Document MJjjwvwjv3J2NENN973qO4Ljx

Serial Ho, KH^Sl-4 . * Copy No, 1. Numerical File Copy to: #1 Nonaries! Pile 2 - Research Office (212) 3 - Idbrary Pile (212) 4 * V, Chalupski - Plant Piles 5 -D.B. Killian 6 - V, F, Spengeman/J. B, Callasr&y/PJM 7 -r Extra 8- hew ahk pl ant < PIGMENT COLOR RESEARCH REPORT Progress Report. i T BASIC ZINC CHROMATE Y-583-B 1 * CEVELOPHEST OP D* E. P, ECONONY PROCESSES SEPTEMBER 1980 - DECEMBER | I960 Charge s A^IC*8 As>H SUBMITTED BP? J4'C. u q r r is o n I4/ DATE SUBMITTED: Jan, 9, 1951 \ H^gHODgOTIQK; 'J J ' 1 r _ ~ "1" 1 T _ 1 f Isminent specification of mandatory use of "Insoluble Zinc Chromate" in several important military primer finishes prompted study directed toward correction of the excessive bulkiness of pressoaks and dry color, and consequent intolerable taanufactuning costs* which bad characterised the production of Basie Zinc Chromate Y-563-B by* previous standard processes. ' . ; / / vY-.--.' : ." *- , SUMMARY AND CONCLUSIOHSi Y .y ^ !- Y/;;Y.YYV '.-t5, , 7 - _ : 77' ;V*V- ''^Y> Y'Y "J y' Previous processes for manufacturing Y~S6~Pivolved, es sentially, chromic acid treatment of thoroughly dispersed sine oxide slurries. The slurries demonstrated pronounced thickening through'* out the successive bichromate and acid treatments* requiring use of relatively large volumes to prevent actual solidification la the . strike vats. Very little, if any* reduction of bulk of the original slurry was e* ffected in subsequent processing. ,, * - A modified process has been developed in whioh the sine oxide prodispersion step has been eliminated, fry sine oxide is now added directly to a solution of chromic acid (actually to a sol** ntion of bichromate, followed by add treatment). This results in an initial predominately surface reaction between the obromto eold and relatively large aggregates of the sine oxide. The final reaction product is sandy and compact, and demonstrates no tendency toward thickening (i.e. - increasing bulk) in slurry form exoept nhan delib erately subjected to prolonged intensive mechanical dispersion - - treatment. The product retains its desirable compactness through subsequent processing. Although obviously not entirely uniform, chemically, in slurry form, the final- pulverised product has demon strated satisfactory performance in tbs laboratory finish evaluations conducted to date. ' - . , : ' ; ' r*r . 4~'- * One plant batch has been manufactured, to enable acceptance of a Mavy Yard order for pigment. This order was filled with pig ment of standard compositive, and a portion of this batch has bseft submitted to Salas as a candidate for replacement standard (lot t . p:-&fcr . V)-', Sent-works performance by the modified process has been V completely satisfactory - processing characteristics being conducive to profitable manufacture if duplicated In the plant. In the case of the single plant batch the goal compactness of the seal-works pigment in presseake form was approached but not completely equalled. At the actual plant press-burden determined as optimum for this batch, the manufacturing cost demonstrates large reduction versus that of the previous prooess, but closer approach to the semi-works press burden goal is required in order to attain a better than mar ginal profit from the manufacture of the product. It is believed that the observed relative bulkiness of the first plant batch can be corrected by decreasing the extant or degree of sine oxide dis persion through more rapid addition of the dry oxide or possibly by decrease in slurry volume oa* intensity of agitation. s*. :tt,,A ;. * * "^Y s* f // 7 A, DUP050068437 A portion of the first batch was experIiseufcally processed continuously in #12 Bldg* Borderline performance was obtained, definitely justifying further trial and .mechanical study to correct the excessive accumulation of pigment in the centrifuge venturis* This program has bean delayed because of the current capacity demand of other codes for production facilities# The new standard (F) process formula and notes* describing the batch process actually used in the plant in manufacturing the , proposed standard lot 21637, Is an integral part of this 'report# Two earlier formulas, appended for reference, are; (E) Plans scale up of semi-works performance, batch " processing* . (p) Plant 12 bldg a sc ale up of seM-works strike, continuous processing* DISCUSSION The (F) formula notes, which foiloar, provide essentially complete information concerning the new process# The results of chemical analyses obtained subsequent., to preparation of the notes provide the basis for the following additional conclusions (KB 1221** page 133) t . *. *- X, There is no indication of significant variation or "drift* in composition among the three successively batch-processed portions of the strike. All are within government speciflostion limits, and agree closely with each other* 2o The gravelly sediment from the floor of the vat is, as anticipated, relatively rich in ZnO# Although still within sped- floation limits, this sediment differs appreciably in composition from the batch processed lots; } ZnO CrO<* lot 21637 WT& Vat sediment 70*8=6 16*3# As the result of the experimental processing sequence, no appreciable quantity of this sediment is present in the batch processed splits, essentially all of it having been transferred to 12 Bldg* with the result that it should be present in continuously processed lot 21639 only* In future production it will be; desirable to sample packed production fairly closely to determine the effect of this sediment on compos! fcion uniformity, and whether the desirability, of its seg regation (end, possibly, reprocessing. Is indicated* Laboratory attempts to eliminate this sediment by- a two-step process involving essentially Initial