Effect of silane coupling agent on filler and rubber interaction of silica reinforced solution styrene butadiene rubber

In the present article, the influence of bis‐(triethoxysilylpropyl)‐tetrasulfide (TESPT) content on the viscoelastic behavior of silica filled Solution Styrene Butadiene Rubber (SSBR) was carefully studied in terms of loss tangent spectrum and bound rubber content. The results showed that both relative tan δ area and tan δ_max of filled SSBR with TESPT were detected to present maximum value at 2.5 wt% TESPT(with respect to silica loading). Larger tan δ area and tan δ_max meant more chains participating in the glass transition in the present system, which is reflected by the variation of effective filler volume with TESPT content. The interaction between filler and rubber can be improved remarkably when a little amount of TESPT up to 2.5 wt% was incorporated, whereas as the TESPT content exceeds 2.5 wt% the filler–rubber interaction was weakened, which was also proven by TEM images and Payne effect. The bound rubber content of this SSBR system studied presents the same tendency as tan δ_max. Once TESPT linked with rubber chains, the condensation reaction between silica and SCA is somewhat hindered because of the difficulty in diffusion of large molecules after SCA is chemically bonded with rubber molecules. The network structure of the filled SSBR was analyzed by applying elasticity model. The consecutive increase of crosslink density compensated the reduction of topological tube‐like constrains and thus tensile strength continued to ascend with TESPT content, but sacrificed the ultimate strain. POLYM. COMPOS., 34:1575–1582, 2013. © 2013 Society of Plastics Engineers     

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.     

Influence of fillers dispersion on friction and wear performance of solution styrene butadiene rubber composites

Development of structure–properties relationships between the fillers/rubber matrix interface chemistry and the dispersion and interfacial adhesion properties of the rubber composites is critical to predict their bulk mechanical and tribological properties. In this paper, three solution styrene butadiene rubber (SSBR) composites containing various fillers with tailored interfacial chemistry were prepared via conventional mixing technique. Subsequently, thermal and structural features of filled SSBR composites were monitored by TG, DSC, XRD, XPS, FESEM and TEM, respectively. Sliding contact experiments were conducted to study tribological properties of styrene butadiene rubber composites under dry and wet conditions. It was shown that the SSBR filled with silicon dioxide nanoparticles significantly reduced both the friction coefficient and the wear against marble block. On the contrary, it exhibited an increased friction coefficient and wear under wet friction conditions due to the specific superior wet‐skid resistance of silicon dioxide nanopartilce filled rubber composites, a good dispersion of silicon dioxide nanopartilce in the rubber matrix and strong interfacial adhesion between nanoparticles and rubber matrix. In addition, the influence of fillers dispersion and interfacial adhesion on friction and wear of styrene butadiene rubber composites was evaluated employing theoretical calculation, and the predicted results were in agreement with the experimental observations. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43589.     

Sulfur‐free lignin as reinforcing component of styrene–butadiene rubber

The potential application of lignin biopolymer as a component of styrene–butadiene rubber was examined with regard to its ability to reinforce the vulcanizates. It was shown that the sulfur‐free lignin preparation improved physicomechanical properties of rubber. The determination of the coefficient of lignin activity confirmed that lignin acts as an active filler. FTIR characteristics of lignin isolated from the vulcanizate containing 20 phr lignin indicated its interaction with the sulfur system, resulting in formation of noncyclic sulfide structures. In the case of higher lignin amount in the vulcanizate, some interfacial interaction between lignin and SBR may occur. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 924–929, 2005     

Properties of tire tread compounds based on functionalized styrene butadiene rubber and functionalized natural rubber

Tire tread compounds based on various rubber types, that is, solution styrene-butadiene rubber (SSBR), functionalized (propylamine and dimethoxysilane) solution styrene-butadiene rubber (F-SSBR), natural rubber (NR), chloroacetate-modified natural rubber (CNR), and their blends, were prepared and used as raw rubbers. Properties of tire tread compounds and tire performance were then investigated. Due to the presence of chloroacetate group on its mainchains, CNR demonstrates increases in glass transition temperature and rubber-filler interaction compared to NR leading to a significant improvement in tire performance, particularly wet grip (WG; ~88%), fuel-saving efficiency (FSE; ~15%), and abrasion resistance (~11%). Similarly, F-SSBR shows a greater tire performance than SSBR (~20, ~13, and ~7% improvements in WG, FSE, and abrasion resistance, respectively). Among the rubber blends, F-SSBR/CNR gives the highest tire performance, followed by F-SSBR/NR, SSBR/CNR, and SSBR/NR, respectively. The results suggest the significant enhancement in properties of tire tread compounds by the presence of active functional groups in NR and SSBR molecules. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48696.     

