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Food Colloids
Contents
1. Introduction
2. Factors in colloid stability
3. Gravitational effects - Stokes law
4. Brownian motion
5. Factors in Brownian motion
6. Sedimentation equilibrium
7. Further reading
8. Return to contents page

Introduction
A colloid is a two phase system in which one phase, the disperse phase, is suspended in the
form of very fine particles in a second phase, the continuous phase. Colloids are
distinguished from other forms of suspension by the size of the disperse phase particles
(typically in the range 1 nm - 1 m and by their apparent stability. In fact, colloids are
inherently unstable systems and, given time, the two phases will separate. The time scale for
separation may range from hours to months and even years. Colloids may take a variety of
forms with both continuous and disperse phases being solid, liquid or gas. Some more
common types of colloid important in a food context are listed in table 1 below
Table 1. Types of colloid
Type Disperse phase Continuous phase Example
Aerosol, Smoke Liquid Gas smoke
Fog, mist aerosol Solid Gas exhaled breath
Foam Gas Liquid Whipped cream,
beaten eggs.
Emulsion Liquid Liquid Milk, Mayonnaise
Sol, Colloidal
solution, gel, paste
Solid Liquid Cloudy beer, milk,
gelatin, tomato paste
Solid foam Gas Solid Ice cream, Meringue
Many foods are colloidal in nature and are generally complex in nature with the continuous
phase being in the form of a true solution and there being more than one disperse phase. A
good example of this is milk which has a continuous phase comprising polysaccharides,
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electrolytes and proteins in aqueous solution and disperse phases comprising both liquid fats
and solid protein.



Factors in colloid stability
There are three key factors which contribute to colloid stability;
- Gravitational effects
- Brownian motion
- Interactions between particles and between phases.
These will be considered in turn.

Gravitational effects - Stokes Law
Gravitational effects are a consequence of differences in density between the disperse and
continuous phase.
If the disperse phase is more dense than the continuous phase, the disperse phase particles
will migrate downwards and tend to settle at the bottom. This is known as sedimentation. If
the disperse is less dense than the continuous phase, the disperse phase particles will migrate
upwards and tend to settle at the top. This is known as creaming. Both phenomena are
essentially the same and are governed by stokes law. This may be illustrated by the following
diagram. (Fig 5.1)

Fig 5.1. Stokes Law
The buoyance force depends the density difference between the disperse and continuous
phase and acts upwards on the particle.
3

The gravitational force depends on the mass of the particle and acts downwards on the
particles.
Depending on the difference between the bouyancy force and the gravitational force, the
particle will move upwards if
L
>
P
and downwards if
L
>
P
.
The frictional force opposes the motion of the particle and depends on the particle velocity.
As a result of the factors influencing these forces, there will arise a velocity at which the
upward and downward forces are equal in magnitude. This is known as the terminal velocity.
By assuming the suspension is a dilute one (ie. neglecting inter-particle interactions), stokes
law allows us to calculate the terminal velocity of a particle.
For a spherical particle, the net force resulting from the buoyancy and the gravitational
effects is


1.1
This applies where
L
>
P
and the particle will move upwards ie. we have creaming. The
motion of the particle is opposed by a frictional force F
F
;


1.2
The terminal velocity, v
S
is reached when F
G
= F
F
. By setting equation 5.1 equal to 5.2, and
rearranging, it is possible to calculate the terminal velocity.


1.3


Brownian Motion
Brownian motion is the apparently random motion of small particles when suspended in a
fluid. It can be seen with the naked eye when dust particles in the air are illuminated by a
shaft of sunlight shining through a window, though it more commonly needs a microscope to
be observed. It is the consequence of the motion of the liquid or gas molecules of the
continuous phase. The molecules strike the suspended particles and exert a small force on
them as a consequence. If the particles are small enough, the force on the particles as a result
of these collisions is sufficient to produce observable motion.
Brownian motion arises as a consequence of the kinetic theory. Very small particles are
"buffeted" by collisions with fast moving molecules. As a result, the particles describe a
random walk continually moving and changing direction. The colloidal particles possess
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kinetic energy ( mv
2
). As the mean kinetic energy of the moving particles is proportional to
the absolute temperature, T then the kinetic energy is given by


2.1
Where k is the Boltzmann constant (= 1.381x10
-23
J K
-1
)
An important consequence of this relation is that as the particle mass increases, its velocity
decreases. This puts an practical upper limit on the size of particles which will display
Brownian motion as the velocity will eventually become too small.



Factors in Brownian motion
1. The motion of colloidal particles will be subject to frictional resistance. This is
proportional to the mean kinetic energy. In fact it can be shown that the mean
displacement of a particle from its point of origin in time, t is given by]


2.2
Where: k = Boltzmann constant = 1.381 10
-23
J K
-1

T = Absolute temperature
f = Frictional coefficient
3. Because of the random motion of the particles, they will diffuse from regions of high
concentration to ones of low concentration. This diffusion is governed by Ficks law
which states


2.3
Where m/t = rate of mass transfer
d = diffusivity of particles
A = -sectional area over which diffusion occurs
dc/dx = concentration gradient.
The sign denotes a flow in a direction from high to low concentration ie a negative gradient.
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By relating the distance moved by a particle in Brownian motion to the mass transferred the
diffusivity for a spherical particle is given by;


2.4
Thus, the distance moved by a particle in time, t as a result of Brownian motion is


2.5


Sedimentation equilibrium
If the colloid particles are sufficiently small, the colloid will be stable as a result of an
equilibrium between the tendency for the particles to fall or rise due to Stokes law and the
rate of diffusion as a consequence of Brownian motion.
As the particles fall (or rise) due to the effect of gravity and buoyancy, a concentration
gradient will be set up. As a result of this concentration gradient, there will be diffusion in the
opposite direction. As the rate of diffusion increases with increasing concentration gradient,
there will a concentration gradient where there is an equilibrium between the terminal
velocity of the particles and the rate of diffusion.
The total mass transferred by particles descending (or ascending) at velocity, v
s
as a result of
gravity/buoyancy is equal to velocity concentration. Thus


2.6
The rate of mass transfer due to diffusion will be governed by Ficks law. At equilibrium this
will be equal and opposite to the mass transferred by the effects of gravity/buoyancy.


2.7
We know that



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and
from Stokes law

Substituting in equation 2.12, rearranging and integrating gives a relationship between
particle displacement and concentration difference at equilibrium.


2.8
Where V
P
= particle volume = 4/3 t r
3
for spherical particles
c
o
= concentration at some point in the colloid
c
x
= concentration at a distance, x from c
o

Note. This is a kinetic equilibrium and not a thermodynamic equilibrium. Colloids are not in
thermodynamic equilibrium and hence are unstable or at best in a metastable state.





Further Reading
Dickinson E, Introduction to Food Colloids, Chapters 1, 2 & 4
Beckett, S T, Physico Chemical Aspects of Food Processing, Chapter 3.


