Marie Emmanuelle, Chevalier Yves, Eydoux Franck, Germanaud Laurent, Flores Philippe
Laboratoire des Matériaux Organiques à Propriétés Spécifiques, UMR 5041 CNRS, Université de Savoie, BP 24, F-69390 Vernaison, France.
J Colloid Interface Sci. 2005 Oct 15;290(2):406-18. doi: 10.1016/j.jcis.2005.04.054.
The crystallization of paraffins from their solution at low temperature was investigated in the presence of ethylene-vinyl acetate (EVA) copolymers that allow the control of the size of the crystals. Depending on the type of solvent and distribution of the paraffin lengths, the mechanisms of crystal formation and growth are different. Precipitation of the EVA prior to the paraffins leads to the nucleation of a large number of crystals, whereas the adsorption of EVA on the surface of the growing crystals slows down the crystal growth. EVA can act either as a nucleating agent or as a growth inhibitor. These two mechanisms were identified from the analysis of the temperature of crystallization (cloud point), the chemical composition of the crystals, and the observations of the crystal habit. The EVA was able to co-crystallize with the paraffins in crystals of an orthorhombic structure and the melting enthalpies of the crystalline paraffin did not depend significantly on their neighborhood. The energies of interaction between the different paraffinlike components are close to each other, so that minor changes of the experimental conditions may lead to dramatic effects. This is the basic rationale for the large behavioral diversity observed in these systems.
在乙烯-醋酸乙烯酯(EVA)共聚物存在的情况下,研究了石蜡在低温下从其溶液中的结晶过程,EVA共聚物可控制晶体尺寸。根据溶剂类型和石蜡长度分布,晶体形成和生长的机制不同。EVA在石蜡之前沉淀会导致大量晶体成核,而EVA在生长晶体表面的吸附会减缓晶体生长。EVA既可以作为成核剂,也可以作为生长抑制剂。通过对结晶温度(浊点)、晶体化学成分以及晶体习性观察的分析,确定了这两种机制。EVA能够与石蜡在正交结构的晶体中共结晶,结晶石蜡的熔化焓并不显著取决于其相邻环境。不同类石蜡组分之间的相互作用能彼此接近,因此实验条件的微小变化可能会导致显著影响。这就是在这些体系中观察到巨大行为多样性的基本原理。