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     

Reinforcement of peroxide‐cured styrene–butadiene rubber vulcanizates by mathacrylic acid and magnesium oxide

Through the neutralization of magnesium oxide (MgO) and methacrylic acid (MAA), magnesium methacrylate [Mg(MAA)₂] was in situ prepared in styrene–butadiene rubber (SBR) and used to reinforce the SBR vulcanizates cured by dicumyl peroxide (DCP). The experimental results show that the mechanical properties, dynamic mechanical properties, optical properties, and crosslink structure of the Mg(MAA)₂‐reinforced SBR vulcanizates depend on the DCP content, Mg(MAA)₂ content, and the mole ratio of MgO/MAA. The formulation containing DCP 0.6–0.9 phr, Mg(MAA)₂ 30–40 phr, and MgO/MAA mole ratio 0.50–0.75 is recommended for good mechanical properties of the SBR vulcanizates. The tensile strength of the SBR vulcanizates is up to 31.4 MPa when the DCP content is 0.6 phr and the Mg(MAA)₂ content is 30 phr. The SBR vulcanizate have good aging resistance and limited retention of tensile strength at 100°C. The SBR vulcanizates are semitransparent, and have a good combination of high hardness, high tensile strength, and elongation at break. The T_g values of the SBR vulcanizates depend largely on the DCP content, but depend less on the Mg(MAA)₂ content and the MgO/MAA mole ratio. The contents of DCP, Mg(MAA)₂, and the MgO/MAA mole ratio have also great effects on the E′ values of the vulcanizates. The salt crosslink density is greatly affected by the Mg(MAA)₂ content and MgO/MAA mole ratio, but less affected by the DCP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2667–2676, 2002     

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     

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     

Possible use of ultra‐fine acrylonitrile butadiene rubber powder as filler in natural rubber vulcanizates

Possible use of ultra‐fine acrylonitrile butadiene rubber powder (UFNBRP) as a filler for natural rubber (NR) was investigated. The UFNBRP was added into NR at various concentrations, and the compound properties were determined. It is found that, with increasing UFNBRP loading, the compound viscosity is increased, whereas both scorch time and optimum curing time are significantly reduced. The results also reveal that UFNBRP has negative effect not only on crosslink density but also on most mechanical properties of the vulcanizate, such as tensile strength, tear strength, compression set, and abrasion resistance. The deterioration of these mechanical properties is thought to arise mainly from the combined effect of large phase size of the dispersed UFNBRP and low interfacial adhesion taking place from the polarity difference between UFNBRP and NR. Interestingly, it is found that, after aging, UFNBRP could promote postcuring phenomenon leading to increases of both relative 100% modulus and relative tensile strength. Oil resistance is also found to improve considerably with increasing UFNBRP loading. This improvement is mainly attributed to the dilution effect, i.e., the higher the UFNBRP loading, the lower the NR portion and, thus, the greater the oil resistance of the vulcanizate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural morphology and properties of star styrene–isoprene–butadiene rubber and natural rubber/star styrene–butadiene rubber blends

Star styrene–isoprene–butadiene rubber (SIBR) was synthesized with a new kind of star anionic initiator made from naphthalene lithium and an SnCl₄ coupled agent. The relationship between the structure and properties of star SIBR was studied. Star block styrene–isoprene–butadiene rubber (SB‐SIBR), having low hysteresis, high road‐hugging, and excellent mechanical properties, was closer to meeting the overall performance requirements of ideal tire‐tread rubber according to a comparison of the morphology and various properties of SB‐SIBR with those of star random SIBR and natural rubber/star styrene–butadiene rubber blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 336–341, 2004     

Use of rice husk ash as filler in natural rubber vulcanizates: In comparison with other commercial fillers

