粘土橡胶纳米复合材料研究进展

简要概述了粘土的有机改性机理、橡胶/粘土纳米复合材料的制备方法、结构与表征和橡胶/粘土纳米复合材料的研究进展.     

Nanoclay distribution and its influence on the mechanical properties of rubber blends

The distribution of modified and unmodified nanoclays inside the rubber phases of immiscible rubber–rubber blends composed of nonpolar–polar natural rubber (NR)/epoxidized natural rubber (ENR) and nonpolar–nonpolar NR/polybutadiene rubber (BR) was investigated for the first time. The distribution of clays at various loadings in the blends was calculated from the viscoelastic properties of the blends. For example, in the 50 : 50 NR/ENR blend, 42% Cloisite 30B migrated to the NR phase, and 58% went to the ENR phase. However, in the same blend, only 7% Cloisite Na⁺ was found in the NR phase, and 93% was found in the ENR phase. Again, in the 50 : 50 NR/BR blends, the NR phase contained 85% Cloisite 30B, whereas 55% Cloisite Na⁺ migrated to the NR phase. All these observations were explained with the help of viscosity, X‐ray diffraction, and morphology analyses. The effect of the distribution of the clay on the mechanical properties was also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

橡胶纳米复合材料研究进展

综述了国内外炭黑／橡胶、白炭黑／橡胶和黏土／橡胶三大类橡胶纳米复合材料的研究进展,对材料的性能特点和制备技术的优缺点进行了总结。     

Novel fabrication of disorderly exfoliated sodium montmorillonite in a styrene–butadiene rubber matrix

Using industrial technologies, we prepared a sodium montmorillonite (Na‐MMT) slurry and an irradiated styrene–butadiene rubber (SBR) latex, and then spray dried them to produce a novel, ultrafine fully vulcanized powder SBR (UFPSBR)/Na‐MMT nanocompound powder in which the nanoscale UFPSBR particles and exfoliated Na‐MMT were isolated and stuck together. When the UFPSBR/Na‐MMT nanocompound powder was mixed with crude SBR, the exfoliated Na‐MMT was disorderly dispersed in the SBR matrix because of the carrier nature of the UFPSBR particle, which is compatible with SBR and disperses easily in the SBR matrix, and the SBR/UFPSBR/Na‐MMT ternary nanocomposite was prepared. When compared with SBR/Na‐MMT binary composites, the SBR/UFPSBR/Na‐MMT ternary nanocomposite has a shorter vulcanization time, higher strength, and better flame retardancy because of the good dispersion of exfoliated Na‐MMT in the SBR matrix with a Na‐MMT loading range of 4 phr. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2013     

Synthesis and characterization of in situ sodium‐activated and organomodified bentonite clay/styrene–butadiene rubber nanocomposites by a latex blending technique

In this article, we describe a method used to prepare an in situ sodium‐activated, organomodified bentonite clay/styrene–butadiene rubber nanocomposite master batch via a latex blending technique. The clay master batch was used for compound formulation. Octadecyl amine was used as an organic intercalate. The clay was purchased from local suppliers and was very cheap. Sodium chloride was used for in situ activation of the clay. The wide‐angle X‐ray diffraction data indicated that the in situ sodium activation helped to increase the intergallery distance from 1.28 to 1.88 nm. A transmission electron micrograph indicated intercalation and partial exfoliation. The thermal properties were relatively better in the case of the sodium‐activated, organomodified bentonite‐clay‐containing compound. A substantial improvement in physical properties such as the modulus, tensile strength, tear strength, and elongation at break was observed in the case of the in situ sodium‐activated compound. A cation‐exchange capacity equivalent (of the clay) of 1.5 times the octadecyl amine was the optimum dose for the modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

