• Polymer(Korea)
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• v.37 no.3
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• pp.308-315
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• 2013

In this study, we performed surface modification of silica nanoparticles with bis[3-(triethoxysilylpropyl)]tetrasulfide (TESPT) silane coupling agent to study the effects of treatment temperature, treatment time, and amount of TESPT used on the silanization degree with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), elemental analysis (EA) and solid state $^{13}C$ and $^{29}Si$ cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR). We found peak area of isolated silanol groups at $3747cm^{-1}$ decreased, but peak area of $-CH_2$ asymmetric stretching of TESPT at $2938cm^{-1}$ increased with the amount of TESPT from FTIR measurements. We also used universal testing machine (UTM) to study mechanical properties of styrene butadiene rubber (SBR) nanocomposites with 20 phr (parts per hundred of rubber) of pristine and TESPT modified silicas, respectively. The tensile strength and 100% modulus of modified silica/SBR nanocomposite were enhanced from 5.65 to 9.38MPa, from 1.62 to 2.73 MPa, respectively, compared to those of pristine silica/SBR nanocomposite.

• Elastomers and Composites
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• v.45 no.2
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• pp.112-121
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• 2010

In this study, styrene butadiene rubber(SBR)/organoclay nanocomposites were manufactured using the latex method with 3-aminopropyltriethoxysilane(APTES) as a modifier. The X-ray diffraction(XRD), transmission electron microscopy(TEM) images, Fourier transform infrared(FTIR) spectroscopy, swelling ratio and mechanical properties were measured in order to study the interaction between filler and rubber according to the mixing temperature in the internal mixer. In the case of SBR/APTES-MMT compounds, the dispersion of the silicates within the rubber matrix was enhanced, and thereby, the mechanical properties were improved. The characteristic bands of Si-O-C in APTES disappeared after hydrolysis reaction in the MMT-suspension solution and the peak of hydroxyl group was increased. Therefore the formation of chemical bonds between the hydroxyl group generated from APTES on the silicate surface and the ethoxy group of bis(triethoxysilylpropyl) tetrasulfide(TESPT) was possible. Consequently, the 300% modulus of SBR/APTES-MMT compounds was further improved in the case of using TESPT as a coupling agent. However, the silanization reaction between APTES and TESPT was not affected significantly according to the increase of mixing temperature in the internal mixer.

• Polymer(Korea)
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• v.39 no.2
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• pp.240-246
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• 2015

Formation of a strong 3-dimensional interfacial network structure via chemical reaction between hydroxyl group on silica surface and NR chain by the addition of bis(triethoxysilylpropyl)tetrasulfide (TESPT) into silica-filled NR compound was observed by using Py-GC/MS and SEM. Addition of TESPT into silica-filled NR compound decreased scorch time ($t_{10}$) due to increased sulfur content, and reduced cure rate index (CRI) via continuous reaction between sulfur atoms in TESPT, which acted as a sulfur donor, and activators and/or accelerators. Addition of TESPT in the compound improved processability and mechanical properties of the compound. Overall, we observed that the addition of TESPT into the silica-filled NR compound formed a silica-TESPT-NR network, and thus the degree of crosslinking was increased resulting in improved mechanical properties.

• Elastomers and Composites
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• v.49 no.3
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• pp.239-244
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• 2014

Reaction between silica and silane coupling agent without solvent was investigated using transmission mode Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Bis[3-(triethoxysilylpropyl) tetrasulfide] (TESPT) was used as a silane coupling agent. After removing the unreacted TESPT, formation of chemical bonds was analyzed using FTIR and content of reacted TESPT was determined using TGA. Content of the coupling agent bonded to silica increased with increase in the coupling agent content, but the oligomers were formed by condensation reaction between coupling agents when the coupling agent was used to excess. In order to identify bonds formed among silica, coupling agent, and rubber, a silica-coupling agent-BR model composite was prepared by reaction of the modified silica with liquid BR of low molecular weight and chemical bond formation of silica-coupling agent-BR was investigated. Unreacted rubber was removed with solvent and analysis was performed using FTIR and TGA. BR was reacted with the coupling agent of the modified silica to form chemical bonds. Polarity of silica surface was strikingly reduced and particle size of silica was increased by chemical bond formation of silica-coupling agent-BR.