preparation of potassium-free sine yellow, followed by addition of glue oxide to attain the standard compo sition, have not been promising* Elimination of sediment has been accompanied by excessive bulk 11221-63) * Plant experimentation along this line will be desirable, however, in case the sediment is found to present a significant practical problem fcom the composition viewpoint* * - ./ . DUP050068438  . , .V 3* `The failure of the continuously processed portion (lot 21639) to Kt specification limits of composition (because of low ZaO, high CrO$ and excessive solubility) appears to be due at least in part to sine yellow contamination, which is indicated by potassium analyses to be of the order of 2-1/2#* (1221, p* 135)* The preliminary laboratory study included trial of many sur face active compounds as possible aqueous dispersants for the plgasnt slurries (1281 -47, 48, 49)* Soso agents were slightly effective* the moat notable being Blanco! and Harasperse CB, but it appeared that at least 4# of agent on the pigment bosis would be required to obtain slurries1 of idle desired fluidity, and this approach to sol-. /ution of the problem was terminated In favor of the economically acre attractive approach ultimately embodied In the new process* Completely -unpromising results were Obtained Xn attests to prepare the pigment by reaction of 2a0 and CrOg in an Abbe* Leaart Mixer be cause of inability to obtain ft fluid slurry at sufficiently high solids coot at to render the process economically attractive* nega tive results were also obtained in an attest to prepare a satis factory product of specified ZnO to CrOg ratio (ignoring potassium) by dry blending sins yellow with sine oxide* The product demonstrated extremely poor film adhesion in primer finish evaluation* BBgSREHCBS .Vi:: -/-*-'.-iy'f Experimental details are recorded in Research Sfotebook 1221, * experiments 47 through 62, 64 throt^b* 61, 'end 6S . Development study records are also filed in Research Hcfce- boofc 1221, under esperlumnts 58, 58 end 60* ^ 4',:;^.,;,, ^ . The chemical analyses of 1948 samples of oompetitive products manufactured by Imperial and by Mineral Pigments are recorded in ' ftotebock 1221, .page 126.; k ; ^.v: ' ;vr >*&<' -: - The followlng correspondence is pertinent* ,,f * letter, "Basic Zinc Chromate*, J* B* Csllawsr to R* E.Pohl, 9*22-50 1 J ... : v - . : I iy ^~r. V . v- TSh 4, "mis. Hayal .Shipyard* 3* A. Rrsdriekson, 10-18-50 ' ktkf, "Y-563-D Economy Process Costs*, J.O.H, to D.B*KillIan, 10-20-50 letter"Basle Zinc Chromate,* 3*0*3. to R* H. Fohl, 11-8-60 letter, *y-S83-B Sampling lot 21637,* j3*Q,K* to **B* BcltOny 12^7-50 letter* "Y-5S3-D Prospective Replacement Standard lot 21637*, jr.O.H* toW.P.Spengemea 12-19-80 .; : ' . y'^- jroxslg . !> DUP050068439 5 VAT PReP l ~W 2 CODE: Jkpfi&sJl, . K#_ iEi GOAL:... J.. .SIZE:. DtAZO VAT: COUPLING VAT:,_______ _________ ,_____ STRIKE VAT*.. 2$Q, 26.U Zfcj. .2.67 STD. HRS. NON-BLEEDING NAME: BASIC ZINC CHROMATE /C.G.6 INSTRUCTIONS 1, n*T* l Hf IND Hfll B AT STR IKS VAT TOR STEP 8 '2, Ru n in t o s c a l e t a n k 36I M ...... 1 ..... _ ^ APPROVED BY: JCM: 11-8-50 h a ; lj-s-50" EM: ii-13-^r JRG: l-'IO-SO USE LBS. N- ACCT. LB! CODE ..... a 5089 S,V. 3 Ru n 48"<4l80G.) w a t e r in t o s t r ik e v a t . 4. Se t AGITATOR AT l6 RPM. f*. He a t t o 74-76*F. 6. Ru n s c a l e t a n k 361 in t o s t r ik e v a t . 7. Ad j u s t s t r ik e v a t To 60" (5223G*) AT 74-76''F 8. We ig h a n d d u mp IN IN 130-150 MINUTES rmTA|NFn in s t e p 1. Re c o r d : Tims St a r t e d . ______________ ______________ Re c o r d ; Time Fin is h e d . p. Ru n in IN 12-15 MINUTES FROM . SCALE TANK 324~ M, . T , t ^3I.64s6 10. St ir 5 min u t e s . n. Te s t a n d . r e c o r d : p H , No r ma l *5.5 - 6.0. 12. Te s t a n d r e c o r d : 13. St ir J HOURS. ____ l4. Te s t a n d r e c o r d : pH T.. "* , n o r ma l 6.0 - 6.5. I?. Fl o o d t o 85" (7399 G.). 12500 525 12500 .3938 ...... 28 1246 16. Pr e s s w it h a s it a t io n ._ AGITATOR MUST NOT BE STOPPED. TIME START ... n ,1 nh TIME FIN ft w . i OPTR n w A * . DUP050068440 KS --CODE: Y-^VP,, GOAL: >7,584# -----(EJ _. PROCESS:-, ______ _______ _________________DATE** 11 "7"^ ___________________________ . EST. LOSS MAKING AREA NOTES JPL 1-10-51 IBS, REMARKS PRESSING AREA JNSTRUCTIONS VAT DATE t ime RELEASED BY....................... . PRESS m 2 NO. OF CAKES 7 K 46 PRESS WITH AGITATION w ash t o *%nnn MAKE FIRST TEST AFTER ' U o h ms HRS. l o ad o n 35 Ca r s . SPECIAL INSTRUCTIONS NOR-BLEEDING. Se e b a c k , or c a r d SAMPLES DELIVER TO PRESSING AREA NOTES DESCRIBH YOUR YIELD RECOVERY CONDITIONS EST. LOSS CAKES USED LBS. HOURS WASHED OfflAS DRYER CARS ACTUAL OR PULP CONTAINERS NOTES ON SPECIAL INSTRUCTIONS SAMPLED BY RELEASED BY TYPE HOURS DRYING AREA INSTRUCTIONS LV. . 27 H.V. 18 HURRICANE 27 *.(M FiHOFB rrn t f s t BEFORE PULLING LUMP CONTAINER Se e CHART. SPECIAL INSTRUCTIONS NON-BLEEDING. SAMPi.ES DELIVER TO GRINDING AREA INSTRUCTIONS GRINDER NO. 10 HSP SPECIAL INSTRUCTIONS NON-BLEEDING Pa c k Fr o m De a d Ta n k SAMPLES J? ENVELOPES AND 1 PINT CAM DRYING AREA NOTES -- -- --LUMP OK WETSALTS CONTAMINATED WITH REMARKS NO. DRYER CARS PULLED EST. LOSS SAMPLED BY XSSI .................. LUMP WEIGHT RELEASED BY GRINDING AREA NOTES -- -- -- --LUMP OK WET SALTS CONTAMINATED WITH REMARKS EST. LOSS IBS. REMARKS d e l iv e r Tp Co n t r o l La b o r a t o r y . DO NOT MIX BEFORE SAMPLING pac k ag in g Se e Ch a r t . ____ SAMPLED BY DATE MIXED QUALITY REMARKS __- DUP050068441 PRESSING AREA - SPECiAt INSTRUCTIONS !. PRESS WITHOUT STRAINER 2, Co l o r vnu f f iss in ,t-i* Min * Po No t Ov e r f il l . 3, SACrtVAS* TO \a? AFTER cACri PUMPIM6. 4, AGITATE CONTiNUCt'Sf.Y ex c ept w h il e me a s u r in g . 