Document ppboQZ4GMd8pxa1v1ryXk5vNw

E. I. DU PONT DE NEMOURS & COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Copy No. ^ Numerical File Period Covered: NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Progress Report THE FINISHING OF PEmtlOCYANINE PIGMENTS I s WET GRINDING STUDIES / NOVEMBER 11,1945 - MARCH 30, 1946 < FILE: DATE: .223 o 4 6/3/46 N41557 Serial No. KN-46-19 Copy No. J Copy to* #1 Numerical File 2 Research Office (223*4) 3 Library File (223.4) 4 Imperial Chemical Industries, Ltd. I 7 D. H.Dawson, Newark 8 A. Siegel. * 9 D. B. Killian, H 10 J. E. Booge, Newport II C. E. Berry, Engineering Dept., Experimental Station, Wilm. 12 - Extra 13 - Extra 14 - Extra NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Progress Report THE FINISHING OF PHTHALOCYANINE PIGMENTS I * WET GRINDING STUDIES NOVEMBER 11, 194? to MARCH 30, 1946. SUBMITTED BYi F. W. LANE APPROVED BY: D. B. Killian ' /rk> DATE SUBMITTED* 4/22/46 DATE ISSUED: N41557.01 DUP050150542 II21I X* Obj@ot: XX* Historical Background XXX* Batura of Problem XT* Pataut Situation V. Summary aad Conclusions VI. Experimental Details: a. General Procedure b. Closed Circuit Grinding 0. Specific Surface Measurements d. Ban Milling a* Mixed Ball Charges f. Dispersion of Ball Milling Slurries g. Mon-aqueous Solvent Grinding h. Choice of Ball Type 1. Choice of Solvent j. Ball Mill Capacity k. Finishing Hydrocarbon Solvent Grind of Crude Polyehloro CPC Green* 1* Soft Powder Finishing - Green G. m. The Szegvari Attributev Table X * Experimental Summary - Solvent Grinding Blue CPC Table IXs Experimental Summary - Solvent Grinding Green CPC APPENDIX X. A. Exhibits A to I pertaining to grinding of CPC Blue* B. Exhibits ^'to M pertaining to grinding of Polyehloro CPC Green. DUP050150543 SOLVENT GRINDING OF PHTHALOCYAHINE PIGMENTS I. OBJECT! T determine whether satisfactory tinting strength in CPC and polychlor CPC can he developed hy grind ing in either water or organic liquid slurries. If satisfactory quality is possible, to obtain capacity estimates for the preferred methods. Period Covered by Reports November 11, 1945 to March 30, 1946 See Newark Research Notebook No. 118? II. HISTORICAL BACKGROUND The development of desired tinctorial properties in the phthalocyanine toners requires a considerable reduction in the particle size of the crude products. Heretofore the only effective methods known were acid pasting and salt milling. Other dry grinding methods have been evaluated and found very unsatisfactory. A few earlier attempts at wet grinding were reported unsuccessful. Discussions of salt milling and finishing may be found in the following reports: JLR-I5I 9-1, ft II No. No. No. No. 59 54 39 41 ft W No. 56 No. 36 If No. 52 Serial No. 19316 18802 17797 17880 19146 17477 19099 The following facts stimulated the wet grinding study at Newark. Acid pasting of CPC is expensive due to low solubility and the consequent high acid consumption. Salt milling of CPC blues is cheaper and satisfactory but is not satisfactory for the green CPC. On the basis of wet pigment grinding experience, wet grinding of CPC has apparent economic and operating advantages over previous methods. III. NATURE OF THE PROBLEM The Initial goal was to develop wet grinding methods for polychlor CPC and chlorine-free CPC made by the urea-phthalic anhydride solvent process. The prime1'* requirement was the develop ment of tinting strength equal respectively to the two current standards GT-486-D and BT-172-D. Electron microscope studies of high strength CPC toners indicate roughly a particle size of about 0.1/44/ This is probably~the largest dimention if the assumption of flake-like paeticle is correct. The crude materials are definitely crystalline, the individual crystals being of the order of 1 x 2 microns to 5 x 30 microns. The blue crudes have more uniformly shaped' needles than the green crude prepared by chlorination in AlCl^-NaCl eutectic melt. DUP050150544 ** 2 * * This degree of particle else redaction to the 0,1range is not, to the writer's knowledge, obtained in present industrial wet grinding installations. The actual strength development required is Indicated by the relative strength of the erodes and standards* BT-172-D, SD-48342 filna IMS-EfflOa 100 25 100 37 iv. mm,.1TOM Although solvent grinding patents exist, the following items may have patentability! 1. Solvent grinding applied to CPC particularly since water grinding is shown to be detrimental in the oass of Green CPC. 2. Speoifio alcohols or alcohol-water mixture. 3* Controlled flocculation to obtain soft powder products* 4. Grinding with a mixture of equal numbers of two ball sizes, the smaller just large enough to fit the spaces between the larger* 5. A fluorineted CPC to obtain solvent stability with a minimum of greenness* 6* Increased ball mill capacity by use of downward magnetic force operating to .increase impact-force and critical mill speed and to prevent floating of small ferrous balls. v. s s mma r i.m..sfigc&mm Ball mill slurry grinding of polychlor CPC and chlorine-free CPC has been successfully employed on a laboratory scale for the development of tinting strength. Water alone is not a satisfactory grinding medium probably because of the poor wetting obtained. Ho wetting or dispersing agent was found effective when used In amounts up to 5% of the pigment. DUP050150545 -- 3 ** Several organic solvents are satisfactory and a choice for plant operation will depend on cost, safety, ease of recovery, etc* The solvents giving full strength on prolonged grinding ares a) for chlorine-free CPC Alcohol 3A Alcohol 23A 2 pts. - water 1 pt* b) jffflP Xylol Mineral Spirits fiip Methanol 99% Kerosene Alcohol 3A Alcohol 23A Isopropanol 99% Isopropanol 3 pts. - water 1 pt. Toluene (carton tetrachloride) Steel balls may be used except with polychlor CPC when water is present. The