Document 6bvVGGJdNBbx0MQ7e1X6gQXL6

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENT5 DEPARTMENT 256 YANDERPOOL STREET NEWARK. NEW JERSEY Serial Ho. KN-50-11 Copy No. X f NEWARK PLANT PICMENT COLOR RESEARCH REPORT f ' A NEW PHASE "NAPHTHANIL" PIGMENT PROM PCONA-* NOL (RT-S66-D) Period Covered: 1945 " 1950 FILE: J.ZL/ DATE-. 8/4/50 NJ0370 mm nt striaa h o . mmm Cw Bo* i mmtfivr pt .a w MOlUHf GOIiOH RESEARCH RBP0B3P Waal Rope*t mittt 4 HEW Ml *HAPESEAH1X#* PICKEST mm p o o k a * h o l <b t *s 8*d ) Porlod Covrdt 1940 * 1989 mmmt u o i*u h o BY I IlfR9V10 BX | CZSr* DAfB SUBBIl JHI* 18. 1950 MfB ISSBBBl 8/4/50 DUP050068103 la 3.945 it waa bbaarwad by th wMm that it fOSSA* 90I waa yottoiod ia^lorofP*a ratharapdlan and aiagkad golwohiiigi Sscr1 wHlPSp*#?P'^- af. .s5Rh5?Sa5r"t tbit aVufct|: SrbyaSay diffraction voocwdo* y w t ^bTw t PW 'w IjPtP%i^impP# :id_ by wyatal aaading : <*f fch* "Msii f a &Ofl)&X*&$HMI Salaa Dlfiifta. o_a_h_ibitod __ 4iVi \ 3(Ppijtw*p`w^pp..j.tP...:r.4.P..Wa CKUr^yW9F 49 iw9 ,:"!' 1 tw atillphd tlfty pyodsuit# -tljit bt * shat# fin bt * lad tbt will b rafan-ad bt at thi it li tiUMM that mm rnm pbaao js*odaot &jm*. tmmmUm of aattas** Hit proaeta far it it jt 'ptaiatbaaiMB^b ta what to baa* a patent appliaatiaa it t? i, o;^rsnt; ^r^gas sr4ssv,ssw*1"' &*** A ratio ot W ml oblorofora yttVtMfltSp oTmat^wiU jlgg ilSPnotlaUow0o^^*Ialoi. A **U of 80 ^ ^***fc** S** 0*40 DUP050068104 8* fhe two steps of solvent treatment and salt milling oaf to ocabined in a single operation wherein the pigment is dispersion allied* A satisfactory mil sbarge consists of 580 9m sodium ohlorids. 55 grams pigment* sad 7 grama chloroform* She action of the mining operation contributes to the pbasa transformation sinee much less solvent is required in dispersion Milling than if tie solvent treatment is given first* followed with salt Milling* 4* Straight salt yflitwg also effeots s o ms chase converslon* 5* Chlorinated solvents with seme exceptions offset a phase transformation* 8* The estlasted alll ooats starting with finished 5fii5*$ using a dispersion ailUng Method described later is #5*50/lb* is cowed fa a mamorandum bp 8* 1* Perkins 8/84/50 Flla 881* ?* The beta pbasa plpent bas tip neeessary transparency to yield attractive metallised finishes* iS^ocapipcuJo^^ei^p^pMiie,!** RS*566-D, it is far yellower in aasstons* ,.m XfcJlux* and in a MMa* Modified alkyd enamel* It is slightly on the defensive in dtarability by weatherometor exposure teste* and slightly on the defensive in reactivity by viscosity asasuremts* If 8M55* (POOHA a 501,) is allowed to reflux la fora for a few minutes and if the ratio of chloroform to pigasut high enough, a narked yellowing of the pigment is observed* it is Important in effecting this phase transformation by solvent that tha ratio of eolveat to pigment be sufftoiently high* appears to bo a Halting value of this ratio below #iien the formation la unoertala* for example* 66 ah of chloroform for pigment sill alios a rapid transformation during reflux of chloroform for 0*46 grass of pigment win show ao apparont during reflux* Solvents other than chloroform else oauae a An exhaustive list of solvents has not boon obtained but that with a few exceptions chlorinated solvents work bast* gives shat information is known to for on the ability of a the to Chloroform frichlorothylene (Trleleae) Ethylene dichlorido Perclone) DUP050068105 figure 1* p*4 shews x*ray psMw oonparieeas of the alpha and beta phases* For PIgw 1A# phase transformation a achieved by refluxing 1*3 gem r t *506*d In 080 ass ohlorofcm for 10 ralnutes. The trimsformed pigment was filtered and dried* It ia believed that very nearly complete phase traruiformat!on has been : achieved* Figure IB* ie the oonventieail alpha phase pcenieiNJW ybe difference in crystal structure between the nev mad eld phis* in quite obvious* Of particular nete is the strong peak at a 0 value of 8?