Accessibility of the Carbon Black Particle Surface to Elastomers

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Abstract
Experimental carbon blacks were prepared with the generally encountered slit-shaped pores of discrete dimensions of 9,12.5, and 16 A˚ width in greatly differing size distribution. Equilibrium adsorption in the saturation range was determined in n-hexane for butadiene—styrene elastomers of the SBR type of average molecular weights of 1500; 2000; 15,000; and 300,000. In attempting to correlate the saturation adsorption values with carbon black surface areas, it was found that a simple linear relation in the range investigated could only be obtained by assuming that pores of 9 A˚ width were inaccessible to SBR of 1500 and 2000 MW; that pores of 9 and 12.5 A˚ width were inaccessible to SBR of 15,000 MW; and that all pores smaller than 20 A˚ width were inaccessible to SBR of 300,000 MW. The data indicated that there are no differences between high, regular and low structure blacks in saturation elastomer adsorption under conditions of equivalent dispersion. Equally, upon breaking the persistent carbon chain structure by dry ball milling in an inert atmosphere and equalizing the chemical surface properties by removal of surface oxides, no difference in elastomer adsorption from solution was observed. It must be concluded that commonly used high molecular elastomers do not have any access to smaller carbon black pores. Since access to the surface is a prerequisite for reinforcement, it is obvious that the surface in the pores of carbon black generally does not participate in reinforcing elastomers. The elastomer adsorbed per unit external black surface area appears to be independent of the carbon chain structure, indicating that the so called surface activity of the carbon black is independent of the chain length.

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