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Scanning Microbeam Small-Angle X-ray Diffraction Study of Interfacial Heterogeneous Crystallization of Fat Crystals in Oil-in-Water Emulsion Droplets

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journal contribution
posted on 01.09.2009 by S. Arima, S. Ueno, A. Ogawa, K. Sato
We performed scanning microbeam small-angle X-ray diffraction (μ-SAXD) experiments, differential scanning calorimetry (DSC) analysis, and optical microscopic observation of palm mid fraction (PMF) crystals in oil-in-water emulsion droplets. The scanning μ-SAXD experiment was performed by irradiating a synchrotron radiation X-ray microbeam having an area of 5 × 5 μm2 onto different positions on a 50 μm diameter emulsion droplet after the crystallization of PMF by chilling the emulsion at 5 °C. The μ-SAXD patterns were recorded with a two-dimensional (2D) detector, which enabled spatial analysis of polymorphic structures and the orientation of lamella planes of PMF crystals at different positions inside the emulsion droplet. Particular attention was paid to compare the crystallization of PMF in two types of emulsion droplets, hydrophilic polyoxyethylene sorbitan mono-oleate (Tween 80) alone (Tween 80 emulsion) and Tween 80 and hydrophobic sucrose palmitic acid oligoester (P-170) (Tween 80+P-170 emulsion). The DSC study revealed that the PMF crystallization temperature in the Tween 80+P-170 emulsion droplets increased by 3 °C compared to that of the Tween 80 emulsion because of the effects of the P-170 additive in promoting PMF crystallization. The μ-SAXD studies revealed the following results. (1) The lamella planes of PMF crystals near the outer edges of the droplet in the Tween 80+P-170 emulsion were mostly parallel to an oil−water interface, whereas the lamella planes of PMF crystals were not always aligned with the oil−water interface in the Tween 80 emulsion droplet. (2) The degree of orientation of the lamellar planes of PMF crystals, which was evaluated from the values of full width at half-maximum of 2D μ-SAXD patterns with respect to azimuthal angle extension, was remarkably higher in the Tween 80+P-170 emulsion than in the Tween 80 emulsion. (3) Polymorphic transformation of PMF from α to β′ in the Tween 80+P-170 emulsion was retarded compared to that in the Tween 80 emulsion. These results confirmed that the P-170 additive caused interfacial heterogeneous nucleation through hydrophobic interactions at the oil−water interfaces in the emulsion, which subsequently influenced the arrangements of fat crystals so that the lamellar planes of fat crystals were parallel to the oil−water interface.