*0 for the beta phase as against a strong peak at lie value of 6*1 for the alpha phase* Also* two prominent peaks at 0^values of 13*2* sad 13*6% for the alpha phase are absent in the beta phase and the beta phase shows two new peaks at 8 values of 14*4% and !.?% : fshle II lists the 0 O values and lnterplanar spacing* ef the dlf"fractio.n....n...t.tw.`fw"s far sash p`hase* Ihf precision of the f ate is wound 6*#* An arbitrary Intercity factor Lven _ from O to 109 to better illustrate the Intensity .. s. Hot too much reliance should be placed m the relative intensities* however* beeanse it is difficult to measure them and the results are sonewhat dependent cn the mounting technique apl< for the sample preparatory tc obtaining a curve* 9hie ie due etal orientation which Is vary difficult to avoid* 03 wi a relative I'ntens"ity of "lees than 6 are not listed* psw II X-RAT 0XFFIUWSIOH OOMJ'AEISOIJ Of fHE TWO PHASES ______ _________ auamam Aim max Bslati mt' 4*13 4*31 14*5810 91 ? ? ll 10 15 S 00 93 3*00 4.06 i:?S 89 y n H tion of Hew fhaee Material m ieai**ei the high ratio of eoJ phase transformation makes the effhit m scale production. It was Cbses * that a li i&ssnt ratio could be tolerated the o a large volume of chloroform* coomapleetteely_ transformed and those new .....,...... would hi crystals would them act as seed to aid in the subsequent phas conversion. fhe DUP050068106 HIFIGORE 1 X-RAY DIFFRACTION RECORDS OF ALPHA AND BETA PHASE PCONAHWOL DUP050068107 batches ware, therefore* made by the stepwise addition of pigment to chloroform. Appendix 1 givea the method usod for tho solvent treatment m & aeml-wwka scale* Ma solvent -treated material la not suitable aa a Mpsul without further processing, because considerable crystal groom mama during solvent exposure* tin product *< fryfimly wne suitable fp use la metallic** It lay therefore* necessary to reduces* .wi ryftyt! (it# tttaa to sowttiiBS eomeMMibio to .v>t. of the o^icinal pigment to attain tha desired propellas* 0* Preparation of Solvent frosted RfS68*D of fo affect a parttola also reduction of this new phase material wet grinding with a 80/8 mixture by volume of math?! alcohol and water was wicdfumt* fhia did not give sufficient petiole alia reduction* homo salt milling waa triad* Salt milling gave sufficient partiole redaction aatnwtalUe* with tha proper "flash* ware obtained* Appendix t gives tha grinding details used to yield an aoceptable product will* a specific surface of 83.7 aq* meter* per gram, as compared to 88*8 at* meters par gram for the original untreated RJ*5S8*D* it waa found possible to combine tha phae* eeawsritem atop through solvent action with the particle also reduction step of call milling in a ainglo operation of dispercion milling, it was further observed that eome phase conversion occurred with foci simple salt milling* which partially explains why phase conversion occur* during dispersion milling at ratios of solvent to pigment far lower than would cause phase conversion during solvent reflux alone* fhe grinding details for dispersion milling given In Appendix 8 arc those used for tmomto&f scale products* in the laboratory dispersion also waa not reduced to the same extent as with straight w*twg 28 gal* seml^works mill* bud; the !w c n i transparent to be satisfactory in sseta&ie*# It is Hie *i* * secular **tea twi!*aii of a **- * w**t #** m>* samples, will result in mors efficient rin&lna ***** ii**.. & bettor reduction in particle else* it was generally observed that the sanUc* the Particle else* the acre transnarent the pigment hence it 1 rather important that the milUng operatic field a particle theft sHe is i mil as possible if one retiree maximum transparency* 4 figure 8 p*6 showo X*ray diffraction records indicating a phase ehangH aid also chows the spooifie surface measurements of the ground products* figure m the alpha phase #as is* 3SN886*!