导电硅橡胶导电性和电热性的研究

对乙炔炭黑作导电填料的导电硅橡胶的导电性和电热性进行了研究。结果表明，由乙炔炭黑用量和渗滤阈可以预测和控制导电硅橡胶的体积电阻率；导电硅橡胶的电阻－温度变化规律符合隧道效应理论模型，导电硅橡胶的电压－电流特性呈非线性欧姆性，且乙炔炭黑用量越大，电压－电流特性的非线性欧姆性越显著；发热量与热损耗量达到平衡时，导电硅橡胶的表面温度可维持140℃，导电硅橡胶可作面状发热体使用；在满足导电性能的前提下，为保证导电硅橡胶良好的物理性能，应控制乙炔炭黑用量。     

Transport properties of natural rubber latex layered clay nanocomposites

Natural rubber latex layered clay nanocomposites were prepared with low loadings of nanoclay using conventional compounding technique. A higher loading of clay resulted in processing difficulties due to viscosity build up. X‐ray analysis showed that nanocomposites in which layered silicate layers were either delaminated or ordered as in an intercalated structure was obtained. Partially exfoliated structure was observed from TEM photographs of nanocomposites with 3 phr nanoclay. The transport properties, sorption, diffusion, and permeation coefficients were measured using the solvent toluene at 303 K. A higher decrease for the diffusion coefficient for nanocomposites directs the presence of tortuous path for the diffusing molecules. Thermodynamic parameters show a better compatibility for the silicates with rubber resulted in the formation of an elastomeric network. Gas permeability results of the nanocomposites suggest a better barrier resistancefor oxygen molecules even in lower loading of nanoclay and different gas transport models (Nielsen, Bharadwaj, Cussler) were applied to describe the behavior of these nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Impact of curing temperature on microstructures and properties of isobutylene–isoprene rubber/clay nanocomposites

In this work, the influence of curing temperature on microstructures of isobutylene–isoprene rubber/clay nanocomposites (IIRCNs) prepared by melt compounding was characterized using wide‐angle X‐ray diffraction and TEM. The gas barrier and tensile properties of IIRCN cured under different temperature were examined. The results reveal that high pressure, curing reactions, and reactions of amine intercalants with curing agents together play important roles on determining the final microstructures of cured IIRCNs. Changing curing temperature would dramatically alter intercalated structure, dispersion homogeneity, filler–rubber interaction strength, and crosslinking density of obtained IIRCN, resulting in great difference in final properties. Finally, some suggestions for the preparation of successful RCNs were proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of clay/styrene‐butadiene rubber nanocomposites

Based on the character of a clay that could be separated into many 1‐nm thickness monolayers, clay styrene‐butadiene rubber (SBR) nanocomposites were acquired by mixing the SBR latex with a clay/water dispersion and coagulating the mixture. The structure of the dispersion of clay in the SBR was studied through TEM. The mechanical properties of clay/SBR nanocomposites with different filling amounts of clay were studied. The results showed that the main structure of the dispersion of clay in the SBR was a layer bundle whose thickness was 4–10 nm and its aggregation formed by several or many layer bundles. Compared with the other filler, some mechanical properties of clay/SBR nanocomposites exceeded those of carbon black/SBR composites and they were higher than those of clay/SBR composites produced by directly mixing clay with SBR through regular rubber processing means. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1873–1878, 2000     

Preparation and properties of styrene–butadiene rubber based nanocomposites: The influence of the structural and processing parameters

Rubber‐based nanocomposites were prepared with octadecyl amine modified sodium montmorillonite clay and styrene–butadiene rubber with different styrene contents (15, 23, and 40%). The solvent used to prepare the nanocomposites, the cure conditions, and the cure system were also varied to determine their effect on the properties of the nanocomposites. All the composites were characterized with X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The XRD studies revealed exfoliation for the modified clay–rubber composites. The TEM photomicrographs showed a uniform distribution of the modified clay in the rubber matrix. The thickness of the particles in the exfoliated composites was around 10–15 nm. Although the FTIR study of the unmodified and modified clays showed extra peaks due to the intercalation of the amine chains into the gallery, the spectra for the rubber–clay nanocomposites were almost the same because of the presence of a very small amount of clay in the rubber matrix. All the modified clay–rubber nanocomposites displayed improved mechanical strength. The styrene content of the rubber had a pronounced effect on the properties of the nanocomposites. With increasing styrene content, the improvement in the properties was greater. Dicumyl peroxide and sulfur cure systems displayed similar strength, but higher elongation and slightly lower modulus values were obtained with the sulfur cure system. The curing of the samples at four different durations at 160°C showed that the cure time affected the properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 698–709, 2004     

