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     

Effect of low molecular weight polybutadiene as processing aid on properties of silica‐filled styrene–butadiene rubber compounds

Because silica has strong filler–filler interactions, a silica‐filled rubber compound shows a poor filler dispersion compared to a carbon black‐filled one. Improvement of the filler dispersion in silica‐filled styrene–butadiene rubber (SBR) compounds was studied using low molecular weight polybutadiene (liquid PBD) with the high content of 1,2‐unit. By adding the liquid PBD to the silica‐filled SBR compound, the filler dispersion and flow property are improved. The cure time and cure rate become faster as the 1,2‐unit content of the liquid PBD increases for the compounds containing the liquid PBD. The crosslink density increases linearly with increase in the 1,2‐unit content of the liquid PBD. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3135–3140, 2003     

Properties of silica‐filled styrene‐butadiene rubber compounds containing acrylonitrile‐butadiene rubber: The influence of the acrylonitrile‐butadiene rubber type

Because silica has strong filler‐filler interactions and adsorbs polar materials, a silica‐filled rubber compound exhibits poor dispersion of the filler and poor cure characteristics in comparison with those of a carbon black‐filled rubber compound. Acrylonitrile‐butadiene rubber (NBR) improves filler dispersion in silica‐filled styrene‐butadiene rubber (SBR) compounds. The influence of the NBR type on the properties of silica‐filled SBR compounds containing NBR was studied with NBRs of various acrylonitrile contents. The composition of the bound rubber was different from that of the compounded rubber. The NBR content of the bound rubber was higher than that of the compounded rubber; this became clearer for NBR with a higher acrylonitrile content. The Mooney scorch time and cure rate became faster as the acrylonitrile content in NBR increased. The modulus increased with an increase in the acrylonitrile content of NBR because the crosslink density increased. The experimental results could be explained by interactions of the nitrile group of NBR with silica. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 385–393, 2002     

Properties of natural rubber composites reinforced with silica or carbon black: influence of cure accelerator content and filler dispersion

Filler dispersion is a critical factor in determining the properties of filled rubber composites. Silica has a high density of silanol groups on the surface, which lead to strong filler–filler interactions and a poor filler dispersions. A cure accelerator, N‐tert‐butyl‐2‐benzothiazole sulfenamide (TBBS), was found to improve filler dispersion in silica‐filled natural rubber (NR) compounds. For the silica‐filled NR compounds without the silane coupling agent, the reversion ratio generally increased with increase in TBBS content, whereas those of the silica‐filled NR compounds containing the silane coupling agent and carbon black‐filled NR compounds decreased linearly. The tensile strength of the silica‐filled NR vulcanizate without the silane coupling agent increased as the TBBS content increased, whereas carbon black‐filled samples did not show a specific trend. The experimental results were explained by TBBS adsorption on the silica surface and the improvement of silica dispersion with the aid of TBBS. Copyright © 2003 Society of Chemical Industry     

分散剂和偶联剂对白炭黑填充硅橡胶性能的影响

研究锌皂分散剂、偶联剂KH-560及其并用对白炭黑填充硅橡胶性能的影响。结果表明,锌皂分散剂和偶联剂KH-560均能弱化填料网络结构,促进白炭黑的分散,减小胶料在低应变下的储能模量,且二者并用效果更佳;结合胶质量分数增大表明偶联剂KH-560和锌皂分散剂并用能够提高填料与硅橡胶间的相互作用;锌皂分散剂的加入明显缩短了胶料的正硫化时间,在保证操作安全的前提下,显著加快了硫化速率;偶联剂KH-560改性白炭黑体系中加入少量的分散剂,硫化胶的硬度、100%和300%定伸应力、拉伸强度呈增大趋势,拉断伸长率减小。     