Dielectric properties of styrene — butadiene rubber/silica mixtures

Rice husk ash (RHA) obtained from rice mill and hydrated silica from RHA were used as a filler in vulcanized SBR 1502 and the dielectric properties were measured at a frequency of 1592 Hz at room temperature. The optimum hydrated silica content giving a good dielectric constant and conductivity was 125 parts/100 parts rubber and the dielectric loss was also high so that it could be a good insulater. There was no significant change in dielectric constant, dielectric loss and conductivity of SBR 1502 filled with RHA which could be used as high frequency dielectric due to low dielectric loss.     

Fly ash particles and precipitated silica as fillers in rubbers. I. Untreated fillers in natural rubber and styrene–butadiene rubber compounds

In this study, we investigated the effects of untreated precipitated silica (PSi) and fly ash silica (FASi) as fillers on the properties of natural rubber (NR) and styrene–butadiene rubber (SBR) compounds. The cure characteristics and the final properties of the NR and SBR compounds were considered separately and comparatively with regard to the effect of the loading of the fillers, which ranged from 0 to 80 phr. In the NR system, the cure time and minimum and maximum torques of the NR compounds progressively increased at PSi loadings of 30–75 phr. A relatively low cure time and low viscosity of the NR compounds were achieved throughout the FASi loadings used. The vulcanizate properties of the FASi‐filled vulcanizates appeared to be very similar to those of the PSi‐filled vulcanizates at silica contents of 0–30 phr. Above these concentrations, the properties of the PSi‐filled vulcanizates improved, whereas those of the FASi‐filled compounds remained the same. In the SBR system, the changing trends of all of the properties of the filled SBR vulcanizates were very similar to those of the filled NR vulcanizates, except for the tensile and tear strengths. For a given rubber matrix and silica content, the discrepancies in the results between PSi and FASi were associated with filler–filler interactions, filler particle size, and the amount of nonrubber in the vulcanizates. With the effect of the FASi particles on the mechanical properties of the NR and SBR vulcanizates considered, we recommend fly ash particles as a filler in NR at silica concentrations of 0–30 phr but not in SBR systems, except when improvement in the tensile and tear properties is required. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2119–2130, 2004     

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     

Synthesis and characterization of maleated glycidyl 3‐pentadecenyl phenyl ether as a functionalized plasticizer for styrene–butadiene rubber/carbon black/silica composites

Maleated glycidyl 3‐pentadecenyl phenyl ether (M‐GPPE) was synthesized from glycidyl 3‐pentadecenyl phenyl ether (GPPE), a renewable derivative from cardanol, with maleic anhydride (MAH) by grafting copolymerization. The resulting M‐GPPE was used as a functionalized plasticizer for a styrene–butadiene rubber (SBR)/carbon black (CB)/silica composite. The effects of M‐GPPE on the development of the filler network, the extent of silica dispersion, the curing characteristics, and the mechanical performance of the composites were studied. Meanwhile, a comparative study was performed between M‐GPPE and aromatic oil, a traditional plasticizer used in SBR filler formulations. Gel permeation chromatography and IR and ¹H‐NMR analysis results confirmed the occurrence of the grafting reaction between GPPE and MAH and the potential structure of M‐GPPE. The thermostability of GPPE was improved by grafting copolymerization with MAH, as shown by thermogravimetric analysis results. The presence of M‐GPPE resulted in a shorter curing time and better aging properties in the SBR composite compared with GPPE. The mechanical properties, dynamic mechanical analysis, and transmission electron microscopy analysis showed that the maleate of GPPE could enhance the compatibility between SBR and silica, improve the dispersion of silica in SBR, and partially replace the aromatic oil in the SBR/CB/silica composite formulation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40462.     

