh~eaas~sssLiaablmmeeelrltieisnniggn ppwooiiitnntht ootffyp22i11c33alCC;t;heiittrimisso,,pltthahseertreei--c apfporrloroopepe,reetrxcitilieiaesbss,is.itfsLiLeisidkkoeemaes.ppooclalhyyattrmeeattcerrtalaetffrluiupsoortrroioocccesettshhwsyyihlblieelencnehe,,raerttshehiniimssowfurlouietrohtoroyctpcyaiapcrraibbclooaonnlfttttyhyspepreepmoppolooypllmlyyaemmsrteieirccr Tanplaahsttoeuurrepeexrtthehhsibaaeninntcsttehhseeoofmpprrteoohpepcehercrathtriliaeeocssrtwiewhnreiihscitachitchsoaamrweedhouuisecsusuhaaliallnlryyetraamossdssouoorccceeiiaatattyeepbddiocwwnaidlitthohoffflliulutoosorwrpoeocorcalaryerbmnboeonernsrgis.yc. ofTtthhhcaaoennmcpemiretehirseeirtncttchaheehleoCCsefi---tg-hrCnCeifcooihrrslonCCre--i-n-FheFabvaboetonomndmosdl.sde.ocTTuehlhseaeirnhctlwhroeoloridrgouohtcttrresiiffaliuuobortorohonecedttrhhoayyfnllgeeloennweeoefpproo3lel0yyn0mme,er0egr0rys0s oH1to0fo.m4c4oo00pm00o,,0m0l00ye00mriewwcrhahisliccshhoigfnaaerirfetcircmmaafunulcccuehhorholoaoewv;tveeherymrlttoehhnlaeacncnuttlhahoroswse eooiffghtththsee iccnoommthmmeerercaricnaigalelllyyofaav3va0ai0ill,ai0bb0ll0ee homopolymers of tetrafluoroethylene. 1. Mechanical Properties Typical noteTiysptihceal fmamcetecchthahaanntiicCcaaTll F1ppE.rrooMpppeeoerrcltthyiieaemssneircaaarhrleeaPsiirnaoncpcrlleeuurldtadieteeiddsveliinyn hTTiaagbbhlleetenLLsiIIVlVe~G~s22t06r,)e.ngOOtfhf wwSnitotirttehhencegilstloohntn;hggeanatatfiiamoocenntliiytnhn,tathhtSeeCH11OT00F00p--E2s2000p0%ao7tl,y0mrr.aaenn2rgg%eeh..aosIIfttshaehata,rsesrleaaAltrsiaevtleaciltyovivmeheplliayygrhhheiidtggehhn1sccioolpemmoplsprtyrer-eessTnssFgiiEvvth,ee strength; namely, 5440 psi at 0.2% offset. As compared to poly-TFE, 33002222..00115555 I3MM_MMNNo044885555226644 #45500 m wer G, BRYCE phpaoorlldyye-r-C,CTaTFnFEdEhhhaaasssmaaucmmhuuchcihhghhheiirgghhreeerrsicsctooammnpcprereetssossidivveeefossrttmrraeetnniggotthnh;uniittdeiisrs ccloosndns,siiddeerraabbllyy hhaorwd(CseCTrT,tFFhaEeEnddppioohfllafyyesmmrmeeenrrucssechhhiaanhvvieregehddseieesrfftiinranenitcseeiesccttarroynysdsctteeaaflltolloiirnnmdeeaetccfohihaorarmnraacaucttnetierdor.en.rTTu<hnh1deeesddrpaaplttloaaiaediindn. FFlioigga.d. 85o44f as11hp00po00rw00osppxsistihimaaeastsdeailfyfffueurnn4eccn0ttcii,oeonnoincofrfryttesetsmeiasltplamiennrcepaetucterooemfrdpfoeoafrarroraetsmdsppaueettcicooirimnmoeeneunenn.odoetfrhtthahaten ppialslpaapsssttlbiiieccowduwhtlihocia6chdh5io%issf ctacrpreypysrsrtaaotlxaliilbnmoel(ani1tdn2eie6lyn)..g 4OOb0b%ebvtviwoioeucuesrnslylyysp,t,oallttlyhihnmeeeerccrcrcyoyshmstataiaplnlallsiri;neneedhessntttocaaettee,ontppehrreoovtvmhiiddauetecsshismmguruacecbhahot..eurtggrrree6saa5i%ttsee-rr tlaatnecrealtobodnefdoinrmgatbieotwn euenndeptollyomaderancdhahiingsh;erhednecnes,ittihse much greater resis- tance to deformation under load and higher densities. TamE Lv TABLE LIV Ym. MRCHARIH, Facets oF PoLCHLomTALEORDETIYLSS 47 25C 'I'YP[CAL ~iECHANICAL ~PRoPERTIES OF POLYCHLOROTItlFLUOIROETHYLENE AT 25~C ST ow) (ZST : 250 sec) rapes Coline Amorphon AStxTNihMod Property Crystalline Amorphous ASTM test Method Speci grmity Specific gravity Tenn emit (on) Tensile strength (psi) Elongation (2) Elongation (%) Vik pon ri YieId point (psi) Yield Sng (ps, 02% offic) Yield strength (psi, 0.2% offset) Nites of iis Modulus of elasticity mie (pi) tensile (psi) Fleirt senshi) Flexural strength (psi) Modus of icy ModuIus of elasticity ore (4) flexure (psi) Comprenie yd rh Compressive yield strength 02: Oty (psi, 0.2% Offset) Modusofcscs Modulus of elasticity Compressive (pd) compressive (psi) Deimos bad Deformation under load hy (24 hr 1000 psi) Haase % at 25C Sane % at 70C Clie % at 125C Impact strength had 5pin. rch) (Izod ft ib per in. notch) Horn kop KNE Hardness, knoop KNP Rood 330 Rockweli S-Scale Trermal conc Thermal conductivity Cpe mt ere per C (cal per cm~ per sec per C ferem per cm) Coticint finer expansion Coefficient of linear expansion Tie -196C otc 0-50C Councat tian sel Coefficient of friction on steel [CE 2,1312 wo4900 os105 m05710 20602660 wae 186 x 103 Tor 10,700 maw 254 x 103 sso5440 50100 180 x 10a om0.20 0300.40 353.57 513.1 10710.7 Hy85 ex 6.32 x 10-4 180000 1.8 x 10 ~ Wien 4.8 x 10-~ 2.1047 so705070 1s175 io4650 jis1940 ax 162 x 103 ie7810 0x 190 x 103 --- -- ox0.37 37.32 025.00 37.3 28.2 "80 Gxt 6.12 10-a os0.43 bingo D792-50 Dessert D638-56T Doser D790-59T Darssh D695-54 Dans D621-59 osss D256-56 Dies D1474-57T rset D785-51 Desa D696-44 33002222..00115566 I3MM_MMNNO044885555226655 sa mrs on rouse cms $1 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 451 he da in 3b LY shows the varision in mechanical prope The data in Table LV shows the variation in mechanical properties ofpoy CTH a cio of semper Ee po THE tin of poly-CTFE as a function of temperature(126,1~7). Like poly-TFE this olin ki ein to mechanic! proper belo 200-Cy pa. polymer also retains useful mechanical properties below -200C, parToy wi pb Big i emg lomo up to ticularly with respect to flexing and resisting deformation up to the limit Se a dete lmnopCTI, hse of the small but definite elongation limits. In the case of poly-CTFE, there rates apd GL properties Ane -C. prey oh is a rather rapid fall-off in properties above !25C, particularly as the meltnei SE app ing point of 213C is approached. 3O er En / 15 VT crystalliny I0 cryst~lline Ll 50 100 150 Fi. 4. Deon vebo ein of rls vente fo 84. Deformation under load us a function of crystallinity and temperature for pa Rn polychlorotrifluoroethylene. he presence of chlorine in is tbswise Saprocbon plc con The presence of cl~lorine in ttiis otherwise fluorocarbon plastic conis Eh rer chen fret psec he sales ml, tributes to much greater cohesive forces between the polymer molecules. For cnn conpating dhe compresive Sees of he poet of For example, comparing the compressive strengths of the polymer of ye i sCEn s ra ndte poet of tetrafluoroethylene, which contains only--CF2 groups, and the polymer of ioerosocmFiroan--CcECal trolute CT Eply: cttlorotrifluoroethylene wittz--CF2--and--CFC1--groups, the CTFE polynerves oopae) 35 otas compared TOPS 1k mer gives values of5400 psi at 0.2//o offset as compared to 1000 psi at 1% offset Tor FFE. Thi, tere much ers ene fr 1 ples doin for TFE. Thus, there is a much greater tendency for the polymer chains he cof TEE pm i nd Ade ny ah er whe in the case of the TFE polymer to slip and slide over each other; whereas line om nthe CIEE pt ed bon he shin oer the chlorine atoms in the CTFE type tend to bond the chains together, ee fe ping and sin. Th srt hs ore bw hence resist the slipping and sliding. This greater cohesive force between 33002222..00115577 aw_nossssass 3M MN04855266 P moc gis 0 II i : 528 138 E:l '| lGeEes HIERER EIRE Hig gd iE | Rado ii - . 2g] fg 2% HfEl]oat i . : $ 33133 lik 33002222..00115588 swnosssszs7 3M MN04855267 INDUSTRINL ASPECTS OF FLUORINE CHEMISTRY I INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 453 ttthhheeeseppoomllayytmmereeirralccehhatiinenssn iitnno CCmaTTiFFntEEaippnoolalyymmmueercrssh iihssigaalhlsseoor eedvevniisddieetnnyc.ceeddThbbyyiitsthheeilfflaauccstttrttahhtaaetdt otbbhfyyesttgehhaeesmeffoaaautccetstrittahmhlaaastttettetrhhnieeadlCCstoTTtmFFhaEEaninppttooahlliyenymmaeperomrslsuyaacmrrheeerhmmsiuguochcfehhrtlldeeeesstssnrsappileteuyrro.mmreToeaeahbtbilhslyeeilste0onilelaauvavsotrrariraiettetehtydye ocpceoforppmgooeallaysybemmioeleurirstyoomftfoattwteeerattirtaaaleffslluvutoaohrpraoooncertthihtyhyslleeehnnopeewonlyasnimnnddeTrashhbeeloxxeafaffLutlueVotorIror.aopfprluorooppryolyeeletnhney.el.enDDeaatotaar forthe for permeability to water vapor is shown in Table LVI. TALE LE TABLE LVI Warn arom Tassos or Vasors Peas ~,VATER ~FAPOR TRANSMISSION OF VARIOUS PLASTICS Atri Materia! Clips Calipcr iim of film nie (mils) Duion_ Duration our of test fy (dab, s) Permsbily Permeability gmp mi per gm per rail per pedi 100 in'z per 24 hr Renee Reference CFE homopance CTFEhomopolymer Godel sow oa Grade II 30 i 3 oo a2 3 CFE boropemer CTFE homopolymer pice (255) wos ox a) plasticizeda (25%) 3.4 3 (FCRamma FD) = = oi as) (C~Fd-CaF6) copolymer (FEP) -- -- (Cit = CO herpes -- 3 os (CH2 - CCI~) homopolymer -- 3 CH, = CH bampobroes. (CH2 = CH2) ho~nopolymer ow demi) - 3 10 (low density) -- 3 0.030 0.034 0.20 0.46 0.80 1.0 (126) (126) (189) Phir wd now olla wight ayes of CFiCFCL Plasticizer used is lo~v molecular weight polymers of CF~CFC1. shoTTwhnheebryraattthhheeerr sfsattrcrotonntgghaiitnnttceevrrmemnoollefecocurullaarrerlacctooihhveeeslsyiivveeloffwoorrwcceeeissgfhfootrr oCCfTT3F0FE0,0aa0r0ee, aatlsshooe spUphooeollywyommtnehererbsrsyhbhaatahnvvedee,ftteaeenncvstseiinllteehwassittttrrheeenvnmeggonttlhhefcoiiunnrlacerrxxecclwaeeetssiissvgeoohlftyf s5Sl0o0o0f0w002,wpp0ssei0i.i.0g,ThT0t0FF0EoEfoppr3oo0lml0yye,mmr0ee0er,0rss,,h, atoohsnnee tthenesioltehesrtrhenagntdh,seovfen20w00ittho4m0o0l0ecpuslia.r weights of 2,000,000 or more, have tensile strengths of 2000 to 4000 psi. 2. Thermal Stability tensW Wilhehiinlleedtthcheeomppprrreeessseeinnvcceee sootffz2ett.hnhgeeTthhccehharllmnoodrraiilnanleSestoaaabtt1o0iolmrictlyoddsooecersspaccoconkntitrnriigbbuubteteetwtteooenggrrpeeaoatlteeyrr mtmTeoenerrsrielccexhhaaaaiminnnpdsls,,ec,iiottamsatllpstoroeemsiinspniettvrrroeaodtdsuuutcrcreeeensssgiiatnnbhhhoeeavrrneeednn2tt6a0lwwseoeCaa,tkkotsshcppeloootCstsseTriinFnpaEtthchkepeionpplgooyllmbyyeemmrtewerurenessdyynessrttpeegommolseys.s-. dpdFeoeoglgrryraemadxdearaatm,tiiopoInnlne,rreTeaiaatgcc.ttteiiom5on5nprreweeressauutlusltteriieennsggraeiibsnnuoltvtthhesee2wff6ho0iormcCrha,tmatihoraeneoteCofxfTipolrFoowewEsenserpreodmmloyiolmnleeectcrueulrulaamnrrsdwweoerfegiioggthehhtest ddpTeeeocwcliytrleemlaaessberee. iinInnontzzeFeedrirgoto.hass8ttt5rrteehnwneggerttehhsieettiimrrmeeaespuiaaldsstsdaaewcffrhuueinncachsctetiiaoiornnnethooeefxf pZttreee5mmsTpsapeeesdrraatittnhuuerrteeteermmaanpnseddroattfitimmutehre.ee. eItxcweieldl sbe3n15oteCd. that there is a rapid decrease in the ZST as the temperature exceeds 315C. 33002222..00115599 I3MM_MMNNo044885555226688 454 H.G. BRYCE Tn this cae the ZT" ser srt ime i mesa of mol In this case, the ZST or zero strength time is a measure of molecular with ad a ershows sore wih he ie sto imi weight and has been shown to correlate with the dilute solution viscosity thd, The vet med ound ih ASTM, DH10AYTOS, method(Z')sL The test method is outlined in A.S.T.M. D-1430-58T(t29). Et, he ZT csr he mimesends el sched Briefly, the ZST is measured as the number seconds required for a notched Senaf sl hing chu dtd coins be ld specimen of the plastic having a carefully defined cross-section to be pulled bys ak eh when poe oe fps 50C. apart by a fixed weight when placed in a furnace at 250C. +RN Ne] T] = 25O ~TF| Homop~lymer ZST = 2S0 260C 500F 277~C 2OO 150 : 1)1) I ---- 5O cF.o15 Ce hrein 257 er of ie nd persfo tan rt~t FiG. 85. Change in ZST as a function of time and temperature for chlorotrifluoro- ethylene homopolymer. "This degradation io owes molar weigh agent presumably This degradation into lower molecular weight fragments is presumably det the Cio of the pres sho Sek so oh due to the cission of the polymer chains at weak spots along the chain. vss ves ts mg ore fo be ofres och ees These weak spots may arise for a number of reasons such as irregularities niodund Sun. fh Tomson pov ened by epics introduced during the polymerization process caused by impurities, nen of term rons ce. Te Fe hn the hk of omni of influence of terminal groups, etc. The fact that the heat of formation of he nb. tcl ond ony 5.5 eh pi mle 4 copa the carbon-to-chlorine bond is only 78.5 kcal per mole as compared to ha Tt th bto ne bond of 11 el er mk regency that for the carbon-to-fluorine bond of 116 kcal per mole respectively i pono wine is also a point of weakness. The heen of cline in he polymer male abo inroduces The presence of chlorine in the polymer molecule also introduces erin dla srt ae ih by en i Gee omof certain dipolar structures as evidenced by the higher dielectric constant of Shor dato param n shckhs vet pei 2.60 over that of polytetrafluoroethylene which has a value of approximately she onc Tab TTT by te ch sp Spon 2.0. This is also indicated in Table LVII by the much larger dissipation 33002222..00116600 aw_nossssass 3M MN04855269 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY. 45 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 4"55 sffcaaecctvtooerrlffeoosrrsttthhheeanCC0T.T0F0EE05oofvvoeerrr ttthhheee TTTEFFEEE, ppoollyymmeerr;; ii.ee.,, 00..00221155 aatt I10000 ecyycleess ppeerr sec vs less than 0.0005 for the TFE. TABLE NT TABLE LVII Euseruca, Proms 07 CFE Hosoroumin br 25C ELECTRICAL PROPERTIES OF CTFE HOiX{OPOLYMEE AT 25~C ST = 30) (ZST = 250 sec) Froanuen Frequency (cps) CDoniarnet Dielectric constant Diwspruin Dissipation factor w Fr aos 10z fo rt oom 104 0 in Sots 10~ Diesen 500 sis per i. Dielectric strength Elen ry Electrical resistivity Volurs > tame Volume Su 35's 10opn eramt Surface Are rence Zaid Arc resistance 2.59 2.41 2.34 0.0215 0.0229 0.0144 500 volts per nail >10z6 ohm cm >5 1017 ohms per cm >360 sec TABLE LVI TABLE LVIII (AST D-1930:55T) CLASSIFICATION OF COMMERCIAL POLYCHLOROTRIFLUOROETHYLENE HOMOPOLYMER (ASTM D-1430-58T) Gude 25T rose Grade ZST range [er Intended usage 2 C30 Exusimoltin bins ambi comin, 2 176 to 300 Extrusion of film, tubing, and wire coating, neon mai injection molding 3 010 Compresion ding nection molding 3 301 to 750 Compression molding, injection molding, 428 ikvaied hick eran Rod, and thick-walled tubing extrusion on t"ThTehheemohhlooemmcuoolppaoorllwyyemmiegehrrtsoo.ff CCThTTeFFsEeEaiissrmmdaeadsdceeriaabvvaeaidillaiibnbllTeeaiibnnlesseeLvvVeerIraaIllL,ggrraaagddaeeissnbbwaaissneegdd.. tothhneet"AAhTehS.SemT.ThoM.lM ae.cmu. lddaaeresspwiiggeonnigaalothtiityfoson.nCmTffTooehFrreErsggerraaiaddsrmeeeassndbbueaasfsscaeercddibtooeundnreittdnhheeTbyZZabSStlThTee..LMiVnInIeIs, oatgaaiMniunisinngg. aPalnnaddstTicMM h.aeanknuoufmafacoctptuuorrliiynnmggerCCooofmmCppaTannFyyE under the trademark, is manufactured by the under the trademark, "KEL-F" Minnesota "KEL-F" Brand Mining Brand Plastic. 35.. CChheemmiiccaall RReessiisttaannccee is sRRheoeswsiinssttaainnncceeTaoobffleCCTTLFFIXEE. ppAoosllyycmmaeenrrssbettoosaaeevvnaarrfiireettoyym ootffhessootllvavbeelnntetssthaainnsddmccahhteeemmriiiccaaallisss ihsigshhloywrnesientaTnsatboleawLiIdXe. vAsacanrofbceihesemeeincayflrsomandthseoltvaebnltes,. tIhtisi munaatefreicatleids highly resistant to a wide variety of chemicals and solvents. It is unaffected 33002222..00116611 I3MM_MMNNO044885555227700 445506 Hn,c.c. sBaRvYeCrE TALE Lx TABLE LIX Crnten. Resemasc or Cisommcomorminass Howonciris CIINIICAL RESISTANCE OF CHLOROTRIFLUOROETHYLENE HOMOPOLXMER ASTM Pres Crpline Anwipton ASTM test py haamgs vchiene ehawndseicsgonosmhee method Property Crystalline % weight o,/; volume change change Amorphous % weight % volume change change [---- Chemical resistance danaCs) (7 days/25C) DIST Acorn or ua es ea D543-56T Acetone 0.1 Bane or izes oe Benzene 0.1 Eta, 952 0 os a Ces Ethanol, 95% 0.0 SNemiawikone 02 0s 0s 01 Methyi ethyI ketone 0.2 Trcorseion Bois a0 1 Trichloroethylene 1.8 Amoriombyo10s%de 00-07 00-03 Ammonium hydroxide, 10% 0.0 Ean Goh Se Ethyl ether 4.4 Fon 113 ac as os Frcon 113 0.9 Brimdsliltr10c% 00-05 00-08 Hydrochloric acid, 10% 0.0 Solum bird 10% 00 03 00-06 Sodium hydroxide, 10% 0.0 Nia00s%fi,g 00 02 00 0s Nitric acid, 90% finning 0.0 Hpbrricacd,mido0u9s 01 00 03 Hydrofluoric acid, anhydrous 0.0 Nigerwrite 00 82 94 99 Hose Nitrogen tetroxide (5C) 8.2 nevedmc! Unsymmetric dimethyl Harn 00 as ero hydrazine 0.0 DST We rpion D570-59T Water absorption or ams) 0 ew ew (21 days!25 C) 0.0 RMD Tose Ligud vse impect RMD Tester Liquid oxygen impact eis (1 pes sensitivity (ff lb per sq in. ron aid) 162 @ for 0.010 in. thick) 162 - 1.1 - 1.2 -0.8 -0.5 1.5 -0.7 7.6a 0.6 -0.5 -0.9 -0.2 --0.1 9.4a 0.8 0.0 0.3 0.2 0.3 - 0.3 0.0 -0.7 0.4 0.1 3.0 1.9 0.0 -0.3 5.8 11.2~ 0.9 0.4 0.0 -0.6 0.0 -0.6 0.0 -0.4 0.0 -0.8 9.9 10.5~ 0.1 0.1 0.0 0.0 162 ee rer Becomes rubber-like. by all tyopfsterosng acids and baseseven at clevsted temperatures. It js. by all types of strong acids and bases even at elevated temperatures. It is not soluble in any of the conventional solvents being only very slightly not soluble in any of the conventional solvents being only very slightly wollen by such material as tichloroethylene, ethyl ether, and nivogen swollen by such materials as trichloroethylene, ethyl ether, and nitrogen tetroxide. By thestandard est procedures for plastic material, the polymer tetroxide. By the standard test procedures for plastic materials, the polymer shows noabsorpotfwiaotenr. shows no absorption of ~vater. 