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PLAINTIFF'S EXHTOff THs DOW CHEMICAL COMPANY DOW-726 n RESEARCH OOW CONFIDENTIAL i TECHNICAL SERVICE AND development___________________ ___________________________ MIDLAND, MICHIGAN DC^aRTmnT section eEPORr number--------------------------------- Designed Products Saran/New Products DP-685 authorisi: K_n R> Rose - chuck W. Glesner 2040 r*. LO co TITLE: FURTHER CHARACTERIZATION OF SAN AND SARAN MICROSPHERES co SUMMARY: r> To further characterize Saran (vinylidene chloride - acrylonitrile copolymer) and SAN (styrene - acrylonitrile copolymer) microspheres, a number of comparative tests were performed. Specifically (1) a paper yellowing test, *(2) resilience in an asbestos sheet, (3) hy draulic compression tests and (4) solvent resistance were the four properties studies. Briefly, SAN MS were found superior in the paper yellowing and re silience tests whereas Saran MS were considered best in the com pression and solvent resistance tests. This report describes the procedures and results of each test. Ecological Considerations: The information contained in this report is simply comparative data between two types of microspheres and consequently has no significant ecological impact. r E ( r. IV2D jUL 31S73 CM N2UM2 ST0284297 DISTRIBUTION: (*=Full cop, of report.) * Midis'.* c. R. I., 566 Bldg. (4 copies) * Corp. Res. & Devel., 2020 A. R. C * RMBartunek-2040 * RLDostal-564 * PSMartin-2040 * AJVogel-684 * PATiffanv-1603 * WARogers-2040 * EVLuoma-1604 * DSMorehouse-1604 * RBIngrahan-566 * RLErratt-B-1603, Frpt. * JHMinsker-3-1603 * TECravens-D-1603 * BEBurgert-1712 * VDFloria-1702 * TOGinter-1712 * RONewman-1702 * RCSimon-Pittsburg * WRNeuendorf-2040. * MADouw-Horgen * KRRose-2040 * DLKenaga-2040 SRVranish-2040 MEWinquist-B-1608, Frpt. RR3umb-2040 * DWilcock-2040 * RMJulier-2040 * JLSticklemeyer, Minnesota *E OF j OaFE '06LEm nuwoEft Lab Report FOOtf COM-O **1NTE0 IN U.L.A. 6- j May 23, 1973 ; 0023999 Pflf* \ DP-685 REPORT NO. PACE 2 DOW CONFIDENTIAL TITLE: FURTHER CHARACTERIZATION OF SAN AND SARAN MICROSPHERES To identify additional, physical differences between SAN and Saran Microspheres. ST0284298 CONCLUSIONS AND RECOMMENDATIONS: Conclusions: 1. Paper yellowing test - Saran microsphere paper shows a greater loss in brightness than SAN microsphere paper when subjected to 94 hrs of intense U.V. radiation. 2. Resilience in an asbestos sheet - Greater bulk was obtained with Saran MS, however the compression set of the SAN MS was far superior to the saran product. For example, a 50% increase in caliper at a compression set of <15% can only be obtained using SAN microspheres. 3. Hydraulic compression tests - Saran microspheres were found to be softer and more flexible than SAN microspheres. Consequently, they collapse at lower pressures, and can survive higher pressures without rupturing than the SAN microspheres. 4. Solvent effects - Saran microspheres were able to withstand aromatic solvents better than the SAN microspheres (at room temp.). At 60C, however, the saran product would also deteriorate. Ali phatic hydrocarbons seemed to be the only organic solvents that do not damage either type of microsphere. Introduction Other than differences in foaming properties and the thermal stabilities of SAN and Saran microspheres, very little comparative data has been generated. So, early in 1973 a list of "comparisons" was drawn up PORKC-Jjoio poinreo B.1./7 A. Paper Yellowing B. Asbestos Sheets, Resilience C. Hydraulic Compression D. Solvent Resistance E. Non-Wovens F. "K" Factor