Producers of Specialty Chemicals Struktol Company of America 1 E. Steels Corners Road P. O. Box 1649 Stow, Ohio 444-649 www.struktol.com High Performance Silica Tread with Next Generation Struktol Process Additives Struktol Rubber Lab Project 844 Paul Danilowicz Benny Bezilla STP64 Phone: (33) 98-188 Fax: (33) 98-876 Technical Services: 1-8-37-8649 E-mail: customerservice@struktol.com
JV46F Blend of fatty acid derivatives DP 8C Zn ~% KK 49 Blend of fatty acid derivatives DP C Zn % CY 48 Blend of fatty acid derivatives DP 97C Zn ~8% Outline Formulations Mix Spec Rheometer Data Physical Property Data Processability/Extrusion Data Conclusions High Surface Area Silica 3 1
Formulations First Pass Batch INGREDIENT MASS MASS MASS MASS DURADENE 71 3. 3. 3. 3. TAKETENE N SCA 98 ZnO.... ST. ACID 6PPD SUNDEX 79 ZS 116MP 7 7 7 7 JV46F 4 KK 49 4 CY 48 4 Total 3 34 34 34 4 Formulations Final Pass Batch MB control 3 MB 1 34 MB 34 MB 3 34 DPG 1.4 1.4 1.4 1.4 CBS 1.7 1.7 1.7 1.7 SULFUR 1. 1. 1. 1. Total 34.3 38.3 38.3 38.3
Mix Spec 1 st PASS MIX ROTOR SPEED FILL FACTOR 7% RAM PRESSURE 3 PSI SECONDS ADD RUBBER 3 SECONDS ADD ½ SILICA AND SILANE 7 SECONDS ADD ½ SILICA AND OIL SECONDS BRUSH AND SWEEP 13 SECONDS ADD BLACK, ZnO STEARIC ACID, ADDITIVES AND 6PPD 18 SECONDS BRUSH AND SWEEP 338 F AUTO RAM LIFT ROTOR SPEED CHANGE TO 8 RPM 7 SECONDS DISCHARGE ND PASS MIX SPEC ROTOR SPEED 77, FILL FACTOR 6%, RAM PRESSURE 3 PSI SECONDS ADD ½ MB, CURES AND ½ MB 3 BRUSH AND SWEEP SECONDS OR 1F DISCHARGE 6 Rheometer Curves 7 3
Rheometer Data 16 C; 3 arc; range; 3 minutes Tech Pro Min Torque Max Torque Ts T T 9 18.34 48.44 4.38 7.9.67 14. 1.8. 8.8.38 Batch 13.4.69.96 9. 11.4 14.6 3.91.71 9.4.83 Higher cure state with all additives Lower minimum torque with all additives Increased scorch safety with all additives T9 approximately equal 8 Mooney Viscosity @ C Initial Vis 3 7 14 8 7.4 78. 1. 8. 13. 86.4 146.4 88. 16.4 9.7 93.8 67.8. 7. 1.3 7.9 14.3 77. 139. 84.3 Batch 89.6 68. 97.7 69.. 7. 113.7 7.1 17.9 78. 98. 7.8 4. 73. 11. 74.7 119.6 76. 134. 8. Decreased viscosity for better processability for all additives Better viscosity control with time providing more stable stock storage 9 4
Tensile Data Unaged Cure time @ 16 C ShoreA Duro Tensile (MPa) Elongation (%) % Mod. (MPa) % Mod. (MPa) 3% Mod. (MPa) 1 6 17.3 67 1.3 3. 6. 1 6 18.8 677 1... Batch 1 6.3 671 1.4 3. 6. 1 63 1. 634 1.6 3.6 6.9 Equal to better tensile, elongation and modulus with KK 49 and CY 48 Better tensile and elongation with JV46F with slightly lower modulus Tear Strength ASTM D 64 Die C N/MM 3ºC ºC 39.8 4. 49.6.3 Batch 3. 4.9.6 49.8 Increased tear at room temperature and C with all additives 11
MER Tension/Compression/Cylindrical / 1 Hz Tan delta/ average of 3 / 3c Tan delta/ average of 3 / c.198.14.1.14 Batch.186.14.183.14 Equivalent rolling resistance 1 Firestone Flexometer Heat Build-up lb. Weight;.3 Throw; 4 min. test Cure Time @ 16 C Duro Temp. C 48 9 19.3 48 9 13.3 Batch 48 6 144. 48 6 148.7 Lower heat build-up for all additives 13 6
