Past exam of the soft condensed matter course of the University of Cambridge 2017 1 a Solution 2026-10-18
Entropic elasticity. A rubber contains flexible polymer strands tied into a network by cross-links. Stretching biases the strands toward relatively extended configurations, reducing their configurational entropy. The restoring entropic force follows from the increase in Helmholtz free energy . For a Gaussian strand with statistical steps of length , its deformation-dependent free energy is approximately . Its stiffness therefore increases with absolute temperature, even if the underlying bond stiffness changes little.
In the ideal affine-network model of rubber elasticity, the shear modulus iswhere is the number density of elastically active network strands. Thus heating increases the modulus approximately in proportion to , provided the network density and rubbery state remain approximately unchanged. Thermal expansion, changing relaxation times or damage can modify that simple trend.
Examples are lightly crosslinked natural rubber, based on cis-rich polyisoprene, and crosslinked polydimethylsiloxane. The crosslinks prevent the long-time macroscopic flow of an unconnected chain solution.
Density estimate and the unspecified modulus convention. With room temperature , the Boltzmann constant gives . If the stated modulus is , thenThe molar value counts moles of active strands. If “modulus” instead means Young's modulus , a nearly incompressible isotropic rubber has , and the inferred value isThus the robust order-of-magnitude estimate is . The cross-link density inferred from rubber elasticity is usually an effective strand density; the actual junction density is for junction functionality in an ideal network without inactive loops or dangling ends. For four-functional junctions this would be half the strand density. The paper supplies neither modulus type nor junction functionality, so a unique chemical junction count cannot be extracted.
Polyisoprene 2026-10-18
A polymer with repeat-unit composition . Its cis-rich form is the main polymer component of natural rubber.