CHM 202

(COLLOID & SURFACE

CHEMISTRY)

LECTURE II
by

Dr Andrew Terhemen Tyowua

Applied Colloid Science & Cosmeceutical Group,
Department of Chemistry,
Benue State University, Makurdi, Nigeria
1
 Lecture Outline
• Detailed description of selected colloidal systems:
▪ emulsions
▪ foams
▪ suspensions

2
 Learning Outcomes
After the lecture, students should be able to give a detailed
description of:
▪ emulsions (and also state the theories of emulsification),
▪ foams &
▪ suspensions, with related applications.

3
 Emulsions
• Emulsions are thermodynamically unstable heterogeneous
mixture of two immiscible liquid phases in which one of the
liquids is dispersed as droplets of microscopic or colloidal
size in the bulk of the other liquid in the presence of
emulsifiers which enhance their kinetic stability.
• The dispersed phase is also known as the discontinuous,
inner or internal phase whilst the continuous phase is also
known as the external or outer phase.
• Emulsifiers (or emulgents) are substances that enable the
dispersion of the dispersed phase in the bulk continuous
phase. Examples of emulsifiers are surfactants, polymer
molecules, small inorganic solid particles, small organic
pigment particles.

4
Examples of Emulsifiers

Surfactants

Fumed silica particles

Sodium dodecyl sulphate (SDS) Soft Matter, 2013, 9,
834-845

Polystyrene particles
5
 dodecane
droplets

water

Photograph and optical micrograph of dodecane-in-water

emulsion stabilised by SDS.

6
Classification of emulsions
• Simple emulsions where liquid droplets are dispersed in
the bulk of another liquid. E.g. oil-in-water (o/w), water-
in-oil (w/o), oil-in-oil (o/o), and water-in-water (w/w)
emulsions.
• Double or multiple emulsions where a simple emulsion is
in turn dispersed in the bulk of another liquid. E.g. oil-in-
water-in-oil (o/w/o), water-in-oil-in-water (w/o/w) and
oil-in-oil-in-oil (o/o/o) emulsions.
• Other complex emulsions like water-in-oil-in-water-in-oil
(w/o/w/o) emulsions are also known.

7
Optical micrograph of a
particle-stabilised o/w/o
emulsion.
Oil
Water
8
Theories of Emulsification
• Emulsification is the process of emulsion formation.
• Experiments have shown that the emulsion type is related
to the properties of the emulsifier.
• According to Bancroft’s rule, dispersing equal volumes of
oil and water in the presence of a surfactant yields o/w
emulsion if the surfactant is more soluble in water and
w/o emulsion if the surfactant is more soluble in the oil.
• For Pickering emulsions (particle-stabilised emulsions);
Finkle and co-workers stated that in an emulsion
containing small solid particles, one of the liquid phases
will probably wet the solid particles more than the other
liquid, with the poorly wetting liquid becoming the
dispersed phase.

9
▪ Particle wettability is quantified in terms of the three-
phase contact angle θ the particles make with liquid
interface.

o/w Bijel w/o

10
• Particle wettability is similar to the concept of hydrophilic-
lipophilic balance (HLB) proposed by Griffin in
surfactant-stabilised emulsions.
• According to Griffin, lipophilic surfactants (with low HLB
values in the range of 1‒7) will form w/o emulsions whilst
hydrophilic surfactants (with high HLB values in the range
of 7‒40) will form o/w emulsions.
• According to Ivanov, both o/w and w/o emulsions are
formed during the homogenisation process but only the
one with lower coalescence rate survives.
• These theories can be extended to cover double and
complex emulsions where more than one emulsifier is
required.

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• During emulsification, the average droplet size of an
emulsion decreases and then becomes constant as the
emulsifier concentration increases. This is due to the two
opposing forces (droplet breakage and droplet-droplet
coalescence) that govern emulsion droplet size.
• At low emulsifier concentration (the emulsifier-poor
regime), the average droplet size rapidly decreases with
increase in emulsifier concentration. This is due to the
process of droplet-droplet coalescence.
• At high emulsifier concentration (the emulsifier-rich
regime), the average droplet size is independent of the
emulsifier concentration and this is due to the process of
droplet breakage.

12
 180
breakage

average droplet diameter/μm

160
140 coalescence
120
100
80
60
40
20 (I) (II)
0
0 1 2 3 4 5
[emulsifier]/wt.%

▪ Region I = emulsifier-poor regime

▪ Region II = emulsifier-rich regime

13
 Foams
(a) Liquid Foams
• Liquid foams are a dispersion of gas bubbles in a liquid
(generally water or an oil). The gas bubbles are the
dispersed phase whilst the liquid is the continuous phase.
• They are kinetically stabilised by surfactants, polymers,
small solid particles or a combination of surfactants and
small solid particles particles.
• Liquid foams are characterised by two structural situations:
▪ Polyhedral gas cells separated by thin liquid films, e.g.
dilute foams and surfactant-stabilised foams.
▪ Spherical or non-spherical gas bubbles, e.g. particle-
stabilised foams.