Rice husk ash is mainly composed of silica and carbon black remaining from incomplete combustion. Both silica and carbon black have long been recognized as the main reinforcing fillers used in the rubber industry to enhance certain properties of rubber vulcanizates, such as modulus and tensile strength. In this study, two grades of rice husk ash (low‐ and high‐carbon contents) were used as filler in natural rubber. Comparison was made of the reinforcing effect between rice husk ashes and other commercial fillers such as talcum, china clay, calcium carbonate, silica, and carbon black. Fourier transform infrared spectroscopy (FTIR) analysis was employed to study the presence of functional groups on the ash surface. The effect of silane coupling agent, bis(3‐triethoxysilylpropyl)tetrasulfane (Si‐69), on the properties of ash‐filled vulcanizates was also investigated. It was found that both grades of rice husk ash provide inferior mechanical properties (tensile strength, modulus, hardness, abrasion resistance, and tear strength) in comparison with reinforcing fillers such as silica and carbon black. However, the mechanical properties of the vulcanizates filled with rice husk ash are comparable to those filled with inert fillers. The addition of silane‐coupling agent has little effect on the properties of the ash‐filled vulcanizates. This is simply due to the lack of silanol groups on the ash surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2485–2493, 2002     

Dynamically vulcanized polypropylene/styrene–butadiene rubber blends: The effect of a peroxide/bismaleimide curing system and composition

Polypropylene (PP)/styrene–butadiene rubber blends were studied with special attention given to the effects of the blend ratio and dynamic vulcanization. Dicumyl peroxide (DCP) was used as the curing agent in combination with N,N′‐m‐phenylene bismaleimide (BMI) as the coagent for the curing process. Outstanding mechanical performance, especially with regard to the elongation at break, and better resistance to compression set were achieved with the dynamic vulcanization; this indicated that the DCP/BMI system also acted as a compatibilizing agent. This phenomenon was also confirmed by Fourier transform infrared spectroscopy of the insoluble material, the crystallinity degree of the PP phase (as investigated by X‐ray diffractometry), and scanning electron microscopy. The dynamic mechanical properties of the nonvulcanized and vulcanized blends were also investigated. The aging resistance of the blends was also evaluated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Nonlinear stress relaxation of silica filled solution‐polymerized styrene–butadiene rubber compounds

The stress relaxation of silica (SiO₂) filled solution‐polymerized styrene–butadiene rubber (SSBR) has been investigated at shear strains located in the nonlinear viscoelastic regions. When the characteristic separability times are exceeded, the nonlinear shear relaxation modulus can be factorized into separate strain‐ and time‐dependent functions. Moreover, the shear strain dependence of the damping function becomes strong with an increase in the SiO₂ volume fraction. On the other hand, a strain amplification factor related to nondeformable SiO₂ particles can be applied to account for the local strain of the rubbery matrix. Furthermore, it is believed that the damping function is a function of the localized deformation of the rubbery matrix independent of the SiO₂ content. The fact that the time–strain separability holds for both the unfilled SSBR and the filled compound indicates that the nonlinear relaxation is dominated by the rubbery matrix, and this implies that the presence of the particles can hardly qualitatively modify the dynamics of the polymer. It is thought that the filler–rubber interaction induces a coexistence of the filler network with the entanglement network of the rubbery phase, both being responsible for the nonlinear relaxation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of chemically modified waste rubber powder as a filler in natural rubber vulcanizates

Waste rubber powder (RP) was subjected to chemical modification by using different concentrations of oxidizing agents such as nitric acid and 30% hydrogen peroxide solution. This treatment leads to introducing some functional groups onto the surface of RP. The chemically modified RP was incorporated in natural rubber mixes either alone or in combination with carbon black (HAF). The physicomechanical properties of NR vulcanizates obtained were studied and compared to NR vulcanizates filled with untreated RP. It was found that the chemically modified RP improves tensile strength and aging resistance of NR vulcanizates compared with untreated RP. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 30–36, 2004     

A novel grafting‐modified waste rubber powder as filler in natural rubber vulcanizates

Polycardanol was synthesized from cardanol, paraformaldehyde, p‐toluenesulfonic acid, phosphoric acid (H₃PO₄), and phosphorus pentoxide (P₂O₅) via a two‐step process. Results indicated that polycardanol is an acid with high molecular weight and can be self‐crosslinked at high temperature. A modified WRP (MWRP) grafted by long chain can be obtained from the reaction between WRP and polycardanol. The sulfur content of MWRP is 0.27%, which is lower than that of WRP by 0.47%. The oxygen content of MWRP is higher by 13% than that of WRP. The phosphorus content of MWRP reaches 5.25%. The water contact angle of MWRP is 91.5°, whereas that of WRP is 123.7°. The properties of the WRP/NR and MWRP/NR composites were also investigated. MWRP/NR possesses higher tensile strength than WRP/NR because of the enhanced interfacial interaction between MWRP and the NR matrix. Post‐treatment is also conducive for MWRP/NR to improve its tensile strength at high MWRP content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42993.     