5. Was h w it h iJu 'F. w at er * <$, RECORD SPLi Tii SSCOVJl Sp l it *- St a r t Oiviac in c h e s _By ,,___ _it T -w < 3 2 USE Jweh e3 INCHES Le f t tt '*11 "ft It Op t r . Al l -4 <J\U1 -t^-O (O DUP050068442 I-563-U (F) STAN PARS FORMULA NOTES .; * , The "P" process represents initial plant modification of the "reverse u * strike reduced-bulking",experimental "3" formula,, J F" replaces "C". as standard formula, end differs; from "C" as. fallouts: 1'. Batch size has been increased from 3200 lbs. to 17,584 lbs. V-w*. 2, Press burden-has been increased from 1067 lbs* to 2512 lbs* (per 78*7 cu.ffc presslgadjo & 1 sine cadde is now. slurried directly in dilute bichromate solution, in.; i street to the "C" procedure in which bichromate liquor* was struck into a ^parately prepared and thoroughly dispersed aqueous sine oxide slurry, * GENERAL NOTES 1 " 1.... 1 - -- ` ' The characteristic excessive bulkines3 (both, as preascake add as dry color} of pigaent produced by the "C" process resulted.in vary unfavorable manufacturing costs which led to obsoletion of the product in 1949o pevelopaant of Basic Zinc Chromate .pigmented Vinyl Resin finishes to positions of major importance is ship and aircraft primers has subsequently provided justification fou study- directed toward development of an economical manufacturing px'oceSs, ' ? . * . ' Z~';\ ; ' <* .rJ The basic zinc .chromate slurries produced by the new process are relatively coarse and granular. They are free from the gelling and solidification tendencies of the more finely dispersed slurries produced by previous prodaeseS^1. These physical changes have permitted increase of slurry pigment concentration frob' 0,93 to *>; 2.2 lbs. per galloa, ;and increase of preS3 burden from 13,,5-tb 31*9 ltd, perreui ft. 'Hie latter approaches but does not equal the "3" process ^emi-vorks press burden , . . of 56 lbs,; per^^rffc, Attainment' of the present 31.9 jareei^'tordea ha provided a very considerable reduction in operating coat, but operatiye earnings-f " ' at this ^ssibuidtea;.leve3. are distinctly development stud^r id order tosetisf&ctory cost positions -,j.r .... C ,? - yy.: _ r as;the mechanism of the cost reducrimopererionjfi^ a major change-.ml%pe of slurry, a very finely divided slurryhavingbeen replaced by a~very' coa^' ^velly ^urry, it is quite probable that a concomitant decrease v has been effected da completeness or uniformity of chemical.' reaction between the ; 7- sine oxide and the chromic acid (bichromate-muriatic acid). She chemical composition of the pulverized end product is -normal, however* and to date no deficiency of the new products has been disclosed by laboratory primer evaluations. . i' STATUS OF PROCESS Reverse-strike process development study to date has consisted of two semi-works strikes and one full size plant strike. All research development notes and records are recorded in Chemical Division Notebook 1221, Kxporiments 57* 58 and 60* In the case of the plant strike (made in 6 Bldg.), three pressloads were processed by batch procedure, permitting accurate determination, of optimum press burden for that particular batch of slurry. The balance of toe slurry was continuously processed through 12 Bldg, equipment. The batch - processing experience i3 considered adequate for preparation of the present "Fw formula as a- firm standard process. The continuous processing experience (lot 21639) was sufficiently favorable DUP050068443 2 - to warrant additional study directed tcard correction of the difficulties encountered - chiefly pijjr^rit accumulation in the centrifuge feed venturis, At present there is sows uncertainty as to the reason for apparent abnomal coapositica of the continuously processed pigment, Analytical study ie in progress to clarify this situation and the results thereof should provide a basis for measures desired to produce standard composition in future continuous process manufacture* `, OPSR.iTB'CU.eOT133 r % i. The reverse-strike D and 8 process slurries obtained in the laboratory, semi-v/orks and plant have been free from, spy observed tendency toward thickening, gelling, or solidification* aha sandy or gravelly character of the pigment produced by the new process introduces entirely different operating problems, arising from sedimentation of the slurry in vat cutlets and transfer lines and hoses* The limited plant experience to date indicates that the sedimentation problem is not serious, provided the agitato? is kept roanirg continuously and provided the transfer lines are backwashed, before and after 'each pumping. A uniform deposit of very coarse particle size pigment does,, however, settle to the floor of the strike vat beneath the agitator blade and final "wash in'* of this coarse sediment presents more than normal difficulty* * . Tho most serious* difficulties encountered to date in plant batch processing resulted from overloading the filter press. The character of the slurry i3 conducive to extremely rapid filtration* The pressing operation must be very carefully controlled to avoid overloading, with resultant excessive washing cycle and excessive difficulty in presscaka removal and handling. . * ! * Contamination with sine yellow must be prevented because of the importance of solubility and chemical composition discussed below, The pulverized product packs readily in 50 lb. paper bags (Jf-566)* It is desirable to avoid tumbling in the' packing operation feed tank (i.e., "pack from dead tank") because the product balls quite readily when tumbled and, unless ' the tumbling operation were closely standardised, considerable variation in bulk density would probably occur. ' QUALXTX NOTES jS- X-563-D is considerably less soluble than sine yellow and-also differs from the latter in chemical composition. Its ZnO/CrOs ratio is *45A*0 and it contains no potassium, whereas the empirical formula for zinc yellow is 4 Z11O.4C1O3* X Kr O. 3H2O. The respective solubility values (KCR-94) are 0.5# for T-563-D (ft&vy Spec* maxumm is 1.0), and approx. 