Effect of crosslink structures on dynamic mechanical properties of natural rubber vulcanizates under different aging conditions

The effects of crosslink structures on the dynamic mechanical properties (DMPs) of unfilled and carbon black N330‐filled natural rubber (NR) vulcanizates cured with conventional (CV), semiefficient (SEV), and efficient (EV) cure systems and having about the same total crosslink densities were investigated before and after aerobic and anaerobic aging at 100°C. The three unfilled NR vulcanizates cured with the CV, SEV, and EV systems had about the same mechanical loss factor (tan δ) values at about 0°C but showed some apparent differences in the tan δ values in the order EV > SEV > CV at relatively high temperatures of 40–80°C before aging. However, N330‐filled NR vulcanizates gave higher tan δ values than the unfilled vulcanizates and showed little effect of the crosslink types on the tan δ at different temperatures over the glass‐transition temperature (T_g) before aging. Aerobic heat aging increased the T_g and tan δ values of the vulcanizates over a wide range of temperatures from ?80 to 90°C that was mainly due to the changes in the total density and types of crosslinks. The unfilled vulcanizates cured with the CV system showed the greatest change in DMP because of their poor resistance to heat aging. Aerobic heat aging of NR vulcanizates caused a more significant change in the DMP than anaerobic heat aging because of the dominant effect of the oxidative degradation during aerobic heat aging on the main‐chain structure, crosslink structures, and DMPs of the vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 710–718, 2001     

The structure change of dynamically fatigued unfilled natural rubber vulcanizates

The submicrostructure of dynamically fatigued unfilled natural rubber vulcanizates was investigated by using scanning electron microscope (SEM) and atomic force microscope (AFM). AFM photographs showed the sample surface roughness became worse after tensile fatigue and the largest surface undulation was as twice that of the unfatigued sample. SEM photographs showed that many micropores of 10¹–10² nm, a sort of defect, occurred on the cross section of samples after tensile fatigue. The surface roughness became weaker and the size of the micropore was reduced to a few to dozens of nanometers with the addition of antiaging agent N‐(1,3‐dimethyl butyl butyl)‐N′‐phenyl‐p‐phenylene diamine (4020); furthermore, the mechanical properties and dynamic viscoelastic properties in the later period of fatigue changed much. E′ decreased greatly and tan δ increased obviously with the extension of fatigue. It indicated that 4020 was only effective in the early period of tensile fatigue.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of liquid isoprene rubber on dynamic mechanical properties of emulsionpolymerized styrene/butadiene rubber vulcanizates

The effect of liquid isoprene rubber (LIR) on the dynamic mechanical properties of emulsion‐polymerized styrene/butadiene rubber (ESBR) vulcanizates was investigated by temperature sweep using dynamic mechanical analysis. The introduction of LIR led to ESBR vulcanizates having higher loss factor (tan δ) in the temperature range ? 30 to 0 °C, and lower tan δ in the range 60 to 80 °C. A small amount of LIR‐403 (LIR with carboxyl groups) led to a significant change in tan δ: the addition of LIR‐403 (3 phr) led to a 7.5% increase in tan δ from ? 30 to 0 °C, and a 24.9% decrease in tan δ from 60 to 80 °C. It was found that the introduction of LIR increased the bound rubber content in the ESBR compound. Equilibrium swelling experiments showed that the crosslink density of the vulcanizates increased after the introduction of LIR‐403 or LIR‐50 (general purpose LIR). The change in tan δ from 60 to 80 °C was related to polymer–filler interactions. The characteristic constant of filler–ESBR matrix interaction (m) was calculated. At a given filler volume fraction, the increase in m in the presence of LIR could be well related to the decrease in tan δ from 60 to 80 °C. The influence of LIR on filler network in the ESBR compound was also investigated by strain and temperature sweeps using a rubber processing analyzer. Copyright © 2011 Society of Chemical Industry     

