Compatibilising effect of carbon black on morphology of NR–NBR blends

Abstract

It is proposed that a non-polar filler can reduce interfacial energies between polar and non-polar polymers. Experiments have been carried out to test this hypothesis using carbon black as the filler in blends of natural rubber (NR) and a nitrile rubber (NBR) with an acrylonitrile content of 45%. Blends of NR–NBR (70/30) were prepared in an internal mixer with varying amounts of carbon black. The dramatic decrease in domain size on addition of carbon black was nonetheless lower than that predicted. Further experiments showed that the amount of carbon black available at the interface for compatibilisation was influenced by preferential incorporation into the lower viscosity elastomer (NBR). Thus, elastomers of similar viscosity should be added to the mixer prior to the carbon black in order to maximise the amount of ‘free’ unwetted carbon black present when the elastomers are blended together. Blending experiments carried out under these conditions resulted in a morphology close to the prediction based on thermodynamic theory.     

Mechanical and sorption properties of poly(ethylene-co-vinyl acetate)(EVA) compatibilized acrylonitrile butadiene rubber/natural rubber blend systems

Poly (ethylene-co-vinyl acetate) (EVA) has been used as a compatibilizer for heterogeneous natural rubber/acrylonitrile butadiene rubber (NR/NBR) blends. NR/NBR (50/50) blends were compatibilized with varying amounts, from 0 to 10 parts per hundred rubber (phr), of EVA. The compatibility of the blend components in presence of EVA has been evaluated in terms of mechanical and sorption characteristics. The mechanical properties were found to be improved by the addition of EVA upto 6 phr. The solvent resistance of the compatibilized samples has been observed to be higher compared to the uncompatibilized blends; attributed to the increased interfacial adhesion between the blend components. DSC studies showed a shift of glass transition temperatures of the blend components towards higher temperatures indicating increased rigidity of the matrix in presence of EVA.     

偶联剂Si 69对NR/BR/NBR共混硫化胶性能的影响

研究了偶联剂Si 69对NR／BR／NBR共混胶体系的硫化特性、交联密度和硫化胶的物理机械性能及动态力学性能的影响。结果表明，偶联剂Si 69在共混硫化胶中可以起到提高聚合物与填料间的相互作用和交联密度的作用，它在白炭黑增强硫化胶中对性能的改善比在炭黑增强硫化胶中的改善更显著。     

Properties of ASA/SAN/NBR ternary blends: effect of AN content in NBR

Abstract

Nitrile–butadiene rubbers (NBRs) with different acrylonitrile (AN) contents were used to toughen acrylonitrile–styrene–acrylic terpolymer/styrene–acrylonitrile copolymer (ASA/SAN) blends. The properties of the ASA/SAN/NBR ternary blends were investigated via dynamic mechanical analysis, heat distortion temperature, Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). The effects of AN content in NBR on physical properties, heat resistance and morphology of the ternary blends were studied. Heat distortion temperature of the blends decreased with increasing AN content of NBR. The impact strength reached the maximum value when 20 phr NBR with 26 wt-%AN content was added. Images (SEM) were in accordance with results of mechanical properties.     

环氧树脂增强聚氯乙烯/丁腈橡胶共混胶的性能

用环氧树脂(EP)增强聚氯乙烯/丁腈橡胶(PVC/NBR)共混胶,研究了EP用量对共混胶力学性能的影响,考察了EP对炭黑增强PVC/NBR共混胶力学性能的影响,并用扫描电子显微镜分析了共混胶的微观形貌。结果表明,用EP增强PVC/NBR共混胶,胶料的力学性能提高,且老化后性能变化不明显。在EP用量为18份左右时共混胶的综合性能最佳。EP对炭黑增强PVC/NBR共混胶力学性能的改善有一定作用。EP在PVC/NBR共混胶中原位聚合生成了直径约为200 nm的纤维。     

Influences of trans‐polyoctylene rubber on the physical properties and phase morphology of natural rubber/acrylonitrile–butadiene rubber blends

The influence of trans‐polyoctylene rubber (TOR) on the mechanical properties, glass‐transition behavior, and phase morphology of natural rubber (NR)/acrylonitrile–butadiene rubber (NBR) blends was investigated. With an increased TOR level, hardness, tensile modulus, and resilience increased, whereas tensile strength and elongation at break tremendously decreased. According to differential scanning calorimetry and dynamic mechanical analysis, there were two distinct glass‐transition temperatures for a 50/50 NR/NBR blend, indicating the strongly incompatible nature of the blend. When the TOR level was increased, the glass transition of NBR was strongly suppressed. NBR droplets of a few micrometers were uniformly dispersed in the continuous NR phases in the NR/NBR blends. When TOR was added to a 50/50 NR/NBR blend, TOR tended to be located in the NR phase and in some cases was positioned at the interfaces between the NBR and NR phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 125–134, 2002     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