26% for Y-539-D. f~563-i) is an essential ingredient of newly developed vinyl resin metal protective finishes for both ferrous and sicm ferrous metals. Two iiaoortant Navy Bureau of Ships specifications ares Metal JPrctreataent (./ash Trimer) Formula I.'o, 117, and Primer No. 120. These two primer coats provide raarksd improvement in adhesion of finishes to underwater sur faces of ships. In these applications the most important pigment properties requiring control are believed to be chemical composition, freedom .front electrolytes (chlorides) freedom from soluble lead, vine, or other similar cations which cause gelation of the Tin/1 dispersion, and dispersion characteristics. Color is of significance only bo ah indication of general process control. : DUP050068444 -3- B-: . . ;--v * ` \ ? s.`. ; * 5 ' : BB ' 1 v. ;; ;-!v- 44 - * '*> ur l'(4 v- Pigaent specification limits included in the Havy's Pretreatment' (Wash .Primers} Specification KXL-P-15323 are: `` rf - - 4 Y>'' -:ft|:4.BB' 4: Constituent CrasCrda', Limits I64L9& Newark Analytical. Method ~ ^, 7 Zn as ZnO 67-7# ' -T/ water soluble salts 4 Kax,.l&-44 _ 7|4 4 KCfc-94 -.7 * '.B'&V Chloride and sulfate content are not limited, as sudb, -by the Navy specification* In the absence of more definite inforraation as to the effects of these, constituents, it is recommended -that shipments be controlled, as diithe .past, below a maximum chloride l^el of 0,05^,as determined ly KCR-125, f / .-'.4 " 4 4 4 ' V A- >:.V?v,3'' > /, .4*;- 5". *4 / The reverse strike products are essentially identical to the obsolete . . standard in chemical composition and have demonstrated satisfactory dispersion and' stability performance in limited laboratory vinyl resin primer evaluations* Available data indicate that the formulated 3 hour" stirring period after acidification and before pressing is Sufficient to^ permit attainment of reaction equilibrium but that a 90 minute period is insufficient, Ko drift in composition: attributable to incomplete reaction was observed- in the case of the three, successive presslcads of Idle first strike, in which an age difference of 3Q hours was, involved between the initial and final filtration* .. - \. - . , ; 4. 44 I' 4... . (','4,. , "... -iijJfe CCHmOl VARIABLES _> . U/B:. - V *** The composition' of the product is controlled by the relative quantities ;|| of sine oxide and of chromic acid (actually bichromate'and muriatic acid) used*' " 1 Decreasing the sine oxide produces a less basic, more soluble product;: increasing 4 the zinc oxide is believed to result in the presence of free aihe* oxide in the a product. The effects of such variations on viqyl resin pigrfflsat dispersion propertie are not known. 444.'4'; . 4-S44B No. other control .variafeleq have been develoj^Ki. for; ^heCher; reverse atrik process* RECOMHEKDATIOKS *1 s m r. -i -r--`aV"tiSA'JV-.',l-y The following program! is recommended: faz^^giatlc^c. '- dsjrdization; 1. Establish r8ascn for abnormal solubility and. slightly; <neeesei^ CrQ3 content of continuously processed stock (lot 21639). This nsay be du,tos4 a. Contamination with zinc yellow (approx, 3 to %)f or!v 4-4, b. lhadsqjiate draining of final centrifuge cake, K --f .. c* Inadequate washing of pigient, or possibly,4- '4 d. Won uniformity of dluivy in vat, witfi early removal of relatively zlnc rich pigment and late retention of relatively chrome-rich pigment* ' * * % : v,' . ' ' " 20 1-^ufacture a full-size batch in 12 Bldg, strike unit, incorporating slight change in zinc-chrome ratio if need is indicated, by results of (l) above. Apply all reasonable and proper physical processing variables to avoid pi accumulation in venturis and to guard against (la) and (ic) above. v. -V . 3* Base choice betvreen eventual batchwise and continuous'type processing on results of me or more 12 Bldg* trials as in 2 above. '* , ' . # Vlv . (i . .V ^r\v4,';. , - 4 BBB DUP050068445 4. The difference in presscake bulk between the initial 6 Bldg. pigment (32 lbs,/ cuo ft,) end the semi-works pigment (56 Iba./cu, ft,) is, probably the result of more complete, or finer,, dispersion of the zinc oxide in the -plant than was obtained in the. semi-works. The only definitely known, factor which would , logically contribute to finer dispersion in the pitot was considerably slower rate of addition of sine oxide to the bichromate (195 minutes in the pitot versus 60 minutes in the semi-works) with resultant considerable prdcnge.tu.cu of the period during which a major portion of the sir.c oxide - bichromate slurry was agitated prior to acidification and completion of reaction. In an attempt to approach the goal density (low bulk) of the semi-works product, which is of course desirable for continuous processing as well as batch processing, it would be desirable to assign sufficient manpower to the zinc oxide addition step to enable addition at a maximum rate, governed only by| prevention of obvious ' lmaxd!ng of the sine, oxide as it is added. No such lumping was observed in the 6 Blag, strike, in which the addition rate was retarded both by non-availabilily of /a helper and Lnteraittsnt delivery of zinc od.de to the making area, # 5. Other suggestions for possible reduction of bulking to the goal-cost semiworks performance level are: Kainiaining zinc oxide addition at amxismm pcrmissable rate, a, Reduce agitator speed (applicable in 6 Bldg, only) to minimum gear setting (previous strike was made with medium speed), r ^ \ ' b. . Reduce initial bichromate volume substantially (say 40#)> Observe batch closely and be ready to flood aLursy if necessary to. prevent stalling . agitator. (This suggestion may possibly operate in the reverse sense to that which is 'desired). 