EGDM01 – Colloid & Interface Science

Professor Huw Summers

h.d.summers@swansea.ac.uk
 ANNOUNCEMENTS
All course announcements will be made at the start of the zoom sessions
NOT
Via the Canvas course pages
 • 18 lectures delivered on zoom
Monday 18.00-19.00
Tuesday 18.00-19.00

• Lecture recording and powerpoint file posted after each session

• Guided problems sessions in mid-semester (1 week)

practise in exam-format questions

• Revision and review in final week of semester

• Weekly online office hour – THURSDAY 9.00-10.00?

NOTE: I did not write this course and have not delivered it before

Aim – to deliver clear information on the essential learning outcomes and

present a good general understanding of colloidal systems
What I want to talk about is the problem of manipulating and controlling things on a small scale.
What would happen if we could arrange the atoms one by one the way we want them? 

Arguably the start of Nanotechnology, in which colloids play a central role.

 1: Introduction to Colloids

• The Colloid State

• Classification of colloidal systems
• Lyophilic and Lyophobic sols: stability and instability
sol - a fluid suspension of a colloidal solid in a liquid
The colloid state
 The colloid state

What do detergents, mayonnaise, paint, cigarette smoke and other products have in common?

BUTTER:
MILK:
Fine oil droplets in
Fine droplets of oil and CHOCOLATE:
suspension in water
micelles of casein in Fine cocoa butter
suspension in whey.
particles in water or
milk

PAINT: BEAUTY CREAM: CIGARETTE SMOKE:

Fine powder of coloured Micelles and/or Fine solid particles in
pigments (organic or particles in suspension suspension in air
mineral) and polymers in in water or oil
suspension in water

All these materials are colloids, i.e. very fine particles (with diameters ranging between a
thousandth and a millionth of a millimetre) dispersed into a continuous medium (gas, liquid,
plastics etc.).
Huge commercial market with success dependent upon stability of these formulations.
 Significance of colloids

 Analytical chemistry: adsorption indicators, ion exchange, blood analysis, precipitate

filterability, chromatography, and decolourization
 Physical chemistry: nucleation, superheating, supercooling and supersaturation, and liquid
crystals
 Biochemistry and molecular biology: electrophoresis, osmotic equilibria, viruses, nucleic acids
and proteins, haematology
 Chemical manufacturing: catalysis, soaps and detergents, paints, adhesives, inks, paper and
paper coating, pigments, thickening agents and lubricants
 Environmental science: aerosols, fog and smog, foams, water purification and sewage
treatment, cloud seeding and clean rooms
 Materials science: powder metallurgy, alloys, ceramics, cement, fibers, and plastics of all sorts
 Petroleum science, geology and soil science: oil retrieval, emulsification, soil porosity, flotation
and ore enrichment
 Household and consumer products: milk and dairy products, beer, water proofing, and
cosmetics
Industrial production using colloids

Almost all the ancient and modern craft industries require colloid science:

Paper making – cellulose fibres used in the meshwork and clay used as a filler to improve opacity and
shinny texture
Pen ink, printer ink, paint and cosmetics – colloidal constituents and their interactions give required
special flow properties to the final product
Ceramics from expensive china models to building bricks – made from clay/water sols
Plastics and textile industries – production controlled through colloidal chemistry
Food processing, preserving and packaging
Brewing of beer / clarifying of wine
Cake mixes
Extracting oil from geological deposits and converting it to petrol
Dispensing of domestic products
Agriculture; delivery of insecticides and weedkillers
Environmental and biological significance of colloids

Many pollution problems can be solved using colloid techniques

The clarification of air and water is essentially a colloidal problem

Biomedical applications

The flow properties of blood are best understood as a colloidal suspension of

(deformable) flat plates (the red blood cells) and a liquid

The flow properties of material in the lower digestive tract must sometimes
be modified using colloidal techniques to treat constipation or diarrhoea

The remarkable lubrication of joints by synovial fluids is due to its colloidal

properties

Adhesion between cells and surfaces.

Historical examples of colloids

Ink on papyrus dating from about 1200BC containing nanoparticles of soot.

