Effect of the amounts of glycidyl methacrylate on the mechanical and dynamic properties of styrene–butadiene–glycidyl methacrylate terpolymer/silica composites

GMA-SBRs with GMA contents in the range of 0.06–0.71 wt.% were synthesized and used to evaluate the properties of the silica composites for fuel-efficient tires. The chemical structures of the GMA-SBRs were analyzed using Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). GMA-SBRs can enhance filler–rubber interaction through covalent bond formation between the silica filler and rubber molecules. After compounding, the cure characteristics and mechanical and dynamic properties of the GMA-SBR silica-filled composites were analyzed. The mechanical properties, including the Mooney viscosity, bound rubber, swelling ratio, and moduli, exhibited obvious differences with increasing GMA content. However, the optimum content of GMA in the GMA-SBR, in terms of dynamic properties such as the Payne effect which represents the change in dynamic modulus against the strain to determine the extent of filler flocculation and tan δ at 60 °C representing tire rolling resistance, was ~0.6 wt.%. These results are due to improved silica dispersion, resulting from increased covalent bond formation between GMA-SBR and the silica surface. This approach assists in the determination of functional group contents in functionalized emulsion styrene–butadiene rubber for fuel-efficient tires, leading to a decrease in vehicular greenhouse gas emission.     

Reduced filler flocculation in the silica-filled styrene–butadiene–glycidyl methacrylate terpolymer

This study presents a method to improve the dispersion of silica in rubber compounds using a styrene-butadiene-glycidyl methacrylate terpolymer (GMA-SBR) synthesized by cold emulsion polymerization. It has been demonstrated that silica particles in conventional rubbers tend to agglomerate during storage, as well as at the onset of vulcanization, because of their polarity. GMA-SBR can improve the compatibility with silica by the formation of covalent bonds between the epoxy groups of GMA-SBR and silanol groups on the silica surface. SBR 1721 and GMA-SBR silica-filled compounds were prepared without curatives by a kneader and a two-roll mill. After compounding, the reaction of the epoxy group, filler flocculation, and morphology of the compounds were analyzed using infrared spectroscopy, a rubber process analyzer, and transmission electron microscopy, respectively. In addition, the content of bound rubber in the compounds was determined by extracting the unbound rubber material with toluene. The GMA-SBR silica-filled compounds had a higher bound rubber content and exhibited significantly different filler flocculation and silica dispersion behaviors compared with the SBR 1721 silica-filled compounds.     

Insights into the Reinforcement of Butyl Rubber by Carbon Black and Silica with the Aid of Their Dynamic Properties

Carbon black (N234) and silica (Vulksail N) with a silane coupling agent Si-69 were chosen as reinforcing fillers in butyl rubber (IIR). The rheological behavior of the IIR compounds and the dynamic mechanical properties of IIR vulcanizates were investigated with a rubber processing analyzer and dynamic mechanical analysis (DMA) to examine the filler dispersion in the rubber matrix and the interaction between filler and matrix. The data indicated that the N234 filled IIR compounds had more filler networks than those filled with silica. Filler networks first appeared at 30 phr N234 and 45 phr silica with silane coupling agent Si-69. The interaction between N234 and IIR was far stronger than that between silica and IIR. However, the silica Vulksail N filled IIR had better wet-grip and lower rolling resistance compared to the carbon black-filled IIR should IIR be chosen as a substitute of styrene-butadiene rubber (SBR) in tire tread. The reinforcing factor, R, R (related to the difference in tan d peak height at T_g for the filled and nonfilled rubbers), also demonstrated that the N234-IIR interaction was stronger than for the silica. IIR with 30 phr N234 exhibited the largest tensile strength, 20.1 MPa, for those vulcanizates examined. The tensile and tear strengths of N234 filled IIR were higher than those of IIR with similar amounts of silica. Thus, it was concluded that N234 is a more active reinforcing filler in IIR than silica (Vulksail N) even with a silane coupling agent (Si-69).     

