CH3E7 Colloidal Materials

Stefan A. F. Bon
University of Warwick

twitter.com/bonlab
www.bonlab.info
youtube.com/bonlabTV
 Structure of this module:
18 interactive lectures
introduction to colloids, production of colloidal particles, droplets and
bubbles. Focus on polymer colloids: (mini)emulsion polymerization. more
complex particles: hybrids, anisotropic, supracolloidal particles

soft matter physics: forces on the colloidal domain, interfacial tension and
Ostwald ripening, how do particles behave in liquids?, particle-particle and
particle-substrate interactions, kinetics of coagulation, rheology of
colloids

physical and mechanical characterization of particles. (Self-)assembly of

macromolecules and particles with a special on using Pickering
stabilization as a tool, from film formation to colloidal crystals and
bandgap materials.

100% written exam

7.5 CATS
Polymer Colloid/Latex
 Emulsion
polymerization
Hybrid biological spores wrapped in a mesh
composed of interpenetrating polymer
nanoparticles as “patchy” Pickering stabilizers

!
N.Ballard, S.A.F. Bon Polym.Chem. 2011, 2(4),
823-827.
Particle Interactions (DLVO)
 Homogeneous Clusters

Science 29 January 2010:

Guangnan Meng, Natalie Arkus, Michael P. Brenner, and Vinothan N. Manoharan Vol. 327. no. 5965, pp. 560 - 563
DOI: 10.1126/science.1181263
 What do we mean with self-assembly?
Spontaneous formation of an organized “supra” structure

Fortuna, S.; Colard, C.A.L.; Troisi, A.; Bon, S.A.F. , Langmuir, 2009, 25
12399-12403 DOI: 10.1021/jp811473q
Equilibrium Self-Assembly vs. Dynamic/Dissipative Self-Assembly
Soft Matter, 2009, 5, 1110-1128 DOI:10.1039/B819321P
(Tutorial Review) [ additional info: DOI: 10.1039/b902046m]
Colloidal Crystalline Opals
Inverse-Opal Photonic Bandgap Material

Y. A.Vlasov et al., Nature 414, 289 (2001).

 Introduction to Colloids
colloid (classical Greek word kolla + “-oid”),
coined by Thomas Graham (1805-1869)
Thomas Graham, On the Properties of Silicic Acid and Other Analogous
Colloidal Substances, J. Chem. Soc. London, 1864, 17, 318-323.

One phase is dispersed into the other phase (e.g. milk)

Q1: let us take two ideal gases, tentatively named A and B. Can we
prepare a colloid of gas A dispersed in gas B, or vice versa?

a) No
b) Yes
 In an ideal gas the molecules do not have a volume and do not have an
interaction with each other. For mixing ideal gas A and B:
The Helmholtz (constant V) free energy of mixing per lattice site for
ideal mixtures is purely entropic:
⎛ φA φB ⎞
Δ Amix = − TΔS mix = kT ⎜ ln φ A + ln φB ⎟
⎝ NA NB ⎠

NA = 10; NB =10
Δ Amix
kT

NA = 10; NB =1

NA = 1; NB =1

φA
Classification of dispersed colloidal systems

Continuous
Gas Liquid Solid
phase
Foam: whipped Solid Foams:
Gas cream, shaving
purnice, styrofoam
cream

Liquid Liquid aerosol Emulsions: milk, Gel: agar, gelatin

hair spray, fog mayonnaise

Solid Solid aerosol Sol: pigmented ink Solid Sol:

cranberry glass
 The dispersed phase retains
some bulk properties, but
can gain new properties
(e.g. a gold sol)

Typical sizes are ca. 2 nm up to a few microns (often

used as indicator: gravitational forces can be neglected)
 Some ancient colloids...

Lycurgus Cup (late Roman 4th

AD) : when lit from the outside
(reflectance) and inside
(transmission).

The Lycurgus Cup – A Roman Nanotechnology

By Ian Freestone, Nigel Meeks, Margaret Sax and Catherine Higgitt

Gold Bulletin, Vol. 40:4, 270-277. (2007)

Egyptian black ink on papyrus (1200 BC):
nanoparticles of soot dispersed with Gum
Arabic

Egyptian Hair dying lead to the formation

of PbS quantum dot clusters in the hair
cortex. Philippe Walter, NanoLett, 1 sept
2006, DOI: 10.1021/nl061493u
 The importance of the surface area
Q2: How many football pitches, N, of
Nou Camp (FC Barcelona) area A with
dimensions 105 x 68 m, can we cover
with a monolayer of monodisperse
spherical polymer particles of diameter
d =100 nm, if the total amount of
particles m sums up to 1 kg (assume
density, ρ, of polymer is 1000 kg/m3)?
Note that P stands for the packing
density of the particles
We are looking at a monolayer of particles, hence it is a 2D problem. We
have to find out how to arrange our particles. Two possible options are:

the area of a circle is (π/4)d2, the volume of a sphere (π/6)d3,

hence area-to-volume ratio for a single particle: 3/(2d)
We have to multiply this with the total volume of all particles (m/ρ) to get
the actual total area covered by the particles

Because of their shape there are interstitial spaces, hence, we have to divide
by the values for the packing densities (square packing, P = π/4; hexagonal
packing P = (π/6)√3) to get a value for the effective area covered.

Finally divide this with A, which yields N = 2.31 (hex), N = 2.67 (sq).
 Capillarity: study of the interfaces between two
immiscible liquids, or between a liquid and a gas (air)

Pioneers: Thomas Young (1773-1829), Pierre-Simon Laplace (1749-1827), Carl

Friedrich Gauss (1777-1855).

Physical origin of interfacial/surface tension, γ:

Cohesive energy, U.

Molecule at interface looses approx: (1/2)U

hence, γ ≅ U/(2a2) with a being measure for

size of molecule
Q3 What are correct units for surface tension?

a) milliNewton per meter (mN m-1)

b) milliJoules per square meter (mJ m-2)
c) milliJoules per meter (mJ m-1)
d) both answer a) and b) are correct
Laplace pressure
Statements:

When we make a droplet of oil in water smaller and smaller (in absence of an
external field) it becomes a sphere as this geometry has the lowest area-to-
volume ratio of possible shapes and hence will minimize the total surface
energy

a) true
b) false

...therefore is this logic prevails all nanoparticles will be spherical!

a) true
b) false
A large variety of shapes

A Transmission Electron Micrograph of the

Cd-based nanoparticles.
aluminium-chloro-hydrate-treated colloidal
Nature 437, 664-670 (29 September 2005) |
gibbsite platelets. The scale bar denotes 500 nm.
doi:10.1038/nature04165
Europhys. Lett., 61 (5), p. 702 (2003)
Tobacco Mosaic Virus
(assembled structure consisting of one Bonlab: amphiphilic triploid
strand of RNA chain wrapped inside a polymer colloids
colloidal armor/coat of 2130 units of a
small protein, stacked together like a
chimney, DOI: 10.2210/rcsb_pdb/mom_2009_1)
Lyophilic colloids: are thermodynamically stable, disperse spontaneously
(e.g. microemulsions, microgels in good solvents)

Lyophobic colloids: thermodynamically unstable, exhibit tendency for

aggregation (coagulation, flocculation, coalescence)