Rheology of Suspensions

Ali Mohraz
Department of Chemical Engineering and Materials Science
University of California, Irvine

Rheology Short Course

Irvine, CA
May 16–18, 2017
 Examples in Nature, Research, and Various Technologies

http://www.puzzlemobi.com https://www.mystorybook.com/books/42892 E. Koos and N. Wellenbacher,

Science 331, 897 (2011)

A. McCoy, C&EN 88, 16 (2010) http://www.healthwellnesscolorado.com G.A. Nunez et al,

Energy & Env. Sci. 3, 629 (2010)
 Principle Factors to Consider

Particle volume fraction Brownian Motion

http://tanakalab.iis.u-tokyo.ac.jp Colloid Science Lab at UCI, unpublished

Talk Progression

Interparticle interactions Particle shape

Colloid Science Lab at UCI, unpublished A. Mohraz, PhD Thesis, Univ. Michigan (2004)
 Outline
1. Non-Brownian Particles
1. Hydrodynamic forces in dilute suspensions
2. Semi-dilute and concentrated systems

2. Brownian Particles
1. Brownian timescale, viscoelasticity
2. Brownian forces in semi-dilute and concentrated dispersions

3. Anisometric (Non-Spherical) Particles

1. Phase behavior
2. Implications for suspension rheology

4. Interparticle Interactions
1. Repulsive interactions and stability
2. Attractive interactions, colloidal gels

5. Thixotropy

6. Brief Overview of More Exotic Systems (if time permits)

1. Ternary mixtures (Pickering emulsions, capillary suspensions)
2. Particles in viscoelastic media
 A Rigid Sphere in a Newtonian Fluid

Uniform Flow Shear Flow

https://en.wikipedia.org G.K. Batchelor and J.T. Green, J. Fluid Mech 56, 375 (1972)

Simplest Form of Hydrodynamic Contribution to Viscosity

The presence of a particle in the fluid will locally disrupt the flow field,
lead to additional energy dissipation, and increase viscosity
 Dilute Suspensions of Non-Brownian Spheres

𝑣$ 𝑦
Assumptions:
– Rigid spherical particles
– Particles large enough to be non-Brownian (2a > 5 μm)
2a
– Simple shear flow y
– No settling (buoyancy-matched system)
– No particle inertia (slow flow, low particle mass) x
– Suspending fluid is Newtonian with viscosity 𝜂" 𝑣$,'()*+,-. = 𝛾̇ 𝑦
– Dilute suspension (volume fraction f < 0.05) 1
Ω'()*+,-. = 𝛾̇
2

Enhancement in viscosity is the additive contribution of individual

particles, each dissipating energy locally as shown on previous slide

Famous (corrected) Einstein relation, nontrivial to verify experimentally:

𝜂 = 𝜂" 1 + 2.5𝜙
A. Einstein, Ann. Physik 19, 289 (1906) and 34, 591 (1911)

If inertia is present, a first correction to the Einstein relation is given by:

𝜂 = 𝜂" 1 + 𝜙 2.5 + 1.34𝑅𝑒'=.>
C.J.-Lin et al J. Fluid Mech. 56, 401 (1972)
 Semi-Dilute Suspensions of Non-Brownian Hard Spheres
Same assumptions as before, however:
– 0.05 < f < 0.15 (approximate limits)
– Particles behave as hard spheres (HS)

https://pixabay.com/
Note: only representing the
form of interactions, not size

At f = 0.1, particles start to feel each other’s locally-perturbed flow fields,

leading to interparticle hydrodynamic interactions.
𝜂
𝜂) = = 1 + 2.5𝜙 + 𝑐@ 𝜙 @
𝜂"
Two-body interactions

But 𝑐@ depends on particle configuration, and can be difficult to determine for shear flow
For extensional flow, c2 = 7.6*; For shear flow, c2 = 5.0 – 6.0**
* G.K. Batchelor and J.T. Green, J. Fluid Mech. 56, 401 (1972)
** N.J. Wagner and A.T.J.M. Woutersen, J. Fluid Mech. 278, 267 (1994); J. Bergenholts et al. J. Fluid Mech, 456, 239 (2002)
 Concentrated Suspensions of Non-Brownian Spheres

