Document G62ex3D73kJ1pJ332GqgDzDjv

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Copy No. I Numerical File-Librai NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Progress Report Title: LIGHT CHROME YELLOWS: STUDIES ON REACTIVITY, COLOR STABILITY, ETC. Period Covered: Charge: JUNE 1948 - JUNE 1949 ilOO-11-3 U-IC-3) 1100-12-3 FILE. 211.1 DATE: July 15, 1949 N42214 Copy tot #1 HMFIftil llii 2 * Offioo 3 4 H_i_a___s^JKltl * Plant - 5 * B Killian, Hemic 6 t* H* Bensiow, * {tee #9 HM 7 sacra . Stria! He* XH-49-33 Copy He* / HHXAHK PLABT PimSf COLOR RESEARCH REPORT Prograas tepept Titles LIGHT CHROME YBLLOJS* STUDIES OH REACTIVITY, COM STABILITY, ETC. Period Cowrodi m& 1948 * JOHE 1949 CJmrgea* 1100*11*3 U*XC3) 1100-12*3 DATE SOlHXTTHHt AW 27, 1949 HATS ISSUED* July IS, 1949 DUP050067343 ISfKOIXJglglOHt This wpojt son?! W|4t oarrlod out during the period J\me 1946 * June 1949* Ths purpose was to inprow* ear Light Yellows* ir*404*D/t405c 1a rospoot to osrtaia properties la order to ant eemi* tltion, particularly the corresponding dale products 40*535S ina w^eis* &aDoratory war* s u m e-ion w#w* troougnout too M?ioa $ imaihfy t%f y*p^i<'w*nfr.y1[ pgjig btVt btlS m4t 111 Ibi 10 and 10 Buitiding milts* soils latter yopk Is not cowered la detail here alnos it is planned to review it la s separate report* 90s the asst part. attention ass toon focussed on *0010* stability9 (behavior of maastone exhibits on drying)# 1nk consistency snd reactivity. 800s work ass slso carried oat on bake resistance (linoleua point point) s property probably related to solos stability* foxtrotf drying (la Ink) sad certain other properties roo touched m la sa Incidental vsy* Products superior to stsadrod y 408d la all important proportits snd apparently at loast equal to the tost ooapotitive material hats boas made la tho laboratory by batch processes* Erodnot# of good color* strength, lightfastness* bake rsaiatanoa color stability hays boon nado h&tohilgo In tho plant. However* thoy were sotaeshat deficient la rhoologioai proportioa against tbs oatabllshad goals sad too reaotive to be aatlefaotory. Products bats boon aads continuously (in 18 Building) which ware superior to standard bat inferior to ths bsst batsb material and competition partloularly in rsapaot to eelor stability. -An important oanso of tho la tbs ^ p_ reei_pittai tod color llfEbtfaatasssi reducing tbs mount of alma y rat at tho a roanst of tbs othor properties* Ths reactivity ean also bo reduced by adding sodlun phosphate (preferably pyro phosphate) to tho partly neutralised slurry. The loo roastivity in this oast Is frequently aoooroanlsd by slower ink drying which In turn bo partly remedied by tho addition of a seoond portion of load nltrato* A relatively loo final pB is also desirable. ia*s. *oolnnfJskl&Uuesosh noaoonssadMdb'bitasya'snvwasadritiovwaunsi**sl0qnki.y^foai^<a*o9fcstnOooay-r^aisfdtt 'FOoa4*fft |ywnghJ!>icwh is mom aortoua with - ` ` feature than with batsb sanufaoturo. The relatilvoet ly poor toxturo of continuously manufactured yellows is probably duo in part at loast to tbs sane factor* Further details art presented in ths body of this report. Tho yellows^ discussed In this roport are treated according to tbs prooodroo spoolflod la our B8 latent 8,818,917 (3*0.Horning?* in oro opinion- none of tbs information developed In tbo present study is of a patentable nature* DUP050067344 #0# mmm. . Since the m#T>aration of tiita roBorfe. eatnh&sls t* %**> shifted to the development of batch products equal to the boat competition bat with special attention to the properties discussed below. The immediate program comprises additional laboratory work along with batch fsa la the plant (Y*S12*D typo) using variables shioh appear likely to give the desired results# A Halted amount of work will be carried out in the soal*worka continuous unit, chiefly to be of assistance to the Hast Quality and control Irenn la their concurrent study of the ease ge neral prOblea la is Building* Policing the