碳包覆白炭黑的制备及其在丁苯橡胶中的应用

以葡萄糖为碳源物质制备碳包覆白炭黑,通过改变葡萄糖在碳包覆白炭黑中占比,研究不同碳含量对碳包覆白炭黑补强丁苯橡胶性能的影响。结果表明:与白炭黑相比,碳包覆白炭黑的分散性及其补强胶料的加工性能大幅改善;葡萄糖质量分数为0.1时,硫化胶综合物理性能最优,耐磨性能提高30%,抗湿滑性能和滚动阻力性能均提高。     

不同填料对丁苯橡胶硫化胶应力软化效应的影响

研究炭黑、白炭黑和白炭黑/硅烷偶联剂TESPT填充丁苯橡胶硫化胶的应力软化效应,并通过扫描电子显微镜表征填料在胶料中的分散程度,探讨填料-填料相互作用、橡胶-填料相互作用、循环加载拉伸及恢复条件等因素对硫化胶应力软化效应的影响。结果表明:炭黑填充硫化胶的应力软化效应最强,白炭黑填充硫化胶的应力软化效应最弱,加入硅烷偶联剂TESPT后白炭黑填充硫化胶的应力软化效应增强;白炭黑填充硫化胶的应变能恢复程度最高,炭黑填充硫化胶次之,白炭黑/硅烷偶联剂TESPT填充硫化胶最低。     

炭黑/白炭黑双相填料的配比对溶聚丁苯橡胶性能的影响

考察了用白炭黑取代部分炭黑作为填充剂对溶聚丁苯橡胶(SSBR)硫化胶物理机械性能和动态力学性能的影响。结果表明,采用炭黑/白炭黑双相填料可以提高SSBR硫化胶的物理机械性能和动态力学性能,原因在于双相填料增强了填料与橡胶大分子之间的相互作用,提高了填料在橡胶基质中的分散性。当用20份白炭黑与30份炭黑组成双相填料时,SSBR硫化胶的各项性能达到最佳。     

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。     

碳纳米管/炭黑/白炭黑混杂增强溶聚丁苯橡胶纳米复合材料的导电性能研究

介绍了通过机械混炼法制备碳纳米管束（CNTB）一元增强,碳纳米管束/白炭黑二元增强,碳纳米管束/炭黑/白炭黑三元增强以复合材料的方法。其中的二元与三元增强复合材料,又研究了Si747的添加与否对复合材料的性能影响。我们进行此研究的目的在于探索在一元,二元,三元以及由Si747添加的几种体系中,碳纳米管束的添加量对复合材料体积电阻率的影响。通过TEM研究了不同复合材料中填料的分散情况,通过导电性能测试,研究了在三种增强体系中,碳纳米管的导电网络效应。经研究我们发现： (1)在碳纳米管束/白炭黑二元增强体系中,当CNTB的填充体积分数一致时,当白炭黑的填充分数从0phr,20phr增加到50phr时,复合材料的导电性能是逐渐变差的。但当白炭黑的填充量到达70phr时,复合材料的导电性发生了突变,其导电性能突然变好,其体积电阻率甚至要好于填充0phr白炭黑的碳纳米管束一元增强的复合材料; (2)在碳纳米管束/炭黑/白炭黑三元增强体系中,我们尝试了用等量炭黑替代白炭黑,当保证CNTB的填充体积一致时,我们发现随着等量替代的白炭黑的炭黑的质量增加,复合材料的导电性能逐渐变好： (3)在碳纳米管束/白炭黑二元增强体系和碳纳米管束/炭黑/白炭黑三元增强体系中,在保证各个填料的质量不变的情况下,我们尝试了用Si747对复合材料进行了改性,结果发现,经过Si747改性的复合材料的体积电阻率要明显好于未经过Si747改性的复合材料。     

氧化石墨烯与白炭黑并用填充丁苯橡胶纳米复合材料的性能

采用乳液共混与机械剪切法制备氧化石墨烯/白炭黑/丁苯橡胶纳米复合材料,并对其综合性能进行研究。结果表明:两种并用填料在橡胶基体中均能达到纳米级分散,且白炭黑粒子填补了氧化石墨烯片层间的空隙。氧化石墨烯的加入延长了复合材料的正硫化时间,改变了其交联密度。氧化石墨烯等量替代白炭黑,可以提高橡胶基体中填料的有效体积分数,改善复合材料的物理性能和动态力学性能。氧化石墨烯的加入使复合材料的耐磨性能显著提高。与白炭黑填充相比,氧化石墨烯/白炭黑填充复合材料的60℃时损耗因子有所降低,能进一步降低滚动阻力,但其0℃的损耗因子也呈现降低趋势,对复合材料抗湿滑性能不利。     

