累托石/NR纳米复合材料的结构与性能研究

研究乳液法和熔体法制备的累托石／NR纳米复合材料的结构与性能。结果表明,乳液法累托石／NR纳米复合材料为层间无高分子插入的隔离型纳米复合材料,熔体法累托石／NR纳米复合材料为典型的插层型纳米复合材料;当应变小于100％时,熔体法制备的复合材料应力较大,当应变大于100％时,乳液法制备的复合材料应力较大;当累托石用量较小时,乳液法制备的复合材料撕裂强度高于熔体法制备的复合材料;乳液法和熔体法制备的两种复合材料热稳定性差别不大,均好于纯NR。     

片层钠基蒙脱土调控炭黑对天然橡胶/丁苯橡胶纳米复合材料性能的影响

采用乳液共混法先制备天然橡胶(NR)/片层钠基蒙脱土(Na-MMT)、丁苯橡胶(SBR)/Na-MMT和NR/SBR/Na-MMT母胶,再制备得到相应的NR/SBR/Na-MMT纳米复合材料,研究Na-MMT对NR/SBR/Na-MMT纳米复合材料的微观形貌、物理性能和耐磨性能的影响。结果表明：采用NR/Na-MMT母胶共混法制备的NR/SBR/Na-MMT纳米复合材料中Na-MMT的分散效果最好,剥离状态的Na-MMT占比最大,炭黑的分散明显改善,片层Na-MMT可在一定程度上调控炭黑在NR/SBR/Na-MMT纳米复合材料中的偏析行为;该橡胶纳米复合材料的定伸应力、拉伸强度和拉断伸长率最大,阿克隆磨耗量最小(0.177 cm³),磨耗表面沟壑最浅,耐磨性能最佳。     

熔体法制备有机黏土/橡胶纳米复合材料的结构及性能

将有机黏土(OC)分别加入到天然橡胶(NR)、丁苯橡胶(SBR)、丁基橡胶(IIR)和三元乙丙橡胶(EPDM)中,通过熔体法制备了纳米复合材料。探讨了橡胶黏度及其分子结构对OC在复合材料中分散状况的影响,研究了复合材料的力学性能。结果表明,在以NR为基体的复合材料中。OC片层分散均匀,且剥离程度较高;在SBR,IIR,EPDM中,OC以插层结构为主,且插层效果从大到小的顺序依次为SBR,IIR,EPDM。与相应的纯胶相比,OC／NR纳米复合材料的定伸应力提高,拉伸强度和扯断伸长率有所下降;OC／SBR,OC／IIR,OC／EPDM纳米复合材料的定伸应力变化不大,拉伸强度和扯断伸长率明显提高,且OC／SBR和OC／EPDM复合材料的撕裂强度提高。     

环氧化天然橡胶对累托石/炭黑/天然橡胶纳米复合材料性能的影响

研究环氧化天然橡胶(ENR)对累托石(REC)/炭黑/天然橡胶(NR)纳米复合材料性能的影响。结果表明:REC/炭黑/NR纳米复合材料中填料分散均匀,REC片层呈纳米级分散;ENR改善了REC与橡胶基体间的界面相互作用,增大了复合材料交联密度,从而显著提高了复合材料的力学性能、抗切割性能和耐磨性能,且各性能增幅随ENR用量的增大而增大。     

一种新型的累托石/SBR纳米复合材料的结构与性能

采用乳液共混共凝法首次制备了累托石／SBR复合材料。TEM研究表明，累托石在SBR基体中的分散尺寸小于100nm。该材料的力学性能与蒙脱石／SBR纳米复合材料水平相当，但由于分散相形状系数略大，气密性和撕裂强度更优一些。累托石可望成为一类新的分散相填料。     

乳液插层法制备丁苯橡胶/蒙脱土纳米复合材料的结构与性能

选用一种能够在水中分散良好的有机改性蒙脱土（OMMT），采用乳液插层法制备了SBR／OMMT纳米复合材料，X射线衍射和透射电镜观察显示制得了半剥离型与插层型共存的纳米复合材料。研究了复合材料的力学性能和耐溶剂性能。测试结果表明，随着蒙脱土用量的增加，复合材料的定伸应力、拉伸强度和撕裂强度均大幅度提高。复合材料具有优异的耐溶剂性能。     