Study on the compatibility of BR/CR/SBS blends by using small amounts of SBS

The structures and properties of BR/CR/SBS blends were studied by using optical, electron microscopy, FTIR methods, etc. Results showed that the addition of a small amount of SBS to the thermodynamically immiscible blends BR/CR could significantly promote fine and homogeneous dispersion of the system, increase crosslink density of vulcanizates and tensile strength, and decrease loss of tan δ of the blends. IR spectra also demonstrated the stronger interaction between SBS and BR, CR. The theoretical prediction of compatibilizing activity of SBS in the BR/CR blends is in excellent agreement with experimental results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 215–220, 1999     

动态拉伸疲劳对SBR胶料网络结构和物理性能的影响

研究动态拉伸疲劳对未填充SBR胶料和白炭黑填充SBR胶料网络结构和物理性能的影响.结果表明,随着拉伸疲劳次数的增加,SBR胶料的交联密度减小,且白炭黑填充SBR胶料的交联密度大于未填充白炭黑SBR胶料;拉伸疲劳后SBR胶料产生共轭的端二烯基结构;随着拉伸疲劳次数的增加,未填充和白炭黑填充SBR胶料的物理性能先提高后下降;拉伸疲劳后SBR胶料的弹性模量降低,高弹态温度区间内损耗因子增大.     

Effect of adhesive‐coated glass fiber in natural rubber (NR), acrylonitrile rubber (NBR), and ethylene–propylene–diene rubber (EPDM) formulations. II. Effect of cyclic loading,abrasion, and accelerated aging

Treated glass fibers (RICS, 3 and 6 mm in length) were added at a concentrations of 10, 20, and 30 phr in natural rubber (NR), nitrile rubber (NBR), and ethylene–propylene–diene comonomer (EPDM) formulations, in both plain and carbon black mixes. The compounds were mixed in two‐roll mill and were evaluated for their resistance to hot‐air aging, abrasion, compression set, Goodrich heat buildup, De Mattia fatigue, and for NR mixes, adhesion in the tensile mode. The vulcanizates of the three rubbers showed resistance to hot‐air aging. Abrasion resistance was poor for NR, and it improved with carbon black addition in the presence of treated glass fiber in NBR. In carbon‐black‐added EPDM vulcanizates, the abrasion resistance and fatigue resistance were better. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1124–1135, 2004     

反式-1,4-聚异戊二烯的结晶性对丁苯橡胶/反式-1,4-聚异戊二烯共混硫化胶动态力学性能的影响

用动态力学分析仪和差示扫描量热仪研究了丁苯橡胶(SBR)/反式-1,4-聚异戊二烯(TPI)共混硫化胶的动态力学性能和结晶性能。结果表明,SBR与TPI的两相相容性良好。随着TPI用量的增加,SBR/TPI共混硫化胶的玻璃化转变温度向低温方向移动,且损耗因子峰值逐渐降低。用炭黑填充CV体系硫化SBR/TPI共混胶的损耗因子峰值低于相应的未填充胶料;而当TPI晶体熔融后,炭黑填充胶料的损耗因子要大于未填充者。不同硫化体系硫化SBR/TPI共混胶的损耗因子峰值和玻璃化转变温度从大到小的变化依次为CV体系、EV体系和DCP体系。     

Mechanical properties,chemical and aging resistance of natural rubber filled with nano‐Al2O3

Al₂O₃ nanoparticles were introduced to natural rubber (NR) to investigate its reinforcement effect on filled NR vulcanizates. The results show that Nano‐Al₂O₃/NR nanocomposites exhibit significantly improved tensile strength, elongation at break, modulus, and tearing strength. Scanning electron microscopy analyses indicate that nanoparticles dispersed in NR matrix at nanoscale and show nano‐reinforcement effect on NR vulcanizates. The aging resistances of filled NR vulcanizates improve. After aging test, tensile strength, tearing strength, and modulus improved, and elongation at break decreased. These attribute to the crosslink maturation reactions, which result in the conversion of polysulfidic linkages into disulfidic and monosulfidic ones. The acid and alkaline resistances of nano‐Al₂O₃‐filled NR vulcanizates improve compared with that of unfilled NR systems. After acid and alkaline test, tensile strength and elongation at break improve, and modulus decrease. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