Colloids Problem sheet 1
Standard constants and selected physical properties
Boltzmann constant, k = 1.381 x 10
-23
J K
-1

Avagadro number, N
A
= 6.022 x 10
23
mol
-1

Universal gas constant, R = 8.314 J K
-1
mol
-1

Acceleration due to gravity, g = 9.81 m s
-2

Standard Atmospheric pressure. P = 1.013 x 10
5
Pa (= 760 mm Hg)
Absolute zero temperature, T = -273.15 C
Viscosity of water at 25 C, q = 8.9 x 10
-4
Pa s (= kg m
-1
s
-1
)
Density of water at 25 C (298 K), = 997.0 kg m
-3

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Download Solutions
1. Calculate the terminal velocity of an oil droplet in milk, 2 m diameter if the oil
density is 900 kg m
-3
and the aqueous phase density is 1035 kg m
-3
. Assume q = 10
-3

Pa s

How long (in days) will it take the droplet to rise from the centre of a milk bottle 16
cm high to the surface assuming the bottle is full of milk?
These calculations should give you some idea of the order of time required for
separation of liquid particles in an emulsion. However, milk is commonly
homogenised nowadays, typically reducing oil droplet size to less than 0.8 m.
2. Calculate the average displacement along a given axis produced by Brownian motion
for a spherical particle of radius 0.1 m suspended in water at 25 C. Given

3. A colloidal suspension comprises 5% wt. spherical particles of mean diameter 40 nm
and density 1015 kg m
-3
suspended in water at 25 C. If 250 ml of the sol is put into a
beaker 8 cm diameter, estimate the concentrations of the particles at the top and
bottom of the beaker if the sol is in kinetic equilibrium. Given

4. Raw milk containing 3.5% wt fat is to be homogenised to reduce the fat globules from
a mean diameter of 4 m to a mean diameter of 0.8 m. Determine the work
required to bring about this change in 1.0 m
3
milk. Given

Oil-water interfacial tension = 20 mN m
-1
Density of milk = 1035 kg m
-3
Density of fat = 920 kg m
-3

5. Determine whether the protein in milk will disperse the aqueous or oil phase given
that

PO
= 10 J m
-2
,

PW
= 0

OW
= 20 J m
-2
.
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9

Interactions Between Particles and
Phases
Contents
1. Introduction
2. Molecular interactions
3. Surface tension
4. Wetting of surfaces
5. Surface activity
6. Critical micelle concentration
7. Electrostatic forces
8. Steric repulsion
9. Summary

Introduction
Interactions between particles leads to disperse phase particles gathering together and
ultimately to separation of the two phases and breakdown of the colloidal structure.
The main interactions between particles are as follows
- Van der Waals forces (usually attractive)
- Electrostatic interactions (ionic interactions, hydrogen bonding) can be attractive or
repulsive
- Hydrophobic interactions (usually attractive) (also main interaction between phases)
- Stearic interactions (usually repulsive)


Molecular interactions
When molecules approach at close range they are subject to both attractive and repulsive
forces. The attractive forces are largely due to attraction between the nucleus and the
electron cloud surrounding the molecule. These are called Van der Waals forces. When
molecules approach sufficiently close, the electron clouds interact to repel one another. (Fig
4.1)


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Fig 4.1 Intermolecular forces
In a similar manner, there are forces of attraction and repulsion between colloidal particles as
a consequence of interactions between the molecules on the surface of the particles. The
energy required to overcome these forces of attraction between particles is inversely
proportional to the square of the distance between the particles.


4.1
The force of repulsion and hence the energy required to overcome the repulsive forces
increases exponentially as the molecules approach


4.2
Hence the total free energy of attraction is

4.3
Equations 4.1, 4.2 and 4.3 may be expressed graphically
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Fig 4.2 Energy of attraction between molecules
As a consequence of this relationship, colloids are inherently unstable and tend to aggregation
unless other factors counteract this.
In a colloid, there will be interaction between the disperse and continuous phase which will
tend to reduce the value of K
att
, which tends to reduce the magnitude of the attractive forces.
Furthermore, viscous forces will tend to resist the motion of particles towards one another.
The effect of both of these factors is to reduce the tendency of colloidal particles to
aggregate, but not to stop it completely.


Surface Tension
Within a liquid, there are forces of attraction between molecules, usually Van der Waals
forces. Inside the liquid these forces are balanced, but at the surface, they are unbalanced. As
a result, there is a net force which tends to pull to the interior of the liquid and which will
tend to minimise the surface area. This is illustrated in Fig 3.1 below.
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Fig 3.1 Attractive Forces between molecules in a liquid
The consequence of this imbalance of forces is to minimise the surface area. For a liquid
droplet, this means that the formation of a sphere. If the droplet were to be broken up an
increase in surface area is involved, as a consequence Energy must be expended overcoming
these surface forces. This energy is in the form of work, so;



3.1
The quantity is called the surface tension and has units of energy/area, in SI units, J m
-2
.
However, the units of surface tension are more commonly expressed as force/distance, N m
-1
.
These units are equivalent.
The surface tension normally quoted is the value at an air-liquid interface. At a liquid-liquid
interface it is called the interfacial tension (which is strictly a more general term). The values
of interfacial tensions for liquid-liquid interfaces are usually intermediate in value between
the values of the two air-liquid interfacial tensions.
Laplace equation
The dimensions of a droplet of one fluid in another are dependant on a balance of forces
between the surface tension and a pressure difference that exists across the droplet surface.
This is expressed as the Laplace equation;



3.3


Wetting of surfaces
Whether or not a droplet of one liquid spreads across the surface of another or forms droplets
on the surface depends on the values of the surface tension at the air and liquid interfaces. A
spreading coefficient for an oil drop on water, S may be defined as

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3.4
Where the subscripts WA, OA and OW refer to the water-air, oil-air and oil-water interfaces.
If S is positive, the oil will spread as a thin layer on the water surface, whereas if S is
negative, the oil remains as lens-shaped droplets on the water surface.
A related property is the contact angle at a liquid-solid-gas interface. The size of the contact
angle determines the wetting properties of the liquid on the solid. The contact angle is defined
below.

Fig. 3.2 Contact angle
The contact angle, u is the angle formed at the junction of the three phases as shown in Fig.
3.2. The contact angle can be determined by resolving the forces in Fig. 3.1 in a direction
parallel to the solid surface.



3.5
Equation 3.5 is known as Youngs equation.
The lower the value of u , the more easily the liquid will wet the solid surface. If the solid
surface is lyophobic, then u >90
0
. With a three phase dispersion such as milk, the dispersion
of the solid particles can be predicted by use of a variant of Youngs equation



3.6
Where PO, PW and OW refer to the particle-oil, particle-water and oil-water interfaces
respectively. If cosu is positive, (u <90
0
) the solid particles are preferentially wetted by the
aqueous phase, so they are dispersed in that phase. The contact angle for casein micelles in
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milk is approx. 60
0
so that milk is a dispersion of oil droplets and casein particles in an
aqueous continuous phase.


Adsorption at the interface and surface activity
Adsorption occurs when solute molecules or particles are present at the interface in
concentrations greater than would be expected from random distribution throughout the
phase. This is represented in Fig 3.3 where there are two bulk phases, o and | each
containing a third, dissolved or absorbed component, i. o represents a region at the interphase
boundary in which the concentration of component i is greater than in the bulk phase.

Fig. 3.3 Surface adsorption
A surfactant is a material that adsorbs strongly at the interface and has the effect of
substantially lowering surface tension when added in small amounts.
The properties of many surface active materials is a consequence of the shape and properties
of their molecules. Many surfactants comprise long chain molecules with a hydrophilic group
at one end. The remaining portion of the molecule is strongly hydrophobic. As a
consequence, the surfactant molecules will align themselves at an oil-water interface with the
hydrophilic group in the water and the hydrophobic "tail" in the oil as illustrated below. (Fig.
3.4)
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Fig. 3.4 Surfactants



Critical micelle concentration
At low concentrations, surfactants will dissolve normally in water. However, at a critical
concentration, there is a sharp change in properties such as surface tension, conductivity,
osmotic pressure and turbidity. At this concentration, the surfactant molecules show a
tendency to associate into micelles with the hydrophobic tails inwards as illustrated in Fig
3.4. The formation of micelles accounts for many of the properties of surfactants, particularly
their ability to solubilise particulate matter. Otherwise insoluble materials are absorbed in the
micelles and held in suspension. This is an important factor in detergency as it is this property
that helps prevent the redeposition of dirt particles. In fact detergency is partly a function of
the wetting properties of surfactants which enables oily dirt to be loosened from the surface
and the micelle formation which suspends the dirt and prevents it from being redeposited on
the solid surface.
Another important property of surfactants is their ability to act as emulsifiers by lowering
surface tension and hence reducing the energy required to disperse one phase together with
their adsorption on the surface which helps to stabilise the emulsion by reducing the tendency
of the disperse phases to coalesce.



