单甲基丙烯酸锌增强丁腈及氢化丁腈橡胶复合材料的热氧老化研究

论文研究了单甲基丙烯酸锌(HZMMA)、HZMMA和炭黑混合物、炭黑增强丁腈(NBR)橡胶及氢化丁腈(HNBR)复合材料的热氧老化行为。实验结果表明:单甲基丙烯酸锌(HZMMA)对丁腈(NBR)橡胶及氢化丁腈(HNBR)均表现出良好的增强作用,丁腈橡胶复合材料的使用温度上限不能超过150℃。氢化丁腈橡胶复合材料在130℃下老化时,由于物理交联点和化学交联点的共同作用,橡胶复合材料老化1周的拉伸强度和100%定伸强度均出现极值点,随着老化时间的进一步延长,材料的力学性能逐渐下降。材料的断裂伸长率随着老化时间的延长,呈单调递减趋势。老化温度越高,HZMMA的耐热氧老化效果愈加显著。HZMMA、HZMMA和炭黑混合物、炭黑等增强的HNBR橡胶复合材料的耐热氧老化能力的顺序为HZMMAHZMMA/炭黑混合物炭黑。     

甲基丙烯酸锌/炭黑增强氢化丁腈橡胶的性能

分别以炭黑、甲基丙烯酸锌(ZDMA)及两者并用为增强剂填充氢化丁腈橡胶(HNBR),研究了HNBR混炼胶的硫化特征,考察了增强剂种类、炭黑与ZDMA并用比、温度对HNBR硫化胶物理机械性能的影响,并评价了用ZDMA/炭黑增强HNBR制得的封隔器胶筒的高温高压密封性能.结果表明,相比炭黑,ZDMA增强HNBR混炼胶的焦烧...     

单甲基丙烯酸锌改性氢化丁腈橡胶老化过程的力学性能演变及其老化动力学

以单甲基丙烯酸锌(HZMMA)为反应型增强剂,制备了HZMMA改性的氢化丁腈橡胶(HNBR)复合材料,研究了无氧、高温条件下HNBR复合材料老化过程的力学性能演变、老化行为及其老化动力学。结果表明,在180℃和200℃的老化温度下,老化前期HNBR/N 990/HZMMA、HNBR/HZMMA复合材料的拉伸强度有所增加,出现极值现象;随着老化时间的延长,材料的拉伸强度呈现逐渐下降的趋势,HNBR/HZMMA复合材料的拉伸强度下降较为缓慢。建立了HNBR/HZMMA复合材料的老化动力学模型,依此模型预测该材料在150℃下的使用寿命超过3年,HNBR/HZMMA复合材料具有优异的耐热老化性能。     

增强剂并用对氢化丁腈橡胶/乙烯丙烯酸酯橡胶性能的影响

采用炭黑、白炭黑、甲基丙烯酸锌（ZDMA）并用增强氢化丁腈橡胶（HNBR）/乙烯丙烯酸酯橡胶（AEM）共混胶,考察了白炭黑和ZDMA并用比例对共混胶硫化特性、物理机械性能、耐热老化性能及动态力学性能的影响。结果表明,当炭黑用量、白炭黑和ZDMA总量不变时,随着ZDMA用量的增加,HNBR/AEM共混胶的硫化速率加快,加工性能改善,拉伸强度和邵尔A硬度变化不大,撕裂强度、扯断伸长率、100%定伸应力和压缩永久变形增大;ZDMA的加入可改善HNBR/AEM共混胶的耐热老化性能和低温性能。     

HNBR胶料结构对复合网络结构的影响

以RPA为主要实验工具,对比了不同结构HNBR中炭黑-炭黑、炭黑-橡胶、橡胶-橡胶间的相互作用。结果表明,丙烯腈含量越高,橡胶极性越大,炭黑-橡胶的界面相互作用小,炭黑的絮凝程度大;门尼黏度越高,炭黑不易分散,但是炭黑在机械力作用下分散后,炭黑橡胶间的相互作用大,炭黑絮凝程度小;HNBR饱和度越高,炭黑网络化程度越大,饱和度对填料-橡胶相互作用影响较小。     

