Stress Relaxation and Thermal Properties of Polymers

Long - term
Mechanical Properties
Stress Relaxation
Stress relaxation is defined as a

gradual decrease in stress with time,
under a constant deformation (strain).
This characteristic behaviour of the

polymers is studied by applying a fixed
amount of deformation to a specimen
and measuring the load required to
maintain it as a function of time.
This is in contrast to creep

measurement, where a fixed amount
Diagram illustrating stress relaxation.
of load is applied to a specimen and
resulting deformation is measured as
a function of time.
Stress Relaxation...
Stress relaxation behaviour of the polymers has

been overlooked by many design engineers and
researchers, partly because the creep data are
much easier to obtain and is readily available.
However, many practical applications dictate the

use of stress relaxation data.
For example, extremely low stress relaxation is desired

in the case of a threaded bottle closure, which may be
under constant strain for a long period. If the plastic
material used in the closures shows an excessive
decrease in stress under this constant deformation, the
closures will eventually fail.
Similar problems can be encountered with metal

inserts in molded plastics, Belleville washer, also
known as a coned-disc spring or multiple cantilever
springs used in cameras, appliances and business
machines.
Stress relaxation measurements can be carried

out using a tensile testing machine. However,
the use of such a machine is not always
practical because the stress relaxation test ties
up the machine for a long period of time.
The equipment for a stress relaxation test

must be capable of measuring very small
elongation accurately, even when applied at
high speeds.
Many sophisticated pieces of equipment now

employ a strain gauge or a differential
transformer along with a chart recorder
capable of plotting stress as a function of time.
A typical stress–time curve is

schematically plotted in Figure. At
the beginning of the experiment,
the strain is applied to the specimen
at a constant rate to achieve the
desired elongation.
Once the specimen reaches the

desired elongation, the strain is held
constant for a predetermined
amount of time.
The stress decay, which occurs

because of stress relaxation, is
observed as a function of time.
Stress–time curve.
If a chart recorder is not

available, the stress values at
different time intervals are
recorded and the results are
plotted to obtain a stress versus
time curve.
One such stress relaxation

curve plotted at various levels of
constant strain is shown in
Figure.
Stress relaxation curve plotted at various

levels of constant strain.
The stress relaxation experiment is often

carried out at various levels of temperature
and strain.
The stress data obtained from the stress

relaxation experiment can be converted to a
more meaningful apparent modulus data by
simply dividing stress at a particular time by
the applied strain.
The curve may be replotted to represent

apparent modulus as a function of time.
The use of logarithmic coordinates further

simplifies the stress relaxation data by allowing
us to use standard extrapolation methods such
as the one used in creep experiments.
Thermal Properties
Thermal Properties
The thermal properties of plastic materials are equally as important

as the mechanical properties.
Unlike metals, plastics are extremely sensitive to changes in

temperature.
The mechanical, electrical, or chemical properties of plastics cannot

be examined without looking at the temperature at which the values
were derived.
Crystallinity has a number of important effects upon the thermal

properties of a polymer. Its most general effects are the introduction
of a sharp melting point and the stiffening of thermal mechanical
properties.
Amorphous plastics, in contrast, have a gradual softening range.

Thermal Properties...
Molecular orientation also has a significant
effect on thermal properties. Orientation tends
to decrease dimensional stability at higher
temperatures.
The molecular weight of the polymer affects

the low-temperature flexibility and brittleness.
Many other factors, such as intermolecular

bonding, cross linking, and copolymerization, all
have a considerable effect on thermal
properties.
Hence, it is clear that the thermal behaviour of

polymeric materials is rather complex.
Therefore, in designing a plastic part or

selecting a plastic material from the available
thermal property data, one must thoroughly
understand the short term as well as the long-
term effects of temperature on the properties
of that plastic material.
Tests for elevated temperature performance
Designers and material selectors of plastic products

constantly face the challenge of selecting a suitable plastic for
elevated temperature performance. The difficulty arises
because of the varying natures and capabilities of various
types and grades of plastics at elevated temperatures.
Many factors are considered when selecting a plastic for a

