Crystalline polymers temperature dependence

After-shrinkage is an additional problem with crystalline polymers and depends on the position of the ambient temperature relative to Tg and T. This was discussed in Chapter 3. 

The results of the temperature dependence on polymerization revealed a noticeable phenomenon. When the temperature was raised from 30 to 80° C, the yield of amorphous polymer remained almost constant, whereas that of the crystalline one increased remarkably. A parallel relationship was observed between the yield and the molecular weight of the crystalline polymer (Fig. 15). These experimental results seemed to tell us the following First, two kinds of catalytically active species, one leading to an amorphous polymer and another to a crystalline one, exist in the polymerizing system. Second, the rate of formation of amorphous polymer is almost independent of the polymerization temperature, while that of crystalline polymer does depend on the polymerization temperature. This phenomenon means that the temperature coefficient of the reaction leading to the crystalline... 

Fig. 23.12. Thermodynam ic conditions assumed for crystallizing polymers Temperature dependencies of the bulk chemical potentials of a mesomorphic and the crystalline phase. The potentials are referred to the chemical potential of the melt and denoted /Apam and Ag c respectively...

Other crystallization parameters have been determined for some of the polymers. The dependence of the melting temperature on the crystallization temperature for the orthorhombic form of POX (T = 323K) and both monoclinic (T = 348K) and orthorhombic (T = 329K) modifications of PDMOX has been determined (284). The enthalpy of fusion, Aff, for the same polymers has been determined by the polymer diluent method and by calorimetry at different levels of crystallinity (284). for POX was found to be 150.9 J/g (36.1 cal/g) for the dimethyl derivative, it ranged from 85.6 to 107.0 J/g (20.5—25.6 cal/g). Numerous crystal stmcture studies have been made (285—292). Isothermal crystallization rates of POX from the melt have been determined from 19 to —50 C (293,294). Similar studies have been made for PDMOX from 22 to 44°C (295,296). 

Master curves can also be constmcted for crystalline polymers, but the shift factor is usually not the same as the one calculated from the WLF equation. An additional vertical shift factor is usually required. This factor is a function of temperature, partly because the modulus changes as the degree of crystaHiuity changes with temperature. Because crystaHiuity is dependent on aging and thermal history, vertical factors and crystalline polymer master curves tend to have poor reproducibiUty. 

In the case of a crystalline polymer the maximum service temperature will be largely dependent on the crystalline melting point. When the polymer possesses a low degree of crystallinity the glass transition temperature will remain of paramount importance. This is the case with unplasticised PVC and the polycarbonate of bis-phenol A. 

The view that the degree of imperfection depends on the amount of supercooling is borne out by the observations of Bekkedahl and Wood on rubber. They showed that the melting range (for fast melting) is lower the lower the temperature at which the rubber had been allowed to crystallize. Other crystalline polymers exhibit parallel behavior. 

In extraction from a polymer/additive solid matrix the rate-determining step in the extraction process is governed by the interaction of the solvent of sufficient dissolution power with the matrix and the removal of the analyte (cf. Section 3.4.1.3). There appears to exist a direct relationship between degree of swelling and efficiency of extraction. The amount of C02 absorbed depends on temperature, pressure and the polymer concerned. Crystalline polymers are-not surprisingly-plasticised less... 

Although Equation (4) is conceptually correct, the application to experimental data should be undertaken cautiously, especially when an arbitrary baseline is drawn to extract the area under the DSC melting peak. The problems and inaccuracy of the calculated crystallinities associated with arbitrary baselines have been pointed out by Gray [36] and more recently by Mathot et al. [37,64—67]. The most accurate value requires one to obtain experimentally the variation of the heat capacity during melting (Cp(T)) [37]. However, heat flow (d(/) values can yield accurate crystallinities if the primary heat flow data are devoid of instrumental curvature. In addition, the temperature dependence of the heat of fusion of the pure crystalline phase (AHc) and pure amorphous phase (AHa) are required. For many polymers these data can be found via their heat capacity functions (ATHAS data bank [68]). The melt is then linearly extrapolated and its temperature dependence identified with that of AHa. The general expression of the variation of Cp with temperature is... 

LDPE affect the dynamic mechanical, as well as other material properties of these polymers. The similarity of the temperature dependence of E between our toluene cast HB film and the quenched LDPE (both of 40% crystallinity) in Figure 14A as compared to our quenched HB film (% crystallinity 30%) is another indication of the importance of the level of crystallinity on properties. (This topic has already been discussed in some length in the section on stress-strain behavior). 

The temperature dependence of the compliance and the stress relaxation modulus of crystalline polymers well above Tf is greater than that of cross-linked polymers, but in the glass-to-rubber transition region the temperature dependence is less than for an amorphous polymer. A factor in this large temperature dependence at T >> TK is the decrease in the degree of Crystallinity with temperature. Other factors arc the reciystallization of strained crystallites ipto unstrained ones and the rotation of crystallites to relieve the applied stress (38). All of these effects occur more rapidly as the temperature is raised. 

Figure 3.10 shows the typical dependence on temperature of the specific heat of an amorphous and a crystalline polymer. For both materials, the specific heat has a steep dependence on temperature, but the behaviour is more complex in the case of the amorphous material. 

Let us now turn to a discussion of the relation of the temperature dependence of the polymer melt s configurational entropy with its glass transition and address the famous paradox of the Kauzmann temperature of glass-forming systems.90 It had been found experimentally that the excess entropy of super-cooled liquids, compared with the crystalline state, seemed... 

Shrinkage and coefficient of thermal expansion are those of semi-crystalline polymers, that is to say, rather high. The absorption and swelling by moisture exposure are high (see Figure 4.54). Creep depends on reinforcement, moisture content and temperature. 

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