combination of metal and water results in dechlorination and marked blueing of the green pigment. Grinding of chlorine-free CPC in hydrocarbon solvents reaches only about 75% of standard strength. This is believed due to crystal growth in these solvents. During this study the importance of producing a non-solvent sensitive blue CPC has become evident. Presumably such a blue will grind to standard strength in hydrocarbons. Initial testa indicate this to be true of semi-chlor material from the phthalonitrlie process* Ball mill capacity tests were made with polychlor CPC and kerosene in a one foot diameter mill. This data has been extrapolated to larger mills up to eight feet. For 3/8" steel balls the extrapolation shows an eight foot diameter mill capacity of 113#/24 hrs/lindar mill foot and a cycle of about 30 hours. These tests were limited and further tests in the proposed semi-works mills will be necessary. See Exhibit I, Fig. 2, A new type of ball mill apparatus, the ,,AttrltorM has been partially evaluated. On a laboratory scale it was found to have a capacity 6 to 10 times that of a normal ball mill of equal volume. The manufacturer states that the rate does not increase in larger equipment. Because of this it probably has no advantage over normal mills of 6 to 8 ft. diameters. However, further investigation would be worth while especially if we wish to grind in the absence of metals. Some work has been done on methods of finishing the ground slurries. Transfer of pigment to water slurries for acid extraction or producing water pastes is readily accomplished by distillation of alcohol slurries. Kerosene does not appear attractive in this respect. A clue to a method of producing a soft bright powder has been found. DUP050150546 4 vi. mmmmmMum a . igais3i.^si^Maias,,. Exploratory grinds wore made In snail mills (1/2 pt. jars to 1/3 gal. parcolatn mills). Steel balls, shot, glass beads and Porox balls mere used as Indicated in the summary. Progressive samples were removed from the mill and air dried at 200SF. Pinal ground slurries were finished by acid and ammonia extraction. Grinds not miscible with water were,dried or steam distilled for the removal of solvent prior to extraction.. Extractions were made by digesting 2 to 3 hrs. in ten volumes of 7% sulfuric acid, filtering, washing, repulping and digesting in 2% ammonia, filtering, washing, drying at 2Q0F. Prom experiment 82 on, 2% sulfuric was used instead of 7%* fluting strength evaluations were made by comparing adjusted extensions with the standards, the samples being adjusted to match the standards atlOOtl 2n0s toner weight ratios* Rubouts were made on a Hoover Muller using 5 x 50 revolutions. All inks rubbed out contained 1 pt. by weight of toner and 2 pts. of varnish drier. Standard inks were extended with 60# ZnO paste; 0.180 gms. of ink being extended with 10 gms. of paste. The quantity of sample ink was varied to make extensions match the standard extension in tinting strength. The sensitivity and reproducibility of the test appear to be of the order of 2$, when there is no marked difference in shade. B. glBfigfl..lgOUlt Grinding Since Ti02 is wet ball milled in a closed circuit system with hydraulic classification, it was proposed that we apply this technique to CPC. The lower limit for separation of T102 particles by aqueous elutriation has been experimentally determined to be about 3 microns. On this basis, using Stokes Law, it may be calculated that the lower sise limit in the case of CPC would be about 7 microns. Liquids of lower density would give negligible advantage. Our studies of the dispersion of CPC slurries resulted in no dispersion satisfactory for such elutriation. Attempts to prepare high strength fractions by elutriation were therefore abandoned. Centrifugal separations in the desired range are of course possible and might be used for academic purposes* The Bird Centrilhges used in Ti02 wet grinding merely serve to remove grit. The lower sizing limit for commercial centrifuge is said to be about one micron. In view of the above, closed circuit grinding has not received further attention. DUP050150547 - 5- The only particle size measurements available for CPC were from electron micrographs of uncertain value because of difficulty in preparing mounts* Several types of CPC's were therefore sub mitted to the Experimental Station for surface area determination. by nitrogen adsorption (Emmett) with the following results. Hue Toner Preparation i(2/Bm. Dla.* BT-172-D A semichlor from phthalonltrlle, 36.5 0.11 SD-48342 acid pasted, soft powder treated 100 B-6091 Salt-milled, urea solvent _ 7.0*6... 10.8 N-384 Drip drowned paste lab* washed with ale*, water, dried 200P. 91.4 0.044 103 H-493 Current BK paste 4/5/45 L.T.drowned. Lab* washed with ale* and ether, dried. Hard 6.7 36 DW-5889 Crude urea solvent 8.6 0.46 25 Green Toner GT-486-D Polyehlor standard SD-48335 DW-5890 Crude Orchem Polyehlor 68*3 14*0 100 37 *Assuming uniform spheres* The T.E.A.