work ea the Y*408*B etude# it ia planned to continue with the lifter product# Y404*B# It ie hoped that the work on Y*40S*B nay aaka this latter a relatively minor problem* WSAWm JUIOBgi la 145# ow current tandard (as of that date# batch material) ea Y*40S*B was teasteod ia B-108 and alkyd against four sas`aham*i; p"le` s of Oaleo'a 40*31B# standard ef Y*404*D Similar against testa were mm two samples of on a temporary Oaleo*s 40*335< included also were samples of improved products made in the semi-works by batChprocedures* namely, MW (Y-404-B type) and K-2024 (MN4 type)* The following results were obtained* la slightly superior to Y-4G4-B la eolor by ...... _ Jit* the superiority la lose marked la alkyd# Xdghtfastneee is better ia both vehloles* compared to MW It 1 approximately equal on fresh H*108 40*3613 ia 1*103 rnibout varies la asaastone oolor Wmmmk to tvs light agaiast Y*405-Bf two of four samples darkened ea drying# Lightfastness was slightly t.o....d.. efinite..l.y, be..t.t..e..rr#* Colaor Hi alkyd wan qpuiittae close to Y~4066**fB># Xdghtfastnesa wmas vs te better# fa H-108, the Cdoo samples war ddkbaesPf^hMdhtdjboa, eew'^^sHB^fptb^BbltiieilgddpiMehdeSfBet-tjlylf. I^wnbifijSAtNMMiBavbet^ldalWKlPbywae 'Hdabiagi asBienewsr^ltvt## *20t#R8*WB4wjaK*,#Smpb^ueiWt^BP: dark ia alkyd* Mghtfastneas (compared with 1*2024) wae slightly worse to worse la iW and definitely worse in alkyd#* Ite was eoncluded that while the Caleo products showed Msofmlfeeansl*u1preiiriinohritym|teItaHil i#em,e4Cxietln**g<sta*nndla*rads*# they#w<el rei#riiynWfe.. rior to Our present (12 Building) standards ea Y-4Q4-B (lot and Y-4G8HD* (lot 10116) wort Ostablishe..d. early ln_1048, Oh time they wore evaluated against netoonnl:y <o q DUP050067345 stands^ but also against new eanplee of 40-3_35S o_s_s_d 40-361_8# Y-404-B, lot 10115,~vm* close in color to tho old standard but o stronger (93/100) and bottom in lightfastaess# Against 40-3355 It was red in aasstont* os stronger {so/iooj and os better in lt$jtfa#inesa# Y-406-D, lot 10116, was also close in solos to tbs old standard* egad in strength and slightly superior in lightfastncss# Its relationship to 40-3618 was substantially -tbs aano as to tins old standard* tn nhsoloffioal properties* Y*404#S initit, yy infanion to both tho old standard and 40-3355# TJm latter two wsre Quito similar, altho the Caleo /allow gave a very slightly softer ink# ta the ease of Y-40S-D. the differences were wuch loss narked altho hors also tho now standard appeared very slightly heavier than tbs old one# . ffco ilaw standards wore worse in texture than ths old sass bob no worse than aenpatitisa* (Referenda - letter H.A.tf# * P.E.B#2-5-40). 3H connection with a sales problen (Armstrong 6osh) a United amount of work was esrrisd out about a /oar ago with tho object of inprovtag. tho bides resistance of Y-408-B (continuous process uatedall to linoleum print paint# Shis resulted in setting op a special standard# Y-677-!?, based on modifications of the standard continuous presses* y*577*D was considered to bo a satisfactory oouutsr-offering altho inferior in baba resistance to certain batoh products# The problem of result of a complaint by If ] , exhibits of Y40S*B darkened m _ their testing vehicle (Cobalt Drier) iron Calco*o 40-3615# Sifcsequiaitly, it was found that Y-404-5 also darkened warn than its counterpart 40-3355# In both oases, the difference is one of dogrooi darkening occurs with the Oaleo yellows but Is lses marked than with our products# Preliminary work on this problem Indicated Y-S77-D (see above) to bo superior to *465*5 in color stability* however, it wee not as good a* 40*3615 and like Y-408-D was considered to be too reactive to bo generally acceptable* Our so-called Y-S19-D type (lots 57926, 6706$] was apparently satisfactory in stability but was even more reactive) niie*ef* it Involved a batch operation and has, therefore, not boon given serious consideration as a per* maaeat solution to tho problem. The work reviewed shove served to set up fairly definite objectives continuous process light yellows to ` sad reactivity. Obviously, ..............., .............. - -........ without any aignificant sacrifice of other properties such as nasstone . odor# tintine strength or li$itfastness# DUP050067346 While Light Yellow fomulas are all superfioially similar to each other* they differ la eertain point# aom of whioh are lull* oated b alow for products of the Y*40B*B typo, Similar products of the Y-404-B typo are node by ohangiag tlio ohroaate/sulfate ratio* 'Y48SB Typo Process Continuous Ohyoffite/sole Development 106 140/160* 1nw04n 140/800* 109 Boil 109 101 189* 128/140* Wash before treatment So so sea So SO Alua/L Llaucr nor soli 17/8 17/8 88/8 88/8 17/8 Second Lead nitrate Ho SO SO Yso, SO Pinal pH Pinal Treatment 0.0/e.x 8*8/M 8*8/6*0 0*8 Bstronate VimSfwavfmP-JIaf 'sMand*trsfPn TRO 6*8/i4 Cl) Kodifiod K<*1882* Pep related fomulas, too K-^1132, K*208SfK2O84* (2) K*818S* (3) AY-S78*D and m*8789 ehioh art included la the tabulation mm So foefmInutrewreansttibaepcalyusae of Mir high tinting strength* laboratory product i tho v^(tos nnf^Qf isa 18 Building but oat never eeopletely rtwadai*diisod Both ooro developed as offerings against Imperials X<*1899# Analytical data on Y*404*B# Y*408*;d and oortata eenpetitIt * light wallows arO urseentsd in tho toaitio? ith seloatad ' electron microscope photographs. nhiip fair* if &BTi serious rosardina oonaiatanev or reactivity ht*o bean received, up Light Yellows (current 18 Building material) are* as indioatsd above, somewhat on the defensive compared to oonpotitiaa produets of this type# xn the oaao of hatch products4^tadsbhowiiin4)gJbtiHhHertfsboilesmtu icsonwldofeMri,tRsiiMtarget nmgm.tooh8 ftaitdnid ligfiJihMiitiMf$aJ8sdttannAe$sfesfa (MYma*hSln19*J> mft*otJdot|mdwWi f /rAVt'hiOtAnnwiHKdPk>twhd*fh4NodePJd/ffkit|:d0lfNfwaMwdifNdWlwhtttJWdtytPAnt-MMnIrd^lKr*fo68a4J*IfPsVVMIfTHaOf#t satisfactory in ideological J^MMdfvOAsTnfsPostodPtvdfkWyaluKWWdabtPfjnJlslmHPMM# troQjflmVmsisfMvvaWn^wl^l|w^fPoytHorawfwe*a'^oUWmliwXnX>9dinsvdi 9 properties nd in establishing variables by idiloh they oan ho controlled* DUP050Q67347  * Reducing th amount of aim used peso EroaoblVElby* but there la a corresponding deterioration la pjaopaiatlaa and lightfastness, while some reduotioa may b possiblei'* it la ques- tionable if tha earn ba reduced below that now used in Y**408*D. Sha introduction f phosphate into the formulation likewise gives a bat with dio?lftitd *f #**nSo.y usually with fw 4ftyyeqffo igi l"o" j"c d* rying tin*'' lb has -b a a s f-o und* that the level phosphate f ie allgddhetfda, atthneeabsesivdat*a'J*jjaWiMrAawjisMiw'flwuw^MlamiadMyre^it lvyVwIj|-mwai.MHthjwhwt*P*hafMWpBloBwaih#naWats. taife pfttMiigldfl!wiwbKS|KhBr> iwcBajHhaiwigMF^tqhMh4eltataPMSi0mi f soda aah (precipitation f hydrous oxides and pH adjustment) prior t adding tha phosphate. l&en don* :1m this way* tha deteriorationiS Tra^wl5^ a wfiifymMt Attempts to add phosphate with tha >iw 1* tiiMfcilla1*r iffeaw t>i* *1 wi mnA WfM rAnnevn %*m*m tAm reiulta. Apparently satisfactory results ware obtained la tha ,4wwwuy wiife by set tha sods aah at th ialat of tha last wat of tha yf^fida >S i^feyaSiintg ah phosphate a a opposite aid of th s u b wat* fh phosphate was addad la a pro^iormtaod aad th soda aah flow adjusted to give tha desired pH. ft t appears lass harmful to lightfastaess thaa orthophosphate and has been used ta .aa| f th plant stadias* However* prodnots of good quality haw ba and la th laboratory with orthophosphate* Previous work a light Yellows (Reference KH4429} has ahosa osrtala advantages la ths "second lead* typs of formula* ! adding laad nitrate after ths lmp idquor before final preoipita* tlon sad adjuatmat with soda a^k Apparently* this has littla or a float a raaotiTity but whaa phoaphata is also praaant* It appeara at laaat partially t remedy th slow isdc drying resulting from ths prsssaos of th* latter* Consistency Is aflostid by th pB t Whloh