1

P O LY M E R
SCIENCE II
Dr A Ndir ipo
VISCOSITY
2
 Viscosity is the resistance to flow
of a substance. Different polymer
melts have different resistance to
flow.

VISCOSITY 3
A Newtonian fluid is a fluid in
which the viscous stresses arising
from its flow, at every point, are
linearly proportional to the local
strain rate—the rate of change of
its deformation over time.
 That is equivalent to saying that those forces are
proportional to the rates of change of the fluid's
velocity vector as one moves away from the
point in question in various directions.

More precisely, a fluid is Newtonian only if the

tensors that describe the viscous stress and the
strain rate are related by a constant viscosity
VISCOSITY tensor that does not depend on the stress state
4

and velocity of the flow.

If the fluid is also isotropic (that is, its

mechanical properties are the same along any
direction), the viscosity tensor reduces to two
real coefficients, describing the fluid's resistance
to continuous shear deformation and continuous
compression or expansion, respectively.
VISCOSITY

Newton's law of viscosity of motion states that:

𝑑𝑣
𝛿=𝜇
𝑑𝑥 5

= viscosity
= stress or shear
𝛿 = 𝜇𝑟 = strain
W H AT I S S T R A I N A N D S T R E S S ?

Definition: 1. Strain is the extension per unit length.

2. The magnitude of a deformation, equal to the change in the dimension
of a deformed object divided by its original dimension.
𝑑𝑣
𝑟=
𝑑𝑥 6

v = the distance covered in direction of x.

Definition: 1. Stress is the force (N) acting on unit cross-section area (M).
2. The degree of stress measured in units of force per unit area .

𝐹
𝛿=
𝐴
W H AT I S S T R A I N A N D S T R E S S ?

Pulling from top, only top part moves while bottom part remains fixed. This is called
shear. 𝐹
𝛿=
𝐴
7
The rate of deformation i.e., strain where v is distance covered (sometime called length)
i.e., % elongation in direction x.

𝑑𝑣
Therefore, strain = 𝑟 =
𝑑𝑥

For all polymer substances that agree with Newton's law of viscosity will have straight line
when graph is plotted against.
NEWTONIAN FLUIDS

All polymers that agree with Newton's law

of viscosity are called Newtonian Fluids

Shear stress (δ)

(NF) in which the viscosity is constant,
thus viscosity is not dependent on strain 8
and stress ( δ = stress and r = strain)
This is mainly true for low molecular
weight substances e.g., benzene, water etc.
But not all polymers as we mentioned
earlier follow (or agree) Newtonian law of
viscosity.
If that is the case, then the graph of δ
against r should look like as follows. Shear strain (r)
 NEWTONIAN FLUIDS

Curve (a) shows viscosity increases NF.

Pseudoplastic
polymer Curve (b) This type of polymer is called DILATENT
c substances.
9
The dilatant substances are a Non-Newtonian fluids
Shear stress

b
that have an increase in viscosity, and they experience
a shear thickening. The viscosity [η] increases in stress.
Curve (c) where the viscosity decreases. This type of
Dilatant polymer polymer is called PSEUDOPLASTIC.
Shear strain
These polymers are experience shear thinning with
time i.e., the viscosity decreases with time.
NEWTONIAN FLUIDS

Dilatant substances that experiences shear thickening (also increase in viscosity) are called
RHEOPECTIC polymer.
Pseudoplastic substances that experience shear thinning are called THIXOTROPIC
polymers.
10
𝛿
Dimension of viscosity: 𝜇=
𝑟
𝐹 𝑁
𝛿= = 2
𝐴 𝑚
𝑑𝑣 𝑚𝑠 −1
𝑟= = = 𝑠 −1
𝑑𝑥 𝑚

𝛿 𝑁 𝑁𝑆
𝜇= = 2 = 2 = 𝑃𝑎𝑆
𝑟 𝑚 /𝑆 𝑚
VISCOSITY

Flow curve: A graph or graphs that are plotted of stress ( δ ) against strain ( r ) are called
flow curves.
They are specific types of curves that broadened between stress, strain and viscosity and
can be used to obtain any one of the three, which is not shown on the graph.
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VISCOSITY

Initial or apparent viscosity is viscosity that depends on shear, stress and strain.
Most polymeric substances have apparent viscosity because they are non -Newtonian
fluids.
Their viscosity depends on stress and strain, and it is sometimes reflected to as initial
viscosity. 12

