Document bBEMr2yQN1nKJZ23zEKjjEKD3

TM TL 5; " CR EL {Te " Handling 1 [1] '* FLUOROPOLYMER RESINS |" RIC RTT ---------------------------------------------- d`Ceotnasiullstotfhperfooplelrowhianngdilnifnogramnatdiuosneoinffifrleueomreorpgoelnycmieerss ainndthoitshGeuriedem.ergQeunecsiteiso.nsBaebsouurteptroorpeevrieuwstehoef fluoropolymer resins should be directed to the resin supplier. Questions about this Guide or the Fluoropolymers Division should be directed to SPI. EMERGENCY RESPONSE + Hazardous fumes may be produced at temperatures above 625F (330C). (See pages I5 and 3) + Toxic fumes may be formed at 840F (450C) and above. (See pages IS and 35) a. Hazardous vapor and fumes will be liberated duringa fire. (See page 36) a= IN CASE OF FIRE 200 1 + Fluoropolymers do not burnwithoutan external sourceof heat. (See page 35) EE T(HhEe),prcianrcbipolnemdoencoomxpiodsei(tCi0o)n apnrdolduocwtsmoinleacufilraerawreeihgyhdtrfolgueonrofplouloyrmiedres(.HE()S,eceaprabgoeny3l6f)luoride + Wearself-containedbreathing apparatus (SCBAt)o protect from inhalation of HF. (See page 35) Wear full turnoutgearor LevelAequipment, to protect skin and eyes from contact with HF. (See page 35) + Decontaminate personnel exposure, as well as ater and equipment with water salvage and overhaul. (See wash-down page 35) after fire and smoke + DSeaetat"he(1N9a9t4ioendaitlioFni)r,e aPrnodte2c9tiConFRAs1s9o1c0i.a1t2i0on(K')s,p"uHbalizcaartdioonu,s NwFasPtAe4o9p,e"rHaatizoanrsdoaunsdCehmeemrigceanlcsy response," for guidance. EMERGENCY RESPONSE NUMBERS + Transportation Emergency (Chemtrec) -- 800.424.9300 eet -- 2 RRR eee AR 226 - 1064 GUIDE TO THE SAFE HANDLING OF FLUOROPOLYMER RESINS The Society of the Plastics Industry, Inc. 1801 K Street, N.W., Suite 600K Washington, D.C. 20006 Third Edition: June 1998 | | B h CONTAIN NO 8 ~ oo Pageii H HI | ! - TABLE OF CONTENTS J NOTETOUSERS + eeeeannnnnnnnnnansssiinneeeee. Pageyv i FOREWORD . ++ vseseeeeeaaeeasseeneiiinennneeePeaegee.l INTRODUCTION ......eeeeeeeennnnnannnnnssiiPeaegee.d FLUO RESR INS..O .....P ceevO uuennL nnannY eerneM ennnnE ... PR ages PRODUCTINFORMATION SOURCES . o-oo Paged POTENTIALHEALTHEFFECTS .........uuunneeeeeeeennnPnangne.l.l | REGULATIONS .......vveeeeeeeaaeaaaaaaaaanennnnnnnPeaegee.l.9 SAFETYMEASURES.....\eeuuueaanarenssinnneeeeeee... Page23 ENVIRONMENTAL INFORMATION AND WASTE DISPOSAL . .... Page 39 FOOD ANDMEDICALAPPLICATIONS ...................P.a.g.e.dl. EMERGENCYMEASURES + evvvvuuuenaaannnnsinnsPnaegeeed.d BIBLIOGRAPHY ........oeenneaeaeaaninnnaaaanensinnPsangne.d.] TFEIN FLUOROPOLY.ME++R+S evvuaaanennsnnnnnenne. PageSO THERMAL PROPERTIES... evvuuuuennnsnnrsinnseeee.. Pages TRADE NAME CROSSREFERENCES ............cooooonn...... Page99 INHALATION TOXICITY. eevvvuuuennannnnsnnneeee. Pagel0l Page iii 1 < Co a - Copyright 1992, 1995, 7998 8 The Society of thePlastics Industry, Inc. All Rights Reserved First Edition: October 1992 Second Edition: October 1995 Third Edition: June 1998 Pageiv | b i @ oo oo ee---- _ NOTE TO USERS This Guide was developed by the Fluoropolymers Division ofThe Societyofthe Pfloarsstaifces Ihnadnudsltirnyg, oInfcf.launodroispoilynmetr eretsnoipnrdsoivenipddreociensfsoirnmga.tiTohneognugiedneelrianlesgupirdoevliidneeds airnetebnadseeddtoonbetheeitchoelrleecxthiavuesteixvpeeroirenincceluosfivmeemofbealrlspoefrttihneentinrdeuqsutriyr,embeunttsa.re Tnhoet rienlfioarblmea,tibount ipsrmoavdideeWd IinTHthOisUgTuiWdAeRisRoAfNfeTrYed,iEn XgPooRdESfaSitEhDaOndRbIeMlPieLvIeEdDt,oAbSe TOROATNHEYMOETRHCEHRAMNATTATBEIRL.ITTYh,e gFuIiTdeNlEiSneSsFprOoRviAdePdAanRdTtIheCeUxLaAmpRlPesURinPcOlSudEe,d asarteisnfoyt ailnl tceunrdreednttolebgealdirreeqcutierdetmoenatnsyrpealrattiecdultaorcpornotdruoclto,fnporrocareesstihnegy ocpleariamtieodnst.o Following thexGuide does not guarantee compliance with any regulation nor safe operationofprocessing facilities. Users are cautioned that the information upon `which this guide is based is subject to change which may invalidate any or all of the comments contained herein. The Guide is not intended to provide specific advice, legal or otherwise, on particular productsorprocesses. In designing and operating processing lines, users of the Guide should consult with their own legal and technical advisors, their suppliers, and other appropriate sources (including but not limited to product or package labels, technical bulletins, or sales literature) which contain information about known and reasonably foreseeable health and safetyrisks oftheirproprietary products and processes. SPI, its members and contributors do not assume any responsibility for the user's compliance with any applicable laws and regulations, nor for any persons relying on the information contained in this Guide. SPI does not endorse the proprietary products or processesofany manufacturer or user of fluoropolymer resins or products. All information about an individual manufacturer's products contained herein has been provided by those manufacturers who are solely responsible for the accuracy and completenessofthe data. CopGyurinde19t5o2.th10e08S.af1e99HaTnediSng oof FlucheorPoapasolymenruRse,sinnsc,.TAhLirRdigEsdiRtoosnario Pagev 7 i CHAPTER FOREWORD E--m ---------------------------------------- Fluoropolymer resins are classified under the U.S. Department ofTransportation (DOT) `Hazardous Materials Regulations' as nonhazardous as shipped and can be safely handled by following the basic safety recommendations of this guide. It is the intentofthis guide to provide an overview ofprocessing and fabricating. Each user is responsible to comply with applicable Federal, state and local laws. Asfar aspossible, this document includes the latest technical and research information currently available and may be updated in the future, but users are cautioned they are responsible for the interpretation and applicability ofall information presented. Dispersions containing solvents may be classifiedashazardous. Consult your supplier of fluoropolymer-gentaining materials for classification information. Another important document that may beofhelp in establishing a safe handling program for fluorocarbon resins is "Criteria foraRecommended Standard...Occupational Exposure to Decomposition Productsof Fluorocarbon Polymers," published in 1977 by National Institute for Occupational Safety and Health (NIOSH). ! 49CFR 171 etseq. 2 NUa.So.naDelpaInrstimteuntteofforHOecacluthp,atEidouncaaltiSoanf,etayndsnWdelHfearael,,PuCrbiltiecriHaeoalrth SRerevciocem,mCeenndteedrSftoarnDdiasreda.se Control, POucbcluipcaattiioonnaNlo.ExpPoBs2u7r4e72to7,De(cWoamsphoisnigtiioonn, PDr.oCd.ucNtTsIoSf,FlSueoprtoecmabrebro1n9P7o7l,ymveirls,+ D11H2EpW. (NIOSH) CopGpuaide19t5o2.th10e05S.af1e39HTaondeiSnog tofoFfluaoraopsoilcymeruRae,sinnc,. AThIiRrdnEadiRtoosnoved Page1 2 i { i Page 2 Guide to Copyright 1962, th19e95S,af1e998HaTnhdeliSnogcofioFeflttuhyoerPolpasotliycsmeInrduRstersyi,nIsnc.,, Third Edition All Rights Reserved i J--------------" CHAPTER - INTRODUCTION Fflouuondroappopllyicmaetriornesiinnsneaarrelpyreovdeurcyedfiaelnddofsomloddweorrnldiwndiudsetrbiyal,setveecrhanlolmoagniucfaalc,tuarnedrss.cieTnthiefiyc:have endeavor. rOefstihsteanmcaentyo hperaotp.ertWiheisltehaftecwhaprlaascttiecrimzaetefrliuaolrsohpaovleymceorntreisniunosu,sosneeorvfictehetemmopsertaitmuproerstmauntchis athbeoivre tohveenbosialnindgipnotihnetoefnwgaitneerc,omfpluaorrtompeonltysmeorfjreetsianisrccraafnt.wiCtohsmtbainndetdhewittehmpcehreamtiucraels rienssiisdteabncaekianngd excellent dielectric stability, the heat resistanceoffluoropolymer resins yields an extremely pVEelererscfatortiirclmaealnfoacvmeeirclhlyaoorafadSchtaegnridinssetiiemcrsiilnnaegreemdmaeetdregriienanlctsih.eeseT.vheenAstsoe fwuinftiihrqeua,eniypnrpfolopuelirydtmiceeorsnitmcaamiyantmeperrniotavlio,droeevxcecerrlhtueasaiitnoindn,egsiorrable thermal degradationofthese resins can produce toxic effluents. "CThhaipstgeuridIIeL.inIctliusdneostiinnftoernmdaetdiotnooanddtrheesssacfoemhpaondulnidnegdanflduporroocpeoslsyimnegrosfotrhreesmiantseriinaltsheifdeonrtmifoifed in micropowders due to the variety and numberofformulations possible. CopyrGiugihdt1e99to2,th19e9S5,af19e9H8aTnhdeSioncgieoyfoFfituhoerPolpasotlicysmeInrdRuests,inIsnc,. AThliRridghEtdsiRteisoenrved Pag3e to Paged CopyGriugihtde19t8o2,t1h9e85S,af19e98HaTnhdelSioncgietoyfoFfituheorPloapsotilcysmInedrusRterys,inIsnc,. AThNiRridghEtdsiRteisoenrved un | CHAPTER Ill FLUOROPOLYMER RESINS MONOMERS Polymers are made from monomers. The monomers commonly used in fluoropolymer resin `manufacturing are listed in Table I. These monomers have various chemical and physical characteristics, and potentially significant health hazards. Table I `Monomers w/ CAS Registry Numbers Tetrafluoroethylene (CF,=CF,) CAS#:116-14-3 Vinylidene Fluoride (CH,=CF,) CAS #: 75-38-7 Ethylene (CH,=CH,) CAS #: 74-85-1 Chlorotrifluoroethylene (FCCI=CF,) CAS #: 79-38-9 HCeAxSaf#l:uo1r1o6p-r1o5py4lene (CF;-CF=CF, ) Perfluoropropylvinylether (C;F,0-CF=CF,) (CAS #: 1623-05-8 Perfluoromethylvinylether CF,0-CF=CF;) CAS #: 1187-93-5 Physical characteristics MW: 100.02 /gas/ b.p.: -76.3/C m.p: -142.5C/Den.: 1.5197 MW: 64.03 /gas / m.p.: <-84C MW: 28.05/gas, mel pr/b.p.:-103.7C/ m.p.: -169 ethC MW: 116.47/b.p.: -26.2C/m.p.: -157.5C/ Den: 2.54 MmpW.: -115560..20/C2/gDaes/n:b.p.1:.-52893.%4C/ |MW: 266/li.qui0d/4 b.p: 35C/ m.p.: <-35C MW: 166.02 / gas/ b.p.: 23C FLUOROPOLYMERS Fluoropolymers are manufactured by connecting individual monomers chemically to form new `substances called polymers. The resulting polymers have vastly different chemical and physical properties than monomers. Consequently, the potential health effects of monomers should not be. confused with thoseofpolymers. This means the potential health effects caused by overexposure CoGruide95to2.th0e5S5a1f6e6H8aTnodlSinegiof oFfluorPoapsoilymer Rneis,innse,. AThirdhEsdRitionr Page 5 i 12 | CHAPTER Ill FLUOROPOLYMER RESINS teofffelctusorcoapuosleydmebrysoavreerqeuxiptoesudirfefetroemntonaonmdertysp.icaCllhyapftaerrleVssdsiisgcnuisfsiecasntthtehpaontetnhteiaplotheenatlitahl ehfefaelctths of overexposure to fluoropolymer resins. The commercial fluoropolymer resins are described below. eFnlvuiorroonpmoelnytmaelrscornedtiatiinounsse.fuMlasntyrenagptphl,icfaletxiiobnislidtye,paenndd odinelfelcutroircopporloypmeretrise"saobvileirtybrtooasderrvaengfeosr of fliirmeiateldarpmerciaobdlse,atflteexmipbelerahtousree,snaobnolvubertihceatreadtebdeavrailnugess,, ae.ngd.,oetlheecrtrcicoamlpaornce-nqtusenwchhiicnhg meqauyipbmeent, subject to sudden changes in temperature. PTFE PTFE is a polymer consistingofrecurring tetrafluoroethylene monomer units whose } fOonrmhuelataiinsg[tChFe,-vCirFg]i,n.rePsiTnF, Eit dfoeos nraoctmlmeesalrtctooalfeosrcmaballeigqeulidatan6d30caFnno5t0be(m3e3l2teCxtr1u0de.d. ; tOhnacnetphartoocfestsheed,vitrhgeingerlespioni.ntIt(oisftseonldreafseraregdratnouelsarthpeowmdeelrt,inag fpionientp)owisdeSrO,For(1a0naCq)uleoowuesr dispersion.' Each is processed in adifferent manner. FEP FEP resin is a polymer of tetrafluoroethylene and hexafluoropropylene with the formula a[(nCdEi(sCFm,e)lt-CpFr,o)c,e(sCsiFb,l-eC.F)I,t]i,s.suIptphlaiseda imnetlhteinfgorpominotf rtaranngseloufce4n7t3pe-lleSt3s6,pFow(d24e5r,-o2r8a0saCn) aqueous dispersion. ECTFE ECTFE is apolymerof ethylene and chlorotrifluoroethylene having the formula [(CHy- aCnHd,)iCsFmCeIl-tCpFr,oc)e,s]si,b.le.ECItTiFsEavhaaislaablmeelintitnhgepfooirnmtorfatnrgaenosflu4c2e8nt p-e4l7le3tsFa(n2d2a0s-a2f4i5neC) powder. PCTFE > tPhTisFfEormma.yCboentsaolcdt iyntouhresfuoprpmlioefrsafmoirctreocphnoiwcdaelr.infTohrimsatGiuonidaenddopersoncoetssaidndgreinsfortmhaetihoanz.ardsofresins sold in "ThHaerbmoerlDtriinvgep,oWinetstdaCtaonwsehroehoocbtkaeinn,edPAfro1m94A28m-e2r9i5c9a.n Society for Testing Materials (ASTM), 100 Barr Page 6 CopyGriugihtd1e89o2,th19e95S,af19e98HaTnhedSinog ocfoFfiituheeorPlotapsotiylcysmeInrduRstersyi,nIsnc,., TAhlliRridghEtdsiRteosnerved 13 CHAPTER Ill FLUOROPOLYMER RESINS PCTEE is apolymerofchlorotrifluoroethylene with the formula [CF,-CFCl),. It has a melting point range of 410- 428F (210- 220C) in the formoftranslucent pellets and powder. and is melt processible. It is available PFA PFA resin is a polymer of tetrafluoroethylene and a perfluorinated vinyl ether having the fPoFrAmumlealt[s(CaFt(5O7R2,)F-(C3F00)(CC)Fm,in- iCFm,u),m],anwdheirs emeOlRt,prroecpersessiebnltes.aIpteirsfalvuaoirloaabllkeoixnytghreoufpo.rm ofpellets, powder, and as an aqueous dispersion. PVDF cPoVpDolFyhmeormoofpovliynmyleirdseonfevfilnuyorliiddeenaendflhueoxraifdeluhoarvoipnrgoptehenefohramvuilnag [thCeH,fo-rCmFu}l,aa[nCdF(CF)CprFo,c)e.s(sCiHb;l-eC;Fiyn)d,]a,rePsVupDpFliepdoliynmtehresfmoerlmtoaftp2o7w3der-,35p2elFlet(s1,3a4nd 1d7is8peCr)s,ioanrse.melt ETFE ETFE is a polymer of ethylene and tetrafluoroethyleneofthe formula [(CF-CFy),(CH,-CHy)],, ETFE melts at 482 and is supplied in pellet and powder form. F(250C) minimum. It is melt processible MFA MFA is a random copolymeroftetrafluoroethylene and perfluoromethylvinylether. It bIteilsoanvgasiltaobtlheeignetnheerifcocrlmaosfsotrfaPnsFlAucpeonltypmeelrlset.sMaFndAaqmeuletosusatd5is3p6ers-i5on4s.F (280- 290C). THY TTHHYY iissametletrpproolcyemsesribolfetwetirtahflmueolrtoientghyploeinnet,shferxaofmlu2o4r0oprtoop3y5l6enFe,(a11n5dvtiony1l8i0denCe) fluoride. depending on grade. Itis available in pellet, agglomerate or aqueous dispersions. TU.hSe.As.uppInlci.e;rsCuosfttohemseCommatpeoruinadlsinignc,lu2dSeutbhseidfioalrlyoowifngD:ynAesoanhiLGLlCa;ssDaAimkeirnicAam,erIincc.a;,AIunsc.i;mDountPont FInlcu. orMoparnoydudcitfsf;erEeInft AgtraodcehseomrNcolrastshesAomfeeriaccah, tIynpc.e; oIfCIflFulouroorpooploylmyemrerress;inasndareSoalvvaialyabPloel.ymPelresa,se contact individual suppliers for specific product information. # Guide to the Safe Handing of Fiuoropolymer Resins, Third Editon `Copyright 1982, 1995, 1998 TheSocofitheePltastyics Industry,Inc., All Rights Reserved Page 7 14 ; ) BN CHAPTER Ill FLUOROPOLYMER RESINS i Guide tothe Safe Handing of Fucropalymer Resins, Third ion H Page 8 `Copyright 1992, 1995, 1998 TheSocietyofthePlastic Industry, Inc, AI Rights Reserved 5 i i i _ _ ~ _ CHAPTER IV PRODUCT INFORMATION SOURCES rFleucoormompeonldymeedrtmhaatnuufsaecrstucroenrtsacptrothdeuicrereasilnarsgueppvlaireirestyfoofrpirnofdourcmtastiaonndrepgraordduicntgftohremss.pecIitfiisc physical properties and other needed product data. Listed below are the addressesofresinmanufacturermembers ofThe Society ofthe Plastics Industry, Inc., Fluoropolymers Division, who contributed to this document: `AGA Chemicals, Inc. (Asahi Glass Group) 2201 Water Ridge Parkway, Suite 400 Charlotte, NC 28210 Product Information: (704) 357-3631 AUSIMONT US.A., INC. 10 Leonards Lane `Thorofare, NJ 08086 Product Information: (800) 221-0553 `CUSTOM COMPOUNDING A Division of Dyneon LLC 50 Milton Drive Bridgewater Business Park Aston, PA 19014 Product Information: (800) 55-HOSTA DAIKIN AMERICA, INC. 20 Olympic Drive Orangeburg, NY 10962 Product Information: (800) 365-9570 Guide to the Safe Handing of Fluoropolymer Resins, Third Ediion `Copyright1982, 1995, 1398TheSocietyof the PiasicsIndustry,Ic.,AllRightsReserved Pag9e 173 a } | CHAPTER IV PRODUCT INFORMATION SOURCES D10U0P7 OMaNrTkeFtLStUreOetROPRODUCTS `Wilmington, DE 19898 Product Information: (800)441-7515 SEpLecFiaAliTtyOCCheHmEicMalNsOGRroTuHp AMERICA, INC. 2Te0c0h0niMcaarlkePtolSytmreeerts Department ] Philadelphia, PA 19103-3222 _ 1 iv | Product Information: (800) 225-7788 (215)419-7520 CICoIncForLdUPOlRaOz--PaOMLcYKMeEanRSIst 1` W3i4l1m1iSnigltvoenr,siDdeER1o9a8d50-5391 Product Information: (800) ICI-PTFE (800) 424-7833 PSeOrfLoVrmAaYncAeDPoVlAymNeCrsEDGrPouOpLYMERS, INC. P3.303.3BRoixch2m7o3n28d Avene Houston, Texas 77227 Product Information: (800) 231-6313 | 1 i Page 10 Guide to the Safe Handing of Fluoropolymer Resins, Third Editon `Copyright 1992, 1985, 1998 TheSocofitheePlatstiycs Industry, Inc. AllRightsReserved | EE | ECE HAPTER V -------- POTENTIAL HEALTH EFFECTS | FLUOROPOLYMER RESINS pFrloupoerrotpieosloyfmtehrerseesicnosmapreouknndoswnarefoarltshoeifravcohreambliec.alTshteabirleistiynsantdhelmoswelrveaecstihvaitvye. deTmhoensttorxaictoeldogliitctle | ifPoalnyyvitnoyxlicflouloorgiidce,acftoirvietxy.amFplleu,orporpoodluycmeedrsnoarsekinneirtehaecrtsikoinns iwrhrietnanttsesntoerd sfeonrsiimtiitzaetrsioinnahnudmans. ! sinensseivteirzaaltisohnoirnt-htuemramnosr.a'l tNooxicaibtnyortemsatlsi.tiOebsseatrtvreibdutraebslpeontosepsolwyetreetraatftlruiobruoteetdhtyoleandediwteirveesopbrseesrevnetd | inthe products tested. | According to Montg-omery, grossly excessive exposure to fluoropolymer resin dust produced || increases in urinary fluoridebutwere below levels considered toxic. || TFhlueoIrnotpeomlaytmieornarlesAignsenhcayvefobreeRnesuesaerdchtoomnanCuafnaccetru(rIeAmReCd)iccaolncilmpuldaendtst*hatfoirnofvoerrmattwieonntywaysears. | insufficient to assess the carcinogenic risk in humans. `As noted above, the available information on the hazards associated with exposure to unheated | fluoropolymer resin dust suggests that the toxicity is low. However, many resins are formulated | wotihtehrahdadziatirvdessitnotphreouvsiedoeftfahveorraebsliens.perFfoorremxaanmcpeloer,pfrloucoersospionlgycmhearraacqteureiosutiscdsiwshpeircshiomnasycocnrteaaitne | osuvrefraecxtpaonstusraen.d Idtiissperresciongmmaegenndtesdthtahte mreasyinpsruopdpulcieerasdbveercsoentpahcytseidolfoogriscpaelceifffiecchtesaalstha irnefsuolrtmaotfion onadditivesused in their products. For substances added by the processor, the supplierofthe additive should be contacted. | 5 eHda,riVsolL2R,,PaatndE,SGarevoardgie,DD.. GC.l,ay"tSoynntahnedtiFcloProelnycmeerEs.,C"lPayatto'ns, IEnddsu.s,t(riNaelwHyYgoirke:neJaonhdn WTiolsiecyol&ogSyo.ns4,h | 1954) Seepage 41 fo discussionofmedical applications. `CopyGriugihdte19t9o2,th19e95S,af19e98HaTnhdeliSnog cofioFfeluhyoerPolpaostliycsmeInrduRstersyi,nInsc.,, Third Editon All Rights Reserved Page 11 8 CHAPTER V PROCESSING EMISSIONS POTENTIAL HEALTH EFFECTS bAelgtihnoutgohgefnleuroartoepeoflfylmueernstsarate laomwonragtetsheat,moorstsitghhetrlmyaalbloyvset,abtlheeiprlansotrimcsa,lfplruoocreospsoilnygmetermspweirlaltures. fTlhueorraotpeoloyfmgeernseraabtoivoen trhiseesmawniutfhacitnucrreerass'inrgetceommpmereantduerde parnodcecasrseinmgulsitmitbse. taOkpeenrantoitotnoohfeat dpreogcreasdsaitnigonoeqfutihpemepnotlyambeorvetothperomdaunucfeapcatrutriecrusl'atreefcuommemaesndweeldl laismittosximcagyasperooudsucbey-spurfofdiuccitesn.t The most common adverse effect decomposition products is widely arsescoocginaitzeeddw"iptholhyummearnfuemxpeofseuvreer"toorfl"uPoFrFo,p"olcyhmaerarcterized by a temporary (approximately man's fever). Symptoms 2c4anhoiunrcsl)udfeluf-elviekre,ccohnidliltsiaonnd,sismoimlaertitmoemse,tacloufghu.me fever (foundry cIonhnatlaamtiinoantoefdetfofblauecnctopmraodyucatlssofcraoumseovpeorlhyemaetredffulmueorfoevpeorl.yImerissrSercafotmemresnmdoekdintghatflsumoorkoiponlgyamenrd- :. dteopbaecncdoinpgroodnuctthse bchearbaacntnereidstiincswoofrtkhaereoapserwahteiorne,flloucaolroepxohlayumsetrvreenstiinlsatairoenpmraocyesbseedr.equIinraedddi(tsieoen, Chapter VI). w`Thhoerehahvaevehabdeernepseeavteerdalepainscooddeostoalfploitleyramteurre freupmoertsf"e!veorf. rIensimdouasltpcuaslemso,ntahreyaeffffeeccttesdiinnidinvdiidvuiadlusals uhnacveertaaihni.stCoormypolficsamtoiknigngf.actBoercsacuasneoifnccloumdep:li(c1a)tmiinxgefdacetxopross,utrhees;va(l2i)diltiymoiftetdheisnefofrimnadtiinogns oisn iprnifoorrmeaxtpioosnuroen hniosntoorcyc;up(a3)tiloinmaitledm,eidfiacnayl,dadtaataoonnsuabcjteucatls.chemical exposures; and (4) limited aRboosvee"3s0u0ggeCst(s57t2hatF)n,oaknndotwhnat,hawzhaernd t"oPhTeFaElthisfhreoamteedxpaobsouvree3e0f0istCs,uandleeqsusattheevpeonltiylmaetrioinsihseated essential." (See Chapter VIL) "Haris, D. K., Lancer 261, 1008, December. 