P-aramid fibers improve truck tire chunk resistance
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1 Technical P-aramid fibers improve truck tire chunk resistance (Part two of two) By R.N. Datta Teijin Twaron B.V. Executive summary When sulfur vulcanized natural rubber compounds are exposed to a thermal aging environment significant change in physical properties and performance characteristics are observed. These changes are related directly to modifications of the original crosslink structure. Decomposition reactions tend to predominate and thus lead to a reduction in crosslink density and physical properties as observed during extended cure normally encountered in curing truck or off-the-road tires. The process leads to high heat generation and ultimately affects prime tire properties, such as flex, cut and chip resistance. The tire industry is therefore continually striving to improve cut, chip and chunk resistance while maintaining a high level of product quality and product performance. Over the years the rubber industry has developed several compounding approaches with varying fillers or optimizing cure packages or altering polymers and blend ratios. Each approach shows improvement with regard to cut, chip and chunk resistance but at the expense of hysteresis, heat buildup and flex properties. This paper provides an outline of available approaches with an emphasis on new avenues for p-aramid (Twaron and Technora) short fibers to improve cut, chip and chunk resistance. It has been confirmed that the addition of 1-3 phr of p-aramid short fibers in a typical truck or off-the-road tread compound significantly could improve hysteresis and temperature developments, thereby reducing cut, chip and chunk resistance. The tire test data show a significant degree of improvements with regard to the performance durability (18 20 percent), heat buildup (10 percent) and rolling resistance (10-25 percent). Optimization of modulus/hardness by partly replacing black with aramid short fibers In general, decrease in the black content diminishes both hardness and modulus and below a certain critical level negatively could influence abrasion as well as strength properties. As discussed earlier, addition of aramid short fibers enhances both modulus and hardness and thereby positively influences the abrasion properties. Having different modulus and hardness makes the systems difficult to compare and for this reason it was our objective to partially replace the carbon black with short fibers, which allows maintaining the hardness and modulus, thus enabling us to effectively compare the dynamic properties. The formulation for this optimization study is shown in Table III (mixes 6-10). The loading of short fibers is selected to be 1 phr, based on our optimization model study. As expected, replacing 2 phr of carbon black with 1 phr of either chopped or dip-chopped fiber (MPIA or PP/ODPTA) virtually maintains the torque, scorch and cure time. The relevant data are tabulated in Table VII. The processing as depicted in Table VII (Mooney viscosity) remains practically unchanged. 1
2 The physical properties of the vulcanizates are shown in Table VIII. It is clear from the table that by optimization by replacing black with short fibers, the hardness as well as stressstrain properties do not alter. With respect to tear and abrasion resistance, short fibers show marginally positive effect. These effects are highlighted in Fig. 4. The most unique feature of using aramid-based short fibers is on hysteresis as reflected in heat buildup data as well as viscoelastic properties. The relevant data are presented in Tables IX and X, respectively. It is worthwhile to stress here that by using dipped chopped fiber derived from PP/ODPTA (Technora), the tangent delta reduction is as high as more than 20 percent. This is expected to improve significantly the rolling resistance of truck tires. The use of PP/ODPTA (Technora DCF, mix 10) on a modified tread recipe also enhances the flex-fatigue resistance in a cut growth test as well as fatigue measured at constant energy. Figs. 5 and 6 clearly demonstrate the advantage of short fibers derived from Technora. In line with the improvement in cut growth and fatigue to failure properties, the samples (control and PP/ODPTA, mix 10) were tested for chip and chunk resistance in a homemade apparatus. The effect shown 2
3 in Fig. 7 is remarkable. By incorporating 1 phr of PP/ODPTA (Technora DCF) the failure is extended from 14 to 18 days in addition to a ranking difference of 2 vs. 4. The fact is shown in Fig. 7. Finally, structural elucidation of the vulcanizates was carried out, which allows correlating the vulcanizates properties and improvements with the fine network structure. The data are shown in Table XI. It is clear from the table that aramid-based short fibers are capable of maturing the network and as a result a fraction of polysulfide crosslinks is converted to monosulfides at equal cure times. This suggests that aramid short fibers such as (poly-(paraphenylene terephthalamide) (PPTA), poly- (metaphenylene isophthalamide) (MPIA) and copoly-( paraphenylene/3,4 -oxydiphenylene terephthalamide) (PP/ODPTA) are capable of participating in the vulcanization mechanism and thereby pave the way to enhancement of the vulcanizates properties. Tire test results The tread wear performance of the compounds tested in the drive axle position is shown in Fig. 8. It is clear that the incorporation of PP/ODPTA (Technora DCF) significantly enhances the tread life as demonstrated by improvement in tread wear. In addition to improvement in tread wear, significant differences were noticed when comparing the pattern of the abraded tread. The control shows a cut, chip and chunking behavior in 90 percen of the tires whereas test tires have a smooth tread surface. This is clearly demonstrated in Fig. 9. 3
4 Heat buildup, endurance and rolling resistance measurements were carried out at a renowned tire company. Results are listed in Tables XII, XIII and XIV. All figures are averages of four test tires. Heat buildup measurements were determined both in the shoulder and crown areas of the tire following a period of 15 hours during which the test speed was increased step-wise from 50 to 110 kph. The tires were run at 80 percent rated load. A significant reduction in heat buildup, more than 15 C, is noted for the tires bearing the tread containing PP/ODPTA (Technora DCF). This reduction in running temperature translates into both increased durability and reduced rolling resistance. Tire durability was determined by continued running at 110 kph and 80 percent rated load until failure. A reduction in rolling resistance from 12 to 24 percent is observed throughout the range of speeds for the tires containing PP/ODPTA (Technora DCF). This level of rolling resistance reduction can lead to a fuel saving of the order of 2 to 4 percent. 4
5 5
6 Conclusions Low levels of short fiber derived from (poly-(paraphenylene terephthalamide) (PPTA), poly-(metaphenylene isophthalamide) (MPIA) and co-poly-(paraphenylene/ 3,4 -oxydiphenylene terephthalamide) (PP/ODPTA) allow compound modifications to be applied that leads to improved cut, chip and chunk resistance, flex fatigue properties, abrasion resistance, hysteresis and heat buildup. These compound modifications involve utilization of lower black loadings, but inclusion of short fiber in the recipe. In addition to improvement in cut, chip and chunk resistance, the above changes lead to a significant reduction in rolling resistance and hence a major contribution to fuel savings. References 1. T.S. Solomen, Rubber Chem. Technol., 58, 561 (1985). 2. B.C. Begnoche, R.L. Keefe and A.G. Causa, Rubber Chem. Technol., 60, 689 (1987). 3. R.L. Keefe Jr., Rubber Chem. Technol., 58, 458 (1985). 4. E. Ellis and G.N. Welding, Rubber Chem. Technol., 27, 571 (1964). 5. P.J. Flory and R.J. Rehner, J. Chem. Phy. 11, 521 (1943). 6. L. Mullins, J. Appl. Poly. Sci., 2. 1 (1959). 7. B. Saville and A.A. Watson, Rubber Chem. Technol., 40, 100 (1967). 8. A.H.M. Schotman, P.J.C. van Haeren, A.J.M. Weber, F.G.H. van Wijk, J.W. Hofstraat, A.G. Talma, A. Steenbergen and R.N. Datta, Rubber Chem. Technol., 69, 727 (1996). 6
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