(Molecular weight and viscosity: Any increase in molecular weight results in increase in
viscosity).
Apparent viscosity η = KMa where M = critical molecular weight
log η = log K + a log M
VISCOSITY

Critical molecular weight is weight

whereby there is no change in η with
increase in molecular weight.
Plot of log η against log M gives following 13
graph.
A sharp increase in η at the critical
molecular weight until η = 1013(critical)
where M does not change.
VISCOSITY

Bingham substances:
These are substances which are
found as being a product of increase
in viscosity and that have an initial
stress or strain to flow. 14

These substances require sizable

stress or strain to flow.
Once the substances begin to flow,
the viscosity remains constant i.e., it
remains a Newtonian type fluid.
However, the fluid cannot be taken
to be Newtonian since it starts at an
initial stress.
 1. Temperature does affect viscosity positively
(increases) or negatively (decreases).
2. Intermolecular interactions are affected in
macromolecular substances and there is
tendency of motion (flow) due to
temperature.
INFLUENCE OF 3. As temperature increases, some polymers
have their macromolecules being loosened
T E M P E R AT U R E and thus easy flow resulting in a decrease in 15
viscosity or as temperature increases polymer
ON VISCOSITY tends to cross link (curing) thus resulting in
an increase in viscosity.
4. As temperature decreases, this result in
hardening of polymer (retard motion of
macromolecules) thus viscosity increases and
approaches a limiting viscosity that of a solid
where it remains constant (i.e., Tg).
INFLUENCE OF PRESSURE ON
VISCOSITY
Effect on viscosity depends on the amount of pressure applied to viscous polymer. Very
small pressure affects very little or no effect at all on viscosity.
The effect of high pressure from 500 to 1000Pa will be felt in Newtonian region of
polymer.
As pressure increases at constant volume, there is a corresponding increase in temperature, 16
which might result in high viscosity or low viscosity depending on nature of polymer.
At high pressure the free volume becomes less and less, and hence there is a tendency of
increasing in viscosity.

ln µ = p ln e

𝜇 = 𝑒𝑃
INFLUENCE OF PRESSURE
ON VISCOSITY

A non-Newtonian fluid is a fluid whose flow

properties differ in any way from those of
Newtonian fluids.
Most commonly, the viscosity (the measure of a 17
fluid's ability to resist gradual deformation by shear
or tensile stresses) of non-Newtonian fluids is
dependent on shear rate or shear rate history.
Some non-Newtonian fluids with shear-
independent viscosity, however, still exhibit normal
stress-differences or other non-Newtonian
behavior.
INFLUENCE OF PRESSURE
ON VISCOSITY

EXAMPLES:
Many salt solutions and molten polymers are non-
Newtonian fluids, as are many commonly found substances
such as ketchup, custard, toothpaste, starch suspensions,
paint, blood, and shampoo. 18
In a Newtonian fluid, the relation between the shear stress
and the shear rate is linear, passing through the origin, the
constant of proportionality being the coefficient of
viscosity.
In a non-Newtonian fluid, the relation between the shear
stress and the shear rate is different and can even be time-
dependent (Time Dependent Viscosity).
Therefore, a constant coefficient of viscosity cannot be
defined.
 C O M PA R I S O N O F N O N -
NEWTONIAN, NEWTONIAN, AND
V I S C O E L A S T I C P RO P E RT I E S 19
 Kelvin material, "Parallel" linearistic combination of elastic and
Some lubricants, whipped cream, Silly Putty
Maxwell material viscous effects

Viscoelastic

Rheopecty Apparent viscosity increases with duration of stress printer ink, gypsum paste

Yogurt, xanthan gum solutions, aqueous iron oxide gels,

gelatin gels, pectin gels, synovial fluid, hydrogenated
Time dependent castor oil, some clays (including bentonite, and
viscosity
Thixotropic Apparent viscosity decreases with duration of stress
montmorillonite), carbon black suspension in molten tire
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rubber, some drilling muds, many paints, many floc
suspensions, many colloidal suspensions
Shear thickening
(dilatant)
Suspensions of corn starch in water, sand in water
Apparent viscosity increases with increased stress
Time-independent
viscosity
Nail polish, whipped cream, ketchup, molasses, syrups,
Shear thinning
Apparent viscosity decreases with increased stress paper pulp in water, latex paint, ice, blood, some silicone
(pseudoplastic)
oils, some silicone coatings
Viscosity is constant.
Generalized
Stress depends on normal and shear strain rates and Blood plasma, custard, water
Newtonian fluids
also the pressure applied on it
 SHEAR
THICKENING
FLUID
The viscosity of a shear thickening
fluid, or dilatant fluid, appears to
increase when the shear rate increases. 21
Corn starch dissolved in water
("oobleck", see below) is a common
example: when stirred slowly it looks
milky, when stirred vigorously it feels
like a very viscous liquid.
https://www.youtube.com/watch?v=m
YTerCbDUzE
SHEAR THINNING FLUID