1951. 1 MoKafSlaPenHs.,OcScN"u.PpoaMtlDiyo,mneaMrlP-HFI.nuhmael"aPFtrieoovgnerreFsAessviseoornc"ioafJtoeCudhrrwnoiantlihcoSfOmbMosetdkriiucncigtnieav.nedP1Uu9sl9e4m:o3onf6aa:r15yM-o7Dd8i.-seRaeAsllecbarafestceehrtS,MparWlaNty.p,CloePnhEi.pDii.rsiondges Polyterafloroethylene." JOccup Med 1987:29.817-819. "Roesde.,BosCteocni:leLAi.t,eI,nhBarloatwinonanFdevCerosm,painnRy,om1,99W2.:Np.., e3d.73E-n38v0i.ronmental and Occupational Medicine, 2nd . n | Page 12 `CopyGruigihdte199t2o,t1h9e95S,af19e98HaTnhdeiSnocgieotfy oFfltuhoerPolpasotlicysmeInrduRstersyi,nisn,c.TAhllirRidghEtdsitRieosnerved CHAPTER V POTENTIAL HEALTH EFFECTS tJhoehynsbeolnieetvealc"a,ntbheeohriizgehltyhattoxhiecattiontgoheflPunTgF,Ecarueslienagsepsuflummoensarcyonetdaienmiang(euxltcreas-sfiivnee pflauritdicilnescewlhlsicihn fthreomlusnmgasl)lwbiltohohdevmeosrserlhsa).gicIninafnliammamlaetxipoenr(ismeevnetrse iinrrwithaitciohnotfhtesheepatritsisculeewsiwtehrreelreeamseovoefdblforoodm the a, signs produced the and symptomssimilarto expected PFF response. thoseof PEF did not develop in the animals. Unfiltered air aFmlouournotpsoolfymeefrflsuemnatys --deceo.gm,pohsyderaotgeelnevfaltueodripdreo(cHeFs)s,incgartbeomnpye!raftluuroersidaen(dCmOFayy),release sufficient ppoetrefnltuioarlohiaszoabrudt.yleTnhees(PeFgIaBs)e,saanrde taeltrtaofxliucoartoeltohwylceonnec(eTnFtEr)at,iaonmsonangdosthhoeursld--nottobpereisnehnatlead (see below). MSDS fBorrimeofrdeisdceutsasiiloednsionfftohrmeateifofne.ctofindividual chemicals appear below. See suppliers oPLfaertgthael1so9ec1c0iunp(da2it9viiCodunFaaRll ec1hx9ep1m0o)is.cuarlReselmcimaoiymtsmb,ee(nOsdEpeeLdc)i,foiccecadullpieandttiPhoeenraUml.iSse.sxipCboolseduerEexopfloiFmseiudtrsee,racLlailmRlieetgdsuTl(ahPtrEieLos)nhs,o,lfdoTriLtsiloemmi2et9., CVoanlfueerse(nTcLeoVf) GoorvReercnommenmteanldeIndduEsxtrpioasluHryegiLeinmiisttss(oRrELb)y,tmheayNatbieoensatlabIlnistsihteudtebyfotrhOecAcmupeartiicoannal tShaefseetysoaunrdceHseaiflatvhai(lNaIbOlSe.H), respectively. Suppliers' MSDS may provide information from all of THERMAL PROPERTIES OFFLUOROPOLYMERS dAelcthoomupgohseflsuloorwolpyolwyhmeenrshaeraeteadmtoonelgetvhaetemdosttemsptearbalteuproesl.ymTehresrkenioswsno,mtehecyonwtirlaldisctatritontoin the dpiufbfliicsulhteydilnitaenraaltuyrzeinasg ttoratcheeeelxeamcetntteemmpiesrsaitounsr.e atHowwheivcehrd,ecsoigmnpiofsiicatnitondeoccocmupros,sirteifloenctoicncgurtsheonly q`uwahnetnitfylouforeofpfolluyemnetresvoarlevehdearteemdaainbsovsematlhleiurnrtielctoemmmpeernadteudrepsroicneesxsciensgstoefmtpheerantuorremsa.l Tprhoecessing temperature for thepolymerare reached. The usual continuous use and processing temperatures for fluoropolymers are given in Table 1 PPJohuhalnrmsmotanocano,rlyCogI1y,n,flFAairnmtkmieaclltseoterNiyon,.Re0J.s2p0No.8n,sGAeeclAaesdsneo,mciRi.ac,tePBdraegwsgisst,,hMRP.aTyFaEn1d9F9Ou6bmredusEtxepro,suGr.e"":ChTaorxaicctoelroigzyaatinodnoAfpEpalrileyd , | 20 il CoGpuiyde13t52o,th19e95S,af15e98HaTnhdeiSnogcoyf oFflhueorPoapsoltyamierncReus,innsc, TAhlirRdhEadiRteosnanved Page 13 i| i CHAPTER V/ POTENTIAL HEALTH EFFECTS Table 1. Continuous Use and Processing Temperatures of Fluoropolymers* Polymer TyTpeimcpaelraCtounrtei,nuoFu(sCU)se Te`TmyppeircaatluPrreo,cesFs(inCg) PVDF/HFP PVDF 255 (125) 300 (150) 480 (250) 450 230) ECTFE wan 300 (150) |wo 540 (280)n| L"Note e that he temm peratur| es in this able arsactwualapomlymer temper[ at--urmew ost ovenoor qumip ] temperatures, which may be significantly higher. TTehmepetryapetourfe,deacvoamiploasbiilttiyoonfporoxdyugcetns,dtehpeepnhdyssiocnalthfeorcmoonfditthieonasrtuincdlee,rawnhdicthhehreeastiidnegncoecctuirmse of ntahteurreeacofttihonepdreocdoucmtpsosaitttihoenhpirgohdutcetmsp.erTahtuerperaerseeancmeoonfgotthheerfascutbosrtsatnhcaetsdmetaeyrmailsnoe atfhfeecutlttihem.ate dneatcuormepoofstihteiodnoecfofmlpuoosriotpioolnypmreordsucatrse. flTuhoreintehrceoemmpaoiunndtsyp,eosoxfipdartoidouncptrsodfuoctrsm,edanidn tlhoe.wmolecular-weight fluoropolymer particulates fIonrtthheecraesaesoonfsPoTuFtEl,innedumaebrovoeu.s sNtIudOiSesHinsutghgeepsutbeldiisnheidtsl1it9e7r7atCurrietreerpioarDtoacwuimdeentvarthiaett,yogefnreersaullltys, mTeFlEtimngoonfotmheerpiosltyhmeerp"ri.ncTihpleeTgFasEeoobusseprrvoedducitn tathetesmtupdeireasturreepsorttheadt jbuystNpIrOoSduHcemasoyftbeenirnesgiodrual !" ONUac.tSci.uopnaDatelipoIannrsamtlieEtnuxttpoofsofruHrOeecacttuohpD,aeiEcodounmcapaltoiSsoainfi,eotanyndParnWodedlHifecaatrlseto,hf,PCuFiblltuirocircoHceafalrotbrhoanSRePreovcliyocmeme,mrCes,enndDteHrdESfoaWrrcD(liNsrIedaO.sS.eHC)ontr, Publication No. PB274721, (Washington, D.C.: NTIS, September 1977) p. 16. Page 14 `CopyGruigihdt e19t92o.th19e95S,af19e98HaTnhdeiSnocgieotfyoFfltuheorPolpasotlicysmeInrdusRtersy.inIsnc,. Third Editon All Rights Reserved os 2 CHAPTER V POTENTIAL HEALTH EFFECTS wmhoinloemteherrethiastliistlteraoprpnedo dinirtehcet erevsiidneannced cisonrfeileramsiendgatshitshehytpeomtpheersaitsu,rteheirnecraeraesetsh.ermHoogwreavveirm,etric data suggesting this is true. hAysdtrhoegetenmfpleuroartiudreebienccoremaesetshetomaaippnrdoexciommapteolsyit8i4o0npFro(d4u5c0tsC.) Cianrabior,nycalrfblounoyrlidfeluhoyrdirdoelaynzdes rapidly in the presence of moist air to the hydrogen of hexafluoropropylene may also be found at these fluoride and carbon dioxide. Small temperatures. The highly toxic amounts `peWrhfelnuotrhoeitseombputeyrlaetnuereharseabceheens daeptpercotxeidmaastealymi1n,o4r70prFod(u8c0t0atC)t,emtpeetrraatfulrueosroambeotvhaen8e9b0egFin(s47t5oC). mfoarnmu.facSteuerealrssooAnpptheenirdifxluBo,ro"pTohleyrmmearlprPordoupcetrst.ies," for information provided by the individual ofWhtihlee htehaetrienagoreffnloufoirnoopwonlyfamtealritrieessidnisreicntrloyuattitnreibhuatneddlitongexopropsruorceetsosifnugm,esit gceonnetriantueeds atso aberesult important to require proper ventilation to prevent worker exposure (See Chapter VII). tIonxdiicviitdyuoaflsexwcietshspirveeexeixsptoisnugrdeissefarsoemsotfhetrhmealludnegcsommpaoysihtaivoenipnrcordeuacstesd. suCsocnesputilbtiltihteyMtaotetrhieal Safety Data Sheets (MSDS) supplied by the resin manufacturer for additional information. fHlauzoarirddeo,ucsargbaosneyslanflduovraipdoer,scaprrboodnucmeodnoinxifdiree,s ainnvdollvoiwngmoflleucourloaprolwyemiegrhst ifnlculourdoepohlyydmrerosg.en 2 mTahteerreiahlassibneeeqnuiopnmeernetpotrhtaetdwafastanloittyptrhoaperrelsyuletqeudifprpoemd tiontheanntdiolnealtlhyebemuimsisnigonfsl.uoNroopcoalsyemsero-ffcaotnatlaiinnijnugryare Known when noma processing temperataruerneots exceeded. Guide to the Sate Handling of Fiuoropolymer Resins, Third Edition `Copyright 1992, 1995, 1998 The Society of the Plastics Industry, Inc., Al Rights Reserved Page 15 22 CHAPTER V POTENTIAL HEALTH EFFECTS HEALTH EFFECTS OF DECOMPOSITION PRODUCTS HYDROGEN FLUORIDE (HF) T"hhoekeifnfge,ctcsouogfhoivnegr,eaxnpodssuerveerdeueeeto,inndohisfaefliaactunilodtnytohifrnohbayrtdeiaritothgaietnnigo,fncl,yupoaronisodsseiisbm,laynyfdoiln`cllpouuwdleemd:oanatsreyyrmbpeydteoammaso. f SHthyyrmdoprutogoghmeltnehesflssukpoirenirdiieonditsoocxfiofcreoavsemrio,vuecnhtiosl.lst,hIeceaynesc,ausksien,dealnadyerdesbpiurmatsortyhacttraamncat,iynajnnuordetmbtaheeyilmbimeveeardbiasanotdreblkeidyd.nveiyssi.ble : or painful. Ti person iAscouvteerocrocmherobnyiecxopvoesrureexptoo shuyedr{o0 gheyndrfolugoernidfel,ueofrfiedcetive medical assistance is needed. | : CARBONYL FLUORIDE (COF) See i i { Tohereffsects ooffoavaehr:exepyoescuorrerotsoiocnarwbiotnhyilctoafmtliueooanrloidfoertmchaoeynjUuipnnpicettriiavlFalEylSpiuInlTccalelurodaert:yiPosnaks(sidaegisertstr;auctotirioo(nnmowpifottrhhaerylens,!} ` ohfatngheineyteatainodn esfufrercotsunwdiitnhgctoiussguhe,s)d;isicromfort, difficulty breathing, or shortness ofbreath. evisailmpohorutrasn.t tIof nthoeteftfheacttshobesfefretvcetensdotiifonnco,lvueidrnecelxsupedovisenrugerebrpteeoarctiahoridbnoognfdyiolfbfsfielcruuvlotaritieidsoe,nm,ianmcyalubydeibndegerlceaoqynuegiderseftdoiron then. mediate medical a TETRAFLUOROETHYLENE (TFE) {tFiEoisna folfatmhmeaublpep,ergraessepoiursatmoroyntonrmtaiceotrnaawnldhmieacyshessim,vaemyiilcndhaauclesanettiraoacnluotfneterehfvefoeucgstassswyrhsetepeonmrtidenedhplaryleepsdrs,ioiodnnuc,clenudaduisngea mcadrdivaocmiatrirnhgy,thamnida,drcyarcdoiuagch.arrIenstte, and death. A report av year has been study on issued by TFE. The tNhiTenhPUa.lsSat.tuiNdoayntirooefpngoaarltseTedoouxksiicdTonFleEoy.gaynTPdhreiovgrererlaamttui(motnohsrehsNipTinoPfr)atoshenastenhdmeefirfeeccsetuslt1s0of a J lpBooteewnitinalegnhlduiemfdeatnbimyreem(sa-pn2ounfysaeecatrhusa)rsernsotwbheoenuseestTabFlEishiend.maAkiwnogrkfliunogrcoetpxeopdloyosmnuerrpeso.tleinmStieitaeolArfp$epspepnopndmsiexhsaAfsobfeToerEnE | i | ee information on the NTP report and research being condu 3 from fluoropolymer processing. Page 16 CopyGrugihtde19t9o2,th1e95S5af19e98HaTnhdeSinog cofioFflutohrPolpaoslicysmeInrduRsets.inIsn,. TAhLiRridghEtdsiRteisoenrved i 3 3 CHAPTER V POTENTIAL HEALTH EFFECTS PERFLUOROISOBUTYLENE (PFIB) The effects of inhalation exposure to PFIB have been studied in animals. Severe adverse effects occurred, including pulmonary edema in animals exposed to high concentrations, which can lead to death. Symptoms in exposed animals include wheezing, sneezing, difficulty breathing, and abnormally deep or rapid breathing. Animals that survive for 24 hours aftr the exposure apparently recover with no after-effects. Little human exposure data exists, but the ACGIH TLV-Cis 0.01 ppm. EMISSIONS FROM FINISHED PRODUCTS Depending upon the material and finished product manufacturing conditions, it is theoretically | possible that small quantities of residual gases, including PFIB, hexafluoropropylene (HF), "TFE, and HF may be trapped and slowly ofsome finished products has confirmed evolve from resins as well that PFIB and HFP can be as finished products. found in the finished Testing | products, but the conditions under which these compounds form, and in what quantities, has not been investigated. Thisunderscoresthe importanceoffollowing manufacturer instructions in sintering and other finishing operations. `The residual gases can accumulate in unventilated spaces (.g., closed storage rooms, closed trucks, etc.) at levels that may be hazardousifthe quantities of fluoropolymer materials and products stored are large. Therefore, it is important to ventilate these spaces before permitting personnel to enter. Sealed packages may also contain significant concentrationsofthese gases, therefore, they should be opened in well-ventilated areas. Fluoropolymer processors should evaluate the potential for exposure to these gases in their operations, taking into account the typeofresins i they handle, the quantities involved, the tasks being performed, and the specific facilities in which the work is performed. 3 DocumentationofTLV, American Conferenceof Governmental Industrial Hygienists, "Perfluoroisobutylene" 1997. CopGyiugihde19t92o,th19e65S,af9e68HTanhdaliSnogciof oFfltuheorPloapsotilcysmeInrdRuests,innsc,. TAhliridghEdsitRieosnerved Page 17 2 i CHAPTER V POTENTIAL HEALTH EFFECTS i i Page 18 CopyrGiughitd1e95t2o.th19e95S,af19e38HaTnhdeiSioncgetoyfoFflhuoerPolpasotlicysmeInrdusRtersyinnsc,. TAhlirRidghEtdsiRteosnerved ------------------------------------------------------ CHAPTER VI -_-- REGULATIONS Regulations exist that apply to the manufacture and use of fluoropolymers and new regulations are announced on a regular basis. Current information about regulations canbe obtained directly from your Federal, state or local regulatory agency or your fluoropolymer supplier. Manufacturers' addresses are listed in Chapter IV. manufacturer or To cite Federal regulations listed below, use title, part and section number. Thus 21 CFR. 177.1550 Perfluorocarbon resins (1b, below) refers to title 21 ofthe Code of FederalRegulations, part 177, section 1550. `GENERAL REGLATIONS VIIL Title 21 Codeof Federal Regulations: Food and Drugs L Part 110 Packing, -- or Current Good Manufacturing Holding Human Food. Practice iMnanufacturing, i a 177.1550 Perfluorocarbon resins. 4 b. 177.2510 Polyvinylidene fluoride. c. 177.1380 Fluorocarbon resins. IX. 29 CFR -- Occupational Safety and Health The following a complete list OSHA standards apply in nearly ofall standards thaat processor every might fluoropolymer have to follow. processor Rather, it facility. includes It is NOT the ones that OSHA is most likely to consider when inspecting a fluoropolymer processor facility. Fluoropolymer processors should make sure that their operations are in compliance with these standards, but fluoropolymer also should processors be a who ware of the have more other st than ten andards that employees affect on any them. day i In na additi given on, year are required to keep and maintain for five years a logofoccupational injuries and illnesses (OSHA Form 200) and the supporting documentation for all serious or disabling injuries and illnesses occurring in their workplace in that year. Copies of the OSHA standards `may be obtained from a local OSHA office, or the Government Printing Office outlet nearest you. A computerized version ofthe standards and official interpretations is included in a subscription service on CD- ROM available from the Government Printing Office for less than $80 per year. A. Recordkeeping 1 Part 1904 -- Recording and Reporting Occupational Injuries and Illnesses 2 Part 1910 -- Occupational Safety and Health Standards a. 1910.147 The control ofhazardous energy (lockout/tagout). b. 1910.1200 Hazard Communication 3. Subpart O -- Machinery and Machine Guarding a 1910.216 Mills and calenders in the rubber and plastics industries. `CopyGruigihdte19t52o,th19e95S,af19e98HaTnhdeiSnocgioeftyoFfltuheorPolpasotlicysmeInrdusRterys,inInsc,, AThlirRidghEtdsiRteosnerved Page 19 26 i CHAPTER VI REGULATIONS b. p1o9r1t0a.b2le41t-o2o4l4s aHnadndeqaunipdmpeonrtt.able powered tools; Guarding; Other 4. aSubpart1S91--0.El7e6ctMriactaelrials Hand--lgeinenragl. bch. 11991100,.115718 PMoedwiecraeldsienrdvuisctersiaalntdrufcikrss.t aid. 5. Subpart a 19--10.P1e4rs5oSnpaelciPfrioctaetcitoinvse Efoqruaicpcmiednentt prevention signs and tags. 6. baS.ubpart"Q1199--1100..W11e40l60d0PieAnrigmr,i-tcC-ourntettqiaunmigirneaadnndctosBnr(faPizenriemndigssspaicbelse. Exposure Limits). b. 1910.134 Respiratory protection. - B. Emergebna..cy Prep11a99r11e00d.3n3e87sMsEempalnosyoefeeegrmeesrsg,egnecneyrapll.ans and fire prevention plans. .. (19H1A0Z.1W2O0PHEaRz)a.rdous waste operations and emergency response : d 1910.157 Portable fire extinguishers. In addition, the following standards affect fluoropolymer coaters operations as well C. Bulk Storage a 1910.106 Flammable and combustible liquids. D. Ventilatai.on b. 11991100..91407VeSnptrialyatifionni.shing using flammable and combustible . m1a9t1e0r.i1a1ls9 Process safety managementofhighly hazardous 4 chemicals. 1910.1450 Occupational exposure to hazardous chemicals in laboratories. The following EPA standards generally apply to fluoropolymer processors: X. A4.0 CFRPParrott2e6c1ti--on IodfenEtnivfiicraotnimonenatnd Listing of Hazardous Waste 3 1. aSubpart2A61--.3 b. 261.7 GDeefnienriatlion of hazardous waste. Residues of hazardous waste in empty containers. :' 2. Saubpart"C261--.21Chtahrraocutgehri2s6ti1c.s24ofChHaarzaacrtedroiusstiWcassotfeignitability, corrosivity, ii 3. SubparretaDct--iviLtiys,tstooxficHitayz.ardous Wastes B. Part 264 -- Standards for Owners and OperatorsofHazardous Waste Treatment, Page20 CopyGuid1e96t2o th19e06S,af19e58HaTnhdeiSioncgtoyfoFflhueorlopaoltymeInrdRuessti,nIsn,c TAhYiRridgEhdsitRieosnerved 27 CHAPTER VI REGULATIONS S1. torageSaunbdpadritspBos--al Facilities General Facility Standards 2. Saubpar2t6l4--.1U5sGeenaenrdalMainnsapgeecmtieonntroefquCiornetmaeinntesr.s 3. aSubpart)264.1T74anIknsSpyecsttieonmss. a 2un6f4i.t1-9fo6r-Ruesseptoannskestyostleemask.s or spills and disposition of leaking or C. 4.Part28A0p--peTnedchinxicValtoSPtaarntda2r6d4s--anEdxCaomrprleectsiovfePoAtcetnitoinalReIqnuciormepmaetnitbslefoWraOstwensers D. aPanrdtO3p0e2ra--toDresosifgnUantdioenr,grRoeuponrdtaSbtloeraQgueanTtaintkiess,(UaSnTd)Notification E. P1. art35350--2.E6mNeortgifeinccaytiPolnarnenqiunigreamnedntNso.tification 21.. a 335555.3400 EEmmeerrggeennccyy rpellaenansiengn.otification. 3." ASupbpsetnadnicceessaAndaTnhdeiBrtTohPraersth3ol5d5 P--lTanhneinLgisQtuaonftEitxitersemely Hazardous F. 1.Part370Su--bpHaarztaDrd--ousInCvheenmtiocraylFRoerpmosrting: Community Right-To-Know G. P1a.rt 372Su--bpTaorxtiDc C--hemSpieccailfiRceTloeaxsiec RCehpeomriticnagl: LCisotmimngusnity Right-to-know 2. Subpart E-- Forms and Instructions `The following DOT standards generally apply to fluoropolymer processors: XL 4A.9 CFRH--azTarradnosupsorMtaatteiroinals Regulations 1. Part a 17117--1G.e1n5eIrmamledIinafotremantoitoinc,eofRecgeurltaatiinonhsa,zaanrddoDuesfimnaitteiroinasls incidents. 2. b. Part 1721--71.H1a6zDaertdaoiulsedMahtaezrairadlosuTsambaltee,rSipalesciianlciPdreonvtissiroenposr,tsH.azardous TMraatierniianlgsRCeoqmumiurneimceanttisons, Emergency Response Information, and 3. a Part 17317--2.S1h01ipPpurepr--osseGeannedraulseRoefqhuaizraermdeonutss mFaotrerSihailpsmteanbtlse and 4. PPaarctka1g7i7n--gsCarriage By Public Highway a b. 117777..881167 SDrhiivpeprintgrapianipnegr.s d. 117777..883374 CGleansesra3l(rfelqauimrmeambelnetsl.iquid) materials. 