加工工艺对ZDMA/N550/HNBR复合材料结构与性能影响

研究了二段硫化、剪切作用时间以及预混工艺对甲基丙烯酸锌（ZDMA）及其与炭黑（N550）并用填充氢化丁腈橡胶（HNBR）硫化胶的物机性能及压缩永久变形性能影响,并用TEM表征了不同工艺条件下填料在胶料中的分散状态。研究结果表明：采用二段硫化和剪切分散工艺能明显改善填料在胶料中的分散,提高硫化胶的综合性能;ZDMA/过氧化二异丙苯（DCP）预混工艺也能显著使反应性填充补强剂ZDMA形成优异的纳米尺度的分散状态。     

ZDMA/白炭黑填充HNBR的结构与性能

以甲基丙烯酸锌(ZDMA)/白炭黑填充氢化丁腈橡胶(HNBR),研究ZDMA/白炭黑并用比、硫化剂DCP用量及硫化时间对HNBR硫化胶结构和性能的影响。结果表明,在填料总量不变的前提下,随着白炭黑用量的增大,ZDMA/白炭黑填充HNBR硫化胶拉伸强度和压缩永久变形先减小后增大,填料分散性下降;随着硫化剂DCP用量的增大,ZDMA/白炭黑填充HNBR硫化胶物理性能和动态性能提高,填料分散性变好。当ZDMA/白炭黑并用比为10/30、硫化剂DCP用量为5～6份、一段硫化条件为160℃×45min、二段硫化条件为150℃×(9～12)h时,ZDMA/白炭黑填充HNBR硫化胶综合性能较好。     

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...     

不同炭黑种类对丁腈橡胶性能的影响

研究炭黑种类对丁腈橡胶物理机械性能、动态力学性能、耐热性能的影响。研究结果表明:炭黑粒径越高,混炼胶口型膨胀率越大,炭黑N550在混炼胶中的分散性较好;炭黑粒径越小,胶料的流动性降低,拉伸强度和硬度越大,补强效果越好,同时压缩生热量越大,压缩永久变形越大;填充N330和N774硫化胶耐热老化性较差。     

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。     

浅色高性能氢化丁腈橡胶密封材料的研制

对比研究炭黑N550和浅色填料(碱性白炭黑AS-70、沉淀法白炭黑255、硅酸铝钾GW-9、硅酸铝钾BS-280和矽丽粉VM-56)填充氢化丁腈橡胶(HNBR)胶料的性能,并制备浅色高性能HNBR密封材料。结果表明:与炭黑N550填充胶料相比,沉淀法白炭黑255填充胶料的门尼粘度明显增大,t10和t90缩短;碱性白炭黑AS-70填充胶料的门尼粘度相差不大,FL和Fmax略增大;其他3种浅色填料填充胶料的门尼粘度、FL和Fmax较小,三者水平相当;浅色填料填充硫化胶的耐热老化性能较好;碱性白炭黑AS-70填充硫化胶的压缩永久变形最小;采用碱性白炭黑AS-70制备的浅色高性能HNBR密封材料综合性能优异且各项性能满足相关标准要求。     

氢化丁腈橡胶配合体系研究

研究了硫化剂用量、不同种类的填料、增塑剂和防老剂对氢化丁腈（HNBR）胶料性能的影响。结果表明：当DCP/TAIC的比例为4:3时,硫化胶的综合力学性能最佳。N774补强HNBR,可以兼顾低的压缩永久变形和良好的力学性能。使用防老剂ZMMBI/防445的HNBR硫化胶压缩永久变形小,耐老化性能优良。增塑剂TP-95对降低HNBR硫化胶Tg的效果最为显著。     

