Short-range Order Research Articles

Decoding Anionic Organization of Hydroxide-Fluorides in a Diaspore-Type Network.

The diaspore-type crystalline structure is historically well-known in mineralogy, but it has also been widely studied for various applications in the field of catalysis, electrocatalysis, and batteries. However, once two anions of similar ionic size but different electronegativity, such as F- and O2- or more precisely OH-, are combined, the knowledge of the location of these two anions is of paramount importance to understand the chemical properties in relation with the generation of hydrogen bonds. Coprecipitation and hydrothermal routes were used to prepare hydroxide-fluorides that crystallize all in an orthorhombic structure with four formula units per cell. By coupling X-ray scattering techniques for both long- and short-range order (XRD and PDF) and by using multiple complementary spectroscopic probes (Raman, FTIR, and 1D/2D 19F and 1H MAS NMR measurements), preferential anionic site occupancy by hydroxyl groups and fluoride ions is demonstrated. Moreover, in the Mg(OH)F diaspore network, 10% of Mg2+ is located in the tunnels, resulting in cationic vacancies in the main site. The preference for OH at the edges is clearly marked in the case of Mg(OH)F, whereas OH is preferred at the vertices in Zn(OH)F, regardless of the allotropic form. The dominant polar low-symmetry Pna21 form of Zn(OH)F has more OH groups at the vertices than the parent centrosymmetric Pnma variety, in agreement with its strongest hydrogen bonds. Given the remarkable flexibility of the diaspore-type network, the thermal stability of these hydroxide-fluorides is perfectly matched to the structural characteristics. The location of anionic groups within the diaspore framework should play a key role in understanding and optimizing physicochemical properties such as proton mobility for alkaline batteries and acid-base properties for heterogeneous catalysis.

Effect of microwave treatment on the structural and physicochemical properties of amylose partially removed sorghum starch.

This study aimed to probe the influence of amylose in starch granules on starch modification. Part of the amylose from sorghum starch was removed through warm water leaching, and the samples were then microwaved. The effects of treatments on starch structure, physicochemical properties, and digestibility were researched. Compared to sorghum starch without partial amylose removal, warm water leaching of amylose resulted in deeper concavity of sorghum starch granules and lower crystallinity, short-range ordering, setback and breakdown values, which disrupted the structure and thus rendered the starch granules more susceptible to microwave radiation, amplifying the advantages of microwave-modified starch. In addition, the ordered arrangement of amylose and amylopectin structures within the microwave-treated sorghum starch with pre-removed amylose were more readily disrupted, allowing enzymes to pass through more readily, thus increasing the fast-digestible starch content and digestibility of the starch. In summary, partial amylose removal can be used as a pretreatment method for modifying and expanding starch utilization in food and non-food industries while providing a new idea for developing baked foods.

Reinvestigating atomic ordering in K0.5Na0.5NbO3 and its impact on ferroelectric properties

In the present work, we reinvestigate the atomic ordering of a Pb-free morphotropic phase boundary (MPB) compositionviz.,K0.5Na0.5NbO3(KNN50) and its vicinity at various length scales using high-resolution x-ray diffraction and pair distribution function data. We have observed a monoclinic phase (Space Group: Pm) at long/short ranges differing from a very recent report by Sahaet al2024J. Phys.: Condens. Matter36425703. Moreover, the ferroelectric (polarization) dominance of short-range ordering (SRO) over long-range ordering (LRO) has been observed and quantified for the very first time using the amplitude of the ferroelectric frozen phonon mode (Γ4-) (corresponding to the high symmetry cubic phase), thereby structure is linked with ferroelectric (or polarization) property for a widely studied MPB systemviz.,KxNa(1-x)NbO3(KNNxforx= 0.40, 0.50, and 0.60). Two uniquely identified monoclinic phases has been observed for SRO (MSRO) and LRO (MLRO) for all the compositions. The amplitude of ferroelectric frozen phonon mode (Γ4-) corresponding toMSROis significantly higher (≈150%-180%) thanMLRO. A peak is observed in the amplitude ofΓ4-and intensity of prominent Raman peaks (ν1andν5) forx= 0.50, which is held responsible for high physical propertiesviz.,dielectric permittivity, piezoelectric coefficient, remnant polarization, electromechanical coupling coefficient, and many more widely reported in literature for KNN50.