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。     

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     

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     

Influence of carbon black on uncompatibilised and compatibilised SBR–NBR blends

Abstract

Elastomeric blends based on SBR and NBR have been prepared, giving emphasis to differences in blend composition. It was observed from dynamic mechanical analysis that the SBR–NBR blends can be compatibilised by addition of 5 pphr dichlorocarbene modified styrene/butadiene rubber. The efficiency of carbon black in uncompatibilised and compatibilised blends was evaluated with reference to their processing characteristics and technological properties and the resistance of the vulcanisates towards thermal and oil aging was analysed. The changes in technological properties have been correlated with variations in crosslink density estimated from stress–strain and swelling behaviour. The swelling studies are also extended to evaluate the reinforcing nature of the filler. The results of the study reveal that compatibilised blends show enhanced mechanical properties in the presence of HAF carbon black in comparison with uncompatibilised samples.     

Studies on conductive silicone rubber compounds

The electrical conductivity of silicone rubber vulcanizates containing carbon blacks [e.g., acetylene black, lamp black, and ISAF (N-234) black] were investigated. The change in electrical conductivity with varying amounts of carbon blacks and the temperature dependence was measured. The mechanical properties like tensile strength, tear strength, elongation at break, hardness, etc., of the vulcanizates were determined. A comparative study of the electrical conductivity of the composites revealed that the electrical conductivity of the composites made with acetylene black was higher than that of the composites made of other blacks. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1043–1050, 1998     

Properties influenced by addition of copoly (ethylene/octene) in BR–NBR blends

Abstract

The effects of copoly (ethylene/octene) (EOM) on rheological, mechanical, and cure properties and on carbon black distribution in each phase of butadiene rubber–nitrile/butadiene rubber (BR–NBR) blends have been investigated. It was found that EOM added to the blends is able to function as a plasticising agent for BR and NBR, and the plasticising efficiency of EOM is more significant in NBR than BR. With increasing EOM content, the deviation of Mooney viscosity from the additive line (interpolated values) reduces markedly. In pure components (i.e. 100 : 0 and 0 : 100), cure rate reduces and cure time increases with addition of EOM. In contrast in the blend systems, cure rate increases and cure time decreases when EOM is added. The distribution of carbon black in each phase of the blends is strongly controlled by the viscosity of each phase in the blend. The lower the phase viscosity, the greater the residual carbon black. Accordingly, dynamic mechanical thermal analysis reveals a slight shift in the glass transition temperature of the BR phase to higher temperature, compared with the NBR phase, as EOM is added. From the results obtained, it is proposed that EOM exists in the interfacial area between the two phases. However, at higher amounts of EOM, saturation of EOM at the interfacial area occurs and the excess EOM starts to migrate to the BR phase. Further increase in EOM concentration leads to saturation of EOM in the BR phase and EOM then migrates to the NBR phase.     

Investigation on the mechanical properties and oil resistance of sulfur cured nitrile rubber/hydrogenated nitrile butadiene rubber blends

Nitrile rubber (NBR)/hydrogenated nitrile butadiene rubber (HNBR) blends with various ratios were compounded with internal mixer and two-roll open mill. Mechanical properties and low-temperature performance (TR10) of the NBR/HNBR blends after aging under different conditions were investigated. Furthermore, equilibrium swelling test and moving die rheometer (MDR) test were used to systematically investigate the effects of HNBR dosage on the crosslink densities and curing behaviors. Vulcanization torque and crosslink densities decreased with an increase in HNBR content. The crosslink density of pure HNBR is higher than that of pure NBR, which is related to the macromolecular structures of the rubber. Compression sets of the NBR/HNBR vulcanizates were correlated with HNBR dosage indicating a linear relationship. Low-temperature performance of the NBR/HNBR blends was improved after being aged in the synthetic hydrocarbon hydraulic oils (SH-1 and SH-2). This work shows that the low-temperature performance and oil resistance could be better balanced by blending NBR with HNBR, while the mechanical properties maintain relatively high level.     

Swelling and mechanical properties of (acrylonitrile‐butadiene rubber)/(hydrogenated acrylonitrile‐butadiene rubber) blends with precipitated silica filled in gasohol fuels

This work studied the effects of hydrogenated acrylonitrile‐butadiene rubber (HNBR) and precipitated silica (PSi) loadings in acrylonitrile‐butadiene rubber (NBR) filled with 60 parts per hundred of rubber (phr) of carbon black (CB) for oil‐resistant seal applications in contact with gasohol fuel. The cure characteristics, mechanical properties, and swelling behavior of HNBR/NBR blends reinforced with PSi before and after immersion in ethanol‐based oils (E10, E20, and E85) were then monitored. This work studied the effects of PSi loading in rubber compounds on the mechanical properties of the rubber blends. The results suggested that the scorch time of CB‐filled NBR/HNBR was not affected by HNBR loading, but the cure time, Mooney viscosity, and torque difference increased with HNBR content. The swelling of the blends in E85 oil were relatively low compared with those in E10 and E20 oils. The recommended NBR/HNBR blend ratio for oil‐resistant applications was 50/50. Tensile strength and elongation at break before and after immersion in gasohol oils increased with HNBR loading, and the opposite effect was found for tensile modulus and hardness. PSi filler had no effect on scorch time, but decreased the cure time of the blends. The swelling level of the blends slightly decreased with increasing PSi content. The recommended silica content for optimum reinforcement for black‐filled NBR/HNBR blend at 50/50 was 30 phr. The results in this work suggested that NBR/HNBR blends reinforced with 60 phr of CB and 30 phr of silica could be potentially used for rubber seals in contact with gasohol fuels. J. VINYL ADDIT. TECHNOL., 22:239–246, 2016. © 2014 Society of Plastics Engineers     

