The reinforcement of elastomers by finely divided fillers, particularly carbon black and silica, is fundamental to the rubber industry. Optimal reinforcement appears to involve both physical and chemical interactions. From a consideration of the effects of particle size as such, it appears that reinforcement, in the sense of tensile enhancement, will occur with any very finely divided filler. Physical factors prevent escape of the polymer from the filler surface (vacuole formation) but allow stress delocalization through interfacial slippage. Occasional stronger bonds may be introduced advantageously to facilitate dispersion, reduce particle/ particle interactions, and optimize practical properties relating to resilience and durability. Several lines of evidence suggest that only a minor amount of strong bonding is necessary or desirable, such that polymer/filler slippage can occur, under stress, over most of the interfacial area.

Polymer-filler interactions in rubber reinforcement

Morphology of aggregates: VI. Effective volume of aggregates of carbon black from electron microscopy; Application to vehicle absorption and to die swell of filled rubber

The reinforcement of elastomers by carbon black is governed by the morphology of the black and its physical and chemical interactions with the polymer. The latter are strongly affected by ...

Reinforcement of Elastomers by Carbon Black

Concepts and conflicts in nanoparticles reinforcement to polymers beyond hydrodynamics

Reinforcement of elastomers by carbon black

The interaction of carbon blacks with high polymers during the mixing process was studied by using fillers having a wide range of surface characteristics. Glass beads, Graphon, high-structure blacks, and heat-treated blacks were mixed with elastomers in the Brabender Plasticorder. With the use as a rubber matrix of a high polymer that did not materially change during the mixing process in molecular weight or viscosity, excellent correlation was found between final torque required for mixing and black structure and between peak torque and bound rubber. Increasing interaction was shown to lead to increased mixing torque, increased Mooney viscosity, increased modulus, and higher state of cure, as measured by swelling. If the high polymer matrix breaks down during the mixing process these influences of interaction are mostly obscured by diminishing molecular weight.

Carbon black–polymer interaction: A measure of reinforcement

The specific surface activity of carbon black, as indicated by amount of rubber bound to the black during the mixing process, has been found to be the major factor in determining the modulus of the vulcanizate at high extensions. However, modulus at low extension is independent of specific surface activity and mostly influenced by other black characteristics, such as “structure” and surface area. Further, a relationship of the Guth-Gold type based upon elastic theory was applied for predicting modulus of filled vulcanizates at high extension from that of an identically cured gum vulcanizate. The relationship is 






where Φ is the reinforcement volume or volume fraction of filler plus volume fraction of bound polymer. This relationship was also used to calculate the actual elongation in a filled vulcanizate to compensate for that portion that does not elongate at all, and this actual extension ratio (α') was utilized in the Mooney-Rivlin equation. The Mooney-Rivlin equation is the theoretical expression for the modulus of a vulcanizate as it changes with elongation and cure level (or number of effective chains per unit volume). The equation has been successfully used previously for gum vulcanizates, but not for filled vulcanizates. With the use of the corrected elongation (α'), experiment and theory are in much better agreement than previously, and a general concept of the influence of black upon vulcanizate properties can be postulated.

Correlation of vulcanizate properties with polymer–black interaction

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Carbon black–polymer interaction: A measure of reinforcement

Correlation of vulcanizate properties with polymer–black interaction