Free Volume of Montmorillonite/Styrene‐Butadiene Rubber Nanocomposites Estimated by Positron Annihilation Lifetime Spectroscopy

Summary: The size and concentration of free‐volume holes of two kinds of montmorillonite (MMT)/styrene‐butadiene rubber (SBR) nanocomposites were investigated by positron annihilation lifetime spectroscopy (PALS). Strong interfacial interaction caused an apparent reduction of the free‐volume fraction of rubber probably by depressing the formation of free‐volume holes in the interfacial region. Interfacial interaction in MMT/SBR nanocomposites was weaker than that in SBR filled with carbon black.

Dependence of normalized o‐Ps intensity of four kinds of composites on filler volume fraction.     

Fabrication of exfoliated graphite reinforced silicone rubber composites - Mechanical,tribological and dielectric properties

The effect of exfoliated graphite (EG) on the mechanical, tribological and dielectric properties of the silicone rubber (QM) composites has been systematically investigated and analysed. Morphological analysis of the composites helps to understand the interfacial interaction between the filler and the rubber matrix as well as wear mechanism respectively. An enhancement in the mechanical, tribological and dielectric properties was observed with an increase in filler loading and better performance was observed at 7 phr of filler loading. The improvement in performance is attributed to the better interaction between the QM chains and the EG layers as evident from the AFM and TEM analysis. It is also evident from the Kraus plot which supports the reinforcing effect of EG in QM matrix.     

Role of epoxidized natural Eucommia ulmoides gum in modifying the interface of styrene‐butadiene rubber/silica composites

Eucommia ulmoides gum (EUG) is a renewable and sustainable polymer, which could be used as rubber or plastic by altering its crosslinking density while the complicated extracting process and nonpolar molecular chains limited its application. In this effort, a novel extraction method was introduced, which could simplify the extraction process of EUG. Then, the extracted EUG‐chloroform (CHCl₃) solution was directly used to prepare epoxidized EUG (EEUG) with an epoxy degree of 40.0% to improve its polarity. The epoxidized natural EUG exhibiting both polar and nonpolar motives had an advantage in working as an interfacial compatibilizer for polymer composites, especially bio‐based composites due to its inherent biocompatibility. Accordingly, the role of EEUG in modifying the interface of styrene‐butadiene rubber (SBR)/silica composites were explored. The results showed that EEUG in SBR/silica composites acted not only as a compatibilizer but also as a constructure generating better mechanical properties than other compatibilizers, such as silane couplings, Si‐69 and KH‐550, and epoxidized natural rubber (ENR). The simplified extracting process and the epoxy modification of EUG would extend its application in rubber materials, medical materials, and biopolymer materials.     

Thermal stability of styrene butadiene rubber (SBR) composites filled with kaolinite/silica hybrid filler

Styrene butadiene rubber (SBR) composites filled with fillers, such as modified kaolinite (MK), precipitated silica (PS), and the hybrid fillers containing MK and PS, were prepared by melt blending. The kaolinite sheets were finely dispersed in the SBR matrix around 20–80 nm in thickness and reached the nano-scale. The SBR composites with fillers exhibited excellent thermal stability compared to the pure SBR. The thermal stability of SBR composites was improved with the increasing of MK mass fraction. When MK hybridized with PS, kaolinite sheets were covered by the fine silica particles and the interface between filler particles and rubber matrix became more indistinct. SBR composite filled by hybrid fillers containing 40 phr MK and 10 phr PS became more difficult in decomposition and was better than that of 50 phr PS/SBR and 50 phr MK/SBR in thermal stability. Therefore, the hybridization of the fine silica particles with the kaolinite particles can effectively improve the thermal stability of SBR composites.     

Interfacial mechano-chemical grafting in styrene-butadiene rubber/halloysite nanotubes composites

SBR/unmodified HNT composites were prepared by open-mill mixing and vulcanization. The results showed that HNT could decrease the scorch and optimum cure time, and play a significant role in reinforcing SBR vulcanizates. Mechano-chemical grafting at the interface between HNT and SBR was investigated by using infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), solid-state ¹³C NMR spectra and bonded rubber content, etc. The results showed the shearing force during the mixing process can impel the grafting reaction of SBR onto the surfaces of HNT, which leads to interfacial chemical bonding between phenyl’s α-H of SBR and the surface groups of HNT with Si-OH or Al-OH. Thus, the mechanical properties of the composites were significantly enhanced.     

