Colloidal Gels:

Formation, Structure & Rheology

Part 1. Colloidal gel formation & structure

Prof. Matthew Helgeson

Department of Chemical Engineering
University of California, Santa Barbara

Society of Rheology Short Course

SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels 1
October 2021
 Learning outcomes
• Understand the colloidal interactions that give rise to gelation behavior

• Identify the three primary gelation mechanisms/morphologies, and their

relation to equilibrium and non-equilibrium colloidal thermodynamics

• Be familiar with aggregation/percolation processes, their theoretical

description by classical models, and how they relate to the process of gelation

• Be able to identify various structural and rheological descriptors of the gelation

process, measurements to characterize them, and their characteristic features
during gelation

• Know how to differentiate gel morphologies based on their distinct structural

and rheological characteristics
SOR Short Course
on Colloidal Gels
October 2021 2
 Whither a gel?
Key questions

What properties and processes encode the ability to form a gel?

What are the routes by which gels can form, and what gel
morphologies do they lead to?

How do these different routes map onto our understanding of other

colloidal phenomena?

SOR Short Course

on Colloidal Gels
October 2021 3
 Colloidal interactions and forces
“Simple” (spherical, isotropic) colloidal particles
a
r
Interaction potential: 𝑈𝑈 𝑟𝑟 “hard”
repulsion
𝑑𝑑𝑑𝑑 𝑈𝑈 𝑟𝑟 𝐹𝐹 𝑟𝑟
Interaction force: 𝐹𝐹 𝑟𝑟 = −
𝑑𝑑𝑑𝑑

Measures of “bond” strength repulsive

between attractive colloids “barrier”
0 r r
0
2a 2a
Minimum potential energy: 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 secondary
𝑑𝑑𝑑𝑑 “well”
𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 𝐹𝐹 = −
Maximum attractive force: 𝐹𝐹𝑚𝑚𝑚𝑚𝑚𝑚 𝑑𝑑𝑑𝑑
primary
attracive 𝐹𝐹𝑚𝑚𝑚𝑚𝑚𝑚
Second virial coefficient: 𝐵𝐵2 “well”
𝑑𝑑 2 𝑈𝑈 ∞
Effective “spring” constant: 𝑘𝑘0 = �
𝑑𝑑𝑑𝑑 2 3 𝑟𝑟,𝑇𝑇 ⁄𝑘𝑘𝑏𝑏 𝑇𝑇
𝑟𝑟=𝑟𝑟𝑚𝑚𝑚𝑚𝑚𝑚 𝐵𝐵2 𝑇𝑇 ⁄𝐵𝐵2𝐻𝐻𝐻𝐻 = 1 − � 1 − 𝑒𝑒 −𝑈𝑈 𝑟𝑟 2 𝑑𝑑𝑑𝑑
SOR Short Course
𝑎𝑎3
𝑎𝑎
on Colloidal Gels
October 2021 4
 Colloidal interactions and forces
“Toy” interaction potentials common to theory & simulation
Square well (Two-)Yukawa/Morse Lennard-Jones
𝑟𝑟 ≤ 2𝑎𝑎 ∞ 12 6
𝑈𝑈 𝑟𝑟 𝑟𝑟 ≤ 2𝑎𝑎 ∞ 𝑈𝑈 𝑟𝑟 𝑈𝑈 𝑟𝑟 2𝑎𝑎 2𝑎𝑎
= �2𝑎𝑎 < 𝑟𝑟 < 2𝑎𝑎 + 𝜆𝜆 𝜀𝜀 =� 𝑒𝑒 −𝑍𝑍1 𝑟𝑟−2𝑎𝑎
𝑒𝑒 −𝑍𝑍2 𝑟𝑟−2𝑎𝑎 = 4𝜀𝜀 −
𝑘𝑘𝑏𝑏 𝑇𝑇 𝑘𝑘𝐵𝐵 𝑇𝑇 𝑟𝑟 > 2𝑎𝑎 −𝐾𝐾1 − 𝐾𝐾2 𝑘𝑘𝑏𝑏 𝑇𝑇 𝑟𝑟 𝑟𝑟
𝑟𝑟 ≥ 2𝑎𝑎 + 𝜆𝜆 0 𝑟𝑟 𝑟𝑟