Electrostatic forces
One factor which may reduce this tendency to aggregation is the presence of charge on the
surface of the particles. This may arise as a result of
- Ionisation of molecules at the particle surface
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- Adsorption of charged species at the particle surface
- Preferential dissolution of ions from the particle surface.
The surface charge on the particles will tend to attract opposite charges to it. As a result there
will be a local unevenness of charge within the colloid although it is overall electrically
neutral. The charge distribution will be something like that in Fig. 4.3 below. The represents
the region near the surface of a particle which bears a net positive charge.

Fig 4.3 Electrical Double Layer
As a consequence of the positive charge on the particle surface, negative ions are attracted to
the particle surface. Because of the motion of the particles, there are two regions of net
negative charge. The region immediately adjacent to the particle surface is strongly
negatively charged with very few positive charges and is called the "Stern layer". Outside the
Stern layer, there is another region of net negative charge which gradually approaches
neutrality as the distance from the particle surface increases. This charge distribution is called
the electrical double layer. The properties of the double layer are governed by Coulombs law
and the Boltzmann distribution law.
Coulombs law states that the force between two electric charges is inversely proportional to
the square of the distance between them. The Boltzmann distribution law defines the
distribution of energy between particles. As a result, an electric charge is said to have an
electric potential, which is a measure of the electrical energy around a charged particle.
In the region close to a charged surface, the concentration of postively charged particles
(cations) is c(+) and that of negative particles, c(-). The net charge will be the difference
between these two concentrations, [c(+) c(-)].
If the region of electrical potential is close to a positive ion, will be positive and [c(+)-c(-
)] will be negative. In the case of a plane surface carrying a uniformly distributed charge (Fig.
4.3), it can be shown that the charge distribution near the surface is

17


4.4
Where z is the distance from the charged surface. Thus the electrical potential near the
surface is exponentially distributed. For z=1, the electrical potential will have fallen by a
factor of 1/e at a distance of 1/k from the charged surface. This leads to a charge distribution
near the surface as is shown in Fig. 4.4. 1/k is known as the thickness of the electrical double
layer.

Fig 4.4 Charge distribution in the electrical double layer
Fig 4.4(a) shows the distribution of positive and negatively charged ions in the double layer
and Fig 4.4(b) the net excess charge in the region of a positively charged plane.
For colloid particles, this means that there is a region of net charge (positive or negative) in
the continuous phase around the particle if the particle surface is charged. As a consequence,
as similarly charged particles approach one another, their electrical double layers will interact
and there will be a repulsive force between the particles which will inhibit the aggregation of
the particles.


Steric repulsion
Steric repulsion is the result of adsorption of molecules, often macromolecules on the surface
of the colloid particles. In the case of macromolecules, the effect is essentially that of a
physical barrier. The particle surface is coated with the macromolecules and the energy
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needed to break this layer is greater than the energy of collision between the particles. In such
a situation the particles behave as if they were hard spheres with a diameter larger than the
diameter of the particles. The slightly larger particle diameter may also have the effect of
reducing interparticle attraction.
Another mechanism of steric repulsion depends much more on molecular structure. This is
often the case where the macromolecule is a protein, a good example being the adsorption of
casein on the surface of the fat globules in milk. Casein has a somewhat random structure
with hydrophobic regions linked to hydrophilic regions. The hydrophobic sections lie close to
the surface of the fat globule whereas the hydrophilic regions "trail" in the aqueous phase. As
a result, when two globules approach, the hydrophilic regions become entangled preventing a
sufficiently close approach of the fat globules to enable them to coalesce. (Fig 4.5). In
addition, the hydrophilic regions will contain charges which may add to the repulsive effect.

Fig 4.5 Steric repulsion



Summary
Although colloids are thermodynamically unstable, nevertheless an important element of
colloid stability is related to the surface free energy of the particles. Colloidal particles are
inherently attracted to one another as a consequence of Van der Waals forces acting between
the molecules on the particle surface. This attractive force results in a negative surface free
energy. On the other hand, there are a number of factors which may lead to particles being
repulsed from one another. The repulsive forces all result in a positive surface free energy. As
a consequence the stability of a colloid may be predicted, in part at least, by the net surface
energy Which is determined from
E = E
att
+ E
rep
+ E
elec
+ E
steric
+ E
other

All values of A G on the RHS except E
att
are repulsive. If the net result is positive the colloid
will be stable.
E
other
may include the effect of surface adsorption and of macromolecules in solution.
Even if E is overall negative, the colloid may be stabilised by adding macromolecules which
act as viscosity modifiers, increasing frictional forces and reducing the rate of approach of
19

particles. Polysaccharides are often used in foods for this purpose.

Colloids Problem sheet 2
Download solutions
Return to colloids index
Standard constants and selected physical properties
Boltzmann constant, k = 1.381 x 10
-23
J K
-1

Avagadro number, N
A
= 6.022 x 10
23
mol
-1

Universal gas constant, R = 8.314 J K
-1
mol
-1

Acceleration due to gravity, g = 9.81 m s
-2

Faraday Constant, F = 9.649 10
4
C mol
-1

Charge on an electron, e = 1.602 10
-19
C
Permittivity of a vacuum, c
0
= 8.854 10
-12
F m
-1

Dielectric constant for water, c /c
0
= 78.5 (at 25 C)
Standard Atmospheric pressure. P = 1.013 x 10
5
Pa (= 760 mm Hg)
Absolute zero temperature, T = 0 K = -273.15 C
Viscosity of water at 25 C, q = 8.9 x 10
-4
Pa s (= kg m
-1
s
-1
)
Density of water at 25 C (298 K) = 997.0 kg m
-3

1. The thickness of the electrical double layer may be found from

Where I is the ionic strength and is defined from

c
i
= Concentration of ion, i (mol m
-3
) and
z
I
= charge on ion i.
Plot graphs of relative charge density ( /
0
) in the diffuse electrical double
layer for the following aqueous solutions at 25 C.
o KCl, 0.1 M
o KCl, 0.001 M
o K
2
SO
4
, 0.001 M
o MgCl
2
, 0.001 M
20

Comment of the effect of ionic strength on the charge density and its
implications for flocculation of a sol.
2. The following data was obtained from particle counting during the coagulation of an
aqueous sol at 25 C after the addition of a 1-1 electrolyte
Time / min 0 2 4 7 12 20
Particle Concentration/10
8
cm
-
3

100 14 8.2 4.6 2.8 1.7
Calculate the observed second order rate constant, k
2
compare it with the value
obtained by assuming ideal conditions. Given;
The integrated form of a second order rate equation

Theoretical second order rate constant
k
2
= 8trD
The particle diffusivity
(k = Boltzmann constant)










21

Breakdown of Colloids
Contents
1. Introduction
2. Electrostatically stabilised dispersions
3. Reversible flocculation
4. Bridging and depletion flocculation
5. Coagulation kinetics
6. Coalescence
7. Ostwald ripening
8. Gels
9. Gel swelling

Introduction
The breakdown of colloids involves particles coming together under the influence of the
attractive forces and forming larger particles. There are various terms for this process
depending on the exact nature of the process.
- Flocculation is a loose association of particles which is relatively easily broken up
and the phases redispersed
- Coagulation is a more strongly bound collection of particles. A Coagulated disperse
phase is not readily redispersed as inter-particle attraction is much stronger than in
flocculation.
- Coalescence is when particles merge to form a single larger particle.
The first two definitions are somewhat loose and the two terms are sometimes used
interchangeably.
In general, flocculation occurs if there is a lowering of the total surface energy as a
consequence.


Electrostatically stabilised dispersions
These are often so-called lyophobic sols i.e. colloids where the disperse phase is insoluble in
the continuous phase. In the case where the continuous phase is aqueous, coagulation has
been found to be a function of added ions known as counter-ions to the sol. There is a critical
coagulation constant (ccc) which has been shown to be largely dependant on the valency of
the counter-ions. This dependency is known as the Schulz-Hardy rule. A more developed
theory is the so-called DLVO theory, named after the two groups who developed it,
Deryagin-Landau and Verwey-Overbeek.
22

The DLVO theory states that the stability of lyophobic colloids is primarily related to Van
der Waals forces and to the electric double layer interactions. By combining these as an
energy of repulsion, E
rep
, and energy of attraction, E
att,
a net interaction free energy is defined.
E
int
= E
rep
+ E
att
5.1
Where


h = distance separating the two particles.
The results of this can be expressed graphically for different colloids.