填料种类对风机主轴用HNBR胶料性能的影响

研究了5种填料(炭黑N330、炭黑N550、炭黑N990、白炭黑和高岭土)对风机主轴用HNBR胶料性能的影响。结果表明,随着炭黑粒径的增大,HNBR胶料硬度略微降低,拉断伸长率、热空气压缩永久变形和热老化稳定性能均增大,拉伸强度和耐磨性能均减小;白炭黑补强HNBR胶料性能与炭黑N550补强胶料性能相差不大,但撕裂强度较高;与炭黑补强HNBR胶料性能相比,高岭土和白炭黑补强胶料的拉断伸长率较高,但热空气压缩永久变形、耐油性能和耐磨性能均较差。     

热空气老化对补强氢化丁腈橡胶性能的影响

研究不同补强剂补强氢化丁腈橡胶（HNBR）在热空气老化过程中的物理性能和动态力学性能变化。结果表明：当补强剂用量均为30份时,甲基丙烯酸镁(MDMA)补强的HNBR硫化胶综合物理性能最好,甲基丙烯酸锌（ZDMA）补强的硫化胶次之,炭黑和白炭黑补强的硫化胶较差;ZDMA和MDMA补强的硫化胶耐老化性能较好;热空气老化后,不同补强剂补强的HNBR硫化胶的损耗因子峰值均有所降低,且老化时间越长,降低幅度越大;炭黑补强的HNBR硫化胶抗湿滑性能最佳,MDMA补强的硫化胶滚动阻力最低。     

碳纳米管增强氢化丁腈橡胶的性能

以碳纳米管(CNTs)为增强填料,考察了CNTs用量对氢化丁腈橡胶(HNBR)混炼胶硫化特性及硫化胶物理机械性能、高温拉伸性能和耐老化性能的影响,并研究了CNTs增强HNBR硫化胶的动态力学性能和加工性能,表征了CNTs在橡胶中的分散状况。结果表明,随着CNTs用量的增加,HNBR混炼胶的硫化效率提高,且具有优异的抗硫化返原能力,HNBR硫化胶的拉伸强度变化不大,邵尔A硬度、100%定伸应力和撕裂强度逐渐提高,扯断伸长率和回弹性减小,高温扯断伸长率减小,高温拉伸强度和100%定伸应力提高;CNTs增强HNBR硫化胶老化后的拉伸强度无明显变化,邵尔A硬度和100%定伸应力提高,扯断伸长率减小。相比未增强HNBR硫化胶,CNTs增强HNBR硫化胶的弹性模量增大,损耗因子峰值减小,加工性能得到改善;CNTs在橡胶基体中整体分散比较均匀,局部存在团聚现象。     

复合型增强剂对氢化丁腈橡胶/氟橡胶复合材料性能的影响

将炭黑（CB）、氢氧化单甲基丙烯酸锌（HZMMA）和碳纳米管（CNTs）进行复配，以改性氢化丁腈橡胶（HNBR）/氟橡胶（FKM）共混胶，制备了HNBR/FKM复合材料，研究了复合型增强剂对HNBR/FKM共混胶硫化特性、硫化胶的物理机械性能、动态力学性能和耐热氧老化性能的影响。结果表明，当加入HZMMA和CNTs后，HNBR/FKM复合材料的硫化速率加快且交联程度提高；在HZMMA和CNTs的协同作用下，HNBR/FKM复合材料的物理机械性能明显提高；与纯CB增强的相比，加入3份（质量）CNTs的HZMMA增强的HNBR/FKM复合材料热氧老化后扯断伸长率的保持率最高，与此同时硬度变化率最低；随着CNTs添加量的增加，HNBR/FKM复合材料的玻璃化转变温度向低温方向移动，同时损耗因子呈逐渐下降的趋势。     

