A Seminar Report on Rheology of non-

Newtonian fluids [2017-18]

CHAPTER 1

INTRODUCTION

Rheometry refers to the experimental technique used to determine the rheological properties
of materials; rheology being defined as the study of the flow and deformation of matter which
describes the interrelation between force, deformation and time. The term rheology originates
from the Greek words rheo translating as flow and logia meaning the study of,
although as from the definition above, rheology is as much about the deformation of solid-
like materials as it is about the flow of liquid-like materials and in particular deals with the
behaviour of complex viscoelastic materials that show properties of both solids and liquids in
response to force, deformation and time.

There are a number of rheometric tests that can be performed on a rheometer to determine
flow properties and viscoelastic properties of a material and it is often useful to deal with
them separately. The first part of this introduction will focus on flow and viscosity and the
tests that can be used to measure and describe the flow behaviour of both simple and complex
fluids. In the second part deformation and viscoelasticity will be discussed.
Definitions:
Strain: deformation in term of relative displacement of the particles composing the body
Stress: measure of internal forces acting within a (deformable) body
Shear: deformation of a body in one direction only (resulting from the action of a force per
unit area =shear stress) and having a given perpendicular gradient (=shear strain)
Most low molecular weight substances such as organic and inorganic liquids, solutions of low
molecular weight inorganic salts, molten metals and salts, and gases exhibit Newtonian flow
characteristics, i.e., at constant temperature and pressure. In simple shear, the shear stress is
proportional to the rate of shear and the constant of proportionality is the familiar dynamic
viscosity. Such fluids are classically known as the Newtonian fluids, albeit the notion of flow
and of viscosity predates Newton. For most liquids, the viscosity decreases with temperature
and increases with pressure. For gases, it increases with both temperature and pressure.
Broadly, higher is the viscosity of a substance, more resistance it presents to flow (and hence

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more difficult to pump). As the viscosity of fluids increases by several orders of magnitude,
and thus one can argue that a solid can be treated as a fluid whose viscosity tends towards
infinity, thus, the distinction between a fluid and a solid is not as sharp as we would like to
think! Ever since the formulation of the equations of continuity (mass) and momentum
(Cauchy, Navier-Stokes), the fluid dynamics of Newtonian fluids has come a long way during
the past 300 or so years, albeit significant challenges especially in the field of turbulence and
multi-phase flows still remain.
During the past 50-60 years, there has been a growing recognition of the fact that many
substances of industrial significance, especially of multi-phase nature (foams, emulsions,
dispersions and suspensions, slurries, for instance) and polymeric melts and solutions (both
natural and manmade) do not conform to the Newtonian postulate of the linear relationship
between and in simple shear, for instance. Accordingly, these fluids are variously known as
non-Newtonian, non-linear, complex, or rheologically complex fluids. Indeed so widespread
is the non-Newtonian fluid behaviour in nature and in, technology that it would be no
exaggeration to say that the Newtonian fluid behaviour is an exception rather than the rule.
This chapter endeavours to provide a brief introduction to the different kinds of non-
Newtonian flow characteristics, their characterization and implications in engineering
applications. The material presented herein is mainly drawn from our recent books. The
assumptions of material isotropy and incompressibility are implicit throughout our
discussion.

Rheological Classification of Fluids:

In classical mechanics, the distinction between liquids and solids was very clear, and separate
physical laws existed to describe the behaviour of solids (Hookes law) and liquids (Newtons
law). However, a variety of products (such as foods) exist that exhibit intermediate behaviour
which needs to be well characterized.
Fluids are initially classified as having Newtonian or Non-Newtonian behaviour, depending
on whether they can be described by Newton's law of viscosity or not. Non- Newtonian fluids
are also classified as time-dependent or time-independent. Fluids in which rheological
behaviour depends only on the shear stress (at constant temperature) are considered time-
independent. Time-dependent fluids are those in which the viscosity depends, not only on the

