Rheology for beginners

Part 2. Viscoelasticity

The sauce is separating, the butter is melting and the marmalade is setting
in the process. These are examples of rheological changes which are
explained best using viscoelastic terms.
In the Rheology for beginners, part 1, viscosity was explained and how it is
used. Unfortunately viscosity can not describe what is occurring when
something is melting or setting because the viscosity is infinite for a solid
material. Then we have to use dynamic magnitudes such as modulus and phase
angel to describe the consistency and character.
If we start with an example which many of us have played with bouncing
putty it is a typical material which can not be described fully by its viscosity
or its elasticity. Bouncing putty can be formed and slowly pulled into long
threads. If it is formed to a ball it will bounce like a bouncing ball. Bouncing
putty together with many foods, for example marmalade, mayonnaise and
spreads, are materials which are both viscous and elastic, viscoelastic. For these
the complex modulus is needed, which for shear is represented by G*. It can be
divided into two parts, the storage modulus G which describes the elastic
properties, and G, the loss modulus which describes the viscous properties.
What is de facto a modulus?
There are a number of different modules and for an elastic material you could
say that the modulus describes the stiffness of a material. The spring constant is
a typical modulus. It describes how much force is needed to stretch a spring to a
certain distance, with other words the force divided with the length. The same
conditions can be applied on the complex modulus but instead force per area
divided with dimensionless deformation is used, see the formula box. The
modulus can be measured in different ways and one of the most commonly used
is shown in the figure below. A viscoelastic material is poured into a cup and a
concentrical cylinder (called bob) is lowered into the material. The cup is
oscillating in a sinus like movement and the force which the material is
transferring is measured with the concentric cylinder. The force will also be
sinus like with the same frequency as the cup, but displaced in comparison to
the movement. The displacement is measured as a phase angel and the
variations correspond to the character of the material. A totally elastic material,
such as steel, has no displacement at all, and the phase angel =0 while a liquid
has maximal displacement and =90. The onset deformation, the measured
force and displacement are used to describe the storage modulus and the loss

The author demonstrats flow

bouncing putty

Formulas

modulus.

Sketch of a rheometer for viscoelastic measurements. Click for an animation.

Viscoelastic measurements at different frequencies can be used to describe the

character for a material in the same way as an optical spectrum is used for
spectrophotometers. A mechanic spectrum is shown for bouncing putty in figure
2. The modules vary dramatically with frequency, which very well describes
how the bouncing putty is experienced during playing. Low frequencies
correspond to when long threads are slowly pulled from the bouncing putty. The
loss modulus which describes the viscous properties is then much higher than
the storage modulus the bouncing putty behaves like a viscous liquid. At high
frequencies the storage modulus is much higher than the loss modulus so the
bouncing putty has an elastic behaviour and bounces. The bounce is quick and
corresponds to high frequency.

A mechanical spectrum for bouncing putty. At low frequencies G dominates and the
bouncing putty behaves like a viscous liquid. At high frequencies G dominates and the
bouncing putty behaves like an elastic bouncing ball.

Viscoelastic measurements are also useful for characterising changes like

melting, crystallisation, and gel formation. The modules are then measured at a
certain frequency while other parameters are changed, such as temperature or
pH. If we use boiling an egg as an example the liquid egg white will turn into
solid material when the temperature is increased. Exactly the same thing can be
performed in our rheometer in figure 1. The egg white is poured into the cup
and the complex modulus is measured while the temperature is increased. The
albumin in the egg white will aggregate and form a gel in the measuring cup
when the temperature is high enough. The same thing is valid for many more
proteins, figure 3 shows how the -lactoglobulin from whey protein forms a gel
when the temperature is increased. (Note that only G and is shown. Only two
parameters are needed to describe a viscoelastic material, which ones chosen
are equal.) At low temperature the -lactoglobulin solution is a liquid which is
explained by the high phase angel. The liquid has a low viscosity why the
measured signal becomes noisy. When the temperature is increasing the protein
aggregates and G increases simultaneously as decreases, which means that
the characteristics for the solution changes from liquid towards a more elastic
material. This happens in two steps and at 75C, G is dramatically increasing
when the protein denaturates.

Gel formation of the protein -lactoglobulin observed using viscoelastic measurements

at 1 Hz. (Stading and Hermansson, 1990).

One advantage with viscoelastic measurements is the extremely small

deformation of the sample, only as much as required for performing a
measurement and yet so little as the material does not change. Because of this it
is possible to perform repeated measurements on the same sample and follow
the changes occurring in the sample. The applied deformation must be tested
utterly thorough so the material does not change during the measures. For the
measurement shown in figure 3 a deformation =10-3 was used which
corresponds to a maximum movement of 8 m. If the movement is increased to
30 m, which still is a very small deformation, the first structure formation will
be destroyed and the final storage modulus will be six times lower! It is
extremely important to use a deformation which is small enough.
Bouncing putty and pure protein solutions may seem far from real food, but the
same methods are used to characterise the processes when the sauce is
separating or when the butter is melting. Pure and simple systems are easier to
use as examples, but a mechanic spectrum for marmalade or yoghurt is as
interesting as for bouncing putty.

Mats Stading

http://projekt.sik.se/rheology/Undre_rheobeginners2.htm