Document oe0BbeJym8D2nyOwJXKq5Nk0X

A A E. I. DU PONT DE NEMOURS & COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOl STREET NEWARK, NEW JERSEY Serial No. Copy No. k *53~12 X Numerical Pile r( !*3L -1 Period Covered NEWARK PLANT CHEMICAL DIVISION - COLORS h p MULim c p wmmmmmm wmmm n mah c s * 1950 to Aim i, A v< NJ *747 PILE: DATE: J Copy to* % #i4 Bollding File 10. Extra 11. Extra [ Serial No. KN-53-12 Copy No. 1 , NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Progress Report m MILLING OF PHTHALOCYANINE PIGMENTS II s t u d ies in wmm, MARCH, 1950 to APRIL 19 1953. CHARGES A-II-C-261, 297 s u b mit t e d it* 7/rr/ri APPROVED BTi J</H: COOPER 7/6/53 DATE SUBMXTTEDs June 15, 1953 DATS ISSUED* July 27, 1953 DUP050069383 X It ms one of the original objectives of the phthaloc^ranine research at Newark to condition the product for pigmentary use by milling in water. Research reports Kl-46-19 and xi-46-55 summarise the discouraging results of that early work, in general, any phthalocyanine pigments, when ground in a ball mill with water alone, did not increase in strength and frequently showed a loss in strength. On the other hand, a few dispersing agents, notably amsonium n&phiienate, .did prevent .any loss in strength and, in sous oases, preached a significant amount of particle size reduction. However, a rather extensive study failed to give results approaching the desired goal, and the method of milling in water ms abandoned in favor of the use of organic solvents, which work ultimately culminated in the acetone milling process now in use at Newport. More recently, Research Report .KN-*&13 has described a new process ("HF" milling) for milling in acetone wherein a mixture of pigment, acetone and a finely divided inorganic salt, such as sodium chloride or borax, was milled in a stirred mill with a high energy input. During the course of this work, attention was turned to the use of water-acetone mixtures and ultimately, again, to the use of water alone. As in the earlier work, water alone in the presence of the finely divided Inorganic salt was not an effective grinding medium. However, certain dispersing agents were shown to promote effective particle size reduction In such a system and the studies covered in this report followed. stmAian A process for the particle size reduction of phthalocyanine pigments by milling in water with selected dispersing agents has been developed in the laboratory and carried through into equipment suitable for full scale plant operation. In this process, a vessel of 100 gallon working capacity and powered with a 30 H.P. motor is capable of milling about 750-1,000 lbs, of pigment per day. This Kess has been proved for both CPC-LB and for polychloro CPC n,and is being used for plant manufacture of specific products at Newark. The end products of this process are two dispersed pastes coded BT-352-P and GT-735-P, which are capable of being converted in the Newark plant to a number of products for sale. The products include two standardized dispersed pastes (BT-353-P and GT-732-P), two dry colors designed for use in latex dispersed paints (BP-358-D and GP-7*+0-D), and a substantial amount of BT-352-P has been con verted to the linoleum lake BL-288-D. Tentative processes have been worked out fof the smnui^ture of water dispersible dry colors comparable to the W.D. colors now purchased for resale from Orcham. products under consideration are the regular grades containing dextrin, and also dextrin-free products suitable for coloring cement. DUP050069384 Substantial progress has been made in the preparation of dry toners comparable to the standards now offered for sale, and in the conversion of such products to other standard phthaleeyanine colors* The best laboratory products lu this work have approached the desired strength, but these results have not been consistent and United studies in the semi-works have left much to be desired* An incidental result of this last work has been, that, one of the dispersing agents tied, though not idle most desirable one, haul given a substantially flocculation resistant toner* mmLwsm* Memorandum deport HLK-53-7 sussaarises the prior art on particle sise reduction of phthalocyanines and related pigments* Although the art is quite dose, it is believed that patentable features exist in the new process, and it was recommended that a patent application be prepared* It should be noted that considerable work has been done by Orehem at Jackson laboratory, substantially parallel to the work at Hewark. but they have emphasized the use of finely divided sand ? as the grinding agent Instead of the finely divided inorganic salts* They also propose a patent application on their modification of the process* U Essentially, the 0 process involves the application of an intensive shearing action to a suspension in a liquid of a mixture of the pigment and a finely divided inert solid* In the modifica tions described in this report, the finely divided inert solid is a water soluble inorganic salt, preferably borax, and the liquid is a saturated aqueous solution of that salt* The liquid also contains in solution a dispersing agent, which is preferably the condensation product of naphthalene sulfonic acid with , variously sold under such trade names as "Blancol" When the desired particle else is achieved as the result of the intensive shearing action, the Insoluble portion of the inorganic salt is separated from the pigment suspension by decantation and the pigment is isolated by flocculation in acid medium, filtration and washing* For most purposes, it is prefer able to retain the pigment in the aqueous paste form. The equipment used is substantially the same as that described in considerable detail In KN-52-13. However, for the plant development studies and the present plant operation, a 100 gallon prefabricated Cowles Dissolver was ibtained and has bean quite satisfactory for the purpose. The tick has an actual capacity of 130 gallons and a diameter of about 32 inches* The agitation Is provided by a 30 H.F* motor operating at about 900 r.p.m. Various types of discs have been used for the shear ing action, but the major part of the work has beau done with a 22 inch smooth disc* DUP050069385 One feature, which has made this process economically attractive on a commercial scale, has been a means for separating the undissolved borax and recovering it for subsequent use in a later operation. Substantial dilution (3-4 times the original volume) with cold water permits the borax to settle rapidly, and a .Dorr rake classifier has proved sn effective means for separating the crystalline borax from the dispersed pigment suspension, fhe recovered borax, in the form of a sludge of about 65f solids con tent, Is used in a subsequent charge with additional new borax to make up the required total* The settling process also serves to remove from the dispersed pigment any over-sise ungrotmd pigment. Generally, this is an advantage to the operation) but it has, on occasion, caused difficulty when there has been a substantial amount of hard particles in the crude pigment, because the un ground pigment tends to accumulate In the borax sludge and reduce the effectiveness of the over-all operation* This has never been significant in operations with CPC Blue LB, but It Is frequently a source of son trouble with CPC Green* The use of the Dorr classifier for separating the borax has been quite successful on the plant scale* Nevertheless, careful observation leads to the conclusion that more effective separation of the borax could be obtained, if there were an opportunity for a brief period of settling without any agitation in the system* There are available types of classifiers which would meet this requirement or it could, perhaps, be done in a simple settling tank with sense special provision for removing the sludge from the bottom* It is believed that investigation of this step is warranted in the future* Although it is not directly a part of the problem) under discussion in this report, mention should be made of the use of the Manton-Gaulin Bosogenizer in the standardization of products made from the pastes resulting from the HP milling operation. The homogenlzer is essentially a device for passing a fluid suspension through a special valve with a very large (approx* 5,000 p.s.l.) pressure drop through the valve* The actual valve comprises two relatively flat surfaces, with the liquid entering through the center