Thermoplastic elastomeric blend of nitrile rubber and poly(styrene‐co‐acrylonitrile). I. Effect of mixing sequence and dynamic vulcanization on mechanical properties

The effects of dynamic vulcanization and blend ratios on mechanical properties and morphology of thermoplastic elastomeric (TPE) compositions, based on blends of nitrile rubber (NBR) and poly(styrene‐co‐acrylonitrile) (SAN), were studied. The TPE composition prepared by adding a rubber‐curatives masterbatch to softened SAN yields higher mechanical properties than that prepared by adding curatives to the softened plastic–rubber preblend. The blends having a higher rubber–plastic ratio (60 : 40 to 80 : 20) display thermoplastic elastomeric behavior, whereas those having a higher plastic–rubber ratio (50 : 50 to 90 : 10) display the behavior of impact‐resistant plastics. DSC studies revealed that NBR and SAN are thermodynamically immiscible. SEM studies of the thermoplastic elastomeric compositions show that SAN forms the matrix in which fine particles of NBR form the dispersed phase. It was further confirmed by dynamic mechanical thermal analysis. Dynamic vulcanization causes a decrease in the size of dispersed particles and improvement in mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1976–1987, 2003     

Effect of anhydride‐modified ethylene–propylene–diene rubber and ethylene–vinyl acetate copolymers on the compatibilization of nitrile rubber/ethylene–propylene–diene rubber blends

The effects of maleic anhydride modified ethylene–propylene–diene rubber (EPDMMA) and maleic anhydride modified ethylene–vinyl acetate (EVAMA) on the compatibilization of nitrile rubber (NBR)/ethylene–propylene–diene rubber (70:30 w/w) blends vulcanized with a sulfur system were investigated. The presence of EPDMMA and EVAMA resulted in improvements of the tensile properties, whereas no substantial change was detected in the degree of crosslinking. The blend systems were also analyzed with scanning electron microscopy and dynamic mechanical thermal analysis. The presence of EVAMA resulted in a blend with a more homogeneous morphology. The compatibilizing effect of this functional copolymer was also detected with dynamic mechanical analysis. A shift of the glass‐transition temperature of the NBR phase toward lower values was observed. The presence of EPDMMA and EVAMA also increased the thermal stability, as indicated by an improvement in the retention of the mechanical properties after aging in an air‐circulating oven. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2408–2414, 2003     

Morphology and dynamic mechanical properties of natural rubber/nitrile rubber blends containing trans‐polyoctylene rubber as a compatibilizer

The use of trans‐polyoctylene rubber (TOR) as a compatibilizer for blends of natural rubber (NR) and acrylonitrile‐butadiene rubber (NBR) was investigated using atomic force microscopy (AFM) and dynamic mechanical analysis (DMA). The NR/NBR blends containing varying proportions of TOR were prepared in an internal mixer. AFM micrographs of NR/NBR blend at 50/50 (w/w) composition showed heterogeneous phase morphology with NR as a matrix and NBR as a dispersed phase. Inclusion of TOR in the NR/NBR blend altered the phase morphology by reducing the size of the NBR phase. DMA of NR/NBR/TOR showed reduction in tan δ peak height of NBR and an increase in storage modulus E′ in the rubbery region for the NR/NBR blends. A comparison of the E′ obtained from experimental data with that from theoretical models was made to deduce the location of TOR in the blend. Based on the fittings of calculated and experimental values of E′, it was inferred that TOR was incorporated into the NR phase at lower proportion as well as at the interfacial region at higher proportion. The Cole–Cole plot illustrated the compatibilizing effect of TOR. Copyright © 2004 Society of Chemical Industry     

Oil resistant thermoplastic elastomers of nitrile rubber and high density polyethylene blends

Different grades of oil resistant thermoplastic elastomers (TPE) based on blends of nitrile rubber (NBR) and high density polyethylene (HDPE) have been developed. Chemical treatment of HDPE to evolve compatibility with NBR and dynamic vulcanization with different curatives have been studied. Determination of physico‐mechanical and thermal properties and relative crystallinity of these blends have been carried out. Oil resistance characteristics of the blends have been evaluated in different commercially used oils and fuels for applications as a substitute for NBR/polyvinyl chloride (PVC) blends.     

