炭黑N134在不同橡胶基体中的分散及其混炼工艺调控

以炭黑N134作为填料,对比了异戊橡胶、丁苯橡胶及仿生橡胶3种体系下混炼工艺对硫化胶性能的影响,并针对仿生橡胶体系炭黑分散度低的问题,对混炼工艺进一步优化,从而提高分散度和动静态性能.结果表明,在所研究的密炼时间范围内,随着密炼时间的延长,异戊橡胶体系和丁苯橡胶体系的分散等级由原本的1级左右提升至6级以上.但延长密炼时间并未明显提升仿生橡胶体系的炭黑分散度.针对该问题引入塑炼和包辊工艺,仿生橡胶炭黑分散性明显提高.随炭黑分散等级的增加, 3种橡胶体系的伸张疲劳性能均得到了较大改善.其中仿生橡胶生胶经塑炼后,门尼黏度和重均分子量均明显下降,表明塑炼对于增强胶料的加工性能有明显作用.相同炭黑混炼时间下,随着塑炼时间的延长,硫化胶佩恩效应也增强,这主要是由于炭黑分散程度的提高使得炭黑与橡胶基体的有效接触面积增加,进而在一定程度上增加了界面结合胶的含量.     

白炭黑填充胶料的硫变动力学研究

轮胎硫化工艺的设定取决于各组成部件的硫化参数,最终决定轮胎的硫化效率、能耗和成品质量,硫化参数的精确性至关重要。橡胶制品的硫化交联反应符合1级动力学方程,白炭黑填充胶料的硫化反应不单有硫磺-促进剂的交联反应,还存在白炭黑极性团聚的物理作用,直接使用硫变仪检测数据无法精确表征其硫变行为。基于此,本文对白炭黑填充母炼胶(未加硫)的硫变行为进行研究,表明了白炭黑团聚作用在硫变测试时对扭矩提升的干扰。最后,对白炭黑填充终炼胶和对应母炼胶的硫变曲线依据“时间-扭矩”数据进行“相减”处理,重新绘制出能够更精确表征硫化动力行为的曲线,更好地指导含白炭黑胶料的轮胎硫化工艺设定。     

白炭黑/炭黑混合填料补强仿生橡胶的性能

白炭黑/炭黑混合填料是近年来发展最快的一种新型橡胶材料补强剂,主要用来改善橡胶材料的动态性能.为了探究混合填料比例和密炼工艺对仿生橡胶动静态力学性能的影响机制,设计了两组实验:(1)固定密炼时间为6 min,采用不同混合比例的白炭黑/炭黑填料填充仿生橡胶,并对其分散、拉伸、疲劳及滚动阻力等性能进行系统研究.结果表明,当白炭黑在填料中的质量分数<50%时,随着白炭黑质量分数的增加,硫化胶拉伸强度显著下降,这是由于混合填料引起的分子链最大交联程度下降所致.进一步增加白炭黑含量,硫化胶的拉伸性能变化不明显,但分散等级由约1级提升至约9级,填料团聚体尺寸的减小使硫化胶的断裂伸长率和伸张疲劳寿命显著提高.(2)在固定混合比(填料中白炭黑的质量分数为75%)条件下,研究了密炼时间对硫化胶动静态力学性能的影响.结果表明,在2～10 min密炼时间范围内, 4 min密炼即显著提升拉伸强度、 300%定伸应力以及断裂伸长率,同时降低滚动阻力.主要原因是此时分子链的最大交联程度较大,分散等级和分散度较高.进一步延长密炼时间(6～10 min),填料在橡胶中易发生重新聚集,聚集体平均粒径增大且分散度...     

炭黑在异戊橡胶中的分散及其对动静态性能的影响北大核心CSCD

橡胶在使用时往往需要在生胶中加入填料颗粒以提高其力学强度,填料在橡胶中的分散状态对其使用性能有显著影响。为了明晰填料分散状态对橡胶动静态性能的影响规律,设计了不同的胶料混炼工艺,进而获得具有不同分散程度的橡胶材料,并对其分散等级、颗粒聚集体尺寸分布、胶料硫化性质、橡胶拉伸以及疲劳等性质进行了系统研究。结果表明,在所研究的密炼时间4~16 min范围内,随着密炼时间的延长,填料在基体中的分散度等级有较大程度的提高,密炼时间为16 min时填料分散等级达到了8.1级,胶料的门尼粘度下降显著,但胶料的拉伸性能变化不明显,而动态疲劳性能得以显著改善。随着开炼包辊时间的延长,填料在基体中的分散度等级呈先升高后降低的趋势,橡胶的动态疲劳性能也先升高后降低,当开炼包辊时间为20 min时,硫化胶的伸张疲劳寿命达到4×10~4次,继续延长包辊时间硫化胶的伸张疲劳寿命下降至2.3×10~4次;但是胶料整体的拉伸性能变化不明显。由此可见,通过调整混炼工艺可以改善填料在橡胶基体中的分散状态,进而提高胶料的疲劳性能。     