ths slurry is flaally adjusted. A low pi glwos lowor Initial oonsiatenoy but there are indications that produets so mads tend to body *%#irapldly in rtaotiw wahlol systmus thaa thoao uhloh ar aad at a higher ps* lb low pB produota art also slower in lab drying. f work bw boon dob with materials added th alurry or dry blended In tha pulveriser 'tflmt bottar^ lnke oonsiatenoy or lower roaotivlty might b attained* loads wort developed. (Beferanoe SB 1145). It Is kaoaa that w* praaant Y*408*B la inferior to ths prowious standard la tosturo. Apparently, ths dsflolonoy la aot oonnaotad with drrimt (to Buildinai *>i samples wore aUbatantlwly aoual to wat oontrola dried at 14C Sa the laboratory. Yeats la laboratory samples containing various amounts of incompletely developed material indicated tha latter to ba an important possible source of wdg grit* DUP050067348 Hi Tltw of o\* limited background on "color stability, considerable feint mo spent in a study of the **>0 t attempts to develop a satisfactory proeednm for evaluating it* tho feoan refers to resistance feo "after-darkening* in eoi vehicles* that it a change la color of masatom exhibit* drying* Uy jjita*b*eMa*nermaAw*!kfcW4 at VawtstkPwa2w&tidSaa2%*a fXttwSaKisSts Mp*'fti'*Mpimwuaa<iiiiiaahjft MIA M*fft;*whpkftflc rGvi'oi,3i^Wj^te8ral#i Yellow apparently darken feo some dogma even if no added drier to mfe oeand differences beattwmeeen pigments naay shew up in * ' of Mtheif type* m geneerraall# however* they are raatthheexr possibly inaigaifioanfe* when driers am addedj the Ink ehowe en tfyiMjtd.lete change in color yy< the change...... " ae the exhibit dries* the ohemotor degree of change the type of drier at shown by the readings of containing drier against a control ink v* drier* Lead A jm Cobalt M re grn ve/a dark* re grn Dry we dark*vs md vs daik, a red dark With.l&e &.? ssr.siir^,.8i^i is ss^i*** incidentally takee plate throughout the film* l roughly proportion al to the mount of drier present* The darkening on drying nay* of Bcomur-sBeP*i bvmo amf.f*ewcctbewdu nmomt B*y by the drier but alee by the pi need* the varnish or other mpmalf of the syefeen* For an ink forwalated to giro Olow drying win ordinarily darl__ Mae mo which dries rapidly* She relation between any two : bo quite different in different vehicles end the exact o depend on tho ago of the exhibit* The eideloor change can bo aeoel<orated bj a mild _ at 140*F# 1ho change in.. OOlOr IP* PM*WB*B| coverings, efee* on baking ia prcfcUbly bInasically the ae tfey after gf lake.* The neohmien of tho change ie not known but the mil teh color suggests that It involves a reduction of luneevalesife ohromlume fieoIfterelvalent` *>~****m- Cchalfe *ia in*:m*-** t-o- b e.af felon of the vahieneriaafeim* Acco should bo oodatod pigment a irfaoo o*g* hydrous oxide treatment) so that'the available fToerr moi o--t-:--- with the vehicle is meet fredeet* relatively large partiele else (docmaeod area In contact with the ) selhould be acre stable than those of extremely emit particle alee# This seme generally true* Of DUP050067349 Which. have been examined, 1-202-D {very small particle also) was ADA WOrat, 1-488-D and Y-31S-X> (because of effective surface coatlug?) showed oaly slight darkening. 1-065-139 end Y-800-D vertverse than 1-469-. Experimental camples containing undeveloped material have invariably shown bad darkening, The color change mama In the dark as noli <ui in the li$it j la the latter ease* the total' coles* change is of course greater. Tbs phenomenon is difficult to evaluate quantitatively* The most satisfactory procedure comprises rubbing out ia a suitable o@bi.ele. drawing down ea metal and ^baking** a portion of the exhibit at sa* 140*F overnight. A comparison of eat end dry readings fur nishes a measure of the darkening. Various vehicles have been needs the most satisfactory was a testing varnish containing cobalt drier. W-l-A obtained from outside the Company* The Change alee Show* m clearly on the masked portions of exposed