0.20 < f < fmax (approximate limits)

Short-range particle configuration can become anisotropic

f = 0.4, Polystyrene particles 𝒂 ~ 𝟐𝟓 𝛍𝐦, suspended in density-matching silicone oils

𝑔 𝑟 represents the average probability to find a particle center at a

distance 𝑟 from a test particle (important in statistical mechanics)

F. Parsi and F. Gadala-Maria, J. Rheology 31, 725 (1987)

 Concentrated Suspensions of Non-Brownian Spheres

𝜂
𝜂) =
𝜂"

J. Mewis and N.J. Wagner, Colloidal Suspension Rheology, Cambridge University Press (2012)

1 + 1.5𝜙 1 + 𝜙 1 + 𝜙 − 2.3𝜙 @
0 ≤ 𝜙 ≤ 0.56
M 1 − 𝜙 1 + 𝜙 1 + 𝜙 − 2.3𝜙 @ Cheng et al, Phys. Rev. E. 65, 041405 (2002)
𝜂),L =
1
15.78𝑙𝑛 − 42.47 0.60 ≤ 𝜙 ≤ 0.64
1 − 1.160𝜙 =⁄V

X@.>YZ[\
𝜙
𝜂) = 1 − I.M. Krieger and T.J. Dougherty, Trans. Soc. Rheol. 3, 137 (1959)
𝜙"($

X@
𝜙
𝜂) = 1 − D. Quemada, Rheol. Acta 16:1, 82 (1977)
𝜙"($
 Concentrated Suspensions of Non-Brownian Spheres

Glass beads suspended in polyisobutylene

Dvs = 235 µm

Dvs = 112.5 µm

Bimodal (and trimodal) size distributions decrease viscosity – may be

rationalized as an increase in 𝜙"($

J.S. Chong et al, J. Appl. Polym. Sci. 15, 2007 (1968)

 Dispersion of Brownian Particles

Solvent “kicks” move the particles randomly, with energy kBT per particle, enables
the mixture to explore its energy landscape and “relax” toward equilibrium
Dispersions of Brownian Hard Spheres: Phase Behavior

l-c
liquid coexistence crystal

0.49 0.54 0.58 0.63 (fRCP) 0.74

f

“supercooled” glass

V. Prasad et al, J. Phys. Cond. Matt. 19, 113102 (2007)

 Dispersions of Brownian Spheres

Two important implications of Brownian motion (small particle size)

1. Relaxation timescale: competes with deformation timescale

𝜏 = 𝑎@ ⁄𝐷` Particle relaxation time

𝛾̇ 6𝜋𝜂" 𝛾̇ 𝑎V Peclet Number

𝑃𝑒 = = (a normalized shear rate)
𝐷` ⁄𝑎@ 𝑘d 𝑇

2. Thermal energy kBT per particle: sets a scale for flow energetics (stresses etc)

𝜎𝑎V Energy per particle from flow

𝜎𝑎V
𝜎) = (a normalized stress)
𝑘d 𝑇
Shear Thinning in Colloidal Sphere Dispersions

Polyvinyltoluene particles suspended in various solvents

Shear thinning, first indirect consequence of Brownian motion

Collapse of data when expressed in reduced form

I.M. Krieger, Adv. Colloid Int. Sci. 3, 111 (1972)

 Shear Thinning in Colloidal Sphere Dispersions

f = 0.38, 0.47, 0.53, 0.55, 0.60

Silica particles 𝒂 = 𝟕𝟖 𝐧𝐦,
suspended in cyclohexane

X@
𝜙
𝜂) = 1 −
𝜙"($

𝜂),` : 𝜙"($ = 0.63

𝜂) − 𝜂),L 1
= "
𝜂),L : 𝜙"($ = 0.71
𝜂),` − 𝜂),L 1 + 𝜎⁄𝜎,

Cross model, here m = 1

C.G. de Kruif et al, J Chem. Phys. 83, 4717 (1985)
Steady Shear Rheology of Colloidal Sphere Dispersions

f = 0.45
Total

Brownian Hydrodynamic

Corn starch monster

http://www.maniacworld.com

H.M. Laun, Angew. Makromol. Chem. 123, 335 (1984)

