Transport of aromatic solvents through nitrile rubber/epoxidized natural rubber blend membranes

The sorption and diffusion behavior of a series of aromatic solvents through blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) have been studied in the temperature range of 28–70°C. The effect of blend ratio, penetrant size and temperature on the transport properties was investigated. The relationship between the diffusion behavior and the morphology of the system was examined. Different transport parameters such as diffusion coefficient, permeability coefficient and swelling ratio have been calculated. Experimental permeability coefficients were compared with various theoretical models. The van't Hoff relation was used to compute the thermodynamic parameters.     

Transport studies of peanut shell powder reinforced natural rubber composites in aromatic solvents

This article investigates the transport behavior of three aromatic organic solvents, viz. benzene, toluene, and xylene in natural rubber (NR) composite membranes containing peanut shell powder (PSP) as filler at different temperatures by conventional weight‐gain experiments. PSP used in compounding the NR was processed in two particle sizes. The solvent swelling characteristics of NR composites containing both untreated and alkali‐treated fillers were investigated. The computed sorption characteristics were discussed in terms of PSP content, particle size, nature of solvent, and temperature. All the NR‐PSP composites were found to decrease with the uptake of aromatic solvents than NR, but the effect was more significant in the case of alkali‐treated PSP composites. Furthermore, the uptake of solvent decreased with decrease in penetrant size. The estimated Arrhenius activation energies (E_D) for the processes of sorption, diffusion, and permeation showed that E_D was generally highest in xylene at the filler contents investigated. The thermodynamic parameters of the sorption process were also evaluated. The relationship between the transport behavior and the morphology of the system was examined. The mechanism of diffusion is found to be close to Fickian trend in toluene and xylene and Fickian trend in benzene. Comparison between theoretical and experimental diffusion results was made to understand the mechanism of diffusion. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Transport of styrene monomer through natural rubber

The diffusion and transport of inhibitor-free styrene through crosslinked natural rubber (NR) have been studied at various temperatures. NR has been vulcanized by conventional, efficient, peroxide and mixed vulcanization techniques. The dependence of diffusion coefficient on the crosslinking system has been studied for all the systems. The influence of temperature on the sorption and the activation energies of sorption have been calculated. The interaction parameter, permeability, sorption coefficient and molecular weight between crosslinks have been evaluated using the diffusion data. The effect of degree of crosslinking on the sorption characteristics of styrene through NR has also been investigated for the different crosslinking systems. The peroxide system showed lowest uptake and the conventional system showed highest uptake.     

Evaluation of kinetics and transport mechanism of solvents through natural rubber composites containing organically modified gadolinium oxide

The solvent transport properties of the prepared composites were analysed using solvents of varying cohesive energy density and the effect of both modified as well as unmodified filler on the sorption and diffusion behaviour of NR vulcanisates has been investigated. It is found that the equilibrium uptake decreases with increase in filler content, as anticipated owing to the restrictions offered by the filler for solvents to diffuse into the polymer matrix. The mechanism of transport in natural rubber composites was carefully tracked and it was found to exhibit an anomalous mode of solvent transport where the polymer relaxation is in par with the rate of diffusion. Theoretical modelling of the swelling parameters was done and the results were found to be in agreement with existing models. The excellent swelling resistance coupled with the simultaneous improvement in mechanical properties would definitely pave way for the utilisation of these composites as barrier membranes.     

Free volume model and diffusion of organic solvents in natural rubber

The concentration dependence of the diffusion coefficients and the equilibrium isotherms of benzene, o-xylene, ethylbenzene, and chloroform in natural rubber membranes at 303 K were experimentally determined. The data were used to critically test the predictive capability of the Vrentas–Duda free volume model. It was found that although the model works well for some polymer–solvent systems such as toluene-polystyrene, the use of some of the parameters from pure component properties yields unacceptably low diffusion rates for the rubber–solvent systems studied. The parameters D_o1 and ξ obtained from experimental zero-concentration diffusivity data, and parameter V?₁^* calculated from the solvent molecular geometries are needed to achieve good predictions. The diffusion coefficients described by the revised model can be used to predict quite well the breakthrough times of the rubber–solvent systems that were also experimentally measured by a permeation method. © 1995 John Wiley & Sons, Inc.     

