Rheology of Colloidal Suspensions

Peter Schall
University of Amsterdam
 Introduction
Soft Matter systems Remarkable
Visco-elastic properties
 Introduction
Soft Matter systems
Visco-elastic properties

Microscopic mechanisms ?

foam ?
colloidal
suspension

gel
DNA
Atoms Polymers Granular
a
10-9 10-8 10-7 10-6 10-5 10-4 10-3 m
 Rheological measurement

Planar Couette Couette

F
x
area A

h colloid

x
Strain =
h
F
Stress =
A

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 Rheology: Simple Liquid

log()
slope 1

.
log()

Viscous liquid (e.g. honey)

.
=

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 Rheology: Complex Fluids

log()
n
y
.
log()

Herschel-Bulkley:
. n
= y + A
n < 1 : shear thinning
n > 1 : shear thickening

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 Rheology : Time-dependent response

(t)
(t)

Applied strain : (t) = 0 sin(t)

Stress response : (t) = 0 (G sin(t) + Gcos(t))
storage loss

G : Elastic modulus
G: Viscous modulus
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 Rheology: Dense Colloidal suspensions

... vary frequency ... vary amplitude

G
0 = 2% = 1rad/s

Elastic Modulus G > viscous Modulus G

Linear response (G, G defined) 0 < 2%
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 Jamming
Pastes,
Suspensions Grains

Liu, Nagel, Nature 1998

Foams Glasses
 Fundamental Transition

Elastic Solid Viscous Liquid

affine non-affine, diffusive
Elastic Modulus Viscosity

Symmetry change:
temporal symmetry

Elastic Viscous
F F
t
-t t
-t
F
F F
-F
Energy storage Energy loss
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 Colloidal Hard Spheres

Hard-sphere Phase Diagram

0.49 0.54 0.74
Volume
Fraction
Fluid Fluid + Crystal
Cryst

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 Colloidal Hard Spheres

Quench
0.58 0.64
Volume
Fraction
Fluid Glass

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 Colloidal Hard Spheres

Scaling of the Moduli

Elastic Modulus Energy / a3

Atoms Colloids
1eV / 13 kT / 1m3
=100 GPa ~1 Pa

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 Observation of Colloidal Systems

Length Scales

Light scattering Microscopy

1cm3
1013 particles 10 mm3
1011 particles

109 particles ~106 particles

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 ~Observation
0.60 of Colloidal Systems
d = 1.3 m
Length Scales

Light scattering Microscopy

1cm3
1013 particles 10 mm3
1011 particles
100 m
109 particles ~106 particles

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3D Imaging and Reconstruction
Colloidal Glasses

Light scattering
van Megen et al. (PRE 1998)

Colloidal glass transition

g ~ 0.57

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 Colloidal Glasses
Particle Diffusion ...
< r2 >

Microscopy
Weeks, Weitz et al. (Science, 2000)

... Single Particle Dynamic heterogeneity

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Application of stress
Particle
displacements
60

z / m
40

20
50d
0
- 0.05 0 0.05 0.1
x / m

Confocal microscopy

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 Strain and non-affine displacements
z
shear
Affine transformation :
x

y r (t)
r = r + r
r(t+t) neighbors

D2min = (r - r)2
Falk and Langer, PRE 57, 1998.

Affine non-Affine

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 Strain and non-affine displacements
z
shear
Affine transformation :
x

y r (t)
r = r + r
r(t+t) neighbors

D2min = (r - r)2
Falk and Langer, PRE 57, 1998.

Symmetric part ...

xx xy xz
Strain tensor ij = yx yy yz
zx zy zz

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 Homogeneous flow
.
~ 1 x 10-5 s-1
. ~ 0.1

Affine part Non-affine part

xz
2
60
Dmin
40
Z(m)

20

0
0 20 40 60 80 100 0 20 40 60 80 100
X(m) X(m)

-0.1 0 0.1 0 0.2 0.4 0.6

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 Shear transformation zone (STZ)

Incremental strain
Continuum elasticity
z
- -
x
- -
x

1
yz slope yz~ 3
-3 r
yz

r / m

(PS, Weitz, Spaepen, Science 2007)

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 Constitutive Models of Flow

Assumption:
flow events independent
Thermal activation

Energy
. (G() - )
= f 0 exp(- kT
)

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 Spatial Correlation in the Deformation

(r+)

(r)

A(r ) A(r + ) ( A )2

C A ( ) =
( A) ( A )
2 2

: difference vector
: spatial average : A =
Strain correlation xz
Non-affine correlation : A = D2min
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 Affine part: Shear Strain xz
Strain Correlation function
z 0.2
30
x

y 15 0.1

z/d
0.02
60 0 0

-15 0.01 -0.1

40
-30
Z(m)

0 -0.2
-30 -15 0 15 30
20 x/d -0.01

0 -0.02
0 20 40 60 80 100

ElasticX(m)
interactions

Self organization of STZ
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 Non-affine part
D2min Correlation
z -1
30
x
0.5
y 15
r

z/d
1
60 0 0

-15 -0.75 -0.5

40
-30
Z(m)

-0.5 -1
-30 -15 0 15 30
20 x/d
-0.25

0 0
0 20 40 60 80 100
X(m)

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Critical Scaling at the verge Elastic
Viscous

100
60

10-1 1.3
CD2min(r) 40
Z(m)
10-2
20

10-3

0
100 101 102
System
X(m)
r/
Size
Power-law scaling
up to system size
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 Conclusions

Colloidal suspensions:
Elastic and viscous properties

Direct observation of particle motion

by 3D microscopy and light scattering

At the verge Elastic 
Dissipative:

Critical correlations, deformation pattern scale invariant

Outlook:
Generic mechanism
Universality classes ?

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