Dispersed Systems

FDSC400
2004 Version
 Goals
• Scales and Types of Structure in Food
• Surface Tension
• Curved Surfaces
• Surface Active Materials
• Charged Surfaces
COLLOIDAL
SCALE
 Dispersed Systems

A kinetically stable mixture of

one phase in another largely
immiscible phase. Usually at
least one length scale is in the
colloidal range.
Dispersed Systems

Dispersed phase

Continuous phase

Interface
 Continuous phase
Solid Liquid Gas
Dispersed phase

Solid Some Sol Smoke

glasses
Liquid Emulsion Aerosol

Gas Solid Foam

foam
 Properties of Dispersed Systems
• Too small to see
• Affected by both gravitational forces and
thermal diffusion
• Large interfacial area
– SURFACE EFFECTS ARE IMPORTANT
 Increased Surface Area

We have 20 cm3 of oil in 1 cm The same oil is split into 0.1

radius droplets. Each has a
volume of (4/3.p.r3) 5.5 cm3
and a surface area of (4.p.r2)
12.5 cm2.
As we need about 3.6 droplets
we would have a total area of
45.5 cm2
cm radius droplets, each has a
volume of 0.004 cm3 and a
surface area 0.125 cm2.
As we need about 5000
droplets we would have a total
area of 625 cm2
 For a Fixed COMPOSITION
• Decrease size, increase number of particles
• Increase AREA of interfacial contact

decrease area
 Tendency to break
• LYOPHOBIC • LYOPHILIC
• Weak interfacial • Strong interfacial
tension tension
• Little to be gained by • Strong energetic
breaking pressure to reduce area
• e.g., gums • e.g., emulsions
Surface Tension
-molecular scale-
 Surface Tension
-bulk scale-
Force, g
Slope g

Interfacial energy

Area, A

Interfacial area
 Surface Active Material
• Types of surfactant
• Surface accumulation
• Surface tension lowering
Types of Surfactant
-small molecule-

Hydrophilic head group (charged or polar)

Hydrophobic tail (non-polar)

Types of Surfactant
-polymeric-

Polymer backbone

Sequence of more water

soluble subunits

Sequence of less water

soluble subunits
 Surface Binding

Equilibrium

ENTHALPY COST ENTROPY COST

Surface concentration /mg m-2 Surface Binding Isotherm

Surface saturation

No binding below a certain

concentration

ln Bulk concentration
 Surface Tension Lowering

Bare surface Interface partly “hidden”

(tension g0) (tension g)

Surface pressure – the

ability of a surfactant to p = g-g0
lower surface tension
 Summary
• Small particles have a large surface area
• Surfaces have energy associated with them (i.e.,
they are unstable) because of their interfacial
tension
• Dispersions will tend to aggregate to reduce the
interfacial area
• Proteins and small molecule surfactants will
adsorb to the surface to reduce surface tension and
increase stability.
Example Dispersion: Emulsions
 Emulsion

A fine dispersion of one liquid in a

second, largely immiscible liquid. In
foods the liquids are inevitably oil
and an aqueous solution.
 Types of Emulsion
mm

Water

Oil

Oil-in-water emulsion Water-in-oil emulsion

Chemical Composition

Interfacial layer. Essential to

stabilizing the emulsion

Oil Phase. Limited effects on

the properties of the emulsion

Aqueous Phase. Aqueous

chemical reactions affect the
interface and hence emulsion
stability
 Emulsion Size
• < 0.5 mm
A • 0.5-1.5 mm
• 1.5-3 mm
• >3 mm
Number Distributions

Very few large

droplets contain
most of the oil

0.5-1.5 mm
1.5-3 mm
< 0.5 mm

>3 mm
•
•
•
•
 35
(Volume in class Total volume measured)
30 Large droplets
Emulsion 3often contribute
25 Median most to
Frequency /%

Emulsion 5 instability
20

15
Emulsion 1
10

0
0.1 1 10
Diameter /mm Note log scale
 Volume Fraction
f=Total volume of the dispersed phase
 Total volume of the system

Close packing, fmax

Monodisperse
Ideal ~0.69
Random ~0.5

Polydisperse
Much greater
 Emulsion Viscosity
Dispersed phase
Viscosity of emulsion volume fraction

= 1  2.5f
0
Continuous 0.8
0.7 Slope=2.5
phase
0.6
viscosity

Viscosity
0.5
Emulsion droplets 0.4
disrupt streamlines 0.3
0.2
and require more 0
0.1
effort to get the 0
same flow rate 0 0.1 0.2
Volume Fraction
 Emulsion Destabilization
• Creaming
• Flocculation
• Coalescence
• Combined methods
 Creaming
Buoyancy pd g
3
(Archimedes) Fb = 
6
d g
2
vs =
18c
Friction  Continuous phase viscosity
(Stokes-Einstein)  density difference

= 3pdv
g Acceleration due to gravity
d droplet diameter
v droplet terminal velocity
vs Stokes velocity
Flocculation and Coalescence

FLOCCULATION

COALESCENCE
 Aggregation Kinetics
• Droplets diffuse around and will collide often
• In fact only a tiny proportion of collisions are
reactive

G
2P
G
kslow=kfast/W
P2

Function of energy barrier

 Interaction Potential
• Non-covalent attractive and repulsive forces
will act to pull droplets together (increase
flocculation rate) or push them apart
(decrease flocculation rate)
 Van der Waals Attraction
• Always attractive
• Very short range
 Electrostatic Repulsion
• Repulsive or attractive depending on sign of
charges
• Magnitude depends on magnitude of the
charge
• Gets weaker with distance but reasonably
long range
 Steric Repulsion

Droplets Protein layers Proteins repel each

approach each overlap other mechanically &
other by osmotic dehydration

What happens when protein molecules on different droplets are reactive?

Rheology of Flocculated
Emulsions
• Flocculation leads to an
increase in viscosity
• Water is trapped within
the floc and must flow
with the floc
• Effective volume fraction
increased

rg
 Gelled Emulsions
Thin liquid Viscous liquid Gelled solid