累托石纳米复合材料的结构和性能

以具有层状硅酸盐结构的累托石(REC)为主体、烷基季铵盐为改性剂合成了有机累托石(OREC)，以有机累托石和环氧树脂复合制备纳米复合材料。累托石含量在0.8％(w)时，纳米复合材料具有最佳力学和热学性能，其中冲击强度增加120％，断裂伸长率增加330％，玻璃化转变温度提高28℃。用X-小角衍射法、透射电镜和红外吸收光谱研究了材料的微观结构，结果表明层状累托石和环氧树脂发生了化学反应，并观测到层状累托石完全剥离和插层两种结构形态。累托石在低含量时容易形成剥离型。     

有机蒙脱土对天然橡胶/丁苯橡胶的补强及增容作用

采用机械混炼法制备了天然橡胶(NR)/丁苯橡胶(SBR)/有机蒙脱土(OMMT)纳米复合材料,采用TEM和XRD对复合材料的亚微观结构进行了表征,并对复合材料的表观交联密度、静态力学性能、动态力学性能和硫化热效应进行了研究。结果表明,复合材料为剥离型纳米复合材料;OMMT能够明显提高纳米复合材料的交联密度和静态力学性能;OMMT导致NR/SBR共混胶动态损耗因子降低,并且能够促使NR和SBR玻璃化转变温度更为接近,起到了增容作用;OMMT实现了NR和SBR两相的同步硫化。     

纳米氢氧化镁在SBR/NR并用胶中的应用研究

研究了纳米氢氧化镁对丁苯橡胶(SBR)/天然橡胶(NR)并用胶的补强性能、阻燃性能及SBR/NR并用比对胶料力学性能的影响.结果表明,纳米氢氧化镁补强效果显著,用量80份时硫化胶拉伸强度可以达到15.1MPa;可显著提高胶料的阻燃性能,且随其用量的增加而增高;SBR/NR并用比为45/55,添加80份纳米氢氧化镁时硫化胶拉伸强度可以达到15.6MPa.     

白炭黑对累托石/天然橡胶纳米复合材料结构与性能的影响

采用乳液法制备累托石(REC)/天然橡胶(NR)纳米复合材料,研究白炭黑对REC/NR复合材料结构和性能的影响。结果表明:白炭黑粒子可以插入累托石片层形成网络结构。加入少量白炭黑后,REC/NR复合材料的物理性能变化不大。随着白炭黑用量的增大,复合材料的抗湿滑性能、抗切割性能和耐磨性能提高,压缩生热逐渐增大,当白炭黑用量为15份时,复合材料的耐磨性能最好;当白炭黑用量为20份时,复合材料的抗切割性能和抗湿滑性能较好。     

Effects of Characteristics of Rubber,Mixing and Vulcanization on the Structure and Properties of Rubber/Clay Nanocomposites by Melt Blending

Summary: Three rubber‐based nanocomposites, natural rubber (NR), styrene‐butadiene rubber (SBR), and ethylene‐propylene‐diene rubber (EPDM) matrixes, were prepared with octadecylamine modified fluorohectorite (OC) by melt blending. X‐ray diffraction (XRD) revealed that the SBR/OC and EPDM/OC nanocomposites exhibited a well‐ordered intercalated structure and a disordered intercalated structure, respectively. In the case of the NR/OC nanocomposite, it exhibited an intermediate intercalated and even exfoliated structure. These results were in good agreement with transmission electron microscopy (TEM) observations. Furthermore, in the NR/OC and SBR/OC systems, the mixing process played a predominant role in the formation of nanometer‐scale dispersion structure, whereas the intercalated structure of EPDM/OC formed mainly during the vulcanization process. The tensile strength of SBR/OC and EPDM/OC nanocomposites loading 10 phr OC was 4–5 times higher than the value obtained for the corresponding pure rubber vulcanizate, which could be ascribed to the slippage of the rubber molecules and the orientation of the intercalated OC. For the strain‐induced crystallization NR, the exfoliated OC efficiently improved the modulus of the NR/OC nanocomposite relative to the pure NR. However, its hindrance on NR crystallization during the tensile process may be the main reason for the decrease in tensile strength of NR/OC.

XRD diffraction patterns of three nanocomposites containing 10 phr organoclay.     