Exploring a highly dispersible silica–elastomer composite for tire applications

In this article, we provide an extensive analyses of various properties that are required for tire tread based on developed highly dispersible (HD) silica‐filled epoxidized natural rubber composites. Silica in an HD form has become a staple filler in tire tread applications because of its inherent advantages. In this study, epoxidized natural rubber with 25 mol % epoxide (ENR 25) and natural rubber were mixed with two different types of HD silica for superior reinforcement. A standard tire tread formulation was used as the base compound. The magic triangle properties were conspicuously influenced by the viscoelastic characteristics of the vulcanizates. The introduction of polar rubber (ENR 25) into the HD silica greatly improved rheological, physicomechanical, bound rubber content, and dynamic mechanical properties, and this led to a better, fuel‐efficient tire. We successfully achieved this, even in the absence of a silane coupling agent. ENR 25 played an imperative role in showing an extraordinary rubber–filler interactions and was primarily responsible for these observations. In this study, we explored the HD silica dispersion with transmission electron microscopy observations. Morphological studies revealed well‐dispersed HD silica with the formation of a rubber–filler network. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43531.     

Reinforcement of maleated natural rubber by precipitated silica

Graft copolymers of maleic anhydride and natural rubber or so‐called maleated natural rubbers (MNRs) were prepared in a molten state with varying maleic anhydride contents from 4 to 10 phr. In this work, the filler–filler and filler–rubber interactions of the MNR and precipitated silica were investigated. The MNR compounds containing 40 phr of silica both with and without 9 wt % of silane coupling agent were prepared. By increasing the maleic anhydride contents, the Mooney viscosity and cure times were increased, but the torque differences and cure rate indices were decreased. Bound rubber was increased with increasing maleic anhydride content, indicating an increase of filler–rubber interaction. In case of the compounds without silane, the MNR with 6 phr of maleic anhydride showed the lowest filler–filler interaction as indicated by a decrease of storage modulus upon an increase of strain in the filled compound i.e., Payne effect. This MNR compound also yielded the optimum mechanical properties. It has been demonstrated that a use of MNR with appropriate maleic anhydride content can reduce filler–filler interaction dramatically and hence improve a silica dispersion, as confirmed by SEM micrographs, resulting in an enhancement of the mechanical and dynamical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of in situ modification of silica on filler network and dynamic mechanical properties of silica‐filled solution styrene–butadiene rubber

The influence of in situ modification of silica with bis‐(3‐(triethoxysilyl)‐propyl)‐tetrasulfide (TESPT) on filler network in silica filled solution SBR compound was investigated. In situ modification greatly increased the bound rubber content. TEM observation of silica gel showed that bridging and interlocking of absorbed chains on the surface of silica particles formed the filler network. Rubber processing analyzer (RPA) was used to characterize the filler network and interaction between silica and rubber by strain and temperature sweeps. In situ modification improved the dispersion of silica, and in the meantime, the chemical bonds were formed between silica and rubber, which conferred the stability of silica dispersion during the processing. Compared to the compound without in situ modification, the compound with in situ modification of silica exhibited higher tan δ at low strains and lower tan δ at high strains, which can be explained in terms of filler network in the compounds. After in situ modification, DMTA results showed silica‐filled SSBR vulcanizate exhibited higher tan δ in the temperature range of ?30 to 10°C, and RPA results showed that it had lower tan δ at 60°C when the strain was more than 3%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Some interesting phenomena in silica‐filled HNBR with the addition of silane coupling agent

Hydrogenated nitrile rubber (HNBR)/silica nanocomposites were prepared by in‐situ modification dispersion technology, and the silane coupling agent γ‐methacryloxypropyl trimethoxy silane (KH570) was chosen to promote the interfacial strength between silica particles and HNBR matrix and further improve the dispersion of silica particles. Rubber Process Analyzer (RPA2000) was used to test the Payne effect of HNBR/silica compounds, from which some interesting phenomena were found: the Payne effect became stronger after KH570 was added to HNBR/silica compound at room temperature, which was a contrary result compared to SBR/silica system. However, after stored for a month at room temperature, the Payne effect weakened, which was contrary to the traditional phenomenon of storage hardening of filled rubber. All these results are related to filler–filler interaction and filler–rubber interaction. The modulus at small strain amplitude of HNBR/silica compound with KH570 gradually decreased with the increase of times of circulatory strain sweep but that of compound without KH570 had almost no change, which was explained by Fourier Transform Infrared (FTIR) results that the reaction between silica and KH570 almost completed at the test condition: 80°C and about 1 h. The effects of silane amount, heat‐treated temperature and time on the Payne effect of compounds and the mechanical properties of vulcanizates were also investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanistic aspects of silane coupling agents with different functionalities on reinforcement of silica‐filled natural rubber compounds

