Millathane® 5004 blends with HNBR - TSE Industries, Inc.

TSE Industries, Inc.Millathane® Millable Polyurethane Division4370 112th Terrace NorthClearwater, FL 33762 (USA)727-573-7676 or 800-237-7634 www.tse-industries.comMillathane® 5004 blends with HNBR(Zetpol 2000L, 2020L, 2030L)ConclusionsMillathane 5004 compounds (100%) generally fared well against compounds madefrom Zetpol HNBR polymers except for boiling water exposure* and high temperaturecompression set.Blends of the two polymers showed that the 70/30 HNBR/Millathane 5004 compoundoffer advantages to 100% HNBR in several properties (volume swell after oilimmersion, improved property retention after oven aging for Zetpol 2030L [only]), andminimal or no disadvantages in other properties. Millathane 5004/HNBR 50/50 and70/30 blends generally showed poorer properties than either polymer alone.RecommendationsMillathane 5004 should be evaluated for applications now using HNBR, especiallythose using higher unsaturation types such as Zetpol 2030L, where compression setat 135C and above and/or boiling water exposure are not factors in the end useapplication.Millathane 5004 should be evaluated as a partial replacement for HNBR. Areplacement of 30 parts Millathane 5004 for HNBR should give a less expensivecompound with characteristics similar to that of 100% HNBR.Thomas L. Jablonowski7/16/2004* This property can be improved by the increase in the level of carbodiimide (Stabilizer 7000 from Raschigor as Stabaxol P from Rhein Chemie).Ref: 40263The recommendations for the use of our products are based on tests believed to be reliable. However, we do not guarantee the results tobe obtained by others under different conditions. Nothing in this literature is intended as a recommendation to use our products so as toinfringe on any patent. Millathane and Thanecure are registered trademarks of TSE Industries, Inc.

Millathane® 5004 blends with HNBR (Zetpol 2000L, 2020L, 2030L)A1 A2 A3 A4 B1 B2 B3 B4 B5 C1 C2 C3 C4A E K B A H F I C A G L DMillathane 5004 100 50 30 100 70 50 30 100 50 30Zetpol 2000L 50 70 100Zetpol 2020L 30 50 70 100Zetpol 2030L 50 70 100Maglite D Bar 4 4 4 4 4 4 4 4 4 4Kadox 911C 1 1.4 2 0.6 1 1.4 2 1 1.4 2Vanox ZMTI 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4N550 40 45 47 50 40 43 45 47 50 40 45 47 50Plasthall TOTM 10 10 10 10 10 10 10 10 10 10TP-95 10 10 10Stabilizer 7000 2 2 2 2 2 2 2 2 2 2TAIC DLCA 2 2 2 2 2 2 2 2 2 2Stearic Acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3Struktol WB-212 1 1 1 1 1 1 1 1 1 1 1 1 1Dicup 40C 6 9 10.2 12 6 7.2 8 8.8 10 6 7 7.4 8159.3 174.7 178.3 181.7 159.3 170.5 173.7 176.9 179.7 159.3 172.7 175.5 177.7Mooney ViscosityML4/100C 52 58 62 77 52 55 54 59 72 52 54 57 71MDR, 30'/160CML, lb-in 0.6 1.5 1.7 1.9 0.6 1.3 1.4 1.5 2.0 0.6 1.4 1.7 2.1dN-m 0.7 1.7 2.0 2.2 0.7 1.4 1.6 1.7 2.3 0.7 1.6 1.9 2.4MH, lb-in 27.7 38.0 36.5 37.7 27.7 41.7 39.0 37.0 43.2 27.7 38.0 37.0 39.7dN-m 31.3 42.9 41.3 42.6 31.3 47.1 44.0 41.8 48.8 31.3 43.0 41.8 44.9ts1, min. 1.0 0.8 0.8 0.8 1.0 0.8 0.8 0.7 0.7 1.0 0.8 0.7 0.6t50, min. 4.2 5.0 5.5 6.2 4.2 5.1 5.1 5.1 5.4 4.2 5.0 4.9 4.8t90, min 8.6 12.5 13.8 16.4 8.6 12.0 12.7 13.6 15.6 8.6 12.7 13.5 14.8Observations1. Zetpol HNBR's, and their blends with Millathane 5004, give higher compound viscosities than Millathane 5004,2. Rheometer data shows the Zetpol HNBR's giving higher states of cure (higher MH values) and slower cure rates (but shorter scorch times (ts1 values))tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 1 of 12