The effect of accelerator contents on the vulcanizate structures of SSBR/silica vulcanizates

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.     

Influence of filler type on wet skid resistance of SSBR/BR composites: Effects from roughness and micro-hardness of rubber surface

The wet skid resistance (WSR) of SSBR/BR(solution styrene-butadiene rubber/butadiene rubber) composites filled with carbon black, silica, and nano-diamond partly replacing carbon black or silica, respectively, was measured with a portable British Pendulum Skid Tester (BPST). A dynamic mechanical thermal analyzer was used to obtain the viscoelasticity of the composites. A 3D scanning white-light interfering profilometer was used and the scratch test performed to characterize surface roughness and micro-roughness, respectively, of the composites. WSR of the silica-filled composite was better than that of the carbon black-filled one, and further enhancement of WSR was obtained by replacing silica with nano-diamond. Tan δ of the composites at 0 °C, 10 Hz, and tensile strain of 2% did not show good correlation with WSR. The surface roughness of the composites had effects on WSR. The scratch test indicated that the higher the hardness of the filler in the composite, the higher the micro-hardness and the better the WSR. Therefore, the surface micro-hardness of the composites is an important factor affecting WSR, besides viscoelasticity and surface roughness.     

Tensile properties of styrene-butadiene rubber/silica composites with mercapto functional silane coupling agents: influences of loading method and alkoxy group number

The influences of alkoxy group number and loading method of silane coupling agents on the mechanical properties of a styrene-butadiene rubber/silica composite were investigated. Mercapto functional silane coupling agents with dialkoxy and trialkoxy structures were used. The pre-treatment method and the integral blend method were compared. Both the fracture stress and modulus at 200% strain were higher in the pre-treatment than in the integral blend for dialkoxy type composites. However, they were higher in the integral blend than in the pre-treatment for trialkoxy-type composites. The interaction between the silane chains on the silica surface and the rubber molecular chains at the interfacial region was estimated by ¹H pulse nuclear magnetic resonance spectroscopy using an unvulcanized silica/rubber mixture. It was found that the binding of rubber molecular chains by the silane chains was higher in the pre-treatment system for dialkoxy-type composites, whereas it was higher in the integral blend for trialkoxy-type composites. The reason is proposed as follows: in the pre-treatment for dialkoxy type, a linear silane chain formed in the case of multi-layer coverage. The silane chain entangled with the rubber chain in the interfacial region and improved the reinforcement effect. For the trialkoxy type, a network structure formed using the pre-treatment method, lowering the amount of entanglement. However, in the integral blend for trialkoxy type, the formation of the silane network and the entanglement progressed simultaneously during the preparation process. A well-entangled interfacial region was formed.     

Characterization of Filler-rubber Interaction,Filler Network Structure,and Their Effects on Viscoelasticity for Styrene-butadiene Rubber Filled with Different Fillers

For styrene-butadiene rubber (SBR) compounds filled with the same volume fraction of carbon black (CB), precipitated silica and carbon–silica dual phase filler (CSDPF), filler-rubber interactions were investigated thru bound rubber content (BRC) of the compounds and solid-state ¹H low-field nuclear magnetic resonance (NMR) spectroscopy. The results indicated that the BRC of the compound was highly related to the amount of surface area for interaction between filler and rubber, while the solid-state ¹H low-field NMR spectroscopy was an effective method to evaluate the intensity of filler-rubber interaction. The silica-filled compound showed the highest BRC, whereas the CB-filled compound had the strongest filler-rubber interfacial interaction, verified by NMR transverse relaxation. The strain sweep measurements of the compounds were conducted thru a rubber process analyzer; the results showed that the CSDPF-filled compound presented the lowest Payne effect, which is mainly related to the weakened filler network structure in polymer matrix. The temperature sweep measurement, tested by dynamic mechanical thermal analysis, indicated that the glass transition temperature did not change when SBR was filled with different fillers, whereas the storage modulus in rubbery state and the tanδ peak height were greatly affected by the filler network structure of composites.     

