Document 1gbJ8Dyjdqek4GB0D6qjR5w75
E. I. DU PONT DE NEMOURS & COMPANY
KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY
V-
Serial No. Copy No.
KF-50-29
Numerical File
K]
ft
&
Period Covered
NEWARK PLANT PIGMENT COLOR RESEARCH
Final u.-v'-ort
REPORT
..
Jtuwr-y lj 194 <5 ~ July 31, 1950
FIEE: DATE:
210* 2 10/24/50
Copy to*
#1 numerical File 2 * Research Office (210.2)
3 * literary File (210.2)
4 - D. B. Killian 5 - . Chalupski * Plant Files o -p 0. Morrison 7 * Extra 8 - Extra 9 - Extra
Serial Wo* i0?-50*29 Copy Bo* 1
HEWBK FLAB? FJOKBSS COLOR RESEARCH BEPOBf
Final Report
wmmiE mem.Mm-3RBimaip.m-n-
January 1, 1948 July 31 1950
CHARGEi A-II-C-250
SUBimED BSf* AFPROT&D BY*
d at e swmmTWt 8/25/50
BAT'S-'
' xo/24/50
DUP050068293
CONTENTS
ISIRQDUCT ION SUMMARY AND COHCLUSIONS PATENT SITUATION GENERAL DISCUSSION
Background Competitive Product Competitive Patent Preliminary Laboratory Study Flushing Process Studies Pigment Process Studies Evaluations Summary Related Products RECOMMENDATIONS REFERENCES EXHIBIT A (B) F-8-F STEPWISE FORMULA (B) F-8-P FORMULA NOTES (A) F-ll-F STEPWISE FORMULA (A) F-ll-F FORMULA NOTES
1
1
2
2
a
3 3
4
i
10
10 10
11
12
DUP050068294
wmmmmi Upon resumption of civilian motor ear production in 1946 there
me a pronounced trend toward the use of highly polychromatic and durable finishes* Impetus to this tread was undoubtedly provided by DuPont's vigorous promotion of the "Hetalllchrome Due* line, in which novel transparency and durability ware obtained by the use of Auric Brown P-4-P, a hydrous ferric oxide manufactured at Jtowark and flushed by the finishes Division*
A companion dry pigment , Auric Brown P-5-D, released by the Pigments Department for lemerai use by finishes manufacturers, was practically incapable of dispersion to the extent required to produce the desired transparency and gained essentially no popularity in the face of competition from lough Sold Paste, a flushed alkyd dispersion of hydrous ferric oxide marketed by the Harmon Dolor Works. Accordingly, research project #250 was undertaken in January 1940 directed toward development of a counter-offering for lough Sold Paste*
Pigment of the desired type was prepared in the semi-works at Newark early in 1948 and flushed into alkyd enamel of generally satis factory quality at the Finishes Division Philadelphia laboratory*
the recognized tinctorial instability of hydrous ferric oxide in aqueous media and the established policy that the product be avail able for unrestricted Sale dictated that tha pigment be marketed as a flushed alkyd dispersion*
Activity directed toward development of a flushing process and eventual standardization of a pigmented dispersion identical in pro perties to the Harmon dispersion was resumed in November 1949*
It was necessary to develop a ferric sulfate type pigment process to replace the unprofitable ferric chloride acetate process originally used, and to develop a flushing process which would avoid infringement of a Harmon patent*
Pigment and flashing processes have been developed which meet the foregoing economic and legal requirements satisfactorily, and which have been carried through the semi-works* the semi-works flashed pro ducts are slightly less polychromatic than Bough Sold Paste but their proximity is sufficient to warrant preliminary trial at plant batch size. Those products will be evaluated for durability. They are very similar to lough Sold in composition and compare as follows in other properties*
1, Typical flushed aiH bases prepared from AF-8-P (chloride acetate) pigment are equal to Rough Gold except for "Slightly light to light" liquid base masstone and "very slight to slight" deficiency in two-tone flash*
DUP050068295
-22* typical flushed bases prepared froa BF-8-P (normal sulfate) pigment differ from lough 0014 in the same properties but to a sig nificantly greater degree than that shown for the chloride pigment bases, and are also definitely light in baked film masstoae. 3. typical flushed bases prepared from a high-concentration triple-caustic process (S.W.-1252) retain the relatively light liquid base masstone and light baked film masstone of the BF-8-P bases, but possess improved two-tone flash of metallized films, at least equal to that of the AF-8-P bases and eery mearly equal to that of lough Sold* they are, however, quite red in hue. the flushing process 1P-11-F has been cleared by the Patent . -Division of the legal Department as free from infringement of the Sermon patent* the proposed process involving use of sulfate process pigment is potentially profitable despite requirements of new capital investment for regular operation. In view of prior commitments of the flushing production facilities, further development and standardisation of the flushed hydrous ferric oxide dispersion has been .indefinitely suspended and the research project terminated as of Inly 31, 1950* io patentable development has resulted from the investigation to date. the only serious competitive patent threat to the proposed development was O.S. 2,384,579 of Fesce, assigned to Harmon Color Works, fhe legal Department, however, has concluded that the proposed process will not infringe any of the Fesce claims, the proposed process embodies prior art specifically disclaimed by Tesee during prosecution of his application and does not infringe his process claims, while his product claims are all of the product-by-process type and expressly limited to the claimed method#
tough Gold taste Is considerably darker in masstone, yellower in tint, and more transparent than Auric Brown P-4-P. fhe yellowness and transparency are quite apparent in metallised colored enamels* Like Auric Brown it produces finishes of outstanding durability. Its manufacture was protected by a patent Cl), issued in 1945 to fesce and assigned to Harmon Color Works, which describes processes both for preparing the hydrous ferric oxide and for flushing it from aqueous to organic media, the claims, however, apply only to the flushing process and to pigmented dispersions produced by the specified flushing procedure; the described preparation of the pigment is not patented.
DUP050068296
3
As initial activity under project #250, the Fesce pigment preparation was carried rapidly through the laboratory. The products possessed qualitatively the desired properties. One snail semi-works batch of aqueous pigment pulp was therefore manufactured in February 1948 and submitted to the Finishes Division for evaluation. Philadelphia laboratory flushed the pigment (AF-8-P) successfully into alkyd res in at a pigment-to-binder ratio (P/B) of 75/100, using W% of linseed oil fatty acids (dry pigment basis) to effect transfer (4), A 250 hoar ball mill grind of the sill base was required to produce satisfactory enamel gloss. The resulting enamel was similar to Harmon's F-95 Hough Sold Paste except for slight ailkiness, ascribed to particle else growth prior to flushing. It was reported that the flushed product containing AF-8-P produced metallised enamels equal in "flash and two-tone* to enamels obtained from Hough Sold (5).
fhe recognised tinctorial instability of the pigment in presscake form and the established policy that the product be available for general sale to finishes manufacturers dictated that the pigment be marketed in flushed form and that the flushing be done as part of an uninterrupted pigment processing sequence.
