Glass Transition Temperature of Plastics

Introduction
Different types of polymers have different stiffness:
Styrene and Plexiglas
Rigid Glasslike

Rubber and Polyethylene

Soft and pliable Almost Ductile

Specific volume vs. temperature for polyvinyl acetate

Transitions in amorphous polymers

Factors affecting Tg
Chain Length Plasticizers Chain stiffness and side groups Copolymers Pressure Test conditions, length of test, and types of impurities in sample Polymer chain factors

Chain Length
As molecular weight increases, Tg also increases As molecular weight decreases, Tg also decreases More end groups Easier movement of molecules More inherent free volume in the polymer

Tg = T g C X

Where: C = constant for each polymer X = degree of polymerization

Plasticizers
Small organic molecules mixed into a polymer having the effect of reducing its Tg Have the effect of increasing the free volume
Their small molecules fit in between the chains Causes chains to be less tight amongst themselves Plasticizers technically do not effect Tg but practically do

Chain stiffness and side groups

Chains that have difficulty uncoiling have higher Tg Chain stiffness is related to higher energy level Bulky side groups hinder rotation

Copolymers
Made from two different monomers Tg will be some kind of average between the two monomeric materials Assuming they were converted into polymer Will be based roughly on the weight % of each material present in the copolymer

Volume Fraction Tg = VFa x Tga + VFa x Tgb 1 = Wf1 + Wf2 Tg Tg1 Tg2

Pressure
A noticeable increase in Tg occurs at several thousand psi. Pressure pushes molecules together Removes free volume

Rate dependence of Tg

Polymer chain conformation

Factors governing conformation
Potential energy hindering internal rotation Repulsive forces and Van Der Waals Forces Electrostatic interactions Hydrogen bonding Packing considerations

Process Temps
Polymer Polybutadiene Polyethylene Polypropylene Nylon 6,6 Polyethylene Terephthalate Polyvinyl Chloride Polystyrene Polycarbonate PMMA Tg F -145 -25 17 122 156 188 212 315 225