热空气老化对补强氢化丁腈橡胶性能的影响

研究不同补强剂补强氢化丁腈橡胶(HNBR)在热空气老化过程中的物理性能和动态力学性能变化。结果表明:当补强剂用量均为30份时,甲基丙烯酸镁(MDMA)补强的HNBR硫化胶综合物理性能最好,甲基丙烯酸锌(ZDMA)补强的硫化胶次之,炭黑和白炭黑补强的硫化胶较差;ZDMA和MDMA补强的硫化胶耐老化性能较好;热空气老化后,不同补强剂补强的HNBR硫化胶的损耗因子峰值均有所降低,且老化时间越长,降低幅度越大;炭黑补强的HNBR硫化胶抗湿滑性能最佳,MDMA补强的硫化胶滚动阻力最低。     

纳米填料填充氢化丁腈橡胶的性能及压缩形态特征

研究了不同的炭黑( N 330,N 550,N 770,N 990) 、甲基丙烯酸锌及炭黑N 770 与甲基丙烯酸锌并用填充氢化丁腈橡胶( HNBR) 的性能,用橡胶加工分析仪和透射电镜分析了填料的分散性、形态变化及其与胶料压缩永久变形的关系。结果表明,随炭黑粒径增大,胶料的力学性能有所降低,Payne 效应减小( 即炭黑的分散性变好) ,压缩永久变形减小。炭黑填充胶料具有较好的耐热老化和耐油性能,相比较而言,炭黑N 770 填充胶料的综合性能最好。在填充30 份( 质量) 炭黑N 770 的HNBR 中并用适量的甲基丙烯酸锌,随其用量增加胶料的强度和扯断伸长率明显增大,压缩永久变形增大,Payne 效应变化不大。透射电镜分析结果表明,高温下长时间压缩后,炭黑粒子间的距离缩短,粒子有聚集现象,但粒子本身未发生变形。这表明炭黑填充胶料的压缩永久变形主要源于橡胶分子结构的变化、炭黑粒子的聚集及分布状态的变化。聚甲基丙烯酸锌在HNBR 中的纳米分散性优异。由于压缩后该离聚体粒子易产生滑移、变形和明显的聚集现象,对大分子网络弹性恢复的阻碍作用远高于炭黑,因而胶料的压缩永久变形比炭黑填充者要大得多。     

Mechanical properties,flame retardancy,hot‐air ageing,and hot‐oil ageing resistance of ethylene‐vinyl acetate rubber/hydrogenated nitrile‐butadiene rubber/magnesium hydroxide composites

The mechanical properties, flame retardancy, hot‐air ageing, and hot‐oil ageing resistance of ethylene‐vinyl acetate rubber (EVM)/hydrogenated nitrile‐butadiene rubber (HNBR)/magnesium hydroxide (MH) composites were studied. With increasing HNBR fraction, elongation at break and tear strength of the EVM/HNBR/MH composites increased, whereas the limited oxygen index and Shore A hardness decreased slightly. Hot‐air ageing resistance and hot‐oil ageing resistance of the composites became better with increasing HNBR fraction. Thermal gravimetric analysis results demonstrated that the presence of MH and low HNBR fraction could improve the thermal stability of the composites. Differential scanning calorimeter revealed that the glass transition temperature (T_g) of the composites shifted toward low temperatures with increasing HNBR fraction, which was also confirmed by dynamic mechanical thermal analysis. Atomic force microscope images showed MH has a small particle size and good dispersion in the composites with high HNBR fraction. The flame retardancy, extremely good hot‐oil ageing, and hot‐air ageing resistance combined with good mechanical properties performance in a wide temperature range (?30°C to 150°C) make the EVM/HNBR/MH composites ideal for cables application. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