Study directed toward development of a profitable, non-patent infringing process for the manufacture of a satisfactory counter offer liag for Hough Gold was resumed in Hovember 1949*
QpiagtlUm-grMasJ The competitive product had been distinctly improved in com parison with earlier samples. The current Hough Gold, F-5850, is an admirable product* completely fluid, mobile (59 X.u.) aon-reactive, seed-free, high gloss, extremely transparent, very dark and Jet in masstone, brilliant red in transmittance, with composition reported to be 33$ pigment, 17$ resin solids, 50$ solvent, and possessing excellent unifomlty of standardization as demonstrated by examina tion of five batches*
The fesca patent stresses the importance of* (1) precipitating the pigment in the presence of a substantial concentration of acetate ion, (2) immediate flashing, (3) preliminary emulsification of the alkyd resin in a large volume of water usings substantial quantity of triethanolamine oleate as stabilizing agent for the aqueous resin emulsion, and (4) effecting transfer of individual pigment particles to the resin by mixing the aqueous pigment dispersion with the aqueous resin emulsion and additional organic solvent, then gradually removing all water from the system by controlled azeotropic vacuum distillation of a mixture of uniter and solvents Particular emphasis is placed on avoiding the characteristic water breakout and decantation steps of prior art flushing procedures. The examples include roller milling of the flushed mill base as a definite step in the preparation of the final dispersion. Hone of the patent examples, incidentally, describes the preparation of dispersions pigmented at the high (2/1) P/B level of the. tsmume rdzftL Hough tGe%8
DUP050068297
4
the initial phase of current activity comprised laboratory attempts to improve the filtering and washing characteristics and tinctorial stability of the AF-8-P pigment (Vesce process) by various surface active treatments, and a brief laboratory variable study of the pigment process. Mo marked improvement in process1st appeared readily obtainable, and development of a satisfactory pro cess for flushing pigment to resin at the required (2/1) P/B con centration appeared to be prerequisite to profitable study of the pigment process variations*
Flushing process study was therefore undertaken using a freshly prepared batch of AF-8-P made by the same procedure as the batch which had been evaluated by Philadelphia in 1948,
Upon the recommendation of the Finishes Chemical Division of Fdf and with subsequent approval of Finishes Management (6), DuPont alkyd resin HC-448 was employed throughout this study, except for limited direct comparison versus the alkyd resin (glyptal GE-2452) now used by Harmon. The results of these comparisons confirm P&F Chemical Division statements that the two resins are interchangeable in this application.
A 3/4 gallon Baker-Parkins vacuum mixer was used in all flushtog studies, the flushing study and the results obtained may be summarised briefly as follows*
1. lo significant quality advantage is obtained by preliminary aqueous emulsification of the resin,
2, Incorporation of triethanolamine and oleic acid or their equivalents (used by Peace as emulsifying agents for the resin) is vital to control of reactivity, transparency and film integrity, the quantity of treating agents required for this purpose is sub stantial - in the range of 10-15$ of the final mill base - but apparently is not significantly greater than the quantities of agent present in sough Cold, the actual FigOq/resto/treating agent compo sition of Sough Cold has not yet been determined. Determination of this ratio to both the wet mill base and in dried films has been requested, and is an essential prerequisite to final standardisation of the product, since at present it is not known whether the non volatile portion of the treating agent is classified by Harmon as "pigment* or vehicle, the reported P/B ratios of experimental mill bases to date have been based on actual hydrous ferric oxide solids and resin solids input, with no assignment of treating agent to either classification.
DUP050068298
3* So apparent quality disadvantage results from conventional prior art breakout and decantation of water, per aet in spite of fesce*s vigorous contention to tfee contrary* incision of this conventional flushing procedure Is not only the principal factor by which the proposed process circumvents infringement of Vesce, but it also effects significant reduction in operating costs versus an "all-d1stillation" procedure*
4. ft is not possible to obtain direct single step water breakout at P/B 2/1, the advertised composition of lough Gold Paste* attainment of this pigmentation level requires stepwise incremental addition of pigment and decantation of water* follow ing initial breakout, which occurs at approximately P/S 80/100 to P/B 120/100. depending upon treating agents present, ami their emulsification tendencies*
5* ill! bases prepared by stepwise flushing to P/B 2/1 are equal in quality to mill bases prepared by *all-d1stillation of ?/8 2/1 emulsions, other factors being constant.
6. To date no method has been discovered for complete clari fication of breakout waters prior to decantation, total solids decanted with the waters have varied fro 10-20$ of the weight of pigment solids. In the single experiment analysed to date, in which the pigment input was 500 grams, the total solids decanted was 56 grams, exposed of 38 grams pigment- 13 grams treating agent ana* by difference, 5 gras resin, volume of decanted liquid has varied from 75$ to 85$ of the total water content of the pigment pulp in typical experiments*
7. Considerable study was directed toward establishment of optimum points and methods of introduction of the treating agent* Considerable further study along this line is desirable for the sake of developing a more economical process as well as possible quality improvement, in the event that standardisation is resumed. Gf the numerous processes investigated to date, none has given consistent all around performance superior to 1351-71, on which the AF-ll-F formula is toed. Briefly, 250 grams (solids basis) of pigment pulp is charged into the mixer and slowly treated with a mixed solution of 84 grams oleic acid end 210 grams of alkyd resin solids, the pigment transfers to the resin phase and the pigmented resin slowly coagulates with eventual separation of cloudy breakout water which is then decanted. The pigment content of the paste is then increased to the final 420 gram input level by stepwise addition in increments of approximately 25 grams tsolids basis). After each pigment addition the water-in-oil paste in the mixer changes to a crumbly oil* in-water mass which eventually reverts to water-in-oil with expulsion of breakout water.
DUP050068299
6 It the final revets Ion does not occur within 15 minutes the crumbly charge is treated with a small quantity of solvent whereupon the breakout occurs instantaneously. After all of the pigment has been added and the water decanted, the charge is treated with 84 grams of triethanolamine, then diluted in the aimer with additional solvent, and the residual water removed by vacuum distillation at 12O~130SF and a pressure of 100*200 millimeters of mercury. An additional 42 grams of oleic acid is added at the first evidence of incipient gelling, or. at the latest, one hour after the - start of distillation. When all water has been removed, evidenced by defegging of distillate receivers and marked drop in rate of distillate delivery, the charge is diluted with additional solvent to approximately 50# film solids content, removed from the mixer and ball milled overnight.
8. Modification of the foregoing procedure by preliminary treatment of the initial charge of pigment with half of the TEA has not affected quality consistently. In this connection, however, it must be mentioned that only one of the 45-50 experimental mill oases was fully equal to Harmon*s product in masstone jetness and clarity of the liquid base, and this base was made by a process involving initial TEA treatment. Hepeated attempts to duplicate this product by the same process, however, were unsuccessful, and no explanation has been obtained for its unique quality superiority to other products.
