Presentation For Polymer Science

POLYMER SCIENCE;
TEX: 103
SECTION: B
TOPIC: GLASS TRANSITION
TEMPERATURE
COURESE ADVISER
DR. ENGR. MD. SAIFUR
RAHMAN
HEAD OF THE DEPARTMENT OF
B.S.T.E
GROUP MEMBERS
NAME ID
Sazzad Hossain 06313200
Md. Shahjahan Ali 06313257
Md. Tajul Islam 06313222
Md. Riyaz-Ul-Islam 06313241
Md. Habibur Rahman 06313077
Mithun Ghos 06313253
Md. Syedur Rahman 06212150

Introduction
The glass transition temperature is different for each polymer,
but many polymers are above Tg at room temperature. In many
cases the polymers are at least partially crystalline at room
temperature and the temperature at which the crystals melt
(Tm) is above room temperature. The graph below shows how
some polymers are above Tg but below Tm at room
temperature. Such polymers are rubbers (so long as they are
largely amorphous) at room temperature. However, the
polymer may flow like a liquid over long time periods as its
amorphous component relaxes under the polymer's weight
Glass transition temperature
The temperature, below which it becomes hard and above which it becomes
soft, is called “glass transition temperature”.
Glass transition temperature is represented by the symbol Tg. At glass

transition temperature the hard, brittle state is known as “the glassy state” and
the soft, flexible state is known as “the rubbery” or “viscous elastic state”. On
heating polymer becomes a highly viscous liquid and starts flowing is known
as “viscous fluid state” (Tf).
Glass state Rubbery or Viscous fluid state
Viscous elastic
state
(Brittle state) (Tough plastics & (Polymer melts)

Rubbers)
Tg Tf temperature
(Glass transition temperature) (Flow temperature)
Fig: change of state with temp. in polymeric materials

Measurement of Tg
There are several methods available to measure the

glass transition temperature, some of which are given
below. Since the value of the glass transition
temperature depends on the strain rate and cooling or
heating rate, there cannot be an exact value for Tg.
Mechanical Methods
It is possible to calculate a value for the glass transition

temperature by measuring the elastic modulus of the
polymer as a function of the temperature, for example
by using a torsion pendulum. Around Tg there is a large
fall in the value of the modulus. The frequency of the
oscillation is important, since Tg depends on the time
allowed for chain segment rotation.
A more common method is dynamic mechanical thermal
analysis (DMTA), which measures the energy absorbed when
a specimen is deformed cyclically as a function of the
temperature, and a plot of energy loss per cycle as a function
of temperature shows a maximum at Tg.
Thermal Methods
As was shown in the thermodynamic approach to glasses, the enthalpy of a
polymer decreases as the temperature decreases, but with a change in
slope in the graph at Tg. Taking the derivative of this graph with respect to
temperature, the specific heat capacity can be plotted, as below. The
specific heat capacity, Cp, can be measured using calorimetry, e.g.
differential scanning calorimetry (DSC). The value of Tg depends on the
heating or cooling rate.
Volume Methods
The changes in conformation that occur above Tg require more
volume, so plotting a graph of specific volume or thermal
expansion coefficient against temperature will give a value for Tg.
The actual volume of the molecules stays the same through Tg,
but the free volume (the volume through which they can move)
increases.
Dielectric Constant
If a varying electric field is applied to a polymeric material, any
polar groups will align with the field. Below Tg rotation of the
bonds is not possible, so the permittivity will be low, with a big
increase around Tg. At higher temperatures the increased
thermal vibrations cause the permittivity to drop again. If the
frequency of the field is increased, the polar groups have less
time to align, so the glass transition occurs at a higher
temperature.
Glass transition temperature of some materials
Polymer Tg (°C)
Nylon 6 50
Nylon 6,6 50
Polyethylene (high density) -125
Polyethylene terephthalate 69
Polystyrene 100
Poly(vinyl chloride) (PVC) 81
Polystyrene 95
Polypropylene (isotactic) 0
Poly-3-hydroxybutyrate (PHB) 0
Poly(methylmethacrylate) (atactic) 105
Chalcogenide AsGeSeTe 245
ZBLAN 235
Tellurite 279
Avatrel; Polynorbornene 215
Fluoroaluminate 400
Tyre Rubber 160
Soda-lime glass 520-600
Quartz glass 1175
Glass transition temperature and molecular weight
The glass transition temperature of a polymer is influenced by
its molecular weight, at least up to around a value of 20,000;
beyond this, the effect of the molecular weight is not
pronounced and this can be seen from Fig. many attempts
have been made to compute mathematical relationships,
among whish the following two are frequently used:
Ts=Ts-K/Mn
1/Ts=1/Ts+A/Mn
Where Ts is the glass transition temperature at infinite

molecular weight and K and A are arbitrary constants.
Tg
Molecular weight around 20,000
Molecular weight
Fig. Plot showing effect of molecular weight on

glass transition temperature of polymers.
Glass transition temperature and plasticizers
Plasticizers are low molecular weight non-volatile substances
(mostly liquids), which when added to a polymer, improve its
flexibility, possibility and, hence, utility. The plasticizer
substantially reduces the brittleness of many amorphous
polymers because its addition even in small quantities markedly
reduces the Ts of the polymer. This effect is due to a reduction
in cohesive forces of attraction between polymer chains.
Plasticizer molecules (being relatively small in size compared to
polymer molecules) penetrate into the polymer matrix and
establish polar attractive forces between it and the chain
segments. These attractive forces reduce the cohesive forces
between the polymer chains and increase the segmental
mobility, thereby reducing the Ts value.
Importance of glass transition temperature
The glass transition temperature is an important parameter of a polymeric

material. It is used as a measure for evaluating the flexibility of a polymer
molecule and the type of response the polymeric material would exhibit to
mechanical stress. The Tg value of a polymer, therefore, decides whether a
polymer at the use temperature will behave like rubber or plastic. As present, it
would suffice to know that polymers above their Tg will be soft and flexible and
exhibit a delayed elastic response (viscoelasticity). While those below their Tg
will be hard and brittle and will possess dimensional stability.
The Tg value along with the Tm value give an indications of the temperature
region at which a polymeric material transforms from a rigid solid to a soft
viscous state. This helps in choosing the right processing temperature, i.e., the
temperature region in which the material can be converted into finished
products through different processing techniques such as molding, calendaring
and extrusion.
Conclusion
Reference Books:
*V R Gowariker, N V Viswanathan, Jayadev
Sreedhar, Polymer Science, 17th Edition.
New Age International (P) Limited, Publishers.
New Delhi,India.
Reference Links:
*www.macrogalleria.com
*www.google.com
*www.yahoo.com
THE END
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POLYMER SCIENCE;

Sazzad Hossain 06313200

Md. Shahjahan Ali 06313257

Md. Tajul Islam 06313222

Md. Riyaz-Ul-Islam 06313241

Md. Habibur Rahman 06313077

Mithun Ghos 06313253

Md. Syedur Rahman 06212150

Glass transition temperature is represented by the symbol Tg. At glass

(Brittle state) (Tough plastics & (Polymer melts)

Fig: change of state with temp. in polymeric materials

There are several methods available to measure the

It is possible to calculate a value for the glass transition

Where Ts is the glass transition temperature at infinite

Molecular weight around 20,000

Fig. Plot showing effect of molecular weight on

The glass transition temperature is an important parameter of a polymeric

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