橡胶补强填料的研究进展

随着汽车行业的发展,在"安全、环保和节能"方面,对轮胎的性能提出了更高的要求,因此对轮胎原料—橡胶的补强研究越来越多。本文详细介绍了补强填料补强橡胶的机理、补强填料的分类及改性途径,概述了传统补强填料炭黑、白炭黑及炭黑/白炭黑双向填料的性能和研究现状,综述了新型补强填料硅酸盐类、碳酸盐类及其它常用新型种类和性能,指出新型填料拓展了橡胶补强技术和功能橡胶材料领域的研究思路,应加强橡胶补强填料的开发、补强机理探讨和拓展补强复合材料的表征和检测手段,以满足橡胶行业发展的需求。     

硅土/白炭黑复合填料对天然橡胶硫化胶性能的影响

硅土主要是由低温石英和粘土矿物组成的非金属矿物,具有独特的粒片叠置结构。本工作采用经改性处理的硅土与白炭黑并用,测定硅土/白炭黑复合填料对天然橡胶(NR)的硫化特性和力学性能,探讨填料并用对天然橡胶性能的影响。实验结果表明:经改性处理,硅土平均粒径减小,疏水性增强。硅土与白炭黑并用,有利于增强NR硫化初期的流动性,延长焦烧时间而不明显降低硫化速率,能改善橡胶的加工性能。拉伸性能测试结果表明,复合填料与白炭黑或硅土单独使用相比,能显著提高填充NR硫化胶的拉伸强度、定伸应力、交联密度,而不降低橡胶弹性。当硅土占复合填料质量为40%时,NR硫化胶的拉伸强度达到最大。动态机械性能测定结果表明,相比白炭黑,硅土更有利于减小硫化胶的生热和滚动阻力。     

反式-1,4-丁二烯-异戊二烯共聚橡胶改性的高性能轿车轮胎胎面胶的结构与性能

研究了新一代合成橡胶-反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)在高性能轿车轮胎胎面胶(溶聚丁苯橡胶/顺丁橡胶(SSBR/BR))中的应用及SSBR/BR/TBIR共混胶的结构与性能.结果表明,相对于无定型的SSBR和BR,TBIR由于具有一定的结晶性而呈现出较高的生胶强度、模量和韧性.但相比反式聚异戊二烯(TPI),由于丁二烯单体单元的引入降低了聚合物链的结构规整性,TBIR的结晶熔融焓、熔点和玻璃化转变温度均明显降低.采用10~20份TBIR与SSBR/BR并用改性,同时加入30份炭黑和45份白炭黑,SSBR/BR/TBIR混炼胶的格林强度和定伸应力提高,焦烧时间(tc10)和工艺正硫化时间(tc90)基本保持不变.SSBR/BR/TBIR混炼胶经过150oC硫化反应,制备的硫化胶物理机械性能优异,抗拉伸疲劳性能提高4.6~6.3倍,压缩强度提高21.4%~23.1%,耐磨耗性能提高10.8%~15.1%,耐湿滑性能提高13.6%~40.4%,滚动阻力维持不变.填料分散仪和透射电镜(TEM)结果表明,相比SSBR/BR硫化胶,SSBR/BR/TBIR硫化胶填料分散度提高7.3%~14.9%,填料聚集体平均尺寸降低1.4~2.7μm.可结晶的TBIR的高生胶强度及模量可显著抑制混炼胶中填料的聚集,改善硫化胶中填料的分散性,最终贡献于SSBR/BR/TBIR硫化胶优异的抗拉伸疲劳性、高的耐磨性、抗湿滑性、压缩强度、定伸模量等性能,TBIR是应用于高性能轿车轮胎胎面胶的一种理想新合成橡胶.     

