Abstract
Highly oriented natural rubber samples of Roberts and Mandelkern, prepared by racking and subsequently crosslinked using γ-radiation, undergo a spontaneous shrinkage upon melting which closely resembles the shrinkage of collagen. If the transformation is arrested by application of a tensile force, a state of equilibrium may be established between two distinct zones, or phases, one being totally amorphous (shrunken) and the other unchanged (i.e., racked). Determination of the stress τeq required for phase equilibrium at various temperatures is described. Extrapolation to τeq=0 gives equilibrium melting temperatures Tmi, which are about 8° below the temperatures Tsi for spontaneous shrinkage. The heat of transformation of racked to amorphous rubber calculated from the dependence of τeq on T is 4.5 cal g−1. Since the degree of crystallinity is only 0.24, the heat of fusion calculated for 1 g of crystalline rubber is ca. 19 cal, which agrees satisfactorily with the value 15.3 cal, deduced by Roberts and Mandelkern through use of the melting point depression method. The shrinkage of racked rubber displays all of the important features associated with the similar contraction of fibrous proteins.
Determination of the Degree of Crystallinity of Poly(2-methyl-2-oxazoline)
