Search

Abstract: The perfection, reorganization, and isotropization of the mesophase of isotactic polypropylene were investigated by fast scanning calorimetry (FSC). The analysis was made at different heating rates, to evaluate the isotropization temperature of the initially grown mesophase and of mesophase which has been perfected or even reorganized into crystals. Mesophase formation is paralleled by formation of a rigid–amorphous fraction which was about twice the mesophase content. While the isotropization temperature of the initially grown mesophase is controlled by the temperature of its formation, the isotropization temperature of perfected or reorganized mesophase was independent on the condition of prior formation. Absence of exothermic heat flow during heating suggests that the mesophase converted gradually into crystals due to the fast heating rate. The discussion of data includes new ideas about nucleation, growth, and perfection of the mesophase, involving nanophase to microphase and rigid–amorphous fraction to mesophase transitions. [Copyright &y& Elsevier]

Phases may be smaller than visible to the human eye. In order to characterize a microphase, a phase smaller than 1 μm, one must consider surface area and free energy in addition to the standard thermodynamic functions. As one approaches nanometer sizes, one also needs to know the changing thermodynamic functions within the phases. The Gibbs-Thomson equation can be used to characterize microphases, but not nanophases. For the latter, the glass transition is needed to assess the properties in the interior. In order to classify condensed phases as liquid, solid, mesophase, or crystal, one needs to consider the molecular motion in addition to the molecular structure. Most important are large-amplitude displacements in form of translation, rotation, and conformational motion. An operational definition based on experiments and an updated classification of the phases is given. The surprising result is the observation that crystals, earlier assumed prime examples of solids, can have order-disorder transitions to more mobile mesophases, as well as a glass transition without change in crystal structure, i.e., under certain condition, they cannot be identified as a solid. To these observations, one has to add the fact that large-amplitude motion may start gradually to a more mobile phase without abrupt changes in structure. These observations limit the usefulness of the 80-year-old classification of transitions as being of first or second order. Quantitative thermal analysis is shown to be an important tool to identify the possible total of 57 different condensed states in terms of their macroscopic properties as well as molecular structure and motion. [ABSTRACT FROM AUTHOR]

Abstract: A number of discussion points are raised concerning the nonequilibrium melting and crystallization as described in the paper by Sommer and Reiter.1 [Copyright &y& Elsevier]

Abstract: The influence of the surface on the thermodynamics of the melting and glass transition of films and fibers is negligible as long as the dimension of the phase is macroscopic, i.e., is more than 1μm in all directions. The influence of the surface on microphases was discovered at the beginning of the 20th century, and is presently developing into the central topic for the description of hard and soft nanophase materials. The central issues of the thermal analysis of films and fibers, thus, are: the assessment of small sample masses, the evaluation of the nature of the surface, the treatment of irreversible phase structures, and the use of fast measurements to avoid reorganization of the metastable material without loss of precision. A short history of the roots of calorimetry of such small systems is used to arrive at a thermodynamic description of linear macromolecules in the amorphous state and, when partially crystallized, in the macroscopic, globally metastable structure which consists of multiple nanophases. [Copyright &y& Elsevier]

The heat capacity of poly(lactic acid) (PLA) is reported from T=(5 to 600) K as obtained by differential scanning calorimetry (d.s.c.) and adiabatic calorimetry. The heat capacity of solid PLA is linked to its group vibrational spectrum and the skeletal vibrations, the latter being described by a Tarasov equation with Θ1=574 K, Θ2=Θ3=52 K, and nine skeletal vibrations. The calculated and experimental heat capacities agree to ±3% between T=(5 and 300) K. The experimental heat capacity of liquid PLA can be expressed by Cp(liquid)=(120.17+0.076T) J · K-1 · mol-1 and has been compared to the ATHAS Data Bank, using contributions of other polymers with the same constituent groups. The glass transition temperature of amorphous PLA occurs at T=332.5 K with a change in heat capacity of 43.8 J · K-1 · mol-1. Depending on thermal history, semi-crystalline PLA has a melting endotherm between T=(418 and 432) K with variable heats of fusion. For 100% crystalline PLA, the heat of fusion is estimated to be (6.55 ± 0.02) kJ · mol-1 at T=480 K. With these results, the enthalpy, entropy, and Gibbs function of crystalline and amorphous PLA were obtained. For semi-crystalline samples, one can check changes of crystallinity with temperature and judge the presence of rigid-amorphous fractions. [Copyright &y& Elsevier]

Linear, flexible macromolecules are long recognized as phase structures limited to micrometer and nanometer dimensions with covalent bonds crossing the interfaces. This special, usually non-equilibrium structure leads to unique properties and a multitude of changes for different thermal and mechanical histories. Analyses that enable the study of these properties are temperature-modulated calorimetry and related techniques which allow the separation of equilibrium and non-equilibrium responses. Research on these topics is reviewed and combined to a model for the nanophases. The new approach to the complex nanophase systems yields a better understanding of the relationship between structure and thermodynamic properties. Special emphasis is placed on the size and surface effects on the glass and melting transitions, the development of rigid-amorphous phases, and the reversible melting within the globally metastable structure. [Copyright &y& Elsevier]