Strain‐induced crystallization behavior of phenolic resin crosslinked natural rubber/clay nanocomposites

Nanocomposites of natural rubber (NR) and unmodified clay were prepared by latex compounding method. Phenolic resin (PhOH) was used to crosslink NR. Crosslinked neat NR was also prepared for comparison. The structure–property relationship of uncrosslinked and crosslinked NR/clay nanocomposites was examined to verify the reinforcement mechanism. Microstructure of NR/clay nanocomposites was studied by using transmission electron microscopic (TEM), X‐ray diffraction (XRD), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering (SAXS) analyses. The results showed the evidence of intercalated clay together with clay tactoids for the nanocomposite samples. The highest tensile strength was achieved for the crosslinked NR/clay nanocomposite. The onset strain of deformation induced the crystallization of NR for nanocomposites was found at almost the same strain, and furthermore their crystallization was developed at lower strain than that of the crosslinked neat NR because of the clay orientation and alignment. However, at high strain region, the collaborative crystallization process related to the clay dispersion and conventional crosslink points in the NR was responsible to considerably high tensile strength of the crosslinked NR/clay nanocomposite. Based on these analyses, a mechanistic model for the strain‐induced crystallization and orientational evolution of a network structure of PhOH‐crosslinked NR/clay nanocomposite was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42580.     

Preparation and characterization of organoclay‐rubber nanocomposites via a new route with skim natural rubber latex

Skim natural rubber latex (SNRL) is a protein rich by‐product obtained during the centrifugal concentration of natural rubber (NR) latex. A new method to recover rubber hydrocarbon and to obtain nanocomposites with organoclay (OC) was investigated. The approach involved treatment of SNRL with alkali and surfactant, leading to creaming of skim latex and removal of clear aqueous phase before addition of OC dispersion. Clay mixed latex was then coagulated to a consolidated mass by formic acid, followed by drying and vulcanization like a conventional rubber vulcanizate. X‐ray diffraction (XRD) studies revealed that NR nanocomposites exhibited a highly intercalated structure up to a loading of 15 phr (parts per hundred rubber) of OC. Transmission electron microscopy studies showed a highly exfoliated and intercalated structure for the NR nanocomposites at loadings of 3–5 phr organically modified montmorillonite (OMMT). The presence of clay resulted in a faster onset of cure and higher rheometric torque. The rubber recovered from skim latex had a high gum strength, and a low amount of OC (5 phr) improved the modulus and tensile strength of NR. The high tensile strength was supported by the tensile fractography from scanning electron microscopy. Thermal ageing at 70°C for 6 days resulted in an improvement in the modulus of the samples; the effect was greater for unfilled NR vulcanizate. The maximum degradation temperature was found to be independent of the presence and concentration of OC. The increased restriction to swelling with the loading of OC suggested a higher level of crosslinking and reinforcement in its presence. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3277–3285, 2006     

Improving heat ageing and thermal properties of silicone rubber using montmorillonite clay

Heat ageing and thermal stability of a silicone rubber (SR) filled with montmorillonite clay (MMT) was investigated. Three types of rubber nanocomposites were prepared with highly exfoliated Cloisite 30B (SR/C30B), intercalated/exfoliated Cloisite Na⁺ (SR/Na⁺MMT), and highly intercalated Cloisite 20A (SR/C20A). This study showed that the SR/C30B nanocomposite exhibited excellent heat resistance in comparison to the other two nanocomposites and neat SR as revealed by higher retention strength. The thermal stability of the rubber in air was strongly dependent on the clay morphology and increased in the following order: highly intercalated/exfoliated SR/Na⁺MMT < highly intercalated SR/C20A < highly exfoliated SR/C30B. The thermogravimetric analyses of the SR/C30B nanocomposite showed a substantial increase in the final residue in comparison with the neat SR. This indicated a major improvement in the thermal stability of the rubber containing the exfoliated clay, which was also supported by the higher activation energy of decomposition measured for the nanocomposite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41061.     

