Assignment No-1

Viscosity
Measurement
&
Rheological
behavior
 Viscosity- An Introduction & Importance
The viscosity and consistency of the paint determine its capacity to level
itself on the surface and not excessively flow, sag or run off during
application. Therefore it is of great importance to study different
rheological behavior to keep a balance in the formulation of paint with its
desired performance properties.

Viscosity is the measure of the internal friction of a fluid. This

friction becomes apparent when a layer of fluid is made to move in
relation to another layer. The greater the friction, the greater the amount
of force required to cause this movement, which is called shear. Shearing
occurs whenever the fluid is physically moved or distributed.

The behaviour of fluid between two very large plates

Here, two parallel planes of fluid of equal area A are separated by a
distance dx, and the top plate is moving in the x direction with velocity u
(or v). Newton assumed that the force required to maintain this difference
in speed was proportional to the difference in speed through the liquid, or
the velocity gradient. The Newton’s Law of Viscosity is as follows:

Where:
τ (shear stress) = (F/A) = µ .(dv/dy)
µ (viscosity) = τ /(dv/dy)
And (dv/dy)is the velocity gradient.

It is a measure of the change in speed at which the intermediate layers

move with respect to each other and it has units of per second.

τ describes the shearing which the liquid experiences and is thus called
the shearing stress

µ is called the Dynamic Viscosity.

Its CGS unit is Poise or dyne.sec.cm-2 and MKS unit is Newton.sec.m-2.
There is another term called Kinematic Viscosity which is defined as:

Where:
µ : Dynamic Viscosity of the fluid.
ρ : Density of the fluid.
v : Kinematic Viscosity.

Role of Rheology in Coatings performance:

Sagging
The sagging of a coating film, when applied to vertical surfaces, is a
function of its rheological properties.
It is basically an extreme form of leveling i.e. a wet paint film flows
excessively if it is too thin to stay/adhere at a particular area of
application after leveling on a vertical wall.

There are two mathematical equations which gives an analysis of

sagging. One of which pertains to the rate of sagging i.e.

V=ρGT2/2√
Where

V: Velocity (Cm/Sec)
Ρ: Density of coating material
G: Gravitational constant
T2: Film thickness (Cm)
√: Viscosity

The distance a wet film will sag in given length of time is:

Distance=vt
On doubling the film thickness change in volume of sagged will increase
by eight times and given by the following equation:

V=ρGT3/3√

Leveling

Leveling is the ability of a brush out paint to flow out and obliterate the
furrows left by the brush bristles.

“Both Sagging and leveling depends on rheological behavior of coating

material. A thin paint exhibits severe sagging problem when applied on a
vertical wall but if we changes its rheological behavior by making it
thixotropic then it does not flow on the other hand a very thick paint does
not level on the surface properly but if we incorporate in it pseudo
plasticity then it levels properly.”

Viscosity Units:
To express the viscosity of liquid materials following units are used
readily:

1. Poise (Centipoises)
 2. Seconds
3. Stokes (Centistokes)
4. Krebs Unit (KU)
5. Saybolt Universal Seconds (SUS)

Below is the viscosity conversion chart which correlates these viscosity

units with each other.

Temperature dependency of Viscosity:

Viscosity varies considerably on varying temperature. It is mandatory to
mention the temp at which viscosity is being measured.

Viscosity is indirectly proportional to the temperature i.e. viscosity

decreases on increasing the temperature and vice versa.

Different Rheological Behaviour

We can classify the rheological behavior as follows:

1. Newtonian Fluids
2. Non-Newtonian Fluids
a. Plastic fluids
b. Pseudoplastic fluids
c. Dilatant fluids
d. Thixotropic fluids
e. Rheopectic Fluids

Newtonian Fluids
Fluids for which the shearing stress is linearly related to the rate of
shearing are designed as Newtonian Fluids. A Newtonian fluid is
represented graphically in the figure below.
 The linear variation of shearing stress with rate of shearing strain

The consistency of viscosity with varying shearing rate.