𝑈𝑈 𝑟𝑟 𝑈𝑈 𝑟𝑟 𝑈𝑈 𝑟𝑟
𝑘𝑘𝐵𝐵 𝑇𝑇 𝑘𝑘𝐵𝐵 𝑇𝑇 𝑘𝑘𝐵𝐵 𝑇𝑇
𝜆𝜆 𝑟𝑟𝑚𝑚𝑚𝑚𝑚𝑚
𝑟𝑟 𝑟𝑟
𝜀𝜀
𝜀𝜀

Advantage: Analytical solutions Advantage: Realistic, versatile Advantage: Smooth, continuous

Disadvantage: Discontinuous Disadvantage: Discontinuous Disadvantage: Unrealistic
(at contact)
SOR Short Course
on Colloidal Gels
October 2021 5
 Colloidal interactions and forces
Sources of colloidal interactions in “real” systems
• Charge-stabilized colloids (DLVO theory)
𝑈𝑈𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝑟𝑟 𝐴𝐴131 𝑎𝑎 64𝜋𝜋𝜋𝜋𝑘𝑘𝑏𝑏 𝑇𝑇 𝐼𝐼 𝜓𝜓𝑠𝑠 𝑧𝑧𝑖𝑖 −𝜅𝜅 𝑟𝑟−2𝑎𝑎
=− + 2
tanh 𝑒𝑒
𝑘𝑘𝑏𝑏 𝑇𝑇 12 2 − 2𝑎𝑎 𝜅𝜅 4𝑘𝑘𝑏𝑏 𝑇𝑇
dipolar attraction electrostatic repulsion
(van der Waals) (Gouy-Chapman)

- - - + - 𝑎𝑎: Particle radius

- - 𝐴𝐴131 : Hamaker constant (particles/solvent)
- - - + -
- - + 𝐼𝐼 : Ionic strength (salt concentration)
- - + - - -
+ - - 𝜅𝜅 −1 : Debye length (salt concentration)
- -
+ - - 𝜓𝜓𝑠𝑠 : Surface potential (~𝜁𝜁-potential)
+ - -
- - -
-
Recommended reading
Intermolecular and Surface Forces
J.N. Israelachvili, 3rd Edition,
SOR Short Course
on Colloidal Gels Academic Press, 2011
October 2021 6
 Colloidal interactions and forces
Sources of colloidal interactions in “real” systems
• Non-adsorbing polymer (Asakura-Oosawa theory)

Depletion interactions 𝑈𝑈𝐴𝐴−𝑂𝑂 𝑟𝑟 4𝑎𝑎 16𝑎𝑎3

= −𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 1 − +
𝑘𝑘𝑏𝑏 𝑇𝑇 3𝑟𝑟 3𝑟𝑟 3

𝑈𝑈 𝑟𝑟
𝑎𝑎 Often approximated
𝑘𝑘𝐵𝐵 𝑇𝑇 by Yukawa potential.

𝑟𝑟 − 2𝑎𝑎
𝑅𝑅𝑝𝑝
Exclusion of polymer between polymers 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚
leads to entropically-driven attraction. Recommended reading
Colloidal Dispersions
Russel, Saville & Schowalter,
SOR Short Course
on Colloidal Gels Cambridge University Press, 1989
October 2021 7
 Colloidal interactions and forces
Sources of colloidal interactions in “real” systems
• Adsorbing polymer (polymer bridging/flocculation)

𝑈𝑈 𝑟𝑟
𝑘𝑘𝐵𝐵 𝑇𝑇

𝑟𝑟 − 2𝑎𝑎

𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚
Preferred size of polymer (Rp) sets transition
from long-range attraction (chain stretching)
to short-range repulsion (chain compression). Recommended reading
Colloidal Dispersions
Russel, Saville & Schowalter,
SOR Short Course
on Colloidal Gels Cambridge University Press, 1989
October 2021 8
 Colloidal interactions and forces
Describing interactions between “complex” colloids

Particle shape

“Patchy” particles Li, Persson, Lund, Bergenholtz & Zackrisson Oskolkova, J Phys Chem B, 2016, 120(34).

