Document 9989KRJ12E2DNk1ojg5V8Qmw5

Indexed Report No.: R-62-42 c. . Theobald, Wilm. F&F) In J. A. Klacsmarm 9 19 12 ) Turn . D. Lawson, )99 99 P. B. Cochran, n 21 ) In Turn D. McBumey, )99 29 J. W. Nestor, R. B. Davis, . F. Kalb, )99 19 99 99 ) In Turn )92 19 Ufa 27 5 2 J. C. Richards, Newburgh 0. H. Bullitt, Jr., Exp. Sta. L. G. Wise, Exp. Station G. I. Mulholland, Flint G. Vaala, Wiltn. F&F R. W. Laurrell, Wilm. File: 1865 JiOTTO 1 i inm s MARSHALL LABORAi* LIBRARY COPY TAKI"^ FROM 1.1 BIRAIRY E. I, du Pont de Nemours & Company, Inc, F. & F., Research Division Marshall Laboratory Research Report V54-MAINTENANCE PRIMERS PROGRESS REPORT Date Issued Period Covered Project No. Previous Reports Notebook Nos. : : : : 5/29/62 12/61-5/62 P-2700-E 62-12 7534 TABLE OF CONTENTS Page Noo INTRODUCTION--------------------------- ------------- ----------------- --------------------- 1 OBJECTIVES------------------------------- -------------------------------------------- 1 SUMMARY AND CONCLUSIONS...... ............. ------------------- --------------------------- 2 ACTION TAKEN OR PROPOSED-------------------------------------------------------------- 2 PATENT SITUATION----------------------- ----------- ------------------------------------------ 3 PUBLICATION STATUS----------------------------------------------------------------------- -- 3 ACKNOWLEDGEMENTS-------------------------------- ---------------------------------------------- 3 DISCUSSION............................. ------- ------------- --------------- --------------------------- 4 Adhesion to Oily Mill Scale---------------- 4 Fast Dry and Wrinkle Resistance------------------ 5 Modification of V54 Primers with THF-MA and RC-384-- Effect of Drier Concentration on the New Vehicle---- Rheological Studies---------- ----- -------- ---- 6 7 8 Drying Characteristics of the New Primer------------ 10 Volatility of THF-MA------------------- 10 Package Stability--12 Corrosion Resistance-------------------- 12 Hardness and Topcoat Adhesion---------------- 14 Thin Film Inhibition---------------- 15 EXPERIMENTAL DETAILS-----------------------------*------------------ ----------- ------- 16 BIBLIOGRAPHY----- ----------- ------------------------------------------------------ ---- 17 APPENDIX------------ ------------------------------------------------------------- ------------- Table I V54 Field Test Inspection Results Table II V54 Field Results (Corrosion Resistance) DUP030009571 ABSTRACTi This report describes the work done to correct the de ficiencies In the V54 primers which were uncovered during the field test program. This report also contains a. list of the V54 field test installations which were inspected by Sales and Research Personnel in April, 1962, DUP030009572 V54-0P V54-I V54-Q V54-Lo RC-384 THF-MA THF-IB TMG SYMBOLS AND ABBREVIATIONS o-phthalate ester of 2-vinyl-1,3-dioxolane-4-n-butanol Itaconate ester of 2-vinyl-1,3-dioxalane-4~n-butanol Oleate ester of 2-vinyl-1,3-dioxolane-4-n-butano1 Linoleate ester of 2-vinyl-l,3-dioxolane-4-n-butanol A dehydrated castor oil alkyd TetrahydrofurfuryImetha.c rylate Tetrahydrofurfurylis obutyrate Tetramethylguaniditie DUP030009573 V54 MAINTENANCE PRIMERS INTRODUCTION; The oldest V54 field tests are now over three and onehalf years old. Judging the results to date specifically for corrosion resistance, and restricting ourselves to the area of adequately controlled tests, the primers are performing satis factorily, We have no absolute basis on which to judge the un controlled tests where failures were observed. The field inspections have uncovered some deficiencies which must be corrected before the V54 primers can be commercialized. The principal deficiencies were: (1) Poor topcoat adhes ion, particularly "Dulux"* Hi-Build Tank White 28-5049; Phenolic Aluminum 354-751; and some vinyls; (2) Poor adhesion of the primers on shop-primed structural steel; this is believed to be due to the presence of oily (hydrocarbon) contamination; (3) The primer was judged to be too hard, based on experience with 'Dulux" primers, although no direct evidence of failure was found which could be traced to hardness as such; (4) Finally the drying time character istics of the V54 primers were judged to be too slow for wide spread commercial acceptance in the maintenance paint market. This report describes the work carried out to correct the deficiencies without sacrificing any of our corrosion resis tance or good application properties. OBJECTIVES: The objectives of this work were to correct the deficien cies of the V54 primers so that the primers would have a commerci ally acceptable balance of properties. Specifically the following objectives were set as product goals. 