Epoxidized natural rubber as a reinforcement modifier for silica‐filled nitrile rubber

Hydrated silicas impart better physical properties to polar rubbers, compared to those of hydrocarbon rubbers. However, to achieve optimum properties silane coupling agents are crucial in such formulations. Epoxidized natural rubber (ENR) in small proportions is used as a reinforcement modifier for silica‐filled nitrile rubber (NBR). Two systems of cure were used: N‐cyclohexyl‐ 2‐benzthiazyl sulfenamide (CBS) alone and in combination with diphenyl guanidine (DPG). In the CBS accelerated system, incorporation of an optimum concentration of about 15% of ENR on total rubber was found to improve technological properties. Addition of a secondary accelerator further improves these properties. Comparable results are obtained with those containing coupling agent and NBR–ISAF. High bound rubber and volume fraction values indicate a high polymer–filler interaction and gel content resulting from the NBR–ENR interaction. Results of this study reveal that ENR could be used as a reinforcement modifier for the NBR–silica system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 292–306, 2002     

氯醚橡胶/丁腈橡胶共混物的结构与性能

研究了不同并用比的氯醚橡胶（ECO）／丁腈橡胶（NBR）共混物的相态结构,力学性能,耐老化性能和耐油性能,透射电镜照片显示：ECO／NBR为70／30（质量份,下同）时共混物呈双连续相：为60／40和40／60时ECO都为分散相,且两相界面清晰。加入NBR降低了ECO的拉伸强度和看断伸长率,以及耐热空气老化性能,随着NBR用量的提高,共混物硫化胶在油中的体积变化率增加,ECO／NBR为70／30时硫化胶在100℃热油中的性能保持率最高,而且体积变化率与ECO的相当。     

Properties of alumina nanoparticle‐filled nitrile‐butadiene‐rubber/phenolic‐resin blend prepared by melt mixing

Effect of alumina nanoparticle (ANP) on the properties of rubber compounds based on nitrile‐butadiene‐rubber (NBR) and NBR/phenolic‐resin (PH) blend is examined. To investigate the surface characteristics of the nanoparticles on the performance of nanoalumina‐filled compounds, trimethoxyvinylsilane (MVS) is attached chemically on the surface of ANP through an appropriate functionalization process. Various NBR and NBR/PH compounds filled with ANP and functionalized ANP (f‐ANP) are prepared via melt mixing using traditional open two‐roll mill. Microscopic analysis carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveals good dispersion of nanoalumina within the rubber matrix, indicating the effectiveness of the melt mixing for fabrication of the rubber/alumina nanocomposites. Nanocomposites of NBR and NBR/PH are subjected to various physical and mechanical tests including swelling, tensile, abrasion, and thermal tests and the role of ANP and f‐ANP on these properties are discussed. The results obtained based on this analysis suggest that as‐received ANP can provide good interaction with NBR possibly due to hydrogen bonding between hydroxyl group present on the nanoparticle surface and acrylonitrile group of NBR. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Thermoplastic polyurethane and nitrile butadiene rubber blends with layered double hydroxide nanocomposites by solution blending

