从绢云母粉看无机填料在橡胶中的补强性能

研究了绢云母粉 MCA-2、MCA-3、MCM-1在天然橡胶、丁苯橡胶及氯丁橡胶的补强性能，并在相同的配方中与半补强炭黑及轻质碳酸钙、陶土、硅铝炭黑、活性硅粉等13种无机填料进行了性能对比。实验证明：绢云母粉在众多的无机填料中具有最好的补强性能，其补强性能仅次于半补强炭黑。在氯丁胶料中绢云母粉与通用炭黑并用具有很好的协同效应，适当的并用比在降低胶料成本的同时全面提升胶料的物理机械性能。     

舰船用高性能密封橡胶研究(Ⅱ)纳米补强填料对氟橡胶硫化胶物理性能的影响

研究了普通炭黑、纳米炭黑、纳米白炭黑以及纳米炭黑／纳米白炭黑复合并用体系对舰船用氟橡胶硫化胶物理性能的影响。结果表明，纳米白炭黑／炭黑并用体系对提高补强效果具有协同作用，当纳米白炭黑在复合填充体系中质量分数在35％左右时氟硫化胶拉伸强度最大，断裂伸长率随填料用量增加而降低。纳米填料补强硫化胶不仅需要补强填料粒子与大分子之间有较强的结合力，而且需要补强填料粒子表面上的分子产生滑移。     

老化温度和炭黑填充量对SBR和NBR老化性能的影响

因填料具有低成本以及广泛的工业应用，填料填充橡胶的研究引起了人们广泛关注。大多数橡胶若没有炭黑等填充剂补强是没有实用价值的。炭黑能赋予橡胶硬度、强度、耐热性、可塑性及其他重要性能，具有较好的补强性能。     

白色填料的进展

无机填料-为将其与炭黑区分开通常称作白色填料，像炭黑一样，许多无机填料具有一系列的补强性能，可以解决工业中的具体问题。     

滑石粉/炭黑协同补强HNBR的研究

采用滑石粉和炭黑N990两种填料协同补强HNBR,研究了滑石粉/炭黑并用体系对HNBR性能的影响.结果表明,炭黑N990填充橡胶的Payne效应更明显;两种填料并用兼顾了炭黑N990对橡胶的补强作用以及滑石粉对橡胶的增韧作用,且压缩永久变形性能较好,力学性能显著提高,具有较好的协同效果.     

原位生成白炭黑对异戊橡胶补强性能与其制备方法和结构的相互关系

弹性体一般需要添加补强填料以提高其基本性能而得到商业应用。炭黑和白炭黑是应用最广的橡胶补强填料。一般说来,与炭黑填充胶料相比,白炭黑填充胶料的撕裂强度较大、耐磨性能和耐老化性能较好。此外,在轮胎工业中,当炭黑补强和白炭黑补强的两种轮胎耐磨性能和湿地抓着     

白炭黑填充环氧化天然橡胶改性丁腈橡胶的物理性能和动态力学性能

通常，大多数橡胶制品通过特定填料的补强来满足具体应用的要求。在传统填料中，白炭黑与炭黑一样是橡胶工业中重要的补强填料。由于混入橡胶胶料中的白炭黑赋予胶料许多优点（如提高了撕裂强度、降低了生热性、良好的耐磨性和更好的胶料粘合性能），因此，近年来自炭黑的使用日益增多。     

一些无机填料特性介绍

对国内面世的ＥＭ，ＸＰＥＭ，ＭＦ－３＾＃等１８种新型无机填料的特性作了介绍，并与现行的碳酸钙、硫酸钡等４种普通无机填料与通用炭黑在补强，填充等方面进行了实验研究，各种无机填料的拉伸强度都不如通用炭黑，但在无机填料中，以新型的活性碳酸钙，超细碳酸钙最优，半补强粉次之；定伸应力以ＭＦ－３＾＃居首，超过其他填料和通用炭黑，其它性能则各有高低。     

MC炭黑在轮胎垫带和夹布胶管中的应用

通过对ＭＣ炭黑的性能试验以及与常用橡胶补强填料的对比结果认为：ＭＣ炭黑是一种密度小，具有一定补强性能的橡胶补强剂，它用于轮胎垫带和夹布胶管当中，取得了明显的经济效益。     

耐低温氟醚橡胶补强体系的研究

研究多种填料对耐低温氟醚橡胶性能的影响,结果表明：硅酸钙和喷雾黑是耐低温氟醚橡胶较理想的补强填料,在相同用量下,煤粉补强的胶料耐空气热老化和耐压缩永久变形性能优于喷雾炭黑,高填充量时其补强性能接近喷雾炭黑     

