Triethoxysilylpropyl Tetrasulfide Research Articles

Reclaiming of waste guayule natural rubber vulcanizate—reclaim rubber for green tire applications: An approach for sustainable development

This article illustrates the reclaiming of guayule natural rubber (GNR) vulcanizate by bis[3-(triethoxysilyl)propyl] tetrasulfide (TESPT), and as-grown reclaim rubber facilitates the silica dispersion in GNR product application without adding any coupling agent. This article deals with the performance evaluation of silica-filled revulcanizates with promising application in green tire. The extent of reclaiming was monitored through the measurement of sol content, cross-link density, Mooney viscosity, and degree of reclaiming. The differential scanning calorimetry study was carried out to evaluate the fraction of immobilized polymer chains and its dependence on cross-link density of the vulcanizates. The Fourier transform infrared study and also sulfur analysis independently indicate the attachment of the fragmented TESPT with the polymer chain and cross-link bonds. The study of mechanical properties clearly shows that in revulcanized GNR, the optimum property is achieved when reclaiming time is set for 40 min. The effect of reclaiming time on dynamic mechanical behavior such as storage modulus and loss tangent was studied. The scanning electron microscopy studies show the coherency and homogeneity of silica-filled revulcanize rubber with reclaiming time.

Cure retardation of peroxide‐cured silica filled natural rubber influenced by organosilane

The influence of silane coupling agent on properties of silica‐filled compounds under peroxide curing was investigated. bis (triethoxysilylpropyl) tetrasulfide (TESPT) was selected in this study and its content was varied from 0 to 12% w/w of silica. It is found that with increasing TESPT content, bound rubber content, tensile strength, elongation at break and tear strength are enhanced. By contrast, magnitude of Payne's effect, modulus at 100% elongation (M100) and heat build‐up are decreased. The changes of such properties are attributed to the reduction of crosslink density in conjunction with the improvements of both rubber–filler interaction and degree of filler dispersion with increasing TESPT content in the peroxide curing system. POLYM. ENG. SCI., 59:42–48, 2019. © 2018 Society of Plastics Engineers

Study on viscoelastic behaviors of bentonite/nitrile butadiene rubber nanocomposites compatibilized by different silane coupling agents

Abstract The influences of bentonite and different silane coupling agents (SCA) on the viscoelastic properties of nitrile butadiene rubber were studied in this work. The silane coupling agents compatibilized bentonite/nitrile butadiene rubber nanocomposites were fabricated by a novel green method. The viscoelastic behaviors of the nanocomposites and their vulcanizates were explored using a rubber processing analyzer (RPA) in the modes of strain sweep and frequency sweep. Storage modulus (G′) and elastic torque (S′) of nitrile butadiene rubber increased significantly with the incorporation of bentonite. In the SCA applied in this work, mercaptopropyltrimethoxysilane (MPTMS) contributed to high storage modulus (G′) of the nanocomposites because of thorough exfoliation of bentonite and short sulfur bonds formed during curing process. Meanwhile, multi-sulfur bonds in bis-[3-(triethoxysilyl)propyl] tetrasulfide (TESPT) and reversible interactions from [3-(2-aminoethylamino)propyl] trimethoxysilane (AEAPTMS) resulted in lower storage modulus of the cured nanocomposites.

Effect of Silane Treatment Methods on Physical Properties of Rice Husk Flour/Natural Rubber Composites

