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application note

Measurement of Tg by DSC
W.J. Sichina

• What is Tg? Tg is the accepted

abbreviation for the glass
transition temperature. All
amorphous (non-crystalline or
semi-crystalline) materials will
yield a Tg during heating and Tg
is the main characteristic
transformation temperature of
the amorphous phase. The glass
transition event occurs when a
hard, solid, amorphous material
or component undergoes its
transformation to a soft, rubbery,
liquid phase. Tg is a valuable
characterization parameter
associated with a material and
can provide very useful
information regarding the end-
use performance of a product.
The ‘classic’ Tg is observed as
an endothermic stepwise change
in the DSC heat flow or heat
capacity.
• What is the Practical Importance
of Tg? The glass transition event
is one of the most important
characteristic properties of a
material. It represents the lower
end use temperature since a
material cannot be processed or
worked with once its temperature increases and will be well above exhibited by a cracker or cookie is
drops below Tg. The Tg of a room temperature after the resin often related to the sugar/starchy
material is related to many cures. In applications involving phase having its Tg above room
important end use properties of a epoxy curing, such as coatings temperature. If the food becomes
wide range of materials. For for motor windings, it is stale, by absorbing water from the
example, a two-part epoxy essential that Tg of the resin be air, the Tg will drop below room
thermosetting resin is initially a well above the operating temperature due to plasticizing
liquid at room temperature temperature to avoid failure of effects, and the food will lose its
because its Tg is well below 25 the motor. For foods containing desired crispness. For clothing
C. As the resin crosslinks, its Tg sugar and starches, the crispness containing polyester, when the
 clothes are ironed, the
amorphous component in the
polyester will exceed Tg and a
crease can be placed into the
garment. When the iron is
removed, the temperature drops
below Tg of the polyester, and
the crease is set in.
• Time Dependency of Tg. When a
viscous liquid is cooled without
undergoing crystallization, the
liquid will (and must) convert to
a solid at some temperature,
which is Tg. The molecular
rotational motions associated
with the viscous liquid material
will 'freeze' at Tg. At Tg there is
a stepwise decrease in the heat
capacity of the sample since the
solid phase must have a lower
value of Cp as compared to the
liquid. Unlike the melting
transition, there is no latent heat
involved in stopping the
molecular motions at Tg. The
freezing of molecular motions is
time dependent and, therefore,
Tg is, as a direct consequence,
time dependent. Factors such as
heating and cooling rates will
have a significant effect on Tg.
Because of the complex nature of
the glass transition event, it transition, T2 is the endset by a polymer is dependent upon
becomes more difficult to assign temperature, and Te reflects the the chemical make-up of the
a true transition temperature to very end of the detection of the material. In general, factors
Tg. In fact, there are actually 5 glass transition event. increasing the stiffness of the
accepted ways in which the Tg polymeric molecular segments will
• Polymers and Tg. Polymeric
of a material can be assigned by tend to increase Tg. As the
materials frequently exhibit a Tg polymeric molecular rotations
DSC, as is represented in the
even if the polymer is semi- become more difficult or hindered,
following figure. Tb represents
crystalline and not totally
the very start of the detection of the Tg will increase.
amorphous. As a rule of thumb,
the change in heat flow or heat
most polymers will have a ratio • Molecular weight and Tg. It is
capacity at Tg, T1 is the onset
of Tg/Tm of between 0.50 and well known that Tg increases with
temperature, Tg is the mid-point
0.75, where Tm is the polymer's increasing molecular weight, M.
temperature and the most
melting point (°K). The glass This is expressed by the Fox and
commonly accepted way of
transition temperature exhibited Flory equation:
defining or reporting the glass

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 Tg = Tg(∞) - Kg/M •

where Tg(∞) is the limiting Tg at

a very high molecular weight and
Kg is a constant.
• Tg and Degree of Cure.
Thermosetting materials are
those which undergo an
irreversible, chemical reaction,
known as curing, which produces applications where strength and
a crosslinked structure. rigidity are important, such as pipes.
Thermosets remain amorphous, If PVC is heavily plasticized with
although, above Tg, the liquid DOP, the PVC becomes soft and
state goes from a freely flowing
state for the uncured material to
a rubbery state for the cured
thermoset. The degree of cure is
a very important parameter in
determining the end-use
properties, such as stiffness or
creep, for the material. The Tg
of a thermoset material is related
to the degree of cure. Tg
increases significantly as the
curing reaction proceeds to
completion due to the
establishment of a crosslinked
molecular structure. Eventually,
as the degree of cure of the flexible since Tg is reduced to well
thermoset approaches 100% or below room temperature. An example
is disposable gloves where the Tg of
complete cure, the Tg of the
the plasticized PVC is approximately -
material will reach a limiting 50 C. Absorbed water often functions
value, Tg(∞). as a plasticizer on many hydrophilic
• Tg and Plasticizers. Plasticizing materials (nylon polymers, starches
agents are sometimes added to and sugars, for example).
polymers to improve its flow,
• Tg and Crystallinity. A semi-
processibility and to reduce
brittleness. Adding a plasticizer will crystalline polymer is composed of
cause the Tg of the polymer to two main phases: amorphous and
decrease. If the Tg of the polymer is crystalline. As a polymer becomes
reduced sufficiently, its properties more crystalline, the fraction of
are change from those of a hard, the amorphous
brittle solid to those associated with
a soft, flexible rubber. As an
example, dioctyl phthalate (DOP) is
added to PVC (polyvinyl chloride) to
reduce its Tg. In its unplasticized component becomes increasingly
state, PVC has a Tg near 80 C and smaller; and, therefore, the change
the unplasticized PVC is used in in the sample's Cp at Tg (∆Cp)