5. Part 397 -- Transportationof Hazardous Materials; Driving and Parking Rules. `CopyGruigihdt e19t8o2.th19e95S.af19e98HaTnhdelSioncigetoyfoFfluthoerPolpaostliycsmeInrduRsiersyi.nIsnc,, TAhlirRidghEtdsitRieosnerved 28 Page 21 CHAPTER VI REGULATIONS CALIFORNIA PROPOSITION 65 In November 1986, California voters overwhelmingly approved an initiative to address growing concerns about exposures to toxic chemicals. That initiative became The Safe Drinking Water and Toxic Enforcement Actof 1986, better known by its original name: Proposition 65. Proposition 65 requires the Governor to publish a listof chemicals that are known to the State of California to cause cancer, birth defects, or other reproductive harm. Agents that causecancerare called carcinogens; those that cause birth defects or other reproductive harm are called developmental and reproductive toxicants (DART). This list must be updated at least once a year. Over 604 chemicals have been listed as of September 1, 1996. ! Proposition 63 imposes certain controls that apply to chemicals that appear on the lists. These i controls are designed to protect California's drinking water sources from contamination by these } chemicals, to allow California consumers to make informed choices about the products they + purchase, and to enable residents or workers to take what ever action they deem appropriate to protect themselves from exposures to these potentially harmful chemicals. For further information, contact the Office of Environmental Health Hazard Assessment's (OEHHA) Proposition 63 Implementation Office at 916.445.6900 or http://www. calepa.cahwnet. gov/oehhal. On May 1, 1997, OEHHA listed tetrafluoroethylene (TFE) as a chemical known to the state to cause cancer based on the work performed by the National Toxicology Program. In accordance with the requirementsof Proposition 65, manufacturers ofproducts using fluoropolymer resins are required to determine if the useoftheir product could cause exposureof the user to TE. Consult Appendix A for more information on TFE and fluoropolymer processing and contact your fluoropolymer resin supplier for detailed information on products you use. i i Page 22 `CopyGruigihdt e19t9o2.th19e85S,af19e98HTahndeliSnog cofioeFflttuhyoerPolpasotliycsmeInrdusRterys.inncs.,, Third Edition All Rights Reserved 29 { ! | CHAPTER VII SAFETY MEASURES --er --------------------------------t--r--e--eet INTRODUCTION In this section, methods, equipment and procedures to reduce and control exposures to `monomer gases and effluent gases produced during processing of fluoropolymers are described. Processors should evaluate their operations in lightof the quantitiesofresin processed, the type of processes used, and the physical plant in which the processing takes place to determine what, ifany,ofthe controls described are appropriate or necessary. Good industrial hygiene practice as well as legal obligations under the Occupational Safety and Health Act (OSH Act) may require processors to adopt one or moreofthe controls described and may require additional actions if air contaminants exceed occupational exposure limits. Following the methods described does not `guarantee compliant or safety; however, the experience of processors and resin manufacturers porvoecretsismiengsuogpgeersattsiotnhsat the controls described are necessary in many, if not most, fluoropolymer E Ifknowledgeable individuals are not employed bythe processor, consultants may be required to `thoroughly assess the operations, evaluate the hazards, and assist in the design ofappropriate J controls. References for qualified consultants can be obtained from your resin supplier. VENTILATION As with most polymers, minute quantities ofresidual gases may diffuse from the resins even at room temperature. Therefore, as a matter of good industrial practice, resin containers should be opened and used only in well ventilated areas. Some resins may require the use of local exhaust ventilation to prevent exposure to hazardous gases that accumulate in the package during storage, shipping, and handling. Consult your resin supplier's MSDS for specific recommendations. All fluoropolymer resin processing (e.g., extrusion, molding, spray coating, and wire and cable coating) will release gases, vapors, or - y fumes that may be harmful to human health,if exposures are high. - The typical continuous use and processing temperatures are noted on page 14. Tm | Figure 1 Exhaust Systems f ! Guitodthee Safe Handlingof `Copyright 1952, 1995, 1998 The Society Fluoropolymer Resins, of the Plastics Industry, Inc, Third Edition AYRights Reserved Page 23 J 20 CHAPTER VII SAFETY MEASURES LOCAL EXHAUST VENTILATION SYSTEMS w`foTrhroekmpmleoaqscutei.epfmTfehenicttsia"vecnadwpatruyermeto"ovcteoenctthhrneoimlqutbehyeisesexcheaamlulisestdsivloeonncsatliliesaxtthiooan"ucsbatepfvtoeurnrteei"tlhatethiyeoanmr(eatLdEtihsVep)eprosiendt ionfrteoltehaese `The reasons LEV is so effective are as follows: ochnelmyiacarlelsatrievleelaysesdmaflrlomamfoluunotroopfolaiyrmeisrrreeqsuiinrsecdotmop"acraepdtutroe"thaenvderryemloavrgeetvhoelauimrebsorne required to try and change the air in an entire area or building, and the proper captureofcontaminants at the source can sigaificantly reduce any exposure to chemicals by workers. . NOTE: The useoffans, ceiling exhaust or open windows is generally not effective because contaminants are allowed to mix with room air. In some cases, they may actually interfere with LEV by creating cross-drafts. PRINCIPLES TO FOLLOIWN USING LEV systems in Fig 1,2 nd 3) L Tfahne(ptaorptsulofaairnaLnEd Vansyycsotnetmamarien:ant1s))a,n e2x)haust (clooncnaetcetdecdlo1s0ae tdoutchteasnodur3c)eaonferxehlaeuasseto"fhood" contaminants [see illustrationof exhaust =--_ ewe. = = = 4| Fare Tpit Sep or Exas 2. Room air will be exhausted by the LEV system and the discharge can be treated in wrveiaqrtuihiorauesndywtaaopyprsleiptcloaacbreleemtolheavweesxchooarnutpsaetrmemidintaasin.r.tsMoarkcea-nubpeaie,xhtaeumspteerdetdo itnhesoomutedroeogrisonisn,awcciolrbdeance } 3. aTlhleowhoaoccdesshsotuoldthbeeesqhuaippemdentto cfoorvenroramnadleonpcelroasteiotnh.e sTohuercheoaosdfsahroausldis bperarcetimcoavlaybeltestoirllbe aAndjaudsjtuasbtlaebldeucdtuctwotrhaktocfatnhibse tmyopveeids caosmimdeerfcoiramlaliynatveanilaanbclee.ortroubleshooting. i y 1| PIBE 20 CaGunide1ato.th1e0sS,af1e58HaTnodmiSnguof FfiuoorPopaoloymer Resins, Ta hird Edition i CHAPTER VII SAFETY MEASURES 4. Tsohuercheooasd iissptrhaectmiocaslt.crTietsitcaslhpaavret osfhothwenLtEhaVt tshyestceamp.turTeheefhfeocotdivsehnoeusslddibmeiansischleosseratpoitdhley as the distance from the hood opening increased (see Figure 4) 5. Ifthe contaminants contain dusts, enough to prevent these materials mists from or fumes, the settling out in air the velocity inthe ductwork. duct must be high `The capture effectiveness ofahood can 10 restrict airflow from above and from be the improved by placing sideofthe hood. flanges around the hood opening -- No|se; - IN Figure 3 Hood an a cE TED o=F] Figure 4 Extrudr Die Hood "wThhiecahircfalnowacatruoalulnydptuhsehartheea wghaseersebtahcekctoonwtaarmdisnaynotus aurnelegsesnyeroauteudseiasnseennsciltoisveurteo c(er.og.s,s-ccuurrrteanitnss,) to help your LEV. 4 Proper DesignofExhaust Systems Properly designed exhaust hoods should be installed to remove all off-gases released from hot epqouliypmmeernst.durFionrgtphrisocpeusrspionsgeoapenruatmiboenrs oifnchlouoddindgeaslilgvnsacaureumshpoawrsn,ipnuFmipgsu,rean5d%venTthseosne pdreosciegsnss opfroefsfe-ngtasseevse.ralSiatlutaetrinoantsivneosrtmo alallyloewncaoduenqtuearteedeaxnhdautshtevcoalputumreesvfeolroceiftfieecsti(vgeencearpattuiroenaonfdariremfolvoawl esxufhfaiucsitenhtotoodr)enmeoevdeedcotnoteaxmhianuasttedallaithiesgsausinegs ffrroomm tthhee svoicuirncietyanodf choatuspionlgymitetro afrleowsuinmtmoaarnized in Table 1.2 A`mReerciocmamnenCdoendfePrraecntciecoe,f G17ohveedm.m, e(nCianlcinInnadtuis,trOiHal: Hyg1i9e82n)i,st4s-,1I0ndu4s-t5.ria(lCVoennstuillattitohne:moAstMcaurarltoefdition) 2 id ConGyiugihde19t92o,th19e05S,af19e68HaTnhdeiSnogocifyoFfutohroPpaosltyemeIrndRuess,innsc,.TAhirRidghEtdsiRteosnerved Page 25 32 CHAPTER VII SAFETY MEASURES `The work situation is selected gases is then used to calculate tfhreomvoTlaubmelteri1 carnadtetohfeacierntfelr-olwinreeqvueilroecditfyorretqhueihroedodtodecaspitgunre all selected from Figure 5. For example, in the extrusion coatingof wire, we may assume a `minimum capture velocity of 200 fpm (1 m/s) is needed. To illustrate how the table isused, consider the following. Assume that a plain opening hood (line 3 in Figure 5) is used, the hood is located giving an 0.5 feet from area of 0.5 . the wire as it The volume exits the extruder, and (3) of air required is given by it has an opening the equation: of1 ft x 0.5 ft, Q=V(10X2 +A) Plugging in the values above gives the following result: Q=200(10 (0.5) +0.5) ! =200(10(0.25) +0.5) =200(2.5+0.5) =200(3) = 600 cubic feet per minute (cfm). | Guide to the Safe Handing of Fuoropolymer Resins, Third Ediion Page 26 Copyright 1952, 1995, 1998 The Society of the Plastics Industry, Inc., All Rights Reserved 5 $ CHAPTER VII SAFETY MEASURES : (Resins by permissionofAmFeirgaunreCo5n:trHnocoofdGDoesningna Indus Hygieniss,nc) HHooooddTTyyppeess DDeessccrriippttiioonn ~~ AsAsppeeccttRRaattiioo, HW/WW AAiirrRRaattee"" C Slot r 020rless Q=37WVX H H-- i 7 H 3 --_-- Flanged slot" 020rless Q=28 WVX Plainopening 0.E 2 or gree ater and TQ=VT (10XR * +A) p & ) ---- Felaenged -- opening' er02-- orgreaterande mQ=C0.75Ve (10X2+AA)) <> | s _3 -- m " Boov th To suit work ; Q=VA=VWH i rl Canopwmy oTowsuAit wwormk QQT=m14aPmDVv + ifWlneocwetsreinocgmphoeesoieod,eDcaloennceissveswnhhcuselsrdnnboescprrosavimndead tro ilxmssia.nlelyie = X= DCeinct(e0ofsovcrloosmcmoieuynsadetXodfcdcaaponfscbeovf,io(o7c)eroomfbToodk, 1r)n i1 neaodntgieceewieidhecmmiaesnencmbutaesblyf9h%e.hoFodrmdos mappolrceasiioentis s06erd QAP===APArolemvserahacntocwfionhrok(o1d17.s9s)8 min)) H "= Nomendaues HDe=HiHegihghsohfohvoeowd.or8km) (m) WnWittofbo, r) `CopyGriugihdt1e99t2o,t1h9e95S,af19e98HaTnhdeiSnocgieotfy FofltuhoerPolpasotlicysmIenrduRstersyi,nIsnc,.ATlhlirRidghEtdsitRieosnerved Page 27 34 CHAPTER VII SAFETY MEASURES Tablee1:piCcapbtyupremeisVieolnoocfiAticescReCocnfoermemnceeonfGdeodveinrVnamrieonustWHyogirenkistS,iitnuc)ations Dispersions of Contaminants into Air Examples Capture Velocity, fpm (m/s) Released with practically no Dryingoffluorocarbon 50-100 velocity into quiet ai. resins--granular, powder, cubes, (025-050) evaporationofsolvents, water, etc. from powders and dispersions i Released at low velocity into Spray coating fluorocarbon 100-200 i moderately still air dispersions or powders. Normal (050-10) : blending of fluorocarbon cub&Gsi i powders. Molding and sintering { ! of fluorocarbon resins into large f | billets. Active generation into zone of rapid air motion. Melt extrusion of fluorocarbon resins on wire and into tubing. Paste extrusion and sintering of fluorocarbon resins on wire and tubing. Injection and transfer moldingof melt-processible resins. 200-500 1.025) Released at high initial velocity into zone of very rapid air motion. Grinding and machining of parts from fluorocarbon resins. Highspeed mixing of fluorocarbon powders in turbulent mode. 500-2000 (25-100) i In each category above,a rangeofcapture velocities is shown. The proper choiceofvalues : depends on several factors: Lower End of Range Upper End of Range 1. Room air currents minimal or favorable to 1. Disturbing room air currents capture. 2. Contaminants of high toxicity. 2. Contaminants of low toxicity. 3. High production, heavy use. 3. Intermittent, low production. 4. Small hood--local control only. 4._Large hood--large air mass in motion. Page 28 Guide to the Safe Handing of Fluoropolymer Resins, Third Edition `Copyright 1952, 1995, 1998 The Society of the Plastics Industry, Inc., All Rights Reserved 5 CHAPTER VII SAFETY MEASURES `The importance of locating the hood opening close to the hot polymer is indicated by the fact the f"oXr"mdeidm)einsseixopnon(etnhteidailstianntcheefarboomvetheequfaatcieoonf.thTehuhso,oidftohpiesndiinsgtatnoctehweeproeindtoautbwlhedicihn tfhuemeasboavree example, the volumetric cfm, a ise of 350%. rateofaif flow required would increase to 200 (10 x 17 + 0.5) = 2100 DESIGNS FOR RESIN PACKAGE OPENING AND MANUAL TRANSFEROFMATERIALS Fluoropolymer resins may contain residues of gases used to manufacture the resins which are released slowly over time. The quantities ofgases in the closedpackagesmay be significant. Opening packagesofresin may require theuseof local exhaust ventilation to control employee exposure to residual gases. Controls for work stations vary depending on a numberoffactors, including: whether bagsordrums are opened; whether the product is liquid or solid (powder); the `nwuhmebtheerrosfmpaallcekragqueasnttiotibeesoapreenteodbae traesmionvgleedtfirmeo;m the package and the package resealed for future uismem;eadnidattehevipcriensietynocfetohfeotphaecrkaacgteivoitpieensiinngtshteation. Typical bag opening and weighing stationare shown Backwalof boo --= Om aeFrySk rom 1111 T I --<. [<0 4comes I PIOURE 613g ojeniugiwelghing siaon in Figures 6 and 7. Local exhaust for drum opening is not normally usedifthere is a pump or other closed method of transfer (such as a self-closing valve). In these cases, employees must be trained to follow procedures designed to minimize exposure. These include, among others: transferring resins only in a well-ventilated area; using a hand pump to transfer resin to another container; and transferring resin directly into the process vessel. Studies by the National Instituteof Occupational Safety and Health (NIOSH) indicate that significant exposure occurs when workers lean over into partially empty drumsof solid materials 10 obtain less than a full-package quantity. Stations designed to control these exposures can similarly be used to prevent overexposure in opening packages. `Whatever methods are used, the processor must be awareofthe potential presenceofresidual monomer gases and their potential hazards and assure that its employees take the steps designed 10 reduce or eliminate the exposure. In some cases, the useofpersonal protective equipment, Guide to the Safe Handing of Fuoropolymer Resins, Third Editon Copyright 1952, 1895, 1998 The Societyof the Plastics Industry, Inc., All Rights Reserved Page 29 C3 CHAPTER VII SAFETY MEASURES ssuupcphliaesrsf'acMe SshDieSldfso,raipnrfoonrsm,agtlioovnesa,boauntdtehveepnrordeuspcitrsationrussmeaayndbethreeqpuriercead.utiCoonsnsnuelctestshaerryestion use the product safely METHODS OF CHECKING AND MEASURING AIRFLOW `YTohueraeiqrufilpomweinnta, vfeanntisliazet,ioincs.ysAtesmimdpulcet cwaanyvtaorymodneipteonrdtihneg on FAjRi performanceofthe system, once itis working properly, is to =|=33 = iCnhsatanlgleasgianutgheistoprmeesassuurree--itnheeistthaetricdiprreescstuiroen--imnetahne etxhhatautshteduct. =| "TY --- = airflow has changed and, therefore, a maintenance check of the fan and/or duct measured with is needed. This "transport" a special flow meter velocity canbe =o FIGURE 7 Weighing Station tAubsei"mp(lNeOTcEhe:ckothfisthsemoLkEeVissnyosrtefmr'osmefafeficrtei)vteonepsrsocdaunceb&a mstardeeamboyfduesinnsgeawvheinttielsatmiookne"satmotkhee elnocoautgiho,n twhheersemotkheehsohtouplladstbiecrwaiplildlreylceaaspetucroendta(mwiintahnitns.1--I2fthseec"ornadnss)pboyrtt"heveelxohcaiutsytisaihfiagnhd swept isnotmoethaedjhuosotdme(nsteeoFfitghuereho7)o.d lIofcsamtoiokneaensdc/aopreasirthveelhoocoitdyawnidllmboevenesediendt.o thIensstualrlrionugnaddidnigtiaoirn,althen enclosures, .g., considered. heavy plastic curtains to surround the operation or sourceofthe gases should be. EQUIPMENTAND TESTDEVICES 4= 1. cVuernrteinltastiaornoSunmdokane eTxuhbaeuss:t thooovdisu(alslcye check figure the 8). air Lev : Good 2. "AciarptVuerleo"civteyloMceittye.rs: to measure airflow and --_R 8 ox | | 3. Static Pressure Gauges. i 4. Portable LEV units, i 5. Adjustable Duct Systems. -- FIGURES: Not Good Use ofSmoke Tubes Page 30 `C op Guide to the Sa yright 1992, 1995, fe Handing of 1998 TheSociety Fuoropolymer Resins, Third of the Plastics Industry. Inc.All Rig Edilion hts Reserved CHAPTER VII SAFETY MEASURES PROCESSING `SofIdNeTcEoRmIpoNsGitOiPoEnRprAoTdIucOtNsSarreeqfuoirrmeedth.e Ousveeonfshmiugsht-theamvpeerfaotrucreedovveentnislaitniwonhiwcihthvasurfifoiucsieanmtoauinrts flowto prevent formed gases from entering the work space during oven operation and when the doors are opened. into the work area. Ovens must be properly maintained to keep gases from the oven from leaking Temperatures in excessof normal sintering temperatures must be avoided. To assist in this, ovens should be equipped with an independent, high-temperature cut-off switch triggered by an increaseof temperatures 50 -- 60F (28-- 33C) higher than the sintering temperature. Both systems need to boealibrated at regular intervals. Ifthe oven temperature exceeds the high temperature cut-off seting, te heaters must be switchedoffand the oven must be cooled to ambient temperature and properly vented before the oor is opened. When opening sintering ovens aftr overheating, appropriate personal protective equipment is recommended, e.g., protective clothing, a self-contained breathing apparatus or supplied-air respirator, gloves, Safety glasses, etc. Processing PTFE fine powder resins requires extrusion byaspecial process, commonly known as : PASTE EXTRUSION. This involves mixing the resin with a lubricant, usuallya volatile petroleum solvent. The useof combustible and flammable liquidsofrelatively low flashpoint | may create a significant potential fire and explosion hazard. In addition, solvents may cause health hazards due to inhalation and/or skin contact. Appropriate precautions must be taken for the safe use, storage, and handling of fluoropolymer resins containing solvent-based lubricants. Follow the recommendationsof the solvent supplier and the information on the MSDS from the PTFE supplier. Removal of the lubricant (solvent) after extrusion may take place in a separate batch drying oven or ina continuous oven fited in-line with the extruder. Appropriate precautions need to be taken to minimize the risk of forming explosive mixtures of lubricant and air, and to prevent ignition. With an in-line operation, the drying operation is immediately followed by high temperature 3 csianrtreireidngi,ntaontdhethseirneteirsitnhgezpoonsesiwbihleirtey tithawtililncaolrmroecstt ocpeerrtaaitniloyn iwgoniutledifacalulsoewfeldatmomaabclceumvualpaotresttoo be. | sufficient concentrations. It is essential to have fire extinguishing equipment available. For ; small fires, portable carbon dioxide extinguishers are usually adequate, but a permanent installation, which can rapidly il the entire oven with carbon dioxide in the event ofa large fire, is advisable. Ventilationofthe drying and sintering operations requires the same precautions as described earlier in this section for operation of sintering ovens in the work place. Consulta fire CoGpuipde19t52o.t1he99S5af1e99HaTnhdaiSnogdoafsFouonroPpaastliysmemruRse.sinnsc,. TAhlirRd sEdiRteosneed Page 31 38 CHAPTER VII protection engineer for specific design details. SAFETY MEASURES rPeromcoevsesiwnagtefrluaonrdopsourlfyamcetranAtQpUriEorOtUoSsiDntIeSriPnEgRtSheIOflNuSornoopromlyamleyr.reqSuoirmees saurhfeaacttianngtspraoncdestshetior dmeugsrtadbaetpironovpirdoedducwtistharfeorfcleadmvmeanbilielaatinodn/otro rpirteavnetnst. aThhaezaorvdeonususbeudiltdo-urpemofovveaptohre.seCpornotdauccttysour dispersion supplier for specific product information. tPhreocuessesionfgcNomObNus-tAibQlUeEaOndUSflDamImSaPbElReSlIiOquNiSdsustiimliizlianrgtfolpuaosrtoepeoxltyrmuesriomnatreersiianlssdmesacyriibnecdorapboorvaet.e i cSoinmtialianripnrgecaasuotlivoennstm-buasstedbeditsapkeernsifoonr tmheedsiaufemuosre,adsdtiotriavgese., aFnodlhlaonwdltihnegorefcoflmumoernodpaotliyomnesrorfestihnes dispersion supplier . MatEpLroTcePsRsiOnCgEtSeSmIpeNrGatuorfefslfuoorreoxptoelnydmeedr rteismiensscaatnexccaeussseivrealpyihdidgehctoemmppoesriattiuorneofstohreexrpesoisnisn.g them Decomposition will produce gases and generate pressures in processing equipment sufficient to ii