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Aramid Short Fiber and Sulfron

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Aramid Short Fiber and Sulfron Aramid fibers enhancing elastomer properties Sveriges Gummitekniska Förenings vårkonferens 10-11 april, 2013 Malmö Ko Arts Technical Sales Manager Teijin Aramid BV Teijin’s high performance fibers Aramid fibers Twaron polyparaphenylene terephthalamide Sulfron Technora co-poly- (paraphenylene/3,4’- oxydiphenylene terephthalamide) Teijinconex poly- (metaphenylene isophthalamide) Why use aramid short fibres in rubber compounds? • Anisotropy • Increase green strength • Increase modulus • Increase abrasion resistance • Increase cut/tear resistance • Lower coefficient of friction • Lower noise generation in dynamic applications • Lower hysteresis and therefore lower heat build up in the compound leading to a longer service life (especially for thick sections) Teijin Aramid’s short fibers • Twaron® : • Chopped fibers (1, 3 & 6 mm) • Dip-chopped fibers (1, 3 & 6 mm) • Pulp • Twaron ® D3500 (new!) • Technora® • Chopped fibers (1, 3 & 6 mm) • Dip-chopped fibers (1, 3 & 6 mm) • Teijinconex® • chopped fibers (1, 3, 6 mm) • dipped chopped fibers (1, 3, 6 mm) • Sulfron® Twaron Technora Twaron will fibrillate and break; mind this aspect Technora gets kink bands, hardly fibrillate during processing or break EFFECTS OF PULP, CHOPPED AND DIP CHOPPED ARAMID FIBER EPDM Formulation Compounds BC1 BC2 BC3 (phr) (phr) (phr) Ingredients Control 3 mm Technora CF 3 mm Technora DCF Keltan 578 100 100 100 Corax N660 70 60 60 Sunpar 2280 10 10 10 ZMMBI-50 1.5 1.5 1.5 Naugard 445 1.5 1.5 1.5 Technora CF, 3 mm 10 Technora DCF, 3 mm 10 Cure recipe Sulfur 0,31 0,31 0,31 Perkadox 14-40 Kdp 9 9 9 Total (in phr) 192.3 192.3 192.3 Influence on Tensile properties Machine Direction Cross Machine Direction 24 24 Control (BC1) Machine direction Control (BC1) Cross-machine direction 3 mm Technora CF (BC2) 3 mm Technora CF (BC2) 3 mm Technora DCF (BC3) 20 3 mm Technora DCF (BC3) 20 16 16 12 12 Stress (MPa) Stress (MPa) Stress 8 8 4 4 0 0 0 50 100 150 200 250 300 0 50 100 150 200 250 300 Strain (%) Strain (%) Influence on Tear (trouser) Compounds BC1 BC2 BC3 Properties Control 10 phr Technora 3 10 phr Technora 3 mm CF mm DCF Average Force (F) [N] 9.3 40.8 40.8 MD Tear strength [kN/m] 4.5 19.7 19.5 Average Force (F) [N] 10.1 33.4 42.5 CMD Tear strength [kN/m] 4.8 16.1 20.3 Influence on Abrasion (other compound) • Twaron CF 3 mm : 130 mm3 • Technora CF 3 mm : 100 mm3 • Control : 170 mm3 3 (> 10 mm is significant, apart from approximately Abrasion 10% spread, 80 mm3 is extreme low) “on end” abrasion (iso 4649, meth A) Twaron will fibrillate more than Technora New! - Twaron D3500 Twaron D3500: aramid pulp masterbatch. A reinforcement additive for rubber compounds. Product details: Product form : Granules Colour : Yellow Specific gravity : 0.980 g/cm3 Twaron pulp type : 1095 p – aramid pulp : 40 wt % Matrix : 60 wt % Twaron D3500 is easily dispersible in rubber compounds. New! - Twaron D3500 Short fibers and pulp Short fibers Pulp 0.1 – 0.3 m2/g 7 (type 1095) – 14 m2/g (type 1091) Fiber length 1 – 6 mm Fiber length 1 - 2 mm New! - Twaron D3500 Mixing and Compounding of Twaron D3500: . Dosage 2 – 10 phr. Twaron D3500 contains 30 % oil. Consider to compensate for this amount of oil in the compound formulation. E.g., For 5 phr of Twaron D3500, 1.5 phr of oil could be reduced. No specific temperature requirements for mixing. Can be used in any type of compounds. Mixing scheme Time Action 0 min Rubber 1/2 min Carbon black or Silica + Twaron D3500 + Rest 2 min Oil 4 min Sweep 5 min Dump the compound New! - Twaron D3500 Test results Model apex formulation Ingredients (Phr) Control Twaron D3500 SMR-10 100 100 Corax N330 35 35 Corax N550 30 30 Nytex 840 5 5 ZnO 10 10 Stearic acid 2 2 Sunolite 240 2 2 6 PPD 