What about polymer melts?

Non permanent crosslinks

Green-Tobolsky Temporary Network Model

Q junction points per unit volume = constant ETE vectors have finite lifetimes when old junctions die, new ones are born newly born ETE vectors adopt the equilibrium distribution \0

Probability per unit time that strand dies and is reborn at equilibrium

1 { O

Probability that strand retains same ETE from t to t (survival probability)

{ Pt ,t
c

Faith A. Morrison, Michigan Tech U.

What is the probability that a strand retains the same ETE vector between t and t+'t?
Pt c,t  't
Probability that strand retains same ETE from t to t (survival probability) Probability that strand does not die over interval 't

Pt c,t  't

1 Pt c,t 1  't O

dPt c,t dt ln Pt c,t Pt c,t e

t  t c 
O

1 Pt c,t O t   C1 O

Faith A. Morrison, Michigan Tech U.

The contribution to the stress tensor of the individual strands can be calculated from,
Stress from strands born between t and t+dt Probability that strand is born between t and t+dt
 

=
dW

Probability that a strand survives from t to t

Stress generated by an affinely deforming strand between t and t

t t c 1 c  O 1 d t e  G C (t c, t ) O

>

G   e f O

t t c 
O

C (t c, t ) dt c

1

Green-Tobolsky temporary network mode (Lodge model)

Faith A. Morrison, Michigan Tech U.

Back where we started! NO!

G   e f O

t t c 
O

1 C (t c, t ) dt c

Green-Tobolsky temporary network mode (Lodge model) We now know that affine motion off strands with equal birth and death rates gives a model with no shear-thinning, no second-normal stress difference. To model shear-thinning, N2, etc., therefore, we must add something else to our physical picture, e.g., Anisotropic drag nonaffine motion of various types

Faith A. Morrison, Michigan Tech U.

Anisotropic drag - Giesekus

In a system undergoing deformation, the surroundings of a given molecule will be anisotropic; this will result in the drag on any given molecule being anisotropic too.
2 Starting with the dumbbell model (gives UCM), replace 8kTE with an

anisotropic mobility tensor . Assume also that the anisotropy in O proportional to the anisotropy in W .

is

BI
Giesekus Model

D W G

W  OW 

DO W :W K0

K0 J

see Larson, Constitutive equations for polymer melts, Butterworths, 1988

Faith A. Morrison, Michigan Tech U.

Constitutive equations incorporating non-affine motion include: Gordon and Schowalter: strands of polymer slip with respect to the deformation of the macroscopic continuum; see Larson, p130 (this model has problems in step-shear strains) Larson: uses nonaffine motion that is a generalization of the motion in the Doi
Edwards model; see Larson, Chapter 5

Wagner: uses irreversible nonaffine motion;

see Larson, Chapter 5

see Larson, Constitutive equations for polymer melts, Butterworths, 1988

Faith A. Morrison, Michigan Tech U.

Reptation Theory (de Gennes)

Retraction (Doi-Edwards)

Faith A. Morrison, Michigan Tech U.

Doi-Edwards Model
W  M (t  t c)Q(t c, t ) dt c
f
t

Q(t c, t )

1 4S

2S S

c F 1 u c F 1 u 5 sin T dTdI c 1 2 0 0 u F
t t c

M (t  t c)

Gi  Oi e i odd Oi

Gi

0 8GN S 2i 2

Oi

O1 i2

c unit vector that gives u

orientation of strands at time t

(Factorized K-BKZ type)

Faith A. Morrison, Michigan Tech U.

Doi-Edwards Model
Correctly predicts:

Ratio of <1/<2 shape of start-up curves shape of h(J0) predicts K=AM3 shear thinning of K, <1 tension-thinning elongational viscosity
Fails to predict:

K=AM3.4 shape of shear thinning of K, <1 reversing flows

Also, calculations of flow fields is quite involved.
Faith A. Morrison, Michigan Tech U.

What about polymer solutions?

Dilute solutions: chains do not interact collisions with solvent molecules are modeled stochastically calculate \(R) by a statistical-mechanics solution to the Langevin equation (ensemble averaging)

Elastic Dumbbell Model

Random force models random collisions

R
R

Drag on beads models friction

Faith A. Morrison, Michigan Tech U.

Elastic Dumbbell Model for Dilute Polymer Solutions results in:

W  OW

K0J

Upper-Convected Maxwell Model

G QkT ] O 8kTE 2
E2 { 3 2 Na 2

number of dumbbells/volume bead friction factor

from random walk

Faith A. Morrison, Michigan Tech U.

Summary
Molecular models may lead to familiar constitutive equations
Rubber-elasticity theory = Finite-strain Hookes law model Green-Tobolsky temporary network theory = Lodge equation Reptation theory = K-BKZ type equation Elastic dumbbell model for polymer solutions = upper-convected Maxwell

Model parameters have greater meaning when connected to a molecular model

G = QkT Gi, Oi specified by model

Molecular models are essential to narrowing down the choices available in the continuum-based models (e.g. K-BKZ, Rivlin-Sawyers, etc.) Caution: correct stress predictions do not imply that the molecular model is correct
Stress is proportional to the second moment of \(R), but different functions may have the same second moments. As always, the proof is in the prediction.

see Larson, esp. Ch 7

Faith A. Morrison, Michigan Tech U.

Rheometry
measurement Shear - capillary, parallel plate, cone-and-plate, Couette Elongational - melt stretching, filament stretching, MBER, lubricated squeezing, stagnation flows, contraction flows

Flow Birefringence - applicable for both shear and elongation flows

What is measured depends on what is measurable.

Faith A. Morrison, Michigan Tech U.

Flow Birefringence - a non-invasive way to measure stresses

no net force, isotropic chain, isotropic polarization

n
force applied, anisotropic chain, anisotropic polarization = birefringent

n2 n1
Faith A. Morrison, Michigan Tech U.