Fadeombter esdiibits pre sumably as a result of the mild baking (llO^P) durlnr exposure* Attempta to measure the change spaotrophotcasetrically . factora,gjfrewvwwmm PnfiwrVia yetWai inyn9a<Q*> r-UTteOnHy4pijedlijtto Aw$*e*dfie 4vdn 9t wm rWiitifl#n j*lawiB*a9it int r8ugIaI 9j*3*t PP-Vte-fwa-mwe **11* *db9*t94*949*u especially the rapid change wprwi]ikHsMttti^ft#Qng db)utifnf afA&<SwfleO41%Xt4vt t shortly after The laboratory study of variables was based for the most part on a batch process similar to the current Continuous) Y-405-B process* It involved a dump strike of a ohromatc/sulfate/salt solu tion into lead nitrate, the two solutions being adjusted to give a slow fi of about 4.7* Development was than effected by heating in 19 minutes to 180* cad holding for 10 minutes at this temperature. The hydrous oxide treatment employed the quantities of alum and & biquw {17 and 9 lbs./mole.respectively) used in the standard fe* followed by enough soda ash to give a pH of 5.7. m a number of series pyrophosphate or ortho phosphate was need la order to obtain better rheological properties (See section above on Consistency,eto) The material given by the above procedure is usually lighter {sl.lt*/lt.) in masst<me batter ia lightfastness and cone siderably bettor in color stability than standard Y-4QS-D when sl*red after baking at 145P and sl.better la lightfastness. The superiority of Worn laboratory material oowparedwith plant production is apparently chiefly the result of acre complete development* in foot. It was possible to approximate the color, Ughtfaetness and stability of standard l-tos-D fairly closely by removing ea 89% orthe slwry after the strike* holding it at room temperature mod adefma' it to who *--* nortlon after *ai.** **f the heat development* The importance of proper development 1st * pact to color stability hea bean indicated in other experiments, variables known to favor development giving better stability* DUP050067350 J)|8ttXtS Of g 9Xf9 fflVfrSVfltVd Hiow* Ihey are concerned with laboratory studiee tm tho most part but plant work la included when relevant* m such of the early work, the formula outlined above, Involving batch (and, . therefore, presumably complete) development, was used and as a ' result the effect of certain variables m stability may bave been masked* In wap $$$# recent experiments, tbe modified faj^n^fiiwiio MUmiASeMoiii#usetCdwHL,efPa m*gma% t'Vi39fwI_^saa*.0j,L gwbdfo*foeAl^aldaieniMiMghatMoadbu'iMtheaaiBege^1^ McisWeMaSea iMWM>e9k^^rdaf OiilQj3l) <TCwr bUf mmmm part m p*eeedares involving the uso of phoaphabe, 1* mo effect of certain anionic and cationic impwi*., bios in mo raw materials was investigated* 3* general , crystal load nitrate was used* mis . usually 'wWJ**i^v"ewWs s**li'g^h*t^ly^*b8ewttwe*mrr. nualiwt.vj^- tfoie* y*i*r>fr. iw>t**m*i*l**u^fw*i> ******F<*ps*rH|BM*j**. , 9mm smiles of the latter bave been satisfactory* Metallic iaiptapi* ties (copper, iron, biemoth) in snail mounts <> 0*005$) ae con* taainants of tbs lead nitrate bave m adverse effect on color but l^it-t- ^~l- mei f* uni eft-VfIf*e* *c>dt I.o**na iS&oJC olor sJimtadbdbh*k*iuli,ai*t!Mykaa*i& VaS,*fcpa*Neace^^tMr*og***rwa^*ph**io**J&teJsjt^ts *s^*hi*o*v,-ie,**dJhno - W^IJHSuErwjSviXy mX^wyLaT^iliiOmaly QJUbATww W*10W VwwlHIfMi WmSt VWJlCIftir dp p ClmNwlnwqSw manufacture os? Calee wallows esnout that the lest bw w m mm* t^ea^*WiFa*meamFd maaseslusi *ianpme wsoomv fewha*ft moreee than tc*r^fa^^cweevr ^ammppoo^uwen*i^vt*wsq,* i*dnewe eAagrp^mjpwmsienvsdieeljnxej,)q*i , t Nitrite in meant* greater than oa* 1*0$ (lb(S%| on fb(N0)) has a decidedly adverse effect on the color (chi initial color) of laboratory batches* It can be eliminated by adding sulfaado acM to the alum solution* Urea was less ,, in a single laboratory trial* In the omi*werk* and plant (one moot each, continuous procedure) aulfaaio acid gave no ` ties* A single laboratory series indicated vanadium .. of chromate liquor) to have little effect on color t* SiM current