高耐磨低生热NBR/TBIR复合材料的结构与性能

采用高反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)对丁腈橡胶(NBR)进行改性, 制备了高耐磨、 低生热输送轮用白炭黑填充的NBR/TBIR橡胶纳米复合材料. 研究了NBR/TBIR橡胶纳米复合材料的交联密度、 物理力学性能及填料分散性, 探讨了材料的结构对性能的影响. 研究结果表明, 与纯NBR相比, NBR/TBIR橡胶纳米复合材料的硫化速率和交联密度随TBIR用量的增加而增大; 在保持NBR硫化胶基本力学性能、 耐老化性能和耐溶剂性能基本不变的前提下, TBIR的加入使NBR/TBIR硫化胶的耐磨性提高15%, 动态压缩生热降低5%, 动态压缩永久变形降低22%, 白炭黑分散水平提高; 与丁腈橡胶/顺丁橡胶[NBR/BR(80/20), 质量份数比]硫化胶相比, NBR/TBIR(80/20, 质量份数比)硫化胶具有更低的动态压缩生热和动态压缩永久变形及更好的填料分散性.     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料性能的影响

本文研究了硅烷偶联剂原位改性白炭黑对溶聚丁苯橡胶(SSBR)性能的影响,结果表明,通过哈克转矩流变仪对含有偶联剂的SSBR/白炭黑混炼胶进行原位热处理后可明显减弱混炼胶的Payne效应,改善白炭黑在橡胶基体中的分散.原位热处理方法能够明显提高硫化胶的300%定伸应力,降低动态压缩温升,同时可使硫化胶在0℃附近具有较高的损耗因子(tanδ),60℃附近具有较低的tanδ.对不同聚合方式得到的丁苯橡胶,即溶聚丁苯橡胶与乳聚丁苯橡胶(ESBR)/白炭黑复合材料的力学性能及动态力学性能进行了研究,结果表明,白炭黑在SSBR2305中分散效果优于在ESBR1502中;采用偶联剂原位改性白炭黑可以使SSBR2305硫化胶获得与ESBR1502硫化胶相当的物理机械性能,更理想的动态力学性能,从而得到力学性能、抗湿滑性、滚动阻力及耐磨性更加均衡的理想轮胎材料.通过对具有不同偶联效率的SSBR/白炭黑体系的微观结构与性能研究发现,随偶联效率的增加,其结合橡胶含量增加,Payne效应减弱;高偶联效率的S-SBR具有较低的动态压缩温升及较好的耐磨性.     

硫化温度对绿色轮胎胎面胶结构与性能的影响

在轮胎的加工和制备过程中,硫化温度是影响橡胶复合材料网络结构和物理机械性能的重要因素之一.本文研究了硫化温度(140、150、160、170和180℃)对溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)(未填充体系)及SSBR/BR/白炭黑(SiO2)(填充体系)纳米复合材料的结构和物理机械性能的影响.结果表明:随硫化温度的...     

Formation of Network by Carbon Black，Silica and Their Mixing Fillers in Isoprene Rubber北大核心CSCD

The network formed by fillers has great influence on the mechanical properties of rubber materials. To understand the formation of network by carbon black,silica,and carbon black/silica mixing fillers in rubber and its influence on the properties of rubber,isoprene rubber/filler composites with different filler loadings are prepared and their micromorphology,rheological and tensile properties are investigated. It is found that the dispersion of fillers is better in rubber after cure than that in rubber before cure for all three rubber systems,and the filler size of silica is smaller than that of carbon black,but the aggregation is more severe in silica filled rubber system. In mixed filler system,the two fillers tend to aggregate separately, leading to the low modulus at small strain than that in single filler system. With the increase of the filler loading,the tensile strength increases first and then decreases,the elongation at break decreases,and the temperature rise in compression flexometer tests increases. Moreover,the temperature rise in mixed filler system is higher than that in single filler system at high filler loading. © 2022, Science Press (China). All rights reserved.     

Thermal characterization of the effect of fillers and ionic liquids on the vulcanization and properties of acrylonitrile–butadiene elastomer

Different thermal analysis techniques were used to study the effect of fillers and ionic liquids (ILs) on the vulcanization process, thermal and dynamic mechanical properties of acrylonitrile–butadiene elastomer (NBR). The products of the studies were composites of NBR filled with hydrotalcite, nanosized silica or carbon black. ILs such as 1-butyl-1-methylpyrrolidinium (BMpyrrolBF₄), 1-butyl-4-methylpyridinium (BMpyrBF₄) or 1-butyl-1-methylpiperidinium (BMpipBF₄) tetrafluoroborates were applied to improve the dispersion degree of the curatives and filler particles in the elastomer and to increase the efficiency of vulcanization. The differential scanning calorimetry results indicated that ILs reduced the vulcanization temperature of NBR compounds and increased the homogeneity of cross-link distribution in the elastomer network. NBRs filled with carbon black or silica exhibited similar thermal stabilities, whereas hydrotalcite reduced the temperature of thermal decomposition. The lowest mechanical loss factors were determined for vulcanizates filled with nanosized silica.

