A full
comprehension of milk fat crystallization is important for
the structural development of dairy products such as butter, ice cream,
and cheese. The influence of triacylglycerol (TAG) composition on
the dynamic of milk fat crystallization and the nanostructure of the
formed crystals was investigated using two chemically different types
of milk fat, namely buffalo and cow milk fats (BMF; CMF). The TAG
composition was determined using liquid chromatography and mass spectrophotometry
(LCMS), whereas differential scanning calorimetry (DSC), small- and
wide-angle X-ray scattering (SAXS and WAXS), and polarized light microscopy
(PLM) were used to characterize the crystallization behavior of the
two milk fats. A total of 37 TAG species were identified in both BMF
and CMF, but in different proportions. In particular, BMF was found
to have a higher amount of low-molecular-weight TAGs in comparison
to CMF. This difference in chemical composition explains the different
kinetics of polymorphic transformation in the two samples. Specifically,
it clarifies the delay in the nucleation of the β′-polymorph
in BMF in comparison to CMF. BMF also showed a higher nucleation rate
due to its higher proportion of saturated TAGs and higher melting
range. Finally, this work presents a novel interpretation of the mechanism
of formation of the β-polymorph (53 Å), which has recently
become the subject of a vivid debate in milk fat crystallization studies.