praetloe of striking at a relativ^ temperature (8Q*P) gives batter results (odor, Xightfaatnees] striking at nil elevated temperature oven though, the total d ' time wad final development temperature are the eme* it is that m oven loser strike tenreratisri might be desirable) able evidence bis net given a definite answer to thie qaei character* (Soe electron microscope phetegrapha In mpendln)* Bliroersed in a vehicle they are dark end green, poor iii Oder stability, pom in llghtfaatzuiss end peer in texture* As the do* velopmeat taperatm*s is increased (strike te8g>erature conetent) redder mi more Intense products (l*o* y-dOg^D typo) of better stability adl lightfastness are obtained* lbs Improvements in color arc accompanied by some lose in strength* iho greatest change occurs / DUP050067351 *4 *10* between W*f end oa* 1S0F j above this temperature Hi* effect, while pretest# is less marked* In tbs laboratory. 180F Ms given products of good quality! developing to 200P gave little or so iww sy^rovseeset xiae os' aevsiopmens sppesvi so save the emoted effect but it bos sot been studied is detail# As would be expected, products developed to a low temperature are similar is color am limtfasbases to those is which a portion of me slurry has been held out mile me rmaiader is developed to the standard temperature. As indicated move# mis latter two been uood is me laboratory to approximate IS Build* im quality sore oloaely mas is' possible by simply developing to ISO*'## the standard plant tenperatare# (See electron mieroseop photographs is appendix.} 4 She standard strike procodur involves reacting a, relatively acid lead solution with as alkaline ehremabe/euifabe/ salt solution, the resultlag slurry having a pH of oa* 4*7* sen the laboratory, this was accomplished by adjusting the lead sols** ties to pH 4*1*4*8, If necessary, ssd the chrome to pH 9#8 a&d men adding a pre*determinal weight of oaustlo based on experience* ihis gave good reproducibility (in strife pH) ssd is bolievod a mere satisfactory procedure than attempting to make any pH adjustment above 9*8# Any desired strifes .pH can be Obtained by varying the quantity of oaustlo* It is, of course* possible to adjust the lead to a loser pH them 4*1 and oeapensate by ***f**g a -.wore *ui,f^ i>* ohrome solution# she pH of the lead oan also be increased subtly but oare is necessary during adjustment to avoid precipitation of lead hydroxide* neither of these latter modifications in technique appear to offer enagf advantage* .8# She slurry pH after the strike should not be less then about 4$ At pH 4# slightly darker and slightly greener material is Obtained* At pH M the effect is even mors marked and the slurry shoes definite evidence of flocculation (thickening and high '' bulk)# Electron microscope photographs (see appendix) show the final pigment in this ease to comprise material which is more aoioular then that obtained at a higher pH# Differences in strifes pH between 4.6 end 8#8 have relatively little effect! pigments made at me letter appear very slightly redder* These variations are chiefly in initial color rathe* man in color stability# ybe importance of strifes pH apparently lies in Its influence on the subsequent development step# A batch struck at low pH finished aim color if me pH was adjusted to the proper value before heating* Similarly, a batch struck at normal pH mowed the characteristic dark maaatone of low pH .material# if acid was added before development* in mm case of batch yellows which are vat warned before treatment (Y*S1*D), mere ere Indies* d&mm- that better settling is obtained if the solutions are adjected --to give me pH required for development directly rather then to strike at a low pH mad then add soda ash as specified In me current formulas* DUP050067352 ik Halted amount of work h* bean dong Oil variations in chromate/sulfate ratio or in (ohromatc/aulfat )/Xead ratio* So mo range investigated, mo differences nor* iHw'. small* A higher chromate/suifate ratio gave