Fig 5.1 Stability of lyophobic colloids


Reversible Flocculation
Because flocculation is generally a loose association of particles, the flocs can be redispersed
relatively easily, usually by agitation. The dispersion process, and hence the conditions for
stability of the colloid in such circumstances can be modelled by considering the process as a
series of addition reactions. Thus;
A + A A
2

23

A
2
+ A A
3

..

A
i
+ A A
i+1

The equilibrium constant for A
i
+ A A
i+1
is given by

5.2
Where x
i
and x
i+1
are the mole fractions of A
i
and A
i+1
respectively.
It can be shown that
If for all i, the dispersion is stable
If for all i, the dispersion will flocculate


Bridging and Depletion flocculation
These both occur as a consequence of the addition of macromolecules to the colloid.
Bridging flocculation occurs when there is a dilute solution of macromolecules in the
disperse phase and these molecules attach themselves to particles at their ends, pulling the
particles together.
24


Fig 5.2 Bridging Flocculation
Whereas in bridging flocculation, the polymer molecules are soluble in the disperse phase, in
Depletion flocculation, the polymer molecules are insoluble.

Fig 5.3 Depletion Flocculation
The polymer molecules between the particles act as a semi-permeable membrane. The
solvent is expelled from the space between the particles as a result of osmosis, causing the
particles to aggregate.




25

Coagulation Kinetics
The rate of coagulation depends on the rate at which the particles come into contact. This in
turn depends on
- The particle concentration, c
- The particle diameter, d
- The diffusivity of the particles in the continuous phase, D
As stated earlier, the process of coagulation depends on two particles associating hence the
process may be represented as
2A A
2

This is a second order process and the rate will be function of the square of the concentration.
The following rate equation applies

5.6
The half life (i.e. the time to reduce the particle concentration to half its original value) may
be found from

5.7
Where c
0
is the initial particle concentration.
This kinetic scheme was developed by Smoluchowski, and strictly speaking applies only to
monodisperse sols and spherical particles. For a spherical particle, k
2
= 8t dD where d is
particle diameter and D is diffusivity.


Coalescence
Coalescence is the combining of two particles to form a single larger particle. The key
distinction is that flocs and coagulated particles retain a distinct identity, but this is not the
case with coalescence.
Coalescence is possible with both liquid and solid particles but is most common with liquids.
The process involves a thinning of the continuous phase film between the particles until all
the continuous phase has been expelled and the two particles merge.
26


Fig 5.4 Droplet Coalescence
The expulsion of continuous phase means that there is an energy barrier to overcome.

Fig 5.5 Energy Potentials for Coalescence
If the continuous phase is sufficiently viscous, there is insufficient energy available to
overcome the energy barrier and the particles will not coalesce.

Fig 5.6 Effect of Viscous Liquid on Coalescence

27


Ostwald Ripening
If the disperse phase has any significant solubility in the continuous phase, the phenomenon
called Ostwald ripening may occur. Owing to surface tension effects, small particles are
generally more soluble than large particles. As a consequence, large particles tend to grow at
the expense of small ones. If the process is sufficiently rapid, the colloid will be unstable. On
the other hand control of this process is useful in production of photographic emulsions. In
frozen foods, it can lead to deterioration during long term storage as the larger ice crystals
will tend to grow at the expense of the smaller ones leading to tissue damage.



Gels
Gels are formed when the interactions between the particles in the disperse phase are strong
enough to form a rigid network. In such a case, the colloid behaves as a solid and under
moderate shear stresses behaves elastically. In effect, a gel comprises a continuous floc filling
the whole system. (Fig 5.7)

Fig 5.7 Gelation
In the case of gels based on macromolecules, there are regions of the molecules where there
is attraction to other molecules often in the form of hydrogen bonding, or via some form of
ionic stabilisation. (Fig 5.8). The result, as in gels based on flocs, is a three dimensional
network which behaves as if it were a solid.
28


Fig. 5.8 Stabilisation of polymer gels
In some cases, the gel stabilisation is based on covalent bonds, for example the formation of -
S-S- bridges in the vulcanisation of rubber or of cystine in proteins.


Swelling of gels
The formation of the 3-D network that comprises a gel results in continuous phase being
trapped within the gel. In many cases, the continuous phase is a solution and the floc network
acts as a semi-permeable membrane. As a result, osmosis takes place and the gel will swell.
The swelling tendency can be counteracted by applying an external pressure, the pressure
required being known as the swelling pressure. This can reach quite high values. For
example, driving wooden wedges into rock and soaking the wood can cause a sufficient
swelling pressure to break the stone.









29


Butter and Margarine
Contents
1. Introduction
2. Butter and Margarine Manufacture
3. Structure and Stability
4. Composition of butter and margarine


Introduction
Butter and Margarine are both water-in-oil emulsions which are used both for cooking and as
spreads on food. They are both high-fat products having 80+% fat. There are also a range of
other "Butter-like" products. These include
- Reduced fat spreads ( <80% fat)
- Low fat spreads ( <50% fat)
Reduced fat spreads are also water-in-oil emulsions, but low fat spreads are oil-in-water
emulsions.
Butter is produced from 100% milk fat and naturally contains vitamins A, D & E plus the
necessary components to form and stabilise the emulsion. A small quantity of salt is
sometimes added, originally as a preservative, but nowadays for the flavour.
Margarine and related products are normally based on vegetable oils, with the aqueous
component usually being a fermented skimmed milk. It is necessary to add emulsifiers,
vitamins and colours to margarine to give it butter-like properties. Preservatives are added to
the lower fat products, but margarine itself is sufficiently microbiologically stable without
added preservatives.
Compositions of some butters and margarines are given here.








30

Butter and Margarine manufacture
Butter is usually produced by the following process (Fig 1)

Fig 1. Butter Manufacture
Concentration. The milk is pasteurised, cooled to then centrifuged at about 40C to produce a
cream of 40% fat content.
Crystallisation. The cream is cooled rapidly to 12 - 16 C and allowed to stand for several
hours while a portion of the liquid fat crystallises to give the cream its proper consistency for
the next stage
Churning. The cooled cream is agitated and air is incorporated. During this operation, much
of the aqueous phase leaches out and a phase inversion occurs the oil in water emulsion
becomes a water in oil emulsion. On completion of churning, the fat content has increased to
81 82%.
Working. The churned butter is cooled again and washed with clean water. The butter is then
kneaded ("worked") to thoroughly disperse the aqueous phase and create a smooth
consistency. If desired, salt may be added at this stage.


Margarine (See fig 2) is produced by mixing a blend of oils and fats with an aqueous phase
comprising skimmed milk fermented with a lactic acid bacterial culture together with
31

emulsifiers, added vitamins, colouring and flavours. This is then worked to produce the
desired consistency of product.

Fig 2. Margarine manufacture


Structure and stability of butter and margarine

Butter and Margarine fats are both mixtures of triacylglycerols. Butter has a much greater
variety of fatty acids (ca 40) than are found in vegetable oils (5 10) from which margarines
are produced.
However, in both cases, the fats present in butter and margarine are a mixture of solid and
liquid fats and it is this, together with the crystal morphology of the solid fat that gives butter
and margarine their particular properties.
The structure of butter and margarine is based on a network of solid fat crystals in liquid fat.
It is this that accounts, at least in part, for
- Emulsion stability
- Microbiological stability
- Rheology
- Hardness/softness
- Mouthfeel
32

The structure may be illustrated in the following diagram. (Fig 3)

Fig 3. Structure of butter/margarine
The emulsion is stabilised by the solid crystal network which holds the water droplets in
place preventing them from migrating and coalescing. It also explains the microbiological
stability as the water droplets are smaller than most common food poisoning bacteria, hence
there is insufficient nourishment for them.
Rheologically, butter and margarine are plastic materials, behaving elastically at low stress.
Above a limiting value of stress, the crystal network breaks down and the oil being liquid will
flow. The hardness and the yield stress of butter are determined by the solid fat content
(SFC). For optimal properties, the SFC should be in the range 20 30% at the temperature of
use.
The mouthfeel of fat-based products is related to SFC and also to crystal morphology. There
are three different types of crystal structure in solid fats which are related to the alignment of
fat molecules in solid fats. A high SFC fat has a cooling effect in the mouth as latent heat is
taken up to melt the fat The melting point of many fats is around, or just below body
temperature.