硅橡胶在电气绝缘方面的应用进展

简述了国内外硅橡胶(高温硫化型硅橡胶、室温硫化型硅橡胶、液体硅橡胶等)在电气绝缘方面的应用情况。     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005     

Effect of iron oxide on vulcanization kinetics and electrical conductance of butyl rubber composites

This paper investigates the effect of iron oxide concentration on the vulcanization process, electrical conductance during swelling in kerosene, and sheds some light on the possible mechanism of vulcanization kinetics. The rate and degree of crosslinking have been evaluated as a function of Fe₂O₃ concentration. It was found that the characteristic time constant during vulcanization decreases as the Fe₂O₃ concentration increases. The activation energy of the crosslinking reaction is calculated. An abrupt decrease in electrical conductance appears after a characteristic time of swelling. A modified model is suggested to calculate the separation distance in the conductive rubber matrix. The effect of microwave irradiation on electrical conductance and separation distance between conductive aggregate of butyl rubber (IIR) composites is also studied. Fe₂O₃ inhibits the degradation of IIR composites and microwave irradiation enhances the texturing microstructure of rubber matrix. © 2000 Society of Chemical Industry     

Styrene–butadiene rubber/cellulose II/clay nanocomposites prepared by cocoagulation—mechanical properties

In this work, nanocomposites of styrene butadiene rubber (SBR), cellulose II, and clay were prepared by cocoagulation of SBR latex, cellulose xanthate, and clay aqueous suspension mixtures. The incorporated amount of cellulose II was 15 phr, and the clay varied from 0 to 7 phr. The influence of cellulose II and clay was investigated by rheometric, mechanical, physicochemical, and morphological properties. From the analysis of transmission electron microscopy (TEM), dispersion in nanometric scale (below 100nm) of the cellulosic and mineral components throughout the elastomeric matrix was observed. XRD analysis suggested that fully exfoliated structure could be obtained by this method when low loading of silicate layers (up to 5 phr) is used. The results from mechanical tests showed that the nanocomposites presented better mechanical properties than SBR gum vulcanizate. Furthermore, 5 phr of clay is enough to achieve the best tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adhesion properties and thermal degradation of silicone rubber

Silicone rubber is suitable for the thermal insulator of the rocket motors owing to its heat resisting properties as well as its excellent elasticity and restoring force. However, the adhesion properties of the silicone rubber should be improved greatly to be used as the thermal insulator because of its poor adhesiveness coming from the low surface tension. Functional groups were incorporated through copolymerization to the silicone rubber to induce chemical reaction with the functional groups in the propellant/liner components to enhance the adhesion properties. Peeling tests results disclosed that the incorporation of amine groups was the most efficient for the adhesiveness enhancement and that addition of carbon black improved the adhesiveness still more. Stability against thermal degradation of the silicone rubber was examined by measuring the activation energy through the thermogravimetric analysis. The results revealed that the compounding of the Cloisite® clays boosted up the thermal stability of the silicone rubber much more greatly than that of carbon black. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2782–2787, 2007     

Characteristics of nitrile–butadiene rubber layered silicate nanocomposites with silane coupling agent

Nanocomposites of organophilic montmorillonite (C18‐MMT), nitrile–butadiene rubber (NBR), and a coupling agent were produced during a melt compounding process at room temperature. During the process, it was clearly observed that organo‐MMT particles were exfoliated into nanoscale layers of approximately 1–30 nm thickness, in addition to their original 40 μm thickness. These MMT layers were uniformly dispersed in the NBR matrix. The effects of a coupling agent such as 3‐(mercaptopropyl)trimethoxy silane in C18‐MMT/NBR nanocomposites were studied. The C18‐MMT/NBR nanocomposites in the presence of the coupling agent were identified and characterized by X‐ray diffraction, transmission electron microscopy, a universal testing machine, thermogravimetric analysis, and IR spectroscopy. It was observed that an additional silane coupling agent, 3‐(mercaptopropyl)trimethoxy silane, enhanced the chemical interaction and was accompanied by the formation of Si? O? Si coupling bonds between C18‐MMT and the coupling agent and Si? C coupling bonds between NBR and the coupling agent. This work resulted in improved properties of organo‐MMT/NBR nanocomposites because of the nanoscale effects and strong interaction of the coupling bonds between NBR and organo‐MMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2633–2640, 2003     