9. Attempts to reduce the initial oleic acid treatment by 50$, either in the vehicle as above, or by direct oleic acid trentaMtiat; of the pigment, were unsuccessful, resulting in serious complications in the transfer process, usually stabilisation of the initial pigamt*invehids-in-water emulsion. Complete (mission of agents until all water is decanted, followed by prod 1st illation addition thereof, was a^so tried but resulted in very light, dull wassione bases.
10. Significant reduction in the total triethanolamine oleic acid treatments invariably results in the formation of fairly rigid gels late in the distillation process. These gels (and, in more aggravated case?, even superficially dry powders) can be refluidised quite spectacularly by treatment with heat and either amine or fatty acid, and, if satisfactorily fluid when distillation is stopped, are noa-reactive. Upon prolonged vacuum distillation the refluldized products again gel; the cycle can be repeated indefinitely. A study Involving heat treatments of such a gel with numerous combinations of agents led to the following observations (1377-25) which appear to have general application in at least a qualitative, and possibly a quantitative sense*
(a) The combination of 5*3# oleic acid and 3*6# TEA <*as is" gel basis). Obtained by actual analysis of the gel, is inadequate to protect the mill base from gelling.
DUP050068300
(b) Best dispersion sad transparency mire obtained by beat treatment of the above gel with 3$ additional oleic acid*
(c) nothing was gained by adding triethanolamine with the oleic acid*
(d) Addition of triethanolamiae alone, rather than oleic acid alone, produced inferior dispersion and opacity* Quantities of triethanolamine In excess of 4% additional treatment induced cracking and general non-integrity of the films ,
(e) Film hardness exceeded that of Bough Gold at 4% or less total additional agent and was equal to Bough Gold at 6% total added agent, but the films were unsatisfactorily soft when the total added agent treatment exceeded 8$.
11, Considerable solid organic asterial collects in the receivers during vacuum distillation of the charge* Also, as indicated in (61 above, a significant quantity or treating agent is unavoidably decanted* Attempts to assay the magnitude of these losses have not been completely successful to date (1351-80). Resumption of such study is recommended in order that the leads reported in (10) can be further confirmed, and satisfactorily applied in ultimate standardization of the process*
12, Various experimental observations as well as the available analytical data indicate that the use of triethanolamine and oleic acid in the ratio of their molecular weights (approx* 35/65) provided the most effective assistance in initial pigment/vehicle transfer as well as the most effective control of final enamel properties* initial attempts to employ this lead in simplification of the flush ing process were promising (1377-37) bat were interrupted by termina tion of experimental study,
13* Available knowledge concerning the role of the treating agents may be summarized briefly as followss
(a) the presence of triethanolamine and oleic acid or their reaction product, or equivalents thereof, is essential}
(b) fhe ratio of amine to acid should be between 35/65 and 45/55}
(e) fhe quantity of combined agent Is to be fixed by the point at which film hardness equals that of the competitive product}
DUP050068301
8*
(d) At least a portion of the agent should he introduced prior to transfer}
(e) The AP-ll-F process (7 above) Includes a sequence of treatments which has beam as cons istently satis factory as any modification thereof}
{f) Further detailed study of the role of agents in the initial transfer is recommended for the sake of possible improvements in economy, quality, or both*
14, On the basis of current information, no apparent effect on quality is definitely attributable to deliberate variation of moisture content of the final mill base In the range of 0.5 to 2.0$, or to deliberate variation of severity of heating of the mixer jacket during distillation. A jacket temperature of X80-2QQP, and maintainane of vacuum until 10-20 minutes after defegging of mixer sightglasses are recommended. A racheck of the effects of moisture is " recommended, however, following fixation of other variables,
15* Although considerable variation has bean observed in the degree of dispersion evidenced by seed content or grittiness of the bases at the conclusion of vacuum distillation, it has not appeared profitable to attempt to correlate this variation with process factors in the study to date, since the best of the bases has been inferior to automotive standards in dispersion and gloss prior to ball milling. The proposed plant process envisages ''HF* processing of the distilled bases, successfully employed in similar applications elsewhere In the Company* Sfo experimentation with this type of processing has been carried out in connection with the present study to date.
16. The Patent Division of the Legal Department has cleared the proposed process <7 above) as free from infringement of the Yeses patent (Bef . 3).
The initial portion of the above summarised flushing study was conducted with semi-works pigment of the AF-8 type prepared by the ferric chloride acetate process published by Yesce. With the exception of one outstaming product (1351-?o) which has never been satisfactorily duplicated, none of the experimental bases were fully equal to Bough doId in jetness of mas stone of the liquid mill base, although many were satisfactory matches in all other mill base pro parties, and were similar, but probably not fully equal, to 9mm Cold in two-tone flash of metallised enamels. Economic evaluation of the prospective processes, however, demonstrated that the use of the Yesce pigment process would result in such poor return as to render further development study unjustifiable, but that a satis factory return should be realised if the product could be standardised on the basis of a pigment ingredient cost similar to that of AUric Brown,
sc.p'M'WrfjNv'y
DUP050068302
Speculative consideration was given to the use of by-product Idgeloor ferric chloride, hat cost and parity data developed by the Production Division (Hef. 8) sere not sufficiently attractive to Justify experimental work along this line*
Based on laboratory process study a semi-works batch was prepared by a process modified by omission of the acetate and replacement of the ferric chloride with ferric sulfate, prepared by the copperas oxidation procedure used for Auric Brown* This process, coded BF-8-P, produced pigment of much lighter color in the form of aqueous presses*# compared to AF-8-P, and yielded flushed mill bases which wire definitely lighter and duller in liquid base masstone, and deficient in two-tone flash of metallised enamels, although quite satisfactory in dried masstone film properties such as transparency, color by transmittance, hardness and gloss*
Several variables were tried in the flushing process in an attempt to darken the masstone of the BF-8-P liquid bases, but none was successful* Bpectrographie analyses revealed no significant difference between the BP-8-P pigment mill bases and Hough Gold, or between the SF-8-P and AF-8-P types of pigment*