 Historical examples of colloids

The Lycurgus cup consists of gold nanoparticles

that create stain glass. Gold has the property of
changing colour when cut into small pieces,
thus giving colour to the glass.
Stained glass at Notre Dame Cathedral
Defining the colloid state
 What is a colloid? – first understandings……
Michael Faraday: Bakerian Lectures 1857
“Experimental Relations of Gold (and other metals) to Light”
In his Bakerian Lectures of 1857, proposed that microscopic particles of silver and gold are responsible for the beautiful
coloration of the famed ruby-gold decorative glasses.

Gold sols had been known to alchemists in the 17th century, but Faraday was the first to present a scientific paper on their
properties and preparation. The preparations of gold sols that Faraday studied were ruby-red in colour: "part of the gold is
reduced in exceedingly fine particles, which becoming diffused, produce a beautiful ruby fluid.“

Faraday discovered that he could turn the preparation blue by adding certain salts. Gold sols coagulate when salts are
added, although this can be prevented by the addition of gelatin.

‘Mesogold is an all
natural mineral
supplement’ !!!
What is a colloid? – first definition

1861 paper - “Liquid Diffusion applied to Analysis” in the Philosophical Transactions,

Thomas Graham described the results of a simple investigation.
Aqueous solutions were placed in a cylindrical vessel the bottom of which was formed by a piece of animal
membrane, like pig’s bladder, or by parchment paper, and the membrane immersed in water. The amount of
dissolved substance which diffused into the outer water was determined from time to time.
Graham found that the numerous substances examined fell into two classes: those which diffused in
appreciable amounts and those which hardly passed through the membrane in perceptible quantities. The
former were without exception substances known to crystallize from their solutions, like various salts or
sugar, while the latter, among which were albumin, gum or gelatine, had never been known as crystals.
Graham called the 1st class crystalloids and the 2nd class colloids (from colla, meaning glue).

Wolfgang Ostwald (27 May 1883 – 22 November 1943)

Colloids: “…any substance consisting of particles substantially larger than atoms or ordinary molecules but too
small to be visible to the unaided eye; more broadly, any substance, including thin films and fibres, having at
least one dimension in this general size range, which encompasses about 1 nm to 1 micron…”

Nowadays other names are used:

Nanofluids, Biocolloids, Nanoparticles
 Generalisation of types of disperse systems
(W. Ostwald)

Disperse systems

suspensions colloidal dispersions solutions

> 1000 nm 1 - 1000 nm < 1 nm

Colloids may be seen as a subset of

specific size range
What is a colloid? – other definitions

A colloid is a type of mechanical mixture where one substance is dispersed evenly throughout another. Because
of this dispersal, some colloids have the appearance of solutions.
A colloidal system consists of two separate phases: a dispersed phase (or internal phase) and a continuous
phase (or dispersion medium).
A colloidal system may be solid, liquid, or gaseous.

All colloidal systems consist of small "particles" of one substance distributed more or less uniformly throughout
another.
The latter phase is continuous whilst the “particles” are discontinuous.
 - Their size should be >> than the solvent molecules.
 - Their size range is typically 1 nm to a few 1000nm (few microns).
 - A very important property is that their surface area is very large.
Discontinuous phase

Continuous phase
It is not necessary that all the dimensions of the dispersed particles be very small for the system to be of interest to
colloid scientists.

1-1000 nm

Textile fibres or cellulose fibres in paper 1-1000 nm

industry

Bubbles in foam e.g. in a head of beer

The only real requirement for a system to behave as a colloidal system is that the surface area be large
The radius, area and volume per particle, number of particles, and total area for an array of spheres after n “cuts” where a
cut is defined to be the reapportionment of material into particles whose radius is half the starting value

Cut Radius Volume per Number of Area per Total area

Number (cm) sphere spheres sphere (cm2)
(cm3) (cm2)
Original 1 4.19 1 12.6 12.6
The exponential
1 0.5 0.524 8 3.14 25.1
expansion in surface
2 0.25 6.55  10-2 64 0.786 50.3
area as size decreases
3 0.125 8.18  10-3 512 0.196 101
4 0.0625 1.02  10-3 4096 0.0491 201
5 0.03125 1.28  10-4 32768 0.0123 403
. . . . . .
. . . . . .
. . . . . .
N 0.5n Ro 0.125n Vo 8n No 0.25n Ao 2n AT o
. . . . . .
Ro original radius . . . . . .
. . . . . .
Vo original volume
13.29 10-4 4.2  10-12 1012 1.26  10-7 1.26  105
No original number of spheres 16.61 10-5 1015
4.2  10-15 1.26  10-9 1.26  106
Ao original area of individual sphere 19.93 10-6 1018
4.2  10-18 1.26  10- 1.26  107
11
AT o original total area
23.25 10-7 4.2  10-21 1021 1.26  10- 1.26  108
13