m"oblldoiwnbgacekq"uitphmreonutg,hptrheessfuereedspcoartn.deIvfenlooepxiwthiiscahvmaialyabrluepftourrethmeesteaglaspeasr,t,aspoisnssioblmyewciotmhpression | ecxopnlsoisdievreedfoarnceu,nsaanfdepporsascitbilcye ctaoussteanidnjiunryfrtoontpeorfsaonnneexltnreuadretrhdeiepfraocceeswshiincgheiqsuipprmoecnets.sinIgt iasny thermoplastic, especially during start up. Tusoedprfeovrepnrtoaccecseslienrgateeqduidpemceonmtp.osiCtointoancotfyfoluurormoaptoelryiamlerssu,ppcloirerrossifoonr-rsepseicsitfainctpmraotdeurcitalisnfmoursmattiboen. dIefgarfalduatoiroonpohlaysmebergruens.in fmealnt obpeegriantsortobdealriekveens, tthhaetctohleorrmcahladneggeraidsaatnioinndiiscoactciuornrtihnagt,tzhoenremal tFelmupoerroaptoulryemsesrhroeuslidnsbsehloouwledrbeed parnodcethsesefdluoonroepqouliypmmeerntrehsainvipnugrgaeccdurfartoem, trheepreoqduuicpimbelnet. temperature control. Temperature cycling should vary less than plus or minus 10F (6C). PIGMENTS AND FILLERS Fhialnldeldiangndflpuiogrmoepnotleydmefrlsuonreoepdotloymbeersobasreerviendw.idInesapdrdeitaidonu,se.useTrhseneneodrmtaolnoptreecaanuytiaodndsitfioornal hfialzlearrsdasnadripsiigngmefnrtosmhtahveeflilolwestooxricpiitgy,mesnotmsethaermesaeblrvaess.iveAalntdhomuagyh cmaaunsyeoifrtrihtaeticonominmoconnltyacutsweidth the skin. offilled orAvpoiigdmesnktiendcofnltuaocrtopwoiltyhmfeirlldeudsto.r pWihgmeenntfelduofrloupoorloypmoelrysmceornstoariniinnhgalcaatidomniourminpgiegsmteinotns i i Page 32 `CopyGruigihdt e19t9o2.th19e95S,af19e9H8 aTnhdeiSnagcoitfyFolfutoheroPlpaostliycsmeInrdusRtersy.inInsc,, Third Editon A Rights Reserved | i. 39 CHAPTER VII SAFETY MEASURES are handled, extra precautions may be necessary and compliance with OSHA standard 29 CFR 1910.1027 is required. Contact your supplierprior to using filled and/or pigmented fluoropolymers for specific safety recommendations. When a user mixes pigments, filles, or other materials with fluoropolymers,a hazard determination as required by the OSHA Hazard Communication Standard (HCS), 29 CFR 1910.1200 must be performed. Health and safety iprnofcoersmsaotriomnumsutsptrebpeaorbetMaiSnDedSffroormatnhdeavfefnidxoarpsporfoptrhieataedhdaezdarmadtwerairanlisn,ganladbetlhse tfolcuoonrtoapionleyrmseorf the filled resin. The processor who makes parts from the filled resins must determine, whether, in the norma circumstances of use, the part wll release hazardous chemicals causing exposure of users. Ifso, an MSDS and appropriate label must be provided. GRINDING AND MACHINING Grinding, sawing, and machining fluoropolymers and fluoropolymer-coated articles are per- | formed routinely in fabricators' shops. All normal high-speed machining techniques can be used | provided the tools have sharp cutting edges. Coolantsare recommended to improve production i rates and quality and they will serve to control any tendency toward overheating, eliminating the need for special ventilation. Dust generated by machining products manufactured from fluoropolymer resins are classified as Particulates Not Otherwise Classified (PNOC) for which the American Conference of Governmental Industrial Hygienists (1997) recommends a Threshold Limit Value (TLV) of 10 mg/m' TWA (inhalable) and 3 mg/m' TWA (respirable). The OSHA PEL (Permissible Exposure Limit) is 15 mg/m' total dust or 5 mg/m? respirable dust. However, machining products manufactured from resins which contain fillers, pigments, or other additives may produce hazardous dusts due to the presence of the fillers and other additives. If the local exhaust cannot reduce air contaminants below occupational exposure limits, wear respiratory protection. Use a NIOSH/MSHA approved respirator equipped with high-efficiency particulate air (HEPA) filters and develop and implemenat respiratory protection program under OSHA's standard, 29 CFR 1910.134. Consult the additive supplier or MSDS for further information for the additives. SOLDERING AND MELT STRIPPING Major uses for fluoropolymers are in electrical insulation for electronics, computers, and in industrial equipment. Tn many cases, soldering or use of aheated element to remove insulation from wire and cable are routine operations. eAxspoinsumroesttiumsee,saonfd fvleunotirloaptoiloynmceornsd,itthieoncsomdubriinnegdseoflfdeecrtisnogfatnedmpmeerlattusrtrei,pqpuianngtairtey iomfrpeosritna,nt | factors for worker comfortand safety. The useof local fume hoods as described in the Guide to the Safe Handing of Fluoropolymer Resins, Third Editon `Copyright 1982, 1985, 1988TheSocietyofthePlastics Industry, Inc.,Al RightsReserved Page 33 | | e #0 Hi CHAPTER VII ventilation section i strongly recommended. SAFETY MEASURES WELDING AND FLAME CUTTING ifitarisedcentewcaieptsphslaimrcoyastttioopnrlaeosmfwtoiecvlse,daiilnncgsluuacdrihcnspgaartnthdsostfeorrfocrmhoeemsqcufauinoprmqoeupniotclkytlomyebrdese.swterloFdyoerdt.hperaWucshteiecfaullnreesassoofns,patrhtserefor, appporpseslviiebenldte,teoxstpuhoceshudraeessiiongnwfoelfluvdoeirnnotgpiololarytmcieounrtifhnuogmoedcsso,aftoTerdhtephaigrsutsi,demleicnheasngiicvaelnveeanrtliileartcioannrseehfofrueeclmtdoivvbeaellyp1rboepvcisded to poPrrpaeeccrtaaiutctieio.onnsscSmaaunfsebtteybfeporuteanckdaeuintniwotnhse psuubclhicaastiaopnp,roipnrdiuastterpiruaerlsppoViserena.ttiolarStypiepocrni,oftiAecctMdieaosnniugaannsldoffofirrRewepercledovimennegtnidnsed hen welding operations are performed, : nHFaisomoertsoopasluoyptmpheorretsscaoounrmdcbteuhssetoifceooxnmtpuronenlmeesnesthstehoaef,relluiusooarrnooppeooxltlyeymmmeaerlrscsooaauntrdicnefglsoufaororexoyp"goselenyf,m-eehxrotcwionegvueirs,hiifnge,x"poes,etdhteey thermally degrade and, like other organic materials, produce toxic fumes, atings wi CLEANING AND MAINTENANCE OF PROCESS EQUIPMENT i J| ibCnelvedoaelnsviienggpnyeardnodltyomsaciiosonmftparlieentsieinldgyuapclraoppctoeulsrysemeearnq.duirpAepmmpeornvotpecriothametpegoanvseeennsttiaslandtdiioepnsa,ratnsicdcurlpearetonetepmcaatcikvse, esqcureiwpsm,enettc.s)hmoualyd vtehnetwiloartkioennvironment. Please reer tothe beginningofthis chapter for additttieonathlatianfrofrmoee. cr PROTECTIVE CLOTHING i p(gearusPnortnolaceletssp)srioantrgeectrteiemvcpeeorcmaqmtueuirnpedmsee,dnftdlu(urPoirPnoEgp)oplirnoyccmelesursdiimnneggl.tsacJfaeentwyeclagluassesesse,vegrleovbeus,rsa;ndthaerremfoprree,vaepnpiroonpriate ry should not be wom, ert AEesdpuist rtatcoar--nynport--otbeec--ativoo--nidfeo--dr uwsheeangahiannsdtlidunsgtsflaonrdompiosltysmhearvriensginapTowLderosf,noNtIOleSsHthaapnpr0o.v0e5dmg/m | PIB"E34pmceormimcaenndCoeGndufPeirrdaecentcitcoeeot,fheG1oStvahfeem,mHea(nnCtdiilsniIgonnodf,uFOslFut:orHoy1pg9oe8l2i)ys,mte4sr,-1Rne0sdi4.n5s.s, (TChVioernndstluEaldiihotnei:onmo4sMt ounmanodfion) cor 652. ov. 195 Tow See co ee re TONG Elon #l CHAPTER VII SAFETY MEASURES sgohgogulledsbeanwdorpnr.oteWcthiivleegplroovceessssihnoguladndbehaspnedcliifnigedf.ilRleesdicnosmcpoonutnadinsi,nginsaodldvietnitonmatoytrheequdiurset tmhaeskuss,e o`CfoNnsIuSltOyHouarpprresoivnedsuoprpglainericfovrapguoirdacnacret.ridges fitted with dust/mist prefilters or HEPA filters. Finlucoonrtoapcotlwyimtehr tdhiespsekrisni.onIst cisonnteacienssraersyidtuoewseoafrfplruootreicntaitveed wgeltotviensgaangdenottshewrhpircohteschtiovueldclnootthicnogme and equipment to prevent skin contact when handling these products. `sTuhietasbplryaeyqaupipplpiecdatsipornoayfabloolthcso.atiOngpse,raitnocrlsudsihnogulfdluwoeraorpopleyrmseornacloaptriontgesc,timvuesctlobtehipnegrfaonrdmed in e0qupriepcmiepnittataes aapnpdrorpergioatvee.thIteissprraeycommismtenfdreomd tthhaetatirhebesipnrgayexbhoaoutshtbede. eqSueieppCehdapwtietrhVaIIwIat(ePrgb3a9t)h for disposal guidance. PERSONAL HYGIENE oWrhuesnedtrianinwionrgkpearresaosn.neSlmiot kisinimgpotrotbaanctcotocoenmtpahmaisniazteedthwatitthobeavcecnovperroyduscmtesllshaomuoludntnsotobfe carried fluoropolymer resin can cause "polymer fume fever (described in Chapter V) by inhalation of (thkeneofwflnueanptpsr.opArfiatteerlsymaosktihneg"csohnatkeasm"i)naatneddottohbearccflou,-ltihkeepseyrmspotnommsa.y Tsuhfefesrysmhpitveormisnginavtatarcikasbly spurbosdiucdteswibtehbinan2n4edtoi4n8wohorukrsa.reFaosrwthheersee rfelausoornospoitlyismerrecreosmimnsenardeedproscmeoskseidn.g and tobacco To prevent traces of fluoropolymer resin powders being carried outofthe work area on clothing, `personnel should be given the opportunity to store their work clothing separate from their street c`lwoatshhiinngg (fadcoiulbitlieesloacnkderbeorenscepoaurraatgeecdhtoanguseertoohmesm).regEulmaprllyo.yees should be provided with adequate FIRE HAZARD CONSIDERATIONS Fluoropolymers, in the absenceofan independent external source of flame, will not continue to bcuarnndwechoemnptoesseteadnidn aacdcdotrodathnecefuwmitehs UbeLin9g4.geneHroawteedv.erS,iniftcehetherepsoisnssibairleitpyreosefantfiinreacfainre,netvheery be AUpnpdleirawnrciets,ers(NLoarbtohrbartooorki,esI,L:TeUssLf9o4r)the FlammabilityofPlastic Materialfor Paris On Devices and Guide to the Safe Handling of Fluoropolymer Resins, Third Edition `Copyright 1952, 1995, 1998TheSocioeftthye Plastics Industry,Inc. Al Rights Reserved Page 35 42 -- re---------- CHAPTER VII SAFETY MEASURES agleenmedreaotusetdibfnrraeoamftahtcihtneogrcya,opmptbhauersalttoiucsoaln(ioSrCetBhsAee)rrvmaiaclnedsfehucloloumltpudornbseiotauidovgnioesaferdf(loffuterhofepiogphlrtyoebrmsae)brleesniantgu.reSoefiffumes pf(ueHmoeApslZeoMroArsTucbltseetaaannmicsne)gs,muupdseitcnobtnehteawmpoirrnemastewinhocenenooffipneovmtoeelnrvtgeideanliclnyyetxrotexisinpcgoufniussmeehspi.enrgsaFonocnlhleomwiicnagolrefLxrepev.oesrluersAecuteioqnuogixpimcent ef1oq2su1oi0c-pi1ma2et0niot(n)a',cscp"ouHrbadlziinacgratdtiooounas,ccwNeaFpsttPeeAdopp4re9ro,acHteiadouznrasersadniodsuesesmsCeehnrtegimaeiln,ccalSseeDathtea"Na(t1ie9ol9ns4a'lepdFiritroieotnPe)r,uotasensdctlioo3nt0:hiCngFRand AppendixD foar technical discussionoth fire hazard pryopreerstpioesnosef,fflourorguoipdoalnycmee.rs.Sec rpIenercffolmouporlre,otieisfaicbnoudmtibyvulisedtnuiea,olcnsoarfabrofenleyu|xopruooospreoidldyeom,eprarsnoddinuocfttihsreeorsfgccaasnoepmsrbiondupuosctetenhitryiodiarlnmloygehfnazrfalrucdooroniutdsaei,qnuianntgities, . edumeoecroromgppeoonlscyiymteimorensa,spurtrohedesuycimtnsafyoorrmnfaeoteridosnkt.irneactomnetnatctfowriitnhhhalyadtrioognoenffhlyudorriodgee.nRfelfueorritdoeCohratphteehr eXrfor atmheaert icEaamnlebrsegaferenetlcyeydasaPetldaasnihnneieenmtgesragonendnctCihoeesmp.mruodnEumicettrysgRieningtchhyetipr-lTfaaonc-siKlsinthoioewuslAadcntdberteodqeiuvdieerlneotsipfceydo,mhpabazaansriededosus(0mpartoevriidales . ppirrneefccoarrugmtaeitnoicnoysnptlioanbntehsethomauaktleedrisinpaeltcshiefsiaecfvaeeltnlytydoiadtfeaansthfiiefreyetttsho, pirgnoactseoecnstjtuthnhacettpmiuoabnyliwcbitefhprrfoeimrseenautthaonrdititehse,apaTpurhoe1psriate toxic smoke ClfuoFbpRrpirco1ap9tr1eid0t.fe1l0uf6oirtFolpparoemlvmyeamnebtrliseoinfatmnhedeacrsoeumribeusasmtpiuobsslsteibblieilqttuayiokdfesin(gwCnhhiaetpantbelsrteoVrvIian)pgo,r/haalnrdlmiinsgs,usaensd fporromciensgs.inSgeeof29 siFghinloiluteliddonfblseuoohuraroncpdeosllewydhmeeinrreacomdmuaspntonuaenirdmsoi,xptirnuervtehesentofcsotcraumtoricf(ec.pgh.o,awrdgmeeirxasicncagunmodupleeasrtpaietcoiionanalsl)nydtehxopsoescuornetationaicngermetals, SvamrailolpuospwamrdetetiraclleedsfiPonfTesFflEmautowerhroiepanlosl.eyxmpeForosrreeedsxioanmstpcelamenp,ebmreeacttauolrmeefsienaxebstor(veeem.eg7.l9ya0clFoumm(bi4u2ns0utmiCb)alnemdainymtahegpnroesne)ncewofd ; producing fire and/or explosion. reset viotondly i emes-- i * Page Internal 36 DuPoGnutdCeomtpoatnhey ScaorfreesHpaonnddeincneg, of Fiuoropolymer Resins, Third Edition `Copyright 1992. 1995, 1998 The Societyohe Plastic Industry. In, All Rights Rearved. > a CHAPTER VII SAFETY MEASURES INCOMPATIBILITY WITH POWDERED MATERIALS Omattheerriafllsuokrnoopwonlytmoercarteasliynzsemtaheysereraecatcattiolnoswienrcolrudheigsihleircat,eTmpieOr,atburroemsi.deIsn,admdeittailolni,c ostalhtesrand glass fibers/beads. materials suppliers fTohresrpeecmiafiyc bienfootrhmeartimoant.erials that can cause such reactions. Contact your Two examplesofsituations where heat generated may be sufficient to cause such a reaction are: > Pumps utilizing fluoropolymer-based packings to pump dispersionsofaluminum flake. > Reclamation ofgarts coated with fluoropolymers by grinding or buffing operations, or by belt sanding or grit blasting with abrasives. SPILLAGE Fmleuaosruorpeosltyamkeernstsoppirlelveedndtutrhiengchraeantdiloinngosafhosullidppbeeryclseuarfnaecde.upItimismaeddviiastaebllyeatnhadtaspoprmoeprfioartme of anti-slip flooring or similar preventive measures be provided in areas where fluoropolymer resins are regularly risks. handled. Slippery surfaces in walking and working areas pose increased accident | Guide to the Safe Handing of Fluoropolymer Resins, Third Edition `Copyright 1902, 1995, 1998 The Socioeftthye Plastics Industry, Inc, All Rights Reserved Py Page 37 CHAPTER VII } SAFETY MEASURES i + i | i { } { i 3 i g i i | 1 i | 12{ t| 1i Page 38 CopyGriugihdte19t92o,t1h9e85S,af1e998HTahnediSnocgioetfyFofluthorPoapsatliysmeInrduRsets,innc,. TAhlilrRdigEhdsiRteosnerved A CHAPTER VIII ENVIRONMENTAL INFORMATION AND WASTE DISPOSAL ENVIRONMENTAL INFORMATION Neither layer. fluoropolymers nor anyof their decomposition products pose any threat to the ozone `Hymdornoocmleorroufsleudoirnocfalruobroonp2ol2y(meHrCsF.C2T2h)eiMsounsreedaals Pfreoetdosctoolck(wihnitchhe dmeaanlusfawcittuhrtehoefctohnetrporlioncfipal ! tozroannes-fdoerpmleedtiinngthseupbrsotcaenscseas)reretchougsnirzeemsotvheatdsfurbosmtatnhceeesnuvsierdonamsencth.emiWchaelnfeuesdesdtotchkiss waanyd, their `ozone-depleting potegial is zero. substances from its regulation, For this reason, the Protocol specifically excludes these DISPOSAL ! Treatment, storage, handling, transportation, and disposalofall fluoropolymer waste must follow applicable Federal, state/provincial, and local regulations. Waste mustnot be mixed with ] pdeormmeistttiecdotro ihnadnudstlreiaalciwdaisctceotmhbautswtiilolnbepriondcuicntesrated unless the facilities are equipped and | Preferred options for disposalofresins, powder, and granular products are recycling and landfill J Incinerate onlyifthe incinerator acidic combustion gases. is fitted and permitted to scrub out hydrogen fluoride and other l`Tihqeuipdrbefyerprreecdioppittaitoinonfoarnddisdpeocsaanltionfgfolruofrilotpeorilnygm.erDiasqpuoesoeuosfddirspyerssoliiodnss iins atolsaenpdafrialttehsaotliisds from } permitted, licensed, or registered by asate to manage industrial solid waste. Discharge liquid afiglrtreaetmeetnotaswwaistthepwuabtliecrltyroewatnmeednttsreyasttmeemntinwaocrkcso.rdSapnecceifwyitihncaipnpelriactaibolneopnelrymiifttsheandi/ncoirnerator is equipped to scrub out hydrogen fluoride and other acidic combustion gases. Pigmented, filled, and solvent-laden waste will require special disposal practices in accordance with Federal, state, and local regulations. Suitable compliance strategies must be observed when storing, handling, and transporting hazardous wastes. | Guide to the Safe Handing of Fuoropolymer Resins, Third Edition `Copyright 1992, 1935, 1398TheSocietyofthePlastics Industry,Inc,Al Rights Reserved Page 39 c | CHAPTERVIIl ENVIRONMENTAL INFORMATION AND WASTE DISPOSAL RESIN PACKAGING A TprhoeviGduesdeinffoorrmthaetiPornofpoerrtDheisfplousoirtioopnoolfymPerTFinEduRsetsriynoPnahckoawgitongdi(sSpPo!secoaftaplaocgknaugmibnegruBsePd-1t0o2) transport PTFE resin. = t | b Page 40 CopyrGiugihdte19t5o2,t1h9e85S,af19e98HaTnhdeiSngoofcoFfiituhoeerPloatpstoilycysmeInrdusRtersy.inIsnc,. AThlirRidghEtdsiRteisoenrved 1 -_ CHAPTER IX -_-- FOOD AND MEDICAL APPLICATIONS FOOD CONTACT ? aUpnpdleicratthieonFseidfetrhaelyFaoroe:d,(1D)runogtarnedasCoonsambeltyiecxpAectc,tesdubtsotbaencceosmceaancboemupsoendeinntfoofodf-ocoodntuancdter the iFnotoedndaenddcDonrduigtiaodnmsinoifstursaet,i(o2n), t(h3e) stuhbejseucbtjoefcatonfaapp"lpirciaobrlseaFnoctoidona"ddoirtiavpeprroevgaullaitsisouneidsbsyuetdhbey the gFeDneAraolrtlyherecUongintiezdeSdtaatsessaDfeep(aGrRtAmeSn)tobyfqAugarliicfuiletduerxepe(rUtsS.DMAa)npyriofrlutoor1o9p5o8l,ymoerrs(4)hadveeebmeeedn rcelgeualraetdiboynsgthoeveUr.Sn.inFgofolduoarnocdarDbroungrAedsmiinnsiasrtera2t1ioCnFfoRr u1se77i.n1c3o8n0tac1t77w.it1h55f0o,od.anTdhe17p7r.i2m5ar1y0 as lainsteesdseinntiCahlapptaretroVftI.heHopwoelvyemre,risztaatbiiloinzeprrso,caenstsiomxuisdtanatlss,ocboelocrlaenatsr,edaunnddeotrhaenr aadpjpurtoapnrtisattheatfoaorde not : raeddaistoinvaeblryegeuxlapteicotne,dbteotbheecsoumbjeecatcoomfapopnrieonrtsoafncftoioodn. orMoapsptroFvDalA, rbeegucloantsiiodnesrefodrGaRntAiSox,idoarntnso,t be stabilizers, and Manufacturers waidsjhuitanngtstoaupspeeafrluinor2o1poClFymRerPsaritn 178. food contact applications must make their own dPeecrissoinosnwciosnhcienrgnitnogustehefsluuiotraboiploiltyymoeftrsheinifnodoivdicdounatlafcltuaoprpolpiocaltyimoenrsfsohrotuhledscpoencsiufilct iwnittehntdheediruse. suppliers to individuals determine whether the experienced in making supplier has a policy such assessments. In governing any event, such uses and with consultation with legal counsel experienced in food additive and clearance requirements is essential. MEDICAL APPLICATIONS SU.oSm.eFfouoodroapnodlDymreurgsAhdamvineibseterantuisoend(tFoDAm)a.nufTahcetumraenumfeadcitcuarlerdeavnidcesselwlheriocfhtahree mreegduilcaatleddebvyictehe adroeesrensoptonaspipbrloevfeorinodbitvaiidnuianlgcaoumtphoonrieznattsi,onsuocrhapapsrfolvuaolrfooprolthyemierrdreevsiicnes(su)seads ainwthhoelem,anaunfdacFtDurAe ocofnmceedrincianlgdtehveicuesse.ofSfPlIuohraospnooltymseourgshtinomrerdeicceailveddevaipcepsr.ovaMlanfurfoamctaunryerresgwuilasthoirnygatuothuosreity finudoirvoidpuoallyfmleurosrionpomleydmiecrasl faoprpluisceatiinotnhseimrupsatrtmiacukleartahpepirliocawtniodne.ciPseirosnornesgawridsihnigngthteo suusietability of fg tmNheuedoyirchoaaplvoedleyavmiepcorelsimciaynttsgeuorcvshe.ranpipnlgicsautciohnsussehs,oualnddcwointshulrtewguiltahttohreyirco`usnupspellieerxspteordieetnecerdmiinneFwDheAther ] CopyGriugihtde19t9o2,th19e95S,af19e88HaTnhdeiSnogcoifoeFfutohyeroPplaosltiycmseInrduRsets.innsc,.TAhDiridgEsdiRteisoenrved Page 41 | %8 || . -- PAGED CGouidep2to.thTesSaf15e50HahnediSngoefFoluoPoaptomleoyr Rnesi.ns, TARideEsdiRtoen s ; q i J - CHAPTER X EMERGENCY MEASURES --------eeeeett-------- EMERGENCY TELEPHONE NUMBERS | AGA CHEMICALS, INC. ! Medical Emergency: Product Information: (704) 357-3631 (Daytime) (704) 357-3631 4 AUSIMONT USA, INC. Medical Emergency: (609) 853-8119 ; Product Information: (800) 221-0553 i CUSTOM COMPOUNDING, A Division of DYNEON LLC i Medical Emergency: (610) 497-8899 | Transport Emergency: (800) 424-9300 CHEMTREC: (800) 424-9300 I Product Information: (800) 55-HOSTA H DAIKIN AMERICA, INC. H Medical Emergency: (914) 365-9500 ] FH Transport Emergency: Product Information: (800) 424-9300 (800) 365-9570 H DUPONT i Medical Emergency: (800) 441-3637 H Transport Emergency: (800) 424-9300 Product Information: (800) 441-7515 Guide to the Safe Handing of Fuoropolymer Resins, Third Edition Copyright 1992. 