4. Radiation Resitance sist(CaCTnTcFFeEE, pppaoorlltyyimmcueelrrassrlhhyaavtvieen4db.beeerReecnanodniiidnanivvttieeoissnottniigRsgaaewttseehidsditcarrhneecccaeeepnnpttlrlyyoxaaissmaottoetththheoierserraaiddniioaauttitioeonrn aosrpefpsaaic1cse0te(a7tnn6lTc.)me.,mRRpeaesrsHtuugi.llctusslTwwahereleryreeduoonabbdatteaaiirinsnceeoiddnncbbdlyyiutideeoexxndppsooiwssnuuhrrTieecahbt1o0lae5p500pLrXkko.vvxiXXmTo-hraraeateyysssethiiornnesaseaulivvntaascocucuuuoturemm-r soreefissnpp1goo0nn-g6ddammqqummuiiatteeHrgeccd.llioosTssteehillyoyen tdtiooantavivaralil0suu2eei0ssn.cwwlAuhhsdiiecccdhkaniwwnbeeerTreesaebooelbbnettaafLiirnnXoeem.dd tTbbhheyyedsooaettthhare,eerrstuhwwletosordrkkcieoesrrrssspuastinigongafmacmtoar rsacduiuaatliloyn sinhoawirs(~a6).siAgshtcandebcreesaeseenifnrovmaltuhee udpaotan, tehxepodsiussrie- pation factor actually shows a slight decrease in value upon exposure 33002222..00116622 33MM_MMNNo04488s5s5227711 oven, vers or own comer 457 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 457 fa5i% 2e33d3 "ES qasa Safft reieee, 3 la I 8ps5858838s 3 Ele i iHE dIlPP FBETLHTBERD gHi |z|8 501 Hi:IE lsi EALILTES 3 3 il I ,R33 : | i 31 SE { | fens 33002222..00116633 awnosssszr2 3M MN04855272 Fe 6. mvc 458 H.G. BRYCE 0 Xeraps, while the tensile nd othe physical properties show loses of to X-rays, while the tensile and. other physical properties show losses of Jes than 20% less than 20/o. . Vile and Ifrred Tranmision 5. Visible and Infrared Transmission CIFE polymers have high tsneision popertis in both the visible CTFE polymers have high transmission properties in both the visible aanndd iinnffrraarreedd rreeggiioonnss.. TTyyppiiccaall IRR aabbssoorrppttiioonn ccuurrvveess aarree sshhoowwnn iinn FFiigg.. 8866.. wT] 10o EER EH 9o T= = NAO - | SENET 70 in6o 50 a inii---- a 40 Ah =IJ 30 20 0 WAVE LENGTH (MICRONS) Fi. 8. ned sirion oct os christy bl 86. Infrared absorption spectrum for chlorotrifluoroethylene homopoIymer. 6. Procesing of CTFE 6. Processing of C TFE Polscloroteiforoethylene molding powder may be converted to a Polychlorotrifluoroethylene molding powder may be converted to a vic of forms by several procedures As has been stated cae, the variety of forms by several procedures. As has been stated earlier, the Tesi has a dente mili oto, harlot, may be covered by po. resin has a definite melting point, therefore, may be converted by proces common to al re thrmoplastic resi, Included sve sompresion cesses common to all true thermoplastic resins. Included are compression molding infection molding, tunics making nd extrusion, molding injection molding, transfer molding and. extrusion. "Nt the meling pint,poly.CTFE ha a very high viesiy; hence, At the melting point, poly-CTFE has a very high viscosity; hence, during compression mobling 1 is necessary to hat he molding powder during compression molding it is necessary to heat the molding powder na vemperaare of 28C under a press of S00 ps befor on be to a temperature of 260C under a pressure of 5000 psi before it can be comerted to 3 dene uniform mass. Injection molding and extrusion converted to a dense uniform mass. Injection molding and extrusion proccss Toque considerably lower vieitics: hence, require even processes require considerably lower viscosities; hence, require even Tihs tmperstore, generally in ences of SIS, Care mit be ake 0 higher temperatures, generally in excess of 315C. Care must be taken to avid overheating he polymer fo excessive periods of time; otherwise avoid overheating the polymer for excessive periods of time; otherwise rious degradation vckure, with ruling poor mechanical poperis, serious degradation occurs, with resulting poor mechanical properties. "The mechanical properties of th Anished article are ho futon of The mechanical properties of the finished article are also a function of the dees of exalt. AC Jest i sltinly thinsections ts posible the degree of crystallinity. At least in relatively thin sections it is possible ary thecxyslinity by hat test followed by quick quenching or to vary the crystallinity by heat treatment followed by quick quenching or ow colin, hick pecnching from above he meng poe, of couse, slleleoaawddss cttooooffloionrrgmm.ssQhhuaaivvciiknnggqutthheeencmmhoiosnstgt aafmmrooomrrpphahbooouuvsseccthhhaaerraacmctteeerlr.t.inOOgnnptothhieent,oottohhfeerrcohhuaarnnsdde,,, ow cooling ves in eaively Nigh Gegrcsof cpl: slow cooling resuits in relatively high degrees of crystallinity. 33002222..00116644 M_uNosess273 3M MN04855273 CEL STSp----T.-- TA INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 459 _~ 65 I TET : TA Ter Tr ct II A FiG. 87. Per cent crystallinity vs spccific gravity for chlorotrifluoroethyIene nd homopolymer. hedge clitma be tind er ms ih The degree of crystallinity may be determined by several means such wt ly pndemiet as X-ray diffraction and density. Figure 87 shows the relationship between Fo CAFE aman per cent crystallinity and density for the CTFE homopolymer. b, rman inns D. POLYVINYI,IDENE FLUORIDE Tahebrnoe yb The homopolymer of vinylidene fluoride has recently been introduced Td ps fe be et on a commerial scale by the Pennsalt Chemical Corporation. The monomer mn a 1 ion. may be prepared by the dehydrohalogenation of 1, 1, 1 chlorodifluoromn Ep A nen ethane(13,131) or the dehalogenation of l, 2 dichloro 1, 1-difluoroethane(in2). i a i nt ba The highly regular structure of the resulting polymer and the similar sizes ly pe tsfbii pds si of the appending fluorine and hydrogen atoms permits close packing of ri the polymer chains. As might be expected, there is considerable hydrogen ende eb pa in bonding between the hydrogen atoms, which produces cross-bonding of Pe ee Se high lattice energies. As in the case of chlorotrifluoroethylene polymers, Sl mm, ne ee this polymer is characterized by the high tensile strength which can be a i ere Tn improved by orientation and exhibits rather rigid structure with high nC, PU EE compressive strength. Typical data are included in Table LXI. The 33002222..00116655 swore 3M MN04855274 60 6. bees 460 t~. Go BRYCE phpioogllyhylmmyeerrdhihapaossleaa mmmaeteulltriienngpofpootiihnsetoopffal11y77m11erCC iccsoommsphpaoarwreenddtutoop 22i11n33thCCe ffuoonrruCCsuTTaFFlElEy.. hTTihhgeeh cddhpiiisegc.lheelcTcyrytripidcicicpccaooolnlnescstltnaaecnanttttruoiofrcfea$l8o4.p4fraaotthp6e6e0r0tpcciopeplssyaamannrdeedrtithhnisecehlshuihidggoehhwdddniiinssuisTppiapabtaiilntioeontnhLefXfaaIcucLtnoturossrauasatl11ly0066hi11g00h9 cps. Typical electrical properties are included in Table LXII. Micausicn. Proviso Porvisvsoess TABLE LXI ~/IECHANICAL PROPERTIES OF POLYVINYLIDENE Terie ares (os) Tensile strength (psi) Elongation (1) Elongation (%) Niobeofshe in enon Modulus of elasticity in tension Compronie em Compressive strength Nichtof cay in compresion Modulus of elasticity in compression pact sth (10d, nord) Impact strength (Izod, notched) Coin of sing foci 10th Coet:ficient of sliding friction to steel Specie rin Specific gravity Futons ar 250m) FLI;ORfDE AT 2.~(~(133) 07000 0300 10000 120,000 noo 10,000 0000 120,000 53.8 oon 0.14 0.17 ne1.76 TamE Lx TABLE LXII Bconcas Prurnis ov Pourvisviaos Fo x 25C ELECTRICAL PROPERTIES OF POLYVINYLIDENE FLUORIDE AT 25C{1an) Dielectric constant wan 0 60 cps Wan pod 10a cps 00 ois 10a cps 8.40 7.72 6.43 Disipsion facer 10~ cps Dissipatiotafactor 2.98 60 cps 0 10a cps fi10~ cps oo 10~ cps 0.050 oo0.019 ed0.159 vio0.110 Volume resistivity [ris (ohm-cm) Didecticsrengn Dielectric strength i ee mi, 0.225 in. (volts per rnil, 0.125 in. Poa thickness) 2a2 10~4 20260 wheW `nWhhicilloeemptthhaiirsseppdoolltyyommeterhrehhaahssydggrrroeecaatateerrrborrneessiiassnttaaanlnoccgeeusse,ttooitssoolilvveencntotnaasnniddderccahhbeolmrycicalaelslsss srwreeuhssciiehssnttaaasnncttotmhttkohpaasannbreadttshheeetdoommontorherete.ezhhhayiifgdglhhruolloyycraoerffbltuuhonoyrnrliiennansanettaeeolddrogcoouhrrel,ohhryiyotddirlrioosuggoerecnnoo-c-nfftsrrhiecdyeeelreappnbooelll.yyymm1leeerrsissss ssssueeuvcvcleeh~rree3allssyynt-hddboeeuggsterryaalbddaeaesdmdeidnbbeyyo.nffIututemmtcriaiannnfbgglueosssuruwollfefeuultrhrliiycecldeaanucceinidddoraapcannrhddtliboabryloylytcrceidefrilrusatapoiiernnoroseoretrghdgayabnlneyiinccaebc.baeastIseotesnsi,es, such as n-butyl amine. It can be swelled and partially dispersed by acetone 33002222..00116666 I3MM_MMNNo044885555227755 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 64611 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY and will form colloidal solutions with such strongly polar solvents as Gimerhylaceumide. and will form colloidal dimethylacetamide. solutions with such strongly polar solvents as E. Pores. Fomor ce"ceTTnhtheleyppoionllyylmmmeerrofooffrvvmii(nn3yy0ll.EfAl.uTuoohPrreOiidLdpeY,,oVl((ICyNCmHYHeLz2r---F-hCLCaHUsHEOaF)R)IgyD~l,aE,sshhaatssrabbneesieetnnimomnaadtdeeemapavevaraiailltaaubblrleee ppureonociaiennfnttetcoolytffe1i1dn5500efviClCe.mn. FFfaoifirlemmmr(1iis3sse4rrv)ee.eppnToohryretteeaerddpso"ttoloyehhmxaapevvoreesuhoorauuesttsstattoaagnnFldadlsiionsnrggitdrwwaaenesasautintthhlioieegnrrhaatbt.beiilmliPttopy,l,eyrbbvaeeituiinnnyrgegl cucIhthnllaoiofsrrfiieaddcleets,e,odoornneevptteohhnreetaeoofdtttehhrteeorrsehhhvaaaevnnnedd.,y,ehssaihhrgsooh'wweueexlddtpaossvseeiurroiriloeoeuuttsso tddFreeaglgonrrsraamidddiasaatstiiisooounnnn.liiingnThhsst.iiexxPfmomiolyonmvntithhnhsays.s.l eepIxtoxclceiyeslvllliaeenlnnysttolfflfrleleexuporroreeirsstdiieessdttaiansnt,coceerehaalannavtddievhheiihlggyihh,gdhdiqciueulileletctrctartvraiiicopslostetlrtraeerntnrgmgaattnhthse..mrAAiisasslsmmioaiinngg.hdhttTebbxhheeeieebfxxiiptplemsecchtthieedgad,hs, pGtdrioieacllydeevetcinrtnraiyimccleccflooounfnoss"rttiTaadnenettdoloisffa,7"7.r.5e5blya3attiEv.66e00l1.yac,dppu.sq.PuoTTinthheteeadpperrpooNoddeluauwcrcottmuiirssastbbeeeariiinnandlggaCoonoffdfmeeprreeaexddnhyiuub.nnidtdseerhittghhhee tradename of "Tedlar" by E. I. duPont de Nemours and Company. F.F. CCOoPoOLLYyMeHEenRxaoOrrFtTTtEEoTTsRAoAAmFTmLLU oUO pOyRRO LOEEaTTeHHY VLLEENNEE AND. AND intrAAodccuoocppeaodllycymommeemrreroocffittaeelttrlrayafltHbuuEyooXrrtoAoheeFettLhhUEyy.OlleRe1nnO.eePdRaauOnnPPddoYnLhhtEeeN xxdaEaeffllNuueoormroooppurrroosppyyallenenndeeChhoaamsspbbaeeneeynn iuuhnenntsddraoeefrdrtuuttchohereedopttrcrraooadpmdeyenmlnaeaemnmreece,i,garl""loyTTueepbffyllioontnnhtre1o10d0E0u0.ceFFI.sEEdPtPh"u"e(P61--o33C5n.)tF. dyAAesssiNmmdeieimggghhorttuourbbspeeaneentxxdoppeeCctcthoteeemddp,p,oattlnhhyyee htmmheeaexrtrafmmoloufololetrecohcuepulrleoep;p;olyhhyleetenncnctecere,ga, iraoaullouterperorciiinntnghtgryolssdeoounmmcceees(ootfTfhEetthh)-ee-CpppFohhly3ysysismiiccedaarell.gccrhIhoanaurrapapccatitrenetrtriioicssutttliihcacesrs,pffortrolhoymim-s tppphrrraoootdbdauuobccfleeyssthbehhyiiggrphheoeedlryurcteisstnttrrgareefntlnuhggoetthrhsoleicctphhhpayaarrlgaeaceonctteeferroii(snsTtteiiFccEssp)o3alptyomllleoyorwmweceehrrra.immnIonoallgeeacpciuaunlrsltaatircrtuhlwweaereio,igtghhthethrtsis.,s, "TpTTrhhhoeeeba-Cb-CClyFFFbsaygsgrirredoodeuuuppgcriaaonllugsspoo,thttoeeefnncsddolssuiprttpsooeaii,gnnedlhioiobbcfiisttonccnreroyytspsttioaanlllytllirimzzoaaedttruiiococennhaaooniffnytthahseigegappniioonfllsiytycmmatnheeterr lcocahatthaieerinnar.l.. cTcphohhalaeiyimnn-e-rtCt.ooFac~crhheasaiiidvnneerbbgyiirnnosdduiiimpnni,gglo:a;rf iicnntoouccrootsnehnso,sseedeqqouueeoesfnnnccetoeh,t,eintthhhtreeoomdggoueepcnnoeeerlraayanllmyeppsrrrigooopnpfeierfritttciieaeetnssrtaooflafuftoerttrhohae-el eepLttohhIlyyyllmeeLnneeer,. Typical are very Typical data comparing the two materials are included in Table similar to those of the homopolymer of tetrafluoro- data comparing the two materials are included in Table tLhaXt"TITIthhIhe.ee pcproriipmmoalarryyymeddriiffofifeerreFennEccPee bibteettawwmeeeeelnnt ttphhreeocttwewsooibmmlaeattereerrsiiaianllsaeenxxdiisshttsseniicnne ttmhheeayffaabccett eteIhtxxattwrtriuultddhleeeddbceooorprnooiitlnnyejjdmee,ccettrihioooonnwfemmvFoeEolrlP,ddeeitddshaabbtyymeccevooletnnnvvpeetrnohntictisieoosnnmsaeialbllltettihhnreegerrsmmpionoopiplanlantasdstitisihccecnottecneceschihmdnneiiaqrqyauubeeblssye.. hIihttiiggiwhsheeinlrrlecttbhehesaasnnanrttoyhhteeeidnhh, ooohmmroodowpeporeovllteyyormm,ehetarrhnadootflfecechvhtlelhooneortotrrtherisiifsfillnuumooirernoolstetitnthhhegyyllmepeennoleeit.n.tcIIonninsdccicootonninssoseeniqqduuteeoernancbucesley,e, ttietemmispBpeenorreahactteuusprrsoecalssryytiienntinreeaxxfoccireeudsosesrrooocftfto3h3y77hl00aennCCde..leantdhethreescionpoinlytmheermofelettrcaofnlduiotiroonethtoyluensee daaenngddrBahhodeetaxhxtaaifpfollonuulooytrrthoeoaptpnrrraootfpplhuyyeollepreononleeeythcaayhrrlleeeonrmmoeotoerarienefdissotttrhaaobebellteechoyttplooeonlccyehh.maaieiInnrnocccfiiostsnsesistoorenanqfuloouerroncrmmoeoeoltolkefecycutluehllinaaser,r degradation than the polychlorotrifluoroethylene. In consequence of this, 33002222..00116677 I3MM_MMNNO044885555227766 40622 HH.GG., mvs BRYCE TABLE Lint TABLE LXIII ComoaPrnoressresoor onxy TEE 0 maComoeTrrasnsosoeminiass COMPARISON OF PROPERTIES OF POLY TFE AND THE COPOLYMER OF TETRAFLUOROETHYLENE oo Hewuomeraorie (FEF) AND HEXAFLUOROPROPYLENE (FEP)(~) Property Property re ver TFE FEP Meling pict Melting point Sect rir Specific gravity Rat nde B.efractivc index Tene ween (0) Tensile strength (psi) Flongaion (2) Elongation (%) Steinofhii Modulus of elasticity Cocticinsof cian Coefficient of friction Dike corsa Dielectric constant Disiption fer Dissipation factor aio ye 60-106 cycles 104106 cycles Compre sent Compressive strength aC at 25C sonenone aban 2.13-2.20 3501.350 soo3000 3 100-350 Ssoi0 58,000 or0.04 202.10 coo -<0.0002 oom<0.0002 ro)600 3% efoto) (1% deformation) nae 285-290C amen 2.14-2.17 oe1.338 25002500 ze 250-330 fo50,00{) So0.08 202.10 <o0 <0.0002 oor 0.0007 foo1400 (2% deformation) (2% deformation) TTreFFquEEiraaenndddfFForEEPPfabccraainncabbtieeonhheeollrdd iaantt ttceeemmrptpeiernraatteuunrrdeessuoosfef 44s00e00rviCCceffoowrritppheeorruiiootddssexoocffesttsiimimveee lrloeossqssuBooiorfftedphphkyyfpsosoirilccyaafmlaIebpprrrrsioocpapeaterrirotetinieerssoe..ravinelcyerstoafitn end and use service without excessive have rather low compressive thsstterresesBsassoemetsseh3assgpessonhhleyoromwawlennarsiinnngaeTTr,aeabbalrlneeedlaLLtbiXXovIteIhlIIyILh.asTvToeefentnessxiaitlnlreedessmttherraleevynnegglttorhhwasstchaaenonrddeleeofllwoofnnggciaaoottcmfiioofipnnrrieeaacscrtnseeiiovtinine.n the same general range, and both have extremely low coefficients of friction. G. CoPoLYMIRS CONTAINING CHLOROTRIFLUGROFTHYLEN. baseSSdeevvoeenrGraa,clloCccmOoobipPpO nooalLlytyYmimMoeeEnrrRsssSohhfCaavO vceheNlToooA rbborItN taariiInN infeeGuddoCrccHoooeLmmtOmimReyOrleTecrncRieiaIaFllaLU nssidiOggRnnvOiiiffEniiTcycalHaninYdccLeeeEnNewwEhfhiuioccrhhidaserr.ec sAAbesasvseemrmdaiilggohwhntatycbbsoaeemsetebxxhinpepeaectciptoteeenrddsc,,eonttfhthaeecghepplrorooorfpopetterhrrietfvtiliiueenssoyrlooofifedtthtehhyneeleecncSooeuppoaoornlilyyddmemveieirsrnssiynlaacirdrreeeeanasaeefffdefe.lccutTtoeehrddeidriienen. dsiisseuvcaaermmaaaplaprwrakkraeeeyddnstaddlseyeccthrrteeeoaatpssheeeerciinpnernettthsaheeegnecrreoeessfiiostsfhttae--annvcCcieenHyt1yol0id--vveaanrgreiirooofuuluusspossriooindllvveteehinnsettissbnacaacrnnekddabsoccenhhdeee.mmToifihccaetalrhlsese `dpmpoueolerlysymamepserpar..ayrDDebeneeptpleyhennadtrdoidinntpgghleauusppptirooecnnssettonhhrceeeappoaahrfrit-tiig-cchCuuelH lraarr2vi-rrna-aynnlgggireedoeuoonpffe ccifnooummotphrpoeisodisbetiatiiccoooknnmb,,poottnshheieetoippfooontllhsyy,e- `mmimlaleauyyrsstaarmppatppaeryrdooaabinccehhthhtatehhroddoasstepealaooisffntieeTcllsaaabssolttrooemmaeLterXsrhIs.i.Vg.ThTehhreevvvinaayrriliiooduuessneppoofiilnnuttossridoofef dificrence are compositions, difference are iillquusAAitstrsaehhtehaadissgbbhinleeyeetnnhcerssyttdsaatattaeteladdliieennaaer;rTlliiaaeebrr,,lenitthfhLteedXhhheIoVmm.ooolepcomulylmaorewroeopfifgcchhohlslooarrloorttroiiyffnluutoormhroocletoethhwyysllrieednneee, stitshlhieeqgrruheetiltiieyss