Filler surfaces

Permanent Set. When an elastomer is stretched and then allowed to relax, it will not completely recover its original dimensions. This divergence from its original form is called its permanent set. It is principally affected by the affinity of the elastomer for the filler surface and is, therefore, primarily a function of the surface energy or wetting of the filler. 

Fluidyibsorbamy. Fluids like ink penetrate into paper during the printing process. The further the ink penetrates, the less glossy the print. The degree of penetration in paper is generally a function of the paper porosity and wettabiUty by the fluid. It can be controlled by the particle size, shape, and chemical nature of the filler or filler surface. In particular, plate-like fillers, such as clays, tend to produce the best fluid holdout because they tend to overlap and reduce the porosity at the paper surface (see Inks). 

Both tear resistance and hysteresis increase on incorporation of silica, but the effect is less pronounced as compared to the stress-strain properties. Tension set of the ZnO-neutralized m-EPDM system is low (around 20%) and incorporation of filler causes only a marginal increase in set due to chain slippage over the filler surface, as previously discussed. Measurement of physical properties reveal that there occurs an interaction between the filler surface and the polymer. Results of dynamic mechanical studies, subsequently discussed, support the conclusions derived from other physical properties. 

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. 

Macromolecular fixation on the filler surface, their orientation in the direction complanar or normal to the surface and condensation result in hard interphases [116]. 

It should be noted that for polymerization-modified perlite the strength parameters of the composition algo go up with the increasing initial particle size. [164]. In some studies it has been shown that the filler modification effect on the mechanical properties of composites is maximum when only a portion of the filler surface is given the polymerophilic properties (cf., e.g. [166-168]). The reason lies in the specifics of the boundary layer formation in the polymer-filler systems and formation of a secondary filler network . In principle, the patchy polymerophilic behavior of the filler in relation to the matrix should also have place in the failing polymerization-modified perlite. 

Finishing of the filler surfaces may also greatly affect the system viscosity. For mica-filled PP [31] and various thermoplastics filled with calcium carbonate [202, 261] it was shown that the relative viscosity of filled systems was lower than that of systems which contained equivalent quantitied of unfinished filler. Note that in contrast to viscosity in shear, the viscosity in stretching is higher for systems with treated filler [202]. 

Organotitanates form regular adsorbed layers on the filler surfaces. This assures a high degree of dispersibility of the solid particles of the filler, removal of moisture and air from the surfaces, a material improvement of the rheological properties of filled compositions. Also, it is possible to use much greater percentages of cheap... 

Thus a strong bond is not always desirable. We can see this from Table 7 and 8. The authors of [100] interpreted their experimental data as follows the rigidity of specimens increases with increasing PVC-filler interaction as a result the rate of relaxation of stresses arising at interphases in the course of deformation decreases. The overstressed states at the interphases may, in the authors opinion, promote separation of the polymer from the filler surface. That is, it is more desirable that the matrix-filler bond is not rigid but labile. 

This relatively new trend in PCM manufacturing business amounts to creating a polymeric matrix out of the liquid or gaseous phase directly on the filler surface which has previously undergone special conditioning aimed at generating active polymerization sites on it. 

As shown for the synthesis of PS [291], the monomer may be localized in the vicinity of the filler surface by previously grafting a polymer capable of swelling in the base monomer. Copolymeric latex of polychloroprenemethacrylic acid was added to the aqueous dispersion of chalk. The acid groups reacted with chalk and the latex particles became chemically grafted to chalk. When further portions of styrene were added they were completely absorbed by modified chalk. 

In polymer regions of PFCM bordering on the filler one typically observes the formation of crystallites as tape-like structures orientated perpendicularly to the filler surface [295, 305, 306]. In real fact these are transcrystallite structures. A morphology of this kind can appear in a mechanical mixture as well [305, 306], but there the layer thickness will be much smaller [306, 307]. 

The enthalpy of interaction of the grafted polymer with the filler surface is given by... 

Quite naturally, novel techniques for manufacturing composite materials are in principal rare. The polymerization filling worked out at the Chemical Physics Institute of the USSR Academy of Sciences is an example of such techniques [49-51], The essence of the technique lies in that monomer polymerization takes place directly on the filler surface, i.e. a composite material is formed in the polymer forming stage which excludes the necessity of mixing constituents of a composite material. Practically, any material may be used as a filler the use of conducting fillers makes it possible to obtain a composite material having electrical conductance. The material thus obtained in the form of a powder can be processed by traditional methods, with polymers of many types (polyolefins, polyvinyl chloride, elastomers, etc.) used as a matrix. 

The model in Figure 3.20a applies to ACM-silica, while Figure 3.20b suits the ENR-silica system. Kraus constant, C, determined from the slope of the plots in Figure 3.19, quantifies the mbber-silica interaction in these systems. CACM/siUca is 1-85 and CENR/siika is 2.30 and these values are significantly higher than the reinforcing black-filled mbber composites [65]. Hydrogen-bonded interaction between the SiOH and the vicinal diols in ENR is responsible for this, whereas dipolar interaction between ester and SiOH in ACM-silica only results in weaker adsorption of the mbber over the filler surfaces. 

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]. 

Prior to the chemical reaction of the silane with the silanol-groups on the sUica surface, the silane molecule has to make contact with the sUica surface by adsorption. Then the chemical reaction of silica with an alkoxy-silyl moiety of the coupling agent takes place in a two-step, endothermic reaction. The primary step is the reaction of alkoxy-groups with silanol-groups on the silica filler surface [4]. Two possible mechanisms are reported ... 

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