Crystallization Behavior of Cocoa Butter Oil‐in‐Water Nano‐Sized Emulsion in the Presence of Sucrose Ester Additives

ABSTRACT The crystallization behavior in oil‐in‐water (O/W) emulsions has been extensively studied due to its significant influence on product properties and functionality across various fields. The presence of small amounts of emulsifiers, called additives, is known to influence the crystallization and polymorphic behaviors in micrometer‐sized O/W emulsions by modifying the surface nucleation of the oil phase. However, in nanometer‐sized emulsions, the influence of additives requires further investigation. In this study, the influence of hydrophobic additives from sucrose esters (SEs): L‐195, P‐170, and S‐170 on the crystallization behavior of cocoa butter (CB)‐based O/W nano‐sized emulsions was investigated. The results demonstrate that the crystallization of CB nano‐sized emulsions was modified by SE additives. Samples with P‐170 (sucrose palmitic ester) and S‐170 (sucrose stearic ester) crystallized at higher temperatures, meaning that the crystallization of CB was promoted due to the similarity of the molecular structure with the major triacylglycerols in CB. Sample with S‐170, however, transformed from Form II (α) to Form III (β′) at an earlier stage. The stability was also affected, with samples containing SEs exhibiting only a slight increase in particle size after 30 days of storage. Furthermore, the combined effects of hydrophilic emulsifiers and SE additives were also investigated. Compared with the corresponding Tween 20‐based emulsions, the combinations of hydrophilic emulsifiers and SE additives having matching hydrocarbon chain lengths (Tw40 + P170 and Tw60 + S170) increased the crystallization temperature, improved storage stability, and suppressed polymorphic transformation of the CB nano‐sized emulsions.