ABSTRACT
In the last decade, research has focused on examining the fundamental interactions occurring in triglycerides, aiming to comprehend the self-assembly of crystalline nanoplatelets (CNPs) and their role in forming larger hierarchical structures essential for fat functionality. Microscopy research on CNPs frequently requires disruptive preparatory techniques, such as deoiling and sonication, to achieve quantitative outcomes. Conversely, X-ray scattering has proven to be an advantageous method for studying triglycerides, as little sample is needed to quantify the system's hierarchical structures. Specifically, ultra-small-angle X-ray scattering (USAXS) has emerged as a fitting technique for studying CNPs, owing to its length scale range falling between 25 nm and 3.49 µm. In this study, we characterized four different 30% fat dilutions of stearic acid-based fats in triolein, with various purities and preparation protocols. Samples were characterized by combining diverse microscopy techniques (cryo-SEM, TEM, polarized light and phase contrast microscopy) with synchrotron-radiation X-ray scattering (WAXS, SAXS, and USAXS). A shape-dependent model for the interpretation of USAXS data is proposed, overcoming some of the drawbacks linked to previously utilized models. CNPs are modeled as polydisperse parallelepipeds, and the aggregates are characterized by fractal dimensionality. This model offers novel insights into CNP cross-section, as well as aggregation. In the long run, we hope that the model will increase our understanding of CNP conformation and interactions, helping us design new fat systems on the mesoscale.
ABSTRACT
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-ß' 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.
ABSTRACT
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.