haeailgssehttvrrlaoyotnnecggdryttetseentnamddlpeleeinnnrcceayyt;uaffronoerrds.ttihfheIethnppeolmmlyayomnmleyeercruattplooaplrcciwrrcyyaesstittigaaolhlnlltsiisz,zeaesruueuppcooohnnnatheesexxppeloxoostwsruuurrsseeiidotteono, zosolaffitgffihiioltlmnlmy'ss,,epttlhhehiveinann--to~ewmvdaealnlltloeeenmdd.pttueulbrbeaiiantnduggsr,,estoo.or Iiiennnmssbuumrlliaaatttniityoolnneampcceoopnaalttitciinanagtgnisdso.noosnnu, lswwiuiiirmcreaeh,t,eattlhshyiissecxrcctrarryyucssksttiiaaonlln.g- lization phenomenon leads to embrittlement and ultimately cracking 33002222..00116688 I3MM_MMNNo044885555227777 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 63 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 463 aparnnoddviccdrraaezzsiinnsggu.f.fTTichhieeentiinniccnootrrepproofrreaartteiinoocnneoowffisstmmhaalnlllorppemerarccleenncttraayggseteassllooiffzvavtiininoyynlliidpdehenneeenffolumuoeorrinidodene: impaap8srorttvoooivdmmeeasatteteshrureiifaabflliallcsyyiiecniinntpccrireneeartaessfreefoerrreeressnmiiscsotateaafnnnwcccteeihteehttoopnoeeolmmrbymbrmiraeitlrtttlcalerefmymaseertnantlatliaazanangtddiionccngrraaipccskkhiciennongngo;c;mehhreeennnneodccn.ee improve the basic TABLE performance of the LXIV polymer as far as aging is concerned. PaoreaTis or Canovoar VinvTiAipBeLxEs FLLXLIoVwDE ab CHLoROTITORORTITAT PROPERTIES OF COPOLYMERS OF VINYLIDENE FLUORIDE AND CHLOROTRIFLUOROETHYLENE MoSovillideene ee Mole % vinylidene fluoride 00 55 :7 525 @50 10065 100 Mling Melting point aM213 92192 i183 hoteue Ta no true Tm Domi TL no true Tm Bote TL no true Tm ic 171 C Form of omy Form of polymer tad pesic Hard plastic Had pic Hard plastic Hed plac Hard plastic Rubber plasic Rubbery plastic Tough easoner Tough elastomer Tough asomer Tough elastomer Hud pic Hard plastic BraPPnodlytomraedrlesomofaftyrthkhiisbsmtytyypMpeieeananrrreeebsboeetsiiannggMmimanadidneegccoaomnmdmmMearecniruaflclaycuitununadrdeilernrtlgthhyCeeo""mKKpEEaLnL-y-FFo""r aBsra"nHdaltorand"emPlaarskicbsybyMtinhneeAsloltiaedMCihneimnigcaanldCoMrpaonruatfiaocntu.ring Company or as "Halon" Plastics by the Allied Chemical Corporation. H. Senixtion mateTTrhihaeelspprrbeeaccseeedddiinngognrreeuvvoiierewiw-neoo-ffcHotthn.heetSaUccihhnMaairMrnaagcActTteemIrOroiiNssnttoiiccmsseroofsf adevvmaaorrniiseetttyyraootfefspposoellyvyemmreaelrr cocmhnhaalartyreaacrccitateaelrrsribissotbtniiac-cssfseudooorffoinnffleluufoloburroooonccrdaianrsrbeb-ooocnntohnemmtraaatietnterihrinaiaganll..mthTToehhnoooissnmeeteerrpps-llacasdostnteiinmccessco,,tniwwsnthhgriaicctcehhasrbccsoooennnv-ttetaaroiian-nl `acoaannrcdlbyboosnncolallvriibennnokktanagg-refeeslsus,,ioseertxxianhhnieicbbei,ibttotatnhhndeedshhtiioghgthehheeeslsrtotwtttehhhseaetrnrmmcatoahlelfessfttiaaicbnbiietilelniitrtt-yyc,o,ofttnhhfneereiggcctrrtieieonaantg.teessctTtahccrhehbeeyommnia-icltcoasaol-l papponoolsdsassreesscsosslvhttehhnaeet rllroeoawwsaieesstsectatvnitddcdieieed,enlleceaecrcndttdriibcctyhccetoohnnelsiostrtwvaaennetrstsstylcaaoonnwedddffiittschhsieeeinptllaeetaaoissfottnfddrfeieacgcgttrirooeernees.. ooTTffhherreeeyssiiinddtauurlsaoaol-l opddruoutclchattrieioocnnchaaoorrffabcosstnooe-mmrteaeosww-hehhvayaidttdreommngocoererneedbbppoyoonlldtaahsrreirllrieinvsnkukeaalrgygseelssionwsstuidhcceihhsls&aiopswaetttrhihoieenngccfaaaorrcfbbtoomonren-sl-t.ttoToi--nchcghehlpolioonriirtinrnnotees.- `oacahnrnaddtiahnlaessl.scoTahirinbniccosrrneee-aaftssofee-csshtyvvreederrrsyyouglggterrseneaaitbntlloyymnuttdhcshehrlleaahsttaueerlrrtdaaslelriccnooahhtnehedsesiimvvlooeewrbbeeoornndindedgsnssobbeefepttmwoweleeleyetnnmineppgroopsllyotymirmnueet-rsr tures, with lower permeabilicyto a chains. This effect results in much tures, with lower permeability to a varity harder variety of gascs, and more of gases, vapors, and solvents. dense polymer struc- vapors, and solvents. 1I. AAvPPrLeIiCcAtTiIOonNsS 1. Electrical The electrical industry has1m. aEdleectwriicdaelspread use of the fluorocarbon wrseresiiifnnTslsh,v, erppoaaecrrlttethiiccyctuulrillecaanarrlllyyainnttddhh,uee shithrnooymmrohoepacpsoeolnlmtyymmadeyeeerrassrwsoo,ifdf etttseheptetrrraeafcafldoulpuouoorrsoloeyeetmtohehfyyrlltehenoneefefalahunneodxdraofcccihhaullrooobrrroooon--- propylene and tetrafluorocthylene. trifluoroethylene and, in recent propylene and tetrafluoroethylene. This usage,of ours,isobvious from. years, the copolymer of hexafluoro- This usage, of course, is obvious from 33002222..00116699 I3MM_MMNN0044885555227788 1 wo. ser 464 H.G. BRYCE vere of the progenies gen pesos sal, Hh es vnc, review of the properties given previously; namely, high heat resistance, Tro moire ans exon: dies popes, high Gilets zero moisture resistance, excellent dielectric properties, high dielectric Coen. niin as ade my Wi cons 2 wel able strengths. Insulation uses include primary wire coating, as well as cable H GSEEE L3 CHH Hi H ee ARGeSs ad 7 Jr \- NBaE Fi L2H J -- Fro. 88. Applications for polychlorotrifluoroethylene. Jick Those pls Has lg Sound wes i. variety of specialised jacketing. These polymers have also found uses in a variety of specialized i epee iets ou forme wars ron soe electrical equipment including coil forms, switchgears, resistor coatings, nd ans uo Sc Fig 8. and many others. See Fig. 88. 2, Clmicl Reston 2. Chemical Resistance "Ihe xcllen combination of chica rexsance and thomal resis: The excellent combination of chemical resistance and thermal resisan i he so of tse Aerob ono 3. sai oF tance has led to the use of these fluorocarbon-type resins for a variety of ons which she Shei vetsants of rie poe applications in which their chemical resistance is of prime importance. oaded se hes 5 sh fof any Shes proce operant nd Included are gaskets and seals for many chemical process operations and in he hain of esc of mile and ode fc soe 0 Ful in the handling of a variety of missile and rocket fuels, such as jet fuels, Tomi sheng vont, pire cr Tn sme PEA, fuming nitric, nitrogen tetroxide, hydrazines, etc. In some applicationsi 33002222..00117700 W_nodssszrs 3M MN04855279 INDUSTRIAL ASPECTS OF FLUOKING CHEMISTRY. 465 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 465 httehhaeetffrleooswwisptparrnoocppeee,rrmttiaieksseoosffthtthihese mTTFFaE:ttteyyappreedepipsooilalayybm mlleeerr,c,hoccioocem m.bbiIinnneeoddthwweirittahhppttlhhieecahhtiiiggohhneesr,r w0hwhehaeevtrrareepeosggrirrsseetaaaonttreecrref, rrumeemssaeiikssstetasainsntccheeriesqttm ouoiarccteooedllr,ddialftfllhaooewdcwehsliiissorarccbioolnnneeccceeshrruonnbieescdtdei.taaIunnntddeodlltehespsessorlppayeepmcrpemmlriescea,aabtbiisoilulnitctsyyh, aftaoosrCCvtTaThpeFFoElr,si,naaiorrnreeg fggouefemnnpeeeirrspaalelilslsyyarppnerrqdeeuffveeirarrelrrdveeedd,s..,tEhExtexattneecknnhsssl,ioivvreeeitncuue,ss-eesuoobffpsaartlilollttutyeytcpeptdeesstphhhoeaalssybmbeaseeeeernns,mm mesatuaadcdleh,e. pfuuoisspruueaatslhl,lleyyvlassitlenecieesnl,,,gfftorrhofoemlpmiiapantteittnsaagccaskknrdffrerovomoamflvtttehehnsee,mcctohhaelenmdmkiesicd,caalielntacapg.g,leeantnctotess;..pwr1Iohnsitemslcmeaotatllthlheeiirteebtmsaess,m,esssu,m uccsehhutac2alhs, papasesiprttseaaisnn,okknvssaclooovrraetsaai,ggnitighttaaesttyoolsirrntieppnamagd--dsdcdlaileretsesh,,oefraatrrebeenasggmeeendonelerodranealdlllayyiqnuccpeooloaatutceesedd;owrbbyyhnioluuenssaiionngtgghceossruuuiisittteaamsbbylslse,etseddumiicsssh-- persion coating system--either based on aqueous or nonaqueous systems. 3. Lubricity coefTTfihhceieenTTtsFFEEofaanfnrddicFFtiEEonPP 5ppsoollcyyommneter3rrs.assLaatrerueedbruuitnncoiiitqqytuuheee iirnnatpphooessrsseehssissgiinnhgg veeaxxltturzceeemmeeflloyyr lltoohwwe accconhhledlooffrrLiiicXnniIeeenToot)srr. ohhTfyyhddifrrsrooi,cggtaeeigonnanissnuu,abbspssottciiionttutunstttereoaddusttcceootduhunenttotfeearcrpttphaaetrrhttassrtat(t(hssheeeeeerCTT--haaiCbgbllhleeossvraXXlCuLLeIIsHXX,f,boarLLnIItdVVhs,e, faiininncttdrtroioLdodnuXu.ccIeeTIIhpp)i.ooslTlaalhrroiwscc,hhcaaoargerafaacfictnitec,erirpieisnsotttiiincoctsfss fowwruhihticitcctihhhoen ggfharraecesstatttlllhyeyadtiitntnohccerrmeeaCaanss-eye-Cttu1hhseeeosrccCfoooeer-ff-iftHichcieicebnnTottnEdoo.sff afairnnnicddvtiaFoFlnEEv.PPeTpphhrraioossddluuboccewttcssocwwomheehefefreirecexiiitennrnetttmhhoeeefliiyrfrliuscismteeipooiinrnntahbbnaeetsaa,rrleiindnWgghstseoaramnneddanhppiyaagcchukkesiriennsgglfssooarffdoostrrhsaesrlleeeTecFvvreeEess eiqqnuauiitvrreeeaddlrveoocsnnohmbbapeesraarerbiisnenigcgvoemmmaatseetrereeriinxaalgtlrstse,,hmffaieillnllyeedrrssirmaeasrrpeieosotortfafanttneceentn. tiiW nonccfhoolreropprweoorraaahnttiedgeddhyeeiirntn loomoraraddidenesrtraattioroneggtiirvhveeee- gorweacteorecfocmenptresssoifvefriscttrieonn.gth and resistance to flow and yet maintain the low coefficients of friction. 44.. 3nni-tiS-Sttiicckk exteTTehhmeeelllyoowwimaapddohhreetssaiinvvtee. qquMuaaallinittyiieessiootffemtthshee uffsllueudoorroiocncaarrhbbaoonnndlrrieenssgiinnbssahhkaaevvreeyaaldlsooougbbheesccoomamreee caeconxoactarteteeemd1d0ewwlsiytittihchkim.pprrpooDoddarurutacicntnttssg. sstuM uhccehahnalayassstTiTtfeFeFmwEsyooerurasrFFesdEE, PPetixntotoeghngiasivnivvedeelianuhhgsiieggbhhhaakddseeerggbyrereeedeenoooumffgahrrdeessesiiassrotte.-f TaTMnaFcFnEeytiiontnysccptooiecaasktti.ionnfDggiussnndriiuccnshhtgriiitttaheelmemrssloa5alsstesfff,rerywyiwinnhyggiecpaphraasnn,assreettxootuesppnerrsdeeivvvteeeonnutatspttephhleehyasssottiicbckhekiiaennnnggdmlooeffadiffoteooeodmod.s.f Many types of industrial rollers, which are used awdhhiecshionno.rmally arc sticky, ar given a coating which normally are sticky, are given a coating ofto of TF. apply TFE toor to prevent this handle items prevent this awdithhAe`sAnpniohiinennn.ttoeelrriescsttiirnneggsiaanppspplaliisccaaptteiioronnmaiinnnevvnaoltlsvcebsseattrhhieenugusseefooorff aTTuPFtoEEmoffbaaibblrrieicc siitmmepeprrrieengggnnaagtteeeaddr wKniuthcklpehejoniontlisc. Trehsinessaares preerpmoratneednntotbetaorninegedfonroramuatlomluobbriilceansttseering gear knuckle joints. These are reported not to need normal lubricants. 5. Moisture Vapor Transmission thosTTehhebeasppeaadcckkoaanggiincnhggloffiriee5oll.tddr3fhhluaoaossirsotmmucatraehddyeeVleaccnpooconn.srsiiddTIeenrraraantbbhslimleseiscuusaisssoeeen,ooffthffeiihlpnmrss,i, mppaaarrryttiiccfuualclaatrorllryys thnmhiaaosvvsseeieobbnb.eeaeescnnehdarrreealloacantttieivvrceeihslaetoaisrcsoeestrooiffffolruhhoeebaraootttehssteehaamytloliieninnsggeta.aunrnIeddn ttahthnheediseeoxxcrttargrseaeemnm,ieectllhyyemallotpowerwrimivvaaaalpp.ryoorrTfyattrpcaaitnncosasr.ls- mission characteristics for both moisture and organic material. Typical 33002222..00117711 I3MM_MMNNO044885555228800 446666 mace H.G. BRYCE eseoxxlaaummtippolnleeso.offTshsuuiccshhuaaseuusrseeeipnilnvavcooelslvvegeslsastthsheewipptahcakcaocgnsiknigdoaeorffagsbsletieecriignllrizzeegaetdderssuucttauusrreeeossfiinhnaaanlldcclooihhnoogll fasaoonnrldduttmmihoueunccsuh.hseTlleehossfisssCdduaaTsnneFggreEeerrpltooayffcpebbesrreefgaailkkalaasmgsgse3e.w. iAAtha sscpiiogrgonnntisieffiicidccteaairnnvatetbaalceppoppgvlelriierccaiaatnttegiiroonefnoarhhsaealssoedfdceehuvvaoeenlllduoolmppiinee-gdd tefnorsearscncetsehnmnetitsuppssaiaenonneeollfollCfiiggThhtthtFsse..EITfntniylpttmhheiicssfoiaalmmppbppsilliniaccesaadttaiioowpnnirtotthhtheeecteteoixxvuttegrrheecnmmoeeevsllesyyrianloongwwdfommgroooieoissldtetuucrsrtreeborvvlauaasmppioooirn-r resistance offer protection transmission of the film resistance offer protection tothesensitive chemical costings. combined with toughness and good to the sensitive chemical coatings. abrasion 6. Cryogenics (CTM MFaEannpyylaaaspptpiplclisiccahattaiivooennssbeiinnentthhdeeevcce6rrly.yooopCggeeredynn.oiicgcOeffnFiieecldspdarfftooircutthlhaeeruunssoeetoeoffibbsoottthhheTTfFFacEEt taahnnaddt tdtChhrTeessoFeegEpperrpnoolddauouscrtctitclsssirqrehuetitaaadviiennhetbthlheieieuienrm.fRdleeeIxxvniiebbaliiodllipdttieyytdiee.ovvneOe,nnftaaphtteayteretmimacprupeeleranrsraotttnuuorsreteessnsaaiissstitolvhoewwetofaaassiclltmiipqqtauhuciiadtdt iahinpnyptdtlhhrioeecgappteirneornsoeserniclsnieqvoeouoflifndvlleiichqqsueueeilaiiddtusmoofxx.oyyrIggnveeannlavdooerdrsi,hhtiiiotgghnhhe,llyytvhaooelxxvyiieddiaibzsrieionndgngyofftiuueecslletssn,yysssiltttiieevpmmessesa.t.losSS,pipmeaesncpiidfaficicc4t vaparpilitcyaotifonsspeicnivaollvpearsse.ats for valves, the valve body itself, lipseals, and a variety of special parts. infaNnNceeye.eddllWeesisssthttoo issnaacyy,r,ettahhseeissneeg nnreeewwscffalruucoohrrooaccnaardrbbaodnen-v-tteyylppoeepmmmeanatttee,rriianalleswaarresnjjudussttdiiinfnfttrhheeeniitrr tsitnyaytfppiaeesnssfcyaayrrm.eeaW ttnoobyibtehereeeiqxxnuppcieerrcecetatmeesdedinniigtnnsttrwhehheseinnaceerhacarhrarffueuattnnuudorete..dmetIevtsteisloboopybbmvvaiienoonyuutss,cottnhnhevatwetnttthhaieenossdneeammldaiahtftfyeeedirrriaeaohnl.sst csaatrisbfoyn mreasniny. requirements which are not met by any conventional hydro- carbon resin. XXIIVV.. FFlluuoorriinnee--CCoonnttaaiinniinngg EEllaassttoommeerrss AA.. Immopucrion 70 Ruseess TongAA,lllflttehhxeeiblsseyynnctthhhaeeitntii-cclirrkuuebbbbmeIoeNrlrsTse,R,cOuaaDlseUwwsCeeTwllIhlOaiaNcshTnnOaaatrtRuuerUraauBlslBuErrauRulbbSlbybeersr,u,baasrreeequffeoonrrtmmleeyddcrffrorososmm. ollloiinnnnekkgeec,ddrfolsettsoxoiibnffloekorrmctmohavaaien-rttlhyihkrrefeeeee-mw-ddoihimlumeneecndnusrslieieoosdnnwacalhlhaiicnnnheectawwatorooerrmkkus..siunTTaahlhlteyeyrrpeesiucbaiislsserqsauppubppebrnreootsslxyoiifmmcaagrtotoeesollsydypSoprnhrooeoppwecerrrtrotiuiseesbssb.l.ienrLLkyiitnnpoeeraoearpvreerpprtyooillefyyesmwmieenhrrsausnsooduffirtessaduubfflcffehiiccatiiieenemnnpttalletyyormahhtsiiuggrihhne aimmntoytoleplereivcccauaulll.laarrruInbwwbteeehiireggsohhefttcgaaaosllosesdoso btsththu~eetowt""heeerunnltbtiaabnnneeggarrllyeemppmoerelonnypttmsese""rtriebbwseeilttiwlnweefaeeonsnwuitatthathbeesluecfchthieacamiiinnepssnetrayaacctthtuirge3ahssintttterreamarnpnvessariileca.nntIttunrccethrr.ooesssUsse-nlicvinnaakkslees.,s, ctbcaeaunmntipizateheereddatlnunianrateetuu,arrraahlplaosrruluoybbnmbbleeeylrrriwiimssiiaaltlellfiidlnonueewsaaerrastppooassullyyfsfmmuiceceirhrenwwbthelhiycicachhuhi,s,gehtthihotoeuRumgoghwhpserrruauatbbtubbhreieegrrsyhy. taaUtet nmroovpoouemmlrataietntmuuerdrepesseb..ryaTTtmuooirxemmi,anahkgkaeewsioaatnhmmlyoaorrlriieemouuuitssseeedfcfuuhullesmeppisrrcooaaddsluuscauctgtc,e,hnntnbsaae,ttcuusraruaualcsl herruuiatbbsbfbleseourrwlfsmmuarsut stohtrigbbpheeertvveouuxmlilccdpaaeennsr-,-aiznedd cbuyrimngixaitngclweviathtevdatreiomupsercahteumreicsal agents, such as sulfur or peroxides, and curing at elevated temperatures. 33002222..00117722 33MM_MMNNo04488s555228811 INDUSTIAL ASPECTS OF FLUORINE CHEMISTRY 67 iNDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 467 rubbTTehhr-eelimmkoeossstttaootebbvviii,oouuosfs caaonnuddr. saa,llssoo htthihgeehmmdoeosgstrteiiemmopfpoorlrtstaatnnittcccdhheaafroraarccmtateebrriiilssitttiicyc oouffndtthehere ttrfhuhoreebbaraecucrttb-iilbooieknnreoosifftsacctseoohmmiopsp,awarnorafatitciinovvueeFlrliysyge.,ssmma8a9ahl.lillgThsstthrrdeeeessgssemresesa.e.xoAiAfmeuttlyymappsiitcciecaaxltldeesnsfsttoricebresmissl--iasstbttyirrlaainiitnyonrumccnauulrdrlvveyeer for rubber is skown in Fig. 89. The maximum extensibility normally 60oi 500 i1i = ii i Fic 30. Type aceexenin ce or slsised sober Percent E|ongatio. 