Sbastien Manneville

sebastien.manneville@ens-lyon.fr

1.

II.

III.

Rheology of soft matter

Sbastien Manneville

sebastien.manneville@ens-lyon.fr

Physics lab Ecole Normale Suprieure de Lyon

Part I. Basics of rheology

Part II. Advanced techniques in rheology

Part III. Current issues in the rheology of soft matter

Introduction
What is soft matter?
What is rheology about?

A few examples of soft solids and complex fluids

cosmetics
oil extraction

pharmacy

detergents

construction

food industry
biology

geophysics

fluid : takes the shape of the container

complex : intermediate between a liquid and a solid

The concept of microstructure

1 1 nm

molecule

simple fluid

1 cm 1 m

container

The concept of microstructure

1 1 nm

10 nm 10 m

complex fluid

intermediate
"mesoscopic"
scale

hydrophilic

1 cm 1 m

+ H 2O
+ ions
hydrophobic

cylindrical micelle

The mixture has a characteristic microstructure

Colloidal scale: thermal agitation ~ particle weight

lcoll ~ 1 m

A first classification attempt

- polymers
macromolecules

(melts or solutions)

- liquid crystals

[ R. Behringer, Duke U. ]

- dry and wet granular materials

- colloids

suspensions
two immiscible phases

- emulsions
- foams
[ A. Colin, CRPP ]

self-assembled fluids
mixtures of solutes

- surfactant solutions

[ P. Snabre, CRPP ]

- bolck copolymers

Thermal vs athermal systems

[ E. Weeks, Emory U. ]

The magic triangle of soft matter

polymers

flexible
polymers
DNA
semi-flexible
polymers

proteins

hard spheres

block
copolymers

liquid
crystals
emulsions

lipids

surfactants

amphiphiles

colloids
[ Gompper et al., Phys. Unserer Zeit 34, 12 (2003) ]

A wide variety of interactions

interaction
potential

What are the forces that lead to the microstructure ?

- Excluded volume: electronic cloud repulsion, very short range

~ a few

- Van der Waals: dipole-dipole attraction, short range:

Lennard-Jones (1931):

for mesoscopic objects:

~ a few nm

for two planes separated by a distance r

- Electrostatics: repulsion, long range, double layer screening

~ 10 nm

lD : Debye length

+ + +

+
+
+ + +
+
+

- Others: hydration, solvation, hydrophilic, hydrophobic Ex. H bonds 10 x van der Waals

The equilibrium phase diagram

The microstructural organization depends on



- the constituent concentrations

- ionic force of the solvent (salt)

- temperature

what is the phase diagram

at equilibrium ?

- pressure

- hard spheres

Some examples

- colloidpolymer mixtures

- surfactant systems

- emulsions

Hard spheres

Brownian
hard spheres

liquid

crystal

liquid
+
crystal

0.494

close
packing

0.545

colloidal
0.58
glass 0.64

Two-phase system

0.7405

random
close
packing

Cristallyzation has an entropic origin

Fast concentration quench metastable glassy state
- Brownian motion suppressed though "caging" effect
- more room for thermal fluctuations in the crystalline state

Colloidpolymer mixtures

Depletion interaction

effective attraction

Posm

Posm

[ Pham et al., Phys. Rev. E 69, 011503 (2004) ]

attractive glass / gel

[ polymer ]

Thermal equilibrium is never

reached: aging phenomena

soft glassy material

repulsive hard-sphere glass

[ colloid ]

Surfactant systems

Sodium Dodecyl Sulfate (SDS)

amphiphilic molecules

hydrophilic head
Cetyl Trimethyl Ammonium Bromide (CTAB)

hydrophobic tail

SURFace ACTive AgeNTS "surfactants"

Surfactant systems

The microstructural organization depends on molecule geometry & environment

packing parameter:
1/3

1/2

a
l

spherical micelles

cylindrical micelles

vesicles
flexible bilayers

inverse micelles

plane bilayers

[ Israelachvili (2011) ]

thermotropic vs lyotropic systems

[ surfactant ]

Surfactant systems

[ Lequeux & Candau, in Structure and Flow of Surfactant Solutions,

C.A. Herb, R.K. Prudhomme, Eds, ACS, Washington (1994) ]

[ salt]

Emulsions

dilute emulsion

concentrated emulsion

1 m

water

huile

huile

surfactant

[ E. Weeks, Emory University ]

glass transition

liquid

solid

Three-phase sytem: oil, surfactant

coalescence, creaming, Ostwald ripening
Intrinsically metastable arrested state

aging phenomena

Introduction
What is soft matter?

What is rheology about?

The elastic solid

Cisaillement dun solide : loi de Hooke

[cisaillement]

[compressibilit]

y
1.
Elasticit-plasticit
1.1.Elasticit-plasticit
Elasticit-plasticit
Trois types de dformation :

1
1
1
=
+
E
9K
3G

[Young]

Three types of deformations three coefficients

Trois
types
dformation
: :
u
ydede
Trois
types
dformation
Youngs modulus
y
=F/S
y
`
extension

`
` `
solide
d
`
==
E E `0`
=E
=
F/s
`0
solide
=
F/s
`de
x
0 Young
solide
module
= F/s
solide
module
dede
Young
module
Young
x
u
x
=x
[dformation]
polyethylene: G ~ 108 Pa
y
d
y
y u
ice: G ~ 109 Pa
shear modulus
u u [loi de
u
shear

F/S
Hooke] = G= =
glass: G ~ 1011 Pa
u
=
G
F/S
= G ud
= F/S
=G
diamond: G ~ 1012 Pa
d
solide
d
dde cisaillement
solide
dd
module
solide
module
de
cisaillement
8
module
de
cisaillement
Module de cisaillement : - polythylne
G
=
10
Pa
x
xx
- glace
G = 109 Pa
y
p
y
p
y
p
G=bulk
1011modulus
Pa
- verre
V
compression

12
V
V V- diamant
p=
G = 10
PaK K V
V
p
=
V0
p
p
=
K
p
V
solide
0
p
p
V0
solide
compressibilit
p
p
solide
compressibilit
compressibilit
x xx
p

oulements

= F/S

The viscous fluid

Ecoulements
ide
Newtonien :

fluide

Fluide Newtonien :y

v
v

shear stress

= F/S
= F/S
[taux de cisaillement]
fluide
d
shear

fluide
d
[viscosit]
x

shear rate

v
d

v
v

=
[taux
dedecisaillement]
5
=: -d air
[taux
cisaillement]
-5 Pa.s
=
2
10
Pa s
Viscosits
air:

~
2.10
d
3
=
Pa s
-310
eau
shear
viscosity:

water:

~
10
Pa.s
[viscosit]
=
[viscosit]
10-3 -3103 Pa.s
10+3 Pa s
- huile silicone
silicon oil: =
~ 10

= 22 10 55 Pa
Viscosits
- air
=
Pass
cosits
: -: air
33
laboratory
= 10
10
Pa
- eauWorlds longest
=
Pass experiment

- eau
+3
= Queensland,
10 33
10
Pa
silicone
University =
of
Australia
- huile
silicone
10
10+3
Pas s
- huile
designed in 1927, flow started in 1930
one drop every ~ 8 years
bitumen: ~ 2.3 108 Pa.s

A definition of rheology

500 bc : Heraclitus : " " = "everything flows"

1929: Bingham: rheology = science of material deformation and flow

logo of the
Society of Rheology

everything flows


if given enough time

a

matter of time scales

relaxation time of

1964: Reiner: Deborah number

the microstructure
after deformation
observation time

A few orders of magnitude

Scales of everyday life

- energy: [ML2T-2] = 10-10 1 J

- length: [L] = 1 mm 1 m

- force: [MLT-2] = 10-2 102 N

- pressure/stress: [ML-1T-2] = 1 104 Pa

- mass: [M] = 1 g 1 kg

- viscosity: [ML-1T-1] = 0.1 107 Pa.s

- time: [T] = 0.1 s 1 h

typical stresses ~ typical modulus of a soft material

easy

to deform

Colloidal scales
- thermal energy: kBT = 10-21 J
- length: l = 10-8 10-7 m
- relaxation time: = 10-3 10 s