A familiar example of the opposite, a shear thinning fluid, or

pseudoplastic fluid, is wall paint: The paint should flow readily off the
brush when it is being applied to a surface but not drip excessively.
Note that all thixotropic fluids are extremely shear thinning, (Yogurt,
xanthan gum solutions, aqueous iron oxide gels, gelatin gels, pectin 22
gels, synovial fluid, hydrogenated castor oil, some clays (including
bentonite, and montmorillonite), carbon black suspension in molten
tire rubber, some drilling muds, many paints, many floc suspensions,
many colloidal suspensions) but they are significantly time
dependent, whereas the colloidal "shear thinning" fluids respond
instantaneously to changes in shear rate.
Thus, to avoid confusion, the latter classification is more clearly
termed pseudoplastic.
SHEAR THINNING
FLUID

Another example of a shear thinning fluid is

blood. This application is highly favored within
the body, as it allows the viscosity of blood to
decrease with increased shear strain rate.
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BINGHAM PLASTIC

z
Fluids that have a linear shear stress/shear strain
relationship require a finite yield stress before they begin
to flow (the plot of shear stress against shear strain does
not pass through the origin).
These fluids are called Bingham plastics. Several 24
examples are clay suspensions, drilling mud, toothpaste,
mayonnaise, chocolate, whipped cream and mustard.
The surface of a Bingham plastic can hold peaks when it
is still. By contrast Newtonian fluids have flat featureless
surfaces when still.
BINGHAM PLASTIC

Mayonnaise is a Bingham plastic. The

surface has ridges and peaks because
Bingham plastics mimic solids under low 25
shear stresses.
 26
BINGHAM PLASTIC
BINGHAM PLASTIC

A Bingham plastic is a viscoplastic material

that behaves as a rigid body at low stresses but
flows as a viscous fluid at high stress. It is
named after Eugene C. Bingham who 27
proposed its mathematical form.
It is used as a common mathematical model of
mud flow in drilling engineering, and in the
handling of slurries.
A common example is toothpaste, which will
not be extruded until a certain pressure is
applied to the tube. It then is pushed out as a
solid plug. Bingham Plastic flow as described by Bingham.
BINGHAM PLASTIC

The figure shows a graph of the behavior of an

ordinary viscous (or Newtonian) fluid in red, for
example in a pipe. If the pressure at one end of a pipe
is increased this produces a stress on the fluid tending
to make it move (called the shear stress) and the
volumetric flow rate increases proportionally. 28

However, for a Bingham Plastic fluid (in blue), stress

can be applied but it will not flow until a certain
value, the yield stress, is reached.
Beyond this point the flow rate increases steadily with
increasing shear stress. This is roughly the way in
which Bingham presented his observation, in an
experimental study of paints. These properties allow a
Bingham plastic to have a textured surface with peaks
and ridges instead of a featureless surface like a Bingham Plastic flow as described by Bingham.
Newtonian fluid.
BINGHAM PLASTIC
The figure on the right shows the way in which it is
normally presented currently.
The graph shows shear stress on the vertical axis and shear
rate on the horizontal one. (Volumetric flow rate depends
on the size of the pipe, shear rate is a measure of how the
velocity changes with distance.
It is proportional to flow rate but does not depend on pipe
size.)
29
As before, the Newtonian fluid flows and gives a shear rate
for any finite value of shear stress.
However, the Bingham Plastic again does not exhibit any
shear rate (no flow and thus no velocity) until a certain
stress is achieved.
For the Newtonian fluid the slope of this line is the
viscosity, which is the only parameter needed to describe its
flow.
By contrast the Bingham Plastic requires two parameters, the
yield stress and the slope of the line, known as the plastic
viscosity. Bingham Plastic flow as described currently.
BINGHAM PLASTIC

