We examined the promotional effects of additives on fat crystallization, such as inorganic (talc, carbon nanotube (CNT), and graphite) and organic (theobromine, ellagic acid dihydrate (EAD), and terephthalic acid) materials. The triacylglycerols (TAGs) of trilauroylglycerol (LLL), trimyristoylglycerol (MMM), and tripalmitoylglycerol (PPP) were employed as the fats. The additives (1 wt%) were added to the molten TAGs, and then the mixtures were cooled at a rate of 1°C/min followed by heating at a rate of 5°C/min. The crystallization and melting properties were observed using differential scanning calorimetry, X-ray diffraction, and polarized optical microscope (POM). Consequently, we found that the above six additives remarkably increased the initial temperatures of crystallization (Ti) on cooling without changing the melting temperatures. For example, in the case of LLL, the increases in Ti were 2.6°C (talc), 3.9°C (CNT), 8.1°C (graphite), 1.1°C (theobromine), 2.0°C (EAD), and 6.8°C (terephthalic acid). Very similar effects were observed for the crystallization of MMM and PPP with the six additives. Furthermore, the polymorphs of the first occurring crystals were changed from metastable to more stable forms by many of these additives. The POM observation revealed that the crystallization was initiated at the surfaces of additive particles. This study has shown for the first time that the heterogeneous nucleation of fat crystals can be greatly promoted by new types of additives. Such additives have great potential to promote fat crystallization by not only hydrophobic but also hydrophilic molecular interactions between the fats and additives.

Polymorphic crystallization of cocoa butter (CB) in a bulk system was examined for the influence of adding talc particles at different concentrations (0.1–5%). While the system was cooled from the melt and subsequently heated, changes in the heat flow and crystal structure of CB were analyzed using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD). Synchrotron radiation microbeam X-ray diffraction (SR-μ-XRD) was employed to determine lamellar-plane directions of CB crystals occurring with talc addition. At any cooling rates (0.1–15 °C/min) applied, talc promoted CB crystallization to elevate the onset crystallization temperature logarithmically with the increasing concentration of talc; this effect became more prominent at higher cooling rates. Talc also acted as a polymorphic stabilizer so that CB crystallized in more stable forms even when cooled at highest rate of 15 °C/min. Moreover, a highly ordered lamellar-plane direction was extensively observed for CB crystals occurring with 0.1% talc addition, which was disturbed by 0.5% talc addition probably due to the spatial dispersion of densely populated talc particles in their randomized orientation. These heterogeneous nucleation effects indicate the potential of talc particles to be used for the quality and productivity control of CB-based products.

This paper reports the precise analysis of the eutectic mixing behavior of 1,3-distearoyl-2-oleoyl-sn-glycerol (SOS) and trilaurin (LLL), as a typical model case of the mixture of cocoa butter (CB) and cocoa butter substitute (CBS). SOS was mixed with LLL at several mass fractions of LLL (w_LLL); the mixtures obtained were analyzed for polymorphic phase behavior using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffractometry (SR-XRD). In melt crystallization with constant-rate cooling, SOS and LLL formed eutectics in their metastable polymorphs, allowing the occurrence of a compatible solid solution at w_LLL ≥ 0.925. With subsequent heating, the resultant crystals transformed toward more stable polymorphs, then melted in a eutectic manner. For mixtures aged at 25 °C after melt crystallization, eutectics were found in the extended w_LLL region, even at w_LLL = 0.975. These results indicate that phase separation between SOS and LLL progressed in their solid solution under stabilization. The crystal growth of the separated SOS fraction may cause fat-bloom formation in compound chocolate containing CB and CBS. To solve this problem, the development of retardation techniques against phase separation is expected.