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shear stress, but also on the amount of time the stress has been applied to the fluid. There are
fluids that present both viscous and elastic behaviour; they are called viscoelastic fluids.
Classification of flowing fluids can be done by means of viscometric functions, defined in the
previous section. For Newtonian fluids, the viscosity function is constant, and the viscosity
(Newtonian viscosity) is independent of shear strain rate and time (() = = constant ).
Mainly fluids are classified into following types:
A). Newtonian flow
B). Non-Newtonian flow
1). Time independent
a) Plastic fluids
b) Pseudo plastic fluids (shear-thinning)
c) Dilatant fluids (shear-thickening)
2). Time dependent
a) Thixotropic fluids
b) Antithixotropic or rheopectic fluids
C) Viscoelastic fluids

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CHAPTER 2

CLASSIFICATION OF FLUIDS

2.1 Newtonian Fluids:

Fluids which obey the Newton's law of viscosity are called as Newtonian fluids. Newton's
law of viscosity is given by

t = mdv/dy

Where t = shear stress

m = viscosity of fluid

dv/dy = shear rate, rate of strain or velocity gradient

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All gases and most liquids which have simpler molecular formula and low molecular weight
such as water, benzene, ethyl alcohol, CCl4, hexane and most solutions of simple molecules
are Newtonian fluids.

Examples:

Water, air, milk, alcohol, glycerol, and thin motor oil are examples of (practically) Newtonian
fluids that have different density properties, which allows a different shear stress and rate
flow graphs within a given interval.

2.2 Non-Newtonian Fluids:

What is Non-Newtonian fluid?

A non-Newtonian fluid is a fluid whose viscosity is variable based on applied stress or force.
The most common everyday example of a non-Newtonian fluid is corn starch dissolved in
water. Behaviour of Newtonian fluids like water can be described exclusively by temperature
and pressure. However, the physical behaviour of non-Newtonian fluid depends on the forces
acting on it from second to second.

Many common substances exhibit non-Newtonian flows. These include:

Soap solutions, cosmetics and toothpaste

Food such as butter, cheese, jam, ketchup, mayonnaise, soup, taffy, and yogurt

Natural substances such as magma, lava, gums, and extracts such as vanilla extract

Biological fluids such as blood, saliva, semen, mucus and synovial fluid

Slurries such as cement slurry and paper pulp, emulsions such as mayonnaise, and
some kinds of dispersions

Although the concept of viscosity is commonly used in fluid mechanics to characterize

the shear properties of a fluid, it can be inadequate to describe non-Newtonian fluids. They

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are best studied through several other rheological properties that relate stress and strain
rate tensors under many different flow conditionssuch as oscillatory shear or extensional
flowwhich are measured using different devices or rheometers. The properties are better
studied using tensor-valued constitutive equations, which are common in the field
of continuum mechanics.

Fig.1 Behaviour of fluids.

CHAPTER 3

TYPES OF NON-NEWTONIAN FLUIDS:

Systems for which the value of at a point within the fluid is determined only by
the current value of at that point; these substances are variously known as purely
viscous, inelastic, time-independent or generalized Newtonian fluids (GNF).
Systems for which the relation between and shows further dependence on the
duration of shearing and kinematic history; these are called time-dependent fluids.

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Systems which exhibit a blend of viscous fluid behaviour and of elastic solid-like
behaviour. For instance, this class of materials shows partial elastic recovery, recoil,
creep, etc. Accordingly, these are called visco-elastic or elastico-viscous fluids.
Each type of non- Newtonian fluid behaviour is now will see in more detail.

3.1 TIME INDEPENDENT FLUIDS:

Also we know that in simple unidirectional shear, this sub-set of fluids is characterized by the
fact that the current value of the rate of shear at a point in the fluid is determined only by the
corresponding current value of the shear stress and vice versa.
Conversely, one can say that such fluids have no memory of their past history. Thus, their
steady shear behavior may be described by a relation of the form,
yx = f (yx)
Or, its inverse form,
yx = f1(yx)
Depending on the above equations there are three types of time-independent fluids.

Shear- thinning or pseudo-plastic fluids.

Bingham plastic fluids.
Shear- thickening or dilatant fluids.