The physical reason for this behavior is that

the liquid contains particles (e.g., clay) or large
molecules (e.g., polymers) which have some
kind of interaction, creating a weak solid 30
structure, formerly known as a false body, and a
certain amount of stress is required to break
this structure.
Once the structure has been broken, the
particles move with the liquid under viscous
forces.
If the stress is removed, the particles associate Bingham Plastic flow as described currently.
again.
SOME KEY DEFINITIONS

The material is an elastic solid for shear stress τ, less than a critical value.
Once the critical shear stress (or "yield stress") is exceeded, the material flows in such a
way that the shear rate, ∂u/∂y (as defined in the article on viscosity), is directly
proportional to the amount by which the applied shear stress exceeds the yield stress:
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SOME KEY
DEFINITIONS

Rheopectic or anti-thixotropic
There are also fluids whose strain
rate is a function of time.
Fluids that require a gradually 32
increasing shear stress to maintain
a constant strain rate are referred
to as rheopectic.
An opposite case of this is a fluid
that thins out with time and
requires a decreasing stress to
maintain a constant strain rate
(thixotropic).
EXAMPLES OF FLUIDS EXHIBITING
N O N - N E W T O N I A N F L OW S
Soap solutions and cosmetics

Food such as butter, cheese, jam, ketchup, mayonnaise,

soup, taffy, and yogurt

Natural substances such as magma, lava, gums, and 33

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

Oobleck on a subwoofer. Applying force to oobleck, by

sound waves in this case, makes the non-Newtonian fluid
thicken.
EXAMPLES OF FLUIDS EXHIBITING
N O N - N E W T O N I A N F L OW S

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EXAMPLES OF FLUIDS EXHIBITING
N O N - N E W T O N I A N F L OW S

35

https://www.youtube.com/watch?v=RkLn2gR7SyE
 An inexpensive, non-toxic example of a non-Newtonian
fluid is a suspension of starch (e.g., cornstarch) in water,
sometimes called "oobleck" or "ooze" (1 part of water to
1.5–2 parts of corn starch).
EXAMPLES OF Uncooked cornflour has the same properties. The name
"oobleck" is derived from the Dr. Seuss book
FLUIDS Bartholomew and the Oobleck.
EXHIBITING Because of its properties, oobleck is often used in
demonstrations that exhibit its unusual behavior. 36
NON- A person may walk on a large tub of oobleck without
sinking due to its shear thickening properties, given the
NEWTONIAN individual moves quickly enough to provide enough force
with each step to cause the thickening.
F L OW S Also, if oobleck is placed on a large subwoofer driven at a
sufficiently high volume, it will thicken and form standing
waves in response to low frequency sound waves from the
speaker.
EXAMPLES OF FLUIDS
EXHIBITING NON-
N E W T O N I A N F L OW S

Flubber is a non-Newtonian fluid,

easily made from polyvinyl
alcohol–based glues and borax.
It flows under low stresses but 37
breaks under higher stresses and
pressures.
This combination of fluid-like and
solid-like properties makes it a
Maxwell fluid.
Its behavior can also be described
as being viscoplastic or gelatinous.
EXAMPLES OF FLUIDS
EXHIBITING NON-
N E W T O N I A N F L OW S

Chilled caramel topping:

Another example of this is chilled caramel ice cream topping (so
long as it incorporates hydrocolloids such as carrageenan and
gellan gum).
The sudden application of force—by stabbing the surface with a 38
finger, for example, or rapidly inverting the container holding
it—causes the fluid to behave like a solid rather than a liquid.
This is the "shear thickening" property of this non-Newtonian
fluid.
More gentle treatment, such as slowly inserting a spoon, will
leave it in its liquid state.
Trying to jerk the spoon back out again, however, will trigger the
return of the temporary solid state.
EXAMPLES OF FLUIDS
EXHIBITING NON-
N E W T O N I A N F L OW S

Silly Putty:
Silly Putty is a silicone polymer-based suspension
which will flow, bounce, or break depending on
strain rate. 39
EXAMPLES OF FLUIDS EXHIBITING
N O N - N E W T O N I A N F L OW S

Plant resin:
Plant resin is a viscoelastic solid polymer.
When left in a container, it will flow slowly
40
as a liquid to conform to the contours of its
container.
If struck with greater force, however, it will
shatter as a solid.
EXAMPLES OF FLUIDS
EXHIBITING NON-
N E W T O N I A N F L OW S

