Coil-stretch transition 2026-10-18
A coil-stretch transition is a sharp change from a coiled to a substantially extended polymer conformation under sufficiently strong extensional flow. The driving extensional strain rate must compete with the chain's relaxation rate, and the available residence time matters. A long polymer relaxation time lets a weak but sustained flow produce a large effect. The Hookean dumbbell in planar extension below isolates this competition; its unbounded growth signals a model limitation, rather than a prediction of infinitely long molecules.
Extensional strain rate Created 2026-10-18 Updated 2026-11-05
The extensional strain rate is the rate of relative stretching along a specified material direction. If a short material line of length follows a principal stretching direction, is the corresponding eigenvalue of the rate-of-strain tensor. For the planar model in extensional flow, ; the two transverse rates are and zero. For uniaxial extensional flow, each transverse rate is .
For steady uniaxial extension of the Giesekus model, the component-first velocity gradient is diagonal, . For a steady spatially uniform diagonal stress, the material derivative vanishes and the convected terms are and . The off-diagonal equations vanish identically, and symmetry permits equal transverse components. The remaining equations are
Set , and , with . For , the branches continuously connected to zero stress at zero rate are
A sufficient nondegenerate range for physical solutions at every nonnegative rate is . Indeed with , so positive conformation implies positive mobility. The longitudinal quadratic equation is nonpositive at and has a nonnegative root of a polynomial. The transverse quadratic equation has values at and at , so its larger root of a polynomial lies in . Thus the displayed branches satisfy , giving . The other algebraic roots do not provide a physical branch connected to the equilibrium distribution. For constant positive diagonal , the associated stationary configuration distribution is a Gaussian with covariance .
For positive on the physical branch, the stretching stress remains finite through . At that rate,
At large extension rate,
Thus the stress continues to grow, but the uniaxial extensional viscosity approaches the finite plateau rather than developing a finite-rate pole. The transverse stress approaches as its conformation tensor variance becomes small. At small rate the two stresses are and , so .
When , the physical steady branch instead is
The stretching stress diverges as from below. Above that threshold its algebraic continuation has and cannot be a conformation covariance. There is no physical finite steady stretching state. The transient equation
gives linear growth at and exponential growth at larger rates, the Hookean coil-stretch failure of the upper-convected Maxwell limit.
Figure 1.
Anisotropic mobility rounds the Hookean extensional-stress singularity
. Dimensionless longitudinal and transverse stresses are plotted against the extension-rate parameter W. Positive dimensionless mobility factors 0.1 and 0.5 give regular equilibrium-connected branches. The isotropic-mobility longitudinal branch is shown only below its physical steady-state threshold W equal to one half. Details.
Parameter qualification. Positivity of alone, without a restriction on , does not ensure real physical steady solutions for the entire tensor. For example , makes the transverse equation , which has no real root. Its diffusion/resistance interpretation is already inadmissible for some conformations. The physically positive-mobility regime stated above avoids that counterexample; the source's positive- case must not be taken as a guarantee for arbitrary parameters.
An original local flow model has velocity for constant extensional strain rate . Its divergence is zero, and its trajectories satisfy the displayed equations. Material approaches along and leaves along . If the idealized observation region ends at , a trajectory starting at has residence time
For chosen , and , this is . Starting ten times farther from the symmetry line halves this particular residence time. The mathematical trajectory never exits in this model; diffusion, imperfect flow and finite apparatus prevent treating that ideal trajectory as a guaranteed infinite exposure in an experiment.