Development of modified expanded graphite‐filled solution polymerized styrene butadiene rubber vulcanizates in the presence and absence of carbon black

Expanded graphite (EG) consists of a huge number of partially exfoliated graphite sheets with the thickness of most of the sheets in the nanometer range. This study analyses the effect of EG and modified EG (MEG) on the mechanical, thermal, and dynamic mechanical properties of solution styrene butadiene rubber (SSBR) with and without carbon black (CB). The surface of the EG was modified to enhance its dispersion in the SSBR matrix. In addition, oil‐extended carboxylated styrene butadiene rubber (XSBR) was used as a compatibilizer to disperse MEG in the base nonpolar SSBR matrix. XSBR/MEG nanocomposites have been prepared by solution mixing. The obtained nanocomposites were incorporated into the SSBR matrix in the presence of CB by melt blending. Morphological properties of the nanocomposites revealed intercalation of MEG sheets in the SSBR matrix. Nanocomposites containing MEG in the presence of CB show improvement in mechanical, thermal, and dynamic mechanical properties. POLYM. ENG. SCI., 54:33–41, 2014. © 2013 Society of Plastics Engineers     

Nanomodified fillers in chloroprene‐rubber‐compatibilized natural rubber/acrylonitrile–butadiene rubber blends

Because of the structural dissimilarity, natural rubber (NR) and acrylonitrile–butadiene rubber (NBR) are immiscible, and compatibilizers are used during their blending. Neoprene or chloroprene rubber (CR) has a polar chlorine part and a nonpolar hydrocarbon part. Also, it has many advantageous properties, such as oil resistance, toughness, a dynamic flex life, and adhesion capacity. Hence, it is not less scientific to use CR as a compatibilizer in the blending of NBR with NR. Because many fewer studies on the use of neoprene as a compatibilizer in NR–NBR blend preparation are available, efforts were made to prepare 20:80 NR–NBR blends with CR with the aim of studying the effect of poly(ethylene oxide) (PEO)‐coated nano calcium silicate along with nano N‐benzylimine aminothioformamide and stearic acid coated nano zinc oxide in the sulfur vulcanization of the blends. The optimum dosage of the compatibilizer was derived by the determination of the tensile properties, tear resistance, abrasion resistance, compressions set, and swelling values. The tensile strength, tear resistance, and abrasion resistance of the gum vulcanizates of the blend were improved by the compatibilizing action of CR up to 5 parts per hundred parts of rubber (phr). In the case of the filled vulcanizates, the tear resistance, 300% modulus, hardness, and abrasion resistance increased with increasing dosage of nano calcium silicate. The elongation at break percentage decreased as expected when there was an increase in the modulus. Scanning electron microscopy was used to study the phase morphology of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fly‐ash particles and precipitated silica as fillers in rubbers. II. Effects of silica content and Si69‐treatment in natural rubber/styrene–butadiene rubber vulcanizates

This article explored the possibility of using silica from fly‐ash particles as reinforcement in natural rubber/styrene–butadiene rubber (NR/SBR) vulcanizates. For a given silica content, the NR : SBR blend ratio of 1 : 1 (or 50 : 50 phr) exhibited the optimum mechanical properties for fly‐ash filled NR/SBR blend system. When using untreated silica from fly‐ash, the cure time and mechanical properties of the NR/SBR vulcanizates decreased with increasing silica content. The improvement of the mechanical properties was achieved by addition of Si69, the recommended dosage being 2.0 wt % of silica content. The optimum tensile strength of the silica filled NR/SBR vulcanizates was peaked at 10–20 phr silica contents. Most mechanical properties increased with thermal ageing. The addition of silica from fly‐ash in the NR/SBR vulcanizates was found to improve the elastic behavior, including compression set and resilience, as compared with that of commercial precipitated silica. Taking mechanical properties into account, the recommended dosage for the silica (FASi) content was 20 phr. For more effective reinforcement, the silica from fly‐ash particles had to be chemically treated with 2.0 wt % Si69. It was convincing that silica from fly‐ash particles could be used to replace commercial silica as reinforcement in NR/SBR vulcanizates for cost‐saving and environment benefits. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

氧化石墨烯与白炭黑并用填充丁苯橡胶纳米复合材料的性能

采用乳液共混与机械剪切法制备氧化石墨烯/白炭黑/丁苯橡胶纳米复合材料,并对其综合性能进行研究。结果表明:两种并用填料在橡胶基体中均能达到纳米级分散,且白炭黑粒子填补了氧化石墨烯片层间的空隙。氧化石墨烯的加入延长了复合材料的正硫化时间,改变了其交联密度。氧化石墨烯等量替代白炭黑,可以提高橡胶基体中填料的有效体积分数,改善复合材料的物理性能和动态力学性能。氧化石墨烯的加入使复合材料的耐磨性能显著提高。与白炭黑填充相比,氧化石墨烯/白炭黑填充复合材料的60℃时损耗因子有所降低,能进一步降低滚动阻力,但其0℃的损耗因子也呈现降低趋势,对复合材料抗湿滑性能不利。     

