Thermodynamic Properties and Polymer Solvent Interaction Parameters for Silicone Rubber Networks

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Abstract
The relationships of the volume fraction of rubber (silica reinforced silicone rubber vulcanizates) at equilibrium swelling to a corresponding solvent-rubber interaction parameter have been found to agree quite well with theory throughout the entire range of volume fractions investigated. Composite sigmoidal curves were constructed from the ϕrs versus μ data for the different vulcanizates. Temperature and solvent effects were found to merely shift the plotting points along the curves for the respective vulcanizates. Contrary to other work linear relationships between ϕrs and μ were found in this investigation only in the range of moderate dilations. Such relationships could lead to serious misinterpretations if the investigations involved ϕrs versus μ data near an inflection point. Thus, the value of μ relative to a corresponding ϕrs not only depend upon solvent (s) and temperature, but also upon the level of vulcanization at moderate to high dilations. The entropy, enthalpy, and free energy changes associated with the configurational changes occurring in the network structure of the rubber were calculated. The thermodynamic properties were found to be consistent and uniform throughout the dilation range. Limiting osmotic pressures were determined to obtain effective number average molecular weights of the crosslinked chains. The molecular weight values were found to average slightly less than three times those obtainable from ve/Vr data. Finally, this investigation has shown that reinforced silicone rubber vulcanizates at equilibrium swelling in a variety of solvents exhibit the swelling behavior predicted by theory. However, swelling behavior at moderate to high swelling was found to be unrelated to the rubber in general, but related more specifically to the network structure of the vulcanizate. At low dilations, the characteristics of the silicone rubber species control the swelling behavior.

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