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。     

原位聚合ZDMA与炭黑并用补强POE的研究

研究了原位聚合甲基丙烯酸锌(ZDMA)与炭黑并用以及体系的填充量、ZDMA理论生成量、ZnO/MMA摩尔比对聚烯烃弹性体(POE)硫化胶性能的影响.结果表明,加入炭黑改善了胶料的拉伸永久变形,当ZDMA与炭黑的用量为50～60份时,填料分散好,对胶料的补强效果显著.ZDMA理论用量为30～40份、ZnO/MMA摩尔比为0.75左右时,胶料的综合力学性能最好.     

原位生成甲基丙烯酸锌对填充天然橡胶力学性能的影响

考察了氧化锌用量和碳酸钙用量对原位生成甲基丙烯酸锌增强天然橡胶的力学性能的影响,以及甲基丙烯酸锌对白炭黑填充天然橡胶和胶粉填充天然橡胶力学性能的影响。研究表明,原位生成甲基丙烯酸钙的增强作用比甲基丙烯酸锌差,与前者的交联反应热很小有关;甲基丙烯酸锌能够大大加快白炭黑填充天然橡胶的硫化速度,对胶粉填充天然橡胶具有明显的增强作用。     

ZDMA补强EVA/CPE/NBR共混型热塑性硫化胶的Payne和Mullins效应研究

采用动态硫化法制备乙烯-醋酸乙烯酯共聚物(EVA)/氯化聚乙烯(CPE)/丁腈橡胶(NBR)共混型热塑性硫化胶(TPV),研究TPV的应力-应变行为、微观相结构、Payne和Mullins效应。结果表明:甲基丙烯酸锌(ZDMA)补强TPV的储能模量随应变的增大而显著下降,表现出典型的Payne效应;TPV存在明显的Mullins效应,相同拉伸比下,与EVA/CPE/NBR TPV相比,ZDMA补强TPV的最大应力、瞬时残余应变、内耗、损耗因子和软化因子均有所提高。     

Prediction of heat build-up behaviour under high load by use of conventional viscoelastic results in carbon black filled hydrogenated nitrile rubber

Abstract

Viscoelastic and heat build-up (HBU) properties of hydrogenated acrylonitrile butadiene rubber filled with various loadings and characteristics of carbon black were determined using RPA2000 and Gabometer 4000 flexometer equipped with high load cell respectively. A correlation of the viscoelastic results measured routinely with the HBU results is drawn. Reinforcement mechanism is proposed as an interplay of hydrodynamic effect, filler transient network, molecular slippage and cross-link density. In addition, the HBU significantly increases with increasing carbon black loading and/or surface area, which is probably the result of hysteretic process. As a prediction of HBU under high load, the loss modulus is superior to the damping factor.     

The Effect of Carbon Black/Multiwall Carbon Nanotube Hybrid Fillers on the Properties of Natural Rubber Nanocomposites

The properties of hybrid multiwall carbon nanotube (MWCNT) and carbon black (CB) in natural rubber nanocomposites were studied. The results show that the scorch and cure time decreased as the MWCNT loading increased in CB/MWCNT hybrid loading ratio but for the maximum torque, the result shown otherwise. As the MWCNT loading increased in CB/MWCNT hybrid loading ratio, the tensile strength, elongation at break and fatigue life are decrease, however the tensile modulus and rubber filler-interaction (Q_f/Q_g) value increased. The SEM results show a dispersion of CB and MWCNT in natural rubber matrix. Furthermore, the thermal stability for the hybrid nanocomposites is enhanced.     

原位生成ZDMA补强HNBR性能的研究

对氧化锌和甲基丙烯酸（MAA）发生中和反应原位生成甲基丙烯酸锌（ZDMA）补强氢化丁腈橡胶（HNBR）进行研究。结果表明，原位生成ZDMA对HNBR具有良好的补强作用；硫化剂DCP用量和ZDMA生成量增大，硫化胶的总交联密度和离子键交联密度均增大；氧化锌／MAA摩尔比为0．8、ZDMA理论生成量为30份、硫化荆DCP用量为4份时，硫化胶的综合物理性能较好。     

原位合成甲基丙烯酸锂增强丁腈橡胶的性能和结构

讨论了在过氧化二异丙苯(DCP)的作用下,氢氧化锂和甲基丙烯酸在混炼过程中原位生成的甲基丙烯酸锂(LiMA)增强丁腈橡胶(NBR)的性能和结构。结果表明,原位生成LiMA对NBR有较明显的增强作用,随着LiMA生成量的增加,NBR硫化胶的邵尔A硬度、100%定伸应力和撕裂强度逐渐增加,拉伸强度和扯断伸长率呈现先上升后下降的趋势;在DCP的作用下,LiMA可显著提高NBR的硫化速率及硫化程度,硫化速率与LiMA生成量呈线性增加关系;随着LiMA生成量的增加,NBR硫化胶的总相对交联密度、离子键相对交联密度增加,而共价键相对交联密度有所下降,说明LiMA改变了NBR的结构。     

