3.1. Color Parameters of Cream-Type Emulsions
Due to the fact that color is the first food feature assessed by the consumer, it was examined how the modification of the lipid phase influenced the color of cream-type emulsions. The color of the emulsion depends on its ability to scatter and absorb light. This is related to the composition and structure of the emulsions as well as destabilization processes [
3,
69]. Interestingly, the physical properties of O/W emulsions are contingent upon the characteristics of the lipids used in the internal phase [
2].
The visual appearance of the cream-type emulsions is shown in
Figure 1 and described by color coordinates in
Table 1. All tested formulations reached equally high brightness (
p-value > 0.05); the values of the
L* coordinate exceeded 90. High
L* values of milk products and milk-like counterparts are connected with the efficiency of ultrasound treatment and the reduction of lipid particles to smaller sizes [
70].
Moreover, the type of lipid phase did not affect the differences in the
a* values (close to 0). In contrast, EC3-5 were characterized by significantly lower
b* values compared to EP. The mean values of the
b* coordinate, which is indicative of the yellowness, varied between 8.61 and 9.26 (
Table 1). Chudy et al. [
52] emphasized that a positive
b* value is a typical feature of the natural color of dairy products.
On the basis of the color components
L*,
a*, and
b*, the whiteness indexes (
WI) and the total color differences in relation to palm oil-based emulsion (Δ
EEP) were determined (
Table 1). The oleogel-based creams were characterized by a slightly higher value of
WI compared to EP. The cause of this observation may be related to the differences in the structure of lipid particles (due to the presence of wax at the interface), causing distinctions in light absorption. A similar tendency was noticed by Javidi et al. [
70], who studied the color of low-fat emulsions with waxy cornstarch nanocrystals used as a fat substitute.
The mean values of Δ
EEP, which ranged from 0.27 to 0.70, indicated no visible differences in color between EP and oleogel-based emulsions. As demonstrated by Chudy et al. [
52], at Δ
E < 1.0, color differences may be imperceptible even to an experienced observer. Thus, it can be assumed that such modification of the lipid phase does not cause changes in the appearance of the potential product, which is the first feature that the consumer evaluates when making a purchasing decision [
71,
72].
Although the examined formulations do not differ in terms of macroscopic appearance, they could show dissimilar internal characteristics. Therefore, in the following part of this research, the emulsions were subjected to microstructural, rheological, and stability analyses.
3.2. Microstructure of Cream-Type Emulsions
The size of dispersed particles is one of the basic indicators of the stability of O/W-type emulsions [
3]. Therefore, the cumulative and differential % number distributions (
Figure 2) show the individual patterns of lipid particle size span in each emulsion tested. The cumulative particle size distribution, i.e., the sum of the differential distributions, appeared as single S-shaped curves with quite steep positive slopes in the middle of the particle size range. The dispersed particles of all the formulations ranged from 0.6 to 6.3 µm in size. The particle size distributions seem to be unimodal with a major contribution of the lipid particles with the sizes less than about 1.6 µm. Differences between emulsions were visible for classes of larger particles, where the slope of the cumulative curves decreased, especially in samples with the highest wax concentration (EC6 and EC7). These systems contain more numerous classes of larger particles (especially in range from 2.1 to 4.0 µm) compared to other emulsified samples. Although all the differential particle size distributions were relatively narrow, they do not have perfectly smooth shape (
Figure 2). This means that the vegan cream-type emulsions have not strong unimodality, irrespective of lipid type incorporated. On the other hand, EC4 and EC5 distinguish from the other samples. Their differential size distributions were shifted to the left, i.e., to lower sizes of lipid particles (
Figure 2). Smaller particles of internal phase usually mean a lower probability of early destabilization of the O/W emulsion [
73]. As shown in
Table 2, the number-weighted mean size of lipid particles in oleogel-based creams with 3–5% candelilla wax (CW) was not significantly different from the palm oil-based emulsion. The use of higher concentrations of wax, i.e., 6–7% for the structuring of oils resulted in an increase in the value of this parameter (
Figure S1). However, the mean particle size is a parameter that is not sufficient to comprehensively conclude about emulsion stability. Therefore, based on the cumulative number distributions of lipid particle size, the
D-values (
DV10,
DV50, and
DV90) were determined, and polydispersity indexes (
PDI) were calculated. The lower value of the polydispersity index, the greater the similarity of the emulsion to the monodisperse system, i.e., showing greater physical stability [
3,
74,
75]. The lowest values of polydispersity indexes (0.80–0.85) were obtained for oleogel-based creams with 3%, 4%, and 5% wax content (EC3–EC5). In turn, creams with other structured lipids (containing 6–7% of CW in a lipid phase) showed significantly higher values of this parameter in comparison with EP (0.92) (
Table 2).