-C^i ester treatment on BT-172-D may blind the surface to If2 -493 dried to a hard grain probably accounting for lew strength* The low area would Indicate that actual particle growth had occurred* Apparently wide range of sizes or large departure from spherical, or both, account for the small calculated diameter of crude DW-5889 as compared with microscopic appearance. If the crude particles are assumed to have needle shape of breadth and thickness equal to one-tenth of the length the particle dimensions are calculated to be 0*32 x 0.32 x 3*2 microns from the surface area measurement. Particles smaller than this would be just about invisible at 625 x. However, if unresolved particles were present on the slide, they did not contribute color to the field as do the full strength particles* Neither electron micrographs nor surface area measurements have been made for solvent ground pigments* DUP050150548 -6- iajiX.Ijl.mBg- Disoussions with Mr* C. E. Berry, attendance at the Brooklyn Polyteeh Symposium on Particle Size, and information from literature all led to the feeling that ball milling is the most successful method of size reduction in sub-micron ranges, Generally, the high speed, high shear type mills do not grind discrete particles but merely disperse aggregates or droplets, This, plus low invest ment, and operating economy, dictated that first efforts be expended on ball milling experiments. Shis report deals entirely with ball milling. However, Mr. A. J. Stratton concurrently investigated numerous types of high shear grinding and found them ineffective except when salts or other extenders were added in relatively large quantities* In the wet ball milling of Ti02 practically no reduction of primary particle size is obtained, the primary particles having been previously formed at about 0.2 micron. The milling is solely the breaking of cemented aggregates and requires only about 10 hrs* grinding in 1/3 gel. lab. mills with flint pebbles. In grinding CPC a longer cycle was expected, hence grinds were continued in most oases until no further increase in strength was obtained} this reached 500 hrs. and generally required 200 to 300 hrs. in 1/3 gal. mills to equal standard strength* S. Mixed Ball Charges Recent literature states that mixtures of ball sizes are additive in their effect. However, it seems reasonable that a special advantage would be obtained by using equal numbers of two ball sizes, the smaller size being just large enough to fill the spaces between the larger. If the large balls are not spread by the smaller, theoretically l33Jf additional contact points will be obtained if we assume hexagonal packing in the active milling zone* Calculation shows that the smaller balls will occupy only about 7* 5jC of the void space between the larger. The high impact force of the large balls should permit handling slurries too thiok for intermediate sized balls giving the same number of contacts per unit volume. Thus it seems possible that the over-all mill capacity would be increased* An experiment was tried comparing a mixture of 3/4" and 1/4" balls with 3/8* balls in 2 gallon mills. One of the mills broke, however, and the experiment has not been repeated. Lifter bars are needed since the 3/4" balls sounded as though excessive slipping occurred* DUP050150549 7 f . itofratea., It is generally known that dispersed slurries give higher mill eapaeities than flocculated slurries chiefly because of better flow and the consequent possibility of employing higher solids concentrations* CPC pigments are notably difficult to disperse and tests covered by this report disclosed no satis factory agents. The use of these agents is noted in the Summary Tables. A more thorough study of wetting and dispersing agents was made by Hr. Stratton* These CPC pigments are so extremely hydrophobic that water grinding actually decreases the strength of the Polyehlor and no significant increase in the blue is obtained unless large amounts of wetting agents are used* <* Hon-Aeneous Solvent Grinding Hydrocarbons i mineral spirits, kerosene, bensene, xylol, or alcohols; methyl, ethyl, Isopropyl, as well as carbon tetrachloride all wet the pigments readily and grinding in them increases strength* Polyehlor CPC has been ground to essentially Tull strength in all of them. CPC ehlorlne....... ...........free blue has been ground to full strength of standard in ethyl (3A) alcohol: and a mixture of 23A alcohol and water. Crystal growth in hydrocarbon solvents is presumed re sponsible for limiting the strength at about 75# of standard. 0-ohlor benzoic acid, benzyl alcohol, and tin phthalocyanine dichloride fail to remedy this situation in kerosene or mineral spirits* CPC blue Pff-5389 was ground to 105$ strength, and slightly greener tint vs BT-172-D in 2 pts. 23A alcohol and 1 pt. water with steel balls* Corrosion of the steel was marked since the ground product before extraction was rated 75% and dirty green. See Exhibit B* h . chaise .aft.MJUam In ball milling, the following factors should be at a maximum to get greatest grind capacity* 1. Humber of ball contacts per unit time per unit volume* 2. Ball Impact force. The first maximum, other mill conditions being constant, implies using very small balls. The second is obtained by balls of nigh density. Starke and others (Micromeritlcs p. 327) have deduced the following relation from experiments in the sieve size ranges (ball dia. DUP050150550 8- Extrapolation to our problem Indicates the following* S8|l.til* n 9 lost. kl| m. '"SP>s ! ]tgtt$a* thfe wffeettveamap of ball# ''t to# the i-* > *7 * *. . - glass beads 1/2 Ineb Perex bills 1/1&H steel shot 1/2" steel shot 3/8 stlel balls. t She effectiveness is measured in terms of unit weight of material ground par unit time per unit volume of mill space, file range was not completely investigated and in larger mills with more concen trated slurries still larger balls may prove more effective. Compatibility with the slurry is another important factor. For example, steel corrodes much faster in slurries containing water, even in small amounts.than it does in kerosene. Polyohlor CPC and steel balls are definitely incompatible when waterris present in appreciable amounts. The water apparently catalysis the dechlori nation of the pigment and the product is very blue. In 99$ Methanol open to air during grind (Exp. 1183-83) the crude polychloro CPC, DW-5890, did not turn blue but considerable rust formed which was removed by extraction. Even though the produfi is satisfactory this may represent intolerable erosion of equipment. See Exhibit M. i* Si?c..Jlsa The relative effect of several solvents is shown in Exhibits B, C, G. It is definite that ohlorine-free CPC