In this study, the effect of silane treatment methods on cure characteristics and mechanical, dynamic mechanical, and morphological properties of rice husk flour (RHF)/natural rubber (NR) composites was investigated. The RHF surface was pretreated with alkali solution and then treated with bis(triethoxysilylpropyl) tetrasulfide (TESPT) solution using the unwashing silane treatment method and washing silane treatment method. The expected difference between these two methods was the silane layers presented on the RHF surface. Unwashed TESPT‐treated RHF (UW‐ST) and washed TESPT‐treated RHF (W‐ST) were incorporated into NR to prepare RHF/NR composites. The TESPT molecules deposited on UW‐ST and W‐ST surfaces were confirmed by the additional peaks appeared in the FTIR spectra of UW‐ST and W‐ST. In addition, the decrement of decomposition temperatures and the changes in the residue amounts of UW‐ST and W‐ST proved the removal of the physisorbed silane layers after washing. The presence of TESPT molecules on the RHF surface enhanced compatibility and adhesion between RHF and NR matrix. This was confirmed by SEM micrographs of both UW‐ST/NR and W‐ST/NR composites. This result was also supported by the improvement of the mechanical and the dynamic mechanical properties of these two composites. According to mechanical properties of the NR composites, the washing silane treatment method was more effective than the unwashing silane treatment method for compatibility improvement between RHF and NR. The modulus, tensile strength, and tear strength of W‐ST/NR composites can be enhanced without deterioration of their elongation at break.

Modulating silica‐rubber interface by a biorenewable urushiol derivative. Synthesis, surface modification, and mechanical and dynamic mechanical properties of vulcanizates therefrom

ABSTRACTHydrogenated urushiol (i.e., 3‐pentadecylcatechol) can be used to directly modify silica particles via surface complexation with silicon. The degree of surface coverage can be varied by experimental conditions. Mooney viscosity and Payne effect studies of uncured rubber compounds show that dispersion of silica filler completely covered by hydrogenated urushiol in the absence of coupling agent bis[3‐(triethoxysilyl)propyl] tetrasulfide (TESPT) is as effective as dispersion of standard unmodified silica in the presence of TESPT under otherwise identical mixing conditions. Low bound rubber content and observation of filler flocculation at the early stage of vulcanization demonstrate that the filler‐rubber interaction is physical in nature as the result of surface modification by hydrogenated urushiol. When silica is partially covered by hydrogenated urushiol, it can be used in conjunction with TESPT. Judicial combination of partially covered silica and TESPT can give optimal properties to the resultant vulcanizate, including reduced Payne effect and improved cut resistance while maintaining other key parameters the same in comparison with a standard silica‐TESPT reinforced rubber. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45937.

PROMOTING INTERFACIAL COMPATIBILITY OF SILICA-REINFORCED NATURAL RUBBER TIRE COMPOUNDS BY ALIPHATIC AMINE

ABSTRACT Octadecylamine (OCT) as an alternative for diphenyl guanidine (DPG) in silica-reinforced NR tire compounds with bis-(triethoxysilyl-propyl)tetrasulfide (TESPT) as silane coupling agent was investigated with focus on the improvement of compatibility between the silica surface and rubber molecules, by taking the amine-free rubber compound as a reference. The quantity of OCT and DPG was varied in a range of 2.4–9.5 mmol per 100 parts of rubber by weight (i.e., 0.5–2.5 phr). Bound rubber contents, changes in heat capacity (ΔCp), and immobilized polymer layer (χim) data prove an enhanced interfacial compatibility as the amines are absorbed on the polar silica surface and catalyze the silanization reaction. Comparing the two different amine types, the rubber compounds with OCT show higher interfacial compatibility than the ones with DPG, because of an additional shielding effect promoted by the long alkyl chain that leads to more hydrophobicity. Thus, the rubber compounds with OCT show higher physically bound rubber contents and consequently higher total bound rubber, a higher immobilized polymer layer, as well as a lower Payne effect. However, the compounds with OCT show a higher flocculation rate constant because the physical interactions between amine and silanol groups decrease under thermal treatment. The compounds with OCT show a lower cure torque difference that indicates a lower crosslink density, but because of the good interfacial interaction combining both chemical and physical interactions, the vulcanized rubber with OCT at optimum loading shows better mechanical properties and tan δ at 60 °C when compared with the DPG counterpart. At high (excessive) loading of amines, the compounds with DPG clearly have higher crosslink density and thus higher modulus as well as tensile strength compared with the use of OCT.

