Normal stress effects (Weissenberg et al.

1947)

4: non-linear viscoelasticity

Main goals Ranges of viscoelasticity: the Deborah number

- To develop constitutive models that can describe non-linear

phenomena such as rod climbing

- To use the equations in practical applications such as

polymer processing and soft tissue mechanics
 A dissappointing point of view Three major topics:
- Non-linear phenomena (time dependent)
- Normal stress difference
- Shear thinning
- Extensional thickening

- Most simple non-linear models

- More accurate models

Normal stress differences in shear Shear thinning

- Data for a LDPE melt

- Lines from the Kaye-Bernstein, Kearsley, Zapas (K-BKZ) model

For small shear rates:

Normal stress coefficients

 Shear thinning & time dependent viscosity Interrelations between shear functions

For small shear rates: Cox-Merz rule

Gleissle mirror rule

Lodge-Meissner; after step shear:

LDPE
Steady shear (solid line)
Cox Merz (open symbols)
Gleissle mirro rule (solid points)

Extensional thickening Extensional thickening

Time-dependent, uniaxial uniaxial extensional viscosity
extensional viscosity versus shear viscosity

Non-linear behavior in uniaxial

extensional viscosity is more
sensitive to molecular archtecture
than non-linear behavior in shear
viscosity
PS, HDPE: no branches
2 LDPEs: branched, tree-like
 Stressing viscosities Second order fluid

Simplest constitutive model that predicts

a first normal stress difference:

Upper convective derivative (definition):

m = uniaxial extension
m = 1 biaxial extension Finger tensor:
m =0 planar extension
with the substantial or material derivative:
Extremely rare results

Second order fluid in simple shear Second order fluid in uniaxial extension

For: extensional thickening for low extension rates

Useful for non-uniform complex flow

More complex model (Criminale-Ericksen-Filby):

Can not predict neither stress

Growth or stress relaxation
 Upper Convected Maxwell model Upper Convected Maxwell model: shear flow

Start-up flow

1-D Maxwell model (linear viscoelasticity):

Homogenous flow =0

- Non-linear viscoelastic model (product of and ) Symmetry:

- Small strain: non-linear terms dissapear, material derivative

- Steady flow, small strain rate: Newtonian flow

- Transient flow, high strain rates: Neo-Hookean.

Upper Convected Maxwell model: shear flow Upper Convected Maxwell model: shear flow

Start-up flow Stress growth, non-zero components:

Steady state results (time derivatives are zero)

Viscosity and first normal

stress coefficient are constant
 Upper Convected Maxwell model:extension Upper Convected Maxwell model

Steady state uniaxial extension Integral form

How to use integral models ?

Different shear histories

.
Extremely extension thickening,
viscosity rises to infinity when : : strain accumulated between t an t

Upper Convected Maxwell model Upper Convected Maxwell model

Step shear strain Start-up uniaxial extension

Start-up steady shear

 Upper Convected Maxwell model Upper Convected Maxwell model

Start-up uniaxial extension Start-up uniaxial extension

Upper Convected Maxwell model Upper Convected Maxwell model

Start-up uniaxial extension Integral form; multi mode

Corresponding differential forms

 Upper Convected Maxwell model Upper Convected Maxwell model

Summarizing: Oldroyd-B constitutive equation (1950)

Including the (viscous) solvent contribution

Pros
- Recaptures all of the linear viscoelastic modelling
- Newtonian / Neo-Hookean behavior for the limiting case (slow / fast flow)
- Predicts first normal stress difference and extensional thickening
HWM polyisobutylene in
Cons
poly(1-butene) / kerosene
- No second normal stress difference
- No shear rate dependence of viscosity and first normal stress difference __ UCM equation
(i.e no shear thinning)
--- Oldroyd-B
- extensional thickening is too severe

Works for very dilute solutions (< 0.5% concentration) and dilute solutions
with very high solvent viscosities (Boger fluids)

More accurate constitutive models More accurate constitutive models

Integral constitutive models Integral constitutive models

Lodge: How to obtain the right energy function:

Lodge, step strain Two invariants IB, IIB and time t:

- lots of experiments required (problem!)
- or guidance from molecular theory

Use general elastic solid:

Time-dependent elastic First, restrict tot simple shear flow

energy function

Special case: Lodge:

 More accurate constitutive models More accurate constitutive models

Integral constitutive models: simple shear Integral constitutive models: simple shear / step strain

The function can be obtained by taking the tome derivative

of the relaxing shear stress after step shear strain

With the expression: one can obtain and

More accurate constitutive models More accurate constitutive models

Time-strain factorabilibty
Simple shear / step strain

- M(t-t) from linear viscoelastic measurements

- Non-linear measurements for U(IB,II B)
- For 12 and N1 the so-called damping function h() needs to be measured

Time-strain factorability!!
(works also for other than shear)
 More accurate constitutive models More accurate constitutive models
Stress growth
Simple shear / step strain /damping function h() With Gi, i and h() known predictions for
various shear flows can be made

Steady state viscosity & first

Wagner (1976) (--) normal stress coefficient

Laun (1978) (__)

Khan & Larson (1987)

Stress relaxation

Notice that the Lodge-Meisner

relation is obeyed ( ) A single damping function captures
a wealth of non-linear shear data for
many polymer melts

More accurate constitutive models More accurate constitutive models

Factorization doesnt work always Concentrated polystyrene solution More general expression:

Also problems with strain

reversal (complete failure)

Doesnt work for other type

of flows (extensional)

Based on a molecular theory,

limited applicability
 More accurate constitutive models Maxwell-type differential equations

Recent integral models:

- Wagner stress function
- Pom-Pom model (Larson-McLeish)

Modifies the rate of stress build up

Modifies the rate of stress decay

Multi-modes required to describe experimental data

Larson model Phan Thien-Tanner model

Maxwell-type differential equations

Maxwell-type differential equations

Step shear

Uniaxial extension

Step biaxal extension

Notice: mostly only one

non-linear parameter!!
 Maxwell-type differential equations Maxwell-type differential equations

Recent differential models Example: viscosity and normal stress

- Pom-Pom differential approximation coefficients for Johson-Segelman model
- eXtended Pom-Pom (XPP)
- Rolie-Poly Steady state:

Some algebra

Summary