Cellulose nanofibres and cellulose nanowhiskers based natural rubber composites: Diffusion,sorption, and permeation of aromatic organic solvents

This article investigates the transport behavior of three aromatic organic solvents, viz. benzene, toluene, and p‐xylene in natural rubber nanocomposite membranes containing cellulose nanofibres (CNFs) and cellulose nanowhiskers (CNWs) isolated from bamboo pulp. The solvent molecules act as molecular probes to study the diffusion, sorption, and permeation through the nanocomposites, and provide information on the nanocomposite structure and matrix–filler interactions. Both the nanocelluloses were found to decrease the uptake of aromatic solvents in nanocomposite membranes, but the effect was more significant in the case on nanofibers compared to nanowhiskers. Furthermore, the uptake decreased with increased penetrant size; being the highest for benzene and the lowest for p‐xylene. Transport parameters such as diffusion coefficient, sorption coefficient, and permeation coefficient have been calculated. Comparison of the experimental values of equilibrium solvent uptake with the predicted values indicated that both the nanocelluloses have restricted the molecular mobility at the interphase and thereby decreased the transport of solvents through the materials; being more significant for nanofibers. The results showed that both the used cellulosic nanomaterials act as functional additives capable of manipulating and tailoring the transport of organic solvents through elastomeric membranes, even at concentrations as low as 2.5 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhancing silica dispersion and interfacial interaction in styrene butadiene/silica rubber composites by using epoxidized styrene butadiene rubber as interfacial compatibilizer

It is usually desired but often challenging to improve the wet traction, and reduce the abrasion and rolling resistance simultaneously in tread rubber, which is referred to as “magic triangle” in tire industry. To fulfill this goal, the filler dispersion and interfacial interaction required to be improved, as they are two essential factors to concurrently govern the ultimate properties of rubber composites. Herein, we synthesized the epoxidized solution polymerized styrene butadiene rubber (ESSBR) with different epoxy level, and used them as interfacial compatibilizer to promote the silica dispersion and silica/rubber interfacial interaction. The epoxy of ESSBR would react with silanol on silica surface and co-crosslink with SSBR simultaneously, therefore build a strong bridge between rubber matrix and filler. By incorporation of 20 phr of ESSBR-15% (15% of double bonds on main chain was epoxidized), the wet grip was improved by 40%, and DIN abrasion and rolling resistance were reduced by 38% and 21%, respectively with hardly sacrifice the mechanical properties. We envisage that this study provides an approach for the fabrication of rubber composites with improved silica dispersion and strengthened interfacial interaction.     

Maleated natural rubber prepared through mechanochemistry and its coupling effects on natural rubber/cotton fiber composites

Maleated natural rubber (MNR) was prepared by blending natural rubber (NR) and maleic anhydride (MA) in an internal mixer at 150 °C through mechanochemistry. The graft reaction of MA onto NR and the hydrogen bonding formed between fiber and MA were confirmed by Fourier transformation infrared spectrometer (FTIR). The quantity of grafted MA increased with increasing MA content. The composites showed better mechanical properties with MNR that contains higher MA content. The MNR with 20 phr MA was used as a coupling agent. Kraus equation showed the incorporation of MNR favored the reinforcement of fiber. The composites with MNR showed higher modulus and tensile strength than those without MNR. The coarse surfaces of the pullout fibers and the high storage modulus of composites with MNR implied the enhancement of interfacial adhesion.     