G. Foamability - Latex & Solvent Based Systems H>-- Cdor-..De.ve.lonment ----- - Peg* 2 DP No. 685 Page 3 DOW CONFIDENTIAL for further evaluation. Although the program is not yet complete/ this report describes the procedures and results of the first four tests. The report is sectioned into four parts, one for each of the four "comparisons" studies. LIGHT STABILITY OF MICROSPHERES IN PAPER The following procedure was used to prepare microsphere-containing paper hand sheets for comparing the U.V. light stability of our SAN and Saran Microspheres. 300 Grams of Great Lakes Bleached Softwood was beat to a Canadian Standard Freeness (CSF) of 454 which gave a 3.0 gm. sheet and a consistancy of 1.5%. In like manner 300 gms. of Bowaters Hardwood Bleached Kraft was beat to a CSF of 479 which gave a 2.7 gm. sheet and a consistency of 1.36%. The two pulp slurries were combined to. give a total of 71 lbs. of slurry with a corrected freeness of 444. A sample hand sheet weighed 2.95 gms. which means we had a consistency of 1.48%. 1% Rosin (based on pulp weight = 4.78 g) was then stirred in followed by 1% Alim (4.78 g). The pH was then adjusted to 4.5 with 1.0 N sulfuric acid (15 ml). One liter of prepared pulp (14.8 gms) was added to the proportionator which contained enough DI water to make four 8 inch hand sheets. In all cases .05% (by wt . of the pulp) Separan CP-7 was added to the proportionator as a retention aid (14.8 cc of a .05% solution) t followed by the appropriate amount of microspheres. The following chart is a summary of the designed experiment. SHEET # C-l Thru C-3 MS 'TYPE None it %MS Controls WT OF MS (gms) Dry Wet 00 1-1 Thru 1-9 2-1 Thru 2-9 3-1 Thru 3-9 SAN SAN SAN 1.0 .148 1.1 2.0 .296 2.2 4.0 .592 4.4 4-1 Thru 4-9 5-1 Thru 5-9 6-1 Thru 6-9 SARAN SARAN SARAN 1.0 .148 1.03 2.0 .296 2.06 4.0 .592 4.12 C-4 Thru C-9 None Controls ST0284299 Based on wt. of pulp DP NO. 685 PAGE 4 DOW CONFIDENTIAL ST0284300 Each of the 63 sheets was checked on the brightness tester to give the following data. Wire Side Felt Side Wire Side Felt Side C-l -2 -3 1-1 -2 -3 -4 -5 -6 -7 -8 -9 2-1 -2 -3 -4 -5 -6 -7 -8 -9 3-1 -2 -3 -4 -5 -6 -7 -8 -9 83.0 82.7 84.2 84.5 82.5 80.0 84.4 82.6 83.5 82.8-85.0 78.6-84.3 85.0 85.2 85.6 85.3 84.0 80.9-84.2 86.5 86.0 86.2 85.7 85.6 87.0 86.8 86.0 84.5 86.3 86.5 86.2 86.3 83.9 -- 82.8 84.7 85.0 86.2 85.7 86.3 87.0 86.3 87.0 4-1 -2 -3 -4 -5 -6 -7 -8 -9 5-1 -2 -3 -4 -5 -6 -7 -8 -9 6-1 -2 -3 -4 -5 -6 -7 -8 -9 C-4 -5 -6 -7 -8 -9 86.2 85.5 86.5 86.6 86.2 85.8 85.8 86.0 86.0 86.2 86.6 86.0 86.3 86.5 87.3 87.6 87.8 87.3 87.8 87.8 87.8 88.0 87.7 87.9 87.9 87.8 87.0 85.4 85.2 85.2 84.9 85.1 85.3 86.4 86.2 86.4 86.9 87.3 87.3 87.9 88.0 88.1 85.6 85.6 To investigate the U.V. stability differences between the SAN and Saran MS, selected hand sheets were subjected to U.V. radiation in the fade-ometer for up to 93.7 hours. The following brightness readings were taken after the U.V. exposure. DP-68 5 PAGE 5 DOW CONFIDENTIAL C-3 C-9 1-9 2-9 3-9 4-9 5-9 6-9 BLANK 81.3 83.1 83.1 83.5 83.0 83.4 83.9 84.4 24 HRS 79.0 81.0 81.2 80.8 81.0 ._ai.2 80.8 82.0 94 HRS 78.8 80.4 80.7 81.1 80.6 80.0 80.7 80.8 A 2.5 No Microspheres 2.7 2.4 2.4 SAN Microspheres 2.4 Lot #110621 3.4 3.2 SARAN Microspheres 3.6 Lot #05182 ST028430I Conclusion Although the bulk of the "yellowing" seemed to occur during the first 24 hrs (indicating the test may have been too severe) the data does show a greater drop in brightness of the Saran MS paper than the SAN. MICROSPHERE RESILIENCE IN ASBESTOS SHEETS To compare the "compression set" characteristics