Filler-elastomer interactions silica

The reinforcement of rubber composites by CB and/or silica is greatly affected by the rubber filler interactions, the agglomeration of the filler particles within the rubber matrices, and the occlusion of the rubber into the internal voids of the dispersed aggregates. Furthermore, filler-elastomer interactions play a major role in the filler dispersion achievable during mixing process. 

M.J. Wang, S. Wolff, J.B. Donnet. Filler-elastomer interactions. Part I silica surface energies and interactions with model compounds. Rubb. Chem. TechnoL, 64, 559-576,1991. 

Elastomer interaction with carbon black or silica is very difficult to estimate and correct. On the other hand, it is much easier to take into account the actual volume of aggregate in the mix, and it has been proposed that a corrected volume fraction 4>c be used, which integrates the influence of filler stmcture as represented by DBF (Medalia, 1974 Kraus, 1970 Medalia, 1973). 

Functionalization of the polymer has been widely employed in binary nanocomposites to improve the polymer/filler interactions and thus maximize the load transfer. Functionalization also serves to enhance the compatibility between the two components of polymer blend. Many grades of functionalized polymers are now available, including maleated grades and silane-grafted polymers. Examples of functionalized matrices studied in ternary nanocomposite studies include PP-g-MA [41], PP-g-VTEOS [27] and examples of functionalized elastomers include SEBS-g-MA [8,49,65], EPR-g-MA [19,44,65], POE-g-MA [75], and EPDM- -MA [64]. It is also important to note that only nonpolar matrices and elastomers require functionalization, as opposed to polar polymers like PA6, which present natural interactions with polar fillers such as silica particles and clay platelets. 

Non-linear viscoelastic properties were observed for fumed silica-poly(vinyl acetate) (PVAc) composites, with varying PVAc molar mass and including a PVAc copolymer with vinyl alcohol. Dynamic mechanical moduli were measured at low strains and found to decrease with strain depending on surface treatment of the silica. The loss modulus decreased significantly with filler surface treatment and more so with lower molar mass polymer. Copolymers with vinyl alcohol presumably increased interactions with silica and decreased non-linearity. Percolation network formation or agglomeration by silica were less important than silica-polymer interactions. Silica-polymer interactions were proposed to form trapped entanglements. The reinforcement and nonlinear viscoelastic characteristics of PVAc and its vinyl alcohol copolymer were similar to observations of the Payne effect in filled elastomers, characteristic of conformations and constraints of macromolecules. ... 

Typical effects obtained by use of these treatments on fillers in elastomer systems can be found in the work of Dannenberg and Gotten [63]. They examined trimethylsilane treatment of a fumed silica and found effects consistent with reduced filler rubber interaction. Thus rebound resilience, modulus, tear strength and bound rubber were all reduced. Surprisingly, the treatment gave a considerable improvement in abrasion resistance, which it was believed resulted from the increased hysteresis. 

Figure 8 (a) Schematic diagram showing distribution of fillers in different parts of anionic elastomer [27]. (b) Proposed structural model showing interaction of silanol groups on silica surface with carboxylale groups [27]. 

Zinc salt of maleated EPDM rubber in the presence of stearic acid and zinc stearate behaves as a thermoplastic elastomer, which can be reinforced by the incorporation of precipitated silica filler. It is believed that besides the dispersive type of forces operative in the interaction between the backbone chains and the filler particles, the ionic domains in the polymer interact strongly with the polar sites on the filler surface through formation of hydrogen bonded structures. 

Before dealing with reinforcement of elastomers we have to introduce the basic molecular features of mbber elasticity. Then, we introduce—step-by-step—additional components into the model which consider the influence of reinforcing disordered solid fillers like carbon black or silica within a rabbery matrix. At this point, we will pay special attention to the incorporation of several additional kinds of complex interactions which then come into play polymer-filler and filler-filler interactions. We demonstrate how a model of reinforced elastomers in its present state allows a thorough description of the large-strain materials behavior of reinforced mbbers in several fields of technical applications. In this way we present a thoroughgoing line from molecular mechanisms to industrial applications of reinforced elastomers. 

A low-resolution proton NMR method is one of the few techniques that have so far proved to be suitable for studying elastomer-filler interactions in carbon-black-filled conventional rubbers and silica-filled silicon rubbers [20, 62, 79]. It was pointed out by McBrierty and Kenny that Many of the basic characteristics of filled elastomers are revealed by low resolution spectra while the more sophisticated techniques and site specific information refine interpretations and clarify motional dynamics [79]. 

The characterization of the elastomer-filler interactions at a molecular level may be cairied out by spectroscopic techniques such as IR and NMR spectroscopy. X-ray and neutron scattering, dynamic mechanical and dielectric spectroscopy, and molecular dynamics simulations [6]. Up to now, the most comprehensive studies of silica filled PDMS [4, 7-22] and carbon black filled conventional rubbers [23] have been carried out by H [4, 7—20, 23], [21], and C NMR relaxation experiments [22],... 

Compression set is an important property of elastomers which is affected by the choice of filler. Studies were conducted on silica in silicon rubber vulcanizates. Figure 8.60 shows the relationship between the surface area of silica and compression set. As the surface area increases compression set increases. The increase surface area contributes to an increase in the number of functional groups on the surface of silica. These groups can potentially react with siloxane. When they do, there is a good interaction of filler with matrix which contributes to reduction of compression set (Figure 8.61). ... 

Compared to morphology, filler chemistry has been only slightly studied, partly because of the difficulty of such characterizations and more probably because since the 1970s reinforcement is broadly considered as a physical interaction between elastomer and filler. So carbon black chemical characterizations mainly date from the 1960s, and few new technical methods have been applied to carbon black surface characterization since then. The situation is somewhat different for silicas, because silica reinforcement is the consequence of a chemical reaction of silane with silica surface. Few studies have been published in the elastomer reinforcement area, probably because silica surface was already well characterized for other applications. 

Fumed silica is widely used for the reinforcement of polydimethylsiloxane (PDMS) elastomers. The intermolecular interaction of the filler surface with the PDMS matrix controls this process [1, 2] so that understanding which factors influence the interaction at the filler/PDMS interface has become a crucial point for further development of the technology. Among the factors of interest there are the... 

For hydrophobic elastomers such as NR and styrene butadiene rubber, carbon black usually has been selected as filler due to the hydrophobic surface characteristics and special particle shapes of carbon black which provide good dispersion. However, the dispersion of polar filler in hydro-phobic rubbers matrix is difficult because of its hydrophilic surface. The hydroxyl groups exist on the surface of polar filler provide strong filler-filler interactions which resulted in poor filler dispersion. The polar surface of filler formed hydrogen bonds with polar materials in a rubber compound. As known, the silica surface is acidic and forms strong hydrogen bonds with basic materials. ... 

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