will not grind to full strength In hydrocarbon solvents. If this type is to be ground, ethyl alcohol or ethyl alcohol-water mixtures are most attractive. See Exhibit E, sample K & L, and Exhibit F. Nothing final can be said at this time regarding the grinding of Blue since the desired solvent stable type has not been developed. There now exist these major possibilities* DUP050150551 - 9- * (a) Grind Cl free CPC in alcohol or alcohol water systems and add a suitable protective agent either during or after the grind* Tin phthalocyanlne dichloride has not proven satisfactory. See Exhibit G. Cont'd. The added agent must survive extraction procedures if present in the grind. If satisfactory post grind ing agents are found, grinding in isopropanol, ethanol, methanol and thdfr water solutions should be further further studied. Bee Exhibit E (samples K & L), Exhibit F, Exhibit G (82 C te H) and Exhibit I (sample B). (b) Use semi or momoehler type. In this case a wider choice of solvents including kerosene is applicable (See Exhibit I (sample B). 2. gttofclfK.QMia Satisfactory quality has been obtained by grinding with steel halls in mineral spirits, kerosene, xylol, toluol,: synthetic methanol (99$) and isopropanol (99$). See Exhibit I,L & H. If ceramic mills are used, an lsopropanol-water mixture will give full strength. The grinding capacity of ceramic ball mills is doubtful for reasons previously discussed. See Exhibit M (A, D, & E). The following are 1946 tank car prices per gallon. Kerosene Mineral Spirits (VM&P) Xylol Toluol Methanol (syn.) Ethanol 190 proof Isopropanol 99$ M . 91$ $0.06 to .08 0.12 0.26 0.27 0.24 0.54 Ho. 1 spec. 0.35 0.31 The initial low cost of kerosene may be offset by the greater ease of recovering any of the other solvents. The alcohols may he preferred because of ease in getting water pastes and slurries and the possibility of a softer, brighter dry product. See Soft Powder Finishing. An unfavorable aspect of the use of anhydrous alcohols for Green CPC in conjunction with steel mills and steam distillation is found in the formation of azeotropic mixtures. DUP050150552 10 4Mi.tsa.3^..S,w.igA^,lrSm Ethanol-water Isopropanol-teter Methanol 4.5# water 12.1# " none listed. Toluol also forms an azeotropic at 13*5# water. Further capacity studies of mineral spirits or kerosene and xylol should be made. Kerosene is now favored only because of its lower fire hazard and lower initial cost. The amount of mill wear seems small, with kerosene and mineral spirits. It may be worth while to Investigate extraction of the crudes only. Certainly the filtration and washing of the erudes is much easier than that of the fine ground products. It oould be employed provided iron contamination is negligible. No effect has been noted on tinctorial properties in the case of these solvents. J. - See Exhibit N and Figs. 1 & 2 The only valid capacity studies were made with Green DW-5S90 in kerosene. See Exhibit N. These data have been extrapolated to mills of larger diameter by use of information found in "A Manual of Ball Milling" compiled by the Engineering Department, Technical Division. The material used. DW-5890, was essentially pure toner having been extracted after chlorination in AlCl-s-NaCl eutectic malt. The effect of by-products solids from solvent chlorination is not known. It is felt that any non-CPC solids present will merely dilute the charge, be ground along with the CPC and decrease millcapacity pro portionately. On this account it may be economical to extract the crudes, particularly the blue, prior to grinding. Similar capacity studies should be made on the blue when the type is established. So far the Indications are that capacity will be of the same order. K. Finishing Hydrocarbon Solvent Grind of PW-5890(Crude Green) In*.flflyJMffiZasSSe..WtBMMA..flAE4Sft The above pigment was ground to full strength in mineral spirits. The mineral spirits slurry aged 35 days prior to filtering and treating according to the following scheme. DUP050150553 11 - .fat Cake , . J2jgAfta...ggfl>aL. V Str. 100% Extracted 7Dried 100% --------- \ Atfluw Ptett 47 n Dried 200F 4^ 98 Extracted Dried 200F vk 98 The pigment is not appreciably damaged tinctorially by the above treatment. Since the crude was essentially pure, no improve* saent is noted on extraction. Bxn..Ho. 1187*60. Kerosene DW-5890 was ground to an average of 97% in Expts. 51, 52, 53* These were composited four days later and treated as follows without filtration. The steps of steam distillation, extracting and drying appear safe. This was frequently verified in later experiments. L. Soft Powder .Finishing - QeS_CPC The products ground in kerosene or mineral spirits, when finished by drying, or by steam distillation, extraction ana drying, *are-unattractive`in appearance. Although they are readily mulled xio full strength, they are dark and granular and inferior salaswise to the standard. In Expt. No. 1187-79, it was found that by washing out the kerosene from the finished mill product with 993? isopropanol and then pouring the Isopropanol slurry into water, small stable floes were formed. These floes persisted through the extraction step, making filtration much easier. The washed product dried to a soft bright green powder freed of lumps by very gentle crushing. Ho strength .was lost. DUP050150554 - 12 - The recovery of 9951 isopropanol fro water is not desirable* Investigation of kerosene removal by washing with the Isopropanolwater azeotrope is suggested. She formation of stable floes is believed to be the effective factor in this process. A cheaper ethod of obtaining the ay be possible* This procedure has not been applied to Blue CPC* To obtain the maximum grinding effect obtainable by the combination of a large number of contacts per unit volume with a high impact force, a combination difficult to obtain in normal ball milling with high slurry concentrations, an apparatus was designed in which steel shot were stirred by wooden paddles* See Exhibit H, Fig. 1. (Sxpts Ho. 1187-70). The agitation was surprisingly easy and the mill was run a week with only slight wear on the edges of the wooden paddles* The experiment was run in a 1/3 gel. mill and the grinding time was about 1/6 of that for normal operation of the mill. Subsequently it was learned that such a device called the Szegvari Attritor was marketadby the Union Process Company, Akron, Ohio. They claim ten times the grinding rate as compared with normal small ball mills. Correspondence with them has disclosed that the #60 mill, approx. 