混炼工艺对偶联剂Si69改性白炭黑填充丁苯橡胶/稀土顺丁橡胶并用胶性能的影响

研究混炼工艺对偶联剂Si69改性白炭黑填充溶聚丁苯橡胶/稀土顺丁橡胶并用胶性能的影响。结果表明,当混炼工艺中有150℃的保温平台且白炭黑为一次投料时,白炭黑在橡胶基体中的分散性较好,白炭黑形成的填料网络得到了抑制,相应硫化胶具有较好的物理性能和耐磨性能。     

白炭黑/溶聚丁苯橡胶复合材料的填料网络结构与动态黏弹性能

用橡胶加工分析仪研究了白炭黑用量和偶联剂Si 69原位改性对白炭黑/溶聚丁苯橡胶复合材料中填料网络结构与动态黏弹性能的影响.结果表明,白炭黑用量为30份(质量,下同)时网络结构尚未形成,不能测定结合胶;填充了50份和 70份的白炭黑复合材料的结合胶含量较低,其网络结构的结点类型以刚性结点为主,混炼胶和硫化胶的Payne效应明显.混炼胶的温度扫描结果表明,随白炭黑用量增加,复合材料中填料的聚集程度加剧.经Si 69原位改性后,复合材料的结合胶含量大大提高,网络结构的结点类型以柔性结点为主,混炼胶和硫化胶的Payne效应明显减弱.在10.04%的大应变下进行频率扫描时,经Si 69原位改性硫化胶的储能模量和损耗因子随频率的增大而增大,且明显低于未改性者.     

原位改性纳米氧化镁/顺丁橡胶复合材料的制备与性能

采用原位改性的方法制备了硅烷偶联剂Si 75 改性纳米氧化镁/顺丁橡胶复合材料,通过橡胶加工分析仪、扫描电镜等研究了其硫化特性、物理机械性能及动态力学性能。结果表明,当改性剂的用量为填料质量的3%时能有效提高纳米氧化镁/顺丁橡胶胶料的硫化速率和交联程度,且硫化胶的综合物理机械性能最好; 与未改性氧化镁填充的顺丁橡胶相比,改性氧化镁与橡胶之间的相互作用得到了增强,纳米氧化镁在橡胶中的分散性有了较大程度的改善,从而提高了改性纳米氧化镁/顺丁橡胶硫化胶的物理机械性能和损耗因子。     

加工配方及工艺对溶聚丁苯橡胶/白炭黑复合材料性能的影响

采用不同加工工艺及配方,制备了溶聚丁苯橡胶(SSBR)/白炭黑复合材料,考察了硅烷偶联剂、白炭黑、橡胶加工工艺及配方对复合材料性能的影响。结果表明,排胶温度和时间对SSBR/白炭黑复合材料的动态力学性能及白炭黑分散性影响显著。升高排胶温度和延长混炼时间均能提高SSBR/白炭黑复合材料的抗湿滑性能、降低滚动阻力,但过高的排胶温度和过长的混炼时间易引起橡胶基体降解。SSBR/白炭黑复合材料的最佳排胶温度为160℃,混炼时间为7 min。随着混合填料中炭黑用量的增加,混炼胶的门尼黏度无明显变化,硫化胶的力学性能增强、抗湿滑性能下降、滚动阻力增加。     

硅藻土/白炭黑复合填料的补强性研究

为拓展硅藻土在高分子复合材料中的应用,将硅藻土/白炭黑填充到天然橡胶/丁苯橡胶/顺丁橡胶中制备了复合材料。通过RPA2000和扫描电镜分析了复合填料的Payne效应和分散性,考察了硅藻土用量对复合材料工艺性能、力学性能、耐磨耗性能影响。结果表明:少量硅藻土的加入有利于白炭黑在橡胶中的分散,能降低复合材料的门尼粘度和Payne效应,提高复合材料的硫化速度,缩短硫化时间,复合填料的补强效果较好;随着硅藻土用量的增加,复合填料容易聚集,其力学性能呈下降趋势,而磨耗性能变化不大;当硅藻土用量10~20份时,复合材料的综合性能最好。     