增强氢化丁腈橡胶的结构与性能

研究了甲基丙烯酸锌(ZDMA)、SiO,和炭黑N 550分别填充氢化丁腈橡胶(HNBR)的流动性、硫化特性、物理机械性能、耐老化性能、压缩永久变形及动态力学性能,表征了填料在HNBR混炼胶及硫化胶中的形态结构.结果表明,3种填料填充的HNBR混炼胶均属非牛顿流体,其中ZDMA填充HNBR混炼胶具有较好的流动性;经过二段硫化后.3种填料填充HNBR具有较佳的物理机械性能、耐老化性能和耐压缩性能;zDMA和SiO2,对HNBR的增强效果显著,但HNBR硫化胶的压缩永久变形偏高,N 550填充HNBR硫化胶的扯断伸长率和压缩永久变形较低;SiO2填充HNBR混炼胶和硫化胶的Payne效应较ZDMA、N 550填充HNBR混炼胶和硫化胶显著;N 550、SiO2种填料在HNBR混炼胶和硫化胶中均能达到纳米尺度,ZDMA在HNBR混炼胶中呈微米尺度,而在HNBR硫化胶中呈纳米尺度.     

HNBR4种补强填充体系的研究

分别研究了炭黑N330,炭黑N550,炭黑N660和炭黑N774对氢化丁腈橡胶（HNBR）硫化特性和力学性能的影响,并考察了4种炭黑在HNBR中的分散度和Payne效应。结果表明,炭黑N550的胶料焦烧时间和正硫化时间均最长,分散度最好。随着炭黑粒径的逐渐增大,硫化胶拉伸强度、定伸应力和硬度均逐渐减小,拉断伸长率却逐渐增大。4种炭黑胶料的Payne效应强弱顺序为炭黑N330〉炭黑N550〉炭黑N660〉炭黑N774。     

Structure,morphology, and properties of HNBR filled with N550, SiO2, ZDMA,and two of three kinds of fillers

The vulcanization properties, mechanical properties of hydrogenated nitrile rubber (HNBR) filled with carbon black (N550), zinc dimethacrylate (ZDMA), SiO₂ independently and two of three kinds of fillers together were investigated, respectively. The filler‐dispersion was characterized by the transmission electron microscopy (TEM) and dynamic mechanical properties. The results showed that HNBR composite filled with SiO₂ or ZDMA displayed high tensile strength, elongation at break and compression set. The HNBR composite filled with N550 displayed low compression set, tensile strength and elongation at break. The dispersion of SiO₂ in HNBR compound was better than that in HNBR vulcanizates because of SiO₂ particles self‐aggregation in vulcanizing processing. ZDMA particles with micron rod‐like and silky shape in HNBR compounds changed into near‐spherical poly‐ZDMA particles with nano size in HNBR vulcanizates by in situ polymerization reaction. The N550 particles morphology exhibited no much change between HNBR compounds and vulcanizates. N550/ZDMA have the most effective reinforcement to HNBR and the appropriate amount of ZDMA is about 25% of total filler amount by weights. The theory prediction for Payne effect (dispersion of the filler) shown by the dynamic properties is identical with actual state observed by TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on wear,cutting and chipping behaviors of hydrogenated nitrile butadiene rubber reinforced by carbon black and in‐situ prepared zinc dimethacrylate

In this study, the wear (Akron and DIN) and the cutting and chipping (C&C) behaviors of hydrogenated nitrile butadiene rubber (HNBR) reinforced by carbon black (N115) and in‐situ prepared zinc dimethacrylate (ZDMA) were investigated. It was validated that ZDMA was more effective than N115 to enhance the wear and C&C resistance of HNBR composites. The Akron wear resistance of the HNBR/N115 composites increased with the content of ZDMA, and the Schallamach ridges observed on the abraded surfaces became less and less clear. With increasing content of ZDMA, the failure mode of the DIN abraded surface underwent the transition from craters to Schallamach ridges, and finally to scratches. The HNBR/N115 composite reinforced by 10 phr ZDMA had the best DIN wear resistance when Schallamach ridges were the dominant failure mode. The use of 30 phr ZDMA can dramatically enhance the C&C resistance of the HNBR/N115 composites. The C&C resistance was suggested to be related to both the variation of the morphology of the C&C ridges and the direction of crack propagation as a function of the content of ZDMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

