Impact of blend ratio on the properties of graphene oxide‐filled carboxylated acrylonitrile–butadiene rubber/styrene–butadiene rubber blends

Carboxylated acrylonitrile–butadiene rubber (XNBR) and styrene–butadiene rubber (SBR) composites with 3 phr (parts per hundred rubber) graphene oxide (GO) were prepared using a latex mixing method. Effects of XNBR/SBR blend ratios on the mechanical properties, thermal conductivity, solvent resistance and thermal stability of the XNBR/SBR/GO nanocomposites were studied. The tensile strength, tear strength, thermal conductivity and solvent resistance of the XNBR/SBR/GO (75/25/3) nanocomposite were significantly increased by 86, 96, 12 and 21%, respectively, compared to those of the XNBR/SBR (75/25) blend. The thermal stability of the nanocomposite was significantly enhanced; in other words, the temperature for 5% weight loss and the temperature of the maximal rate of degradation process were increased by 26.01 and 14.97 °C, respectively. Theoretical analysis and dynamic mechanical analysis showed that the GO tended to locate in the XNBR phase, which led to better properties of the XNBR/SBR/GO (75/25/3) nanocomposite. © 2017 Society of Chemical Industry     

Overall properties of fibrillar silicate/styrene–butadiene rubber nanocomposites

The mechanical properties, heat aging resistance, dynamic properties, and abrasion resistance of fibrillar silicate (FS)/styrene butadiene rubber (SBR) nanocomposites are discussed in detail. Compared with white carbon black (WCB)/SBR composites, FS/SBR composites exhibit higher tensile stress at definite strain, higher tear strength, and lower elongation at break but poor abrasion resistance and tensile strength. Surprisingly, FS/SBR compounds have better flow properties. This is because by rubber melt blending modified FS can be separated into numerous nanosized fibrils under mechanical shear. Moreover, the composites show visible anisotropy due to the orientation of nanofibrils. There is potential for FS to be used to some extent as a reinforcing agent for rubber instead of short microfibers or white carbon black. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2725–2731, 2006     

改性Kevlar纳米纤维对羧基丁腈橡胶/丁苯橡胶共混胶力学性能的影响

采用环氧氯丙烷对Kevlar纳米纤维（KNFs）表面进行改性,制备了表面改性KNFs（m-KNFs）,考察了m-KNFs对羧基丁腈橡胶（XNBR）/丁苯橡胶（SBR）共混胶力学性能的影响。结果表明,m-KNFs可以增强XNBR/SBR共混胶的拉伸性能及撕裂性能,提高硫化胶的热稳定性和耐溶剂性能。添加5份m-KNFs后,共混胶的拉伸强度和撕裂强度分别提高102%和207%。     

Structure and properties of hollow carbon black and filled rubber nanocomposites

Abstract

Hollow carbon black (HCB) is introduced in this work. It has a special hollow structure, high specific surface area, high structure and high electric conductivity. Hollow carbon black is used to fill styrene–butadiene rubber (SBR). The bound rubber test results show that the bound rubber of SBR/HCB can be measured when the HCB content reaches 25 phr because a strong filler network is formed, which indicates good electric conductivity of SBR/HCB. In comparison, the bound rubber of SBR/N330 can not be measured even when the N330 content is 40 phr. The mechanical measurements show that HCB has very good reinforcing effect on SBR especially when the filler content is low. The electric conductivity and thermal conductivity increase with the increase in filler content. At the same filler content, the properties of SBR/HCB nanocomposites are better than those of SBR/N330 nanocomposites, which suggests that HCB has good application potential.     