• Rubber Technology
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• v.9 no.1
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• pp.1-12
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• 2008

Effects of silane modifier, bis(triethoxysilylpropyl) tetrasulfide (TESPT(S4)) and bis(triethoxysilylpropyl) disulfide (TESPD(S2)), on silica filled compound were investigated upon processability, dynamic, mechanical, heat build-up, blowout properties, and silica dispersion in natural rubber (NR). The temperature of the S2 treated silica compound generated higher than that of the S4 treated compound during internal mixer compounding. The shear viscosity of the S2 compound exhibited lower than that of the S4 compound and the viscosity measured in dynamic mode was close to each other. The elongation modulus of the S2 compound exhibited lower than that of the S4; however, the tear resistance strength of the S2 compound exhibited higher than that of the S4 compound. The loss tan$\delta$ values of the S2 compound exhibited higher than those of the S4 at room temperature. The augmentation of the test temperature lowered the tan$\delta$ values of each compound, which results in close tan$\delta$ values to each other at $100^{\circ}C$. The S2 compound deformed less than the S4 compound, and the blowout time of each compound was close to each other. The S2 compound generated more heat build-up than the S4 compound. The abrasion loss of the S2 compound was less than that of the S4 compound. The size of the silica agglomerate reduced on both S4 and S2 compounds upon vulcanization. The addition of the bifunctional silanes (S2 and S4) on silica filled NR compound improved the processability of each compound and their effects were more significant on the S2 compound than the S4 compound. After vulcanization the silica agglomerate size of each compound reduced compared with before vulcanization.

• Elastomers and Composites
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• v.55 no.1
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• pp.26-39
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• 2020

The physical properties of silica-filled SBR compounds (WSBR) prepared using silica-SBR wet masterbatches (WMB) were systematically investigated to understand the effect of the surface treatment of silica on the reinforcement performance of SBR. Treatment of silica with bis(triethoxysilylpropyl)tetrasulfide (TESPT) in the liquid phase, followed by mixing with an SBR solution and recovery by water stripping, easily produced silica-SBR WMB. However, insufficient surface treatment in terms of the amount and stability of the incorporated TESPT led to considerable silica loss and inevitable TESPT elution. Pretreatment of silica in the gas phase with TESPT and another organic material that enabled the formation of organic networks among the silica particles on the surface provided hydrophobated silica, which could be used to produce silica-SBR WMB, in high yields of above 99%. The amount and type of organic material incorporated into silica greatly influenced the cure characteristics, processability, and tensile and dynamic properties of the WSBR compounds. The TESPT and organic material stably incorporated into silica increased their viscosity, while the organic networks dispersed on the silica surface were highly beneficial for reducing their rolling resistance. Excessive dosing of TESTP induced low viscosity and a high modulus. The presence of connection bonds formed by the reaction of glycidyloxy groups with amine groups on the silica surface resulted in physical entanglement of the rubber chains with the bonds in the WSBR compounds, leading to low rolling resistance without sacrificing the mechanical properties. Mixing of the hydrophobated silica with a rubber solution in the liquid phase improved the silica dispersion of WSBR compounds, as confirmed by their low Payne effect, and preservation of the low modulus enhanced the degree of entanglement.

• Elastomers and Composites
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• v.47 no.1
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• pp.54-64
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• 2012

Acrylonitrile was introduced in the emulsion SBR to increase compatibility between silica and rubber. AN-SBR/silica compounds showed faster vulcanization time and higher delta torque values than SBR 1721/silica compounds because interaction between nitrile group of AN-SBR and silanol group on the silica surface could make hydrogen bond that prevented adsorption of the accelerator on the silica surface, which improved the vulcanization reaction efficiency and enhanced the degree of crosslinking. AN-SBR/silica compound showed higher values in minimum torque than SBR 1721/silica compound during the vulcanization because AN-SBR has higher molecular weight than SBR 1721 in the raw material. When PEG was added to the SBR 1721 and AN-SBR compounds, vulcanization time was faster than SBR 1721 and AN-SBR compounds without PEG because PEG has a large number of ether linkages which show high compatibility with silanol group on the silica surface that prevented the adsorption of the accelerator and the ingredients on the silica surface, which improved the vulcanization reaction efficiency. In the mechanical properties, AN-SBR compounds showed higher modulus values at 100%, 300% than SBR 1721 compounds because interaction between nitrile group of AN-SBR and silanol group on the silica surface enhanced the degree of crosslinking. In the dynamic properties, AN-SBR compounds showed lower tan ${\delta}$ values at $0^{\circ}C$ than SBR 1721 compounds in accordance with the $T_g$ values. AN-SBR compounds showed lower tan ${\delta}$ values at $60^{\circ}C$ than SBR 1721 compounds because interaction between acrylonitrile and silica caused strong filler-rubber interaction that induced low energy dissipation by the filler-filler interaction.