33


Scope of Rheology,
elastic solids & Newtonian liquids
Contents
Introduction
Stress and Strain
Newtonian Liquids
Laminar and Turbulent Flow
Problems
Return to Home Page

Introduction
Rheology may defined as "the study of the deformation and flow of matter". It is concerned
with the effects of stress on fluids and materials having fluid-like properties, usually under
the effect of shear forces. The province of rheology is usually considered to be the properties
of materials which lie between two ideal states; the perfectly elastic solid and the Newtonian
fluid. In order to identify the nature of the rheological properties of materials, we need to
examine these two ideal states.
The perfectly elastic solid
Types of force
Materials may be subjected to three major types of force.
a. Tensile forces - These are forces that tend to stretch the material

b. Compressive forces - These forces tend to squash the material

34

Both tensile and compressive forces are known as direct forces since both the opposing
forces act along the same line.
c. Shear forces - These forces tend to distort or displace the material in some
way.

Shear forces do not act along the same line and are consequently known as indirect forces. In
the study of rheology, shear forces are the most important type of force.
Elasticity
When a material is subject to a force, it tends to deform. The size of this deformation is
known as strain. If a material returns to its original shape when the load is removed, it is said
to be elastic. An elastic material is one which obeys Hooke's law which states that the
magnitude of the deformation is proportional to the applied force. This means that a graph of
deformation vs force is a straight line.


Stress and Strain
The slope of a graph of deformation vs force will vary with the material and the dimensions
of the specimen. In order to be useful, it would be necessary to produce hundreds of such
graphs for the various materials of interest. In order to reduce the quantity of data needed it is
usual to standardise the axes so that they are independent of the dimensions of the specimen.
The slope of the graph then becomes a property of the material only. In order to do this, the
quantities stress and strain are defined.
Stress is defined as force per unit area
Strain is defined as deformation per unit length.
For a material in shear, these are defined as illustrated below.

Fig 1.1 Elastic shear
35

Fig 1.1 represents a block of solid that has been subjected to shear forces, F. As a result it has
been deformed, as shown, by an amount o x.
Shear stress is defined as


ie.

(eq
n
1.1)
Shear Strain is defined from


ie.

(eq
n
1.2)
If a graph of shear stress vs shear strain is drawn, we get a straight line through the origin.
Thus shear stress and shear strain are related by
t = G or (eq
n
1.3)
The quantity, G is the slope of the straight line and is called the shear modulus


The Newtonian fluid
Viscosity
Viscosity is a measure of the frictional forces within a fluid. The principle of viscosity may
be described with the aid of the following diagram. (Fig 1.2)

Fig 1.2 Shear in Fluids
Fig 3.1 represents a small element of fluid resting on a flat, solid surface. The fluid is
imagined to be built up in layers and a force is applied to the topmost layer. The topmost
layer will move under the influence of the force and will drag the layer below with it.
36

However, because of the frictional resistance between the layers, the second layer will move
a little slower than the top layer. This repeats itself down the fluid until the layer in contact
with the solid surface is reached. Because of friction between the fluid and the solid, this
layer is in fact stationary. This results in a velocity gradient in the fluid with velocity
increasing, the farther the fluid is from the solid surface.
It can be shown that, in a Newtonian fluid, such as water, the shear stress is proportional to
the velocity gradient. Thus we can write, in symbols;
(eq
n
1.4)
But, since velocity is rate of change of distance with time, then the velocity gradient is the
rate of change of shear strain, or the shear rate. Thus, equation 1.4 becomes;
1.5
(eq
n
1.5)
The quantity is the gradient of a graph of shear stress vs shear rate and is called the
viscosity of the fluid.
For a Newtonian fluid, the viscosity at a given temperature and pressure is a constant and the
graph of shear stress vs shear rate is a straight line.


Streamline and turbulent flow
There are two basic patterns of fluid flow called streamline and turbulent flow. These differ
in the degree of cross mixing occurring when the fluid is flowing.
Streamline flow
At low flow velocities, no mixing of the fluid takes place in directions perpendicular to the
direction of flow. This is called streamline or laminar flow. Fig 1.3 illustrates streamline
flow in a pipe.

Fig 1.3 Streamline flow
The velocity profile across the pipe is parabolic with a maximum velocity at the centre of the
pipe. It can be shown that the average velocity is half the maximum velocity.
Turbulent flow
37

As the flow velocity increases, the fluid in the centre of the pipe starts to behave erratically
and to break away and form small eddies. This causes some cross mixing of central core of
the fluid. This flow behaviour is known as turbulence. You may have seen it in a river in
flood or in a fast flowing stream. As the flow velocity increases, this turbulent core increases
until it leaves only a very small layer of fluid next to the pipe wall in streamline flow. This
thin layer is called the boundary layer. Fully developed turbulent flow is illustrated in Fig
1.4

Fig 1.4 Turbulent flow
The onset of turbulence does not only depend on the velocity, u of the fluid, but also on the
pipe diameter, d, the viscosity, , and the density, .
These properties are related together by Reynold's Number, Re and it is the value of
Reynold's number which determines whether the flow is streamline or turbulent.
Reynold's number is defined as
(eq
n
1.6)
This is an example of a dimensionless group. ie it has no units (Check this).
The relationship between the type of flow and Reynold's number is as follows;
- When Re < 2000 (approx), flow is streamline.
- When Re > 3000 (approx), flow is fully turbulent.
- Flow in the range 2000 < Re < 3000 is said to be transitional.
The flow pattern in fully developed turbulent flow is very much flatter than in streamline
flow. In fact most of the velocity gradient is in the streamline boundary layers.
Many foodstuffs are very viscous. As a result, when they flow, they are usually in streamline
flow, so streamline flow is of importance in food rheology.


Exercises
Download Solutions
1. Describe streamline and turbulent flow. Explain the difference to your neighbour.
38

60% sucrose solution is being pumped along a pipe of 50 mm diameter at an
average velocity of 0.5 m s
-1
. The density of the sucrose solution is 1290 kg m
-
3
and the viscosity of the solution is 0.059 Pa s. Calculate the Reynolds
number of the flowing sucrose. Is the flow streamline or turbulent?
2. Define shear stress and shear strain. Explain how the velocity gradient
arises in a flowing fluid. How does this relate to shear stress and shear strain?
A flat plate of dimensions 5 mm x 10 mm is resting on a flat surface separated
from the surface by a film of olive oil 0.8 mm thick. A constant force is
applied to the plate which results in its moving along the surface on the film of
olive oil at a velocity of 0.8 m s
-1
. If the viscosity of olive oil is 0.084 Pa s,
what force was applied to the plate?
3. Sketch graphs to show the relationship between
a. Shear stress and shear strain in a perfectly elastic solid
b. Shear stress and shear rate in a Newtonian fluid.
What is the property defined by the slope of each graph called?
A glue for use in food packaging is tested by gluing together two rectangular
specimens 50 mm wide such that there is a 75 mm overlap using a layer of glue 0.2
mm thick. The glued joint is then subjected to a shearing force by pulling the two
specimens apart. The joint failed with the application of a force of 2 kN at a deflection
of the glued joint of 0.03 mm. Calculate;
a. the shear stress at the point of failure
b. the shear modulus of the glue in the joint










39

Non-Newtonian flow
Contents
Introduction
Non Newtonian Flow
Time Independant fluids
Apparent Viscosity
Time Dependant fluids
Effects of Temperature and Concentration
Problems
Return to Home Page


Introduction
The elastic solid and the Newtonian fluid are not normally considered the province of
rheology. Rheology is concerned with materials which either exhibit behaviour which has
components of both the elastic solid and Newtonian fluid and/or displays behaviour which
deviates from one or other of these ideal states.
The principal deviations from ideality are:
1. in fluid systems, the viscosity is not a constant. In many fluids, viscosity varies as a
function of applied shear stress and/or of time.
2. solids, when subject to stress, continue to deform after the initial (elastic) extension.
This behaviour is called creep and solids displaying such behaviour are call visco-
elastic.
These behaviours are discussed below.


