CHEM F325: Polymer Chemistry

Lecture 20A
Solid State Properties-III
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 Thermal Transition and Properties
of Polymers
Background
• Many of the commonly used techniques to determine Tg and Tm can be
understood on the basis of the thermodynamic definition of a phase transition
originally proposed by Paul Ehrenfest in 1933.
• A first-order transition is defined as one for which a discontinuity occurs in the
first derivative of the Gibbs free energy (G). According to the first law of
thermodynamics for a reversible, closed system, the Gibbs free energy can be
expressed in differential form as a function of temperature and pressure, G(T, p),
as,

where S is entropy and V is the system volume.

• The free energy may be differentiated with respect to temperature (at constant
pressure) OR with respect to pressure (at constant temperature) as

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 Thermal Transition and Properties
of Polymers
• In terms of describing transitions in polymer
systems, the most useful of the preceding
relationships is the first derivative with respect to
p, which indicates that a first-order transition
should occur as a discontinuity in volume, as
illustrated here
• Volume is easily measured as a function of
temperature by a technique called dilatometry,
which is described in the next section.
• The dependence of volume on temperature in the
region about the crystalline-melting temperature
approximates such a transition

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 Thermal Transition and Properties
of Polymers
Second-Order Transitions.
• The glass transition approximates an Ehrenfest second-order transition. This
means that a discontinuity should be observed in the second derivatives of the
Gibbs free energy. Three possible second derivatives can be used to provide a
basis for the experimental measurement of Tg. From eqs. (4.11) and (4.12), the
corresponding second derivatives are

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 Thermal Transition and Properties
of Polymers
Second-Order Transitions.
• Since entropy is not an experimentally measurable quantity, eq. (4.13) may be
recast into a more useful form in terms of the specific heat at constant pressure,
Cp, which is defined as

• From the first law of thermodynamics, a relation between Cp and entropy can
be obtained as

• Substitution of eq. (4.17) into eq. (4.13)

indicates that a second-order transition
should occur as a discontinuity in
specific heat, as illustrated

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 Thermal Transition and Properties
of Polymers
Second-Order Transitions.
• The other two second derivatives indicate that second-order transitions should
occur as discontinuities in the slope of volume as a function of pressure (eq.
(4.14)) or volume as a function of temperature (eq. (4.15)). These slopes
define two useful parameters—the isothermal compressibility coefficient, b,
and the (isobaric) thermal-expansion coefficient, a

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 Thermal Transition and Properties
of Polymers
Second-Order Transitions.
• This means that a discontinuity in a
plot of a or b versus temperature, or
alternatively a change in slope of a
plot of volume versus temperature
(at constant pressure) or a plot of
volume versus pressure (at constant
temperature), marks the occurrence
of a second-order transition as
illustrated in Figures 4-11A and 4-
11B, respectively. Both coefficients
may be obtained by dilatometric
measurements, although the
constant-pressure experiment is the
easier and, therefore, more
commonly used.

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 Thermal Transition and Properties
of Polymers
Second-Order Transitions.
• The magnitudes of the discontinuities in Cp, a, and b at the second-order
transition may be expressed as,

where the subscripts, 1 and 2, represent values at temperatures below and above
the transition, respectively
• the glass transition is not a true thermodynamic transition but, rather, it is
considered to be a pseudo-second-order transition that is influenced by the
kinetics of glass formation (i.e., the rate of heating or cooling).
• Both volume and specific-heat data for polymers closely approximate second
order transition behavior; however, the discontinuities or changes in slope are
more gradual and are affected by the heating rate.

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 Thermal Transition and Properties
of Polymers
Measurement Techniques.
• SELF Study these topics
• Topics to be overed – Dilatometry, Calorimetry, and Heat- Distortion
Temperature – formulae and numericals

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 Thermal Transition and Properties
of Polymers
Structure –Property Relationships.
• Both Tg and Tm are strongly influenced by the chemical structure of the
repeating unit.
• In general, both Tg and Tm increase with decreasing flexibility of the polymer
chain. Flexibility decreases with increasing aromatic composition of the main
chain or by incorporation of bulky substituent groups or non-rotational groups
in the main chain.
• This is illustrated by the relation of Tm to repeating-unit structure for an
analogous series of polyesters in Table 4-8. Replacement of the aliphatic
sequence (CH2)4 of compound A with an aromatic ring (compound B)
increases Tm by 220°C.
• Replacement by two coupled aromatic rings (compound C) further increases
Tm by 85°C, but incorporation of a flexible –CH2–CH2– group between
aromatic rings lowers Tm by 135°C (compound D). By contrast, incorporation
of a non-rotational, unsaturated linkage between aromatic rings (compound E)
results in the highest Tm.