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     

Radiation induced modification of NBR and SBR montmorillonite nanocomposites

Nanocomposites of two different kinds of rubber (acrylonitrile-butadiene rubber NBR and styrene butadiene rubber SBR)/organo-montmorillonite nanocomposites modified by hexadecyltrimethyl ammonium bromide were prepared by the reactive mixing intercalation method in the presence of trimethylolpropane trimethylmethacrylate (TMPTMA). The influence of gamma irradiation on the morphology and properties of the rubber nanocomposites was investigated. Intercalated polar or unsaturated matrices (e.g., NBR and SBR)/OMMT nanocomposites can be obtained, which was confirmed by X-ray diffraction (XRD). The clay layers could be uniformly dispersed in the rubber matrix on the nanometer level. Mechanical tests showed that the nanocomposites had good mechanical properties as compared to the neat composites. The results also showed that the irradiated NBR/OMMT nanocomposites had higher thermal stabilities than irradiated SBR/OMMT nanocomposites.     

Studies on the Mechanical,Electrical Properties and Interaction of Petroleum Fuels with SBR/ Manganous Tungstate Nanocomposites

A novel nanocomposite based on styrene butadiene rubber (SBR) and manganous tungstate (MnWO₄) nanoparticles was prepared by a simple and inexpensive open two-roll mixing mill. The interaction of the nanoparticles with SBR matrix was studied by different characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and electrical properties. The effect of loading of MnWO₄ nanoparticles on the processing characteristics of mixed rubber compounds, mechanical properties and the transport properties of nanocomposites through petroleum fuels were also analysed. XRD of nanocomposite revealed that the addition of nanoparticles imparts a semi-crystalline or regular arrangement of chains in the composite. SEM analysis showed good dispersion of nanoparticles in the polymer matrix. Also it has been observed that the dispersion of nanoparticles decreases with increase in its loading. TGA analysis indicated better thermal stability of all nanocomposite and thermal stability increases with the loading of the nanoparticles. The AC conductivity and dielectric properties were greatly enhanced in the whole range of frequencies studied. The processing properties of rubber compounds like cure and scorch time decreases with increase in concentration of MnWO₄ nanoparticles and the maximum enhancement in torque was observed for 10 phr loading. The tensile strength, modulus, tear resistance, hardness and heat build-up of the composite increased whereas the resilience, compression set and elongation at break decreased with the loading of nanoparticles. Solvent penetration studies of nanocomposites were done in petroleum fuels at different temperatures.The solvent uptake was the minimum for composite with 10 phr of MnWO₄ and penetration of solvent increased with further addition of nanoparticles.     

Effect of silane coupling agent on the structure and mechanical properties of nano‐dispersed clay filled styrene butadiene rubber

In rubber nanocomposites containing inorganic clay, the reinforcement effect has always been relatively insignificant due to the poor interfacial interaction between the rubber matrix and clay fillers. In this work, the silane coupling agent bis[3‐(triethoxysilyl)propyl]tetrasulfide (Si‐69) was employed through mechanically blending with styrene butadiene rubber (SBR)/clay (100/30) nanocompound that was prepared by combined latex compounding and spray‐drying technique, to serve as the molecular bridge between SBR matrix and clay filler and strengthen the interfacial interaction. TEM and XRD characterization indicated that Si‐69 significantly improved the dispersion of the silicate layers in the SBR matrix. The RPA analysis and the mechanical property study of the SBR/clay nanocomposites revealed that the filler network interaction was weakened while the filler–rubber interaction was strengthened upon the addition of Si‐69. POLYM. COMPOS., 37:890–896, 2016. © 2014 Society of Plastics Engineers     

Enhancement of thermal,morphological, and mechanical properties of compatibilized based on PA6-enriched graphene oxide/EPDM-g-MA/CR: Graphene oxide and EPDM-g-MA compatibilizer role