of one of them and passing out between them it3 tlN*p on a ring which surrounds the cM** of the valve* Although there ha# been little evidence of actual particle size reduction in such an operation, it has proved exceedingly effective in dispersing products which appear to have been agglomerated, and thus has significantly improved the effective strength of many of the products which have been made available for sale* DUP050069386 b In the later staged of this work, consideration has been given to alternative equipment which might be effective in re* duelng the particle site of phthaloeyanine pigments within the general frame-work of the process described here* For instance, the relative merits of single and double discs have been explored in the laboratory, and there has been little evidence thattun discs are significantly more effective than one* Heeent work in the F&F Department and at faeksoa laboratory suggests that a series of discs, perhaps 6 to 3, spaced fairly close together, may give a marked improvement for continuous operation over one or two discs* this has not been explored at Newark* It has been suggested that a long cylindrical grinding agitator operating with relatively close clearance within a cylindrical vessel might be more efficient In an over-on operation than a disc type agitator* Such a device was con structed, but not tried out during the period covered by this report* This type of operation was simulated to some extent by repeated passes through a colloid mill with a conical rotor, which operation has given a substantial degree of particle sine reduction, but offers no economical advantage over the process described above* It appears safe to conclude at this time that there is no obvious alternative equipment which offers any economic advantage over the Cowles Dissolver for large scale operation of this process* AL RESULTSi The experimental results will be considered first in a very general way including the historical aspects of the work and the use of some new testing techniques* Subsequently, more details will be given on a number of individual topics. During the work on HP milling with acetone, which is reported in detail in KN-52-13, consideration was given to milling tdie crude pigment in the fora of an aqueous paste* This resulted in the presence of some water, and was successful when a crude paste substantially free of kerosene was available*.,' This led to experiments with further dilution with water mod it was possible to mill CFG Blue in a 50$ acetone - 5C$ water mixture (by volume) with only a slight loss in efficiency from pure acetone. Below 50$ acetone there was a serious drop in efficiency, but even 10$ acetone was markedly better than pure water* In March. 1950, a critical experiment (1191-50) suggested that the right dispersing agent would permit the complete elimination of acetone* With 2$ high viscosity Carboxy Metbyl Cellulose (CMC) in a 2 hour grind with borax, followed by decantation and flocculation with C11CI2 plus HCl, there was obtained a dry color which was about 15$ weaker then BT-lw-D, DUP050069387 -5 but ftpee from dullness. Subsequent work has not supported the use of CSC as a preferred agent, hut these Indications of success did lend hope to that line of research. It was *wiw* w m* jajtommvj. ~ , a poljwerised _____ition pi___ of ph.hft*! ana awl fV>w< acid egg form* was sore'effective than CMC 'In promoting particle --*- la aqueous ml with borax. Beginning with the obsi thefollovlng la the development e he recognlzea. ! The in a dry color of other agents and combination of agents 2. The recognition that many products made with a large amount of dispersing agent, although weak as dry c olors, were quite strong in the paste form* 3* The development of a particle sine index and the demonstration that* with large amounts ot dispersing agent, the particle else index continued to decrease with tine of milling. and went considerably below that of the tf.D. plgnents obtained from Orchea for resale. *+ The development of tentative processes for W.D. colors, hut the ultimate decision to set these colors aside because of their high sodium content. pastes and their translation te plant operations. Tide also included the tentative standardization of products for sale and considerable assistance to the plant in the standardization of these processes. 6. The re-Hexaaination of some dispensing agents recognition that some of them ware especially promising preparation of dry colors. The following table summarizes the various dispersing agents used In these studies. DUP050069388 -6 t - sggtj&taiai Blancol ftoTWMl li Tamal 5 Compound 8 Mp b Us s General Dewey & Alaqr Bohm & Haas DuPont I Polymerised condensation product of naphthalene 0 sulfonic acid and ) formaldehyde II -j Poatas^ine,, Past Turquoise 8GSi* DuPont - CPC polysulfonic acid* Zndulln XB-3 Industrial Chem.Sales Dir* (Sulfonated Lignin (West Va.Pulp A Paper Co*) (3-sulfonic acidgroups. ' Lignins with sulfonatlon *ii of value* Orzan Crovn-Zellerbach Marasperse CD) Marasperse % ) Marathon Corp. Ammonium f.tgt^w sulfonate.' Lignin Sulfonates. Ill- CMS Fetronate Indulin Muroaic P-68 Sodium Hosinate DuPont A others* Sonneborn industrial Chem.Sales Atlas Wyandott Carhoxy Methyl Cellulose Petroleum Sulfonate Lignin Polyoxyethylene-Lauryl alcohol Polypropylene oxide derivatives I?- Triton X-100 Aerosol Of Bohm & Haas Amer. Cyanaalde Aerosol CMfe Seen 20 Victawet 12 Victawet 35 Santomerse DT Igepon f Arctic Syntax T Ammonyx CO AO km Amer* Cyanamide Atlas PiBeter Chetlmical Monsanto General Dyestuffs Colgate Palmolive Onyx Oil A Ohio. m m Montanto Ferro Chem* Corp* Ucon Carbide A Carton 4 Polyethylene oxide derivative Dioctyl ester of saiSMa sulfo succinate A quaternary salt* Sorb!tan monolaurate non-ionic phosphoric acid ester Phosphate* higher alcohol " Sulfonated amide of oleic acid .Same as Igepon f A quaternary iodide Dodecyl diaethylamlne oxido a Dihutyl phenyl 3 sodium Acid ester* of pelybesic acids A their amine salts* Polyalkylene DUP050069389 7 Atlas G BOO Lustrex 820 TEAC^g st* Hai^O^ Sodium Folyphos Hethyl Cellulose Ammonium Styrene Maleamate Aromatic Sulfonates ff<athfliml iMtm> Tltanate Atlas Monsanto DuPont fietor C Dow Da Pont wyaadott Da Boat Probably ail andne derivative Styrene Maleic add fw afr-hannl amrf tyi ester Of lauric add See formula Sodium polyphosphate See See' Considering sone of these agents in nor detail, the In the first group are all similar In chemical composition, differ somewhat in the ratio of the alpha and beta isomers of naphthalene sulfonic acid present. There are only minor differences In effectiveness* The agents in the second group are less effective than Blancol for aqueous dispersed pastes, hut have beta more effective (especially Indulin XS-3) in the preparation of dry colors. Foliated lignins have seemed to offer peculiar advantages in products* The value of the sulfonated CPC ("Pontaadne" Past Turquoise GL) as a dispersing agent in such a system was and offered the additional advantage of a flocculation reels The high cost, however, makes its use economically unattractive The agents in the third group have shown just enough promise to list as of potential value. CISC has given some good products, hut the results have been undependable. It is speculated that It may hydrolyze to varying degrees during the flocculation stags, but this has not been confirmed. Petronate and sodium rosinate have given evidence of particle else reduction, but this has been accom plished with severe foaming .which reduces the effectiveness of the milling operation. If the foam could be controlled, it is believed these agents might have definite veins In the preparation of late. The nan-lonlc agents, Brls 35 and Pluronie P-6B have seemed mere effective than other agents of this general type. There was also some evidence that they were beneficial in cdsbinatlcui with Hansel. They may, therefore, deserve more study. Some of the agents in the last list, aotsaHy Tictawet M, Arctic Syntax T end tetra sodium pyrophosphate, gave some alight evidence of value when used in combination with Blancol, bat Ihtt . improvements were slight and not always consistent. Many of the agents were not tried in such combinations? hence it is lack of information, rather than negative results, which is reported in these cases. DUP050069390 8 In studied on the effect of the amount of agent, particularly Blancol. it was noted that an optimum strength of dry color existed at about % agent. Above this point there was a serious drop off in dry color strength, yet flushed color strength continued to rise. This led to testing these colors as dispersed pastes by casein brushout,and colors with 10% or wore agent were found to exhibit high quality in this use. When the amount of agent exceeded about log. however, there was considerable difficulty in flocculation and filtration, hence the great bulk of the work was done with 10g of agent. On the other hand, it was known that the W.D. colors (BP-192-D and 0P-501-D), which are nado by Orchem, contain the agent in an amount of about 60% the weight of the color coni Some charges were milled with large amounts of Blancol, and __ both as aqueous suspensions and as dry colors obtained by simple evaporation of the water in Ike suspensions. At about this tHis the Physics Group at Newark proposed a method for a particle sis# index based on a spectrophotometric transmission curve of a dilute sus pension of the dispersed color. This nsthod is described in detail in KN-51-^3 and the theory back of it will not bo repeated hero. It will suffice to point out that the particle's!