60 gallons, the largest available, has a capacity equal to a 500 gal. mill. They also stated that the grinding rate does not vary with the Attritor size. From this it appears that ball mills having diameters greater than 4*5 ft. will have greater capacity per unit volume than the Attritor. The Attritor consists of a ceramic container, small pebbles and a steel shaft agitator fitted with specially hardened arms which are readily replaceable. The device might have valuei (a) in experimental work where short cycles are desired to hasten results. (b) by replacing the steel agitator with "micartaw or wood, the green CPC could be ground in alcohol-water slurries. Laboratory experiments disclosed that glass beads were nearly as effective as steel shot in this type of grinding. Our laboratory device of this type is referred to in the data tables as the "Ballitator". Further evaluation of the Attritor is suggested because of the possibility of capacity advantage to be gained by using small pebbles or shot. See Exhibit H, Fig. 1 and accompanying discussion* DUP050150555 13 .i.i 1 mm amupiro The following pages contain a tabulated summary of all grinding experiments. Many of them are exploratory and have very little capacity significance. Those having more conclusive capacity data are given more fully elsewhere. Coin am telaBaMm,,,<?. ..yhRls, M XtibM.I Agents: oeba * ortho chlor benzoic acid SnCl2PC * Pigments* DW-6076 Tin Phthalocyanine bichloride The MD-958 signifies Orchea product. Others are Hewark preparations. Urea solvent CPC. Supposedly equivalent of l>W-5889. Str. a 2# vs BT-172-D. Balls t 1201-5A DW-6091 Crude PH 1191-7-B DW-5890 g* s ** Hewark chlorine-free CPC ex. Urea-phthalic anhydride kerosene. About 65# CPC dry basis. Chlorine-free CPC salt milled. Orchem semi-ehlor crude. Ho. 33246 Hewark CPC ammon. extracted. Standard Orchem crude green. Stri * 37JC vs GT-486-D 6 mm glass beads. 2-3 am steel shot S 3/8" etc. Steel balls of indicated dia. in inohes. P = 1/2" Porox balls. Miscl.j "Ballitator" = grinding by stirring ball charge in vertical vessel. DUP050150556 p o $ t< * PU N 0IQNfcOnrOvOrOC<^<Ofr iN* B H MH J*S \0 p *H *!lo Is j p PW* OHO*PPo Hm** goo *fefl CP o w W CO mmvo^p o n aw c m c m c m cococo\o d & t e rl *0 tn m p AA3SR o n o > \d<^ ov s M 4 *400 PO CO H $ w m *4 cO 0 O us U\\OsO C^C^ 4 g dd tan P*0i PtuDi * WW O UN IN Cv % St?ci gg d WM * * o &a HH WW i *a m P g JIN Op UN <*OHOOU\\r\ o tt\U\UMr\ C^-VO IN IN IN INIS o n $tn P W *4 d IrvOOOHCOH ^ C^CNf'OxOOO ro Vrvoo o^ft CM OCO o OvOO fOt fOCO Q O Pi 5 CM CM H CM CM CM W" CM HI m 3 p HO oa t HoUeCIOMH6tHtECdoNM14 a Of 3 H SOI e*0 6S ( w w w o * eg c * M Hf fad s CM > COCO W 0 s ff pm > p sOsfa CM H rH as s c* is H **f CM CMNOV0CM * ss u n Gn Cn .CS * rO ^ CM CM >> 11 CM CM m -a *?p 4N HcO COON ft* 8f 2 35 ft ft? 1P CO (d o I ii d *4 * &0 HH wm d u m H W QttxOOQ'CN ^tlrwo IN\0 o \0 MuwMnTco0 oo NV0\O>CM 00 trsliwo rOUNUNOm CM CM CM ft fv H CMCMHCM CM 0OrOrOrH ft ft l es8 s s CM CO 00 0000 00 ^S?> i \ H COCOCO CO 0 CO 0 CO CO co co co m ftWWk z zp tr\lr\lK C^Cn .C^IN CStNCv s s * *2 CO CO r <4* CO eON 00 fts mQ1 * vnqJOON b Q <C lf\ Or-ls CHM *dWdvOHooN *4 f oa p jd p o s$io* CO iS1 i-l *s co co co s ms ss; SSB m p is e ao CO *4 43 tf o, os A a 10 P P M Sag 88 CM CM HH o t otaoi 3o* MM.**. to VfNlfSO rt r-t 8 CM H <8* co ** O H m m o u Q) H S SO oi H DUP050150557 s H w m 0 43 O 0 i H *0 H CD *> X* I *0 *8 0 H go & mm *a a o CD 3 tr Hm HMog & x4-s> S$ 33$ g 3$m o m am g$RR ^NOvOsD vO IN 8S3 SR OQCO CO tN r0MOv0v0v0 ej gg ^ un p ^ cs % uno n o co fi fie m mm Un Un ^T* cm cm o un h h h Un unun unco m *a ^ CO VO VD CM _ _ . . b1 c m ro ro RR$ HHH Un O ro uncn Oco rocM *p Q o Wl *fr h g a M to ft s go oo co ro ro co co co co ft CO cftocfto \ CO coro ta w wr CO coco a gal o Rg g N ft ft Un Un HI H H * Un ft Un cO tv * tN IN *+ sc ft ft co com IN (NiUN* <<MN Vtvp 0O0N 0 go vO Un 1i VO a rrCooM H $" CV I 0 , ft Ov B ai h h ot* E & && d 4. ,4 a ocy ow -P S Hm H* Sr Sr H ON H Ov 3 fSa co Si <Si m & 0?3 UN 'g-X * 39 ro y a% H 43 Ocol 0 XH0O3 O gg 60 60 6O # HHH ca c& m <3.M88 aa && *# Hm Hm co CIO UN INQO \0s0 ct&SU CM CM ft ft CO 00 ro^ C0 CQ W* tNCv ft ft ...Os oo * u0p I 1 t ^ ro JST CM HO JO02 aOo 60 gg UNlfN 00 IN fi * 60 m SCS voO'oO o vO 60 * & faa 60 4 $m4 * Hm pop ININ Ow0 (Nn Os O 60 Otv O O Un ^>vOCM CM CM ro ft ft ft CM CM 00 r^r^rO fro ca co co Un Un CM CM roco fgto fcto rOrO COCO Un c o CM CM rocM ft ft 00 NT rOH COCO dSRRR H CM CM CM CM ft ft S ft oo 00 CO CO rOrO^Nrn 10 UN UN UNUN & CM 10 UNUNUN tNCvfs. '*?H'*?*& Un Un CvlN * ft ft* R> st rO Un Sn Sn cvcvcs.es ENO * -( ** NO VO < tPv U*n. v0 ft H IO aa <aj -a$ VIy UIn HH OO CM CM HH <vo UIn EoN HmD Oi CM & HO a a* Q oa oo Soo { c mu n c mu n I H On I HONft Ift % Bq O c m m S coS IOh O0vn o C0 M 0V\O0\ CO tvCO RSR.ft ft SSE OO 9 9 I 00 rT o ON 00 R * m*3 Sh o H X3 O H &U4 DUP050150558 8 4> 0 + < Xrs>0U\CO<X>ClOQO o h o o m CM CM u% moo no it n u> H d&Jf H 0 <*> o CO ass8swa&^s^5iP5i 1 c H MR i0 m IN m 3 H n| 0 SS 0 0 d r*i *0 r-4 h 0s *0 O o ioiNCNINOlrvOIN m & o d H 2R *R & } "0'RS*gSS|gSS pHI iH ffHI rn pH* f*4 P"H pHI H CM CM s CD \ m Rco m w> w o ft. ft. o &. &o boa, O mmv0'D^0v0>D o *> 0*0^4) c m CM \fN fHHrtO OOO O <t INM? 0MN\0\4>c O HCMCMCMCMCMCMCMHCM^-M- COH H *: CM Ol wo, co n ta w w w m 0 ft. w mwo ss ss e s tc e s s s s MMfnncyMM-MMMOl I <$* UMrslr\UMr\UMr\ C^CvCv(S.