What this means in practice is that at a given temperature the

viscosity of a Newtonian fluid will remain constant regardless of which
Viscometer model, spindle or speed we use to measure it.
Non-Newtonian Fluids
Fluid for which the relationship τ/(du/dy) is not constant. In other
words, when the shear rate is varied, the shear stress doesn't vary in the
same proportion (or even necessarily in the same direction). Thus, the
experimental parameters of Viscometer model, spindle, speed etc. all
have an effect on the measured viscosity of a non-Newtonian fluid. This
measured viscosity is called the apparent viscosity of the fluid and is
accurate only at the same parameters.

Psuedoplastic Fluids
This type of fluid will display a decreasing viscosity with an
increasing shear rate, as shown in the figure below. Probably the most
common of the non-Newtonian fluids, pseudo-plastics include paints,
emulsions, and dispersions of many types. This type of flow behavior is
sometimes called shear-thinning.

Dilatant Fluids
This type of fluid will display a increasing viscosity with an
increasing shear rate; see the figure below. Although rarer than
pseudoplasticity, dilatancy is frequently observed in fluids containing high
levels of deflocculated solids, such as clay slurries, candy compounds,
corn starch in water, and sand/water mixtures. Dilatancy is also referred
to as shear-thickening flow behavior.
Plastic Fluids
These type of fluids will behave as a solid under static conditions. A
certain amount of force must be applied to the fluid before any flow is
induced; this force is called the yield value. Tomato ketchup is a good
example of a plastic fluid; its yield value will often make it refuse to pour
from the bottle until the bottle is shaken or struck. After impact, the
ketchup flows out of the bottle. Once the yield value is exceeded and flow
begins, plastic fluids may display Newtonian, pseudoplastic, or dilatant
flow characteristics.

Ideal plastic substance.

So far we have only discussed the effect of shear rate on non-Newtonian
fluids. Some fluids will display a change in viscosity with time under
conditions of constant shear rate. These are:

 Thixotropic Fluids
As shown in the figure below, a thixotropic fluid undergoes a decrease in
viscosity with time, while it is subjected to constant shearing.

 Rheopectic Fluids
 Rheopectic behaviour is essentially the opposite of thixotropic
behaviour, in that the fluid's viscosity increases with time as it is sheared
at a constant rate, as shown in the figure.

Both thixotropy and rheopexy may occur in combination with any of

the previously discussed flow behaviours, or only at certain shear rates.
The time element is extremely variable; under conditions of constant
shear, some fluids will reach their final viscosity value in a few seconds,
while others may take up to several days.

Rheopectic fluids are rarely encountered. Thixotropy, however, is

frequently observed in materials such as greases, heavy printing inks, and
paints.

Viscometers
A viscometer (also called viscosimeter) is an instrument used to
measure the viscosity of a fluid. For liquids with viscosities which vary
with flow conditions, an instrument called a rheometer is used.
Viscometers only measure the viscosity under a single flow condition.

Types of Viscometers:
“U-tube” Viscometers (Ostwald or Ubbelohde type)

These viscometers are based on the measurement of the rate of flow of a

definite volume of liquid through a capillary of definite bore.

These instruments can be used for the comparison of the viscosities of

two liquids.
 Various types of glass capillary viscometers.

Rotational Viscometers
 Rotational viscometers use the idea that the force required to turn
an object in a fluid, can indicate the viscosity of that fluid. The viscometer
determines the required force for rotating a disk or bob in a fluid at
known speed.

'Cup and bob' viscometers work by defining the exact volume of

sample which is to be sheared within a test cell, the torque required to
achieve a certain rotational speed is measured. There are two classical
geometries in "cup and bob" viscometers, known as either the "Couette"
or "Searle" systems - distinguished by whether the cup or bob rotates.

