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In many food applications, the mechanical properties of fats play a critical role in determining the processing performance of fat-rich products. In fact, fat crystal networks form a particular class of soft materials that exhibit viscoelastic properties. The uniqueness of the mechanical response is intricately linked to the hierarchical nature of the system, as fats possess a complex architecture encompassing features at different scale levels (i.e., length scales). Since the discovery of crystalline nanoplatelets (CNPs), it has been hypothesized that CNPs are the basic building blocks of lipid networks and that CNPs are the responsible units for the mechanical properties of fats. This hypothesis, however, has only been partially tested. In this article, we examine which units could be responsible (e.g., lamellae, CNP, CNP aggregates) for the mechanical breakdown of fat crystal networks, through Rheo-USAXS in beamline ID02 (ESRF, Grenoble, France). Time-resolved USAXS profiles were acquired during the three steps of a three-interval thixotropy test (3iTT), namely, pre-shear, shear and recovery. The results were then utilized to evidence which specific length scale is arranged (i.e., orientated) during rheological breakdown. The findings suggest that, at the tested shear rates, orientation is only visible from 250 nm onwards, suggesting that the rheological breakdown of triglycerides is primarily driven by the orientation, and possible disruption, of CNP aggregates. These results reveal the critical role of CNP aggregates in the mechanical properties of fats. In the longer term, we believe this study will steer future research toward a more focused understanding of CNP aggregation and disaggregation dynamics.

Palm oil (PO), a semi-solid fat at room temperature, is a popular food ingredient. To steer the fat functionality, sucrose esters (SEs) are often used as food additives. Many SEs exist, varying in their hydrophilic-to-lipophilic balance (HLB), making them suitable for various food and non-food applications. In this study, a stearic–palmitic sucrose ester with a moderate HLB (6) was studied. It was found that the SE exhibited a complex thermal behavior consistent with smectic liquid crystals (type A). Small-angle X-ray scattering revealed that the mono- and poly-esters of the SE have different packings, more specifically, double and single chain-length packing. The polymorphism encountered upon crystallization was repeatable during successive heating and cooling cycles. After studying the pure SE, it was added to palm oil, and the crystallization behavior of the mixture was compared to that of pure palm oil. The crystallization conditions were varied by applying cooling at 20 °C/min (fast) and 1 °C/min (slow) to 0 °C, 20 °C or 25 °C. The samples were followed for one hour of isothermal time. Differential scanning calorimetry (DSC) showed that nucleation and polymorphic transitions were accelerated. Wide-angle X-ray scattering (WAXS) unraveled that the α-to-β′ polymorphic transition remained present upon the addition of the SE. SAXS showed that the addition of the SE at 0.5 wt% did not significantly change the double chain-length packing of palm oil, but it decreased the domain size when cooling in a fast manner. Ultra-small-angle X-ray scattering (USAXS) revealed that the addition of the SE created smaller crystal nanoplatelets (CNPs). The microstructure of the fat crystal network was visualized by means of polarized light microscopy (PLM) and cryo-scanning electron microscopy (cryo-SEM). The addition of the SE created a finer and space-filling network without the visibility of separate floc structures.

Palm oil (PO) is still widely used for the production of all types of food products. Due to its triacylglycerol (TG) composition, PO is semisolid at ambient temperature, offering possibilities for many applications. In order to tailor the fat crystal network for certain applications, it remains imperative to understand the structural build-up of the fat crystal network at the full-length scale and to understand the effect of processing conditions. In this study, PO was crystallized under four temperature protocols (fast (FC) or slow (SC) cooling to 20 °C or 25 °C) and was followed for one hour of isothermal time. A broad toolbox was used to fundamentally unravel the structural build-up of the fat crystal network at different length scales. Wide-angle and small-angle X-ray scattering (WAXS and SAXS) showed transitions from α-2L to β’-2L over time. Despite the presence of the same polymorphic form (β’), chain length structure (2L), and domain size, ultra-small-angle X-ray scattering (USAXS) showed clear differences in the mesoscale. For all samples, the lamellar organization was confirmed. Both cooling speed and isothermal temperature were found to affect the size of the crystal nanoplatelets (CNPs), where the highest cooling speed and lowest isothermal temperature (FC and 20 °C) created the smallest CNPs. The microstructure was visualized with polarized light microscopy (PLM) and cryo-scanning electron microscopy (cryo-SEM), showing clear differences in crystallite size, clustering, and network morphology. Raman spectroscopy was applied to confirm differences in triglyceride distribution in the fat crystal network. This study shows that both cooling rate and isothermal temperature affect the fat crystal network formed, especially at the meso- and microscale.

This research aims to explore the potential of waxes as ingredients in the formulation of food-grade water-in-oleogel emulsions without added emulsifiers. The effects of the wax type, wax concentration and water concentration were tested on systems containing exclusively water, sunflower oil, and wax. Beeswax and carnauba wax were used in the formulation of water-in-oleogel emulsions with 20%, 30% and 40% w/w of water. For the continuous phase, three different levels of wax were used, namely 50%, 100%, and 150% of the critical gelling concentration. More specifically, carnauba wax emulsions were prepared at 2.5%, 5.0% and 7.5% of wax, while concentrations of 0.75%, 1.5% and 2.25% of wax were utilized for the beeswax experiments. Samples were assessed over time regarding stability, rheology and microstructure (polarized light microscopy, cryo-scanning electron microscopy and confocal scanning laser microscopy). Our findings suggest that, if present in sufficient concentration, carnauba wax and beeswax can stabilize emulsions in the absence of additional added emulsifiers. The resulting systems were inherently different based on the wax used, as crystal morphology and droplet configurations are determined by wax type. The yield strain was dictated by the nature of the wax, while the complex modulus was mostly influenced by the wax concentration. To test the scaling-up potential, systems were crystallized in a pilot-scale scraped surface heat exchanger, resulting in notably smaller crystal sizes, reduced rigidity and a storage stability of over one year. These findings represent a starting point for the formulation of scalable water-in-oleogel emulsions without added emulsifiers.