Acoustic analysis of bound rubber formed in silica/SBR compounds

The compressibility of the bound rubber around the silica particle was evaluated by an acoustic technique. The density and the longitudinal wave velocity of a silica/SBR compound were measured as a function of the silica content. The density increased linearly with the filler content. The longitudinal wave velocity was almost constant within the experimental error. The mass ratio of the bound rubber to the silica in the silica/SBR compounds was 1.08+/-0.03 kg kg(-1) which was measured by a thermal gravimetric analysis (TGA). The partial specific adiabatic compressibility of the silica was estimated as (0.1+/-0.5) x 10(-10) Pa(-1) on the basis of a three states model. The adiabatic compressibility of the bound rubbers in the silica/SBR compounds was (4.6+/-0.5) x 10(-10) Pa(-1). The compressibility was almost the same as that of the SBR, and the value was twice larger than the compressibility of the bound rubber formed in a CB/SBR composite.     

Effect of High Aspect Ratio Fillers on the Performance of Styrene-Butadiene Rubber

Among the many material performance properties of vulcanized elastomers for tire tread application, rolling resistance and wet traction are particularly important since both greatly impact fuel efficiency and traction of a vehicle. Rolling resistance and wet traction are generally negatively correlated, i.e., with the increase in rolling resistance of a tire, its wet traction decreases. Silica nanofillers are often used for achieving the desired balance of wet traction and rolling resistance. However, the high cost of silica limits its wide spread application. In this research we studied the effects of using fillers with different aspect ratios (calculated by dividing the long dimension of a filler by its short dimension) on the performance of vulcanized styrene butadiene rubber (SBR), a common rubber for tire tread application. Three high aspect ratio fillers were used: aragonite calcium carbonate, wollastonite and carbon nanofiber. For comparison purpose, spherical silica filler was also included. We found that the high aspect ratio fillers were efficient in improving the wet traction and rolling resistance as well as enhancing the mechanical energy dissipation of SBR. Among the three high aspect ratio fillers studied, wollastonite provided the best wet traction and rolling resistance balance due to its high aspect ratio and compatibility with the base rubber. The effects of fillers induced crosslinking on the dynamic performance were also discussed.     

Improved Dispersion of Carbon Nanoparticles Modified by Poly(Sodium 4-Styrenesulfonate) and Its Influence on the Properties of Natural Rubber Latex

A novel strategy of radical polymerization of sodium 4-styrenesulfonate on the surface of carbon black (CB) in the solid state was developed to prepare hydrophilic carbon nanoparticles (PNASS-CB). A high performance natural rubber latex (NRL)/PNASS-CB composite was produced by the latex compounding technique. Scanning electron microscope shows considerable improvement in the dispersion of PNASS-CB in rubber matrix. The lower degree of filler–filler networks and the stronger filler–rubber interaction of PNASS-CB in rubber matrix were confirmed by dynamic mechanical thermal analysis. Rheometric properties of NRL/PNASS-CB, like scorch time and optimum cure time, decreased. Tensile strength, tear strength, and elongation at break increased due to stronger interaction between the PNASS-CB and rubber matrix. Dynamic mechanical properties of the modified carbon nanoparticles further corroborated a significant contribution from the better dispersion and efficient load transfer of PNASS-CB on the static and dynamic mechanical properties of composites.     