In this study, a series of elastomeric nanocomposites based on specific amounts of polyamide6 (PA6)/chloroprene rubber (CR) blends which are compatibilized with ethylene propylene diene monomer-grafted-maleic anhydride (EPDM-g-MA) and different amounts of graphene oxide (GO) were prepared with melt mixing method. The effect of compatibilizer and reinforcement concentration in the PA6/CR blend matrix was investigated using theoretical and experimental analysis. Dispersion of nanoplatelets within rubber blend matrix was proven with transmission electron microscopy and field emission-scanning electron microscopy. The modified microstructure of samples showed the significant effect of EPDM-g-MA and GO on the size reduction of CR droplets in the PA6 continuous phase. The results from differential scanning calorimetry and dynamic mechanical thermal analysis revealed the effect of EPDM-g-MA and GO as an effective nucleating agent in PA6-enriched GO/CR (PA6EGO/CR). The findings obtained from thermogravimetric analysis displayed that the GO in the presence of an EPDM-g-MA as a compatibilizer can cause a higher thermal stability in PA6EGO/CR. From mechanical properties, by adding a compatibilizer to the PA6/CR blend, the tensile strength changed from 39.0 to 45.1, the Young's modulus altered from 522.2 to 716.0 and the elongation at break changed from 246.8 to 222.2. While incorporation of 5 phr of GO to the compatibilized blend, the tensile strength increased by 25.2%, the Young's modulus increased by 36.6% and the elongation at break decreased by 20%. The Christensen–Lo model used for analyzing the stiffness of PA6EGO/EPDM-g-MA/CR with emphasis on the influence of the interphase region to predict the effect of various loadings of GO and EPDM-g-MA of Young's modulus. The rheology and creep tests showed a significant effect of EPDM-g-MA and GO content on the rheology behavior of nanocomposites.     

黑液/高岭土复合物在丁腈橡胶和丁苯橡胶中的应用研究

通过絮凝沉降法制备了一种复合补强剂——黑液/高岭土复合物(CLK),将其分别与丁腈橡胶(NBR)和丁苯橡胶(SBR)共混制备了NBR/CLK与SBR/CLK复合材料。考察了CLK的添加量对橡胶复合材料硫化特性、交联密度、力学性能、热氧老化性能以及热降解性能的影响。结果表明:随着CLK含量的增加,在NBR/CLK复合材料体系中,焦烧时间、正硫化时间和硫化速度指数先增加而后逐渐降低;交联密度和力学性能则逐渐增大;老化性能及热性能没有显著改善。在SBR/CLK复合材料中,焦烧时间、硫化速度指数先增加而后逐渐降低,正硫化时间先减少而后逐渐增加;交联密度和力学性能则逐渐增大;老化性能没有显著改善,但热性能得到了提高。     

黑液-硅藻土共沉物在丁腈橡胶与丁苯橡胶中的应用研究

通过絮凝-酸沉降法制备了一种复合补强剂——黑液-硅藻土共沉物(CLD),将其分别与丁腈橡胶(NBR)和丁苯橡胶(SBR)机械共混制得NBR/CLD与SBR/CLD复合材料。考察了CLD的含量对橡胶复合材料硫化特性、交联密度、力学性能、热氧老化性能以及热性能的影响。结果表明:随着CLD的加入,焦烧时间与正硫化时间逐渐降低,硫化速度逐渐提高;交联密度逐渐增加;力学性能逐渐增强;但老化性能及热性能没有得到改善。     

The toughening effect and mechanism of styrene‐butadiene rubber nanoparticles for novolac resin

In this article, phenolic nanocomposites were prepared using styrene–butadiene rubber (SBR) nanoparticles with an average particle size of about 60 nm as the toughening agent. The mechanical and thermal properties of phenolic nanocomposites and the toughening mechanism were studied thoroughly. The results showed that when adding 2.5 wt % SBR nanoparticles, the notched impact strength of phenolic nanocomposites reached the maximum value and was increased by 52%, without sacrificing the flexural performance. Meanwhile, SBR nanoparticles had no significant effect on the thermal decomposition temperature of phenolic nanocomposites. The glass‐transition temperature (T_g) of phenolic nanocomposites shifted to a lower temperature accompanying with the increasing T_g of loaded SBR, which showed there was a certain compatibility between SBR nanoparticles and phenol‐formaldehyde resin (PF). Furthermore, the analysis of Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy indicated that there existed a weak chemical interaction between SBR nanoparticles and the PF matrix. The certain compatibility and weak chemical interaction promoted the formation of a transition layer and improved the interfacial bonding, which might be important reasons for the great enhancement of the toughness for phenolic nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41533.     