机械共混法制备NR/SBR/OMMT纳米复合材料及其性能

选择不同牌号的有机蒙脱土（OMMT）,利用机械共混法制备了NR/SBR/OMMT纳米复合材料。测试了复合材料的力学性能,选择出了最佳牌号OMMT。不同含量的OMMT与共混胶复合后力学性能的测试结果表明：当OMMT含量仅为3份时,拉伸强度和断裂强度分别提高了90％和63%;利用X射线衍射和透射电子显微镜研究了复合材料的亚微观结构,观察结果显示制备出了分散均匀的剥离型NR/SBR/OMMT纳米复合材料,同时OMMT在轮船工业配方中的优异性能预示其良好的应用前景。     

Preparation of graphene oxide/natural rubber composites by latex cocoagulation: Relationship between microstructure and reinforcement

Graphene oxide(GO) has recently attracted substantial interest as a possible reinforcing agent for next generation rubber composite materials. In this research, GO was incorporated in natural rubber(NR) composites through latex co-coagulation technique. The microstructures of GO/NR composites were characterized through a combination of transmission electron microscope, scanning electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and Differential scanning calorimeter. The results showed that highly exfoliated GO sheets were finely dispersed into NR rubber matrix with strong interface interaction between GO and NR. The mechanical properties of the GO/NR composites were further evaluated. The results showed that the tensile strength, tear strength and modulus can be significantly improved at a content of less than 2 phr. Especially,GO exhibited specific reinforce mechanism in NR due to the stress-induced crystallization effects of NR. The stress transfer from the NR to the GO sheets and the hindrance of GO sheets to the stress-induced crystallization of NR were further displayed in stress–strain behavior of GO/NR composites. These enhanced properties were attributed to the high surface area of GO sheets and highly exfoliated microstructures of GO sheets in NR.     

SBR-clay-carbon black hybrid nanocomposites for tire tread application

Styrene butadiene rubber-organoclay nanocomposites were prepared with Cloisite 15A via melt intercalation. X-ray diffraction and transmission electron microscopy indicated that the nanostructures are partially exfoliated and intercalated. The nanocomposites exhibited great improvements in tensile strength and tensile modulus. The incorporation of organoclay gave rise to considerable reduction of tan delta and increase in storage modulus in the rubbery region. It is shown that after 6 phr (parts per hundred rubber) clay loading there is not much increase in the properties. The effect of carbon black (N330) on mechanical properties, dynamic mechanical properties, heat build up, abrasion resistance in the nanocomposites having the optimized clay level (6 phr) was investigated. Optimum results were obtained with the addition of 25 phr carbon black. For comparison with the 6phr nanoclay and 25phr N330 (high abrasion furnace carbon black) filled SBR composites, 40 phr N330 filled SBR composites was used. The 6phr organoclay and 25phr N330 filled SBR nanocomposite showed better properties than 40phr carbon filled SBR compound. These results indicate that 6phr organoclay can be replaced by 15 phr carbon black from the conventional SBR-carbon black based tire tread compounds. The Dynamic mechanical analyzer (DMA) results revealed that the new tire tread compound gives better rolling resistance and comparable wet grip resistance and lower heat build up than that of conventional tread compound.     

Preparation,characterization, and application of NR/SBR/Organoclay nanocomposites in the tire industry

The natural rubber/styrene butadiene rubber/organoclay (NR/SBR/organoclay) nanocomposites were successfully prepared with different types of organoclay by direct compounding. The optimal type of organoclay was selected by the mechanical properties characterization of the NR/SBR/organoclay composites. The series of NR/SBR/organoclay (the optimal organoclay) nanocomposites were prepared with various organoclay contents loading from 1.0 to 7.0 parts per hundreds of rubber (phr). The nearly completely exfoliated organoclay nanocomposites with uniform dispersion were confirmed by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The results of mechanical properties measurement showed that the tensile strength, tensile modulus, and tear strength were improved significantly when the organoclay content was less than 5.0 phr. The tensile strength and the tear strength of the nanocomposite with only 3.0 phr organoclay were improved by 92.8% and 63.4%, respectively. It showed organoclay has excellent reinforcement effect with low content. The reduction of the score and cure times of the composites indicated that the organoclay acted as accelerator in the process of vulcanization. The incorporation of a small amount of organoclay greatly improved the swelling behavior and thermal stability, which was attributed to the good barrier properties of the dispersed organoclay layers. The outstanding performance of co‐reinforcement system with organoclay in the tire formulation showed that the organoclay had a good application prospect in the tire industry, especially for the improvement of abrasion resistance and the reduction of production cost. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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