Colloidal Gels:

Formation, Structure & Rheology

Society of Rheology Short Course

SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels 1
October 2021
 Instructor Bios
Prof. Matthew E. Helgeson
Associate Professor, Chemical Engineering
Tool Development Co-Lead, BioPACIFIC MIP
University of California, Santa Barbara
biopacificmip.org
Society of Rheology Short Course
SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels
October 2021
Education
B.S. 2004 Chemical Engineering, Carnegie Mellon
Ph.D. 2009 Chemical Engineering, U. Delaware
Postdoc Massachusetts Institute of Technology
Research Interests
• Design and flow/thermal processing of colloidal
particles and solids
• Rheology of colloidal dispersions, emulsions and
polymers
• Development of in situ measurements (scattering,
microscopy, microrheology) for probing fluid
structure and dynamics in flow
2
 Instructor Bios
Prof. Safa Jamali Education
Assistant Professor, Chemical Engineering B.S. 2008 Polymer Engineering, Amirkabir (Tehran)
Northeastern University Ph.D. 2009 Macromolecular Sci., Case Western
Postdoc Massachusetts Institute of Technology

Research Interests
• Physics and dynamics of colloidal systems at
different concentrations and interactions
• Data-driven methods for complex fluid modeling:
rheology-informed machine learning
• Hemorheology and hemodynamics, from blood
rheology to liquid biopsy for cancer diagnostics

Society of Rheology Short Course

SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels 3
October 2021
 Instructor Bios
Prof. Roseanna N. Zia Education
Associate Professor, Chemical Engineering B.S. Mechanical Engineering, Univ of Missouri
Stanford University Ph.D. 2011 Mechanical Engineering, Caltech
Postdoc Princeton University

Research Interests
• Theoretical modeling of flowing colloidal
suspensions
• Computational modeling of hydrodynamically
interacting suspensions
• Vitrification and gelation – fundamental aspects of
arrested phase transition

• Combining mesoscale physics, chemistry, and

cellular-level biology into models of biological cell
Society of Rheology Short Course function
SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels 4
October 2021
 Agenda
Saturday, October 9 (all times EST)

8:30 – 8:45 Introduction & Overview 1:00 – 2:30 Part 2. Linear viscoelasticity,
aging and yielding
8:45 – 10:00 Part 1. Colloidal gel formation
& structure 2:30 – 3:00 Break

10:00 – 10:15 Break 3:00 – 4:00 Part 2. Linear viscoelasticity,

aging and yielding
10:15 – 12:00 Part 1. Colloidal gel formation
& structure 4:00 – 5:00 Wrap-up & discussion

12:00 – 12:50 Lunch (outside tent)

Society of Rheology Short Course

SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels 5
October 2021
 Agenda
Sunday, October 10 (all times EST)

8:30 – 10:00 Part 3. Nonlinear rheology & 12:45 – 2:30 Live Demos
flows of colloidal gels

10:00 – 10:15 Break Option 1. Rheological measurements of

10:15 – 11:50 Part 3. Nonlinear rheology &
flows of colloidal gels
11:50 – 12:40 Lunch (outside tent)
colloidal gels: experimental design
Option 2. In silico simulation of colloidal
systems: gel formation and flow

Society of Rheology Short Course

SOR 2021 Annual Meeting
October
SOR Short Course 9-10, 2021
on Colloidal Gels 6
October 2021
 What is a gel?
Gel (n): A volume-spanning (percolated) Chemical gel: Bonds between elements are
network of bonded elastic elements. irreversible, creating a permanent
network. (e.g., crosslinked polymer - rubber)

Physical gel: The bonds between elements are

reversible, resulting in a network that
rearranges over observable time scales.
(e.g., associative polymer - gelatin)

Distinguishing features/properties

Chemical gel Physical gel

Network structure Static Dynamic

Elastic over Viscous at (sufficiently)

Linear viscoelasticity
all frequencies low frequencies
Colombo & Del Gado, Soft Matter, 2014, 10: 4003-4015.

Mechanical failure Typically Ductile/

SOR Short Course mode brittle yielding
on Colloidal Gels
October 2021 7
 What is a colloidal gel?
Colloidal Gel (n): A volume-spanning
physical network of bonded colloidal
objects (particles, droplets, proteins, etc.).
Simulation rendering from Roseanna Zia group
SOR Short Course
on Colloidal Gels
October 2021
Common rheological features
• Elastic-dominant linear response: Network is
sufficiently rigid so as to resist deformation and flow
• Aging: Because of the physical nature of the
network, gel structure and rheology are intrinsically
age-dependent.
• Yielding: After sufficient stress is applied to the
network, it begins to rearrange and flow.
• Shear thinning: Once broken densification,
breakdown and alignment of aggregates reduces
material viscosity.
• Thixotropy: Interplay between thermal and flow-
induced structural rearrangements lead to significant
history and time-dependence of response to
nonlinear deformations.
8
Common applications and rheological design of colloidal gels
Texture Workability Locomotion

R. Mezzenga et al., Nature Mater., 2005 B.Y. Ahn et al., Science, 2009 “Robosnail”, Peko Hosoi Lab, MIT

Better design principles for the structure and rheology of colloidal gels could have a
significant impact in numerous contemporary technologies.

Mechanics Photonics Adhesion

1 mm 10 μm

SOR Short Course 9E. Filippidi et al., Royal Soc. Interface, 2015
G.E. Fantner et al., Nature Mater., 2005 E. Dufresne et al., Soft Matter, 2009
on Colloidal Gels
October 2021 9
 Learning outcomes
Part 1. “The birth of a gel” – Colloidal gel formation & structure
• 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 10
 Learning outcomes
Part 2. “The life of a gel” – Linear viscoelasticity, aging & yield
• Understand the structural basis of why gels stiffen with age

• Understand the role of particle dynamics in gel formation and aging

• Identify common features of glasses and gels

• Be able to describe gel yield from both mechanical and phase

behavior perspectives

• Be able to identify various modes of gel yield and re-solidification,

and particle-scale strategies that can affect both

SOR Short Course

on Colloidal Gels
October 2021 11
 Learning outcomes
Part 3. “The death of a gel” – Nonlinear rheology & flow behavior
• Understand the mean field predictions for linear and weakly non-linear rheology of colloidal gels:
elastic modulus, yield stress, limit of linearity

• Be able to identify thixotropic behavior and its rheological consequences: hysteresis curves, time
dependent stress response

• Familiarity with different thixotropic constitutive models, and recovery of thermokinematic memory

• Identify methods of thixotropic timescale measurement, and appropriate dimensionless groups that
describe gel rheology

• Understand flow-structure coupling in colloidal gels, and familiarity with the concept of leveraging
this coupling to tune properties

SOR Short Course

on Colloidal Gels
October 2021 12
 Learning outcomes
Demo 1. Rheological measurement of colloidal gels
• Design experiments for careful, interpretable rheological measurements on
colloidal gels

• Understand the impact of sample loading and pre-shear on gel structure and
rheology

• Design rheometric experiments to minimize and assess the influence of wall slip

• Perform measurements to characterize various gel processes and rheology

(formation, aging, yielding, flow) using common flow protocols

• Interpret rheological data on colloidal gels

SOR Short Course

on Colloidal Gels
October 2021 13