D.R. Foss and J.F. Brady, J. Fluid Mech. 407, 167 (2000)
N.J. Wagner and J.F. Brady, Phys. Today 62, 27 (2009)
E. Brown and H.M. Jaeger, Rep. Prog. Phys. 77, 046602 (2014)
Steady Shear of Concentrated Colloidal Sphere Dispersions

f = 0.515

Structural anisotropy present even in the shear thinning

regime, but dramatically increased in shear thickening
D.R. Foss and J.F. Brady, J. Fluid Mech 407, 167 (2000)
D. Kalman, PhD Thesis, University of Delaware (2010)
 Viscoelasticity in Colloidal Sphere Dispersions
PMMA particles, 𝒂 = 𝟎. 𝟑 𝛍𝐦, suspended in dioctylphthalate (DOP)

𝛾̇ = 124 s X=

Onset of shear thickening

M. Lee et al, J. Rheol. 50, 293 (2006)

 Viscoelasticity in Colloidal Sphere Dispersions

silica, a = 37 nm in ethylene-glycol/glycerin, f = 0.37

𝑎V 𝐺LM
𝜂M
@ L
≈ 0.78𝜙 𝑔 1, 𝜙
𝑘d 𝑇 𝜂"

Notable features:
low- and high-frequency viscosities, finite elastic modulus with high-frequency plateau

T. Shikata and D.S. Pearson, J. Rheol. 38, 601 (1994)

 Principle Factors to Consider

Particle volume fraction Brownian Motion

http://tanakalab.iis.u-tokyo.ac.jp Colloid Science Lab at UCI, unpublished

Talk Progression

Interparticle interactions Particle shape

Colloid Science Lab at UCI, unpublished A. Mohraz, PhD Thesis, Univ. Michigan (2004)
 Anisometric Particles: Axisymmetric Shapes

2a 2a L
L
d
2b
2b d
Prolate Spheroid Oblate Spheroid Rod Disk

𝑎 𝐿
Aspect ratio 𝑟 = or
𝑏 𝑑

Soft Condensed Matter Group A. Mohraz, PhD Thesis, A. Kuijk et al, Faraday Discuss.
Utrecht University Univ. Michigan (2004) 159, 181 (2012)
Anisometric Particles: Ubiquity (Here Only Rods Shown)

M.J. Solomon and P.T. Spicer, Soft Matter 6, 1391 (2010)

Anisometric Particles: Phase Behavior

Sphere volumes carved out by

1
Dilute 𝜈< V rod rotations do not overlap,
𝐿 particles freely rotate
Number of particles per unit volume

Rotational motion becomes

1 1 halted, but no excluded
Semi-Dilute ≪ 𝜈 ≪
𝐿V 𝑑𝐿@ volume restrictions (much
more common than dilute)

Concentrated 3.3 Excluded volume interactions

Isotropic 𝜙"($ = become important, crowding
𝑟
(Onsager)

1 Crowding leads to
Nematic 𝜈~
𝑑𝐿@ orientational ordering

L. Onsager, Ann. NY Acad. Sci. 51, 627 (1949)

M. Doi and S.F. Edwards, The Theory of Polymer Dynamics, Oxford Press (1986)
 Anisometric Particles: Random Packing

sphero-
cylinders

S.R. Williams and

A.P. Philipse,
Phys. Rev. E 67,
051303 (2003)

https://www.123rf.com
r

biaxial
oblate prolate

P. Chaikin and
S. Torquato

A. Donev et al. Science 303, 990 (2004)

 Anisometric Particles: Interaction with Flow Field

Flow field will affect particle orientations

𝑣$ 𝑦

2𝜋 𝑎 𝑏
Tumbling motion called Jeffery Orbit, has period 𝑇= +
𝛾̇ 𝑏 𝑎

Rod

Disk

Note: absent in irrotational flows (extensional or compressional), but alignment present

H.L. Goldsmith and H.G. Mason, in Rheology: Theory and Applications, New York Academic Press, 1967
 Anisometric Particle Dynamics

Thermal energy results in both translational and rotational motion. Flow field interacts
with particle orientations. These have important consequences (next four slides)