89. "I'ypical force-extension curve for a vulcanized rubber. effaaxlltllessnwwsiiitothhniinnoftththeheeSSo00r00deotor o11f00010040%9Ibrrpaannrggeei,,0w3wi0itt,hh tthhee YYoouunngg''ss mmoodduulluuss ffoorr ssmmaallll extension of the order of 14 tb per in~(137~. B. FLuonine-Contaiixg Bustos tetsTTahhfeueoroooueutttsshttyaalnnedndBeiinn.gga~n'LccdUhheeOcmmRhiIlicNcoaaErllo-CtrOaafnnNlddTuoArttIhoNheeeItNrrhmGmyalalEelLnAepp,SrrTooOptpeM oergrEtetRiiteeShsserooffwipptoohllyymmteheerrss ioonf-f ctcaerprteepraalaissfciilnauntggoirooiinmemst,pphoohyrralttevaanenneccreeeasnuooldffteeedcvvheeirlnroarhhoiivtggerhhirfeyelrurlottareoermegmtpphreeyersrlaeeatnauierrec,ehsstaoiinngndetmmdhieeilvlrliettalawrroyypitmhaaennnddtthefooftthohinreetrrtabtoouptpmmlaioacnkkaleetyiofffnluuosoou,rrrihinnaheeva--evcceoornenatstuauasiliitnneniidnneggdinceaalanasysvttoeocmrmoyemremlsrae.sr.rgceM Miaraaelnnsyyesaissrgycynhssiftteiaecmnmadsnscedhh.aeavvvTeeehlobbeepeseemenneanssrtttcuu:eddfiifeeoddr,,t but only four have attained any commercial significance. These are: 33002222..00117733 I3MM_MMNNo04488s555228822 448688 Hn.eG.. pBaRYvCeEs ("((K11))ELCCooPppooBllryyammneedrrssBlooaffstccehhrllosor?rot)tcriiffluuoorrooetthhyylleennee and and vinylidene vinylidene fluoride fluoride ((""KV@(EI2))LTO-CCFNoo"p'po}oBllyyraammnnededrrs"sEFlaooLsfftUomOhheReerxxEsaa*Lfl)l.auTMoorrBoorpparronopdpyyEleelnnaseetomsaennrdds) vviinnyylliiddeennee fflluuoorriiddee ("V(2(I33T)))OHPHNoooml"mo]y"pmooepalronyldmyoefm"raFemfrLe1oUtf,Oh1,R113E--,ddLi3hh",y*yddSrBruooerbbafuunurtdoyyrlsEaocclparrrsylotlaopatmtyeele((r1ssF4)i.4loBBxrarnaaenn,ddvEEill,asstt(ooCmmFeierrC)*e,)-. HIS(CHa) 0) (*Slsic L553"). (4) Polymer of methyl 3, 3, 3-trifluoropropyl siloxane, viz, (CFaC~- H4Si(CHa)--O)r,, ("Si.lastic LS-53%). C. COPuLYMERS OF CHLOROTRIFLUORGAENDTVINVYLIEDNENEE C. COPOLYMEllS OF CHLOROTRIFLUOROETHYLENE AND VINYLIDENE Fuooune FLUORIDE Tino elastomers are availabe, one kna o"KwEL-nF" Band Elastomer Two elastomers are available, one known as "KEL-F" Brand Elastomer 5500, and the othr know2ns "KEL-I" Brand Blastorr 370003033.150, 5500, and the otker known as "KEL-F" Brand Elastomer 3700(13s,1~9,140). "The forme ea 50; 3 copolymerof chlrotfuoroethylene and vinlidene The former is a 50:50 copolymer of chlorotrifluoroethylene and vinylidene fluwheorearthie tdere3,30:70 f thesm monomer. Elatcty has fluoride, whereas the latter is a 30:70 of the same monomers. Elasticity has been artined by incorporation of methylene groups, -- CH in the been attained by incorporation of methylene groups, --CH.)--, in the nomial rigid, highly fuorinaced polymer chin normally rigid, highly fluorinated polymer chain. "X-raydiaghravaeshmowsn tha he polymerse morphs temper X-ray diagrams have shown that the polymers are amorphous at tempersuresse low as --40C. On stretching (0 300%, typical ier diagrams re. atures as low as -40C. On stretching to 300%, typical fiber diagrams are obicrved, indicating suscepti to orientation and crystal formation. observed, indicating susceptibility to orientation and crystal formation. TTAaBLmE LLXXVV Gus GUM Buona PROPERTIES or OF Tare TYPES 300 3700 aAEvNDou5555r0000oCCHH~ACCFP~s AvAND CFCC] CF~CFCI Courata COPOLYMER ELASTOMERS Peover Gade 700 Gre 559 Property Grade 3700 Grade 5500 Sout gir sas Specific gravity 3 Fare by nigh 5% 5% % Fluorine by weight Cor Ofc Oe Color Shor A bardoen i u Shore A hardness Tid -i o Tg (c) Erna pene (0) 4 51 Embrittlement temperature (C) Tamia prperin of eened gor Tensile properties of pressed gum: Tete sen (om) sow 00 Tensile strength (psi) Fiogeion (2) Ei Elongation (%) Low penta ios, Low temperature stiffness, ST Bos ASTM D-1053-52T: Geman (0 Gehman (C) or ar T~ 7 a8 T~ To 4 T10 1.85 50 Off-white 45 - 15 -64 350-600 500 800 --7 -ll -14 1.85 50 Off-white 45 0 --51 350-600 500-800 +7 +3 +1 "Mins Ming at Vaafictring Company Se. Po, Mirco. *Minnesota Mining and Manufacturing Company, St. Paul, Minnesota. TET. ot de NounrdCompany. 1. Wingo, Dow. "~E. I. duPont de Nemours and Company, Inc., ~,Vilmington, Delaware. owComing Corvin, Midian, cs, :~Dow Coming Corporation, Midland, Michigan. 3300222..00117744 33MM_MMNNo0d488s555228833 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 0 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 469 cT"Tihhseeiopponollyoyrmmeehrrassloaagrreeensslttoaasbbs.llee ttoo tteemmppeerraattuurreess ooff 222277CC,, tthheerree bbeeiinngg nnoo cchhaaiinn sAesis"csTTiaaoanbnbllbeeoerLLsheXXaelVVnogfggeriinvoveemlssostddsha.aettaadaootann,ttbhhoeethgguupmmolppyrmrooeppreesrrttciioeensstaooiffntthaheebottuwitoo0ccoo%ppoolflylymumeorreisrns.e. gaAalnnsaddscsayhhnaasvvabeeteeeesetmmrebabnrnrisifittrttolliemeommnetethnneettmpdtteaeertmmaap,tpeuebrrroaaettthuuorfrpeeo--ssl1ybb5meelleCoor,wswwcho---i5nSlt00eaitCnCh.a.atbGGfoorurraatdGd5ere0a%33d77e00f00lSu5hho0ara0isnsi1eas glassy state transition temperature of - (twCo.grTahdees.Gehman temperature show 0C. The Gehman temperature show 2 similar 15C 15C, while that a similar 15C diffrence for Grade difference for the 5500 is for the tlwlorBBg,oortatahhdnedggsr.roaatddheeessr oocffom""pKKoEuEnLLd--iFFn""g iEEnllgaarssettdooimmeneetrrs ccoaannnstbbaeendmmairixxdeerddubwwbieittrhh pccruuorcraaettsiisvvieens,g, feetihqqlleuueiirgppsum,memanesntnd.td. ooAAthllnettohrhtoocuuboggrmhehaptktohhueednyyodwcicnnaagnn oibbnnoogttprhherdobblieeeonnbbtgsaaenndoddneemiddsltlarrineendaagd.dairilldyGy rrooaunndbeb2ae5rrru5upb0br0bboeecsrrehsmmosiuilinllllgd,, tbhee mgiullmesd adto Sn0o-t65brCe,akwhdiolwenGroandepro3l7o0n0gesdhoumlidllibneg.haGnrdaldeed 5a5t0705-s5h0ouCl.d be milled at 50-65C, while Grade 3700 should be handled at 75-90C. 11. . VVeualcnainziazattiioonn readSSiilinnyccveeultthchaeensseiezeppdoollybyymmeenrrossrmddaool nrroouttbbppeoorssssecesussraaatnniyyveuunsnsusaactthuurraaattiisoounnl,,futteh.heeyHyoaawrreeevennroo,tt tctrhehyaeeadyynialtycceaa,vnnulabbcneeadnivvzuiuelsldceoaacbnnyyiiazzneenaddoterm-wwaiaimttlihhnreuoobrrcbggoaeamnrnbiiicccnuarptpaeietroriovnoxsexi.siddesesuAs,,chcppoooamlslypysaaaummrliifinsuncoers.ns,,Hoppofoowlltyyehiviessesooer.-., cscceuyuerarniinnnatggthesassyty, sspttaeeenmrmdossiiiidssseosschhayoonawwdnnnaptoeiinn-layTTmaaamibbnilleneeeLcLcoXXumVrVIeb.Iii.ncaFFtrritoooonmmsb.etthhApeersseeefceddoramartetapda,iitribccsoaoatnnnhbbefoerfccolltmeehaaetrrshlleyey sssettaeannn"ddTtpphhoeoaiitnnpttpereooorffovixccdiuuderreeevauttnliimcdmaeenpioaazlninynddagmppsihhnyyyesssticieccuamarlletppaarkrroeoepspeteorartdtibiveeeassnptoorafefgfeetthhrreoeefdvv,tuuhllbeccoaantpnhirizeazfsrtaeeoesnms(c~(ea3ths9oLe.f tbthhyee Tdhhehyycdedorrmooppggeoereosnnixanaidttgoeommovsrsuglooacnnnaincttihhzeepineccrghhoaxasiiyinnds,e,tseww,mhhititchcauhhkseiisngneaaandebbvraaaassntiiticcanggsseyyassocttetfemimvtheaaerrseepirasaebb,sssettnUrracnacecdtteeeodrdf bplpiryrnookppdaeeegrrcesoccmoobnenpdtdoiwitsteiiinooegnnnss,c,ohrttaghihaneesns.eeicTaaccphtteeiirvvoeemxecicdthheasasii,nnossxtihaadureess iiignnnettentrrherrerceaaaftciconttregemddualttcoaotipffvoreoorrmvsmiitde--es.CthU--e nbCdas--eer sslittnrrekeBnanegggnetthzshobrryeeeltqqwuupieirreeeernddoxct0ihodaeiaanccscci.eselTleethrrhaaeteteemtmtehhoteeasltccouuxrreieefd.cecstiinvetheanfdormcounlavepnrioevnitdeptehreoxbiadsee cfcuourrraatBttihievveene,z.ionTTyihlhiaeelprreoeerrcocoxommimodmlmedeeinninsddgeetddshctauecgure.riminnogTgschtcoeondenpifdftrietiecioostinnvscseuaarrraeeenid11s55--fc33oo00lnlmmvoeiwinenndieaatntbyt1111ap00ne--r11oa22fx55eidrCCe. fccouurrreeTthhiienneaainonnittohoiavevlreennorraeatatmc11toi55lv00deinCCsgtffooosrtmragttoiiemnm. eeTssthhuueepppp1toor0lesy11s66mebchrrurrddieseeipptseehnnefoddl--iilnnoCggw,eoodnnwbtthhhyiiicccakkhnnneesrassefs.at.cetrs- rrleiesaatddeTidill,hyyehwweioxitttahhhmeessrtttrhrroeoynnalggceltlniyyveebbdaaisasiaticocm,,minssettoe,errniitccetaathllrlelyaycptuuohnnylhhyliiemnnnddeeererpreieesddntthaaammmeiiinn-nee-eCs,s..1a,OOnFdwf httthihrceeihetaahrmmeyilainneceentsses tldteiisettaraeamdmmi,ininenheeetxhaeiimmmbpeepsatahtrryttblaelntthaehenecdeihhaiiimgnghhisneetsesrt,testsett-etesrnntassreiiatlliheenylpssettrnrreeoennpggptetehhn.r.ttaimiW Wsiianittcehhh,icahhvneeedxxdaatmmwrieieetttthhhhyyytlllheeernnneeeee ddppiaiabarratmtsssiincooeffctaaahmmdeiinnpbehe.eo.sstM Mpbehaetalttaaaelnl,cooerxxieiidndeeussss,t,eredsssuustcc-ohhsmtr1aoassdinezirinpnscrctoeopoxxteihridtdeieeeasamaninisdndeacllehveaauieddlvcsaseaandllitszws,a,ittssihuounccthhhsrne1ade6s dttooibnnaAeesumuitctirrnaaleleliaizzdesetpaaohcccioikddssiipccshbhbayoyte-u-,pplrdraoordedbueucuctsctsesu.d.retod moderate the in the press amine for 0.5 vulcanization and he at 150-175C andAimn itnhee ostvoecnksatsh1o75uldC bfoer c5u-r1e6dhri.n the press for 0.5 hr at 150-175C and in the oven at 175C for 5-16 hr. 33002222..00117755 I3MM_MMNNo044885555228844 mn no. BRYCE 470 H, G. BRYCE TABLE LxvI TABLE LXVI Cuno Svar ron Types 3700 and $500 CH,CF, ao CELCEC] Cororsan CURING SYSTEMS FOR TYPES 3700 and 5500 CHzCF2 AND CF2CFC1 COPOLYMER Erno ELASTOMERS Type af care Persie Polynit bocysrac: Type of cure-(ede amen ne (stock number) --_-- wm -- 1 Compound Freasmer 3700 wow -- = Elastomer 3700 Flame $500 202 ww Elastomer 5500 Zine wide wooow ls s Zinc oxide Dyphos wow SC Dyphos Beran pers y oz Benzoyl peroxide TMEIRDAdoo 4- o=o 3 5$ MID-100~ TEPAb Haba 5-2 HMDAc Low molec weight polyiylnes 025 Low molecular weight polyethylenea Peroxide 89 Polyamine Isocyanate 282 1 Isocyanateamine 98 100 100 -- -- -- -- 100 100 10 10 5 5 10 10 -- -- 3 -- -- -- -- -- 5 5 -- -- -- 1 -- 3 -- -- -- 0.25 -- -- cuPeres (a) ye se aw uo Press (hr/F) Oven) ro nto m2 wm Oven (hr/F) Physical properics Physical properties SirSe50s donation (5) mo m0 wo eo Stress at 300% elongation (psi) "Temi stn (| some swe ow Tensile strength (psi) Fongaion C9) wwe ww Elongation (%) Harboe (Shore A) ss aw Hardness (Shore A) Comprenionse 1 br 4 21F) BB pen mow Compression set (16 hr at 212CF) Se ae ~ di(4-phenyl isocyante)methane. ~ tetraethylene pentamine. Primm c Hexamethylenediamine. Prot a Plaskon 8416. 1/2/300 16/300 1/41350 16/300 11260 72/212 lj260 16/212 1300 3500 500 58 25 1500 2000 400 58 29 600 800 320 61 rupture 630 1280 580 60 rupture Among the che22m..icPPahhlyyssiiaccnaadll aahnneddatCChhreeemmsiiicscataallntPPrrroouppeberbrtetirieesss, "KEL-F" Brand gEEolloasdsAtteoomxmmtoeeennrrsgssibtaaihrrleeeitynncooh(tteaambb3llieeca0lffoorra0nttdhah-eenihidrr6egahhotii0oggrdhhe0ssbittseret%nanasssniiitl)loeernussrbtterbrseeiennsrtggsat,tnhhc"e.K((22ET00h00Le00-s--F33e5"5r00u00Bbrbppaessnir))ds,, ghohfoaavvoteedheebbixreetecetnnennsasaiiggbleeieldditsyfftoor(rre3n066g000t-h--6880a000n%dddaa)cyylssaonnaadgttag44toi00oo00dnFaFabnrwwdaiisttwihhoioontuuhrttenslloioossstaiianpnngpgcremem.coToirraheebelstteehhaiarnnnucbr22be55ea%sr%se inof in hhth"aaTerrhdidernneethessinssg.shiledesgtrreeengotfh and elongation and with stfincss developed st its no appreciable corresponding increase 7, value ((001toT0"Thh-ee11ph55oiglCChy))mdemmeraagsyyrbesbeseecoanafdodstetetiaftrfrfinifmemecseetsnnetddt ettbovoyesslfoooumpmmeeeidnaagapptpnpliiittclsraiictciooc3rnrasieotdsofpifaotntonhhddenesistnseehgemmaTpate~etrerovrixiaaaillludssee.. vcvauunlliccTzaashnntieiezzsapatoteaelsrymoofsfelrGGsorraaaqrddeueeinteo5$t55r00ae00fsfiesaactrrtaeeendtsswwbteyoelllflheeuyddmdrioononngcllayynribaatrobbinoocuutamtciin22de00r-a-a3n3l0d0%%ot.ih.se,TTphhseeierloixvvciouudnllee-- canizates are also quite resistant to hydrocarbon mineral oils, silicone 33002222..00117766 I3MM_MMNNo044885555228855 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY ru INDUSTRIAL ASPECTS OF FI.UORINE CHEMISTRY 471 ocoalilnssi,,zsaatnnedsd assriielliichcaaittgeeh--blbyaassesedwdolsslyyennntthhebetytiiccthffelluuiidddiss.e.steHHroowwaenevdveerrp,,hottshhpeehaggtueummesaatnend-dbavvsuueltd-efuilasduneisdidz.sa.2tseTTsrhheaeefriegeeellhraaiassgnttohtomlsmyeearrsnsswdoaapclrlreeeonpaaelllbsslooyanhhtthiisgeghhallndyydiesssawtwlesoorollllafeenlnnudobbrpyyohcaoccrshhbplloohonrraootfefflluuueioodsrrstooeccsraa-ubrrcbabhosoernadsss uFaFsnCCed--d77t55ahsaearnnreddfrsiFFtgrCCeo4r-na34gn.3lt.ys TTabnhahsdeeiyycpraaaorrmpeeienlaaelllasssn.ootsaaTttyattpnaaicdcckkaeaeldldsodqqauuftiliautteoeraossreeecvvaeerirbrneeocllnlyyufdbbleuyydidhhsiyyndsdrurTaacazzhbiinlnaeees and other strongly basic amines. Typical data are included in Table LXVIL Tam xvi LXVII. Cuenca CHEMICAL RREaSsIS(rTaAAsSNcCTeEMOorFDCC AH HTL2,CCMFFeztTA4hAN0oDBdCCLBFFE;~ECITC.tyX"]CpeI-CICSIOo0P0Or,LPYoeMrnEotil dEELeuAsCStTuOorMn)ERVerena. VULCANIZED (ASTM D-471, Method B; Type 5500, Peroxide Cure) tin wo) Media Time (days) ------] 2s Red fuming nitric acid 27 Fuming ites 7 i Fuming sulfuric acid 27 Hydrocchdl(o3r63i70c) 31 i Hydrochloric acid (36.5/o) 27 Propionic acd (85%) 7 i Phosphoric acid (85%) 27 Hrdrotoors sid (at) 32 FH Hydrofluoric acid (48%) 32 Petes eit = i Petroleum ether 27 Ed skatel 5 H Ethyl alcohol 27 Tohene z is Toluene 27 Anne = i Aniline 27 Coven thirds 7 a Carbon tetrachloride 27 aan luene (030) 27 a Iso-octane/toIuene (70/30) 27 ASOT 7 0 ASTM Oil No. 1 7 Shae vr hid J Silicate ester fluid 14 Prope cr uid 14 50 Phosphate ester fluid 14 Dicer brant z is Diester lubricant 27 Soper 7 50 So~r crude 7 Siaoe DC-100 2 0 Silicone DC-200 7 ercicren i = CF~CICFCI~ 1 Temperature (C) 25 25 25 25 20 25 25 25 25 25 25 150 150 150 25 150 150 25 i -- Volume swell Co(%) Py24 |1 16 \1 515 513 .6 555 `5 533 oo30 2-2 =25 fo70 @600 rg10 \1 i180 highAA,lltththhooeuuygghhcatthhnee bvveiissccocososiimttpyyroeofsfsttihhoeen ""KmKoEElLdLe--dTF,"" tEErllaaansssttfooemmreermrssoliidsseccdoo,mmppaerxaatrarttuiidvveeedlly,y qchcaaiugllieehpnn,ddmeeetrhrneeed.dy,, ddCciioappsnppteeidbdn,e,g aaacnnnodddmsspdpprirreepesapasdidioncgncooasamotteleodudltdiuueossdniisn,nggotrrssatanacnnesdfdmeaearenrddtmsrrouuhlbbadbbveeeedrr,bppeerrexooncctreeumssdsiaeindndgeg., fuefrsqroeuomdmipmb5b8ooettnthhht.eGGCrpraaroddiaemetisasnrg$3y77a00sn00odlvaaednnndditpsp:5Si55n0a00gn0..dsoKKaleluetittopoiohnnaenetsssi,,coeerassnttceederrssma,,reoaanmnntasddtihcccayycvclehliiyccdbreeeotetchhnaeerrrmbssoanaadsrree.e `uasneddalacsohtholes parriemsaartyisfsaocltvoernytsd;iluaenndts.aliphatic and aromatic hydrocarbons and alcohols are satisfactory diluents. 3. Aplications andTTvhhueelca""nKKizEEeLLd--sFFt"a"tesEE.hlasTstntoommtheeer3rss.unAhhvpaaupvvlleeciacnaffoitoizuouennnddds fuuossreemss, iiintn ibbsoouttshheduunnavvsuulalccaabnniinizsdeeeddr and vulcanized states. In the unvulcanized form, it is used as a binder 33002222..00117777 I3MM_MMNNO044885555228866 4m7n2 6. mee H.G. BRYCE ffaoosrrtccheeerrtthaaiiignnhppdrreoonppseeilltllyaanntatnaadnnddiseexxhppillgoohssiifvvleeuossryyissntteeemmcsos,n,twwenhhtee,rreearttehheeimsspttoaarbbtiiallniitttyy.,, aaIssnwwteelhllel 10vaVsuuplltccuhaaemnniiphzzeiegdadhvssatdaaretitene,,tsyiiiotttyfhacaaossnrdfrfoooiusutinsnvddheissageechrvivdifiicclcueeoma4raistne3aerillciainolneensrrtieffnnooctrrl, ua2adriccenhhgereimmmeidipccfaoalurltmappinuuntmm.gppInnuiutsstcheeidedc antaoicctiirpddi,,ucfmfuuapmcmiidain,nvggiastsruiuhlelaftfyusurrobiifcececaanoccridrrd,oe,spttioivitrtaetaneanidciuiumtdmhicattteemttraraaatc"cehhKrllioEoarlrLisidd-eieF.n.c"OlOunEndlihhnaasagnntdrodelmldiiennrfggulmrrieeniddendgffuupnmmuiitimrnnipggc nhnhoaaittssriiccbbeeeaaeebcnlnied,rrsuuwitnenlnnhliianinsngggbocecoeonnncttoiirrnenruupoooosuuirstoselnldyy. tIffhtooarrhta11sa44a,,"77sK00o00E,,f0L0o00-u00Fn"dfflleueExxsleaccsayytsocclmlseeessearlW wsliiinittnhehodosuyutpstutaaemnnmpyys hhnaaonntidAdclsleiiannbwggleeccoossrwrhrraeoollssliiivnvseegeeccohhrleaecmtmoei,irccraoatllshssieoiinncn.chclllIutoudrdhiitnanrsggifattilhhsoooorssofeeeotummhneyednlnettuniioesoe-nnveeaiddsnysaalebbiaoodlvvseeeni.en systems fluoride cicnootpphooAellsyyammwreeeerar seoehllfaaasrlsltetososmimeseeetrarssnlacteaaertrreo,sssttuuhrppeeoernrciighoolrrcoorttroortorooistftitlh~vueeeormrrioffnleluetuhoroyrraololeccanaacrerib-bdvo.oinnnTyttyhlyippedeeecnecoellpaaofsslltutoyoommmreeiedrrresss toionoff thbhhoeeetxxhaaarlfeluhuaoiorgorohfopprraeroonspipdsyytlalleenonncwcee ttaaoennmsddptreovvrniiangntyyucllriioeddrerenosneeserivvffiellcuuemoorriaiindsdeeerawelaalrraleecid2gg5.eennTegerheranealellrlcyyaolpssouuslpaypelmervrieeioonrrtsr resistance. to both high resistance. and low temperature service as well as general solvent DD.. CCOoPrOoLYrM yEVaRsaS nOoFFiH HaEEXX:AATFFLLU UoOORRoOOPPnRROOPPYYLLEEN N.E ANDAND mleAAtrttahthieeo ppcrroeesspeeonnlttymttehhreesmmooosfVstIthNeuuYsxsLeaefIffDuullEluN oecrElloaapsFsrtLtooUompmOyeeRlrreIssDnEeooffattnhhdiiss vttiyenppyeeliasdrreeenetthhfeelu22o0r0i:d8$:e00. These elastomers are mole ratio copolymers These elastomers are available commercially of hexafluoropropylene available commercially under the trade names, and vinylidene fluoride. under the trade names, Tame vin TABLE LXIII Turan Baw Geos Promos 1 CuFoCHCEs Cours Euros TYPICAL RAVe' GUM PROPERTIES Ot, C~F,CHgCF2 COPOLYMER ELASTOMERS Specie srry Specific gravity rrr we % Fluorine by weight Color Hires (Stare 8) Hardness (Shore A) Ernbrittlement temperature Eo onpertae n Low temperature stiffness ATVDis 521) ASTM D1053-52T) Gehman "ErT2 byT5 7Tio 1s1.85 Fe > 60% off-white I)40 -- 45 we -- 10C Sie --15C Ee --17C ""IVnVcII)TTOaOnNNd"""FFFllLuuUoorrOooRccaaErrLbbo"onn BEErllaaanssdttooPmmleearrsto((EEr.s.erI1..