Bending/torsion 𝜙𝜙

𝐹𝐹 = 𝑘𝑘0 𝑎𝑎 𝜙𝜙 − 𝜙𝜙𝑒𝑒𝑒𝑒
SOR Short Course
Pantina & Furst Physical review letters, 2005, 94(13), 138301.
on Colloidal Gels
October 2021 Bonacci, Chateau, Furst, Fusier, Goyon, Lemaître, Nature materials, 2020 19(7), 775-780. 9
 Measuring colloidal interactions in experiment
Cantilever-based optical methods Colloidal Probe AFM,
a = 3.1 µm sulfate latex in KCl solution
Surface Forces Apparatus (Israelachvili and co-workers) (lines = DLVO theory)

Finessi et al., J Phys Chem B,

J. Zhang and H. Zeng, Engineering, 2021, 7(1): 63-83. 2011, 115(29): 9098-9105.
SOR Short Course
on Colloidal Gels
October 2021 10
 Measuring colloidal interactions in experiment
Laser-tweezer based optical microscopy (active “microrheology”)
Pair distance
distribution, Silica, a = 1 µm in
𝑔𝑔12 𝑟𝑟 water-2,6 lutidine

Boltzmann
inversion,
Φ 𝑟𝑟
− 𝑇𝑇
𝑔𝑔12 𝑟𝑟 = 𝑒𝑒 𝑘𝑘𝑏𝑏

Pair interaction
potential,
Φ 𝑟𝑟

SOR Short Course

on Colloidal Gels
Paladugu, Callegari, Tuna, Barth, Dietrich, Gambassi & Volpe, Nature Communications, 2016, 7: 11403.
October 2021 11
 Measuring colloidal interactions in experiment
Small angle light/X-ray/neutron scattering (SALS/SAXS/SANS)
𝐼𝐼 𝑞𝑞 = 𝜙𝜙𝑝𝑝 𝑉𝑉𝑝𝑝 Δ𝜌𝜌 2 𝑃𝑃 𝑞𝑞 𝑆𝑆 𝑞𝑞 octadecyl-grafted silica in cyclohexane

P(q) 40 °C 25 °C
θ S(q)
q I(q)
Sample

40 °C

I(q)
Wave vector: Note:
4𝜋𝜋 sin 𝜃𝜃 2𝜋𝜋 φ
𝑞𝑞 = 𝐿𝐿~
𝜆𝜆 𝑞𝑞
log(q)

Pair interaction Liquid state Structure factor,

potential, theory, 𝑆𝑆 𝒒𝒒 = 1 + � 𝑔𝑔 𝒓𝒓 − 1 𝑒𝑒 𝑖𝑖𝒒𝒒⋅𝒓𝒓 𝑑𝑑𝒓𝒓
𝑈𝑈 𝑟𝑟 𝑔𝑔 𝑟𝑟 = 𝑓𝑓 𝑈𝑈 𝑟𝑟 , 𝜙𝜙
A.P.R. Eberle et al., Langmuir, 2012, 28: 1866−1878.
SOR Short Course
on Colloidal Gels
October 2021 12
Colloidal gelation – the morphological perspective

Key observation: gels reported in the early literature follow

three different types differentiated by their morphology
(i.e., the arrangement of their structure).