An intensive laboratory study of pigment process variables was rapidly conducted, using color comparison of the presscakes for screening evaluation, laboratory pigments prepared by the chloride acetate process were considerably lighter in aqueous pulp appearance than were the pigments prepared by the same process in the semi-works, being equal to the seal-works sulfate type products, and no darker than laboratory sulfate products* So appreciable effect on the color of the laboratory slurries or jnrssseak# was produced in the case of either type of process by major variations in several physical and chemical factors (agitation, strike rate, concentration, presence or absence of acetate, chloride versus sulfate, direction of strike, temperature), but pronounced darkness was produced by the introduction of from 1 to 5$ ferrous ion, or by the introduction of from 1 to 5% manganous ion, or by the combination of high strike concentration and large excess of hydroxyl ion* The product containing ferrous ion drifted lighter on storage in pulp form. The product containing manganese produced a metallized enamel which demonstrated exceptionally good two-tone flash but was undesirably dark and dull. Consequently, only the combination high concentration - high alkali process has been taken to the semi-works to date. The semi-works pigment obtained from the latter process (S.W.-1252), while much darker than the normal BF-8-P in aqueous pulp appearance, disappointingly produced mill bases which were not appreciably darker in liquid masstone than normal BF-8-1'.bases. Evaluation of the bases in metallized enamel, however, indicates that the modified procedure has apparently definitely improved the two-tone flash, almost to equality with Hough Gold, and has definitely reddened the hue, providing a lead for further study in case the Finishes Division renews its previously expressed interest in a hypothetical red-toned product*
DUP05P068303
- 10 *
IgiOmUGM^ai .fiaansx. Evaluation of most of the experimental flushed products consisted of inspection of baked .003" films of the unreduced mill bases on transparent plastic. Key bases ware reduced with RC-103 to P/B m 14/100, metallized at V&% aluminum content, sprayed and baked. Serious difficulty was repeatedly encountered with poor reproducibility of the metallized enamel evaluations. The results summarized below, however, are based on several series of tests and are believed to have been established beyond reasonable doubt 1377*31)* 1. Typical flushed mill bases prepared from AF-8-P (chloride* acetate) pigment are equal to lough Gold except for "slightly light to light1* liquid base mass-tone and "very slight to slight1* deficiency in two-tom flash. 2. Typical flushed bases prepared from BF-8-P (normal sulfate) pigment differ from Bough Gold in the same properties but to a sig nificantly greater degree than that shown by the chloride pigment bases, and are also definitely light la baked film masstone. 3. Typical flushed bases prepared from the high-concentration triple-caustic sulfate process (S*f.-12523 retain the relatively very light liquid base masstone and light baked film mas-stone of the BF-B-P bases, but possess improved two-tone flash of metallized films, at least equal to that of the AF-8-P bases and very nearly equal to that of lough Gold* They are, however, quite red in hue. Typical samples of each of the two sulfate types (BF-8-P and S.W.-1252) bases have been submitted to the Finishes Division for evaluation (1377*33)* Their results, received after initial drafting of this report, confirm the Hewark evaluations* They conclude that neither of the bases could be used as a general replacement for Harmon's #5850, but only for new developments, or in colors which do not utilize the full transparency of #550 (Exhibit A). The same two bases are included in a metallic enamel exposure series being prepared by the Sewark Sales Service laboratory. P.th3.g-g^.^s,t, During the course of the experimental program, a sample of flushed Auric Brown (1351-74B) was prepared by the proposed flushing process. This product also is to ba evaluated by Sales Service* At the request of the Finishes Division the experimental program also included preliminary study directed toward preparation of a lough Gold type dispersion in a non-drying alkyd resin. Although this work has been discontinued by agreement with the Finishes Division, the results demonstrated that the AF-11-? process should be adaptable to preparation of a satisfactory product of the desired type, provided that the necessary treating agents (as used in Hough Gold) have no deleterious effect on properties of the ultimate finish. Concern regarding the latter possibility was expressed by F&F. (Bef. 9)*
DUP050068304
11 * The experimental project has been terminates because of the demand of other products on the limited capacity of production flushing facilities* Tentative plant formulas for the current experimental processes are appended* with notes indicating the items of new plant equipment which would be required for routine manufacture of the products* The following program is recommended in the event that develop ment and standardisation studies are resumed* 1. Complete the analysis of lough Gold and of the present counter-offerlag (1377-33A) for determination of FepOq/resln/treatlhg agent composition both of the liquid bases and of baked mass tone films prepared therefrom. 2. Hush a batch of freshly prepared plant (or maximum slas semi-works) pigment in the plant flushing unit. Ho preliminary variable study is essential as a prerequisite to plant trial* but, if desired, brief study along the line suggested under item (12) "flushing Process Studies"*; above* is suggested. It would be necessary to dispose of this pilot batch of flushed product on an *m is" flushed basis since no suitable dispersion equipment is available at the Uewark plant* 3* Several suggestions of laboratory flushing experiments which might contribute helpful information to the development program are included in the items under "Flushing Process Studies" above* 4. It is strongly advised that all pigment process develop ment variable studies be conducted at semi-works scale - i.e* larger than laboratory* It may be desirable to investigate the effect of caustic excesses and concentration increases- intermediate between those represented by S.W.-1252. as well as the effect.of introduction of manganous ion in quantities less than $$ (1377-12-1). Experimental details are recorded in Chemical Division research notebooks 1351 and 1377 and in DSS-50-4.
DUP050068305
12 *
1. U.S.Patent 2,384,579 (9-11-45). "Iron Pigments*5 Vesce to Harmon Color Works (Application 8-20*41).
2. Major Experimental Project #250. December 30, 1947. 3. Letter J. P, Hancock to A. J. Stratton, July 18, 1950*
"?esce U.S.Patent 2,384,579". 4. Letter W. H. Toole to G. Grimm, July 23, 1948.
"Experimental Flushing Procedures". 5. Letter W, H. Toole to 8. 1. Denslow, April 15, 1948.
``Hydrous Iron Oxide AF-8". 6. Letter J. B. Bullitt to I. Shrawder, Jr., June 19, 1950*
"itlkyd lies in HC-448". 7. Letter J. 0, Morrison to p. B. Killlan, July 5, 1950.
"Flushed Hydrous Ferric Oxides - Estimated Costs". 8. Letters, C. B. Bosses to J. 0. Morrison, June 28 and
July io, 1950. "Ferric Chloride". 9. Letter f. fU Matthews to J. 0. Morrison, March 22, 1950,
"Flushed Hydrated Ferric Oxides".
DUP050068306
Philadelphia Laboratory August 21, 1950.
J. 0. MOBBISOI . tmmmB wusamm SEWARK, MW JERSEY
FLUSHED HYDROUS 1H0I OXIDE JfeUdt__________ _________
We have completed our preliminary evaluation of the
subject product. Results relative to Hanson*s Hough Gold
Paste #5850 are tabulated below
Gloss
Ms.
Sslsx tas&Ssm Saiaiia
5850
95 Std. 10(6 td)
'
1377-33A
96
Std,
8 Milky
1377-330
96
s.redder 8
llllky and
Panels of these enamels at % and 15$ aluminum levels, which demonstrate the above two-tone deficiencies, are being enclosed* 1377-33A is closest to the Harmon product; however, with it we are unable to match established colors originally developed with the Harmon product. We could not use X377-33& as a general replacement for Harmon's #5850 but only for new developments or In colors which do not utilise the full trans parency of #5850-. Of course, we would not be justified in. carrying two such products unless there was a substantial cost advantage.*
Soutine exposures are being made of these products and we will inform you of any significant results* Please advise if you require additional information*
PHILADELPHIA LABORATORY '
H. GODSHALK
DUP050068307
Code
W <B) F*8-P Approved by*
Goals Theor. 2200# SIZE*.
J.Q.S, 6/30/50
1st.Prod.fid. 1877# Coupling fat
Strike fats Steel fat <Repl.l82)
m .Isa,tost loos, 422 1. Run 33* (11150.) eater into vat 422*
2. Dump in 10 loads (Hough Payloader) of crystal copperas.
3. Heat to 80-lOQOF, 4. Stir to dissolve.
M
Pomp vat 422 into vat 283. Stir 5 minutes. fake 16 os. sample for analysis. . Stop agitator. 9. Check and records ,............ *. 0. Deliver sample to laboratory.