Molecular-level dispersion of graphene into epoxidized natural rubber: Morphology,interfacial interaction and mechanical reinforcement

The interfacial interaction of composites dominates the properties of polymeric/inorganic nanocomposites. Herein, epoxy and hydroxyl groups are introduced into the natural rubber (NR) molecular chains to anchor oxygenous functional groups on the surface of graphene oxide (GO) sheets and therefore enhance the interfacial interaction between GO and rubber. From the morphological observation and interaction analysis, it is found that epoxidized natural rubber (ENR) latex particles are assembled onto the surfaces of GO sheets by employing hydrogen bonding interaction as driving force. This self-assembly depresses restacking and agglomeration of GO sheets and leads to homogenous dispersion of GO within ENR matrix. The formation of hydrogen bonding interface between ENR and GO demonstrates a significant reinforcement for the ENR host. Compared with those of pure ENR, the composite with 0.7 wt% GO loading receives 87% increase in tensile strength and 8.7 fold increase in modulus at 200% elongation after static in-situ vulcanization.     

乳液共混法制备天然橡胶复合材料研究进展

天然橡胶的应用十分广泛,在其应用过程中,一般需要通过共混改性制备综合性能更加优异的天然橡胶复合材料。本文总结了近年来国内外使用乳液共混法制备天然橡胶复合材料的研究进展。介绍了天然橡胶与炭黑、粘土、白炭黑、碳纳米管、石墨烯等填料乳液共混的新方法。对比了乳液共混法及传统机械共混法制备的橡胶复合材料在加工流程、填料分散情况、材料力学性能等方面的差异;说明了乳液共混法制备天然橡胶复合材料的优势。并对乳液共混法的发展前景进行了展望。     

超支化有机蒙脱土阻燃剂的制备及其在天然橡胶中的应用

采用超支化及有机改性技术成功制备了超支化有机蒙脱土阻燃剂(HFR-OMMT)。通过X射线衍射(XRD)和热失重分析(TGA)手段分析了HFR-OMMT的结构与性能。制备了天然橡胶(NR)/HFR-OMMT复合材料,研究了其阻燃和物理机械性能。结果表明,NR/HFR-OMMT复合材料的力学、耐磨和阻燃性能均得到一定程度的改善。     

马来酸酐接枝天然橡胶对纤维素纤维增强天然橡胶复合材料的增容作用

在无引发剂的熔融状态下,利用剪切力将马来酸酐接枝于天然橡胶分子链上,并将马来酸酐接枝天然橡胶(MNR)作为增容剂添加到纤维素纤维增强天然橡胶复合材料中,研究其对复合材料性能的影响.结果表明,在熔融状态下利用剪切力能够发生自由基反应或Diels-Alder反应,将马来酸酐接枝于天然橡胶分子链上而制得MNR.添加了MNR的纤维增强天然橡胶硫化胶的物理机械性能,尤其是定伸强度比未添加MNR的硫化胶有明显提高,应力弛豫程度减小;扫描电镜分析也说明添加MNR使填料与橡胶基质之间有了更强的界面黏合力.     

Improvement of the properties of natural rubber/ground tire rubber composites through biological desulfurization of GTR

The surface desulfurization of ground tire rubber (GTR) had been carried out via a biological treatment by Thiobacillus sp. with strong sulfur oxidizing capacity. The bonding states and element content on the surface of GTR and desulfurated GTR (DGTR) were evaluated using an X-ray Photoelectron Spectroscopy (XPS). The contact angle of GTR was 120.5° and decreased down to 93.5° after treatment. The cure characteristics, swelling behavior, and crosslink density of natural rubber (NR)/GTR and NR/DGTR were examined. The improvement in mechanical properties was observed for NR/DGTR vulcanizates, which was attributed to the enhanced interfacial interaction between DGTR and NR matrix. The dynamic mechanical analysis (DMA) results showed that NR/DGTR vulcanizates had a reduction of molecular chain friction resistance during glass transition region and Scanning electron microscopy (SEM) studies further indicated a good coherency and homogeneity between DGTR and NR matrix.     