Synergistic reinforcement of nanoclay and carbon black in natural rubber

The synergistic reinforcement of nanoclay (NC) and carbon black (CB) in natural rubber (NR) has not been much studied. Therefore, the reinforcement mechanism was probed using synchrotron wide‐angle X‐ray diffraction and transmission electron microscopy (TEM) observation and analyzed in terms of tube model theory. A synergistic effect in reinforcement between NC and CB was proved by the marked enhancement in tensile strength from 11.4 MPa for neat NR to 28.2 MPa for NR nanocomposite with 5 wt% NC and 20 wt% CB. From a study of crystallization under deformation it was found that crystallization plays a less important role in the reinforcement of NR/NC/CB. Analysis using tube model theory provided more evidence for the synergistic effect. NR containing a combination of NC and CB exhibited an increase of topological tube‐like constraints in comparison with NR/CB. That is to say, in NR/NC/CB nanocomposites, a CB–NC local filler network, as indicated by TEM images, induced a more entangled structure in which mobility of rubber chains was hindered for lateral fluctuations by the presence of neighboring chains. The synergistic reinforcement of NC and CB in NR/NC/CB nanocomposites can be reasonably understood as due to the formation CB–NC local filler networks. Copyright © 2010 Society of Chemical Industry     

Viscoelastic properties of natural rubber composites reinforced by defatted soy flour and carbon black co‐filler

Filler mixtures of defatted soy flour (DSF) and carbon black (CB) were used to reinforce natural rubber (NR) composites and their viscoelastic properties were investigated. DSF is an abundant and renewable commodity and has a lower material cost than CB. Aqueous dispersions of DSF and CB were first mixed and then blended with NR latex to form rubber composites using freeze‐drying and compression molding methods. A 40% co‐filler reinforced composite with a 1 : 1 DSF : CB ratio exhibited a 90‐fold increase in the rubber plateau modulus compared with unfilled NR, showing a significant reinforcement effect by the co‐filler. The effect, however, is lower than that observed in the carboxylated styrene–butadiene rubber composites reported earlier, indicating a significant effect from the rubber matrix. The co‐filler composites have elastic moduli between those of DSF and CB reinforced composites. Stress softening and recovery experiments indicated that the co‐filler composites with a higher CB content tend to have a better recovery behavior; however, this can not be simply explained from the recovery behaviors of the single filler (DFS and CB) composites. CB composites prepared by freeze‐drying show a strain‐induced reorganization of fillers. Strain sweep experiment data fit with the Kraus model indicates the co‐filler composites with a higher CB content are more elastic, which is consistent with the recovery experiments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

From the Volume‐Filling Effect to the Stress‐Bearing Network: The Reinforcement Mechanisms of Carbon Black Filler in Natural Rubber

Using synchrotron‐radiation X‐rays for nanoscale computed tomography (X‐ray nano‐CT), the structure and corresponding reinforcement effects of carbon black (CB) filler at various amounts in natural rubber (NR) are studied during cyclic loading. All structural parameters of the CB filler, which are extracted from X‐ray images—such as the destruction and reconstruction ratios of the aggregates and the network connectivity, show a transition point with the CB content at around 30 phr (phr = parts by weight per hundred parts of rubber). When the CB content is above the transition point, the effective volume fraction exceeds the percolation threshold, and a stress‐bearing filler network can form; this network can effectively transmit the external stress to the entire sample and abruptly enhance the reinforcement factor. Below the percolation threshold, the CB filler is mainly disconnected aggregates, where its reinforcement of the rubber matrix can be mainly described by the volume‐filling effect. Using the dynamic cluster–cluster aggregation (CCA) model, calculations of the mechanical properties related to the CB content suggest that the network structure plays a major role in the reinforcement of the NR.

     

超细改性矿物粉体增强硅橡胶

采用材料物理化学和复合材料的方法,系统地研究了８种矿物及其超细粉体和改性粉体与硅本的相互作用。结果表明,湍石、石英和硅灰石对硅橡胶基体具有较好的增强作用。粒径小、比面积大、长径比大等粉体性质好的填料,其增强性能高。界面粘附功与界面张力比值大的复合材料的力学性能好。具有表面活性基团（通过表面改性）、表面缺陷和一的表面羟基是提高粉体增强性能的重要因素。复合粉体的增强性能与粉休性质、混炼胶中的结合橡胶、     

Dynamic mechanical properties of styrene‐butadiene composites reinforced by defatted soy flour and carbon black co‐filler