of the SAN and Saran MS# a series of asbestos hand sheets were made containing from 1 to 7% (by wt) microspheres. The following procedure was used for pre paring the hand sheets: Asbestos H20 57.9 g 2340 ml Latex (10% Soln) Ethomeen C-15 (5% Soln) Drew 169 A (DeFoamer) Microspheres (Foamed wet cake) 87.0 g 2.5 ml 2.5 ml As Needed The crumbed asbestos was agitated in 2340 ml of H-O with an air driven agitater for 1 minute. The latex was then poured in and agitated for 3 more minutes followed by the addition of the Drew 169 A (defoamer) and the Ethomeen C-15 (surfactant) and an additional 1 minute of agitation - total of 5 minutes of agitation. The microspheres were then slurried in just prior to pouring the formulation into the sheet former. After each sheet was pressed and dried, four two-inch squares were cut out for compression set analysis. DP-685 Page 6 DOW CONFIDENTIAL This test is performed by subjecting the samples to 50% compression at 70C (158C) for 22 hours. The sample is then allowed to recoil at room temperature for 30 minutes before the final thickenss is read. The following data was generated - SARAN MICROSPHERES'LOT #05182 14.4% SOLIDS 1.24 ATP Sample Wt.(g) Int. Thick. Final Thick. Set % Set 1% Saran 1 2.3595 MS 2 2.3252 3 2.3517 4 2.3030 .0540 .0510 .0540 .0545 .0430 .0380 .0435 .0415 .0110 .0130 .0105 .0130 20.4 25.5 19.5 24.0 1 2.2675 2% Saran 2 2.3227 MS 3 2.3101 4 2.3165 .0730 .0770 .0785' .0800 .045 .051 .053 .054 .028 .026 .0255 .026 38.4 33.8 32.6 32.5 3% Saran MS 1 2.5165 2 2.2208 3 2.1828 4 2.2231 .1100 .1120 .0925 .0900 .077 .0765 .062 .060 .033 .0355 .0305 .030 30.0 31.8 33.0 33.3 1 2.3714 4% Saran 2 2.4382 MS 3 2.4089 4 2.3912 .1255 .1240 .1240 .1105 .0950 .0960 .0950 .0850 .0305 .0280 .0290 .0255 24.3 22.6 23.4 23.1 ST028U302 DP-685 Page 7 DOW CONFIDENTIAL SAN MICROSPHERES LOT #110621 13.4% SOLIDS 3.00 ATD ST0284303 1% SAN MS 2% SAN MS 3% SAN MS 4% SAN MS 5% SAN MS 6% SAN MS 7% SAN MS Sample Wt. (g) 1 2.1610 2 2.3850 3 2.4430 4 2.3660 1 2.2-129 2 2.2800 3 2.4410 4 2.4982 1 2.0630 2 2.3887 3 2.2683 4 2.3151 1 2.4739 2 2.4421 3 2.4251 4 2.3667 1 2.2978 2 2.3660 3 2.6070 4 2.3055 1 2.4850 2 2.4962 3 2.4958 4 2.4660 1 2.7168 2 2.6621 3 2.4480 4 2.5526 Int. Thick. .0405 .0450 .0445 .0445 .0475 .0495 .0585 .0560 .0555 .0570 .0535 .0570 .0645 .0700 .0675 .0695 .0795 .080 .081 .080 .089 .088 .087 .087 .100 .101 .094 .096 Final Thick. Set % Set .0400 .0400 .0415 .0420 .0005 .005 .003 .0025 1.2 11.0 6.7 5.6 .0415 .0450 .0450 .0500 .006 .0045 .0135 .006 12.6 9.1 23.1 10.7 .0440 .0470 .0460 .0460 .0115 .0100 .0075 .0110 20.7 17.5 14.0 19.5 .053 .060 .053 .057 .0115 .010 .0145 .0125 17.8 14.3 21.5 18.0 .064 .061 .063 .058 .0155 .019 .018 .022 19.6 23.8 22.2 27.5 .066 .067 .0665 .067 .023 .021 .0205 .020 25.8 23.8 23.6 23.0 .074 .074 .072 .073 .026 .025 .022 .023 26.0 24.7 23.4 24.0 DP-685 Page 8 DOW CONFIDENTIAL The following charts display this data graphically. il0 |}8 2 0 iS % Microspheres (By Wt.) This first diagram shows the relationship between amount of micro spheres added and the additional thickness of the sheet. The dra matic difference in slopes between the SAN and Saran MS is probably due to their different densities - the SAN has a density of 3.00#/ft3 whereas the Saran only a 1.24#/ft^density. The next two graphs show the amount of compression set compared first to % microspheres and then to % increase in caliper (bulk). % compression Set vs^ i Microspheres % C om pression S et ST0284305 Com pression S et % Compression Set vs. % Bulk 50 100 150 200 % Bulk (Increase in