Material Characterization

Rheology: Rheology is the science that studies the

deformation and flow of materials in liquid, melt or solid
form in terms of materials elasticity and viscosity.

Elasticity: Elasticity is the ability of material to store

deformational energy, and can be viewed simply as the
capacity of material to regain its original shape after being
deformed.

Viscosity: Viscosity is the measure of materials resistance

to flow.

Viscoelasticity: Materials respond to an applied

displacement or force by exhibiting either elastic or viscous
behavior or a combination of these, called Viscoelasticity.
Ideal Fluids (Newtonian fluids): The fluids for which the
applied stress () is proportional to the strain rate or shear rate
 i.e., follows Newton’s law are called Ideal fluids.
Let us imagine two parallel plates of very large area
A at a distance of y apart by an ideal fluid. A shear force F
is applied to the top of the plate and the top plate moves
with uniform velocity u. (as shown in Fig.-1).

Moving plate with surface area ‘A’

The viscosity of a Newtonian
fluid is dependent only on
temperature but not on shear
rate and time. e.g. Water, Milk,
Sugar solution, Mineral Oil
etc.
Most cases, the relationship
between shear stress () and
shear rate () is not linear and
these fluids are called Non-
Newtonian Fluid.
In contrast to Newtonian
Fluids, these fluids show
either time dependent or time
independent behavior.
Non-Newtonian Fluids, Time Independent
The viscosity of a Non-Newtonian time independent fluid is
dependent only on temperature and shear stress () and shear
rate ()
Depending on how viscosity () changes with shear rate () the
flow behavior is characterized as
Shear Thinning – the  decreases with increased .
Pseudoplastic Fluids
Shear thinning fluids are also called pseudoplastic. e.g. Paint,
Shampoo, Slurries, Polymer Melts, Ketch up, etc.
The  -  and  -  relationship for pseudoplastic fluids is shown
below
 Shear Thickening – the  increases with increased 
Dilatant Fluids
Shear Thickening fluids are called dilatant. Examples are
wet sand, concentrated starch suspensions, etc.
 Bingham Liquids– exhibits so-called yield value. i.e. a critical
shear stress must be applied to cause the fluid flow.
Bingham Fluids / Plastic
These fluids are believed to have an internal structure, which
resists the flow of fluid at lower shear stress. Therefore, a
certain shear stress value needs to be applied to help the
fluid flow.
Examples: - Tomato Paste, Tooth Paste, Hand Cream,
Grease, etc.
The important type of Non-
Newtonian fluid is the
psudoplastic one and
polymer melts and rubber
components behave in this
way.
Melt Flow Index Test (MFI)

Definition: It is defined as the measurement of the rate of

extrusion of molten resin through a die of specified length &
diameter under prescribed conditions of temperature and
pressure in 10 min. The unit of MFI is g/10 min.
Test Methods:
ASTM D 1238
ISO 1133-1991
Test Apparatus:
• Test Sample
• Steel Cylinder
• Die
• Heater
• Piston
• Load
• Thermometer
•Weighing Balance
Test Sample: The test specimen should be in the form of powder,
granules, strips or film or moulded slugs of Thermoplastics
material

Steel Cylinder: The Steel Cylinder shall be 50.8 mm in Dia., 162

mm in length and a straight hole 9.5504 ± 0.0076 mm in Dia.. It is
a thermal sensor one and thermometer is provide in it.

Die: The outside of the steel die shall be 9.5504 ± 0.0076 mm in

diameter that it will fall freely to the bottom of the steel cylinder.
The die shall have 2.0955 ± 0.0051 mm in inner Dia. And 8 ± 0.025
mm in length.

Heater: The heater must have the capacity to heating the

apparatus and maintain the temperature ± 0.2°C at 10 mm above
the die.
Piston: The piston shall be made of steel with an insulating bush
at the top as a barrier to restrict the heat flow from the piston to
load. The land of the piston shall be 9.4742 ± 0.0076 mm in Dia.
and 6.35 ± 0.13 mm in length.

Load: The cylindrical steel load has different weight in size

based on the material such as 0.0.325 kg, 1.2 kg, 2.16 kg, 3.8 kg,
5.0 kg, 10 kg, 12.5 kg, 21.6 kg, 31.6 kg.

Note: The combined weight of piston and load shall be within a

tolerance of ± 0.5% of the selected load.

