New ways to improve the damping properties in high‐performance thermoplastic vulcanizates

The incorporation of viscoelastic materials represents an effective strategy to reduce the vibratory level of structural components. Thermoplastic vulcanizates (TPVs) are a special type of viscoelastic material that combines the elastomeric properties of rubbers with the easy processing of thermoplastics. In the present work, we propose innovative ways to improve the damping properties of high‐performance TPVs by using rubbers with carboxylic functionalities. For that, TPVs from physical blends of carboxylated hydrogenated acrylonitrile butadiene rubber (XHNBR) and polyamide 6 (PA6) were prepared. The chain dynamics of different mixed crosslink systems containing peroxide, metal oxides and hindered phenolic antioxidants were investigated in order to find the most suitable strategy to design a high‐performance TPV system with upgraded damping properties. The results indicate that the damping performance of the TPV system can be tailored by controlling the type and magnitude of the bonding interactions between the mixed crosslink system and the XHNBR rubber phase. Therefore, this study demonstrates the potential of TPV systems containing carboxylic rubbers as high‐performance damping materials. © 2020 Society of Chemical Industry     

三元乙丙橡胶/聚丙烯热塑性硫化胶细观力学数值模拟分析Ⅱ.三元乙丙橡胶结构对细观力学性能的影响

通过建立三元乙丙橡胶(EPDM)/聚丙烯(PP)热塑性硫化胶(TPV)的细观尺寸多颗粒随机分布的RVE模型,研究了分散相EPDM粒子形状及大小、间距对TPV应力和弹性模量的影响。结果表明,在分散相EPDM体积分数不变的条件下,EPDM粒子形状越接近圆形,TPV的应力值越低,EPDM粒径的减小可提高TPV的弹性模量;EPDM粒子间距增大,TPV的应力值下降,TPV中EPDM体积分数越高,其应力值受EPDM粒子间距的影响越显著。     

增容高抗冲聚苯乙烯/高乙烯基聚丁二烯橡胶热塑性硫化胶的Mullins效应及其可逆性

采用动态硫化法制备了苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)增容高抗冲聚苯乙烯(HIPS)/高乙烯基聚丁二烯橡胶(HVPBR)热塑性硫化胶(TPV),考察了SBS用量对TPV物理机械性能的影响,表征了TPV的微观形貌,并研究了TPV的Mullins效应及其可逆性。结果表明,SBS可显著改善HIPS/HVPBR体系的相容性,其用量为12份时,TPV的物理机械性能较好;SBS增容TPV的断面平整、结构致密,界面相互作用明显增强;SBS增容TPV在循环单轴拉伸过程中出现明显的Mullins效应,提高应变速率时,TPV的最大应力和内耗呈增大趋势,瞬时残余形变则减小;当拉伸比相同时,TPV经第1次拉伸热处理后,第2次单轴拉伸中TPV的最大应力和内耗均增大,瞬时残余形变则减小。     

混炼型聚氨酯橡胶/聚十二内酰胺热塑性硫化胶动态硫化历程与性能

采用动态硫化方法制备了混炼型聚氨酯橡胶（MPU）/聚十二内酰胺（PA 12）热塑性硫化胶（TPV）,通过控制动态硫化时间探究了该TPV的动态硫化历程,同时研究了不同动态硫化阶段共混物的物理机械性能和动态力学性能。结果表明,随着动态硫化时间的延长,MPU/PA 12 TPV逐步完成相转变,在温度和剪切作用下,MPU相由连续相转变为分散相,而PA 12则由分散相转变为连续相;随着动态硫化时间的延长,MPU/PA 12共混物的储能模量升高,损耗模量降低,损耗因子减小。此外,随着动态硫化时间的延长,MPU/PA 12共混物的综合力学性能提高。     

Swelling behaviour of rubber vulcanizates: 2. Effects of tensile strain on swelling

The effects of tensile strain on the swelling behaviour of acrylonitrile-butadiene copolymer rubber vulcanizates were studied by real-time pulsed nuclear magnetic resonance (n.m.r.) measurements and volume swelling measurements at equilibrium. It was shown that tensile strain causes an increase of the initial swelling rate evaluated by n.m.r. measurements and of the swelling ratio of the rubber matrix at equilibrium. This behaviour was discussed qualitatively in terms of the molecular mobility of the network chains on the basis of Treloar's theory for swelling under deformation. It was suggested that the presence of reinforcing fillers in the rubber matrix exerts two noticeable effects on swelling under deformation: (1) a transient effect through some oriented structure induced by stretching, which restricts the increase of the swelling rate; (2) a strain amplification effect, which causes the increase of the average local strain in the rubber matrix and enhances the swelling ratio more remarkably proportional to the filler concentration as compared with that of the unfilled system.     