SOR Short Course

on Colloidal Gels
October 2021 13
 Early observations – “stringy” gels
Electrostatically (de)stabilized PMMA spheres, a ~ 2 µm with PS
gold, a = 7 nm in water, φ ~ 10-3 “depletant” in water, φ ~ 0.02

“Stringy” gels tend to form for:

• Low-moderate particle volume

fractions, φ ~ 0.02 – 0.10

• “Strong” interparticle bond

strengths, 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 > 8𝑘𝑘𝑏𝑏 𝑇𝑇

• Short-range interactions, 𝜆𝜆 < 0.1𝑎𝑎

• Solid particles

Weitz and Oliveria, Phys Rev Lett, Eric Weeks lab,

1984, 52(16): 1433-1436. http://www.physics.emory.edu/faculty/weeks//lab

SOR Short Course

on Colloidal Gels
October 2021 14
 Early observations – “clumpy” gels
PMMA spheres, a = 25 nm with PS PMMA spheres, a ~ 0.5 µm with PS
“depletant” in decalin, φ ~ 0.11 “depletant” in index solvent, φ ~ 0.05

“Clumpy” gels tend to form for:

• Moderate particle volume

fractions, φ ~ 0.10 – 0.40

• “Weak” interparticle bond

strengths, 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 ~2 − 6𝑘𝑘𝑏𝑏 𝑇𝑇

• Short and longer-range

interactions

• Solid and deformable particles

Aarts and Lekkerkerker, J Phys Cond Matt, Lu, Zaccarelli, Ciulla, Schofield, Sciortino &
2004, 16: S4231. Weitz, Nature, 2008, 453: 499-504.

SOR Short Course

on Colloidal Gels
October 2021 15
 Early observations – “dense” gels
PMMA spheres, a ~ 0.5 µm with PS
“depletant” in index solvent, φ = 0.59

“Dense” gels tend to form for:

• Large particle volume fractions,

φ > 0.4

• “Moderate” interparticle bond

strengths, 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 > 3𝑘𝑘𝑏𝑏 𝑇𝑇

Pham, Egelhaaf, Pusey, Poon, Phys Rev E,

Simeonova et al., Phys Rev E, 2006, 041401. 2004, 69: 011503.

SOR Short Course

on Colloidal Gels
October 2021 16
 Summary – the three morphologies
“Stringy” gels “Clumpy” gels “Dense” gels
Dilute concentration, strong attraction Moderate concentration, weak attraction Large concentration, moderate attraction

SOR Short Course

Key question: what determines which type of morphology forms?
on Colloidal Gels
October 2021 17
 Colloidal gelation – the thermodynamic perspective
Colloidal thermodynamics – “colloids as big atoms”
Ensatz (effective medium assumption): Stable colloidal dispersions can be
thought of like atomic fluids, where it is assumed that the only influence of the
suspending medium is to determine 𝑈𝑈 𝒓𝒓 .
Gibbs energy: 𝑑𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + Π𝑑𝑑𝑑𝑑 Osmotic pressure:

Helmholtz energy: 𝐴𝐴 = −𝑘𝑘𝑏𝑏 𝑇𝑇 ln 𝑄𝑄 𝑁𝑁𝑘𝑘𝑏𝑏 𝑇𝑇 2𝜋𝜋 𝒓𝒓𝒊𝒊𝒊𝒊

Π= − � 𝒓𝒓3 𝑔𝑔 𝒓𝒓 𝑑𝑑𝒓𝒓
𝑉𝑉 3
𝑉𝑉
𝐸𝐸
− 𝑁𝑁𝑘𝑘𝑏𝑏 𝑇𝑇
𝑄𝑄 = � … � 𝑒𝑒 𝑘𝑘𝑏𝑏𝑇𝑇 𝑑𝑑𝒓𝒓 𝟏𝟏 … 𝑑𝑑𝒓𝒓𝑵𝑵 ≈ 1 + 𝐵𝐵2 𝜙𝜙 + 𝐵𝐵3 𝜙𝜙 2 + ⋯
𝑉𝑉 𝑉𝑉
𝑉𝑉
𝑁𝑁 𝑁𝑁 𝑁𝑁, 𝑉𝑉, 𝑇𝑇
𝐸𝐸 = � � 𝑈𝑈 𝒓𝒓𝒊𝒊𝒊𝒊 Volume fraction:
𝑖𝑖>𝑗𝑗 𝑖𝑖=1
𝑉𝑉𝑝𝑝 4𝜋𝜋𝑎𝑎3 𝑁𝑁
𝜙𝜙 = =
SOR Short Course 𝑉𝑉 3𝑉𝑉
on Colloidal Gels
October 2021 18
 Colloidal gelation – the thermodynamic perspective
Equilibrium phase behavior of attractive colloids
purely repulsive

