## 3 Results and Discussion  
### Crystallization Behavior  
Figure 1 depicts the wide angle X-ray difractograms of neat waves. Most waves showed a degree of crystallinity (DC) ranging from 67 to 71%, except for beewax (BEW). The lower DC in BEW is attributed to the poor crystal network ordering of the solid phase, due to the diverse presence of esters, fatty acids (FAs) and hydrocarbons (HCs). The last two families of compounds introduced a greater disorder conferring the lowest melting temperature of 37.8 \({}^{\circ}\)C (Table 2). Thus, BEW had the weakest and less stable crystal structure. On the contrary, carnauba wax (CRW) has virtually no hydrocarbon compounds prevailing wax ester (WEs) compounds, rendering a more ordered system resulting in a large DC and melting temperature (82 \({}^{\circ}\)C). All of the waves exhibited very similar wide angle diffraction patterns with one strong reflection (110) peak at 0.28 nm, followed in intensity by a second peak at 0.31 nm (200). The (110) reflection peak corresponds to a triple chain length stacking (3L), while the other peak (200) is indicative of a 2L packing. These results indicate a \(\beta\) orthorhombic crystalline sub-cell arrangement that is known to be the most stable allomorph [17]. Figure 1: Wide angle X-ray diffraction for waxy emulsifiers. (**A**). carnauba wax, (**B**). candellila wax, (**C**). beewax, (**D**). ozokerite wax, (**DC**). Degree of crystallinity. Figure 2 depicts the thermograms that result from the crystallization profile (dotted lines) and melting profile (straight lines) of the neat waves (left panel) and their matrix systems (right panel). The presence of different peaks is related to the heterogeneous chemical nature of the lipidic matrixes. For instance, CRW is mainly composed by several types of WEs forming one large and wide melting event, whereas other materials, such as BEW and candelilla wax (CLW), also had a considerable amount of low molecular weight HCs, FAs, and fatty alcohols (FAIs), which resulted in melting events at lower temperatures. Thus, BEW showed a broad and intense melting peak at 37.8 \({}^{\circ}\)C due to the short-chain FAs, mostly stearic acid C\({}_{18}\), oleic acid C\({}_{18:1}\), and palmitic acid C\({}_{16}\), whereas at 57.9 \({}^{\circ}\)C showed a broad band probably attributed to the long chain WEs and HCs fraction. Interestingly, neat OKW is considered to be a mono-component wax, mainly comprised in 92% of HCs (Table 1), which explains the intense and narrow melting peak at a high temperature (76.6 \({}^{\circ}\)C) probably attributed to ceresin and resin fractions. Conversely, CLW exhibited two intense endothermic peaks at 29.3 and 67.4 \({}^{\circ}\)C, which could be due to melting of low molecular weight FAs and FAls fractions, and mid melting point compounds, such as HCs and WEs, respectively. Further, OKW showed a large fusion enthalpy that was attributed to the small steric interference of ceresin cyclic rings, petroleum resins, and alkane compounds favoring the formation of a compact structure. On the other hand, the crystallization peaks of neat waxes were smaller in magnitude than the melting peaks. The presence of more than a single exothermic peak is also a result of the heterogeneous chemical composition. BEW, CRW, and OKW upon cooling crystallize, showing small bands without co-crystallization. Thus, crystallization in two different stages is a consequence of the degree of crystalline disorder, since, first, a group of compound crystals (mainly long chain WEs) is formed at a high temperature (68-71 \({}^{\circ}\)C), and then at a lower amount of energy a second arrangement by another set of compounds complete the crystal network. This could result from hindered crystal growth, due to the low compatibility between major and minor components. The second and most important exothermic peak of BEW and CRW is shown at 53.9 and 61.5 \({}^{\circ}\)C, respectively, being possibly ascribed to the crystallization of the FAc and FAl fraction, respectively [24].