Millathane® 5004 blends with HNBR (Zetpol 2000L, 2020L, 2030L)A1 A2 A3 A4 B1 B2 B3 B4 B5 C1 C2 C3 C4A E K B A H F I C A G L DMillathane 5004 100 50 30 100 70 50 30 100 50 30Zetpol 2000L 50 70 100Zetpol 2020L 30 50 70 100Zetpol 2030L 50 70 100Original Properties, Test at RT (23C)Press Cure, minutes at 160º C 12 20 20 20 12 18 20 20 20 12 20 20 20Hardness, Shore A 69 70 68 68 69 71 70 68 70 69 68 68 68100% Modulus, psi 760 940 720 770 760 1020 940 840 910 760 1020 820 770MPa 5 6 5 5 5 7 6 6 6 5 7 6 5300% Modulus, psi 2300 2000 3240 2300 2300MPa 16 14 22 16 16Tensile Strength, psi 2820 2870 2790 3360 2820 2770 2850 3010 3400 2820 2830 2710 3440MPa 19 20 19 23 19 19 20 21 23 19 20 19 24Elongation, % 490 290 320 310 490 290 280 290 270 490 270 260 290Specific Gravity 1.31 1.23 1.20 1.16 1.31 1.26 1.23 1.19 1.16 1.31 1.23 1.20 1.16Original Properties, Test at 135CHardness, Shore A 72 73 71 71 72 73 73 72 72 72 72 70 71Change 3 3 3 3 3 2 3 4 2 3 4 2 3100% Modulus, psi 450 540 470 470 450 590 580 540 610 450 590 540 530MPa 3 4 3 3 3 4 4 4 4 3 4 4 4% Change -41 -43 -35 -39 -41 -42 -38 -36 -33 -41 -42 -34 -31Tensile Strength, psi 1200 1200 1010 1060 1200 1280 1260 1190 1320 1200 1090 1000 1210MPa 8 8 7 7 8 9 9 8 9 8 8 7 8% Change -57 -58 -64 -68 -57 -54 -56 -60 -61 -57 -61 -63 -65Elongation, % 210 160 160 150 210 160 150 150 160 210 140 140 160% Change -57 -45 -50 -52 -57 -45 -46 -48 -41 -57 -48 -46 -45Observations1. 100% Zetpol HNBR's had higher tensile than 100% Millathane 5004 and their blends (roughly 500 psi/4 Mpa higher). (See Chart 1)2. All Zetpol HNBR's gave similar tensile strengths.3. Elongations of HNBR and HNBR/M5004 compounds were lower than that of 100% Millathane 5004, both at room temperature and at 135C.4. Physical property tests at 135C showed similar drops in properties for all polymers and polymer blends. Properties of all compounds at 135C were similar.5. The tensile strength for the Millathane 5004 compound is lower than typical; this compound normally tests 3000 psi (20 Mpa). The compound may have been undercured.tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 2 of 12

Millathane® 5004 blends with HNBR (Zetpol 2000L, 2020L, 2030L)A1 A2 A3 A4 B1 B2 B3 B4 B5 C1 C2 C3 C4A E K B A H F I C A G L DMillathane 5004 100 50 30 100 70 50 30 100 50 30Zetpol 2000L 50 70 100Zetpol 2020L 30 50 70 100Zetpol 2030L 50 70 100Oven Aging, 168 hr/135CHardness, Shore A 74 73 74 75 74 77 77 76 77 74 79 76 76Change 5 3 6 7 5 6 7 8 7 5 11 8 8100% Modulus, psi 1130 1230 1150 1100 1130 1400 1280 1390 1360 1130 1710 1530 1500MPa 8 8 8 8 8 10 9 10 9 8 12 11 10% Change 49 31 60 43 49 37 36 65 49 49 68 87 95Tensile Strength, psi 3250 2700 3190 3430 3250 1990 2710 2970 3410 3250 2670 2820 2750MPa 22 19 22 24 22 14 19 20 24 22 18 19 19% Change 15 -6 14 2 15 -28 -5 -1 0 15 -6 4 -20Elongation, % 340 240 290 310 340 160 200 220 250 340 170 180 160% Change -31 -17 -9 0 -31 -45 -29 -24 -7 -31 -37 -31 -45Oven Aging, 70 hr/150CHardness, Shore A 74 76 77 77 74 77 76 77 76 74 78 79 78Change 5 6 9 9 5 6 6 9 6 5 10 11 10100% Modulus, psi 1160 1400 1340 1200 1160 1360 1610 1570 1520 1160 1930 1930 1860MPa 8 10 9 8 8 9 11 11 10 8 13 13 13% Change 53 49 86 56 53 33 71 87 67 53 89 135 142Tensile Strength, psi 3310 2520 3080 3380 3310 1590 2500 3200 3330 3310 2540 2480 2010MPa 23 17 21 23 23 11 17 22 23 23 18 17 14% Change 17 -12 10 1 17 -43 -12 6 -2 17 -10 -8 -42Elongation, % 320 200 260 270 320 130 170 220 220 320 140 120 105% Change -35 -31 -19 -13 -35 -55 -39 -24 -19 -35 -48 -54 -64Observations1. Millathane 5004 had better heat resistance than Zetpol 2030L and slightly deficient heat resistance than Zetpol 2000L and 2020L. The deficiency is with higherpercent elongation losses,but the absolute levels of elongation with heat aged Millathane 5004 was still higher than that for the HNBR polymers.2. Blends of the polymers generally showed that the replacement of 30 phr of HNBR with Millathane 5004 gave improved heat aging when Zetpol 2030L wasthe HNBR, and roughly comparable heat aged properties when Zetpol 2000L and 2020L were the HNBR polymers.tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 3 of 12