* index (PSI) is defined as the ratio of the optical density (Di) at the point of maximum transmission to the optical density (Dg) at the point of minimum transmission. Since this ratio Is always loss than 1, it has usually boon multiplied by 100 to give a whole number. Tie formula then becomes: PSI * Jh X 100 "TS------ This number becomes smaller as the particle sine becomes smaller, but no correlation has been established between actual particle sine and the P.S.I. When the particle alee index was obtained on the experimental products ground with a large amount of Blancol, it was found to he less, in many cases, than those of dispersions of the W.D.enters. It was also shown that the P.S.I. in such cases was a function of the time of grinding, and it was utilised as a routine testing method to follow the degree of particle sine reduction. It then became apparent that, when small amounts of agent are used, the particle else reduction did not proceed smoothly. For instance, with % agent, the cupeeomparing particle sise index vs tine would reverse after about 15 nlnutes and the P.8.1, would increase sharply. Using 10% agent, the decrease In P.S.I. would continue for about ho-45 minutes and then a slow Increase would start. With about X% or more of agent, there was no evidence of Ike reversal in P.S.I. with tine of grinding, though there was a tendency to level out sooner with lower amounts* During the time of actual grinding the slope of the curve was more or less ini of the amount of aent present, so that one may conclude that increasing the amount of agent functions largely by Increasing time of effective grinding. M DUP050069391 Another important observation regarding the effect of idle amount of agent say he made when additional agent is added after idie particle size index has started to increase markedly as in a charge ground with % agent. The charge will he seen to beeome much thinner, and within one or two minutes the P.S.I. will drop to a point approximating that whieh it would hare reached in that time if all the agent had been present throughout. The fallowing explanation appears to fit the observed facts. As new surfaces are formed by fracture of particle, the agent fi " "" " there is any free agent in the solution* inuring this interval, the system is well dispersed and thin, the particle size index decreases with time. When, however, the agent has been adsorbed on new surfaces, any further new sur faces which are formed attract each other and the absence of dispersing agent results in a flocculated system, wherein the particles tend to grow in effective size, even though some of them continue to bo fractured. If , now, one adds more agent, a minimum of work is required to redisperse the system and to take advantage of ail the fractures which have occurred in the meantime. So serious conflict with this explanation has been found. Figure 1 shows curves relating the P.S.I. to the time of grinding and to the amount of Blaneol used. When colors, which have boon ground beyond the point of minimum particle size index, are tested by casein brushout in the normal maimer, they become weaker with increasing tins of grind. It is believed, though not fully established, that such colors are inherently strong and this strength can be realized by applying a certain amount of work, as in the homogenlzer, with additional agent present. It has also been argued that strength as a dry color should increase with continued grinding after reversal of the P.S.I. There have been observed trends in this direction, but not to the exthnt hoped. However, there has never been any significant decrease in strength as a dry color in these samples which do show decreases in casein broshout strength. DUP050069392 P a rticle Size Index Figure I DUP050069393 5# Blaneol * 1055 Blancol *15# Blancol # 25% Blancol % Blaacol added at points of sharp inflection on first two curves. P a rticle Size Index 51015 20 30 35 *560 65 90 Tim of Hilling (Minutes) Figure I 120 DU P050069394 11 * Before continuing with a detailed discussion of tbs process as it applies to different types of colors and to specific codes* It is veil to consider! in a general way, some of toe operating variables which have been studied* The following statassents are quite general mid applicable to the process as a whole* In the first place, it is necessary that the crude pigment which Is used -in this process shall he in a'" powder form before attempting to .dll it* Any.leaps of pigment are if at SIi, in this process, and it is therefore necessary that t! product he pulverised at the beginning* Xn cost of the work* * simple low speed pulverization was used, and proved quite satis factory. However, sons samples of crude pigment, particularly CPC Breen crude, have shown a considerable content of very snail, but very hard particles, which do not readily find themselves to further sub-division in this process. A partial solution to this problem has been high speed pulverization* Xt would appear, however, that the basic solution to ths problen goes further back in the process in avoiding the formation of such very hard particles. This problen has not been significant with CPC Blue* and low speed pulverization has been satisfactory there* Substantially all of the evidence accumulated in this work points to the rather clear conclusion that the rate of particle size reduction bears a direct relationship to the amount of power applied to the system* Hence, most of the ordinary operating variables are effective only in so such as they influence the amount of power which can be applied to the system. For instance, the rate of application of power to such a system is in direct relationship to the speed of the agitator and, high speed agitation, other factors being held constant* always gives a faster rats of particle size reduction. Xn the laboratory equipment* speeds of 1250 r.p.m. and 2**50 r*p*m* have been readily available, and the higher speed has given a substantially higher rate of milling at all times. As the else of the equipment has been increased, it appears that the peripheral speed of the agitator disc should be kept mere or less constant at a value somewhere above 2,000 ft./min. Xn the small laboratory vessels * the diameter of ths disc does not seem to be a critical factor, although nearly all of the work has been done with a 4 disc in a 5* vessel* Also, most of the work has been done with two discs whereas recent evidence Indlcatac that a single V-l/2" disc is fully equal to the two discs* Hi a lb" diameter vessel in the semi-works, discs of 8" and 10* diameters* operating at speeds of about 1750 r.p.m. and 1500 r.p.m. respectively* have given results substantially equal to the laboratory results. When the diameter of the vessel was Increased to 18 with these same discs, ths rat of milling was lliierfefiy v reduced but, since the charge was larger, the rte per pcciS of color was not markedly different* Using still larger vessels, a 32* vessel with discs from 18* to 22* operating at about 900 r.p.m. gave results comparable to these smaller vessels in terms of rale of mining. DUP050069395 12 * The ratio of borax to the pigment being ground has varied over a considerable range with rather interesting results* Much of the early nosh was done with ten