fluid
0 Colloidal
gas

crystal
𝐵𝐵2 or CP
𝑘𝑘𝑏𝑏 𝑇𝑇⁄𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚
gas liquid Colloidal
liquid- liquid
gas-liquid
crystal
coexistence
co-
existence
𝜙𝜙
strongly attractive
Colloidal
Recommended reading crystal
SOR Short Course Weeks lab,
on Colloidal Gels E. Zaccarelli, J Phys Cond Matt, 2007, 19: 323101.
October 2021
Emory University 19
 Colloidal gelation – the thermodynamic perspective
Gel morphologies as non-equilibrium “arrest” transitions
Percolation (topological): Drawing a line
purely repulsive
connecting primitive sub-units of nc
fluid “bonded” particles within an aggregate
0 produces a line that spans the system
volume, V.

crystal Pair percolation:

𝐵𝐵2 or CP nc = 2 “bonds”
𝑘𝑘𝑏𝑏 𝑇𝑇⁄𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 Rigidity percolation:
gas liquid nc = 6 “bonds”
liquid- (isostatic cluster)
gas-liquid
crystal
coexistence
co-
existence Percolation transition (topological): The
𝜙𝜙 threshold defining conditions that, on
strongly attractive
average, produce a percolated network
Recommended reading at an arbitrary “snapshot” in time.
SOR Short Course
on Colloidal Gels E. Zaccarelli, J Phys Cond Matt, 2007, 19: 323101.
October 2021 20
 Colloidal gelation – the thermodynamic perspective
Gel morphologies as non-equilibrium “arrest” transitions
Glassy dynamics (entropic): “Crowding”
purely repulsive
repulsive of particles in a dense system slows
fluid glass diffusion to the point where fluctuations
0 become heterogeneous.

crystal
𝐵𝐵2 or attractive
CP glass
𝑘𝑘𝑏𝑏 𝑇𝑇⁄𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚
gas liquid Weeks and Weitz, Phys Rev Lett, 2002, 89: 095704

gas-liquid
liquid- Repulsive glass: “Cages” formed by
crystal steric repulsion with neighboring colloids.
coexistence
co-
existence Attractive glass: “Cages” form by nearest
𝜙𝜙 neighbor particle “bonds”.
strongly attractive
Glass transition (dynamic): Sufficient
Recommended reading
SOR Short Course slowing of long-time dynamics leads to
on Colloidal Gels E. Zaccarelli, J Phys Cond Matt, 2007, 19: 323101. “arrest” of structure out of equilibrium.
October 2021 21
 Colloidal gelation – the thermodynamic perspective
Gel morphologies as non-equilibrium “arrest” transitions
Arrested phase separation: Fluid-fluid
purely repulsive
repulsive phase instability produces a dense state
fluid glass whose formation is “interrupted” by the
0 attractive glass transition.