炭黑填充NR和S—SBR硫化胶动态性能及屈挠破坏性的研究

探讨炭黑种类及用量对天然橡胶（NR）和溶聚丁苯橡胶（S—SBR）硫化胶的耐屈挠破坏性及动态力学性能的影响。结果表明,随着炭黑N234、N330用量的增大,NR和S—SBR两种硫化胶的耐屈挠破坏性降低;随炭黑粒径增大,炭黑用量对两种硫化胶的耐疲劳破坏性的影响逐渐减小;NR硫化胶的耐初始疲劳破坏性明显优于S—SBR硫化胶,随屈挠次数的增加,两者间的差距逐渐减小。炭黑用量增加,NR和S—SBR硫化胶的损耗因子峰值（tanδmax）减小,高于10℃时（高弹态）的tanδ值增大,S—SBR较NR具有更好的抗湿滑性和相差无几的低滚动阻力。炭黑粒径减小,NR和S—SBR硫化胶的tanδmax减小,填充30质量份炭黑时,N660增强的两种硫化胶在0℃时tanδ值较高,60℃时最低,具有较好的动态性能。     

Influence of phenolic curative on crosslink density and other related properties of dynamically cured NR/HDPE blends

Dynamically cured 60/40 NR/HDPE blends with various amounts of phenolic curative were prepared in an internal mixer at 160°C. A simple blend (i.e., the blend without curative) was also prepared using the same materials and blend proportion for comparison purposes. Mechanical, dynamic, and morphological properties; swelling resistance and crosslink density of the blends were investigated. It was found that the thermoplastic vulcanizates (TPVs) gave superior mechanical and dynamic properties than the simple blend. Furthermore, the mechanical properties in terms of elongation at break, modulus and tensile strength and elastic response in dynamic test in terms of storage modulus increased with increased loading amount of the curative. The complex viscosity also increased but the tan δ and tension set decreased with increased loading level of the curative. The crosslink density of the TPVs was estimated based on the elastic shear modulus. It was found that the crosslink density of the blends increased with increased loading levels of the curative while the degree of swelling decreased. This correlated well with the trend of mechanical and dynamic properties. SEM micrographs were used to confirm the level of mechanical and dynamic properties. It was found that the simple blend at a given blend ratio exhibited co‐continuous phase morphology. However, the TPVs showed micron scale of vulcanized rubber domains dispersed in a continuous HDPE matrix. The size of vulcanized rubber domains decreased with increasing amounts of the curative. This led to greater interfacial adhesion between the phase and hence superior mechanical and dynamic properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

促进剂种类对NR硫化胶动态性能的影响

探讨促进剂NS、CZ、DZ对天然橡胶(NR)硫化胶动态性能的影响。结果表明,由不同的促进剂得到的硫化胶的交联密度不同,硫化胶的动态性能对频率、温度和应变的依赖性也不完全相同。由NS和CZ得到的硫化胶的交联密度较高且相近,其储能模量(G′)随频率和温度的升高而增加的变化趋势几乎重合,但在较低的应变下硫化胶的G′随应变振幅的提高而降低;而由促进剂DZ得到的硫化胶,由于交联密度较低,其G′随温度的升高而略有增加。     

RPA分析硫黄用量对天然橡胶动态性能的影响

用橡胶加工分析仪(RPA)分析硫黄用量对NR动态性能的影响。结果表明:不同硫黄用量的混炼胶的动态模量随频率的升高和温度的降低而增加,损耗因子降低;应变超过28%,混炼胶的储能模量下降。不同硫黄用量的硫化胶随交联密度的提高,动态性能对频率的依赖性变小,对应变的依赖性变强;而温度越高,硫化胶的"橡胶弹性"越明显。     

Influence of rubber composition on change of crosslink density of rubber vulcanizates with EV cure system by thermal aging