Proton Exchange Membrane with Dual-Active-Center Surpasses the Conventional Temperature Limitations of Fuel Cells.

High temperature-proton exchange membrane fuel cells (HT-PEMFC) call for ionomers with low humidity dependence and elevated-temperature resistance. Traditional perfluorosulfonic acid (PFSA) ionomers encounter challenges in meeting these stringent requirements. Herein, this study reports a perfluoroimide multi-acid (PFMA) ionomer with dual active centers achieved through the incorporation of sulfonimide and phosphonic acid groups into the side chain. The fluorocarbon skeleton and multi-acid side chain structure facilitate the segregation of hydrophilic and hydrophobic microphases, augmenting the short-range ordering of hydrophilic nanodomains. Furthermore, the introduction of a rigid segment-benzene ring is employed to decrease side chain flexibility and raise the glass transition temperature. Notably, the prepared membrane exhibits a conductivity of 41 mS cm-1 at 40% relative humidity, showcasing a 1.8 times improvement over that of PFSA. Additionally, the power output of the H2-air fuel cell based on this membrane reaches 1.5W cm-2 at 105°C, marking a substantial 2.3 times enhancement compared to the PFSA. This work demonstrates the unique advantages of perfluorinated ionomers with multiple protogenic groups in the development of high-performance high-temperature electrolyte materials.

High-entropy assisted capacitive energy storage in relaxor ferroelectrics by chemical short-range order

Next-generation advanced high/pulsed power capacitors rely heavily on dielectric ceramics with high energy storage performance. Although high entropy relaxor ferroelectric exhibited enormous potential in functional materials, the chemical short-range order, which is a common phenomenon in high entropy alloys to modulate performances, have been paid less attention here. We design a chemical short-range order strategy to modulate polarization response under external electric field and achieve substantial enhancements of energy storage properties, i.e. an ultrahigh energy density of ~16.4 J/cm3 with markedly improved efficiency ~90% at an electric field of 85 kV/mm in Nb doped (Bi0.2Na0.2K0.2La0.2Sr0.2) TiO3 system. Atomic-scale scanning transmission electron microscopy observations show that Nb exhibits a chemical short-range order structure, with Nb enriched regions displaying ultrasmall polar nanoregions and more flexible polarization configurations, which is conducive to achieving high maximum polarization and low residual polarization. Moreover, refined grain size of ~0.25μm, suppressed oxygen vacancies and enhanced bandwidth contribute to a high breakdown field strength. These collective factors result in exceptionally high energy storage density and efficiency. This short-range order strategy is expected to enhance the functional performances in other high entropy relaxor ferroelectrics.

Two dimensional confinement induced discontinuous chain transitions for augmented electrocaloric cooling

Overheating remains a major barrier to chip miniaturization, leading to device malfunction. Addressing the urgent need for thermal management promotes the development of solid-state electrocaloric cooling. However, enhancing passive heat dissipation through two-dimensional materials in electrocaloric polymers typically compromises the electrocaloric effect. In this work, we utilize two-dimensional polyamide with porous structure and hydrogen bonding to achieve multiple polar conformations with short-range order in the electrocaloric composite polymers. The structure minimizes intermolecular interactions while reducing energy barriers for field-driven polar-nonpolar conformational transitions. The electrocaloric polymer exhibits doubled cooling efficiency at electric fields as low as 40 MV m−1. Additionally, the electrode design achieves a vertical deformation of 2 millimeters, demonstrating the feasibility of self-driven electric refrigeration devices. This porous organic two-dimensional material resolves cooling efficiency limitations from spatial confinement, advancing the integration of two-dimensional materials in flexible electronics.