parte of borax per part:- of pigment, bnt substantial reductions have been possible in the nee of boras without any major changes in the effectiveness of tie operation* reduction in borax without other changes results in a thin nixtore which does not grind well, bnt ifthe pignent is f sanewhet9 pea the water reduced so that the over--all aharg* in the vessel is t in volume and viscosity as with tbs original ten parts of r. .im ate of per pound of nisowiit ie' very close- to - ___JmBm* JPB&FXy i.i O* . ww XArgff 908X0 Op9Tlra33S have 'been carried oat with a maxlmm of five parts of borax per part of pigment, and a few charges using somewhat lower mmm*. of borax haws been successful. It is believed possible that the amount of borax night bo reduced to as little as throe parti per part of pignent if mam additional work were done* She particle site of the horn; appears to he rather critical in this operation* Crystalline borax which has a particle also of roughly 20-30 nosh# has been quite poor in this process as oca to the finely powdered borax, noeh of which is finer than 100 Very little is known about the particle also of the which has bsen used again and again in the commercial Generally, it is believed to be quite mil and comparable to j powdered borax which is used in the beginning* however* it is suspected that sons charges which have been allowed to 1 hot have grown larger crystals of borax* and there have m*w wgur indications that such charges of borax do not grind as wall as the store conventional fine particles* The influence of the temperature of the grinding charge has been rather Mysterious In the laboratory, there has been no dlfflc^Lt^in^keeping^the chargesjiool,jtad sutotantlall^ sll^. cooling^water^whichllas beaa^below roomPtai^j^ttire On the*?' ' other hand, in the larger vessel used for commercial operation, it has not hu possible to prevent sense temperature rise* It is not believed that such a temperature rise has say effect on the pigment as such, but it 'has two effects on the over-all systei both of which -ash undesirable* ' In the first place, act of t! borax^goes into^aol^ionjat^^w^higher takerstures^and is- higher temperature reduces the viscosity of the ad* reduces tft* ability of 'to absorb afe* allied to the agitator* Consequently, it has been oba all charm which exceed abqutWC In temperature show a lower rate of grinding. llso, in the large vessel at thei temperatures, a cowpjiex system aevexops an wmen oorax goes solution m lie main body of the liquid.but tends to out near the cold walls and build up a layer of which becomes an effective Insulator and reduces the rate of heat transfer from the sain body of the liquid, this, of DUP050069396 13 becomes a viseious circle and the main body at these conditions, may beat up quite rui-rfeiw- 1 to avoid these drastic conditions by e. material from the malls between batches, w general tltfeFi# in the vessel such that an erature bulld*uo cannot occur* It has been generally acceptedthat the viscosity of this system should be kept fairly high* However, the system is quite thistropic, end very little is known .as to the exact viscosity which exists or which should exist* Obviously, the viscosity " w*pa*n b*f e^* <<>n*< f l HflWn4 >w lu> t^f o**TMa*m**^*i*i*.iwawimeslivn* 9. airf W,eayr tahnwaerne eeepemviFUnsauna ua'*ftp**ppm of either the pigment or the borax, or both, in the liquid of the system. It also shoes- an apparent increase during the grl as the particle sise of the pigment becomes smaller* In " tory grinds with small amounts of treating eg , the a^^^Fpfl*F9p)F:^^aF^*r.^e^F1n****tF viscosity shoes a very marked increase coincJ with the point where the particle else index begins to Increase, and presumably corresponding to the point where all of the die* parsing agent has been adsorbed on the particles of the pigment. Substantially all -of these variables influence the with which energy is absorbed by the system* and tbs of the variable which increases the absorption of the energy ii>* been the desired direction. Tims, with a thin s a disc, large aomr owunittholfowposwpeeredtoatghietastyiostne,mitanidsthime proastseibolef grinding is always slow. On the contrary, a thick high speed agitation resulted in consumption of id, invariably, in a more rapid rate of dVwise |VtlifSl| dAt *pki- appears to require very close to 0.5 B.P* meat to result in the desirable particle ...... a plant charge of 125 lbs* using about 25 B.P. 2 hours applies 0.*f B.P. hours per posutd of been on the border edge th# power consumption 'bee 'but even this consumption of power in it was shown tiet the perM^e efiT p & smodmct ground with relatively large amounts of dispersing agent was actually loss that of either the water dispersible 'dry *(BFf -o1.9V2-Do aenad 0P-5H-D) purechnaseda from Orche* for yesaSn, m immediately suggested that the nons product afo***^1* be eepyb^e of. being converted into satisfactory 'water eolmm. &s. thefirst attempt in this directicj q . ijytt 0P "the Ingredients of- tbs W.D. colors' (CPC about 30, Blaneol about 20g, end Dextrin about fof> were charged to the miser with water to give a fluid mass and sand as the grinding aid* In the absence of cooling, this Mature became quite hot -in the HP mixer and there was sufficient evaporation to cause the mixture to bosoms quite viscous* However, ilfcea starting with CPC in the form of a * a fcffch'la development of DUP050069397 the resulting product v&s elvers **irBrny vea^er tva^> :atpdrd seoiaenerree suspension, ana mm particle same indices approctabiy lower than those obtained from suspensions of the standard color. As.*w*r exoece ted. theso go*<r*oducetes*v. e--xhibited *s-- tra--*ea>ezs wtht hr.e^as Tpeaao<MSN*iMwNi brushoutawn waareenewnaa ijy better than to* standard colors nos wean* Bnifl, t nearly every ease, however, this strength could he appreciably in* . creased by adding soe dextrin prior to drying 'Hie products. this process Has studied rather extensively on both the laboratory and the seat-works scale and, in general, the process variables outlined above apply throughout. In the laboratoryf grinding tines of froa one to two hours ware quite satisfactory with a Stage which included 6Qp Blancol on a pigaent basis and about ten parts of borax per part of pigment. However, the particle else index and the strength would show additional advantages up to four hours or more of grinding. The seal-works appeared to require somewhat longer grinding time,with two hours a hare minimus, and a somewhat longer tlao definitely advantageous. It would appear that the Blancol could be reduced considerably below the 60J( level,which was used in most of this work, and it is believed probable that there is little advantage in the use of mere than k&t and tint it might wall be reduced to around 25-30JS .Host of the semi-works studies were carried out on CPC Green and a tabulation of all of the batches Bade in the semi-works is included as a part of the appendix to this report* (See Table 1) Although tentative laboratory standards were set up on both the bine and the green, end although a rather slseable amount of material was prepared in the semi-works, end made available for evaluations* several difficulties resulted In this work being abandoned for the present. In the first place, all ef the crude pigment available for our pee is contains a: rather ^aewnt of ewyepf -isfe* Met- **f**t of which is a significant amount of iohle copper. " The process, as described above, does not provide for any farther purification - by extraction, end these impurities fiv find theft* way into the final product. It was iudiad that, before this process could be successful, it would to necessary to obtain a purified crude pigaent, and this was .not then available. . DUP050069398 15 The second difficulty lay In the finding of a practical naans for separating the borax from the ground pigment without excessive dilation and consequent solution of some of the borax* On a small laboratory scale with a wall tion from the borax can be readily effe< either through a porous stainless steel _ filter cloth. This filtration can be accomplished with only that aslant of dilution .necessary /it wash out the grinding vessel, is <ia'waifi'iy ^s>s than one vdtsse of water| a iigh with water leaves a relatively colored borax cake on the filter* ` ` - - .........................