- modulus: G = kBT / l 3 = 1 104 Pa

- viscosity: = G / = 0.1 107 Pa.s

Time scales and rheology

accessible

10-12
water, simple liquids

De << 1

10-3

to rheology

1s

polymers, surfactants

De ~ 1

103

soft glassy systems

tsedim =

106
solids

6ph
103 108 s
rg` De >> 1

r`2
tmomentum =
10 10 10 8 s t
h
Characteristic time scales besides the microstructural relaxation time
6ph 1/2 3
tsedim
= r`5
10 108 s t
tinertia = rg` 6ph 10 39 108 6 s t
10 10 s t
- gravity: sedimentation/creaming over length l: tsedim
kB T=
rg`
r`2
8
10
tmomentum = 6ph`3 10
10
s2 t
2
5
h
r` 10 10
tviscous =
s10< t
- viscous damping of thermal kinks:
8
tmomentumk=

10
10
st
T
B
h
56ph
1/2
8
1
t
=
103 10
s t
r`
sedim
= 0.1 s
g
9
tinertia =
10 10 6 s t
- inertia force due to thermal kinks:
rg`5 1/2
kB T r`
tinertia =
10 9 10 6 s t
2
r`
k T
= B3 10 510 102 8 s t
- viscous diffusion of momentum over l: tmomentum6ph`
h 10 10 s t
tviscous =
kB T6ph`3
tviscous
=5 1/2 10 5 10 2 s t

r` kB T
g = 0.1 s 1
tinertia =
10 9 10 6 s t
1

A gallery of non-Newtonian fluid motion

Viscosity depends on shear, on stress, on elongation, on time, etc.

mud over an inclined plane

[ Coussot et al., Phys. Rev. Lett. 88, 175501 (2002) ]

bubble rising in a liquid

Newtonian

non-Newtonian

Elasticity evidenced through "normal forces" depending on flow geometry

Weissenberg effect
or
"rod climbing effect

A gallery of non-Newtonian fluid motion

Viscosity depends on shear, on stress, on elongation, on time, etc.

mud over an inclined plane

[ Coussot et al., Phys. Rev. Lett. 88, 175501 (2002) ]

bubble rising in a liquid

Newtonian

non-Newtonian

Elasticity evidenced through "normal forces" depending on flow geometry

Weissenberg effect

polymer swelling
upon extrusion

elastic recoil "memory" effect

A gallery of non-Newtonian fluid motion

all-in-one: polyvinyl alcohol crosslinked with sodium tetraborate

Weissenberg effect
rod-climbing

Kaye effect
leaping shampoo

Borus effect
die swell

https://www.youtube.com/watch?v=nX6GxoiCneY

Rheology of soft matter

Part I. Basics of rheology
Part II. Advanced techniques in rheology

Part III. Current issues in the rheology of soft matter

Main reference books

- H. A. Barnes, J. F. Hutton, K. Walters, An Introduction to Rheology, Elsevier (1989)
- C. W. Macosko, Rheology, Principles, Measurements, and Applications, Wiley-VCH (1993)
- R. G. Larson, The Structure and Rheology of Complex Fluids, Oxford University Press (1999)
- J. N. Israelachvili, Intermolecular and Surface Forces, Academic Press (2011)
- R. A. L. Jones, Soft Condensed Matter, Oxford Univ. Press (2002)
- P. Oswald, Rheophysics: The Deformation and Flow of Matter, Cambridge Univ. Press (2009)
- R. Piazza, Soft Matter: The Stuff that Dreams are Made of, Springer (2011)
- J. Mewis, N. J. Wagner, Colloidal Suspension Rheology, Cambridge University Press (2012)
- R. B. Bird, R. C. Armstrong, O. Hassager, Dynamics of Polymeric Liquids, Wiley (1981)
- P. G. de Gennes, Scaling Concepts in Polymer Physics, Cornell University Press (1979)
- M. Doi, S. F. Edwards, The Theory of Polymer Dynamics, Clarendon Press (2001)
- J. D. Ferry, Viscoelastic Properties of Polymers, Wiley (1980)

Part I. Basics of rheology

I.1. Fundamental formulation from continuum mechanics
I.2. Linear viscoelasticity

I.3. Nonlinear viscoelasticity

I.4. Practical implementation: rheometry

I.5. Some examples

A short reminder from continuum mechanics

Stress tensor: such that

dS

isotropic material is symmetrical

M
Strain tensor:

A short reminder from continuum mechanics

Elastic solid:

Hookes law
Lam coefficients

Newtons law

Simple liquid:
shear viscosity

bulk viscosity

strain rate tensor

incompressibility
for rheology

incompressible Navier-Stokes
equation
negligible inertia

hydrostatic pressure

ideal liquid
(inviscid = 0)

liquids

linear viscous liquid

(Newtonian > 0)

rheology

nonlinear viscous liquid

elasticity

continuum mechanics

hydrodynamics

A second classification attempt

complex
fluids
soft
solids

solids

viscoelastic material

nonlinear elastic solid

"memory"

examples

water
alcohol
oils
dilute polymers
dilute suspension

surfactant
concentrated polymers
concentrated suspensions
plastics
natural rubber

linear elastic solid

(Hookean)

indeformable solid
(G = )

metals
minerals

Part I. Basics of rheology

I.1. Fundamental formulation from continuum mechanics

I.2. Linear viscoelasticity
I.3. Nonlinear viscoelasticity

I.4. Practical implementation: rheometry

I.5. Some examples

Linear viscoelasticity

Typical observation: "solid" at short time and "liquid" in the long run

Intuitive approach: elastic deformation + viscous flow

dominates at high frequencies

(t) =

low frequencies
(!) at
sin(!t)
+ G 00 (!) cos(!t)

Oscillating deformation at :
(t) =
G
! (rad/s)

linear response theory

0 sin(!t)

00
0.5
(!)
!sin(!t)
(t)=G 0(!)
G 0
(!)
+ G 00 (!) cos(!t)
in phase

in phase quadrature

elastic (or storage) modulus

(t) =

Rg3 1/

viscous (or loss) modulus

0 sin(!t)

a2 6
Pe =
=
D
D=

Rg
a

df

1( )

Rg3 1/

kB T
6

= s (1 +P2

loss angle:

I(q) q

a
kB T

( )

0 viscosity:
Gd00f (!) ! 0.5
complex
G
(!)

