TG and Factors Affecting PDF

Glass Transition Temperature (Tg): Most polymers are either completely amorphous or have an amorphous component even if they
are crystalline such materials are hard, rigid below a fairly sharp defined temperature known as glass transition temperature (Tg). At Temperatures above the glass transition temperature the amorphous polymer is soft and flexible and is either an elastomer or a very viscous liquid.
Glassy Brittle & Hard Tg
Viscoelastic Rubbery & Soft
Viscous fluid melt
Tm
Mechanical properties show profound change in the region of Tg. For example, the elastic modulus may decrease by a factor 1000times as the temperature is raised through the glass transition temperature. Therefore, Tg is the most important material characteristic of a polymer as far as the mechanical properties are concerned. Tg values of several polymers are given in reference [1]. Elastomeric or rubbery polymers have a Tg, or a softening temperature value, below room temperature. Brittle, rigid polymers have Tg values well above the room temperature. The other physical properties which change rapidly with temperature in the glass transition region are: Coefficient of thermal expansion Heat Capacity Refractive index Mechanical Damping Electrical Properties.
The glass transition temperature is usually measured by experiments (which measure the volume, specific heat, and mechanical strength as a function of temperature) such as Dilatometry (Volume) Thermomechanical Analyzer (TMA) (Expansion or modulus) Differential Scanning Calorimetry (DSC) (Specific Heat) Dynamic Mechanical Thermal Analyser (DMTA) (Modulus)
Effect of chemical structure on Tg: The repeat structure of a polymer has influence on the stiffness and flexibility of the polymer which in turn decides the Tg of the polymer. If stiffness of the polymer is high then Tg of the will also be high, if flexibility of the polymer is high then Tg of the polymer will be low. Aliphatic groups, ether linkages and dimethyl siloxane groups present in main chain
Main-chain aliphatic groups, ether linkages and dimethyl siloxane groups build flexibility into a polymer and lower the Tg. Poly (dimethyl siloxane) rubber has the lowest Tg value, -143C than any other polymer.
Rigid groups in the back bone or main chain of the polymer
When rigid groups such as phenyl rings constitute the polymer backbone, chain flexibility decreases thereby increase in Tg results. This can be seen from the following comparision. Polymer Polyethylene Polycarbonate Structure Tg(C) -80 147
Poly(ethylene terephthalate)
70
Large or rigid groups present in the pendent positions
Large or rigid groups such as substituted aromatic structures and pendent tertiary butyl groups raise the Tg of the polymer. The effect of decreasing the molecular flexibility by the substitution of bulky side groups onto a polymer chain is illustrated by the following example Polymer Polyethylene Structure Tg(C) -80
Polypropylene
-10
Polystyrene
95
Poly(2,6-dichlorostyrene)
167
Length of the side chain
Aliphatic side chains lowers Tg, the effect of the length of aliphatic side groups is illustrated by the methacrylate series.
Backbone symmetry, tacticity and chain conformations
The backbone symmetry has great influence on the value of Tg. It affects the potential energy barrier for bond rotations. This effect is illustrated by the following pairs of polymers.
Asymmetric Polymer Polypropylene
Symmetric Polymer Poly isobutylene
Tg = -10C Poly (vinyl chloride)
Tg = -70 C Poly (vinylidene chloride)
Tg = -19 C Tg = 87 C The symmetrical polymers have lower Tg values than the asymmetric polymers despite the extra side group. This could be attributed to the cancellation of intermolecular forces due to the presence of same group or atom on either side of the chain. Lower the intermolecular forces higher the flexibility and hence low Tg. However, tacticity plays a very important role in asymmetrical polymers. Thus syndiotatic and isotactic Poly (methyl methacrylate) have Tg values of 115 C and 45 C respectively. Isotactic polymers assume helical conformations to accommodate bulky pendent groups which are all lying on the same side of the polymer chain. These helical conformations may impart flexibility to the backbone which results in low Tg. Secondary bonding between the chains
The secondary bonding such as hydrogen bonding restricts the mobility of segments which results in higher Tg. This can be illustrated by the following examples Polymer Poly (methyl methacrylate) Structure Tg C 3
Poly (acrylic acid)
106
Poly (methyl methacrylate) is incapable of forming hydrogen bonding and hence has lower Tg than Poly (acrylic acid) which form intermolecular hydrogen bonding between the chains.
Primary bonding between the chains
The segmental mobility is restricted by the presence of covalent bonds between the chains in the form of crosslinks. Therefore crosslinking (primary bonding) increases the Tg values. For instance, Poly (styrene-co-divinyl benzene) has crosslinks between the chains to have higher Tg than polystyrene. Similarly, polyethylene is cross-linked using peroxides such as dicumyl peroxide to increase its Tg and mechanical properties. Intermolecular forces(Cohesive energy density due to polar group)
Molecular polarity increases the intermolecular forces or cohesive energy density which makes the chains stiff and hence shifts the Tg to higher temperatures. This is illustrated with the help of following examples Polymer TgC Polypropylene -10 Poly (vinyl chloride) 87 Polyacrylonitrile 101 The size of the side group in all the above polymers is about the same, but the polarity increases. The non-polar Polypropylene has the lowest Tg than Poly (vinyl chloride) and Polyacrylonitrile. Molecular weight
Tg increases with number average molecular weight to a limiting asymptotic value of Tg infinite molecular weight. In practical range of molecular weights, Tg is given by: Tg = Tg
for
- (K/Mn)
K constant (related to free volume) characteristic of each polymer. For Polystyrene K=1.75 x 105, so its Tg value increases from about 83C for a molecular weight of 104 to 100 C infinite molecular weight. Higher the chain end concentration (low molecular weight) more the free volume for segmental mobility and hence low Tg. The Tg of cross-linked polymer is given by Tg Tg 0 = (3.9 x 104 / Mc) Mc The number average molecular weight between crosslinks. Tg0 The glass transition temperature of uncross linked polymer.
Copolymerization
Tg of a copolymer depends on the Tg of the individual homopolymers of monomers which constitute the copolymer and on the mole fraction of the monomeric units. The Tg of a copolymer can be expressed by the following empirical relation: 1/Tg = (WA/TgA) + (WB/TgB) Tg glass transition of copolymer. TgA glass transition of homopolymer of monomer A. TgB glass transition of homopolymer of monomer B. WA , WB weight fractions of the monomer components which constitute the copolymer.
REFERENCES [1] J.Bauder Up and E.H.Immergut Eds. Polymer Hand Book , John Wiley, New York, 1975. [2] Plastics Materials by J.A.Brydson. [3] D.W. Van Krevelen And P.J. Hoftyzen, Properties Of Polymer, 3rd Edition Elsevier Scientific Publishing Company Amsterdam Oxford New York. 1990. [4] R.J.Samuels, Structured Polymer Properties, John Wiley & Sons, New York, 1974.

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How does the chemical structure of a polymer affect its glass transition temperature?

What factors influence the glass transition temperature of a polymer?

Glass Transition Temperature (Tg): Most polymers are either completely amorphous or have an amorphous component even if they

Glassy Brittle & Hard Tg

Viscoelastic Rubbery & Soft

Viscous fluid melt

Rigid groups in the back bone or main chain of the polymer

Large or rigid groups present in the pendent positions

Length of the side chain

Backbone symmetry, tacticity and chain conformations

Asymmetric Polymer Polypropylene

Symmetric Polymer Poly isobutylene

Tg = -10C Poly (vinyl chloride)

Tg = -70 C Poly (vinylidene chloride)

Poly (acrylic acid)

Primary bonding between the chains

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