crystal
𝐵𝐵2 or attractive
CP glass
𝑘𝑘𝑏𝑏 𝑇𝑇⁄𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚 Gas
Liquid “pore”
gas liquid “strand”
x?
liquid-
gas-liquid
crystal
coexistence
co-
existence
𝜙𝜙
strongly attractive
Padmanabhan and Zia, Soft Matter,
Recommended reading 2018, 14: 3265-3287.
SOR Short Course
on Colloidal Gels E. Zaccarelli, J Phys Cond Matt, 2007, 19: 323101.
October 2021 22
 Colloidal gelation – the thermodynamic perspective
Gel morphologies map onto non-equilibrium “arrest” transitions
purely repulsive “Stringy” gels
repulsive
fluid glass “Dense” gels
0

crystal
𝐵𝐵2 or attractive
CP glass
𝑘𝑘𝑏𝑏 𝑇𝑇⁄𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚
gas
*
arrested
liquid
liquid-
“Clumpy” gels
crystal
phase
co-
separation existence
𝜙𝜙 *
(Here be dragons…)
strongly attractive

Recommended reading
SOR Short Course
on Colloidal Gels E. Zaccarelli, J Phys Cond Matt, 2007, 19: 323101.
October 2021 23
 Whither a gel?
Key questions
What properties and processes encode the ability to form a gel?
The ability to form a gel is determined by the shape/strength of the interaction
potential, by encoding the formation of colloidal “bonds” AND by setting
conditions for arrest of colloidal structure.
What are the routes by which gels can form, and what gel morphologies do
they lead to?
Percolation → “stringy” gels
Attractive glass transition → “dense” gels
Arrested phase separation → “clumpy” gels
How do these different routes map onto our understanding of other colloidal
phenomena?
Where/when these morphologies occur is currently understood to arise from the
location of various arrest transitions relative to equilibrium phase boundaries in
a colloidal phase diagram (but this is an active area of research).
SOR Short Course
on Colloidal Gels
October 2021 24
 How a gel?
Key questions

What are the kinetic processes by which colloidal gels form in time,
and how do we model them?

What measurable descriptors are available to track the gelation

process, and what is their expected behavior during gel formation?

How does solid-like rheology emerge from gelation process(es), and

what sets the gel point (i.e., when does a gel become a gel)?

SOR Short Course

on Colloidal Gels
October 2021 25
 Describing chemical gelation
Chemical gels – sol-gel processes and percolation
Theory for the formation of chemical gels is mature, and involves the use of
diffusion-reaction models to track the evolution of the size and structure of a
network over time from the earliest stages through the percolation transition.

Meakin, PRL , 1983

Question: Can theories and concepts for the formation of

SOR Short Course
on Colloidal Gels chemical gels apply to physical/colloidal gels?
October 2021 26
 Kinetic models for aggregation & gelation
Population balances and Smoluchowski theory
Consider aggregates containing nk particles, which form by collisions between
collisions and successful “bonding” between two aggregates containing i and j
particles…
j=1
diffusion
j=4
𝑟𝑟𝑐𝑐

k=2
i=1 reaction
k = 10
𝒓𝒓𝒄𝒄 : “capture” radius i=6
(set by 𝑟𝑟𝑚𝑚𝑚𝑚𝑚𝑚 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚

SOR Short Course

on Colloidal Gels
October 2021 27
 Kinetic models for aggregation & gelation
Population balances and Smoluchowski theory
Consider aggregates containing nk particles, which form by collisions between
collisions and successful “bonding” between two aggregates containing i and j
particles…
𝑘𝑘−1 ∞
𝑑𝑑𝑛𝑛𝑘𝑘 1
= � 𝑘𝑘𝑖𝑖𝑖𝑖 𝑛𝑛𝑖𝑖 𝑛𝑛𝑗𝑗 − � 𝑘𝑘𝑖𝑖𝑖𝑖 𝑛𝑛𝑖𝑖 𝑛𝑛𝑘𝑘
𝑑𝑑𝑡𝑡 2
𝑖𝑖=1;𝑖𝑖+𝑗𝑗=𝑘𝑘 𝑖𝑖=1 j=4
“birth” rate “death” rate

