Microstructural studies for rheology

John Hinch
DAMTP, Cambridge University

22 July 2008

Microstructural studies for rheology

To calculate the flow of complex fluids, need governing

equations,

Microstructural studies for rheology

To calculate the flow of complex fluids, need governing

equations,

in particular, the constitutive equation relating stress to flow

and its history.

Microstructural studies for rheology

To calculate the flow of complex fluids, need governing

equations,

in particular, the constitutive equation relating stress to flow

and its history.

Either ad hoc, such as Oldroyd-B differential equation and

BKZ integral equation,

Microstructural studies for rheology

To calculate the flow of complex fluids, need governing

equations,

in particular, the constitutive equation relating stress to flow

and its history.

Either ad hoc, such as Oldroyd-B differential equation and

BKZ integral equation,

Or look at microstructure for highly idealised systems and

derive their constitutive equations.

Microstructural studies for rheology

To calculate the flow of complex fluids, need governing

equations,

in particular, the constitutive equation relating stress to flow

and its history.

Either ad hoc, such as Oldroyd-B differential equation and

BKZ integral equation,

Or look at microstructure for highly idealised systems and

derive their constitutive equations.

Most will be suspensions of small particles in Newtonian

viscous solvent.

Outline
Micro & macro views
Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Separation of length scales

Essential
Micro

`  L Macro

Micro = particle 1m

Macro = flow, 1cm

Micro and Macro time scales similar

Need ` small for small micro-Reynolds number

Re` =

`2

 1,

otherwise possible macro-flow boundary layers 6 `

But macro-Reynolds number ReL =
I

If ` L, then non-local rheology

L2

can be large

Two-scale problem `  L

Solve microstructure tough, must idealise

Extract macro-observables easy

Here: suspension of particles in Newtonian viscous solvent

1. Macromicro connection

Particles passively move with macro-flow u

Particles actively rotate, deform & interact with

macro-shear u

both needing Re`  1.

2. Micromacro connection
Macro = continuum = average/smear-out micro details
E.g. average over representative volume V with `  V 1/3  L
Z
1
=
dV
V V
Also ensemble averaging and homogenisation
To be used in averaged = macro momentum equation


u

+ u u = + F
t
NB micro-Reynolds stresses (u)0 u0 small for Re`  1.

Reduction for suspension with Newtonian viscous solvent

Write:

= pI + 2e + +

with pressure p, viscosity , strain-rate e,

and + non-zero only inside particles.
Average: = pI + 2e + +
with
+

1
=
V

Z

dV = n
V

dV
particle

with n number of particles per unit volume

types of particle

Reduction for suspension with Newtonian viscous solvent 2

Inside rigid particles e = 0, so + = .

Also ij = k (ik xj ) xj k ik , so ignoring gravity k ik = 0,
Z
Z
+ dV =
n x dA
particle

particle

so only need on surface of particle. (Detailed cases soon.)

Hence

Z
= pI + 2e + n

n x dA
particle

Homogenisation: asymptotics for `  L

Easier transport problem to exhibit method

k T = Q
with k & Q varying on macroscale x and microscale = x/,
Multiscale asymptotic expansion
T (x; ) T0 (x, ) + T1 (x, ) + 2 T2 (x, )

Homogenisation 2

2 :
k T0 = 0
i.e. T0 = T (x)
Thus T varies only slowly at leading order, with microscale making
small perturbations.

Homogenisation 3

1 :
k T1 = kx T0
Solution T1 is linear in forcing x T0 , details depending on k():
T1 (x, ) = A()x T0

Homogenisation 4
0 :
k T2 = Q x kx T0 kx T1 x k T1
Secularity: hRHSi = 0 else T2 = O( 2 ) which contradicts
asymptoticity. (Periodicity not necessary.) Hence
0 = hQi x hkix T0 x hk

A
ix T0

Hence macro description

k T = Q

with

k =

A
k +k

and Q = hQi

Homogenisation 5
NB: Leading order T0 uniform at microlevel, with therefore no
local heat transport
NB: Micro problem forced by T0 . Need to solve
k Tmicro = 0
Tmicro x T0
Solution
Tmicro = (x + A)T0
Hence heat flux
hqi = hkTmicro i = hk + kAi T0

Micro & macro views

Separation of length scales
Micro Macro connections
Case of Newtonian solvent
Homogenisation
Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Einstein viscosity

Simplest, so can show all details.