Polymer blending coupled with nanofillers has been widely accepted as one of the cheaper methods to develop high‐performance polymeric materials for various applications. In the present work, dodecyl sulfate intercalated Mg? Al‐based layered double hydroxide (DS‐LDH) was used as nanofiller in the synthesis of polyurethane blended with nitrile butadiene rubber (PU/NBR; 1:1 w/w) nanocomposites, which were subsequently characterized. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the partial dispersion of Mg? Al layers in PU/NBR blends at lower filler content followed by aggregation at higher filler loading. In comparison to the neat PU/NBR blend, the tensile strength (156%) and elongation at break (21%) show maximum improvement for 1 wt% filler loading. The storage and loss moduli, thermal stability and limiting oxygen index of the nanocomposites are higher compared to the neat PU/NBR blend. Glass transition temperature and swelling measurements increase up to 3 wt% DS‐LDH loading in PU/NBR compared to either neat PU/NBR or its other corresponding nanocomposites. XRD and TEM analyses indicate the partial distribution of DS‐LDH in PU/NBR blends suggesting the formation of partially exfoliated nanocomposites. The improvements in mechanical, thermal and flame retardancy properties are much greater compared to the neat blend confirming the formation of high‐performance polymer nanocomposites. Copyright © 2009 Society of Chemical Industry     

Polymer blends of carboxylated butadiene‐acrylonitrile copolymer (nitrile rubber) and polyamide 6 developed in twin screw extrusion

Polymer blends of carboxylated butadiene‐acrylonitrile copolymer (nitrile rubber) and polyamide 6 (PA6) were developed in twin screw extrusion. The rubber was cured with SP 1045 methylol phenolic resin during melt mixing in twin screw. Effect of degree of carboxylation in the rubber phase on blend properties has been assessed. Phase morphologies have been characterized using transmission electron microscopy. A compatibilizing NBR‐g‐Nylon 6 graft copolymer generated in situ during melt mixing via interfacial reaction between the ? COOH groups in NBR and the ? NH₂ end groups in nylon 6 has been effective in generating a fine and stable dispersion of the rubber within the polyamide matrix. The graft copolymer has been characterized by DMTA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 372–377, 2007     

共混比对丁腈橡胶/氯醚橡胶性能的影响

研究了共混比时常规共混及动态硫化共混丁腈橡胶(NBR)／氯醚橡胶(ECO)的力学性能及加工流变性能的影响。结果表明,共混比对NBR／ECO胶料的力学性能及加工流变性能影响显著。NBR经动态硫化后,压缩永久变形及挤出胀大明显减小,拉伸强度提高,表现黏度随ECO用量的增大而减小。共混比对常规共混胶的表观黏度影响不大。动态硫化有利于改善NBR／ECO胶料的加工性能。     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005     

Aluminum powder filled nitrile rubber composites

Effect of aluminum powder on the properties of nitrile rubber (NBR) composites and the role of bonding agent viz. hexamethylene tetramine‐resorcinol has been investigated. Shore A hardness of the aluminum powder filled composites is lower than that of high abrasion furnace (HAF) and acetylene black (ACB) filled nitrile rubber composites and can be increased by the addition of bonding agent. Equilibrium swelling decreased considerably by the use of hexamethylene tetramine‐resorcinol, suggesting an improved nitrile rubber–aluminum powder adhesion. A marked increase in thermal conductivity is obtained with the incorporation of aluminum powder. Increased thermal conductivity reduced the additional time needed for the vulcanization of thick rubber articles and imparted uniform curing throughout the material. In nitrile rubber, the modulus and tensile strength followed the order HAF > ACB > aluminum powder. Combination of HAF and aluminum powder in NBR gave composites with good thermal conductivity and mechanical properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3156–3161, 2004     

Reactive compatibilization of a nitrile rubber/phenolic resin blend: Effect on adhesive and composite properties

Resole phenolic resins containing various p-cresol (PC) to phenol (P) mol ratios were prepared and characterized. These phenolic resins were blended with nitrile rubber (NBR) and the measurements of adhesive joint strength, stress–strain properties, DSC, TGA, DMA, TEM, and SEM were performed using a 50 : 50 NBR/phenolic resin blend. It was observed that the adhesive joint strength and the mechanical properties of the blend enhanced significantly on incorporation of p-cresol into the phenolic resin, and the optimum p-cresol/phenol mol ratio was in the vicinity of 2 : 1. Observation of a more continuous phase and the increase in T_g of the rubber region in the blend indicated increased reactivity and compatibilization of NBR with phenolic resin as p-cresol was incorporated. The effect of silica filler on the properties of the nitrile rubber/phenolic resin blend was also studied without and with p-cresol modification and the results suggest that silica filler take not only the role of a reinforcing filler in the nitrile–phenolic–silica composite, but also a role as surface compatibilizer of the blend components. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1187–1201, 1998     