Carboxylated styrene‐butadiene (SB) composites reinforced by a mixture of defatted soy flour (DSF) and carbon black (CB) were investigated in terms of their dynamic mechanical properties. DSF is an abundant renewable commodity and has a lower cost than CB. DSF contains soy protein, carbohydrate, and whey. Aqueous dispersions of DSF and CB were first mixed and then blended with SB latex to form rubber composites using freeze‐drying and compression molding methods. At 140°C, a single filler composite reinforced by 30% DSF exhibited roughly a 230‐fold increase in the shear elastic modulus compared to the unfilled SB rubber, indicating a significant reinforcement effect by DSF. Mixtures of DSF and CB at three different ratios were investigated as co‐fillers. Temperature sweep experiments indicate the shear elastic moduli of the co‐filler composites are between that of DSF and CB composites. Strain sweep experiments were used to study the fatigue and recovery behaviors of these composites. Compared with the DSF composites, the recovery behaviors of the 30% co‐filler composites after the eight consecutive deformation cycles of dynamic strain were improved and similar to that of 30% CB composite. Strain sweep experiments also indicated that the co‐filler composites have a greater elastic modulus than the CB reinforced composites within the strain range measured. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effect of oxidized carbon black on the mechanical properties and molecular motions of natural rubber studied by pulse NMR

The mechanical properties such as elastic modulus and stress-relaxation and spin-spin relaxation time T₂ from pulse NMR were measured for surface-oxidized carbon-black-filled natural rubber. The extent of reinforcement increased with CB volume percent in the range of 0–30%. At a given CB percent, this quantity increased by surface oxidation of fillers and decreasing filler size. From pulse NMR experiment, it was found that there were three components in rubber molecules which have different values for T₂. Stress-relaxation time and elastic moduli fitted one master curve against effective volume, fraction which is the sum of filler and bound rubber fraction. It was found that the distance between particle surfaces is the most important factor influencing reinforcing properties of filled polymers.     

改性矿物填料增强橡胶/聚氯乙烯共混体系

研究了橡胶、增塑剂、矿物填料和表面处理剂对橡胶／聚氯乙烯(PVC)共混物力学性能的影响,用扫描电镜分析了有机胺类表面处理剂改性高岭土／丁腈橡胶(NBR)／PVC的界面结合状况。结果表明,当NBR用量为30份,邻苯二甲酸二辛酯用量为60份,有机胺类表面处理剂质量分数为3％,填充60份的超细碳酸钙或高岭土或牌号为SMF的蒙脱土时,可得到力学性能较佳的NBR／PVC共混物;不同矿物填料对NBR／PVC共混物的增强作用不同,经有机胺类表面处理剂改性后,以超细碳酸钙、高岭土和蒙脱土SMF的增强效果最为明显。     

Effect of modification conditions of coal gangue on properties of natural rubber composites

The purpose of this work is to study the reinforcement effect of modified coal gangue (CG) on natural rubber (NR); carbon black (CB) was taken as reference filler. The addition of CG and CB to NR with the total filler loading fixed at 35 phr. The orthogonal experiment was employed to reveal the modification conditions on reinforcing properties. The results show that modification conditions such as weight ratio of coupling agent (CA), calcining temperature (CT), and calcining time (CM) affect the strengthening properties of CG, and CA is the most important factor influencing the tensile strength of NR, the order of influence can be expressed as CA > CT > CM. The optimum modification conditions are CT 800°C, CM 1 hr, and CA 2%. 300% modulus of NR composites filled with modified CG (17.5 phr)/CB (17.5phr) hybrid filler is similar to NR filled with CB alone at same filler loading, while elongation at break increases significantly for existent of CG. The effect of heat treatment and modification conditions of CG were tested by particle size distribution, scanning electron microscopy, Fourier transform infrared spectra, and X‐ray diffraction. The results show that the specific surface area of CG increased and hydroxyl group in crystal structure of CG removed under heat treatment. Dynamic mechanical analysis results show that the storage modulus and tan δ of CG filled NR composites are higher while T_g is less than that of CB, indicating the existence of a strong and stiff interface between filler and NR matrix. POLYM. COMPOS., 35:1911–1917, 2014. © 2014 Society of Plastics Engineers     

Thermal and mechanical enhancement of styrene–butadiene rubber by filling with modified anthracite coal

Anthracite is the highest rank of coal with a layered structure similar to that of graphite. Here, styrene–butadiene rubber/modified anthracite (MA) composites were prepared and analyzed. The microstructure and dispersion of the anthracite were improved by ball milling with the modifier bis-(γ-triethoxysilylpropyl)-tetrasulfide (KH-Si69). The particle size of the modified coal was decreased significantly to ~3 μm, while surface interactions with the modifier yielded enhanced lamellar morphology and hydrophobic surfaces. The anthracite lamellae were well dispersed in the rubber matrix, providing good reinforcement; the tensile strength of the composite exceeded that of a composite with carbon black (CB) N660 filler (16.65 vs. 14.68 MPa). Moreover, low-level CB or silica compositing further promoted the dispersion of coal particles in the rubber, effectively enhancing the mechanical reinforcement behavior of the coal particles as well as the thermal stability of the rubber composite. Notably, it led to a 10.63% improvement in tensile strength and a 9.96 °C increase in the 5% mass loss temperature compared to the composite with a single MA filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48203.