1995, 1988 The Society of the Plastics Industry, Inc., All Rights Reserved Page 43 i Jo CHAPTER X ELF ATOCHEM NORTH AMERICA, INC. EMERGENCY MEASURES Medical Emergency: Transport Emergency: Product Information (303) 623-5716 (800) 424-9300 (800) 225-7788 (215) 419-7520 ICI FLUOROPOLYMERS Medical Emergency: (800) 228-5635 Ext. 181 Transport Emergency' (800) 424-9300 - Product Information: (800)ICI-PTEE (800 424-7833) i SOLVAY ADVANCED POLYMERS, INC. { ; Medical Emergency: (713) 479-2381 | CHEMTREC: Product Information (800) 424-9300 (800) 231-6313 rae SR IE S TE H <1 i i CHAPTER X 1 EMERGENCY MEASURES 1 FIRST AID INHALATION cIonnhdailtaitoinosno.Iffflafufoercotpeodlybmyeirnhdaulsattiisonnooft ldiuksetl,yctoonsbuelthaazpahrydsoiucsiaunn.der normal handling J| J Ipfaatfifenetctweadrbmyafnudmeatsrfesrt.omIhnantdhleienvge,nhteaittiisngn,ecoerscsoamrbyutsotiroensc,umeoavveicttoifmroesvheraicr.omKeebey.p the fumes or otherwise unconscious in a contaminated area, a self-contained breathing ap- | 8 tphaera"tuHsE(ASIC#BHA)HmAuZstAbReDusIeNd.FOCRonMsAuTltIaONph"ysfiocriafnl.uoTrhoepoplhyymseircsiainncslhuodueldd ibneCahdavpitseerdVo.f Because overexposure to hydrogen fluoride requires specific medical treatment, the I 7 tprreeasteinntgipnhsyuscichisaintusahtoiounlsd. beFoilnlfoowrimnegdotfhtehreescpuosesoipbielriattyiotnh,atThHydOrRogOeUn GflHuoLriYdevmeingtihltatbee the room. ] 3 vIfioctviemrctoomfreesohraaifrf.ecKteeedpbythienahiarlaptaisosnaogfe scollevarenatnvdaapdomrisn(itsotleurenaert,ifxiycliealner,eseutcs.c)i,tarteimoonvief the necessary. Calla physician. J fIufamepserosrognaisseso,vmeerdciocmaelotrreaadtvmeernsteliys arefqfueicrteedd. bMyeidnihcaallatpieornsoofnnfelluosrhoopuolldybmeeradpvriosceesdstihnagt 3 5 thhyadtrtorgeeantmfelnutorsihdoe,ulpdercfolnusoirdoeirsotbhuetpyolsesnieblaendefoftehcetsroffltuhoersineatseudbsgtaasnecsesm.aSyeebeCphraepsteenrt Vanfdor briefdescriptionsofoverexposure, or the fluoropolymer resins manufacturer's MSDS for 3 more details. ; EYE CONTACT ES FLUOROPOLYMER POWDERS AND PELLETS i:y PFrlouvsihdeeyethsewpihtyhsipclienatnywoiftchlaeacnopwyaotefr.theCaMllSaDpShyfsoirctihaenipfriordruictta.tion develops and persists. FLUOROPOLYMER AQUEOUS DISPERSIONS In caseofeye contact, immediately flush the eyes with plentyofclean water for at least Guide to `Copyright 1992, the Safe Handiing of 1995, 1998 The Society Fuoropolymer Resins, ofthe Plastics Industry, Inc. Third Editon All Rights Reserved Page 45 La CHAPTER X EMERGENCY MEASURES w1i5tmhinauctoeps.yofCaltlheaMpShyDsiScifaonritfheiiptraotdiuoctn(dse)vienlouspes. and persists. Provide the physician SKIN CONTACT FLUOROPOLYMER POWDERS AND PELLETS uFsleuoirsoapdovlisyambelres. a[rfemnoolttleinkeployltyombeerhgaeztsarodnoutshebsykisnk,incocoolnttahcet,afbfuetctceldeaanrseianrgatphiedlsykiwnitahfter 1 cold wate. Do not attempt to pe a polymer from skin. Oblain medical treatment fora | thermal bum : . FLUOROPOLYMER AQUEOUS DISPERSIONS } Flush skin with water aftr contact, Wash contaminated clothing before reuse. The | saobloivdes from aqueous solutions should be treateda resin powders and pelets a described INGESTION FLUOROPOLYMER POWDERS AND PELLETS No specific intervention is indicated as fluoropolymers are not likely to be hazardous by ingestion. Call a physician iirritation develops and persists FLUOROPOLYMER AQUEOUS DISPERSIONS | aIfsnywtahlilnogwbeyd,moiumtmhedtioaatenluynctaoknesctiwoous(2p)ergsloans.sesCoafllwaatpehrysaincidani.nduce vomiting. Never give Page 46 Guide tothe Safe Handing of Fuoropalymer Resins, Third Editon `Copyright 1992, 1995, 1998 The Society of the Plastics Industry, Inc., Al Rights Reserved : $3 i | CHAPTER XI BIBLIOGRAPHY `AMmaenruiaclaonfCRoencfoermemnecnedeofdGPorvaecrtincmee,nt1a7l% eIdn.d,usCtirnicailnnHaytgii,enOiHst,s,19I8n2d,us(tCrioanlsuVletnttihleatmioons:t A J current edition). American Society for Testing and Materials (ASTM), 100 Barr Harbor Drive, West | Conshohocken, PA 19428-2959. | ASTM D1430 "Standard Specification for Polychlorotrifluoroethylene (PCTFE) Plastics." | AST D1457 "MSotladnidnagrdanSdpeEcxiftircuastiioonnMfaotrePrioallyst.e"trafluoroethylene (PTFE) ASTM D2116 "Standard Specification for FEP-Fluorocarbon Molding and ASTM D3159 Extrusion "Standard Materials." Specification for Modified ETFE-Fluoropolymer ASTM D3222 M"SopledciinfigcaatnidonExftorruPsoiloyn (MVaitenryilaildse.n"e Fluoride) (PVDF) Molding, ASTM D3275 Extrusion "Standard and Coating Materials." Specification for ECTFE-Fluoroplastic Molding, Extrus- ASTM D3307 ion and Coating Materials." "Standard Specification for PFA-Fluorocarbon Molding and ASTM D4441 Extrusion "Standard Materials." Specification for Aqueous DispersionsofPolytetra- ASTM D4745 fluoroethylene." "Standard Specification for Filled Compounds of ASTM D4894 Polytetrafluoroethylene "Standard Specification (PTFE) Molding and Extrusion Materials." for Polytetraflucroethylene (PTFE) - Granular Molding and Ram Extrusion Materials." ASTM D4895 "PSrtoadnudcaerdd Specification for Polytetrafluoroethylene from Dispersion." (PTFE) Resin ASTM D5575 "Standard Specification for Copolymersof Vinylidene Fluoride (VDP) with Other Fluorinated Monomers." Baker, ative." BA. naBl.yatincdalKaCihseemr,isMt.ryA,.,pp."A6n3a,lyTt9icAa,l Approach 1991. -- Understanding what happens in : Baker, B.B.,and in Air," Polymer Kasprzak, D. Degradation Ja.,n"dTShteabrimlaitly,DeVoglr.ad4a2t,iop.n of Commercial 181, 1993. Fluoropolymers : CopGuyi:de19t9o2.th15e65S,af19e9H8aTnhdeiSnogcoifoFfluheorloaposltysmeInrduRsets,inisn,c TAhIirRdiEscRoesnerves Page 47 Sk CHAPTER XI BIBLIOGRAPHY CD.laJrk,eM,aFk.oBv.e,cv,anG.KTu.i,jkS,eiHd.elM,,W.VaCl.e,nHtienrep,olR,.,C.BaHk.e,ra,nBd. JBa.n,ssBeonnse,stMe.e,l,"TJ.hKe.,toKxiacsiptryzoafk, smoke from fires involving Science, pp.10, 488, 1992. perfluoropolymers: Full-Scale fire studies." Journal of Fire Clayton, 1,1967. J. W., "Fluorocarbon toxicity and biological action." Fluorine Chemical Review HarrisD,. K., Lancet 261 1008, Dec. 1951 Internal DuPont company correspondence. J"Cohhanrsatcotne,riCzaIt,ioFninokeflEsatreilny,PJ.ulN.m,onGaerlyeiInn,fRl.a,mBmaagtgosr,yRR.e,sapnodnsOebrAdsussotceira,tGe.d,with PTFE {- Fume Press, Exposure." 1996 Toxicology andApplied Pharmacology, Article No. 0208, Academic | KMaulletsi,plSeNE,pMisDo,deMsoPHf.an"OPcrcougpraetsisoinoanloIfnChhalraotniiocn OFbesvterru.c"tiJvoeurPnuallmoofnMaerdyicDiinsee.ase1a9f9t4e.r AolfbareMcohltd,-WReNl.e,asPeh.DS.p,raMySCPoHn.tai"nPionlgyPmoelyrt-eFturmafeluFoervoeerthAyslseoncei.a"teJdOwcictuhpSMmeodk.ing19a8n7.d Use KMaeptlhaond,s,H.NaLt,ioGnraalnBdu,rAe.auFo.,faSntdaHnadratrzdesllM,eGt.hoE.d,""RCeovmibeuwsotfioPrniTncoixpilceolLoagbyo-ratProirnyciples `and Test Methods, Lancaster, PA: Technomic Publishing Company, 1983. Kthaeplsamno,kHe. pLr.o,dGurcaendd,byA.fiFv.e,hSawliotgzeern,atWe.d pC.o, lyamnedrsG"adJ,. FS.irCe.,Sc"i.Ac2u,te198i4n.halation toxicity of Levin, B. C, development Fowell, ofa test A. J, Birky, M. method for the M., Paabo, assessment M,, Stolte, A., and of acute inhalation Malek, toxicity D., of "Further `combustion 2532,1982. products" National Bureauof Standards Technical Report (U.S.) NBSIR 82- Mvooln.i2g,oGmeeorryg,eRDu.tChlRa.y,t"oPnoalnydmeFrlso"rePnactetyE'.s ICnldauysttorni,alEHdysg.iNeneewaYnodrTko:xiJcoohlnogWyi,ldetyh&ed., Sons, 1994, ROocsceu,paCteicoinlaelAM.,edi"cInihnael,at2inodn eFd.e,veBross,t"oinn:RLoitmt,le,W.BNr.o,wned.anEdnvCiormopnamnenyt,al19a9n2d. Page 48 (CopyGruigihdt e19t8o2,t1h9e95S,af19e98HaTnhdeliSnocgisotfyoFfltuhoerPolpasotlicysmeInrdu Resins, stry. Inc. Third Edition A Rights Reserved F s I I EE 4 CHAPTER XI BIBLIOGRAPHY pSycrhoeleyls,iLs.pDr.o,duLcatnse,- iWn.clCu,diangndcaCrobloenmyalnf,luWo.ridE.e,a"nTdhaerteoaxcitciiotny oprfopdoulcytt,etsrilaifclounorocthylenc tetrafluoride" American Industrial Hygienists Association Journal 29, 1968. pSehiydseilc,alW,.aCn.d tSocxhiecroelro,giKc.alV.,chaCrlaicntee,rDi.zaJtri,onOolfsfoun,meA.s Hp.r,odauncdeBdonbeystheeealt,inJg. K., "Chemical, tpeetrrfalfulouroorporeotphyyllveinneylheotmhoerp)o"lCyhmeemr.anReds.itsincoTpooxlicyomler4s, w1i9t9h1 hexafluoropropylene and UD.iSs.easDeepCaornttrmoeln,tNoaftiHoenaallthI,nsatnitdutHeufmoar nOcSceurpvaitcieosn,aPlubSlaifcetHyeaanldthHSeearlvtihc,e,"CCrietnetreira ffoorr a Recommended Standard .. Occupational Exposure to decomposition products of GFlPuOo,toSceaprtbeomnbPeorly1m9e77r.s." DHEW (NIOSH) Publication No. 77-193, Washington, D.C. US. Departmentof Health and Human Services, Public Health Service, National ) I(nCstAiStuAtesNoof. H1e1a6l-t1h4,-3")ToixniFc3o4lo4g/yNaRnadtsCaarncdiBnoEgCe3nFes1isMiStcuedi(eIsnohaflaTteitornafSltuuodircose)t,h"ylNenTeIS Publication No. PB 97-208508. Underwriters Laboratories (UL) 94, Testsfor the FlammabilityofPlastic Materialsfor 1 Parts on Devices and Appliances. Warheit, D. B, Seidel, W. C., Caracostas, M. C., and Hartsky, M. A., "Attenuation of Mfollu.orPoaptohloyl.mer52f,u1m9e90t.oxicity: effect of filters, combustion method and aerosol age" Exp. Williams, S. J, Baker, B. B., and Lee, K. P, "Formationofacute pulmonary toxicants aftomlolsopwihnegritcherremaacltidoeng"rFaodaotdioCnhoefmipceralluTcorxiincaolt.ed25p,olpy.me1r7s7:, 1e9v8i1d.enceforacritical mWioldleiaomfs,prSo.dJu.ctangednCelraartkieo,n"F.FiBr.e M"aCtoemrbiuaslt6i,o1n9p8r2o.duct toxicity: Dependence on the 3 CoGmuipde95t2o.th1e98S,af16e98HTanadSingtofoFlouraPpaoslysmenryRe.sinms,ATbhei Erditeon d Page 49 3 APPENDIX A -_-- 0 TFE IN FLUOROPOLYMERS dAitstchuessFilnugotrhoeproelsyulmtesrofDivthiesiNoantiFoanllal1T9o9x6iCcoonlfoegryenPcreo,graamse'rsie(sNoTfP)praesneinmtaaltisotnusdywoafsthmeadeeffects of ienxdpiovsiudruealtoprteesternatfaltuioornosetphryelpeanree(dTbFyE)Gegrasr.y This written summary is Kennedy, DuPont, Colin based on Kinnear, the attached ICI, and David oSragravnadiiz,atKieolnlerresapnodnsHieblcekmfaorn.regTuhlaetsoerymactoemrpilailsanscheo.uld be shared with the individuals in your . mBriineuftley,qTuaFnEtiitsyothfeTmFoEnommaeyrruesmeadintoimnatkheerceesirnt.ainThfleuroeroispoallysmoetrhse. poEtvenetniatlhtohuagthsiotmiseaTgFaEs,maay be formed during heat processing or overheatingoffluoropolsmersofall kinds. . Treessitnsi.ngTihs eunqduaenrtwiatiyestoo fdeTtFeErmionbesewrhveetdheirn ptrheelriemiisfiaanryy aTnFaElyesevsoolfvesdodmuerirnegsiunsseaonfdfplruoodruocptoslywmeerre described in conclusions. the second Following of the presentations, after that, a descriptionofthe paobtreinetfiadlesrcergiupltaitoonroy fobtlhiegaNtTioPnssotfudpyroacnedssiotsrs sanudmmraersiinzepreoadcuhcepresrswoan'sspprreesseenntteadt.ionT.heTthheryeedpoapneortsredpirsecsuesnsttohfefsiecisaulbpjoescittsiionnsgroefattehre detail, and Fluoropolymers Division. ` `The major points made during the presentations were: !: { + NTaetuiaofnlaulorTooextihcyolleongeymPornoogmreamr wusaisngtessttaenddfaorrdittsecchanricqiuneosgefnoircitthye tbyypreessoefaracnhiemraslatsttuhdeies performed; } | * oTfhcearsctiundoygreensiucltascwtievrietyi"ntienrbportethedrabtsy the and NTP peer mice; reviewers as showing "clear evidence i * pLoetveenltsioalflTevFeElsmpornodoumceerd iinnrpersoicnessasriengbeairngailnsvoesbteiignagteedv,albuuatteadr,e eaxnpdescatmepdltiongbetveecrhynilqouwe;s : aocncduplaatbioorantaolreyxmpeostuhroed;sofanalysis are being developed to allow measurement of * aTrheebpeoitnegntiinavlesetxipgoastuerdesbyinthperorceseisnsimnagnuafnadctuusreeorfsriensginrseaatnedr dfeltuaoilroipnoalypmreorgrpraomdcucotnsducted dtehvroeulgohpmtehentAsosfoncieawtiaonnaloyftiPclaalstmiectMhaondusfatcotduerteercts linowEulreoveples (oAfPTMFEE),moinncolmuedirngin resins 3 Page SO conyGrigdne19t82o,th15e05S,af19e98HaTnhdeiSnogctoyf oFflhuoerPopootlsymenruRte.sinns,cTA.hlirRdohEdsitRieosnerved . 57 APPENDIX A and fluoropolymer products; TFE IN FLUOROPOLYMERS The resin manufacturers have parts per million (ppm)of TFE rebcasoemdmeonndaendeainghotc-chuopuarttiiomnealweexipgohstuerdeavliemriatge(OiEnLt)hoeifr 5 facilities that produce and use TFE monomer; 4 = oUrnteivlotlhveedrefsrinomm,antuhefarcetsiunrse,rsnonostpiefcyifpircoocbelsisgoartsitohnastatrheeriempmoasyedbeonsopmroeceTsFsoErsm;onomer in, + Asinformation their employees develops, have the processors may have to evaluate potential for exposure and, ifso, their operations to to provide training determine under the if E Occupational Safety Standard (HCS); and Health Administration (OSHA) Hazard Communication + `ImfeiansfuorrambalteioqunabnteictoiemsesduarvianiglaubsleeofspugrgoedsutcitngstfhaabtriTcFatEedmofnroommeflrumoraoypobleymreelreraesseidnsi,n # apprporcoepsrsioartsemmaatyerhiaavlestaofeatsysedsastathsehiereptrsoadnudctlsabuenlds.er the OSHA HCS and prepare eSxipnocesutrhee tmoeeTtFiEngw,iitthhathsecoocmceurtroenocuer oatftpeontliyomnetrhaftusmoemfeeveemrp(lPoFyFe).esoAfspryoocuesksnoorws,mPaFyFciosnafuse: `| PcoTnFdiEtiaonndtohtahtesrofmleutoirmoepsolryemseulrtsrewshinesnarpeerosvoenrsheaarteeedxopros"ebdumtmoetdheofffu."meAsltthhaotuagrhe igteinserthaetoerdetwihcaelnly :3 phoysdsriobgleenthfaltuosroidmee, TpeFrEflmuoaryoibseobpurtyoldeuncee,dfiinnethpearetfifcluuleantetsg,eannerdacteadr,boontyhlerflsuuobrsitdaen,caerse, kinncolwunditnogbe : produced and are present in quantities that may be hazardous. may be attributable to heated ultra-fine particlesofpolymers. Current There is data suggests that PFE no known relationship rbeevtiweewenthPeFiFnfaonrdmatthieocnaarbcoiuntogPenFiFcirneCsphoanpseteiVnrroadnedntvsenetxilpaotsieodn itno CThFaEp.tePrrVoIcIestshoerisr sehmopullodyees and make employee sure they exposure. use appropriate controls, such as enclosures and ventilation, to limit potential DInriandkdiintigonW,atoenrMaanyd T1,ox1i9c94E,ntfhoercSteamteenotfACcatlioffor1n9i8a6li(sPtreodpTosFiEtimonon65o)m.e"rThuinsdelrawthreeq"uTihreesStahfee (CaOlEifHoHrnAi)a EtonvpiurbolnimshenatalilstoPrfotcehcetmiiocnaAlgsewnhciychOfafrieckenoofwEnnvtiortohnemeStnattaeltHoecaalutsheHcaaznacredr oArssessment reproductive toxicity. `CopyGruigihdt e199t2o,t1h9e95S,af19e98HTanhdelSiongcoifoeFfutthoyeroPplaosltiycsmeInrdusRtersy.iInnsc,.,TAhllirRidghEtdsitRieosnerved SE Page 51 RhCOXea itaad ------ CCctt--. `The Societyofthe Plastics Industry, Inc. i i i | Summary of TFE Presentations FPD Fall `97 Conference Atlanta, GA -- October 7, 1996 i -_-- Presented by the : Fluoropolymers Division The Society ofthe Plastics Industry, Inc. Presentation to SPI Fluoropolymers Section i| PAGE SZ CopyGiugihtde19t92o,th19e05S,af19e90HaTnhdeliSnogcioyfoFflhuoerPopiosloymenruRse.sinnsc,.TAhlirFidghEtislReosnerved -- 9M BE Gerry Kennedy, DuPont Haskell Laboratory Atlanta, GA. October 7, 1996 Toxicology of Tetrafluoroethylene Monomer-Workplace Control Guides i The purpose of this talk was to give the participants an overviewofthe toxicologic properties of i3 ctoenttrraoflluloervoeelst,hyPlaernteicmuolnaromatetrenatinodn twoadsisgciuvsesnhtoowthtehirsesiunlftosormfatthieonreccoeunltdlybereupsoerdtetdo lsoetngw-otrekrpmlianchealaaitribonome studies in rats and mice and the implications ofthese findings to the above. i3 Abebruinedferisnttorooddutcotiaopnp/regcrioautneditnhge ienxpteheridmeefnitniatliodnaotfa wtaosxigciovleon.gyIanncdlusdoemdewoafsthaedimsaciunsspiroinoncfitplhees dwihfifecrhenncee.ed to ; between toxicologic properties (inherent inthe chemical) and hazard (which combines the former with exposure potential). A discussionofdose-response relationships and the typesoftoxicity studies (acute, : intermediate, chronic) and routes used to conduct these tests (ora, dermal, inhalation) was presented for : gwrhoautnrdoiuntgepoufrepxopsoessuarTehedotewsiotmtaaikne qtuoepsrtoidouncsethtehne befefcecotmse"?whatcan the chemical do? and how much and by ` Earlier inhalation studies (TFE monomer is a gas) showed that the rodent kidney isthe frst target ofTFE 3 minornaotsmethre twooxrickiptlya. cBeacsoendtroonl dloesveel-rweassposnusgegecshatreadctteoribseti5c0s pfpolmlo(wsihnogulidntbeermaesdsioactieatdeudrawtiitohn neoxpaodsvuerresesthuedailetsh 3 effects for a normal working lifetime in man). i Work conducted by the National Toxicology Program (NTP) and reported late 1995 confirmed that TFE monomer was not very toxic following acute inhalation exposures and tha the kidney was the target tissue. NfoTlPloswtiundgieisntweerrmeedpiraetseelnetnegdthinedxeptaoislu.reNso. Tobhseeqruvaendtiatdavteirvseeaenfdfeqcutallietvaetlisv(e NasOpAeEctLs)ofwtehreeidnetteerrmmeidnieadtetolebnegt3h12 ` ppminthe rat, 625 ppm inthemouse. 5 In two year (chronic) inhalation studies, exposureofrats to 312 ppm or greater produced an increase in both i bluivterthaendeffkeicdtnseayt ctahnecleorwseasltolnegvewlittehsttihnege(x1p5e6cptepdmk)iwdneeryensolnig-hcta.nIcnerthteoxmiociutsy.e,AsuNrvOiAvaEl Lwawsasrendoutcdeedtearnmdine. # kidney damage was seen at the lowest level tested-312 ppm. In addition, increases in liver cancers, i particularly hemangiosarcomas, was seen in both male and female mice. Genetic toxicity testing conducted ]` bgeyneNtTicPal(lmy-iaccrtoinvuec.leus test) and those found in the literature suggest that TFE monomer is not : A follow-up-up program looking at metabolic comparisonsofrodent and human tissues along with toxicity i comparisons following exposure to TFE monomer metabolites will help to place these findings in a more appropriate human perspective. The aim ofthese studics, which will begin in early 1998, is to validate the 1 acceptability (or no)ofthe current workplace airbome control limit of ppm. b CopyGriugihtde19t92o.th19e65S,af19e98HaThnedSioncgiofoFfltuhorPolapsotlicysmIenrdRuests,innsc,. TAhliridghEidsiRteisonoved Page 53 60 3 PRESENTATION TO SPI FLUOROPOLYMERS SECTION COLIN KINEAR -- ICI FLUOROPOLYMERS ATLANTA, GA. OCTOBER 7, 1996 TFE in Fluoropolymers `There are four areasofpotential concern for the processor or user of Fluoropolymers possible presenceoftetrafluoroethylene monomer (TFE) in fluoropolymer. arising from the i How much TFE is there in polymer from the polymer manufacturer? Is TFE formed from processing Fluoropolymers? (e.g. sintering) Is there any TFE in sintered or melt processed articles? Can TFE form when the product is used at its maximum continuous service temperature? 3 MIannfuorfmaacttiuornerosnitnheEsuerotpoep)i.csThhaissbpereenseanstsaetimobnlesdumbmyatrhiezePsTFsoEmgerooufpthoefaAvaPiMlaEble(Aisnsfoocrimaattiioonn.of Plastic | Sources of information } Studies of the TFE content of fluoropolymers have been conducted since about 1979. Most of the i historic data comes from work commissioned in the TNO laboratories in the Netherlands orPIRA in the | UK, both internationally recognized authorities in the fieldofpolymer testing. Mostofthe recent data i comes from analyses carried out by the polymer producers as they have expanded the data base of i information. i |i TFE in polymer from the polymer producer i | The results, summarized in TABLE 1, show the concentrations of TFE found in solid polymer (powder | or granule) or aqueous dispersionsas supplied by the polymer manufacturers. As can be seen from the able TFE is not normally detected in powder or granules with limitofdetection which varies rom 0.0110 1 ppm on 2weight/weight basis. TFE is always found in aqueous dispersion as TFE is soluble | im water, Messed valuetso dateae below | ppm on weightveight basis on the dispersion andre { typically around 0.5 ppm. These results are at present based on a limited number of measurements and the manufacturers are committed to developing more data. $ Sigaificanceofthe TFE Monomer in Polymer data for the converter Page 54 Guide to the Safe Handing of Fluoropolymer Resins, Third Edition `Copyright 1992, 1995, 1988 The Society of the Plastics Industry, Inc., Al Rights Reserved - 2 4 i i APPENDIX A TFE IN FLUOROPOLYMERS :; wItoriskpploascseibklneotwoincaglctuhleaqtueanrioiutgyhloyf ptohelycmoenrceunsterda,tiaosnsuomfintgetrarfelausoornoaebtlhyylceonnesewrhviacthivmelayyhiagrhisevailnuethoef ; TFE contained in polymer and the size and ventilation in the workshop. A later presentation will provide much more information on the methodology. Calculations need to be done for each individual | case but the indications are that values are likely to be well below the 5 ppm 8 hour TWA standard which the polymer manufacturers have generally adopted for their own workplaces. 