Past exam of the quantum condensed matter course of the University of Cambridge / 2009 / Section A / A2 / c

A polymer melt has an observation-time-dependent response because chains need time to rearrange. Short compared with their terminal relaxation time, entangled chains constrain one another and can store elastic free energy. Long compared with that time, chains escape their original constraints by reptation and the uncrosslinked melt flows. A permanently crosslinked elastomer instead retains a long-time elastic modulus.

A single-time approximation is the Maxwell fluid: a spring of shear modulus $G$ and a viscous dashpot of viscosity $\eta$ in series. Their common stress and additive shear strains give $\dot{\gamma }=\dot{\sigma }/G+\sigma /\eta$, with relaxation time $\tau =\eta /G$. For sinusoidal deformation proportional to $e^{i\omega t}$, the storage modulus and loss modulus areAt low frequency $G^{\prime \prime }\simeq \eta \omega$ dominates; at high frequency within this coarse-grained model $G^{\prime }\simeq G$ dominates. Real melts have a spectrum of relaxation times and additional segmental or glassy regimes, so the single-time model does not describe every frequency. A step-strain experiment measures the decay of stress, whereas oscillatory rheometry separates stored energy from dissipated energy through the phase of the response.