&* figure m Hews tho^a# ii* S8 salt milled* i*o* no solvit added* Hots that sens phase slon has occurred* It is difficult to estimate the extent of conversion because the converted material will have a larger crystallite sice and yield a stronger diffraction peak* and alee iaterferonce of the diffraction maxima of the DUP050068108 FIGURE 2 X-RfiZ DIFFRACTION RECORDS OF MILLED RT-566-D Specific Surface Square Meters/gram A* "As Is" 32*3 B, Salt Milled C, Dispersion Milled with Chloroform D, Dispersion Milled with "Triclene" 14.9 22.4 21,1 DU P050068109 Sven so* it eppears that considerable conversion has taken slats* Figure 0 shews to result of dispersion milling with shierofcra ' ss the solvent and Figaro 2D shows to result with Srisleae* 'll. ail oases phase conversion has occurred, altho it is difficult to say if to 9t*iai is complete, ft. is also of iatareet to m `' to apeoifia surface of to milled product ie actually leas original pliant hat they are still acceptable in metallic* emeieat grinding should increase the apeeifie surface to more nearly oonparable to to original pigment. fhat salt capable of reducing thepartiole alee ia apparent torn to ream already mentioned where salt filing to feetajhase a_ a specific surface of 83*F so* msters/graau, fils ie a toreaee overtof1gure of 32.5 eg* raeters/graa for to eri alpha phase Bf*S60-*B. fhe oatlm&ted millooate ft with finished BfS00*O using dispersion milling in _i 6* diameter n containing 151 to* of plgseat per cl ie #5*50 covered in detail in a memorandum by B* H* Perkins mmmf fRffWHBMt to beta phase product is far yellower in -alpha phaaeproduet* m baked overstripe bleed in : 20/jsleina, it is superior to the alto toss but it classed as a h color* Weatheromet li or and duller to a si' the ial. m reactivity the beta is to alpha phase as oan be seen from to: IIS* ....t be 9mM in sgtowTO tmmiam Adjusted Initial 5 8SIffIX*-KSIAHUE Hading MpSJlSU^ MJi tose (sf*see*i>) Beta Jhase FGGM*S01 83MWHH& 20 32 20 43 22 .. 23 34 02 33 m f? m 38SBSL Alpha Phase PCOE&^GL 4 CBf-see-D) B$lSsjrSoL 21 4 32 20 30 *1 if 22 - 24 u m m l m m 28 si* thin* . v# * no.: imfm. .teahse* no no . * DUP050068110 All Initial viscosities ware tee hlgb fur ford Cup an the viscosities vara pre-adjusted to about the sane value by thinner# it la not valid# therefore* to eeroare initial readings* The results appear sssmdiaA inconsistent* which serves to Illustrate that the time differeneea w p* not great and tbe actual differances will depend to a considerable extent on tbe vehiole* end foe cow aonditiona the new phase may be better in reaotlvtty than the 'did phase* fhe Farlin ou used foe tbe tSsmteat* at one iMm****** iarnffi* eient enamel remained to make e Pond tap needing but it ia valid tb tMe one noMtti reading with *be 7 day Farlin way reading* So ovfcdoer exposure results are available ea yet but an outdoor exposure series is under way and the results will be given in a later report* Samples have also bean sent to F & P* at iaflin and Ph* t*<wiWh<* fa* valuation s t o b s t io h s f o h mrnrnm w o e s So detailed study has been made to establish tho optima conditions for the dispersion milling method* During the 16 hr* grind# very nearly complete phase conversion occurred. Further work my shoo that less grinding effects Just ae complete a eonversion* So etudy was uedo of the solvoat requirement in dispersion milling* Further work; may show that lass solvent than ? grams for S$ grams of HT-866* will give Just as complete phase conversion* Further work may show that the partial# else nedwlbien my be mare effestively achieved by milling in two steps* The first atep in the pretense of a solvent will cause tbs phase conversion# and the second step wilt be milling after evaporation of the solvent Which will allow a rapid reduction in partial# site* Perhaps a balanea of pigaent/solvent oan bo achieved which will allow both rapid phase conversion and sufficiently rapid reduction in particle site to oeour In a single stop* Far this work# finished standard Hf-566-D was uaad* In actual praetioe HT*6g6d> dried pressoake should be suitable* There e houldbe no need to pulverise this* slthe this point was not studied* I. t nay . be possible to eliminate any special treatment