6. Batch size has been arbitrarily fixed at a'value slightly greater than that of zinc yellow, lab. and seed-works results indicate that it nay be possible to increase the size by from 20 to 60#; this is subject to confirmation in the plant. > 7* St, Joe's Zinc Oxide, IT-617, has been used exclusively in the semi-works and plant because of supply conditions. Trial of cheaper types of zinc oxide is recommended in the interest of econcsy.- y STANDARD LOT Pending completion of the standardization program, lot 21637, an optimum (standard) size batcfe~procs3Sed portion of the single plant strike to date, has been selected for use ag temporary sampling material. Its composition is compared below with that of the cbsoleied previous T-563-E standard: New Zt l as ZnO , #lot 21637 68 6 Cr as CrOg ie.3# ZnO/Cr03 IIol Ratio 4.62# Solubility 0,45# ei 0,0075*' St>3 0.061# K (flame photometry) 0,05# Na ' less than 0,025# Obsolete Lot 80166 67.8# 18.4# 4.52# 0.85# 0.020# 0.181# mm DUP050068446 ... .. *Sr >' -`i*,V/v*V *< ' * XESLD Pending development of additional plant experience, and analysis of filtrates and wash vjater effluents for soluble sine content* the original estimated goal yield for the "AB process has been retained* Scaled to the present batch .sine,. x 12500.. ZnO -s~ 2275 2n0),. this. yield4s 17,5fc- Jfca* "V For costing purposes, the 96.125 performance factor of the obsolete ffCB: process is recamended. > X $ ,,. * t * "3 jaitcc SUEHITTSD BXs ~ APPROVED BX S' 1. j .o , mo h b is c k u 12/A/50 H, ARHOBL 12/5/50 i": . - , /* r r * "'I ~ ' *< rr - . * -- ~ - 'i?aa&&vdiH.'' fcr4. .vll^Sr - , irr .' ,* vT$-'/* /d> ' - * ,F - i'- "- c -.V .?/ .. . .. -.` vr-s*ttf* VN i' * **>* *' ' *.' ' -:V WM**, / > v 1. ., ,- r.$**;; t TV 'r V _i t&T.'V -: n;- ;b - r ti;fOS? *;ffr| r+v .* "* A 4* w.. * 3m ;. r? :7t-iii~ ** -. f ' .,- v. >7^'. 'Iff*'*? S-iMa ' Tv DUP050068447 VAT Woup * oPr at Pn. ..... WOSfc / ^ c o d* nn*i 17584# ............K*..(P) Y-563-P. s ize . ^MAZO VAT: . COUPLING VAT: ^ ^ STRIKE VAT: 12 &LDG, lllxll 2IA, 2IB, 22A. (3334) APPROVED BY: 00M: IO-I6-5O HA; ' JRG: -12-51 NAME: b a s i c ZINC CHROMATE INSTRUCTIONS lr INSERT FOOT PLUG IN STRIKE VAT OUTLET. ?, Ru m li5" (11320G.) WATER INTO STRIKE VAT. 3, Ru m i n 4, Aft.iiisr t o 5s*" (^28o g .) a t 74~78F, M f> 5* St a r t Ag i t a t o r . 6- Sp o t N-525 NEAR CHUTE AREA. Y. WnoR AND DUMP IN IN no-150 MINUTES Re c o r d : Ti me St a r t e o __________ . _________________ _____________________________________________ RFrowp: Ti me Fi n i s h e d . R pM >U Imirniiwi* IN Re c o r d : To t a l 12-15 M Mi n u t e s + ?l.64 -..., Re c o r d : Ti me s t a r t e d Re c o r d : Ti me Fi n i s h e d a St i r 5 MINUTES. in. Te s t a n d Re c o r d : pH ^ No r ma l 5*3"O.O.o p t H USE LBS. N- CODE ACCT. LBS. 8 5089 12500 w 12500 3938 28 1246 t 11. St i r 12. Te s t 3 Ho u r s . and r ec o r o : pH ... No r ma l .. . 6.0-6.5.0PTR 13. Te s t a n d r e c o r d : *F. ", l&T Fl o o d t o 83" (7968Q.). 15. St i r u n t i l 'f i n i s h e d c e n t r i f u g i n g . IS. Re mo v e f o o t p l u g f r o m s t r i k e v a t o u t l e t . 17. Ce n t r i f u g e w i t h a g i t a t i o n a t 16" / h o u r . 18. Co u n t e r c ur r ent w as h as . Re c o r d : f o l l o w s; Ti me s t a r t e o . A. 45 GPM COTRu n d il u t io n w at er a t in t o c e n t r if u g e 67 w a s h p o r t . B. Ru n c e n t r i f u g e 68 e f f l u e n t i n t o c e n t r i f u g e 66 w a s h . PORT................................... ... ............ C. Ru n 30 GPM o f c e n t r i f u g e 67 e f f l u e n t t o s e w e r RUN REMAINDER INTO CENTRIFUGE 66 HEAD TANK. D. Ru n c e n t r i f u g e 66 e f f l u e n t t o s e w e r . an d 19. Se t f i n d r u m i n d i c a t o r to , and pr es s u r e t o 20. Ad j u s t t e mp e r a t u r e o f 1s t . Se c t i o n . 2n d . Se c t i o n . 3r d . Se c t i o n . 4t h * Se c t i o n . dr y er s e c t io n a s f o l l o ws: # 21. 22. 23, Se t SET Ru m DRYER DRYER col or bel t in d ic a t o r to DISCHARGE DAMPERS t o s t o r a g e g in TO HSP24. Gr in d and pac k . . ...'. . * TIME START II II ti it TIME FIN II If ti 11 OPTR II c o n t i n u e d ON PAGE 2. DUP050068448 VAT P*6l: 2 Co o e:(D)Y-563~D Lbs : 17584 In s t r u c t io n s ' USE LBS. NCODE ACCT. LBS. * * C Lo c k Time W IN VAT CENTRIFUGING RATE ' v 1 1 . . ..... El aps e .11 \ ' 1. .... ?.. t Cl o c k ! " in >El aps e Time Cen t 1 Time 1 Vat Time l1 1 Cen t : *1\ 1 ' i...... . A .. Ij...... , .... u...... ...... 1 _ . | ... ...... j-- * \1 ! .. .. } .. _ i ) . i .... . * > . * - >A K13731 DUP050068449 563-3 KffiWJW H01SS 12 BLDG* BAUCH STRIKE ~ C02j'XIKl)GUB PKQCESSBIG The nDtr nrocesa represents tentative plant formulation of a semi-work3 process developed to correct the characteristic excessive bulkiness of previous production (presscPka as well as dry color) which restilted in unfavorable manu facturing costs, leading to bsdetion of tha product in 1949. Justification for economy process study is- provided by recent development of basic zinc chromate pigmented vinyl resin finishes to positions of major importance as primers fur ships ana aircraft. Both the "'D" process and its eqpgjanion *8* process (identical. except for 6 Bldg, strike and batch processing) represent 40 scale up of SJ lot 1311, Research Notebook 1221-5* H . I. /The "D" process differs from the obsolete standard BCn process as follows: 1# Bat^h size hag been increased from 3200 lbs. to 17,534 lbs* 2. 12 'Bldg, batch strike end continuous processing have been substituted for the previoxisiy formulated 6 Building strike and batch processing. 