OMMT/ZDMA协同增强HNBR复合材料的性能研究

以离子聚合物(ZDMA)、有机蒙脱土作补强剂,采用机械混炼法制备了氢化丁腈橡胶/有机蒙脱土纳米复合材料,研究了OMMT/ZDMA协同作用对氢化丁腈橡胶纳米复合材料性能的影响,并使用扫描电镜(SEM)、热失重分析(TG)、差示扫描量热分析(DSC)及力学性能测试等方法分析了复合材料的结构和性能。结果表明,有机蒙脱土用量较少可达到纳米级分散,材料力学性能得到相应改善;用量较大时,OMMT团聚几率增大,可能形成应力集中点,影响复合材料力学性能。热性能分析表明,加入有机蒙脱土在一定程度上提高了HNBR的热稳定性。     

乳液压力附聚法制备炭黑/NR胶料的研究

采用乳液压力附聚法制备炭黑/NR胶料,并对其微观结构、热稳定性能、硫化特性和物理性能进行研究.结果表明:高压均质机处理后的炭黑分散体分散性好,沉降量小,贮存稳定;压力附聚处理后炭黑/NR混合乳液具有稳定分散性;与纯NR和压力附聚前炭黑/NR母胶相比,压力附聚后炭黑/NR胶料门尼粘度较大、炭黑分散性较好、热稳定性提高;与传统机械混炼法制备的炭黑/NR硫化胶相比,压力附聚后炭黑/NR硫化胶定伸应力、拉伸强度和撕裂强度增大.     

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。     

Prepared hydrogenated nitrile rubber (HNBR)/organo–montmorillonite nanocomposites by the melt intercalation method

The polymer, Hydrogenated Nitrile‐Butadiene Rubber (HNBR) was melt compounded with organophilic montmorillonite (OMMT). The dispersion of the OMMT in the HNBR matrix was characterized by X‐ray diffraction (XRD), which indicated that at the temperature of 100°C, the organoclay belong to the exfoliated and interlayer structure. The effect of sulfur on the dispersion of OMMT in the polymer matrix was also studied. The vulcanization changed the dispersion of OMMT in polymer matrix greatly and the basal spacing of clay layers is decreased after vulcanization. The mechanical properties, Akron abrasion and the crude oil medium aging‐resistant of HNBR nanocomposites were examined as a function of the OMMT content in the matrix of polymer. The results of the test show remarkable improvement in tensile strength, tear strength, aging‐resistant, and hardness of HNBR nanocomposites than that of unfilled HNBR. It is obvious that the 10 phr of OMMT filled nanocomposites have the best mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

丁腈橡胶/黑液-蒙脱土复合材料压缩永久变形的研究

以造纸黑液和蒙脱土为原料制备黑液-蒙脱土复合物(BL-MMT),并将其作为填料,通过机械混炼制备了丁腈橡胶/黑液-蒙脱土(NBR/BL-MMT)复合材料。考察了BL-MMT用量、硫化体系、填充体系对NBR/BL-MMT复合材料压缩永久变形的影响。实验结果表明:当BL-MMT的用量为50 phr时,使用过氧化物硫化体系的硫化胶压缩永久变形优于硫磺硫化体系,且随着过氧化物含量的增加,硫化胶的压缩永久变形减小。当过氧化物为1.5 phr时,综合性能较好。无机填料填充NBR/BL-MMT(100/50)复合物,将导致硫化胶的压缩永久变形增大。在添加相同量的无机填料时,填充白炭黑的硫化胶压缩永久变形最大,其次为轻质碳酸钙、重质碳酸钙。     

甲基丙烯酸锌补强氢化丁腈橡胶耐老化性能的研究

试验研究甲基丙烯酸锌（ZDMA）补强氢化丁腈橡胶（HNBR）热空气老化前后的物理性能和动态力学性能。结果表明:随着ZDMA用量的增大,HNBR胶料的t₁₀和t₉₀缩短,M_L和M_H增大,硫化胶的邵尔A型硬度和100%定伸应力增大,拉伸强度和拉断伸长率先增大后减小;经热空气老化后,随着老化时间的延长,HNBR硫化胶的邵尔A型硬度和100%定伸应力增大,拉伸强度和拉断伸长率减小;延长老化时间或增大ZDMA用量,HNBR硫化胶的储能模量和损耗模量增大,损耗因子峰值逐渐减小,损耗模量峰值和玻璃化温度逐渐向高温方向移动。     

Effects of γ-Radiation Treatment on the Reinforcing Properties of Carbon Black in Rubber Compound

Abstract

Commercial graphite flakes and carbon black grade N234 have been subjected to γ-radiation treatment to a total dose of IMGy. The resulting radiation-damaged materials were studied by Raman spectroscopy. Raman spectra have revealed that graphite underwent substantial changes in its structure with formation of hexagonal diamond sites as well as onion-like and amorphous carbon domains. Changes also in the Raman spectra of irradiated carbon black have been observed which could be interpreted in the light of the results on irradiated graphite.