Highly hydrated poly(allylamine)/silica magnetic resin

The creation of multifunctional nanomaterials by combining organic and inorganic components is a growing trend in nanoscience. The unique size-dependent properties of magnetic nanoparticles (MNPs) make them amenable to numerous applications such as carriers of expensive biological catalysts, in magnetically assisted chemical separation of heavy metals and radionuclides from contaminated water sources. The separation of minor actinides from high-level radionuclide waste requires a sorbent stable in acidic pH, with ease of surface functionalization, and a high capacity for binding the molecules of interest. For the described experiments, the MNPs with 50 nm average size were used (size distribution from 20 to 100 nm and an iron content of 80–90 w/w%). The MNPs that have been double coated with an initial silica coating for protection against iron solubilization and oxidation in nitric acid solution (pH 1) and a second silica/polymer composite coating incorporating partially imbedded poly(allylamine) (PA). The final product is magnetic, highly swelling, containing >95% water, with >0.5 mmol amines g^?1 available for functionalization. The amine groups of the magnetic resin were functionalized with the chelating molecules diethylenetriaminepentaacetic acid (DTPA) and N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) for separation of minor actinides from used nuclear fuel.     

凹凸棒石/硅橡胶复合材料的热氧化降解和老化性能研究

本文采用高压均质结合对辊挤压工艺对天然凹凸棒石进行棒晶解离得到了纯度较高和比表面积较大(133.7 m²/g)的纳米解离凹凸棒石. 进一步通过机械共混法分别将天然凹凸棒石和纳米解离凹凸棒石与硅橡胶生胶复合制备了天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶材料,研究了天然凹凸棒石和纳米解离凹凸棒石对凹凸棒石/硅橡胶复合材料热氧化降解和老化性能的影响. 结果表明,天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶在300 oC热氧老化处理0.5 h后,相比于纯硅橡胶,初始5%失重温度从385 oC提高至396∽399 oC. 系列表征结果表明,天然凹凸棒石和纳米解离凹凸棒石增强了纳米粒子与硅橡胶之间的相互作用从而抑制了纳米颗粒聚集,并且可显著提高硅橡胶侧链Si-CH₃的保存率,从而提高了该复合材料的热氧化降解和老化性能. 此外,纳米解离凹凸棒石可大大抑制纳米粒子的长大;因此老化后,纳米解离凹凸棒石-硅橡胶表现出了比硅橡胶(10.6%、7.4%和5.0%)更高的拉伸强度、断裂伸长率和撕裂强度保留率(40.6%、34.9% 和30.1%).     

Interactions Between an Ionic Liquid and Silica,Silica and Silica,and Rubber and Silica and Their Effects on the Properties of Styrene-Butadiene Rubber Composites

An investigation of the effect of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMI), on the properties of silica reinforced styrene-butadiene rubber (SBR), aimed to correlate the interactions between the ionic liquid and silica, silica and silica, and silica and rubber with the macro-properties and microstructure of SBR and SBR/silica vulcanizates is described. The interaction between the ionic liquid and silica was characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), the interaction between silica and silica was characterized by a rubber processing analyzer (RPA), and the interaction between rubber and silica was characterized by the bound rubber content. The FTIR analysis revealed that BMI can react with the hydroxyl groups on the surface of silica, improving the compatibility between the rubber and silica. The RPA and bound rubber testing indicated that the interactions between silica and silica particles were weakened and the interaction between silica and rubber increased with the incorporation of BMI into the SBR rubber. The bound rubber content showed a maximum with a BMI content of 3 phr. At the same time, the dispersion of silica in SBR was improved with the incorporation of BMI. With the increase of BMI content, the curing rate was greatly improved and the crosslink density increased. BMI also increased the tensile strength and abrasion resistance of the SBR vulcanizates. Most important, the BMI significantly improved the dynamic properties of the rubber composites, especially the wet-skid resistance and rolling resistance. However, excessive BMI (beyond 3 phr) acted as a plasticizer and was detrimental to the mechanical properties, resulting in a decrease of tensile strength and abrasion resistance.     