3o The order of addition of sine oxide and bichromate has been reversed. In the obsolete ,lGn -process, bichromate liquor was struck into a separately prepared aqueous sine oxide slurry# In the new process tha dry sine oxide is, slurried directly in the (diluted) bichromate solution# . '\ BCCtlCHr PRINCIPLE . She basic zinc chromate slurry produced by the new reverse process is relatively coarse and granular. It io free from the gelling and solidification tendencies of the more finely dispersed slurries produced by previous processes. These physical changes permit increase of slurry pigment concentration from 0a93 to 2,2 lbs# per gallon, and increase of press capacity from 1066 lbs, ("0 process) to 4400 lbs<> (semi-works performance) * laboratory centrifuge tests indicate that, whereas slurry made by the old MCrt process `doss 'hot settle at all - roaaining stable at full initial volume approximately 6 times the cake volume of zinc yellow, the new type slurries Settle to approximately i/3 their initial volume, or to double idle normal cake volume of zinc yellow,, STATUS OF PROCESS The "Dn (12 Bldg. - Continuous Processing) and "E11 (6 Bldg. - Batchwise Processing) formulas were written primarily for use in calculation of estimated manufacturing costs and were based on process development study consisting of 2 semi works strikes. One 175S4 lb# plant hatch has subsequently been struck in 6 Bldg# Approximately half of the slurry was continuously processed through 12 Bldg# equip ment as lot 21639. As indicated in the following section, additional experience is necessary before final decision can be reached as to the practicability of continuous processing. OPERATING NOTES >' . The reverse-strike D and S process slurries obtained in' the laboratory* semi-works and plant have been free from say observed tendency toward thickening, felling, or solidification# The sandy or gravelly character of the pigneni produced y the new process introduces entirely different operating problems, arising from _ excessive sedinsntatdcn of the slurry in vat outlets and transfer lines and hoses. DUP050068450 The limited plant experience to date indicates that the sediiaentaticn problem / is net serious, provided tfcs .agitator is kept'running continuously; .and provided the transfer lines are backwashed before and after each pumping, % vaaktvm deposit of very coarse particle else pigment does, however, settle to the floor of the. 4 strike vat beneath the agitator blade and final tf\<ash in** of this coarse sediment presents more than normal difficulty, ; .. In the 12 Bldg, continuous processing trial, the abet serious difficulty encountered was. frequent accumulation of pigmsnt in the centrifuge venturis. . Additional study is necessary to correct this trouble* Processing conditions fe (instructions 17 through 22) remain to be established during the course of this study, Caitandnation. with zinc yellow must be prevented because of the importance , of solubility and chemical composition discussed below* . ^ cmia KOT33S ` I-563-D is considerably less soluble than zinc yellow and also differs from the latter in chemical composition. Its Zn0/Cr03 ratio is +4,5/L0 and it contains no potassium, wheroas the empirical formula far bine yellow is 4 2n0.4Cr03. 1 KaO, 3ife0. The respective solubility values (KCR-94) ore 0.55 for y-563-3 (Navy Spec, maximum is 1.055), and approx. 265 for Y-539-B. Y-563-B is an essential ingredient of newly developed vinyl resin metal protective finishes for` both ferrous and non ferrous metals. Two important Navy Bureau of Ships specifications aret Ketui Pretreatment (bash Primer) Formula No, 117, and Primer No* 120, These two primer coats provide marked improvement in adhesion of [finishes +0 faces of ships. In these -applications the most important pigment properties requiring control are believed to be chemical composition, freedom from electrolytes (chlorides), freedom from soluble lead, zinc; or other similar cations which-cau'se. gelation of the vinyl dispersion, and dispersion characteristics. .Color is of.. significance only as an indication of general process control, i j ,f*L| * . . . . .V ' V- , & * jjf i * >x"7' < :.4- V . J ri**'*' * . ..x-'J , * Pigaent specification limits included in the Kaby's Pretreatment Ofash Primers.) .Specification....KQ-P-3..5.3.2..8.ares -... Constituent / Limits : 1 - '.w*affevrr..'- . `fr-wr'm* -* ^Newark" fcical Kethoir* Cr a3 CrOs ' Zn aaZaO water soluble salts 16-1955 67r>72& Max. 15b t KCH-I57 KCE-94 -* ' Chloride .and sulfate content are not limited, as such, by the Navy apecificatiha0 Hi the absence cf more definite information as to the affects of these- constituents it is recommended that shipments be controlled, as in the past, below a maximum:.. chloride level of Q.05& as determined by KCR-125* , */" , The reverse strike products are essentially identical to the obsolete standard in chemical composition and have 'demonstrated satisfactory dispersion and stability performance In limited laboratory vinyl' resin primer evaluations. Batch size has been arbitrarily fixed at a value `slightly greater than that of zinc yellow. Lab. and semi-works results indicate that it may be possible to increase the size by from 20 to 60^j this is Subject to confirmation' in the plant St. Joe13 Zinc Gxido, N-617, has been used exclusively in the semi-works and plant because of supply conditions. Trial of cheaper types of zinc cotide is recommended in the interest of economy. DUP050068451 Pending completion of the standardisation program, lot 21637, a portion of batch-processed pignent from the single plant strike to date, has been selected for use as temporary sampling material* Its casqsoaition is included in the new 7-563-0 (F) standard foxnula notes* , COIJTP.OL VARIABLES Ihe composition of the product is controlled by the relative quantities of ainc ordLde and of chromic acid (actually bichromate and muriatic, acid) used. Decreasing