'Cone and Plate' viscometers use a cone of very shallow angle in

theoretical contact with a flat plate. With this system the shear rate
beneath the plate is constant to a modest degree of precision; a graph of
shear stress (torque) against shear rate (angular velocity) yields the
viscosity.

Rotational viscometers fall into two main types:

1. Synchronous (Stepper) Motor / Spring

2. Servo Motor / Digital encoder

The first type uses a stepper motor to drive the main shaft. A spring
& pivot assembly rotates on the shaft. The spindle or rotor hangs from this
assembly. As the spindle rotates the spring is deflected by the viscosity of
the sample under test.

The second type uses a precision servo motor to drive the shaft. The
Spindle or rotor is attached directly to the shaft. High speed
microprocessors measure the speed from a digital encoder and calculate
the current required to drive the rotor at the test speed. The current
required is proportional to the viscosity of the sample under test.

A rotating body experiences a viscous drag, or retarding force, the

amount of which varies with the speed of rotation. In rotational
viscometers, the viscosity is determined by measuring the drag on a
spindle rotating in the material. The chief advantages of these
instruments are:-

• They are simple to use.

• Continuous measurements can be made at a given rate of shear or
stress.
• The dependency of viscosity on time can be readily determined.
• Yield stresses can be determined.
Examples are the Brookfield Synchro-Lectric, Rheometrics, Stormer,
MacMichael, Bohlin, Haake, and Brabender viscometers.
 “Cone & Plate” (Couette type) Viscometer

Stormer Viscometer
This viscometer employs a paddle that measures the viscosity of a fluid
based on the resistance to flow while stirring.

Cone & Plate Measurement of Viscosity (Accuracy)

The accuracy of the cone and plate viscometer depends upon the
instrument’s ability to hold temperature, accuracy of the cone’s angle; the
cone’s setting to the plate and the speed of the instrument.

Other parameters also affect the accuracy and these are listed below.

1) Wear on the cone and plate.

2) Size of sample.

3) Time taken to allow the sample to stabilize on the plate before

taking a reading.

4) Cleanliness of cone and plate.

5) Material Nature - Newtonian? high or low viscosity, particulate

size.

6) Cone type - lower range cones give higher accuracy.

7) Shear Rate applied to sample.

The achievable accuracy for a cone and plate viscometer across its scale
is ± 2% of the full-scale range. e.g. 0-10P the accuracy should be
within ± 0.2P.

In practice, the accuracy between the 10% and 90% of the scale is
normally ± 0.1P for a 10P scale.

Efflux Viscometers
They usually consist of a metal cup with parallel sides and with an
accurately machined orifice at the center of the base.The time for the cup
to empty through the orifice is noted and the results expressed in
seconds.
 But these viscometers are unsuited to paints which possess any
degree of thixotropy.

Ford Cup No#4 Viscometer

The Ford viscosity cup is a simple gravity device that permits the
timed flow of a known volume of liquid passing through an orifice located
at the bottom of the cup. Under ideal conditions, this rate of flow would be
proportional to the kinematic viscosity (expressed in stokes and
centistokes) that is dependent upon the specific gravity of the draining
liquid. However, the conditions in a simple flow cup are seldom ideal for
making true measurements of viscosity.

Zahn cup Viscometer

A Zahn cup is a viscosity measurement device widely used in the

paint industry. It is commonly a stainless steel cup with a tiny hole drilled
in the center of the bottom of the cup. There is also a long handle
attached to the sides. There are five cup specifications, labeled Zahn cup
#x, where x is the number from one through five. Large number cup sizes
are used when viscosity is high, and low number cup sizes when viscosity
is low.

To determine the viscosity of a liquid, the cup is dipped and

completely filled with the substance. After lifting the cup out of the
substance the user measures the time until the liquid streaming out of it
breaks up, this is the corresponding "efflux time".
Conversion:

One can convert efflux time to kinematic viscosity (cSt) by using an

equation for each cup specification number, where t is the efflux time and
ν is the kinematic viscosity.

