Glass transition temperature

Glass transition temperature T

g
is a characteristic temperature that marks the transition Irom
the glassy state (hard and brittle amorphous state) to the rubbery or Ilexible state because oI
the onset oI segmental motion. At temperature beloq T
g
, there is no segmental motion, expact
Ior the sretching or distartion oI covalent bonds. As such, the Ilexibility oI amorphous
polymer is reduced drastically when they are cooled below T
g.
The melting point, T
m
is the
temperature range where total or whole polymer chain mobility occurs Ior many polymers, T
g

is appoximately one-halI oI T
m
(expressed in Kelvin). The glass transition temperature is
characteristic (oI a particular polymer in much the same way that a melting point in
characteristic oI ordinary low molecular weight compounds.
The glass transition temperature oI amorphous polymers is a Iunction oI the chemical
structure oI the polymer chain. It varies widely with the types oI skeletal atoms present, with
the types oI side groups, and with the tacticity oI side groups along the polymer backbone.
Table 14.11 demonstrates the eIIects oI structural variations on the crystalline melting
temperature and glass transition temperature Ior several polymers.
In general, polymers with Ilexible backbone and small substituant groups have low T
g
,
whereas those with rigrid backbones, such as polymers containing main-chain aromatic
groups have T
g
. Thus, poly (dimethyi.....) bas a very low T
g
(-125
0
C), presuinably because the
silicon-oxygen bonas have considerable homobility. On the order hand, polymers with highly
rigrid aromatic backbones such as the












igh-modulus Iiber poly |2,2`-(m-phenylene)-5,5`-bibenzimidazole| has a reported T
g
in the
range Irom 427 to 500
0
C. Likewise, aromatic nylons, called aramids, have greater T
g
values
than aliphatic nylons counterparts. Bulky substituent groups hinder rotation and thereIore
raise T
g
. For example, the bulky phenyl group in polystyrene restricts rotation, and hence its
T
g
is higher than thaat Ior polyethtylene. Also, as shown in Table 14.11, T
g
decreases as the
size oI the ester groups increase in polyacrylates and polymethacrylates. The T
g
oI poly
(ethylene terephthalate) is 69
0
C, which is higher than that oI poly(ethylene adipate) by 132
0
C
demonstrating the eIIect oI the phenylene stiIIening group. Chain, which will repel oI attract
each other. Also, polar interactions between neighboring chains could raise the T
g
. As shown
in Table 14.11, T
g
increases as the degrec oI crystallinity increases; the T
g
value oI isotactic
polypropylene is 100
0
C, whereas atactic polypropylene (less crystalline) has a T
g
value oI -
20
0
C. The presence oI other nonrotational groups such as unsaturated groups in the main
chain decreases Ilexibility oI the polymer chain. Trans geometric isomers have higher T
g
than
cis isomers, as Ior example, in the case oI cis-polybutadiena (T
g
-102
0
C) compared to trans-
polybutadiene (T
g
-58
0
C), or in the case oI cis-polysoprene (T
g
-67
0
C) compared to trans-
poylsoprene (T
g
-70
0
C). Table 14.12 even the chain lenght has an eIIect. For low polymers.
The T
g
generally rises with increasing chain lenght until a limiting value is reached where
Iuther increase in molecular weight has very little eIIect on T
g
. T
0
a very large extent, the
practical utility oI polymers and their diIIerent properties depend heavily on their glass
transition temperatures. Amorphous plastics perIorm best below T
g
, but elastomers must be
used above the brittle point or T
g.


14.5.2 Mechanical properties
Mechanical properties oI a polymer depend on many variables-molecular weight, molecular
weight distribution, morphology, additivies, temperature, time, and so on. Mechanical
properties oI polymers are much more dependent on molecular weight over a very board
range, yet they too level oII at high molecular weight. The leveling oII molecular weight
depends on the polymer structure. For very polar polymers, such as polyamides, the leveling
oII may occur at a molecular weight in the range 20.000 to 50.000. Whereas polyoleIins such
as polyethylene, in which mechanical strenght is mainly because oI dispersion Iorces, the
leveling oII occurs at much higher molecular weight (above 10
5
). The dependence oI
properties on molecular weight is shown Ior a hypothetical polymer in Fig. 14.17
Mechanical properties oI a polymer are mainly determined by how much stess a sample will
withstand beIore the sample fils. At low strain (i.e..1 percent), the deIormation oI most
polymers is elastic where deIormation is homogeneous and Iull recovery can occur over a
Iinite time. Among the mechanical properties that are oI Iundamental interests in commercial
polymers are :
1. Tensile strenght : it is a measure oI resistance to streching. Anything that contributes to
chain stiIIening such as the presence oI bulky side groups. Cyclic units, cross-linking,
and crystallinity, will increase the tensile strenght, but decrease the tensile elongation.
2. 425ressive strenght: it is the extent to which a sample can be compressed beIore it
Iails.
3. lexural strenght: it is a measure oI resistance to breaking, or snapping, when a sample
is beni (Ilexed).
4. 25act strenght: it is a measure oI toughness that is, how well a sample will withstand
the sudden onset oI stress, like a hammer blow. Usually, chain stiIIening lowers the
impact strenght and increases embrittlement.




