Filler, fillers

Fillers. Fillers are not commonly added to CR adhesives. Calcium carbonate or clay can be primarily added to reduce cost in high-solids CR mastics. Maximum bond strength is obtained using fillers with low particle size (lower than 5 [jim) and intermediate oil absorption (30 g/100 g filler). In general, fillers reduce the specific adhesion and cohesion strength of adhesive films. Although polychloroprene is inherently flame retardant, aluminium trihydrate, zinc borate, antimony trioxide or... 

There is currently considerable interest in processing polymeric composite materials filled with nanosized rigid particles. This class of material called "nanocomposites" describes two-phase materials where one of the phases has at least one dimension lower than 100 nm [13]. Because the building blocks of nanocomposites are of nanoscale, they have an enormous interface area. Due to this there are a lot of interfaces between two intermixed phases compared to usual microcomposites. In addition to this, the mean distance between the particles is also smaller due to their small size which favors filler-filler interactions [14]. Nanomaterials not only include metallic, bimetallic and metal oxide but also polymeric nanoparticles as well as advanced materials like carbon nanotubes and dendrimers. However considering environmetal hazards, research has been focused on various means which form the basis of green nanotechnology. 

In addition to increases in high-strain loss modulus, reductions in low-strain loss modulus are also observed. This may be attributed to the improvements in polymer-filler interactions which may reduce the amount of filler networking occurring in the compound. The low-strain losses are dominated by disruptions in the filler-filler network, the Payne effect. 

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. 

Flocculation studies, considering the small-strain mechanical response of the uncross-hnked composites during heat treatment (annealing), demonstrate that a relative movement of the particles takes place that depends on particle size, molar mass of the polymer, as well as polymer-filler and filler-filler interactions (Figure 22.2). This provides strong experimental evidence for a kinetic cluster-cluster aggregation (CCA) mechanism of filler particles in the mbber matrix to form a filler network [24]. 

For a consideration of filler-network breakdown at increasing strain, the failure properties of filler-filler bonds and filler clusters have to be evaluated in dependence of cluster size. This allows for a micromechanical description of tender but fragile filler clusters in the stress field of a strained mbber matrix. A schematic view of the mechanical equivalence between a CCA-filler cluster and a series of soft and hard springs is presented in Figure 22.9. The two springs with force constants... 

FIGURE 22.9 Schematic view demonstrating the mechanical equivalence between a Hller cluster and a series of soft and stiff molecular springs, representing bending-twisting and tension deformation of filler-filler bonds, respectively. (From Kluppel, M. and Heinrich, G., Kautschuk, Gummi, Kunststojfe, 58, 217, 2005. With permission.)... 

The surface of silica is covered by a layer of acidic silanol and siloxane groups. This highly polar and hydrophilic character of the filler surface results in a low compatibihty with the rather apolar polymer. Besides, highly attractive forces between silica particles result in strong agglomeration forces. The formation of a hydrophobic shell around the silica particle by the sUica-sUane reaction prevents the formation of a filler-filler network by reduction of the specific surface energy [3]. 

A minimum shrinkage of 5% or less, more typically 1% or less, has been specified in order to maintain excellent seal transference in the cured mass. This requirement has been met through much experimentation involving various levels of filler. Fillers typically result in lower shrinkage with lower bulk viscosity. Fillers also present difficulty in this application due to the inherent problem presented by a fibrous mass with its high surface area. The present formulation has avoided the use of fillers. 

Filler Vol% Filler Filler Epoxy Resin Composite... 

In order to understand the effects of filler loading and filler-filler interaction strength on the viscoelastic behavior, Chabert et al. [25] proposed two micromechanical models (a self-consistent scheme and a discrete model) to account for the short-range interactions between fillers, which led to a good agreement with the experimental results. The effect of the filler-filler interactions on the viscoelasticity... 

Presuming that within each unit volume of rubber the filler platelets are segregated in such a way that the filler-filler interactions are negligible, the swelling deficiency for all N particles can be designated as AV — N Av. 

The interaction between two fillers particles can be investigated by measuring the Payne effect of a filled rubber compounds. In this measurement, dynamic properties are measured with strain sweep from a very small deformation to a high deformation. With the increased strain, the filler-filler network breaks and results in a lower storage modulus. This behavior is commonly known as the Payne effect... 

Another attempt by Tricas et al. to modify the surface of carbon black was by the plasma polymerization of acrylic acid [34]. Treatment with acrylic acid made carbon black hydrophilic. Plasma-coated carbon black was mixed with natural rubber and showed increased filler-filler interaction. The bound rubber content was reduced after the surface treatment of the filler. The authors also concluded that the surface of the carbon black was completely covered by the plasma polymer film, preventing the carbon black surface from playing any role in the polymer matrix. 

Filler-filler interaction (Payne effect) - The introduction of reinforcing fillers into rubbery matrices strongly modifies the viscoelastic behavior of the materials. In dynamic mechanical measurements, with increasing strain amplitude, reinforced samples display a decrease of the storage shear modulus G. This phenomenon is commonly known as the Payne effect and is due to progressive destruction of the filler-filler interaction [46, 47]. The AG values calculated from the difference in the G values measured at 0.56% strain and at 100% strain in the unvulcanized state are used to quantify the Payne effect. 

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