Report to Group Supervisor for calculations based on analytical .results.
x 64.5 x
J/Gal. x flOO * $ Pe-ne
100
*
Total.
Record at
.F 11 Get Inside strike vmt and brush and hose
. top, wall, agitator, etc., thoroughly clean.
12 Run 20*25* (j; 26250*) water into strike vat
with agitation.
13. Slow steam lines. *4. Hun wash water to sewer with agitation.
283 4
15. Adjust
i 8*24 in vat 23J to 6250# total, by running in from scale ianS
Or by 16. Mittst to 25* (16120. ). 17, Run in from scale tank
.383 18 Run 14..16*' (+ 1$0G.) water into vat 383.
..,5 19. Turn on agitator and steam. 20 Weigh and dump In 21 Adjust to 21* (257G.) at 120-130P. 22 Stir 10 minutes or longer to dissolve.
24
27 12
1200
428'
DUP050068308
amuL
gflBfa...
ST 23. When strike vat runs empty hose top, wall, 6 agitator, etiTr frm outs ide of vat sad run to sewer. 24. Bun 5-15" (& 1050 0.) water into strike vat 25. Weigh and run into strike vat from vat 348
V--____________ J*
26. ismtall chart in temperature recorder 27. Start agitator 28. Adjust to 44* <4620 0,) at 78-02?.
283 When step 22, Stirring completed, run vat
7 383 Into vat 283 In 3-5 minutes.
Seat to 138-142?*
Stir 15 minutes at 138-142%*
fast and record s Fe
, Must he - a
if Fe-M- test still * stir ah additional
15 minutes at 138-142?.
fast and records Fh
, must to -
if Fe+e test still +, add additional
Stir to complete oxidation.
test and records !!..,,_____ , must toe -
Adjust to 36" <2322 CJ at 138-142?.
Strike vat 283 into strike vat on the surface with agitation in 28-30 minutes*
Beeords Time .Started ................ Records Total Minutes
Becord* Temperature '................%
39. Stir 5 minutes.
40. Test end records pH ....... ...... normal
7*4-7.8
41. If necessary, adjust to pH 7*4-7,6 with
H-7 or H-27
Records pH
.... .....
42. Check and records
.
43. Press Mediately without agitation.
Time Start ........Time Fin*......... .... Optr Time Start '..........-JEime Fin. .:........ :0ptr Time Start .............-Time Fin.^_______ Optr
7 2t>
DUP050068309
I3 Code ___ _ ___goals Process <B)F-8-FDatet
iV^siiSS^^ntW
miim abba nsTBtrcf:ions
:!W*
)l|MWI>lIWIIIIIWirc^^
mum a b m wmm.
osmm .a s m tmmmiom
i^peo34,1,. i^ui3s.^r,iio^ii^^QJ5^v
h/tia^wi*tfag*^.we'UjN*ws^^
S&UsftfeJ10 Polios, j k 19K&8
SJ0BUI
gijg.wwiwwtfgaw n*ft?rsvr.' S>*5J
GBtBMBS *** JSQfgs
DUP050068310
1
Jtefcft 1fO&U mBWjamLmsL.mL meson
wowmiA sens This product is inteennddeedd primarily for Hewark manufacture of AF-ll-F, a flushed alkyd dispersion similar to Harmon* s lough Gold F-5850. In presscake fora the pigment rapidly under particle growth with loss of transparency and masstone dap _ Manufacture and flushing must, therefore, be scheduled as an integrated uninterrupted operation* The (B) process has been developed to provide a more economical process than that described by the (A) formula* neither of the processes has been operated at larger than 30 lb, semi-works batch size to date, neither process can be tried in the plant without some equipment changes. The equipment needed for the (B) process is detailed below. In the <A) process, translated directly from a process published (but not patented) in a Harmon patent (U.S. 2,384,579), a dilute solution of ferric chloride Is mimed with sodium acetate and struck into caustic soda. In the (B) process the sodium acetate has been emitted and the ferric chloride has been replaced with ferric sulfate prepared by oxidation of copperas as in F-4-P(C.). As reported in JOT-50-29, metallised alkyd enamels prepared from BF-8-P, at the present stage of semi-works development, are not fully equal in two-tone flash to those prepared from either the Harmon dispersion or from AF-S-P, but the quality differences are such that trial of the (8) process at plant or maximum semi-works size, and pilot flushing in the plant, have been recommended The <B) process is based on s,1,-1222 and is essentially identical therewith, except that the volume of the initial caustic solution has teen reduced 2500 gal,, fro 7120 to 4620 to enable full utilisation of the ferric sulfate vat capacity, (see section on '"Variables** MAKIBG For regular manufacture of BF-8-P it will be essential to provide a caustic resistant strike vat. Based upon discussions with Production Division Area Supervisors (letter, J.O.M. to D.B.Killlam, 7/5/50 - 'Flushed Hydrous Ferric Oxide - Fstimated Costs*'), the process has teen written and costed on the has is of anticipated replacement of Fat 182 with a steel tank of identical dimensions for exclusive neutral or alkaline service, Cains tie liquor will be delivered to the strike vat from existing scale tank 348, requiring installation of a delivery line from the scale tank to the strike tank. Existing equipment is available and adequate for the other making area operations.
DUP050068311
; p* 2 .
Preparation of the ferric sulfate solution, terminating at step |?f is identical with that of F-4-P(C) except that the copperas oxidation temperature has Seen reduced from 180F to 140%, which was satisfactory in 3.1.-1222. Complete oxidation of the copperas is essential.
Preparation of the strike vat has Seen modified by omission of the acid treatment specified for F-4-Kc). The specified cleaning treatment may or may not be adequate, depending upon the thoroughness with which it is carried out and the sensitivity of the slurry to seeding influences, not yet established. wms&im
Pressing characteristics are expected to be similar to those for Auric Brown, but it is anticipated that the BF-8-P washing cycle will be from id to 24 hours longer* Wo fundamental difference in operating technique or in maintenance characteristics can be foreseen on the basis of limited semi-works experience to date, flBUBLBS
Incomplete oxidation of the copperas, to an extent greater than 0,5#, will result in darker masstooe pigment but duller metallised flushed enamel, fhe darkness of the pulp slowly disappears on aging*
Introduction of manganous ion with the ferric sulfate has effects similar to those of ferrous ion except that the resulting dark pigment is stable. Additional study of the effects of manganous ion in quantities between 1 and 5# is suggested. *
Ho significant effect was obtained in the semi-works by omitting preliminary dilution of the caustic liquor (equivalent plant tf-7 volume +425 gal.), tripling the quantity of caustic, together with omission of caustic dilution (plant equivalent 8400 lbs. H-7, +1300 gal.) yielded a product S.W.-1252 which was very dark in aqueous presscake color and produced metallized enamel of improved ties-tone flash bat distinetljr redder hue than Bough Bold. Further study of this variable, at inter mediate caustic excess and intermediate concentration, is also suggested.