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761 Main Avenue
Norwalk, CT 06859-0010 USA
Tel: 80O-762-4000 or PETech-09
(1+) 203-762-4000 Thermal Analysis
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 becomes smaller. Eventually, if temperature well below Tg and
the polymer becomes highly then immediately heated at the
material, it is important to specify the
crystalline, the DSC instrument same rate as used for cooling, a
particular experimental conditions that
may no longer have the simple 'classic' stepwise change
were used to analyze the sample.
necessary sensitivity to detect in the DSC heat flow will be
Tg. In general, the Tg obtained at Tg, without the • Tg and Copolymers. Block
temperature will increase occurrence of the enthalpic copolymers are those where the
somewhat as the crystalline relaxation peak. The Tg polymer main chain consists of
content of the polymer increases. observed during the 2nd heating alternating long sequences of two
segment reflects the chemistry chemically different polymers.
• Tg and Orientation. When a
of the molecules or material, Block copolymers behave as two-
molten polymer is subjected to
while the 1st heating step phase systems with two distinct
stretching during processing,
represents the physics as well as sets of physical properties
orientation of the polymer chains
the chemistry of the as-received analogous to physical mixtures of
occurs. Orientation can cause
the Tg of a polymer to increase
substantially due to the hindered
rotations of the molecules.
Highly oriented polymers, such
as films or fibers can yield a Tg
that is 20 to 30 C higher than the
unoriented, amorphous polymer.
• Tg and Aging. If an amorphous
polymer yields its Tg above
room temperature, physical
aging can occur if the material is
stored at room temperature for a
prolonged period. The effects of
aging will be observed as an
endothermic peak at Tg in the
DSC data. The magnitude of this
relaxation peak at Tg will
increase, as the aging time at
room temperature becomes
longer. The peak can become
large enough that it takes on the
appearance of a melting peak;
but the transformation does not
involve melting processes
whatsoever. The peak is simply
a consequence of the molecules
acquiring a longer overall
material. When reporting the Tg the two different polymers. Each
relaxation time as the amorphous
of a phase will exhibit its own distinct
material is permitted to
Tg. Thus, if the Tg's of the two
physically age at room
polymers are different enough, the
temperature. If the aged material
block copolymer material
is heated to a temperature above
its Tg, cooled back to a

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761 Main Avenue
Norwalk, CT 06859-0010 USA
Tel: 80O-762-4000 or PETech-09
(1+) 203-762-4000 Thermal Analysis
Fax: (1+) 203-762-4228 2000 PerkinElmer, Inc. Printed in U.S.A.
 using the following suggested contact and to give a larger
guidelines: sample mass
will exhibit two Tg's during heating
• use a sample mass between 10 • if the Tg is very weak, increase
by DSC. Random copolymers are
and 20 mg the sample mass
those which consist of random
alternating blocks along the main • keep the sample as thin and as • better identification of weak Tg's
polymer chain. For random flat as possible to minimize the can be obtained by subtracting
copolymers, there are no longer two occurrence of thermal out the baseline results (empty
distinct phases and the random gradients DSC cell) from the sample data
copolymers will exhibit a single, • heat the sample at a rate of 10 file
broad Tg which lies somewhere to 20 C/min • a heat-cool-reheat DSC
between the two Tg's of the • start the experiment so that experiment yields a 'cleaner',
individual polymer comprising the three minutes of 'run time' are easier to interpret Tg during the
copolymer. The relationship obtained before the onset of reheat or 2nd heating segment
between Tg and composition is not the Tg is encountered, as this • StepScan DSC provides a clearer
always linear for a random provides a better baseline evaluation of Tg from the
copolymer system. response storage Cp signal
• when analyzing powder,
• Experimental Tips for compress the powder into the
Measuring Tg by DSC. Best pan with a glass or metal rod
results, when testing a sample to provide better thermal
for its Tg, are obtained by

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PerkinElmer Instruments
761 Main Avenue
Norwalk, CT 06859-0010 USA
Tel: 80O-762-4000 or PETech-09
(1+) 203-762-4000 Thermal Analysis
Fax: (1+) 203-762-4228 2000 PerkinElmer, Inc. Printed in U.S.A.