|N.OwCS $ # & c m <r nr <t '& <* c m 5-s & Cv N c s e a S S SSttSSSSS .. oI 0N VO 00 cscsss^ s * tt-s s r s I* a o a%. .M CO 00*8* 40 ro H rl^ d* 0 0 iFFCO 3m O % _M^ o2od8i ^ 23q o^fr $ aa h q Km 0 cao. cas CQ CtoO oCOac0i^&*i"c* oO&-HirsC&Ms0 H 0 qN 0 4 am o *H -t f O CO iI DU P050150559 74B DW-5890 4 .7 5 " 3 3 /8 " 210 100 s o f t a Oto oto Pm po$ Pp *4 <0 MS P<8 P H H p0a 02 OOff KRR&SSgRK&5g i% g* CO > i 4I3k oo $4 o Oto pP <0 p p<0 n M tOo Pm p eno*H COCO Cv H H *H *rl ^ *4 *4 *4 43,0 43 CO O It s CM 0^00 rH rH O lr\v0\3\0 Cn . H H H tvCSC^CO P* >* CO P0 CO# rH fk 43 .OP IfN CM o <v*o H iH M<J H00 sf st rH lf\IN C^ st:et: ITNOOOOVTN g& On OOOn QO OO >* P *fH0k ft OlAO IfNQ ON oH Pd p d ft ft 00 CM ft ft CM ft CO 00 ro CM H rnrnirvH 3CO SCiQ W CO w CO feQ CO CQCacOtfttQ P%m fk 8 Ik fk d4 ft ft \t n tr\ H OB ft C^ V I CM CM NO @ Cv* 000 > COOON^OOSON H rH OH & iusOavOOOsOOCn ON'vCO^Wf-J'CtcDHC'\^J -SPICGO^HO'sof H H rS"4 CfMtCfMtf<MtftfHtftfCtQftfHtfHt NO 00 OJ NO H CM ft 00 \ro co ca iCnN ft 8 <*00 ON rovO <* CM GO \ ro W CQ ^5% UNCn . o ON 00 Xrsss 8 * 0 CO p r-l Ik 43P <a p to <H JS s UNO OtfNfr* VNrO ^VNfOON ONOD oO Un m3 Xr\ 00 0NOO rH <* c m^ ft s: CM CM & Ok 0* CO CO 00 00 \AC O CO H CM CM CM S ft 0000 00 COCO ro ftOCQCO CO ft ft ft \r\lrs\r\ CNCNtN ft -ft -ft <* M* * <* <* t CM ft \lr\tf\ H CvO* * CM M* *t lf\ CV *t oo ON 00 On lTVS ft ft ft ft Rc ife A o ON R & 6-4 d PS 0 m o h*3 ik otn * iro r-m Q On d on o as * 43 43 d o p >* CO jHo < Jf< o o CM CM !O P co cm A cd H lr\lr\ Id OCM CM CM d rH O O^. 43 to ON O PON O Ow rH W < H4 Si" rH a 0 1 H 0 rH > Toluol - DUP050150560 APPENDIX I A. EXHIBITS A to I Pertaining to Grinding of CPC BLUE DUP050150561 JKMMfrA BEHAVIOR OF VARIOUS fXPIS OF BLUB IN MINERAL SPIRITS EXPT. HO. 1187-46 OBJECT* To note the relation Between type of CPC and strength development in mineral spirits in the light of known crystal growth phenomenon. GRINDING: Pint Jars, steel shot, 20 pu CFC, 110 cc H-287 PIGMEHT* AB BT-172-D DW-5839 semi-chlor crude 61s Ureaphthalo- solvent nitrlle C DBF D-5315 crude D-5316 crude Seml-chlor Mono- via PH cblor via m D-6094 D-6091 BX Paste Salt milled Mono- Urea chlor solvent dried 200? HRS. 0 119 213 380 Strength vsi Standard BT-172-D 100 25 39 100 75 90 90 75 90 95 62 95 41 68 58 78 50 108 5 75 50 75 60 80 DUP050150562 EXHIBIT J3. COMPARISON OF SOLVBHTS FOR GRIHDHIG DW-5889 BXPS. HO. 1187-54 OBJECT: To make a direct comparison of solvent. GRINDING: 1/2 pint jars, 500 g. steel shot, 10 g. CPC, 55 co solvent. IRS: A. Mineral Spirits B. Alcohol 3A C. lAOr^Uayl Acetate 0. Dloxane E. Mono ethanolamlne F. Morpholine * Acetone H. Kerosene (Deo Base) 1. Benzol . Xylene Strength vs BT-172-D 52 Idi 207 70 75 72 SO 32 85 75 85 85 75 85 90 50 56 50 58 72 72 82 36 85 58 75 75 70 82 82 60 75 75 CONCLUSIONS: Alcohol appears the most desirable solvent for grinding solvent sensitive CPC. 3A is ethanol plus 5% methanol. Samples were too small to gat tests on extracted products* See Exhibits C, E and F. DUP050150563 . jnaanjL - EFFECT OP 80LVEUT SHX1DIMQ OK HIGH STRENGTH SALT MILLED CPC. IXPT. HO. 1187-64 OBJECT; To subject: B-6091* a salt milled urea solvent process type CPC, f the same type as DW-5889 crude, to solvent grinding action. It is postulated that if solvent does not produce crystal growth no strength loss will occur. MILLS* 500 ce jars, 3 1/8" O.D. turned at 135 H.P.M. BALLS* Steel shot. 1165 gas. POL. SOLVENT* 120 cc. 60 ec added later when thickening occurred. 0-6091 -- 20 gms. - Orig. Str. 108# vs BT-172-D GRINDING TIME; M 134 177 hrs.' la|. Ageing after Grinding 5 days 11 days feato-BjL. A. Mineral Spirits B. Kerosene C, C CI4 D. Perchlorethylene E. Acetone, dried P. Ale* 3A. dried G. Turpentine B. Water EH OH I. Ale. 3A + 5% HOH J. Mono ehtanolamine Strength versus BT-172-P 78 75 78 82 90 90 72 78 90 85 120 130 70 86 50 50 120 120 85 82 85 90 90 78 95 125 105 50 125 75 m 75 * 80 130 67 130 m CONCLUSIONS* 1. 3A alcohol, (methanol denatured ethanol} appears the best candidate for grinding CPC. 2. The amount of water which can be tolerated Is an Important feature. See Exhibit E. DUP050150564 .Mi, ORTHO CHLOR BENZOIC ACID AS A GRIM)IRQ AIR. , EXPT. HD. 1187-65 OBJECT; Since o-chlor benzoic acid has been found to decrease flocculation of CPC In paint systems, It may have dispersing action in solvent grinding. She slurries used here were deliberately made rather thick to show any dispersing of the o.c.b.a* treated samples* MILLS; 1/3 gal* Pore, containing 2500 g. 3/8* steel balls* CHARGE: 100 g. DW-5889 and 300 cc solvent. GRXMDIHG TIME: jgsizarB ia 22 186 256 Hrs litegji A. C Cl4 B. C Cl4 4- 1 gm oeba C. C CI4 4- | gm. oeba D. Kerosene 1. Kerosene + 5. g* oeba F. C Cl4 CDW-6076 used) G. 23A Alcohol H. 23A 4- 5 g. oeba 45 55 45 57 45 50 45 50 45 50 45 47 45 55 45 55 60 60 55 55 60 55 60 60 7 67 67 55 60 60 60* 65 Residue of G on steam distillation and extraction = 860 str* COECLUSIOHSi 1* oeba does not aid grinding* 2. Since additional solvent was required after 90 hrs* it appears that a higher solvent;pigment ratio will be required for the blue than for the green. DUP050150565 oo t>9- IM-Ijiy.B FURTHER TRIADS WITH 23A ALCOHOL AND ORTHO CHLOR BENZOIC ACID, BXPT. HO, 1187-66 lILLi* 1 qt* porcelain,containing 700 g, 1/2W Porox Balls, except K & L which had 232? . steel shot (eq, vol!) PISHSHTf DW-5889, 50 gas. per mill. strength varans bt -172-d 2M I&S Qcha Hrs t & m m m* 300 - 0*5 ga. 200 100 ,5 150 150 0.5 100 200 0.5 45 45 45 47 45 50 45 50 55 60 60 60 300 2.5 200 100 2.5 150 150 2.5 100 20 2.5 40 45 40 45 40 45 45 47 50 5 55 60 300 0.0 100 200 0. 