Ho other variables, were found effective in the laboratory, /where evaluation was limited to comparison of color of aqueous presscake. TESflHQ
She only authentic test available at present involves laboratory vacuum-mixer flushing into alkyd resin with subsequent preparation of metallized enamels. When the process is reduced to plant practice it will undoubtedly be possible to screen "flop batches" by inspection of the color of the aqueous pulp* it may be desirable t establish a micro-flushing test in lithographic varnish as is now used for batchwise classification of Auric Brown, but this is questionable. The present tentative manufacturing plans involve quality classification, and standardization blending, of the flushed dispersions rather than of the aqueous presscakes.
DUP050068312
i p. $ rmw
Based on Fes* analysis of a single sample of dried seal-works presseake, the theoretical goal yield Is 97.8 lbs. pliant solids per mol of copperas, equivalent to 2200 lbs. per plant batch, determined by drying to constant weight at l60C in the Brabender Sols tare fester.
the single laboratory yield recorded to date was 96# of the above. Semi-Works yields have ranged below this level, with a maximum of 83.5$ of theory* MimimmomnaOJiliS (Reference 1377-40).
The estimated production yield of 1877 lbs. is obtained by assuming a production yield equal to 95# of the current production yield of Auric Brown F-4-P corrected for omission of treating agent (2026 - 59 1976 x .95 1877)5 this is 85.4# of the theoretical yield above. PREPARED BYs J,, 0. Morrison
8/28/50
DUP050068313
Cod,
m (A)F-U-? Approved by*
Goal
Else
J.O.M, 8/28/50
FLuaana
2L
mm.
Drrn
'monmomt oma al l f l u s h na *qumw 1. Weigh into (two) clean 55 gal* drums
2. Weigh and ran in 3, Mix thoroughly
M, ii
01ei Acid
m
Baker 4. Install recorder chart in temperature controller Perkins 5 Set temperature controller at 10OC. Mixer 6. Weigh and shovel into mixer.
F-8-P
Lot____
.. net at ... ..
%
Lot fro
net at
$
Lot
from
.... __ net at ... ......... _*
Lot from.......... ..... . net at ...
Lot . . from ....... ...... net at-......
Lot....... from. * ....
net at _____ f
7. Start mixer with top raised, 8. Hun mixed resin-oleic acid solution prepared
in Step 3 into mixer during 20-25 minutes. 9. Continue mixing until water separates and
flushed pasta is firmly coagulated, . 10, Decant repeatedly until all separated water
has teen removed from mixer, 11, Weigh and shovel into mixer
Lot from
net at ... ...Jg
Lot from
net at
&
12. Start mixer. A. When water sheds, decant repeatedly until all separated water has teen, rasoved, or B. If charge in mixer Becomes crumbly and does not shed water within 15 minutes, add add mix until Breakout occurs or
C. If charge in mixer remains pasty, ate does not shed water within 15 minutes, check ( ), stop mixer, and proceed with Step 13.
DUP050068314
BSB m____ 1m*J.A-.....CQBlt (A)F-ll-F.....LBS.* 19m..........
13* Weigh and shovel into mixer
hot . ....,, .from............... net at ........
Lot.iri[_.......... from............ . net at ........ ...
14* Repeat Step 12. Circle A or B or C haloes 1. Water shed and completely decanted, or B. Crumbly after 15 min. Added 100 lbs* H-690. or C* Pasty.after 15 min.
15* Weigh and shovel Into mixer*
Lot , from
net at ,
.Lot. .,..........from.......... ...... net at ...,
16* Repeat Step 12* Circle A or B or C Belovs A* Water shed and completely decanted, or B. Crumbly after 15 min* Added 100 lbs* 1-690, or C* Pasty'after 15 min*
j17* Weigh and shovel into mixer*
Lot, ,,
. fro.... ....... net at ..........m
Lot ,
from............ . net at .......,.
18. Repeat Step 12. Circle A or 8 or C below* : A. Water shed and completely decanted, or 1. Crumbly after 15 min* Added 100 lbs* 1-690, or C. Pasty after 15 in*
19. Weigh and shovel into mixer.
Lot ,, , from...,,. ...... met at
Lot.............. from....,..... ... net at ..
20. Repeat Step 12. Circle A or B or C below* A. Water shed and completely decanted, or B. Crumbly after 15 min. Added 1O0 lbs. I-690. or C. Pasty after 15 min.
1 emm *
..fib' 50
690 F-8-P . :
690 -- f~8-f ; 50
'690 ; ' : m -'...V ' .1
690
1........ :.. ;....
DUP050068315
mm
ssUde__ m^rno, 21. Weigh and shovel into mixer
Lot from net at . &
Lot
from
net at
4
.22 Repeat Step 12. Circle A or B or 0 below?
4. Water shed and completely decanted, or B. Crumbly after 15 min. Added 100 lbl.
W-69O, or
C, Fasty after 15 aim.
Start mixer Weigh and poor la daring 5-10 minutes Close mixer top and continue mixing. Ban in very slowly through 2" line
;. Ijvf 400
Inspect charge frequently through sight-
glasses. If lumps appear, stop W-690 at
once until charge is again uniform, then
resume 1-690 addition. If necessary, the operation may be shut
II
down, at this point only, for 16 hours f
or less*
I
A. Stop mixer, still closed, and lock out 1 drive#
B. Bun in through the 2* line a 1/2* layer, of S-690 onto the surface of the charge.
C. When ready to proceed, start mixer, still closed.
,
27. Brain distillate exhaust lines behind
mixer.
28. Open condenser spray valve 1/S turn.
29. Close distillate drain valves.
30. Start vacuum.
31. Bet temperature controller at 55C*
See Hots 31.
32. Continue mixing under vacuum at 550
I
until mixer sight-glaases are free fro
fog* Capprox. 1 to 2 hours). See Step 34* f
Weigh into clean 10-15 gal. drum and hold | 73
33.
on second floor for rapid addition
I
through 2* line to mixer.
f
Mjm, F*8-F
690 695 690
oleic acid
w 400
73
.x.
DUP050068316
if.IMS
HJL
JLSM-
34. A. Impact charge la mixer frequently through sight glasses ehHe dis tilling.
1, Also, check temperature of distillate exhaust lines 'behind mixer and drain condensate when necessary*
C, When charge starts to gel add 0M0 acid weighed in Step 33 if no gelling occurs, add oleic acid as soon as sight glasses are clear*
35# As soon as sight glasses hare cleared, set temperature controller at 10C, shut off heating steam and start cold water running through mixer Jacket*
3d* fifteen minutes after sight glasses have cleared, run in B-690 to total of 3-1/2 drums (1650 lbs.) for entire run#
37. Shut off vacuum steam and condenser spray. 38* Stop and open mixer* I39. Check gelling. Add oleic acid if I necessary* Soto 39* |40* Take two 4 os. samples for duplicate | moisture and solids tests* 41, Decant entire batch from mixer. Sec Botes.