- on a larger the filter i diseersed pinssiit1 to llliite with water to a sufficient degree to obtain separation by settling results in dissolving a large amount of borax, all of which appears In the final dry color* Host of the seal-works charges were finished by the latter process and contained approxi mately 50 borax in the final dry color* For some purposes, this borax is not objectionable, except for the fact that in the drying operation at normal drier temperatures some of the water of crystallisation is lost, and if earn la not exercised In diapersing the pigment in water, there is a marked tendency for caking as the borax is rehydrated* Hueh more serious, however, is the presence of the large amount of sodium which has bean found to ba vary objectionable in certain applications of such colors, particularly in paint based on rUbbar latex as thevehiele, wherein such a large sodium content invariably tends to result in efflorescence in the final paint film* On the other hand, colors containing dextrin as in the current standards of the water dispersed colors, have been quite objectionable because of the tendency for the dextrin to faction of paints containing such pigment, and to at to surfaces painted therewith. Also, ec dextrin are unsuitable for use in eelerimg products Portland Cement, because they result in a serious loss of structural strength of the cement, the products containi* borax and no dextrin are free fro* these defects, but the _ 'Sodium content does not permit their general acceptance. It is. apparent that the desired type of and be substantially sodium-free* An approach to such products has been made by ,,------0 additional dispersing agent to the dispersed paste colors (which will be described In the next section), end subsequet them out either with or without mechanical treatment --. drying* fhe Orcbem process involves the evaporation of from a mixture of the pigment and dispersing agent, and quent plastic milling in a kneading type mixer* As a w.___ sent for this expensive equipment, an alternative procedure tried involved evaporating the water from such a mixture in the W mill *iw i Mng the clastic milling in this machine. Such pro- .duets aouroached ^ Wfth eiaieaO%fitfye epppfts'fffr- lng 50*, but the operation was- not particularly attractive from DUP050069399 - 16 * Some further work on this type of A more practical approach involi of a mixture of the dispersed paste and added dispersing agent, followed by drying of the pigment paste. This has resulted in products which elosely approach Hie strength, on a pigment Oasis, of the present W.D. colors. Pro ducts of this type have been node rod proposed for use in coarot. The general effect of varieties in the Billing operation has adequately covered above. However, two closely related it not specifically a part of the Billing operation, groo study before this phase of the problem could be established m a ' al scale. As already pointed out, the efficiency of increased markedly with increases in the a*ount of Blaneol mover, this -increase also resulted in a narked increase in the difficulty of isolating the pigment from the dispersed slurry. In the laboratory, products ground with % of Blaneol were relatively easily filtered froo an acid slurry. Products aade with IGjC of Blaneol coUld be filtered, bat the operation was apt to cause considerable difficulty, in tbs first semi-works study with 109S Blaneol, filtration proved Impossible, am* it vas necessary to search for better naans of flocculating the dispersion. It has been reported elsewhere that products similar to Blaneol can be precipitated by means of aany cation active c Multivalent natal salts such as barium chloride or aluminum sulfate" have been said to precipitate the Blaneol type product, but in this work such agents have not precipitated Blaneol in acid solution. (hi the other hand, many cationic organic agents have been success fully used. Such products as quaternary ammonium salts and diphenyl guanidine have been especially successful, and the choice turned to diphenyl guanidine as a readily available product of moderate Thus, upon the addition of a small amount of a solution of dl guanidine sulfate or diphenyl guanidine hydrochloride to the____ slurry of the dispersed product obtained iy milling with log or more of Blaneol, the SLurry is completely dispersed rod can be readily filtered and washed. Although this product is flocculated and readily filtered, the saddled cake is readily redispersed to a fluid slurry which remains completely in suspension. There i* frequently some loss in strength compared to products which have been filtered without the flocculation, but, even with this logs of stroll, the final products, which have been ground wlthlH Blaneol, have been ropy*durably stronger roo more Intense ' standards which 'had been heretofore available far sale as__,, pastes, namely BT-287-P rod GT-675-P. the blue dispersed past obtained by this process is alias's greener tl..~ * * -' green diffparsed has generally 1 previous standard. iiUaiatA these hue deviations from standards are considered to be in the undesired direction, theless, the marked intensity of tie products has * '* desirable than the previous standards. DUP050069400 - 17 - falila TT xiwimnHnnita 4w fan '* aiftmmm a^Wee .. . ,_ _.,___ _ ,,_, _ during the development study of a dispersed paste of CPC-ts. of those batches wore made in a 13 gallon ismt on the Covies Dissolver using a single 10" disc at 1500 r.p.m. foes of were made vith % Blanch, and some of them with 10% Blanco ___ of the batches vere node vith 10 parts of borax per part of pigment? ftnft 'ha^tuftfo 119ml ;five parts Of ^MfMwyv aM |]gp| i " ** o ^--*0f1* bora'* eer oar*t* of nlzsent. sit of ^ei^M^ppSiP.sesS9ps^O> ... .,........ -- '^jg'pidtob'sKf all^s^s!il^r~idtli 1% Blaacol than it was vf nf nftiMlI if>aawwn^w^ oj| bhe q j j || amperes, vttMn t3ai# ramgs there was me tide sise index by variation in power. There was \ impression of more efficient grinding with high pom but positive proof of this was not readily obtained, % Table TT? summarizes the experience in of CPC Breen designed as a development study on the preparation of dispersed pastes. Tbs equipment was the same as that used in tbs Bits#* but all but two of the charges were ground vith % Hasted and only a fev of titan vere tested for particle sise index, i the use of 10% Blasted gives a markedly smaller particle sise and distinctly better strength. However, all of the products stronger titan GT-689-P) except one, in which case the test is believed to be inconclusive, because it did not mm to detract from the strength of a mix in which It waa included. In this study, for the first time, borax sludge from vious batch was re-used with a aaice~ig} of fresh borax mod results were completely satisfactory* _ s based on the excellent results obtained with tt Codes Dissolver la the sesd-worka. a auch larger mit with i operating capacity of 100 gallons (actual capacity about 130 and powerbd with 30 B.P* motor was purchased and installed tike end of 1951. The vessel has a diameter of about 32" and the BaaaracwgBr rocosaBnaM io" or xo" toowKa discs as smooth discs of 18", 20", 22* and WJpmmm XSJt^ ftpiKrOXXmMIXtlXeyev .tAvHvit JPmJIm'tSauwt.e in 'diamstar*: The jyfber -*-< <* toe..iSktlbA borax ana rordO*k^Mlk meifcib, ! p-- -i*gment DU P050069401 - 18 -- faids '1? mmmHsm the experience in the use of tide equipment with nine batches of CPC Green as dispersed paste, followed by too batches at a somewhat later date. The first throe of these hatches were made with an 18* -toothed Cowles disc with a maximal power usage of stout 25 amperes* The- pro ducts obtained were, however, universally of excellent quality* in attempt to use an 18* smooth disc in the next batch deaon- strated that it would not Impart the desired amount of to the batch, and it was replaced by a' has haen used since that tine* It has haen possible disc to use from 30-85 amperes in most of the charges. -first nine charges were i with a ratio of -ten parti -par part of pigment* ill re-used the borax sludgo on an analyzed basis, with___ added to glee the desired figure. The usage of for make-up purposes 'was about three parts par part of pigment, but the average us# was In the vicinity of two 'inerts par port of pigment* The charge used in these batches was 75 lbs* of dement and 750 lbs* of borax with IQp Blancol* In the last ses ande at a later date, the pigment charge was 120 lbs* the borax 600 lbs* with lOjf of Blancol* Particle size index measurements were