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Thermal Transition and Properties
of Polymers

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 Thermal Transition and Properties
of Polymers
• Chain flexibility is particularly important in determining Tg.
• Flexible chains, as may be obtained by incorporating an oxygen atom into the
main chain (e.g., polydimethylsiloxane), are capable of large-scale molecular
motions at very low temperatures and, therefore, have low Tg.
• Bulky substituent groups hinder chain rotation and therefore raise Tg as shown
by structure–Tg comparisons for several vinyl polymers in Table

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 Thermal Transition and Properties
of Polymers
• For comparably sized substituent groups, increasing polarity, which may
enhance intermolecular interactions, can elevate Tg. This is illustrated by Tg
data for the vinyl polymers—atactic polypropylene (Tg = -20°C), poly(vinyl
chloride) (Tg = 89°C), and polyacrylonitrile (Tg = 100°C)—given in Table 4-9.

• As illustrated in Table 4-10, increasing flexibility of the side group can lower
Tg, as is evident by comparison of the chemical structures of poly(methyl
methacrylate), poly(ethyl methacrylate), and poly(propyl methacrylate).
• Syndiotacticity increases Tg as illustrated by data for poly(methyl
methacrylate) (PMMA) prepared with different tacticities: i-PMMA (Tg =
45°C), a-PMMA (Tg = 105°C), and s-PMMA (Tg = 115°C).
• Trans geometric isomers have higher Tg than cis isomers, as for example in the
case of cis-polybutadiene (Tg = -108°C) compared to trans-polybutadiene (Tg
= -18°C) or in the case of cis-polyisoprene (Tg = -73°C) compared to trans-
polyisoprene (Tg = -53°C).

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Thermal Transition and Properties
of Polymers

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 Thermal Transition and Properties
of Polymers
Effect of molecular weight on T g
• The glass-transition temperature increases with molecular weight at low
molecular weight but reaches a point at moderate molecular weight where
further increase in molecular weight has very little effect on Tg. This is an
example of a limiting-property relationship.
• The crystalline-melting temperature, Tm, follows a similar dependence on
molecular weight.
• The particular molecular-weight average most relevant to Tg is the number-
average, Mn (see Section 1.3.2). This dependence can be rationalized on the
basis of the free-volume theory of the glass transition. Since larger free volume
is associated with the ends of long polymer chains than with other chain
segments, free volume increases with an increasing number of chain ends (i.e.,
decreasing molecular weight).
• The form of dependence of Tg on molecular weight is approximated by the
Fox–Flory eq

• where Tg∞ is the limiting value of Tg at high molecular weight (obtained from
the intercept of a plot of Tg versus reciprocal number-average molecular
weight) and K is a constant for a given polymer. BITSPilani, Pilani Campus
 Thermal Transition and Properties
of Polymers
Effect of molecular weight on T g
• Equation (4.27) has been found to give a good fit of experimental data for
many polymers; however, there is evidence that K may not be constant for
molecular weights below about 10,000. Representative values of the Fox–
Flory parameters, Tg∞ and K, for some well-characterized polymers are given
in Table

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 Thermal Transition and Properties
of Polymers
Effect of Composition on Tg
• When a second component, either a low-molecular-weight additive or a second
polymer, is blended to form a homogeneous mixture, the Tg of the mixture will
depend upon the amount of each component and upon the Tg of the second
component.
• The form of the Tg–composition dependence may be approximated by several
theoretical or semiempirical models. An approximate relationship between the
Tg of a miscible mixture and composition is given by the simple rule of
mixtures, which for a binary mixture.

• where W1 is the weight fraction and Tg,j (in Kelvins) is the glass-transition
temperature of the ith component (i.e., component 1 or 2 in a binary mixture).
For a multicomponent mixture, we can write.

• The simple rule of mixtures is a good approximation for blends of two or more
polymers but overestimates the Tg of polymers plasticized with a low-
molecularweight organic compound such as an ester or phthalate
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 Thermal Transition and Properties
of Polymers
Effect of Composition on Tg
• Improved predictive capability is available through a number of other empirical
or theoretical relationships. One of the earliest theoretical expressions is the
Kelley–Bueche equation, which is derived from the isofree volume model of
the glass transition. At constant pressure and at a temperature, T, above the glass
transition, the fractional free volume, f, is given as

• where fg is the fractional free volume at Tg (fg ~ 0.025), af is the (isobaric)

thermal expansion coefficient (eq. (4.19)) of the free volume of the melt, and f
is the volume fraction of the diluent(1) or polymer(2), where f1 + f2 = 1
• Since the thermal expansion coefficient of free volume was not a parameter
available at the time,* the assumption was made that it was the same as that of
the bulk melt state, a, which can be determined by dilatometry or estimated
with good confidence. (e.g., eq. (4.24)). By equating T with the Tg of the mixture
(whereby f = fg), eq. (4.29) reduces to

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