Document ByKaBDDK3Vk6p12gggxpKkaRJ

E. 1. DU PONT DE NEMOURS &- COMPANY PIGMENTS DEPARTMENT 256 VANDERPQOL STREET NEWARK, NEW JERSEY i Serial No. Copy No- / nmtz NEWARK PLANT CHEMICAL DIVISION - COLORS FUAL RSPORT bu mbl e o r at fimmus - mmumsm o p *tmmr m,v* h Period Covered 1950 - 1953 CHASCSS: 1100-11-272 :? #.l 210 a/17/53 NJ 8747 Copy to: #1 - Baaerleal Ilia , 2 - Research Office (210} I - literary Hie (210) 4 * I. Araonl Plant Piles 5 - J.H. Tully/A. Siegel - B* R. Onslow 7 - W.P. Spengeman 9 * Extra Serial So* KH-53^14 Copy Ho. / HIMARK PLABT CHEMICAL DI7XSIGH - COLORS FXML REPORT TITLE: DURABLE GRAY POTEBfS - BEmOFMEST OF "ARGEHT GBAT* A*4*l PERIOD COTOED: 1910 * 1951 CHARGE: 1100-11-272 SUBMITTED BT: mm DESSLOSf DATE SUBMITTED; 7/21/51 DATE ISSUED: S/17/53 DUP050069313 -1- KE-53-14 im.OPUCTIijK; This report covers tbs work started early in 1950 on gray inorganic pigments leading to the development and standardisation of "Argent Gray. ATbs major portion of the study mas carried out under Experimental Project #872* mmm..mmtmm* In a search for new pigments which could he used to formulate metallic gray enamels superior to those in commercial use, a number of inorganic compounds were investigated* A number of promising candidates were found* Of these, the one of most interest to P & P and Sales was the material obtained by the addition of sodium hydroxide/aodium phosphate to a solution of copper sulfate* This product was coded A-6-D and subsequently released to the trade as "Argent Gray** The process wee carried through the Semi-works and plant with out noteworthy difficulties and has been accepted by the Production Division* An active Sales promotional campaign was undertaken and the material is under test by a number of customers* Evaluation work has given generally favorable results* iseeat teste have indicated certain deficiencies, the most serious being gloss retention* in which it is apparently surpassed by other products, via. PefcCh/CroOa and OuO/CrgOj combinations. Any decision as to future promotional activity must await the results of current customer tests and the completion of numerous exposure series now in progress. A product/process patent application baa been filed on A-6-B. TABia.pr .pamra* The problem is discussed below under the following heading*; Historical - Development and standardisation of A-6-D Patent Situation Ghemietry of A-6-D and mechanism of its formation Composition aii field Variable Studies Evaluation Studies and Sales Promotional Work Improved Products of the A-6-D type Argent (buy Pulp A-7-P References Appendix Electron Hie Color Chips A X-ray -- A--6--D D'and other products (S-10192) curves DUP050069314 HISTORICAL jSM314S5M; aJHbll Some years ago (circa 1940-1941), F & F (Parlin) prepared experimental transparent finishes from special black iron oxide pigments* These ferroso-ferrlc oxide combination# gave attractive metallica .Including both colors and grays, with a high degree of "two-tone" flash* On exposure, however, they were found to be unsatisfactory because of their tendency .to go from blacit-'tosbrown, presumably as a result of oxidation of the ferrous iron in the pigment. A cooperative study (with Parlin) was carried out in 1944 aimed at the development of a pigment which would give color effects similar to those obtained with the ferroeo/ferrie oxide products but with better resistance to color change on exposure* A partial solution to the problem was obtained by reducing the amount of ferrous iron present by treating the pigment slurry with bichromate. Material prepared in this way was coded as AF-7-P and is claimed* as part of a coating composition, in U*S. Patent 2,466,770. Develop ment studies were carried as far as the Semi-works but subsequently discontinued for two principal reasons! (1) the pigment was similar to P-4-P in respect to color drift of the pulp on storage. (2) it was not a true black but rather a dark brown* Furthermore, indications