改性钢渣-矿粉复合橡胶填料补强-阻燃机理的光谱学分析

钢渣作为炼钢过程中产生的固体废弃物,矿渣作为高炉炼铁过程中的副产品,其存在难以利用与附加值的问题。面对上述问题,利用钢渣与矿渣开发一种价格低廉的复合橡胶填料用于橡胶领域。采用磁选热闷渣、未磁选热闷渣、矿粉和助磨-改性复合剂制备改性钢渣-矿粉复合橡胶填料,并且用于复合橡胶体系。研究磁选热闷渣用量、未磁选热闷渣用量、矿粉用量和助磨-改性复合剂用量对改性钢渣-矿粉基橡胶复合材料性能的影响,并且分析其影响机理。结果表明,以磁选热闷渣用量150 g、未磁选热闷渣用量150 g、矿粉用量150 g和助磨-改性复合剂用量9 g制备的改性钢渣-矿粉复合橡胶填料补强-阻燃性能最优。按改性钢渣-矿粉复合橡胶填料∶炭黑质量比20∶30制备的改性钢渣-矿粉基橡胶复合材料,其拉伸强度为21.83 MPa、撕裂强度为46.23 kN·m-1、邵尔A硬度为62、磨耗量为159 mm3、极限氧指数为19.8%与燃尽时间为187 s。助磨-改性复合剂不仅降低粒径尺寸、提高粒径均匀性,而且改善钢渣-矿粉复合橡胶填料的表面结构与性质,有利于改性钢渣-矿粉复合橡胶填料在复合橡胶体系中均匀分散,提高相容性。钢渣与矿粉在助磨-改性复合剂的作用下发生化学反应,改变了钢渣与矿粉的物相组成,提高补强性能与阻燃性能。     

Natural rubber nanocomposites using polystyrene-encapsulated nanosilica prepared by differential microemulsion polymerization

In this study, nanocomposites of natural rubber (NR) and polystyrene (PS)-encapsulated nanosilica were prepared by latex compounding method. The nanolatex of PS-encapsulated silica was synthesized via in situ differential microemulsion polymerization. The resulted hybrid nanoparticles showed core-shell morphology with an average diameter of 40 nm. The silica hybrid nanoparticles were subsequently used as filler for the NR nanocomposite. The properties of NR were found to be improved as a result of the incorporation of PS-encapsulated nanosilica at 3 and 3-9 parts per hundred rubber (phr) for tensile strength and modulus at 300% strain, respectively, except the elongation at break, and up to 9 phr for flammability. The results from dynamic mechanical analyzer showed that the elastic properties of NR near the glass transition temperature increased with the inclusion of increasing concentration of the PS-encapsulated nanosilica, causing by the semi-interpenetrating nanostructure in the NR nanocomposites.     

Natural fibre composites from polyethylene waste and hazelnut shell: dimensional stability,physical, mechanical and thermal properties

Within the framework of this study, the physical modification of high-density polyethylene waste foil was performed using finely ground hazelnut flour to produce a composite whose physical, mechanical and flammable properties make it possible to use inside and outside of buildings. Three mixtures were produced with filler shares of 11, 26 and 42 vol.% using equipment that is normally used in polymer processing, and no refining additives were applied. The produced materials were analysed for their processing (mass flow ratio), physical (density and moisture content) and mechanical properties (tensile strength, elongation at break and dynamic thermal analysis) and resistance to environmental factors (swelling and water absorption, thermogravimetric analysis and combustion heat). The particle size distribution of the filler and morphological properties of the composites (scanning electron microscopy) were also investigated. It was vital to obtain an inexpensive material with low absorptivity. The resulting materials are characterised by a low density, acceptable low absorptive and good mechanical properties; also, they can constitute an important fuel once their practical properties have been exploited.     