Spiral Mold Batch Cure Time @ 3 F 1 1 1 1 1 1.68 1.83 1.9 1.86 1.633 1.881 1.96 1.86 3 1.97 1.863 1.97 1.7 Avg. 1.69 1.88 1.9 1.797 Better flow characteristics with all additives 14 Capillary Rheometer Data C, 18 sec preheat Die L/D ratio: 1:1: 9 entrance angle: 1. mm orifice Stress (Pa) Viscosity (Pa-s) Stress (Pa) Viscosity (Pa-s) Batch /s 71,13 43,6 3,7 44,87 /s 4.9 487.33 471.4 489.77 /s 3,94 79,7 69,9 8,9 /s 3.9 79. 69.89 8.7 Reduced apparent viscosity with all additives Better extrudability Less scrap/workaway 1 7
Conclusions All additives provide increased cure state and increased scorch safety. Reduced viscosity for better processability. Better viscosity control with time. Superior tensile, elongation and modulus. Equivalent rolling resistance. Lower heat build-up. Flow and extrusion characteristics improved. 16 High Surface Area Silica First Pass Batch INGREDIENT MASS MASS MASS MASS DURADENE 71 3. 3. 3. 3. TAKTENE N SCA 98 ZnO.... St ACID 6PPD SUNDEX 79 ZS P MP 7 7 7 7 JV46F 4 KK 49 4 CY 48 4 Total 3 34 34 34 17 8
High Surface Area Silica Final Pass MB 3 Batch MB 1 MB MB 3 DPG CBS SULFUR Total 1.4 1.7 1. 34.3 34 1.4 1.7 1. 38.3 34 1.4 1.7 1. 38.3 34 1.4 1.7 1. 38.3 18 Rheometer Curves 19 9
Rheometer Data 16 C; 3 arc; range; 3 minutes Tech Pro Min Torque Max Torque Ts T T 9.73 43.9 4.38 7.8 1.8.14 41.97 6.96 1. 18. Batch 19.74 46.7 7.38 13.1 18.46. 4. 6.63 11.4 14.79 (Compared to ZS 116 MP) Significantly reduced cure amount Longer cure times High surface area silica adsorbing more of the curatives/additives Mooney Viscosity @ C Initial Vis 3 7 14 8 137.. 14.3 6.9 16.8 11. 17. 117.3 198.4 1.8 116. 87.1 16. 89.6 13. 9.4 141.9 97.7 19.1.6 Batch 119.3 89.1 13. 9.1 136.8 93.9 147. 98.9 164.6 6.1 119.3 89.7 131.8 94. 14.6 98. 17.6.4 17.9 1. Decreased viscosity for better processability for all additives Better viscosity control with time providing more stable stock storage 1
Tensile Data Unaged Cure time @ 16 C Shore A Duro Tensile (MPa) Elongation (%) % Mod. (MPa) % Mod. (MPa) 3% Mod. (MPa) Batch 16 19 19 16 61 6 6 6 6.4 1.4 13.3 18. 46 644 63 79 1.3 1.1 1.3 1.8.7..7 3.9 4. 3.8 4.6 6.9 (Compared to ZS 116 MP) Significantly lower tensile and modulus values Curatives and additives being adsorbed on silica Poor dispersion? Tear Strength ASTM D 64 Die C N/MM Batch 3ºC.1 3.7 37.3 44.9 ºC 19.7 4. 41.6 49.8 Increased tear at room temperature and C with all additives 3 11
MER Tension/Compression/Cylindrical / 1 HZ Batch Tan delta/ Average of 3 / 3c.8.6.. Tan delta/ Average of 3 /c.166.161.163.168 Equivalent rolling resistance 4 Firestone Flexometer Heat Build-up lb. Weight;.3 Throw; 4 min. test Cure Time @ 16 C Duro Temp. C 64 64 183.7 76 6 18.7 Batch 76 6 171.9 64 61 8.3 Lower heat build-up for all additives except (CY 48). This compound had very high modulus and tensile values as well as the highest cure amount. 1
