Transition in Polymers
The glass transition
• Amorphous polymers may exhibit 2 distinctly different
types of mechanical behaviour at room temperature:
• 1) Glassy :
Hard, rigid
Eg; polymethyl methacrylate (Lucite, Plexiglas) & polystrene
• 2) Rubbery :
Soft, flexible
however;
i. polymethyl methacrylate + polystrene are heated to
about 125°C, they exhibit typical rubbery properties,
and
ii. when a rubber ball is cooled in liquid nitrogen, it
becomes rigid & glassy, and shatters when an attempt
is made to bounce it
So there is some temperature an amorphous polymer will
become glassy or rubbery, is know as glass-transition
temperature Tg.
• The glass-transition temperature is a property of the
polymer ; glassy / rubbery
depends on its application temperature is above or
below its glass-transition temperature
*Tg = glass transition temperature
You may have experienced the glass transition of chewing gum.
At body temperature the gum is soft and pliable, which is characteristic of an
amorphous solid in the rubbery state.
If you put a cold drink in your mouth or hold an ice cube on the gum, it becomes hard
and rigid.
The glass transition temperature of the gum is somewhere between 0oC and 37oC.
Polymer Tg (oC)
Polyethylene (LDPE) -125
Polypropylene (atactic) -20
Poly(vinyl acetate) (PVAc) 28
Poly(ethyleneterephthalate) (PET) 69
Poly(vinyl alcohol) (PVA) 85
Poly(vinyl chloride) (PVC) 81
Polypropylene (isotactic) 100
Polystyrene 100
Poly(methylmethacrylate) (atactic) 105
Molecular motions in an
amorphous polymer
• There are 4 categories of the molecular motions in an
amorphous polymer:
1. Translational motion of entire molecules, which permits
flow
2. Cooperative wriggling & jumping of segments of
molecules approximately 40 to 50 carbon atoms in
length, permitting flexing & unwilling
3. motions of a few atoms along the main chain (five or
six, or so) or of side groups on the main chains
4. vibration of atoms about equilibrium positions, as occur
in crystal lattices, except that the atomic centers are not
in a regular arrangement in an amorphous polymer
• Motions 1-4 above are arranged in order of decreasing
activation energy; i.e, smaller amounts of thermal energy
(kT) are required to produce them
• Motions 1,2 are “frozen out” or in other word is quite weak
• Motion 3,4 have sufficient energy for motion
* Not all molecules possess the same energies at a given
temperature. The molecular energies follow a Boltzmann
distribution & even below Tg there will be occasional type
2 & even type 1 motions, which can manifest themselves
over extremely long period of time
Determination of Tg
• By observing the variation of same thermodynamic
property with T, e.g; the specific volume
• Fig 8.1: Specific volume versus temperature for polyvinyl
acetate
From the figure:
• Note: The slope of the v versus T increase above the Tg
• The value of Tg determined in this fashion will vary
slightly with the rate of cooling & heating
• This reflects the fact that long, entangled polymer chains
cannot respond instantaneously to changes in
temperature & illustrates the difficulty in making
thermodynamic measurement on polymers
Often, very long to reach equilibrium, if indeed it is ever
reached, & it is difficult to be sure if & when it is reached
Strictly speaking, the Tg should be defined in terms of
equilibrium properties- or at least those measured with very
low rates of temperature change
Refractive index may also be used to establish Tg
In contrast to a change in slope at the glass transition a
thermodynamic property such as specific volume exhibits a
discontinuity with temperature at the crystalline melting
point in polymers as in other materials
• The determination of Tg for amorphous materials, including polymers, by dilatometric
methods (as well as by other methods) are found to be rate dependent.
• This is schematically illustrated in the figure below, again representing an amorphous
polymer, where the higher value, Tg2, is obtained with a substantially higher cooling
rate than for Tg1.
• Transition in polymers are rapidly & conveniently studied
using DTA (differential thermal analysis) & DSC
(differential scanning calorimetry)
• The glass transition is therefore known as a second-order
thermodynamic transition (v versus T continuous dv/dT
versus T discontinuos)
• In DTA, small samples of the polymer & an inert reference
substance (one that undergoes no transition in the
temperature range of interest) are mounted in a block with
thermocouples to monitor temperature
• The thermodynamic property monitored here is the
enthalpy. The block is heated at a constant rate, & the
difference between the sample & reference temperatures
is plotted versus the sample temperature
• At Tg, Cp= (2H/2T)ρ increases (the slope of an H versus T
plot increases) dropping the sample temperature below its
previous level relative to the reference
• At Tm large amounts of heat are required to melt the
crystals at constant T, & the ΔT shows a sharp dip
• DSC provides the same sort of information. The device
measures the differential power input necessary to
maintain the sample & reference at the same
temperature as they are heated. This technique is
something more amenable to quantitative measurement
of ΔHm, & other properties
• Both DTA & DSC are also useful techniques for studying
oxidation (exothermic) & degradation (endothermic)
• May provide useful information on transitions
Technique
Compounds Analyzed
Nature of Sample
FACTORS AFFECTING GLASS TRANSITION
TEMPERATURE
• The glass transition temperature there is a large-scale
cooperative movement of chain segments.