环保丁腈橡胶与传统丁腈橡胶的性能对比

对环保型与传统丁腈橡胶(NBR)进行了微观结构、相对分子量及其分布、硫化胶的物理机械性能、混炼胶硫化特性、压缩永久变形、耐老化性能以及制品的性能进行了对比研究。结果表明,环保型NBR 3305 E、2907 E与传统NBR 3305、2907的相对分子质量及其分布、微观结构组成略有不同,混炼胶硫化特性、物理机械性能、压缩永久变形以及耐老化等性能相当。使用NBR 3305与NBR 3305 E制备密封制品时物理机械性能和预期使用寿命基本相同,使用NBR 2907 E制备发泡橡胶制品的密度比NBR 2907制品的略低。     

不同结构氢化丁腈橡胶的性能研究

从氢化度和丙烯腈含量角度对不同结构氢化丁腈橡胶(HNBR)的性能进行研究。结果表明:在HNBR丙烯腈含量相同的条件下,随着HNBR氢化度的升高,填料的分散性降低,胶料的混炼升温速率减慢,流动性降低,硫化速率变慢,硫化胶的定伸应力下降,拉断伸长率提高,压缩永久变形增大,高氢化度HNBR硫化胶可采用二段硫化来提升抗压缩永久变形性能;在HNBR氢化度相同的条件下,随着HNBR丙烯腈含量的增大,填料的分散性提高,胶料的混炼能耗和排胶温度显著降低,流动性提高,焦烧时间延长,硫化胶的定伸应力和拉伸强度提高,拉断伸长率降低,耐油性能显著提高,压缩永久变形增大。     

ZSC/氢化丁腈橡胶并用的性能研究

采用热重分析方法计算HNBR和甲基丙烯酸锌(ZDMA)聚合物合金(ZSC)中ZDMA的质量分数,研究ZSC/HNBR胶料的物理性能、耐热老化性能和动态力学性能,并与ZDMA/HNBR胶料进行对比。结果表明,ZSC中ZDMA质量分数约为0.5;在ZDMA用量相同的条件下,ZDMA/HNBR胶料的物理性能略优于ZSC/HNBR胶料,且适量的ZSC能够减小ZSC/HNBR胶料的压缩永久变形,两组胶料耐热老化性能均较优;当ZDMA用量为30份时,两组胶料的综合性能较好。动态力学性能分析结果表明,ZSC在混炼胶中的分散效果优于ZDMA,在硫化胶中则相反;当ZDMA用量大于30份时,ZDMA在ZSC/HNBR和ZDMA/HNBR胶料中的分散效果均较差。     

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     

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。     

生物质硅炭增强改性氢化丁腈橡胶的性能及老化规律

以生物质硅炭(Si/CB)取代部分N550炭黑为补强剂、HNBR为基体制备了生物质硅炭改性的HNBR复合材料。研究了硅炭对HNBR的补强行为,高温真空介质中橡胶的热老化行为及主链老化结构的演变。与传统炭黑的增强效果相比,生物质硅炭增强的HNBR表现出更好的韧性、撕裂强度、较低的永久变形及高温力学性能。160℃下老化20 d,材料的拉伸强度保持率大于100%,生物质硅炭表现出较好的耐老化能力。链接-CN官能团的α-碳原子高温下易均裂氢原子生成自由基,连续加氢还原使-C■N转化为-C■NH,直至形成化学交联结构,导致橡胶的玻璃化转变温度升高。氢化丁腈的CN含量越低,耐老化能力越突出。依据分子主链老化的结构演变信息,提出了HNBR的可能老化机理。     

Aspects of producing hydrogenated nitrile butadiene rubber (HNBR) nanocomposites by melt compounding processing

Industry is constantly demanding for materials with differential properties that explores nanoscale fillers functionality. Unfortunately, most of the papers present processing methods that are hard to scale up. Effects in addition different amounts of multiwall carbon nanotubes (MWCNT) and few-layer graphene (FLG) on cure behaviour, viscoelastic, mechanical and electrical properties of a hydrogenated nitrile butadiene rubber (HNBR) are investigated and compared with those composites having carbon black (CB) as filler. Looking for scale up the produced nanocomposites, rubber composites were produced in a closed mixing chamber by melt mixing with unmodified fillers. Addition of nanotubes reduces curing time. Microstructural analyses indicate that FLG cannot be easily dispersed by this methodology. Significant improvement in mechanical properties is observed with MWCNT addition, with 940% modulus increment regarding to the pure polymer and also, in lower intensity, in HNBR/FLG composites. Moreover, HNBR/MWCNT composites presented a sharp reduction in electrical resistivity at low loading level.     