Weighing Balance: The weighing balance should have the

capacity to measure the four decimal of weight of the sample.
Test Procedure: Place the thermometer on the hold provided.
The set temperature stabilizes for 5 min. than charge the
material using tool without any air gap. Then apply the load
over the piston. Allow some time for material to melt and
soften and purge the material up to the lower mark of the
piston. Then start the stopwatch and start cutting off the
extrudate depending upon the flow.

Calculations: 30 Sec., 1 min, 3 min, or 6 min intervals and

tabulate the weight of the extrudate.

Flow rate = (m/t) x 600

Where m = mass of extruded, t = time of piston travel for

length L. (sec), 600 = conversion factor to convert in sec.
9.3.2.1.1.9 Factors Influencing:

1. Preheat Time. If the cylinder is not preheated for a specified

length of time. This causes the flow rate to vary considerably.
2. Moisture. Moisture in the material, especially a highly
pigmented one, causes bubbles to appear in the extrudate. The
weight of the extrudate is significantly influenced by the
presence of the moisture bubbles.
3. Packing. The sample resin in the cylinder must be packed
properly by Pushing the rod with substantial force to allow the
air entrapped between the resins Pellets to escape. Once the
piston is lowered, the cylinder is sealed of air can escape. This
causes variation in the test results.
4. Volume of Sample. In order to achieve the same response
curve. Repeatedly, the volume of the sample in the cylinder
must be kept constant. Any change in sample volume causes
the heat input from the cylinder to the material significantly
Summary of test specimen for MFI

Physical form of test materials Preferably pellets or performs

(thermoplastics) samples charges – 2.0 – 8 g
Test equipment Extrusion plastometer
Test Condition Dead load on piston varying from polymer
to polymer and Temperature varying from
polymer to polymer
Measuring range Test observation are made between two
specified scribe marks on the piston
Measurement Extrude cut at uniform time intervals are
taken and weighed
Conclusion Melt flow index as the weight of extrudate
(average in 10 min is calculated and
reported.
Dilute Solution
Viscosity
Dilute Solution Viscosity (DSV)
Ostwald-Fenske Method by using Ubbelohde Test Tube

Definition: It is defined as the measurement of

viscosity of the dilute solution of polymer. This
gives the correlation between dilute solution
viscosity and molecular weight or chain length.
Test Methods:
ASTM D 2857-95(2007)
ISO 1628
Test Apparatus:
• Volumetric Flask
• Transfer Pipet
• Constant Temperature Bath
• Viscometer
• Stopwatch
• Thermometer
Procedure:
 This method is applicable to all polymers that dissolve
completely without any chemical reaction with the solvent or
degradation to form solutions that are stable with time at a
temperature between ambient and 150°C.
 Weigh an appropriate sample into a volumetric flask and
then add 50 cm³ of solvent and shake it.
 A suitable quantity of the solution is transferred into the U-
tube viscometer by using transfer pipette. The test
temperature is maintained in a constant temperature bath.
 After temperature achieved their set temperature, the liquid
level of viscometer is brought above the upper graduation
mark in the bulb A by means of gentle air pressure. Then allow
the solution to drain down through the capillary.
 The efflux time (t) is measured between the two marked
points using a timer. The efflux time for solvent (t0) is also
measured under similar conditions. In order to measure the
intrinsic viscosity, solutions of different concentration are
used.
The presence of small amount of a polymeric
material dissolved in a solvent significantly
increases viscosity of the solvent. Such an
increase in viscosity is dependent on the
concentration and molecular weight of the
polymer and its interaction with solvent
In order to determine the molecular weight of a
polymer, viscosity of polymer solutions at
different concentrations relative to that of the
solvent is measured.
Since only relative measurements are required,
capillary viscometers are well suited. The most
convenient viscometers are Ostwald viscometer
and Ubbelohde viscometer.
 The viscosity of dilute polymer solutions may be related
to the molecular weight of the polymer. This method
involves the measurements of viscosity of dilute polymer
solutions over a concentration range (usually up to 2 g
dl-1). The polymer is usually separated into narrow
molecular weight distribution fractions, which are
characterized by absolute molecular weight methods. The
molecular weight is related to the intrinsic viscosity by
the Mark-Houwink relationship.
 The molecular weight is related to the intrinsic viscosity
 relationship.
by the Mark-Houwink M 

 Where k and  are empirical constants and are

characteristic for a polymer solvent pair at a given
temperature.
Huggins
Kraemer Equation
Equation
sp / C      '   C
2

(ln rel ) / C     "  C

2
Definition of Different viscosity terms:

Relative Viscosity, rel:

It is the ratio between the solution viscosity () to the solvent
viscosity (o). rel   / o  t / to

Specific Viscosity, sp:

It is related to the fluid viscosity increase due to all polymer
sp  (  o) / o  rel  1
solute molecules.