Emergent quasicrystal in fermionic superradiance

Quasicrystal is state of matter with multiple crystalline orders, displaying a short-range density-wave order and a long-range disorder. As an exotic state lying in between crystals and Anderson insulators, its dynamical formation is little discussed. Here, we study the emergence of quasicrystalline order in fermionic superradiance, where Fermi statistics plays a crucial role, being distinct from its bosonic counterpart where interaction is the stabilizer. Owing to quasicrystalline orders, there exist multiple energy gaps opening at different quasicrystalline order strength, which can modify the density of states in excitation spectrum. As a result, the effective ground-state energy is strongly modified and the superradiant quasicrystal transition becomes first order and density dependent. This new mechanism leads to a linear V-shape kink of the fermionic superradiance transition line near a filling which uniquely relates to the quasicrystalline order. Our findings demonstrate that quasicrystal can be realized in fermionic superradiance as a result of Fermi statistics and be verified by characteristic density-dependent phenomena. Published by the American Physical Society 2025

Morphology remodelling and membrane channel formation in synthetic cells via reconfigurable DNA nanorafts.

The shape of biological matter is central to cell function at different length scales and determines how cellular components recognize, interact and respond to one another. However, their shapes are often transient and hard to reprogramme. Here we construct a synthetic cell model composed of signal-responsive DNA nanorafts, biogenic pores and giant unilamellar vesicles (GUVs). We demonstrate that reshaping of DNA rafts at the nanoscale can be coupled to reshaping of GUVs at the microscale. The nanorafts collectively undergo reversible transitions between isotropic and short-range local order on the lipid membrane, programmably remodelling the GUV shape. Assisted by the biogenic pores, during GUV shape recovery the locally ordered DNA rafts perforate the membrane, forming sealable synthetic channels for large cargo transport. Our work outlines a versatile platform for interfacing reconfigurable DNA nanostructures with synthetic cells, expanding the potential of DNA nanotechnology in synthetic biology.

The Derivation of CRSS in pure Ti and Ti-Al Alloys

The work focuses on the determination of the critical resolved shear stress (CRSS) in titanium (Ti) and titanium-aluminum (Ti-Al) alloys, influenced by an array of factors such as non-symmetric fault energies and minimum energy paths, dislocation core-widths, short-range order (SRO) effects which alter the local atomic environment, and tension-compression (T-C) asymmetry affected by intermittent slip motion. To address these multifaceted complexities, an advanced theory has been developed, offering an in-depth understanding of the mechanisms underlying slip behavior. The active slip systems in these materials are basal, prismatic, and pyramidal planes, with the latter involving both 〈a〉 and 〈c+a〉 dislocations. Each slip system is characterized by distinct Wigner-Seitz cell configurations for misfit energy calculations, varying partial dislocation separation distances, and unique dislocation trajectories—all critical to precise CRSS calculations. The theoretical CRSS results were validated against a comprehensive range of experimental data, demonstrating a strong agreement and underscoring the model's efficacy.

Enabling Type I Lattice-Matched Heterostructures in SiGeSn Alloys Through Engineering Composition and Short-Range Order: A First-Principles Perspective

Enabling Type I Lattice-Matched Heterostructures in SiGeSn Alloys Through Engineering Composition and Short-Range Order: A First-Principles Perspective

Effects of extrusion temperature on structure and physicochemical properties of proso millet starch.

Due to its thermal stability, and high viscosity, proso millet starch has limited practical applications. Extrusion can alter the functional properties of starch by pre-gelatinization, but the specific effects of extrusion temperature on starch behavior are not clear. In this study, proso millet starch was modified using extrusion at varying temperatures (70°C, 90°C, 110°C), and its structure as well as physicochemical properties were evaluated. As the extrusion temperature increased, the starch granules were gelatinized, and the particle size increased significantly. The relative crystallinity of extruded starch decreased and the short-range order was enhanced notably, but the starch still exhibited an A-type structure. Starch chains degraded, migrated, and aggregated, showing an increase in the double helix content, but there was no difference in the single helix structure with temperature. With the increase of extrusion temperature, the amorphous layer of extruded starch thickened. Moreover, the peak viscosity, breakdown viscosity and setback viscosity initially increased and then decreased, the peak temperature and enthalpy change increased. The water absorption index, water solubility and swelling power significantly decreased with increasing temperatures. The freeze-thaw stability and transparency of extruded starch decreased, and showed a downward trend with prolonged time. The above results indicate that extrusion treatment effectively modifies the thermal stability and viscosity of proso millet starch, laying a foundation for applying it different industrial applications.