     

Radiation effects on polymers—IV: Straight radiation vulcanization of styrene-butadiene rubber mixes

Vulcanization of styrene-butadiene rubbers was carried out by gamma radiation in air. For unloaded unextracted rubbers, the dose required for optimum cross-linking was about 40 megaroentgens (MR). Elimination of foreign materials and stabilizers and also incorporation of filler affected the vulcanization. Loaded samples gave vulcanizates with best complex physico-mechanical properties for filler content of 50 (phr) and a dose of 30 MR. Evaluation of various fillers has shown that the best properties were obtained with HAF among the black fillers and silica in the case of white fillers.     

Effect of silane coupling agent on the polymer‐filler interaction and mechanical properties of silica‐filled NR

The effects of filler loading and a new silane coupling agent 3‐octanoylthio‐1‐ propyltriethoxysilane (NXT silane) on the polymer‐filler interaction and mechanical properties of silica‐filled and carbon black‐filled natural rubber (NR) compounds were studied. Silica (high dispersion silica7000GR, VN2, and VN3) and carbon black (N330) were used as the fillers, and the loading range was from 0 to 50 phr. The loading of NXT silane was from 0 to 6 phr. Experimental results show that the maximum and minimum torques of silica and carbon black‐filled NR increase with increasing filler loading. With increasing filler loading, the scorch time and optimum cure time decrease for carbon black‐filled NR, but increase for silica‐filled NR. The minimum torque, scorch time, and optimum cure time decrease because of the presence of NXT silane. For the carbon black and silica‐filled NR, the tensile strength and elongation at break have maximum values, but the hardness, M300, M100, and tear strength keep increasing with filler loading. The mechanical properties of silica‐filled NR were improved in the presence of NXT silane. With increasing filler loading, the storage modulus of filled NR increases, but the loss factor decreases. Carbon black shows the strongest polymer‐filler interaction, followed by VN3, 7000GR, and VN2. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 573–584, 2005     

Insights into the Payne Effect of Carbon Black Filled Styrene-butadiene Rubber Compounds

As a widely used reinforcing filler of rubber, carbon black(CB) often enhances the nonlinear Payne effect and its mechanism still remains controversial. We adopt simultaneous measurement of rheological and electrical behaviors for styrene-butadiene rubber(SBR)/CB compounds and CB gel(CBG) during large deformation/recovery to investigate the contribution of conductive CB network evolution to the Payne effect of the compounds. In the highly filled compounds, the frequency dependence of their strain softening behavior is much more remarkable than that of their CB network breakdown during loading, while during unloading the unrecoverable filler network hardly affects the complete recovery of modulus, both revealing that their Payne effect should be dominated by the disentanglement of SBR matrix. Furthermore,the bound rubber adjacent to CB particles can accelerate the reconstruction of continuous CB network and improve the reversibility of Payne effect. This may provide new insights into the effect of filler network, bound rubber, and free rubber on the Payne effect of CB filled SBR compounds.     

Activity of fillers in elastomer networks of different structure

The paper deals with interactions between low molecular weight substances and silica. Activity of SiO₂ towards ethylene-propylene-diene rubber (EPDM) also depends on the kind of crosslinking system used. Calcium carbonate, the filler exhibiting low interactions with elastomers does not show any changes in activity, due to application of different crosslinking systems. In our opinion, the observed increase of the fillers activity results from the modification of elastomer chains by crosslinking agents, influence of the latter on the formation of its own network (the so called “structure”) in the elastomer matrix, and above all from nanoheterogeneous distribution of network crosslinks in vulcanizates. The non Gaussian probably bimodal distribution of crosslinks is likely to influence positively properties of elastomers. A similar effect is observed in peroxide vulcanizates of EPM produced with the use of the crosslinking coagents of polar nature. Behaviour of different kinds of carbon black in natural rubber (NR) crosslinked with dicumyl peroxide (DCP), sulphur donors or sulphur with accelerators is discussed. Reinforcing action of carbon black, particularly the active ones, showed to be more effective in sulphur than in peroxide vulcanizates.     