In general, the characteristics of the creams were influenced mainly by the high efficiency of emulsification via ultrasonic homogenization. Whereas the microstructural diversity of vegan creams resulted mainly from the composition and the phenomenon of lipid recrystallization during static cooling. The presence of numerous, large lipid crystals in the emulsion favors the joining of lipid particles into larger aggregates [
3,
76]. As we have shown in another study, palm oil was characterized by the largest lipid crystals compared to candelilla wax-based oleogels [
39]. Higher values of polydispersity indexes for EC6 and EC7 could result from a larger number of crystals compared to other structured lipids. Therefore, it can be concluded that the concentration of candelilla wax in the lipid phase of the emulsion at a level of ≥6%
w/
w hindered the dispersion of structured lipids in the aqueous phase. Munk et al. [
77] proved that after the emulsification of oleogels with the aqueous phase at a temperature above the melting point of these lipids, the original structure of the oleogels is not rebuilt, but most of the molecules of the structuring substance migrate to the lipid-water interface, where they form a shell of lipid particles (
Figure 3).
Based on the above microstructural characteristics of cream-type emulsions, it can be concluded that the concentration of candelilla wax (CW) had a significant effect on the size of dispersed particles and their distribution. The use of 3–5% CW allowed to obtain the O/W emulsions with similar microstructural properties to the palm oil-based emulsion. Higher CW concentrations contributed to presumably worse properties. Nevertheless, this could be explained by further research involving rheological analyses.
3.3. Rheological Characteristics of Cream-Type Emulsions
In order to comprehensively assess the rheological behavior of cream-type emulsions, both non-invasive and invasive techniques were used. Firstly, the samples were examined in their natural (undamaged) state. For this purpose, the formulations were subjected to the micro-scale analysis by means of the non-invasive diffusing wave spectroscopy method, which is based on the migration of particles due to Brownian motion [
59]. The evolution of Mean Square Displacement (
MSD) in the function of decorrelation time was determined for each sample. It allows to characterize the viscous and viscoelastic properties of the creams. The linear increase in the
MSD value informs about the free movement of particles, which is characteristic of a “purely viscous” system [
78,
79].
Figure 4 shows the
MSD curves of all cream-type emulsions 24 h after production. The curves resemble a straight line. Thus, it was concluded that all the creams exhibited liquid behavior. Similar conclusions were reached by Xu et al. [
79], analyzing the microrheological properties of O/W emulsions stabilized with whey protein isolate with the addition of 0.1%, 0.2%, or 0.3%
w/
w or without the addition of the linseed gum.
The palm oil-based cream (EP) did not differ from the oleogel-based cream with 3% candelilla wax (EC3) in terms of the average elasticity index (
EI). Other oleogel-based creams (EC4–7) were characterized by higher EI values compared to the above-mentioned samples. There was no significant relationship between the CW concentration in the lipid phase and the average elasticity index of the cream-type emulsions. The EC5 was characterized by the greatest microstructural elasticity, i.e., about two times higher than EP (
Table 3). It was found that the cream-type emulsion with 5% CW in the dispersed phase had the highest degree of packing of molecules in the internal structure as well as greater physical stability. According to Degrand et al. [
56] and Medronho et al. [
80], the increase in the elasticity of the system may be associated with a reduction in the size of lipid particles and, at the same time, an increase in the number of these particles, limiting the free movement in the structure.
The mean values of the coefficient of solid–liquid balance (
SLB) of tested creams were above 0.5 (
Table 3), which confirms that the liquid-like behavior of these samples was dominant [
59]. The lowest
SLB values were obtained via EC6 and EC7 (
Table 3). Thus, it was noticed that the concentration of candelilla wax had a significant influence on the microrheological properties of oleogel-based creams. Moreover, a strong positive correlation was found between the mean
SLB values and the flow index
n (
ρ = 0.90;
p-value = 0.0064). Therefore, it can be stated that the higher the
SLB value, the greater the fluidity of the cream-type emulsion. According to Wang et al. [
81], a high
SLB value, which indicates high mobility of dispersed particles, may be related to sedimentation and phase separation of the emulsion.