Strength of flow field should be scaled with particle rotational diffusivity

𝛾̇
𝑃𝑒) =
𝐷)

ln 2𝑟 − 0.5
𝐷),` = 3𝑘d 𝑇 For spheroids
8𝜋𝜂" 𝑎V

ln 𝑟 − 0.8
𝐷),` = 3𝑘d 𝑇 For rods
𝜋𝜂" 𝐿V

3𝑘d 𝑇
𝐷),` = For disks
4𝜂" 𝑑 V

H.J. Brenner, Int. J. Multiphase Flow 1, 195 (1974)

(other expressions also available, see for example F. Perrin, J. Phys. Radium 5, 497 (1934))
 Anisometric Particle Dynamics

Brownian forces contribute to viscosity even in dilute systems (competition of rotary

diffusion and flow). Stresses scale with sphere volumes carved out by rod rotations (flow
is disturbed on this scale). Addition of rods can significantly enhance dispersion viscosity.

Tobacco
Mosaic
Viruses

Glass fibers

M.A. Lauffer, J. Am. Chem. Soc. 66, 1188 (1944) J. Mewis and A.B. Metzner, J. Fluid Mech. 62, 593 (1974)
 Anisometric Particle Dynamics

Rod dispersions can show more pronounced shear thinning than spheres due
to flow-induced orientation

Xanthan gum, PBLG, FD Virus (rods) Kaolin (platelets)

𝜎 = 𝜎y + 𝑘𝛾̇ z

𝜎 (Pa) Newtonian

𝛾̇ s X=
J.K.G. Dhont and W.J. Briels, S.M. Jogun and C.F. Zukoski,
Colloids Surf. A. 213, 131 (2003) J. Rheol. 43, 847 (1999)
 Anisometric Particle Dynamics

Available empirical relations for viscosity of dilute dispersions

Prolate spheroids:

1 + 𝜙 2.5 + 0.408 𝑟 − 1 =.>`~ 𝑟 < 15

𝜂),{.| →` = 𝑟@ 1 1
1 + 𝜙 1.6 + + 𝑟 > 15
5 3 𝑙𝑛 2𝑟 − 1.5 𝑙𝑛 2𝑟 − 0.5

W. Kuhn and H. Kuhn, Helv. Chim. Acta 28, 97 (1945)

Rods:
8𝑟 @
𝜂),` =1+ 𝜙
45𝑙𝑛 𝑟

M
2𝑟 @
𝜂),L =1+ 𝜙
45𝑙𝑛 𝑟
J.K.G. Dhont and W.J. Briels, Colloids Surf. A. 213, 131 (2003)

… and many more

 Anisometric Particle Dynamics

Dispersions of long slender rods can show finite elasticity at

vanishingly low volume fractions

Tobacco Mosaic Virus

Extrapolated to infinite dilution
M
3 𝜔@ 𝜏 @
𝐺 = 𝜈𝑘d 𝑇
5 1 + 𝜔@𝜏 @

3 𝜔𝜏
𝐺 MM − 𝜔𝜂" = 𝜈𝑘d 𝑇 + 𝑐𝜔𝜏
5 1 + 𝜔@𝜏 @

Basically a Maxwell Fluid with a

limiting high-frequency viscosity

with (single) relaxation time:

𝜏 = 1⁄6𝐷),`

For rods, c = 1/3; for spheroids, c = 0.4

N. Nemoto et al, Biopolymers 14, 409 (1975) J.G. Kirkwood and P.L. Auer, J. Chem. Phys. 19, 281 (1951)
 Anisometric Particle Dynamics
A review of cases where elasticity is seen in rod suspensions:

M.J. Solomon and P.T. Spicer, Soft Matter 6, 1391 (2010)

 Principle Factors to Consider

Particle volume fraction Brownian Motion

http://tanakalab.iis.u-tokyo.ac.jp Colloid Science Lab at UCI, unpublished

Talk Progression

Interparticle interactions Particle shape

Colloid Science Lab at UCI, unpublished A. Mohraz, PhD Thesis, Univ. Michigan (2004)
 Interparticle Interactions: Beyond the Excluded Volume

Repulsive
Repulsive

Interaction Potential (Energy), F

– Electrostatic
– Steric Can Provide Kinetic Stability
– Electrosteric Distance, r