made on all of these batches, and showed a rather uniform reduction of particle size to substantially tha sane point which was obtained in tha seml-vorks charges. ' The jppfuMag time was four hours, but there * 'little evidence of benefit beyond about 2 or 2-1/2 brs. it was re- contended that subsequent operations bo conducted at a 2-1/1 hr* cycle using the 125 IMjshirge with 600 lbs* of borax* The unstandardised CIO Green dispersed paste obtained by this proms was coded GT-735-P* A mix of most of these charges -was made in the plant Abbe' Lenart mixer, thickened with barium chloride and standardised at about 195 solids* This mix ms coded GT-732-P, and at 195 solids was approximately equal in strength to the GT-689-F standard which contained about 225 solids. Subsequently, 'this batch of material mam stirred urn and pm through the hoaoganizer to give a slight additional strength advantage, and it was decided that future batches should be treated with a preser vative such as Dowicide to inhibit mold .growth# This product ham shown two deficiencies in -use not yet been completely corrected* - The first is a develop a slight acidity on prolonged staidiprig* that this can be corrected by the addition' of the proper salt to the system* ^ A potassium phospharo^^H^rad hip teca^ bj^reason of*the faot'lhat'ttie barium chloride used^for*thid ing the paste also causes, some flocculation .and, on shsklmg or vibration of the * ........ `..... . of more or less clear water uu mw uri*c. sized that this settling is a soft settling readily redispersed as contrasted to the very is sometimes observed with type of Settling is very difficult to reincorporate in tha paste* Here recent attempts to solve these problems will be eoverci in DUP050069402 19 kith the successful development of a proca for making a groan dispersed paste In the Conies 100 gallesfttiipr attention' was tnmed to a process for CPCAM as a dispersed taste, and Table summarizes the experience in seven bat<;h** of CPC/LB made Immediately following the work on the jflaiKr followed by two batches at a somewhat later date. All aspics batches wars " made with 10 Blancol, three of then using yf lbs* of pigment, and 790 lbs* of 'borax, and the remainder using 120 lbs* of pigment and either 750 or 600 lbs* of borax* The average power consumption in these batches was about 30 amperes and all of them showed excellent particle size reduction as Judged by tbs particle size indices. Evaluation of the final dispersed -pastes, ceded BT-352-P, showed all of them to be stronger than BT-321-F on an equal pigment basis. A mix of several of these batches was standardized in the plant Abbe* Lenart mixer at about 19$ solids content, and thickened with barium Chloride substantially as described above for the green paste* This product was aJLittle stronger than BT-321-P, at a solids content of about 22$, when tested on the equal commodity basis* After careful study of competitive products* this strength was Judged a little deficient to meet average competition* and it was increased rather markedly by putting the whole batch through the homogenlzer* The tendency to develop a slight acidity on standing has also boon noted with this standard (BT-353-P) but the tendency to show a separation of water on the surface Is very much less than has been observed with the green. Another difficulty, however, which has developed in recent experience with plant manafacture,l8 a serious foaming tendency. The efforts to solve this problem and other problems in connection with this color will be reported elsewhere. CPC-LB appears to grind a little more rapidly in the Cowles unit them dose the Green, and a time of about 2 hours has appeared to be adequate for this operation* The separation of the borax following the grinding, using the Dorr rake classifier, has substantially come up to expectations The equipment used during most of this process and continuing up to the present Is not ideally adapted to the use, but has served the purpose. The charge from the Cowles dissolver has been pumped to a vat on the third floor of #10 building, where it lms been diluted to approximately 350 gallons and kept in vigorous agita tion until the classification can bo carried out* Failure of the agitator in this vat on a few occasions has been serious is that very rapid sottling occurs and the agitator cannot than bo storied again* The charge has been run from this vat to the rake classifier by gravity at a rate between 3 end 3*5 gallons per minute. Control of this flow is difficult, because there is a tendency fey the borax to clog ths small valve opening. Various conditions were used in the classifier, with changes in the slope of the classifier having relatively little effect on the condition of the sludge discharged* (hi the other hand, the speed of the rakes did have a marked ^effect, and it was necessary to rsdnes the speed to About seven or eight strokes per minute to obtain borax in the desired high concentration in the sludge* There Is always s o bs borax in *, DUP050069403  20 the pigment overflow, and It la believed that this will always he true as long as there Is a significant amount of agitation in the settling hod. Perhaps sons other equipment night he more efficient for this purpose* Possible improvement might include the nee of a combination of howl and rake classifier which is a standard pises of equipment, or it is possible that a simple settling tank from which the dispersed pigment could he syphoned, and which contained sene device for removing the sledge tram tin bottom might he successful in the operation. Such modifications should he studied in the future. the sludge obtained during these operations was analysed on several occasions and found to contain between about 70% and 75% of borax. On the basis of these analyses, it was specified for later operation that the borax sludge he weighed and estimated as 72jf for the purposes of calculating the additional borax to add# However, recant plant experience has demonstrated that the sludge In practice is not as high in borax content as had originally bean estimated, and that it is nore apt to he about 69% then the originally estimated 7S$ gone effort during this work was expended tnwird obtaining a borax with less water by means of sons filtration operation to remove the water from the sludge near the upper end of the rake classifier. A device was built and installed to use a short vacuum bed, about 6H in length, beyond the end of the classifier as originally designed. Although the liquid in a small amount of sludge is readily filtered in the laboratory through #8 duck filter doth, no such filtration could be achieved in the actual operation, for the doth seemed to blind immediately. Wien the doth was re placed, by a small wire screen, approximately 4o mesh, it was possible to remove a substantial amount of liquid from the sludge. However, this then caused the dry borax to build up on the rakes from which it did not readily drop off and tbs over-all advantage was very slight. This was not deemed sufficiently successful to contlimfr ixi t2JM . In estimating the consumption of borax in these operations, it Is noted that eleven batches of CPC Green, all but two of ..'them ' using the 10*1 borax/pigment ratio, totalling approximately 900 lbs* of pigment, used about 2100 lbs* of borax. On the other hand, nine batches of blue, only four of them at the 10*1 ratio* totalled approximately 900 lbs* of pigment , and consumed about IhQQ 1bs. of borax* Zt is believed that an over-all realistic consumption of borax will be slightly less than 2 lbs* per pound of pigment ground. DUP050069404 21 - It lias been difficult to estimate the recovery of In this work for too reasons. Zn the first place, the ' ment Kith which we start is not pars end has been of m purity for ths asst part*- 'la tha second place, all of tha pigment is never recovered, for seas of it recycles with the henna sludge. Another difficulty is that of obtaining aceurata solids on large hatches of paste* However, the test estinate o work, which le boras out hr later slant axoarience. is that over-all recovery of pigment is substantially quantitative. ImMBsSapWawBulHmWMaMieSipieiaehsli^ltMsHwe-rt pt -mw arPRa-rases Several phases of the plant experience in the of the processes for BT-352-P .and for GT-735at this time* There are two problems in the practical ,, of the unit which appear to be closely related* Zn the procedure as originally specified, it was somewhat difficult to obtain the desired viscosity of grind at all times, because the original specifications called for controlling it by the addition of water during the grinding cycle* On the other hand, the viscosity will change with grinding and also with the development of host so that the ordinary plant operaittoor focund it quite difficult to trd this situation* Ultimately, the situation was brought ........ control by specifying the addition of a definite amount of water to be followed after about one-half hour grinding with additional borax, if necessary* to develop the proper viscosity and the sequent proper utilisation of power* * As noted earlier in this report, the cooling facilities on the plant unit have never bean adequate to prevent soae t porature rise during the grinding cycle* Sometimes this has gotten seriously out at hand and has resulted in a marked for crystallisation of borax against the cold walls of the vessel* This crystalline layer in turn becomes a good Insulator and ihe heat accumulation proceeds more rapidly so that a vicious cycle results, and tbs temperature rise becomes quite large* This situation has been seriously aggravated on occasion by adding more borax to e charge which had become hot instil seme charges have actually set up to almost solid crystalline masses when allowed to cool slightly after the agitation is Stopped. Careful removal of the crystalline layer from the walls of the vessel between charges has been quite successful in avoiding tenperatiire rises if tbs water * * Another problem which has seriously handicapped the grinding of CFG Green in this process has been the tendency of many batches of CFG Green crude to contain substantial amounts of undispersime pigment in the form of quite wngl, butjgrf^ hard, granules or pellets* These pellets do grind slight^ fut the borax sludge. This has been controlled somewhat speed pulverisation of the crude, and it is believed can be kept under reasonable control by avoidiiqf exet use of the borax sludge* Rather, this sludge should be dissolved and the pigment tesevefed and pulverised^for further use after a DUP050069405 22 As to capacity, it is believed that tha Cowles unit now installed is capable of milling at least six charges par day of 125 lbs* each or a total of f$0 lbs* of pigment par day. tilth careful scheduling, it seass reasonable to believe that seven batches could be done, and it is not impossible to conceive of eight batches if the grinding cycle is no more than two hours* At present, the plant is able to accumulate five Conies charges for filtrationi but the filtration and the washing have proved to be the bottleneck in the process and the contemplated over-all capacity has not been, in general, achieved* Thus, with every* thing considered, it seems reasonable to conclude that the capacity of one Cowles unit operating under optimum conditions approximates that of two ball mills inthe Newport plant. Moated The two dispersed pastes described above have been con verted to colors especially designed for use in rubber base latex paints by the addition of. other ingredients, particularly a special resin compatible with the latex paint vehicles and subsequent drying. These products have been coded BP-358-D and GP-7M5-D, and mere details on their preparation mill be reported elsewhere. They con tain approximately 65* pigment and show excellent dispersion and strength development in latex paints, but are less desirable for other aqueous thinned systems. A substantial amount of our phthaloeyanine production is sold in tiie form of the "Ramapo" Lakes, BP-173-D end GP-501-D* It was, therefore, considered highly desirable to convert the aqueous ground dispersed pastes to such "Bamapo" lakes. Although the first attempts in. this direction were somewhat promising, it has not been possible to make consistently satisfactory lakes in this way, whether one starts with products ground with % of Blancol or products ground with icp of Blaneol. Substantially all such lakes have been markedly weak and also quite poor in texture* The strength deficiency can ba overcome by using higher tinier content in the lakes, bat such product* are even worse in . texture than the products with the normal toner content. This experience is in line with earlier experience on attempts to make "Ramapo" lakes from phthslocyanine pastes containing Blaneol, and it seems quite probable that such lakes will not hemade until some other dispersing agent Is found suitable for milling CPC tm water* DUP050069406 23 la contrast to the experience with the roalasted "BamapB lakes. It has been possible to stake ISkes siailar to BL-288-D from the CPC/LB dispersed paste with relatively simple modification in the process. Some dispersed pastes ground with % Blaneol have bees used in the BL-288-D process without any changes to give pro ducts of excellent strength. However, this has been somewhat undependable and attempts to use products ground with 10# Hansel in the standard process were quite unsuccessful, because such pro ducts would not absorb the Resinous Oil X-l, and the latter invariably floated to the surface during the drying step. However,, by adding a small amount of barium chloride during the lake forma tion, this difficulty has bees largely avoided and products of rather good strength have been obtained. By increasing the toner content slightly, products fully equal to BL-288-D were obtained, and. for some months past, a substantial portion of the m.-288-D production in the Newark plant has been mads by this method. The only deficiency appears to be a slight deficiency in texture and it has been the established policy of the plant that all such products which may be slightly poor in texture, and which may contain slightly more than the standard amount of toner, shall be consumed by blending with products made in the normal manner. This use has consumed a major shart of the BT-352-P manufacture and continues in active operation* ms COLORS It is noted above that all of the early experiments on aqueous milling of phthalocyanino pigments were evaluated by rubout comparisons of the dried colors with our standard phthalocyanine toners. Although the quality of these products was pro mising. the general strength level was, at best, from 15-20# below that of the current standards. Nevertheless, occasional products showed strength approximately equal to BT-30M). A study Of these few strong samples shoved that all of them had been obtained from relatively long grinds with 5# Blaneol, which had been carried beyond the point of minimum particle else index, further experiments of this sort wore then carried out both in the laboratory and the semi-works, but it has not been possible to confirm the hypothesis that effective particle else reduction with respect to ultimate dry colors continues beyond this point of minimum particle size index* However, one set of experiments with 5# Blaneol, in which the borax/pigment ratio was increased substantially above the usual lOsl ratio (actually 800 grams borax to 60 grams pigment),did give products which approximated the strength of BT-28MD. By carrying the borax ratio somewhat higher, dispersed pastes containing only % Blaneol mere obtained which approximated the strength of the standard paste from 10# Blaneol* These conditions appeared impractical and have not been followed up* Nevertheless, they demonstrate that it is possible to obtain dry colors of satis factory strength in aqueous milled processes. : %... DUP050069407 --^ Since some of the early experiments lied been made with carboxy methyl cellulose* the use of this dispersing agent was reviewed again, both as the sole agent In the sdxer and when 1 used together with other agents# Carboxy met^i cellulose has continued to give erratic results, and dees not appear to deserve further attention# - In some of 'the earliest work on particle sine reduction at Newark, copper phthalocyanine polysulfonate ("Pontamlne" Past Turquoise 8GL) was tried as a dispersing agent In aqueous Billing,a it was found to be quite effective In bringing about particle sins reduction in the HP process. It is a water soluble dye which can be precipitated with a metal salt, such as aluminum sulfate; and this method of precipitation has been used to flocculate the din* persion and to enable the products to be filtered without sig nificant bleeding* Products ground in the presence of about 1(# of "PoatanSne" Past