Preparation and properties of ethylene–propylene–diene rubber/organomontmorillonite nanocomposites

Ethylene–propylene–diene rubber (EPDM)/organomontmorillonite (OMMT) nanocomposites were prepared with a maleic anhydride grafted EPDM oligomer as a compatibilizer via melt intercalation. X‐ray diffraction and transmission electron microscopy indicated that the silicate layers of OMMT were exfoliated and dispersed uniformly as a few monolayers in nanocomposites. The change in the crystallization behavior of the nanocomposites was examined. The nanocomposites exhibited great improvements in the tensile strength and tensile modulus. The incorporation of OMMT gave rise to a considerable reduction of tan δ and an increase in the storage modulus. Moreover, the solvent resistance of the nanocomposites increased remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 440–445, 2004     

Improvement of cutting and chipping resistance of carbon black-filled styrene butadiene rubber by addition of nanodispersed clay

A novel, effective approach to improve the cutting and chipping resistance (CCR) of carbon black (CB)-filled styrene butadiene rubber (SBR) composite was reported in this study. CCR of SBR was dramatically improved more than 30% by addition of 4 phr nanodispersed clay (NC), while not decreasing the stress at 100% and the Shore A hardness of the composite. The curing characteristics, loss tangent (tan δ), and the strength of filler network of the composites were further measured by a Disk Oscillating Rheometer and a rubber processing analyzer, respectively. It was found that the addition of NC led to a slightly lower crosslink density, higher tan δ, and stronger filler network, which contributed to the higher CCR. Therefore, the novel layered NC is more efficient in improving CCR when compared with CB. The results are expected to promote the application of NC in rubber industry. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of resol–layered silicate nanocomposites by reaction exfoliation with acid‐modified montmorillonite

Resol–layered silicate nanocomposites were prepared by the intercalative polymerization of phenol and formaldehyde in the presence of acid‐modified montmorillonite (HMMT). The nanocomposites were studied by means of X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), and rheological measurements. The exfoliation of HMMT was promoted by the intragallery reactions catalyzed by protons in the galleries of the clay, whereas the extragallery polymerization catalyzed by ammonia went on simultaneously. The nanocomposites showed higher glass‐transition temperatures in the DMA diagram compared with the resol counterparts. The impact strength was improved significantly by the incorporation of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 791–797, 2004     

Melt‐compounded natural rubber nanocomposites with pristine and organophilic layered silicates of natural and synthetic origin

Composites based on natural rubber (NR) and containing organophilic and pristine layered silicates of natural and synthetic origin were produced by melt compounding and sulfur curing. The curing, thermomechanical, and mechanical properties of the mixes, which contained 10 phr (parts per hundred parts of rubber) silicates, were determined. The dispersion of the silicates was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Organophilic clays accelerated the sulfur curing of NR, which was believed to occur because of a complexation reaction in which the amine groups of the clay intercalants participated. The property improvements caused by the fillers were ranked as follows: organophilic clays > pristine synthetic layered silicate (sodium fluorohectorite) > pristine natural clay (purified sodium bentonite) > precipitated nonlayered silica (used as a reference). This was attributed to partial intercalation of the organophilic clay by NR on the basis of XRD and TEM results and to the high aspect ratio of the fluorohectorite. Apart from intercalation, severe confinement (i.e., the collapse of the interlayer distance) of the organoclays was observed. This peculiar feature was traced to the formation of a zinc coordination complex, which extracted the amine intercalant of the organoclays, thus causing the collapse of the layers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 813–819, 2004