Non-Newtonian fluids
Most low molecular weight fluids obey the Newtonian model over a wide range of shear rates
- typically over several log cycles of shear. However, with high molecular weight liquids and
40

more complex liquids including many solutions and most colloids, deviations from the
Newtonian model start to exhibit themselves. There are a variety of non-Newtonian models
of behaviour, the main categories of which are;
a. Fluids which will not flow until a minimum shear stress is achieved.
b. Fluids whose viscosity varies with rate of shear
c. Fluids whose viscosity varies with time
Fluids in categories a) and b) are usually referred to as time independent fluids and fluids in
category c) as time dependant fluids


Time Independent models
Most low molecular weight fluids obey the Newtonian model over a wide range of shear rates
- typically over several log cycles of shear. However, with high molecular weight liquids and
more complex liquids including many solutions and most colloids, deviations from the
Newtonian model start to exhibit themselves. There are a variety of non-Newtonian models
of behaviour, the two simplest of which are the Bingham and the Power law models.
Fluids showing Bingham type behaviour show little or no strain until a critical value of shear
stress is reached, when they start to flow, displaying Newtonian behaviour. Such behaviour is
often referred to as ideal plastic behaviour and fluids that conform to the Bingham model as
"Bingham Plastics". Bingham behaviour may be expressed as follows:


2.1
where t
o
is the yield stress and
p
is the plastic viscosity. Foods which are high in fat content
such as butter, margarine and chocolate and also beaten egg white display Bingham
behaviour over a moderate range of shear - typically over about 1 log cycle.
For many fluids, the coefficient of viscosity is not a constant, but is a function of shear rate.
Such fluids may often be modelled by means of the power law.


2.2
Where K is called the consistency coefficient and n is the power law index. If the power law
index, n = 1, the power law equation simplifies to the Newtonian model
By combining the Bingham with the power law models, the Herschel-Bulkley model is
obtained:


2.3
41



Apparent viscosity
If the power law equation is rearranged


2.4
The term in brackets, , is often referred to as the apparent viscosity,
app
. Thus, the
power law equation simplifies to


2.5
Hence, the form of the power law equation parallels that of the Newtonian model, though the
apparent viscosity,
app
is a variable, not a constant. The Herschel-Bulkley may also be
rewritten in a similar manner, taking the yield stress to the LHS of the equation


2.6
By writing the equations in this form, the graph of apparent viscosity vs shear rate is a
straight line on log-log co-ordinates.
If the power law index, n < 1, the apparent viscosity falls as shear rate increases and the fluid
is said to be shear thinning. Such fluids are often known as pseudoplastic. The converse
situation is where n > 1 when the fluid is shear thickening and such fluids are known as
dilatent. The terms shear thinning and shear thickening are to be preferred in current usage
and will be used here.
The effects of power law behaviour are illustrated graphically in Fig 2.1.
42


Fig. 1 Apparent viscosity - shear rate relationship for time-independent fluids
These models are essentially empirical and have been derived by a process of curve fitting to
experimental data, although the constants in the various equations are though to be related in
some way to the structure of the system, especially in the case of disperse systems.
Casson derived a model based on a consideration of the structure of a disperse system. He
assumed that the disperse phase formed flocculated particles in the form of long chains which
may be modelled as rod-like structures. The resulting model was of the form


2.7
Where t
o
is the yield stress. The two parameters t
o
and K express relationships between the
length and orientation of the rods, the volume fraction of the disperse phase and the viscosity
of the continuous phase. The Casson model has proved useful in describing the rheology of
chocolate
The power law, Herschel-Bulkley and Casson models effectively describe the rheology of a
wide variety of foodstuffs.


Time Dependent Behaviour
There are two major classes of time dependent fluids, thixotropic where the apparent
viscosity decreases with shearing time and rheopectic (or anti-thixotropic) where the
apparent viscosity increases with time.
43

Two other characteristics of time dependent fluids is that they tend to relax to their original
properties when shearing is stopped and there is usually a limiting shear stress ie. the shear
stress tends to a constant value at infinite time. This is illustrated in Fig 2.2.

Fig 2.2. Time dependent behaviour
Thixotropic behaviour may be accounted for in equations such as the Herschel-Bulkley by
means of an extra, time dependent parameter, which is a measure of the structural
breakdown of the system.

2.8


Effect of Temperature and Concentration on Viscosity
Viscosity (or apparent viscosity) is affected by both temperature and the concentration of
both solute and solid particles in the system. In general, viscosity decreases with increasing
temperature and increases with increasing concentration.
Temperature effects may be modelled by an Arrhenius type equation. This may be expressed
in terms of viscosity or of the consistency coefficient.
44



2.9
is the viscosity at temperature, T (Kelvin),
o
is the viscosity at a reference temperature, E
a

is an activation energy term and R is the universal gas constant.
Viscosity data for a number of foods is given in Table 2.1 below
Table 2.1 Rheological Properties of some Food Products
Product Temp n K/ t
o/

/C Pa s
n
Pa
Apple Pulp 25 0.084 65.03
Apple Sauce 20 0.302 16.68
Apricot Puree 26.6 0.35 11.2
Orange Juice concentrate (40%) 25 0.585 4.121
Tomato Ketchup 25 0.27 18.7 32.0
Tomato Puree 25 0.236 7.78
Mayonnaise 25 0.54 6.6
Milk; homogenised 20 1.00 0.002
Whipping Cream 40 1.00 0.00238
Double Cream 40 1.00 0.00690
Molten Chocolate 46 0.574 0.57 1.16
Olive Oil 10 1.0 0.1380
40 1.0 0.0363
Sunflower Oil 38 1.0 0.0311


Problems
Download Solutions
45

1. Show that a graph of log t vs for a power law fluid will produce a
straight line. What are the slope and intercept? Sketch such graphs for shear
thinning and shear thickening fluids
Calculate the apparent viscosity of apricot puree at rates of strain of 10 s
-1
, 100
s
-1
, and 1000 s
-1
. By how much does the apparent viscosity vary? Do other
fruit purees vary similarly? What do you think are the implications of this for
the processing of fruit purees?
2. The Data below relates to Quorn' paste. Quorn is a high protein food
which is derived from the fermentation of a fungus, Fusarium graminearum
A3/5. Prior to processing into the final products it takes the form of a thick
paste. The data below is based on a series of rheological measurements carried
out on Quorn paste.


Shear stress vs shear
rate
apparent viscosity
vs temperature
Power law parameters vs
concentration
shear
rate
shear
stress
Temp.
app
Conc
n
K n
s
-1
Pa deg C Pa s Pa s
n

0 194
0.5079 348 5 307 13.1% 99 0.336
1.0033 4352 10 245 15.0% 154 0.359
1.5127 516 20 146 16.0% 215 0.316
2.0000 599 30 94 17.5% 362 0.339
2.5097 663 40 65 19.6% 458 0.337
2.9453 700 50 47 21.3% 808 0.278


a. Plot a graph of log shear stress, (t -t
o
) vs log shear rate.
Suggest a non-Newtonian flow model for Quorn paste?
Determine the parameters of the model
b. Plot a graph of log apparent viscosity (
app
) vs 1/temperature
(in Kelvin). Does the Quorn paste conform to the Arrhenius
model? Calculate the values of
o
and E
a
, given a value of the
universal gas constant, R = 8.314 J mol-1 K-1.
c. Plot graphs of log consistency coefficient vs concentration
and power law index vs concentration. Suggest a relationship
between the rheological properties and concentration for Quorn
paste.
46

d. The above measurements were based on short time tests. The
Quorn paste was then subjected to a constant shear stress over a
more extended time period and the apparent viscosity was
recorded at approx. 50 second intervals. The results are
summarised in the table below.
Time /sec 10.5 52.5 100.5 150 201 250.5 298.5
visc. /Pa.sec 509.6 388 332.6 299.4 284.9 260.2 252.9
Plot a graph of apparent viscosity vs time and identify the type
of behaviour exhibited by the Quorn paste. Sketch the graph
you would expect for measurements of shear stress vs shear
rate if the shear stress was increased from zero to a maximum
then reduced back to zero.

