PSEUDO-PLASTIC OR SHEAR THINNING FLUIDS:

In rheology, shear thinning is the non-Newtonian behaviour of fluids

whose viscosity decreases under shear strain. It is sometimes considered synonymous for
pseudo-plastic behaviour, and is usually defined as excluding time-dependent effects, such
as thixotropy. Shear-thinning behaviour is generally not seen in pure liquids with
low molecular mass, or ideal solutions of small molecules like sucrose or sodium chloride,
but is often seen in polymer solutions and molten polymers, and complex fluids and
suspensions like ketchup, whipped cream, blood, paint, and nail polish.

EVERYDAY EXAMPLES:

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Modern paints are examples of pseudo-plastic materials. When modern paints are applied the
shear created by the brush or roller will allow them to thin and wet out the surface evenly.
Once applied the paints regain their higher viscosity which avoids drips and runs.

Ketchup is a shear-thinning fluid, caused by the addition of a relatively small amount

of Xanthan gum - usually 0.5%.

POWER LAW OR OSTWALD DE WAELE EQUATION:

Often the relationship between shear stress ()shear rate() plotted on log-log co-ordinates
for a shear-thinning fluid can be approximated by a straight line over an interval of shear rate,
i.e.,
= m()n

or, in terms of the apparent viscosity,

= m()n1

Obviously, 0 < n < 1 will yield (d/d) < 0, i.e., shear-thinning behaviour fluids are
characterized by a value of n (power-law index) smaller than unity. Many polymer melts and
solutions exhibit the value of n in the range 0.3-0.7 depending upon the concentration and
molecular weight of the polymer, etc. Even smaller values of power-law index (n
0.10.15) are encountered with fine particle suspensions like kaolin-in-water, bentonite-in-
water, etc. Naturally, smaller is the value of n, more shear-thinning is the material. The other
constant, m, (consistency index) is a measure of the consistency of the substance.
Although, eq. (12) or (13) offers the simplest approximation of shear-thinning
Behaviour, it predicts neither the upper nor the lower Newtonian plateaus in the limits of 0
or . Besides, the values of m and n are reasonably constant only over a narrow interval

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of shear rate range whence one needs to know a priori the likely range of shear rate to be
encountered in an envisaged application.

THE CROSS VISCOCITY EQUATION:

In order to rectify some of the weaknesses of the power-law, Cross presented the following
empirical form which has gained wide acceptance in the literature. In simple shear, it is
written as,

0 1+m()n

It is readily seen that for n < 1, this model also predicts shear-thinning behavior.
Furthermore, the Newtonian limit is recovered here when m 0. Though initially Cross
proposed that n=2/3 was satisfactory for numerous substances, it is now thought that treating
it as an adjustable parameter offers significant improvement in terms of the degree of fit.
Evidently, correctly predicts = 0 and =in the limits of 0 and respectively.

THE ELLIS FLUID MODEL:

While the two viscosity models presented thus far are examples of the form of eq., the Ellis
model is an illustration of the inverse form of equations of time independent. In
unidirectional simple shear, it is written as

= 0
1+ (1/2)^1
In above eq., 0 is the zero shear viscosity and the remaining two parameters 1/2 and > 1
are adjusted to obtain the best fit to a given set of data. Clearly, > 1 yields the decreasing
values of shear viscosity with increasing shear rate. It is readily seen that the Newtonian limit

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is recovered by setting 1/2 . Furthermore, when (/1/2 )1, above eq. reduces to the
power-law model.

Structural changes due to the forces changes in viscosity: ordering of molecules or

particles.

BINGHAM PLASTIC FLUIDS:

This type of non-Newtonian fluid behavior is characterized by the existence of a threshold

stress (called yield stress or apparent yield stress, 0) which must be exceeded for the fluid to
deform (shear) or flow. Conversely, such a substance will behave like an elastic solid (or flow
en masse like a rigid body) when the externally applied stress is less than the yield stress, 0.
Of course, once the magnitude of the external yield stress exceeds the value of 0, the fluid
may exhibit Newtonian behaviour (constant value of ) or shear-thinning characteristics, i.e.,
(). It therefore stands to reason that, in the absence of surface tension effects, such a
material will not level out under gravity to form an absolutely flat free surface. Quantitatively
this type of behavior can be hypothesized as follows: such a substance at rest consists of
three-dimensional structures of sufficient rigidity to resist any external stress less than |0|
and therefore offers an enormous resistance to flow, albeit it still might deform elastically.