Effect of zinc oxide nanoparticles as cure activator on the properties of natural rubber and nitrile rubber

Zinc oxide (ZnO) nanoparticles were synthesized by homogeneous precipitation and calcination method and were then characterized by transmission electron microscopy and X‐ray diffraction analysis. Synthesized ZnO was found to have no impurity and had a dimension ranging from 30–70 nm with an average of 50 nm. The effect of these ZnO nanoparticles as cure activator was studied for the first time in natural rubber (NR) and nitrile rubber (NBR) and compared with conventional rubber grade ZnO with special reference to mechanical and dynamic mechanical properties. From the rheograph, the maximum torque value was found to increase for both NR and NBR compounds containing ZnO nanoparticles. ZnO nanoparticles were found to be more uniformly dispersed in the rubber matrix in comparison with the conventional rubber grade ZnO as evident from scanning electron microscopy/X‐ray dot mapping analysis. The tensile strength was observed to improve by 80% for NR when ZnO nanoparticles were used as cure activator instead of conventional rubber grade ZnO. An improvement of 70% was observed in the case of NBR. The glass transition temperature (T_g) showed a positive shift by 6°C for both NR and NBR nanocomposites, which indicated an increase in crosslinking density. The swelling ratio was found to decrease in the case of both NR and NBR, and volume fraction of rubber in swollen gel was observed to increase, which supported the improvement in mechanical and dynamic mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

溴化丁基橡胶/丁腈橡胶并用胶微观结构及性能研究

用改性沥青作相容剂,研究溴化丁基橡胶(BIIR)/丁腈橡胶(NBR)并用胶的微观结构和性能。结果表明:与未添加改性沥青CJ-100的BIIR/NBR并用胶相比,添加改性沥青CJ-100的BIIR/NBR并用胶的相容性较好,加工性能改善,气密性、耐屈挠和耐臭氧性能提高;添加5份改性沥青CJ-100的BIIR/NBR(并用比为80/20)并用胶物理性能、气密性、耐屈挠和耐臭氧性能较好,气密性接近全BIIR胶料,有望用于全钢载重子午线轮胎气密层。     

Preparation and characterization of acrylonitrile–styrene–methylmethacrylate terpolymer as a compatibilizer for rubber blends

Acrylonitrile‐co‐styrene‐co‐methylmethacrylate (AN‐S‐MMA) terpolymer was prepared by bulk and emulsifier‐free emulsion polymerization techniques. The bulk and emulsion terpolymers were characterized by means of Fourierr transform infrared spectroscopy, ¹³C nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, thermal gravimetric analysis, and elemental analysis. The kinetics of the terpolymerization were studied. The terpolymers were then incorporated into butadiene—acrylonitrile rubber (NBR)/ethylene propylene diene monomer rubber (EPDM) blends and into chloroprene rubber (CR)/EPDM blend. The terpolymers were then tested for potential as compatibilizers by using scanning electron microscopy and differential scanning calorimetry. The terpolymers improved the compatibility of CR/EPDM and NBR/EPDM blends. The physicomechanical properties of CR/EPDM and NBR/EPDM blend vulcanizates revealed that the incorporation of terpolymers was advantageous, since they resulted in blend vulcanizates with higher 100% moduli and with more thermally stable mechanical properties than the individual rubbers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3143–3153, 2003     