47

Visco-elasticity
Contents
1. Introduction
2. Modelling Visco-elasticity.
3. Oscillatory shear
4. Problems
5. Download Solutions

Introduction
A visco-elastic material is one which exhibits properties of both viscous fluids and elastic
solids. Many materials exhibit properties of elastic and viscous behaviour dependant on
stress. Examples include metals and Bingham plastics. However visco-elasticity describes a
material which exhibits a combination of viscous and elastic behaviour simultaneously.
Visco-elastic materials can appear to be either solid or liquid, depending on whether the
dominant property is elastic or viscous. Visco-elasticity is common among macromolecular
materials and is often the result of molecular entaglement between macromolecules. Visco-
elastic materials are characterised by two particular behaviours
- Creep and
- Stress relaxation
When a sudden load is applied, there is an initial rapid extension but instead of there being a
fixed extension as with an elastic solid, it continues to extend with time. When the load is
removed, there is an initial rapid contraction which quickly slows down. This is illustrated in
Fig 3.1 below.
48


Fig 3.1 Creep in visco-elastic solids
Conversely, the stress required to maintain constant strain decreases with time. This is known
as stress relaxation.
Visco-elasticity may also be exhibited in liquids. One manifestation is die swelling in
extrusion processes. Extrusion is involves application of high shear stress through the die and
when the stress is released on the liquid leaving the die, there is some elastic recovery
resulting in an increase in diameter of the stream of fluid from the die.



Modelling Visco-elasticity.
A common approach to modelling visco-elastic behaviour is by means of combining elements
representing ideal elastic behaviour and ideal viscous behaviour. The usual method of doing
this is using a spring and dashpot analogy. The spring represents ideal properties and the
dashpot, ideal viscous properties. The simplest combinations are to put the two elements in
series and in parallel. This leads to the so-called Maxwell element and the Kelvin or Voigt
element. These are illustrated in Fig 3.2 below.
49


Maxwell Element Kelvin-Voigt Element
Fig 3.2 Spring and Dashpot models for visco-elasticity
The Kelvin element explains creep. When a force is applied to the element, the spring
attempts to stretch but is slowed by the effect of the viscous liquid in the dashpot. For a given
initial stress, t it can be show that the strain,
t
after time t is given by


3.1
Thus the strain approaches a limiting value,
o
exponentially. Similarly, when the stress is
released, the element approaches its original state exponentially. The quantity t
R
is known as
the retardation time and is equal to /G
The Maxwell element explains stress relaxation. If a force is applied to the element, the
spring causes a rapid initial strain. If this strain is now held constant, the spring attempts to
relax and is able to do so as a result of viscous flow in the dashpot. As the spring relaxes, the
force required to maintain the constant strain reduces. It can be shown that the stress, t
t
after
time t, required to maintain the strain is given by


3.2
In this case, t
R
is called the relaxation time, but is defined in the same way as the retardation
time for the Kelvin element.
The Maxwell and Kelvin elements thus explain aspects of visco-elastic behaviour, but neither
on its own explains the whole story. To achieve this, various combinations of Maxwell and
Voigt elements have been proposed. Two of the simpler ones are illustrated below. (Fig 3.3)
50


3 element model 4 element mode
Fig 3.3 More complex spring and dashpot models.



Oscillatory shear
If a shear force is applied to a material there may be a delay before the material responds.
With a perfectly elastic material, the response is instantaneous, whereas the response time is
maximum with a viscous material. Visco-elastic materials have an intermediate response
time. This is exploited as a method of characterising visco-elastic materials by applying an
oscillating shear force in the form of a sine wave and monitoring the response (Fig 3.4). In
practice, the stress response to an applied strain is monitored so that the stress is leading the
strain rather than vice versa.
The response curves are show in Fig 3.5. From Fig 3.5, it can be seen that for a perfectly
elastic material the output is in phase with the input and for visco-elastic and viscous
materials, the response is out of phase. A a purely viscous material exhibites a maximum 90
o

out of phase response. The quanities
m
and t
m
are the maximum values of the applied strain
and the stress output respectively. For a visco-elastic material, the amount by which the strain
leads the stress is defined by a phase angle, o . The relationship between the applied strain,
51

the stress response and the phase angle delta are expressed for a visco elastic material by
dividing the response into its elastic and viscous components and defining two shear moduli,
G' and G". These are known as the Storage modulus and the Loss modulus respectively.

Fig 3.4 Oscillatory Shear

Fig 3.5. Stress response to a sinusoidal applied strain
The loss modulus, G" is the in phase component and is defined by

52


3.3
and the storage modulus, G' is the out of phase component and is defined by


3.4
3.3 and 3.4 can be combined to express the relationship between G' and G" as


3.5
The loss modulus, G" is sensitive to the vibrational state of molecules so that a graph of G" or
tan o vs either temperature or log vibration frequency can be used to investigate the
relationship between the rheological properties of a material and its molecular structure.
The storage and loss moduli represent the response of a material to stresses that vary with
time and are thus dynamic properties of the material. An overall dynamic modulus, G* may
be determined from the storage and loss moduli as follows.

3.6
G* arises naturally out of a mathematical derivation of the dynamic behaviour of materials,
but is of less use to us than its components, G' and G".



Exercises
Download Solutions


1. What is meant by creep and stress relaxation in a visco-elastic solid? Are the
3- and 4- element spring and dashpot models capable of explaining both
creep and stress relaxation? Justify your answer.


2. Define the phase angle, o in oscillatory shear. How is the phase angle related
to the storage and loss moduli of a visco-elastic solid.

A solid food was subjected to an oscillatory shear test with the following
results
53


stress,
t
m
/ Pa
strain,

m
/s
-1

phase
angle,
o
o

300.0 1.20E-2 20
400.0 1.50E-2 15
500.0 1.67E-2 13

Calculate the values of tan o , G' and G" in each case. What trends are
exhibited by the data?


3. A creep test was carried out on a solid food by applying a constant stress of
1500Ps for 400 seconds and then removing the stress. The results recorded
are as follows
time/s 0 10 100 200 300 400 500
strain 0.000 0.042 0.097 0.147 0.173 0.186 0.135
time/s 600 700 800 900 1000 1100 1200
strain 0.0936 0.0661 0.0476 0.0352 0.0269 0.0213 0.0176

a. Plot a graph of strain vs time. What evidence is there that this
material exhibits visco-elastic behaviour?
b. Assuming the strain after 10 s is a sufficient approximation to the
elastic strain of the material, Calculate the shear modulus G

4. The material in question 3 was subjected to a strain relaxation test. The
material was subjected to a stress of 1500 Pa for 100 s. At this point, the
strain was held constant and the stress required to maintain the constant
strain was measured with the following results

time/s 0 50 100 150 200 250 300
stress/Pa 1500 1075 770 552 395 283 203

a. Show that a graph of ln stress vs time will be a straight line. What are
the slope and intercept of the graph?
b. Plot a graph of ln stress vs time. Determine the slope and hence find a
value for relaxation time.
c. Assuming the value of shear modulus, G is as for question 3,
determine the viscosity of the material.