Small size mesoporous organosilica nanorods with different aspect ratios: Synthesis and cellular uptake

In the work, small size thioether-bridged mesoporous organosilica nanorod (MONRs) are successfully synthesized using cetyltrimethylammonium bromide (CTAB) as structure-directing agent and bis[3-(triethoxysilyl)propyl]tetrasulfide (TETS) and tetraethoxysilane (TEOS) as co-precursors. The MONRs have tunable aspect ratios of 2, 3, and 4 (denoted as MONRs-2, MONRs-3, and MONRs-4), small and controllable lengths (75–310nm), high surface area (570–870cm2g−1), uniform mesopores (2.4–2.6nm), large pore volume (0.34cm3g−1), and excellent biocompatibility. The uptake of the MONRs by multidrug resistant human breast cancer MDR-MCF-7 cells is related to their aspect ratios. The MONRs-3 shows a faster and higher cellular internalization compared to the MONRs-4 and MONRs-2, respectively. Thanks to the high cellular uptake, doxorubicin (DOX) loaded MONRs-3 show obviously improved chemotherapeutic effect on MDR-MCF-7 cancer cells. It is expected that the MONRs provide a useful platform for drug delivery and therapeutics.

Influence of the silanes on the crosslink density and crosslink structure of silica-filled solution styrene butadiene rubber compounds

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.

Crack growth behavior of natural rubber influenced by functionalized carbon nanotubes

ABSTRACTIn this work, the silane coupling agentbis‐(triethoxysilylpropyl) ‐tetrasulfide (TESPT) is used to modify the carbon nanotubes. After modification, carbon nanotubes can be well dispersed in the natural rubber (NR) matrix and form a strong and flexible network. Based on the original real‐time crack tip morphology monitoring, crack propagation and scanning electronic microscopy tests, it is revealed that modified carbon nanotubes filled NR samples (NR/F‐CNTs) have better crack resistance. It is found that modified carbon nanotubes can resist the cavitation process during cyclic loading. Crack tip morphology monitoring tests indicate that the crack tip of NR/F‐CNTs is rougher and the ligaments are thinner and densely distributed. A crack branching phenomenon is also observed. It proves that F‐CNTs increase the energy consumption of NR during cyclic loading. It is concluded that the F‐CNTs used in this work improve the crack resistance of NR in two ways: the one is cavitation resistance and the other is the increase of energy consumption for crack propagation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2017,134, 44527.

ENHANCEMENT OF ELECTRICAL CONDUCTIVITY AND FILLER DISPERSION OF CARBON NANOTUBE FILLED NATURAL RUBBER COMPOSITES BY LATEX MIXING AND IN SITU SILANIZATION

ABSTRACTCarbon nanotube (CNT)-filled natural rubber (NR) composites were prepared by melt and by latex mixing methods. Also in situ functionalization of CNTs with a silane coupling agent, namely bis(triethoxysilylpropyl)tetrasulfide (TESPT), was done to improve the filler–rubber interactions between CNT surfaces and rubber molecules. The grafting of TESPT molecules on CNT surfaces was confirmed by attenuated total reflection (ATR)–Fourier transform infrared (FTIR) spectroscopy and by the improvement of composite properties. Tensile properties were determined to assess the reinforcement efficiency of the CNTs in the composites. Also, electrical conductivity of the composites was measured to assess the formation of CNT networks (or connected conductive CNT pathways) in the rubber matrix. The results indicate that the composites prepared by latex mixing, in particular with the TESPT, had better tensile properties and electrical conductivities than the composites made by melt mixing. The lowest percolation threshold concentration, about 0.55 phr of CNTs, was observed in the latex–CNT composites, and three-dimensional network formations of CNTs in the rubber matrix were found with added TESPT, used by in situ functionalization. The improvement of filler–rubber interactions with the addition of TESPT was also examined by temperature scanning stress relaxation measurements, revealing the relaxation modulus, the relaxation spectrum, and an estimate of the cross-link density.