2 2 TMQ 1 1 Cofill 11/gr* 6 6 Twaron D3500 (Pulp MB) 0 12.6** Insoluble Sulfur 6.5 6.5 CBS 1.0 1.0 PVI/CTPI 0.1 0.1 HMTA (Hexa-80) 1.8 1.8 Total (phr) 202.4 215.0 *Cofill 11/gr: 50% resorcinol on 50% silica carrier ** corrected for 5 phr pulp New! - Twaron D3500 Hardness New! - Twaron D3500 Tensile Strength (machine direction) • Hot air aging, 72 hrs, 100 °C New! - Twaron D3500 Tensile Strength (cross-machine direction) • Hot air aging, 72 hrs, 100 °C New! - Twaron D3500 Tear Strength (Crescent type) New! - Twaron D3500 SUMMARY • Twaron D3500 is an aramid pulp masterbatch • A reinforcing additive in rubber compounds • Gives strong increase in low elongation modulus • Dispersion of Twaron D3500 is very important to achieve good properties EFFECTS OF SULFRON Sulfron® Sulfron is based on Twaron, which is modified by chemicals. polyparaphenylene terephthalamide Sulfron D3001 Sulfron D3515 – new grade Sulfron reduces hysteresis in carbon black filled compounds. Sulfron can be used in CB filled compounds. Most pronounced effects are seen in NR based compounds. Main Sulfron® effect 0,220 0,200 0,180 0,160 ) d 0,140 tan tan ( 0,120 0,100 0,080 loss factor loss 0,060 0,040 0,020 Dynamic strain: 2 % Frequency: 10 Hz 0,000 0 10 20 30 40 50 60 70 80 90 100 110 Temperature (o C ) Adding Sulfron® to a compound improves hysteresis because tan δ reduction! Sulfron D3515 – new grade Based on aramid pulp masterbatch Granular shaped Contains 40 % aramid pulp (type 1095) Easily disperses in rubber compounds Reduces hysteresis ( tan d at rolling conditions) Mixing recommendations Sulfron has to be added together or just after carbon black addition. The compound temperature has to be kept in the range of 145 – 160 °C for about 1.5 – 2 min. The optimum dosage can vary depending on formulation. However, it is most usually around 1.5 – 2 phr. Natural rubber (NR) based tread formulation Phr Ingredients Control Sulfron D3001 Sulfron D3515 Natural rubber 80 80 80 Butadiene rubber 20 20 20 Carbon black N234 50 50 50 Nytex 840 5 5 5 Zinc Oxide 4 4 4 Stearic acid 2 2 2 Sunolite 240 2 2 2 6 PPD 2 2 2 TMQ 1 1 1 Sulfron D3001 0 2 0 Sulfron D3515 0 0 2 Sulphur 1,75 1,75 1,75 TBBS 1,5 1,5 1,5 TOTAL 169,25 171,25 171,25 Mooney Viscosity Control S3001 S3515 Temp req. [°C] 100 100 100 Time req. [min] 5 5 5 Test type "visc" "visc" "visc" Rotor "large" "large" "large" Initial [MU] 86 84,9 87,2 ML [MU] 53,7 51,3 51,7 Cure Characteritics Control S3001 S3515 Temp req. [°C] 150 150 150 Time req. [min] 30 30 30 Osc. angle [°] 0,5 0,5 0,5 ts2 [min] 5,03 5,52 5,7 t5 [min] 4,23 4,72 4,96 t50 [min] 6,21 6,58 6,77 t90 [min] 9,79 9,15 9,33 ML [Nm] 0,23 0,21 0,21 MH [Nm] 1,9 1,83 1,88 Delta S [Nm] 1,67 1,62 1,67 RH [Nm/m] 0,066 0,07 0,072 tRH [min] 0,58 0,63 0,65 Dynamic mechanical analysis Tan d DMTA Control Sulfron D3001 Sulfron D3515 Temperature (°C) 60 60 60 Frequency (Hz) 10 10 10 Storage modulus (E') 6,7855 6,517 6,6755 Loss modulus (E'') 0,9497 0,7896 0,7865 Tan d 0,13995 0,12115 0,1178 % reduction Tan d - 13 16 Control S3001 S3515 Tensile strength [Mpa] 29 27,5 26,9 Elongation at break [%] 554 515 494 Tear strength [kN/m] 114,4 121,3 100 Reduction in tan d (60°C, 10Hz and 2% DSA) 25 20 Reduction d [%] tan in Reduction 15 10 5 0 120 125 130 135 140 145 150 155 160 165 Dump temperature [°C] -5 Effect of Sulfron with different loadings N234 0,18 0,17 Control 0,16 1 phr Sulfron D3515 0,15 A 0,14 B 2 phr Sulfron D3515 0,13 Tan d Tan 0,12 0,11 0,1 47 50 53 56 N234 content [phr] 31 Effect of Sulfron with different loadings N234 - Din Abrasion - A B Sulfron D3515 Conclusions Sulfron in NR model compound shows: Improvement of: Hysteresis (tan δ) a slight effect on cure, processing and mechanical properties. Examples of applications that could benefit from Sulfron: • Tires • Conveyor Belts • Vibrational dampers .
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