Rheology

Introduction
Rheology is the study of the flow of matter, primarily in the liquid state, but also as
'soft solids' or solids under conditions in which they respond with plastic flow
rather than deforming elastically in response to an applied force. We are generally
more concerned with soft solids when we talk about rheology. The flow of soft
solids behave in an interesting or unusual manner. For example, oil and water
flow in familiar, normal ways, whereas mayonnaise, peanut butter, chocolate,
bread dough, and Silly Putty flow in complex and unusual ways. In rheology, we
incline our attention towards the flows of unusual materials. It applies to
substances which have a complex microstructure, such as muds, sludge,
suspensions, polymers and other glass formers (e.g., silicates), as well as many
foods and additives, bodily fluids (e.g., blood) and other biological materials or
other materials which belong to the class of soft matter.

Rheology generally accounts for the behavior of non-Newtonian fluids, by

characterizing the minimum number of functions that are needed to relate stresses
with rate of change of strains or strain rates. For example, ketchup can have its
viscosity reduced by shaking (or other forms of mechanical agitation, where the
relative movement of different layers in the material actually causes the reduction
in viscosity) but water cannot. Ketchup is a shear thinning material, as an increase
in relative velocity caused a reduction in viscosity, while some other non-
Newtonian materials show the opposite behavior: viscosity going up with relative
deformation, which are called shear thickening or dilatant materials. Since
Sir Isaac Newton originated the concept of viscosity, the study of liquids with
strain rate dependent viscosity is also often called Non-Newtonian fluid mechanics.

The term rheology was coined in 1920s, and was inspired by a Greek quota) on,
"panta rei", "everything flows". In practice, rheology is principally concerned with
extending the "classical" disciplines of elasticity and (Newtonian) fluid mechanics
to materials whose mechanical behavior cannot be described with the classical
theories.
Factors affecting rheology
Rheology is the science of materials flow behavior and deformation. When a
material flows we have to consider three basic things.

1. The first essential factor is the materials inner structure.

This factor is concentrates on how the material is built. For example, if there
is space between its molecules the materials will flow easier, if molecules
are more tightly linked it will stick together even if the material is deformed.
2. The second factor is the Outside forces that stress the material.
The outside forces either deform the material or make if flow. The
magnitude of force applied, the rate of application of force on materials
heavily influences how the material flow.
3. The third vital factor is the Ambient conditions in which the material is
kept.
This factor deals with the situation in which the material is kept, the
surrounding temperature, pressure, humidity etc.

Rheological Behavior
The two extreme rheological behavior are:

ELASTIC behavior e.g. perfectly rigid solids where any deformation reverses
spontaneously when an applied force is removed. Energy is conserved, first stored
in the system and then released.

NEWTONIAN or VISCOUS or PLASTIC behavior e.g. ideal Newtonian liquids

Where any deformation ceases when the applied force is removed. Energy is not
conserved, it performs work on the material

In between elastic and viscous behavior lies the real world of most substances,
which are viscoelastic materials. Materials like jelly, cream, honey etc. which are
mixtures of viscous and elastic portions come under this category.
Definitions and Common Terminology used
in Rheology

Laminar Flow
Laminar flow is a type of flow in which fluid flow in parallel layers, with no
disruption between the layers i.e. no exchange of any particles occurs between the
two parallel layers, one layer slides over the other. In laminar flow the motion of
the particles is very orderly with all the particles moving in straight parallel to the
pipe wall.

Turbulent flow
Turbulent flow is a type of flow in which the fluid undergoes irregular fluctuations
or mixing in contrast to laminar flow in which the fluid flows in layers.

Shear Stress
Shear stress is defined as the ratio of force acting parallel to the surface of a
material to the area of the surface
Shear rate
Shear rate is the rate at which a progressive shearing deformation is applied to
some material. The shear rate for a fluid flowing between to parallel plates, one
moving at a constant speed and the other one stationary is defined by

Viscosity
Viscosity of a fluid is a measure of its resistance to gradual deformation by shear
stress or tensile stress. For liquids, it corresponds to an informal notion of
thickness. Viscosity is due to friction between neighboring particles of fluid that
are moving at different velocities.

Newtons Law
According to Newtons law viscosity is defined as the ratio of shear stress to shear
rate.
Newtonian (or viscous) behavior
For ideal viscous material, the rate of deformation is proportional to the force
applied. Deformation ceases when the applied force is removed. The apparent
viscosity is constant with changing shear rates. This behavior is seen in liquids like
water.