1 TFE formation in processing Fluoropolymers? (e.g., during sintering) i Nslootwlmyucanhddiattraeqiusiarveasisloapbhleisbteiccaatuesdeaenavleynsiast tporodceetsesrimnignetetmhpeenraattuurreesa,nFdlquuoarnotpitoileysmeorfsthdeegsruabdsetanvecreys i formed. It is known, however, that TFE is one of the degradation products when PTFE and other Fluoropolymers are heated. | It is recognized that any analytical work on the decomposition of Fluoropolymers needs to be treated `with great caution. The products are very dependent on the conditions, especially temperature, amount ofair, time gas is a temperature, etc. A studyofthe literature shows that even at very high temperatures, where analysis is simpler, there is agratdealofvariation in the substances formed. Nonetheless some indiccanabetobitaoinned from the resofusolmetvesry recent work on the formation ofTFE during the decompositionof PTFEattemperatures from about 260-400C are shown in FIGURE 1. In this experimental work PTFE was heated ina streamof ir or inert gas (helium) and the TFE was t1r-a3p0ppedpomuvthoaunrdtwhte/nwatnoanlypzoeld.ymeTrhededpaetnadpelnotttoend itnemFpiegruarteu|resuagngdeswthethtahteTrFdEeciosmfpoorsmietdiaotnataakteesopflaabceouitn ai or inert gs. The formation of TFE during melt processing or sintering should not be acauseofspecial concen. It is already well recognized that other components, such as hydrogen fluoride and the agent causing polymer fume fever, which have acute toxic effects, are formed at normal processing temperatures. Ventilation to protect against exposure to these acute toxicants will also offer protection against exposure to TFE. TFE in articles "The levelofTFE in the product or articles sold by the converter is one ofthe key pieces of information for the industry. Resuls of measurements made to date are shown in TABLE 1. This indicates that, using techniques with detection limits generally down to about 0.01 ppm weight/weight, TFE has not been found in articles, manufactured using standard recommended processing conditions. `While this is basically very good news it must be emphasized that the data on which itis based in very limited and further work is planned to develop a more extensivedatabaseof information CopyGriugihtde15t5o.1t9h8e5.Saf15e38HTahnedSinogcoafoyFfutoeroPpaosltyemenruRte,sinInsc,. TAhlirRdigEsdiRieosnerves Page 55 62 APPENDIX A TFE IN FLUOROPOLYMERS TFE formation at maximum continuous service temperatures TahndeleyxspierfoirmeTntFaEl awtortekmpdeersactr0uirbeeCsd. aiUnrsotiuhnnegdsaeancnatdliyotanibcooanlveTteFtchEhenfimoqaruemxsaitwmihouinmcihncogpnartvoiecneduseostuiesncgtsiePornvIilcEiemititsenmcoplfeurrdaeotduunardne 0a.0l5lpypmrteoc0o.m0m1epndpemdpoefr2h6our (weightweight basis on polymen), the following observations vere made: I. TfoEuEndfiirnstobneeocafmtewdoetreucntsaabtlethaatttteemmppeerraattuurree.s of 320C when PTFE was heated in ir, being i 2 oWfhtewnoPrTunFsEawtatshahtetaetmepdeirnaatnurneest gas TFE first became de--tectable at 280, being found none : This data is consistent with the higher temperature data shown in Figure 1 bWeitshigtnhiefivcearnyt elxopwocsounrceenfotrTaFtEio.nsAonfyTFpEastiitciusldrifcfoincudlittioonesncvaisnabgee cchierccukmesdtbanyctehseicnawlchuilcahtitohner`eme`tmhiogdhts described in the paper by David Savardi. i Page 56 CopGyiugihde19t5o2,th19e85S,af19e9H8aTnhdeiiSnocgioefty FofltuhoerPolpaostliycsmeInrduRstersyi.nIsnc,. Third Edition Al Rights Reserved APPENDIX A TFE IN FLUOROPOLYMERS TABLE 1- TFE CONCENTRATION IN POLYMER Data collected by APME) [Powder [aqueous [sinterea| ppm (vw) ppm vi) TMO 1979 val nd lod 0.01 nd 0.01 i PIRA 1987 val || lod | TNO 1994 - val lod nd 03 024 i Producers 1996 | val lod | nd 001-100 02.07 || va I= lod = VLailmuietof Detection !| nd = NotDetected | a Fi TEEFORMATION ROMFIFE | ww ww ww || CoomGruhitde19t52o,th19e95S.af1e908HTanhdeiSngoocfoFafuioyeroipsaltysmenreRyes,inIsn., TAhlirRdigEsdiRteosneed Page 57 n 1 Regulatory and Product Safety Obligations and Guidelines Fall Meeting SPI Fluoropolymers Division October 1996 Presented by David G. Sarvadi --_heer Kela ler n and d Hect kmane ,LLc LLPPkma0n 00, tTehterafrleupoorrtoetohfyltehnee N(aTtiFoEn)alinTdoicxaitceoslotghayt Ptrhoegrflaumor(oNpToPl)ymesrtudiynduosrttryhefaccaenscear-pcoatuesnitnigalphotaeznatridalnootf - dpreegvriaoduastliyonidoenftiffliueod.ropToFlyEmeisrsa cwhheemincatlhueyseadretohemaatkede afbluoovreoptoelmypmeerrastuarneds iastalwshoipcrhotdhuecepdolbyymtehresrmaarle nusoerrmsatlolythperirocoewsnseedmaplnodyueseesd.anTdhicsupsatpoemrerdseusncdreirbetshteherreegguullataotryoiofobtnlhisegaOtcicounpsoatfipoonlaylmSearfeptryoadnudceHresaalnthd Administration (OSHA) and good practices under product stewardship principles. Regulatory Obligations to Employees and Customers TcohmepaOnSy'HsAreHsapoznasridbilCiotmiemsuwniitcharteisopnectSttaonTdFarEda(nHdCiSts)emipslothyeeemso.stThiempHoCrtSanitncroergpuolraattieosnrgeoqvueirrneimnegntas i cfhoremtircaianlinsguabbsotauntctehse thoazdaorwdnssttorwehaimchemepmlpolyoeyresesviaaremaetxeproisaeld,saafnedtyfodratcaomsmheuentisca(tMiSnDgSt)heahnadzalradbselos.f i; Oitbslifagcaitliitoiness,to(2a) ciodmepntainfyy'sthoowsen teompwlhoiycehesitrseequmiprleoayeceosmpaarenyextpo:os(e1d),id(e3n)tiqfuyatnhteifcyhetmhiocsaelsexipnoussuereisn qualitatively comparedto for purchased chemicals the levelsofexposure to the from suppliers; (5) develop chemicals which are hazardous; MSDS for chemicals made or (4) obtain produced MSDS during tprraoicneesmspinlgoyoereusseionfthpeuhraczhaarsdesdopfrcohdeumcitcsaalns,d hmaokewtothreeamdaavnadilsabeleMtoSeDmSplaonydeelasbealns,dacnusdttohmeerlso;caatniodn(o6f) i MSDS and related regulatory information. | cInhetmriacinailnsgaerempulseody,eethseahnedalptrheapnadripnhgysMiScaDlSh,azeamrpdlsoofyetrhse acrheemriecqaulisr,edmetothdoesdcsroifberetchoegjnoibzsinign cwhheimcihcatlhse (MsSuDcSh aasnoddolraboerlscomluosrt),aaccnudramteetlhyoadnsdefmapirlloyyreeeflsecctatnhefohlalzoawrdtso aasvsooicdiattheedewfifetchtsthoefuosveeorftexhpeoesumrpel.oyeTrh'es products Page 58 (CopyGruigihdte195t2o, t1h9e95S,af19e98HTahnedSioncgieotfyoFfituhoerPolpasotlicysmIenrdusRterys.inInsc,. AThlirRidghEtsdiRteosnerved F APPENDIX A" TFE IN FLUOROPOLYMERS i mAannuefmapcltouyreerr'ssaroeblriegqautiiroendsunudnedrerprtohdeuctHCliSabilciotnytlianuwetoaskenepewupiwniftohrmtaetcihonnoldoegvyelaonpds.knoGwelneedraglelyi,n hthaeziarrsdpseocfitahleiizerdpfrioedludc.tsT.hisWihnecnludneeswfionlfloorwmiantgitohne albitoeurtatcuhreemaincdalsscbieenctoifmiecsdekvenloowpnm,enthtes mraenluatfeadcttourtehre emmupsltoryeeveissetoittshMe eSxDteSntarnedqluaiberltesodwiitnhfionrm90thdeamyosfatsheapnperowprdaitaat.e MfoSr DthSe mnueswtitnhfeonrmbaetsieonnt,taoncdusttraoimneirtss with the first shipment afte the MSDS is revised. `EmployeeExposureAssessment andControl ; Employees must evaluate the new information about chemicals in light of the exposures to their : employees under normal circumstancesofuse and in foreseeable emergencies. They must consider: + Magnitude gg levelofexposure + Durationofexposure ] Frequency (per day, week, month, year) ofexposure + Presence and efficacyofengineering controls. VFIoIr pfrlouvoirdoepsolgyumiedranpcreocoensssiunigt,abtlheeeSnPgIinFeleuroirnogpcoolnytmreolrs,Dipvriisnicoinp'asll(yFePnDc)loSsaufreeHsaannddlivnengtiGluaitidoen.ChTahpetseer are the kindsofcontrols that shouldbeconsidered, and discussed with employees, in complying with the OSHA HC. Airsiitsatwienglla-nkdntoowxnicwigtahsienstmheaiyndbuestermyitatneddibs dyesfclruiobreodpoilnyCmhearpstaetrtVeompfetrhaetuSraefseaHbaonvdelinnogrGmuaildeop,ehriagthilnyg `tepmhpeenroamteunroenfkor enquaiospm"epnowtlysmnuecrh fausmeextfreuvdeerrsisaancdonmdoiltdiionngwheiqcuhiipsmebnetl,ieavneddtoibnesicnateursiendgboyveinnsh.alaTtihoen of some of these gases and fine particulates generated in thermal decomposition of fluoropolymers. The general reasonably principle possible. to be followed in Once that has regard to employee exposure is been accomplished, exposures to keep exposures are compared to as low as existing qguoalvietrynmteonatsasulroetrhvaotleuqnutairpymestnatnodpaerrdastoesfpsraofpeetryl.y.TIhfetsheesctoamnpdaarrdissoanrsehtohwesn uthsaetdtahsegeumipdleosoyefewoexrpkopsluarcese reexscpeieradtotrhse,repgruotleacttoirvyelicmliottsh,itnhgeonradodtihteironaaplpcroonptrrioaltse, gienacrl,udmiunsgtpebresounsaeldprtootercetdiuvceeeqeuxippomsuernetssutochtahse existing limits. Guide to the Safe Handing of Fluoropolymer Resins, `Copyright 1992, 1995, 1998ThaSocioeftthye Plastics Industry, Inc., Third Editon A Rights Reserved 3 Page 59 APPENDIX A TFE IN FLUOROPOLYMERS Engineering Controls: Enclosures and Ventilation Engineering controls described exhaust ventilation, and general in the Safe mechanical Handling Guide in Chapter VII include isolation, local ventilation. Isolation involves the creation oaf physical bEanrcrlioesrurinestchaenpsauthrobuentdwteheensotuhrecep,otaesntwiiatlhlya ceaxbpionseetduseemdptloohyoeueseangrdittbhleasstoiunrgcoer ootfhetrhemectoanltacmlienaannitn.g `apparatus for small parts, or to surround the employee, as with the operator's booth on a crane. oNrotromaclolnytr,oelnhcelaots.urWehseinnceoxrhpaoruasttevsenotmielatkiionndiosfcovennnteicltateidont,oaeiptahretriatlo ocrapftululreenacnldosruerem,oviteisccoanltlaemdi"nlaonctals exhaust ventilation" or "LEV." Examples of LEV used in the fluoropolymer industry are found in the Safe Handling Guide, 3rd edition. : cGeonnetraamlinmaenctshainnitchaelwovernktpillaatcieonby(sGlMowVl)y rreefmeorsvitnogtchoentuasemionfateexdhaaiursatnadnddilsutuipnpglythseycsotnetmasmitnoancotnwtirtolh 1c0lecaonnaitrr.ol Fclaorobroenxhmaounsotxsicdoemamnodnlotyhesreecnominbufsltaimomnabglaeselsiqfuriodsmsitnodruasgtreiralootmruscokrs waarlelefxaanmspliensw.arGehMouYseiss vseurcyh iansesffeivceireentimaittcaotnitorn.ollAicncgoredxipnogsluyr,esthteoShaifgehlHyantdoxliicngmaGtueriidaelsd,ooerstnhootserewchiocmhmepnrdodGucMeVacfuotreceofnftercotls of chemicals emissions in fluoropolymer processing. GstuainddealridnseasnfdorputhbelidceastiigonnsooffpLrEivVattehaotrgmaanyizabteiounsse.d OinSfHlAuosrtoapnodlayrmdesrinp2ro9ceCsFsiRngPaarrte1f9o1u0ndwhiincOhSmHaAy | apply to fluoropolymer operations, include: 1910.94(c) Ventilation for spray finishing operations; ( 1910.107 Spray finishing using flammable and combustible materials (various paragraphs); 1910.108(b) Dip tanks containing flammable or combustibleliquids -- ventilation. || These standards set minimum design criteria for various kindsofoperations and are legally enforceable. oPfriGvoatveerorngmaennitzaatlioInndsuessttraiballiHsyhgdieesniigsntsgu(iAdeClGiIneHs)f,orlovcenattieldatatio1n3s3y0stKeemmspaelsro.MTehaedAomwerDiricvaen, CCoinnfcienrneantcie, OVeHnti4la5t2i4on0, A(5M1a3.n7u4a2l.2o0f2R0e/cFoaxm:me5n1d3.e7d42P.r3a3ct5i5c/eh,ttwph:i/c/hwiwsw.tahcegpirhi.nocrigp)l,e spouubrlcieshfeors iandubsotorika,l hIyngdiuesntirsitasl and engineers regarding exhaust ventilation systems. It contains design information and principles for industria} exhaust systems, The American National Standards Institute (ANSI), located at 11 West 42 St, New York, NY, issues Page 60 CopyGiugintde19t9o2th1e99S5af19e98HaTnhdeiSnocgieotfy FofltuhoerPoapsoilcyameinrduRstersy.innsc,. TAhlirRdighEtdsitRieosnerved i 67 | APPENDIX A TFE IN FLUOROPOLYMERS | vFiarreioPursotsetcatnidoanrAdsssofocriatthieodne(sNigFnPaAn)dinopBeorsattoinonosifmilinadrulsythraiaslstveanntdialradtsifoonrvseynsttielamtsioans,wperliln.ciTpahlelyNdaitrieocntaeld at fire hazard control, but also at life safety. Assessing Employee Exposures ICnalecuxlaamtiinoinnsgcapnotbeentuisaeld,exbuptosmueraessu,raenmeenmtpslaoryeerpr'esfecrornecd.luIsnidounsstrmiaulshtygbieenbeasseadmpolnin"gobcjaencbteivoeb"tadiantead tsoampprloveiadnealtyhzeedd.ataArleisqtouf icroend.suTlytpaincatlslyin, tshuecfhiesledrcvaicnebsecoobstta$i8ne0d0--frSo$m20t0he0 Apmeerrdiacya,naInnddu$st2r5ia--lSH1y5g0iepneer : 1 ``gAesnseorcailatpiroanctiinceFaainrdfawxh,oVihragsihnaiad (e7x0p3e.r8i4e9n.c8e8i8n8e)v.alLuoatoikngfolroawnleivnedlusetxrpioasluhryegsiteoniosrtgawnhicociosntcaermtiinfainetdsi.n ISnoutrhceesa,bsperonvciedoefdtshpeecriefiisca rdeataasoonnaabcloesmhpoawniy'nsgtohpaetratthieodnas,tacaslcuulaptiopnstohcearcnabltecubilaastneidognosnwdearteatfarkoemnoftrhoemr substantially similar Kinds tetrafluoroethylene (TFE) of operations. The most released from the process, important piece of information which can normally be based is on the the amount number of of poundsofresin processed, or the rate ofprocessing. The following example illustrates the calculation, assuming; V350exftoroutdxer4s,0 cfooontsupmroicnegss2i0n0g0rkogo/mdawyitpher1e5xtfrouodtecre;ilings; p V1 part per million (weight basis) TFE in resin (e.g., 1 mgofresidualTFEreleased for ]i c0.a1cmhgkrgeofgreneesriantperdocTeFsEspede)r;kgresin processed (e.g., | mgTFEproduced for cach kg of resin processed); / Complete mixing in room air; and / No freshair replacement; o"fThferelsahst, ausnscuomnpttaimoinnaisteidmpaoirrthaanstobnetchaeusmeagtniigtnuodreesantdhedvuerraytiiomnopofrtexapnotseufrfeesct. tThahteainsfsiultmrpattiioonnatnhdatsutphpelrey iascncooufnrtesfohraviarrcioatmiionngs iinnttohetohtehwerorpkaraarmeeateirssh,igshulcyhacsonesmeirsvsaitoinveraatneadnpdropvriodxeismaitwyiodfecmxaprogsiendoefmspalfoeytyeetso 1 1 tcootnhseersvoautricveeoafstshuempctoinotnasm,inparnotc,etshsaortsccoaunlbderreseualstoinnaebxlpyossuurreesthhiatgahcetrutahlaenxptohsousreecsalwciulllatbeed.leGssitvheanntthheossee predicted by the following mathematical model. Based on the above assumptions, the total TFE released into the workroom from the residual TFE in the resin is: Guide to the Safe Handingof Fuoropolymer Resins, Third Edition `Copyright 1952, 1995, 1998 TheSocietyofthe Plastics Industry, Inc., AllRightsReserved Page 61 68 APPENDIX A TFE IN FLUOROPOLYMERS 3 extruders x 2000 kg resin processed/day/extruder x | mg/kg resin = 6000 mg TFE. Similarly, the total regenerated TFE from processing is: 3 x 2000 x 0.1 = 600 mg, giving a total TFE released each day in the workroomof6600 mg. Ifthe total volumeofthe room is 850 cubic meters (see box nearby), the average TFE concentration would be approximately 1.0 ppm. The calculation and conversion from weight per unit volumeof room air to parts per million is as follows: 6600 mg = 7.8 mg/m'; 850m' 1 ppm = 4.17 mg/m' TFE; 7.8/4.17 = 1.87 ppm TFE. Compared to the level which the resin manufacturers are using as a.guideline for employee exposure in their facilities, which is 5 ppm, the processor employees are likely 10 be exposed to levels well below that criterion. This woubelthde average exposure ovawoerkirng period in which the employee spends | asignificant amountof time in the workroom, but is not constantly exposed near the dieofthe extruder, i the location where mostofthe TFE is likely to be released. Note also that the calculation assumes that | thereisno LEV over the dic head, as is recommended in the Safe Handling Guide. Similar calculations i can be madeofother typesofprocessing equipment and general exposures. |i Product Stewardship ay TEERoa i i Product stewardship principles and OSHA (15x40x50) dm = = gsom standards require manufacturers to examine| their products and to produce MSDS for the 353F 353 - products they make which are hazardous. Mixtures or products which contain more than 0.1% (w/w)ofsubstances listed or regulated by NTP, OSHA, or the Intemational Agency for Research on Cancer (IARC) as carcinogens should be presumed to present acancer hazard,unlessthe product s tested as a whole and found not to produce cancer in a comparable test. The product MSDS and labels must reflect these hazards, and may require a specific cancer warning on the label. Whether such wamings are required depends on the hazard determination made by the manufacturer. The specific procedure to follow for plastic materials and products is described in detail in SPI's "Guidance Document for Preparing MSDS for Plastics." Contact SPI's publications department at (202) 974-5200 for pricing and availability. `When performing a product assessment, manufacturers must answer the following questions: Is there residual TFE in my product? 7 Ifso,isit more than 0.1%? Page 62 Guide to the Safe Handing of Fluoropolymer Resins, Third Edition `Copyright 1992. 