Characterization of effects of thermal-oxidative aging on styrene-butadiene rubber/silica composites with vitamin C-lanthanum complex

A novel rubber antioxidant, vitamin C-lanthanum complex, was prepared and applied in styrene-butadiene rubber (SBR)/silica composites. The anti-aging behavior of SBR/silica composites with vitamin C-lanthanum complex was systematically investigated by mechanical property retention after aging, oxidation induction time, exothermic enthalpies of thermal oxidation, and thermo-oxidative degradation kinetics. The highlight of this work lies in the fact that several thermal analysis techniques were successfully applied to fully evaluate the thermal-oxidative aging of SBR/silica composites and the vitamin C-lanthanum complex was found to endow SBR/silica composites with better protection against aging than commercial antioxidants, which may be beneficial for better characterization of rubber aging and fruitful for the preparation of highly aging-resistant rubber composites, respectively.     

MORPHOLOGY,INTERFACIAL INTERACTION AND PROPERTIES OF STYRENE-BUTADIENE RUBBER/MODIFIED HALLOYSITE NANOTUBE NANOCOMPOSITES

 A natural nanotubular material, halloysite nanotubes (HNTs), was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube (SBR/m-HNT) nanocomposites. Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier. The structure, morphology and mechanical properties of SBR/m-HNT nanocomposites, especially the interfacial interactions, were investigated. SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix at nanometer scale, but also enhance the interfacial combination between HNTs and rubber matrix. FTIR and XPS investigations confirmed that a number of hydrogen bonds were formed between the phenol hydroxyl groups in resorcinol-formaldehyde resin derived from RH and the oxygen atoms in Si―O bonds or hydroxyl groups on HNTs surfaces. The m-HNTs modified with RH have significant reinforcing effect on SBR vulcanizates. RH as a good interfacial modifier can remarkably improve mechanical properties of SBR/HNT composites. The substantial improvement of comprehensive properties for SBR/m-HNT nanocomposites can be attributed to good dispersion and orientation of HNTs in SBR matrix at nanometer scale and the enhanced interfacial interaction between HNTs and rubber matrix.     

Improvement of properties of silica‐filled styrene‐butadiene rubber composites through plasma surface modification of silica

The performance of plasma surface modified silica filler in styrene‐butadiene rubber (SBR) matrix has been analyzed. The conditions of plasma modification have been optimized by taking secant modulus as a standard parameter and the occurrence of the modification has been confirmed by surface area determination and Fourier transform infrared spectroscopy. The plasma‐modified surface of silica has been found to be composed of carbon–carbon double bonds and carbon–hydrogen bonds. Silane treatment also has been carried out on silica filler surface for a comparative assessment of its influence in the curing behavior and filler–rubber interaction. The cure reactions of all the rubber compounds have been found to be proceeded according to first‐order kinetics. A reduction in the cure reaction rate constant has been observed with the loading of unmodified and surface modified silica, emphasizing the cure deactivation of the matrix rubber by the silica filler. The filler dispersion, as revealed by scanning electron microscopy, has been found to be greatly improved by the plasma as well as silane treatment. The filler–rubber interaction has been found to be greatly improved by both surface treatments, but the best balance of mechanical properties has been observed with plasma surface modification only. Copyright © 2004 John Wiley & Sons, Ltd.     

Structure and properties of star‐shaped solution‐polymerized styrene‐butadiene rubber and its co‐coagulated rubber filled with silica/carbon black‐I: morphological structure and mechanical properties