(MddiuunPPnooennsttotddaee MNNienemimnooguurarssnd&&MCaCono...,, Inc.) and "FLUOREL" Brand Elastomer (Minnesota fofac--tu5r0ingt0C3o0m0paCn.y). They are wable over the wide ufacturing Company). They are usable over the wide temperstre Mining and temperature range Man- range of -"5Ty0picatol p3r0o0peCrt.ies of th ra gum stock are incliundTaeblde LXVILL, Typical properties of ttte raw gum stock are included in Table LXVIII. 33002222..00117788 I3MM_MMNNo044885555228877 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 473 1. Vulcanization The copolymer structure consists of alternating methylene and difluoromethylene groups interspersed with very short branched fluorocarbon chains, the latter resulting from the hexaituoropropylene molecule. HEThe structure may be represented as: CF ettysy tfeetynetre] , i ee The chemical stability conferred by this structure, while valuable in the cross-linked molded elastomer, makes the problem of forming cross links difficult(141). ae ene Three general methods are known by which cross links may be intro- duced into these elastomers. They are: (1) the action of aliphatic amines; ERrE (2) tl~e action of high energy radiation; and (3) the action of peroxides. For this class of elastomers the action of amines is by far the most important. Except for some specialty peroxide cures, all tlxe commercial curing formulations contain organic bases of some kind. Smith has shown that the cross linking of C3F6 and CH2 = CF2 copolymers takes place by a three-stage process(142L Bases, high energy radiation, and other radical generators, in conjunction with metal oxides, react with the elastomer chain at the poly(vinylidene fluoride) segments to form double bonds. During press cures at or around 150C difunctional cross-linking agents such as diamines or dithiols may react with these double bonds to form some partially cross-linked structures. During the oven post-curing cycle at 200C, conjugated double bonds systems are formed by dehydrofluorination at points adjacent to the double bonds formed in the first stage. These unsaturated centers then react to form direct carbon to carbon linkages between chains. The resulting vulcanizate is largely stable to heat, the centers of instability having been removed by the oven cure. For example, these rubbers maintain their properties EopyEeEmER ts8 A fnT ds well even when subjected to temperatures of 300C for times up to 100 hr. Oven post-curing is recommended for nil fluorocarbon elastomers, not because good properties cannot be obtained by a direct press cure, but because the centers of instability produced during press curing must be removed in order to obtain a vulcanizate which is stable at high temperature. After the post cure, subsequent heating of the vulcanizate at 200C for prolonged periods of time causes no further degradation or crosslinking. Amine cures are the best method for processing the polymer to a vulcanizate which is stable, both to high temperatures and to chemical 33002222..00117799 3M MN04855288 a vows 474 ~. G. BRYCE eh shoes http pi, rio gol attack, and has the best obtainable physical properties. Amine compounds me friedyyey such as the carbamates and diamines confer additional advantages of A processibility and are thus preferred. 2 Compan 2. Compounding The ge con be coy smo vl ill and i The gum can be easily compounded on a two-roll mill and can be em od elil dn fe successfully extruded on standard rubber tubers. A typical general puriypdm Sd i er mlpele pose compound with good mechanical properties is shown in Table LXIX. GENRAL I TABLE LXIX rm ms er rs PURPOSE FORMULA AND PROPERTIES FOR C~Fs,CH~CF~ ELASTOMERS i Recipe Parts by weight ---- I Base Elastomer 100 fo, 3 Magnesium oxide 20 Er= B Medium Thermal Carbon black 15 Cot . Hexamethylene diamine Carbamate 1 hr in press 24 hr in oven 150C 205C TT eemenze Properties at 25C ST Stress at 100% elongation smn EE Tensile strength a 3 Elongation (%) Erk. 3 Hardness (Shore A) = JC Tear strength 320 psi 2300 psi 320 65 180 lb per in. 13ers sre Te 2 Sey sch The formula represented in the above Table has a Mooney scorch i ed ds Tite be 2 ey ot rating of 8 min to a 10-point rise. For safer processing, modifications can BtnMe Bor prem odin mn be made so as to increase the scorch rating to the 20-30 min range for a fom 10-point rise(144,145,146). ee ote a ass ote ls All compounds for these elastomers contain at least three different a a lr in fn types of compounding ingredients. These are acid acceptors, fillers, Et aptrls The med amr, Sey and curing agents. Plasticizers may also be used. Metal oxides such as Fe fe Me ie magnesium and lead and combinations of zinc oxide and dibasic lead Spi 2 nk ontonsof oeoe phosphate are commonly used as acceptors. A number of fillers, including 33002222..00118800 mons 3M MN04855289 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY os INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 475 abbmoototkhuncctaasrrbbooofnnfibbllllaearcckkaraaennuddsemmdiinnteehrraaanll iffniillllecerossn,,veccnaatnniobbnees]uuseseehdds..toGGmeeenrneseraraltlollyy,a,vossmimdaalllelexer.r accemesssoi`iuvvAneeitssdstteiiofffffvnnaefersisslisl.et. ryoafrpeoluyseadmitnheasn in conventional elastomers will cur the CyFeCH= CF to avoid elastom ex- ers, bbcauurttbAaoomnnwaeetideoo.effvttaShhrieeinectmmyeooosstftthpispporrlayacccauttmriiiccinaanlglesiiassgwetthinhletel chhtuiiernnendddeetshrreeetddoCpparoFoel6layyc,CaatmmHiri2nanpe=ei,,dClhhyFee,2sxxa1eamlmaeesitttnhohcymyrlleeeeanrnsesee., pcpraroorbccPeaeesmsrssoaiinxtnegig.dsseSaa,ffientstcyyuecaahthccaioossppppbceeeurrnrizniionngshh]iiabbgipitteeoornrrotx((itrrdeeeentt,adarrsdwdieetlrrol)) ariiselssauvocsetecddurarpiiennidtsshlyoeo,msmeeetoelffoaoisrnrmtmcouruemlleaaarssses. cbbauunttiPawwaeitrietot.hhxisdsPoeoemsmr,oeessiudddicifefhffiicccauuusllrttyebydeeennnzsccooooycuulknnstpteeerrgreoeeddnxeidriinaenl, lppywrreeivlvhleaenvnatletsiinonpggocopuproorerrooctsshoiimettyspyernieneslsattisihltoeeonmvvuueslerl-st- Acrreeassnhiiisisztugaaahtnnecc.see,t,Peebbruuootftxicdddueooreececxuxharhienibdbisittlsotggooocbookedds degrrveeeessniilessotrtapaanelnldccyeebhyttaooevxerrpeeodpdsouofrfureummtciioonnmgghipgnnrheiitscrisiiniccotenanasccisiddte.y.t beAbRteEtahaPiogorhfrogslgatlaaommtwememdoaafbrrcyaauddrihieaeatatciitooainnnn..galFFasootorr2b0eee0xxadamme2pv5ple0leleo,,Cpaaeydi]fe3-bl-aydrdsaiedaxpiathptyioisoosinnucraeddlootsspoaarggohpeeiegroohtfif1ie1nstexcnos11im00t-y77 pRaEraPblfeolltoowtehdosbeyohbteaaitinnagblaet w2i0th0~b5e0nzCoylyiepledrsovipdhey.sical properties com- parable to those obtainable with benzoyl peroxide. 3. Physical Properties and Chemical Resistance of Vdeanizales 3. Physical Properties and Chemical Resistance of Vulcanizates In Table LXIX sre included typical values for some of the physical In Table LXIX are included typical values for some of the ph.ysical properties of the vulkanizate, Table LXX shows the per cent swell of a properties of the vulcanizate. Table LXX shows the per cent swell of a TABLE LX TABLE LXX Chesien, Rissoe C.F CHLCF, Evsstovass i Vesa Sear, our CHEMICAL RESISTANCE OF CzFmCH~CFz ELASTOMERS IN VULCANIZED STATE, POLL- a Con (evnda neers) AMINE CURE (seven-day immersion) Meta Media Sodium tydroide (165%) Sodium hydroxide (46.5 %) Faring Sur sid Fuming Sulfuric acid Hyder cd (483) Hydrofluoric acid (48/~) Hpdrchioric acd (363%) Hydrochloric acid (36.5/~) Glial see sid Glacial acetic acid Rel fami nie sit. Red fuming nitric acid Coben biol Carbon tetrachloride rivwing Ethyl alcohol in Aniline Benen Benzene fr -- Tricresyl phosphate Mey ea ere Methyl ethyl ketone Iocan (7030) Isooctane-toluene (70/30) AST OF ASTM:~3 Oil Slice ur id Silicate ester fluid Slice sur hid Siiicate ester fluid [------ Temperature CS wal (C) = a 25 x i 25 = i 25 x i 25 = pn 25 x EY 25 i 13 25 = i 25 x 30 25 i we 25 sto aio 300 ES nro 25 = 25 25 sto i 300 S00 is 300 io fixt 400 Volume swell (%) 2.1 4.8 4.8 7.3 61.6 74.0 1.3 1.7 3.0 19.6 24.0 287.0 2.5 4.3 1.8 11.1 Phosphate ater fuid Diester lubricant Phosphate ester fluid 300 200 400 19.6 300 270.0 33002222..00118811 I3MM_MMNNO04488555522%900 47766 Hn.oG.. oBRaYeCrE apptoolltyyeaammmpieinnreea--tccuuurrreeesddspvveuuclilccfaianendii.zzaattTee,, waaiflftlteerbesseenvvoeetnne--dd.daatyyhiiammmhmeeerrsssiiooolnnveininnt ttrhheeesismmteaenddciieuumims sHagteiendnte.eerrmallApllnyyeoratvvteheurreryyresggooousooptddsetcwwaifiniitdethhdin. ttghhIetechweeaxxriclaclceetppbetteriiioosnnntoiotoceffdikks etehattobaoinntlecitssthyeaanntsoddolaraveeppcnhohtvooesrsreppshhifasaotttlaeelnoceewesistnteegirsr. cfloumidp.reAssniootnheart o1u50ts-t2a0n0diCn.g characteristic is ability to recover following compression at 150-200C. 4. Applications aloTThthheee CCvu3FlFc6aC,nCiHzHaa2t=e=sCCFFp;o2sseeellsaass4st.togomoAmoepedrrpsslaiclaaalrrt-eeiroonrrueesnllaadttiivpveheyllysyiccesaa]ssyyprttoooperpptrriooecsc,eessssThaaenndyd aha5la0vsvo0eeCtuuhsseaeenffvuudulllgcppearrnnooeiprpzeaearlrttletiyiseessrpeobbssieesstttewwseesceehnnegmotitohhcdeealattelelamm-nrppodeuerrnsaaodttluuvrpreeenhtyeesxxiactttraareclemkm.peerssoCpoooeffnrsti---ee5qSsu0.0enTCCthleyttyo,o tt3mkh0ieel0ssieeCareeyllaaanassdnttodomgmceeeinrrvseslriahhslaanlyvveeaprpeaalsttiitasactiaintniceeohddnesm.ccooiIncnsnasilciddleaeurnrdaadebbdllseeaomlccvoooenmmnmgtmetraehctrteciaiacmalkla. nuwCysaaogganeepspelffqioocurraetbnbiotoolttnyhhs, maaarrueietliotOOma-or-rytriiinnavggnessd,,trcssaievanailsllmsisainsffsooairropnpvvlaaifllclvvaueetissido,,sn,ssscae.aialrIlscsn.rcafflfouotrrdaeccndoodnnattimaanccdottunsgtwirttiihtahhel mahaioisarsccnerr,ayaftfpa.tpuffpmuuleiepcllsasctiaaoonnnmdds apuontoenmtos,tivteantkranlsimninisgss,ionanfdluigdass,keatiircnrgafmtataenrdialisn.dustrial hose, pump com- ponents, tank linings, and gasketing materials. E. Fuuomye-CONTAINING SiticoN Russin E. FLUORINE-CONTAINING SILICONE RUBBER contTahienincgosmimlearnec,ially available product is derived from The commercially available product is derived from the the fuorine fluorine containing silane, cCFrscCiHu2cChH;z7cCHs \ / d/siu\ CI C1 Taahnnidds iipssrodddeeussciigtgnnhaaatteseddthaaessty""pSSiicillaaalssttviiccyLLSlS-o-5w53Yo"p'..er((aDtDioonwwg tCCemoopmrenirinnaggtuCCroeorrpopofroasrtaiiltioiocnno)n.)e. Truhbisbeprrsoditucctanhabsetuhseetdypoivcearl tvheeryanlogwe -70C to 250C, operating temperatures of silicone rubbers; it can be used over the range -70C to 250C. TABLE Lxxt TABLE LXXI Pron or Fuzososuicons Rowson PROPERTIES OF FLUOROSILICONE RUBBER Specie grit i Specific gravity Toke (hoe) 50 Hardness (Shore A) Teme sens (300 Tcnsilc strength (psi) Elongation (4) 0 Elongation (%) Be point Zoe Brittle point To erste ios Low temperature stiflhess Gehrnah a "we T~ 5 Zac Ts 1.4 50 800 250 - 68C - 18C -47C Tlo -- 60C 33002222..00118822 33MM_MMNNo044885555229911 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 7 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 477 atom"TsTh,heeheppaootllyysmmteaebrrleccoognnrssioisusttpsss oobffeillonongnggatccthhaaaciihnnessdootffoaaellttaeecrrhnnaasttieelissciiollniiccoaontnomaa.nndd oxygen oxygen wathoimT"cThshh,eechaccenooammt mbmseetraecbrvcilueialalclgarppnoriruozopedddusuccbtitneiissn$gsmsuuiappntpptlaliicaeehtdded13a2ss5to2aC.ffeuuallcllTyhyhccseioolmimcrpoeponcououamnntmddoeeemnddd. emmda.atteerpriioaasl,t, oaworvvheeeinncshhccouucwrraneen iiisnsb2eT24a4vbhhulrrlecaaaLtntXiz11Xe551d00.CCi.n. Typical properties of the cured ehstomer 5 min at 125C. The recommended post Typical properties of the cured elastomer are shown in Table LXXI. Tang Lx Souvess RessTeAoBrLEFuLsXonXoIsI ions Eamonn SOLVENT RESISTANCE OF FLUOROSILICONE ELASTOMER Nein Conditions. Media Conditions Hone Iso-octane one Xylene Coron nhs Carbon tetrachloride Faby satel Ethyl alcohol ere Acetone i ctr eiene G30) Iso-octane/toluene (70/30) AST ai 3 ASTM oil @ 3 Dies brant Diester lubricant Prrapate eer Phosphate ester Shen rr Silicate ester dase 7 days at 25C amuse 7 days at 25C 7dam C 7 days at 25C amuse 7 days at 25C Taman 25 7 days at 25C 3dors C 3 days at 25C Tamaiiec 3 days at 150C Samui 3 days at 175C Jamie 3 days at 120C 3dr 3 days at 175C Volume wel Volume swell (2(%) as+ 15 Tn+ 19 ia+21 =+ 5 +i+ 180 2+20 Sw300 rl+ 5 oan+ 11 %--5 resiTTshhaneecfAelouorovirenirne-etc-hcoeonntgtaeaininenirinanlgg spsiiulliricpcoaonnseeeeeslliaalssittcooomnmeeerrclkhsaatssommmeuurcsc.hk iiTmmypppriroocvvaleedddasstoolalvveeanrntet shown in Table LXXIL. resistance over the general shown in Table LXXII. purpose silicone elastomers. Typical data are 1. Applications certTTaihhneecffaluuloorrifinnoree-.cacioornnctrtaaiifnntiinnwgghessr1iil.eliicAcaoopnncpeeolimcecballaitaisnsotatontomsimoeenrr hhofaasssoffloovuuennndtd raaeppsppilsliitccaaanttciieoonnaniindn enceoxxettrtrtraeaeimsnmeesselleoroavwwlisctteefeaommbrplpeeaerir2aracttruutarrhfeeteCffwleaeihxFbeiibr,leiilCittayyHcaaaorreemCiibmFmipnpoaeortlritoataasnnnttto.o.mfIIettssroigssle1vgne0een,nrtearlraellslyyi,s,tahhnoocwweeevvaeenrrd,, not as serviceable as the CaF6,CH~= CF2 elastomers(15). F. FuuoaneCONTAINING AckyLaTe ELASTOMER comm"TeThrheecihhaoollmmyoFop.p4ooFllLyy"UmmFOeeLRrrIUNooOfEf -RC11,,OO1N1R--TUddAiiBhIbNyByIddNErrGooRhkAeeIpCptFRtaa4Yff"LlluAubooTyrrEooaMEaccLirrAnyynSllaeTttsOeeoMtwwEsaRassMiiinnnttirenoogdduusccneeddd MtcMhoaeamnnumufusafeeacrcctotiuaufrlrliiypnnogglaysCCaom"omFimpnLpeaUasnnOyya.Rs. OTTcuRhhreeIiSnBbbgeeBssattEgeRppnhhtysy1s.sFiic4cAa"all btppyyrprooiM pcpeaelrirnttniireeeesscsioapatveraee iMsaattisttnaahiiinnongeweddnabnbiydyn tTThaaebblTlueehsieLLsXXocXfXlIapIIsIotILl.oymaemrinheass as co curing agents. A nsiderably lower typical tensile recipe is steengths shown in than the CaFCaFan3FgTa,eh,CCoiHsfH,~--e1=Cl3aCsFCtFos~mteocerll2aah0ss0attosomCm.ecerorssn..sidIIettrakhbaalssy 3 maximum lower tensile a maximum useful temperature strengths than the useful temperature ' range of - 13C to 200C. 33002222..00118833 I3MM_MMNNo044885555229922 ea no. oRvee TABLE LXXI TABLE LXXIII Cums or 1, 1,DovosoreanvosoncTv. Actas Eustousn CHARACTERISTICS OF 1, 1,-DIHYDROPERFLUOROBUTYL ACRYLATE ELASTOMER Reine Por Recipe Parts Pore iw Polymer 100 Sto id 1 Stearic acid 1 Suhr ' Sulfur 1 Cian hack 5 Carbon black 3S Trchtumine rane 1 Triethylamine tetramine 1 Cor mn SC Cure--60 rain at 155C Physical properties 125C Physical properties at 25C -- Specific gravity Foie wrth Tensile strength Elona Elongation Heres (Share 3) Hardness (Shore A) Genin Silos, To Gehman Stiffness, T10 ete pint Brittle point 1st1.54 0 1250 psi Sut, 300% =55 =9C - 9C Tre -7C TALE LXV TABLE LXXIV Camen. Ressrascs on 1, 1Dirvosormsonomrys, Acsiare Evstonan CHEMICAL RESISTANCE OF I, 1,-DIHYDROPERFLUOROBUTYL ACRYLATE ELASTOMER Metin Contin Volu2me)sll Media Conditions Volume sweIl (%) f= Amwrsc 2s Benzene 72 hr at 25C 25 Acne Abie @ Acetone 72 hr at 25C 60 ieacters (030) 72 he 25C I Iso-octane/toluene (70/30) 72 hr at 25C 15 Atha 4 Them 0c o ASTM oil ~ 3 72 hr at 150C 0 Diet co S001 150 ` Diester base oil 500 Inr at 150C 6 Phase coer 100 et 100C 2 Phosphate ester 100 hr at 100C 25 Sous r 080 1S0C i Silicate ester 750 hr at 150C 15 Bolo id 065%) 72 4 2 5 Hydrochloric acid (36.5~,~) 72 hr at 25C 5 Contented ssid 72 1 25C. o Concentrated nitric acid 72 hr at 25C. 49 Coenincd for id 72 be m 3G 100 Concentrated sulfuric acid 72 hr at 25C 100 Selim mydronie (0%) 73 hem 25C o Sodium hydroxide (50~)) 72 hr at 25C 60 unesIIttterihhfaaissedbbaeeceernnylirrceeppaoocrirtdteedmdotnthhoaamtteccrrrooussnssi-t-llsi,innkwkiihnniggchooccaccruuerrpssreiinnsettthhiiissn ppthooellyyommrieegrrinaaaltt `mumnooen"nsotToemhmreieefrirceohodreramaaircrcreeyafllfioocrrrmaemcseeiidddstmaddnuuocrreniinonigmgs tteihhrleeluuccsntuuirtrrsaii,tnneggwdprhpiorinocccheTessaassbrOel4Se1pl.,r11Le55sX%2e,)Xn.ItVi.n tke original The chemical resistance is illustrated in Table LXXIV. 