were that reproducibility of the process left acmething to he desired. Among the other black pigments investigated at the same time was Cupric oxide, prepared by the addition of sodium hydroxide to cupric sulfate. It showed some promise in Parlin9* preliminary teste and was later exposed in lacquer in our Series 6972* also with promising results* Ho further work on blacks was carried out until 1950* In March of that year, the technical representatives of F & F indicated that there was a definite need for pigments to make gray finishes (particularly metallic#} which would be superior to existing products in color and durability* Conventional pigmentations were said to be unsatisfactory in respect to film chalking and fading, making refinish ing difficult* Gloss lose of conventional grays was particularly serious since it was impossible to bring back the original gloss by polishing* Laboratory work was undertaken covering a general survey of blaek/gray compounds to select one or more eandidatss for evaluation in respect to the properties mentioned above. On the basis of the earlier work* further attention was given to precipitated cupric oxide* This la easily made from copper sulfate and 8odium hydroxide. Semite variation in color and strength can be obtained by changes in the method of precipitation* thus making it possible to produce grays of different types when aluminum is added* It was found to give self pigment (masstone) enamels of only moderate transparency and* as a result, the metallics showed considerably less DUP050069315 flash than those made from F-4-P or AF-7-P* To correct this deficiency, experimental samples were by coprecipitating copper oxide with other insoluble products lower opacity but which would be expected to hare s' Products wars also made comprising precipitated (M oxide alone or In combinations. (Work on these latter later since they usually showed rather severe color Preliminary teste for color were made by snail alkyd and panels were exposed in the leaitiarQmeter* On the basle~of discussion of the results with F & F representatives, snail Sesai*works batches were made of the following for further teste* ML. PCLP m M-f-P 3 id if 12 13 $ 15 13 20 21 Copper oxide Conner oxide/____ ,___..__ but higher in Cud (stronger] 'Copper oxide . ____ #e oxide Cooner/Zinc Oxide like A-14 but lower in CuO (lighter) Copper oxide/lead sulfate Copper/Kagnesium oxide In aaestone color, these were all gray or black; with aluminum, they gave attractive finishes, varying from brownish to relatively neutral "metallic grays". these metallica were exposed in S-10192 against metallies from Mapico Black. Lamp Slack, "Ti-Pure"/laap black blends and three commercial automotive refinish enamels* (see exhibits in appendix}* The following samples showed better performance than the others; AA-4-D, AA-6-D, AA-3-D, AA-10-D, AA-14-D. AA-16-D. AA-6-D and AA-10-D were considered as the most promising, AA-6-D being preferred by P & F and Sales because of its more neutral (less brown) color* the outstanding properties demonstrated in this series for the better products were; Color and does retention * unpolished film Color retention - polished film doss recovery upon polishing back three additional Semi-works batches of A-6-D were made si blended (Lot 1421} to supply material for complete evaluation by Sales Service and the preparation of Sales* promotional exhibits. Initial plant manufacture was undertaken in March 1952, three 1450 lb. batches being made* An equal part mix of these was made up as lot 35493 which served as a tentative working standard and to supply samples and fill orders from manufacturera of automotive finishes* Compared with lot 1421* lot 35493 was vs/s light In masstone, very slightly strong (ea 95) and vs/s rad in tint* Additional manufacture (3 batches) was carried out in December 1952, without sny serious difficulties* A new mix (39671/39672) was made up from this material