Attractive
Can result in Weak Aggregation

– van der Waals Total

– Depletion
– Polymer Bridging (electrostatic)
Attractive
– Solvent-induced
– Capillary
– etc…

Shape of the combined potential determines

net interparticle interactions, phase behavior, rheology
𝑑Φ 𝑟
𝐹=−
𝑑𝑟
 Electrostatic Interparticle Interactions

– + – –
+ –
– + –
– + +
+ –
– +
– + –
– –
– + +
+
– –
+ +
– + + –
+ –
–

Accumulation of counter-ion cloud near charged surface results in osmotic pressure

𝑛L,+ : concentration of ion species i (number density)

= ⁄@ e: fundamental electron charge
𝑛L,+ 𝑒 @ 𝑧+@ zi: valence of ion species I
𝜅= „
𝜀𝜀` 𝑘d 𝑇 e: dielectric constant of medium
+
e0: permittivity of space

k –1 is called the Debye length (typically in tens of nm),

sets the range of electrostatic interactions
 Electrostatic Interparticle Interactions

Ion cloud around the particle increases

its effective size, volume fraction

V
‰Š
𝑑.ˆˆ
𝜙.ˆˆ ≈𝜙 , where:
2𝑎

1 𝛼
𝑑.ˆˆ ~ ln Distance where Φ.-., ~𝑘d 𝑇
𝜅 ln 𝛼 ⁄ln𝛼

𝜀𝜀` Φ`@ 𝑎@ 𝜅exp 2𝑎𝜅 Location of nearest neighbors

𝛼= at equilibrium
𝑘d 𝑇

>
3 𝑑.ˆˆ
𝜂) = 1 + 2.5𝜙 + 2.5 + 𝜙@ (semi-dilute)
40 𝑎

‰Š X@.>YZ[\
𝜙.ˆˆ
𝜂) = 1 − (effectively concentrated)
𝜙"($

W.B. Russel, J. Fluid Mech. 1, 540 (1978); W.B. Russel et al, Colloidal Dispersions, Cambridge University Press
 Electrostatic Interparticle Interactions

Electrostatically stabilized polystyrene particles

a = 50 nm a = 34 nm

F.M. Horn et al, J. Coll. Int. Sci. 225, 166 (2000) R. Buscall et al, J. Chem. Soc. Faraday Trans. 1.
78, 2873 (1982)

Divergence in viscosity and onset of finite elastic modulus at

much lower volume fractions than Hard Spheres
 Steric Interparticle Interactions
2a

Colloidal (possibly even thermodynamic) stability

can be imparted by grafting of a polymer layer to
particles, suspending in good solvent for polymer

Polymer layer increases effective single particle

size, even impacts dilute viscosity
d

‰Š 1 L Φ 𝑟
Φ 𝑟 ‰Š
Φ.ˆˆ 𝑟 𝑎.ˆˆ = 𝑎 + • 1 − 𝑒𝑥𝑝 − 𝑑𝑟
2 @( 𝑘d 𝑇
𝑘d 𝑇 𝑘d 𝑇 4
‰Š ‰Š V
𝜙.ˆˆ = 𝜋 𝑎.ˆˆ
3

Φ 𝑟 Note:
‰Š
𝑘d 𝑇 Φ.ˆˆ 𝑟 represents the effective HS potential
r ‰Š
𝜙.ˆˆ represents the effective HS volume fraction

J.A. Barker and D. Henderson, J. Chem. Phys. 47, 4714 (1967)

 Steric Interparticle Interactions

2a

2a

G. Biebaut, PhD Thesis, Katholieke Universiteit Leuven (1999)

 Steric Interparticle Interactions

2a

2a

G. Biebaut, PhD Thesis, Katholieke Universiteit Leuven (1999)

 The Ubiquitous van der Waals Interactions
Induced by transient molecular dipoles, naturally present in all materials,
responsible for cohesion, phase transitions in pure fluids, etc.