Viscosity = Shear stress / Shear rate

Non-Newtonian Behavior
A fluid shows non-Newtonian behavior when its apparent viscosity changes with
change in shear stress.
Thixotropy and Rheopexy (Work Hardening)
A thixotropic material becomes more fluid with increasing time of applied force.
The applied force could be stirring pumping or shaking. This effect is sometimes
called work softening. It is often reversible, so that if left undisturbed for some
time a thixotropic slurry regains its viscosity. Quicksand is an example of
thixotropic material.
A rheopectic material becomes more viscous with increasing time of applied force.
This effect just the reverse of thixotropy and sometimes also called work
hardening.

Dilatancy (Shear Thickening)

A dilatant material resists deformation more than in proportion to the applied force.
For example, the more the effort you put in stirring a dilatant material, the more
resistant it becomes to stirring. This is usually an indication that the applied force
is causing the material to adopt a more orderly structure. A thick slurry of wet
beach sand is often dilatant.
Plastic or Pseudoplastic (Shear thinning)
Plastic material initially resist deformation, until a yield stress is reached. When
the stress exceeds the yield stress, the shear rate becomes measurable. Further
stress finally leads to linear (Newtonian) behavior.
Pseudoplastic materials exhibit shear thinning without the initial resistance to
deformation. Like plastic materials, they also show linear (Newtonian) behavior at
the highest level of stress and shear rate.

Rheometry
To measure flow behavior we need to create flow. The easiest way to create flow is
to let gravity do all the work on the material. Flow cup and capillary are few
examples where gravity is used to measure kinematic viscosity.
But such measurements only work for a
limited range of materials, although gravity
is highly reliable it effects cannot be
controlled. For non-Newtonian liquids the
value of viscosity changes with increase in
shear rate. We need several values under
several shear conditions. So, to precisely
measure a parameter related to viscosity for
non-Newtonian liquids we need controlled
shear conditions and gravity do not serve
this purpose. By use of rheometry we measures many viscosity values in a
continuous run under changing conditions. This can be done by the use of
rheometer which uses principal of rheometry.
Rheometer
Rheometer creates a controlled and workable flow conditions. The two most
essential tests a rheometer performs are rotational tests and oscillatory tests.

The difference between these two tests is the way the material is sheared. In
rotational tests liquids are stirred or turned, oscillatory test on the other hand work
on very small back and forth oscillation. With oscillation we determine values for
the viscoelastic behavior of all types of materials varying from viscous end to
elastic end. Rotation test are used to measure viscosity function of liquids as in
liquids the viscous portion dominates and elastic portion is very less and can be
ignored.
Various Geometries used in a Rheometer
The most common measuring geometries used to measure various parameters in a
rheometer are concentric cylinders, cone and plate system and the parallel
plate system. All geometries consist of a measuring bob and lower plate /
cylindrical cup. The measuring bob is turned by the instrument motor whereas the
lower plate or cup stands still.

The measuring bob shears the liquid while it is rotating. We decide how fast the
measuring bob should turn. This is known as measurement preset. Depending on
the liquid viscosity the measuring bob will require certain amount of torque for
maintaining this speed and this required torque is our measurement result. It is
depicted in the fig below.

We can also preset certain torque and then measure

the speed of the measuring bob rotation as result.

By using the torque value we find the shear stress

and rotational speed gives shear rate. By taking the
ratio of shear stress to shear rate we determine the
shear viscosity.
Various test modes used in a rheometer
A rheometer has two essential test modes speed control and torque control.

Tests where the speed or shear rate is controlled is known as the Controlled Shear
Rate (CSR) Test. In this test the shear stress is measured. Various process
conditions can be stimulated by CSR test like spraying pipe flow or painting.

Alternatively tests where the torque or shear stress is controlled is known as the
Controlled Shear Stress (CSS) Test. In this test shear rate is measured. The CSS
method is used to measure the viscosity of dispersion, gel or pastes.

Rheological Curves
Rheological curves are drawn in order to express the viscosity parameters in an
effective way. To draw these curves we need to set the presets properly so that we
can obtain the results. The preset in case of rheology is defined in such a way that
it varies linearly with time as shown in fig below. We either control the shear stress
or the shear rate. For example if we perform a CSR test a rheometer usually starts
at a shear rate or rotational speed of zero, then the shear rate is gradually increased
step by step right up to the maximum of our defined period of time and we
measure how the viscosity will change under these defined conditions.
We can find the viscosity of the material using flow curve which are curves of
shear stress on ordinate and shear rate on abscissa. The slope of the flow curve at
any point gives the viscosity at that point. When viscosity measured at various
points from the flow curve are plotted on ordinate and the some other quantity
varying the viscosity like shear rate, time or shear stress on abscissa, the curve
obtained is a viscosity function. Various flow curves and viscosity function are
drawn below for both Newtonian and Non Newtonian materials.