DUP050069316 together with sotoe of the earlier manufacture. and eet up aa the flret official standard. Zt was el dark, re intense; rr* weak (101); re yellow re 05498 and aleo close to an equal part nix of the six plant batches. The process was taken oyer by the Production Division, March 2, 1953* PSiJAS^hTS5E(GNi S*T*w<i8Ssi ijBIwTRP>iSCAShTiRdISOi3S3NS*^s^ An application (Case 1227-K) for a product and process Ment on A~6*D has been filed* The product data* are baeed essentially oh the unexpected amorphous character of the product* This lack of crystallinity la obtained only in a narrow range of composition and by carrying out the reaction under specified conditions* Coating compositions claims hare also been made* The patent concerned with the iron oxide black" pigment, AF-7-I mentioned earlier in this respect in U.S, 2,466,770 (Rucks and Benslow), go consideration baa been given to the possibility of obtain* ing protection on the other gray/brown pigments {A-10-D, etc*) mentioned above. mmmx m,.xomnmi A-6-D is prepared by the addition to copper sulfate (1 mol) of a mixed solution of sodium hydroxide (1*5 mole) and dieodlum phosphate (0*5 mols), thb two solutions being at an elerated temperature It was originally assumed that this would giro a mixture of oxide and phosphate according to the following equation which involves 1.0 mol of caustic, leaving an excess of 0*5 mol* 0.5 Ra(^*25 0u(<)2<),2ibg0k* 0.25 H2O CUSO4 0*5 taOH + 0*5 Na2HP04*0.25^Cu3(POj,j2 Zt has been found that the additional 0*5 mol caustic is necessary to obtain the color characteristics of A~6~D* If only me mol is the product is not black or gray but bluish green end hie been identified as a'definite basic .sail, (CuO:P2054117 corresponding to the and giving the m characteristic diffraction pattern as the latter. tl moi 58SJ tto under specified conditions* it is substantially amorphous, giving only a* slight indication 0 ^ 0uo X-ray lines and no indicatiihi of tbs characteristic l1l1b1ethenlte lines* (See appendix). The particle else is very small* Visual examination of electron micrographs (see appendix) indicate* ft to average less than 0.1 micron. DUP050069317 *5 It is believed that the mechanism of the formation of A-6-D involves, as a first step, the precipitation of the basic phosphate {Cu0/P205*4/1) together with sene copper oxide/hydroxide. As the alkalinity builds up towards the end of the strike, there is a change in color froa hluiah/green to a gray which becomes somewhat darker at higher temperatures or upon aging. Presumably, this color change is the result of the reaction of the excess sodium hydroxide on seii if the basic phosphate as indicated in the following equations, (for simplicity, ths starting material has been assumed to be a normal rather than a basic phosphate } (a) Cu 3(P04)2*6 PaOfH CuO 3 H20 2 (b) Cu 3(P04)2*4 KaOH-3 CuO H2Q f 2 Ka2HP04 According to reaction (1). the quantities of ingredients used in A-6-D would yield, as a filial product, material of the composition 6 CuO/l P2O5 with a substantial amount of phosphate in the backwater. Reaction Tb1 would give $ CuO/l P2O5, As mentioned earlier, of typical have given approximately 7 CuO/l F2O5, the presence of phosphate in the A~6~D filtrate has been shown by the quantitative determination of the ingredient balance in a laboratory experiment, as well as by simple qualitative tests on plant filtrates. The degree of hydrolysis is determined by the amount of caustic used, the concentration of the reactants, the temperature, ami possibly other factors, and is quite critical if an amorphous product of standard analytical composition is to be obtained. With too liitj* caustic, the product is light and greenish, weak end shows to some extent the X-ray lines of the 4/1 basic phosphate. With too much caustic, the product is dark (brown) and strong and there is evidence (X-ray pattern) of the presence of free copper oxide. Co-precipitation appears essential; attempts