000 300 0.0 200 100 0*0 45 47 40 45 45 53 70 78 58 53 55 32 75* After 231 hrs, L was diluted with more solvent soli ------------ The product at 359 hrs. was dirty green but on extraction cleaned up to 105#f si, green. DUP050150566 ALCOHOL GRIND OF NEWARK MADS CPC EXP?. HO. 1187-68 OBJECT: MILL: CHARGE: To high spot grinding characteristics of freshly prepared CPC made by urea solvent process. Sample used was a dryammonia extracted crude coded 1191-7-B^ 500 cc jar, 3 1/8" Q.D. containing 250 cc steel shot. 20 gm. 1191-7-Bi 120 cc 3A Alcohol, dried with soluble anhydrite.* i.t^Bg.tk.vSgag.l..lfelZgrI 43 hrs. 90# 113 " 103 si. dull 166 *' 103 si. dull Extracted 115 equal or vvs green. It is suspected that the CsSO. used did not remove the water. Since strength development ItrExhibit H was not obtained the presence of 5 to 10# of water may be desired. DUP050150567 EVALUATION OF TIN PHTHALOCIANI8E BICHLORIDE 1XPT. 1187-77 OBJECT: Addition of SnClgPG to grind as a crystal growth preventive to permit grinding to full strength in hydrocarbon solvents. PROCEDURE: Hills - 500 cc jars, containing 1 kg. 1/4*' steel balls. Charge- 300 cc solvent, 27 g. DW-6076 and 3 g. HD-*58. Sis. ^ Solvents 47 127 180 228 Extracted Residue fiftMJMflb.yersua. .Sir,172-3 Kerosene JL Xylol -fi JL ls opropanol . Methanol 5 62 60 62 60 grn. 53 60 53 . 60 grn. 5 . 64 64 70 s.grn. 75 53 75 60 75 grn. 90 A and B were steam distilled before extraction C and D were poured into water, filtered, before extraction There is some indication that DW-6076 is slightly harder to grind than BW-5889. On acid pasting and flushing it is 105$ while BW-5889 is somewhat higher. l. * DUP050150568 SXPT. HQ. 1187-82 OBJECT} To observe grinding of Hewark made CPC in several solvents with and without 10$ of Orchea Tin Phthalocyaaine Bichloride. FBOCSMB} Hills - 1/3 gal* containing _ 3/8* steel balls. Charge* 40 g. CPC - crude (65$ 1201-51 'm a dry basis. 4 g. 110-958 Solvent added to give total of 175 ce The kerosene pulp used was 69$ total solids. ABCD1P 0H 1201-5& Pulp, gs 58 52 58 52 1201-54 Dry crude 4 36 HD-9581 gns. - 4 4 4 Kerosene, cc 153 150 Isopropaaol 99$ cc - - 153 150 175 175 Alcohol 3At cc 58 52 ee 4 2.53 15 ilaggsg|^a.,Jl.-:JL22=a BErsn* 94 161 229 325 icted Hrs. 45 42 51 43 45 45 ,, 53 53 6 55 55 55 67 65 55 64 oO 60 60 143 56 53 60 60 62 60 239 305 80 g 75 g 95 g 90 g 90 g 85 g 50 50 53 lo 60 II55 82 g g DUP050150569 PMPAMTIOH OF FULL WIf ALCOHOL GROUHD HEWAHK CPC m*. BO. 1187-88 OBJECT* To prepare a fair sized sample of Hewark CPC for stadias in solvent stabilisation# PRQCBDOBSs Anhydrous 3A alcohol was prepared by refluxing with and distilling from quick lime. H. this case the last traces of water were not removed. The CPC used was received as a kerosene palp. 1201-5A. ## solids and 45# CPC. It was dried at 200% aad ex tracted with 7# H2S04 than with aqueous anemia and dried, fields verified tie Shove analyses. A m gallon mill containing 11.8 kg of 3/8" steel halls (50# load) was charged with 278 pas. of the dry CPC and 750 ae at the prepared alcohol. ftB,4a8MW,yiMeJtela ' ttrensth.vs lf-172-D 67.5 ll 200 cc dry 3A added 287 extracted 325 * Masstone rather light but not dull. in the grind may effect masstone. See ishibit I. The presence of water DUP050150570 SOLVENT GRINDING WITH SBTHANOL. 1XPT. 0,U87-S9 OBJECT* To evaluate synthetic methanol,99$, as a solvent for grinding both green and blue. Two kerosene grinds are Included as controls. PSOCEDtfRBi Mills 1/3 gal. porcelain with 2500 g of 3/8" steel balls. 300 ee solvent, 75 g* pigment. S was included 24 hrs. after start of grind. PIGMENTi JL DW-5890 DW-5889 SOLVENT; Methanol Methanol SnClgPC, MD-958 - - C DW-5889 Methanol 10 g JL. DW-5890 Kerosene - JL Crude E, PH (33246) Kerosene - GRINDING TIMS* BPS. 95 86 146 95 189 100 268 105 d 316 Extracted* 105 SJtUUlKttL'VS-J1=122=1 dr GT-486-3 6 60 6730 70 80 grn. 55 gr. 62 " 63 w 65 " 65 M 75 " 75 90 122 100 165 100 144 282 100 65 75 75 86 82 80 .. d dirty. Methanol shows promise of somewhat faster grinding of polyohlor CPC than kerosene. Although contamination with iron occurs it is removed on extraction. DUP050150571 .1.....IMP J to H PERTAINING TO GRINDING OP POLYCHLOR CPC GREEN 4. , DUP050150572 mrntij; SFFBCT OF VISCOSITY OF LIQUID, SLURRY COMC. AND BALL SIZE KM. 1187-58 Shis experiment is a test of the idea that a lew viscosity liquid gives faster grinding. At the same time it is a quick survey of mill leading conditions to indicate the probable ranges for ball mill capacity studies* Mills 1/3 gal. porcelain. 4.75" I.. Ballss 2500 g. steel Solvents 200 cc as indicated. &$gag$fo..Y3.0%: agfefc. mil.,Mm Salami S=52 Sis* 65 uz m A 3/w B 3/8" C 3/8 D 3/8* E 3/8* F 3/8 0 1/8* a 1/2* I 3/8* Kerosene 50 gms. 60 * " Nujol 75 100 50 " 75 Kerosene 75 75 C Cl4 75 85 90 100 82 90 100 80 90 100 67 87 98 47 50 50 55 56 55 78 85 95 63 82 90 69 85 . 95 CONCLUSION* 1. Conditions of D give highest rate of grinding in terms of gms. pigment ground per hour. See calculation of relative rates in Monthly Report 1/30/4$. 2. More viscous liquid of same chemical type gives slower grinding probably due to protection of small particles by the viscous liquid film. 3* 3/8" ball size seems most efficient. DUP050150573 jamas. & BALL MILLING DW-5890 IN KEROSENE B2PT.N0. 