redder wassteae material as lid also a redaction in me lead excess* in the latter ease, there appeared to be a tendency towards U^MMM also, 7* A number of a .apartments mere carried out In whichv . sodium fluoride ms added to me chrome solution* la yellows *4MMl at a low pH (3,6), me fluoride gave a marked improvement in 'initial, goto and lightfastness mad..some improvement In color stability. At a more normal strike pH (4,6) the offeet is much lees-narked* -He#* tram microscope photographs Indicate that the particle shape is altered slightly (wider crystals) and It was, therefore, hoped mat sodium, fluoride would he effective in accelerating development, es* facially in IS Building, gome improvement was obtained hut it was rather small* fhe action of fluoride appears similar to that of chloride except mat a lesser amount is required* 4s might be pro* dieted, it is mere effective men present daring the strike .than-if added later# Sodium blfluorlde has hem need in a few experiment* hut offered no obvious advantage in respect to quality. Omitting sodium chloride results in dark doll products of high strength, poor llghtfastnass and heavy ink consistency# Increases above the amounts normally used are relatively ineffective. 8, me precipitation of hydrous alumina in the slurry ha* been used for many years as a means for controlling color, light stability and certain working properties of chrome yellows* Sub* ssquently, it was found (H,3* Patent 2*212,917) that a somewhat similar effect could ho Obtained with hydrous titanium oxide# mi* had the added advantage of giving less reactive products than those obtained with alum# m th* effort to Obtain th* optimum in light* fastness, seminations of the two treatments were developed imvelv* lag the use of large amieouumnets orf aximurn* anda tciivtaannyyz! suurlrfaaete# i(st* Ux&.fquuoorr>/#* me Y~319-D formula far example employs* 32 lbs* o*f a"lum and 8 lbs* of % Liquor per mole* iIn developi `ing our present Y*40d*# and Y-dQS-D formulae (continuous mmanauff&acettuurree!). It was found necessary to reduce of alum to 17 lbs# (hitting the alum gave better ink consistency and lower reactivity but lightfastness and stability were worse, . Omitting the t Liquor had a similar effect| initial color was not tspaired quite so much but stability appeared even worse* moreas* the alum over the standard amount improves color, color stability lightfastness but result* in higher consistency and greater re* activity* Adding the alms before the L Liquor (standard pro* eodure) appeared to give somewhat better results than th* reverse procedure but the result* were -not elean*eub* Adding a mixed solution of the two ingredients gave as satisfactory results as the standard sreoedure in a nipple experiment. DUP050067353 *12* phoaphot*. Pm tbto **oooa oad booouoo of tbo favorablo offoat oa working proportion (ospooiolly roootlvity) which tumolly oo* aulta, oonl<!U>rblo iitmion ho# bwa given to fommlotloao containing pjrophoephoto er orthophosphate* Sblo to diiouiaod in on earlier aeotion of the report* J0# boon HfidO ftbOVI Of tht Of o wOfflTHl MftOtiviiy woo lONWist greaser wood iu a itoxiti oofo 'goon ^owo nitrate wa wood* Further study of both prooeduroa to reooantnded* m flow of the aagneaiua found proaent fa Celaoa iO-SSlt, the uoo of aagaefiua aulfate tsiotood Of loud m sine oolto woo tORfOottgotod in o preltelaary way* fa the limited amount of wood which woo douo .00 afewtewe dtffereae frea the oubrei woo 11* While tbo ofloot of olim/t Liquor on Ughtfastnesa afid other properties to bellowed to bo duo largely to o coating offoot by the hydrous oxide* formed when oodo ah to added* tbo pigment may oloo bo offoetod by tbo low pi wbtob prevails prior to tbo neutralising stop aa o rsault of thtir uoo* fhat this mm oo woo Indicated by axsarlaanba la ehiah wo* iiw* tod/iw L t .4*** woo partly neutralised before addition to tbo follow slurry* oo OtfS -pH ^wy<wp treatment remained ObOWO tbS Q*Q*ff value* $hS material