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For stress levels above |0|, however, the structure breaks down and the substance behaves
like a viscous material. In some cases, the build-up and breakdown of structure has been
found to be reversible, i.e., the substance may regain its (initial or somewhat lower) value of
the yield stress.
A fluid with a linear flow curve for || > |0| is called a Bingham plastic fluid, and is
characterized by a constant value of viscosity B. Thus, in one-dimensional shear, the
Bingham model is written as:

yx =B0 +B yx |yx| > |B0|

yx = 0 |yx| < |B0|

On the other hand, a visco-plastic material showing shear-thinning behavior at stress levels
exceeding |0| is known as a yield-pseudo plastic fluid, and their behavior is frequently
approximated by the so-called Herschel-Bulkley fluid model written for 1-D shear flow as
follows

yx =H0 +m(yx)n |yx| > |H0|

yx = 0 |yx|< |H0|

Another commonly used viscosity model for visco-plastic fluids is the so-called Casson
model, which has its origins in modeling the flow of blood, but it has been found a good
approximation for many other substances also It is written as:

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Shear stress-shear rate data for a meat extract and for a carbopol solution displaying Bingham
plastic and visco-plastic behaviours respectively.

EXAMPLES:
Blood, yoghurt, tomato puree, molten chocolate, tomato sauce, cosmetics, nail
polishes, foams, suspensions, etc.

SHEAR THICKNING OR DILATANT FLUIDS:

A dilatant (also termed shear thickening) material is one in which viscosity increases with
the rate of shear strain. Such a shear thickening fluid, also known by the initialism STF, is an
example of a non-Newtonian fluid. This behaviour is usually not observed in pure materials,
but can occur in suspensions.

A dilatant is a Non-Newtonian fluid where the shear viscosity increases with applied shear
stress. This behaviour is only one type of deviation from Newtons Law, and it is controlled
by such factors as particle size, shape, and distribution. The properties of these suspensions

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depend on Hamaker theory and Van der Waals forces and can be stabilized electrostatically or
sterically. Shear thickening behaviour occurs when a colloidal suspension transitions from a
stable state to a state of flocculation. A large portion of the properties of these systems are due
to the surface chemistry of particles in dispersion, known as colloids

EXAMPLES:

Corn starch and water (oobleck):

Corn starch is a common thickening agent used in cooking. It is also a very good example of
a shear thickening system. When a force is applied to a 1:1.25 mixture of water and corn
starch, the corn starch acts as a solid and resists the force.

Silica and polyethylene glycol:

Silica nano-particles are dispersed in a solution of polyethylene glycol. The silica particles
provide a high strength material when flocculation occurs. This allows it to be used in
applications such as liquid body armour and brake pads.

Quicksand:

Quicksand is a natural case of a shear thinning, non-Newtonian fluid. This is the opposite of a
dilatant. As its strain rate increases, its resistance to shear will decrease causing the system to

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act more like a liquid than a solid. Hence, as one thrashes about in quicksand one sinks faster
as the mixture's resistance decreases.

APPLICATIONS:

Traction control:

Dilatant materials have certain industrial uses due to their shear thickening behaviour. For
example, some all wheel drive systems use a viscous coupling unit full of dilatant fluid to
provide power transfer between front and rear wheels. On high traction road surfacing, the
relative motion between primary and secondary drive wheels is the same, so the shear is low
and little power is transferred. When the primary drive wheels start to slip, the shear
increases, causing the fluid to thicken. As the fluid thickens, the torque transferred to the
secondary drive wheels increases proportionally, until the maximum amount of power
possible in the fully thickened state is transferred. See also: limited slip differential, some
types of which operate on the same principle..... To the operator, this system is entirely
passive, engaging all four wheels to drive when needed, and dropping back to two wheel
drive once the need has passed. This system is generally used for on-road vehicles rather than
off-road vehicles, since the maximum viscosity of the dilatant fluid limits the amount of
torque that can be passed across the coupling.