Caliper) 250 DP-685 Page 10 DOW CONFIDENTIAL Both graphs show that the Saran MS containing sheets reach a maxi mum compression set of 35% at the 2% MS level. Also, the SAN MS sheets seemed to have reached a maximum of 25% set at the 6-7% level, however the experiment wasn't carried far enough to confirm whether this is indeed a maximum or a plateau. Conclusion SAN Microspheres show superior compression set characteristics to Saran Microspheres in the asbestos sheet formulation. The Saran MS do add more bulk to the sheet, but the corresponding compression set is much larger than that of the SAN MS sheets. For example, a 50% bulk with <15% set can only be achieved using SAN Microspheres. HYDRAULIC COMPRESSION TESTS Compression bulking tests were run on both the SAN and Saran expanded microspheres. The first series of tests were run in a thick walled, glass bomb with a 60 psig pressure limit. Both dry microspheres and a MS-glycerin slurry were subjected to pressures up to 60 psig in this apparatus. In general, the procedure was to place the MS sample in a calibrated test tube, which was then sealed in the bomb. As the pressure in creased (by the introduction of air) the volume of the sample would decrease due to the buckling of the microspheres. When the pressure was released, the sample would again assume its original volume. The following data was collected when each sample was run in dupli cate. ST028U306 DP-685 Page 11 DOW CONFIDENTIAL SAN (Freon) Microspheres Lot #110621 Air Dried Initial Wt. Initial Vol.. Initial Density = 0.3459 gins - 23.0 ml , = 15 x 10 gns/cc Press.(psig) Vol. (cc) Density (10 -3.qms/cc) 5 21.2 9 20.5 13 20.0 15 19.5 19 19.0 25 18.5 29 18.2 39 17.5 46 17.1 56 16.4 16.3 16.9 17.3 17.7 18.2 18.7 19.0 19.8 20.2 21.1 % Increase in Density 8.5 12.1 15.0 17.9 21.0 24.3 26.3 31.4 34.5 40.2 initial Wt. Initial Vol. Initial Density = .3504 g = 23.2 ml t *3 = 15.1 x 10" gms/cc ST0284307 2 22 4 21.5 9 20 13 19.4 16 18.9 22 18.3 27 17.8 36 17.0 50 16.5 59 16.2 15.9 16.3 17.5 18.1 18.5 19.1 19.7 20.6 21.2 21.6 5.4 7.9 16.0 19.5 22.7 26.7 30.3 36.5 40.6 43.2 DP-685 Page 12 DOW CONFIDENTIAL Saran Microspheres Lot #05182 Air Dried Initial Wt. Initial Vol. Initial Density = 0.1895 = 22.7 ml .. = 8.35 x 10 g/cc Press, (psig) 2 10 14 16 22 25 27 33 39 46 57 Vol. (cc) 20 19.5 19 18.5 16.4 15.5 15.0 14.0 13.0 12.1 11.0 Density (10~3g/cc) 9.5 9.7 10.0 10.2 11.5 12.2 12.6 13.5 14.6 15.7 17.2 % Increase in Density 11.1 13.9 16.9 20.0 35.5 43.5 48.1 58.7 70.9 83.7 102.0 ' ST0284308 Initial Wt. Initial Vol. Initial Density = 0.1775 = 21.5 ml = 8.26 x 10~Jg/cc 4 19.2 11 17.6 15 16.8 20 15.5 24 14.6 27 14.0 31 13.0 38 12.0 47 11.0 57 10.0 9.2 10.1 10.6 11.4 12.2 12.7 13.6 14.8 16.1 17.8 11.9 22.2 28.0 38.6 47.1 53.6 65.3 79.2 94.9 115.0 DP-685 Page 13 DOW CONFIDENTIAL When this data is presented graphically, one can readily see the more pronounced effect of pressure on the Saran Microspheres compared to the SAN product. % b e n sity Increase ST0284309 Gauge Pressure DP-685 Page 14 DOW CONFIDENTIAL A similar set of data was generated using a glycerine slurry of expanded microspheres instead of the dry material. Here, too, we see the same pronounced effect of pressure on the Saran micro spheres . ST0284.310 D ensity Increase) The following charts show the raw data used to generate this graph. DP-685 Page 15 DOW CONFIDENTIAL Saran Microspheres Lot #05182 14.4% Solids Initial Wt. Initial Vol. Initial Density 16.5 gms of MS - Glycerine Slurry 21.2 ml 0.778 g/cc Press, (psig) 20 23 27 32 37 44 51 59 Vol. (cc) 19.4 19.0 18.5 