1995, 1998 TheSociey ofthe Plastics Indust, Inc. AllRights Reserved. - 69 | APPENDIX A TFE IN FLUOROPOLYMERS | | If not, can enough TFE be release under normal conditions of use or foreseeable | emergency to cause exposures to exceed an established limit or to otherwise present a ! health hazard? Processors may wish to use the manufacturers' ppm criteria as a guideline in health hazard evaluation. | Conclusion Ptoroctheessocrasncsehrousltdudbye ppreerpfaorremdetdo rbeyceNiTveP.MSDItSisfrnoomtthcelierarresfirnosmuptphleiedrasttahaptrmeaseyntceodntationdaryeftehraetncaelsl | mTaFnEufianctmueraesrusr'aMblSeDqSuanwtiiltileisn.facSto,mce oresninthmtiastreaerfieairlesnnmceayortnohta.taTlhlutsy,petshoefirruessienbsywiallprcooncteasisnoorrrmealyeansoet ! i rreesauclhtiinng eexxpceosssuirveeoofpetrhaetpirnogcteesmspoerr'sateumrepsl,oyreeseuslttiongTFinE,reugnelneesrsatuinounosufasligcniirfciucmasnttaanmcoeusnetxsisot,fsTuFcEh basy : dsepegcriafdiacticoansoefatnhde fpoorlyamsesri.staPnrcoecienssaonraslyszhionugldtcheoinrsuplatrtwiictuhltarheoiprersautpipoline.rsEfxotrrmudoerresdaetnadilostahbeoruhtetahteeidr pbreoicnegspsrioncgeessqeusi,pamsenrtecsohomumlednbdeedrebvyietwheedmatonuafsascutreurtehratofmathxeirmesuimn, service are not temperatures exceeded. for the resins TCoFaEteirnsthaenidroppreorcaetsiosnosr.s tThhateyussehofiullldedc,arleubfruilclayteed rxesinasthmemaiyr iobpeermnaotrieeonlsikteolaystsourheavtheatreusniunssuwailtehxrpeossiudrueasl aVernetailvaotiedde.d,Gaennderwaolrlyk,wiitfhthtehesiorlsvuepnptliceornscteontarsastuiroentshartesthuelitrinsgprianytfhienissphrianyg ooppeerraattiioonnsaarree acodnetqruoaltleeldy, chances are that the residual TFE levels will also be controlled adequately. Ovens will require more careful analysis, particularlyifthey are operated at or near the maximum { treegmepneerraattuerde. reAcgaoimnm,enddateadabrye tlhiemistuepdp,liseor iotftihs eimrpesoirnt.anOtthteorwcoinsseu,lstigwniitfhicsaunptpalmieorusntfosrofmoTrFeEsmpeacyifbiec guidance. In any event, processors should review their oven operating procedures and not exceed | temperatures recommended by the resin supplier. || | `CopyGruigihdt e19t9o2,th19e95S,af19e98HaTnhdeiSnocgieotfyoFfltuhoerPolpasotlicysmeInrduRstersy.inIsnc,.,TAhllirRdigEhtdsitRieosnerved 70 Page 63 APPENDIX A . ;| i 3 TFE IN FLUOROPOLYMERS ; Guidtothe Safe Handing of Fucopoymr Resin, Third Eon Page 64 `Copyright 1962, 1995, 1988 TheSociely of the Plastics Industry, Inc., All Rights Reserved an J APPENDIX B THERMAL PROPERTIES J S--- fTohretdhaetirasipnectihfisicApprpoednudctisx,haanvde, bceoennsepqruoevnitdlye,d bthyeianpdpiveindduiaxl imsantoetriianltseunpdpeldiearssa p`rcoomdpulcettecosmopuarrcies=oInts.shoDualtdabceouusleddvfaorryisnifgonrifmiactainotnlayldpeuprepnodsiensgoonnlythaend notfor `Icnofnodrimtaiotnisonunpdreorviwdheidchhetreestisinngoits icnatrernideeddotuotbaendustehde sinpepcliafciecopfropdruocdtucttested. sapveaciilfaibcldeaftraopmrtohveidsuepdpliinetrhse. reCsopnetcatcitvethMeatspeerciiaflicSamfaetteyriDaaltsauSphpeleitesrf(oMrSDS) z% pgruoidduacntcsecoonnttahienuesdeoinftthhisesAeppdeantdaiaxn,dofrofroarddiintfioornmaaltiionnfoornmfaltuioornoopnoltyhmeer resins notfound in this Appendix. `GopyGruiihtde19t52o,th1e995S,af19e98HTahnediSnogcoiftoFyfutohreoPplaosltiycmseInrduRsets,inIsnc,. ATlhiRrgdhtEdsitRieosnerved 72 Page 65 3 i | 3 i Page 66 CopyGriugihtd1e99t2o,th19e95S,af1e998HaTnhdeiSngoofcoFlfiuthoeerPolaptsotliycysmeInrdusRtersy,inIsn,c. ATlhlirRidghEtsdRietsoenrved 73% | APPENDIX B PART 1 -- DUPONT | | THERMAL PROPERTIES THERMAL APNEDRFTOORXIMCAINTCYEOFOFDEDGURPAODNATTFILONUOPRROOPDOULCYTMSER RESINS DuPont fluoropolymer resins are very stable at their recommended continuous use temperatures, i c`hoomwpelveetre,dthaesytduodyex?htiobidteastmearlmiln.ea them ratoo eoffddu eeggrran daadtat itoinonaotfhisgehveerraplroofcetshseiinrgctoemmmpeerractiuarlesf.luDouroPpoonltymhears 1 Ii resins over the range of continuous use and processing temperatures and examined the nature and amountofthe gases evolved. Six DuPont fluoropolymer resins were evaluated, including Teflon 7A. | | Granular PTFE, Teflon 6C Fine Powder, Teflon PFA 340, Teflon PFA 440 HP,Teflon FEP 100, || and Tefzel 200. All the resins were tested in the physical form in which they are commercially | supplied. - Tohfeflrueocroompmoleynmdeartsiomnasyofvdairfyfetroeantdefglrueoer,oTpaoblylmeerI (prPogd6u3c)erisncalsutdoesthtehetevmapleureastuirnediscfaotredcobmymDeurcPioanlt ufsoer the resins used in this study. | Figure II (Pg 66) shows the results of weight loss data from the rateof degradation experiments. `TWheeirgmhotgrloasvsimdaettariwcerAenaolbytzaeirne(dTGuAs)i.ng TahTeAduIrnasttirounomfentthseThruenrmwaalsAunsaulaylslyt 62510m0i,nuetqeusi.ppBeedcawiutsheoaft95h1e | low rate long as 1o2fhdoeugrrsa,duastiinognoafPherokmionp-oEllmyemrerth(eTremfoglroanvim7Ae.traincdbTaelafnlcoen,M6oCd)elsoTmGeA-r7u.ns were made for as. { | i } 2 pBoakleyrm,eBr. DBe.,gJrard,atainodnKaasdpSrztaakb,ilD.y,J,Vo"l.Th4e2r,m1a9l9D4e,gr18a1d-a1t5i8o.nofCommercial Fluoropolymers in Air" | | orn to cp se ndea.r asiteeecdomoefipotowinn st.ovTehendcihcikcsoSf hle foirmaotiwonnicrotti4ocn send is0k.oThee Ddorko 3 eeommisdaton 0 ing, rypnofDuFto ohr ||i - `CopyGruigihdte19t52o,th19e95S,af1e99H8aTnhdeliSnogcofioFefltthueyorPolpaostliycsmeInrduRstersyi.nIsnc,,TAhlirRidghEtdsiRieosnerved Page 67 | APPENDIX B THERMAL PROPERTIES CONTINUOUS USE AND TYPICAL TABLE | POLYMER PROCESSING TEMPERATURES RESIN CONTINUOUS USE DEGREES C TYPICAL PROCESSING DEGREES C Tefzel 150 310 Teflon FEP 205 360 Teflon PFA - 260 390 . Teflon PTFE 260 400 A 60 ml/min streamofair from acylinderwas:split so "en recombined to yield 50% relative `humidit that one-half passed througha water bubbler and 208 liter "Tedlar" polyvinyl fluoride gas y air. sampling This bag. stream was directed through the TGA and A samofp pollyme er `weighing 25-80 mg into was laced run on the platinum panofthe TGA, was begun by moving thefumace whose furnace had been over the sample ont heated tothe desired temperature and couained for the durationofthe run, usually 65 minutes. hebalance pan. Weight loss data was then A 2 ml portion was removed from the. Perfluoroisobutylene). The column `sample was 10 bag and feet by examined 1/8 inch by GC (Gas Chromatography) for PFIB 2aracil C Durapak, run isothermally at 35C. The PFIB , n-octane/dinonyl retention time with 18 phthalate/Krytox on psi head pressure was = minutes. ch. 25% The identification di(2-ethylhexyl) was. confirmed by running one sebacate on 100/120 mesh sample on a second column: 20 feetby 1/8 <eaditions; the PFIB retention time was 10.4: `minutes. Chromasorb P-AW, using the same GC Measurement wasbyan.electroncapture detector "%72 a detection limit of about 0.001 ppm. <ontentsofthe gas sampling bag were then transferred to an evacuated 10 meter path length infrared <F22xr1ca1uml2a1ptre2.de2 .violuitselrys evsotlabulmiesheadn.dcatlhiebrsapteicotnrduamtao,fthteh`evagraisoeuss rcuonmpoonnaenNtiscowleerte2i0dSenXtiifniferdaarneddtshpeeicrtarmomoeutnetrs. 1 ! I L2TETSirSammeeesie seoafffertedhl witGhoiusan espLhsirnii s eodorp otfn Dounbnc onn'spo setmrvievothteheo mcustdomo erss , botthhee yncannotBguraSnee foevkTelEslDiill 1 aPaze 68 ideto the Safe Handing of Fiuoropoymer Resins, Trird Eton `CopyRight 1992, 1995. 1998 The So cietyof the Plastics Industry, Inc. Al Rights Reserved 2s ; sy APPENDIX B THERMAL PROPERTIES FIGURE II PERCENT WEIGHT LOSS ON HEATING IN AIR E| nnne ee eee- >-- C =-- Z ---------------- > = ly Ne : = R= 4U 0.001 : R 250 275 300 325 350 375 400 425 450 475 500 525 55C DEGREES CENTIGRADE & *TEFZEL PFA 440HP = FEP 100 x *TEFLON'6C * PFA 340 TEFLON'7A is nfos oferd wuschargea puto DuPon' serieo heictor, bt hey sot ga vos rss will Cmenduion 0 ngs, pttofufonShee. CopyGiugihde19t92o,th19e95S,af16e90HaTnhdeiSngoocfoiFfltuyhorPoapsotileysmeInrduRsets.innsc., TAhliRrdigEsdiRteosnerved Page 69 26 --~ APPENDIX B" THERMAL PROPERTIES C`OTFh.e..priTnchiipsalcoemvpolovuenddgtahsenwhheydnrofllyuzoersoptoolaymseigrnsifairceanhteaetxetedntininaitrhaet 400 50% deg C is carbonyl RHairto HF and fluoride, CO,. HF tisheaquwaeratkz iTnfGrAaretdubaebsaonrdbeitrsapnrodpiesnsdiiftfyictuoltabtsoomrebassturroengblyy ootnhesorlmideasunrsfaacsesw.elTl,hebreecfaourseeowfermeeaacstuironedwitthhe amount of un-hydrolyzed measurement. COF; by IR and calculated the amount of hydrolyzed COF; from CO, Foverriaftiyepdibcyalfi6ll5inmgitnhuet2e.2rulnitterheIRvocellulm, eruonfnignags tinhethsepescatmrpulme, bevaagcsuhaotuilndg thhaevecelbleaennd3.t9ralnistefresr.riTnhgiasllwtahse craelmcauilnaitniognogfasthteo tthoteaIlRamceolul.ntTohfegparseisnsutrhee biangt.heTcheelslewmaesatshuernemreeandtswigtahvea gvaaluugeesornantghiencgeblle,tawleleonwi3n.3g aalnldth4e.2salimtperlse, vferrosmusthtehebaegxpaencdtesdom3.e9.inTachceurdaifcfyerinentchee ipsrepsrsoubraeblmyeadsuuerteometnhet,difWfeicuhlatyveoneltercatnesdfetroruisneg 1 the expected 3.9 litaes in our calculations of the amountofthe various gases evolved. i `bTeatbwleeeInI t(hPege7a1r)lygiavnedsltahteewweeiigghhttlloossssdraattaef.orTthhee vsailxuseasmfpolretshaenTd,Ew(htehreermiatlexeiqsutsi,lisbhroiwums)tthoe d1i5ffmeirneuntcee i| i awnads u1s5utaoll6y5rmeiancuhetdeilon3ssorrat4esmiwneurteest.akTehneffrionmaltchoelsulmopneo(TfEthpeluTsG60A) icsutrhveeaocvteuralthweeitgihmtelionstserovvael.r tThiEs i optehreirosda(roer,awvheerargeeisondfitcawtoed,oratlhornegeemrepaesruiorde)m.enStos.meWoefitghhetTlEos+s6r0epmrienseuntteavtiaolnueosf a"r<e0.f0r5o"m iansdiincgatleesrtuhne; limitof detection in that particular experiment. | `"bCToihimnspeiandnfyofrsomammtiheoeissnefofobfelidcghiaiodouassr. cIaharidg 5einpdcuornofnfeocDtrionbowyiptenhrsonvssiic.havtTehihneegidcsihooimnca,lofsbthtofhoemkymcaotvnonGgrunaetrvaen nanvsdoFr1oa0k.loeeTsherlDsunPwdolnelt or ecommendiononige, ny peofDutPont ors `Guide to the Safe Handing of Fluoropolymer Resins, Third Edition Page 70 `Copyright 1992, 1995, 1998 The Societyofthe Plastics dusty, Inc. All Rights Reserved 77 i APPENDIX B THERMAL PROPERTIES ! Resins 5if rerem20 Temp "C 216500 332080 350 TABLE Il WEIGHT LOSS DATA % Weight Loss/Hr TEto 15 min. 1510 65 min. 004321 000096 2 TE +60 min. <o0l0l5 001647 68 Teflon 100 320080 33550 "00 003 <<0000ss 04s 013 001687 32 3 Teflon PFA 340 260 300 j1 3a500 018 005 008 007- 002328 i Teflon PFA 440 260 300 8 30500 <00s 00s 012 003 000256 Teflon 6C 0a0s 000165 a52ss 255" 9o5o 0 i Teton 7A 335500 000020s a000 0000036" aass 000066" *#HoHuourrllyyrraattee ffrormo3.mt3o 01.86.h6ohuorurssaafefrebbeeggiinnninnigunrnug.n. ++ Gross decomposition in one hour. Initial ate 255% per hour. TiChoinmspeiandnfyorrammamtieoissanfepelrfeisdgcwhaidtihaoosun.tca1h1ai5rgple aIdnpctofoonfeDsoicnhtio'pnerssseorwvneisc.heavTtienegsceccsoiurar,ioflbuhsetihnehfyoimcaoatwinnodndgis roaetrneensfnvedoris1bkl.peTsehueelDuuPnwoidlnelkrboer eomnendaiofno ine, 8 pcof DuPork oes. Guide to the Safe Handling of Fluoropolymer Resins, Third Editon `Copyright 1892, 1995, 1998 The SocofitheePlatstiycs Industry, Inc., Al Rights Reserved Page 71 7% ~~ APPENDIX 8 THERMAL PROPERTIES "The data on the evolved gases from the four resins that have significant amounts of effluents are presented in Table III (Pg 68). The numbersare all weight percent so that the sumofthe gases can be comparedwith TGA weight loss shown in Table ITI. Table values have the weight ofoxygen subtracted assuming the oxygen came from air and should not be considered when comparing weightofoffgases with TGA weight loss. Where no value is given for the seven gases measured by IR, none was detected. "The detection limit is variable, typically about 0.05 ppm in the 10 meter cell (about 0.02%). Formation of PFIB (perfluoroisobutylene), even in small amounts, is noted because ofitshigh toxicity (2 hour LCs forratsis | ppm). FEP polymers branched chain would be expected to produce PFIB more readily than PTFE. [twas found that FEP produces PFIB at 400C, but PTFE does not. PFIB is produced by heating PTFE to 525C, where gross decomposition occurs, well above normal processing temperature. No PliFmIitBowfa<s1fpoprbmeidn tfhreoemvFolEvPedatga3s50saCm.plTe,hewheilecchtrcoonrrceaspptounrdesgtaosacyhireolmdaotfogarbaoupth 0u.s5edpphamd(a0.d0et0e0c0t5i%o)n ona polymer basis. Fluoropolymer resins when decomposed at high temperatures evolve toxic products.** While several i stopxeicciiftiyc ddeecpoemnpdoosinttihoenmpertohduocdtsusheadvetobfeoenrmidtehnetipfrioeddu,ctthse,stemppereatoucrfed,ettchoemrproatsueiotfimotnemppreordautcutrsearnidsethaenidr | ! potohleyrmceornddietcioomnpsoosfiptyiroolnypsriosd.uctsThisewmiodsetlyardveecrosgeniezfefdecatsas"spoocliyamteedr wfiutmhehfuemvearn,"ecxhpaorsaucrteertiozefdluboyroa- ; temporary (approximately 24 hours) flu-like condition similar to metal fume fever ("foundry man's fever') | | 2 Clayton, 1. W. "Fluorocarbon toxicity nd biological action," Fuorine ChemicalReview I, 1967, 233-252. Wgeinlelriaatmiso,n,5". FJi.raenMdatCelarrikael,5F,. 1B9.8,2,"C1o6m1b-u1s6t2.ion product toxicity: Dependence on the mode ofproduct Hams, D.K. Lancer 261 1008, Dec. 1951 CTvoiimspnoadnmyfsnoeiesfoneepe8ofdeshhaoGnsuot. ah1ib1lGyEmpScutnoofueDttunwpsiescAosisic.avtToihtnehesccchuosarmlersofs,hibleokOecyHrCaonAwnngd7us1rroenEavsndeoi0kro.TpehrsDuaPwnoidnltrbeo 3 econo to ing. nt peofnDuPtont ror. Page 72 `CopyGriguht i19t5od2t,he1e995S,af19e88HaTnhdeliSnocgieotfyoFfltuheorPolpasotlicysmeInrduRstersyi.nIsnc,.,TAhllirRidghEtdsitRieosnerved 2 APPENDIXB THERMAL PROPERTIES (RevisedTSAepBtLemEbeirl 18. 1995) COMPARISON OF ONE HOUR TGA WEIGHT LOSS WITH WEIGHT OF EVOLVED GASES, Ms CCTENP TGA WIWPEEISGHT OWFEEVOLVWEPD GASEHSCEA,S 4 OFFEsTabPMLesECsORCle CO SM RC Loss TRE 0S 006 0 o25n 0s am 0 pepo a0 2s 06-006 03 019 os12t ao ne PAZ a 06 oss oo os we ee PAM 0 026 12 PSTeAhriiosfrcostbauomtfyitnlhceeltuhadnyealsley1ntei7c.a%lCteOc,hnfirqoumefoorxvaliuedsofa1t0h0t%ee.tihyolenne units. Includes 0.19%ofCF.COF. mon tf drs toutec cmea8rontaonoertere r adhe e See Handiengyof FoooarPopoaymansReesini,. ATdhsi Edeitonr Pages &o -------------------------------------- ~~ APPENDIX B THERMAL PROPERTIES (InNB1S9,82r,eanasmmeadllNastciaolneacloImnbsutisttuiteoonftSoxtiacnidtayrdtessatnddevTeelcohpneodloagtyth[eNIUS.ST.] iNnat1i9o8n7a,lsBhuorweeaduPoTfFSEtarnedsainrdtso phraovteocaonl,ulnaebxopreacttoerdylryathsiigehdanfirmoamla(l3a0bmoriantuotrey erxatpso)stuorxeitcoitpyy"rolWyhsiesnprPoTduFcEtswfarsotme0s.te0d4umsginogftphoelNymBeSr fpeirrmLeodfthcehNaBmbSerresvulotlsu.meH.oweInvveers,ticghaetmioincaalt aannaluymsbiseorfotfhelaebxopreactotreidecsounstienngtotfhtehNeBfSumpersoftroocmotlheNcBonS(tetsettraapfplauroraoteutshycloeunle)d annodtCeOxFpl;ai(ncawrbhoynylthfeluroartisded)i.edT. FETihsereplratiinvceilpylenopnrtoodxuicct,sanddetCecOte,d wwaesrefoTunFdE, obuftPaFtIcBon(cpeenrtfrlautoiroonissofbaurtbyellenoew)wwhhaitcihs ilesthkanl.owAn steoabrechvweraysttohxeinc.inNitoinateedwtaostrdyetaencdtedd.etect the presence eInxpeoarsleidertosttuhdeieNs?B,Spatrestticmuolastpehmeatreeritahlrwoaugshifmipltleircsattoerdeamsocvoentpraritbiuctuilnatge.to Rtaoxtiscietxyp,otsheedretfoohree,sreatfsilwteerreed {g0astehse dciodncnloutseixohniBthTattapnarutniucsuluaatletwoaxisctrheespproonbsaebwlheiclaeutsheoosef uenxepxopseecdtteoduhnifgihltteorxeidcgitaysedsisdpilda,y"edleiandtihneg | oNfBuSlttroaxifciintey pteasrtt.icSltesud(y2o0f-t3h0enmmi)nuptreofdruaccetidonbryetmhoevecdombbyusfitliteorns roefvePaTleFdEthraetsiancsonisdelnestahatliotnoareartossoiln | 1 i{ 5 Leesvtimn,etBh.Co,dFfoowrehlel,asAsJe.ssmBeinrtko,fcMu.tMe,inPhailaabtioo,nMt,oxtictiltey,ofAc,omabnudstMailoenk,prDod,uc"tsF,u"rNartidoenvaellBouprmeeanut ooffa } Standards (Technical Report] NBSIR82-2532, 1982. 2 Kparpoldaunc,edHbLy.fiGverahnadl,ogAe.naF.t,edSwpitozleyr,meW.rsCJ".. aFinrde SGacdi,en5.ceC.2,, "1A9c84u,te15in3h-a1l7a2t.ion txiciy of the smoke. 53 KBaupleaan,ofH.SLt.aGndraarndds,MeAt.hFo.d,a"ndCoHamrbtuzseltli,oGn. TEo.x,i"cRoelovgiyew--oPfriPnrciinpclipelseaLnadboTreasttoMreytMheotdhso,dLsa,ncNaasttieorn,alPAS Technomi Publishing Company, 1983. 5% Wdieglrlaidaamtsi,o.n oJ,f pBearkleuro,iBn.atB.,edapnodlyLmeeer,s:K. EP.v, id"eFnocremaftoironroifaicaulteatpmuolsmpohnearircy rteoaxcitciaonnt,s" fFololoodwiCnhgert.hermal Toicol 25, 1987, 177-185. 3 tWoaxrihcietiyt:, DE.ffBec.tSoefidfeilll,erWs., cCo.mCbaursatcioosntamse,thMo.dCa.n,danaedrHosaorltsakgye,."M.ExAp.. "MAotlt.enPuatahtoilo,no5f2.f1l9u9o0r,op30l9y-m3e2r9.fume eT a THEO ; i formeatisonsnafstoffbwawiiodthotocbharimgeansdpeotdnoofnt eiioonwpsiehsseorsvaishc.aveTithnhgidccashoimsrcs,fahbsetanheroykramonwanndnasnrrtiocncrdaskv1.0reTrrheeseuDsuonwcdiletlrboeF 4 ecommenaion 0 Ang, ry pan ofDuo othe ! Page 74 Copynght 1952 1995, 1998 The Sucety of he asics Indust. In. Al Rights Reserved i 2 i APPENDIX B THERMAL PROPERTIES i concentrations of the order of 107-10" particles per milliliter* The unique conditions of the NBS i toxicity protocol result in formation ofthisaerosol from combusting fluorocarbon resin PTFE. I : bAeorronsooult pbayrtsitculdeiseasgogflofumlelrsactaelerefiardeislyatitnhethSetaptreesUennicveeorsfitsymoofkGehefnrtominotBheelrgmiautmer7i2al4s Ctahbatlebsurinn,sualaftaecdt with fluoropolymers were installed in a bum room overhead in a ray simulating a plenum. The design { `1c2o0nnkeicltoegdrtahmesb(u2r64rpoooumndtso)aocofrwroiododr twharsoubogluhrnwehdicash athheecaotmsbouusrtcieotnosbmuorkne25trakvielleodg.raImnsa(5ty3yppipicoaulndtess)t cable insulation. As the smoke passed down the corridor, samples were drawn to chambers containing rats. Over the course of twenty tests, the rats showed no evidence of exposure to the toxic acrosol `generated by the NBS toxicity protocol. These results are consistent with the absenceoffield reports of unusual toxicity associated with the presenceoffluoropolymers in real fires. i +- i Seidel, W. Scherer, Cline, D. Olson, A. & Bones, J, "Chemica, physica nd toiclogca |: hchaersxceraizfatilonuofofurmneodsppperrrfolduouocrpeod(ypbrylohpeyealtvniinngeylteettrhaefrlu,o"rCoehtehymlnReesh.oimnoTpooxlicyomle.r4,an1d99i1s,c2o2p9o-2l3y6m.ers with i 7 Baker, B. B. nd Kaiser, M. A, "Analytical App--rUnoderastacndihng what happens ina fir," Analytical Chemisty, 63, 9A 1991 : : 3 C.laSrekied,elF.,BW,.vaCn,KuHiejrkp,l,HC..M.,H., VaalnedntJiannes,seRns,,BMa.,ker",ThB.e tB.o,xiBcoinysotefels,mJo. kK.e, fKrroamsfprizraski,nvD.olJv.inMgakovec, G. t `perfluoropolymers: Full-scale fire studies," JournalofFire Science, 10, 488, 1992. i hniseidnforomamtionivft otfshwhiu.t hIcgAputoofrDuiPonyt'os vniceAtnegiEuBteCsS,lbsooey cvncrge 4v7rk.sTehsDluPwoinltbe eCoammpmaennyimaicons0 goeb .gaisoyn pTbiloa tfyDnon cronoshoo0nenw. is. The dcoof he formation cr 0 ere under, or3 Guide to the Safe Handling of Fluoropolymer Resins, Third Edition `Copyright 1952, 1995, 1938 The Socioeftthye Plastics Industry, nc. Al Rights Reserved Page 75 8x APPENDIX B' nl THERMAL PROPERTIES imNseymdaoaamineensfodhaneodwni.hpytht4neFertdosDo0buecrres vooTtlhctsdaso0tfsOsBhoeckoo ontSsneecscA cliotnt4 1 PIZET6 CoGpuiede1t.o th1e35S.a1f9e50HTaonmdSinog oyf FtioorPopaosliymeir R,esinsne,. ATbhieEsdRioonars 3 5 8% i APPENDIX B PART 2 -- ELF ATOCHEM THERMAL PROPERTIES Sample ELF THERMAL PERFORMANCE OF ATOCHEM KYNAR PVDF FLUOROPOLYMER RESINS KL2o7t5808C8056 K2800 Lot 87C8163 K2850 Lot 87C8080 TGA Run# 1334B 13358 Aum, Air Air 5%wt. loss 4316 4274 temp., C EL 10% wt. loss 4406 4420 temp, C Deriv. Peak 4790 469.7 Temp, C 1 wt. loss region, C 40010478 40010478 9%wt. loss 582 90.1 2% wt. loss region, C 47810625 47610 625 % wt. loss as 99 Samples were heated 10C/min. in air to 1000C 13368 Air 4487 | 4576 ans 40010 481 794 48110625 206 I ST ASnES `CopyGruigihdte195t2o,t1h9e95S,al19e98HaThnediSoncgietoyfoFfltuheorPolapsotilcysmIendrusRterys.iInnsc.,. ATlhliRridghEtsdiRteisoenrved sx ay racer Page 77 APPENDIX B Sample K2750 Lot 88C8056 K2800 Lot 87C8163 TGA Run # Atm. 2652B N, 2653B N, 5% wt. loss temp., C 4513 459.4 10% wt. loss temp., C Deriv. Peak . temp., C 465.6 491.2 469.7 4932 Residual mass% 11.9 ns at 1000C 1* mass loss region, C 399 to 508 38210 510 % mass loss 81.9 823 2"massloss. region, C 508to 1000 510to 1000 % mass loss 6.2 6.4 Samples were heated 10C/min. in N; to 1000C THERMAL PROPERTIES K2850 Lot 87C8080 2654B N, 461.5 470.6 485.5 244 421 to 506 66.7 506 to 1000 89 TE PAGE TB Se STS ------e i er copGuid1e98t2o.t1h5e5S,a1f5e88HaTnedSliongyoffFlouorPopsolymeor Rtesil ns,ATLhc igrdsEdiRtionr s APPENDIX B* THERMAL PROPERTIES : Sample K730 K740 K760 K2750 Lot89C6025 Lot89C6021 Lot86C6049 Lot 88C8056 TGA Run # 26498 26508 26518 26528 Atm. N, N, N; Ny 5% wt loss 466.0 4594 468.0 4573 temp., C 10% wt. loss 4746 469.7 4787 465.6 temp, C Deriv. Peak . o 489.5 4846 915 4912 Temp. C i Residual mass% ~~ 224 298 24 19 at 1000C 1%mass loss I1t0S13 4000505 36910510 39910508 ] region, C 9%mass loss 692 616 689 819 3} 2% mass loss 513101000 505101000 510101000 50810 1000 region, C i 9%mass loss 84 86 87 62 | Samples were heated 10C/min. in N; to 1000C i '5 a mnfat rntr nf 7At i ic tmni, sctarnpetrer1rHnrndeaprrctnaSy0oaorn Guide to the Safe Handling of Fluoropolymer Resins, Third Ediion `Copyright1952, 1995,1998TheSocioeftthye Plastics Industry, nc. Al RightsReserved Page 79 g nm--------------mmm-- ---- -- APPENDIX B THERMAL PROPERTIES Sample K2800 Lot 87C8163 K2850 Lot 87C8080 Kynar SL Lot 86J8003 Kynar ADS Lot 8422 TGA Run# Am, 2653B N 2654B N, 2655B N 2656B N, t5e%mpw,t.lCoss 459.4 461.5 4744 4573 | i 10% wt. loss 469.7 temp., C 4706 4826 4720 i| Deriv. Peak - 4932 485.5 501.8 4976 i Temp., C Residual mass% 113 244 28 0.0 i at 1000C i r1e%gimoans,slCoss 38210510 421 to 506 43410516 379to 542 ! 