Solvent-Modulated Nucleation and Crystallization Kinetics of 12-Hydroxystearic Acid: A Nonisothermal Approach

• Published in: Langmuir Vol. 25; no. 15; pp. 8556 - 8566
• Main Authors: Rogers, Michael A, Marangoni, Alejandro G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.08.2009
• Subjects: Algorithms; Calorimetry, Differential Scanning - methods; Chemistry - methods; Crystallization; Glycerol - chemistry; Kinetics; Light; Materials: Nano-and Mesostructured Materials, Polymers, Gels, Liquid Crystals, Composites; Models, Statistical; Oleic Acids - chemistry; Probability; Solvents - chemistry; Stearates - chemistry; Succinates - chemistry; Surface Properties; Temperature; Thermodynamics; Time Factors
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la8035665

The solvent type strongly affects the nucleation behavior of 12HSA and therefore strongly influences the peak nucleation rate, fiber length, spatial distribution of mass, and degree of branching. Using nonisothermal kinetic models, a correlation was established among the activation energy of nucleation, fiber length, and induction time of 12HSA nucleation in different solvents. However, there was no correlation between any measurable parameter and solvent polarity. Activation energies varied from 2.2 kJ/mol in methyl oleate to 15.8 kJ/mol in glycerol. Nucleation behavior and structure were strong functions of the cooling rate, with distinct regions observed above and below 5−7 °C/min for fiber length, induction time, rate constant, and peak nucleation rate. The abrupt changes in the rate of nucleation, crystal growth rate constant, and degree of branching around this cooling rate are related to whether the nucleation and crystal growth processes are governed by mass transfer or thermodynamics. Furthermore, the Avrami equation accurately predicted several structural features of the fibrillar network such as fiber length and, to a lesser extent, induction time.