Highly idealised many generalisations
I

Spheres no orientation problems

Rigid no deformation problems

Dilute and Inert no interactions problems

Micro problem
I

Isolated rigid sphere

force-free and couple-free

in a general linear shearing flow U

Stokes flow

Stokes problem for Einstein viscosity

u=0

in r > a
2

0 = p + u
u=V+x

in r > a

on r = a

u U + x U

with

F=

Z
n dA = 0,

r =a

as

V , consts

x n dA = 0

G=
r =a

Split general linear shearing flow U into symmetric strain-rate E

and antisymmetric vorticity , i.e.
x U = E x + x
NB: Stokes problem is linear and instantaneous

Solution of Stokes problem for Einstein viscosity

F=0
G=0

gives V = U
gives =

i.e. translates with macro flow

i.e. rotates with macro flow

Then
a5
5(x E x)
u=U +Ex+xEx 5 x
r
2r 2
3
(x E x)a
p = 5
r5

a3 a5
5
r3
r

Evaluate viscous stress on particle


5
nr =a =
Ex
2a
Evaluate particle contribution to macro/average stress
Z
4
n x dA = 5E a3
3
particle

Result for Einstein viscosity (1905)

= pI + 2E + 5E

with volume fraction = n

4 3
a
3

Hence effective viscosity



5
= 1 +
2

Result independent of type of flow shear, extensional

Result independent of particle size OK polydisperse

Einstein used another averaging of dissipation

which would not give normal stresses with : E = 0,
which arbitrarily cancelled divergent integrals (hydrodynamics
is long-ranged)

Micro & macro views

Einstein viscosity
The simplest example
Stokes problem
Stokes solution
Results
Rotations
Deformations
Interactions
Polymers
Others

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Rotation of particles rigid and dilute

Spheroid: axes a, b, b, aspect ratio r = ba .

rod r > 1

disk r < 1

Direction of axis p(t), unit vector.

Stokes flow by Oberbeck (1876)

Rotation of particles

Microstructural evolution equation

Dp
=p+
Dt

r 2 1
r 2 +1

[E p p(p E p)]

(Last term to keep p unit, so can discard sometimes.)

2 1
Straining less efficient at rotation by rr 2 +1
.

Long rods

r 2 1
r 2 +1

+1

i.e. Upper Convective Derivative A

Flat disks

r 2 1
r 2 +1

i.e. Lower Convective Derivative

Micromacro link: stress

= pI + 2E + 2 [A(p E p)pp + B(pp E + E pp) + C E]

with A, B, C material constants depending on shape but not size
A

r2
2(ln 2r 23 )

6 ln 2r 11
r2

r 0

10
3r

8
3r

8
3r

Rotation in uni-axial straining

U = E (x, 21 y , 21 z)

rotates to

Aligns with stretching direction maximum dissipation

rotates to

Aligns with inflow direction maximum dissipation

Effective extensional viscosity for rods

ext


= 1+

r2
3(ln 2r 1.5)

Large at  1 if r  1. Now =
ext


= 1+

4
2
3 ab

and r = ba , so

4na3
9(ln 2r 1.5)

so same as sphere of radius a its largest dimension(except for

factor 1.2(ln 2r 1.5)).
Hence 5ppm of PEO can have a big effect in drag reduction.
Dilute requires na3  1, but extension by Batchelor to semi-dilute
 1  r 2


4na3

ext = 1 +
9 ln 1/2

Effective extensional viscosity for disks





10
10nb 3
ext = 1 +
= 1+
3r
9
where for disks b is the largest dimension
(always the largest for Stokes flow).
No semi-dilute theory, yet.

Behaviour in simple shear

U = (y , 0, 0)

rotates to

Rotates to flow direction minimum dissipation

rotates to

Rotates to lie in flow minimum dissipation

Both Tumble: flip in 1/, then align for r /
= /r 2 )

( = 1/r with

Effective shear viscosity

Jeffery orbits (1922)
=
=

(r 2 cos2 + sin2 )
r 2 +1
(r 2 1)
sin 2 sin 2
4(r 2 +1)

Solution with orbit constant C .

tan = r tan t,

Effective shear viscosity

shear

r
,
r 2 +1

tan = Cr (r 2 cos2 + sin2 )1/2

Leal & H (1971)

(
0.32r / ln r
= 1+
3.1

rods
disks

numerical coefficients depend on distribution across orbits, C .

