The effects of three silane coupling agents, triethoxy(octyl)silane (TEOS), bis[3-(triethoxysilyl)propyl]disulfide (TESPD), and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) on the filler-rubber interaction, crosslink density and crosslink structure of the silica-filled solution styrene butadiene rubber (SSBR) vulcanizates were studied. High dispersion silica, 7000GR, was used as the filler, and the loading range was varied from 0 to 60 phr. Crosslink density was measured by the swelling method. Experimental results showed that Kraus plot can be applicable to the silica-filled SSBR vulcanizates to separate filler-rubber interaction from the measured swelling data. Filler-rubber interaction increased by increasing sulfur rank in the silane as TEOS < Silica without silanes < TESPD < TESPT. Sulfurless silane, i.e. TEOS, only worked as a covering agent for hydrophobating silica surface. Silica without silane show high filler-rubber interaction than TEOS system because chain-end functionalized SSBR was used in this study. Unfilled system showed similar amounts of poly, di, and mono-sulfidic crosslinks. On the contrary to this, all of the silica-filled vulcanizates showed high mono-sulfide contents due to longer cure time.

Styrene-butadiene-glycidyl methacrylate terpolymer (GMA-SBR) was synthesized by emulsion polymerization for the fuel efficient tire tread composite. The chemical structure of the GMA-SBR was analyzed using infrared spectroscopy, ¹H NMR, gel permeation chromatography, and differential scanning calorimetry. The GMA-SBR/silica composite is the first instance introduced covalent bonds between silica filler and rubber molecules by in-chain modification of styrene-butadiene molecules. After compounding, the curing characteristics, the mechanical and dynamic mechanical properties of the composites were analyzed. The GMA-SBR/silica composite exhibited higher wear resistance of 32.9% and lower rolling resistance of 25.7% than the styrene-butadiene rubber 1721/silica composite. These results are due to the improvement of silica dispersion in the composite as the covalent bonding increased the filler–rubber interaction and the countervailing effects of less filler flocculation. The proposed approach assists in finding a solution to improve the performances of tires for fuel efficiency and the reduction of greenhouse gases from the vehicles.

Silica compounds were prepared using non-functionalized solution styrene-butadiene rubber (SSBR) to investigate effect of the functional group of silanes on the silica modification and properties of SSBR/silica compounds. Bis-[3-(triethoxysilyl)propyl]disulfide (TESPD), 3-mercaptopropyltriethoxysilane (MPTES), 3-aminopropyltriethoxysilane (APTES), vinyltriethoxysilane (VTES), and 3-chloropropyltriethoxysilane (CPTES) were used as silane agents. Bound rubber contents and vulcanizate structures were analyzed, and physical properties, cure characteristics and viscoelasticities were evaluated. MPTES and TESPD have chemically reactive functional groups with rubber chain. Particulary, as thiol group is more reactive than disulfide, the filler–rubber interaction is outstanding when applying MPTES. The bound rubber content of the MPTES applied compound was 30% higher. Vulcanizate structure analysis exhibited that the filler–rubber interaction of the MPTES applied compound is more than twice as high. As amino group of APTES can form hydrogen bonds with other amino or silanol groups on silica surface, strong filler–filler interaction which leads to easy agglomeration and accelerator adsorption, resulting in flocculation and marching. VTES cannot hydrophobize silica surface owing to its short carbon chain. Therefore, the compounds that apply APTES or VTES had high Payne effect, indicating poor silica dispersion. CPTES has polar functional group but behaves as covering agent because of its weak interaction with rubber.

Physical properties of rubber compounds are affected by the filler–rubber interaction, filler dispersion in the rubber matrix, and cross-link structure formed during vulcanization. In particular, the cross-link structure is closely related to the physical properties of vulcanizates and has been analyzed using the swelling test and Flory-Rehner equation. However, the relationship between the structure and physical properties of vulcanizates cannot be explained by the cross-link density obtained using these methods. The cross-link density obtained from the swelling test is a complex result of the filler–rubber interaction occurring during the compounding as well as the chemical cross-link structure formed by sulfur during the vulcanization. Moreover, the rubber vulcanizates that use silica need to be separately analyzed for each factor as its physical properties are affected more by the filler–rubber interaction than by carbon black. Therefore, this study determines the factors that contribute to the total cross-link density of vulcanizates into chemical cross-link density and filler–rubber interaction via quantitative analysis using the swelling test results and Flory-Rehner and Kraus equations. The vulcanizates used for the analysis were carbon black-filled and silica-filled non-functionalized SSBR compounds with varying cure accelerator for each filler loading. Their chemical cross-link density was measured and the effect of the filler–rubber interactions on their mechanical and dynamic viscoelastic properties was investigated. Furthermore, the relationship between the structure and physical properties of rubber vulcanizates was elucidated.

Energy loss in carbon black (CB) filled vulcanizates can be reduced by decreasing the CB volume fraction, reducing the localized deformation of rubber molecules between low-structure CB fillers, and increasing the crosslink density of vulcanizates. However, the decreased volume fraction and the use of low-structure CB degrade the mechanical properties of the vulcanizate. Furthermore, the increased crosslink density leads to drawbacks, such as the decrease of dynamic fatigue property. In this study, considering the performance trade-off from the energy loss reduction of CB-filled vulcanizate, the CB coupling agents (CCAs) system was introduced and its vulcanizate structure and mechanical properties were investigated. The coupling effect between CCAs and natural rubber molecules was confirmed by analyzing the vulcanizate structure using Flory–Rehner and Kraus equations. The vulcanizates with CCAs showed an increase in total crosslink density (TCD) compared to vulcanizates without CCAs. This increased TCD was attributed to the increase in crosslink density by the CB–rubber interaction (CRCD) and the increase in crosslink density by vulcanization reactions between vulcanization agents and matrix rubber (VRCD). The increase of TCD by CCAs improved the mechanical properties of vulcanizates. In particular, the energy loss characteristics were improved by increasing CRCD.