𝒌𝒌𝒊𝒊𝒊𝒊 : rate kernel for successful collision

and reaction of ni with nj (includes
both diffusion and reaction) k = 10
i=6

Note: Smoluchowski’s original theory is for irreversible aggregation. New

terms appear in the master equation if reversible bonds are considered.*
SOR Short Course
on Colloidal Gels *Rouwhorst, Schall, Ness, Blijdenstein, Zaccone, Phys Rev E, 2020: 022602
October 2021 28
 Kinetic models for aggregation & gelation
Results from adaptations of Smoluchowski theory
Higashitani and Matsuno,
J Chem Eng Japan, 1979
fraction of clusters having size k

𝑛𝑛𝑐𝑐
k
Rouwhorst, Schall, Ness, Blijdenstein, Zaccone, Phys Rev E, 2020: 022602

Key problem: To describe percolation, we need a theory to

SOR Short Course
on Colloidal Gels relate the number of particles in an aggregate to its volume.
October 2021 29
 Kinetic models for aggregation & gelation
Fractal theory and its application to colloidal aggregation
Consider an aggregate consisting of particles, each
with volume 𝑉𝑉𝑝𝑝 , enclosed by a fictitious sphere of radius
𝑟𝑟 𝑟𝑟 and volume 𝑉𝑉. If the topology of the aggregate is
described by a fractal, then the number and volume
of particles enclosed by the sphere is described by:

𝑑𝑑𝑓𝑓
𝑛𝑛𝑝𝑝 𝑉𝑉𝑝𝑝 = 𝑉𝑉 𝑛𝑛𝑝𝑝 = 𝑉𝑉 𝑑𝑑𝑓𝑓 −1 𝜙𝜙 𝑑𝑑𝑓𝑓
Fractal dimension, 𝒅𝒅𝒇𝒇 : the “dimension” of the fractal
that describes how particles are distributed along the
aggregate.

1 𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
Originally applied to
𝑑𝑑𝑓𝑓 = �2 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
colloids by by J Texeira
3 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 − 𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
SOR Short Course
on Colloidal Gels
October 2021 30
 Key predictions of kinetic theories of gelation
Diffusion-limited aggregation (DLA) vs. reaction-limited aggregation (RLA)

Observed fractal dimension depends sensitively on the rate-limiting birth rate

(j = 1 vs. j ≠ 1) and rate-limiting step (diffusion vs. reaction) of aggregation.

j=1
diffusion

𝑟𝑟𝑐𝑐 Friedlander, “Smoke,

Dust and Haze”, 2nd Ed.,
2000, Oxford
k=2
i=1 reaction

𝒓𝒓𝒄𝒄 : “capture” radius

(set by 𝑟𝑟𝑚𝑚𝑚𝑚𝑚𝑚 𝑈𝑈𝑚𝑚𝑚𝑚𝑚𝑚

Key observation: These predictions tend to be consistent with

SOR Short Course
on Colloidal Gels experimental observations on percolation-type gels.
October 2021 31
 Measurement methods to track the gelation process
Optical/electron microscopy and particle-scale structural descriptors

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SOR Short Course

on Colloidal Gels
October 2021 32
 Measurement methods to track the gelation process
Small angle scattering and meso-scale structural descriptors

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SOR Short Course

on Colloidal Gels
October 2021 33
 Measurement methods to track the gelation process
Linear viscoelasticity and continuum-scale mechanical descriptors
• Conventional methods: small amplitude oscillatory shear

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Key question: Since viscoelastic response evolves across a spectrum
SOR Short Course
on Colloidal Gels of time scales, which frequency do I choose to measure?
October 2021 34
 Measurement methods to track the gelation process
Linear viscoelasticity and continuum-scale mechanical descriptors
• Advanced methods: “Chirp” protocols

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Key consideration: Probing rheology during gelation requires careful
SOR Short Course
on Colloidal Gels selection of parameters so as not to disturb the nascent gel structure.
October 2021 35
Measurement methods to track the gelation process
Microrheology and meso-scale mechanical descriptors