Spiral Mold Cure Time @ 3 F 1 3 Avg. 16 1.491 1.9 1.47 1.3 19 1.748 1.74 1.648 1.713 Batch 19 1.67 1.661 1.644 1.64 16 1.649 1.64 1.91 1.61 Better flow characteristics with all additives 6 Capillary Rheometer Data C, 18 sec preheat Die L/D ratio: 1:1: 9 entrance angle: 1. mm orifice Stress (Pa) Viscosity (Pa-s) Stress (Pa) Viscosity (Pa-s) Batch /s 91,8 6,63 86,39 8,78 /s 8.6 31.3 7.83 71.6 /s 3,9 98,6 31,7 313,87 /s 3.7 98.9 31.69 313.86 Slightly reduced apparent viscosity with all additives Slightly better extrudability 7 13
Three Pass Mix for High Surface Area Silica Low cure amount with pass mix Longer cure times Lower modulus Possible poor dispersion 8 Mix Spec 1st pass mix spec (6 rpm, fill factor 7%) SECONDS ADD RUBBER 3 SECONDS ADD 1/3 SILICA 6 SECONDS ADD 1/3 SILICA 9 SECONDS ADD SILANE, OIL, CARBON BLACK, ADDITIVES AND REST OF SILICA 18 SECONDS OR 66F RA LIFT 3 SECONDS OR 3F BRUSH AND SWEEP 4 SECONDS OR 3FDISCHARGE ROTOR SPEED 6 RPM AT DISCHARGE 3 PSI nd pass mix spec for batch rotor speed started at 1 rpm, at 3F changed rotor speed to 6 rpm fill factor 7%) SECONDS ADD all MB 3F AUTO RAM LIFT, CHANGE ROTOR SPEED TO 6 RPM DISCHARGE 7 MINUTES AFTER ROTOR SPEED Mix spec final pass for batch (6 % fill factor) SECONDS ADD ALL RUBBER 1 SECONDS ADD CURES 6 SECONDS BRUSH AND SWEEP 1 SECONDS OR 6F DISCHARGE ROTOR SPEED 77 RAM PRESSURE 3 PSI 9 14
Rheometer Curves 3 Rheometer Data 16 C; 3 arc; range; 3 minutes Tech Pro Min Torque Max Torque Ts T T 9 19.79 4.87 4.8 7.83 1.17 1.19 41.33 6.96 1.67 17.7 Batch 14.61 4.18 7.38 13.9 18. 1.7 39.41 7.17 13.79. Higher cure amount than pass mix except for (CY 48) T9s approximately equal to pass mix except for (CY 48) significantly longer Reduced minimum torque with all additives 31 1
Mooney Viscosity @ C Initial Vis 3 7 14 8 11.4 81.4. 83.6 86.6 86.7 136.6 91. 1.6 99.7 9.8 7.3 98.8 7.4 74.6 74.6 111.8 78.1 13.3 83.8 Batch 9. 7. 97.9 73. 73.6 73.7 114.1 78. 13. 8.4 98.9 7.1 4. 7.3 77.3 77.3 117.7 8.6 17.3 87.6 Decreased viscosity for better processability for all additives Better viscosity control with time providing more stable stock storage 3 Tear Strength ASTM D 64 Die C N/MM 3ºC ºC 7.1.7 44.7 64.9 Batch 48.3 81. 44. 64.8 Increased tear at room temperature and C with all additives 33 16
Spiral Mold Batch Cure Time @ 3 F 18. 18. 18.. 1 1.66 1.839 1.811 1.813 1.69 1.868 1.81 1.73 3 1.687 1.7 1.86 1.791 Avg. 1.67 1.81 1.89 1.776 Better flow characteristics with all additives 34 Capillary Rheometer Data C, 18 sec preheat Die L/D ratio: 1:1: 9 entrance angle: 1. mm orifice Stress (Pa) Viscosity (Pa-s) Stress (Pa) Viscosity (Pa-s) /s /s /s /s 86,39 7.83 31,6 31.64 3,4 6.87 8,78 8.77 Batch,.4 84,6 84. 8,9 17.86 87,6 87.6 Reduced apparent viscosity with all additives Better extrudability 3 17
Conclusions Lower cure amount with high surface area silica. Longer cure times with high surface area silica due to cure and additives adsorbing onto silica. Significantly lower modulus values than would be expected for a high surface area silica. Lab program to evaluate increased cure/additive package has been initiated. 36 18