Turquoise 8G1 (about 50g purity so thatactual dye content is only about 550 can be flocculated with alua, so that they are substantially free of any bleed during the filtra tion step# However, as the soluble salts are washed out of the precipitate, some tendency to bleed frequently develops. The dry colors obtained in this manner are close in strength to BT-28^-0 by rubout, and fully equal to BT-2w--D in alkyd enamels* Further more, they are substantially free from flocculation in alkyd enamels# The dispersed pastes from these products sue on the defensive against the Blancol ground products, but are of rela tively good quality. They are quits poor in texture in either varnish drier or alkyd roller mill grinds, and appear to be poorly wet by oil in substantially the same maimer as products ground with Blancol are poorly wet in oil* Two seal-works charges made with this dye as a dispersing agent were markedly Inferior to their laboratory counterparts. Another agent showing soms premise in the early work was Petronate, (a petroleum sulfonate), and its use was reviewed at this time without mush evidence of promising results* it had also been suggested that sodium rosinate might function as the dispersing agent mad permit the preparation ef a rosinated "Bamapo* type lake directly from the crude* This agent does appear to promote particle else reduction in a rather efficient maimer during the first few minutes of a grinding operation* However, it develops rather copious amounts of foam in the process, and any further particle else reduction is greatly inhibited thereby* The best .products were at least 2Q5& ump against BP-173-D on an equal toner basis* Several anti-foam DUP050069408 25 - Another group of agents, which lias consistently shown results of interest in this work, comprises the lignin sulfonates which are widely available as by-products free tbs paper pulp industries, These are typified by the "Maraaperse" products of the Marathon Corporation and by "Orzan" from the Crown Zellerbach Corporation. These products have been a little inferior 'to Blancol .-as a dispersing agent, when judged by have not shown the * ' to be on the defensive with respect to the properties -colors obtained from their use. More recently- the West Pulp & Maps* Company submitted to ns four samples of sulfonal limn under the designations "Indulin* XS-1, 3-2, 2&-3f -end mch ware said to have been obtained by directly sulfonatf " relatively pure lignin and to contain respectively 1, 2, 3, sulfonic sold gronps per lignin molecule* When lip of ihes ducts was used in aeneous grinds, the resulting pigments exhii the best strength of any products heretofore obtained la aqt milling, Differences between the four products were the Insulin 308-3 was selected as giving the nost consistently strong product. - The best strength in such products has bona sub stantially equal to that of BT-28M)$ they have' dart masstones. Intense undertones and grew but intense tints* The first agents -were obtained in the fora of solutions, but the supplier has since given us dry powders Which have been in every way equivalent to the original solution supplied* Charges mlliei with io5 of 3 103-3 and 10 parts of borax per part of pigment for about one in the laboratory, have given very interesting results at about the strength level mentioned shove* Increasing the time of grind' to two hours has shown only a very Slight advantage* Increasing the amount of agent beyond the up level has not given consistent improvement. - Three semi-works chargee have been made* The was rather poor in results for reasons unknown. The second was ground for six hours and gave rather good quality mat but appeared to require at least four tours to equal the quail! obtained in the laboratory in one hour. The third charge was ground 'With 205 Indulin XB-3 and gave weak products. Farther work in the semi-work# is obviously required if this to be made practical* ' Mixtures of Indulin 308-3 .-and' Blancol have shown proniso of superiority over either one alone, but this fie! not been thoroughly explored. For Instance, one sample with % Indulin XS-3 end 35 Blancol was actually on m: aids of BT-284--D. Another In the .addition of a substantial amount of sodium strong side of. >, but It was not reproduced in a ____ Other salts such as sodium citrate, radium or 'urea gave no advantage in 'this type of experi ment. Another agent* which proved harmful whether used along or in combination with Indulin, was dimethyl forwaadde. DUP050069409 26 It is obvious fro those tether sketchy results that the work on the use of Indulin X8-3 in the preparation of dry colors is incomplete, said any additional experiments arm suggested by the results reported. Several experiments, including one charge in the Cowles 100 gallon unit (S.W.3031)* Mere carried out In an attempt to develop a green shade dispersed blue paste. The results were disappointing in two respects. In the first place, although the product was considerably greener than BT-353-P* it lets also markedly duller. In the second place, the strength developed was considerably less than had been anticipated from the work on CPC/IB. The crude used in these experiments was the "EFM type of chlorine-free crude and was bslieved to b# 100^ in the beta fora. Nevertheless, the degree of greenness was considerably less than was anticipated. Thm over-all properties led to a loss of intsrest and the work was not carried further. More recently, efforts hare been directed to the prepare* tion of a counterpart for BT-297- by milling the same chlorinefree/EF crude with Indulin XS-3. These products did develop fairly good strength with respect to BT-297-B, but were very each redder, being only slightly greener than CPC/LB ground in the same manner. Very limited work was done on this problem during the period covered by this report and further work will be reported elsewhere. The use of Indulin XB-3 as the dispersing agent for milling CPC Green has been explored very briefly. The products obtained were appreciably weaker than GT-67*f-D (about 10% weak), but there was only a trace of dullness and this definitely re presents the best CPC Green toner obtained in any aqueous milling operations. Since the very early attempts to ball mil phthalocyanine colors in water had been unsuccessful, it was considered desirable to review some of this work after it was demonstrated that particle size reduction could he brought about in the HP mill ha water. The poor results obtained by ball milling with water alone or with water plus Blancol were amply confirmed. However, whan both Blancol and borax were introduced in the hall mil, the results of the grind were markedly superior to anything hitherto obtained with either pure water or with either agent alone. It was also found that borax would similarly Improve the results obtained with a number of other dispersing agents, among Which irij. 35 (Atlas Powder Company) gave results substantially comparable to those with Blancol. Carboxy methyl cellulose was also similar to Blancol 'in this process.' Several materiel*' ware 'tried in placa of the borax, .and only trlsodium phosphate showed comparable properties. DUP050069410 27 - In spit of a considerable msaber of experiments with this typo of ball mill operation, there seemed to bo a limit beyond which significant particle sis# reduction was not obtained, and this Halt was still very much weaker than the product which could be obtained by HF willing in the awl wanner, A Halted anount of work on the green was even less successful experience with CPC/UB. Accordingly, this work and there is no apparent reason for giving it f The experiments 3g notebooks# Jf#B* 115 This information is classified in wore detail as follows * 1191 - 26f 0, 53, 55, 66, 71, 78 13^5 * Ha, 51, 9+9 69, 100, 103,107, 108, 110 11 * ft ft ft ft ft ft 8: ft ft ft ft a,1393 * 10,12, f*. 1ft* - 2, 6, 7, U-20, 22, 25, 29, 32,3ft, 56, 57, 60, 63. lft* - 1-ft, 6, 10, U, -22, 2ft, 33, 37, ft), ft*. ftf, SO, , 53, 55, 56,58, 60, 62, 63,67-70, 72, ,, 76. 1393 ift, 35i 38, ft5, ft9, 59, , , 75, 76. lft* - ft, 23, 2ft, 27, 3l 35-ftl, ftft-55, 57, 58, 6ft. lft2ft - 5, 7, 9, 23, 3ft, 35,36, 38,39, ftl, ft8, 59, 6ft, 75. lft39 - 16, 17, aft. 27. 36, 38*2, ft5. DUP050069411 * 28 * MtiftitmiiyiffiE .r.fS.ISM3ML* 1383 - 56* 61, 75, m, 83* 84, 85, 88, 89, 90 1393 * 4, 6, 7, 9, 57, 68* l4fi4 21* 33, 34. 1424 * 29, 30, 54* 60. 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