The binary phase behavior of 1,3-dilauroyl-2-stearoyl-sn-glycerol and 1,2-dilauroyl-3-stearoyl-sn-glycerol

The binary phase behavior of purified 1,3-dilauroyl-2-stearoyl-sn-glycerol (LSL) and 1,2-dilauroyl-3-stearoyl-sn-glycerol (LLS) was investigated at a slow (0.1 °C/min) and a relatively fast (3.0 °C/min) cooling rate in terms of melting and crystallization, polymorphism, solid fat content (SFC), hardness and microstructure. Much of the behavior of the system is explained by its polymorphism and the influence of thermal processing. The α-form and the β′-form of a double chain length structure were detected in the mixtures cooled at 3.0 °C/min, whereas only the β′-form was detected in those cooled at 0.1 °C/min. X-ray diffraction data as well as thermodynamic data propose that the most stable phases are promoted by the symmetrical LSL. The measured trends in structural characteristics, thermal properties, SFC, relative hardness and microstructure delimit three groups of mixtures which imply a competition between the stabilizing effect of LSL and disordering introduced by kinetic effects: (a) LLS-rich mixtures with LSL molar fractions (X_LSL) less than 0.3, (b) mixtures with X_LSL clustered around 0.5 and (c) LSL-rich mixtures with X_LSL ≥ 0.7. The balance between ordering and kinetic effects determines the polymorphism of the mixtures, which in turn determines the behavior of the LSL/LLS system. The kinetic phase diagram of the LSL/LLS binary system constructed using heating differential scanning calorimetry thermograms displayed a singularity at the 0.5_LSL molar fraction which delimits two distinct behaviors: eutectic behavior in one region and monotectic behavior in the other. The molecular interactions, as depicted by a non-ideality parameter of mixing obtained from a thermodynamic model based on the Hildebrand equation, suggests an almost ideal mixing behavior and a moderate tendency to the formation of unlike-pairs in the liquid state.