AID .STDgl*
Weigh flushed batch from mixer. See Botes.
Grind batch until gloss test is O.K, n
Standardise color*'-
See lotes.
Standardise drying and film hardness. **
46* Standardise solids*
See Botes.
47* Pack through felt filters, into shipping
drums.
liii
3
690
raUEHSPJTORoqS FERRIC OMMt seaM
this product is a flushed alkyd dispersion of hydrous ferric oxide, similar to Harmon's Bough Sold Paste P-5S5Q, Intended for use in polychromatic durable automotive finishes*
the "AH process represents a paper scale-up of a selected laboratory procedure based on 1351-71. As discussed in teport KS-50-29, this procedure has given results in the laboratory which hare not been consistently improved by any of several investigated variations, but additional study directed toward improvements in economy, and possibly to quality, is desirable in the event that the process development and standardization program to resumed. In scaling the formula up to plant batch size it has been necessary to rely solely on limited experimental plant flushing experience with a similar product A-3-F, Many of the details of the A formula are therefore far from firm - the more important of these are noted below. A pilot flusheat in the laboratory should precede the first plant trial. Attention should be given to the possibility of utilizing the lead indicated in KH-50-29 (Item 12 under "Flushing Studies*'! if time permits,
the experimental 4-3-F plant flushing experience has demonstrated the need for certain equipment modifications to the plant, prior to trial manufacture of F-ll-F. thebe also are noted below.
Chemical analysis of the Harmon product, as well as of baked films thereof, for inorganic pigment, organic resin, and organic treating agent to a definite prerequisite to any further work directed toward preparation of a specific counter-offering, Although the advertised composition of the Harmon product is 33m pigment. 17% res to solids, $0$ solvent, It apparently contains 13p of organic treating agents, and laboratory study has demonstrated that similar treatment of F-ll-F to essential to produce the desired properties. In the A formula, the treating agents have not been classified as either pigment of vehicle, and have been ignored to the calculation of estimated yield, pigment and resin input are set at the 200/100 solids ratio corresponding to the advert toed Harmon composition, treating agents are added as required, and solvent content to adjusted at the end of the process to produce the desired 59f actual non-volatile film solids content in the final product (determined by analysis of product).
DUP050068318
Af-ll-f:,foil*.Jam p* 2
OWMMS 0? PROCESS
'4
Approximately 59-60$ of tha total pigment presscake is initially flushed into a mixed vehicle solution contalaing all of the resin and a large quantity of Oleic acid. Following decantation of breakout water (which unavoidably contains some pigment, oleic acid and resin)) the balance of the pigment presscake is added in six equal stepwise portions with breakout and decantation after each addition of pigment* Attainment of the stepwise incremental breakouts frequently requires the addition of a small quantity of solvent. When all of the pigment has bbee<en incorporated, the heavy paste is treated with triethanolamine, reduced to fluid consistency by addition of solvent, and subjected to vacuum distillation until its residual water content has been reduced to &1$. .during the latter portion of the distillation step it is necessary to add a second portion of oleic acid to prevent gelling in the mixer and reactivity on storage.
the distilled fluid dispersion must then be ground to enamel fineness, standardised for color, drying, film hardness and solids content, and finally felted into shipping containers*
mumsaim
tegular manufacture of the finished product for general sale will require installation of paint grinding, blending and filtering equi`pment (letter, d,0,M'. t*o DD.B.B.3.milan 7/5/50 ^"FFlulushse*d---h--y-d- rous Ferric Oxide - Estimated Costs").
The following changes in existing plant flushing equipment are suggested for the reasons given (the first Is required)*
1. Provide steam-water mixer to supply heat to the vacuum mixer jacket and blades. Must be controllable in range from 140F to 200P (preferably 240? if convenient) and must also be able to supply unheated main-water for cooling, {present direct steam heat supply is excessive and uncontrollable by existing controller installation),
2. Change drainage system to eliminate delivery of flammable solvent to open storm sewers.
3. install monorail and hoist with overhead scale to permit direct discharge of pigment presscake and' viscous resin solutions from shipping drums into mixer., Addition of resin through- existing line from second floor is very time consuming and also jeopardises quality through possibility of skinning, while the existing pressoaks loading chute from the second floor Is virtually useless. (Betain line from second floor for solvent). The monorail and hoist should also be adequate to support an entire batch of flushed product
DUP050068319
< p. 3 ) (2000 lbs. ) in a 250-300 gallon mixer-discharge hopper. provision of which would be required for the contemplated dispersion process (previous section).
4. Modify connections at top end of 2** line from second floor to permit simultaneous connection to too solvent druse and to a 10 gallon funnel for addition of treating agents while ;.mx#y is under vacuum.
5* install grating platforms around mixer to facilitate safe operation*
6. Provide suitable means for discharging condensate' from bottom of distillate lines behind mixer without breaking vacuum. 'this condensate must not be allowed to drain into mixer because of danger of contamination with rust and sludge*
7* Provide Fahrenheit scale and charts for mixer temperature controller recorder to conform with all other process instruments on the plant.
1-413
Batch Size - To insure against the possibility that the process aay hSve besa scaled up too optimistically it is suggested that the initial batch be started at 80$ of formula size. Decision as to increasing batch to full formula size can be readily made.on basis of observation of initial transfer (steps 8, 9 and 10)* It is also suggested that the initial pigment be cut further, in the first batch, to 72$ of the weight of 1-693* this will give a P/S solids ratio of 100/100 for initial breakout, rather than 433/367 ( 118/100) as formulated, minimizing possibility of difficulty in obtaining breakout. Specifically, the suggested procedure for the first batch is as follows*
Step 1. Oleic Acid 118 lbs.
Step 2* H-693
408 lbs. (as is)
Step 6* F-8-P
294 lbs* (solids)
If breakout is satisfactory, decant, then add 53 lbs* F-8-P, to 347 lbs. total, the second breakout should oe obtained without difficulty. If it is then decided to increase batch to fall size, decant, and add 86 lbs. F-8-P to 433 lbs. total, and prepare and add a mixed solution containing 29 lbs. Oleic Acid and 102 lbs. H-693* theft follow standard formula starting with Step 9.
Battlement - 411 equipment must be completely clean to protect the trensperency and non-bleeding properties of the product*
DUP050068320
4fcUrr.-teattAa-Ja.ts.a^ p. 4 cud the mftdiitaneoIutslyshhouultdsheopaproastesilby,leatvooidodindgththeeOplereicpaArcaitdion of the specified mixed solution. This, however, must first be established by trial in the laboratory, the two ingredients must not he added in sequence - this seriously complicated the transfer process in the laboratory.
S.tfiflS.. 11+,13* it may be possible to materially increase the quantity of pigment added in the first increment, simplifying the process by reducing the number of operations required to attain final pigmentation.
