Silica-Filled Conventional Rubbers

The mobility in both tightly and loosely bound BR and isoprene rubbers increases, and the fraction of bound rubber decreases with a decreasing concentration of silanol groups on the silica surface [124], This led to the suggestion that the silanol groups on the silica surface are active sites for the chain adsorption. The grafting of aliphatic chains to the silica surface leads to a decrease in BR-silica interactions [125]. The effect is less pronounced in BR filled with carbon black containing aliphatic chains at the surface. 

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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 estimated thickness of the PDMS-silica interface is about 1 nm [105, 109, 110], which is comparable with that of carbon-black-filled conventional rubbers. The adsorption... 

Contrary to carbon-black-filled conventional rubbers, which form a semi-rigid interface at the carbon black surface, PDMS chain units at the silica surface are not rigidly linked to the silica surface. Two types of dynamic processes are thought to occur at the interface relatively fast anisotropic reorientation of chain units in the interfacial layer and slow adsorption-desorption of chain units (Figure 10.13) [108, 113]. 

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],... 

Micron-sized fillers, such as glass fibers, carbonfibers, carbon black, talc, and micronsized silica particles have been considered as conventional fillers. Polymer composites filled with conventional fillers have been widely investigated by both academic and industrial researchers. A wide spectrum of archival reports is available on how these fillers impact the properties. As expected, various fundamental issues of interest to nanocomposites research, such as the state of filler dispersion, filler-matrix interactions, and processing methods, have already been widely analyzed and documented in the context of conventional composites, especially those of carbon black and silica-filled rubber compounds [16], It is worth mentioning that carbon black (CB) could not be considered as a nanofiller. There appears to be a general tendency in contemporary literature to designate CB as a nanofiller - apparently derived from... 

Analysis of rubber filled with conventional filler and an in situ filled siloxane sample displayed three levels of structure in the size-range observed [51]. In another study, growth mechanism and structures of siloxane composites containing silica, and silica-titania were studied by Breiner et al. using SAXS. Both systems were found to yield dense particles. 

This solid product was incorporated into SBR/butadiene rubber (BR) blends at various levels, and the mechanical and dynamic properties were compared with those of conventional silica/carbon black (2 1 ratio) filled SBR/BR compounds. The results showed that the physical properties, and the dynamic ones (such as heat build-up and tan 8), of the two types of compound were comparable. Their work showed that the recovered silica had a similar particle size to virgin silica, and its ability to disperse evenly within the rubber matrix was also similar. 

Figure 6.10 shows typical dynamic properties of vulcanized PDMS-silica systems, as investigated through strain sweep experiments at constant frequency and temperature. As can be seen, dynamic strain softening is observed in a qualitatively similar manner to other filled polymers. It follows that models, which successfully fit conventional filled rubbers (e.g., carbon black filled compounds), are expected to well suit such data. This is indeed the case, as shown by the curves in Figure 6.10, drawn by fitting the Kraus-Ulmer equations, i.e.. 

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