Comparison of Some Soft Unplasticized Cast Polyurethane Rubbers

Different types of unplasticized cast polyurethanes with hardness around 60 Shore A have been compared. The tensile properties, tear strength, resistance to hydrolysis, and swelling in solvents and water were examined. The influence of composition on the properties of cast polyurethanes prepared from a polyadipate polyol and diisocyanates, including the effect of a range of fillers, was investigated in detail. Fumed silica, fumed alumina, and carbon black significantly increased the hardness and tensile strength of the rubber, whereas kaolin and talc gave small increases. Ground silica, calcite, and rutile had no effect. No significant increases in tensile strength were obtained with silane and titanate coupling agents with a fumed silica filler. The rate of hydrolysis or extent of swelling in xylene was unchanged by fillers.     

Mechanical properties of composite heterogeneous gels

Composites with a matrix of poly(2-hydroxyethyl methacrylate) (PHEMA) and 10% by volume of various crosslinked PHEMA polymer fillers (prepared by copolymerization with 0.1, 0.4, 1.0, and 20.0% by weight of ethylenedimethacrylate) of particle size about 1 μm were prepared. Some polymer matrixes were prepared from soluble branched PHEMA (Hydron S), and others by copolymerization, in the presence of the filler with 0.4 and 1.0% of ethylenedimethacrylate as a crosslinking agent. In the case of the uncrosslinked matrix, a linear polymer–crosslinked polymer system, resulted; in the case of the crosslinked matrix, a composite heterogeneous network was formed (in the latter case, the particles of the filler were swollen with monomer during the crosslinking polymerization). Stress–strain, equilibrium, and ultimate characteristics were measured at 3, 10, 25, 40, 60, and 80°C on samples swollen to equilibrium in water (T_g ≈ ?50°C) and at 80, 110, and 140°C on dry samples (T_g ≈ 100°C). Depending on experimental conditions, above all on the distance from the main transition region and on whether the polymer is dry or swollen, it was found that the measured hydrophilic composite systems behaves as a filled system (with the polymer filler acting mostly as solid particles, irrespective of the crosslink density) or as a system with crosslink density fluctuations (where both networks, the matrix and the filler, contribute roughly additively to the properties of the system), or finally as defect heterogeneous systems (where the properties depend primarily on the character of the polymer–filler interface).     

Understanding the reinforcement and dissipation of natural rubber compounds filled with hybrid filler composed of carbon black and silica

The performance of reinforced rubber compounds depends on the filler composition while the reinforcement and dissipation mechanisms still remain unclear.Herein linear and nonlinear dynamic rheological responses of carbon black/silica hybrid filler filling nature rubber compounds are investigated.The rheological contributions of dynamically retarded bulk phase and filler network are revealed to be crucial at high and low frequencies,respectively,and the bulk phase is shown to be of vital importance for the occurrence of nonlinear Payne effect at mediate frequencies.A framework for simultaneously solving reinforcement and dissipation varying with filler composition and content is suggested,providing a new perspective in understanding the filling effect for manufacturing high-performance rubber materials.     

Influence of Carbon Black and Silica Filler on the Rheological and Mechanical Properties of Natural Rubber Compound

Rubber compounds are reinforced with fillers such as carbon black and silica. In general, filled rubber compounds shows smooth rheological behavior and mechanical properties. Variation in rheological behavior and mechanical properties was studied in terms of the filler composition using natural rubber compounds filled with both carbon black and silica CB/Si = 0/60, 20/40, 30/30, 40/20 and 60/0 phr (parts per hundred rubber is parts of any non-rubbery material per hundred parts of raw gum elastomer (rubbery material)). The rheological behaviour can be showed in measurement of Mooney viscosity and cure time. The Mooney viscosity of rubber compounds increase with the increasing the carbon black in the compounds. The compound filled with CB/Si of 30/30 and 60/0 showed abnormal rheological behaviour in which the cure time decreased suddenly and the increased at certain ratio during the measurement. The mechanical properties such as hardness, abrasion resistance and tensile stress at 300% elongation were studied. In the hardness and abrasion resistance measurement, the higher ratio CB/Si decrease contribution of silica, which resulting smaller of hardness value. Ratio CB/Si 40/20 gives an optimum filler blended. It is also clearly understood that higher abrasion resistance mainly due to the lower hardness value under the same condition. The tensile stress at 300% elongation of rubber compound increased with the increasing carbon black filler.