Obtained by tbto technique woo redder ey* wowoo In eeiey stability god lightfaetnaas than o control mods ill tbo usual way# ^frtfmif ttytaidi &jb|aewe JIM Pit #ys dtbedfc drtlifllMA^L td woes lnooncluaiwe* it to ottU uador oto&y* DUP050067354 3.8* The importance of the final pH to which the slurry Is adjusted before filtration has toon mentioned elsewhere in eonmotion with Ink properties It likewise has a marked offset on color, llghtfastneaa and stability. The desirability of a low pH (ea.5) la especially evident In eontlnuoua manufacture where there aye also Indications that the adverse effest of low pH on Ink drying H lose serious* in the laboratory there is in improvement In drying in going from 5*0 to 5.7 without significant ehangos in other proper* tils* 15* Esther large differences have been observed in certain 18 Building runs between samples taken at different points, via* 58 Vat (final pH adjustment, ample washed in laboratory}* 71 Vat (final repulp, Betronate treated) and grind* The reason for these differ* enees has not been established definitely* In the laboratory (com pletely developed material}, the presence or absence of Petronate haa very little effeot on oolor* Raising tbs drying temperature from 140 to 180 gavo a vs darkor maostonej this difference is lest than the difference* referred to above whieh were obtained in the plant* 14* A limited amount of work on atriko concentration has been carried out in the laboratory, semi-works end plaint but the re* suits have been inconclusive* Some further attention to this variable is probably Justified. notebook 3145 * This cover; the latter part of the work on AY-578, K*811Orep5rted la KN-45-29 and the early stages of work on the present problem. The specific ii oaa include t Work on bake resistance. Evaluation of competitive produets* Llvering chiefly Y-519-D typo* General work on oolor stability and Its evaluation* Development of laboratory formula * Y-40S-D, Variable studios on above* Hotebook 1350 * The entire content* of thia notebook Is conoerned with worm on thia problem* It inoludea t Variable studies on laboratory formula* Effect of raw material quality. Effeot of undeveloped pigment on texture* Evaluation of 18 Bldg* and 10 Bldg* runs* a is*.. HMHtHIlASPto MS f5v.Si,il"tfi.S?J.W >S.jS H the slum solution disoussed in the present report* Bolewant rosoareh reports include,KH-45-10 Semi-works Development of a Gontlnuoua process for the manufacture of Bxeeleior Chrome Yellow* HE*45*89 Idgbt Chrome Yellow K-3152 Development of a Strong Canary Yellow * Laboratory Work. DUP050067355 IV **14* ' 1*47-3 Chrome Yellows * Hheologioal properties of continuously manufactured products nod develop* wmt of tostlag methods* K2J-47-37 * Laboratory study of the Application of Con* tiauous Floe Tubular Reaotor to the Manufacture of Medium Yellow, mmmm mia Competitive Light Yellows. Report of 8*18-49. . Currdht Standards, informatIda from Plant Analytical Laboratory* not yet reported. Speotrographio Analysis Lotten Dunlop * Denslow 1*20*49. DUP050067356 ANAOTICAL m m APPENDIX DUP050067357 Std* Y-405-D Lot 10116 (Plat 781) Y-519-D Lot 57928 / (Plat 1004) Oalco 40-3615 0#51301 (Plat 782) Imperial X-1S09 C#47450 PIG* 1;- Miscellaneous Light Chrome Yellows. Magnification approx. 16000 x (Plat 500) DUP050067358 Immediately after strike* Ho beat development* (Plate 983) SkMI ` Finished Pigment* Standard (180WF) precipitation and development conditions* (Plate 791) Low temperature (140F) Development 25$ of slurry held out at room (Plate 1011) temperature until after 180F* development of main portion was completed* (Plate 1012) FIG. 2s- Lab. Light Yellows (Y-405-D type). Effect of heat development* Magnification approx* 15000 x DUP050067359 Effect of striking and developing *t low (3.5) pH* Compare with Plat 791 (Pig* s). (Plate 821) Effect of sodium fluoride on material struck and developed at low (3*5) pH* (Plate 820) PIC* Sj- Laboratory Light Yellows (Y-405-D Magnification approx* 15000 z DUP050067360