The type of lipid phase also affected the macroscopic viscosity (at zero shear) of the obtained creams. The oleogel-based emulsion with the lowest wax content (3%
w/
w) was characterized by an approximately 1.5-fold higher
MVI value (2.19 × 10
−5 nm
−2), compared to EP. In addition, an increase in the candelilla wax content in the lipid phase resulted in an increase in the viscosity of the cream-type emulsions. The mean
MVI value for EC7 was about 67% greater compared with EC3 (
Table 3).
After investigating the microrheological properties of the samples using the non-invasive method, they were also subjected to shear forces. As a result, flow curves and viscosity curves were obtained. Increasing the shear rate resulted in a decrease in apparent viscosity (
Figure 5a) and an increase in shear stress (
Figure 5b). However, these changes were not directly proportional. The greatest decrease in viscosity was observed at low shear rates, when the particle flow was turbulent. As flow rates increased, viscosity decreased as shear broke larger particles into smaller particles until the structure became ordered, and at the highest shear rates, the viscosity stabilized at a relatively constant level. Such behavior is typical for non-Newtonian shear-thinning (or pseudo-plastic) fluids. In addition, the shape and course of the flow curves, intersecting the origin of the coordinate system (
Figure 5b), prove that examined formulations did not have a yield point [
82]. The shear thinning phenomenon is associated with a change in the orientation of particles (including proteins) in the direction of the induced flow in order to reduce the friction force. At the same time, weaker intermolecular bonds (e.g., hydrogen, hydrophobic) may be broken and the internal structure of the emulsion irreversibly disturbed [
83]. Additionally, the presence of crystals in the lipid phase of the emulsion is responsible for crystalline particle–particle interactions, which are also favored by their irregular shapes. However, these interactions are relatively unstable and susceptible to mechanical forces [
84]. To express numerically the degree of change in apparent viscosity under shear, coefficients of variation were determined for each emulsion variant. High values of coefficients of variation of apparent viscosity
Vc (>20%) indicated a significant sensitivity of the creams to shear forces. The value of
Vc was higher for the systems with higher initial apparent viscosity, e.g.,
Vc for EC7 it was about twice as high as for EC3 (
Table 4). A similar relationship was also found by Quintana-Martinez et al. [
85], who analyzed the rheological properties of O/W emulsions with different contents of guar gum and lecithin.
Therefore, to expand the rheological properties of cream-type emulsions, the experimental data were described with a power law model with a high degree of fit (
R2 ≥ 0.95). The overall consistency coefficients (
K) and flow indexes (
n) were determined. All the creams were characterized by the value of the flow index
n < 1.0, confirming a non-Newtonian shear-thinning characteristics. Compared to the oleogel-based creams, EP was characterized by a greater fluidity (
Table 4). Zhang et al. [
66] also noted that the oleogel-in-water emulsions showed higher viscosity than traditional emulsions. In turn, the rheological behavior of the oleogel-based creams was sensitive to a change in candelilla wax concentration. When CW content increased, a significant increase in the consistency coefficient and decrease in the flow index were observed (
Table 4). It was mainly due to the increase in viscosity of the lipid phase as a result of the oleogelation [
38]. As reported by Elik et al. [
86] a lower value of
n means a higher degree of shear thinning. Thus, a higher wax concentration could have increased the pseudoplasticity of the emulsion. According to the interpretation proposed by Goyal et al. [
87], EP belongs to emulsions with low pseudoplasticity (0.77–0.80), while EC6 and EC7 be-long to emulsions with high pseudoplasticity (0.56–0.59).
Both non-destructive and destructive analyses allowed for a quite complex characterization and comparison of the rheological properties of cream-type emulsions. The results of non-destructive test showed that the use of candelilla wax for structuring the lipid phase of the O/W emulsion promoted strong intermolecular interactions. In turn, as observed in destructive test, these bonds are sensitive to shear forces, causing significant changes in the macroscopic viscosity of the systems. Therefore, the next step in the research was to analyze the stability of these formulations.