to form this product by successive addition of phosphate and .sodium hydroxide have, so far, been unsuccessful. Striking at an elevated temperature (rather than striking cold and heating afterwards) also appears to be essential* cmpmmim mm* A-6-D is apparently not a definite compound but more likely a mixture of amorphous cupric oxide apd basic (4/1) cupric phosphate. The copper content, expressed as J5 CuO", runs about 66-i9f and the phosphate, content, as *$ P2O5*. about 16-18& these figures correspond to a CUO/P2O5 mol ratio of M/l Sark products are higher in copper content than the light ones. In addition to the above, the products contain a little over 1# (as *SCft*) of sulfate, most of which is in water insoluble fora and presumably present ae basic copper sulfate. Sodium is also present DUP050069318 (ca 2-3# as "HagO*), probably combined with some of the phosphate as a result of the hydrolytic action of water and/or alieali on tbs basic phosphate as discussed in the section on the mechanical 'of formation of the product* A typical analysis (Lot 25498} la Shown below: Copper ae "CuO" Phosphate as "P2O5" Sodium as '"Kagflm Sulfate as HO** Water aa "ifeO" "Combined water" etc 66<4^ 16.9 i6:.i 5.5 IO0.0 Correspond to mol ratio Cu 0/P2057/1 Chiefly "acid soluble^* By toluene distillation, difference* The "lesion The goal yield (analytical) given in the standard "e formula la: 1527# (aa is) ex. 3250# H-629. The specific gravity of A-6-D is 3*7* The discussion of the mechanism by which A-6-D is formed will serve to indicate in a general way the effects of formulation and process variables on the final product. Any specific information is based on laboratory work; Semi-works and plant batches wert made on substantially identical formulas* The moat important variable influencing composition and color is the amount of caustic used* A slight decrease (eg* 5#/mol CuSOU yes a lighter, greener and weaker product: a similar increase gives rdarker, browner and stronger product* (In general, light products are greenish, dark ones are brown). This change ie associated with the ratio of GuOiPgOs in the product and is also reflected in the yield which decreases as ths percentage of copper is ineihassd* Increased strike concentration gives lighter, weaker material* Decreasing the strike temperature .gives lighter, If the temperature is Increased above the standard figure la a slight increase in depth* However, the difference be _________ and 200* samples is less than that between samples rads at 160* and 120** Development after the strike has considerably less effect than the actual strike temperature, for example, it is not possible by striking at a low temperature and heating subsequently to a boil to equal material struck hot * km atirriM or tends to give slightly DUP050069319 darker products, presumably as tbs result of increasing tbs amount of copper oxide in the ` ...... Increasing tbs strike time appears to have a similar effect to that of long stirring*A very rapid (dump} strike was unsatisfactory; apparently the conversion of basic phosphate to odds was under these conditions* Adding sodium phosphate end sodium hydroxide successively did not give the .earns results as. the standard coprecipitation pros* Indications were that the final product was a simple mixture of ph< and oxide such as is obtained by slurrying these two substances together* In most of the work, tint standard amount of phosphate mail Attempts to make the product with substantially lower 'were not successful* However, the few experiments in' which the phosphate was varied do hot lustily positive conclusions on this point, Triaodium phosphate can be substituted for disodiras phosphate provided that a suitable adjustment in the amount of sodium hydroxide is made* Pyrophosphate gives a product quite different from A-6-D. Experiments to compare direct and reverse precipitation gave inconsistent results* the standard procedure in