Reduced Viscosity:
The ratio of the relative viscosity increment to the mass
concentration of the polymer
red  sp / c
inherent Viscosity inh:
The ratio of natural logarithm of the relative viscosity to the
mass concentration of the polymer
inh  ln rel / c
Intrinsic Viscosity, : The limiting value of the reduced viscosity
or the inherent viscosity as the polymer solute concentration
approaches zero.
  lim (sp / c)  lim inh
c 0 c 0
Significance:
 It is giving the information about the molecular
characterization of polymers.
 Viscosity is dependent on molecular weight distribution. So
we can determine the molecular weight and chain length of
polymers.
 It is used to differentiate the polymer grades based on the
molecular weight distribution.
Limitations:
 The polymer type, molecular weight and its distribution will
affect the flow time.
 Concentration of the solution and air bubbles present in
the solution will also affect the flow time and viscosity.
 Temperature is also affect the viscosity of the solution.
 Dilute solution viscosity data are dependent upon the
purity of the ingredients in solution and type of viscometer.
So at the beginning of each experiment, the viscometer to be
washed with acetone.
9.3.1.2.5 Brookfield Viscometer

9.3.1.2.5.1 Definition:
The viscosity defines the flow behaviour of plastisol
under low shear. This viscosity relates to the conditions
encountered in pouring, casting, molding and dipping
process. The Brookfield instrument is a commercially
used rotating spindle type viscometer.
9.3.1.2.5.2 Significance:
The suitability of a dispersion resin for given
application process is dependent upon its viscosity
characteristics. The test standard for viscosity
measurement of plastisols / organosols, epoxy resin and
emulsion etc.
9.3.1.2.5.3 Test Methods:
ASTM D-2393, ASTM D 1824 and ISO 2555.
9.3.1.2.5.6 Procedure:
1. Select the spindle in middle or upper portion of viscometer
dial at the highest rotational speed to be used. Insert the
spindle approximately at 45° angle. Move the sample so as
to center the spindle, adjust the depth to the immersion
mark.
2. Start the viscometer at its lowest speed. Allow it to run 2
min. record the scale reading during the next rotation.
3. Placing it in a constant temperature bath at the specified
test temperature preconditions the sample. The proper size
spindle is allowed to rotate in the sample for 30 sec. The
instrument is stopped through the use of a clutch and the
reading is taken from the dial. The test is repeated until a
constant reading is obtained. Record the sample
temperature at the conclusion of viscosity reading.
 Conversion table from centipoises to factor

Range (cP) Spindle Speed (rpm) Factor

100-400 1 20 5
400-800 1 10 10
800-1600 2 20 20
1600-3200 2 10 40
3200-4000 3 20 50
4000-8000 4 20 100
8000-16000 4 10 200
16000-20000 3 4 250
20000-40000 4 4 500
40000-80000 4 2 1000
80000-160000 5 2 2000
160000-200000 6 4 2500
200000-400000 6 2 5000
400000-800000 7 4 10000
800000-2000000 7 2 20000
9.3.1.4 Dilute Solution Viscosity & K-Value
9.3.1.4.1 Ostwald-Fenske Method
9.3.1.4.2 Ubbelohde
9.3.1.4.2.1 Definition:
Inherent Viscosity, inh: The ratio of natural logarithm of the
relative viscosity to the mass concentration of the polymer; c:
inh =(In r)/c.
Intrinsic Viscosity []: The limiting value of the reduced
viscosity or inherent viscosity at infinite dilution of the
polymer [ ] = lim (i /c) = liminh
c 0 c 0