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SOR Short Course

on Colloidal Gels
October 2021 36
Experimental determination of the gel point
Tracking percolation using particle-scale and meso-scale descriptors

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SOR Short Course

on Colloidal Gels
October 2021 37
Experimental determination of the gel point
Tracking dynamic arrest using meso-scale descriptors

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SOR Short Course

on Colloidal Gels
October 2021 38
Experimental determination of the gel point
Tracking emergence of elasticity using rheological descriptors

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SOR Short Course

on Colloidal Gels
October 2021 39
 How a gel?
Key questions
What are the kinetic processes by which colloidal gels form in time, and how do we model them?
Gels form by attractive “bond” formation and attraction-hindered diffusion, which can be
modeled as a reaction-diffusion process and resulting fractal behavior.
What measurable descriptors are available to track the gelation process, and what is their
expected behavior during gel formation?
Particle-scale descriptors: p(Nc), p(Vc), cluster analysis
Meso-scale descriptors: S(q), f(q,t), MSD
Continuum-scale descriptors: linear viscoelasticity
How does solid-like rheology emerge from gelation process(es), and what sets the gel point (i.e.,
when does a gel become a gel)?
Although analogies to chemical gels are useful in understanding the gel point as a singularity
(with associated critical scaling of structure and viscoelasticity), there is no clear unique definition
of the gel point, and answers differ depending on the descriptor used

SOR Short Course

on Colloidal Gels
October 2021 40
 What a gel?
Key questions

How well does the reaction-diffusion picture of gelation describe the

gelation process for the three canonical morphologies?

What are the characteristic structures and dynamical processes

associated with ?

How does solid-like rheology emerge from gelation process(es), and

what sets the gel point (i.e., when does a gel become a gel)?

SOR Short Course

on Colloidal Gels
October 2021 41
 Reminder – the three morphologies

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SOR Short Course

on Colloidal Gels
October 2021 42
 Dilute / percolation / “stringy” gels

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SOR Short Course

on Colloidal Gels
October 2021 43
 The role of bond “reversibility” in gel formation
Irreversible vs. thermoreversible gelation (“cold” and “hot” gels)

Primary/secondary minima,
attraction-hindered diffusion,
thermoresponsive interactions

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Key observation: Reaction-diffusion models tend to work best for irreversible
SOR Short Course gels. RLA-type models capture some features of reversible gels, but new
on Colloidal Gels physics emerge… 44
October 2021
 Arrested (?) phase separation
Kinetics of phase separation processes – a primer

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SOR Short Course

on Colloidal Gels
October 2021 45
 Arrested (?) phase separation
Length scales of phase separation and their evolution during gelation

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Key question: How does emergent elasticity influence the mechanics
SOR Short Course
on Colloidal Gels of phase separation (and vice versa)?
October 2021 46
 Arrested (?) phase separation
The influence of viscoelasticity on the phase separation process

Tanaka – viscoelastic phase separation

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SOR Short Course

on Colloidal Gels
October 2021 47
 Arrested (?) phase separation
The influence of viscoelasticity on the phase separation process

Cipelleti – intermittent, “superdiffusive” behavior

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SOR Short Course

on Colloidal Gels
October 2021 48
 Arrested (?) phase separation
The influence of viscoelasticity on the phase separation process

Helgeson – coarsening by “microyielding”

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SOR Short Course

on Colloidal Gels
October 2021 49
 Learning outcomes
• Understand the colloidal interactions that give rise to gelation behavior

• Identify the three primary gelation mechanisms/morphologies, and their

relation to equilibrium and non-equilibrium colloidal thermodynamics

• Be familiar with aggregation/percolation processes, their theoretical

description by classical models, and how they relate to the process of gelation

• Be able to identify various structural and rheological descriptors of the gelation

process, measurements to characterize them, and their characteristic features
during gelation

• Know how to differentiate gel morphologies based on their distinct structural

and rheological characteristics
SOR Short Course
on Colloidal Gels
October 2021 50