26.58 10-8 4.2  10-24 1024 1.26  10- 1.26  109

15
Classifying colloid states
Classifying colloid systems

Colloidal systems may be grouped into three general classifications:

 Colloidal dispersions are thermodynamically unstable owing to their high surface free
energy and are irreversible systems in the sense that they are not easily reconstituted after
phase separation.
 True solutions of macromolecular material (natural or synthetic) are thermodynamically
stable and reversible in the sense that they are easily reconstituted after separation from
the solvent.
 Association colloids which are thermodynamically stable and involve the formation of
micelles.
Dispersions
 Particles are large enough for definite surfaces of separation to exist between the
particles and the medium
 Simple dispersions are 2 phase systems: dispersed phase and dispersion medium
 Physical nature of a dispersion depends on the roles of the constituent phases e.g. an
oil-in-water (O/W) emulsion and a water-in-oil (W/O) emulsion could have almost the
same overall composition, but their physical properties could be notably different
 Sols are the most important type. The term sol is used to distinguish colloidal
suspensions from macroscopic suspensions. When water is the solvent the term
hydrosol is used
 Foams are different as it is the dispersion medium which has colloidal dimensions
The importance of the interface
 Characteristic feature of colloidal dispersions is the large area to volume ratio for the
particles
 At the interface, surface properties such as adsorption and electric double layer
effects, play an important part in determining the physical properties of the whole
system
 The material within the molecular layer close to the interface exerts the greatest
influence on particle-particle and particle-dispersion medium interactions
 Substantial modification of the bulk properties of colloidal suspensions can be
effected by small quantities of a suitable additive
 Surface science is closely linked with colloid science
Classification of Colloidal systems
What type of colloidal dispersions are the following?

Ice Cream Solid emulsion or a solid foam

Milk Emulsion of fat(oil) in water
Hairspray Aerosol (liquid in gas)
Bitumen Solid emulsion
Insulation Foam Solid foam (gas solid dispersion)
Fruit Jelly Colloidal sol (solid polymer in liquid)
Blood Colloidal sol (solid polymers and cells in liquid)
Ink Colloidal sol (solid polymers in liquid carrier)
Swansea Bay Beach (on a Colloidal sol (silica particles and water)
wet day)
Quantum dot labelled Solid in a gel (colloidal sol)
cell
Thermodynamic stability
of colloids
Colloids are traditionally divided into two classes called lyophilic and lyophobic depending on the ease of re-
dispersing the system (when water is the solvent they are known as hydrophilic and hydrophobic)

Lyophilic colloids can be dispersed simply by Lyophobic colloids can only be dispersed by
adding a suitable solvent rigorous mechanical action
ie. making jelly with Gelatin

Discontinuous phase / Disperse Phase

Continuous phase / Dispersion Medium

Lyophilic colloids "solvent loving"

 
Easier to disperse
Disperse by adding a suitable solvent to the dry colloid which will first swell as it takes up liquid and will
finally form a homogeneous colloidal solution.
Thermodynamically stable The solution has a lower Gibbs free energy than the separated components.
Such a sol can be stable indefinitely. Very stable colloidal systems not obviously affected by electrolyte
concentration unless it is high.
Lyophobic colloids "solvent hating"

Harder to disperse
There is an attractive force (van der Waals) between colloids, thus if they get too close they will be linked
together
Thermodynamically unstable The system can be made to appear stable for some time if some force is
present which can reduce the chance of the particles closely approaching one another in the course of
Brownian motion. That is, they are kinetically stable.
Stability in this case is a relative concept there are some highly stable lyophobic colloids that remain stable
for months however they will ultimately form aggregates.
Stability can be altered by controlling the electrolyte concentration, if repulsive forces between particles
not high enough they will flocculate.
 LEARNING OUTCOMES

• General appreciation of the importance of colloids to a broad range of sciences

• Knowledge of specific examples of colloids and industrial products using them

• Provide a definition for what is a colloid?

• Be able to classify colloids into different classes of:

aerosol, sol, hydrosol, emulsion, foam, dispersion, solid emulsion & solid foam