Synthesis of spin labelled silica and EPR molecular dynamics study at silica–polymer interfaces

Information concerning the interface structure in filler/polymer composites is of key importance for the rationalization of reaction mechanisms in mechano‐chemical (extrusion, blending, etc.), thermal or radiation induced free radical processes and for elucidating the factors underlying the reinforcing mechanism. The analysis of the chain dynamics is a suitable tool for undertaking such investigations because any reactivity parameter (rate constants, collisional frequencies, activation energies) and bonding interactions are strictly related to the mobility of the interacting centres. EPR spectroscopy coupled with specific spin labelling at the filler/polymer interface is a tool for making such novel perspective available. In this work, a spin labelling study of the molecular motion at the filler–rubber interface in a silica–SBR blend is reported. Spin labels of different length, spanning a 9–11 Å depth and linked to the surface of silica particles, were prepared and used for determining the rotational diffusion tensors, the T₅₀ and order parameter in silica/SBR interfaces. The measurements carried out as a function of the temperature in comparison with unbound spin probes dispersed in the rubber matrix have afforded information consistent with the structure of the interfaces predicted by molecular–level theoretical models. Copyright © 2010 John Wiley & Sons, Ltd.     

Abrasive Wear Behavior of LDPE Filled with Silane Treated Flyash Cenospheres

Lightweight, high mechanical strength insulating materials exhibiting high resistance to corrosion, solvents and abrasive wear are desired for wire and cable insulation as well as protection. Polyethylenes are generally used for such applications owing to their good electrical insulation properties and being inert to solvents at room temperature. However, their abrasion resistance is quite poor. Hence, in the present work, an attempt has been made to improve the abrasive wear resistance of low-density polyethylene (LDPE) by incorporating hollow microspheres, known as cenospheres, in the base polymer to form composites. These cenospheres are obtained from flyash particles, a thermal power plant waste, and do not tend to increase the weight of the polymer composite when used as a filler. The composites were developed by changing the weight fraction of untreated as well as silane treated cenospheres to the extent of 5 wt%. Tribological characterization of these composites was done in abrasive wear mode by varying the operating parameters, such as speed and sliding distance against silicon carbide paper. It was found that 10 wt% silane treated cenosphere filled LDPE composite showed the maximum wear resistance (～×10^?11 m³/N m) among the six composites. However, a further increase in filler concentration decreased the wear resistance. The improvement in wear resistance was supported by scanning electron microscopy and attributed to the strong interaction between silane treated cenosphere and LDPE molecules which resisted the elongation and shearing of polymer chains by the abrasive grits.     

Composite Material Based on Polytetrafluoroethylene and Al–Cu–Fe Quasi-Crystal Filler with Ultralow Wear: Morphology,Tribological, and Mechanical Properties

Samples of composites with polytetrafluoroethylene as the matrix and a powder of 0, 1, 2, 4, 8, 16, and 32 vol % Al–Cu–Fe quasi-crystal as the filler are prepared. Electron microscopy studies of the sample structure are carried out, the influence of the filler on the degree of crystallinity and the melting and destruction temperatures of the samples is investigated; mechanical tensile tests and tribological tests are performed. The composite samples with filler contents of 4, 8, 16, and 32 vol % show ultralow wear with the coefficient K < 5 × 10^–7 mm³/N m. The highest wear resistance exceeding that of unfilled polytetrafluoroethylene by 2200–3100 times is recorded in composites with 16 vol % filler. An increase in the wear resistance is associated with formation on the friction surface of a thin crust containing quasi-crystal particles 0.2–0.3 μm in size, revealed by scanning electron microscopy in combination with energy dispersive analysis.     

Water at the interface modified silica filler-polydimethylsiloxane: quantum-chemical modelling

Intermolecular interactions determine the reinforcement of polydimethylsiloxane (PDMS) elastomers by fumed silica, and a water interlayer on the fumed silica/PDMS interface may act as a lubricant, decreasing the interaction energy and promoting the PDMS molecule motion over the filler surface. A quantum-chemical (QCh) modelling has been performed to study a microscopic aspect of water impact on the intermolecular interactions in the system. The results obtained for a series of superclusters simulating fragments of the real silica filler surface, both hydroxylated and silylated, interacting with five-member PDMS oligomer in presence of individual water molecules and of a 'water drop', of several H-bonded water molecules, are in good agreement with results from IGC adsorption experiments.