high-temperature application.
i) The material must be able to support a design
load under operating conditions without objectionable creep
or distortion.
ii) The material must not degrade or lose necessary
additives that will cause a drastic reduction in the physical
properties during the expected service life.
Tests for elevated temperature performance... Thermal Properties...
All the properties of plastic materials are not

affected in a similar manner by elevating
temperature. For example, electrical properties
of a particular plastic may show only a
moderate change at elevate temperatures,
while the mechanical properties may be
reduced significantly.
Thus, it is quite clear that a single maximum-

use temperature that will apply to all the
important properties in high-temperature
applications is simply not possible.
When studying the performance of plastics at elevated temperatures,

one of the most important considerations is the dependence of key
properties such as modulus, strength, chemical resistance, and
environmental resistance on time.
Therefore, the short-term heat resistance data alone is not adequate

for designing and selecting materials that require long-term heat
resistance.
For the sake of convenience and simplicity, we divide the elevated

temperature effects into two categories:
1. Short-term effects 2. Long-term effects

a. Heat deflection temperature a. Long-term heat resistance test
b.Vicat softening temperature b. UL temperature index
c. Torsion pendulum c. Creep modulus/creep rupture
tests
Short-Term Effects
A. Heat Deflection Temperature (HDT) (ASTM D 648, ISO 75-1 & 75-2)
Heat deflection temperature is defined as the temperature

at which a standard test bar (5 × 1/2 × 1/4 in.) deflects
0.010 in. under a stated load of either 66 or 264 psi.
The heat deflection temperature test, also referred to as

the heat distortion temperature test, is commonly used
for quality control and for screening and ranking materials
for short-term heat resistance.
Heat distortion temperature, however, does distinguish

between those materials that lose their rigidity over a
narrow temperature range and those that are able to
sustain light loads at high temperatures
Short-Term Effects
A. Heat Deflection Temperature (HDT) ... Thermal Properties...
Apparatus
The apparatus for measuring heat deflection temperature consists of an
enclosed oil bath fitted with a heating chamber and automatic heating
controls that raise the temperature of the heat transfer fluid at a uniform
rate.
A cooling system is also incorporated to fast cool the heat transfer medium
for conducting repeated tests.
The specimens are supported on steel supports that are 4 in. apart, with the
load applied on top of the specimen vertically and midway between the
supports.
The contact edges of the support and of the piece by which pressure is
applied is rounded to a radius of 1/4 in.
A suitable deflection measurement device, such as a dial indicator, is normally

used. A mercury thermometer is used for measuring temperature. The unit is
capable of applying 66- or 264-psi fiber stress on specimens by means of a
dead weight.
Short-Term Effects
A commercially available heat

deflection measuring device with a
closeup of a specimen holder is
illustrated in Figure
Short-Term Effects
Test Specimens
The test specimens consist of test bars 5 in. in length

and 1/2 in. in depth by any width from 1/8 to 1/2 in.
The test bars may be molded or cut from extruded

sheet as long as they have smooth, flat surfaces and are
free of excessive sink marks or flash.
The specimens are conditioned employing standard

conditioning procedures.
Short-Term Effects
Test Procedure.
The specimen is positioned in the apparatus along with

the temperature and deflection measuring devices and the
entire assembly is submerged into the oil bath kept at
room temperature.
The load is applied to a desired value(66- or 264-psi fiber

stress).
Five minutes after applying the load, the pointer is

adjusted to zero and the oil is heated at the rate of 2 ±
0.2°C/min.
The temperature of the oil at which the bar has deflected

0.010 in. is recorded as the heat deflection temperature at
the specified fiber stress.
Short-Term Effects
Factors Influencing HDT
• Residual Stress. The specimens consisting of a high degree of

“molded-in” residual stresses or a high degree of orientation
have a tendency to stress relieve as the temperature is
increased. The specimen warpage occurs in a downward
direction owing to the external loading. The warpage due
to stress relaxation and deflection, occurring from the
softening of the specimen, combined together, yields a false
heat deflection temperature.
However, if the specimens are annealed in a controlled

oven atmosphere prior to testing, the stresses can be
relieved and warpage can practically be eliminated. Heat
deflection temperature of the unannealed specimen is
usually lower than that for a comparable annealed
specimen.
Short-Term Effects
Factors Influencing HDT

