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TMA – Thermomechanical Analysis is the measurement of a change of a dimension or a mechanical property of the sample while it is subjected to a temperature ramp. Increased thermal vibrations produce thermal expansion characterized by the coefficient of thermal expansion (CTE) that is the gradient of the graph of dimensional change versus temperature. CTE depends upon thermal transitions such as the glass transition. CTE of the glassy state is low, while at Tg increased degrees of molecular segmental motion are released so CTE of the rubbery state is high. Changes in an amorphous polymer may involve other sub-Tg thermal transitions associated with short molecular segments, side-chains and branches. The linearity of the sf-TM curve will be changed by such transitions. Other relaxations may be due to release of internal stress arising from the non-equilibrium state of the glassy amorphous polymer. Such stress is referred to as thermal aging. Other stresses may be as a result of moulding pressures, extrusion orientation, thermal gradients during solidification and externally imparted stresses.

Semi-crystalline polymers are more complex than amorphous polymers, since the crystalline regions are interspersed with amorphous regions. Amorphous regions in close association to the crystals or contain common molecules as tie molecules have less degrees of freedom than the bulk amorphous phase. These immobilised amorphous regions are called the rigid amorphous phase. CTE of the rigid amorphous phase is expected to be lower than that of the bulk amorphous phase. The crystallite are typically not at equilibrium and they may contain different polymorphs. The crystals re-organize during heating so that they approach the equilibrium crystalline state. Crystal re-organization is a thermally activated process. Further crystallization of the amorphous phase may take place. Each of these processes with interfere with thermal expansion of the material. The material may be a blend or a two-phase block or graft copolymer. If both phases are amorphous then two Tg will be observed if the material exists as two phases. If one Tg is exhibited then it will be between the Tg of the components and the resultant Tg will likely be described by a relationship such as the Fox or Kwei equations. If one of the components is semi-crystalline then the complexity of a pure crystalline phase and either one or two amorphous phases will result. If both components are semi-crystalline then the morphology will be complex since both crystal phases will likely form separately, though with influence on each other.

Crosslinking will restrict the molecular response to temperature change since degree of freedom for segmental motions are reduced as molecules become irreversibly linked. Crosslinking chemically links molecules, while crystallinity and fillers introduce physical constraints to motion. Mechanical properties such as derived from stress-strain testing are used to calculate crosslink density that is usually expressed and the molar mass between crosslinks (Mc). The sensitivity of zero stress TMA to crosslinking is low since the structure receives minimum disturbance. Sensitivity to crosslinks requires high strain such that the segments between crosslinks become fully extended.

Zero force TM will only be sensitive to changes in the bulk that are expressed as a change in a linear dimension of the material. The measured change will be the resultant of all processes occurring as the temperature is changed. Some of the processes with be reversible, others irreversible, and others time dependent. The methodology must be chosen to best detect, distinguish and resolve the thermal expansion or contractions observable. The TMA instrument need only apply sufficient stress to keep the probe in contact with the sample surface, but it must have high sensitivity to dimensional change. The experiment must be conducted at a temperature change rate slow enough for the material to approach thermal equilibrium throughout. While the temperature should be the same throughout the material it will not necessarily be at thermal equilibrium in the context of molecular relaxations. The temperature of the molecules relative to equilibrium is expressed as the fictive temperature. The fictive temperature is the temperature at which the unrelaxed molecules would be at equilibrium.