Short-range order and hidden energy scale in geometrically frustrated magnets

In geometrically frustrated (GF) magnets, conventional long-range order is suppressed due to the presence of primitive triangular structural units, and the nature of the ensuing ground state remains elusive.

Physicochemical characterization and in vitro digestibility of resistant starch from corn starch sugar residue.

This study sought to investigate the thermal stability and digestibility of corn starch sugar residue resistant starch (CSSR-RS) through comparative analysis of the physicochemical properties and structural characteristics among CSSR-RS, high-amylose corn starch (HS), and normal corn starch (NS). CSSR-RS contained 51.76% resistant starch (RS), with 42.6% remaining after high-temperature treatment, which was significantly higher than HS, demonstrating strong resistance to gelatinization. CSSR-RS is characterized by highly ordered aggregation of small molecules with a C-type crystalline structure, and irregular granular structures with wrinkled surfaces. Compared with NS and HS, the short-range and long-range order of CSSR-RS were significantly higher, indicating excellent thermal stability. In vitro simulated digestion revealed that the total hydrolysis rate of CSSR-RS was significantly lower than those of NS and HS, and the residual digesta of CSSR-RS also showed better resistance to digestion than HS. CSSR-RS exhibited significant development prospects in healthy food.

Enhancing the mechanical properties of TiZr-based multi-principal element alloys via leveraging multiple short-range orders: an atomic-scale study

Enhancing the mechanical properties of TiZr-based multi-principal element alloys via leveraging multiple short-range orders: an atomic-scale study

Tensorial interaction model for the effect of short-range order on single crystalline medium entropy alloys

Tensorial interaction model for the effect of short-range order on single crystalline medium entropy alloys

Theoretical and Experimental Research on the Short-Range Structure in Gallium Melts Based on the Wulff Cluster Model.

In this paper, the short-range ordering structures of Ga melts has been investigated using the Wulff cluster model (WCM). The structures with a Wulff shape outside and crystal symmetry inside have been derived as the equivalent system to describe the short-range-order (SRO) distribution of the Ga melts. It is observed that the simulated HTXRD patterns of the Ga WCM are in excellent agreement with the experimental data at various temperatures (523 K, 623 K, and 723 K). This agreement includes first and second peak positions, widths, and relative intensities of patterns, particularly at temperatures significantly above the melting point. A minor deviation in the second peak position has been observed at 523 K, attributed to the starting of the pre-nucleation stage. These findings demonstrate that the WCM can effectively describe the SRO structure in melt systems exhibiting a certain extent of covalency.

Using the Radial Distribution Function to Analyze Atomic Force Microscopy Images of Colloidal Systems

Biomacromolecules generally exist and function in aqueous media. Is it possible to estimate the state and properties of molecules in an initial three-dimensional colloidal solution based on the structure properties of biomolecules adsorbed on the two-dimensional surface? Using atomic force microscopy to study nanosized objects requires their immobilization on a surface. Particles undergoing Brownian motion in a solution significantly reduce their velocity near the surface and become completely immobilized upon drying. Using radial distribution function (RDF) methods, it is possible to obtain information about the presence of short-range or long-range order in the arrangement of immobilized colloidal particles. In this work, RDF is applied to immobilized gold nanoparticles (AuNPs) and horseradish peroxidase molecules on mica. It is shown that AuNPs maintain mobility on the mica surface when water is present. Upon immobilization, AuNPs organize into an amorphous structure exhibiting short-range order. Protein molecules are immobilized randomly, and their surface density is well described by the Poisson distribution.