N M Rdf
! (rad/s)

=
d

2e
R3

Relaxation function

: elastic solid

Generalization :

: viscous fluid

G(t ) = relaxation modulus

with

or

- Memory function:

- Strain step at t = 0:

- Shear-rate step at t = 0 :

- Flow cessation:

Creep and recovery

Imposed stress (t):

J(t ) = creep compliance
- Stress step at t = 0:

unrecoverable strain
t

- Relationships between J(t ) and G(t ) :

The Maxwell model

Mechanical model: spring and dashpot in series

single characteristic time:

Viscoelastic moduli

G0 : elastic
modulus

G ()

G()

1 / : relaxation time
G ()

Cole-Cole representation

G0/2

G0/2

G()

Models derived from the Maxwell model

Ex.: "particles"

in a Newtonian solvent of viscosity

r = 0.05
Gp
G ()
solvent

G()

1 / p
r = 0.05
G ()

Jeffrey model

G()

Models derived from the Maxwell model

Generalized Maxwell model: n Maxwell elements (Gi, i ) in parallel

n characteristic times:
discrete distribution of relaxation times

and

Continuous distribution of relaxation times: H( )

: contribution of Maxwell elements with relaxation

times [ ; + d ] to the viscosity

then

Kelvin-Voigt model

Viscoelastic solid : "liquid" at short time and "solid" in the long run

Ex.: natural rubber
single characteristic time:

Viscoelastic moduli

G()

G0

G()
1/

Part I. Basics of rheology

I.1. Fundamental formulation from continuum mechanics

I.2. Linear viscoelasticity

I.3. Nonlinear viscoelasticity

I.4. Practical implementation: rheometry

I.5. Some examples

Validity of the linear approximation

Until now: linear response theory

linear

: only depends on time on frequency

viscoelasticity cannot explain non-Newtonian behaviours

But in general : the response depends on

viscous

- time frequency

- the deformation amplitude

- the deformation rate

nonlinear
viscoelasticity

elastic
solid

liquid

Newtonian

linear
viscoelasticity

Hookean

Validity of the linear approximation

concentrated emulsion

Influence of 0 at fixed

= 1 Hz

linear viscoelasticity

nonlinear
viscoelasticity
if

large-amplitude

oscillatory shear

(LAOS)

.

Influence of 0
polyethylene

linear viscoelasticity
+ (poise)

shear-rate step at t = 0

see Part II.4

nonlinear
viscoelasticity
if

t (s)

Simple shear flow

v0

solution of the equations

of motion in steady state

Assumption:

Shear rate:

y
z

+
elongation at 45

Rheological functions :

rotation
.

three components of are independent and function of

viscosity

1st normal stress difference

2nd normal stress difference

The constitutive relation

Flow curve

yield stress fluid

shear-thickening:
Newtonian: = cst

flow-microstructure
coupling

shear-thinnning:
.

linear regime:

generalized
Newtons law

Case of a nonlinear viscous liquid

steady state
+
homogeneous flow
flow stability

TABLE 1.7.1. I Equations of Motion*

Rectangular CoordiMtes (x, y, z)
x-Component

y-Component

z-Component

The continuity equation:

v . v = -av,+ - + av,,
-=o
ax

ay

avZ

az

Cylindrical Coordinates (r, 8, z)

r-Component

Elongational flow

Assumption:

solution of the equations

of motion in steady state

Elongation rate:

Stress tensor

difficult to implement in practice

Elongational viscosity

= 3 for a Newtonian fluid

Trouton ratio:
up to 104 in the non-Newtonian case

Elongational flow

Filament stretching

v(t )

constant elongation rate

View Article Online

Capillary breakup:

surface tension
2R (t )

ed on 05 October 2011. Downloaded by Bibliotheque Diderot de Lyon on 02/01/2015 23:34:52.

[ Hassager et al., TU Denmark ]

[ Erni et al., Soft Matter 7, 10889 (2011) ]

Capillary breakup of a reference silicone oil and corresponding fit to the similarity solution for capillary thinning of a viscous Newtonian fluid

Fig. 4
thread.31 Here the capillary thinning flow proceeds until the fluid filament breaks up; the extensional viscosity he 3h0 is constant with a value of three
times the shear viscosity. Due to the high viscosity even the recoil of the cusped threads after capillary breakup takes several seconds to complete. Data
from t 0.75 s to t 4.4 s were used for curve fitting. Time stamp for video images is indicated in seconds; 0.00 s is the time at which axial pre-stretching
ceases.

Droplet detachment

is derived from the kinematics of the thinning slender

filament.16,18,32
The quantitative description of the transient fluid dynamics
associated with the necking process for a complex fluid remains

polyacrylamide +
glycerol +
brine

a challenge for capillary thinning rheometry, even in the absence

of mass transfer.19 The time-evolution of the material functions
and of the kinematics, in particular the extension rate, has been
discussed elsewhere.17,19,23,34 Based on these previous

ADN
[ Wagner et al., PRL 64, 823 (2003) ]

Classical phenomenological models

Shear-thinning fluids

n = 1: Newtonian
power-law (Ostwald - de Waehle):

0 < n < 1: shear-thinning

not realistic for 0 or

characteristic time:

Carreau law:

CPCl-NaSal

Yield stress fluids:

Bingham law:
Casson law:
Herschel-Bulkley law:

Parameters strongly depend on T :

Most yield stress fluids are thixotropic:

[ Ponton et al., Coll. Surf. A 145, 37 (1998) ]

The upper convected Maxwell model

Generalization of the Maxwell model to large deformations

Maxwell model
integral formulation in terms of the Finger tensor

under simple shear

where

differential formulation

rheological functions

where
upper-convected derivative

qualitatively correct

but no shear-thinning

The Oldroyd-B model

Generalization of the Jeffrey model to large deformations

"particles"

solvent
with
"delay time"

rheological functions

still not shear-thinning

kinematic nonlinearities are not enough

add material nonlinearities

The Giesekus model

Oldroyd-B model with a quadratic term

shear-thinning for
increase of e for

correct behaviors for 1 and 2

Part I. Basics of rheology

I.1. Fundamental formulation from continuum mechanics

I.2. Linear viscoelasticity

I.3. Nonlinear viscoelasticity

I.4. Practical implementation: rheometry
I.5. Some examples

Practical implementation: rheometry

not

so easy to achieve experimentally due to edge effects, finite sample volume, etc.

Principle of a drag-flow rheometer

sample is confined between
a fixed wall and a rotating tool
torque sensor and measure
of the angular displacement
controlled-stress (30-70 k) or
controlled-strain (150-300 k) rheometer

TA Instruments
AR G2

Malvern
Bohlin CVOR
Anton Paar
MCR 301

Practical implementation: rheometry

proportionality coefficients depend on the geometry

stress-controlled
TA Instruments DHR

strain-controlled
TA Instruments ARES G2

Stress-controlled rheometer

optical encoder for

displacement measurement

The next generation of strain measurements

Optical Encoder Dual-Reader

All DHR systems feature optical encoders for high resolution displacement measurements.

normal force
transducer

The HR-3 features a patent-pending optical encoder with dual reader. This new
technology provides ultra high displacement resolution of two nanoradians, reduces
noise, and enhances phase angle measurements. The benefit is better data and higher
sensitivity when running challenging materials over a broad range of conditions, or even
extreme conditions.

magnetic bearing to
reduce frictional torques
drag-cup motor

requires to correct

for system inertia

vertical position sensor

to ensure gap width and
compensate thermal effects

DISCOVER
radialPOWERFUL
air bearings for high
NEW
INNOVATIONS
stiffness
and low friction
4

[ from TA Instruments DHR product brochure ]

ARES-G2 TECHNOLOGY

Strain-controlled
Only ARES-G2 provides independent
measurements of stressrheometer

and strain rate
When it comes to making the most accurate rheological measurements, two heads are simply better than one! Consider that the rheological behavior of materials is
described by material functions such as the modulus or viscosity. Modulus is the ratio of stress to strain and viscosity is the ratio of stress to strain rate. In order for a
rheometer to make the purest and most accurate rheological measurements, it is best to measure the fundamental parameters of stress and strain or strain rate
separate motor and transducer technology independent strain and stress measurements

independently. The ARES-G2 provides rheological measurements free of instrument artifacts over wide ranges of stress, strain, and frequency.