the zinc c&cide produces a less basic, wore soluble product; increasing the j-inc oxide is believed to result in the presence, of free zinc oxide in the product. The effects of such variations on vinyl resin pigment dispersion properties are not known* { /No other control variables have been developed for the new reverse strike process,/ /7I8LD > Pending .development of additional plant experience, and analysis of centrifuge effluents for soluble zinc content, the original estimated- goal yield for the "Aw process has been retained* Scaled to the present butch size, (3200 x 12500 ZnO-f 2275 ZnO), this yield is 17,5% lbs* l 'V . For costing purposes, the 96,1/S performance factor of the obsolete wC" process is recoasnended. `* dCXi:CC SUHKI7T3D ST: J* Oil KORniSOK-ll/lt/SO APPROVED B7 j H, ARNOIg. - 11/22/50 DUP050068452 Cost Group - 6 (5300) CODE; APPROVED BY? 3# (E)Y-565-D JOM; 10HL8-50 GOAL: 17.584# SIZE? HA: 10-19-50 COUPLING VAT: STRIKE VAT: 260-261-262-267 STD* HRS* 4,7 NON-BLEEDING VAT Rrep, X ~ 36l 2 S.V, 3 * HARE: BASIC ZINC CHR0RATE/G*G*6 L flbfc*la, ina hold .t etrik. TOl: USE7LBS. " J . N. CODE 525 / for Step 9* /""SV Run into scale task 361 U T ; .......... $ .7 8 3, Insert foot plug In strike rat outlet* 4, Run 48" (4180 Go) water into strike vat*, y ' So Agitator at 87 RIM, I 6, Heat to 74-76F, ' 7o Hun scale tank 361 into .strike vat* ir 8 Adjust strike Vat to 60" (5223 G.) ... - . \ ' '... i. ?r ; V at ?4-76F* 9* Weigh and duam in 130-150 mn* Obtained in Step 1* Records Time Started ' Record: Tints Finished lo Run in. 12-15 min, from scale tank 324 M T *31.64* 11, Stir 5 minutes* f: 12, Test and record: pH. . . .. Normal 5,5-8o.O '".T;.- . 13, TastranS record: F*. , 14o Stir 3 hours, 15, Test-and recdrd: pH* Normal 6,0-6*5 . 16, Flood G,)* 12,500 , ""ji ' 525 i . \7l 3,938 '-y. _.. ''v;'V>W> . - r ; "il't-iV. i- V",. S&Sf. , 28 - / -jPM" ^ ,, 17, Press with agitation. ' ' ' . : "V . ACCToLBS, ' >>" 5089 - 7' *! *>' ' 12,500 '..''."7'.'.' 7,1,246 ;7 j Y'V.r *' * ; lv*s" .** ^ ' * v ^ V ' ' ,* /-1 t t* ' ' Agitator Mua.t NoirBe Stopped* V, Press Operator to remove Foot. Plug from Vat Outlet, .- ' Time Start nn Time Fin, v nn nn Optr, . .p i " * r DUP050068453 COAL?K*b 17. 84# KiOCESS: {E)Y-S63-D DATE: JOMs HA * mr-ig-50 PRESSING AREA INSTH0CTI0R3 vats . Cate: Time: Released By: Brass Ho* 2 No. of^-Cakes: 4 x 46 W with Agitation 23 4 x 46 Wasli to: Chloride Erse* at 110P Nak first tost alter Era. load on 20 oars Special instruction: NON-BLEEDING Bust press with agitation. Remora foot, plug from rat outlet * *000 acidified silver nitrate solution. Do not contaminate with zinc yellow;, i > } '$ # DRYING AREA INSTKP0TI0N3 Tjpes Hows: Temp* L.V* 18 ' 220*F, H.V. 12 220F. Hurricane 18 , 220F. Lump Container: See chart. Special Instructions: Samples: Deliver To: NON-BLEEDING GRINDING AREA INSTRUCTIONS Grinder No& 10 H.S.P. Special Instructions: NON-BLEEDING. Do not contaminate with sine yellow*Avoid tumbling In mix tank - balls readily* Samples:. 2 envelopes and 1 pint can. Deliver To: Control Laboratory* Do Not Mix Before Sampling. Packaging:* See Chart. ' * DUP050068454 <E) T-563-D ' _ s: FORMULA n o t es #6 BIDC-'S1RIKK - BATCH PROCESSING / * The "Sn process represents tentative plant, formulation of, a sesd-works : process developed to correct the characteristic excessive bulkiness of previous production (presscalce as well as dry color) which resulted in unfavorable nem*-' facturing costs, leading to obBoletion of the produebia 1949- Justification for econoey process study is provided by recent development-of basic, zinc chromate pigaented vinyl resin finishes to positions of major importance as, primers for . 1-* ships and aircraft. Both the flSn process:ahd its c^psniaa "SM* procass (identlcEl except for1? Bldg, batch strike and continuous processing) represent 40 Z scale . ./ up of SVf 2ot 1311, Research Notebook 1221-5P* , .;C >' ; * - / The ,s2n process differs from the: obsolete standard BCW process as follows* / \ * '.'. -v s-l m- j** .,v * 1, Batch size has been increased fro 3200 lbs# to 17,584 lbs# 2. Press burden has been increased from 1067 lbs. to 4,4^1lhs# per 78.7 cu. ft#, pressload* . ^ .. ; . Vv;. 3# The order of addition of zinc oxide and. bichromate has been reversed.\ 2h the obsolete `<0" process, bichromate liquor was struck, into a separately.prepared aqueous sine cad.de slurry. In the new* process the dry zinc oxide is slurried directly in the (diluted), bichromate sciutioa. v, ;' fr ' %1 ECONO&r PRINCIPLE' The basic zinc chromate slurry produced by the new reverses process is' relatively coarse and granular. - It is free froa the geUing^aad solddification tendencies of ihe aspre finely dispersed slurries proceed by previous processes# * ,, These physical, changes permit increase of sluny pigmentconcentration frc-Oi93'~'iiV to 2,2 lbs. per gallon, and increase of press capacity from 1067 lbs.! ("C* process) *: to 4400 lbs. (semi-works performance). : Laboratory centrifuge tests indicate that,/ ^ whereas slurry made by the old;ttC" process does,not seiils at.aTf ykaadivtng. taa>ii&T- at full laiti&.voi2xp^ . ^ .new type slurriee settld'-to'appa^mtkj^^l^'their^initiaZ,.^^ to-double-^ the normal cake voluue^bf zinc--'yellow, . ? STATUS OF PROCESS -'$rJ>' H*$s*f&rr&*'; 'Ui v rh*:-r?V~ fi*!*3rars ,,,, r3 .sdfR -The "Dtt (12 Bldg. i. Continuous Processing) an< 3 (6? Bldg# - Batchwiso lh?oeeiAg)-'.formnlajs were writton ptinarily fiwr y$ estimated ' manufacturing costs and were based m process devalopmant studf cchsisting of 2 semi-works strikes* (hie 17,584 lb. plant batch, has. subsequently been struck in 6 Bldg. 