Effects of air flow micro pulverized wheat bran dietary fiber on physicochemical, structural, and digestive properties of wheat starch.

The effects of wheat bran dietary fiber (WBDF) treated by air flow micro-pulverization on gelatinization, thermal, rheological, structural properties, and in vitro digestion of wheat starch (WS) were investigated. Different particle sizes of WBDF were obtained by conventional knife grinding and airflow micro-grinding. Compared with conventional knife grinding, the particle size of WBDF treated by air flow micro-pulverization decreased, the particle size distribution was concentrated at small particle sizes, the specific surface area increased, and the hydraulic and oil-holding power decreased, which was mainly related to the change of WBDF spatial structure and the increase of solubility. At the same time, the peak viscosity, setback, breakdown, and resistant starch content short-range order degree and relative crystallinity of WS were increased by adding WBDF treated by air flow micro-pulverization, whereas the gelatinization enthalpy value and apparent viscosity were decreased. This indicated that the air micro pulverized WBDF promoted gelatinization and inhibited digestion while reducing the thermal stability of WS, leading to short-term recovery. This study provides a theoretical reference for the production and processing of gluten-containing flour products. PRACTICAL APPLICATION: In this study, the physical and chemical properties and spatial structure of air flow micro pulverized dietary fiber of wheat bran were analyzed, and its effects on the properties of wheat starch were studied. Therefore, this study provides a theoretical basis for the industrial application of gluten-containing flour products.

Magnetoresistive and magnetocaloric properties of polycrystalline Sm0.50Sr0.50MnO3 compound with short range magnetic ordering

In this study, the magnetic and magneto-transport properties of polycrystalline Sm0.50Sr0.50MnO3 have been investigated. The presence of short-range magnetic order plays a crucial role in influencing electron transport, making it a promising pathway for tuning magnetoresistive properties for specific applications. This research focuses on the effects of magnetic nanoclusters on spin-dependent scattering and their impact on magneto-transport and magnetocaloric properties in polycrystalline Sm0.50Sr0.50MnO3. Experimental results reveal a significant magnetocaloric effect and notable magnetoresistance within the liquid nitrogen temperature range. At 100 K, the magnetoresistance reaches approximately 70% under an external magnetic field of 20 kOe. The magnetocaloric entropy change is calculated to be 3.5 J/kg-K for a 70 kOe magnetic field, with the entropy change curve exhibiting a broadened peak, leading to a substantial Relative Cooling Power (RCP). These findings enhance our understanding of the material’s behavior and highlight its potential for various technological applications.

Theoretical Study of the Stability of CdSn Liquid Alloy at Different Temperatures

The quasi-lattice theory (QLT) is utilized for the prediction of the temperature and concentration dependence of the thermodynamic properties of the molten CdSn alloys. At first, the analytical expressions are employed to reckon the excess Gibbs free energy of mixing, Gibbs free energy of mixing, activity, enthalpy of mixing and entropy of mixing as well as concentration fluctuations, short range-order parameter and excess stability function ofCdSn melts at 773 K. For this, the model parameters i.e. size ratio and order energy parameter are assessed using the experimental data of the free energy of mixing for CdSnmelts at 773 K. The theoretical values of the thermodynamic functions are in well harmony with the interrelated experimental values. The theoretical values of the structure function like concentration fluctuations are in unison with the experimental values for molten CdSn system at 773 K. Again, the optimization procedure is applied to explore the excess Gibbs free energy of mixing, activity, concentration fluctuations, short-range order parameter and excess stability function at different temperatures for CdSnmelts. The present study discloses that the stability as well as the segregating nature of CdSnmelts decrease with the elevation of the temperature from 773 K to 1123 K. Further, the temperature dependency of the excess stability function reveals that there is a probability of transition from segregating character to the ordering character of CdSn melts near 1162 K. Keywords: Gibbs free energy of mixing; entropy of mixing; concentration fluctuations; short-range order parameter; excess stability function