Silane coupling agents containing different specific functionalities are studied to gain understanding of their roles in silica‐filled natural rubber (NR) compounds. Five different silane coupling agents, that is bis‐(triethoxysilylpropyl) tetrasulfide (TESPT), bis‐(triethoxysilylpropyl) disulfide (TESPD), octyltriethoxysilane, vinyltrimethoxysilane, and bis‐(trimethyl‐silylmethyl) tetrasulfide (TMSMT), are comparatively investigated, by taking the most commonly used TESPT as a reference. The results reveal that alkoxy‐based silanes can effectively reduce the filler–filler interaction and lower compound viscosity owing to the effect of silane‐to‐silica hydrophobation which contributes to better compatibility between silica and NR. The alkoxy‐silanes with a sulfur moiety, that is TESPT and TESPD, show more pronounced improvement in overall properties as a result of filler–rubber interactions. The use of TMSMT which has no alkoxy groups but contains only a sulfur moiety elucidates that there are three reaction mechanisms involved in systems with sulfur‐alkoxy‐based silane. These are as follows: (1) the silane‐to‐silica or silanization/hydrophobation reaction; (2) the silane‐to‐rubber or coupling reaction; and (3) rubber–rubber crosslinking originating from active sulfur released by the polysulfide‐based silane TESPT. These simultaneous reactions are temperature dependent, and show an optimum level at a dump temperature of approximately 140–150°C, as depicted by filler–filler and filler–rubber interactions, as well as mechanical properties of such compounds. POLYM. ENG. SCI., 55:836–842, 2015. © 2014 Society of Plastics Engineers     

Tailoring Silica Surface Properties by Plasma Polymerization for Elastomer Applications

The surface properties of reinforcing fillers are a crucial factor for dispersion and filler–polymer interaction in rubber compounds, as they strongly influence the final vulcanized properties of the rubber article. Silica is gaining more and more importance as reinforcing filler for rubbers, as it allows for a reduction of rolling resistance and thus energy losses in tires, compared to the use of carbon black as filler. However, silica and common elastomers differ greatly in polarity and, therefore, are difficult to mix and thus have little interaction. In the present study plasma-coating of silica-filler with acetylene, thiophene and pyrrole is applied, and the surface-treated silicas are blended with S-SBR rubber, in an attempt to enhance the compatibility between the two. The dispersion and reinforcing effects of the modified silicas are investigated and compared with untreated and silanized silica. The relative rankings of the various coatings in reduction of filler–filler interaction, improved dispersion, enhanced polymer–filler interaction, apparent crosslink density and tensile mechanical properties are mutually different. Where the best silica dispersion and largest reduction in filler–filler interaction are obtained with polyacetylene coating and the worst with polythiophene coating, but the tensile properties achieved with the polythiophene coating are far better than all others. Apparently, the sulfur contained in the thiophene-moiety enhances the filler–polymer interaction and contributes to the degree of crosslinking. Unmodified silica performs worst in all aspects, also because its acidic nature harms the preferably alkaline vulcanization process. Silane treatment of silica has a positive effect on reduction of filler–filler interaction and improved dispersion, but has little effect on polymer–filler interaction in the still unvulcanized state. Its tensile properties after vulcanization are comparable with polyacetylene- or polypyrrole-coated silica. This investigation shows that the compatibility and interaction of silica with a polymer can be controlled by tailoring the surface energy of the filler by coating with plasma polymers. An appropriate monomer for the plasma polymerization process allows to improve the cured rubber properties.     