• Zahn Cup #1 : ν = 1.1 * (t - 29)

• Zahn Cup #2 : ν = 3.5 * (t - 14)
• Zahn Cup #3 : ν = 11.7 * (t - 7.5)
• Zahn Cup #4 : ν = 14.8 * (t - 5)
• Zahn Cup #5 : ν = 23 * t

Falling Sphere and Bubble Rise Viscometers

In these instruments, the time required for a sphere of some sort to

pass through a liquid is measured. The sphere may be a falling ball or a
rising bubble. This method is particularly good for low-shear
measurements. Examples are the Hoeppler rolling-ball viscometer and the
Gardner-Holdt comparative bubble tubes.

Stokes' law is the basis of the falling sphere viscometer, in which

the fluid is stationary in a vertical glass tube. A sphere of known size and
density is allowed to descend through the liquid. If correctly selected, it
reaches terminal velocity, which can be measured by the time it takes to
pass two marks on the tube. Electronic sensing can be used for opaque
fluids.

Knowing the terminal velocity, the size and density of the sphere,
and the density of the liquid, Stokes' law can be used to calculate the
viscosity of the fluid. The technique is used industrially to check the
viscosity of fluids used in processes. It includes many different oils, and
polymeric liquid solutions.

Stokes' law

Where:

F : frictional force,
r : radius of the spherical object,
η : fluid viscosity, and
v : particle's velocity.
 If the particles are falling in the viscous fluid by their own weight,
then a terminal velocity, also known as the settling velocity, is reached
when this frictional force combined with the buoyant force exactly
balances the gravitational force. The resulting settling velocity (or
terminal velocity) is given by:

Where:

Vs: particles' settling velocity (m/s) (vertically downwards if ρp > ρf,

upwards if ρp < ρf),
r: Stokes radius of the particle (m),
g: gravitational acceleration (m/s2),
ρp : density of the particles (kg/m3),
ρf : density of the fluid (kg/m3), and
μ: (dynamic) fluid viscosity (Pa s).

Bubble viscometer
Bubble viscometers are used to quickly determine kinematic
viscosity of known liquids such as resins and varnishes. The time required
for an air bubble to rise is directly proportional to the viscosity of the
liquid, so the faster the bubble rises, the lower the viscosity.

The Alphabetical Comparison Method used in the Gardner Tubes

uses 4 sets of lettered reference tubes, A5 through Z10, of known
viscosity to cover a viscosity range from 0.005 to 1,000 stokes. The Direct
Time Method uses a single 3-line times tube for determining the "bubble
seconds", which may then be converted to stokes.

Bubble Tubes
 A bubble rising in a fluid.

Saybolt Viscometers
They are used to express the fluid’s viscosity, in Saybolt universal
seconds or Saybolt furol seconds. The glass capillary viscometers,
shown in the figure are examples of the second type of viscometer used.

These viscometers are used to measure kinematic viscosity. Like

the Saybolt viscometer, the glass capillary measures the time in seconds
required for the tested fluid to flow through the capillary. This time is
multiplied by the temperature constant of the viscometer in use to
provide the viscosity, expressed in centistokes. The following
formulas may be used to convert centistokes (cSt units) to
approximate Saybolt universal seconds (SUS units).

For SUS values between 32 and 100:

For SUS values greater than 100:

Rheometers
A Rheometer is a laboratory device used to measure the way in which a
liquid, suspension or slurry flows in response to applied forces.
Viscometers that can measure fluids with high viscosity or molten
polymers are usually called rheometers or plastometers.

It is used for those fluids which cannot be defined by a single value

of viscosity and therefore require more parameters to be set and
measured than is the case for a viscometer. It measures the rheology of
the fluid.

It can be of two types:

Shear rheometers (apply shear stress)

Pipe or Capillary Rheometers

Rotational Cylinder Rheometers
Cone and Plate Rheometers

Extensional rheometers (apply extensional stress)

Acoustic Rheometers
Pulled string Rheometers
Capillary Rheometers

*****