CHAPTER 7:
Non-Equilibrium Phase Transformation in Solids
7.3 Crystallization, Melting, and Glass Transition Phenomena in Polymers
Crystallization
-is the process by which, upon cooling, an ordered (i.e., crystalline) solid phase is
produced from a liquid melt having a highly random molecular structure.
Concept:
For polymers, upon cooling through the melting temperature, nuclei form where small
regions of the tangled and random molecules become ordered and aligned in the manner
of chain-folded layers
At temperatures in excess of the melting temperature, these nuclei are unstable because of
the thermal atomic vibrations that tend to disrupt the ordered molecular arrangements.
The time dependence of crystallization is the same as for many solid-state
transformations; that is, a sigmoidal-shaped curve results when fraction transformation is
plotted versus the logarithm of time (at constant temperature)
Usually, the extent of crystallization is measured by specimen volume changes
Rate of crystallization is equal to the reciprocal of time required for crystallization to
proceed to 50% completion.
1
𝑟=
𝑡0,5
where 𝑡0,5 = time required for crystallization to proceed to 50% completion
This rate is dependent on crystallization temperature and also on the molecular weight of
the polymer; rate decreases with increasing molecular weight.
For polypropylene (as well as any polymer), the attainment of 100% crystallinity is not
possible.
Melting
- reverse process of crystallization that occurs when a polymer is heated. It corresponds
to the transformation of a solid material, with an ordered structure of aligned molecular chains,
to a viscous liquid in which the structure is highly random. It occurs, upon heating, at the melting
temperature (Tm).
Concept:
Melting of polymers takes place over a range of temperatures.
The melting behavior depends on the history of the specimen, in particular the
temperature at which it crystallized.
The thickness of chain-folded lamellae will depend on crystallization temperature; the
thicker the lamellae, the higher the melting temperature. (↑ 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠, ↑ 𝑇𝑚 )
Impurities in the polymer and imperfections in the crystals also decrease the melting
temperature ( 𝑝𝑟𝑒𝑠𝑒𝑛𝑐𝑒 𝑜𝑓 𝐼𝑚𝑝𝑢𝑟𝑖𝑡𝑖𝑒𝑠, ↓ 𝑇𝑚 )
Finally, the apparent melting behavior is a function of the rate of heating; increasing this
rate results in an elevation of the melting temperature (↑ 𝑟𝑎𝑡𝑒 𝑜𝑓 ℎ𝑒𝑎𝑡𝑖𝑛𝑔, ↑ 𝑇𝑚 )
Glass Transition
-occurs in amorphous (or glassy) and semi-crystalline polymers and is due to a reduction
in motion of large segments of molecular chains with decreasing temperature.
Upon cooling (gradual transformation), liquid → rubbery material → rigid solid
The temperature at which the polymer experiences the transition from rubbery to rigid states is
termed the glass transition temperature (Tg).
Concept:
Abrupt changes in other physical properties accompany this glass transition: for example,
stiffness heat capacity, and coefficient of thermal expansion.
Melting and glass transition temperatures are important parameters relative to inservice
applications of polymers.
They define, respectively, the upper and lower temperature limits for numerous
applications, especially for semi-crystalline polymers.
The glass transition temperature may also define the upper use temperature for
glassy amorphous materials
Furthermore, Tm and Tg also influence the fabrication and processing procedures for
polymers and polymer-matrix composites
FACTORS THAT INFLUENCE MELTING AND GLASS TRANSITION TEMPERATURES:
Melting Temperature:
Molecular chemistry and structure
Chemical bonds
Size and type of side groups
The presence of polar groups
Molecular weight
Degree of branching
Glass Transition Temperature:
Molecular characteristics
Molecular weight
Branching