The progress of solid-state phase transformations can generally be subdivided into three overlapping mechanisms: nucleation, growth and impingement. These can be modelled separately if hard impingement prevails. On that basis, an overview has been given of recent numerical and analytical methods for determination of the kinetic parameters of a transformation. The treatment focuses on both isothermally and isochronally conducted transformations. To extend the range of transformations that can be described analytically, a number of more or less empirical submodels, which are compatible with experimental results, has been included in the discussion. It has been shown that powerful, flexible, analytical models are possible, once the concept of time or temperature dependent growth exponent and effective activation energy, in agreement with the existing experimental observations, has been adopted. An explicit (numerical) procedure to deduce the operating kinetic processes from experimental transformation-rate data, on the basis of different nucleation, growth and hard impingement mechanisms, has been demonstrated. Without recourse to any specific kinetic model, simple recipes have been given for the determination of the growth exponent and the effective activation energy from the experimental transformation-rate data.
Monolayers of amphiphilic melamine derivatives are good candidates for the formation of supramolecular structures by hydrogen-bonding of nonsurface active species dissolved in the aqueous subphase by molecular recognition. In the present work, the thermodynamic and structural properties of the Langmuir monolayers of a homologous series of a selected amphiphilic melamine-type are characterized. Good candidates for such studies are the decyl, undecyl, and dodecyl homologues of the 2,4-di(n-alkylamino)-6-amino-1,3,5-triazine (2CnH(2n+1)-melamine) monolayers because of their two-phase coexistence region in the accessible temperature range. The characterization of the structural and phase behavior is performed by a combination of surface pressure studies with Brewster angle microscopy (BAM) imaging and Grazing incidence X-ray diffraction (GIXD) measurements. A comprehensive thermodynamic analysis provides good agreement between the experimental surface pressure - area (Pi-A) isotherms and the theoretical curves that were calculated on the basis of equations of state for a large region of monolayer stages developed by us in J. Phys. Chem. 1999, 103, 145. Theoretical curves calculated by application of equations of state only for the fluid monolayer state proposed recently by Rusanov (J. Chem Phys. 2004, 120, 10736) are in good agreement with the experiments in a limited temperature range. A rigorous equation is derived and applied to the experimental results for the calculation of the enthalpy of two-dimensional phase transition. The combination of BAM and GIXD illustrates that the microscopic long range ordering of the condensed monolayer phases is related to the lattice structure of the condensed monolayer.
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