Preparation and properties of octadecylamine modified graphene oxide/styrene‐butadiene rubber composites through an improved melt compounding method

Octadecylamine modified graphene oxide/styrene‐butadiene rubber (GO‐ODA/SBR) composites are prepared by a novel and environmental‐friendly method called “Improved melt compounding”. A GO‐ODA/ethanol paste mixture is prepared firstly, and then blended with SBR by melt compounding. GO‐ODA sheets are uniformly dispersed in SBR as confirmed by scanning electron microscope, transmission electron microscopy, and X‐ray diffraction. The interfacial interaction between GO‐ODA and SBR is weaker than that between GO and SBR, which is proved by equilibrium swelling test and dynamic mechanical analysis. GO‐ODA/SBR show more pronounced “Payne effect” than GO/SBR composites, indicating enhanced filler networks resulted from the modification of GO with ODA. GO‐ODA/SBR composite has higher tensile strength and elongation at break than SBR and GO/SBR composite. The tensile strength and elongation at break for the composite with 5 parts GO‐ODA per hundred parts of rubber increase by 208% and 172% versus neat SBR, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42907.     

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。     

Research of styrene‐butadiene rubber/silicon‐aluminum oxides nanotube binary nanocomposites

A novel silicon‐aluminum oxides (Si‐Al) nanotubes with length ranging from 500 to 1000 nm were introduced to fabricate the styrene‐butadiene rubber (SBR)/Si‐Al nanotube binary nanocomposites. Scanning electron microscope observation showed the Si‐Al nanotubes up to 20 parts per hundred parts of rubber (phr) loading level were dispersed well in SBR matrix. Mechanical properties tests, thermogravimetry analysis and dynamic mechanical thermal analysis revealed that the Si‐Al nanotubes have the effects on improving shore A hardness, tensile strength, tear strength, initial decomposition temperature, and storage modulus while lower the maximum loss factor (tan δ) of the SBR/Si‐Al nanotube binary nanocomposites. FTIR spectra analysis showed that new Si O bond was generated between the hydroxyl group of Si‐Al nanotube and the coupling reagent Si69. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of silica/styrene butadiene rubber masterbatches by latex co‐coagulating technology

Silica/styrene butadiene rubber (SBR) masterbatches were prepared by co‐coagulating SBR latex and silica aqueous suspension. The X‐ray diffraction patterns and scanning electron microscopy were employed to characterize the microstructure of the composite. The content and utilization of silica of silica/SBR masterbatches were also investigated. The highest content of silica was achieved when amount of silica is 50 g. Then the cure characteristics, swelling ratio, thermal stability, and mechanical properties of vulcanizates prepared from the masterbatches were compared with those prepared by a conventional direct mixing method. The results revealed that higher maximum torque, shorter cure time, and better swelling resistance of silica/SBR masterbatches were obtained than conventional silica filled composites. The mechanical properties of silica/SBR masterbatches exhibited greater tensile strength and hardness compared to the corresponding conventional mixes. Additionally, the silica/SBR masterbatches vulcanizates exhibited better abrasion resistance, rolling resistance and heat build‐up to those of the conventional composite. POLYM. COMPOS., 35:1212–1219, 2014. © 2013 Society of Plastics Engineers     

氧化石墨烯/氯丁橡胶复合材料的制备及性能研究

通过乳液复合方法制得氧化石墨烯/氯丁橡胶纳米复合材料。研究氧化石墨烯/氯丁橡胶复合材料的硫化特性,力学性能,动态力学性能,耐磨性能。采用扫描电镜研究氧化石墨烯和无机填料在橡胶基体中的分散性。结果表明,氧化石墨烯在氯丁橡胶中具有良好分散性以及改善其他无机填料的分散性,氧化石墨烯的加入可以明显改善加工安全性,提高氯丁橡胶的力学性能,提高氯丁橡胶储能模量及耐磨性。当氧化石墨烯填充量为5phr时,氧化石墨烯/氯丁橡胶的综合性能最佳。     