Spheres
attraction 𝑎𝐴–
Φ’“” ≈ − for D << a
12𝐷
D otherwise:
2a @ @
𝐴– 4𝑎@ 2𝑎 2𝑎
Φ’“” =− + + 2ln 1 −
12 4𝑎𝐷 + 𝐷 @ 2𝑎 + 𝐷 2𝑎 + 𝐷

attraction
Flat surfaces (e.g. disks, platelets)

D 𝐴–
Φ’“” =−
12𝜋𝐷 @

AH is Hamaker constant (material-specific)

W.B. Russel et al, Colloidal Dispersions Cambridge University Press (1989)

 Polymer-Induced Attractive Interactions
Depletion interactions, caused by a non-adsorbing dissolved polymer

4𝜋 V
3𝑟 𝑟V
Φ = − 𝑎+𝐿 1− + V
Π
3 4 𝑎+𝐿 16 𝑎 + 𝐿
where:
P is osmotic pressure caused by dissolved polymer
(can be set to nkBT if dilute)
L is the thickness of the shell from which polymer
center of mass is excluded (grey shell in cartoon)

S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)

A. Vrij, Pure and Appl. Chem. 48, 471 (1976)

Bridging, caused by an [electrostatically] adsorbing dissolved polymer

Interparticle interactions can be heterogeneous,

and depend on polymer concentration, particle
size, and mixing protocol.
 Solvent-Induced Attractive Interactions

2a

d
Steric stabilization in a good solvent Aggregation in a poor solvent

Interaction potential often related to a Baxter sticky parameter, tB

L
Φ @
1
𝐵@ 𝑇 = 2𝜋 • 1 − 𝑒𝑥𝑝 − 𝑟 𝑑𝑟 = 𝑏` 1− Second virial coefficient
𝑘d 𝑇 4𝜏d
`

16𝜋𝑎V
𝑏` = Second virial coefficient for hard spheres
3

R. Baxter, J. Chem. Phys. 49, 2770 (1968)

 š›
𝑚 ~ 𝑅, mass of cluster

Df: fractal dimension < 3

š› XV
𝜌 ~ 𝑅, density in cluster
D.A. Weitz and M. Oliveria, Phys. Rev. Lett. 52, 1433 (1984)
 Gelation: A Rheological Transition

Silica particles 𝒂 = 𝟏𝟒 𝐧𝐦, grafted with octadeyl alcohol, in cyclohexane, f = 0.12

Frequency sweep curves are offset vertically for clarity

At the gelation point, 𝐺 M ≈ 𝐺 MM ~ 𝜔z
A.P.R. Eberle et al, Phys. Rev. Lett. 106, 105704 (2011)
 Qualitative State Diagram
F/kBT
Fluid-fluid Phase Separation
6
Increasing strength of attraction

Crystallization
Gelation
Glass Transition
1 2

Ergodic Non-ergodic 3 4
Systems Systems
4

5 6

1 2 3
f
Adapted From: Pham et al Science (2002); Trappe et al COCIS (2004); Zaccarelli JPCM (2007);
Lu et al Nature (2008), Ruzicka et al. Nature Materials (2011)
 Colloidal Gels in Shear Startup r



Even at Very Low Particle Volume Fractions... 
ω,
∇, z

y v, x

Polystyrene particles, 2a = 41 nm PMMA particles, 2a = 1.01 µm

Aggregation by vdW interactions Aggregation by depletion interactions

f
sxy (Pa)

𝛾̇ = 0.56 s X=
𝛻

𝑣⃗ 𝛾̇ = 0.07 s X=

g
A. Mohraz and M.J. Solomon, J. Rheology 49, 657 (2005) B. Rajaram and A. Mohraz, Soft Matt. 6, 2246 (2010)
 Effect of Particle Shape

(from light scattering measurements)

Normalized Structural Anisotropy

Large bending moments between aggregated rod

particles result in “brittle” behavior

A. Mohraz and M.J. Solomon, J. Rheology 49, 657 (2005)

 Fractal Models for Elasticity

http://www.ifpan.edu.pl/ON-2/on22/staff/mariusz.html

š›
𝑚 ~ 𝑅, mass of cluster
$ For strong flocculation:
𝑛' ~ 𝑅,‰ no. particles in a chain
X =¡$
Rc: cluster radius, Rch: chain length 𝛾` ~ 𝜙 VXš› Limit of linearity
Df: fractal dimension < 3 V¡$ Zero-shear
VXš›
x: backbone dimension 𝐺`M ~ 𝜙 elastic modulus
Both depend on aggregation kinetics, and
characterize cluster’s tenuous morphology W-H Shih et al, Phys. Rev. A 42, 4772 (1990)
 Power-law Scaling of Rheological Properties