33002222..00118844 I3MM_MMNNO044885555229933 ousTR Asrcrs OF von CUBSTRY 479 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 479 1. Applications 1. Applications "Fluoronabber 154" is infer 10 CaF Cls--CF clsomers in "Fluororubber IF4" is inferior to CaF~,CH,~-CF2 elastomers in fey ot low temperatures, och fei at High serpent, and flexibility at low temperatures, is much inferior at high temperature, and tached rach more by eomcuted. ii and Sufi ail, I is attacked mucll more by concentrated nitric and sulfuric acids. It ttas, Bowne to est stone 12 ils ofof solvent of an of he however, the greatest resistance to a wide range of solvents of any of the Bunrocatomrs. I ha found ned ee in specaly miliary srice fluoroelastomers. It has found limited use in specialty military service in diner typ ica, in diester type lubricants. XV. Mises and Rockets XV. Missiles and Rockets A. Prunus Gove Jo Bans A. PRINCIPLES GOVERNING JET ENGINES In gen, je engines sce propels dics which cs based on In general, jet engines are propellant devices which are based on Noort Tint Law of Motion which sarc tat the mous action ofay Newton's Third Law of Motion which states that the mutual action of any avo odie vay equal and oppose The propulive fre s ger two bodies are always equal and opposite. The propulsive force is generSed i thee devices by th reson, of mass which are Gecie n 2 ated in these devices by the reaction of masses which are ejected in a dicho oppo to he vetooftion of he deicr Th estioonf direction opposite to the direction of motion of the device. The ejection of teow 2 cere af ance ah th corso of voor mass requires a source of energy and then the conversion of this energy into Kine nergy of the mse 0 be. iced. Akhough ther atc many into kinetic energy of the mass to be ejected. Although there are many sowces of pers hich Ter console homes hain cles sources of energy which offer considerable promise, including nuclear actors, se adain and charge oe, 1 dae the shemale reactions, solar radiation and charged ions, to date the chemical proTeas ete os igs develope pellants are the most higllly developed. "The devcopment of misled focket. dics has becn character The development of missile and rocket devices has been characteronl By parton or Tagen shone fe vo. gent ized by requirements for increased performance from the propellant ete, Fagin a copeelly Acie component of 4 oct amen system. Fluorine is an especially attractive component of a rocket system ee ab goes ot bee ot en sown me Tot sry since its oxidizing power is the highest of any known element. The energy eins with tre bf ora Fc bea of he ow meeuior release with fluorine is also favorably effected because of the low molecular gi ofthe soba pode, I ett ears rs Ep dh oo weight of the combustion products. In recent years research and development wrk has een very xine, and appear a id Ruin ment work has been very extensive, and it appears that liquid fluorine is que praca tow. In abdion, the tenis performane of kd quite practical to use. In addition, the theoretieai performance of liquid Soong and ater Bunene compounds has bo lly demo fluorine and other fluorine compounds has been clearly demonSrna. An excllen summary of recent work given by Ki stratedO.~a,l~v). An excellent summary of recent work is given by Kit od Ered and Evered(l~4). Newrons Second Law of Motion sates that fre i progorional Newton's Second Law of Motion states that force is proportional 0th mera of ching of momeor, Tos low ia corre method to the time rate of change of momentum. This law is a convenient method forthe evaluation of rocket engin tt Amiandy at pertions for the evaluation of rocket engine thrust. Assuming steady state operation, Wi bo propellant fow re nd bait veloc bing omtons, then with both propellant flow rate and exhaust velocity being constant, then he thrust, 7, 5givenby th following sqstons the thrust, F, is given by the following equation: PB am 8 WC~ F = + Ae(pe - p~) (lS) g 3300222..00118855 W3M_nMoNd0s4s8s55z2o9s4 wT "0 wo. es 480 II. G. BRYCE where where 31 = propels flo at, I pe sec W = propellant flow rate, lb per sec CCee == eexxhhaauusstt vveelloocciittyy,, fftt ppeerr sseecc = gravitational sceleuion, f per sect g = gravitational acceleration, ft per sec2 Ay = nome xi ea, 0 Ae = nozzle exit area, ft2 pe = morale chat pres, pik Pe = nozzle exhaust pressure, psi Fo = ambien resre, pt Pc~ = ambient pressure, psi a' th theoretical caloiations the thrust is greatest when pe = fo In the theoretical calculations the thrust is greatest when pe = Pa, Hones, hence, I:wTe, [1 WCe } F = (19) g "The specific impulke Ly is defined ss the ths in pounds force The specific impulse I~; is defined as the thrust in pounds force resulting from the xpulio of ane pound mis per second resulting from the expulsion of one pound mass per second. Fb fore I~p : ~F(lb ~orce-s_ec~ (20) W\ lb mass ]" Pounds fore and pounds mass sre generally canceled, and hens, ry i Pounds force and pounds mass are generally canceled, and hence, Is~ is expres in soni, expressed in seconds. Combining equations (19) and (2) sbove, the equation for specific Combining equations (19) and (20) above, the equation for specific impulie he the orn impulse takes the form, tn== G2 ee a) Iav= -- sec (21) g Using the Tw of conservation of energy, i cn be casly shown that Using the law of conservation of energy, it can be easily shown that the spec impuli in eed to th heat cnegy made svaabe for the specific impulse is related to the heat energy made available for propubion by the folowing cquation: propulsion by the following equation: Lo = Ja [EpRn= [f25HH 2@) = 4 ~ ' (22) where where he = specific enthalpy of propelant gascs within socket chambers he - specific enthalpy of propellant gases within rocket chambers, BTU pero BTU per lb = specie enthalpy ofgases afc they have bn discharged from he - specific enthalpy of gases after they have been discharged from Tociet esate, BTU pr rocket nozzle, BTU per ib = mechanical silent of hes, 778 Ib pes BTU J - mechanical equivalent of heat, 778 ft Ib per BTU J = hea er ole selcsed ding expansion, FT pes mole AH = heat per mole released during expansion, BTU per mole 7 svceage cee wightof hegases, I per mol, .~-I = average molecular weight of the gases, lb per mole. According the Eq. (2) sbov, the specie impale abtsined from According to the Eq. (22) above, the specific impulse obtained from chemical propellant i proportions the square ook ofthe hes made a chemical propellant is proportional to the square root of the heat made Svabl by the operstion of he roe. available by the operation of the rocket. 33002222..00118866 M_MNose55295 3M MN04855295 INDUSTRIAL ASPECTS OF BLUOKIN CHMISTRY 1 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 481 oxidUiUzsseuura,allllbyyuttthhteeherccehheeammrieiccaacllertrraeeiaanccttiitooynnpesccooonnfssiismsttossnoiipnnrobbpuuerrlnnliinnnggisaawhffuiueecllh wwdieitvthheloaapnn. hphoerexaoaitdcteizbbsesyyr,dcdabeenccuootmbmteplpaooevsrsiieisnnugagarleiiinzncettodoertssaaiismimnpspltlteeyarrrpieppnsrrgoooddwfuuiccmttthsso..ntohIInpenroggdepiensenerlerluraapanltl,t,isottnhwheeohficccoohmmmobdlbueeuscvstuetililoooepnns pnbinirttnoooacteiaasottsonommcosasf,n, taahbnneeddavtaaiosumccasoolnnizcwceoiodmtmihtiattasahnnetsttapaarrbbtoissdnoougrrcppttwtsiioiotonnhf ooctffhoemeebnnudeesrirstggriyyuo,,pnt,ffiooollrnlleosowouwlfeetddimnbbgoyyleincccouotmlmhe.esbrPlerielnoeaacastseieeosnsoosffoieefsnnetgehrirgegvyey.an.toVVimnaallTsuuacewbssliftefhoorrLttthXhheeeXpeVernno0eedrr)uggcyytsrreeolleefaascseeoddmiibnnusatiunoumnm,bbereersruoolftfinoogxxiiddinaattiitohonen processes is given in Table LXXVOa~). Tans LxXY TABI.E LXXV I.IBERATION OF HEAT DURING OXIDATION PROCESSES{156) Tener l~eaction KTelrprrsimemsole Heat released kcal per gm mole rr Ha + 0a -+ HaO (g) F$1i0s1 VChEEci)te Ha + [ Fa ~ HF (g) o357.8 "a1o64.2 Ha + ~ Cla -> He1 (g) BEE ERE B + 1 F= ~BFs(g) 2A3E1I1R7.00ARAuGn ) 2 A1 + 1 Oa ~ AlaOa (c) 21.9 309256.9 miioe 398.0 SIIann0 S0RoGve A1 + ~ Fa -~ AIFa (g) Si + 2 Fa ~ SiF4 (g) ssie0a1r 329.0~ 360.1 ldT~ TiihnnisShieis oorb=sgoofad3vcoofrmproopkeal. 2 P + 2 Oa -~ P~Os (c) not a good value for propellant sApirnsa,psiynce FAoTs0coevevs corsn o8f 360.0a systems, since A1Fa (c) never occurs as a Csoolmidplienx tess the exhaust of AF, SEF, a conventionaI ed Pi. rocket. Also entropy effects cause dissociation of compiex molecules such as A1Fa, SiF4, and P=O~. decrEEeqqausuaiatntigioonnmo((l22e22c))ulaaallrssoowiienniddgiihcctaatteeossf tttbhh.aaett ptthrhoeedusscppteescc.iiffiiTcchiiimsmppurulelssqeeuiiirnneccmrreeenaatsseessmawwkiietthsh ditittheacpptrrreaascactostiiimcnceaaglllloymyf oaatlllhewwecaauhyylsysadrddreeowssgieierrinagabbhlclteeonotttfooaitoohnppeeeedrrpaairttnoeedtaauhttcetaasf.uffeuulTeelhlr--ierrsiimccarhhienqmmsuiiixx3rte1tuumsrreueecnhrrtaattimiono,a,ktssheooes tcchooammtbIbnusuossmtgteiieononcnoafpplr,rtoohdedtuuhchectrystse.d.roargeena contained in numb of the fi~ei remains as requirements which such in govern the the hacIne ogfeneeffriacli,enttherroeckeatrepraopnelulmanbtes,r vis.of requirements which govern the choi(((c112e))) oAALfoelh~wfifiggicmhhioehlhneeetacatrutolvvcaaakrlleuuwteeepiiirgnnohpooterrlddoleafernrtthtsto,eo vggciiiozvvm.eeb: uhhsiiggthhiossnppeepccriioffdiiccuciitmms.ppuullssee. redu(((235c)))inALAgotwhhhiieggmhhsiozhhleeeecoaautftltaoohrffewccroeooimmcgkbhbeurtus.stotifiootnnheppeecrromuunbniuittstvviooonlluumpmreeodiiunnctoosrr.ddeerr to to permit permit redu4((45c)))inHCgHioitgmghhbheuhshsieetzaaiettooccnfaptahparecoiptrdyouoccaokftfescctco.omimnibubasuttsigtiyaoosnneoppurrsooddufucoctrstsm.., in order 10 insure sati(s5f)actCoorymcbuosntiovnerporsofdihueocatnts einneragygiansteooukisneftoicrmn,erigny.order to insure ssapeticsT"iffTahihcecetrotreroyaarbrceo,o,tnohofvcfseocoruolsriuiodsrsneea,o,nfdmmahalenniayqytuoioetdtnhhepeerrrrgoypooeppileenlrrtaaaotntitikooisnnnyaaelslttioocerrmeseen.cceoornngooymm. iicc requirements requirements specific to both solid and liquid propellant systems. 33002222..00118877 I3MM_MMNNO044885555229966 a2 482 Hn.o.G, pBRavYeCsE B. Liguio Prorstoaxs. ofthLLriiuqqsuutiiddarpperroonppoeewllllbaannittnppgoowcw]~oee.nrrsLtppIrlQluaaUcnnttItDsesdddPeaeRlnlOiidvvPeeEtrreLiisLnntAgegdN.ooTnnSTeehmmeisillellioodnnevooerrlommpoomrreeentppsoouuhnnadvdses noeoxofttttrhbbermeeueeeslnntyawwricietothhmnoopouulwttexdbdiieffdiffeniivcgciuuclclettosiieen,sss;;atrniiunndctffetaadhccet,,anpllridiqoquputeeiidlsdlteappdnrrt.oosppTeehlullselaaesnnedtt dfrrerooveccqekkuleeoettnpteemlnnyeggniipnntsreeesshsaeaavnreete eSexrtrieomusehlyancdolminpgplerxobdleevimcses1, .and the propellants used frequently present serious handling problems(158). TamLE LxxvI TABLE LXXVI Tuma. Prone o sow Lig Prorziats THEORETICAL PERFORMANCE OF SOME LIQUID t~ROPELLANT8 Onder Oxidizer Yad OCmine I Fuel O]F ratio (weight) (see) HNO rdtming 4 150 a HNO~ (red fuming) JP-4 3.50 242 HNedOfo.m) Hydraive 120 uo HNOa (red fuming) Hydrazine 1.20 260 1.0, I 70 a HaO~ JP-4 7.00 243 Ho. Byline 15 B50 H~O~ Hydrazine 1.89 256 cin Hodes 220 6 C1F~ Hydrazine 2.20 246 No. Hyde 103 He N20~ Hydrazine 1.03 266 combAusllitiqiquuoiindd cpprhrooappmeelbllelaarnntt3,,sbb4yy lddieeqffuiiindn.iittiooMnno,,siitss oolnniqeeuiwwdhhiipccrhhopieisslliiannntttrroodrduouccckeeeddt iiennntgoointthehese ocnnxoooimwwdibziiuennsrtooiaoppnenerdraacttahiioaolmnniqbuuuesisreed afllsiuiqqeauu,iidldicqabbuciiihppdrr.oaopfpMeelwolllhsaaitnncttlhiiqssyyussidtteiemnmpjssre,o,ctpcceeodolnnlsassienipsstattirirnanogtgceklooyeff.t &aeLnlliigiqqiqunuuieiiddds obb(ihxippyidrprooeizprpeegelorllllaaiancnnt)td ssoayyrssltiteqremuominssdspmmfouanaeytyl,unbbeceaeocuhsddilivovyifiddeweidd.ghniciiihnnbttlooise ttiwnswyjooesctetccemlldaasss.ssseeessp,,Tahressa.pptooennlhytty.aapnneLeerooigquousulsliildyyc ss(Whyyhyssetptreeeemrmagsssoliitigcghnn)eiitteneoornsssppnpoooonnnnttsaatpnnaoeenonocutouasuslnlsyyeosuoyosnsnltyeccmoosinngttnraaiectcqatubiliirnene ttsshhyueeistteaccmboolmmseb.ubisugTtsnihtiioetonen'r.ttccyhhpaaemmrgbboeerlir,c, ofwhperIIrennesaeTsTnaattbblhllyeeeuLLnsoXXendXXslVpVioIqInuitaaadrrneeperssoohhupoosewwlslnnyanstttthheeemsyssssppteeerccemiisqff.iiucciriiemmppsuuuliltssaeeblvveaalluiugeenssitffeoorrrs.2a number number of presently used liquid propellant systems. C. Soun Proves is t"ThTehhiere mmsiaamiipnnliaacddivvtaa.nnttTaahggeeeoyofCfs.hsoaolSvliOeiddLnIppDorrooPpmpReoeOllvllPiaaEnnnLtgtLrAroopNcacTkrkeSset,tssonovoveerrtallniikqqsuu,iidd7pprrooippnejeellclaatnnitotsns ssifsyyassctttheeeemdmisrsb,,esfaaiomnnrddpelttiihchnieetcyyyh. irreTenqqghuu.eiiyrreeAhsa2a6saveaarerrnsuuoulleel,,tmnnotoovheinccyoogoaollrpiinnagrgc,t.ass,TTlhnyheoesyyttoarddneookd,srn,iohonttaonhhdaalivvneeejde,cttotaoionbbdene fffiuirreeelddSe.odlibdefporroepellaluanncthrinocgk.eAtss a al result, o have they are easily stored, a number of disadvan handled, and tages in com pfpaoarrriimSssaooonnlncidett,oopprllooiiqpoqureuiildldtahnprpturrsoortpopececlklollenaattnnsrttoalrrl,soooccakkenhetdastvs..perTTeachhineesueyymthhbeaaervvmreeionifianntdiiggoseenanndeeivrsraaadlnlitfaaaigcuelllosotww.ienerrHcoppoewemrr-.-- efoverrm,ainmcper, opvoeomrenthtrsuastecroanptirdolly, baenidngprmeacidsee itnertmheisneatdieofniciisendciifefsic,ualtn.dHsoolwid- ever, improvements are rapidly being made in these deficiencies, and solid 33002222..00118888 I3MM_MMNNo044885555229977 INDUSTRIAL ASPECTS OF FLUGRINE CHEMISTRY INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY " 483 pprrerooqpupeielrllleaamnnettnrrtoosccakkneettd ssuyysssattgeeem.mss aarree oofftteenn ffirrsstt cchhooiiccee bbeeccaauussee ooff ssppeecciiffiicc rroocckkeett preeqlluAAairttteyymgpprieiaccniaatnlls;ssao(on2lidi)ddutpphsrearoogpipeeg.elnllilataennrtt; rraoonccdkkeet(t3)eennhggaiirnndeewhaharases,tthhTrrheeeee pphaaacrrttds::wa((r11e)) tithhneeclppurdroeo-s- ttphheeellTaccnhootemmrbgbeurusaastintiei;oonns(e2vcc)ehhrtaaahmlmebbieiemgrrpnoiaartnnetddra;neetxxahnhcadahuausr(s3tat)cnntheoorazrirzsdl.etw.iacroef. The solid hard,yore includes propellats which `immnaugssTttrahbbteeeer,eccrooaannrtsseeiiddoseeefrvreeepddrr,ao, lpaaeimmlmlooapnnnoggtrtttcahhoneentsmmcuohomsasptrttaiiicmomtnepp,rooirsrtgttiaracannsittnooofsffhswwaohplhieidi,cchhparnaaordepeetllllihiannrneeuatasrrstwbbsuhu,rircnnh- einargliBBreeeras,stieidd,aeersssaotlttehhdeoepfrggpoeeprnneoeelprrlaeaalllnlatnrrmteeqqscuuotiinrreseamulmsmeeonnpttptssoiosnsffoeo,rrsgsrrrgaooioccnokkedestthmaeppprcreoho,papeanelinlllcdaaannlttthssrpurrorstpee(evv~ri5iet4ewi)we.eesdd, `tewawhhheriilcictehhre,mmmpaueusrsstaottlibbudereepuurrnnoaiipfnfoegorlerlmasmnitttnhhvmrroooluuuvsgegtdhhaldttshuhoreeipggnorrgsaasiisenntsosaarnnagddgoeommdourusmstateccbtbhueeaalnmmaiocaipainenlrttaapatiirinnooeepndd.erootviveeesrr, the temperature ranges involved during storage or actual operation. D. Buovextac Frvomse whiEEclhleem hmeaenvntetaalbleffellunuooirrininvneeesiitssiDttghha.eeteEm mdLoEosiMsnttEtppNhooeTwwAeUeLr.rffSFuu.LllAUoo.fOflRTalIhlNliEccshhecemlmieicmcaealnltrroohccakkseettmooaxxixiddaiannmttssa,, weemnonhlceierrcgcghyuylhasraerevlleewaaesbsieeegehddntuuroirnifinvntggehsetcciogcoomm amtbebbuduussstittinioiotnonhneaapnnUrddo.Sdaau.ttActt.thh.TeeWhssiiasatmmheeelbeym ttidimermneuetinmmhaeaai,sinntm wtahaaiiinxncssihmlliuosomww tm nnhoooannlncceaacwrruibbltaoohrnnaaswccyeecsiootguuehsmstsmmoauftasettihernrieigaalcOl,,osmtthhobeerusssOpptesiec.ocinifWfiiipcctrioihmmdpcupuaculrtlsssbe.eo,,nWa[sscsipte,h,ouiihsssyssdfuuubrbeassltzstaia,nnntsetiu,iaaclwlhllyhy2ihchshiiJggPihhs-ee4rar otoHhrreannggcaaesws,ooilltiiihtnneesi,,ys sCgCteoFFmo4dsffupoorsrram imncstsgicOddeuu2rrtioionnrgguOs~cce.oomm mWbibsuiuttshsuttriiccooasnnrbooaafnnnaddfcleuddooeeruccirsrneeefaaussaeeenlsssd, ppsoeeuxrrcyffhogorreammnsaanJwncPicet-e.4h. Hence, it is good practice swuiftfhiciheyndtroogxeyng.en 10 oxidize sufficient oxygen to oxidize the carbon, thus to use mixtures the carbon, thus leaving fre fuorine to of fluorine and oxygen leaving free fluorine to reactwith react owfitlh"TiTqhhhueyeiddssrppooeexcgciyeifgfniiec.cnggrroaarvviilttiyyquooiffdlliuiqqeuuoiindde;fflluuvooirrzii.nneethiises ccsoopnnescsiiifddieecrraagbbrllayyvggirryeeaostfterrftuthhoaarnninttehhaaitst To1!,.hf5illsi,qwwuihsihidiallleeottxothhyaaagttefonoaffvooooxrxryaylgbigqleeeunniidfissaco11tz.o11or4,n,ieaan;nndtdvhiaozev.z,oopnnethereifissosr1pm.e14ac.6ni4fc6ai:ect nngooofrrrammvuaioatllyrbbiooonifielliifnlniuggnopprrooioinicnnekttessit.s. fafTuluelhelilsssp..raiEEsctxxiappclesaerolriieeafnnuccfealeesv,oiinnrtdadhibicculaaestteefossabcvttthihoaaartttiifnfnlgoutrohsirepinencepeieasirlsfohhiryygmpnpieaetrnriggcoooenlliioccsfyuusftpplueoomonnsr.iccnooeTnnhtiteanarccettrfowwocirkitetehh,t imiannellsaahpddadrdnaiiicttcitiaoioclnnallyttoofsuittehhmleepsl, hhetirihgguhhaesenrrdoppmbeevorrifrfaooetrrimnmrgaealnnicscapeeb,el,ecffialtuulhooarirniginnnteeiht--eippoioornwwoeesxrryyeesgddteemnrroosccc.kkoeueTtntsshteem