54

Rheological Measurement
Contents

1. Measurement of Shear Viscosity
2. Wide gap concentric cylinder viscometer
3. Parallel plate viscometer
4. Capillary flow viscometer
5. Measurement of visco-elastic properties


1 Measurement of shear viscosity
There are three basic types of viscometer for measuring viscous flow; rotary, flow and falling
sphere. These are summarised in Table 4.1.
The rotary viscometers comprise three basic types, i) the narrow gap concentric cylinder, ii)
the wide gap concentric cylinder, iii) the cone and plate and iv) the parallel plate. In types i
and iii, the shear rate is approximately constant over the rotating element whereas in types ii
and iv it is not.
Table 4.1 Summary of basic methods viscosity measurement

Viscometer
Type
Variable to
Change
Measurement Convenience Robustness
Rotary
Viscometers
Speed and
diameter of
rotating element
Couple * * *
Flow
Viscometers
Tube or orifice
diameter
Efflux Time * *
* *
* *
* *
Falling ball Ball diameter Velocity * *

* *

Source: adapted from Barnes et al, 1989
The main types of flow viscometers are the capillary viscometer which is well suited to the
measurement of viscosity at high shear rates. The other type comprises various cup and
orifice viscometers. These latter are usually calibrated against known standards and are often
used to determine the viscosities against these standards for quality control purposes.
55

Falling ball methods - and the related rising bubble methods are convenient if no other
viscometer is available as they can usually be assembled from standard laboratory equipment.
The rely on determining the time taken for a ball to fall between two fixed points such that
when the ball reaches the upper point, the terminal velocity has been achieved. Viscosity may
be determined by application of Stokes law.
For disperse systems, the most suitable types of viscometer are the wide gap concentric
cylinder, the parallel plate and the capillary viscometer.


1.1 Wide gap concentric cylinder viscosity
The wide gap concentric cylinder viscometer two concentric cylinders, the inner one of which
is rotated. The fluid under test is in the annulus. The rotational speed and the applied torque
are measured.
For the wide gap concentric cylinder viscometer, the shear stress at the wall of the inner
cylinder is given by




4.1
Where e is the rotational velocity and r
1
/r
2
is the ration of the inner to the outer radius.
The shear stress at the wall of the inner cylinder is given by




4.2
Where T is the torque, r
1
is the radius of the inner cylinder and L is the height of the inner
cylinder.


1.2 The parallel plate viscometer
56

The parallel plate viscometer comprises two parallel, circular plates, one of which is rotated
and the other is fixed. Like the concentric cylinder viscometer, the rotational speed and the
applied torque are measured.
The shear rate varies across the radius of the plate, but the usual value of concern is at the rim
where shear rate is a maximum. The shear rate at the rim is given by




4.3
Where r is the radius of the rotating plate and h is the gap between the two plates.
Shear stress is given by




4.4


1.3 Capillary flow viscometer
The capillary flow viscometer functions by forcing the fluid to flow from a cylinder through a
capillary by means of a piston acting on the fluid. The volume flow of fluid and the pressure
loss across a section of the capillary are measured. Providing the length to diameter ratio of
the capillary is sufficiently large, (L:d > 100), the entrance and exit losses are negligible and
the pressure loss may be taken as the difference between the applied pressure on the piston
and the pressure on discharge from the capillary. The determination of shear stress and shear
rate is based on the Hagen-Poisseuille equation for laminar flow in pipes. For a Newtonian
fluid this states




4.5
Where r
i
is the inside diameter of the capillary, A P is the pressure loss across length, L of the
capillary.
The shear stress at the pipe wall, t
w
may be determined from a force balance.

57




4.6
By combining equation 4.6 with the basic equation for Newtonian flow (equation 2.2), the
shear rate in the capillary may be determined




4.7
However, equation 4.7 only applies to Newtonian fluids. For non-Newtonian fluids, it is
necessary to apply a correction. For power law fluids, the corrected form of equation 4.7
usually used is




4.8
The term in brackets in equation 4.8 is called the Rabinowitch correction, (Reilly, 1997)


2 Measurement of visco-elastic properties
The properties of visco-elastic solids are most commonly measured by one of two techniques;
Static and oscillatory methods.
The static methods are basically similar to standard tensile and compressive testing methods.
The material is clamped and subjected to a stress and the resulting strain is measured. In the
case of visco-elastic solids, a means of monitoring creep is need so that a strain-time curve
may be produced. Alternatively, if stress relaxation is under investigation, a means of varying
stress is required to maintain constant strain so a stress-time curve may be produced. With
small samples, creep tests may readily be carried out using a cone and plate or parallel plate
viscometer.
For low strength solids, oscillatory shear is most often employed. This is carried out using
rotary viscometers adapted to apply and measure oscillating shear. The cone and plate and
parallel plate are the most commonly employed types. Most modern instruments are
58

connected to computers and the data collection and analysis software will produce values of
G and G" directly.






















59


Food Additives
What are food additives?
"Any substance not normally consumed as a food by itself and not normally consumed as a
typical ingredient of a food."
Additives are incorporated into foods so as to modify the properties (including the processing
properties) of the food in some way.
A distinction should be made between food additives and food contaminants.
A contaminant is an undesirable substance present in the food which it is not feasible to
completely remove (either for technical or economic reasons).
An additive, on the other hand, is a substance which is added deliberately for some specific
purpose.
Why use Food Additives?
It is important to note that food additives are not all bad. There are often good and proper
reasons for using additives in the commercial preparation of foods. Unfortunately, additives
have received a bad press because they are used on occasions to disguise inferior products.
When deciding whether or not to use additives, it is useful to ask the following questions
"Would I use this substance if I were preparing the same food in the kitchen at home?"
If the answer to this question is No, then ask the follow up question
"Is the use of this substance justified?"
The answer to this question can be determined with reference to the following two check
lists, one of positive reasons for using additives and one of negative reasons.
Food additives may be justified when they serve the following purposes:
1. Maintenance of the nutritional quality of food.
2. Enhancement of the keeping quality or stability of foods leading in a reduction of
losses.
3. Making foods attractive to the consumer in a way that does not lead to deception.
4. Providing essential aids in food processing.
Additives should not be used in the following circumstances:
1. To deceive the consumer.
2. To disguise the use of poor ingredients or faulty processing and handling techniques.
3. When the result is a substantial reduction in the nutritional value of the food.
60

4. When the desired effect can be obtained by good manufacturing practices which are
economically feasible.
In recent years there has been a considerable reduction in the number and quantity of food
additives being used as a result of consumer pressure.
Finally, it should be noted that most undesirable uses of additives arise out of lack of thought
rather than intention to deceive.
Major Categories of Food Additives
Under EC legislation, additives bear "E" numbers. Broadly speaking, the first digit of the E
number indicates the type of additive. The main E-number categories are given below.
E number Type of additive
E1xx Colours
E2xx Preservatives
E3xx Antioxidants, Emulsifiers, Stabilisers and Thickeners
E4xx Sweeteners
E5xx Mineral Salts
E6xx Flavour Enhancers
E9xx Waxes and glazing agents
There are variants on this set of categories, though the main categories are pretty much the
same. Jukes in "Food Legislation in the UK" categorises additives in a slightly different way.
Under UK and EU legislation, additives are mostly approved on a "positive list" system. That
is; if it is listed, you can use it. One exception to this is flavourings. There are such a large
number of flavour compounds, that a negative list system is used. That is you can use a
flavouring unless it is specifically prohibited.
Natural and Synthetic Additives
A distinction is often drawn between natural and synthetic additives. Often the association in
peoples minds is "natural = good" and "synthetic = bad". However, the situation is not as
simple as that as there is actually a third category, often referred to as nature identical. The
distinction basically is as follows
An additive can be called natural if it is actually isolated from a plant or animal source (using
those terms broadly) or occurs in a plant or animal extract
If an additive is identical chemically to a compound occurring in nature but has actually been
chemically synthesised, it referred to as nature identical
61

A synthetic additive is one which does not occur in nature and must be produced
synthetically.
This still leaves a grey area. How does one categorise an additive produced by means of a
fermentation process or by other biotechnological means?
Suggested Reading
Coultate T P, (1996), Food, the chemistry of its components 3rd Edition, RSC Paperbacks
Dickinson E, (1992), An Introduction to food colloids, OUP
Hanssen M, (1987), The New E for Additives, Thorsons
Jukes, D J, (1993), Food Legislation of the UK, 3rd Edition, Butterworth Heinemann
Russell N J & Gould G W, (1991), Food Preservatives, Blackie