Silica particles, grafted with polymer (octadecyl alcohol)

Aggregation (gelation) induced by reducing solvent quality for grafted chains

a = 40 - 80 nm a = 50 nm

Changes the
solvent quality

M. Chen and W.B. Russel, C.J. Rueb and C.F. Zukoski,

J. Coll. Int. Sci. 141, 564 (1991) J. Rheology 41, 197 (1997)
Mode Coupling Theory

𝐺 M 𝑎V 𝜙𝑎@
= 0.29 @
𝑘d 𝑇 𝑟-£,

J. Bergenholtz and M. Fuchs, Phys. Rev. E. 59, 5706 (1999)

Y.-L. Chen and K.S. Schweizer, J. Chem. Phys. 120, 7212 (2004)
M. Siebenburger et al, J. Rheology 53, 707 (2009)
 Viscosity of Aggregated Systems
Silica particles, grafted with polymer (octadecyl alcohol)
Aggregation (gelation) induced by reducing solvent quality for grafted chains

V
a = 47 nm 𝑎+Δ
𝜏dX= = 4 𝑒 ¤⁄¥¦ § − 1 −1
𝑎

Φ 𝑟 𝚽𝒔𝒒.𝒘𝒆𝒍𝒍
𝑘d 𝑇 𝒌𝑩 𝑻
𝜂),` − 𝜂),L

2a
𝜂) − 𝜂),L

D 𝜖

square-well potential
𝑎ª 𝜎
6𝜙Δ𝜖
A.T.J.M. Woutersen and C.G. de Kruif, J. Chem. Phys. 94, 5739 (1991)
 Shear-induced Changes in Aggregated Systems

PMMA particles, 2a = 1.25 ± 0.06 μm, f = 0.035

Aggregation by depletion interactions (dissolved PS with MW = 777,500 Da at rp = 4.48 mg/ml)

From top to bottom: 𝛾̇ = 0.00, 0.07, 0.14, 0.56, 2.24, 8.96 s–1 100 μm

B. Rajaram and A. Mohraz, Soft Matt. 8, 7699 (2012)

 Yielding in Colloidal Gels and Glasses

PMMA particles, a = 130 nm, Depletion interactions induced where

noted using PS with MW = 143400 Da

rp = 0 rp = 10.4 mg/ml rp = 19.8 mg/ml

f = 0.6 f = 0.6 f = 0.4

2 1 2 2 1
1 3 1 6 2
6 3 3 4
6 6 5
4 5 4
5 4 5 3

Two-step yielding in attractive concentrated dispersions

K.N. Pham et al, Europhys. Lett. 75, 624 (2006)
 Viscoelasticity of Concentrated Colloidal Gels

Silica particles, 2a = 493 nm, grafted with polymer (octadecyl alcohol)

Attraction induced by suspension in poor solvent for polymer (DMSO/water)

𝜎 − 𝜎y (Pa)
𝜎y (Pa)

𝜎 (Pa)
𝜎 = 𝜎y + 𝑘𝛾̇ z Herschel-Bulkley model: a power-law fluid with a yield stress
𝜙 @ 𝑑Φ
𝜎y ~ @ W.H. Bulkley and A.R. Herschel, Kolloid-Z. 39, 291 (1926)
𝑎 𝑑𝑟 "($ M.T. Roberts et al, Langmuir 23, 8726 (2007)
 Polymer-Bridged Systems

Silica particles, 2a = 545 nm, f = 0.3, aggregation by

addition of oppositely charged PEI, MW = 1200 Da

Non-uniform interparticle interactions can lead to highly heterogeneous dynamics

K.L. Pickrahn et al, Langmuir 26, 2392 (2009)
 Polymer-Bridged Systems
20 20
Mobile
Arrested

15 15

R (µm)

Y (µm)
10 10
g

5 5

0 0
200 400 600 800 1000 0 5 10 15 20
N (frames) X (µm)
tracked
arrested subpopulation:
(Pa)