given &MHMHI to mm it suitable as a finished pigment* it may be possible te simplify Abe . formula for asking M*$$g*# if It is to be converted to Abe hew phase* This point was not studied* ' Since tho now phaso pigment will present a lower energy level for the crystal lattioe# it is at least thermodynamically sound so suppose that the new phase crystals oan be formed directly in the coupling procedure* Ho work of this sort was dons* Crystal seeding and/ca; the use of solvent present during coupling may allow the direct fcarnation of the. new phase crystal* DUP050068111 9* X Procedure for Phase &smereien of Alpha Phase Chare# the 75 gallon glass Hand Pfaadler reaotor with 178 Xbe# teobnieal grad# chloroform* Addl/8 3b* ||f*SS8*I>* Moat to reflux with aglteatloa# This wilt require about 1*5/4 hours*: Add a seoond 1/2 It* portion of pignisi and after a time Interval of of an boon aid a third inereaanfc of 1/9 lb# nigtaant* After law add a fourth inortrwnt of 3/8 lb** #ig|y^g a 9 lbs* pigment* continue refluxing .for 4 hows* Pistil chloroform* ' faon off hoot and discharge slurry into paste* t i remaining chloroform at room temperature (ventilated hood) anti olaost dry* Transfer to the vacuum dryer {8* 10* vacuum b#at) for overnight drying# Pigment la dry and nooda no aant other than partial# ala# reduction# Procedure for and Finishing Solvent Treated Beta Phase PCQli^Qi fFXa##te#jtfeja Wm 9Sshat p#^*#4#li fUJBtt s9h41U#fl| #|j#t %9aaIaJ%U'tl mSAIU*1 #fnl>8od*hl*l .. mixture of stool balls and rivets. Add 88*1/2 lbs# wen dried hot sodium chloride# Grind briefly to osra up mill* Add t*3/9 lbs# pigment (solvent treated BT566**D)* Orind 78 hours# Bnpty tbs will in tt># ocaveatiooel manner* time approximately 8 .hoars# Remove salt and iron using a wooden barrel equipped with a non corrosive stssm line and mixer* For the solvent, dissolve 18 3bs* concentrated OF hydrochloric aoid in about 88 gals# water contained in the barrel# Add "mill powder*# agitato and host with steam to 800*F# Maintain temperature for about 1 hour# Press using Mo# 888 proas (8 frames}# Press wash with oold water until ohlorids free (13 hrs#}# Dry at 140*F# for 22 hours# It dries to a soft powder# f * Procedure for Planersion Milling and * Phase PCCfHi**goXi 70 Producs beta Phase _ _ a one gallon paint esn with 5885 balls (a mixture of i/8* and 1/8*}# 1800 grams rivets# iso grams dry sodium chloride, 88 grama RfS66*Dt and 7 grams solvent* only two eolventa have been triad so fir# ohloroform and Trie w aI3> TSMP U AOtfiMt# wNI9 CmTJF tt# OJULlfl MWm t 3U|$# % powder in a four liter beaker and extract the salt and iren ta boiling with a hydroehiorte aoid solution made by adding 8 wL trated hydrochloric aoid to 1 liter of water* Afterboiling 1 filter and wash with warm water toil ohlorldo^free* try at it dries to a toft powdar# DUP050068112 *I0 of Bbdstenae of Sow Fbaae FCOSMOL* 9B 1132-48 j>*lS4f 159 <Mrfor Solubility of "Saphtbaail ISgjMN*VI***'8 m2-$rp*17i Cryctal Soeding Experiment*.333 1268 p. 51 ' First. lap^ijBont to fpepsro aa6 S'xamina Hew Phase ******** ** * *************##*****$$ 1286 p 9? Hetfcyl noohol/HgO Killing of Hew Fhaas Material* ,HB 1881 p* 143 Methyl Aleobol/HgG Milling of tow Basse Material..*.! 1386-1 p. 26 First S.w. Mai of 0HC1S treatment of iwm-fJGL****! 188$ p* 184 Seoona S#W* Mol of 0S8% freataeat of WOmmot$99m 188$ p* 188 Determining Batio of CHC1* to Pigaont Heeesaary for Conversion*..*$#.....*,*,.*.}& 188$ p* 18$ Aoetooo Mfttmesit of h j q m*o l , NB 1888-8 p. 8i First Laboratory Salt Milling S^erisssat* ********** IB 1336-6 p 88 g 1 1 1 i Sseona Laboratory Salt Mining Ssperimsnt ** , * *,, ,SB 1888-18 p* S*W, salt Milling Eacperipent***************:*.***i$ 1888-12 p. Seeking Solvents that Danse Ffcaee Conversion, *BB 3868-11 p* First msperalm Mining of FCOM-^OL*.*,****,,****.BB XS$8-18p* Cornplete Conversion to' Beta mas# for Furposo Of X-ray*.plffraotio,t Cbaraoterisation****, ****1B 1856-20 p* Evaluation Stagy of Sew mass n^ont******..**MB 1888-17 p* DUP050068113