Remarks
Alignment gives shear  ext
and this material anisotropy will lead to anisotropy of macro flow.
Important to Turbulent Drag Reduction

Three measures of concentration of rods

2 .
3

for ext
r = na
.
r = na2 b for shear

.
= nab 2
for permeability

Brownian rotations for stress relaxation

Rotary diffusivity

Drot =


kT

kT
8a3

8a2
3(ln 2r 1.5)

for spheres,
rods,

kT

8

3 b

disks

(NB largest dimension, again)

After flow is switched off, particles randomise orientation in time
1/6D 1 second for 1m in water.
State of alignment: probability density P(p, t) in orientation space
= unit sphere |p| = 1. Fokker-Plank equation
P

+ (pP)
= Drot 2 P
t

p(p)
earlier deterministic.

Average stress over distribution P

Averaged stress
= pI + 2E + 2[AE : hppppi
+ B(E hppi + hppiE ) + C E + F Drot hppi]
Last F Drot term is entropic stress.
Extra material constant F = 3r 2 /(ln 2r 0.5) for rods and 12/r
for disks.
Z
with averaging:
hppi =
ppP dp
|p|=1

Solve Fokker-Plank: numerical, weak and strong Brownian

rotations

Extensional and shear viscosities

ext

ext

1/3
X r^2/ln r

Small
strain-hardening

4/15

6
shear

E/D

l Orientation effects

4 r^2/15ln r

Large
shear-thinning
r^2/2ln r (D/) 1/3

Also N1 > 0,
N2 small < 0.

0.32 r/ln r
6

r^3

/ D

The closure problem

I

Second moment of Fokker-Plank equation

D
hppi hppihppi
Dt


2 1
= rr 2 +1
[E hppi + hppiE 2hppppi : E ]6Drot hppi 31 I
Hence this and stress need hppppi, so an infinite hierarchy.

Simple ad hoc closure

hppppi : E = hppihppi : E

Better: correct in weak and strong limits


hppppi : E = 15 6hppiE hppi hppihppi : E 2I (hppi2 : E hppi :

New idea Brownian fields: simulate many random walks in

orientation space for each point of the complex flow.

Micro & macro views

Einstein viscosity
Rotations
Rotation of particles
Macro stress
Uni-axial straining
Extensional viscosity rods
Extensional viscosity disks

Simple shear
Shear viscosity

Anisotropy
Brownian rotations
Macro stress
Viscosities
Closures

Deformations

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Emulsions - deformable microstructure

Reviews: Ann. Rev. Fluid Mech. Rallison (1984), Stone (1994)
4 3
3 a

Dilute single drop, volume

T = surface tension (in rheology and not possible)

Newtonian viscous drop int , solvent ext

Rupture if ext >

T
Ea

(normally)
time

time

Irreversible reduction is size to a = T /ext E , as coalescence very

slow.

Rupture in shear flow

T
ext Ea

int
ext
Experiments: de Bruijn (1989) (=own), Grace (1982)
Theories: Barthes-Biesel (1972), Rallison (1981), Hinch & Acrivos (1980)

Rupture difficult if int  ext

Too slippery. Become long and thin. Rupture if

(
T 0.54 (ext /int )2/3 simple shear
ext E >
a 0.14 (ext /int )1/6 extension
but tip-streaming with mobile surfactants (makes rigid end-cap)
ext E >

T
0.56
a

Rupture difficult is simple shear if int > 3ext

If internal very viscous ( int  ext ),

I
I

If internal fairly viscous (int & 3ext ),

I
I
I

then rotates with vorticity,

rotating with vorticity, sees alternative stretching and
compression,
hence deforms little.
then deforms more,
if deformed, rotates more slowly in stretching quadrant,
if more deformed, rotates more slowly, so deforms even more,
etc etc

until can rupture when int 3ext

Theoretical studies: small deformations

Small ellipsoidal deformation
r = a (1 + xA(t)x +

higher orders)

Stokes flow with help of computerised algebra manipulator

DA
A + A = 2k1 E + k5 (AE + EA) + . . .
Dt
T
ext
a (k2 A + k6 (AA) + . . . )

= pI + 2ext E + 2ext k3 E + k7 (AE + EA) + . . .

