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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) 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.

ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke–Watzky model with slow, continuous nucleation followed by autocatalytic growth.

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.

ZnO inverse opals combine the outstanding properties of the semiconductor ZnO with the high surface area of the open-porous framework, making them valuable photonic and catalysis support materials. One route to produce inverse opals is to mineralize the voids of close-packed polymer nanoparticle templates by chemical bath deposition (CBD) using a ZnO precursor solution, followed by template removal. To ensure synthesis control, the formation and growth of ZnO nanoparticles in a precursor solution containing the organic additive polyvinylpyrrolidone (PVP) was investigated by in situ ultra-small- and small-angle X-ray scattering (USAXS/SAXS). Before that, we studied the precursor solution by in-house SAXS at T = 25 °C, revealing the presence of a PVP network with semiflexible chain behavior. Heating the precursor solution to 58 °C or 63 °C initiates the formation of small ZnO nanoparticles that cluster together, as shown by complementary transmission electron microscopy images (TEM) taken after synthesis. The underlying kinetics of this process could be deciphered by quantitatively analyzing the USAXS/SAXS data considering the scattering contributions of particles, clusters, and the PVP network. A nearly quantitative description of both the nucleation and growth period could be achieved using the two-step Finke-Watzky model with slow, continuous nucleation followed by autocatalytic growth.