Synthesis and characterization of 3‐benzothiazolthio‐1‐propyltriethoxylsilane and its reinforcement for styrene–butadiene rubber/silica composites

A novel block mercaptosilane (3‐benzothiazolthio‐1‐propyltriethoxylsilane) (Silane‐M) was synthesized and characterized by Fourier transform infrared spectra, ¹H nuclear magnetic resonance, and elemental analysis. Styrene–butadiene rubber (SBR)/silica composites were prepared with Silane‐M, and its effect on the properties of materials was studied. Results show that Silane‐M can substantially improve the dispersion of silica and strengthen the reinforcement of silica for SBR vulcanizates like anchors of silica to rubber matrix. As expected, it enhances the tensile, tear strength, dynamic compression property, and resistance to abrasion of SBR/silica composites. By adding Silane‐M into the system, SBR/silica composites get superior skid resistance and high glass transition temperature (T_g). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Plasma surface modification of silica and its effect on properties of styrene–butadiene rubber compound

The effects of surface modification of silicas by plasma‐polymerization coating, together with modification using a silane coupling agent for a comparison on the dispersion and physical properties of styrene–butadiene rubber (SBR) are reported. The chemical compositions of the plasma‐polymerization coating were characterized using FTIR and Auger spectrometer and it was found that the plasma coating was composed of C?C and C? H bonds. The surface modification of silica by either plasma polymerization or silane greatly improved the dispersion of silica particles in SBR vulcanizates. The plasma‐polymerization modification of silica improved the tensile modulus of SBR vulcanizates without deterioration of important basic properties such as tensile strength and elongation at break. © 2002 Society of Chemical Industry     

Improvement of properties of silica‐filled styrene–butadiene rubber compounds using acrylonitrile–butadiene rubber

Since silica has strong filler–filler interactions and adsorbs polar materials, a silica‐filled rubber compound has a poor dispersion of the filler and poor cure characteristics. Improvement of the properties of silica‐filled styrene–butadiene rubber (SBR) compounds was studied using acrylonitrile–butadiene rubber (NBR). Viscosities and bound rubber contents of the compounds became lower by adding NBR to the compound. Cure characteristics of the compounds were improved by adding NBR. Physical properties such as modulus, tensile strength, heat buildup, abrasion, and crack resistance were also improved by adding NBR. Both wet traction and rolling resistance of the vulcanizates containing NBR were better than were those of the vulcanizate without NBR. The NBR effects in the silica‐filled SBR compounds were compared with the carbon black‐filled compounds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1127–1133, 2001     

Dynamic mechanical properties of styrene‐butadiene rubber vulcanizate filled with electron beam modified surface‐treated dual‐phase filler

The influence of the electron beam modification of a dual‐phase filler on the dynamic mechanical properties of styrene‐butadiene rubber (SBR) is investigated in the presence and absence of trimethylol propane triacrylate or triethoxysilylpropyltetrasulfide. Electron beam modification of the filler results in reduction of the tan δ at 70°C, a parameter for rolling resistance, and an increase in the tan δ at 0°C, a parameter for wet skid resistance of SBR vulcanizates. These modified fillers give significantly better overall performance in comparison with the control dual‐phase filler. This variation in properties is explained in terms of filler parameters such as the filler structure that leads to rubber occlusion and filler networking. These results are further corroborated using the master curves obtained by the time–temperature superposition principle. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2992–3004, 2003     

Mechanical aging behavior of styrene‐butadiene rubbers evaluated by abrasion test

The ring‐shaped styrene‐butadiene rubbers (SBRs) test pieces ran on a rotating stainless‐steel ring using an abrasion tester to evaluate the changes in the mechanical properties, such as the tensile storage modulus and tan δ values, the modulus at 300% elongation, and the strength and extension ratio at the breaking point, after a mechanical aging process. The surface of the SBR test pieces and the formed rubber debris after the running experiment was investigated using scanning electron microscopy. A change in the crosslinking density of the SBRs and the analysis of the isolated free polymers showed the occurrence of bond scission of the copolymer chains. On the other hand, the mechanical properties of whole SBR samples showed only a small change during the mechanical aging test. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Processing optimization of latex‐compounded montmorillonite/styrene‐butadiene rubber–polybutadiene rubber