Variation of the crosslink density of a rubber vulcanizate depending on the rubber composition after the thermal aging was studied with single rubber, biblend, and triblend vulcanizates of natural rubber (NR), butadiene rubber (BR), and styrene‐butadiene rubber (SBR). The efficient vulcanization (EV) system was employed to minimize the influence of free sulfur in the vulcanizate on the change of the crosslink density. Thermal aging was performed at 40, 60, and 80°C for 20 days with 5‐day intervals. The crosslink densities of the vulcanizates after the thermal aging increase. For the single rubber vulcanizates, variation of the crosslink density by the thermal aging has the order: SBR > BR > NR. For the biblend vulcanizates, variations of the crosslink densities of the NR/SBR and SBR/BR blends are larger than that of NR/BR blend. Variation of the crosslink density of the vulcanizate increases by increasing the SBR content in the vulcanizate. Variation of the crosslink density of the rubber vulcanizate depending on the rubber composition was explained by miscibility of the blends, combination reaction of the pendent groups, and mobility of the pendent group. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1378–1384, 2000     

Creep and stress relaxation of natural rubber vulcanizates. Part I. Effect of crosslink density on the rate of creep in different vulcanizing systems

The physical creep of unfilled natural rubber vulcanizates, prepared with different vulcanizing systems, has been studied. For each of the three vulcanizing systems chosen there is a strong dependence of creep rate on crosslink density, but the rates for accelerated sulfur vulcanizates are two or three times higher than those of peroxide vulcanizates of similar crosslink density. Supplementary experiments, in which the crosslink structure of sulfur vulcanizates is modified either by chemical treatment or by variations in the vulcanizing conditions, show that the nature of the crosslink itself is not a determining factor in the type of vulcanizate. Other features, such as the type and quantity of extranetwork material arising from the vulcanizing process, contribute significantly to the viscoelastic behavior of accelerated sulfur vulcanizates.     

Bis(trifluoromethylsulfonyl)imide Ionic Liquids Applied for Fine-Tuning the Cure Characteristics and Performance of Natural Rubber Composites

The goal of this work was to apply ionic liquids (ILs) with bis(trifluoromethylsulfonyl)imide anion (TFSI) for fine-tuning the cure characteristics and physico-chemical properties of elastomer composites based on a biodegradable natural rubber (NR) matrix. ILs with TFSI anion and different cations, such as alkylpyrrolidinium, alkylammonium, and alkylsulfonium cations, were applied to increase the efficiency of sulfur vulcanization and to improve the performance of NR composites. Thus, the influence of ILs on the vulcanization of NR compounds, as well as crosslink density and physical properties of NR vulcanizates, including tensile properties, thermal stability, and resistance to thermo-oxidative aging was explored. The activity of ILs seems to be strongly dependent on their cation. Pyrrolidinium and ammonium ILs effectively supported the vulcanization, reducing the optimal vulcanization time and temperature of NR compounds and increasing the crosslink density of the vulcanizates. Consequently, vulcanizates with these ILs exhibited higher tensile strength than the benchmark without IL. On the other hand, sulfonium ILs reduced the torque increment owing to the lower crosslinking degree of elastomer but significantly improved the resistance of NR composites to thermo-oxidation. Thus, TFSI ILs can be used to align the curing behavior and performance of NR composites for particular applications.     

反式-1，4-聚异戊二烯硫化胶及其共混硫化胶的研究

研究了反式－１，４－聚异戊二烯（ＴＰＩ）硫化胶及其与ＢＲ，ＳＢＲ，ＮＲ共混硫化胶的性能。结果表明，通过控制硫黄用量即交联密度，可使ＴＰＩ硫化胶具有优异的力学和动态力学性能；ＴＰＩ与ＢＲ，ＳＢＲ，ＮＲ共混，工艺性能良好，当ＴＰＩ／ＢＲ，ＴＰＩ／ＳＢＲ和ＴＰＩ／ＮＲ共混比小于５０／５０时，共混硫化胶的力学和动态力学性能优于ＢＲ，ＳＢＲ和ＮＲ硫化胶，特别是拉伸疲劳寿命大大延长，这正是高性能轮胎所需要的     

Comparative study on natural antioxidant as an aging retardant for natural rubber vulcanizates