Steps,., 12 t ,ZZ* these stepwise breakouts usually proceed as follows. Addition of pigment presscake followed by 5 to 10 minutes mixing converts the initial smooth pasty water-in-oil emulsion to a coarse granular, or "crumbly* oil-in-water emulsion, the latter slowly coagulates and finally reverts to asmooth pasty water-in-oil emulsion, simultaneously expelling breakout water; the coagulation and breakout are accelerated by addition of small quantities of solvent to the crumbly charge. Generally, no solvent is needed for the first few incremental steps; occasionally two or even three portions of solvent are required for the later incremental steps. Excessive solvent must be avoided since it would reduce the plasticity of the batch to a point where subsequent presscake additions are no longer adequately dispersed.
Step. 24. As discussed in SH-50-29 ("Flushing Studies" item 8), It may be desirable to add a portion of this triethanolamine to the Initial pigment charge in the mixer but further study is necessary to establish this point firmly. Also, it may be possible to reduce the quantity of triethanolamine, based on further study.
Stan 26. Rate of addition of solvent for predistillation reduction of viscosity should be controlled to prevent formation of plastic lumps in the batch, the quantity of solvent added at this point is to be more firmly established on the basis of future plant experience. It is suggested that in early batches the consistency be reduced liberally, possibly with from 2 to 3 times the quantity of solvent specified, to a rather sloppy consistency.
Step 'U. in the laboratory excellent control of distillation at satisfactory rate, is obtained by supplying water to the mixer jacket at a temperature of 180F to 190F. ; the batch temperature remains at >122bF. until all of the water has been evaporated. Past experience in the plant with distillation of A-3-F has shown that the existing temperature Indicator registers essentially the temperature of the inner wall of the mixer which is in turn more nearly a function of the temperature of the jacket than of the batch. For this reason, a temperature of 131F (55C) has been suggested for the controller setting. Past experience has also shown, however, that the high pressure steam supply to the plant mixer produces serious over-heating of the jacket and blades, and that efforts of the instrument to control this heat are ineffective. It is virtually imperative that facilities be provided for duplicating the laboratory heating con ditions. using manual control of inlet water temperature until optimum plant conditions are established. The present Instrument
DUP050068321
may possibly be useful as a recorder daring this period, although the significance of its readings in terns of actual batch temperature remains to he determined,
atep-32. Under laboratory heating conditions described . above * distillation time has var ied from 1 to 2 hours depeniiiig upon degree of vacuum obtainable (vacuum gauge variation +23-268).
aisp_31 dee recommendation 4, preceding section* for a<iuipaentV iee following note for quantity*
Step 14. (a) It is essential that the batch be observed carefully and frequently during distillation. Interior solvent** spray winder washers have been provided for this purpose - a high power spot or flood light Is also necessary, it may be desirable to add solvent continuously at a uniform rate throughout the dis tillation. Ho definite indication was obtained in the laboratory concerning the relative quality effects of maintaining the batch in a highly fluid condition and of concentrating it down to e semi-plastic mass prior to final reduction. delation of the batch will occur late in the distillation process unless treating agent concentrations are maintained at a sufficiently high level, the necessary quantities of agents must be established on the basis of plant experience. If gelation occurs in the mixer it cea be readily corrected by titration of the gelled batch In the mixer with either oleic acid or triethanolamine, The former is recommended on the basis of present Information.
(b) Considerable distillate condenses in the 40 ft. unhealed 6* distillate exhaust line, collects at the U bends behind the mixer, and eventually forms a liquid trap which seriously retards further distillation. Closure of a line with collected condensate is evidenced by drop in temperature of the line - this can be detected by feeling with the hand* Is the interest of uniform quality and efficient operation the II bends should be kept open, leans should be provided for draining liquid condensate from the lines without breaking vacuum in the mixer. The condensate is contaminated with sludge from the exhaust line it mast not be permitted to return to the charge in the mixer.
stn
The total formulated batch quantity of solvent
(1650 lbs.) S Subject to revision based on plant experience. The
quantity used in step 36 should be lust adequate to adjust the film
solids content of the batch to 50$, This must be determined by test
in early batches before discharging the mixer.
,
step 39. The batch must be carefully checked for false body or gelling. If these properties or tendencies exist they should be titrated out with Oleic Acid in 5 lbs. increments $ no more than 20-25 lbs. should be needed, based on laboratory experience.
DUP050068322
/iS-Urg.,.Ep.raa3va-^otas < p.^ 6 ;
*
Slbep% 4041. Following establishment of satisfactory control of heat and vaeuSTfotes 31 and 33b) it #111 undoubtedly he possible to establish time cycles and solvent quantities (Step 36) with sufficient accuracy to permit discharging the batch from the miser without waiting for moisture and solids tests# Pending such process standardisation, however, each batch should be left In the mixer until it has been established that no further distillation is needed.
All products flushed in the laboratory have required sub sequent dispersion grinding to develop satisfactory gloss and fineness. Ball milling has been satisfactory - no other method has been experimentally evaluated to date, (the products are completely uasuited to roller milling).
The final steps included in the (A) process are intended only as a listing of properties which must be standardised, the following speculative process is suggested. Installation of the following items of equipment would be required. A 250 gallon vessel on hoist and monorail would receive the flushed product discharged from the existing vacuum mixer and would also serve as a gravity feed hopper to a 15 gallon continuous dispersion unit to be in stalled at the north wall of the first floor of the flushing area, the dispersion unit would discharge product of G.X. fineness and gloss into an agitated 500 gallon stainless dual function surge and standardisation tank. If the batch is 0.1. in color and transparency, and if it is standardlzsble to 0.X, film hardness -and solids by addition of oleic acid and solvent, it would bo self standardized and run through a felt filter into shipping drums. If, however, the batch is not self-standardizable it would be packed from the surge tank into sub-standard stock drums, without felting. Standardization blends of the sub-standard stock should be formulated to standard color, avoiding low hardness and low solids, adjusted if necessary to standard hardness or solids in the 500 gallon.tank, then felted into the shipping drums. MUU.
Except for the powerful effects of oleic sold and triethanol amine on rheological and film characteristics (Kl-50-29 * ''flushing Process Studies1, items 2-13) no flushing variable has produced sig- ^ aifleant effects on quality in the laboratory. It is unquestionably desirable to resume laboratory study in the event that plant standardIzation Is undertaken. Such study should await determination of quality obtained in a pilot run in the plant flushing unit, however. VflwTwRiwHtnw
The estimated production yield of 1980 lbs., as Is, at 50% film solids content, assumes 90$ performance based on a hypothetical goal yield of 2200 lbs. The latter is arrived at by assuming that 39$ of the total solvent used (Including that In the alkyd solution)
DUP050068323
gr.l3,.rF^gM3,a.JaJ.gs f p. 7 ' Is evaporated (the condensate being used for cleaning purposes and that the solids decanted in the breakout eater are compensated by the as yet undetermined non-volatile content of treating agent in Weed films. In other words, both the decantation losses and the treating agent in dry films are ignored* She reasons for the obvious uncertainty as to composition have been given on page 1 of these notes. It is believed that the allowances which have been provided for this uncertainty are conservative. PREPARED Sfi J. 0. MORRISOJf
1/29/50
DUP050068324
