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Over the years, there has been a steady stream of publications on the influence that minor components and additives have on the physical properties of fat continuous systems. These have been reviewed here. Both indigenous and added components are taken into account. The various materials have been discussed, ranging from partial glycerides and phospholipids to esterified sugars and polyols. Within the publications in this area, the (sub-)micron effects that these minor components have on nucleation, crystal growth, morphology, heat capacity and polymorphic stability have been described and discussed and, sometimes, explained. Similarly, the effects on a macroscopic level, such as visual aspects, melting profiles, posthardening and rheology have been the subject of research. Although limited compositional information, especially of additives, hinders appropriate discussions of the relevant mechanisms, some generic guidelines as to what type and strength of effect can be expected have been derived. As a general rule, a more significant influence is observed when the acyl group of the minor component (where present) is similar to those present in the fat itself. Additives may have different effects depending on the fat they are added to, their concentration and the temperature, especially with increasing undercooling (which typically reduces the effect of additives).

The crystallization behavior of milk fat was investigated by varying the cooling rate and by isothermal solidification at various temperatures while monitoring the formation of crystals by differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD). Three different polymorphic crystal forms were observed in milk fat: γ, α, and β′. The β-form, occasionally observed in previous studies, was not found. The kind of polymorph formed during crystallization of milk fat from its melted state was dependent on the cooling rate and the final temperature. Moreover, transitions between the different polymorphic forms were shown to occur upon storing or heating the milk fat. The characteristic DSC heating curve of milk fat is interpreted on the basis of the XRD measurements, and appears to be a combined effect of selective crystallization of triglycerides and polymorphism.Milk fat is one of the main constituents of milk and determines the specific properties of butter and cream. It is also an important ingredient in many bakery and confectionery industry applications. The various applications require different properties of milk fat, which in turn requires improved functionality control. The functional properties of milk fat are strongly related to the amount and type of milk-fat crystals at the temperature of application. The crystalline part of the fat determines to a large extent the firmness of products in which fat is present as the continuous phase, such as butter and butter oil, and the stability of products containing an emulsion of milk fat, such as cream. Milk fat has a broad melting range due to a large number of triglycerides with a wide range of chain lengths and degrees of saturation. Moreover, the phase behavior is complicated because of the polymorphism of the solid phase.Polymorphism of the crystallized phase is a general feature of triglycerides. The different polymorphic forms can be identified by X-ray diffraction (XRD). The polymorphic forms are characterized by the d-spacings (short-spacings) of the crystal lattices (typically between 3 and 6 Å) as observed in XRD patterns, which correspond to the distances associated with the lateral packing of the fatty acid hydrocarbon chains. Polymorphs with similar packing of the fatty acid hydrocarbon chains were found for pure tristearin (1), and for natural oils and fats (2), including milk fat (3). The d-spacings are characteristic for the type of polymorph, and this has led to the nomenclature given by Larsson (4) that is now widely accepted. Table 1 lists the d-spacings of the polymorphs of triglycerides (2). In general, the stable polymorph of triglycerides is either a β′-or a β-crystal form. The density of the β-crystal form is higher than that of the β′-crystal form, and this leads to more severe packing constraints for the first form as compared with the latter (5). As a result, asymmetrical triglycerides, i.e., triglycerides of the SSU or UUS type, in which the single unsaturated (U) or saturated (S) fatty acid resides in either the sn-1 or ...

The crystal structure of the beta polymorph of tripalmitin (1,2,3-trihexadecanoylglycerol, beta-PPP) has been determined by single-crystal X-ray diffraction. The molecules crystallize in space group P1; in an asymmetric tuning-fork conformation. This structure and the already-known crystal structures of beta-tricaprin (beta-CCC) and beta-trilaurin (beta-LLL) could be matched in an overlap model. Apart from a difference in chain length, the three structures are almost identical. The overlap model can be used to predict the crystal structure of the other members of the C(n)C(n)C(n)-type (n = even) TAG series reasonably accurately. This is demonstrated by predicting the crystal structure for beta-trimyristin (beta-MMM) and successively comparing the experimental and calculated X-ray powder diagrams.

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