A comparative study of rice husk ash and siliceous earth as reinforcing fillers in epoxidized natural rubber composites

Rice husk ash (RHA) and siliceous earth (SE) were compared as alternative reinforcing fillers in epoxidized natural rubber (ENR) vulcanizates. The effects of RHA and SE on processability, curing characteristics, mechanical, thermal and morphological properties, and thermoelastic behavior of vulcanizates were studied, in the presence and absence of bis(triethoxysilylpropyl) tetrasulfide (TESPT) silane coupling agent. The results indicated that the RHA offers processing advantages over the commercial SE. The filled ENR vulcanizates without TESPT provided higher tensile strengths than the unfilled ENR vulcanizates, but had lower elongations at break. This is attributed to physical interactions between filler particles and rubber matrix, which affects the reinforcement by the filler. The modification of filler surfaces with TESPT resulted in further improved properties of the rubber vulcanizates. This is attributed to the coupling of polymer matrix and filler particles via TESPT linkages that increased the polymer–filler interactions. It was also found that the RHA filler, a renewable resource, exhibited similar reinforcement to the conventional SE. This indicates that the RHA has great potential as a reinforcing filler that can substitute for conventional SE in polymer composites. POLYM. COMPOS., 39:414–426, 2018. © 2016 Society of Plastics Engineers

Surface functionalization of rubber latex nanoparticles with sulfidosilane moieties

ABSTRACTPolybutadiene latex particles were functionalized with bis[3‐(triethoxysilyl) propyl] tetrasulfide (TESPT) in the presence of zinc oxide as an activator and ethanol as a co‐solvent. The success of this reaction was confirmed both by the peaks attributed to Si‐O groups at 1085 and 1110 cm−1 and C‐S bond at 630 cm−1 which appeared after reaction in Attenuated Fourier Transform Infrared (ATR‐FTIR) Spectra and also by increasing in the particle size diameter of latex particles (from 95 to 127 nm) in Dynamic Light Scattering analysis. X‐ray Diffraction results also showed changes in crystalline structure of the modified particles (as a strong decrease in the intensity of peak at 2θ=19.54). The effect of reactant concentration in a constant amount of TESPT (by varying the water and ethanol content), reaction time, activator size (micro and nanoparticles), and pH (≈7, 8.5) were investigated on degree of grafting (obtained from thermogravimetric analysis and ATR‐FTIR spectra), particle size diameter, cross‐link density, and swelling ratio of the samples. The amounts of silane grafting and cross‐link density of polymer particles were increased by an increase in the reaction time. The highest grafting degree was observed at low concentration of TESPT. Silane functionalization was also improved in a slight basic condition (pH=8.5) rather than neutral pH. The grafting reaction took place such as sulfur pre‐vulcanization and the possible mechanism of this reaction was discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43268.

Effects of silane coupling agents on the properties of bentonite/nitrile butadiene rubber nanocomposites synthesized by a novel green method

Effects of different silane coupling agents on the mechanical strength, tribological properties, thermal behaviors, swelling properties and rheological properties of bentonite (Bent)/nitrile butadiene rubber (NBR) nanocomposites were explored. The nanocomposites were fabricated with an innovative green method in NBR latex. The composition of the nanocomposites was determined by Fourier transform infrared spectroscopy (FT-IR). The intercalated/exfoliated structure and the dispersion of Bent in rubber matrix were characterized with X-ray diffraction (XRD) and field emission-scanning electron microscopy (FE-SEM). It is revealed that different functional groups from the silanes were effective to the properties of the nanocomposites mainly because of their different interactions with the rubber matrix. Mercaptopropyltrimethoxysilane (MPTMS) showed attractive effects on mechanical modulus, tribological properties and swelling properties. Incorporation of bis-[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) resulted in the highest elongation at break. With octadecyltrimethoxysilane (OTMS), the degradation temperature of the nanocomposite was noticeably elevated due to its “barrier effect”.