Organo‐montmorillonite was incorporated into model tire tread formulations through latex compounding methods, to evaluate its effects on elastomer reinforcement and dynamic properties. An intercalation structure was obtained by applying latex compounding method to prepare organoclay‐emulsion stryene butadiene (E‐SBR) masterbatches, for compounding with organoclay loading levels of 0–20 parts per hundred rubber (phr). Microstructure, curing properties and tire performance of the compounded rubber were investigated with the aid of X‐ray diffraction, rheometor and dynamic‐mechanical analysis, respectively. The results showed that organo‐montmorillonite filler provided effective reinforcement in the elastomer matrix, as indicated through mechanical and dynamic mechanical properties. Tread compounds using higher organoclay loadings displayed preferred ice traction, wet traction, and dry handling, but decreased winter traction and rolling resistance. Model compounds using 15 phr of organoclay loading levels were preferred for balanced physical and dynamic properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41521.     

Mechanical properties and morphologies of polypropylene composites synergistically filled by styrene‐butadiene rubber and silica nanoparticles

The mechanical properties and morphologies of PP/SBR/SiO₂ nanocomposites have been studied using mechanical testing, wide‐angle X‐ray diffraction (WAXD), polarizing optical microscopy (POM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The mechanical properties of neat polypropylene can be considerably improved by synergistically filling with SiO₂ and SBR nanoparticles, especially for the notched Izod impact strength. The results from the WAXD, POM, SEM, DSC, and TGA measurements reveal that: (i) the β‐phase crystal structure of PP is formed when SiO₂ and SBR nanoparticles are synergistically filled with polypropylene and its formation plays a role for the enhancement of the impact strength for PP/SBR/SiO₂ nanocomposites; (ii) the dispersion of SiO₂ and SBR nanoparticles in PP/SBR/SiO₂ composites is homogeneous, indicating that synergistic incorporating method decreases the aggregation of nanoparticles and thus increases the sites for dissipation of shock for impact energy in PP/SBR/SiO₂ nanocomposites; (iii) the thermal analysis shows high thermal stability for the PP/SBR/SiO₂ nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of palm ash loading and maleated natural rubber as a coupling agent on the properties of palm‐ash‐filled natural rubber composites

Natural rubber composites were prepared by the incorporation of palm ash at different loadings into a natural rubber matrix with a laboratory‐size two‐roll mill (160 × 320 mm²) maintained at 70 ± 5°C in accordance with the method described by ASTM D 3184–89. A coupling agent, maleated natural rubber (MANR), was used to improve the mechanical properties of the natural rubber composites. The results indicated that the scorch time and cure time decreased with increasing filler loading, whereas the maximum torque exhibited an increasing trend. Increasing the palm ash loading increased the tensile modulus, but the tensile strength, fatigue life, and elongation at break decreased. The rubber–filler interactions of the composites decreased with increasing filler loading. Scanning electron microscopy of the tensile fracture surfaces of the composites and rubber–filler interaction studies showed that the presence of MANR enhanced the interfacial interaction of the palm ash filler and natural rubber matrix. The presence of MANR also enhanced the tensile properties and fatigue life of palm‐ash‐filled natural rubber composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Styrene–butadiene rubber/cellulose II/clay nanocomposites prepared by cocoagulation—mechanical properties

In this work, nanocomposites of styrene butadiene rubber (SBR), cellulose II, and clay were prepared by cocoagulation of SBR latex, cellulose xanthate, and clay aqueous suspension mixtures. The incorporated amount of cellulose II was 15 phr, and the clay varied from 0 to 7 phr. The influence of cellulose II and clay was investigated by rheometric, mechanical, physicochemical, and morphological properties. From the analysis of transmission electron microscopy (TEM), dispersion in nanometric scale (below 100nm) of the cellulosic and mineral components throughout the elastomeric matrix was observed. XRD analysis suggested that fully exfoliated structure could be obtained by this method when low loading of silicate layers (up to 5 phr) is used. The results from mechanical tests showed that the nanocomposites presented better mechanical properties than SBR gum vulcanizate. Furthermore, 5 phr of clay is enough to achieve the best tensile properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011