• It is therefore to be expected that any structural features or
externally imposed conditions that influence chain mobility
will also affect the value of Tg.
• Some of these structural factors include chain flexibility;
stiffness, including steric hindrance, polarity, or interchain
attractive forces; geometric factors; copolymerization;
molecular weight, branching; cross-linking; and crystallinity.
External variables are plasticization, pressure, and rate of
testing.
Factors effecting Tg
Chain Length
• Each chain end has some free volume
associated with it. A polymer with
shorter chains will have more chain
ends per unit volume, so there will be
more free volume. Hence Tg' for
shorter chains will be lower than Tg for
long chains. Note that the shorter-
chained polymer also has more free
volume frozen in below Tg than the
long-chained polymer.
Factors effecting Tg
Chain Flexibility
• A polymer with a backbone that exhibits
higher flexibility will have a lower Tg. This is
because the activation energy for
conformational changes is lower. Therefore,
conformational changes can take place at
lower temperatures.
Factors effecting Tg
Side Groups
• Larger side groups can hinder bond rotation
more than smaller ones, and therefore cause an
increase in Tg. Polar groups such as Cl, CN or
OH have the strongest effect.
Factors effecting Tg
Branching
• Polymers with more branching have more
chain ends, so have more free volume, which
reduces Tg, but the branches also hinder
rotation, like large side groups, which
increases Tg. Which of these effects is greater
depends on the polymer in question, but Tg
may rise or fall.
Factors effecting Tg
Cross-linking
• Cross-linking reduces chain mobility, so Tg
will be increased. It also affects the
macroscopic viscosity of the polymer, since if
there are cross-links between the chains, then
they are fixed relative to each other, so will not
be able to slide past each other.
Factors effecting Tg
Plasticisers
• Small molecules, typically esters, added to the
polymer increase the chain mobility by
spacing out the chains, and so reduce Tg.
Factors effecting Tg
Time Effects
• The properties of an amorphous polymer above Tg can change
with time
– At very short loading times the polymer can still be glassy
because there is not time for the chains to move.
– At intermediate times the polymer may be rubbery - i.e.
chains can uncoil and recoil between entanglements, which
remain stable.
– At very long times, the chains can move past each other
permanently, and so the polymer behaves as a viscous
liquid.
Methods Of Measuring Transitions
• Definitions of the Terms “Transition,” “Relaxation,” and
“Dispersion”.
– The term “transition” refers to a change of state induced by changing
the temperature or pressure.
– The term “relaxation” refers to the time required to respond to a
change in temperature or pressure. It also implies some measure of the
molecular motion, especially near a transition condition.
– The term “dispersion” refers to the emission or absorption of energy—
that is, a loss peak—at a transition. In practice, the literature sometimes
uses these terms somewhat interchangeably
Methods Of Measuring Transitions
Experimental Methods
Dilatometry Studies
• A mercury-based dilatometer. Bulb A
contains the polymer (about 1 g),
capillary B is for recording volume
changes (Hg + polymer), G is a
capillary for calibration, sealed at
point F. After packing bulb A, the inlet
is constricted at E, C contains
weighed mercury to fill all dead
space, and D is a second constriction
Dilatometry Studies
DSC Method
Theories of Glass Transition
• The Free-Volume Theory
• The Kinetic Theory
• Thermodynamic Theory
Summary of the Theories
• Free-Volume theory provides relationships between
coefficients of expansion below and above Tg and yields
equations relating viscoelastic motion to the variables of time
and temp.
• The kinetic theory defines Tg as the temp. at which the
relaxation time for the segmental motions in the main polymer
chain is of the same order of magnitude as the time scale of
experiment.
• The thermodynamic theory introduce the notion of equilibrium
and the requirements for a true second-order transition.
Free-Volume Theory
The important point is that
molecular motion cannot
take place without the
presence of holes. These
holes, collectively, are
called free volume.
• Aquasi-crystalline lattice exhibiting vacancies or holes. Circles represent
molecules: arrow indicates molecular motion
• The free volume of polymer, Vf. Free volume is the volume of the
polymer mass not actually occupied by the molecules themselves;
i.e,
Vf = V – Vs
Where,
V= specific volume of the polymer mass
Vs= volume of the solidly packed molecules
• The higher the Vf, the more room the molecules will have in which
to move around & the lower the Tg
Kinetic Theory
• The kinetic concept of glass transition considers the glass transition as a
dynamic phenomenon since the position of the Tg depends on the rate of
heating or cooling.
• It predicts that the value of Tg measured depends on the time scale of the
experiment in relation to that of the molecular motions arising from the
perturbation of the polymer system by temperature changes.
• This theory permits a description of the approach to thermodynamic
equilibrium.
• When a polymeric material above Tg is cooled, there is sufficient
molecular motion for equilibrium to be achieved.
• However, the rate of approach to equilibrium, and hence the Tg , depends
on the cooling rate employed in the experiment.
Thermodynamic Theory
• The equilibrium concept treats the ideal glass transition as a
true second order thermodynamic transition, which has
equilibrium properties.
• The ideal state, of course, cannot be obtained experimentally
since its realization would require an infinite time.
• The glass transition temperature, Tg , therefore approaches the
true transition temperature as the time scale of experiment
becomes longer.
Kinetic Theory