Dynamically vulcanized nitrile rubber/polypropylene thermoplastic elastomers

A new compatibilized method was used to prepare thermoplastic elastomer (TPE) of nitrile rubber (NBR) and polypropylene (PP) with excellent mechanical properties by dynamic vulcanization. Glycidyl methacrylate (GMA) grafted PP/amino‐compound was used as a compatibilizer. The effects of the curing systems, compatibilizer, PP type, and reprocessing on the mechanical properties of NBR/PP thermoplastic elastomers were investigated in detail. Experimental results showed that the addition of amino‐compound in the compatibilzer can significantly increase the mechanical properties of the NBR/PP thermoplastic elastomer. Compared with other amino‐compounds, diethylenetriamine (DETA) has the best effect. PP with higher molecular weight is more suitable for preparing NBR/PP thermoplastic elastomer with high tensile strength and high elongation at break. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2862–2866, 2002     

累托石/丁腈橡胶纳米复合材料的结构与性能

用乳液共混共凝法制备了累托石／丁腈橡胶(NBR)复合材料,分别进行了透射电镜分析和X射线衍射分析,研究了其力学性能和气体阻隔性能。结果表明,累托石以厚度为10．00nm左右的晶束均匀分散于NBR中;累托石／NBR复合材料属于隔离型纳米复合材料;与传统的炭黑／NBR复合材料和白炭黑／NBR复合材料相比,累托石／NBR纳米复合材料具有高的邵尔A型硬度和300％定伸应力．尤其是其气体阻隔性能得到了显著提高。     

Study on polypropylene/natural rubber blend with polystyrene‐modified natural rubber as compatibilizer

Polystyrene‐modified natural rubber (SNR) was prepared in the laboratory and subsequently used as compatibilizer in polypropylene/natural rubber (PP/NR) blends. The effect of SNR (at 5%, 10%, 15% and 20% by volume) in PP/NR (70/30) blend was studied by maintaining the rubber volume while PP volume was replaced by SNR accordingly. The sequence of mixing was found to affect the blend morphology and tensile properties. The effect of curatives on the tensile properties of the blends was also investigated. The addition of curatives into the rubbers in PP/NR/SNR improved the tensile properties significantly compared with the PP/NR reference blend. For a semi‐efficient curative system, SNR loading at 10% gave the best overall tensile properties, while for an efficient curative system, 5% SNR loading resulted in improvements in tensile strength and stiffness of over 20% and 40%, respectively, compared with the reference. © 2002 Society of Chemical Industry     

Improvement of the homogeneity of SBR/NBR blends using polyglycidylmethacrylate‐g‐butadiene rubber

Polyglycidylmethacrylate grafted butadiene rubber (PGMA‐g‐BR) was synthesized by a graft solution copolymerization technique. The PGMA content was determined through titration against HBr. The PGMA‐g‐BR was blended with styrene butadiene rubber/butadiene acrylonitrile rubber (SBR/NBR) blends with different blend ratios. The SBR/NBR (50/50) blend was selected to examine the compatibility of such blends. Compatibility was examined using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and viscosity measurements. The scanning electron micrographs illustrate the change of morphology of the SBR/NBR rubber blend as a result of the incorporation of PGMA‐g‐BR onto that blend. The T_gs of SBR and NBR in the blend get closer upon incorporation of PGMA‐g‐BR 10 phr, which indicates improvement in blend homogeneity. The intrinsic viscosity (η) versus blend ratio graph shows a straight‐line relationship, indicating some degree of compatibility. Thermal stability of the compatibilized and uncompatibilized rubber blend vulcanizates was investigated by determination of the physicomechanical properties before and after accelerated thermal aging. Of all the vulcanizates with different blend ratios under investigation, the SBR/NBR (25/75) compatibilized blend possessed the best thermal stability. However, the SBR/NBR (75/25) compatibilized blend possessed the best swelling performance in brake fluid. The effect of various combinations of inorganic fillers on the physicomechanical properties of that blend, before and after accelerated thermal aging, was studied in the presence and absence of PGMA‐g‐BR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1559–1567, 2006