Reduced Viscosity: The ratio of the relative viscosity

increment to the mass concentration of the polymer i.e. (i /c)
Relative Viscosity: The ratio of the difference between the
viscosities of solution and solvent to the viscosity of the
solvent i.e.   (   ) / 
i s s
9.3.1.4.2.2 Significance:
# Measuring the viscosity of dilute solutions prepared in
suitable solvents can be useful for understanding the relative
molecular characteristics of polymers. When viscosity data
are used in conjugation with other molecular parameters, the
properties of polymers pending on their molecular structure
can be better predicted. It is also possible to obtain a
satisfactory correlation between dilute solution viscosity and
molecular parameters such Molecular weight or chain length
of linear polymers.
# The viscosity (kinetic) determination of dilute solutions
involves the use of all efflux viscometer having a capillary
bore or small orifice that drains by gravity. The values
strongly dependent on density or specific gravity of the
liquid, and is measured in stocks (S) and centistocks (cS).
The value in poise is obtained on multiplication of measured
value with specific gravity.
 The viscosity of dilute polymer solutions may be related
to the molecular weight of the polymer. This method involves
the measurements of viscosity of dilute polymer solutions over
a concentration range (usually up to 2 g dl-1). The polymer is
usually separated into narrow molecular weight distribution
fractions, which are characterized by absolute molecular weight
methods. The molecular weight is related to the intrinsic
viscosity by the Mark-Houwink relationship.

The molecular weight is related to the intrinsic viscosity by

the Mark-Houwink relationship.

    M 
Where k and  are empirical constants and are
characteristic for a polymer solvent pair at a given
temperature.
9.3.1.4.2.3 Procedure:
# A suitable quantity of the solution is transferred into the
viscometer suing transfer pipette. The test temperature is
maintained in a constant temperature bath.
# The liquid level of viscometer is brought above the upper
graduation mark in the bulb A by means of gentle air
pressure.
# The efflux time (t) is measured between the two marked
points using a timer. The efflux time for solvent (t0) is also
measured under similar conditions. In order to measure the
intrinsic viscosity, solutions of different concentration are
used.
# The presence of small amount of a polymeric material
dissolved in a solvent significantly increases viscosity of
the solvent. Such an increase in viscosity is dependent on
the concentration and molecular weight of the polymer and
its interaction with solvent
# In order to determine the molecular weight of a polymer,
viscosity of polymer solutions at different concentrations
relative to that of the solvent is measured.
# Since only relative measurements are required, capillary
viscometers are well suited. The most convenient
viscometers are Ostwald viscometer and Ubbelohde
viscometer.
Definition of Different viscosity terms
sp / C      '   C
2

Huggins Equation

(ln rel ) / C     "  C

2

Kraemer Equation
9.3.2 Flow Properties of Thermosetting Materials

Factor Affecting Flow:

1. Resin Type: All resin flow differently because of basic
differences in the structure of the polymer e.g. melamine
formaldehyde exhibit longer flow than urea formaldehyde.
2. Type of filler: The small particle size filler e.g. wood floor,
mica, and minerals creates less turbulence and less frictional
drag during mold filling. The size of the glass fibre and long
fibre can adversely affect the flow.
3. Storage Time: All resins have a natural tendency to
polymerize in storage, causing partial precure, which reduces
flow.
9.3.2.1 Cup Flow (ASTM D 731)