Ketchup (tomato sauce):

Ketchup is a shear thinning fluid.
Shear thinning means that the
41
fluid viscosity decreases with
increasing shear stress.
In other words, fluid motion is
initially difficult at slow rates of
deformation but will flow more
freely at high rates.
MOLECULAR WEIGHT
D E T E R M I N AT I O N B Y
SOLUTION VISCOSITY
MEASUREMENTS:

42
MOLECULAR WEIGHT
D E T E R M I N AT I O N B Y S O L U T I O N
VISCOSITY MEASUREMENTS:

Polymers due to their randomly coiled chain molecules

produce viscous solutions.
The intrinsic viscosity [ η] of a solution (obtainable
experimentally) is related to the viscosity average 43
molecular weight of the polymer, M v by the Mark-
Houwink-Sakurada (MHS) relationship (equation);
Where K and a are constant for a given polymer, solvent
a
and temperature.
Mv is the viscosity average molecular weight
[n]
[η] = KM v
 M O L E C U L A R W E I G H T D E T E R M I N AT I O N B Y
SOLUTION VISCOSITY MEASUREMENTS:

Procedure: Arm A Arm B

1. First clean using acetone to get rid of any residue. Upper

point
2. Now add the solution in the side where’s there a large bulb (arm A) and the other as
arm B.
Lower 44
3.Now Arm B has 2 markings on it one on top and on one on the bottom usually point
before or after the capillary section.
4. Now start sucking the liquid out from arm B using an appropriate apparatus till the
upper point on arm B.
5. When it reaches there, start the timer and let the solution fall until it reaches the
other lower marking.
6. Note there is a small bulb between two markings on arm B and use that time and
the ratio of densities, time and coefficient of viscosity with respect to your pure solvent
to calculate the coefficient of viscosity of the solution.
The apparatus must be placed in a temperature-controlled bath at all times.
MOLECULAR
WEIGHT
D E T E R M I N AT I O N
BY SOLUTION
VISCOSITY
MEASUREMENTS: 45
M O L E C U L A R W E I G H T D E T E R M I N AT I O N B Y
SOLUTION VISCOSITY MEASUREMENTS
[η] is related to measurable quantities by the Huggins equation, which may be written
as:
ηsp/C = [η] + K1[η]2C + K 1[η]3C2 + -------
Or alternatively:
46
ln ηr/C = [η]+ K1[η]2C + K 1[η]3C2 + -------

where ηr = relative viscosity of solution = t/t 0

ηsp = specific viscosity of solution = ηr – 1
t and t 0 are measured efflux times of solution and solvent and C is the concentration of
polymer solution in kgm -3.
MOLECULAR WEIGHT
D E T E R M I N AT I O N B Y
SOLUTION VISCOSITY
MEASUREMENTS

At low concentration:
[η] = ηsp/C = lnηr/C
i.e. [η] is the intercept at C=0 of the plots of 47
ηsp / C or ln ηr/C against C at low
concentrations, when such plots should be
linear.
If both plots are made on the same graph and
extrapolated to zero concentration they should
yield the same intercept, the intrinsic viscosity
[η].
EXAMPLE

In a solution viscosity experiment the efflux time for the pure solvent was 84.2 seconds.
The efflux time for the solution of different concentrations are given in the table below:

Concentration 0.40 0.50 0.67 1.00

g/cm3 48
Efflux in sec. 112.7 121.4 134.6 164.6
Find the viscosity average molecular weight (M v) of the polymer if:
K = 1.34 x 10 -4 dlg-1 and a = 0.71
EXAMPLE
Calculation:

Concentration nr = t / ln nr ln nr / C nsp = nr – 1 nsp / C t

gcm-3 t0
0.40 1.3385 0.291 0.7288 0.3385 0.846 112.7
0.50 1.4418 0.366 0.7318 0.4418 0.884 121.4 49
0.67 1.5986 0.469 0.7002 0.5986 0.893 134.6
1.00 1.9549 0.670 0.6700 0.9549 0.995 164.6

A plot of ln ηr / C against C and that of ηsp/C against C should give two straight lines which intercept
on the Y axis and this intercept value gives the value of the viscosity [η].
From the graph:
[η] = K = 1.34 x 10 -4 dlg -1 a = 0.71
[η] = K Mva
 THE END

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