The modified silica at different temperature (MSaDT) with bis(3-triethoxysilylpropyl)tetrasulfide (TESPT), and MSaDT filled solution styrene butadiene rubber (SSBR) composites were prepared to investigate the effect of temperature on surface modification of silica. The results showed that TESPT was successfully bonded on the surface of silica by chemical bonds. The grafting degree ( K ) of MSaDT of 50 °C was 62.2% and higher than that at the other temperatures. The thermal weight loss and the size distribution of MSaDT showed that the silanol of TESPT hydrolysates reacted with the surface hydroxyl groups of silica, decreasing the average size and agglomeration of modified silica. For 50 °C modified silica/SSBR composite, the static mechanical properties and rubber–filler interaction of the composite were better than those of the others. As far as dynamic mechanical properties are concerned, the 50 °C modified silica/SSBR composite owned a best combination of low rolling resistance and high wet skid resistance.

Effect of the temperature on surface modification of silica and properties of modified silica filled rubber composites

In a rubber/filler composite, the surface chemistry of the filler is a critical factor in determining the properties of the composite because it affects the dispersion of the filler and the interfacial adhesion between the filler and rubber. In this study, we primarily focus on how graphene surface chemistry affects the dispersion of graphene and interfacial adhesion in butadiene–styrene rubber (SBR)/graphene composites and on the resultant properties of the composites. Composites that contain graphene with tailored surface chemistry are prepared via the chemical reduction of graphene oxide (GO) in situ. Subsequently, the dispersion of the graphene and interfacial adhesion are fully investigated in relation to the graphene surface chemistry. As revealed by dielectric relaxation spectroscopy, the bulk segmental relaxation is independent of the graphene surface chemistry, whereas the interfacial relaxation mode is retarded in the composite with stronger graphene–rubber affinity. The contribution of the grap...

http://pubs.acs.org/doi/pdf/10.1021/ma502201e

Rational Design of Graphene Surface Chemistry for High-Performance Rubber/Graphene Composites

Simplified silica (Zeosil 1165 MP) and SBR (140k carrying silanol end-groups) nanocomposites have been formulated by mixing of a reduced number of ingredients with respect to industrial applications. The thermo-mechanical history of the samples during the mixing process was monitored and adjusted to identical final temperatures. The filler structure on large scales up to micrometers was studied by transmission electron microscopy (TEM) and very small-angle X-ray scattering (SAXS). A complete quantitative model extending from the primary silica nanoparticle (of radius \approx 10 nm), to nanoparticles aggregates, up to micrometer-sized branches with typical lateral dimension of 150 nm is proposed. Image analysis of the TEM-pictures yields the fraction of zones of pure polymer, which extend between the branches of a large-scale filler network. This network is compatible with a fractal of average dimension 2.4 as measured by scattering. On smaller length scales, inside the branches, small silica aggregates are present. Their average radius has been deduced from a Kratky analysis, and it ranges between 35 and 40 nm for all silica fractions investigated here (\phi_si = 8-21% vol.). A central piece of our analysis is the description of the interaggregate interaction by a simulated structure factor for polydisperse spheres representing aggregates. A polydispersity of 30% in aggregate size is assumed, and interactions between these aggregates are described with a hard core repulsive potential. The same distribution in size is used to evaluate the polydisperse form factor. Comparison with the experimental intensity leads to the determination of the average aggregate compacity (assumed identical for all aggregates in the distribution, between 31% and 38% depending on \phi_si), and thus aggregation number (ca. 45, with a large spread). Because of the effect of aggregate compacity and of pure polymer zones, the volume fraction of aggregates is higher in the branches than \phi_si. The repulsion between aggregates has a strong effect on the apparent isothermal compressibility: it leads to a characteristic low-q depression, which cannot be interpreted as aggregate mass decrease in our data. In addition, the reinforcement effect of these silica structures in the SBR-matrix is characterized with oscillatory shear and described with a model based on the same aggregate compacity. Finally, our results show that it is possible to analyze the complex structure of interacting aggregates in nanocomposites of industrial origin in a self-consistent and quantitative manner.

Multiscale Filler Structure in Simplified Industrial Nanocomposite Silica/SBR Systems Studied by SAXS and TEM

Simplified silica (Zeosil 1165 MP) and SBR (140k carrying silanol end-groups) nanocomposites have been formulated by mixing of a reduced number of ingredients with respect to industrial applications. The thermo-mechanical history of the samples during the mixing process was monitored and adjusted to identical final temperatures. The filler structure on large scales up to micrometers was studied by transmission electron microscopy (TEM) and very small-angle X-ray scattering (SAXS). A complete quantitative model extending from the primary silica nanoparticle (of radius ≈10 nm), to nanoparticle aggregates, up to micrometer-sized branches with typical lateral dimension of 150 nm is proposed. Image analysis of the TEM-pictures yields the fraction of zones of pure polymer, which extend between the branches of a large-scale filler network. This network is compatible with a fractal of average dimension 2.4 as measured by scattering. On smaller length scales, inside the branches, small silica aggregates are presen...