9.3.2.1.1 Definition: The measurement of the molding index

of thermosetting plastics ranging in flow from soft to stiff by
selection of appropriate molding pressure within the range
from 4.1 to 31.9 MPa
9.3.2.1.2 Significance: This test is specifically designed for
thermosetting molding compounds. This test is primarily
useful for determining the minimum pressure required to
mold a standard cup and the time required to close the
mold fully. The material is molded using a mould of
specified cup-shaped cavity dimensions. The method
provides the guide for evaluating the mold ability of
thermosetting powders.
9.3.2.1.3 Test Methods: ASTM D 731
9.3.2.1.6 Test Apparatus: The test apparatus shown in
Figure
9.3.2.1.7 Procedure:
1. The rate of flow is sensitive to the condition of the mold
surface. First two reading has to be discarded and after two
successive reading the mold flow can be accepted. The
preferred mold temperature is given below:
Phenolics: 165  1 °C
Melamine: 155  1 °C
Urea: 150  1 °C
Epoxy: 150  1 °C
Diallyl phthalates: 150  1 °C
Alkyd: 150  1 °C
# Take the weight and begin the test with proper load to close
the mold to the fin thickness specified for the type of material.
The load can be applied to the mold is as given below:
Total Load Molding Pressure (MPa)
1112 4.6
1601 6.6
1124 9.0
1686 13.6
2248 18.0
3372 21.2
4496 36.3
11120 45.4
# If a 2248 N load applied to make initial cup and required
fin thickness is obtained, the next lower load 1686N is
applied as indicated above. If the mold close to the
required thickness again then next 1124 N load applied. If
the mold then does not close, the ‘molding index’ is close
to 1686 N load.
# The time of flow in seconds shell be measured from that
the hydraulic gage indicates an applied load of 454 kg to
the instant that the fin has reached 0.20 mm I thickness for
material with an izod impact strength of 27 J/m of notch.
9.3.2.2 Spiral Flow
9.3.2.2.1 Definition: The spiral flow of a thermosetting molding
compounds is a measure of the combined characteristics of
fusion under pressure, melt viscosity and gelation rate under
specific condition.
9.3.2.2.2 Significance: This is a high shear-rate test for
thermoplastics and is widely accepted in the molding industry
and quality control test. The test is performed on an injection-
molding machine under specified condition and using a spiral-
flow mould.
9.3.2.2.3 Test Method: ASTM D 3123-98
9.3.2.2.4 Procedure
Molding condition:
1. Temperature: A temperature of 1503°C shall be maintained
on the mold and transfer plunger.
2. Transfer Pressure: The actual pressure applied to the
compounds at the base of the pot shall be 6.900.17MPa.
3. Charges Mass: The mass of the compounds shall be
determined empirically so that the thickness of the molded
compounded on the top of the sprue plate of the mold.
4. Transfer plunger speed: The transfer plunger speed without
load shall be controlled between 25 and 100 mm/s.
5. Pressure Cure Time: sufficient cure time shall be used to
facilitate easy removal of spiral from the mold.
Spiral flow data of polypropylene.
3
Spiral flow (cm ) at 260°C barrel
MFI of polypropylene (g/10min at 230°C 2
temperature, 700 kg/cm injection
and 2.16 Kg load
pressure
1.7 25.0
3.0 32.0
5.6 36.0
10.0 46.25

9.3.2.3 Disc Flow Test

Resin Temperature (°C 5°C) Pressure (MPa 10%)

Polyester 120 1.4
Epoxy 160 1.4
Silicones 175 1.4 – 6.9

( w1  w2 )
Flow  100 percent
w1
( w1  4 w3 )
Flow  100 percent
w1
9.3.3 For Elastomer
For vulcanisable compound a measure of the time to
the incipient vulcanisation and rate of curing can be
determined for elastomeric material using Mooney
viscosity.
9.3.3.1 Mooney Viscosity
9.3.3.1.1 Definition:
Mooney viscosity is defined as the shearing torque
resisting rotation of a cylindrical metal disk (or rotor)
embedded in rubber within a cylindrical cavity.
9.3.3.1.3 Test Method: ASTM D 1646, ISO 289
9.3.3.1.2 Significance:
1. By this method molecular mass and viscosity can be
determined because rubber is non-newtonian fluid.
2. These mooney viscosities of polymers will normally
relate to how they will be processed. Lower Mooney
viscosity materials (30 to 50) will be used in injection
molding, while higher Mooney products (60 to 80) can
be more highly extended and used in extrusion and
compression molding.
3. The onset for vulcanization can be detected by
increase in viscosity. The curing rate also can be
detected for rubbers.
4. Test Apparatus:
 9.3.3.1.6 Procedure:
1. Select the rotor to be used and select the test
temperature table given below:
Type Rubber Test Temperature °C Running Time (Min)
NBS 388 1000.5 or 1250.5 8
NR, BR, CR, IR, NBR,
1000.5 4
SBR
BIIR, CIIR, IIR 1000.5 or 1250.5 8
EPDM, EPM 1250.5 4
Synthetic Rubber black
1000.5 4
master batches
Compounded stock
1000.5 4
reclaimed material

1. Adjust the torque indicator to the zero reading while

viscometer running in the unloaded condition with the
rotor in place.
2. Remove the hot rotor and place the test piece and
replace the viscometer and start the viscometer and
recorder.
Case Study:
Following can be obtained from the recorder
a) Minimum Viscosity
b) The time required for a specified increase
above the minimum viscosity.
c) Cure Index:

Typical curing characteristics curve using large rotor

 Scorch assessed by plasticity test on rubber sample
when sample heated and an increase in stiffness with
heating time was observed (The results shown in Fig.).
Rate of cure is still assessed by vulcanising samples for
various times and following the change in tensile
properties, hardness, set, swelling etc

Determinations of scorch and cure characteristics

Thank You Very Much for Your Kind
Attention