1. Reformulate the V54 primers to obtain adhesion (initial and retained) of "Dulux'' 28-5049, Phenolic Aluminum 354-751, at levels which are at least equivalent to 67-Line controls. 2. Improve the adhesion of V54 primers to unweathered, oily, scale-bearing metal to a level equal to 67-Line primers, 3. Improve the hardness/flexibility balance of the V54 pri mers so that they are comparable to 67-tine controls. ^-Registered Du Pont Trademark DUP030009574 2 4. Improve the drying time /wrinkle balance of the V54 primers to obtain minimum wrinkle resistant film thicknesses of 7.0 dry mils and maximum drying times of 16 hours at 40F . The minimum wrinkle resistant film thickness must be applicable up to 130F and under all conditions of relative humidity. SUMMARY AND CONCLUSIONS: We have modified the V54 maintenance primer vehicle (V54OP/V54-I, 1:1) by replacing part of the V54-OP with a blend of de hydrated castor oil alkyd (RC-384) and V54 oleate to obtain improved oily metal adhesion and improved adhesion of !5Duluxn 28-5049 topcoats to the primer. The new vehicle also contains a. substantial amount of tet- rahydrofurfuryl methacrylate for an improved dry/wrinkle balance and a new combination of driers based on cobalt, zirconium and tetra- methyl guanidine* The new vehicle contains V54-0P/V54-I/V54-0/RC- 384/THF-MA in the following ratio: (24/32/8/20/16). The new primers are equal to the old primers in wetting and application properties but have much superior drying rates, im proved adhesion to oily mill scale and improved adhesion of }'Duluxn (28-5049) topcoats. Initial laboratory screening indicates that we have not hurt the corrosion resistance of the primers at operating film thick nesses, 4-5 mils, but below that our salt spray resistance is poorer than that of the old formula. We are starting small scale field tests, in Company plants, to confirm the application properties and drying characteristics that we obtained in the laboratory, because we do not have good correlation between laboratory tests (e.g., sun wrinkling) and field performance. ACTION TAKEN OR PROPOSED : Work is continuing to characterize the new vehicle in terms of optimum pigmentation (corrosion-inhibitive), mechanical properties (initial and aged), adhesion under topcoats and over contaminated substrates, storage characteristics and corrosion resistance. DUP030009575 --3 PATENT SITUATION: The paint compositions discussed in this report are covered generally by U.S. Patent 3,010,924 (to Du Pont), The V54-I/V54-0P are covered by U.S, Patent 3,010,923 (to Du Pont). V54-01eate is the subject of patent application FFD-1732. THF-MA is disclosed ganerically in U.S. Patent 3,010,924 (to Du Pont) as: "the presence of polymerizable monomers in V54 esters which are used as metal pro tective paints". Zirco driers are the subject of patent application FFD-1744. Tetramethyl guanidine is the subject of patent application FFD-1730 and cobalt butyl phthalate is covered by U.S. Patent 3,010, 945 (to Du Pont), PUBLICATION STATUS: The subject matter of this report is not suitable for pub lication at this time. ACKNOWLEDGEMENTS: The writer wishes to acknowledge the helpful discussions with L. A. Henderson and J, G. McNally, R. VS, LaBerge suggested the use of RC-384 for promoting oily metal adhesion. DUP030009576 -4 - DISCUSSION: The field test results (Table I, Appendix) have shown that the V54 primers (7067-5001 and 7067-5002), which are based on a 1:1 blend of V54-0P/V54-I, have an acceptable level of