Molecular architecture, amorphous and crystalline phases, glass transition,

plasticization, crystallization, melting, factors affecting Tg and Tm:

GLASS TRANSITION:
 The 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, the glass transition corresponds to the gradual transformation from a liquid to a rubbery material and finally
to a rigid solid.
 The temperature at which the polymer experiences the transition from rubbery to rigid states is termed the glass
transition temperature, Tg.
 Of course, this sequence of events occurs in the reverse order when a rigid glass at a temperature below Tg is heated.
 In addition, abrupt changes in other physical properties accompany this glass transition: for example, stiffness (Figure
15.7), heat capacity, and coefficient of thermal expansion.
MELTING
 The melting transformation is the reverse process that occurs when a polymer is heated.
 The melting of a polymer crystal corresponds to the transformation of a solid material, having an ordered structure of
aligned molecular chains, to a viscous liquid in which the structure is highly random.  This phenomenon occurs, upon
heating, at the melting temperature, Tm
 There are several features distinctive to the melting of polymers that are not normally observed with metals and ceramics;
these are consequences of the polymer molecular structures and lamellar crystalline morphology.

Concept:
 First of all, melting of polymers takes place over a range of temperatures; this phenomenon is discussed in more detail
shortly.
 In addition the melting behavior depends on the history of the specimen, in particular the temperature at which it
crystallized.
Tg
TG of polymers or TG polymers is the glass transition temperature. At this temperature, the hard, glassy state of an
amorphous polymer converts into a rubbery state. Specifically, the thermosetting polymers undergo this conversion, while
thermoplastic polymers undergo melting rather than converting into a rubbery state.

Thermosetting polymers show a very hard and rigid glassy state. However, the rubbery state is viscous and pliable.
Furthermore, pure crystalline polymers do not have this glass transition temperature because they melt rather than
converting into a glassy state. Therefore, amorphous and semi-crystalline polymers have glass transition temperatures. There
are some factors that affect this conversion; chemical structure of the polymer, molecular weight of the polymer, the
presence of plasticizers, flexibility, etc. The TG determines the applications of the polymer; for instance, a rigid polymer with
a low TG is suitable for high-temperature applications.

Tm
TM of polymers or TM polymers is the melting temperature. At this temperature, the crystalline phase of a polymer converts
into a solid amorphous phase. Therefore, this is different from the usual melting process of other materials in which sold
phase converts into liquid phase. This term applies regarding thermoplastics because thermosets undergo decomposition at
high temperatures rather than melting.
DIFFERENCE BETWEEN Tg & Tm
FACTORS THAT INFLUENCE MELTING TEMPERATURES
Molecular chemistry and structure:
During melting of a polymer there will be a rearrangement of the molecules in the transformation from ordered to disordered
molecular states. Molecular chemistry and structure will influence the ability of the polymer chain molecules to make these
rearrangements and, therefore, will also affect the melting temperature.
Chemical bonds: Chain stiffness, which is controlled by the ease of rotation about the chemical bonds along the chain, has a
pronounced effect.
The presence of double bonds and aromatic groups in the polymer backbone lowers chain flexibility and causes an increase in
Tm. Size and type of side groups: Furthermore, the size and type of side groups influence chain rotational freedom and flexibility;
Bulky or large side groups tend to restrict molecular rotation and raise Tm. For example, polypropylene has a higher melting
temperature than polyethylene
The CH3 methyl side group for polypropylene is larger than the H atom found on polyethylene. The presence of polar groups: 
The presence of polar groups(C l, OH, and CN), even though not excessively large, leads to significant intermolecular Bonding
forces and relatively high TmS. This may be verified by comparing the melting temperatures of polypropylene and poly vinyl
chloride. Molecular weight:
At relatively low molecular weights, increasing (or chain length) raises Tm Furthermore, the melting of a polymer takes place
over a range of temperatures; thus, there will be a range of Tms, rather than a single melting temperature. This is because every
polymer will be composed of molecules having a variety of molecular weights (Section 14.5), and because Tm depends on
molecular weight. For most polymers, this melting temperature range will normally be on the order of several degrees Celsius.
10. Degree of branching:  The introduction of side branches introduces defects into the crystalline material and lowers the
melting temperature. High-density polyethylene, being a predominately linear polymer, has a higher melting temperature than
low density polyethylene which has some branching.