Crack growth of natural rubber filled with functionalized silica particles

In the present work, functionalized liquid isoprene rubber (FLIR) was used to improve the filler dispersion and filler–rubber interaction in the silica filled natural rubber system. By the infrared spectra and scanning electron microscopy, it was proved that the FLIR was successfully grafted on the silica and the functionalized silica was dispersed in the NR matrix homogeneously. Based on the real‐time crack tip morphology monitoring method, the influence of FLIR on the crack growth behavior of NR filled with silica was analyzed. By the adding of FLIR, the crack resistance of the natural rubber embedded with functionalized silica is remarkably increased. When the weight ratio of FLIR to silica is 3:10, the NR composite has the best crack resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42972.     

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     

Use of epoxidized rubber seed oil as a coupling agent and a plasticizer in silica‐filled natural rubber compounds

To obtain good reinforcement by silica filler in nonpolar rubbers, it is almost essential to use coupling agents, such as bis(triethoxy silyl propyl) tetrasulfane (TESPT). Chemicals that can interact with the silanol groups on the silica particles and reduce their network formation are also expected to enhance reinforcement. We made a comparative evaluation of TESPT, epoxidized rubber seed oil (ERSO), and their combination as a coupling agent and a plasticizer in silica‐filled natural rubber compounds. The results indicate that compounds containing ERSO showed physical and mechanical properties between that of TESPT and naphthenic oil. The action of ERSO in the improvement of the properties was expected to be bifunctional and similar to that of TESPT; that is, it caused the hydrophobation of silica, which increased its degree of dispersion and the formation of chemical bonds with the rubber, thereby ensuring strong polymer–filler interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3531–3536, 2004     

Application of rice husk ash as fillers in the natural rubber industry

Rice husk ash (RHA) obtained from agricultural waste, by using rice husk as a power source, is mainly composed of silica and carbon black. A two‐stage conventional mixing procedure was used to incorporate rice husk ash into natural rubber. For comparison purposes, two commercial reinforcing fillers, silica and carbon black, were also used. The effect of these fillers on cure characteristics and mechanical properties of natural rubber materials at various loadings, ranging from 0 to 40 phr, was investigated. The results indicated that RHA filler resulted in lower Mooney viscosity and shorter cure time of the natural rubber materials. The incorporation of RHA into natural rubber improved hardness but decreased tensile strength and tear strength. Other properties, such as Young's modulus and abrasion loss, show no significant change. However, RHA is characterized by a better resilience property than that of silica and carbon black. Scanning electron micrographs revealed that the dispersion of RHA filler in the rubber matrix is discontinuous, which in turn generates a weak structure compared with that of carbon black and silica. Overall results indicate that RHA can be used as a cheaper filler for natural rubber materials where improved mechanical properties are not critical. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 34–41, 2005     

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     

The role of devulcanizing agent for mechanochemical devulcanization of styrene butadiene rubber vulcanizate

More or less universally, bis(3‐triethoxysilyl propyl) tetrasulfide (TESPT) has been used as a coupling agent during dispersion of silica filler in a virgin nonpolar rubber compound. It is for the first time that TESPT has been used as a devulcanizing agent and as‐grown devulcanized rubber facilitates the silica dispersion in nonpolar rubber compound without any coupling agent. Dual functionalities of TESPT have been modeled and validated in this work. Various factors like the role of sol‐gel content, inherent viscosity of sol rubber, crosslink density, and degree of devulcanization were investigated as a function of devulcanization time and amount of TESPT to optimize devulcanization time and TESPT amount. To study the silica reinforcement, revulcanization of devulcanized SBR was carried out with silica filler and the curing characteristics of the material were evaluated. From the mechanical properties and thermogravimetry analysis the optimum time for devulcanization is determined. Further, scanning electron microscopy (SEM) studies were undertaken to check the coherency and homogeneity of the material. POLYM. ENG. SCI., 58:74–85, 2018. © 2017 Society of Plastics Engineers     