'Approximately half of the slurry was continuously processed through : 12 Bldg, equipment. As indicated in the ''P* formula notes, additional experience is nscessaay before final decision can be reached as to the practicability of continuous processing. Experience developed in connection with plant scale batch processing has been incorporated in the nFM formula, recently established as the". standard process. -f QPgaATgg H0T33 nr_ --r-, -r-" 7 .9 ; ; . t. -i/..;. ' The revorse-strilce D and process slurries obtained in th lahorstoiy, ssjoi-'lorte and plant have been free from any observed tendency toward thickening. DUP050068455 galling, or roHdifi<^ tiers, The sandy or gravelly character -of the pigment produced by the new prccsscs introduces entirely different operating problems, arising fro. excessive cadfucniabior. of the slursy in rat outlets and transfer lines and hoses* The limited plant experience to date indicates that the sedi- mcntatica prchlea is not serious, provided the agitator is kepi running continuously and provided the transfer lines are backwashed before and after each pumping. It was found unnecessary in the plant to use the formulated foot-plug technique which had been 'essential in the semi-works, A unifora deposit of very coarse particle size pigment does, however, settle to the floor of the strike vat beneath the agitator binds and final "wash in" of this coarse sediment presents store than normal difficulty, I, f hi the plant baichr-processing trials, the most serious difficulties encountered resulted fro.2 overloading the wash press, viz,; excessive washing cycles ,end excessive difficulty in removing the prsoscake from the press and in loading drier pans, Tfce character of the , sluriy is condncivo to extremely rapid filtration as well ac to excessive cake packing. Pressing must be carefully coatrc&Xed to avoid overloading, - ' Contamination with -sine yeilcw must bs gravented because of the importance of solubility sad chemical coraposition discnsse^Selew,' ' QUALITY NOTES '* i y-563~$ is considerably less soluble than zinc yellow and-also differs from the latter in chemical composition. Its SnO/CrOs ratio is +4,5A0 and it contains no potassium, whereas the empirical formula for zinc yeTlow is 4 2n0e4Cr03 1 K2O, 3HaQ. The respective solubility values (ICCR-.94) are 0,5^ for Y-563-D (NavySpec* maximum is l.Q^), and approx, 26}j for Y-539-*G,, X~5&3-N is an essential ingredient of newly developed vinyl raain metal protective finishes for both-ferrous and non ferrous metals, Two important Navy Bureau of Ships* specifications ares Hetal Pretreatment ('wash Primer) formula Ko, 117, and Primer No, ,120. These two primer coats provide marked improvement in adhesion of finishss to underwater sur faces of ships, 2h these applications the most important pignent properties requiring control are believed to be .chemical composition, freedom from electrolytes (chlorides), freedom from soluble lead, zinc, or other similar cations which cause gelation of the vinyl dispersion, and- dispersion characteristics. Color- is of significance only as an indication of general process control. '- f ` Pigment specification limits included in the Navy*s Pretreitment flash Primers) Specification KE,-P-1532$ are: Constituent Cr as Cr03 Za as ZnO viator odubl-3 salts limits - 16-19% 67-723 Kax. 1% < ' Newark Analytical Ksthod ECR-157 KCE-133 KCR-94 Ghloride and sulf&fce content are not limited, as such, by thd Ravy apeciftcation. Hi the absence of more definite information as to the effects of these constituents it is roccafneudcd that Eh.tpnjsn.ts be controlled, as in the past, below a maximum chloride level of 0,053 as determined by KCR-125. The reverse strike products are essentially iderttical to the obsolete standard in chemical composition and have doaoastrated satisfactory dispersion and stability performance in limited laboratory viigrl resin primer evaluations. DUP050068456 Batch size hag bead arbitrarily fixed at a value aligijtly greater than. that of zinc yellow, lab, and seni-works resulta indicate that'it may be possible to increase the size by from 20 to 60j this is "subject to confirmation in the plant. St, Joe's Zinc Oxide, N-617, has been.used exclusively in the semi-works. and plant because of supply conditions. Trial of cheaper types of sine'oxide ia - recojanended 3r. the interest of econcay, ' ! j. .. r J ;**'/ *-- *: ' ; * ;. '.-v > ,',W< ` . '.V" '* V. rv:|*b ' ' . ' ^Pending completion of the, standardization prcgra|i, lot 21637* a portiosj ------------- , ^- *-----:jjwji-.date, I1&3 been aelecteefr',',";' " for nso/ta tenrooraxy sar^ling material*; , Bfr:o6mj^iii<^ nm '--ZK-: * Y-563-y (P) standard formula notesy .* *: $ * -dr--'::' * r.^Vv*-. l- -A CONTROL VARIABLES The composition of the product is controlled by the relative ".quantities ' of zinc ojrf.de and of chrcsic acid (actually bichromate and muriatic acid) used. Decreasing the zinc oxide produces a less basic,' -more soluble product} increasing the sine ccd.de ia believed to result in the presence of free zinc oxide inf.the product. The effects of such variations on vinyl rbsin pigpent dispersion properties aC re notM m4> ?kMnMo.wMn. t . < J: process YIELD Ho other control Variables have been: *4. .'i. the new reverse strike \ \ . : -v* ': tei.. :*>** S---. r,; ( VS:* . r. ? ..Uft.-,'. _ i ^ : .-v- of additicnal pla^t ^perieni3p,.JhadSJVI3ycta of v filtration and wash water effluents;fbr scitobi^rfnc .content,, the^ orispuel estimated goal yield for the,"A!* process has.bean retained;.5/ Scaled to the mesjsrefc batbh size,.,. "C^r- ' : . ~;.-i :J^-MAv.yc srr*jf*.!\f * < *$&*&& Z'-} 1 OSOOxli^OO , For costing purposes, the 96,1^`performance factor-of the obablete BC^ v-tet r> process is recossaRidsda. ' ."- * ' ^ ^'S^SdSfcSfc-. /.* 1 ' J . :.i:; `* ' M k'- ' - iTii. * . Sf'>iSV #mt.''.*%! s ' * *' ' . *-1%, < 'fJtfti i'T ., l "j- r/ JCKsCG ,ry x ^ -r.-i-.r i \ * Vi . .-irri i- "rf? r,<, fr `: DUP050068457