T
ext a (k4 A

+ k8 (AA) + . . .

with kn depending on viscosity ratio, k1 inefficiency of rotating by

straining = int /ext
k1 =
k3 =

5
2(2+3) ,
5(1)
3(2+3) ,

k2 =
k4 =

40(+1)
(2+3)(19+16)
4
2+3

Theoretical studies: small deformations 2

Equilibrium shapes before rupture
extension
shear
internal circulation,
tank-treading

Rheology before rupture

Small strain-hardening, small shear-thinning, N1 > 0, N2 < 0.
Repeated rupture leaves
= constant. Einstein: independent of
size of particle, just depends on .
Form of constitutive equation
d
(state)
dt

&

linear in

E &

T
ext a

Numerical studies: boundary integral method

deformation

xy

angle

N1 , N 2

Different . No rupture for = 5 (*)

Flexible thread deformable microstructure

Position x(s, t), arclength s, tension T (s, t)
x = xU + T 0 x0 + 21 T x00
with T 00 12 (x00 )2 T = x0 Ux0

and T = 0 at ends

Snap straight
H 76

Electrical double layer on isolated sphere

another deformable microstructure

Charged colloidal particle.

Solvent ions dissociate,

forming neutralising cloud around particle.

Screening distance Debye 1 , with 2 = i ni zi2 e 2 /kT .

In flow, cloud distorts a little

very small change in Einstein 25 .

Micro & macro views

Einstein viscosity
Rotations
Deformations
Emulsions
Rupture
Theories
Numerical

Flexible thread
Double layer
Interactions
Polymers

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Hydrodynamic interactions for rigid spheres

Hydrodynamic: difficult long-ranged

Rigid spheres : two bad ideas
Dilute between pairs (mostly)

Reversible (spheres + Stokes flow) return to original streamlines

But minimum separation is 12 104 radius sensitive to roughness
(typically 1%) when do not return to original streamlines.

Summing dilute interactions

1
Divergent integral from u 3
r
Need renormalisation: Batchelor or mean-field hierarchy.


= 1 + 2.5 + 6.02

6.0 for strong Brownian motion

7.6 for strong extensional flow

= 5 for strong shear flow, depends on distribution on closed

orbits

Small strain-hardening, small shear-thinning

Test of Batchelor 2 result



= 1 + 2.5 + 6.02

slope 6.0
Einstein 2.5

Russel, Saville, Schowalter 1989

Experiments concentrated

Effective viscosities in shear flow

0

a3 /kT

Russel, Saville, Schowalter 1989

Stokesian Dynamics
(mostly) pairwise additive hydrodynamics
Jamming/locking clusters across the compressive quadrant

Brady & Bossis (1985)

Fragile clusters if include soft repulsion or Brownian motion

Stokesian Dynamics 2
Effective viscosity in shear flow

Foss & Brady (2000)

Stokesian Dynamics Brady & Bossis

Ann. Rev. Fluid Mech. (1988)

Electrical double-layer interactions

Interaction distance r :
6ar =

 2 a2 (r 2a)
e
r


 r 5 

= 1 + 2.5 + 2.82
a
 r 5

= velocity r

force distance r
 r 3

volume
a

2 coefficient as function of

r
a

Experiments concentrated
Stress as function of shear-rate at different pH.
Suspension of 0.33m aluminium particles at = 0.3

Ducerf (Grenoble PhD 1992)

Note yield stress very sensitive to pH

Interactions van der Waals

Attraction aggregation
gel (conc) or suspension of flocs (dilute)
Possible model of size of flocs R
I

I
I
I

I
I

 d
R
, d = 2.3?
Number of particles in floc N =
a
 3
R
Volume fraction of flocs floc =
a
Collision between two flocs
Hydro force 6RR = Bond force Fb number of
bonds N Ra
Fb
Hence floc =
6a2
So strong shear-thinning and yields stress Fb /a2 .

Breakdown of structure in rheology ()

Interactions fibres

Cannot pack with random orientation if

r > 1
leads to spontaneous alignment, nematic phase transition
Note extensional viscosity r 2 can be big while random,
but shear viscosity r is only big if aligned.
Disk not random if 1r > 1.

Interactions drops

No jamming/locking of drops (cf rigid spheres)

I
I

small deformation avoid geometric frustration

slippery particle, no co-rotation problems

Faster flow more deformed wider gaps in collisions

Deformed shape has lower collision cross-section

so dilute at = 0.3, blood works!