The morphological structure and mechanical properties of the star‐shaped solution‐polymerized styrene‐butadiene rubber (SSBR) and organically modified nanosilica powder/star‐shaped SSBR co‐coagulated rubber (N‐SSBR) both filled with silica/carbon black (CB) were studied. The results showed that, compared with SSBR, silica powder could be mixed into N‐SSBR much more rapidly, and N‐SSBR/SiO₂ nanocomposite had better filler‐dispersion and processability. N‐SSBR/SiO₂/CB vulcanizates displayed higher glass‐transition temperature and lower peak value of internal friction loss than SSBR/SiO₂/CB vulcanizates. In the N‐SSBR/SiO₂/CB vulcanizates, filler was dispersed in nano‐scale resulting in good mechanical properties. Composites filled with silica/CB doped filler exhibited more excellent mechanical properties than those filled with a single filler because of the better filler‐dispersion and stronger interfacial interaction with macromolecular chains. N‐SSBR/SiO₂/CB vulcanizates exhibited preferable performance in abrasion resistance and higher bound rubber content as the blending ratio of silica to CB was 20:30. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface modification of silica nanoparticles by a polyoxyethylene sorbitan and silane coupling agent to prepare high-performance rubber composites

The interfacial interaction between nano-silica and rubber matrix is very important for the preparation of high-performance rubber composites. In this paper, we first proposed the use of TWEEN-20 as a new silica modifier, it has four long arms consisting of three polyether chains with terminal hydroxyl group and a fatty chain. The oxygen on the polyether can form a hydrogen bond with the silanol groups on silica surface, and the terminal hydroxyl groups can chemically react with the silanol groups without any VOCs. Moreover, the long fatty chain can weaken silica polarity to obtain a better compatibility with rubber, so that silica modified by TWEEN-20 with chemical reaction and physical absorption can homogeneously disperses in rubber matrix. Nextly, we prepared high-performance natural rubber (NR) composites by adjusting the ratio of TWEEN-20 to TESPT to adjust the physical and chemical interaction between nano-silica and rubber molecular chains. The results indicated that the performances, including the filler dispersion, static mechanical properties, and dynamic heating (viscoelastic self-heating), were optimal when the ratio of TESPT to TWEEN-20 was 2:1. In addition, one-third of TESPT was replaced by TWEEN-20 to prepare silica/rubber composites, which can reduce one-third of VOCs, improve “scorchy”, and achieve high dispersion of silica.     

平衡溶胀法研究谷氨酸二硫代氨基甲酸镧对SBR/SiO2复合材料界面作用的影响

通过合成一种含有二硫代羧基,羧基和镧离子的新型稀土促进剂——谷氨酸二硫代氨基甲酸镧(简称La-GDTC),并利用平衡溶胀法研究了La-GDTC对丁苯橡胶(SBR)/SiO2复合材料界面作用的影响.交联密度测试表明,SiO2的加入能够有效提高SBR/La-GDTC/SiO2复合材料的交联密度;而SBR/La-GDTC/S...     

Influence of filler type and content on properties of styrene‐butadiene rubber (SBR) compound reinforced with carbon black or silica

Rubber compounds are filled with reinforcing fillers to improve their physical properties. Carbon black and silica have different surface chemistries to each other. Differences in properties of carbon black‐ and silica‐reinforced styrene‐butadiene rubber (SBR) compounds were studied. Variation of properties of carbon black‐ or silica‐filled compounds with the filler content was also investigated. The silica‐filled compounds without any coupling agent and dispering agent were prepared to investigate the influence of polar materials‐adsorption on the silica surface. Viscosity and crosslink density increased with increase of the filler content. Hardness, modulus, tensile strength, and wear property were improved more and more by increasing the filler content. Viscosity of the silica‐filled compound was higher than that of the carbon black‐filled one. Cure rate of the silica‐filled compound became slower as the filler content increased, while that of the carbon black‐filled one became faster. Difference in properties between the carbon black‐ and silica‐filled compounds were explained by the poor silica dispersion and the adsorption of cure accelerator on the silica surface. Copyright © 2004 John Wiley & Sons, Ltd.     