Motor

Transducer

Lower Geometry Mount

Force Rebalance and

Magnetic Suspension
Non-Contact Temperature
Sensor Electronics

Thrust Air Bearing

Radial Air Bearing

Torque Rebalance Motor

Torque/Normal Force
Rebalance Electronics

Brushless DC Motor

Radial Air Bearing

Optical Encoder
Non-Contact
Temperature Sensor
Electronics

Upper Geometry Mount

[ from TA Instruments ARES G2 product brochure ]

Standard accessories

solvent trap to
minimize evaporation

lots of geometries

Peltier plate for temperature

control of bottom plate

double wall ring

for interfacial rheology

Cone-and-plate geometry

e 1 mm

0 = 2
R = 25 mm

and

advantages

drawbacks

- homogeneous deformation

- cone positioning

- gives access to high viscosities

- evaporation

- normal force N1 measurement

- meniscus surface tension

Spherical Coordinates (r, 9 , d )

r-Component

9-Component

&Component

The continuity equation:

* r has not been assumed symmetric.

r
Parallel plate geometry

(r ) =
e

e 1 mm

R = 25 mm

R
e

2 (r ) = r
=
e
R3
r
R
6
(r
)
=
3 = 8
sedim =
10 10 es
g` e

2e
R3

(r ) =

r
e

R
2
=`2
=
8
momentum = e 10 10 10
R3 s
R

=
e
2
6
advantages

=sedim 3=
drawbacks

103 108 s
5 R
1/2 g`
2
`
- non-uniform
strain
field
9
6
- easy to vary the gap width
=
=

10
10
s

inertia
2
R3
6
kB T 3 - evaporation
`
8
10
8
- gives access to high viscosities
sedim = momentum
10 =
10 s 10

10 s
g`

6
surface
tension 3
- normal force (N2-N1) measurement
6`3 - meniscus

=
10 108 s
sedim
5
2
viscous `
=2

10 10
s < g`
10
8
k
T
momentum =
B10
510
1/2 s

`
9
`62 s 10

10
10
= 0.1 s 1inertia =
kB T momentum = 10 10
5 1/2
`
9 3 6
inertia =
106`
10 s 5 2
10 10 5 s 1/2
<
kB Tviscous =

The continuity equation:

v . v = -av,+ - + av,,
-=o
ax

ay

avZ

az

Cylindrical Coordinates (r, 8, z)

r-Component

-Component

z-Component

The continuity equation:

i a
V.v=--(rv,)+-r ar

1 ave av,
+-=O
r ae
az

Couette geometry: concentric cylinders

,

R1 = 24 mm

h = 30 mm

R2

v0
r
e = 1 mm

advantages

drawbacks

- gives access to low viscosities

- non-uniform if e / R1 > 0.15

- good for high shear rates

- requires large volumes

- limited evaporation

- edge effects Mooney-Couette

Vane geometry

?
plug

advantages

drawbacks

- designed for yield stress fluids

- non-uniform deformation field

- works with large particles

- secondary flows between vanes

- prevents wall slip

- difficult to model the flow

Vane geometry

FLOWS AND HETEROGENEITIES WITH A VANE TOOL

streamlines visualization in glycerin

particle migration under shear (MRI)

[ Baravian, Appl. Rheol. 12, 81 (2002) ]

[ Ovarlez, J. Rheol. 55, 197 (2011) ]

advantages

drawbacks

- designed for yield stress fluids

- non-uniform deformation field

- works with large particles

- secondary flows between vanes

- prevents wall slip

215

- difficult to model the flow

FIG. 11. 2D magnetic resonance image of a suspension of particles in a yield stress fluid in a vane-in-cup
geometry: !a" after a 1 h shear at ! = 100 rpm !corresponding to a macroscopic strain of order 75 000" and !b"
before any shear. The crosses in !a" correspond to the limit between rigid motion and shear for the Newtonian
oil of !b". The white rectangle in !b" shows the slice in which the volume fraction profiles of Figs. 10!a" and 12
are measured. !c" is a zoom of image !a" near the edges of a blade. The images are taken in the horizontal plane
of the geometry, at middle height of the vane tool, and correspond to vertical averages over 2 cm. The vane tool
rotates counterclockwise.

Part I. Basics of rheology

I.1. Fundamental formulation from continuum mechanics

I.2. Linear viscoelasticity

I.3. Nonlinear viscoelasticity

I.4. Practical implementation: rheometry

I.5. Some examples

Polymer rheology

Colloidal suspensions

Modeling of polymer molecules

Microscopic model

- Edwards model: Gaussian chain

- equilibrium properties:

elastic

v > 0 : repulsive (excluded volume or good solvent)

v < 0 : attractive (bad solvent)

- ideal chain (v = 0) vs chain with interactions

- radius of gyration:
- dilute solution vs semidilute solution vs polymer melt

Rouse model:

continuous version:

polymer melt with short chains (screened interactions)

Modeling of polymer molecules

Normal modes:
Brownian particle with

Brownian particles in a harmonic potential

In a homogeneous flow:

Maxwell fluid with discrete relaxation times

3.1. T i m e d e p e n d e n c e

For simple shear flow the weil known relations

for the shear stress Pa 2 and the primary normalstress difference Ps I - P22

Polymer linear rheology

~3

p12(t) = ~ fl(t -- t') 7t,,' d(t - t ' ) ,

[3]

Laun, Description of the non-linear shear behaviour of a low density polyethylene melt

superposition of Maxwell models

105

, i , , , u

, , , , , u

, , , , , u

, i , , , , i

, i , , , u

, t , , , u

,i

oo 3

[Ps l - Pzz] (t) = ~ fl(t - t') 72 d(t - t')

0

....

low-density polyethylene melt

G
106

tO~
E

[4]

To each relaxation time z~ a relaxation stre

fli = a~.z~ is attributed. Figure 1 shows m
urements of G'(o) and ~"(co) performed
Z o s e l (10). The moduli measured at diffe
temperatures are plotted as functions of
reduced angular frequency arco to get toa
curves at a reference temperature of To = 15
(11), aT being the shift factor. For the approx
tion of the memory function eight relaxa
times z~ between 1 0 - 4 S and 103 s with dec

102

o~

o~
10~

105

E I0 4

tO1

~
1C
I0 -3

10.2

10-1

100

101

102

103

103

104

o~
1061

,i,,,,,

,i,,,,~

,c,,,u

, i , , , u

, l , , , u

' l ' ' " l

'

'

l51
E

' l ' ' " J

lO~

101
10-3

10-2

10 4 '

o~

100
101
102
angular frequency a T t.u ES-1.7

103

104

[ Laun,
17,of1 the
(1978)
] angular ffequency. Reference temperature
Fig. 1. Shear moduli of
LDPE Rheol.
Melt I asActa
functions
reduced
150C. The full lines were calculated according to [6] and [7] using the constants of table 1

//s

! oI

Maxwell model with discrete relaxation times

provides good modelling of viscoelastic moduli

102

101|
10-3

10- I
reduced

10-2

10-I

100

tO1

102

lO3

104

angular frequency cogs-1]

Fig, 2. Frequency dependence of the shear moduli at T = 150C as represented by a sum of eight terms with
decimal spacing of the time constants ~. The contribution of the term with z~ = 103 s is not seen in the diagramm

Polymer linear rheology

short PS melt
[ Gray et al. (1977) ]

0.5?
1

1
2

Zimm model account for hydrodynamic

interactions in dilute solutions
: Maxwell with relaxation time 1
:

0.5 ?

Doi-Edwards model
for semidilute solutions and long polymer melts
account for chain entanglement
reptation model

quisition system.
calculated curve, is practically the same for
and t~l. The strain at departure, 7a = )ra, is
6.2. Relaxation of stress from stead
virtually independent
of
shear
rate.
At
interPolymer nonlinear rheology

mediate and long times the data agree with reRelaxation of the stress com
sults reported earlier (2). The time to peak for t~l steady state when the flow is stop
polybutadiene in a hydrocarbon oil
=.0214

sec -=

linear viscoelasticity
prediction

;,,

~ - - . . . ~ -'----- ~.36

<g---

shear-thinning

(.9
0
J

stress overshoot

/

/
r
-5

I
-2

I
-I

I
0

I
I

I
2

I
3

LOG T I M E (SEC)

[ Menezes & Graessley, Rheol. Acta 19, 38 (1980) ]

Fig. 9. Stress growth da

stress growth function ~
are experimental data a
indicated and dashed lin
FLV prediction

this is only true for t z~..... z~. . . . being the

longest relaxation time of the memory function
) ( t - t'), whereas at high shear rates even for
t z~. . . . a steady-state is reached if for the
magnitude of shear % t >> 1/n is valid.
The viscosity function r/~(~)0)and the primary
normal-stress function Os(To) as calculated according to eqs. [27] and [28] are compared

and Os are predicted by means of a memory

function which has been determined by measuring quite different quantities, namely the frequency dependenc e of the complex shear
modulus G*(co) and the strain dependence of
the shear relaxation modulus G(t; ~o). In order
to compute the viscosity function for a wide
range of shear rates it is necessary according to

Polymer nonlinear rheology

low-density polyethylene melt

,o z

I0 ?