corrosion resis tance (Table II, Appendix) under controlled field conditions, but they are deficient in other properties. The three properties which have to be corrected before the V54 primers can be commercialized are: (1) more foolproof topcoat adhesion; (2) greatly improved ad hesion of the primers over contaminated mill-scale, such as found under shop-priming conditions, and (3) improved drying character istics under field conditions, The drying problem has been studied by McNally (1). He found that a combination of cobalt, Zirco, TMG and THF-MA would, when added to V54-0P/V54-I primer formulations, provide a balance of wrinkle resistance and dry that was better than anything then available. The writer, following the suggestion of R. W* LaBerge, found that incorporating RC-384 into V54 primers (7067-5001) would bring about an improvement in oily metal adhesion. The problem was to combine the drying system of McNally with the adhesion promoting system based on RC-384 and to determine whether the beneficial properties of both systems would remain intact or be mutually harmful. Also it was necessary to determine what effects these compositional changes would have on topcoat adhesion, corrosion resistance, recoat time, application properties, mechanical properties, package stability and wetting characteristics. Adhesion to Oily Mill-Scale (NJB. 7534-72, 73) Three field tests involving V54 shop primed steel have shown early failure. Two of these were known to have oil contamina tion on the metal at the time of painting. A fourth test which was over oil-free, blue scale is not failing. These results, coupled with the known incompatibility of V54-OP/V54-I with aliphatic hydro carbons led us to check the performance of V54 primers and controls over clean and contaminated (cutting oils or lubricating oils) un weathered, smooth, blue, mill-scale. The scale was degreased with xylene and coated lightly with a "cutting5" oil. The V54 primer had no adhesion to scale which had been oiled but had equal adhesion to 67-Line controls over oil free scale. The V54 (7067-5001) could be stripped cleanly from the oiled areas by using an adhesive tapetest, but it could not be stripped by this method over oil-free scale. DUP030009577 -5- We found that by replacing 5-25% (volume) of the V54-0P in the primer vehicle with V54 oleate, V54-linoleate or V54-eleostearate we could make the primers compatible with aliphatic hydro carbons. However, the use of these levels of mono esters did not give us a level of oily metal adhesion that was equal to the con trols * We also found that by replacing 5-25% volume of the V54-0P with a dehydrated castor oil alkyd we could obtain a level of adhes ion equal to 'Dulux8' 67-Line primers over oily mill scale bearing metal. These results over oily, scale bearing metal were confirmed both initially and after oven aging the cured primed panels for one month at 150F. Fast Dry-Wrinkle Resistance (N.B, 7534-91) McNally established that we had to use at least 15% THF- M& to replace V54-OP in the primers to obtain fast dry and wrinkle resistance. To check the effect of THF-MA. on primer formulations we prepared paints based on THF-M& and THF-IB and various combinations of cobalt, Zirco and TNG. The THF-IB was used to evaluate the effect of a model compound which had similar solvent properties, boiling point and peroxidizability, but which lacked the polymerizable double bond of THF-Mk, on drying time and wrinkle resistance. The results ore tabulated as follows: DUP030009578 -6TABLE I THE EFFECT OF THF-MA ON DRYING TIME AMP WRINKLE RESISTANCE Vehicle Comoonents'L V54-OP/V54-1/THF-MA/THF-IB 50 50 0 0 50 50 0 50 50 0 0 0 42 42 16 0 42 42 16 0 42 42 16 0 42 42 16 0 42 42 0 16 42 42 0 16 42 42 0 16 42 42 0 16 Driers'3 Co^/Zirco/TMG 0.075/0/0 0.150/0/0.50 0.150/0.20/0.50 0.100/0.20/0.50 0.100/0/0.50 0.100/0.20/0 0.150/0.20/0.50 0.100/0.20/0.50 0.100/0/0.50 0.100/0.20/0 0.150/0.20/0.50 Dryinj Maximum Time2 Wrinkle (Zapon #2) Free Fill (Hours) Thicknes; (Mils) 8-12 10,0 6 5.0 7 5.0 3 7.0 4 7.0 5 7.0 3 5.0 7 7.0 8 7.0 8 7.0 7 7.0 CD All paints at 30% PVC <Pb30^j Iron Oxide, 1:5) (2) Drying time data taken at 77F and 50% R.H. (3) Percent based on vehicle solids. These data show that a model compound which has similar peroxidizing characteristics, solvent power and volatility to THFMA will improve the wrinkle resistance of the primer, but that it will not speed up the dry rate. Also these results indicate that there is an interaction between cobalt, Zirco and TMS which cannot be obtained without the combination of all three. Modification of V54 Primers with THF-MA and RC-384 <7534-98) Primers were prepared from a 7067-5001 mill base using THF-MA, RC-384 and cobalt, Zirco and TMG drier systems. From these studies we established that it was possible to obtain the oily metal adhesive characteristics of the RC-384 and the rapid cure and wrinkle-resistance of the THF-MA modified systems in the same formula. DUP030009579 7 The data from these studies are given below: TABLE II OILY METAL ADHESION OF MODIFIED V54 PRIMERS Oily Metal^ Dry^ Vehicle Components Adhesion Time V54-0P/V54-I/V54-0/RC-384/THF-MA/V54-L0 (Hrs.) Wrinkle Resistance (Mils) 50 50 0 0 42 42 0 0 42 42 0 0 25 50 25 0 25 50 0 25 25 50 0 0 25 50 5 20 25 35 0 24 25 35 24 0 25 35 0 0 24 32 8 20 00 16 0 0 16 00 00 0 25 00 16 0 16 0 16 24 16 0 Very poor** Very poor Fair Fair Good Fair Good Good Fair Fair Good 8 3 8 8 8 8 8 5 5 5 5 74 7 7 7 4 7 4 7 7 7 7 1. Panels contained 0.5 mil of T'Rigid" cutting oil. 2. Ratings based on adhesive tape test of scored area. 3. Dry time at 77F and 50% R.H, 4. All paints at 30% P.V.C. From Table II it can be seen that the blends of V54-OP/V54-I V54-0/RC-384/THF-MA give the best balance of dry, wrinkle resistance and oily metal adhesion. Effect of Drier Concentrations on the New Vehicle (N.B. 7534) The effect of several levels of cobalt on the drying time/ wrinkle balance of the new vehicle pigmented with 25 volume per cent iron oxide and 5 volume per cent red lead is given in Table III: DUP030009580 -8TABLE III DRYING TIME VS. CATALYST CONCENTRATION Drier Composition Percentages1 Co Zirco TMG Drying Time 9 1 (77F & 50% R.H.) (Hours) Maximum Wrinkle Free Film Thick. (Mils) 0.150 0.125 0.100 0.081 0.063 0.044 0.150 0.150 0.150 0.150 0.100 0.100 0.100 0.100 0.20 0.20 0.20 0.20 0,20 0.20 0.30 0.10 0.20 0.20 0.10 0.30 0.20 0.20 0,50 0.50 0.50 0.50 0.50 0.50 0,50 0.50 0.75 0.25 0.50 0.50 0.25 0,75 4.5 5.0 5.0 6.0 6.5 8.0 5.0 6.0 5.0 6.0 6.0 6.0 6.0 4.5 4-5 5-6 9-10 8-9 8-9 8-9 3-4 3-4 3-4 4-5 5-6 6-7 9-10 5-6 1. Percentage based on vehicle solids, 2. Paints are at thirty percent pigment volume, 3. Vehicle composition - V54-0P/V54-I/V54-0/RC-384/THF-MA, 24/32/8/20/16. From these data the level of 0.1% Cobalt, 0.2% Zirco and 0.5% TMG were selected as being best for drying time and wrinkle resistance. Rheological Studies (N.B, 7534-120, 121, 129) Because of the gross change in the polarity of the new vehicle the old flocculating agent (VM-5617, a polyethylene dis persion) was no longer useful. We did not have an adequate sag/ flow balance. We found that by using soya lecithin in the new vehicle we could control our flocculation index from 1.07 to above 37. The effect of soya lecithin on flocculation index, gloss and sag-resis tance is given below in Table IV. DUP030009581 Printer 1 2 3 4 5 6 7 8 9 10 11 -9. TABLE IV EFFECT OF FLOCCULATION ON SAG RESISTANCE Percent Soya Lecithin Gloss (20) Sag Test Flocculation (Shell Sag Blade) Index(Wet Mils) 0 0.23 0.46 0.69 0.92 1.15 1.38 1.51 1.75 1.97 2,30 60 65 55 5-7 (Flat) 5-7 (Flat) 5-7 (Flat) 5-7 (Flat) 5 (Flat) 5-7 (Flat) 5-7 (Flat) 5-7 (Flat) 1.06 1.15 1.23 10.81 29.4 32.9 37.1 37.4 37.5 37.0 32.7 Sag Sag Sag Sag Sag Sag Sag Sag Sag Sag Sag 4 4 4 5 5 5 5 5 5 5 5 From the data in Table IV it is seen that the control of sag/flow balance is not simply a matter of the degree of flocculafcioru L. A. Henderson observed that aluminum stearate (G-217) was effective in promoting a good balance of sag/flow characteris tics in the topcoat formulations. We repeated his work in the pri mer formulations with the same success as he had in the topcoat program. We found that two percent