Effects of silane coupling agents on tribological properties of bentonite/nitrile butadiene rubber composites

In this work, effects of silane coupling agents on the tribological properties of bentonite/nitrile butadiene rubber (NBR) composites were investigated. The composites were fabricated with a facile method. Three silane coupling agents, (3‐mercaptopropyl)trimethoxysilane (MPTMS), bis[3‐(triethoxysilyl)propyl]tetrasulfide (TESPT) and [3‐(2‐aminoethylamino)propyl]triethoxysilane (AEAPTMS) were employed in our research. The short sulfur bonds formed between MPTMS and macromolecules in the matrices limited the extension of the contact interface between rubber matrices and glass plate, which contributed to the reduction in friction coefficient. With TESPT and AEAPTMS, the adhesion force of the composites was remarkably reinforced, further leading to the increase in friction coefficient. In the wear test, bentonite/silane/NBR composites showed better wear resistance compared to the specimens fabricated without silanes. By investigation on the morphological features of the worn surfaces, different wear mechanisms for composites with/without silane coupling agents were illustrated in detail. Generally, the effects of silanes to adhesion force, hysteresis loss ratio, and hardness all contributed to the friction coefficients of the composites. In wear test, the effects of the silanes on hysteresis force were prominent. Incorporated with MPTMS, the composite showed poor wear resistance due to its high hysteresis loss ratio. POLYM. COMPOS., 38:2347–2357, 2017. © 2015 Society of Plastics Engineers

Effects of in‐situ functionalization of carbon nanotubes with bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 3‐aminopropyltriethoxysilane (APTES) on properties of epoxidized natural rubber–carbon nanotube composites

Composites of carbon nanotubes (CNT) and epoxidized natural rubber (ENR) were prepared by in‐situ functionalization of CNT with two alternative silane coupling agents: bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 3‐aminopropyltriethoxysilane (APTES). The reactions of ENR molecules with the functional groups on CNT surfaces and with the silane molecules were characterized by Fourier transform infrared. Furthermore, cross‐link density, relaxation behaviors, curing, mechanical, electrical, and morphological properties of pristine ENR and the ENR composites were investigated. Very low percolation thresholds, at CNT concentrations as low as 1 phr, were observed in the ENR–CNT and the ENR–CNT–TESPT composites. This might be attributed to improvements in the chemical linkages between ENR molecules and functional groups on CNT surfaces that led to a homogenous dispersion of CNTs in the ENR matrix, with loose CNT agglomerates. POLYM. ENG. SCI., 55:2500–2510, 2015. © 2015 Society of Plastics Engineers

MORPHOLOGY OF SILICA-REINFORCED NATURAL RUBBER: THE EFFECT OF SILANE COUPLING AGENT

ABSTRACT A good dispersion of silica in a rubber vulcanizate is important as it influences the filler-to-rubber interaction and consequently the final properties. This article presents an investigation into the morphology of silica-reinforced natural rubber (NR) in the presence and absence of a silane coupling agent, bis(triethoxysilylpropyl) tetrasulfide (TESPT). Micro- and nano-dispersion morphologies of silica in NR and deproteinized natural rubber (DPNR) are studied by using atomic force microscopy (AFM). Using a special network visualization technique based on transmission electron microscopy (TEM), insight into the silica and rubber interaction in the NR and DPNR is gained. In the absence of silane, vacuoles around the silica particles are formed as a result of a weak filler–polymer interaction, whereas the presence of silane leads to strong filler-to-rubber bonding, which prevents formation of vacuoles. Improvement of the micro-dispersion of silica in the NR and DPNR vulcanizates with the use of TESPT is observed from AFM phase imaging. The correlation between the filler-to-rubber interaction as analyzed by TEM and AFM and bound rubber contents as well as the Payne effect is discussed.