18.0 17.5 17.0 16.5 16.2 Density (g/cc .85 .87 .89 .92 .94 .97 1.00 1.02 % Increase in Slurry Density 9.3 11.6 14.6 17.8 21.2 24.7 28.5 30.9 ST02843 I I Initial Wt. Initial Vol. Initial Density = 17.6 gins slurry = 22.8 cc = .772 g/cc 17 21.5 .82 20 21 .84 22 20.5 .86 26 20 .88 30 19.5 .90 34 19 .93 39 18.5 .95 46 18 .98 57 17.5 1.01 6.1 8.6 11.2 14.0 16.9 20.0 23.2 26.7 30.3 DP-685 Page 16 DOW CONFIDENTIAL SAN Microspheres Lot #110621 13.4% Solids Initial Wt. Initial Vol. Initial Density Press (psig) 28 35 40 48 59 = 22.3 g of MS-Glycerine Slurry = 22.6 cc = .987 g/cc Vol. (cc) Density (g/cc) % Increase in Slurry Density 22 21.5 21 20.5 20 1.014 1.037 1.062 1.088 1.115 2.7 5.1 7.6 10.3 13.0 8T0284312 Initial Wt. Initial Vol. Initial Density 34 40 46 58 = 21.7 g of Slurry = 21.9 cc = .991 21 20.5 20 19.5 1.033 1.059 1.085 1.113 4.3 6.8 9.5 12.3 DP-685 Page 17 DOW CONFIDENTIAL At these low pressures, 0-60 psig, no permanent damage, or rupturing, occurred to the microspheres. In order to deter mine the maximum pressures these spheres can withstand, experi mentation was done in a small, (50 ml.) Parr tomb equipped with a 1000 psi pop valve. A glycerine slurry of known microsphere concentration and density was poured into the bomb and subjected to 900# psig (air pressure) for 15 minutes. The sample was re moved and the density checked. Theory: If a significant number of microspheres are ruptured, their loss of volume will cause the slurry density to increase. In this manner the following data was collected. $10284313 Effect of 900# Air Pressure on Microspheres Time = 15 Minutes Temp. = Room Temp. Initial Density Final Density % Change Saran Lot #05182 1.24#/ft3 1.12#/ft3 -9.6 Saran Lot #111811 1.78#/ft3 1.77#/ft3 -0.5 SAN Lot #110621 2.54#/ft3 5.23#/ft3 +105.9 SAN Lot #092021 1.84#/ft3 2.13#/ft3 +15.8 SAN-Neo Lot #1553-15 1.53 #/ft3 1.67#/ft3 +9.2 Microscopic examination of all five samples confirmed that rupturing had occurred with the Saran Microspheres, but the SAN samples showed unusual looking platelets, presumably the ruptured microspheres. Conclusion Saran Microspheres buckle at lower pressures than SAN and can survive higher pressures without rupturing. Saran Microspheres, in general, seem to be a softer, more flexible sphere than SAN Microspheres. DP-685 Page 18 DOW CONFIDENTIAL SOLVENT EFFECTS ON MICROSPHERES The solvent compatibility of microspheres has been a major concern of many of our customers doing developmental work in non-aqueous systems. To examine the solvent effects on micro spheres, a series of test tubes were filled with dry, expanded microspheres and treated with the solvent in question. The following table shows the effect of fourteen different solvents at room temperature and at 60C. Conclusion Aliphatic hydrocarbons seem to be the only organic solvents that do not soften or solvate the microsphere shell. The saran product is more resistant to aromatic solvents than the SAN material at room temperature, but at 60C it too will decompose. CO o ro GO to BPC ? 68.7 80.7 64.7 78.4 82.4 80.1 110.6 140 56.2 79.6 118 40.2 113 SOLVENT RESISTANCE OF MICROSPHERES SOLVENT Mineral Spirits Hexane Cyclohexane Methanol Ethanol Isoprcpanol Benzene Toluene Xylene Acetone Methyl Ethyl Ketone Methyl Isobutyl Ketone Methylene Chloride Trichloroethane SARAN R.T. 60C Good Good Good Good Good Good Good Poor Good Good Good Good Good Poor Good Poor Good Good Poor Poor Poor Poor Good (Slight Color) (?) SAN R.T. Good Good Good Good Good Good Poor Poor Poor Poor Poor Poor Poor Poor 60C Good Good Good Poor Poor Poor