Microstructure and properties of styrene‐butadiene rubber based nanocomposites prepared from an aminosilane modified synthetic lamellar nanofiller

In this work, a novel nanocomposite series based on styrene‐butadiene rubber (SBR latex) and alpha‐zirconium phosphate(α‐ZrP) lamellar nanofillers is successfully prepared. The α‐ZrP lamellar filler is modified at the cation exchange capacity by γ‐aminopropyltrimethoxysilane and the filler surface modification is first discussed. A significant improvement of the mechanical properties is obtained by using the surface modified nanofillers. However, no modification of the gas barrier properties is observed. The impact of addition of bis(triethoxysilylpropyl)tetrasulfide (TESPT) as coupling agent in the system is discussed on the nanofiller dispersion state and on the filler–matrix interfacial bonding. Simultaneous use of modified nanofillers and TESPT coupling agent is found out with extraordinary reinforcing effects on both mechanical and gas barrier properties and the key factors at the origin of the improvement of these properties are identified. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1051–1059     

Chemical modification of carbon fiber with diethylenetriaminepentaacetic acid/halloysite nanotube as a multifunctional interfacial reinforcement for silicone resin composites

In the present research, a multifunctional hierarchical reinforcement was prepared by chemical modification of carbon fibers (CFs) with halloysite nanotubes (HNTs) by the bridging diethylenetriaminepentaacetic acid (DTPA) for improving interfacial microstructures and properties of composites. Surface structures and groups of modified HNTs and CFs were characterized systematically. The uniform distributions of the introduced DTPA and HNTs helped to increase fiber polarity, surface energy, and wettability. As a consequence, significant enhancements of interfacial properties and hydrothermal aging resistance of composites were achieved, and interfacial reinforcing mechanisms have also been studied. Moreover, the storage modulus showed a 17.95% improvement, and the glass transition temperature was enhanced by 17°C by dynamic mechanical analysis testing.     

Styrene butadiene rubber/carbon black composites modified by imidazole derivatives

In this study, the imidazole derivatives such as 2-undecylimidazole (UI) and 2-mercapto-1-methylimidazole (MMI) are utilized to work as novel additives for modifying styrene butadiene rubber (SBR)/carbon black (CB) composites. The imidazole groups on UI and MMI can be hydrogen-bonded with oxygen-containing groups on the surface of CB, and the undecyl or thiol groups can be reacted with the SBR chains via physical entanglement or thiol-ene chemistry. The results demonstrate that the static and dynamic mechanical performances of SBR/UI and SBR/MMI composites are significantly improved over those of the SBR composite. Compared with blank SBR composite, the tensile strength, modulus at 300% elongation, and tear strength of SBR/MMI-1.0 are greatly improved by 30, 42, and 18%, respectively. The rolling resistance of SBR/MMI-1.0 is reduced by 10.4%, and the wet grip property is increased by 4.0%. The superiority of appropriate MMI content (1.0 phr in our work) in the enhancement for the overall performance of SBR composites is attributed to the promotion of a good dispersion of CB throughout the SBR matrix and the enhanced interfacial interactions between CB and the SBR matrix. This work may enlarge the potential applications of modified CB to fabricate high-performance rubber composites.     

Properties of ethylene propylene diene rubber/white and black filler composites cured by gamma radiation in presence of sorbic acid

The effect of incorporating sorbic acid (SA), an echo-friendly curing agent, and silica or carbon black (CB) filler, as well as gamma irradiation on the physico-chemical, mechanical and thermal properties of ethylene propylene diene monomer rubber (EPDM) was investigated. The results indicated that the developed composites revealed improvement in the studied parameters over the untreated samples. Filler incorporation into rubber matrix has been proven a key factor in enhancing the swelling resistance, tensile strength and thermal properties of the fabricated composites. The improvement in tensile strength and modulus was attributed to better interfacial bonding via SA. Alternatively, a comparison was established between the performance of the white and black fillers. The utmost mechanical performance was reported for the incorporated ratios 10 phr SA and 40 phr white filler into a 50 kGy irradiated composite. Meanwhile, the incorporation of CB yielded better thermally stable composites than those filled with silica at similar conditions.     

Stepwise strain-induced crystallization of soft composites prepared from natural rubber latex and silica generated in situ

Novel biphasic structured in situ silica filled natural rubber composites were focused on their strain-induced crystallization (SIC) behavior from the viewpoint of morphology. The composites were prepared by in situ silica filling in natural rubber (NR) latex using a sol–gel reaction of tetraethoxysilane. Simultaneous time-resolved wide-angle X-ray diffraction and tensile measurements revealed a relationship between the characteristic morphology and tensile stress–strain properties of the composites associating with the SIC. Results showed stepwise SIC behaviors of NR-based composites for the first time. Pure rubber phases in the biphasic structure were found to afford highly oriented amorphous segments and oriented crystallites. The generated crystallites worked as reinforcing fillers together with the in situ silica to result in high tensile stresses of the composites. The observed characteristics are useful for understanding a role of filler network in the reinforcement of rubber.     