Millathane® 5004 blends with HNBR (Zetpol 2000L, 2020L, 2030L)A1 A2 A3 A4 B1 B2 B3 B4 B5 C1 C2 C3 C4A E K B A H F I C A G L DMillathane 5004 100 50 30 100 70 50 30 100 50 30Zetpol 2000L 50 70 100Zetpol 2020L 30 50 70 100Zetpol 2030L 50 70 100Oven Aging, 70 hr/100C ASTM 903 OilHardness, Shore A 75 70 69 64 75 72 70 69 65 75 70 70 70Change 6 1 -4 6 1 1 -5 6 2 2 2100% Modulus, psi 810 940 740 670 810 940 1060 850 850 810 1130 840 740MPa 6 6 5 5 6 6 7 6 6 6 8 6 5% Change 7 3 -13 7 -8 13 1 -7 7 11 2 -4Tensile Strength, psi 2770 2690 2940 3220 2770 2290 2630 2920 3350 2770 2510 2520 3200MPa 19 19 20 22 19 16 18 20 23 19 17 17 22% Change -2 -6 5 -4 -2 -17 -8 -3 -1 -2 -11 -7 -7Elongation, % 470 285 330 325 470 225 240 280 280 470 215 250 280% Change -4 -2 3 5 -4 -22 -14 -3 4 -4 -20 -4 -3Weight Change, % -4 1 4 6 -4 0 0 1 6 -4 0 3 5Volume Change, % -5 2 5 8 -5 0 0 2 8 -5 1 2 6Oven Aging, 70 hr/135C ASTM 903 OilHardness, Shore A 75 68 68 65 75 69 70 69 65 75 69 70 65Change 6 -2 -3 6 -2 1 -5 6 1 2 -3100% Modulus, psi 810 660 630 635 810 710 740 720 800 810 900 770 760MPa 6 5 4 4 6 5 5 5 6 6 6 5 5% Change 7 -30 -13 -18 7 -30 -21 -14 -12 7 -12 -6 -1Tensile Strength, psi 2600 1680 2170 3160 2600 990 1620 2350 3210 2600 1680 2020 3100MPa 18 12 15 22 18 7 11 16 22 18 12 14 21% Change -8 -41 -22 -6 -8 -64 -43 -22 -6 -8 -41 -25 -10Elongation, % 480 250 300 310 480 150 205 270 280 480 180 230 290% Change -2 -14 -6 0 -2 -48 -27 -7 4 -2 -33 -12 0Weight Change, % -4 0 2 7 -4 0 0 2 6 -4 0 2 6Volume Change, % -4 1 3 9 -4 0 2 2 8 -4 1 2 8Observations1. ASTM 903 Oil aging, both at 100C and at 135C, gave comparable property changes for 100% Millathane 5004 and the Zetpol HNBR polymers. Blends ofthe polymers, especially those with 50-70% Millathane 5004 and 30-50% HNBR, gave poorer properties and property retentions after oil immersion.2. Weight and volume changes after oil aging showed the HNBR polymers to give higher weight and volume changes than Millathane 5004, with intermediateblends giving roughly intermediate values. The 100% Millathane 5004 compound used a plasticizer, TP95, that appears to be more extractable than the plasticizerused in the HNBR and HNBR/M5004 blends (TOTM); this resulted in a small weight and volume loss after the oil immersions. (See Chart 2)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 4 of 12