mrrapeaafyyortrbbesee, vmaerci"TohTuaaasbnbllifeceuaellLLl.yXXCXsXoiVmV mIppITalIerrgigisiavvoneendss wm ttihhtoeehrettthhhreeeeooldriraeaettbtiailccegaaliltvheappnneerrpfftrohoerevrmiimroaaunnosccxleeyygiooenfnfTffacllbouuluooernriitnLneeerXpXwwaiVritttIshh. sivshnhaocroiwewoesusassttfhhuaaietntlstt.shhpCeeecouuimfssieepcaoorififsmoffplnluuulow osrreiiitnnheeotfhaassecoaadnnnavteaoonxxgtiiiiddvoiienzznaeelrrprrreleevissqiuuoulliuttdssslyiisnnyisn8taeTmfiaisff.btyyleAppLeeXrrdiXccreeeVncnttIt cicLnooXcmmrXpepVaaarIsrieIissLooinnn between specific between liquid Suorine and liuid impulse of conventional liquid fluorine and liquid oxygen liquid oxygen is shows systems. is shown inA in Table direct Table sLtXorX IienndVssaIppnIiiItdt.e hooaffnttdhhleeeeedxxuttrsreiemnmgeecrreeoaamcctmtiiovviinttyycoooffnseetlleuemmcetenintotaanll mffallutueoorrriiiaunlees,,.iittTmmnaatyyhebbeecasssaaeffeeollyyf sfmmtroooosrsmtetdfmmeuaetrnattadlhlses,hr, aaaantmm dtaelceetktda.alluMffsleuiuntoogarrliidcsdoeewmlfhim ilmmcohniissmcffaoooynrrmsmbteereuddcuwwtsiheohidniccshhmafppaerrtleooytrtieeawcclittstss.httIhhnfeelutbbhoaareissneeceam msceeevtteaoanlfl from further attack. Metals which may be used safely with fluorine even 33002222..00118899 I3MM_MMNNO044885555229988 a WG. weve. TABLE LVI TABLE LXXVI 1 Tuaonrmcas Puerco Foose win Vasioss Fis THEORETICAL PERFORMANCE OF FLUORINE WITH VARIOUS FUELS i OFe (vSDipoek)c Simppelce Fuel O]F ratio Bulk (Specific gravity) Specific impulse uy as on m H2 4.5 0.32 373 u i om 535 Li 2.19 0.83 335 Nm 20 30 sm NzH4 2.0 1.30 318 ba So i" in B~H6 5.0 1.07 309 Nh 30 16 w NHa 3.0 1.16 307 anon 2m om 5 CHaOH 2.37 0.99 297 wi 29 iw Ho JP-4 2.9 1.19 280 TABLE LXXVII TABLE LXXVIII Coransonor Thence, Pasomcasrosr Fitostt xD Ones With Vanes COMPARISON OF THEORETICAL PERFORMANCES OF FLUORINE AND OXYGEN WITH VARIOUS FUELS/159,160,161) Fut wi 1Rls with Iyoen Fuel Is~ with fluorine Is~ with oxygen I 7 a JP-4 276 262 Sy io us NHa 320 268 ie 2 F N~H4 324 281 iy io @ H~ 376 363 taatetcec!lleevvHaaitteegddhttesemimippceoernraa-ttcuuorrneetssaiiinnniccnllguuddaeellnnoiiyccskkeelal,r,cMMnooontneelrl,,ecccoooppmppmeeerrn,,daaellduummdiiunneuumm1,0, aatnnhdde sellititbebheeeylrrl.aaettniHioeoningsohonffds.ttihhleiepcoogglnaayss-cceehoooiuunorsstaoStiSnieiFiFinsfa.gi.vTToarhlholeoeeytffhslyuuloaoerrrneooccc,naaorrabbtroeo.rnnecppsoallatamissstmtificaecsc,n,tdoppreooydllyytftdeeoutrtreraafutllosuseoortrhooae-terCreetahllraaybttlioievvnneeleltyyyplaloenowdwoilccspooaommnlbydbucusghstrltieoiaoorsonnetsrttieefamlmrupepoeurerosraaeetfttuuhurlyreealsesnaaelnn,uddbraipprcreraeensstssssauutrurieesnsfsd,a.ecSSrtoiicmrymeillarfraoaly,r,tuffelisumveoporreooar--t ctaatuurrbrFeeoonaarnntryddopcppekrreeoetssilsssfuuuarrceneldccuoosgnenrd,ediatifstiuieooosnnrsais.r.neeucsaenfubleassulupbplriiceadnt2s uanldieqruicde.rtTarinantsepmorptesr-tftiiooonnFtaaornnarnddsropssocttoroktrreaaatgtgifeeuoneiinlnavvuoonslldevv,eesfttltouhhroeeargiuuensseeeofcooafflnittaqabunneikkdsssuowwpxhyphigliceicenhhd.saaerAseelasstiihlmmioiqiullugaairhrd.tttooThettrhhaoohnssaseepnoduurisstnceaddgfoGooiffrfqllitsqureauinnicddsepsffo,luurotoparartiriinntoeiencuiislasanggrdelenynseetrioranarllallrgyyeegttahhoreefdslssiaaqtmmoueeidvesaanostxffiyoongrrgellntii.qhqueuAiiddlathtooomxxuyoyggsgehepnnh,t,hesse,oomhmmaeuensdbbtalaissnbiigecc `odnitionfedtfe,eddr.He.ennITcncneetst,h,hesepyacesaratstsieeecmousoflafwrffhlllyiuucoorihrniinanreere,e, vgcvealenrondtstseiidnntggoottovotehttnehhteeaintmagmtoomstshoppeshhpeaehrteremreemousmmsputhusbestrtebebu,eesmeaadvvuooswiitdidbeteddhe <aqnudi, phmeenncte,fosyrscteomnsdwenhiscihtnhaegregcalsoesoeudstofltuhoerianetmbooislp-hofe.reAlmsuosrtobcekeutseexdhwauistht equipment for condensing the gaseous fluorine boil-off. Also rocket exhaust 33002222..00119900 I3MM_MMNNO044885555229999 INDUSTRIAL ASPECTS OF FLUONINE CHEMISTRY 8 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 4-85 goganasseeessofffrtrohomem pffrluiuonocrriiipnnaeel ccpoorommdbubucuststst.iioonnTsshirsreeqcquauinirreeusssuppaeleclciyiaallbehhaarnnedaddlliiilnnygg assciicnnoccmeeplHHiEsFheiidss obobfynyeowwuoatafseshrhthiisnnepggapcrwweii,nittchhsipiwmwaaplatltpeeerrro,,ddiclcuuhhcteetismmo.iniccTaiahlnlisntnehecueuattnraraatlulmiisozzusaaatptliihlooyennr,,be.eoorrrSeiiiafnfdcaaieltythhhaiiecggchhsopmaailllpttlilitgituseuhddeeoedssf olpliirfqqeuousiiueddntetffrluusospopirrlaiilncnseeea, swwsmoiomuuulpclddlhe aaadlkssioolpuotsbbisoeeinblaaei.nhhaatzzhaaerrdd,a,tmddeeosssiipgghnnessreaa.rreeSiuunsscuueaallltlhyye bbseepssittllawwghheiiccohhf prevent spills as much as possible. E. Coupounos or Frome dueAAtonnuuthmmebibererrcaoosffeccooofmmphpaoEonuu.dnnlCdidO nssgMo,oPffOaffnU lluduNooDrrbiSiennceOeaFhuhsaaFevvLeeUoO bfbeeRteehIN nnisE,ccoomnnassiyiddeeorrfeefeddraaassdoovxxaiinddtiiazzgeeerrsss ioodfvvuleeeurrotorlliiiqtdqhuueeii,ddirCffIelluaFusoo;erriinpnoeeef.,rhcaIihnnnlcdclolluiurnddgefe,ldduaonaarimdmdoeob,nneggCcIaOutthQshFeee:;ommfanoisthstttriso,isimymmlppoauoryorttraoainnfdftteer,aaarrNedOvccaFhhnlUlotoarrgii)nen;ese tnnAruiietforylryu]ilodreAfi,lduuoeoor,riiCFdde1e;,F, 3;NNanpOOde2rFEed(hi1Sfl6of7:ur)yo;rliinfnltieutcroomoroggidneeeonn,xiCitrdlIieOful,ou~roFFir;2id0dne.ei,t,roNNsyFFl3;f;luddoiirnniiditterro,ogNgeeOnnF(tt1ee6ttrr7aa)--; fluoride, N2F4; and difluorine monoxide, F20. 1. Chlorine Trifluoride termCCshhllooofrriipnneeerftroriirffmliuauonorcrieddeewiootffhf1fe.erfrssCewhmmeloorosrssitntteooorffTagrttiehhfleeuaonqqrduuiadahleliaitntiideelssinoogff plliriqqouubiilddemffllsuuoobrreiicnnaeeusiinen toobefofriimitltsisshnhgioiggfphhopeieernrrctfcroroiriftmticc1aal1nl3ctteeeCmm.wppieteIrhraatfateluuwsrroeeerbaaannsstddoarbbaoohgiiiellgiinahngngsdpppeoohiciniantfn.tid.clTTignhrhgiaivssiptrccyoo,obmmlmeppamoomueuslnnbydde,chha1aua.ss5ase2a aabattnodi22li00nfglCCu..oproCCiin1IneFtF3goccfaaa1nns1.bb3aeerCcpp.rrpeIeaptspasaareleesdddo tbhbhyayrsoa2augoohhnniege-h-ssttrseeepppaeccpptifirriooocncceegscsrssahvawwimthyhbe,eerrrneeabbfmyyilelcclehyhdl,loowr1riii.n8tn2hee Saspiinrllvdovde-urf-pclputlloiaaorttineenddechccglooaoppsippeneeserr atccrrhheiiifpplpssuaotarstisde22ed880c0tohCuC.rl.oduIIbttgehsims aeeasdstteriiemfmaoaacrttteieoddlnetsthshcathtthaaaamnllbaa$err1grgeepfivvleooleIllrdubum.mweeiotohff pforrodHHfualaucnnotddirloiliinnnnegcgwhiaaltonnhrddinossebttovotrirraiaofgguleeusooocrffaidrCCee1IcFtFoo~uarrledveqoqbiuudeiriemcssoanmdmteauuccfctohhrwttilhehtseehs ssotaharmmagnaeenip$pc1rreecpccoaaemuurpttliioboou.nnnssdsaa.ss infilnocikcrleluuffdlduiuionnorggirnggierrneewaeassaieetsehs,,2ooob2ii1lsv6s4,,i,oppuaasiinntctssa,,reeettctc.o. The general toxicology isalso very much avoid contact with organic compounds The general toxicology is also very much like fluorine(16Z,l~3,1~4). 2. Parchiory! Fluoride is oPPneeerrccohhfllootrryhsel fffllluuuooorrriiiddneee,, cCCoII2mOO.pG~oFPFt,e,urnciisdshslaaorwccyhoollilFoocrlrhulleeoossrssfideeggraasss swwoiitmthhe aaofsswwteheeeett aototddrooarrc..tivIIett fiffseeeaawotteuunrrreeepssoroofffothlliiebqquulofiilddufeosffrtllruiounoronearrgiisnence,eo,,mhiianpnnodttuelenrirmndmgsss, wooaffnhdirrceehtaaoccxtotiiicfvvfiiietttryyys.,, Iswwohhbmiiolleeeilopprafrteetssh--eee4nnt6tiia.nnt5gtgraCmmcutuaicnvcdhhe. fhhaeaanwssdieaasr ddpneeronontsbsiiflttelyymamoosmffaob11fl..6s6et66.oraaatHtgottewhh,eeehvbbaeonoridi,llliiiinnntgggr,eppaoaoidninintdl.ty.tosCCuxI1pi0cOp-iSo~tyrFFt. isiIsstcnnbooomottbilsusseseantntsisio-iti4niv6vea.n8ttodoCsfshhooaorcnmckdks. fCAalnaIadmmOmSimsaFabncbloaleetnflabaanenmddsmteeoaxxrbppelledloo.sisHiinvvoeegwlaemmsvisixexotrt,ruurirmteeessrteaawwldiiittslhyhysstoouexxpimipddsi;oizzraatwsbbhllceeeomvvawabpepuotor,srstsi.h.oonwW Weahvhneeedrnn,foddirtrmryyi.s, vvSCeyeIrsrOyytaeFccmoosrcrrratoonhssiaibvnveee.l.sitqTTouhhiriedissduccoinoormimgnplpeaoo0suusensno1ddr66imis,emmtauulccshhyslltoeowmweesrr; in performance in rocket when wet, however, it is in performance in rocket systems than liquid fluorine(16~,i66L 33002222..00119911 33MM_MMNNO044885555330000 84866 WG. waver ~. G. BRYCE 3. Nitrogen Triftoride thanNNioitttrrhooeggreenintttrrroiifgfleluunoo-rrciidodeen,,taNNi3FFn. i3,nN, giiisthrsaoalgiccdeooenlsloo.rTrllrIeeissflssuisgogaaarilssdswweohhrieicclahhtiiisvsemmlyuueccahhsymmtooorreeprssettpaaabbrlleee actahannuaddsntiohhceethnnaecclerke,a,nliitppersooo,ttgeeentntnctii-.aacllollIynyttaiiiinsnneeibxnxeppgseetnhnsasiplivivrdeeee.p.sa.rNNeItFdF3isbayddlooscoteshsreennleaooltttievcetrrrleeyoaalccyettsaissywwiiotttofhhpmrwweaopatlteaerrere,, abacmaerumssmtcoicoonoiumauplmrklailbLsiieihffsell,uduooerrbtiicdyd.ee pIaatatts2sais5isnllbgooewwsotvtteepermmreppmpeaerarnaragettdauunrreeebsssyseasstphdopieosoxssieisdlbieebl.cleter..oItlPPyuusrhriiasiffsiicoc#aafttiimbooonnoillcctieaannnng point of ~129Cen, be aceompIished by passing point of - 129C(16s). over manganese dioxide. It has a boiling +. Dinirogen Tetrafuoride defiTTnihhteee iccntooemmrpepsootuunndd8,, rNNoec24FkF.se4t,,Dfihhneaailstsr0o6rrghee.eccneennTttlleyytrabbfeleueeonnridpperreeppaarreedd aanndd asppppeesasrss ooff definite interest as a rocket fuel(leg). F. Sout Proves fluoTTrhihneeerrceeowwmopouoululddndaaspppieneatrhetFtoo.bibbSneeOdeLaarIddDsvvaoaPfnnRttsOaaogPglEeedsLsLpttAroooNpTbbeSeellgganratiinnseyddstbbeyyms,iinnpccaoorrrtppioocruralatatiirnlngyg tatfhlhnuoodossreehinywwdehrhcioiocgcmhhenp.ccocoounontnntatadiaisnniinnlliiigntghghhettcbmomiemnetpdtaaoellusrssnssdouu.fccshhoaliads lithium, aluminum, or boron, propellant systems, particularly lithium, aluminum, or boron, aanndd"ThTchhyoeendsrceioaasgrrtlleeyynd-sscoooollfiinddtmaappitrnreooirpnpiegealllllcsaaonnmtctssopmwwopeueornreeudnsaa.dddeaadpptteefddroffmrroomnmitttehhoeeglxeypxclpeorlsoiinsvieveesasinnidnddunusittsrrtroyy- acpcerenloldllpuuellclooolssaneen..stis.TTtehhOdeetsshoeeefrmmmaoatxateietredririiaaizlalisslnsgffocomorarmmtmeeeprddioaulttnhshd,eeesdbbuaacfsshriiosamsffooprrnoitpptarrroseegsssileeyunncmtte--dprdieaanryyechddalooonuurdbbaltleene--ibbtaraanossde-e paaamrnmodmmpoteoalnrnlsaii,nuumwtmsh.iOncrihittthrrwaaetotreeu,,olxdwwideheriarzeerindgemmnimisxueaepdtdoenriwwasilittstha,hnsduvviacanrrhgiioooauusrssphaollititqaiquunsiisgddi.uss,,mThsspeuuesccrehhchpaalrossorpaaaetslseplphahaananltldtst abbneecdcaMatmomarerese,kkwnnsoohuwiwictnnhabaawlsseoccusoolummdbpsophtsoaiisrttdiuetteesens.s.ufpoorn tshteanadsinphgalotrsheaantdingt.arTshheaseveprboepeenlladnet-s vvtyeeplloeoMppeeeoddlraeiisnttsothumhieeetrasffb,oolrermpmosloouyffbupsprotoeilttluyyhmatmeneseerrsii,fzzoaarpbbolteelhyebbaiicnnarddsyeeprlrhsts,a,el,iitnsnccplalouunldddyiidnnitggaernbbsucut,thyylal<vtaace.nnddbIettnhheitiinoioakkldoolleyl-,-- tttthyhhpeeeeccpoooelmmlypapmsotoesorismiittzeeeassrbsclc, oeonpnsbosiiilnssydttueeerrdde. tpphRrraeiinmcmeeaasnrr,tiilllpyyyo,oolyhffaeaacnnraydooladxxtiiietddsiii,zozinipnnogoglyfssaadaliltletinghheheestll,ddmeettttoocagg.lee,hIhneseriurticwawhliiltty1hh5, `atahplloueusmimptieionnlpuyurmmompeeriilinnlzaaaanbtlseffiinhnbaeeillsnyydieddmriip.vvriiRoddveeeceddednssttttlaahytte,eer,,thptteoeorafbbdooodrttmihhtainottcnhheee.ofddTooahuublebilgleeih--ntbbcmaarsseeeestsaaal,hnnaddssucccbhooemmea.ns- cbpchhuoiisseeitffilleoyynpddroouufpeetehttloleoanatththlseeuhmhhaiiisgngihhummeepnntreeoorrvgigetyysd opptxheeieedreir.uunnpiieTttrhfwwioesreimiggeahnhntetcrerrgee.yssTuuhllhettaieintnsgigntcffhrrreoeoammcseomtthhhbaeeusscctbooiemmoe.nn- gobgaxausissedetsisiozen1tro0opfaaretshhheeiinggtahh,eleurrmttieenmmupmpeerrtaaottuuirtrsee than oxide. than that produced by This energy heats that produced by thethe the binder and combustion binder and eonxeidrAAgiszsyeriwwsapatrssheesrreemenvvati.iexewiweemddumeeaavrrallilieeurre,, fttohrheethiiemmeppxooprrrtteaasnnsttionppaairrnaammEqee.tteer(r2)ff.oorrThppirrsooppmeelelllaaannnstt poeprfnrooerppreegealylclltaaiinsnottnthiiwneniggtmrrheeaddxliioieemnnwttussmmommlaveuscastultuleiiannrfccollwuruedditeehghecctooemcxmopppmrooebuusunsnsiddtossinottinhhnaagtEtasqwwei.sill,l(l2t2yyoi)ig.eeellTdtdhhhheiirisggwhhmiethhaehenaatsat minimum amountofsolido liquid particles. of reaction with low molecular weight combustion minimum amount of solid or liquid particles. gases, together with a 33002222..00119922 33MM_MMNNo044885555330011 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 7 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 487 the TTfooollooobbwtitaaniignncr2aitsseoorliliaiddmuppsrrotoppbeeelllaamnnettt:wwhhiicchh wil will yield yield a a high high performance, performance, the (((f112o)))lloTTTwhhhieeengmmaamcatroteierutreiniraatillamommfuusulstsittqhhubiaaedvvemoearaetshh:oiilggihhd hhpeeaaartttioocflferrseeaafccottriiomonnedppeedrruruuinninitgt wwteheieigghhct.to.m- bbuusst(t(ii23oo))nnTApplhrrlooeccpeearssmosspoemmluulnusatsntttobbfeielnissgqmmruaeialddllil.e.ontrssoslhidoupldartnicelers formed during the com- the combustion process aanndd((3c4c))oonnATttrrhliilebbuupattreveorpttaoeoglltteahhneemtoaalivvneaacgiilurlaelbbdallireeenweetennsieegrrsghghytyo.uofldtheentgearsetshemuscotmbbeulsotwio.n process highT(T4hh)aeevTishlseeaeaabrrlaccevhhereanffgoeoerrrgmisseuuosiiltteaaacbbgullaeleianrggwaalsseeeeaioodguushssttoommfeettththaaeell gfccauoosomemrsbibunmusestutiisaoottnnobmep.prtroooMwddou.uscctttss mwewtiiatthlh orhooxixgciikdhdeeetssavchhaoaaimvvlabeebulshhetiigigehohnnevvrtaageppimoeoprsrieizrzaaaagtttiaiuooirnnnestt.leeemaTmdphpseeerrtaaomtteuuttrraheeless faafllnunuoddoriraaidnereese,ssaoootnlloiimddtssh.eooM rrotollhiiseqqtruuiihmddassentdaaa,ttl `araaorrteecukruueessst,uuacTalolhllmeyyrbppeurrfseeotssireeo,nnntthtieienncmhaapiehheirfiagghtahullyrydesssv.ttaaaTbbllhneeeotggfmaaassseeegitooanuuelgssflfofuoororrrimimdneaaestt,itthnohenessseteohlsseiaadmom-tpeehreottrepeemmhlpapienaerndr.t-, afAfotouurromrmreuiusld.laeaTtstiihoaoesnnreeiifxssohrttaehhu,eestthrreeepssrcuuohldltiuteaacfnnttsat.dffvooTarranmmbtaaaltgteiieooLnnofXoouXffsIihhnXiiggghhfglliluyyvoerseeinnnteeehrregigneehttaeiiaccstosgglaiaodssf-eepoforouuorsspmemmaletletiataonalntl offlusoorimdees laisghetxmheatuaslt poxroiddeusctasn. dTfalbuloeriLdeXsXIX gives the heats of formation of some light metal oxides TABLE LX and fluorides. Hers orFomuaorrSieoTnAsnBLLEicwLrXMXeIrXa Ostots axaFiona HEATS OF FORMATION OF SEVERAL LIGIIT METAL OXIDES AND FLUORIDS(1701 FT Oxide H2ssK Fluoride -- /~/298 K Lio wo LifO bow Cie BeO (c) Bow Dm B~O~ (c) MOO Dw MgO (c) Now Cw AI~O~ (c) - 142 - 146 -302 - 143 -399 Ee ow LiF (c) mRG mm BeF~ (c) BR ous BF~ (g) Mo a MgF2 (c) AB A1Fa (c) - 146 - 227 -265 -- 264 -356 fashIIittommnitiggohhttthaeappeppneeeaarrrgytthhoaautttaapufftlluudoourroeocc0aarrbbtoohnne mmvieirggyhhtsttnnaoobtlteccoConn--ttrrFiibbuubtotenedii.nn aHapoopwsoeisstietiirvv,ee wwfaahnhsdehenniorneuudtttiiuollciizitzehnededg eiicnnnoemaarpgppoyrrnooeoppnueetltlpsllaa,unntttidtffuooeirrsmtmoutulhtlaehatteiinoovennteraayassvsaaatialbbbaiilbnenlddeCeerr-e-nffFoeorrrbgoooyttnhhdwee.hrriHoocxoxhiiwddieiizzsviiennorggf, waiimmnhpdipocorhrrtetaacdnnocucnecet.i.anigCCnooncbnsoosemteqhqupueoCennnt--etlnlFyyt,s,,awwnhihtdeenniCsil--itgghHhhett mbmneoeetnttadalslas,svaaaiirrtleeaibsaalddepddoeesedsdniebttrologeybbiitnnowddseherhircohsswyyssiattseemnmoesscf Wiwinnhhccrrieceenhaassee+coiifnnnltuaeeoinnnreeorrcbggaoyyrtbhrroeenllCeebaa-iss-eenF,,deddaruneeidsttCouos-tte-hhdHee iffnoboorr4mnmadratostcii,okoinenttooipsffrHpHopoFFeslsooilbrarlnemmtetestotyaaslsltheffollmuwu,oorrtaiihddeneersese..t sW s`hwheoohiuueglhlnddt aobbffeeluAooouttrohhoreecirranreffb,aaovvnoo1r9rb,aaibbnlvldeeaetreehffiafiesetcctoustsf.s.ehdIIynndinrttohhageeernoff,iicr1skstte,tdppplelaarcccoreepe,,ealsttlhehaesentthhhsiiyeggshhtceeeorrmnc,aaetttonhomtmeririaecc wtttiihoeoeningfoholftfuttoohhrfeeofcrlraueerlloaabrttioiinvnveee,llhyya1vii9nen,eeffvhfesiecgctththiievvareet odccefaanrrshbbiyootdninerosaagttoaeomnnmd,ss 1iian,nredtthehtceehreessrayymsssaettelsemlmty.h. eImInnocroaaendddcdiesittntiiatoobrnanl,e-, tthheanflhuyodrrooccaarrbboonnss.have higher densities and are thermally more stable than hydrocarbons. 