Numerical studies: boundary integral method

= 0.3, Ca = ext a/T = 0.3 = 1, t = 10,

12 drops, each 320 triangles.

Numerical studies: boundary integral method 3

deformation

xy

angle

N 1 , N2

= 1, different = 0, 0.1, 0.2, 0.3. Effectively dilute at = 0.3.

Numerical studies: boundary integral method 4

Reduced cross-section for collisions

into flow

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Hydrodynamic
Dilute
Experiments
Numerical

Electrical double-layer
Dilute
Concentrated

van der Waals

Fibres
Drops

Micro & macro views

Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others

Bead-and-Spring model of isolated polymer chain

simplest, only gross distortion, Kuhn & Kuhn 1945, Kramers 1946

Flow distortion = Stokes drag = 6a(R U R)

1
0.5
0.6
a = 6 bN N

Resisted by entropic spring force = R,

3kT
Nb 2

Hence
R = R U

1
2 R

with

= 0.8kT /(N 1/2 b)3

Bead-and-Spring model of isolated polymer chain 2

Adding Brownian motion of the beads: A = hRRi



1
Nb 2
DA
T
AU U A =
A
I
A
Dt

3
= pI + 2E + nA

with n number of chains per unit volume.

Oldroyd-B constitutive equation with UCD time derivative A

Rheological properties
Shear
I

= constant, N1 2 , N2 = 0.

Distortion xy : a a

Extension
I

0.5

!
1

Distortion e (2E )t

For TDR: small shear and large extensional viscosities

Refinements
1. (boring) Spectrum of internal modes: Rouse 53, Zimm 56
with pre-averaged hydrodynamics
2. (boring) Polydisperse molecular weights
3. (important) Finite extensibility to stop infinite growth
1
e (2E )t
I

Nonlinear spring force inverse Langevin law

 
kT 1 R
with L(x) = coth x
F (R) =
L
b
Nb
F.E.N.E approximation
F (R) =

1
x

kT
R
Nb 2 1 R 2 /L2

with fully extended length

FENE-P closure


RR/(1 R 2 /L2 ) = hRRi /(1 hR 2 i/L2 )
but molecular individualism

L = Nb

FENE-P constitutive equation

1
L2
A= 2
L trace A


a2
A I
3
2
L
= pI + 2E + n 2
A
L trace A

ext
1 + naL2

More refinements
4. Nonlinear bead friction
Hydrodynamic drag increase with size 6(a R)
ext = 1 + nL3

and hysteresis

5. Rotation of the beads simple shear not so simple

Couple balance

Afine

A non-affine A

inefficiency of straining

trace A
(AE + E A)
3 + trace A

One more refinement

6. Dissipative stress nonlinear internal modes

Simulations show growing stretched segments
segment length

R2
,
L

number

L2
,
R2

dissipation

R4
L



(trace A)2
L2
A
= pI + 2 1 + n
E + n 2
L
L trace A
Good for contraction flows

Unravelling a polymer chain in an extensional flow

Simulation of chain with N = 100 in uni-axial straining motion at

strains Et = 0.8, 1.6, 2.4.

Growing stretched segments

Two ends not on opposite sides

Simplified 1D kinks model

I

t = 0: 1D random walk, N steps of 1

t > 0: floppy inextensible string in u = Ex

arclengths satisfy
si = 41 E (si+1 + 2si si1 )

Large gobble small

Kinks model 2

Distribution of lengths `(t)

Number of segments n(t)
scaled by e 2Et
Scalings
(
(
n` = N
n = Ne 2Et
Et

n` = R = Ne
` = e 2Et
H 94

Evidence of a dissipative stress

Original data of Sridhar, Tirtaatmadja, Nguyen & Gupta 1991 plotted
as viscosity as function of time

Replotted a function of strain = strain-ratetime

Improved algorithms for Brownian simulations

1. Mid-point time-stepping avoids evaluating D
Keep random force fixed in time-step, but vary friction
2. Replace very stiff (fast) bonds with rigid + correction
potential

kT ln det M 1

with

M 1 ab =

X
i beads

mi1

g a g b

xi xi

where rigid constraints are g a (x1 , . . . , xN ) = 0 and stiff spring

energy 12 |g a |2
3. Stress by subtraction of large t 1/2 term with zero average
1 n
2 (x

