Narrow molecular weight fractions of Poly(ε-caprolactone) were successfully obtained using the successive precipitation fractionation technique with toluene/n-heptane as a solvent/nonsolvent pair. Calorimetric studies of the melting behavior of fractions that were crystallized either isothermally or under constant cooling rate conditions suggested that the isothermal crystallization of the samples should be used for a proper evaluation of the molecular weight dependence of the observed melting temperature and degree of crystallinity in PCL. The molecular weight and temperature dependence of the spherulitic growth rate of fractions was studied in the context of the Lauritzen-Hoffman two-phase model and the Strobl three-phase model of polymer crystallization. The zero-growth rate temperatures, determined from spherulitic growth rates using four different methods, are consistent with each other and increase with chain length. The concomitant increase in the apparent secondary nucleation constant was attributed to two factors. First, for longer chains there is an increase in the probability that crystalline stems belong to loose chain-folds, hence, an increase in fold surface free energy. It is speculated that the increase in loose folding and resulting decrease in crystallinity with increasing chain length are associated with the ester group registration requirement in PCL crystals. The second contribution to the apparent nucleation constant arises from chain friction associated with segmental transport across the melt/crystal interface. These factors were responsible for the much stronger chain length dependence of spherulitic growth rates at fixed undercooling observed here with PCL than previously reported for PE and PEO. In the case of PCL, the scaling exponent associated with the chain length dependence of spherulitic growth rates exceeds the upper theoretical bound of 2 predicted from the Brochard-DeGennes chain pullout model. Observation that zero-growth and equilibrium melting temperature values are identical with each other within the uncertainty of their determinations casts serious doubt on the validity of Strobl three-phase model. A novel method is proposed to determine the Porod constant necessary to extrapolate the small angle X-ray scattering intensity data to large scattering vectors. The one-dimensional correlation function determined using this Porod constant yielded the values of lamellar crystal thickness, which were similar to these estimated using the Hosemann-Bagchi Paracrystalline Lattice model. The temperature dependence of the lamellar crystal thickness was consistent with both LH and the Strobl model of polymer crystallization. However, in contrast to the predictions of Strobl’s model, the value of the mesomorph-to-crystal equilibrium transition temperature was very close to the zero-growth temperature. Moreover, the lateral block sizes (obtained using wide angle X-ray diffraction) and the lamellar thicknesses were not found to be controlled by the mesomorph-to-crystal equilibrium transition temperature. Hence, we concluded that the crystallization of PCL is not mediated by a mesophase. Metallocene-catalyzed linear low-density (m-LLDPE with 3.4 mol% 1-octene) and conventional low-density (LDPE) polyethylene blends of different compositions were investigated for their melt-state miscibility and concurrent crystallization tendency. Differential scanning calorimetric studies and morphological studies using atomic force microscopy confirm that these blends are miscible in the melt-state for all compositions. LDPE chains are found to crystallize concurrently with m-LLDPE chains during cooling in the m-LLDPE crystallization temperature range. While the extent of concurrent crystallization was found to be optimal in blends with highest m-LLDPE content studied, strong evidence was uncovered for the existence of a saturation effect in the concurrent crystallization behavior. This observation leads us to suggest that co-crystallization, rather than mere concurrent crystallization, of LDPE with m-LLDPE can indeed take place. Matching of the respective sequence length distributions in LDPE and m-LLDPE is suggested to control the extent of co-crystallization. / Ph. D.

The crystallization and melting behavior of linear polyethylene and of a series of random ethylene/styrene copolymers was investigated using a combination of classical and temperature modulated differential scanning calorimetry. In the case of linear polyethylene and low styrene content copolymers, the temporal evolutions of the melting temperature, degree of crystallinity, and excess heat capacity were studied during crystallization. The following correlations were established: 1) the evolution of the melting temperature with time parallels that of the degree of crystallinity, 2) the excess heat capacity increases linearly with the degree of crystallinity during primary crystallization, reaches a maximum during the mixed stage and decays during secondary crystallization, 3) the rates of shift of the melting temperature and decay of the excess heat capacity lead to apparent activation energies that are very similar to these reported for the crystal ac relaxation by other techniques. Strong correlations in the time domain between the secondary crystallization and the evolution of the excess heat capacity suggest that the reversible crystallization/melting phenomenon is associated with molecular events in the melt-crystal fold interfacial region. In the case of higher styrene content copolymers, the multiple melting behavior at high temperature is investigated through studies of the overall crystallization kinetics, heating rate effects and partial melting. Low melting crystals can be classified into two categories according to their melting behavior, superheating and reorganization characteristics. Low styrene content copolymers still exhibit some chain folded lamellar structure. The shift of the low melting temperature with time in this case is tentatively explained in terms of reorganization effects. Decreasing the crystallization temperature or increasing the styrene content leads to low melting crystals more akin to fringed-micelles. These crystals exhibit a lower tendency to reorganize during heating. The shift of their melting temperature with time is attributed to a decrease in the conformational entropy of the amorphous fraction as a result of constraints imposed by primary and secondary crystals. To further understand the mechanism of formation of low melting crystals, quasi-isothermal crystallization experiments were carried out using temperature modulation. The evolution of the excess heat capacity was correlated with that of the melting behavior. On the basis of these results, it is speculated that the generation of excess heat capacity at high temperature results from reversible segmental exchange on the fold surface. On the other hand, the temporal evolution of the excess heat capacity at low temperature for high styrene content copolymers is attributed to the reversible segment attachment and detachment on the lateral surface of primary crystals. The existence of different mechanisms for the generation of excess heat capacity in different temperature ranges is consistent with the observation of two temperature regimes for the degree of reversibility inferred from quasi-isothermal melting experiments. In a second project, the chain length and temperature dependences of spherulitic growth rates were studied for a series of narrow fractions of poly(ethylene oxide) with molecular weight ranging from 11 to 917 kg/mol. The crystal growth rate data spanning crystallization temperatures in regimes I and II was analyzed using the formalism of the Lauritzen-Hoffman (LH) theory. Our results are found to be in conflict with predictions from LH theory. The Kg ratio increases with molecular weight instead of remaining constant. The chain length dependence of the exponential prefactor, G0, does not follow the power law predicted by Hoffman and Miller (HM). On this basis, the simple reptation argument proposed in the HM treatment and the nucleation regime concept advanced by the LH model are questioned. We proposed that the observed I/II regime transition in growth rate data may be related to a transition in the friction coefficient, as postulated by the Brochard-de Gennnes slippage model. This mechanism is also consistent with recent calculations published by Toda in which both the rates of surface nucleation and substrate completion processes exhibit a strong temperature dependence. / Ph. D.