33002222..00119933 I3MM_MMNNO044885555330022 TM ic. vce H.G. BRYCE deveIItlt ommpamaeyyntbbeeofaannnesticwciipptaaytpteeedds,,oftthhpeeorrelffyoomrreeer,,isttahhbaaltte ffRuuuttouurrrieenerr-eecssoeenaatrraccihhniwwnigillllmassteeeeerittahhlees dfoerveulsoepminesnotliodf pnreowpeltylpanets rocket propulsion systems, of polymerizable fluorine-containing materials for use in solid propellant rocket propulsion systems. XVE. Catalysis A. HXvVoLsoCanatsalFyusviosnios A hasbeen 1. PhyAs.icHalYDaRnOdGCEhNemFiLcUalORPrIDopEerties poin1t.edPhoyusticbayl aSnidmoCnsh,emtihcealchPermoipcearltieasnd physical proper- ttHiiIee,ssAooHsffBhrhhay,ysddorrbrooeggeHeennnCpfuIoloiun.rotrieidddIeenouddgtooenbnneyoroatSliffmootllohlloenowswp,rtttohhhpooeessreecthiooecffmstooitchfba_elherryandhhrdyyoddpgrrheooynggseeinnfclauhhloaarplliiridoddeepeseasrr----e- HI, HBr, or HCl(173!. In general, the properties of hydrogen fluoride are TmhoirsecilossehloywrnelianteTdablweatLeXrXaXn.d ammonia than theothrhydrogen halides. more closely related to water and ammonia than the other hydrogen halides. This is shown in Table LXXX. TamLE LX TABLE LXXX COMPARISON OF PHYSICAL PROPERTIES(17s) Frociog | Baling Mow ben Sela beiol | Didearc Freezing point OnE CE TR C Boiling point C Molar heat of fusion kcal Molar heat of vaporization kcal Dielectric constant nr ca me HF FE HC1 He Teo Zor HBr i He Th HI tio oe H20 Meo We NHs -83 - 114 -86 -53.6 0 --77 19.9 - 85.8 -67.1 -36.0 100 --38.5 ee ew sao) 1.09~ SE 0.50 om do ima 0.62 om vam 0.72 an ean 1.34 mW Whe 1.84 6.02~ 3.6 4.0 4.4 9.72 5.6 85.3 (0) 4.60 (27.7) 3.82 (24~7) 2.9 (21.7) 80 (20) 14.9 (24.5) Fate ~ For 20 gm. + For 6330 gm. fom vapor rere curve. Calorie menared le i 0 For 63.36 gm from vapor pressure curve. Calorimetrically 03 Cpe. Toi ais wi oh seperate and press, See fh Hen of 97.5 cal per gin. This varies with both temperature and pressure. Nomoretins of Wphogn Fonte" by Ss sod Takrgh Vaporization of Hydrogen Fluoride" by Simons and Bouknight. measured value is See the "Heat of solvTTehnhtee fhhoiirgghshaddsii,eelleeaccnttdrriiccthcceoonnrssetsaaunnltttieennngaasbblaleetssshholyyuddtrrioooggnesennacffcluugooorrioddie cttooondbbueectaaorggsoooooddf sselooleellcvcurbteriinicccticcfunourrrrrlesenantlitt,.s,HHqoyaydnfdrdurohoictchiaaertrbybdropoenenss.usalAatnninndhdgyssdsiirmamoilitlulaassrronhnlouyontdnpiropoonolgslaearanrrllfeiiuqqoguuroiiidoddsdse,aacrehoenonnwodoeuttvcueutsrosu,urasialsllloyy3f svieonerlruyiytbsslsettrrreoionnnmgagalaadiccqeiiuddi,s,doaalonnufbddtlheaalilsllttchcyoropommeup.pgoAohuunncnhhddyessdmicrcoacaupapalsabbhlilyneetdeoorrfofagceetexxihnohinifb.bliuictoAiinrnsiggdeabb,aacshsoiionccwscceehhqvaauerreraa,ncccittseee,rar simmnoalanunitbyylaeoorreriggnamannhaiiydccderccooosgommelpupnoboulufenlnuddotrshsirdttoehh.uaagtthFsaorrcreeheeooxmnnaliymycpavlvleeer,irnyytaesscrlloaiigbgchohttiltollsyyn,.sspooAhlleusunbboallleesc,iionnncswwaearaqtbtuoeeesrrnyalacrireeec, soluble in hydrogen fluoride. For example, alcohols, phenols, carboxylic asiclitsd., Ecxiacm,plaects aare:bases 0 hydrogen fluoride and hence form ionizing acids, etc., act as bases to hydrogen fluoride and hence form ionizing salts. Examples are: 3300222..00119944 I3MM_MMNNO0A4B8555330033 INDUSTRIAL ASPECTS OF FLUORING CHEMISTRY 4 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY 489 (CHLCOOM = HF CHACON + F a CH~COOH -~ HF ~ CHoCO~H2 + F (23) CHO + HE COM + 5 an Ofthethree liquids, aCm~mHognOiHa,+ wHatFe~ r,Ca~nHd~OhHy~d+ro+geFn- fuoride, ammon(2i4a) is is tthhOIeenfmmtthohoeetsttvhbbaarapessoieirccl,,isqtwwauhthiiedil,lsee,hhhyayymdddrmrrooogoggeneeninna,fffulwuouaortireoiddre,eriaeisnxsdtidtshhetheseymimdnoroos@sgtteuaancmciifbddliuiecc.or.ridoef, ammonia moleculae ffoorr`mmIWnsshitoolhnneeeeavonoafhfpywwodhrrhioisccutahhstehhh,yaahdssryaaodnngreoaangppepfpnalarrufeelounnrostiriffddooeerrsmmevuuxellirasay,t,sstHoirn6oFFna6(gTn"aMucm)db,((ssewecrheeeoCnCfhdhmaiaposptlsteeeocrrluvl11ea)),dr. aiinnvwweWraythaeirpleioitttwaeeenxrxehhfhiyubidblirrtiotsdsuetsthhhyheedyrppdarrrtooopipgeneergrnttiiafeeglsuseonootrffidaafewwoieseaafarkkveeeaacrcydwid.as.tterHHoryynddgrIrcaoocggaileedonn,owfflfhvuoeoornrrmidddseies4siioswlaavilledssdoeo aries a very variety opofof wmmoeolrlefeuccluulldaaerrhccyoodmmrpapltlieennxgcessa,,gsseoonmtmeefooorff fwwrheheiiccwhh aaatrreeer.vveeIrrtyyassltstrrooonnfgog.r.ms a wide 2. Catalytic Effects "The first disclosureofth2e.uCseatoaflythiycdEroffgeecnts fluoride as a catalyst for an oorrggSaaTinnhimicceorrnfeeisraasaccttntiidodoinnsccwwoloa-aswssuorrmmekaaeoddrfeesthhbbeayyvuSeSsiiepmumoobfnolsihn(syt7hsde5r.d)o.agesnerfileusoorfidpeapaesras coantatlhyestgefonerraanl swsuuobbrjjkSeecicmhttaooosnffbshheayyenddndrropocgguoeeb-nnwliofulsruokhoreeriridsdd)eeh.1aav5se 2 condensing agent. A good published a series of papers a condensing agent. A good review of this on the general review of this work has been published(176L veryaa..efAAflelkckytylilavatetiicooannt..alOyOsnnteeisooafflkttyhhleeatrrieeoana,ccttiTioohnnisssiffoorreswwshehinitccihhalhhlyyyddtrrhooeggpeernnepffalluruaootrriiidodene oiissf aa pvp{orernoortyddhuueeccftfmteottclhhteiaavctteucclcooeannstttaaaoliiyfnnssstthooiesnneesaolkoouryrrlcmametrioomrenaet. eaaTrllkkihyyail.ls ggisrrUooseuuisppnssseginithniyaiildttlsrsyommtgoheolenleecpcAuruuellopeerssairdttaheht,aiaonnintwwoweefarrseea Sfimnooaututennhrddeiattlmhsaohtclaeoagcuagrulerdleteasabtteommfuasatnehnydyetssosooosuuuurrrpccceepelmmmyaatatteteherreriiiaaaalllls.kyccUloouguslirlnddogubbpeehsyaadillknkroycyllglaauettdneeiddnfglaaunnaolddrkiyttdhlheaa,httailmtmiadwaennasyy,s omolleeaffti`iennArsssi,a,'laaasnllccceoooxhhuoaollmdlsps,,bleeee,ssuttesebresesd,n, zteeeottnhhseeeurrspsm,,paletyyctc.tb.hee alkyl groups reacted with including alkyl butyl chloride. halides, Tn the cbeaaussteeyAloosfcftheatlernortrtieiiaaxdreray,ymabbptuulte2ty,y5llbCcce;hhnlalzoonerrndiiddeieef,,m1tt-ahhbyeeutrbryeeelaaccrcttehiiaoloconntretitdaadkkeweeasstit1pph0lla0abccueeCt.ayattlT0ncthCChloe;isrifiefsdeserec.ecoaoIcnntndidaoatnrhrsyye, btthhhyueedtyrhhloyygcddherrlnoooggrfeeidnnocehc,rlhaoldtor2rii5iddseeCnees;cscaecansapsdpeaesirsfyaansfs-obaaruggttaayhs,le, caarhnenladdocortoniindlolenyy.aaat relatively small 100C. In these relatively small amount of reactions, amount of mhyadyBBroebegnenezznereennfaeelcutmmoeradaiydyaetaaillssrsoeonleabbtceeievsaaeslllakkyryyylllaaofttwoeerddttehuumesspiienrnreggaatcaautnniroeoonsll.e.effiiAnn.S. BtBhuuettyyollleeennfeeinoosrrppporlrooyppmyeylrleeinnzeee rwmreeiaaaldydiipllbyrye,o, cttreheheeaedycytmesaedureecahaatddrmddeoeelddrateiwwvireitatlhphyissdltotliiwyrrrrtiitnhenaggmnttptooehtrtehahtpeeuorblbeyeesmnn.ezzreAeinnzseea;t;thihheoeennno.ccleee,f,lntthshepoaalllkykyymllaaettriiiozonen wmoilslAtApllrrccoeooachhdeooiellldssy;mmmaauanyycdh3aplm1rssoiomrbbaeeerryauuptsseheiddedlyltteooatshtaa.allnkkCyyotllhanaettseeipdbboeeelrynna~szbenelnenyerei;;zmaotttereiorrettnii.haaryrydy raaollgccoeohhnooflllssuorrereiaadccett miiasssodrrse,etqqruuTeiinarredetdidhleyww;fhhiaerensnndpsaplllarcccioomehhoaowlrlasystaatehrrieeesfuulesosaeersddmt.ettChdhaaonwnnhswwiidhcheheernnatbeaalnlyldkksyynllmtohhraaedliliihldduyeetdssertooohrgreeoonhlleeyfffdliiunrnossorgiaaedrrneee ufAtlhusueeoosdrrei.iddIreene;;dtuahacnneeddftirshsseeetcccopoanlntaddacllleyyy,t,wicaaalltacceotorihhiovoslilfssyo.rttemenneddd to add which to add hydrogen fluoride; both of tends to dilute the hydrogen hydrogen fluoride; both of these reduce the catalytic activity. 33002222..00119955 33MM_MMNNO044885555330044 49900 HH.oG.. wBRaYvCeEr in aW `mWhhaeennnnaaennsieemssitteelrrairistouuspseerddo,p, yss)uucaclhhcoaahssolpp;rroohppoyywllesaaeccreet,taatiteen,,tththihsee crraeesaaec,cttiaioconentippcrrooaccceeiededdsis.s pipnrrooaddEmtuuhccaeeenrddnseiinmnr apspilylmaaccaieellasoorofftobwweapattreueorsrp.eydl alcohol; however, in to alkylate benzene; this for case, acetic acid is example, dipropy] geetrthhoeeuErrpt,wwhielillrellsarrvemeianaacgtyt piirannolseepoiiyttlhhbeeearrlocuofosfhettodwwlootsoswwaa2aylykbssyy----li-apittrteommdbauaeycyntz.rreeeOanaccentt; sstfohoeraosoetotxohaea.marddpdhdlaeaon,nnded,eipppitrrrooompppayyyyl.ll aaglrsooourTrpiee,aaicslcett5ans0voo.itn2agsnet0pocreo3aspdsdydarltwywalooctpooprhruooosplpeyaylslhiggagrrhbooluuyypp-sps,pr,uollrdeeiaaufvviciietnn.dggOucononnlmlytyphwoeawutanoetdtrehsre,2arssthfthoahernedpcp,roroiomtsdmumuotca.nty. icimamtppaIuultryrisiitsittessnidroedeotsaodninnleooyctterddseseecaaaorccvytetiirvvteoaadtt.eeuTstthheheeehecciqaagtuthaailllypyytmtiipeccunaartcicfttiiieoordnneloocafoftimhhvyyepddloyrrusooinggmdeepsnnl, efffll.ouuoroIrnriicgddoeee.m.nmTeThrhoe,ne ctthaheetaAyylyinieesyltlddissssuraaberrsaeetdaveilnerycryyerehhctihoigagvthherwcweoidintt.thhTalilhintiestlleeaqtlluoooispmsssmoofefonfpptrrhioosydddruuercclotatgtiddevuuneeelyttthosotimssiiadpdreleee.rreseIuaanfccfttgiiiecooinnneessn.r.tally, anaccattpiihvAvteenhayfflooesrrnuerrb,eespptaallannacdcceeemmmtaeehnnnattyt rroceetoaahnccetttraiioionnansrssoamcctaaaotnnmicbbseecoorrfmeeahpaccoyttudeenrddod..sg.`eTTnhhiitsshaiintnccallurueddeesssufppfhihceeinneonoltlslsy,, naphthalene, and many other aromatic compounds. latiob0n... AAFccoyyrllaalciixooannm..plHHeyy,ddrrbooeggneeznnenffelluumoorariiyddeereiissacaatllsswooitaahnn 8eeffcffaeercctbtiiovvseeylcciaacttaaallcyysdstt, ffaoonrr aaacccyiy-dlhnraeaatallicioddtneie,.o,nF,aannotrhaaecceiixgddarmoaannuphphleyy,didrnbritiededneoe,zd,euooncreredaamnnianeeytsosttreeterrha..ecFFtbooewrrniztceheiintthaeeerrcraiaarnllbgkkoyygxlloyaacttlsiiioconpnarcooiirrmda,aarccalyynlylaataitiincootindno rtehaecptiaornt, ptohseitgiroon.up introduced into the benzene ring goes primarily into the para position. succhc.. RRreeeaaacrrtrriaaonnnggseemmaesnetnsits.n.gHHycydldrorsoouggreeenns fSalunodurirdeeoacrcaraannrnagalelissmooebnbtdeseu.useseeIdtdaiasss aaaciacotaataallyyusssetefffooolrr osccfuaattcaahhllyyydssrrtetoaiigcnnteinssouunlflsffloounaonasratitidrioioennn.gt.oBBcfleeoonnsrzzumeernnebeseenarreeznaaedccnttsesr.eswwauirilrttafhhonngssiuueclmlffauuecrriniditc.cs.aaAccItiitddhiiiisnnghattelhhsroee tppaerrmeeupssseeeernnfaccu.eel ottfulufurroeehrsyiddddierip,ophgheteeonnnlyyuflelnussueuollrffirodoenenaeecttioisss fffwoooirrrtmmmheeddbb..eennFFzzooeerrnneeeexxaassmmuupllpflfoleeon,,niceiinnaattchhcieded.ppArteortsefhneoicgreshmoeofrfethhhtyeeyndmdrmrcpoioegxgreeeeandn- sulfone, p-tolyl phenyl sulfone. fluoride, toluene reacts with benzene sulfone, p-tolyl phenyl sulfone. sulfonic acid to form the mixed ce4da.. NNwiiittrrhaattbiooennn,.zeHHnyeyddarrtooggsueebnnseffsluuooortriieddmeepeaarllasstoourcceaastsalltyyozzeefssornnmiittmrraaottniiooonnni..tsNNoiitbtreriincczeaancceii.dd reacts with benzene at subzero temperatures to form mononitrobenzene. achiee.c. vCeCodommmimtesreirlicacaragllesUUtssaawggeae,g. eOOnninaatcchooemmmamlelreycrlciaiatalilonssccaoallfee,,ishhoyypddarrrooagfgieennns,fflluwuoohrriiicddhee hhaaarssc iacmhpoiervteadntitisn lparrogdeusctinugsahgieghinoctthaeneaalvkiyaltaitioonnanodf aisuotpoamroatfifivnes,gawsohliicnhe.are important in producing high octane aviation and automotive gasolines. B. Tuastuonoxceric Aci AND ANHYDIDE B. 1. Properties TRIFLUOROACETIC ACID AND ANHYDRIDE the TTmrriiinffleluurooarrlosaaaccceietdtiisccsaauccciihdd 2siss aaHCvvIee1Grr.yy7P4ssr7ttorr9opo.nenrggtTiehaasciciisdd,,stccrooommnpgpaararcaaibbdlileetyiinnis ssdtturreeennggttothhthttoeo pthreesiennicneeroafl tahceidsrfsluucohroamsetHhCy1](1g77r,otvusp). wTithhistsstrsotnrgonagciedlietcytrisondautetratoctitnhge. presence of the trifluoromethyl group with its strong electron attracting 33002222..00119966 33MM_MMNNO044885555330055 INDUSTAIAL ASPECTS OF FLUORINE CHEMISTRY 1491 INDUSTRIAL ASPECTS OF FLUORINE CHEMISTRY pTpooewwserer.re. pTTorrritffelludootrroooahcaaevcteiecgtaaoiccoiicddd salolssloovehhnaatss phhoiiwgghehrssooflolvvreenhntatlppoogoewwneesrrtiffTMoo,rr many many materials. materials. pIrtoitsM Meriaeannpnsy;oyrsstueaapldlottssntoaarreheevaaddvpiieosssrsgoaooltlovvideeoddnsoiionlnvftterrtniihftflelupuoosororwoloaevaeccreneftttoi,icrc thachacieldiod.g.perITnottst(lae1li7ssno9s).rreweaaeddriiellyyrddeiicssossvooellrvveeedss pihfnoraroawtsewapietnacetsief;rricussoopplloouulnbbyllmeeeevccraosopn.noddrtiatisitotinoui(ns1oe8not,f)o. tdTThirresiifslsfouollolevoroertnaeotcr,seetcptihhceteatahcaicpilicdrdaotiitesesipannonsleeyxwexcscecterlelelrleesnrnethtcassosoovllbevvereeeenndntt described, for specific polymers. described(ZSl). Its use to dissolve terephthalate polyesters has been Trifuoroacetc acid has22.b. eCCeanattaarlelyypttoiircctEEefdfffeetccottssbe an excellent catalyst for `ccCeearrtttTaaaliirynnizfeludooortrgrghoaaenaniecisccetteicrrrieefaasiccccittadiotoninohsns.a.sofbMMmeoeaornrnggyaraennapoffrlotoeuudnncddtaosowttbhheeaalthtlanaCCsoceFFexaSlcClleCuOllOleoOsOsneHtHcwaeeiftftaffheelycctastiictvvefeetolilyycr casnanhtay`hldyCrzyoidevddee(rrltShdSeet,~eeasnlte,riffiocuantidonthoaft mCaFnysCalOcoOhHolsorasitws eallnhays dcreildluelopserowmiottheadcetthiec eegssrttoeeuCrriipoffsiioecivaanetttiriooonnetlhooeaffl.p,ppooofllolyyyuvmvnieidnwsys1lthhaaa.lltccooChhFoolalCwwOiitOthhHoouuttortthhietes iiannnttrhroyoddduurcicdttiieoonnprooofmf oCCtFFesdaCCtOOh-e- groups into the polymer(.84). . Boson Tirivompe C. 1. Properties BORON TRIFLUORIDE wortBBhooytrootnnhafftoorrtmmhess BtthheeFvveerbryyonssdttaabibsllee1r.eccpooPommrrpotppoeoeduurantnsided,s,haBFvFsia,n,gwwiaittbhhoffnlluduooreriinnneee.r.gyIIttoiifs n1noo4tt0ee6-- kkbwcocoaailrllthppayeterrt--hmma1oto0ll1eteh,,eCccBaoonmm-d-phpFaaarrsbeeoddanmdtteoolist11ir11ne66gppkokoecriatanelltdppoaeefsrr hmm~aovo1lile3neg0ffooarrCb.ttohhIneetdiCCse---vn-eeFFrrygbbysooononldfdu..b1l4BBe0FFi.6an bbwwoaoratiitleescrraacaatinnd-dd, 1ll0iHkk1BeeFCss.iilaliinccdoBonnFhyatteseittarsraamsfflouelloolutrrbiniilddgeee piiinossinomontonlsloyytf pp-oaarrr1tgti3aiaan0lli.ll7cyyChlh.iyyqdIdurtrioodislsly;yvzzeeefroddyr stoolufuboleroi-n teoxuflmupolreo,- aibitttoiirmssicpssraooecllsuiusdbbu,lrleeeH.iiBnnIFtnnd-f-.ppoeerBnnmFttsaaancnoeeisorttsoodoilttnuhhabeetlieeeoxxnittneecnnomttmpoooosfftv33io00nrdgggsammnwiicppteehlsriqalluivttieedrrrsy;aattlfao55rrg55eeCCxnauaammnnbpddlee3r3, oyaoftdfmrooorrpcggryaaenansinisccuircnnei.iattcrIriotodg,gfeoeennrtmhaaesnnrsddc,ooooaxxrlddyyieggnheeaynntdieoccsnoo,mmcapopnomoduupnknodedustson,,ndessssuu.wcchhiTthhaai5saspvaameomrmwmyoonlanioriagfa,e,conaaomumrimdirnicbenses:,r, Cahaattyitidoaorlnnoyscuutynnadidnnooiuucmbbatatnecediyddll,yyoreagathcaccnecioroscuu,nnrtatessladcfeftoohirryondttshehese, eeafenfcedtcitkivveeetnoncnesessss.ooTff hbbioosrroopnnowttrreiirffloluufoorrciioddoeerd3assin3a- catalyst in many organic reactions. 2. Catalytic Effects BF, as a feaBcFiaonas9,a ccHaaottwaalelyyvssettr,rreessienemsmtbb2ell.aeedssCoaaaftllauuolm>cmc'iitnufcnruurmEimfnfgeccchhwtllsiootrrhiiddoeergiinannitthcheehaFFlriridieeeddseewlli--CtCrhraatffhttess ereeeltliaihmecmrtiiisnno,aantte(iitsoaotnsneLrsoofHfanoHHdwCCIse1,pv,ietBrFs,Fsoianfsaatccwetaasstdewwroi.iftthhocoocxxuyyrggreiennng compounds such as with organic halides compounds such as alcohols, with the alcohols, eftrhoemBBroso,rraooelnncstoehetrroisilffsailucnooadrrniisdddpeeliatiicsssiodeefsfff;ffeewcceatttiitvehveeer.r3sa5s+2a acccaaittdaasll;yyssttaniidnn. ttahhleecoffhooorrlmsmaa+ttiiooannmioodffeseesdstteeDrr.ss ftriosmalaolcoefhfoelcstivaendin tarcaindssf;erreithngerasn+alkayclidosf; 47anadcyalgcroohuoplsfr+omamaindeosx(~yag6e}n. It is also effective in transferring an alkyl or an acyl group from an oxygen 33002222..00119977 I3MM_MMNNO044885555330066 I wo mer 492 H.G. BRYCE attachment to one with carbon, Many examples ofthis are reported in the attachinent to one with carbon. Many examples of this are reported in the [res literature(186). Fs will ho ctl dir dion olen. For xampl, propyl BF3 will also catalyze direct additions to olefins. For example, propylene canbeadded to acid to form props] ser: ais can 50 be reacted can be added to acids to form isopropyI esters; olefins can also be reacted il benene to form alkyl subst besene, BFS wil alo. ayes witll benzene to form alkyl substituted benzene. BFa wilt also catalyze he polsmeeationof leo. tb.e polymerization of olefins. Tameric changes can sho be cred by BF in 8 manner simile Isomeric ctlanges can also be catalyzed by BFa in a manner similar to AIC Example ae the Deckman reaction, th bensidine rasfore to AIC13. Examples are the Beckmann reaction, the benzidine transformation, snd the cq of ci and ranten0s. mation, and the equilibrium of cis- and trans-stilbene(186). 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