aluminum stearate gave good sag resistance up to ten dry mils and gave sufficient "drag" to insure thick film application with no sacrifice in penetration characteristics. The data for some of the other rheological conTM trol agents that were tried are given in Table V. TABLE V RHEOLOGICAL CONTROL AGENTS USED IN V54 PRIMERS Component ________ _____ Brushir. Sag Resistance Penetration Ease VM-5617 (polyethylene dispersion) (G-12) Soya Lecithin W-98 (Talc) W-1003 (Bentone) (G-217) Aluminum Stearate VM-5617 in 7067-5001 (Control) 5 5 10 10 10 10 10 Good 10 Good 0 Poor 0 Poor 10 Good 10 Good Sag and Penetration ratings are based on control being rated 10. DUP030009582 - 10 - Prying Characteristics of the Hew Primer (N.B. 7534-104,106) Tabulated in Table VI are the drying times and minimum wrinkle free film thicknesses of the new primer vehicle as a. func tion of temperature and humidity* TABUB VI PRYING TIME VS . RELATIVE HUMIDITY Temperature Maximum Wrinkle Free HumidityFilm Thickness Dry Time (Zapon #2) 120F 100 F 95 F 77F 77F 50F 40 F 40 F 50% 90% 50% 50% 20% 50% 50% 25% 7.0 Mils 12.0 9,0 9.0 9.0 12.0 12.0 12.0 ft n if H n tt tt 1.0 hrs. 4.0 hrs. 2,75 ii 5.0 ii 2.5 ti 16 ti 31 ii 20 ii Volatility of THF-MA (N.B. 7534-146,150) Because of the volatility of THF-M4 we felt that it was necessary to check weight losses which occurred on clear films dur ing curing under various conditions of temperature and humidity. In this study we used tetrahydrofurfuryl isobutyrate as a model compound which would not be expected to cure into the film and which should provide us with a built-in indicator as to the amount of tetrahydrofurfuryl methacrylate that was being retained in the film. The data are tabulated in Table VI. DUP030009583 - 11 - TABLE VII LOSS OF WEIGHT STUDIES Vehicle Components Curing Condi- tions Film (Air Thickness Dried Mils 1 Week) Solids V54-0P/V54-I/V54-0/RC-384/THF-MA*1/Xylene2 10.0 4.0 10.0 4.0 10.0 4.0 V54-0P/V54-I/V54-0/RC-384/THF-IB/Xylene 10.0 4.0 10.0 4.0 10.0 4,0 77F+50%R.H. (,84.8% 77F+50%R.H. (' 40*F+25%R.H. ( ,5% 40F+25%R.H. (' 150C X 1 Hr.C 150*0 x 1 Hr.( 77F+50%R.H. ( 77F+50%R.H. (77.5% 40F+25%EUH. 40oF-f-25%R.H. ( ( 70.1% 150C 150C X X 1 1 Hhrr..(( 69.2% (1) Theoretical solids if all xylene is lost 81,..66%% (2) Theoretical solids if all xylene and THF-MA. or xylene and THF-IB are lost - 68.2%. From the data, in Table VII it can be seen that the rapid curing rates obtained with THF-MA are not obtained due to volatility; because if this were the case the primers containing THF-IB would cure just as rapidly. Also the films containing THF-IB lose the theoretical amount of weight due to combined solvent and THF-IB volatility when cured at 150C for 1 hour (solids found: 69,2%; theory 68.2%). However, under the identical conditions the films containing THF-MA lose only 50% of the THF-MA that is in the film initially (solids found: 74.9; theory 81.6). These data suggest that under the severe curing conditions of temperature, 150C, 50 percent of the THF-MA remains in the film but all of the saturated analog is distilled out. DUP030009584 - 12 - The second abuse condition is that of long open times at 40F and 25% R.H. The long drying time under these conditions will provide ample opportunity for the THF derivatives to evaporate if that is characteristic of them. Again from Table VI we can see that under these conditions the THF-IB is in fact being lost but the THF-MA is not. It must be pointed out that these weight loss studies do not positively identify the volatile component. It is possible that we are co-distilling a mixture of THF-MA/xylene out of the film and that the amount of THF-MA that is indicated to be left in the film by these studies is illusory, except in the case at 150C, However, based on the relative boiling points and volatilities of xylene and THF-MA. the assumptions made regarding the composition of the residual material appears to be not unrealistic* We will confirm the composi tion of the volatiles by gas chromatography in further studies. Package Stability (7534-161) We now have two months shelf and oven stability (120F) on the new primers with no change in drying characteristics or viscosity increase* We are stabilizing the system with 100 ppm of hydroquinone, based on THF-MA, and we obtain anti-skinning properties from 0.05% methyl ethyl ketoxine (Exkin #2). The new primers skin badly in partially filled containers but not in filled cans. The skinning tendencies of the new primer are more like semi-alkyd (67-739) and short oil phenolics (373-759) than they are like straight linseed oil primers* Corrosion Resistance (7534 - 139,140,141) Although there is no reliable test, short of field expo sure, which will predict the corrosion resistance of coatings, we felt that by comparing the performance of the new formulations against 7067-5001 and "Duluxn* primers in salt spray, humidity cabinet and fresh water immersion we might be able to make rational judgements about the effects of compositional changes on corrosion resistance. We studied the salt spray resistance, humidity cabinet and fresh water immersion resistance of the new vehicle as a function of substrate, inhibitive pigment concentration, film thickness and vehicle components. DUP030009585 - 13 The salt spray results over oily mill-scale indicate that the new vehicle has better wet adhesion to scale after 1000 hours than the old formula (7067-5001). Tfie new formula appears to be equal to 67-739, and superior to 67-746 over these substrates. Primers formulated from the new vehicle appear to have about 1 mil less corrosion resistance than the old V54 formulation at equivalent pigmentation and after 1000 hours exposure to 5% salt spray. This deficiency disappears at 5 mils film thickness. At 5 mils film thickness both the new formula and old formulations show superior wet adhesion to substrates using ,!Duluxn 67-739 and 67-746 as controls. The "Oulux" 67-746 films are very poor in salt spray, humi dity cabinet and immersion tests. They have practically no wet ad hesion but the corrosion resistance is very high. This is probably due to the soluble chromates which are bleached out of the film. The greenish-yellow color of the chromate solutions are clearly visible after the films are removed. The effect of various levels of red-lead in the new vehicle was evaluated by salt spray testing. The corrosion resistance of the films (2-3 mils) was optimum for ten volume percent red lead (1-7-349) and 20 volume percent iron oxide (Gif-870). The worse system was thirty volume percent iron oxide (W-870). Because of these results we will field test the primer at the ten percent level of red lead. However, we are also checking these levels by panel exposure (Series #18972). The immersion resistance (1000 hrs.) and humidity cabinet resistance (blistering) of the new vehicle is directly proportional to film thickness. This is in contrast to the old formula (70675001), whose blister resistance is inversely proportional to film thickness. The new formula appears to be equivalent to 67-739 and superior to 67-746 over these substrates. We have two large panel exposure tests out in Belle, W. Va. and Niagara Falls plants to check the corrosion resistance of the new formula as a function of film thickness, inhibitive pigment level, substrate (sand-blasted and rusted) and topcoated and untopcoated. We have Florida exposures out to cover all the initially important compositional variables over sandblasted steel. DUPQ30009586 - 14 Hardness and Topcoat Adhesion (7534-141) We have one month Florida exposure panels and 1000 hours accelerated weathering panels on the new formula for comparative hardness measurements. We observed that the new formula was initi ally softer than the old vehicle; however the AWC-2 results showed that after 330 hours the new formula became just as bard as the old formula. The one month Florida panels do not confirm this and what we may be observing so far is just a rate phenomena. It is interest ing to note how hard ,sDuluxn 67-739 gets and particularly how slowly 67-746 gets hard. Standard printers containing red lead pigmentation get much harder than those which contain zinc chromate as the inhibitive