Crystallization kinetics study on higher homologues of benzylidene aniline compounds: impact of phase variant on nucleation process

Abstract

A systematic kinetic study leading to the crystallization process from the kinetophases (which occur prior to crystal phase) smectic B, crystal G and smectic F is performed on representative compounds of the homologous series p -phenylbenzylidene-p′-alkylanilines (PBnA) and p-n -alkoxybenzylidene-p′-alkylanilines (nO.m) these compounds are p-phenylbenzylidene-p′-nonylaniline (PB9A), p -phenylbenzylidene-p′-tetradecylaniline (PB14A), p-n -pentadecyloxybenzylidene p′-tetradecylaniline (15O.14) and p-n -octadecyloxybenzylidene-p′-nonylaniline (18O.9). The molecular mechanism and dimensionality in crystal growth from the kineto phases are computed from the Avrami equation, while the characteristic crystalline time (t ^*) at each crystallization temperature is deduced from the individual plots of log t vs. Δ H. The low magnitudes of the dimensionality parameter n infers the occurrence of diffusion-controlled transformations leading to the formation of plates or needles of finite size possessing impinged edges. The degree of variation in the value of n at each crystallization temperature also reveals the existence of an independent nucleation mechanism for any individual member of the series. The influence of the terminal alkyl chain lengths on the rate of crystallization is determined from a comparative study with the reported analogous compounds.