The research aim is mainly to investigate the effectiveness of natural antioxidant (NA) obtained from oil palm leaves (Elaeis guineensis) as an aging retardant in natural rubber (NR) vulcanizates. Comparison of NA with other commercial antioxidants, trimethyl quinoline (TMQ) and butylated hydroxy toluene (BHT), is investigated. The effect of natural and commercial antioxidants on NR vulcanizates was explored before and after aging. Aging test was carried out at 70°C for three different periods, 4, 7, and 14 days to determine aging property by performing the tensile and tear tests. NA shows lower tensile properties, crosslink density, tack strength but high tear strength compared to the commercial antioxidants, BHT and TMQ. However, upon aging NR vulcanizates with NA retains its properties equivalent to that of commercial antioxidants, BHT and TMQ. Thus, NA can be used as an aging retardant for short‐term protection in application requiring moderate tensile properties and can be used as alternative source for commercial antioxidant. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

ESBR硫化胶交联结构及动态粘弹性在拉伸疲劳过程中的变化

研究炭黑和白炭黑填充乳聚丁苯橡胶硫化胶拉伸疲劳过程中交联结构和动态粘弹性的变化。结果表明,炭黑填充胶料的拉伸性能在拉伸疲劳次数低于50万次时下降明显,而白炭黑填充胶料在50万～100万次之间下降幅度较大;随着拉伸疲劳次数的增加,两种胶料的交联密度均减小;拉伸疲劳次数达到200万次时,炭黑填充胶料的tanδ峰宽明显增大,而白炭黑填充胶料在拉伸疲劳次数50万次以上tanδ峰就明显增高、增宽;炭黑填充胶料疲劳后高弹态的tanδ变化不大,而白炭黑填充胶料tanδ显著增大;白炭黑填充胶料的Payne效应较炭黑填充胶料大,且拉伸疲劳后Payne效应明显减小。     

三种微生物脱硫废乳胶及其填充天然橡胶的力学性能比较

利用三种微生物鞘氨醇单胞菌、脂环酸芽孢杆菌和酵母菌对废乳胶(WLR)进行了脱硫再生,考察了脱硫过程中微生物的生长情况以及脱硫前后WLR溶胀和交联密度的变化,并将WLR和脱硫WLR(DWLR)以不同份数填充到天然橡胶(NR)中,对比了DWLR/NR硫化胶和WLR/NR硫化胶的力学性能和交联密度。结果表明,利用鞘氨醇单胞菌脱硫的WLR溶胀值较高,交联密度较低。随着乳胶用量的增加,填充NR硫化胶的拉伸强度和交联密度逐渐降低,扯断生长率逐渐增加。DWLR/NR硫化胶的力学性能明显优于WLR/NR硫化胶,且鞘氨醇单胞菌脱硫的DWLR/NR的力学性能明显优于其它两种微生物脱硫的DWLR/NR硫化胶。     

硫化时间对绿色轮胎胎面胶交联网络结构与性能的影响

针对以溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)并用胶为主体材料的绿色轮胎胎面胶,研究在不同硫化时间下未填充白炭黑的SSBR/BR并用胶(简称未填充白炭黑体系胶料)及填充白炭黑的SSBR/BR并用胶(简称填充白炭黑体系胶料)形成的交联网络结构与性能变化。结果表明:对于未填充白炭黑体系胶料,随着硫化时间的延长,硫化胶的交联密度略有降低,硬度、定伸应力、拉伸强度和回弹值等变化不大,撕裂强度提高,拉断伸长率和耐伸张疲劳性能降低;对于填充白炭黑体系胶料,随着硫化时间的延长,硫化胶的填料网络结构化程度逐渐提高,交联密度略有增大,键能较低的多硫键减少,键能较高的单硫和双硫键增多,硫化胶的拉伸强度、回弹值、耐伸张疲劳性能和耐磨性能基本不变,生热和滚动阻力降低;未填充及填充白炭黑体系硫化胶的耐老化性能均随硫化时间的延长而逐渐提高,这表明以SSBR/BR并用胶为主体材料的胎面胶即使在高温下硫化较长时间,仍具有较好的性能。