Carbon nanotubes‐filled thermoplastic polyurethane–urea and carboxylated acrylonitrile butadiene rubber blend nanocomposites

This article reports the preparation and characterization of multiwalled carbon nanotubes (MWCNTs)‐filled thermoplastic polyurethane–urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blend nanocomposites. The dispersion of the MWCNTs was carried out using a laboratory two roll mill. Three different loadings, that is, 1, 3, and 5 wt % of the MWCNTs were used. The electron microscopy image analysis proves that the MWCNTs are evenly dispersed along the shear flow direction. Through incorporation of the nanotubes in the blend, the tensile modulus was increased from 9.90 ± 0.5 to 45.30 ± 0.3 MPa, and the tensile strength at break was increased from 25.4 ± 2.5 to 33.0 ± 1.5 MPa. The wide angle X‐ray scattering result showed that the TPUU:XNBR blends were arranged in layered structures. These structures are formed through chemical reactions of ? NH group from urethane and urea with the carboxylic group on XNBR. Furthermore, even at a very low loading, the high degree of nanotubes dispersion results in a significant increase in the electrical percolation threshold. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40341.     

橡胶助剂Silane-M对丁苯橡胶/白炭黑复合材料硫化性能的影响

用硫化仪考察了橡胶助剂3-苯并噻唑硫代-1-丙基-三乙氧基硅烷(Silane-M)对丁苯橡胶/白炭黑复合材料硫化性能的影响.结果表明,Silane-M可明显缩短丁苯橡胶/白炭黑复合材料的正硫化时间,但不影响其焦烧时间.Silane-M具有一定的促进作用,可以加快硫化速率.未添加和添加6份(质量)Silane-M的丁苯橡胶/白炭黑复合材料在135～160 ℃的硫化温度系数和硫化反应表观活化能均比较接近,2种复合材料的硫化性能对温度的依赖性基本一致.     

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     

Effect of pulverized coal/carbon black hybrid fillers on mechanical properties and thermal stability of styrene butadiene rubber composites

Pulverized coal (coal) possesses a layered structure similar to graphite and is a potential reinforcing filler. In this paper, ball milling is used to reduce the particle diameter of coal. The coal is modified with KH-560 to obtain K-COAL and prepared K-COAL/styrene-butadiene rubber (SBR) composites. In addition, carbon black (CB) is modified to obtain CB-Si69, K-COAL and CB-Si69 are added to SBR in different ratios to prepare COAL/CB/SBR composites. The results show that the addition of K-COAL can improve the vulcanization performance, thermal stability, and mechanical properties of SBR composites, but the reinforcing effect is weak. In the COAL/CB/SBR composites, the vulcanization and mechanical properties of the composites gradually increase with the increase of CB, while those of the thermal stability decrease. The tensile strength of the 10 phr COAL/30 phr CB/SBR composite is 24.1 MPa, which is elevated by 1105% and 205% compared with the pure SBR and 40 phr K-COAL/SBR composites, respectively. The composites maintain high elasticity while the tensile strengths are greatly improved, and the mechanical properties are significantly enhanced. In conclusion, this paper provides a reference for the clean utilization of coal and shows new possibilities for finding new fillers to replace CB.     

Grafting hydroxy‐terminated polybutadiene onto nanosilica surface for styrene butadiene rubber compounds

Hydroxy teminated polybutadiene (HTPB) was grafted onto the surface of nanosilica particles via toluene di‐isocyanate (TDI) bridging to reduce filler–filler interactions and improve dispersion of nanosilica in rubber. Also, this prepolymer as modifier contains double bonds which participate in sulfur curing of styrene butadiene rubber (SBR) matrix to enhance filler/polymer interaction and reinforcement effects of silica. The reactions were characterized by titration and Fourier transforms infrared spectroscopy. Thermogravimetric analysis was utilized to evaluate the weight percentage of grafted TDI and HTPB. About 60% of the hydroxyl sites of silica were reacted with excess TDI in the first reaction. In the second reaction, HTPB as desired reactive coating was grafted on the functionalized nanosilica to constitute about 24 wt % of the final modified silica. The sedimentation experiments showed good suspension stability for the modified nanosilica in the organic media. Scanning electron microscopy revealed nanoscale dispersion of modified silica aggregates in the SBR matrix at concentration of about 14 phr. Also, vulcanization characteristics and mechanical properties of compounds demonstrated that HTPB grafting improved dispersion of nanosilica as well as its interaction to the rubber matrix as an efficient reinforcement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011