Pressure Response through Valve for Continuous Oil-Water Separation Based on a Flexible Superhydrophobic/Superoleophilic Thermoplastic Vulcanizate Film

Highly efficient oil-water separation shows urgent demand in industrial applications, especially in oil-spill accidents and organic solvent separation. Herein, a novel method is proposed for continuous oil-water separation by a pressure response through valve, which is loaded in a flexible convolute superhydrophobic/superoleophilic film based on low-density polyethylene (LDPE)/ethylene-propylene-diene terpolymer (EPDM) thermoplastic vulcanizate (TPV). The superhydrophobic/superoleophilic LDPE/EPDM TPV film (with contact angles of oil and water are 0° and 161.9°± 2.2°) is prepared only via a molding process where sandpaper is used as the template. The superhydrophobic/superoleophilic property of the TPV film shows robust performance in the activity endurance test. More importantly, the flexible LDPE/EPDM TPV film can be easily rolled up and loaded in through valve, which is the pressure response channel in oil-water separation. The typical separation pressure of oil and water is 3.01 and 6.17 kPa, which means the oil can be completely separated from the oil-water mixture under proper pressure in the pressure response through valve.     

The tensile properties of strain‐crystallizing vulcanizates. III. The superiority of conventional over peroxide vulcanizates in terms of network microstructure

It is proposed that, when vulcanization is performed using peroxides, crosslinking leads to a simple network, whereas in conventional vulcanization crosslinking a partially interpenetrating polymer network (PIPN) is formed. Two unfilled polyisoprene networks of similar crosslink density, produced with dicumyl peroxide and 2‐bisbenzothiazole‐2,2′‐disulfide/sulfur formulations, were compared with respect to the effect of strain rate on their stress–strain and hysteresis curves at room and elevated temperatures. At high elongations, the stress–strain curves for peroxide vulcanizates show a steeper upturn than for conventional vulcanizates, but have lower tensile strength and elongation at break. On increasing the extension rate, stress–strain curves for peroxide vulcanizates rise less steeply, while conventional vulcanizates rise more steeply. For both vulcanizates the hysteresis ratio decreases on increasing the rate at which samples are extended and retracted. The effect on conventional vulcanizates is less than on peroxide vulcanizates. It is suggested that chains in peroxide networks disengage increasingly rapidly at higher strains, allowing increased strain‐induced crystallization. Rapid strain‐induced crystallization leads to low ultimate tensile strength (UTS). In more complex PIPNs, the disengagement and alignment of chains are retarded. The increased nonuniform extension of chains promotes early strain‐induced crystallization at low extensions, but overall it reduces the rate of crystallization, which occurs over a wider range of strains. This improves UTS and elongation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 876–884, 2006     

增塑剂对丁腈橡胶/聚丙烯热塑性硫化橡胶性能的影响

研究了邻苯二甲酸二辛酯(DOP)、偏苯三酸三(2-乙基己酯)(TOTM)、聚酯和邻苯二甲酸烷基.苄酯4种增塑剂对丁腈橡胶(NBR)聚/丙烯(PP)热塑性硫化胶(TPV)邵尔A硬度、耐油性能和流变性能的影响,并用透射电镜分析了4种增塑剂对NBR/PP TPV相态结构的影响。结果表明,TOTM的增塑效果最好,可制备出低硬度、高耐油和流动性好的NBR/PP TPV,并且分散相的粒径小、大小均匀;随着TOTM用量的增加,NBR/PP TPV的邵尔A硬度降低,流动性提高,但TOTM用量不宜超过50份。     

Influence of 1,2‐unit contents on retraction behaviors of SBR vulcanizates

Styrene‐butadiene rubber (SBR) has four different repeat units of styrene, cis‐1,4‐, trans‐1,4‐, and 1,2‐uints. Influence of the 1,2‐unit content on the retraction behaviors of SBR vulcanizates reinforced with silica or carbon black was studied. The retraction behaviors were compared in terms of the filler systems and the microstructures of SBR. The silica‐filled vulcanizates containing a coupling agent showed nearly the same retraction behaviors as the carbon black‐filled ones, but the silica‐filled vulcanizates without a coupling agent were recovered slower than the carbon black‐filled ones. The vulcanizates with lower 1,2‐unit content started to recover at lower temperature than that with higher 1,2‐unit content. The recovery rate increased with increase of the 1,2‐unit content of SBR. The experimental results were explained with the polymer‐filler interactions, filler dispersion, glass transition temperature, and modulus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4707–4711, 2006