( )

in

10 6

10 6

1( )

normal forces

~k 10 5

~s

7Is

~,
.~

ie

o
m
zx
0

)
1 ( 130
I 50
170
t90
210

2e
R3

[ Laun, Rheol. Acta 17, 1 (1978) ]

,o;~

r
(r
)
=
Io-3
~o-2
e

Io-I

Im

103 ~
b

tO 2

fO 1

7o I

~c;

" ~3

" io~

reduced shear r a t e a T ~o E s - l ]

K-BKZ

lO g

"6

R
e

2
R3
i0o

la

shear-thinning

r
(r ) =
e

T EC J
115

10 3 - _ _
:

10 5 ~

2e
=
R3

( )

to ~

sedim
=
10 sviscosity
(12) and steady-state primary normal
Fig. 7. Temperature invariant
representation
ofthe10
steady-state
R
g`
stress coefficient as functions
of the reduced shear rate. Reference temperature To = 150C. The viscosities at
=
high
shear
rates
were
obtained
by
a capillary rheometer.
The tic denotes measurements
with a modified
geomee
approach
provides good predictions
for
shear-thinning
and
normal
stress gap
differences

try similar to that used in (23). (
) prediction
of
[27]
and
[28]
using
the
experimentally
determined
damping
2
`single
function. (- - -) calculated by means of the
exponential
10 damping
8 function
momentum
=
10
2

10

Surfactant wormlike micelles as model Maxwell fluids

Reptation-reaction model

[ Cates, Macromolecules 20, 2289 (1987) ]

CPCl-NaSal

-1
2

[ Rehage & Hoffmann, J. Phys. Chem. 92, 4712 (1988) ]

2 relaxation mechanisms

reptation:
reversible scission:

Surfactant wormlike micelles as model Jeffrey fluids

EHUC NH4Cl

[ Yesilata et al., JNNFM 133, 73 (2006) ]

r = 0.05

r = 0.05

G ()

G()

solvent
G ()

Gp

1 / p

G()

Part I. Basics of rheology

I.1. Fundamental formulation from continuum mechanics

I.2. Linear viscoelasticity

I.3. Nonlinear viscoelasticity

I.4. Practical implementation: rheometry

I.5. Some examples

Polymer rheology

Colloidal suspensions

Colloids as big atoms

particles of radius a 20-200 nm with 3 basic interactions:

steric repulsion vs electrostatic repulsion vs van der Waal attraction

model systems to study basic physics with direct microscopic visualization

spherical colloids

non-spherical colloids

[ Bechinger et al. ]
[ van Blaaderen et al. ]

play with interactions, volume fraction, shape, chirality, patchiness, etc.

Electrostatic interactions

salt
concentration
wiikipedia.org

screening

of the electrostatic repulsion

Colloidal (in)stability

steric repulsion vs electrostatic repulsion vs van der Waal attraction

[ Malescio, Nat. Mater. 2, 501 (2003) ]

DLVO theory: Derjaguin & Landau (1941),Verwey & Overbeek (1948)

Colloidal (in)stability

force

barrier

[ Israelachvili (2011) ]

diffusion-limited

or reaction-limited particle aggregation

Colloidal (in)stability

cluster formation

wiikipedia.org

diffusion-limited

or reaction-limited cluster aggregation

fractal dimension df

ramified clusters
df ~ 1.8

compact clusters
df ~ 2.3

Brownian hard spheres

a2
6s a3
Pe =
=
D
kB T

steric repulsion + hydrodynamic interactions + Brownian motion

D =

kB T
6s a

Dilute suspensions are Newtonian and follow Einsteins law:

= s=(1+
2.5
) )
+ 2.5
s (1
Concentrated suspensions: hydrodynamic interactions more complicated beahviour

( )( )

In practice: optical index matching + polymer grafting

1 ( )1 ( )
[ Pusey et al. ]

2e
= =3 2e
R R
3
r r
(r ) =
(r )e=
e

R
= = R
e e
2
= =3 2
R R3

glassy states

crystal

66 3
8
liquid +crystal
=
1010
s 8 s
sedim
sedimg`
=liquid
103 10
g`

Rheology of Brownian hard spheres

r =

Effect of shear reduced viscosity r =

vs reduced stress

s

I:ig. 10. Relat&vc viscosities

particle sizer of crossfinked

26

22

spheres.

kB T k T
a2
6s a3
B
D
=
P
e
=
=
D
=
6s a6s a
limiting low-shear
D
kPS
B Tspheres at = 0.5
viscosity r,0

kB0T 8 Z Ol -i
D=
6ls am-CFESOL

20-

a = 77 nm

= s(1
=+s2.5
(1 +) 2.5 )
a = 110 nm
a = 108-180 nm

( ) ( )

= s (1 + 2.5 )

7, IS -

shear-thinning

16 -

(0
QOI

3
a3
= r= a
kB T k T
B

2 s 6
a2 6
a3 s a3
a3
a
P e = P e ==
r =
foror
=T different
Pclet number

stress
in D
m-cresol of
kB T50%vs monodispersions
D kBfour
kB T

vs. shear
polystyrene

12 -

=
sr
s

1( ) 1( )

( )

[ Krieger, Adv. Colloid Interface Sci. 13,( 111

) (1972) ]
*
003

Fig. 11. Relative

various sizer in
Fig. 7.

I
at0

0.30

1
LO

f
30

2e r
= shear3 stress fog 50%
viscosities
vs. reduced
R
different
media. Points are taken from Pigk
shear

rr

limiting high-shear
viscosity
r,
2e
2e
= =
R3 R3
I
a0

t
3QO

r
(r ) = (r ) = r
e p o l y s t yer e n e
monodispersions of
9 and

10; solid iine from

spheres o f
aqueous data of

disrupts the equilibrium microstructure

R
R
r
=
(r ) =

e = e

indicated that
.... 10the system did not change during the eight
b
months over which measurements were made. That the optilaD"-33'C
smaller
than the Stokes-Einstein or hycal radius is slightly
-W'C

Rheology of Brownian hard spheres

-W'C

O.5"C

10-1

r,0 r,1
1 + ( / c )m
C. Specific viscosity and
speCific
volume
r,1
r,0
r =viscosity
r,1 + is defined

mr,1
The intrinsic
+ ( r,0/ c )as
r = r,11+
1 + ( / c )m
lim (1]r - 1)/ = [1]] .
4>-..D
( / c )m m
( / c)

.+
3
silica spheres=a = 78
nm

3
1
+

160
e
+
1a
+
e =
in cyclohexane
a

10 spheres:
10 All measure103 2
TABLE I. Optical and hydrodynamic10
radii of silica
w/rads'
ments at 25 C.
(a)
r = 1
0

-dependence
of r: two popularmax
relations

lOS

Optical Optical
Hydrodynamic

b
radius'
radius
c
radiusc
3)
104 '
(g cm-Krieger-Dougherty
(nm)
(nm)
r(nm)
= 1

-SI'C

-44C

-33'C

Date

.. max
.