which caustic/ phatc is added to copper sulfate la believed to be preferable* Some further discussion of variables will be found in the formula notes on the "B" process* EVALUATION AND SALES A-6-D has been exposed in the foll< wise noted, the vehicle was of the baking motive series* type used for auto* S-10192 Gray metallica on miscellaneous products, inclv Semi-works batch of A-6-D (lot 1270), together with , controls. It showed excellent performance (12 mons. This series is discussed in the "Historical* section of this report 3*10271 Includes lot 1270 (ess above ) as well as lot 1421 which was used in the preparation of .Shies promotional exhibits* Siasstones and Metallic** Performance good but goes retention slightly worse than that shewn in 3-10192. S-1Q26A this doss not include A-6-D hut compares copper, oxide (A-4-D) samples mad* respectively by direct and reverse precipitation* These are quits' different from each other 'in color but not markedly different in performance on exposure* 8-10239 Film fortifier study covering 0*203 end and other products* A-6-D included as a control* Masstones. DUP050069320 S-10290 Metallics corresponding to 203139* 1*40304 Sales Service Series. Pigment volume and aluminum ladders. Also includes tints. 1*10305 Sales Service Series* Metallies of blends of a*6*B uitfc other durable plgmenta. l*103j? Sales Service Series, Masstone and Metallics in $ vehicle systems. % of aluminum varied* 1*10325 Evaluation of AGI-734-D. A*6*D included ae a control* 3*10329 A*6*D included as a control in evaluation of 0uO/Or2Si pigment (cf 3*10250). 1*10339 Svaluation of experimental samples of various CuO/PgOj ratios. 1*10342 Comparison of A-6-P and other products for color and film fort;ifying properties in Green and Tallow metallics* 1*10365 Sales Service Series* Svaluation of A*6*D in "Duco* and Rinahed Mason lacquer vehicle. 1*10392 Svaluation of official plant standard (19671/2) 1*10346 Comparison of A*6*8 and other products in blue trim paints. 2=12122 automotive gray metallic is included in this series. further details. Tbs results of presented in a letter. on lot Iton. DUP050069321 A sample was submitted to Grassalli for evaluations as a pesticide. The Glidden Co. in a di: film hi that A-6-B improved fleaf and However, difficultiosi sse below.} A-6-D has been favorable SMiffa*re5TMInd*oictalatendobfelow, gy4Bdiwcr(i3fa3Cfctira) - in our work A-d-D bee been found; to disperse without difficulty. Sons received from the trade. These do not appear eertone since farther work has shown such complaints to be unjustified. Laboratory work has indicated that the texture can be improved somewhat by of certain treating agents. Details have not been worked oat. - F & F reported that workers handling large amounts of A-b-3) complained thaitt i..t....h.a..d...a..n. ..i..r.r..i.tating_ effect. This has not been observed at Fewexk in oar own lank, teste by the Haskell Laboratory confirmed the fact that undue exposure might result in serious irritation and it is planned to label the product accordingly, the precautions normally followed with irritating materials* that is the use of gloves end respirators should mini,mine this hasard. Reactivity * Viscosity stability has been satisfactory in most vehicles* OccasiLcocal difficulties have bsen reported, however* in .specific systems. fflf " Difficulties have been reported on drying properties by three customers - Rinahad Mason, Ferbert Sehorndorfer and Glidden. that this isatioa ini ,, . ............ w . . _ _ _ ...... film. As in the case of reactivity, the effect appears to be rather Specific, varying with the vehicle system used. A change in itspB or ins ajjcya 8 niTmiMW isfffli9# prooiMuinw . ifr 'd.htae w t v m wwVwsD sbwneMevetsl' imo naitVsoyw wteedm^wse^ 'VfcessjMvM'ft'Wt to correct the difficulty hy changee in drier have* sc far* ` Gloss Betention * ^ have a series that tea gloss retention of ............ . Igyeu| as fffd been believed from thy iwwlts of early btf*** (S-10192). More data are necessary before positive conclusioas c be drawn. Exposure series 10397 should xlve more definite information and suggest possible alternatives if A-6~0 fails 'to be generally accepted. BgaOVEP PBODPCTS Qg THE_A-6^D TEFg Hhllo It 1* too mxOjr to ate . rollabl. forocoot of tte ftltnwi of A--6--.fW. oftn.4 rut tm-jj >a.n Kt mb tO Other o_ar s_ji|m_.n! e__r color wnicn )n,ave to,Benenn made a4mn t n'- Tiijs.1xoaloiinotrinattory enJd *wJUm4mcVn teittkfe be superior in n# or more respects* he cf * DUP050069322 -10- special mention, namely (1) combinations of hydrated iron and chromic oxides sad (2) cupric/chrooic oxide combinations. Preliminary results {S-1025S, 10329, 10290) bats indicated that theca types which are similar is color to A-6-D may bo cuperlor is durability. Additional exposure tacts arc is .progress which should sake a dofinita conclusion possible. While A--6--0 was orixinally developed primarily for use is the production of grays, it has been found possible to see it in the production of novel colors; part of it# salsa in such usage may lia in film fortifying properties. Whether it can compete with otter pigments (P-A-p7f **13-D, A-33-D, etc.) in this fldld is still open to quaetions. The F&2O5/GTZO3/CuO pigment A-1Q-D shewed excellent performance in S-10332 and other series. It lacks the relatively neutral color of A-6-D but might find application share the exact color-of the .latter is not essential. &v`tsmnir. Qfa? *fe<m filtered xives a vult) of 30$ solids content ; thi is coded as A-7-P. laboratory (spatula) flushouts indicate it to give results .are <y idNisMtieel with with the dry product* Flushed enamels wens made by F & F .in' their early evaluation studies* Apparently no advantage was obtained by -bf teefaniaua since their later work wae based entirely on the dry product# An attempt was -made to flush the pulp into alkyd resin in our small Semi-works &f mixer. The experiment was unsuccessful .in that a transfer was not obtained and the * *. wmmtfiffa-y*r-^ryt Due to tea presmare or other items on the program, no further work was dene to work cut more suitable conditions* A-7-P has bssn flushed into pyroxylie without difficulty, .ho detailed (2 roll ,, .made with mourns this -can be cowering the worfc #272 as well as the laboratory to evaluate Project So further work on A-6-B is planned aside from what may be in an way in the development -mad evaluation -of pr^d^ts .ffUidh as t-b"**** mentioned wader the section Improved Products of the A-6-D Type". DUP050069323 i* on "Gray*. i* 1372-11, 13, 15, 16, If, 2, 23, 24, 29, 31, 35, ^ 37, 47, 50, 52, 56, 60 1369-15, 17, 20 " ` ` of 1-6-8 is 1220-50C Experiments on Cu/Cr Qxlds SB 1369-39, 45, 64. 74, 75, 76 Expos. Series UB5 10329, 10397 Seal-works and Plant Davoloposent - 4-6-8 D8S 53-7 1372-423 1369-58, 59, 62, 63, 731 1441-69 Standardization DSB 53-7 ____ __ (Miacollaneoi -4-^72. % fL,.sri4 'hU'd: U*5*- I, 19, 21* *--*' Analytical Data - 4-6-8 1441-6, 9, 40, 69 Patanfc Stadias (inciting X-ray diffraction studies). 1369-77} 1441-4, 12, 16, 20, 71, 72, 73 Sse alao correspondence in Texture - 4-6*8 1441-70? DSS 53-7 HUWrtTMJfMSfWcii AUYH"*?* WnOwfll jPMl'nTat^flalkiiwra t2#Si. with Haskell laboratory (1953) Baa alsc"DSN-53-7 DUP050069324 %jsm%vti aAx-y&x&x DUP050069325 Figtms 1 X-ray d iffr a c t ion Curve o f Cupric Oxide I 1 ) 1 >t m ')M DUP050069326 & ! I 1 i * 1M W <*S 8vft DUP050069327 ri DUP050069328 trpj #fW|ilKEK dT**S trpj aps-ag @trp| wdeot& oppjg #18*9 -- OSt'C^ *m*i ^tqdosH o'es'sfii mjq ajpwplsoqa OT*^ rpj pp0 joddoo up*j oprpto <s<M0 0X6*2-- 2^9*2-- CtS02- 22~ />< ---V-- -~f-- - S8 \o0 oft O^ .. &o\ 0W uCppeas^wj 3Axq.rt;8H 4 DUP050069329 mm HBTA3LL1CS - S-10192 ID A4-9 (2) A-&-D (4) A-10-D (5)A~12~P (6JA-14-D C7)A-l6-0 (14)Ll&a tan *49 Lineola (15) Sunaiat Qyay *50 Buick (16) Guruaefcal *50 Chrysler DUP050069330 mmmm g ea i a ^b Magnification 35OOX. DUP050069331