Specimen Thickness.
Thicker specimens tend to exhibit a
higher heat deflection temperature.
This is because of the inherently low Fiber Stress. The higher the fiber
thermal conductivity of plastic stress or loading is, the lower the
materials. The thicker specimen heat deflection temperature. The
requires a longer time to heat difference in heat deflection
through, yielding a higher heat temperature values resulting from
deflection temperature. different fiber stress varies
depending upon the type of
polymer.
Specimen Preparation.
Injection-molded specimens tend to have a
lower heat deflection temperature than
compression-molded specimens. This is
because compression-molded specimens are
relatively stress-free.
Short-Term Effects
B. Vicat Softening Temperature (ASTM D 1525, ISO 306)
The Vicat softening temperature is the temperature at

which a flat-ended needle of 1-mm2 circular cross
section will penetrate a thermoplastic specimen to a
depth of 1 mm under a specified load using a
selected uniform rate of temperature rise.
This test is very similar to the deflection temperature

under the load test and its usefulness is limited to
quality control, development, and characterization of
materials.
The data obtained from this test is also useful in

comparing the heat-softening qualities of
thermoplastic materials.
However, the test is not recommended for flexible

PVC or other materials with a wide Vicat softening
range.
Short-Term Effects Thermal Properties...
Vicat Softening Temperature (ASTM D 1525, ISO 306)...
The test apparatus designed for

deflection temperature under load
test can be used for the Vicat
softening temperature test with
minor modification.
The flat test specimen is molded or The test is carried out by first
cut from a sheet with a minimum placing the test specimen on a
thickness and width of 0.12 and 0.50 specimen support and lowering the
in., respectively. needle rod so that the needle rests on
the surface of the specimen.
The temperature of the bath is raised

at the rate of 50 or 120°C/hr
uniformly.
The temperature at which the needle

penetrates 1 mm is noted and
reported at the Vicat softening
temperature.
Short-Term Effects Thermal Properties...
Vicat Softening Temperature (ASTM D 1525, ISO 306)...
A commercially
available test
apparatus for
measuring the Vicat
softening
temperature is
illustrated in Figure
Vicat softening point apparatus.

Long-Term Effects
During long-term exposure to heat, plastic materials may

encounter many physical and chemical changes.
A plastic material that shows little or no effect at elevated

temperature for a short time may show a drastic
reduction in physical properties, a complete loss of rigidity,
and severe thermal degradation when exposed to elevated
temperature for a long time.
Along with time and temperature, many other factors such

as ozone, oxygen, sunlight, and pollution combine to
accelerate the attack on plastics.
At elevated temperatures, many plastics tend to lose

important additives such as plasticizers and stabilizers,
causing plastics to become brittle or soft and sticky.
Long-Term Effects
Three basic tests have been developed and accepted by the

plastics industry.
If the application does not require the product to be exposed

to elevated temperature for a long period under continuous
load, a simple heat-resistance test is adequate.
The applications requiring the product to be under

continuous significant load must be looked at from creep
modulus and creep rupture strength test data.
Another widely accepted method of measuring maximum

continuous use temperature has been developed by
Underwriters Laboratories.
The UL temperature index, established for a variety of plastic

materials to be used in electrical applications, is the
maximum temperature that the material may be subject to
without fear of premature thermal degradation.
Long-Term Effects
A. Long-Term Heat-Resistance Test (ASTM D 794)
The long-term heat-resistance test was

developed to determine the permanent effect
of heat on any property by selection of an
appropriate test method and specimen.
In ASTM recommended practice, only the

procedure for heat exposure is specified and
not the test method or specimen.
Long-Term Effects
Any specimen, including sheet, laminate, test bar, or molded

part may be used.
If a specific property, such as tensile strength loss is to be

determined, a standard tensile test bar specimen and
procedures must be used for comparison of test results
before and after the test.
The test requires the use of a mechanical convection oven

with a specimen rack of suitable design to allow air
circulation around the specimens. The test is carried out by
simply placing the specimen in the oven at a desired
exposure temperature for a predetermined length of time.
Long-Term Effects
The subsequent exposure to temperatures may be increased