The Figure represents the flow curve and

the viscosity function for water. It this
case CSR test is performed i.e. the shear
rate is measurement preset and the shear
stress is the result. The shear stress
constantly varies with shear rate and the
slope of this curve i.e. viscosity is
constant when plotted against time as
seen from the viscosity function curve.

This figure shows the behavior of shear

thinning material like ketchup in a CSR
test. The shear stress for this type of
material decrease with increase in shear
rate. The viscosity for this type of
material decreases with increase in time.
The above figure represents the behavior of shear thickening material like
suspension of starch in water in CSR test. the shear stress increases at faster rate
compared to increase in shear rate.

The above figure shows the shear stress v/s shear rate relationship for toothpaste in
an CSS test which flows only after it has reached certain yield point. Once the
shear stress comes below the yield point stress value the material stops flowing.
Rheology Influencers

Temperature
Temperature is a very powerful influencer of viscosity so it is very important to
control temperature in a rheometer. Viscosity decreases as the temperature
increases. A rheometer should be capable of performing temperature dependent
tests so that effect of change of temperature can be studied as well. The fig below
depicts the change in viscosity of ice cream with time. Temperature dependent
tests are used in the food industry and are also very important for the petroleum
industry where the pour point of the oil needs to be determined.

Some other factors are

1. Pressure
2. pH value
3. Strength of magnetic / electric field around the material

But the effect of temperature on viscosity is much greater than the above three.
The Painting Trouble
Rheology is very important in manufacture of paint as for any paint we require it to
have high viscosity while it is at rest, low viscosity while it is being applied and
again a high viscosity after the paint is applied. So, a paint passes through three
stages in its lifetime rest, application and recovery. The time for which the paint
can hold on to its properties in respective stages is determined by testing it
rheologically. A curve is drawn between time on abscissa and viscosity in ordinate
and various stages of paint are determined by studying these curves

If the time required for recovery of paint is low, there will be sagging problem and
the curve will be obtained like
If the paint recovers too quickly there will be brush marks on the surface of
application and the curve obtained will be like

So to obtain a glossy finish on a paint we require that the recovery time of the paint
is neither to loo nor too fast. The curve for a paint with optimum finish is shown
Applications of rheology and areas of use
1. Pumping slurries materials transport.
2. Thickening and dewatering of mineral slurries.
3. Filtration the materials with more viscosity are filtered with less speed
4. Production of brick and ceramic products. The slurry used for production of
brick and ceramic products should be rheologically tested for production of
accurate finished products
5. Manufacture of paint. Rheological studies of the paint is done so that the
paint becomes more viscous in optimal time.
6. Rheology is used in reactions involving mineral slurries e.g. gold extraction
7. Soil chemistry e.g. effect of clay rheology on soil friability and structure

A through rheological understanding of any slurry system is required as it directly

influences the flow of the slurry or paste. If proper rheological data is available
then an accurate process can be selected for mixing or producing the mixture or
slurry. This can save a lot of time and cost.

Highly reliable and accurate principle of rheometry is so vital so that we precisely

know how our flow will occur
Factors affecting the rheology of concrete
As stated earlier, workability and other flow properties are related to the rheology of
concrete. What are the principal factors that influence the rheological parameters of
concrete? The first factors are the composition of the concrete, including the chemical
and mineral admixture dosage and type, the gradation, shape and type of the
aggregates, the water content and the cement characteristics. The same mixture design
can result in different flow properties if secondary factors are not taken into account.
These are:

mixer type: pan, truck; (These may induce various levels of deflocculation and
air entrainment);
mixing sequence, i.e., sequence of introduction of the materials into the
mixer;
mixing duration;
Temperature.

To determine the rheological characteristics needed for a specific application, the

following items need to be considered:

method of delivering the concrete to the forms, e,g., pumping, bucket;

method of consolidation, e.g., vibration, tamping, none;
Type of finishing method.

In considering the application, some of these items will be automatically selected. For
instance, if a structure with a very high amount of reinforcement is built, the concrete
needs to be self-consolidating because it will be impossible for a vibrator to reach all
the concrete.

Another variable that should be addressed is the time dependence of the rheological
parameters. This phenomenon is often described as "slump loss" or excessive
retardation. The placement of the concrete becomes either difficult (slump loss) or the
demolding is retarded and strength development is delayed.

A detailed review of how the various factors mentioned above will influence the flow,
and specifically the Bingham parameters, will not be attempted here but a good
review is given by Khayat et al.