改性淀粉对炭黑填充丁苯橡胶/顺丁橡胶并用胶性能的影响

用改性淀粉替代部分炭黑填充丁苯橡胶(SBR)/顺丁橡胶(BR)并用胶,考察了改性淀粉用量及偶联剂种类对混炼胶硫化特性及硫化胶物理机械性能和动态力学性能的影响.结果表明,用改性淀粉替代部分炭黑可对SBR/BR混炼胶的硫化产生明显的延迟作用,但改性淀粉用量的变化对焦烧时间与正硫化时间影响不大;添加偶联剂KH-570或NDZ-201延迟了混炼胶的硫化过程,KH-550能大幅度地促进硫化作用,Si-69对于体系的硫化性能略有影响;随着改性淀粉用量的增加,SBR/BR硫化胶的拉伸性能、耐磨耗性均有所降低,但弹性、动态生热和滞后性能得到了明显改善,改性淀粉最佳用量为5～8份;各种偶联剂均可提高SBR/BR硫化胶的拉伸性能,硅烷偶联剂Si-69和KH-570对弹性和动态生热也略有改善,添加偶联剂KH-550改善了SBR/BR硫化胶的抗湿滑性能,但滞后性能变差,添加偶联剂KH-570或Si-69对SBR/BR硫化胶动态力学性能的影响较小,综合考虑,以添加偶联剂KH-570较好.     

Nanocomposite materials based on zinc sulfide nanoparticles reinforced chlorinated styrene butadiene rubber

The effect of zinc sulfide (ZnS) nanoparticles in chlorinated styrene‐butadiene rubber (Cl‐SBR) was analyzed by X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM), Differential Scanning Calorimetry, and impedance analyzer. The cure time, mechanical properties, and solvent transport of petroleum fuels through the Cl‐SBR/ZnS nanocomposites at different temperatures were evaluated. XRD and SEM studies showed that ZnS nanoparticles were well‐placed in the polymeric structure of Cl‐SBR. The increased glass transition temperature of the composite with the loading of nanoparticles indicated the increased molecular rigidity. Rheometric torque, alternating current conductivity, dielectric property, tensile strength, tear resistance, modulus, hardness, abrasion resistance, heat build‐up, and compression set were increased with the loading of nanoparticles, however, cure and scorch time, elongation at break, and resilience were reduced with the loading of nanoparticles. The diffusion results have been explained in terms of the size of liquid molecules and the diffusion mechanism was found to follow the anomalous trend. The activation energy for diffusion, sorption and permeation process was evaluated. These activation energy parameters were increased with the size of the penetrant molecules and also with the loading of nanoparticles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46538.     

Cellulose nanocrystal-mediated assembly of graphene oxide in natural rubber nanocomposites with high electrical conductivity

This study reports a green and powerful strategy for preparing cellulose nanocrystal (CNC)/graphene oxide (GO)/natural rubber (NR) nanocomposites hosting a 3D hierarchical conductive network. Due to good dispersibility and amphiphilic nature of CNC, well dispersed CNC/GO nanohybrids were prepared. Hydrogen bonding interactions between CNC and GO greatly enhanced the stability of the CNC/GO nanohybrids. CNC/GO nanohybrids were introduced into NR latex under sonication and the mixture was cast. Self-assembled CNC/GO nanohybrids preferentially dispersed in the interstice between latex microspheres allowing the construction of a 3D hierarchical conductive network. By combining strong hydrogen bonds and 3D conductive network, both electrical conductivity and mechanical properties (tensile strength and modulus) have been significantly improved. The electrical conductivity of the nanocomposite with 4 wt% GO and 5 wt% CNC exhibited an increase of nine orders of magnitude compared to the nanocomposite with only 4 wt% GO; meanwhile, the electrical percolation threshold was 3-fold lower than for NR/GO composites.