5. atigue: it is a measure oI how well a sample will withstand repeated application oI
tensile, Ilexural, or compressive stress.
6. ree5: it is the cold Ilow oI a polymer. It is a measure oI the change in strain when a
polymer sample is subjected to a constant stress (such as gravity).
7. $tress relaxati4n: it reIers to the decrease in stress when a sample is elomgated rapidly to
a constant strain.

14.5.3 Solubility
Solvents are Irequently used during the polymerization processes, during Iabrication (i.e.,Iilm
casting, Iiber Iormation, and coatings), and Ior the determination oI molecular weight and
molecular weight distribution. Dissolution oI a polymer sample in a solvent accurs in two
stages. The Iist stage is a solvation process in which the solvent molecules diIIuse slowy
through the polymer matrix to Iorm a swollen, solvated mass called a gel. The second stage
oI dissolution consists oI a breakdown oI the swollen gel to give an actual solution oI
polymer molecules in the given solvent. In general, liniear and branched polymers remain in
a swollen condition. owever, lack oI solubility does not necessarily mean that the polymer
is oI network type; some liniear polymers deIy all aattemps to dissolve them.
General rules Ior polymer solubility. A number oI structural parameters oI the polymer aIIect
the ease and speed oI the polymer solution. Thease include.
1. he2ical structure.polar polymers tend to dissolve in polar solvents, and nonpolar
polymers tend to dissolve in inpolar solvents (like dissolves like). ThereIore, chemical
similarity oI a polymer and solvent is a Iair indication oI solubility. For example, ethanol
can disolve poly(biny alcohol) but not polystyrene, whereas toluene can dissolve
polystyrene but not poly(vinyl alcohol).



2. 4lecular weight. in a given solvent at a particular temperature, the solubility oI a
polymer decreases s its molecular weight increases.
3. r4ss-linking: iI a polymer is cross-linked to a signiIicant degree, it will only swell s a
result oI taking liquid into network, but complete dissolution does not occur.
4. rystalinity. in general, solubility oI a polymer decrease with an increase in the degree
oI crystallinity, but it is possible to Iind solvents capable oI overcoming the crystalline
bonding Iorces and hence dissolving the polymer. Also, solubility is enchanced by
heating the polymer to a temperature close to its crystalline melting point.
5. ranching. in general, solubility increase with increasing polymer branching.

!70/icitions of polym07s solubiliti0s. Dissolution oI polymer in a solvent occurs iI the
solvent-solvent and the polymer-polymer cohesive Iorces are similar to adhesive Iorces
betweeen the solvent and polymer molecules. Solubility oI polymers is usually predicted
using parameter called s4lubility 5ara2eter, o. The solubility parameter is related to
cohesive energy density, or the molar energy oI vaporization oI a pure liquid. Cohesive
energy density is deIined as the energy needed to remove molecule Irom its nearest
neighbors. The magnitude oI the cohesive Iorces may be described simply by the amount oI
the energy needed to vaporize a certain volume aI a subtance, and is deIined by Eq.2
Cohesive energy density (CED) o
2
=
L
0
v
0
..........................................(2)
Where E
0
molar latent heat oI vaporization
V
0
molar volume
o solubility parameter
ildebrand |12| showed that the enthalpy change per unit volume Ior endothermic dissolution
(the usual case Ior polymers) is expressed as
AE
disolution

1

2
((o
1-
o
2
)
2
................................................................(3)
Where
1
volume Iraction oI solvent in the solution

2
volume Iraction oI polymer in the solution
o
1
solubility parameter oI the solvent
o
2
solubility parameter oI the polymer