+ x n+1 )f n 12 x n f n
Grassia, Nitsche & H 95

Relaxation of fully stretched chain

Long times - Rouse relaxation

Short times finite

Stress relaxation: Decay of [1,1] stress component vs t: Short times

Stress relaxation: Decay of [1,1] stress component vs t: Long times

(stress-final stress)/(initial stress-final stress)

10

(stress-final stress)/n

0.1

0.1

0.01
0.01

0.02

0.03

0.04

0.05
t/n^2

0.06

0.07

0.08

0.09

0.1

10
n^2 t

15

/ 13 N 3 vs N 2 t

/N vs t/N 2 (Rouse)
Stress relaxation: Decay of [1,1] stress component vs t: Intermed. times

(stress-final stress)/n^2

10

Intermediate times
kTN 2 t 1/2

0.1
0.001

0.01

0.1
t

20

Constitutive equation options

1
f (A I )
h
= pI + 2E + G f A
A=

I
I
I
I

Oldroyd B f = 1
FENE-P f = L2 /(L2 trace A)
p
Nonlinear bead friction h = traceA/3
New form of stress

= pI + 2E + 2d (A : E )A + G trace AA
I
I

Last term for finite stress when fully stretched

d term ( N 1/2 ) for enhanced dissipation

Good for positive pressure drops and large upstream vortices

in contraction flows.

Reptation model of De Gennes 1971

often reformulated

Chain moves in tube defined by topological constraints from other

chains.
*

*
*

*
*

*
*

*
*
*

*
*
*

Chain disengages from tube by diffusing along its length

D =

L2
M3
D = kT /6L

Modulus G = nkT = G D M 3

(expts M 3.4 )

Diffusion out of tube

At later time:
*

*
*

*
*

*
*

*
*
*

*
*
*

Fraction of original tube surviving

X 1
2
e n t/D
2
n
n
Diffusion gives linear viscoelasticity G 0 1/2

Doi-Edwards rheology 1978

Deformation of the tube by a shear flow.
*

*
*

*
*

*
*
*

*
*

*
*
*

*
*

*
*

Unit segments of the tube u aligned by flow:

u Au

with Finger tensor A

Stress
Z
(t) = n
0

X 1
2
e p s/D
2
p
p
surving tube

Nsegements



3kT
A u A u
a
ds
a
|A u|2

segment tension

with relative deformation A = A(t)A1 (t s).

A BKZ integral constitutive equation
Problem maximum in shear stress

Refinements
1. Chain retraction
deform

retract

Chain returns in Rouse time to natural length loss of

segments
2. Chain fluctuations
3. Other chains reptate release topological constraints
Double reptation of Des Cloiseaux 1990. bimodal blends
2 & 3 give M 3.4
4. Advected constraint release Marrucci 1996
1
D

1
D

+ u : huui

5. Flow changes tube volume or cross-section

Chain trapped in a fast shearing lattice

Lattice for other chains

more shear

central section pulling chain out of arms high dissipative stresses

Ianniruberto, Marrucci & H 98

Branched polymers

typical in industry

Very difficult to pull branches into central tube

exp(Marm /Mentangle )
Pom-Pom model of Tom McLeish and Ron Larson 1999
= g 2 S

Orientation: S = B/traceB
Stretch: = u : S

1
S (

1)

B = 1O (B I)
while

< max

with O = arm (MC /ME )3 and S = arm (MC /ME )2 and

arm
= exp(Marm /ME ) where MC = Mcrossbar and ME = Mentanglement .

Test of Pom-Pom model

Blackwell 2002

Fit: Linear Viscoelastic data and Steady Uni-axial Extension.

Predict: Transient Shear and Transient Normal Stress

IUPAC-A data Muntedt & Laun (1979)

Polymers
Polymers
Bead-and-spring model
Refinements
FENE-P constitutive equation
Unravelling a polymer chain
Kinks model
Brownian simulations

Entangled polymers
rheology
Refinements
pom-pom

Other microstructural studies

Electro- and Magneto- -rheological fluids

Associating polymers

Surfactants - micells

Aging materials

GENERIC

Modelling Molecular individualism and closure problems

Outline
Micro & macro views
Einstein viscosity
Rotations
Deformations
Interactions
Polymers
Others