Body armour:

Various corporate and government entities are researching the application of shear thickening
fluids for use as body armour. Such a system could allow the wearer flexibility for a normal
range of movement, yet provide rigidity to resist piercing by bullets, stabbing knife blows,
and similar attacks. The principle is similar to that of mail armour, though body armour using
a dilatant would be much lighter. The dilatant fluid would disperse the force of a sudden blow
over a wider area of the user's body, reducing the blunt force trauma. However, against slow
attacks which would allow flow to occur, such as a slow but forceful stab, the dilatant would
not provide any additional protection.

In one study, standard Kevlar fabric was compared to a composite armour of Kevlar and a
proprietary shear-thickening fluid. The results showed that the Kevlar/fluid combination

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performed better than the pure-Kevlar material, despite having less than one-third the Kevlar
thickness.

Four examples of dilatant materials being used in personal protective equipment are
Armourgel, d3o, ArtiLage ( Artificial Cartilage foam) and 'Active Protection System',
manufactured by Dow Corning

TIME DEPENDENT FLUIDS:

Many substances, notably in food, pharmaceutical and personal care product manufacturing
sectors display flow characteristics which cannot be described by a simple mathematical
expression of the form of equations of time independent fluids. This is so because their
apparent viscosities are not only functions of the applied shear stress () or the shear rate
(), but also of the duration for which the fluid has been subjected to shearing as well as
their previous kinematic history. For instance, the way the sample is loaded into a viscometer,
by pouring or by injecting using a syringe, etc. influences the resulting values of shear stress
or shear rate . Similarly, for instance, when materials such as bentonite-in-water, coal-in-
water suspensions, red mud suspensions (a waste from alumina industry), cement paste, waxy
crude oil, hand lotions and creams, etc. are sheared at a constant value of following a long
period of rest, their viscosities gradually decrease as the internal structures present are
progressively broken down.
As the number of such structural linkages capable of being broken down reduces, the rate of
change of viscosity with time approaches zero. Conversely, as the structure breaks down, the
rate at which linkages can re-build increases, so that eventually a state of dynamic
equilibrium is reached when the rates of build-up and of break down are balanced. Similarly,
there are a few systems reported in the literature in which the imposition of external shear
promotes building up of internal structures and consequently their apparent viscosities
increase with the duration of shearing.

TYPES OF TIME DEPENDENT FLUIDS:

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There are two types of time dependent fluids.

Thixotropic Fluids.
Rheopectic or Anti-Thixotropic fluids.

Now we will see each type in detail.

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Typical experimental data showing thixotropic behaviour in a red mud suspension

THIXOTROPIC FLUIDS:

A material is classified as being thixotropic if, when it is sheared at a constant rate, its
apparent viscosity = / (or the value of because is constant) decreases with the
duration of shearing, as shown in Fig. 9 for a red mud suspension containing 59% (by wt.)
solids [33]. As the value of is gradually increased, the time needed to reach the equilibrium
value ofis seen to drop dramatically. For instance, at = 3.5 s1, it is of the order of
1500 s which drops to the value of 500 s at = 56 s1. Conversely, if the flow curve of
such a fluid is measured in a single experiment in which the value of is steadily increased
at a constant rate from zero to some maximum value and then decreased at the same rate, a
hysteresis loop of the form shown schematically in Fig. 10 is obtained. Naturally, the height,
shape and the area enclosed by the loop depend on the experimental conditions like the rate
of increase/decrease of shear rate, the maximum value of shear rate, and the past kinematic

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history of the sample. It stands to reason that, the larger the enclosed area, more severe is the
time-dependent behaviour of the material under discussion.
Evidently, the enclosed area would be zero for a purely viscous fluid, i.e., no hysteresis effect
is expected for time-independent fluids. Data for a cement paste shown in Fig. 11 confirms its
thixotropic behaviour. Furthermore, in some cases, the breakdown of structure may be
reversible, i.e., upon removal of the external shear and following a long period of rest, the
fluid may regain (rebuilding of structure) the initial value of viscosity. The data for a lotion
shown in Fig. 12 illustrates this aspect of thixotropy. Here, the apparent viscosity is seen to
drop from 80 Pa.s to 10 Pa.s in about 510 s when sheared at = 100 s1 and upon
removal of the shear, it builds up to almost its initial value in about 5060 s. Barnes has
written a thorough review of thixotropic behaviour encountered in scores of systems of
industrial significance

Thixotropy in a cement paste

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