https://hal.archives-ouvertes.fr/hal-00767771/document

Rubbers are strategically important due to their indispensable applications in the daily life and high-tech fields. For their real-world applications, the covalent cross-linking, reinforcement, and malleability of rubbers are three important issues because they are closely related to the elasticity, mechanical properties, and recycling of the rubber materials. Herein, we demonstrate a simple way to prepare covalently cross-linked yet recyclable and robust elastomeric vitrimer composites by incorporating exchangeable β-hydroxyl ester bonds into the elastomer–nanoparticle interface using epoxy group-functionalized silica (Esilica) as both cross-linker and reinforcement in carboxyl group-grafted styrene-butadiene rubber (CSBR). The Esilica-cross-linked CSBR composites exhibit promising mechanical properties due to the covalent linkages in the interface and fine silica dispersion in the matrix. In addition, the interface can undergo dynamic reshuffling via transesterification reactions to alter network topolo...

Engineering of β-Hydroxyl Esters into Elastomer–Nanoparticle Interface toward Malleable, Robust, and Reprocessable Vitrimer Composites

In material science of elastomers the influence of nanoscale and nanostructured filler particles is of utmost significance for the performance of innovative rubber products, i.e., passenger car tires with ultralow rolling resistance but high wet-grip performance. A better understanding of the physical characteristics of the filler–rubber interface and the filler–rubber interphase as well is necessary to improve the overall macroscopic properties of these elastomeric nanocomposites. Therefore, the surface energies and polarities of filler particles with different modified surfaces were measured by a modified Wilhelmy technique. In all cases the rubber matrix consisted of a solution - styrene butadiene copolymers, filled with 20 or 40 phr pyrogenic or precipitated silica grades with different surface modifications by silanes, and a carbon black sample as reference. A moving die rheometer was employed to observe the filler flocculation at elevated temperatures (160 °C) in rubber mixtures containing no curati...

Impact of Filler Surface Modification on Large Scale Mechanics of Styrene Butadiene/Silica Rubber Composites

Algorithm of constant definition for a visco-elastic rubber model based on cyclic experiments, stress relaxation and creep data

In the deformable solid mechanics, there are concepts associated with continuum points (displacements, relative elongations, shifts) and a set of continuum points – an elementary volume (mass, energy, stresses). The role of such volume in the mechanics of composite materials is played by the representative volume element (RVE).This concept was first introduced by R. Hill (1963). Modern authors use the W.J. Drugan, J.R. Willis (1996) formulation. Based on the analysis of the RVE concept, we formulated its essential features: RVE is the minimum possible sample for numerical tests to determine the effective material parameters of the composite; under any RVE loading, its macroscopic stress-strain state is uniform. Its significance for the mechanics of composite materials is revealed: the existence of RVE for a composite is a criterion for applying the effective modulus theory to the analysis of its stress-strain state; the dehomogenization of a stressed-state composite material at a point is a solution to the micromechanics problem of the RVE stress-strain state determination; the characteristic size of RVE limits the size of the sampling grid in the numerical study. An iterative algorithm for constructing a representative volume of a periodic structure composite and its effective material thermoelastic characteristics is proposed. It is shown that the geometric shape of such a composition is a rectangular parallelepiped. The RVE construction algorithm for periodic compositions is extended to the composites statistically uniformly reinforced with continuous fibers. A method for modeling such materials with a following regular structure is suggested described: in the section perpendicular to the fibers, fiber centers should be located at the vertices of regular triangles. Examples of constructing RVE and thermoelastic material characteristics of specific compositions are given. The calculation results are compared with the data obtained using certified software products.

/pdf/representative-volume-and-effective-material-characteristics-t321jya7.pdf

Representative volume and effective material characteristics of periodic and statistically uniformly reinforced fiber composites

This article is devoted to the effect of ion-plasma treatment on the surface morphology of various formulations of medical grade polyurethanes. In this work, we study single-layer polyurethane samples synthesized by molding and solution technology, as well as two-layer samples using the proposed technology. Optical and atomic force microscopy were used to study the surface morphology. The influence of production technology, ion fluence of treatment and mechanical loads on the surface morphology of polyurethane samples was studied. It was shown that the use of two-layer technology has a positive effect on the morphology of the plasma-treated surface. 

A. G. Pelevin

Papers

Impact of Filler Surface Modification on Large Scale Mechanics of Styrene Butadiene/Silica Rubber Composites

Algorithm of constant definition for a visco-elastic rubber model based on cyclic experiments, stress relaxation and creep data

Representative volume and effective material characteristics of periodic and statistically uniformly reinforced fiber composites

Surface morphology of a carbon layer on polyurethanes synthesized by two-layer technology