14
Photograph and optical micrograph of a
surfactant-stabilised foam.
15
Photograph and optical micrograph of a particle-stabilised
foam.
16
(b) Biliquid Foams
• They are cellular materials and are made up of liquid-filled
arrays of cells separated by thin films of another liquid.
• Their structure is similar to that of ordinary liquid foams in
all respect, except that the cells contain a liquid instead of a
gas.
• There are two types of biliquid foams:
▪ oil-lamella biliquid foams where the thin films contain an
oil.
▪ water-lamella biliquid foams where the thin films contain
water.
• Biliquid foams are stabilised by surfactants or small solid
particles.

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• They are made by only concentrating (via evaporation) an
emulsion or followed by centrifugation to deform the
emulsion droplets in some cases. As a result, they are
sometimes called high internal phase emulsions or
emulsion gels.

Confocal laser scanning microscope image of a particle-

stabilised biliquid foam. 18
• Complete removal of the continuous phase usually leads to
the collapse of the cellular network of the biliquid foams
especially if they come from a surfactant-stabilised
emulsion.
(c) Solid Foams
• Solid foams are cellular materials and are considered as a
dispersion of gas bubbles in solids. Two-dimensional and
three-dimensional solid foams are known.
• Unlike in liquid foams where the cells are filled with a gas
and the cell walls are interlinked by films, the cell walls of
solid foams are solid and the cells are filled with either a
gas (e.g. bread, sponge, polymeric cushion) or a liquid
(e.g. animal tissues and honeycomb).
• The honeycombs are good examples of two-dimensional
solid foams whilst the rest examples are three-
dimensional.
19
• The size (diameter) is ≥ 1 μm whilst the cell wall varies
from 1 to 10 μm in thickness depending on the foam.

Photograph of a honeycomb (2-D solid foam)

20
 gas-filled
cells

solid cell
wall

Scanning electron microscope image of a

solid foam.

21
Liquid-filled cells
Alveoli (pl. alveolus)
▪ Example of a biological
solid foam.
▪ They are tiny sacs within
the lungs that allow the
exchange of O2 and CO2
between the lungs and the
bloodstream.

22
• Aerogels (also frozen smoke, solid smoke, solid air and
blue smoke) are another class of solid foams.
▪ Aerogels are ultralight, synthetic porous materials
obtained by replacing the liquid component of a gel with
a gas.
▪ They are ~98% air and their cell sizes are as small as
0.1 μm.
▪ They have extremely low relative density (0.002) and
extremely low thermal conductivity.

An aerogel

23
Properties of Solid Foams
Solid foams have:
▪ low density,
▪ low thermal conductivity,
▪ low stiffness,
▪ low strengths,
▪ large compressive strains.
Selected Applications of Solid Foams
• Their low density allows the design of light, stiff
components like sandwich panels and large portable
structures and other buoyancy applications.
• Their low thermal conductivity permits fabrication of
cheap and reliable thermal insulators.

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• Their low stiffness makes them suitable for a wide range of
cushioning applications.
• Their low strength and large compressive strains make
them idea for energy-absorbing (or shock absorbing) and
packaging applications.
• They are used as filters for different purposes.
• Some are used as car exhaust catalysts and other related
applications.

25
 Suspensions
(a) Colloidal Suspensions
• Colloidal suspensions are a dispersion of colloidal particles
in a liquid. The shape of the particles varies from spherical
to non-spherical and the suspensions themselves may be
aqueous or non-aqueous.
• Suspensions are considered to be dilute when the particles
do not interact and concentrated when the particles interact.
Many concentrated suspensions are viscoelastic compared
with dilute suspensions which are usually fluid.
• The particles in the suspension may be monodisperse or
polydisperse.
• Because of the density difference between the particles and
the bulk continuous liquid, dilute suspensions often tend to
separate out into their component phases.
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(b) Capillary Suspensions
• Capillary suspensions are formed through the action of
attractive capillary force, leading ultimately to particle
bridging and network formation when a small amount of a
secondary immiscible liquid is added to a colloidal
suspension.
• They are ternary particle-liquid-liquid systems where the
two liquids are immiscible like in Pickering emulsions.
• Compared to Pickering emulsions where the liquid droplets
are larger than the particles by several magnitudes and the
volume fraction of the liquid phases is significantly large,
the liquid droplets in capillary suspensions are smaller than
the particles and the secondary liquid is a small fraction of
the total volume of the suspension.

27
• Capillary suspensions have been divided into the:
▪ pendular and
▪ capillary states
• In the pendular state, the minority (secondary) liquid
preferentially wets the particles more than the bulk
(primary) liquid and the particle network is formed through
individual particles and linked by capillary bridges.
• In the capillary state, the bulk liquid wets the particle more
than the secondary liquid. Here clusters of particles
surrounding the droplets of the secondary liquid are linked
together.
• Based on the wetting behaviour of the secondary liquid
phase, it is speculated that particle contact angles < 90° give
the pendular state whilst those > 90° give the capillary state.
• Capillary suspensions are characterised by high viscosity.
28
liquid primary primary
liquid liquid

secondary liquid secondary liquid

particles

(a) Colloidal (b) Pendular state (c) Capillary state

suspension

29
 Confocal scanning
microscope image
of capillary
suspension

Langmuir 2016, 32,

1489-1501.

Selected Applications of Capillary Suspensions

• Preparation of novel food products with reduced fat
content and improved temperature stability.
• Can serve as precursors for ceramic or glass filters with
high porosity and simultaneously small pore size.
• Can be used to improve polymer blends and slurries for
printable electronics with accurately moulded edge shape
and good charge-transfer properties. 30