Recent developments in rubber processing,leading to new applications such as the “green tyre”

Rubber articles derive most of their mechanical properties from the admixture of reinforcing fillers. Most commonly, carbon black is used as reinforcing filler. If silica is used instead, tyres made with such rubber compounds may exhibit a rolling resistance reduction by ca. 30%, which translates in substantial fuel savings of a car. Such silicas are far more difficult to mix with rubber than carbon black. Coupling agents are used as a surface modification of the filler to enhance compatibility with the polymer. Additionally they improve the ease of mixing with the rubber. The development of proper coupling agents combined with improved mixing techniques has contributed to the final break-through of the silicareinforced “Green Tyre”.     

Morphology and performance of styrene butadiene rubber filled with modified graphite nanoplatelet and carbon black

In our work, effects of 2‐mercapto‐1‐methylimidazole modified graphite nanoplatelet (MMI–GN) and carbon black (CB) on static and dynamic mechanical properties of styrene butadiene rubber (SBR) composites were studied. MMI–GN is synthesized by ball‐mill process, and the result reveals that π–π interactions existed between MMI and GN. The results demonstrate that the static and dynamic mechanical performances of SBR/CB/MMI–GN composites are significantly improved over these of SBR/CB and SBR/CB/GN composites. Compared with SBR/CB, the tensile strength, tear strength, and modulus at 300% elongation of SBR/CB/MMI–GN–3 are greatly improved by 45%, 27%, and 4%, respectively. And the rolling resistance of SBR/CB/MMI–GN–3 is reduced by 3.7% with remaining almost unchanged in the wet grip property. The superiority of MMI–GN in the enhancement for the overall performance of SBR/CB composites is attributed to the well dispersion of GN throughout the SBR matrix and the enhanced interfacial interactions between GN and the SBR matrix. This work might expedite synthesis of the graphite‐based materials for enhancing rubber composites, and enlarge the potential applications of modified graphite to fabricate the high‐performance rubber composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Plasma polymerization of acetylene onto silica: an approach to control the distribution of silica in single elastomers and immiscible blends

Surface modification of silica by acetylene plasma polymerization is applied in order to improve the dispersion in and compatibility with single rubbers and their blends. Silica, used as a reinforcing filler for elastomers, is coated with a polyacetylene (PA) film under vacuum conditions. Water penetration measurements show a change in surface energy due to the PA‐film deposition. The weight loss measured by thermo‐gravimetric analysis (TGA) is higher for the PA‐coated silica compared to the untreated filler, confirming the deposition of the PA film on the silica surface. Time of flight‐secondary ion mass spectrometry (ToF‐SIMS) shows the well‐defined PA cluster peaks in the high mass region. Scanning electron microscopy (SEM) measurements show silica aggregates, coalesced by the coating with smooth and uniform surfaces, but without significant change in specific surface area. Elemental analysis by energy dispersive X‐ray spectroscopy (EDX) measurements also confirms the deposition of the polymeric film on the silica surface, as the carbon content is increased. The performance of single polymers and their incompatible blends based on S‐SBR and EPDM, filled with untreated, PA‐ and silane‐treated silica, is investigated by measurements of the bound rubber content, weight loss related to bound rubber, cure kinetics, reinforcement parameter, Payne effect, and mechanical properties. The PA‐ and silane‐modified silica‐filled pure S‐SBR and EPDM samples show a lower filler–filler networking compared to the unmodified silica‐filled elastomers. Decrease in the reinforcement parameter (α_F) for the plasma‐polymerized silica‐filled samples also proves a better dispersion compared to silane‐modified and untreated silica‐filled samples. On the other hand, the PA‐silica‐filled samples show a higher bound rubber content due to stronger filler–polymer interactions. Finally, the PA‐silica‐filled pure EPDM and S‐SBR/EPDM blends show high tensile strength and elongation at break values, considered to be the result of best dispersion and compatibilization with EPDM. Copyright © 2008 John Wiley & Sons, Ltd.