pigmentation. The Tukon Hardness data are given in Table VIII, Primer Vehicle TABLE VIII Pigment Exposure Conditions; Tukon Hardness (Knoop Units 7067-5001 V54-0P/V54-I (1:1) Pb304:Fe25 Initial(1 wk.air dry) 1 month 456S Fla. AWC-2 330 hrs. 7067-5010 V54-0P/V54-I/ V54-0/RC-384/ THF-MA i? Initial 1 month 45S Fla. 330 hrs. AWC-2 5.0 <5.0 mil 14,0 18.0 tt II If 3.0 (5.0 mil 8.0 ii 18.0 if If 67-739 LO Alkyd/ Linseed Oil (1:2) Pb304:Talc Initial 1 month 45S Fla. 330 hts, AWC-2 1.0 14.0 16.1 (21.1 0 m11 il tl (1 67-746 LO Alkyd/ Linseed Oil (1:1) Fe?0q: Initial 2nCr04:Talc 1 month 45 S Fla. 330 hrs. AWC-2 1.0 (2.5 mil 2.4 4.5 if 11 it 11 We expected that the use of V54-oleate and RC-384 in the . new vehicle would make the 'Thilux'8 topcoats 28-5049 adhere better to the new primer because the softness of the new primer would en able the topcoat solvents to bight in better* This was confirmed initially and after 2 months Florida exposure in Series #190021, Other series which are in exposure covering the new vehicle are: #19023, 18972, 19028, 19036, 19027 and 19089. These studies will be reported on as results develop. DUP030009587 - 15 Thin Film Inhibition (7534 - 181) The new vehicle appears to be more susceptible to thin film inhibition than the old formula (7067-5001). Under labora tory conditions under which a 5.0 mil film of the primer formulated from the new vehicle dries in four hours, a film of the same material less than 0.4 mils thick took 16-18 hours to cure. This problem has not manifested itself on primed edges (thin films) in laboratory studies. We first observed it when we obtained tbin films during sag tests. We will look for this deficiency in our field test pro gram. EXPERIMENTAL DETAILS: The experimental details of paint preparations, panel pre paration and drying time measurements are standard procedures outlined in other reports or standard Marshall Laboratory Test Methods. Drying times are reproducible to one half hour with the Zapon Method. The data tabulated throughout this report have been gathered from studies made with at least two different hatches of plant mater ials. Other materials used in this work were standard raw materials wherever possible. Weight Loss Studies (N.B. 7534, 146, 150) The weight loss studies which were carried out in this work were accomplished as follows: Pieces of aluminum foil 4" x 6" x 0.002" were pre-cut and weighed to the nearest milligram on an automatic balance in the con stant temperature room. Immediately after weighing drawdowns of the catalyzed clear vehicle were made using a one inch wide Bird Applica tor of 20 and 5.6 mil clearance. The strips were carefully and imme diately re-weighed on the automatic balance. The strip was then placed on a flat surface and allowed to dry in the desired atmos phere. The weight of the aluminum strips ranged from 1.1910 grams to 1.4350 grams. The weight of clear applied to these strips ranged from 1.2820 grams to 1.0490 grams. The amount of xylene in the film . was 18.35 percent and combined weight of the xylene and Tetrahydrofurfuryl methacrylate amounted to 31.8 percent of the total film. Therefore, the weight losses we are measuring are 10-20% of the total initial weights which makes our weighing measurements on an analyti cal balance fairly accurate. DUP030009588 16 Preparation of Tetrahvdrofurfurvlisobutvrate (N.B. 7534-88,89,90) Tetrahydrofurfurylisobutyrate was prepared by direct esteri fication of tetrahydrofurfuryl alcohol (DS-48258) with isobutyric acid (Maithe son Coleman & Bell #12890) using 0.3 percent p-toiuene sulfuric acid as catalyst and toluene as an azeotroping agent for the by-product water. The water was removed from the reaction mixture as soon as it formed. The l.R, Cure of the product can be found in N.B. 7534-90. The yield of distilled product (B.P. 80-85C at 1-1.5 MM of Hg) was 94 percent based on isobutyric acid charged. Saponification number: found 324.8, 326.6; calculated 325.2, Nfp 1.4350. DUP030009589 17 BIBLIOGRAPHY 1, McNally, J. G., Marshall Laboratory Report 62-43. 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