Flame retardance of montmorillonite/rubber composites

The effect of dispersion of clay in rubber on the mechanical properties and flame retardance of rubber/montmorillonite (MMT) nanocomposites and rubber/MMT microcomposites were investigated in the present article, and the results were compared with the performance of silica reinforced rubber composites. Cone calorimeter test and limiting oxygen index test were employed to evaluate the flame retardance. From the results, it could be seen that the rubber/MMT nanocomposites always possessed the best flame retardance, such as lower peak heat release rate and higher fire performance index value. In addition, the rubber/MMT nanocomposites also showed better mechanical properties than the pure rubber and the other composites, especially in tear strength. With the rubber/silica composites, as expected, the silica could appropriately endow the rubber with flame retardance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of carbon black in polychloroprene organoclay nanocomposite with improved mechanical,electrical and morphology characteristics

Abstract

The effect of carbon black on nanoclay filled polychloroprene (CR) composites has been investigated. The nanoclay loading is fixed at 5 part per hundred rubbers (phr), and carbon black loading varied from 5 to 20 phr in rubber compounds. The rubber nanocomposites are prepared in laboratory by mixing in two-roll mill. The addition of nanoclay enhances mechanical properties especially tear strength and decreases water absorption without change in electrical properties compared to gum rubber vulcanisates. Wide angle X-ray diffraction and transmission electron microscopy are used to study the microstructure of CR nanocomposites. The addition of 5 parts of nanoclay to 15 phr carbon black filled samples shows synergistic effect between the fillers and suggests that the reinforcement is due to a more developed filler network formation in hybrid filler system than that in single phase filler. Significant improvement in mechanical, electrical and low water absorption properties has been obtained with these nanoclay and carbon black filled rubber nanocomposites. The paper concludes that nanocomposites containing a mixture of organoclay and carbon black in right proportion can be a substitute for rubber components used in underwater cable and device encapsulation applications.     

Role of in situ generated silica for rubber science and technology

Filled rubbers have a long history in rubber technology. Filler morphology in the rubber matrix significantly influences the performance of filled rubber products. Therefore, we have to achieve a certain morphology of filler in the rubbery matrix in order to enjoy good reinforcement. However, it has not been sufficiently known what kind of morphology is necessary for the reinforcement, because preparations of adequate models for the characterization of filler morphology have been difficult. The in situ silica filling of the rubber matrix can be modeled for the preparations. In this paper, the characteristic features of in situ silica generated in diene rubbers are reviewed, citing recent reports. Two important models are presented. One is a homogeneous silica filling in situ, producing soft rubber nanocomposites. The other is the formation of an in situ silica filler network, creating stiff rubber nanocomposites. The controlled in situ silica filling is useful to evaluate the reinforcement effect of filler in a rubber matrix. © 2016 Society of Chemical Industry     

Structure–property relationships of silica/silane formulations in natural rubber,isoprene rubber and styrene–butadiene rubber composites

The mechanical performance of natural rubber (NR), synthetic poly-isoprene rubber (IR), and styrene–butadiene rubber (SBR) composites filled with various silica/silane systems is investigated. The results are analyzed by referring to micro-mechanical material parameters, which quantify the morphological and structural properties of the polymer and filler network. These are obtained from fits with the dynamic flocculation model (DFM) describing the strongly nonlinear quasi-static stress–strain response of filler-reinforced elastomers as found from multihysteresis measurements of the investigated compounds. We focus on the reinforcement mechanisms of silica compounds with coupling and covering silane, respectively. The fitted material parameters give hints that the coupling silane provides a strong chemical polymer–filler coupling, which is accompanied by improved strength of filler–filler bonds for all three rubbers types. This may result also from the chemical coupling of short chains bridging adjacent silica particles. It implies larger stress values for the coupling silane and, in the case of NR and IR, a more pronounced “Payne effect” compared to the covering silane. In contrast, for SBR, the coupling silane delivers a lower Payne effect, which is explained by differences in the compatibility between rubber type and silane-grafted silica surface. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48435.     

Attributes of Polymer and Silica Nanoparticle Composites: A Review

In this article, polymer microspheres and silica nanoparticles have been discussed as important filler in polymer composites. Their synthesis methods, properties, and application were particularly stressed. Silica is usually used as nucleating agent, surface enhancement mediator, and as templates and cores. Among polymer/silica composites, various categories including polyaniline, polypyrrole, polystyrene, epoxy, rubber, and acrylate polymer were discussed in detail. It was observed that silica nanoparticles enhanced mechanical strength and overall performance of composites. Furthermore, composites having carbon nanotube along with silica particles possess high electrical and mechanical performance. These composites are important in nanoelectronic devices, nanomedicines, and defense-related applications.     