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 and reinforcement mechanisms of hydrogenated acrylonitrile butadiene rubber composites containing fibrillar silicate nanofibers and short aramid microfibers

Short‐fiber‐reinforced rubber composites (SFRCs) with hydrogenated acrylonitrile butadiene rubber (HNBR) as the matrix and fibrillar silicate (FS) nanofibers and short aramid microfibers (DCAFs) as the fillers were developed, and their tensile properties, compression moduli, and mechanical anisotropies were investigated. The results indicated that the properties of the HNBR/DCAF/FS composites were determined by the loadings of the FS nanofibers and DCAF microfibers. A small amount of the microfibers combined with an appropriate amount of the nanofibers resulted in synergetic reinforcement and imparted to the SFRCs significantly improved mechanical properties without substantially compromising the rubbery characteristics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of a small amount of sulfur on the physical and mechanical properties of peroxide‐cured fully saturated HNBR compounds

Sulfur can be used as crosslink coagent in unsaturated elastomer. In this work, a fully saturated HNBR with 39 wt % nitrile content was selected to investigate the effect of a small amount of sulfur acting as crosslink coagent on the physical and mechanical properties of peroxide‐cured vulcanizates. First, selective cleavage of polysulfide (? Sx? ) and monosulfide(? S? ) bond by combined thiol‐piperidine treatment were performed and the existence of poly/monosulfide bond in sulfur‐contained HNBR compounds was verified. Then, no‐filler HNBR compounds with various content of sulfur were investigated to detect the influence of sulfur on the crosslink density and cure kinetics. The MDR results showed that the crosslink density of HNBR compounds reduced only when the amount of sulfur is 0.25 phr and above. Besides, the curing rate of no‐filler HNBR compounds increased with the increasing of the amount of sulfur and reached a maximum at a dosage of 0.25 phr sulfur. Finally, physical and mechanical properties of fully formulated compounds were evaluated and it was found that the addition of small amounts of sulfur in fully saturated HNBR compounds could improve the dynamic properties of peroxide‐cured HNBR compounds remarkably but at a cost of slightly higher compression set values and a small loss in heat aging resistance. In a conclusion, small amount of sulfur can impart the peroxide vulcanizates some “sulfide properties” like dynamic property, tensile strength, but at the same time, due to the introduction of sulfur, some “peroxide vulcanizates property” like heat‐resistance property, hot air resistance were weakened slightly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41612.     

氢化丁腈橡胶／超细全硫化粉末丁腈橡胶共混物的结构与性能研究

采用熔融共混工艺制备了氢化丁腈橡胶（HNBR）／超细全硫化粉末丁腈橡胶（UFPNBR）共混物,研究了共混物相态结构、动态力学性能、力学性能及老化性能,并与HNBR／NBR共混物作了对比。透射电镜观察表明：在HNBR／UFPNBR体系中,HNBR容易形成连续相,UFPNBR为分散相;在HNBR／NBR体系中容易形成双连续相结构。DMA动态力学性能分析表明：2种共混物都只有一个tanδ峰,且相容性较好。HNBR／UFPNBR共混物在玻璃化转变区的tanδ峰值逐渐降低,而HNBR／NBR体系的tanδ峰值先减小后增大。加入适量的UFPNBR能降低HNBR／UFPNBR共混物的压缩永久变形;与常规共混胶相比,HNBR／UFPNBR具有低脆性温度和良好的耐老化性能,但力学性能略低。     

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