A compound evaluation of γ-treated carbon black has been performed in comparison to a pristine sample. The results show a spectacular increase in the reinforcing effect as measured by the 200% and 300% modulus, hence an increase of the filler-to-polymer interaction, a reduction of the Payne effect and of the hysteresis (measured by tand at 70[ddot]C).     

炭黑的物化性质及表征

炭黑是一种微观结构，粒子形态和表面性能都极为特殊的炭素材料，炭黑原生粒子是由同心石墨层排列组成，炭黑含有氢，氧及硫等元素，它们基本上位于炭黑表面，形成具有化学活性的表面官能团，决定了炭黑的化学性质，仪器分析技术的发展，为人们研究炭黑表面性质提供了有效的手段，进一步认识了炭黑粒子的表面形态。     

炭黑对丁基橡胶硫化动力学的影响

本文主要研究了炭黑N330、N660和N990对丁基橡胶(IIR)硫化动力学的影响。研究表明,用三种不同炭黑填充的IIR其硫化反应均包含n=1级反应和n≠1级反应两个阶段。当n=1级反应时,反应速率常数K1均随着温度的升高而增大;当n≠1级反应时,反应速率常数K2则随着温度的升高而减小。同时,在硫化反应过程中活化能Ea随着炭黑粒径的增大而增大。     

偶联剂改性炭黑对橡胶性能的影晌

研究了偶联剂ＢＮＡＨ［Ｎ，Ｎ＇＝双（２－甲基－２－硝基两基）－１．６－二氨基己烷］和偶联剂ＴＥＳＰＴ［双（３－三乙氧基硅烷基丙基）四硫化物］改性炭黑对橡胶性能的影响。试验结果表明，偶联剂ＢＮＡＨ可以明显改善橡胶的动态性能。偶联剂ＴＥＳＰＴ次之，两者均可保持或提高橡胶的力学性能。     

Novel role of polymer-solvent and clay-solvent interaction parameters on the thermal, mechanical and optical properties of polymer nanocomposites

Solvent-polymer and solvent-clay interactions are very important in determining the properties of polymer-clay nanocomposites. In the present work, hydrogenated nitrile rubber-sepiolite nanocomposites were prepared and the interaction parameters of various solvents with rubber (χ_AB) and clay (χ_CD) were studied. Nine different sets of solvent combination were chosen based on their solubility parameter. A correlation between thermal, mechanical and optical transmittance properties of polymer-clay nanocomposites and the difference in their interaction parameters with various solvents (χ_AB − χ_CD) was analyzed for the first time. This study helped to identify chloroform/methyl ethyl ketone as the best solvent combination, where temperature at which maximum degradation of the polymer took place was raised by 65 °C and tensile strength and modulus at 100% elongation were enhanced by almost 200% over the neat rubber. The results were correlated with the data of X-Ray Diffraction study, Atomic Force Microscopy and Transmission Electron Microscopy. Finally, thermodynamic interpretation was made to explain the results.     

Zn(MMA)_2对硫黄硫化天然橡胶性能的影响

甲基丙烯酸锌(Zn(MMA)_2)在自由基存在下可以与橡胶发生接枝和交联反应,在橡胶中引入金属离子键交联结构,发生自聚合反应生成纳米聚盐粒子等,使得硫化橡胶具有多元的交联网络结构和多元的填充网络结构,这使得硫化胶的物理力学性能大大提高。为了获得Zn(MMA)_2所给出的优异性能,需采用过氧化物硫化体系,虽然过氧化物与硫黄并用的体系有很多报道,但是都没有单纯采用过氧化物硫化时的性能好。由于硫黄硫化是不饱和橡胶最广泛采用的硫化体系,因此在硫黄硫化条件下,获得Zn(MMA)_2的优异性能,无疑是非常有意义的。从化学计量角度设计了胶料中硫黄的摩尔用量远远大于Zn(MMA)_2的摩尔用量(14:1/mol:mol)的情况,对比了三种硫化体系(S、Zn(MMA)_2/S、Zn(MMA)_2/S*)硫化天然橡胶的特点。结果表明Zn(MMA)_2/S体系硫化胶料的物理力学性能显著提高,这使在硫黄硫化体系中实现Zn(MMA)_2的优异性能成为可能。论文分析阐述了产生这些结果的原因并提出了可能的机理