or decreased in steps of 25°C until a failure is observed.
Failure due to heat is defined as a change in appearance,

weight, dimension, or other properties that alter plastic
material to a degree that it is no longer acceptable for the
service in question.
Failure may result from blistering, cracking, loss of plasticizer,

or other volatile material that may cause embrittlement,
shrinkage, or change in desirable electrical or mechanical
properties.
Long-Term Effects
Many factors affect the reproducibility of the data.
The degree of temperature control in the oven, the

type of molding, cure, air velocity over the
specimen, period of exposure, and humidity of the
oven room are some of these factors.
The amount and type of volatiles in the molded

part or specimen may also affect the reproducibility.
Long-Term Effects
B. Creep Modulus/Creep Rupture Tests
The tests developed to determine creep

modulus and creep rupture values of plastic
materials are discussed earlier.
Both creep modulus and creep rupture

strength decrease significantly as the
temperature is increased.
Before selecting a material for a load-bearing

application at an elevated temperature, one
must carefully evaluate the published creep
modulus and creep rupture strength test data.
This is accomplished by using bar charts.
Long-Term Effects
In one chart, creep

modulus of various
thermoplastics at three
different temperatures is
compared.
Creep modulus versus temperature.

Long-Term Effects
A similar comparison is made

using creep rupture strength
for the same set of
thermoplastic materials.
A study of the charts reveals

that while most of these
thermoplastics have
substantial rigidity and
strength at room
temperature, only a few retain
enough of these properties at
elevated temperatures to bear
significant loads
Creep rupture strength versus temperature.

Stress Relaxation and Thermal Properties of Polymers

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Long - term

Stress relaxation is defined as a

This characteristic behaviour of the

This is in contrast to creep

Stress relaxation behaviour of the polymers has

However, many practical applications dictate the

For example, extremely low stress relaxation is desired

Similar problems can be encountered with metal

Stress relaxation measurements can be carried

The equipment for a stress relaxation test

Many sophisticated pieces of equipment now

A typical stress–time curve is

Once the specimen reaches the

The stress decay, which occurs

If a chart recorder is not

One such stress relaxation

Stress relaxation curve plotted at various

The stress relaxation experiment is often

The stress data obtained from the stress

The curve may be replotted to represent

The use of logarithmic coordinates further

The thermal properties of plastic materials are equally as important

Unlike metals, plastics are extremely sensitive to changes in

The mechanical, electrical, or chemical properties of plastics cannot

Crystallinity has a number of important effects upon the thermal

Amorphous plastics, in contrast, have a gradual softening range.

The molecular weight of the polymer affects

Many other factors, such as intermolecular

Hence, it is clear that the thermal behaviour of

Therefore, in designing a plastic part or

Tests for elevated temperature performance

Designers and material selectors of plastic products

Many factors are considered when selecting a plastic for a

All the properties of plastic materials are not

Thus, it is quite clear that a single maximum-

When studying the performance of plastics at elevated temperatures,

Therefore, the short-term heat resistance data alone is not adequate

For the sake of convenience and simplicity, we divide the elevated

1. Short-term effects 2. Long-term effects

Heat deflection temperature is defined as the temperature

The heat deflection temperature test, also referred to as

Heat distortion temperature, however, does distinguish

A suitable deflection measurement device, such as a dial indicator, is normally

A commercially available heat

The test specimens consist of test bars 5 in. in length

The test bars may be molded or cut from extruded

The specimens are conditioned employing standard

The specimen is positioned in the apparatus along with

The load is applied to a desired value(66- or 264-psi fiber

Five minutes after applying the load, the pointer is

The temperature of the oil at which the bar has deflected

Factors Influencing HDT

• Residual Stress. The specimens consisting of a high degree of

However, if the specimens are annealed in a controlled

Factors Influencing HDT

The Vicat softening temperature is the temperature at

This test is very similar to the deflection temperature

The data obtained from this test is also useful in

However, the test is not recommended for flexible

The test apparatus designed for

The temperature of the bath is raised

The temperature at which the needle

Vicat softening point apparatus.