Diffusion of water and artificial seawater through coir fiber reinforced natural rubber composites

The diffusion of water and artificial seawater through cross‐linked coir fiber reinforced natural rubber composites was analyzed. The effect of fiber loading, chemical treatment, and bonding agent on liquid sorption was investigated. Based on the experiments, it is suggested that the probable mechanism of transport in gum compound is Fickian and that in composites is anomalous. The liquid uptake of all the composites is higher in water than that in artificial seawater. The composites showed increased swelling with fiber loading in water and artificial seawater. The influence of silica in the bonding system on swelling of the composites was also analyzed. In the case of gum compound, the desorption process is also Fickian, similar to the absorption of water and seawater. But the desorption of composites exhibited deviation from Fickian behavior. The effect of chemical treatment of coir fibers on the swelling was analyzed and found that the uptake of water and artificial seawater is reduced further in composites containing treated fibers. POLYM. COMPOS., 26:136–143, 2005. © 2005 Society of Plastics Engineers     

Molecular transport of aromatic hydrocarbons through lignin‐filled natural rubber composites

The diffusion and transport of organic solvents through lignin‐filled natural rubber composites have been studied in the temperature range 25–45°C. The diffusion of aromatic solvents through these samples were studied with special reference to the effect of filler concentration, penetrant size, and temperature. Transport coefficients such as diffusion, permeation, and sorption coefficients were estimated. The van't Hoff relationship was used to determine the thermodynamic parameters. The first order kinetic rate constant has been evaluated. A correlation between theoretical and experimental sorption results was evaluated. POLYM. COMPOS., 28:15–22, 2007. © 2007 Society of Plastics Engineers     

腰果酚功能化液体1,2-聚丁二烯橡胶的制备及其对丁苯橡胶/白炭黑复合材料界面作用的增强

采用烯烃复分解法将生物基腰果酚（CA）接枝到1,2-聚丁二烯橡胶（1,2-PB）上制备了苯酚官能化的液体1,2-PB（1,2-PB-g-CA）。结果表明,CA成功接枝到聚丁二烯上,并且在开放体系下可得到官能度大于10%的接枝产物。将1,2-PB-g-CA作为白炭黑填充的丁苯胶轮胎胎面胶配方体系的增塑剂可提高白炭黑在基体中的分散性。同时,此改性低聚物羟基的存在有利于增加白炭黑和橡胶基体的相互作用。且该硫化胶具有较低的滚动阻力和生热性能。     

Enhanced interfacial adhesion of aramid fiber reinforced rubber composites through bio-inspired surface modification and aramid nanofiber coating

In order to improve the interfacial adhesion between aramid fiber (AF) and rubber matrix, a simple and facile method of aramid nanofiber (ANF) coating is demonstrated in this article. Tannic acid (TA) and polyethyleneimine (PEI) are polymerized in an alkaline solution to form a thin TA/PEI (TP) layer that is deposited on the surface of AF to introduce functional groups such as hydroxyl and amino groups. Then, the ANF coating is utilized to construct nanostructures on the surface of AF to improve the interfacial adhesion between the fiber and the rubber. Through hydrogen bonding and/or π-π stacking between the TP layer and the ANF, the ANF coating is firmly attached to the surface of AF. Compared with the untreated fiber, the interfacial adhesion of AF coated with ANF after 1, 3, 5, 7, 9 deposition cycles is increased by 27.8%, 29.1%, 31.5%, 43.1%, and 30.3%, and the mechanical properties of the fibers remain almost unchanged. This method shows its advantages of simple, facile, and time-effective, which is of great significance for industrial applications.     

淀粉/天然橡胶复合材料的力学性能研究

采用不同偶联剂对淀粉活化改性,通过直接共混法制备淀粉/天然橡胶复合材料。研究了淀粉种类、添加量及偶联剂对复合材料的拉伸性能、硬度、耐磨性的变化规律。结果表明:改性后淀粉/天然橡胶复合材料的拉伸性能、硬度、耐磨性明显增加,而改性后木薯淀粉/天然橡胶复合材料的力学性能最佳;采用质量分数为3%的有机硼偶联剂对橡胶材料的改性效果最好。