Past exam of the soft condensed matter course of the University of Cambridge / 2021 / Section B / 4

Use a rheometer, for example a cone-and-plate rheometer or a parallel-plate rheometer, to impose a small deformation and measure the required torque, or impose a torque and measure the deformation. The apparatus geometry converts these into shear stress and strain. First check that reducing the imposed amplitude does not change the normalized response; this identifies the linear regime and avoids yielding or structural rearrangement.

Three complementary protocols characterize the material's memory. In a stress relaxation experiment impose a small step ${ϵ}_{0}H(t)$ and hold the deformation fixed. The output is the relaxation modulus $G(t)=\sigma (t)/{ϵ}_0$, revealing how stored stress decays and whether an elastic plateau remains. In a creep compliance measurement impose a small stress step ${\sigma }_{0}H(t)$ and record $J(t)=ϵ(t)/{\sigma }_0$. Removing the load also distinguishes recoverable deformation from permanent flow.

In small-amplitude oscillatory shear, impose sinusoidal strain over a range of frequencies and measure both stress amplitude and phase. With $ϵ={ϵ}_0\cos \omega t$, fitThe outputs are the storage modulus $G^{\prime }$ and loss modulus $G^{\prime \prime }$, or equivalently amplitude ratio and loss tangent $\tan \delta =G^{\prime \prime }/G^{\prime }$. These measure elastic storage and dissipative response, respectively. The step experiments give time-domain information and the oscillatory experiment gives the corresponding frequency-domain response. All comparisons must use the same deformation convention and controlled temperature.

The dynamic modulus, or complex viscoelastic modulus, is the ratio of complex stress amplitude to complex strain amplitude in the periodic steady response:This defines the sign convention; for passive response the loss modulus is nonnegative at positive frequency. A Newtonian fluid obeys $\sigma =\eta \dot{ϵ}$, while a Hooke's law solid obeys $\sigma =G_0ϵ$. HenceThe first is purely dissipative and the second purely elastic. Here $ϵ$ denotes the scalar deformation used in the problem, with any shear-versus-extension geometric factors already included in its modulus and viscosity.

Parallel elements have the same strain, while their stresses add. The spring supplies $G_0ϵ$ and the viscous element supplies ${\eta }_0\dot{ϵ}$, so the Kelvin-Voigt model has constitutive equationFor the oscillatory deformation this givesPhysical stress and strain are the real parts of these expressions. Thus the storage modulus is $G_0$, independent of frequency, and the loss modulus is $\omega {\eta }_0$. The equation is the quasistatic material law; an inertial equation for an attached mass would require additional mechanical data.

For elements in series the stress is common and the strains add. If ${\widehat{ϵ}}_K$ and ${\widehat{ϵ}}_1$ are the Kelvin element and added spring amplitudes, thenThe compliances therefore add, yieldingThis is a standard linear solid model. DefineWriting $x=\omega \tau$, its storage modulus and loss modulus areThus $G^{\prime }$ increases from the low-frequency plateau $G_L$ to the high-frequency plateau $G_H$. The loss modulus has low-frequency slope $+1$ and high-frequency slope $-1$ on a log-log plot, with maximum $\Delta G/2$ at $\omega =1/\tau$. At that frequency $G^{\prime }=(G_L+G_H)/2$. There need not be a crossing of the two curves for arbitrary spring constants.

A Kelvin-Voigt model has no finite instantaneous elastic compliance: the viscous element prevents a sudden deformation under a finite stress step. Its creep compliance isConversely an ideal strain step requires an impulsive stress,After the impulse the held-strain response is simply constant. There is no finite stress-decay interval, and the loss modulus grows without bound as $\omega \to \infty$. This fails to represent a material with both a finite instantaneous stiffness and delayed stress relaxation.

The added series spring resolves this particular defect. At the instant of loading the Kelvin element cannot move but the added spring can. The standard linear solid model consequently hasandIts instantaneous stiffness is $G_H=G_1$, its long-time stiffness is $G_L$, and it exhibits genuine stress relaxation as well as delayed creep. The creep retardation time ${\eta }_0/G_0$ differs from the stress-relaxation time $\tau ={\eta }_0/(G_0+G_1)$. These properties also follow directly from its constitutive equation,It remains an idealized solid with one relaxation mode: it cannot describe unrestricted long-time viscous flow, nonlinear response, or a broad spectrum of relaxation times.