硫化时间对HNBR/ZMMA复合材料形态结构及性能的影响

采用炭黑和单甲基丙烯酸锌(ZMMA)并用作补强剂制备了氢化丁腈橡胶(HNBR)复合材料,使用X射线衍射法和透射电子显微镜法分析了ZMMA在HNBR硫化过程中的结构和形态变化,并研究了一段硫化时间对复合材料力学性能的影响。结果表明,在硫化过程中,ZMMA发生了复杂的化学反应;随着一段硫化时间的延长,氢化丁腈橡胶复合材料的拉伸强度和100%定伸应力变化都不大,而撕裂强度先增大后减小,拉断伸长率减小。X射线衍射结果表明,ZMMA由结晶态转变为非结晶态。透射电子显微镜分析结果表明,在硫化开始阶段,ZMMA聚合反应已经完成,有大量的纳米级粒子分布在橡胶基体中。     

橡胶/炭黑复合材料的压敏性和时间响应性

以炭黑（Ｎ３３０,Ｎ５５０）为导电相,橡胶（ＮＲ,ＥＰＤＭ,ＮＢＲ）为基质制备压敏导电复合材料。研究了复合材料的压敏性和不同压力条件下复合材料的时间响应性,讨论了对复合材料性能和压敏性的影响。     

Effects of partial replacement of commercial fillers by recycled poly(ethylene terephthalate) powder on the properties of natural rubber composites

Commercial fillers, including carbon black (N550), halloysite nanotubes (HNTs), and precipitated silica, were replaced by recycled poly(ethylene terephthalate) powder (R‐PET) in natural rubber (NR) composites. Five different compositions of NR/N550/R‐PET, NR/HNTs/R‐PET, and NR/silica/R‐PET compounds, i.e., 100/20/0, 100/15/5, 100/10/10, 100/5/15, and 100/0/20 parts per hundred rubber (phr), were prepared on a two‐roll mill. The curing behavior, tensile properties, and morphological characteristics of the natural rubber composites were investigated. The results indicated that the replacement of carbon black, HNTs, and silica by R‐PET decreased the tensile strength and tensile modulus, such that NR/silica/R‐PET composites showed the lowest effect, followed by NR/HNTs/R‐PET and NR/N550/R‐PET composites. The negative effect on these properties can be explained by the decrease of crosslink density. The curing results revealed that with the replacement of carbon black by R‐PET, the scorch time and cure time decreased, but that the NR/HNTs/R‐PET and NR/silica/R‐PET composites exhibited the opposite trend. Scanning electron microscopy investigation of tensile fracture surfaces confirmed that the co‐incorporation of N550/R‐PET improved the dispersion of R‐PET and enhanced the interaction between the fillers and NR matrix more than R‐PET and silica/R‐PET hybrid fillers. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

Filler–rubber interactions in α_cellulose‐filled styrene butadiene rubber composites

In this study, the interactions between rubber and fillers in α_cellulose‐filled styrene butadiene rubber (SBR) composites were investigated. The results obtained from the tensile and tear strength, abrasion resistance, and hardness indicate that addition of 5‐phr α_cellulose into compound not only does not affect rubber–carbon black bond but improves the mentioned physicomechanical properties. In this study, the type of carbon black was changed from N 330 to N 550. The main purpose of this investigation was to observe the possible changes in physicomechanical properties due to this change. Obtained results show that overall observation of the trends of results do not change with type of carbon black. It can be concluded that the presence of α_cellulose does not have significant influence on the performance of carbon black in the compounds used. POLYM. COMPOS., 28:748–754, 2007. © 2007 Society of Plastics Engineers