环氧树脂增强天然橡胶/顺丁橡胶并用胶的性能

采用低相对分子质量的液体环氧树脂(EP)与固化剂混合作为增强体的前驱体,比较了其填充天然橡胶(NR)、顺丁橡胶(BR)及两者并用胶的物理机械性能,考察了EP用量对并用胶及炭黑增强并用胶物理机械性能的影响,并通过扫描电子显微镜表征了填充后的NR、BR及并用胶的微观相态结构。结果表明,EP的加入均可提高NR、BR、NR/BR并用胶的物理机械性能,其中并用胶的拉伸强度提高幅度最大;当EP用量约为24份时,NR/BR并用胶的综合性能最佳;EP可以提高炭黑增强NR/BR并用胶的物理机械性能,但提高幅度不大;EP在NR/BR并用胶中呈现规整的圆球形状,直径为1.0～2.5μm。     

Compatibility studies on some polymer blend systems by electrical and mechanical techniques

Systematic electrical and mechanical studies were carried out on natural rubber (NR) blended with different types of synthetic rubber such as styrene‐butadiene rubber (SBR), polybutadiene rubber (BR), and ethylene‐propylene‐diene monomer (EPDM) as nonpolar rubbers and nitrile‐butadiene rubber (NBR) and chloroprene rubber (CR) as polar rubbers. The NR/SBR, NR/BR, NR/EPDM, NR/NBR, and NR/CR blends were prepared with different ratios (100/0, 75/25, 50/50, 25/75, and 0/100). The permittivity (ε′) and dielectric loss (ε″) of these blends were measured over a wide range of frequencies (100 Hz–100 kHz) and at room temperature (∼ 27°C). The compatibility results obtained from the dielectric measurements were comparable with those obtained from the calculation of the heat of mixing. These results were confirmed by scanning electron microscopy and showed that NR/SBR and NR/BR blends were compatible while NR/EPDM, NR/NBR, and NR/CR blends were incompatible. To overcome the problem of phase separation (incompatibility) between NR and EPDM, NBR, or CR, a third component such as SBR or poly(vinyl chloride) (PVC) was added as a compatibilizing agent to these blends. The experimental data of dielectric and mechanical measurements showed that the addition of either SBR or PVC could improve the compatibility of such blends to some extent. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 60–71, 2001     

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     

Effect of fillers on morphological properties in NR/SBR blends for OTR tyres

Abstract

The blends of styrene butadiene rubber (SBR) and natural rubber (NR) are prepared using a two-roll mixing mill in the presence of different types of carbon blacks as reinforcing filler. The effects of fillers on cure characteristics and thermal, dynamic–mechanical, morphological properties of the blends are studied. The ISAF N231 type of carbon black shows a significant effect on tensile, tear and modulus properties by reacting at the interface between SBR/NR matrixes. The dynamic characteristics and storage modulus of SBR/NR with SAF N110 and SRF N774 types of carbon black show distinct characteristics in respect to all other blends in this system. The thermal stability of the rubber vulcanizates containing SAF N110 and SRF N774 types of carbon blacks is higher than other blend types. With the increasing percentage of SBR to NR, the thermal stability of the blend is increased. However, the heat buildup of the blends increases with the increase in SBR percentage.     

Changes in morphology and properties of NR–NBR blends. Effect of viscosity ratio modified by liquid natural rubber and epoxidised liquid natural rubber

Abstract

Changes in rheological properties, morphology, and oil resistance in NR–NBR blends by viscosity ratio have been investigated. In this study, the viscosity ratio was modified by mechanical mastication and addition of liquid natural rubber (LNR) and epoxidised liquid natural rubber (ELNR). The results reveal that as viscosity ratio increased from 0·5 to 1·0, Mooney viscosity of the blends increased, and then decreased sharply as the viscosity ratio further increased from 1·0 to 2·0. The addition of LNR and ELNR for plasticising NR and NBR, respectively, does not significantly affect cure properties of the blends. The phase size of the NR dispersed phase depends strongly on the viscosity ratio. The high viscosity of the matrix and/or the low viscosity of the dispersed phase promote breaking up of the dispersed phase. Unexpectedly, a decrease in size of the dispersed phase by the modification of viscosity ratio via the use of low molecular weight rubber (i.e. LNR and ELNR) did not result in an improvement in oil resistance.