9% mass loss 823 66.7 898 977 ! 2%mass loss 51001000 506101000 516101000 region, C % mass loss 6.4 89 6.8 6.2 Samples were heated 10C/min. in N; to 1000C EBEE , Guide tothe Safe Handlingof Fuoropolymer Resins, Third Ediion |: 87 ii i Page 80 Copyright 1962, 1985. 1998 TheSocofitheePlt asty ics Industry, Inc... All Rights Reserved ii APPENDIX B THERMAL PROPERTIES | pf Ereen, LSso-- w S ,Nun oTaGr sAr GBaEtehastse one 4 Pr - i roo wat ome ro 3 5 3 eo =: :i mar - 4 i- sas.7mn w& TTT me a wBe issos To ads slo ie fr : Guidetoth Sale Handing of Faoropeymer Resins, Thi Edin nTRE Copyright 1992, 1995, 1998The Societyofthe Plastics Industry, Inc., All Rights Reserved Page 81 &% APPENDIX B i ii i THERMAL PROPERTIES : ra man ocen m ns oeaaa rfs 1rAera oosnereenoosrC3ss cauira,, iEL n oanre wey n l1eHnstcS en rna r |i Page 82 (CopyGruioindte19t5o2.th19e95S.af19e98HTahnedSioicnigetoyfofFtlhueoPrloasptoiclsymIendrusRtreys.inncs., ATlhiRridghEtsdiRteisoenrved j 8 APPENDIXB THERMAL PROPERTIES PART 3 -- SOLVAY THERMAL PERFFLOUROMRAONPCOELYOMFESRORLEVSAIYNSSOLEF PVDF Weight Loss ofFluoropolymer Resin: Dynamic Thermal Gravimetry Analysis Conditions: Material: Solvay Solef PVDF Fluoropolymer Resins Atmosphere: air Meliing Pot in Pt- area: 0.4 cm' Output: 60 mlimin Form: tray Load Sarple: 10 mg Form: pellets . Temperature Profile: initliianleatremhpeeartaitnugrer:ate3:08CC(/86miFn)(46F/min) [ T | wees| i | sotere rorouamn Velingtempera=tu17r4eC (45F) "oo weclle mosl|eme wowl ow | Bo 4 [4s zs laee 21 2 `Average processingtemperature = 230C Bo a2 |s ze lew 22] 3 ?i i SaAmpppeln)deilxoad:1.10mg | [ Ms`eAolvLeiernarggeetsepmroporecre0as0tsui0rn0egt=em1p7e3raCtu(r4e3=%)230C 7o7tas Bs 44324[2sz zzow 39 us|s2 mee w20e0|) 2s) 21 3 Sawmipslneload: 10mg Append ':2_ 11 i T1 T2 = = Difference Difference between between TGA TGA temperature temperature a--nAdvmeerlatgiengptreomcpeesrsaitnugret.emperature. Allinformation is given in good faith but without guarantee. neet hems coi ce, le iroy Rts we e ee iee ncima.Cs hei sion4. ome mt re oerei (CopyGriugihtde195t2o.t1h9e95S,a1f9e98HaThnediSnogcoifoefFttlhuyeorPloapsotilcysmIenrdusRte,siInncs.,ATlhRiirgdhtsEdRieisoernved. Page 83 qo EEE EE a yy APPENDIX B ~ THERMAL PROPERTIES THERMAL PERFFLOUROMRAONPCOELYOMFESRORLEVSAIYNSSOLEF PVDF Weight Lossof Fluoropolymer Resin: Dynamic Thermal Gravimetry Analysis Conditions: Material: Solvay Solef PVDF Fluoropolymer Resins Atmosphere: air Melting Pot in Pt - area: 0.4 cm? Load Sample: 10 mg Output: 60 mU/min Form: tray Form: pellets Temperature Profile: initial temperature: 30C (86F) linear heating rate: 8C/min (46F/min) MSeOtLiEngFtm1p1e0r0a8t1u0r0e03= 160C 220) | eAverrage processing temperature = 20C: L Sample load: 10mg TAT TM Ia vole lew ooos0s 0mlar draws 22wl07|228 113%0 1a T1= Difference between TGA temperature and melting temperature. T2 = Difference between TGA temperature -- Average processing temperature. All information is given in good faith but without guarantee. S erThebedet oavm eceefyeocsI nm ensnoSfesiSAirihce.eHoi eewae FoSe yAvhunes Resoi ness eei sy Guide o the Safe Handing of Fuoropolymer Resins, Third Editon Page84. `Copyright 1982, 1995, 1998TheSocofitheePitastycs Industry.Inc..All Rights Reserved. Ki) APPENDIXB THERMAL PROPERTIES 3 THERMAL PERFFLOUROMRAONPCOELYOMFESRORLEVSAIYNSSOLEF PVDF Weight LossofFluoropolymer Resin: Dynamic Thermal Gravimetry Analysis J Conditions: Material: Solvay Solef PVDF Fluoropolymer Resins 8 Atmosphere: air Output: 60 ml/min Melting pot in Pt area: 0.4 cm Form: tray Load Sample: 10 mg Form: pellets Temperature Profile: initliianletaremhpeeartaitnugrera:te3:08CC(/8m6iFn)(46F/min) . MSeOlLiEnFgte3m1p0e0r8a1t0u0r03= 169C (36%) wAvaerea)ge processing temperature = 230C Samppelndeilxo'a:d:410mg N`eStOiLnEgFte3m1pe0r8a/t0u0r0e9= 166C (3367) `wAaveera)ge processing temperature = 230C Sample load: 10mg ppendxn 5 _ - 03 - cle eoau sera|woe ee a0 e7s0 aeriae|ame wo ime - - ole w m|zae 20128 2202022 22fzs wl ow awmw 12 || w0| 3 13 I te reee a T1 = Difference between TGA temperature and melting temperature. T2 = Difference between TGA temperature --Average processing temperature. All information is given in good faith but without guarantee. A Ta ne wepe betmao ceist earilisscaae,nsH debsio FohSeo w eygAocos seoy3e4ee r.,yomrysomlasm egosomsse ooeeyn neclteys ee Guide to the Safe HandingofFluoropolymer Resins, Third Editon `Copyright 1952, 1995, 1998 TheSocoftihePleastiycs Indust, Inc. All Rights Reserved. Page 85 5 7s LT 0 I ~ APPENDIXB ~ THERMAL PROPERTIES THERMAL PERFORMANCE OF SOLVAY SOLEF PVDF FLUOROPOLYMER RESINS Weight LossofFluoropolymer Resin: Dynamic Thermal Gravimetry Analysis Conditions: Material: Solvay Solef PVDF Fluoropolymer Resins Atmosphere: air Melting pot in Pt - area: 0.4 cm? Load Sample: 10 mg Output: 60 ml/min Form: tray Form: pellets Temperature Profile: initial temperature: 30C (86F) linear heating rate: 8C/min (46F/min) w Sionregrop3a15r00s0e003 165 0957) wwoo hSormbrieey 10mg Average processing temperature = 230C 696 | SMpoisnrp papan--es--10--5--30%v)c wo|on (46F) Lopes g=o II wle m|olme 369| 392 smWollEe EE To | wemoss| wmoi|le|mme wwoo 200| 282 139 wu || i womimEm ooiweE J T1 T2 = = DDiiffffeerreennccee bbeettwweeeenn TGA TGA tteemmppeerraattuurree a--nAdvmeerlatginegptreomcpeesrsaitnugret.emperature. All information is given in good faith but without guarantee. EEt St EsE 4E , -- o dp oet rfee my Guide to the Safe Handingof Fucopolymer Resins, Tid Eon Page 86 Copyright 1992, 1995.1998 TheSocofithe ePlatstiycs Industry, Inc.,All Rights Reserved. 95 SE wyi APPENDIX B . THERMAL PROPERTIES THERMAL PERFORMANCE OF SOLVAY SOLEF PVDF FLUOROPOLYMER RESINS Weight Lossof Fluoropolymer Resin: Dynamic Thermal Gravimetry Analysis Conditions: Material: Solvay Solef PVDF Fluoropolymer Resins Atmosphere: air Melting pot in Pt - area: 0.4 cm? Load Sample: 10mg. Output: 60 ml/min Form: tray Form: pellets Temperatugg Profile: initial temperature: 30C (86F) . linear heating rate: 8C/min (46F/min) or | Tween | skoivneroepsazruhnangos2 165% 0367) Hee o----oc | S(C4o4m6meFm)eont:s10mg *wor mBcllEm wm|mE wB<m % [6s |W HEB |r | SsoLteree 32r008e100'08e65e% 33n6%)s 6o|9S4 | mE 368| 390 mmEm 199| 280 oe138 | Com (446F) ant 10mg LAgpondencs wn ---- - T1 = Difference between TGA temperature and melting temperature. T2 = Difference between TGA temperature -- Average processing temperature. All information is given in good faith but without guarantee. fE rm rninoC a T ey eS,g LmP 5 e E s m AAeS `CopyGriugihtde199t2o,t1h9e95S,a1f9e98HaTnhdelSioncigetoyfoFf lthueorPloapstoilcsymInedrustRrey,siinncs.,, ATlhliRrigdhtEsdiRtesieornved. 9H Page 87 | ---- APPENDIX 8 THERMAL PROPERTIES ham tohebootorf boGee temseiecdsfrCoolneosSiofdtbt ia edo cnpn. imn acieenrcteo.nHootwecrs,d Fe4rd0SkeeoyeAednvisedoe Ffoatrwtse, etSteyeyoE fes n ckitty Page 88 `CopyrGiugihtd1e96t2o,t1h9e95S,a1f9e98HTahnedSoicnigetyofofFlthue oPlraosptoilcsymInedrusRtreys.iIncs.,.AlTlhiRrigdhtEsdRietsieornved. r APPENDIX B THERMAL PROPERTIES = 2 5 gs 22 Jof &8 $= 1i2 :i ga Fgis- i! 33 u2e3 | = 1 g 7. 8 : 2 . 3 - Ton Ea 5 of 38 | Lf 8 sf88 3% TT I % = in 2.58 g 8 8 8 8 5 5 & &g i1224345 x urn 28 { ; E ee tyeta GoaS tiT e nessod.3 Fo o0tash. ssmo-- meWisn--oo b--ed-- k ] Guttoter Sto Handingof Fcrcpoymer Resin, Thi Eton Copyright1992, 1995, 1998TheSocietyofthePlasticsIndustry, Inc...AllRights Reserved. Page 89 I 7 _ I oo APPENDIX B THERMAL PROPERTIES = g vesant te. 31 B=g 5s 3 2 2 5 8- 8 5 FFoEB =3 | 258 ES = nz od := gseizst BBiEgL g2s52 fs 82 t : : 8 g ic 238 2 &4% 3:5 23 gs Elo. st a Page 90 ofoo iSpa a Eo A i 50a. e-- A Sier Seam Why Guide to the Safe Handing of Fluoropolymer Resins, Third Editon `Copyright 1992, 1995, 19 TheS9 oci8 ety of the Plastics Industry. Inc., All Rights Reserved. ul I a _ ! | APPENDIXB i i ! | THERMAL PROPERTIES PY of atzs =is3 2 g= 8 uf ie B 23 z agfcld | | =i } gE", : : - : : 2 if 3 - iy |e =i - gg58 LI= # 35% s os a = a I a Fv Tes i g 8 8 8 8 5 5 8 85 57e3%83 x aw stan a B m e S r T STT,A ---- SS `CopyrGiughitde199t2o,t1h9e95S,a1f99e8HTahnedSloicnigetoyfofFtlhueoPrlaosptoiclsymInedrustRrey,siInncs..,ATlhRiirgdhtEsdRietsieornved. Page 91 || 78 APPENDIX B THERMAL PROPERTIES 5 g Wesgne ve. x) F g d3f jd : B-z8 58 =2 2= 88 8& 88 82 3 FFiElEs ~2 = sed B Br | E o 7 os " 8 . & 3 g gs 3 sap sPrs ald EK 4 i88 i] EX 5 et at " = 2 a gE 2 T e oh Betemo ioo cmsn driio scmc.oHI roesntC Fo oobytAoE b IofBbeyoesyosA sor yihStei soress Oo PAB92 ConyGnuainde165t2o.th1e99S.a1f0e0HaThndSioncgoafoFnuecrPoapsailymedrueRe,siInns.,AThiRrd EdtRietisoasn 21 -- __ _ " APPENDIXB THERMAL PROPERTIES : iB ! - - - ii 3 a [a 8 3 2: 8=5 fH223 fs > 5 88%2 =5 i 3 i 88& 27g $ "iEf EE[4a S5g2ir nr sz g2& 23% ws 8 CaM) 3ubTeN 53 55 i sk =o if .2 8 83 i fT r oo tema sen ndoe moceinn.oNs e e odseoybat tSsr.a t 2 mth asawi s 7bee2e CoGmupiad95o.6t8h.e165S8ate HaTnodiSng oofoFloouoPronpsolymerrRye.sins,AThigrdsEdiRtoiosnes Page 93 lov J aI a APPENDIX B THERMAL PROPERTIES i]_ Mesone (ve. 1 Bgigsr;e Bg5 or oz oz os 2 0s os FB td %3 gE S25. i gs] | && [ = n= #8 Ed = Sa z = 55 = : 8 s Py] zsizz28% i 888 58=8 338 Bo Ee Be EE = - EI Te E eta tme ss e oe sR te,Yor seLbysetedr .wAy3 IT ateweE yyms Page 94 Guido tothe Safe Handingof Fluropolymer Resin, Tic Editon Copyright 1992, 1995, 1998TheSocietyofthePlastics Industry, Inc.. All Rights Reserved. a I Iol } . 1 i: APPENDIX B. - THERMAL PROPERTIES : i -iBion i i ef= ed- joi f 2a - 8a2z =iz 58 fs g28 i2e3 ms =3 yiue 5 8, 1 :z: :. .i 38 - =3o ifs of 55B8i%r 3or 5: 3 5 3 8 i&z feds g 8 8 8 8 5 5 Er 5s2i3:8k ew ween 2, # o plisteu tebevcyre cJ t, Howe se Ae eyArdaye Tr eor mne eteseoet ts Sern Guidetothe Safe HanofdFluioopnolygmer Resins, Third Edition j Copyright 1992, 1995, 1398TheSocietyofthePlasticsIndustry, Inc., AYRightsReserved. Page 95 | 162 APPENDIX B = 8 B52 5 = = =5 || i or | Tz oe $ g gs | LR wm aE Ef Wotan no 30 sg 8 3 THERMAL PROPERTIES 8 g58l% =: gsegz:t gf. i5=}. S47: :5 8 a TAte ISeio I o LSRoyo m5Bntnh i sb PAGE 96 CosyGruginde15t2o t1h5e85.Sa1f9e9HTaonedSinagoraFuhorPopsoltymneirtR.esinncs.,AThihrdsEdRioansa - 02 _ _ APPENDIX B THERMAL PROPERTIES 8# : Weighs te. x) wBreoosfoxos oo F4 oro2sg FB Sgg2gi5g ?3 g B BogsFi2t " 8=E;I 2g,e,3s i. 3S - z I i : gt -~ |; | B13F & oo Br & 8s 5 if FoF3= 8 SS S m LeeSE r STEn re rt et y CSu8ds1to5h Safe HoandSa ing of Eurcpoymr ResiA n, ToL ra EatE in Page 97 0H -- APPENDIX B THERMAL PROPERTIES Page 98 i i| 10S i I APPENDIX C - TRADE NAME CROSS REFERENCES FLUQORQPOLYMER ECTFE ETFE - FEP MFA PCTFE PFA MATERIAL SUPPLIER 'AUSIMONT USA, INC. AGA CHEMICALS, INC. AUSIMONT USA, INC DAIKIN AMERICA, INC. DUPONT FLUOROPRODUCTS 'DAIKIN AMERICA, INC. DUPONT FLUOROPRODUCTS AUSIMONT USA, INC. ALLIED SIGNAL DAIKIN AMERICA, INC. 3M AGA CHEMICALS, INC. AUSIMONT USA, INC. DAIKIN AMERICA, INC. `DUPONT FLUOROPRODUCTS DYNEON LLC TRADE NAME "HALAR" "AFLON" COP "HALON ET" "HYFLON" "NEOFLON" | "TEFZEL" "NEOFLON" "TEFLON" "HYFLON" "ACLON" "NEOFLONTM "KEL F* "AFLON" PFA "HYFLONTM "NEOFLON" "TEFLON" "HOSTAFLON" Cop 1 Guidet the tSaSfe Handionfg oPfFiluoropolymer RAesiRnisbs Rese ------------ 06 TE---------------- Page 99 -- APPENDIX C PTFE TRADE NAME CROSS REFERENCES DAAUIKSIINMOAMNETRUISCAA,,IINNCC.. DUPONT FLUOROPRODUCTS "DAIKIN"-APLOGLOYFFLLOONN"" "TEFLON" ICI FLDUYONREOOPNOLLLYCMERS "HOST"AFFLLUOONN"" PVDF DAAUISKIINMOANMTERUISCAA,,IINNCC.. ELF ATOCHEM NORTH AMERICA, INC. "NE"OHFYLLOANR" "KYNAR SOLVAY ADVANCED POLYMERS, INC. "FOR"ASFOLLOENR"" THY - DYNEON LLC 000 "DYNEON" Fluoropolymer Coating Materials fSoereatlhisetFoPfDflFulruooproalpyomlyemrecroaCtoiantgintrgasdeGlnoasmseasr,y (SPL publication BP-104) orwwwcustomeoaters.org PAGE 100 conpig 95G2u,i1d9e91,1t9h9eTSeaSHeayndoinfgoPflsuornopsolymer Rmesinss Rese 107 ii a APPENDIX D INHALATION TOXICITY A numberofstudies have been conducted overthe past two decades to investigate the toxicityofthe pcroomdbuucsttsi-oinn/tchleurdmianlg dheygdrraodgaetinofnluporroidduecatsndofcaPrTbFoEn.yl Pfrliuoorritdoe 1-9w82e,reitrweasspobnesliibelveefdorthtahtetthoexmicajeoffrects on rats exposed to the evolved combustion products of PTFE (a toxicity approximately 10 times greater than the combustion productsofwood). However, in 1982, Levin, et al., using a newly developed National Bureau of Standards (NBS) small-scale test method for assessing the toxicology ofcombustion products, reported an unexpectedly high toxicity when testing PTFE. They found an LCy, of 0.045 mg/l for PTFE products, compared to 20-40 mg/l foar standard sampleofwood (Douglas fir). This unexpected result, which could not be explained in termsofthe expected combustion productssed to extensive investigation by a number of laboratories. - S1e9v9e0r;aCllraervkie,ewvsoafntKhueijske,settuad.i.es1w9e9r0;e Cplraerskeen,teSdeaitdetlh,eetInatl.er1f9l9a0m).`9T0ocgoentfheerrenwcieth(Pruercseenrt p1u9b9l0i;caFatridoenlsl (Warheit et al. 1990, Lee and Seidel 1991), an interesting explanation for the extreme toxicity easmseorcgieast.ed exclusively with thermal degradation productsofPTFE or similar perfluoropolymers In brief, there are a few critical parameters essential for expressionof extreme toxicity. Thermal degradation must occur under nonflaming conditions. Experimental design must allow for the recirculationofevolved fume through the combustion area, as in the NBS apparatus, or for rapid exposure to freshly generated fumes, as described by Warheit et al. (1990). `The particulate phaseofthe degradation products is clearly responsible, specifically with regard to the sizeofthe particles evolved. When fumes are generated ina temperature rangeof 450 to 800C (840 to 1,470F), the particles generatedare extremely fine, typically less than 0.05 microns. In an apparatus such as the NBS chamber, the particles will be confined to a relatively small volume. `They will rapidly undergo thermal coagulation, producing fume particlesofgreater size and lower number concentration that will spread throughout the 200-liter exposure chamber. As they recirculate through the furnace, they may undergo deaggregation and dispersal, stabilizing at the ultrafine particle size and producing extreme toxicity. In a dynamic system, such as that described by Warheit et al. (1990),ifexposure is effected before coagulation occurs, extreme toxicity is also `seen; butif coagulation is allowed to occur initially, the toxicity is reduced considerably. It has been suggested that the specific requirement for fresh or recycled fume to induce extreme toxicity may also be related to free radical production during pyrolysis. Indeed, relatively stable railtkiyclafllufoarctoopreraopxpyearrasditcoalbseatrheerseipzoerotfetdhteo hpaarvteicbleesenwhdeetnecitnehdal(eFda.rdeTlhlis19d9i0c)t.ateNsotnheethperloepsosr,titohne tmhoastt Guide to he Safe HandingofFloropalymer Resins i `Copyright 1992, 1995, 1998TheSocietyofth PlasticsIndustry,Inc. AllRightsReserved. Page 101 i1 108 APPENDIX D INHALATION TOXICITY wiinltlerdaecptoisoniotfitnhtehepaarltviecollearwirtehgitohne,ewphiethreelidalamcealglse. isThseeerne,ibsuitncproesassiibnlgyeevviednenmcoerethiatmpuolrtrtaafnitn,e:the ptairttainciluemsodfisoixzidees,laerses stuhbasntaanptpiraollxyimmaotreelyto0x.i0c5tmoitchreolnusnogftehvaennlhariggehrlypairnteirctlemsat(eOrbiearldso,rsstuecrh,aest al 1990) due to direct penetration into or reaction with the epithelial cells. The extreme toxicity of PTFE pyrolysis products is consistent with this picture. TPhTeFEtoxdiucietytoofdiPreTcFtEexptyrraoploylsaitsioins tionfrleuale,nclianrgged-escciaslieofnisrebsycerneagurliaotsowrsheornemhaunmyanpostemnatiyalbeuseexspoofsed to cthoamtbeuxsttrieomneptrooxdiuccittsy.haHsowbeevenerd,emcoanusttiornatmeudshtabsebeexeenrcuinsdeedricnlsosueclhyecxotnrtarpoolllaetdioenxsp.erTihmeenotnally time conditions. Althoughsuck conditions could possibly be reproduced in a real fire, other factors must also be considered. F`inrusmt,beerxpoefrsitmuedniteaslosntumdiixesedhamvateesrihaolwsn--efffeocrtesxoanmlpylew,hePnTFusEincgomPbTuFstEeodrwfiltuhorwoopoodly(mPeurrssearlo1ne9.90)A-- d`miidxtnuortepsorofdmuacteereixatlrseamnedtolxaircgietry.smTohkies ipsarmtoicrleesaptphratopmraiaytetetnodrteoalsfciarevse,nwgheiacnhdgdeenteorxailflyyfiinnveoPlvTeFE particles. Sinescuolnadt,edincafbullels-s(cCallearfkier,e vteasntsKuusiin,g aetnalu.mb1e99r0o),fptohteetnotxiiaclitiygnrietpioorntseodurincersatfsoerxppeorsfelduotrootphoelymercmoomnbouxsitdieo,nhpyrdordougcetns fwlausorcidoen,siasntdenctawribtohnytlhaftlueoxrpideec)t.edoThfetrheewparsinncoipilendtiocxaitcioangoefnetsxt(rcearmbeontoxicity. Therefore, contribute it to is more likely in areal fre situation that anyofthe the toxicity by virtue of normally expected thermal fluoropolymers present will degradation products, but will not dominate the toxicity due to productionof extremely toxic products. REFERENCES CG.laJr.keM,aFr.oBv.e,,H.J. vKa.nBKouniejskt,eeRl.,VMa.leJnatnisnsee,nGs., Ta.ndMaC.koHv.eHce,rpWo.l,C.19S9e0i.del",TBh.eBi.nhBaalkaetri,onDt.oxKiacsiptryaozfak, smoke from fires involving perfluoropolymers: Full scale fires." Proceedings of Interflam `90, 287295. Cidleanrtkief,yFa. nBd.,coWa.guCl.atSieoindselo,fVf.luSocrhoeproel,yImre,,r-Dd.erCilivnesd,sAm.oOkleseane,roasonlds.J. Bonesteel, 1990. The relationship "Formation, between aerosol behavior and observed toxicity of fluoropolymer smoke." Proceedings of Interflam `90, 297- 304. Guide tothe Safe HandlingofFluoropolymer Resins Page 102 Copyright 1992, 1995, 199 The Sit ofthe lic nus, In. Al RghsResred 101 a | APPENDIXD . INHALATION TOXICITY Fardell, P., 1990. "UK studiesofthe toxic smoke potential of PTFE in fire." Proceedings of Interflam ;90, 257-271. Laened,tKe.trPa.f,lauonrdoeWt.hylCe.neSehiedexla.fl1u9o9r1o.pr"opPouplymloennaercyorpeoslpyomneseroffurmaetsanedxpiossoeldatteod ppoarltyitceltersa.f"luIonrhoaeltahtyiloenne Toxicology 3, 237-264. i : aOsbe2rdmoordsetelrf,oGr.s,tJu.dFyienrginov,J.erFlionakde-lrsetleaitne,dS.meScohdaenrihsomlsm.,"aJndAeRr.oGseolleiMne,d.1939,0.79,"Ultrafine TiO, particles Pduergsreard,atDi.oAn.pr1o9d9u0c.ts"."RecPernoctedeedvienlgsoopmfeInnttserifnluanmd`e9r0s,ta2n7d3i-n2g8o6f.the toxicity ofPTFE thermal }1 `Wpaerrhfeliuto,rDo.polB.,ymWer.f&umeSepiudellm,oMna.rCy. toCxaircaitkyo:stEafsf,ecatnsdoMf.fiHlaterrtss,kcyo,mb1u99s0t.io"nAmtetetnhuoadtsioanndofaerosol age." Exp. Mol. Path. 52,309-329. i Cop Guide 019th8eTSoafeS Handloifngn ofiFsluoropolymer RAesRinsSRese no :SU Page 103 Cg TN NT The Society of the Plastics Industry, Inc. [LTT I TY TTT Washington, DC 20006-1301 202.974.5200