降低负重轮天然橡胶基复合材料生热的研究状况

概述负重轮天然橡胶(NR)基复合材料的生热原理及表征方法,重点介绍交联结构和填料包括炭黑、硅烷偶联剂改性白炭黑、新型碳材料氧化石墨烯和多壁碳纳米管对复合材料生热影响的研究状况。指出将新型碳材料部分取代炭黑,采用胶乳共沉法制备新型碳材料母胶有利于将新型碳材料均匀分散在NR基复合材料中,在有效提高NR基复合材料强度的同时降低其生热。新型碳材料制备成本高,需要进一步探讨其放量制备的简易方法及分散工艺,以开发能够工业化生产的应用于负重轮的高强度和低生热NR基复合材料。     

Effect of silane integrated sol–gel derived in situ silica on the properties of nitrile rubber

Nitrile rubber/silica composites are prepared by a sol–gel process using tetraethoxysilane as precursor in the presence of γ‐mercaptopropyltrimethoxysilane as a silane coupling agent. Here, we follow a novel processing route where the silica particles are generated inside the rubber matrix before compounding with vulcanizing ingredients. The effect of in situ generated silanized silica on the properties of the rubber composite has been evaluated by studying curing characteristics, morphology, mechanical and dynamic mechanical properties. Enhanced rubber–filler interaction of these composites is revealed from stress–strain studies and dynamic mechanical analysis. Excessive use of silane shows an adverse effect on mechanical properties of the composites. Due to finer dispersed state of the in situ silica and enhanced rubber–filler interaction, the mechanical properties and thermal stability of the composites are improved compared to corresponding ex situ processed composite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

Contribution of physico-chemical properties of interfaces on dispersibility, adhesion and flocculation of filler particles in rubber

Reinforcing fillers are added to elastomeric compounds to improve and adjust several mechanical, dynamical, tribological, etc. properties with respect to different applications, i.e. for automotive tires, or technical rubber goods. Carbon black and precipitated silica are widely used as rubber reinforcing fillers; however, some new classes of nanosized substances like organophilic modified clay or carbon nanotubes are presently intensive studied as possible future filler systems in combination with carbon black or silica.An important parameter for the dispersibility and compatibility of the filler in the polymer matrix of rubber compounds is the surface energy and surface polarity of the solid filler particles. Therefore, we systematically measured and compared the dynamic contact angles of a collection of different filler types (carbon blacks, silica, carbon nanotubes and organoclays) using the Wilhelmy method, whereby the particles were fixed as a thin layer at a double-sided adhesive tape. From the contact angle values the polar and disperse part of the surface energies of the filler particles were calculated by fitting Fowkes formula. For an estimation of the compatibility of the fillers with different types of rubber polymers we additionally analyzed the surface energy and polarity of the gum (unfilled) elastomers. From the evaluated surface energies and polarities, thermodynamic predictors for the dispersibility (enthalpy of immersion), the adhesion between filler particles and polymer matrix in the nanocomposite, and for the flocculation behaviour of the particles in a rubber matrix (difference in the works of adhesion) were derived. These thermodynamic predictors improve considerably the compounding process of novel rubber nanocomposites with respect to target-oriented adjustment of rubber properties.     

Preparation of dispersible nanosilica surface-capped by hexamethyl disilazane via an in situ surface-modification method and investigation of its effects on the mechanical properties of styrene–butadiene/butadiene rubber

Silica has been established as one of the most promising materials in green tires. The filler–rubber interactions can increase the comprehensive performance of rubber composites. In this study, sodium silicate was used as the silicon source and hexamethyl disilazane (HMDS; molecular formula: C₆H₁₉NSi₂) was used as a modifier to synthesize dispersible silica (DNS) via an in situ surface-modification method. The effects of the HMDS-capped silica on the properties of rubber–matrix composites made of styrene–butadiene rubber (SBR) and high-cis-polybutadiene rubber (BR9000 or BR) were investigated with Zeosil 1165MP (Z1165-MP; a commercial highly dispersible silica produced by Rhodia for the production of green tires in the rubber industry) as a reference. The results show that the SBR–BR–DNS composite was before the SBR–BR–Z1165-MP composite in increasing the tear strength and elongation at break and reducing the compression heat buildup. On the basis of the resulting properties, the reinforcing behaviors in the rubber–matrix composites were analyzed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47763.