Millathane® 5004 blends with HNBR (Zetpol 2000L, 2020L, 2030L)A1 A2 A3 A4 B1 B2 B3 B4 B5 C1 C2 C3 C4A E K B A H F I C A G L DMillathane 5004 100 50 30 100 70 50 30 100 50 30Zetpol 2000L 50 70 100Zetpol 2020L 30 50 70 100Zetpol 2030L 50 70 100Water Immersion, 7 days/100CHardness, Shore A 49 61 70 70 49 54 63 70 71 49 59 70 69Change -20 -9 2 2 -20 -17 -7 2 1 -20 -9 2 1100% Modulus, psi 210 380 480 610 210 360 480 550 710 210 530 590 610MPa 1 3 3 4 1 2 3 4 5 1 4 4 4% Change -72 -60 -33 -21 -72 -65 -49 -35 -22 -72 -48 -28 -21Tensile Strength, psi 1050 1220 1880 3180 1050 490 1080 1930 3220 1050 1100 1840 3310MPa 7 8 13 22 7 3 7 13 22 7 8 13 23% Change -63 -57 -33 -5 -63 -82 -62 -36 -5 -63 -61 -32 -4Elongation, % 550 240 310 370 550 110 190 260 300 550 170 260 350% Change 12 -17 -3 19 12 -62 -32 -10 11 12 -37 0 21Weight Change, % 10 -9 -1 2 10 -15 -10 -3 1 10 -8 -1 1Volume Change, % 12 -5 3 2 12 -11 -6 2 1 12 -4 2 1Compression Set22 hr/135C 84 40 28 21 84 53 38 28 20 84 35 26 2122 hr/150C 98 41 29 24 98 61 38 29 26 98 35 26 24DIN Abrasioncu mm lost 61 102 84 76 61 109 104 90 79 61 106 82 81Abrasion Res. Index 178 107 129 145 178 99 104 121 137 178 102 131 134Observations1. Water immersion for 7 days at 100C showed the Millathane 5004 compounds to have much inferior properties after this aging condition. The 70/30 Millathane5004/Zetpol 2020L gave especially poor properties after the immersion. Higher levels of the water stabilizer, Stabilizer 7000, may be required to obtain goodresistance to boiling water for this time period.2. Compression set for the HNBR polymers was much better than for Millathane 5004, but 70/30 HNBR/Millathane 5004 blends still had very good set,even at 22hr/150C. (See Charts 3 and 4)3. Abrasion resistance for Millathane 5004 was better than for the HNBR polymers, with the polymers ranking being Millathane 5004>Zetpol 2000L>Zetpol 2020L>Zetpol 2030L.Abrasion resistance of the Millathane 5004/HNBR blends was poorer than the individual polymers. (See Chart 5)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 5 of 12

4000Millathane® 5004/HNBR BlendsTensile Strength, Original at Room Temp (23C)350025Tensile, psi30002500200015002015MPa1000500HNBR 2000HNBR 2020HNBR 20301000 10 20 30 40 50 60 70 80 90 100% Millathane 5004 (of M5004/HNBR blend)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 6 of 12

Millathane® 5004/HNBR BlendsTensile Strength, Oven Aged 70 hr/150C10080Tensile change from unaged, %6040200-20-40-60-800 10 20 30 40 50 60 70 80 90 100HNBR 2000HNBR 2020HNBR 2030-100% Millathane 5004 (of M5004/HNBR blend)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 7 of 12

Millathane® 5004/HNBR BlendsElongation, Oven Aged 70 hr/150C10080Elongation change from unaged, %6040200-20-40-60HNBR 2000HNBR 2020HNBR 20300 10 20 30 40 50 60 70 80 90 100-80-100% Millathane 5004 (of M5004/HNBR blend)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 8 of 12

10Millathane® 5004/HNBR BlendsASTM 903 Oil Immersion, 70 hr/135C8Volume Change, %6420-2HNBR 2000HNBR 2020HNBR 20300 10 20 30 40 50 60 70 80 90 100-4-6% Millathane 5004 (of M5004/HNBR blend)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 9 of 12

90Millathane® 5004/HNBR BlendsCompression Set, 22 hr/135C807060Set, %504030201000 10 20 30 40 50 60 70 80 90 100% Millathane 5004 (of M5004/HNBR blend)HNBR 2000HNBR 2020HNBR 2030tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 10 of 12

120Millathane® 5004/HNBR BlendsCompression Set, 22 hr/150C10080Set, %604020HNBR 2000HNBR 2020HNBR 203000 10 20 30 40 50 60 70 80 90 100% Millathane 5004 (of M5004/HNBR blend)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 11 of 12

200Millathane® 5004/HNBR BlendsDIN Abrasion180Abrasion Resistance Index16014012010080604020HNBR 2000HNBR 2020HNBR 203000 10 20 30 40 50 60 70 80 90 100% Millathane 5004 (of M5004/HNBR blend)tlj 40263_HNBR_M5004_Copy.xls 7/16/2004 Page 12 of 12