First-order transitions crystalline polymers

The four-parameter model is very simple and often a reasonable first-order model for polymer crystalline solids and polymeric fluids near the transition temperature. The model requires two spring constants, a viscosity for the fluid component and a viscosity for the solid structured component. The time-dependent creep strain is the summation of the three time-dependent elements (the Voigt element acts as a single time-dependent element) ... 

The first-order transition or melting point (Tm) is energywise larger than the Eg. Entirely crystalline polymers will have only a whereas a totally amorphous polymer will have only a Tg. Since most polymers are a combination of amorphous and crystalline regions, they have both a Tg and a T -... 

Both kinetic and thermodynamic approaches have been used to measure and explain the abrupt change in properties as a polymer changes from a glassy to a leathery state. These involve the coefficient of expansion, the compressibility, the index of refraction, and the specific heat values. In the thermodynamic approach used by Gibbs and DiMarzio, the process is considered to be related to conformational entropy changes with temperature and is related to a second-order transition. There is also an abrupt change from the solid crystalline to the liquid state at the first-order transition or melting point Tm. 

The T of crystalline polymers may be determined by observing the first-order transition (change in heat capacity value) by DTA or by DSC (ASTM-D3418). Some comparative information on thermal properties of polyolefins may be obtained from the melt index. To determine the melt index, the weight of extrudate or strand under a specified load and at a specified temperature is measured. Melt index values are inversely related to the melt viscosity. 

The most common applications of DSC are to the melting process which, in principle, contains information on both the quality (temperature) and the quantity (peak area) of crystallinity in a polymer [3]. The property changes at Tm are often far more dramatic than those at Tg, particularly if the polymer is highly crystalline. These changes are characteristic of a thermodynamic first-order transition and include a heat of fusion and discontinuous changes in heat capacity, volume or density, refractive index, birefringence, and transparency [3,8], All of these may be used to determine Tm [8],... 

We note here that gel is a coherent solid because its structure is characterized by a polymer network, and hence, the above theoretical considerations on crystalline alloys should be applicable to gels without essential alteration. It is expected that the curious features of the first-order transition of NIPA gels will be explained within the concept of the coherent phase equilibrium if the proper calculation of the coherent energy and the elastic energy of the gel network is made. This may be one of the most interesting unsolved problems related to the phase transitions of gels. 

First order transition temperature in crystalline polymers. J. Appl. Phys. 34, 2442—2445 (1963). 

Melting is known as a first order transition. Unlike crystalline polymers, amorphous polymers do not melt when heated but undergo a dramatic reduction in flexibility when they are cooled below a characteristic temperature known as the glass transition temperature (Tg) (Figure 4.11). Below Tg, the... 

Polymer crystallinity and melting were discussed previously. Crystallization is an example of a first-order transition, in this case liquid to solid. Most small molecules crystallize, an example being water to ice. Thus this transition is very familiar. 

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