..
.= a.s'c

2.5 max

(13)

120

r,0 :
max = 0.63

:
r,0
max = 0.63
-W'C 2, 1984
78.8
0.0507
75.4
73.7
Jan.
F
ine
r,1 :
max = 0.71
0.0299
78.1
75.9
77.2
c
+
r,1 :
80
b80.2
r
2
max = 0.71
0.0254
79.0

t
s
77.6
0.0199
79.1

2
102 Qumada

=
1
r79.4
0.0147
77.1
76.0

2
max
r = 1
a3
40

.0
78.3
77.5
0.0102

=
1
=
max
r
0
r

0.0049
77.9
77.5
81.0
101
k T2.510 3max
max
10- 2
10-1
101
laD
102B
....
0.0010
74.5
Viscoelasticity

= 0.1
/rad s1
.,
1
....
+-"''''_'''II'.*'2.5 2.5max max
r =
w76.6
0.0280 (bl69.5
68.6
Feb. 14, 1984 3
2
=
r = 1
amaxFeb.6
s a
0.0149 105
14, 1984
75.2
r.2= 1.3max .4
P
e=
=
0
.1
.6
0.005
1984
77.2
<II .5
silica spheres a = 60
nm D Sep. 8,
max
kB T
r =

4 at = 0.37
10
ks T
[ de ofrelative
Kruif et al.,
J.Chern.
Phys.
83, 4717
(1985)
FIG. 6. Plot
viscosity
fraction
at T =] 293.15 K .
volume
r =against
Static light scattering at A = 546 nm.
B

=
s
r 'Tfr = (I The dotted lines represent equation
with
= 0.63
bStatic light scattering at A = 436 nm.
D= 3
s
Dynamic light
scattering
at
A
=
488
nm.
6
a
and 0.71.
09
a s
3
110
viscosity diverges
a3 3 at max

=
liquid-like

-0
r
G"
",,p
G
......
a
r =
kChern.
"
.
B T Phys.,
b
k
T
J.
Vol.
83,
No.9,
1
November
1985
=
B
r
= s (1 + 2.5 )
kB T
!3 102
This article is copyrighted
as indicated in the article. Reuse
of AIP content
is subject to the terms at: http://scitation.aip.org/termsconditions.
Downloaded to IP:
2
3

a
6

a
2
3
s
b
glass
transition
III.3)

a 2 6(see
18.111.109.226
On: Mon, 29 Dec 2014
16:47:58
s a Part
P e ()tJ
=
=
3
P
e
=
=

a
6

a
s
D
1']0 co a,.
(1 {) "
G' ( )kB T
D
Pe =
= kB T
101
D
kB T
kB T
o@
kB T
D
=
--I .. ",,!,

relaxation
through
Brownian
motion

D
=
kB T
2 ( a
)
10
6
101
106
1 s )103
D
=
sa
/rad S-1
6s a
(c)
implies viscoelasticity

-20'C

..

{i!

= (1 +2e
2.5 )
=
t six different temperatures from 0.5 to - 51 'c. The closed symbols for the
R3 lowest
two temperatures depict
esults obtained with a small cone-plate fixture. (c) The Master curve of G' and G" as functions of
after

FIG. 1. The dynamic storage modulus

0'&(a)
and the loss
modulus
0"601
(b) as
functions
[ Shikata
Pearson,
J. Rheol.
(1985)
] of frequency (J) for the
s38,
uspension of STI in a mixture of ethylene glycol and glycerol at volume fraction, = 0.37. Data are shown
waT

= s (1 + 2.5 )
= s (1 + 2.5 )

0.417
0.447
0.486

Rheology of

Pe =

a2
D

D=

0.542
0.579
0.626

1932
1966
2017

2303
2416
1882

[Leesurprisingly,
& Wagner,that
Ind.theEng.
Chem.
Res. size
45, 7015
(2006) ]
indicates, not
effective
particle
is
greater than the hydrodynamic size due to repulsive electrostatic
interactions.
Using an approach successfully applied for similar particles,5,36 we fit the data to eq 5 by using an effective particle

a3
kB T

3.9
3.8
3.7

the effective particle radius aeff due to the electrostatic repulsive

forces.
(b) For 446 nm Silica Particle
0.30
5.8
55.5
0.39
31
We0.35compare
our experimental
results 32.5
obtained from the
6.1
53.2
0.45
32
53.2
stable
colloidal
0.40
50.7suspensions

0.51
rolling
ball6.4
viscometer
with dilute 33
limiting54.4
predictions for the
0.44
6.7
48.5
0.56
35
55.6
0.51
7.3
44.3 in Figure
0.63
38 relative
90.9 viscosity exceeds
zero shear
viscosity
8a. The
0.55
7.8
41.7
0.68
41
92.9
0.58
8.2
39.6
0.70
62.6 eq 3 to the data,
predictions
for hard
spheres.
The 43
best fit of

charge-stabilized silica spheres a = 32 nm

r =

6.0
6.1
6.3

a3

6s
kB T

kB T
6s a

r r,1
1
=
r,0 r,1
1+( /
r = r,1 +

c)

r,0
r,1
Cross
model
1 + ( / c )m

Figure 10. Critical shear stress for shear thickening as a function of volume
fraction for 32 and 446 nmmparticle dispersions.

( / c)
sedim =

m
2
3
of (a) the particle
( / `
)
Figure 9. Relative zero shear viscosity as a function
c
= particle1 +
volume fraction and (b) e
effective
volume fraction for 32 nm

=
10 10 10 8 s
momentum
nanoparticle dispersion.
a
for 32 nm nanoparticle
( )
Figure 7. Mastercurve
of
the
3 viscosity curve

= reduced
1 + stress in eq 2 (solid line). 3
dispersione
using
or the relation35
momentum
1+
a
e =
a
1( )
0 max = 0.63

-2.0
1/2
r0 )
) (1 - /m)
(5)
`5 are defined
9
m spheres
similar to hard
provided
effective
size
and
volume
fraction
6

10
10
s
2e
max = 0.63inertia =
=
0.71
max
=
0.63
max
=
k
T
B
R3where
m is the maximum packing fraction (typically on the

order of 0.58-0.64 for hard spheres). Here, we use m ) 0.58,

=
=
0.71
inertia
max
max = 0.71
which
corresponds to the
colloidal glass transition
2 for hard
k
r
3
(r ) =

= s (1 + 2.5 )

spheres.

,2o

,3,o, ~,~ ~o~,o ~,~ ,o

N M R

M, (0

NaC1 concentration asdthe

independent variI(q) q f of sizes. Electronic part
distribution
able (Fig. 12) indicate a slight initial weakening vs s
counting
could
not be employed
to determ
FIG. 13. Determination of fractal dimensionality
of thefrom
floc due
to added
electrolyte,
followed
~< 1
the
distribution
of
floc
sizes
because
such

1
light
scattering,
unsheared
(#3'
~<
10
dyn/cm
2)
flocs.
((3,
r
r,1
by379a significant strengthening
at higher con- resp
F L O C B R E A K U P . II. T H E O R Y
[3) Flocculated in water at 0.4 M, (A, 0, V) flocculated
in vices=
m as large as 5000 d
generate
stresses

