Mathematical Models of Viscoelastic Behaviour

In these models springs and dashpots are used to simulate the elastic and viscous components of the stress/stain response. The spring (elastic component of the response) obeys the relations for tensile and shear stress

The dashpot (viscous component of the response) obeys the relations for tensile and shear stress

Simple models using combinations of springs and dashpots do not correspond directly to discrete molecular structures, but they do aid in understanding how the materials will respond to stress/strain variations. In general, the more complex the model the better the experimental fit, but the greater the number of experimental constants required. We shall only describe the simplest of these models, developing these only for tensile stress. (a) Maxwell Model This consists of a spring and dashpot in series

Figure: Maxwell Model

Equilibrium Equation Assuming constant area, equilibrium of forces gives

Deformation Equation

or from above

giving

This is the governing equation of the Maxwell Model. (i) Creep For a constant applied stress,

ie the strain increases linearly with time, being given by

(ii) Relaxation For a constant strain

Solving this equation with

at t = 0,

(iii) Recovery When the stress is removed there is instantaneous recovery of the elastic strain.

This model is acceptable as a first approximation to relaxation behaviour, but is inadequate for prediction of creep and recovery. (b) Kelvin or Voigt Model This consists of a spring and dashpot in parallel

Figure: Kelvin or Voigt Model

Equilibrium Equation The applied load is supported by the spring and the dashpot

Deformation Equation

Thus

giving

This is the governing equation of the Kelvin or Voigt Model. (i) Creep For a constant applied stress,

Solving this differential equation for total strain,

(ii) Relaxation For a constant strain

ie the stress is constant, with the predicted response being that of an elastic material - no relaxation (iii) Recovery When the stress is removed

Solving this equation with the initial condition removal

at the time of stress

This model is acceptable as a first approximation to creep and recovery behaviour, but is inadequate for prediction of relaxation. Various compromises involving aspects of both models have been proposed. All involve increased complexity. In general, equations of the form

are favoured to model viscoelastic behaviour. >From these simple models, we can obtain some insight into the criterion by which we can judge whether the polymer melt system will be predominantly viscous or elastic in its behaviour. Using the Maxwell model, for constant stress ( strain in time t is ) the

The terms on the right hand side contribute equally to the strain when when is . , the relaxation time. For shear stresses this relaxation time

: i.e.,

For processing times, t < tr, the system is predominantly elastic. For processing times, t > tr, the system is predominantly viscous. Effect of Elasticity When a tensile or shear stress is applied to a polymer melt, the molecules partially uncoil becoming preferentially aligned in the direction of the applied stress. On removing the stress the molecules tend to regain their random configuration. This recovery leads to a contraction in the direction of stress, and in the case of shear. in the case of tension

The elastic modulus depends not only on the polymer but also on the processing conditions. Its effects are observed in die-swell (most significant in short dies - why?) and in the Weissenberg effect (polymer appears to climb rotating shaft in stirred tank - cf. normal vortex).

David Balmer Last modified: Thu Dec 3 16:27:13 GMT