양기능성 커플링제 실란에 의한 실리카-천연고무 복합소재의 계면간 결합 고찰

양기능성 실란 커플링제인 bis(triethoxysilylpropyl)tetrasulfide(TESPT)가 실리카/천연고무 복합소재 내에서 실리카의 hydroxy기와 고무 계면간에 화학적 결합반응을 하여 실리카-실란-고무간의 3차원 사슬구조를 형성한 것을 열분해 가스 크로마토그래피 질량분석기(Py-GC/MS)와 주사전자현미경(SEM)을 통해 관찰하였다. TESPT의 첨가로 배합물 내의 황 함유율이 증가하여 스코치 시간(<TEX>$t_{10}$</TEX>)은 감소하고, TESPT 내 sulfur donor 역할을 하는 황이 활성화제 및 촉진제와의 복합반응으로 가교반응이 지속적으로 이루어짐에 따라서 가교속도지수(CRI)의 값이 감소하였다. 또한 TESPT가 첨가된 컴파운드는 첨가되지 않은 컴파운드에 비해 가공성 및 기계적 물성이 향상되었다. 결과적으로, 실리카로 충전된 천연고무 복합소재에 실란 커플링제(TESPT)가 첨가되어 화학반응으로 실리카-실란-고무간의 3차원 사슬구조가 형성됨을 관찰하였고 이에 따라 가교밀도가 증가하여 복합소재의 물성 증가에 기여함을 보여주었다. 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 (<TEX>$t_{10}$</TEX>) 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.

Compatibilization of silica-filled natural rubber compounds by combined effects of functionalized low molecular weight rubber and silane

Epoxidized low molecular weight natural rubber (ELMWNR) with 28 mol% epoxide groups and weight average molecular weight of 49,000 g mol−1 was prepared by oxidative degradation of epoxidized natural rubber (NR) using periodic acid in the latex state. ELMWNR-28 was used at 10 parts per hundred parts of rubber (phr) loading in combination with bis-(triethoxysilylpropyl) tetrasulfide (TESPT) as the silane coupling agent in the range of 0–4.5 phr in silica-reinforced NR compounds. The use of TESPT in combination with ELMWNR-28 gives lower mixing torques and compound viscosities compared with the use of TESPT alone and the system without any compatibilizer. The bound rubber content, modulus, and tensile strength of the compounds with only TESPT strongly depend on the TESPT loading. The use of ELMWNR-28 as a compatibilizer clearly improves such properties compared with the non-compatibilized systems. By adding TESPT into the compound with ELMWNR-28, the properties further improve with increasing TESPT loading. The combined effect of ELMWNR-28 at 10 phr with a small amount of TESPT at 1.5 phr results in compounds with superior processability (i.e. low Mooney viscosity and Payne effect), and only slightly lower modulus and reinforcement index (M300/M100) compared with the use of the optimum content of TESPT. This compatibilizer/TESPT combination has the environmental benefits that the ELMWNR is a naturally based product, and that the reduced amount of TESPT silane coupling agent emits a greatly reduced amount of ethanol during processing.

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

ULTRA SMALL-ANGLE X-RAY SCATTERING STUDY OF FLOCCULATION IN SILICA-FILLED RUBBER

ABSTRACT The flocculation of silica during vulcanization is monitored using the ultra small-angle X-ray scattering technique for two different types of silica: a highly dispersible silica (HD) and a conventional silica (CV), mixed into a blend of S-SBR and BR rubbers. The cutoff length of the silica aggregate Rss and the mass fractal dimension Dm, which indicate the degree of flocculation of aggregates, are estimated according to the modified unified equation. The aggregate radius Ra is estimated to be related to the lower cutoff length Rss, indicating the radius of gyration of the mass-fractal structure. For both silicas, Ra increases during vulcanization. For the CV silica, an increase of Dm is observed, whereas no significant increase of Dm can be seen for the HD silica. The Ra of CV is relatively high compared with that of HD. On the other hand, the CV silica shows a relatively lower Dm compared with that of HD. These results indicate that CV has a larger size of aggregates and lower degree of agglomeration of its aggregates. The presence of di(tri-ethoxy-silyl-propyl)tetrasulfide (TESPT) as coupling agent between the silica and rubber decreases the aggregate radius of silica. However, in the absence of TESPT, a low mass-fractal dimension, which means a low degree of agglomeration of aggregates, is observed. This results from a lower mobility of silica aggregates, depending on the size of the aggregates. The silica loading also has an influence on the flocculation process. The aggregate radius increases as the silica loading is increased. At the same time, a higher mass-fractal dimension, and therefore also a higher degree of agglomeration, can be seen at higher silica loading.