Structure of Filler Particles

It is well known that the particle size, structure, and surface characteristics are important parameters that determine the reinforcing ability of filler particle size is important because a reduction in size... 

In a search for the defining structural parameter of a composite, the free volume of disperse system proved to be the most sound one from the physical standpoint Presumably, for disperse systems the free volume is a measure of the mobility of filler particles, just as for liquids it is a measure of the mobility of molecules. But as applied to highly-loaded coarse systems of the type solid particles — liquid — gas this notion requires a certain correction. In characterizing the structure of such specific systems as highly-loaded coarse composites, it should be noted that to prevent their settling and separation into layers under the action of vibration, the concentration of the finest filler fraction with the largest specific surface in dispersion medium should be the maximum possible. Because of this and also because of the small size of particles (20-40 pm), the fine fraction suspended in the dispersion medium practically does not participate in the formation of the composite skeleton, which consists of coarser particles. Therefore... 

This paper is devoted to the study of a part of the complex phenomena of reinforcement, namely the behavior of the host elastomer in the presence of filler particles. The results of solid state NMR experiments and some other methods for filled PDMS are reviewed. The short-range dynamic phenomena that occur near the filler surface are discussed for PDMS samples filled with hydrophilic and hydrophobic Aerosils. This information is used for the characterization of adsorption interactions between siloxane chains and the Aerosil surface. Possible relations between mechanical properties of filled silicon rubbers on the one hand and the network structure and molecular motions at flie PDMS-Aerosil interface on the other hand are discussed as well. 

A large number of macroscopic properties of elastomer networks are closely related to the density of network junctions and the extent of their fluctuations. Qualitatively, any increase of network density causes an increase in stress, whereas fluctuations of network junctions leads to a decreasing stress. It is generally believed that a formation of additional network junctions resulting fi-om the presence of filler particles in the elastomer matrix is one of the reasons for the improvement of mechanical properties of filled elastomers. However, the application of macroscopic techniques does not provide reliable results for the network structure in filled elastomers. Furthermore, a lack of information exists on the dynamic behavior of adsorption junctions. The present study fills the gap of knowledge in this area. 

Considerable effort has been spent to explain the effect of reinforcement of elastomers by active fillers. Apparently, several factors contribute to the property improvements for filled elastomers such as, e.g., elastomer-filler and filler-filler interactions, aggregation of filler particles, network structure composed of different types of junctions, an increase of the intrinsic chain deformation in the elastomer matrix compared with that of macroscopic strain and some others factors [39-44]. The author does not pretend to provide a comprehensive explanation of the effect of reinforcement. One way of looking at the reinforcement phenomenon is given below. An attempt is made to find qualitative relations between some mechanical properties of filled PDMS on the one hand and properties of the host matrix, i.e., chain dynamics in the adsorption layer and network structure in the elastomer phase outside the adsorption layer, on the other hand. The influence of filler-filler interactions is also of importance for the improvement of mechanical properties of silicon rubbers (especially at low deformation), but is not included in the present paper. 

The presence of filler in the rubber as well as the increase of the surface ability of the Aerosil surface causes an increase in the modulus. The temperature dependence of the modulus is often used to analyze the network density in cured elastomers. According to the simple statistical theory of rubber elasticity, the modulus should increase twice for the double increase of the absolute temperature [35]. This behavior is observed for a cured xmfilled sample as shown in Fig. 15. However, for rubber filled with hydrophilic and hydrophobic Aerosil, the modulus increases by a factor of 1.3 and 1.6, respectively, as a function of temperature in the range of 225-450 K. It appears that less mobile chain units in the adsorption layer do not contribute directly to the rubber modulus, since the fraction of this layer is only a few percent [7, 8, 12, 21]. Since the influence of the secondary structure of fillers and filler-filler interaction is of importance only at moderate strain [43, 47], it is assumed that the change of the modulus with temperature is mainly caused by the properties of the elastomer matrix and the adsorption layer which cause the filler particles to share deformation. Therefore, the moderate decrease of the rubber modulus with increasing temperature, as compared to the value expected from the statistical theory, can be explained by the following reasons a decrease of the density of adsorption junctions as well as their strength, and a decrease of the ability of filler particles to share deformation due to a decrease of elastomer-filler interactions. 

The information in the table shows that the shape of filler particles is determined by their crystal structure and cleavage. The surface area of crystal is increased by milling but it retains the original features of the mineral. This... 

This sphere of influence includes the nature of chemical bonding, properties of the formed structure, and the concentration of filler particles... 

FIGURE 17.20 The effect of filler particles on gel properties, (a) Relative modulus (Gm/G0) as a function of particle volume fraction (broken lines are calculated for various values of the ratio Gp/Go, indicated near the curves. The drawn lines are average experimental values for acid casein gels (C) and polymer gels (polyvinyl alcohol, P), with emulsion droplets that are either bonded (B) or nonbonded (N) to the gel matrix, (b) Highly schematic pictures of the gel structure. Shaded area denotes primary gel. Particles are nonbonded (1) bonded (2) bonded but with intermediate layer (3) bonded and aggregated (4). (Adapted from T. van Vliet. Colloid Polymer Sci. 266 (1988) 518.)... 

Figure 19b shows the results of mPDMS composites filled with carbonyl iron. The concentration of filler particles is 30 wt %. One can see the breaking of the pearl chain structure at X = 0.95. 

This chapter considers a study of two types of composites based on polyhydroxyether and graphite with various amounts of a filler. Using various methods it is possible to estimate the adhesion characteristics and interfacial layer, including its thickness and tensile strength and the interdependence between these values and the adhesion properties. The results were treated on the basis of the theory of irreversible aggregation, cluster theory of the polymer structure and fractal analysis. It was established that all the important characteristics of adhesion, the interfacial layer and mechanical properties are interconnected by the fractal dimensions of the surface of the aggregates of filler particles and of the polymer matrix, whose structure is distorted under the influence of the filler surface. 

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