Influence of polymer–filler interactions on retraction behaviors of natural rubber vulcanizates reinforced with silica and carbon black

In general, silica‐filled rubber compounds contain a silane coupling agent to improve the filler dispersion and polymer–filler interactions. The silane coupling agent modifies the silica surface and makes crosslinks between the rubber and the silica. Influence of the modification of silica on the retraction behaviors of natural rubber (NR) vulcanizates reinforced with silica and carbon black was studied. Variation of the retraction behaviors of NR vulcanizates with filler composition was also investigated. The vulcanizates containing the silane coupling agent were recovered faster than those without the silane coupling agent. The recovery difference between the vulcanizates without and with the silane coupling agent increased with increased silica content. For the vulcanizates containing the silane coupling agent, the retraction behaviors were nearly the same, irrespective of filler composition. But, for the vulcanizates without the silane coupling agent, the vulcanizate was recovered more and more slowly as the silica content increased. The experimental results are explained with the polymer–filler interactions, modification of silica surface, and formation of crosslinks between silica and rubber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 691–696, 2006     

Nonlinear viscoelasticity and stress‐softening behavior of chloroprene rubber reinforced by multiwalled carbon nanotubes

The viscoelasticity and stress‐softening behavior of chloroprene rubber (CR) filled with multiwalled carbon nanotubes (MWCNT) and carboxylated multiwalled carbon nanotubes (MWCNT‐COOH) were studied using a Rubber Process Analyzer 2000 (RPA2000). In the strain sweep measurements, it is found that CR/MWCNT and CR/MWCNT‐COOH compounds have different behavior on storage modulus (G′). With increasing strain, G′ of CR/MWCNT (100/8) compound decreases at strain less than 2°, while G′ of CR/MWCNT‐COOH (100/8) compound stays at constant, indicating that MWCNT‐COOH has stronger filler–filler network and filler–rubber interactions as compared to MWCNT in CR matrix. CR/MWCNT (MWCNT‐COOH) vulcanizates have higher G′ but lower loss modulus (G″) than the corresponding uncured compounds. Repeated strain sweep scans were carried out to study the stress‐softening behavior of CR compounds. A stress‐softening effect of the filled CR compounds is observed and becomes more pronounced with increasing loading of MWCNT or MWCNT‐COOH. The correlation between the Payne effect and stress‐softening effect of CR/MWCNT (MWCNT‐COOH) vulcanizates is also studied. It is found that the difference of the storage moduli at 0.1° and 10° strain amplitudes and the difference of storage moduli of first and second strain sweeps at 0.1° strain amplitude show a positive linear correlation. POLYM. COMPOS., 35:2194–2202, 2014. © 2014 Society of Plastics Engineers     

A comparison of white rice husk ash and silica as fillers in ethylene–propylene–diene terpolymer vulcanizates

White rice husk ash (WRHA) and silica filled ethylene–propylene–diene terpolymer (EPDM) vulcanizates were prepared using a laboratory size two‐roll mill. Curing characteristics and physical properties of vulcanizates were studied with respect to the filler loading and filler type. Filler loading was varied from 0–50 parts per hundred resin (phr) at 10 phr intervals. Curing was carried out using a semi‐efficient vulcanization system in a Monsanto rheometer. Enhancement of the curing rate was observed with increasing WRHA loading, whereas the opposite trend was observed for silica‐filled vulcanizates. It was also indicated by the maximum torque and Mooney viscosity results that WRHA offers processing advantages over silica. Compared to the silica‐filled vulcanizates, the effect of filler loading on the physical properties of WRHA‐filled vulcanizates was not significant. According to these observations, WRHA could be used as a diluent filler for EPDM rubber, while silica can be used as a reinforcing filler. © 2001 Society of Chemical Industry