𝜎y (Pa)

0.3 0.4 0.8 Cp (mg/m2)

Regime I Regime II

Cpc ~ 1.4 mg/m2 1.6 11.7 19.6

K.L. Pickrahn et al, Langmuir 26, 2392 (2009)
 Thixotropy and Ageing

Intermittent flow startup tests

Carbon black in mineral oil, f = 0.032

Sample response will change depending on its history (age, pre-shearing, etc)

K. Dullaert, PhD. Thesis, Katholieke Universiteit Leuven (2005)

 Soft Glassy Rheology (SGR) Model
1
𝐸 − 𝑘𝑙 @
Characteristic yield time of a mesoscopic element 𝜏 = 𝜏` 𝑒𝑥𝑝 2
𝑥
𝜏` a characteristic time for activated dynamics
k a spring constant (linear elasticity of element prior to yielding)

𝑙 the local strain imposed on element

Relaxation modulus after linear step strain

silica particles,
2a = 80 nm

𝑙
𝑙

P. Sollich, Phys. Rev. E. 58, 738 (1998)

G. Yin and M.J. Solomon, J. Rheology 52, 785 (2008)
 Capillary Suspensions

Ternary mixtures of solid particles and two immiscible fluids

E. Koos and N. Willenbacher, Science 331, 897 (2011)

Droplet Bridging by Colloidal Particles

Aqueous
Organic

θ > 90°

θ > 90°
Aqueous

ΔG = π r 2γ OW (1 ± cosθ ) ~ 10 3 − 10 6 kT

E.J. Stancik and G.G. Fuller, Langmuir 20, 4805 (2004)

 Microstructure of Bridged Emulsions

Tenuous arrangement of aqueous droplets bridged by a

percolating web of adhesive solid particles

M.N. Lee et al, Langmuir 28, 3085 (2012)

 Zero-Shear Elastic Modulus
4
5 10
φa = 0.3
4 104
G' (Pa)

3 104
G0′ ~ φ
0

4
2 10
G0′ ~ φ 1.9

4
1 10

0
0 0.04 0.08 0.12 0.16
φφ p
M. Kaganyuk and A. Mohraz, Soft Matter 13, 2513 (2017)
 Zero-Shear Elastic Modulus
4
5 10
φa = 0.3
4 104
G' (Pa)

3 104
0

4
2 10

4
1 10

0
0 0.04 0.08 0.12 0.16
φφ p
M. Kaganyuk and A. Mohraz, Soft Matter 13, 2513 (2017)
Shear-Induced Transitions, Effects of Bridging

5
10

104
before shear
3
10
Shear
102
G'
G" 101
(Pa) after shear
100

10-1 G'
G"
10-2
10-4 10-3 10-2 10-1 100 101 102 103
τ (Pa)

Dramatic shear-induced rheological transition

accompanied by loss of bridges
Colloid Science Laboratory at UCI, unpublished
 Particles Suspended in a Viscoelastic Medium

Background fluid: surfactant solution, 100 mM CPyCl in electrolyte

PMMA particles, 2a = 15 µm, f = 0.008 PS particles, 2a = 2.8 µm, f = 0.008

R. Pasquino et al, Langmuir 26, 3016 (2010)

 Summary

The rheology of dispersions involves hydrodynamic and Brownian contributions to

viscoelasticity. For large particles, Brownian forces are insignificant.

Particle shape matters. Non-spherical particles can rotate and the flow will interact
with their orientational distribution, which contributes heavily to their rheology.

Interparticle interactions are key to suspension rheology. Colloidal dispersions are

typically stabilized by means of electrostatic or steric interactions.

Aggregation can have dramatic consequences for suspension rheology, including

gelation, which is commonly defined as a rheological transition from liquid-like to
solid-like viscoelasticity.

Colloidal gels often show signs of ageing and thixotropy.

Multiphase mixtures can exhibit very interesting rheology, including capillary gelation.

Suspending solid particles in a viscoelastic background can lead to additional

interesting phenomena including migration, particle chaining, and assembly of
ordered 2D structures.
For More on Suspensions and their Rheology:

Mewis and Wagner Russel, Saville, Schowalter

Larson Macosko