1
+
(
/
)
r,0
r,1
c
centrations.
A si
(Rg/a) 3 = 5.25 106(//,3') -1"06 55.2%
[2] glycerol at 0.4 M.
p ( r ) 1 if r is within a particle
cm
2
at
the
orifice
when configured to meas
C-bC
of sheared flocs. at U
r,0particles.
r,1
(=
~
L
~
~
= 0 if r is within fluid (c) Fractal dimensionality
gold colloids
df Stresses of this magnit
1- to 3-1zm
for 17.5 < tz~, < 60N/m 2. Here u is the viscosity
R
=sheared
dr,1
+ at ~z-y
g > 150 mdyn-cm -2 were
The flocs
of-2
a = 15 nmof the suspending fluid and 3' is the shear rate.
f
Ntoo
small
M r toRwould
rupture
1
+ ( / even
c ) the strongest flocs. Th
exhibit thea power-law dependence dyn
A comparison of the two results shows that
6. DISCUSSION
fore, the light
scattering results must be in
of scattering intensitym on wavenumber deN = 0.455(Rg/a) z48.
[3]
(d
solely
on knowledge of the nature
(
/
)
Small-angle light scattering from a suspen- preted
c
scribed by [10]
at
angles
less than in
10 the
, soRayleigh-Ga
sev- The
The exponent of [3] characterizes the indf
the
averages
embodied
sion
of
flocs
provides
mean
values
of
the
floc
I(q)

q
terior structure of the floc. For a uniform inq~( r ) is determined by integratingeral
p ( r ) similar samples were sheared less severely
from
7. 3
size
about the Debye-5theor
ternal porosity independent of floc size,
theand mass, with noalonginformation
this spherical surface area.
PS
spheres
a
=
70
nm
at

=
10
in
glycerol
and then observed.
A logarithmic plot of/tot(0) form
exponent would be 3. Structures for which the
e =Due 1to+their weighting of the larger si
FIG. 1. Definitionof the averagelocal volumefraction.
a (1986)
exponent is less than the dimension of space
[ Sonntag & Russel,
Interf.
113, 1
399
]
df theSci.
r J.RColl.

massand
z-averages
indicate, to hyd
ag
r,1
are often referred to as fractals. Other defini- rupture location. Differentiation
g
=
d
of
[5]
then
f
mos
m maximum floc mass
the
r,0 r,1 approximation,
tions, or other indications, of the fractal di- yields 4O N M R
1 + ( =/ 0.63
c)
a

:
laps
mensionality of an object exist as well (3, 4).
light scattering

r,0size
o
inmax
the suspension. Therefore, we comp
ddNf / dfrom
R = 3R2~(R)/a
3.
[6]
For example, for hr ~> 1 the light scattering
those
values
directly
to N, the numberonto
of
However,
r,0
r,1
intensity should follow I oc h -D with h = (4~-/

:
=
0.71
2 o ~ 'for
\ , \a floc with fractal dimension
r,1
max
3
d
square of thestre
f= r,1 +
oglet particles,
o R
X)sin[0/2], with 0 the scattering angle and X D
and
2, the
rad
gmR 1/
I(q) q r [7]
N = No(R/a) D
1
+
(
/
)
the wavelength of the incident radiation. Inc
ofgyration, predicted
by Adler and Mills
12
deed this measurement leads to D = 2.5 for and
2
I0
"o,\\'~
[ Weitz & Oliveria,
PRL 52,
] with the
a single uniformly porous
d N / d R = (NoD/aD)R D-l.
[8]
the sheared
flocs 1433
(1), in (1984)
agreement
spherical
df floc

=
1
r
m
r,1 is reached
1 ( the
value from [3]. Here we consider the impli- Equating [6]
Rof
r an
suspension
F
g such flocs.3O0O
/monodisperse
) Mmax
and
[8] angle
determines
the local voldf
ctangential
when
for which
grav=
N

E
cations of a value of D less than 3 on the floc umez fraction,
6
::k
m
floc
Ra
with constant in
oof radius
r,0 force
r,1per unit
1+
( at
/ the
itational
area
of the
iso
breakup process.
c ) bottom
spherical
pile
2.5 max
Th
~(r) = ~,o(r/a) D-3
[91
A floc is a porous cluster of particles with a
=- 2
. 0 6= [3/5]R 2.
2000
larger
than the yield stress,
gh
sin nal
theRg3 with Rg
y , with
> porosity
N3 oc

1
vr =
number density o(r) of unity within a particle
(N)

the volume
fraction of dsolids within the f
with ~oo =density
NOD/3. Since
the material,
removalof
of the
g ther,1
gravitational
acceleration
r,0mass
max
and zero in the fluid. Defining a spherically does not2affect
=
1
+
e
I(q)
q f
the
local
volume
fraction
within
hr =
height
r,1 +of the depositedm material.
~int, is a
symmetric local volume fraction ~p(r) by
and
the
In
reality,
I000
the floc, [9] applies to 0 < r ~< R. 1 + ( / c )
( P i n t ---~ (3/5)3/2N(a/Rg) 3.
however,
inclined
plane
tests
reveal
For such
a floc, the
radius of
gyration
is on a clay suspension
o
r =
~p(r) = ( l /A) fA p(r)dA,
[41 related to the actual radius through

s
that for a given pile height
there is a critical
slope
above
r,1
Therresults
of
Figs. 9 and1 10 produce f0
2
3 4 5 6 8
I0 m
:
=
0.63
r,0
max
sedim16
(
/
)
R2g
:
[D/(D
+
2)]R
2
[
10l
=400
I
I
n
I
I
I
I
I
11
I
c
which the sample starts
flowing, and[20]
once
it does,
the
with r defined with respect to the center of
26ointernal
3~ofloc
' 1 +' (6010
volume
fractions
m (Fig.
0.4
1.0
2.0

/
)
r,1
c
mass and A the area of the spherical shell at which, upon
s [ dyne/cm2]
P'mox
substitution
intoto [3]
with D in viscosityr,0
thixotropy
leads
a decrease
which
accelerh [~m-']
-1
which increase only slightlyFIG
w
r,1 : 0.037-0.050
= 0.71
radius r (Fig. 1), permits the total number of = 2.48, leads to q (m )
max
ates
the
flow,
since
fixing
the
slope
corresponds
to
fixing

rate.
particles in the floc to be expressed as
PIG. from
10.
of shear
stress on floc size,
3 Effectshear
at sev
r,0low electrolyte
r,1

FIG. 14. Determination

of fractal
dimensionality
= 0.218(R/a)
2"48.
[11]
the Nstress
(Coussot
et
al.,
2002a).
This
in
turn
leads

+
The
variation
of
floc
size
with
electro
concentration.
~Psh~
=
(O)
0.5
X
10
-5,
(I-1)
1.0
X
10
-5.
=
1
+

dictio
r= /r,1
momentum
light[51scattering, flocs sheared
in 55.2% disrupts
glycerol. #~ =the
(O) floc
e
shear
m
decrease
rstructure

sand
N = (3/47ra
3)
47rr2~o(r)dr.

1
+
(
/
)
Then from
[9]
and
[5] more pronounced
a
[ Bonn & Denn, Science
324, 1401
(2009) ] 90 dyn/em
to
an
even
viscosity
so
c
2
2, ([3) 200 dyn/cm 2.
concentration (Fig. 11) can be rationalized
FIG. 8 A colloidal gel (A) at rest, with a percolated structure
Jo
~p(r)
= O.
181 (r/a) -'52.results,[ 121
on.
An
avalanche
which
transports
the fluid over
r1986= 1
We make two assumptions concerning
the of Colloid and Interface Science, Vol. 113, No. 2, October
Journal
and a yield stressflocofstructure.
5 Pa, First,
and the
(B)short-range
just aftervan
flow,
with
3
large distances.
By ~<
contrast,
stress
der
a (fluid
max
The experiments
detected 5960
(Rg/a) 3 a simple yield
/ )m
0.4

1.0

h [~,'n"]

2.0

Fractal colloidal flocs

SLOPI]-I
i~

Routes to gelation

J. Phys.: Condens. Matter 19 (2007) 323101

Topical Review

J. Phys.:
Matter 19, transition
323101 (2007)
]
Figure [2.Zaccarelli,
Schematic
pictureCondens.
of the percolation
in physical
gels, where the formation of a
transient network does not have any implication for gelation.