1187-73 OBJECTS A preliminary study of mill loading vs capacity. PROCEDURES Mills 1/3 gal. mill containing 2000 g. 3/8" steal balls, rotation 47$ of critical speed. Charge made up with kerosene and BW-5890. DW-5890, gms. -J- JSL JL 100 100 125 150 Kerosene, cc 300 500 500 500 Slurry cone, g/1 280 180 220 254 Tiatiag-^irength vs GT-486-D 70 75 65 60 88 82 82 75 75 159 90 88 82 80 207 95 95 95 86 Grinding rates are calculated by the formulas gms. pigment/hrs. x increase in str. and tabulated below for the different periods. HRS. A JL _L JL. 46 88 72 51 82.6 51 7564 75 65 159 33 32 35 46 207 28 28 35 35.5 CONCLUSIONS Unfortunately the grinds were not carried to 100$ Str. However, since D rate is dropping off rapidly at the end, the C slurry is judged best and serves as a guide for further capacity studies. These results relate only to slurry concentration and may not be translated to larger mills with lifter bars. DUP050150574 mmsji COMPARISON OP SOLVENTS FOR GRINDING BW-5890 BXPT. NO. 1187-74 OBJECT* To compare solvents more readily removed by steam distillation with kerosene. PROCEDURE* Mill* 1/3 gal. porcelain containing 2000 g. 3/8M steel balls, 100 g. DW-5890, and 500 cc solvent. Solvent* HRS. |I||1I lllWIIW 47 115 163 210 -A. Xylol B, ri Toluol JL. c ei4 Kero: Tintina Str. VS.GT-486-D 69 67 56 69 90 88 75 86 97 97 82 90 105 100 86 92 The final slurries were dried at 200F. E was hard. A & B were at least as soft as D. CONCLUSIONS* Xylol or Toluol appear to give considerable capacity advantage over kerosene. Further comparison with mineral spirits and methanol (See Exhibit I) should be made. DUP050150575 EVALUATION OP ISOPROPANOL 1XPT.NO. 1187-76 1/3 &&1* mills, 2000 g. 1/2rt steel balls or 760 g. glass beads* 100 g. pigment. Rail charge Isopropanol, 99*, cc Water Pigment, DWf mm&rn* Steel 500 JL Steel 500 JL. Steel 400 5890 6076 100 6076 D Steel 400 100 5890 HRS. 45 93 212 260 372 446 Extracted: * strength vs. QT-486-D 60 36 39 36 69 45 43 blue 82 90 50 50 53 53 v b11 lue 9 95 105 53 dull 60 dull JL Glass 400 100 5890 S ll 87 95 102 DUP050150576 BifflLI BALL MILL CAPACITY FOR ORIHOIHO D-5890 IN KEROSENE EXPT. NO. 1187-78 OBJECT* To make a high spot mill capacity test in a 12" die. mill equipped with lifter bars* PROCEDURE; Mills 12" die. by 6" steel mill at Experimental Station. Engineering Department Laboratory fitted with 1 1/4" bars. Ball chart# used* Materials; 47.2? lbs. 3/8" steel 1.125 lbs. (510 gas.) DW-5890 1.14 liters kerosene .3 liter added at 29 brs. 3 liter more at 40 hrs. The mill was operated almost continuously and small progress samples withdrawn for immediate test. The addition of more solvent was governed by the sound of the mill. It was thus judged that the run was made with a slurry of close to optimum concentration. Maximum mill temperature was 40-45*0. HRS. STR. 20 II 40 93 60 93 78 100 This operation is compared graphically with small mill grinds in ixh. N, Fig. 1 and the mill conditions tabulated. DUP050150577 Bxtrapolatlon of Data of Expt. II87-78 to Large Kills. By assuming the mill conditions of the Expt. calculations for larger diameter mills are shown below. The basic assumptions taken from known ball milling practice ares 1. Materia! capacity proportional to B2 2. Grinding capacity proportional to the power input. 3. Power input proportional to 4. Grinding cycle proportional to B*5 The following quantities are given for one foot of mill length for easy conversion to mill of any length. Kill Dim. ft. Ball charge,lbs Figment, lbs. Gycle, hrs. Loading, etc. Total Cyole # Pig/24 hrs. 1 94.5 2.25 80 2 82 1.3 a . 3*5 JL 378 115 1512 3400 9 27.4 36.1 81 57 42.8 40 32 2 222 ?9 44.6 42 34 3.67 14.85 20.8 56 8 6050 144 28.4 2 30.4 113 This bold extrapolation is shown graphically in Exhibit N,Fig.2 DUP050150578 it o * .. Lmmb A-- I 5 Expt. 1187-27 small mineral spirits grind of GT-486-D using steel shot, fhis is Included to show that hall milling has inherent characteristics suitable for the degelopment of high strength. In this case ball milling is super-imposed upon acid pasting. 0 Sxpt. Il87~70 Kerosene grind of DW-5890 in Ballitator with steel shot. x Sxpt. 1187-78 Kerosene grind of DW-5890 in 1 ft. dia. mill at the Experimental Station. f*T| Sxpt. 1187-79 Same as 78 but using steel shot and more solvent. /X Sxpt. 1187-58C A fairly comparable grind in 1/3 gal. mill. v See Exhibit J. * This point represents theoretical conversion of the 279 hr. <> cycle to the conditions of Sxpt. 78. Corrections are made for till dia., mill speed, and ballspigment ratio. The remaining discrepancy is thought due to slipping of the ball charge in the porcelain mill. DUP050150579 i&k.smmQm.gpR f ig * 0 Expt. Bo. 1137- Mill dia., inches $ Grit, speed Ball dia., inches (steel) Ball Load % MsV vol. BallsPig. wgt. KerosenesPig. ec/ga. Lbs.Pig./ou.ft. mill space Grinding rate in #/ou.ft./hr. at 100$ Str. 20 4.75 1/8 70 lsl 33 4.15 4.75 .091 X 28 12 66 3/8 40 lsl 42 3.9 2.89 .037 22 12 66 5/32 40 2t 1 42 6.5 2.89 58c 4.7! 47 3/8 50 lsl 33 4.77 3.36 .025 .012 REMARKS 8 She sharp breaks in the 73 and 79 carves costs at the point where thickening occurred and in each case about 20$ additional solvent was added at this time* Further evaluation with semi-works mills may show a shorter cycle and a major increase in capacity by using thicker slurries and larger balls* If the grinding rate in terms of #pig. ground/hr./cu.ft. of total mill space (last line) increases in a ball mill with the square root of the diameter, it may be calculated that a 73 inch mill is required to equal the Ballitator rate* DUP050150580 / * " -ftfP 444' 5:1.4: Ex h ibit N Fi*. TnT^^T^rrt F [rrrr [Vi 55 .. -- :4 .i ' 4;; ITT?!"?::; r 1;V. :.v':;|n:; lifil pd If>; 54.44 j(;. ;;;. ;I444: ;r :: :i ' 4j44 :hj 44 tek * Zs' " i-.3 p |ji: Vjr:; r.:|y4 44 V-f Try" ^TiT ' 33 r; t -- 5s 44 i ::rlv hr. 54 . * *H: 4h hi;: -.T-*.. .. ;|r H;i i..t 4:4:4 - _53 ~.T.i *iv" 15?* :44 ;1 *! -fi X;4 :*: 45 45 Vrf hijh;-;;: 4Ti]TM` 44r 53 .ITT. i'-jiL S|n? `r>PS 35 45 4:` :-4: -55 '44 55 rtr; :' 4;r 54 54 rtrr !d ~-4-- .rLd j * ir: ZZZ1' }.zni 55 45 : :::!Vi.* '.r*; HfJ V* *#4W* if:: 44:44: 55` 4:' r;.h;. 34 V:f. j 55 44 :: :1 45 4-7 - i.. :: 4 5 53 34 hr f::: iff.p.:; liil ip: mi. 54' 44 44: **.iv mi :r r T:Th 44 <? r 14': . r r. t Ht ; ;44ii .nif r-V t v ~ in 55 :ih % 45 44 btM m ur. hj ri 45 44 Tiff; ':rr 45 44 *. TT' r35 .441^. :--JL~ 44)3 r .i y.T;\ 55 4 *S MUi : i | :::] :{:;;: : :;5 rr:1; W. 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