soft

solids even at very low volume fractions

information, it is still possible to locate the line in the phase diagram where a spanning transient
cluster first appears, which plays the role of percolation transition locus. Analysis of the cluster

Routes to gelation

J. Phys.: Condens. Matter 19 (2007) 323101

Topical Review

glass transition

(see Part III.3)

[ Zaccarelli, J. Phys.: Condens. Matter 19, 323101 (2007) ]

Figure 3. Schematic picture of the interrupted phase separation or arrested spinodal scenario. A
quench into the two-phase region may lead to an arrest of the denser phase. It is not yet clear how
the glass linebetween
continues thermodynamics
within the spinodal and
region.
The figure
shows dynamics
the case where
competition
kinetics:
arrested

the density
fluctuations freeze before they reach the final spinodal value, a scenario that is supported by a study
on lysozyme [67]. Alternatively, the glass line might merge with the spinodal on the high density
branch.

sol

gel

max

1457

max

sol

gel

FIG. 1. Phase diagram of CJRS5 octadecyl silica particles (2a 5 1006 5 nm) suspended in decalin. For
temperatures above the solid line, the suspension is a fluid with a measurable, zero shear rate viscosity and
unmeasurable elasticity. Below the solid line, the zero shear rate viscosity is not measurable and the suspensions
are elastic. A space filling gel can be reached at volume fractions as low as 0.10, below this volume fraction
particle associations cause the network to settle.

with the onset of the glass transition where the creep behavior is characterized by a
stretched exponential relaxation behavior. The gel line depends weakly on shear history
@Rueb and Zukoski ~1997!#. However all measurements reported here were made on
samples which had thermally equilibrated after experiencing a hard shear at the required
temperature. Small angle neutron scattering in the velocityvorticity plane indicated no
substantial anisotropies in dense sheared gelled suspensions @Rueb and Zukoski ~1997!#.
From Fig. 1, we extract a gel volume fraction f G at each temperature studied and a gel
temperature T G for a given volume fraction.
At elevated temperatures (T . 10 C), the density dependence of the relative viscosity follows the predictions made for the hard spheres of Eq. ~1! ~Fig. 2!. Using volume
fractions up to 0.06 with the 25 C data, the intrinsic viscosity has a value of 2.560.2
while the Huggins coefficient is 7.962. Note that volume fractions used in Fig. 2 are
those determined from mass fraction using the gravimetrically determined particle density indicating that q 5 1/r . This result is surprising as the particles used in this study
are similar to those of de Kruif et al. ~1985!, van der Werf and de Kruif ~1989! and
Verduin and Dhont where r 5 1.44 g cm is reported in contrast to the value of 1.89
g/cm3 found here. Note that a best fit through our data using r 5 1.89 g/cm3 yields the
Einstein value of @h#. Thus while we cannot explain why our values of r and those
reported earlier are different, in this system the gravametrically and hydrodynamically

floc suspension

FIG. 10. Gel point determination for CJRS3 (2a 5 125 nm) (T G 5 7.5 C). This plot shows the rapid change
[ Rueb & Zukoski, J. Rheol. 41, 197 (1998) ]
in h 0 with temperature. The shear test is a destructive test so a second method of determining T G is from a plot
of G 8 vs T2T G which shows the appearance of an elasticity at T G .
FIG. 9. Relative viscosity vs applied stress for CJRS5 ~2a 5 100 nm, f 5 0.517, T G 5 5.6 C! at several
temperatures. As the temperature is reduced to 6 C, attractive interactions cause the low shear viscosity to
diverge and the sample becomes strongly shear thinning.
coefficient assuming D/2a 5 0.1!. h 0 doubles
of 1 3kT ~estimated from the Huggins

upon gelation: build up of elastic modulus and yield stress

2.5 max

2
1465

kB T

D=
r = 1 6s a

a = 50 nm

r,0 :

r = /s

WEAKLY ATTRACTIVE PARTICLES

r =
s

( max
/ c )m

WEAKLY ATTRACTIVE PARTICLES

a2
6s a3
P e== 1=
r D
kB T

a3
r,1 r: = max = 0.71
kB T

= 0.63

3
1+
a

yield stress

r = 1

r,0
max

r = 1

2.5 max

r,1
r = r,1 +
1+ ( / c )m

r,0

max

df
I(q)

q
:
= 0.63

silica spheres
in decalin

:
max = 0.711
rr,1r,1
=
r,0 r,1
1 +( /

c)

df
g
df R
3
N M R
a
1+
e =

( /

c)

gel transition

RUEB AND ZUKOSKI
as T decreases

Rg3 1/

1466

r,0 r,1
r = r,1 +
1 + ( / c )m

m
c)

r r,1
1
=
r,0 r,1
1+( /

I(q) q

Rheology of colloidal gels

between 25 and 6 C ~e grows from . 0 to . 3kT.! At 4 C the flow behavior is

dramatically altered. A zero shear rate plateau viscosity is no longer observable and shear
These studies are important as they indicate a wide range of materials where gelation
thinning covers at least 4 decades in viscosity. A second example of the extremely rapid
~i.e., a rheological transition where relaxation times increase rapidly for small changes in
increase in h near T is shown in Fig. 10 for a suspension where f 5 0.41 and 2a

cates that partially cured samples were homogeneous and representative of intermediate stages of the continuously cross-linking
samples. In addition, the temperature stability of the poisoned
samples allowed the application of time-temperature superposition" from - 50C to + 140C. The PDMS samples crystallize
below -50C and their dynamic moduli were too low to enable
accurate measurements above + 140C. The frequency dependence of the reduced storage, G'(aTw, tJ, and loss, G'va-, t,),
moduli at different times, t., on the curing curve are presented in
Figure 3. An evolution of the rheological properties comparable to
crosslinking PDMS

to define the gelation temperature. Because this is a physical gel, there is evidence of the expected low frequency
Rheology
relaxation
as of
a critical
deviation gels

from this power-law behavior.
However, the sample will support its weight in gravity at
this temperature and flow at higher temperatures.

'-I

.5
+ 2db
iii <!l

+12
.
b

-0

,f".jl'5'8'

....,

>.0
0'

- 3.0
I;

++:$0

100
.;.;@c9
.; e
sol

.,..;"
10

>-

+bo

r"'..'

..::*'

#' CY'iP
....-t&CY'.;tt!'g

a O

.2

f0
++.F or
++ 0 8

00
0

-18

+1

+1.2

0
-1
-2

1
o

0.1

+ log war (rcd/s)

+2

+25

o
A

t.t,1

-30

1
0.1
0.01

!(b)
(rad/s)
1

1/2
o

28.2 C

0.0001

0.01

gelation:

28.1 C

26

at

28.0 C

0.001

Fig, 3. Reduced
storage&and
loss moduli
at intermediate
states of] conversion
[ Winter
Chambon,
J. Rheol.
30, 367 (1986)
for PDMS with imbalanced stoichiometry. t; is not the instant of intersection (see
A) to avoid overlap.
Fig. 2) of G' and G". The curves were shifted sideways (factor
0.001

gel

27.9 C

10

-F.p-c9

.D

-18

+.J<5

gel

.!-

! 1000
is

1"'1,

G, G" (Pa)

c min)

G, G" (Pa)

1-1 (

r"'0.91

a..

(a)

GEL POINT

time

RDMS

silica spheres a = 14 nm

100

sol

10

w (rad/s)
! (rad/s)

28.4 C
100

[ Eberle et al., PRL 106, 105704 (2011) ]

28

30

32
C)
T(
0
00
0.5
G (!) G (!) !

34

36
N M Rdf

30 C

ibution subject to SOR license or copyright; see http://scitation.aip.org/content/sor/journal/jor2/info/about. Downloaded to IP: 216.165.95.74 On: Mon, 07 Apr 2014

Rg3 1/

I(q) q

28.2 C
r r,1
28.1
C

Rg
a

df