Structural Properties Research Articles

A brief review on Ce and Zr-based phase-separated metallic glasses

AbstractPhase-separated metallic glasses (MGs) have attracted a lot of interest recently because they offer a unique opportunity to design composites or alloys with hierarchical microstructure at various length scales. Phase-separated MGs differ from other MGs in terms of their structure and physical properties. Though a lot of theoretical work has been done, there is still a lack of understanding regarding the mechanism underlying phase separation in MGs. In general, phase separation in many MG systems is explained on the basis of nucleation and growth or spinodal decomposition mechanisms. On the other hand, the phase separation in Ce-based MGs is examined based on changes in the electronic structure of Ce atoms. This opens up a new direction of research for delineating issues pertaining to phase separation in amorphous systems. The present brief review aims to provide a comprehensive overview of the phase separation phenomenon in Ce- and Zr-based MG systems. It is broadly divided into two sections: the first section gives a brief introduction into the phase separation in MG systems, mechanisms of phase separation, micro-structural and thermal characteristics, and advantages of phase separation. The second section discusses some of the recent work on Ce- and Zr-based phase-separated MGs with respect to their design and properties. Graphical Abstract

First-principles study and mesoscopic modeling of two-dimensional spin and orbital fluctuations in FeSe

We calculated the structural, electronic, and magnetic properties of FeSe within density-functional theory at the generalized gradient approximation level. First, we studied how the bandwidth of the d-bands at the Fermi energy is renormalized by adding simple corrections: Hubbard U, Hund's J, and by introducing long-range magnetic orders. We found that introducing either a striped or a staggered dimer antiferromagnetic order brings the bandwidths—which are starkly overestimated at the generalized gradient approximation level—closer to those experimentally observed. Second, for the ferromagnetic, the striped, checkerboard, and staggered dimer antiferromagnetic order, we investigate the change in magnetic formation energy with local magnetic moment of Fe at a pressure up to 6 GPa. The bilinear and biquadratic exchange energies are derived from the Heisenberg model and noncollinear first-principles calculations, respectively. We found a nontrivial behavior of the spin-exchange parameters on the magnetization, and we put forward a field-theory model that rationalizes these results in terms of two-dimensional spin and orbital fluctuations. The character of these fluctuations can be either that of a standard density wave or a topological vortex. Topological vortices can result in mesoscopic magnetization structures. Published by the American Physical Society 2024

Experimental and computational studies on possibility of using glucose diazacrown cryptand as a carrier for anticancer drugs busulfan and lomustine

AbstractDrug carriers play a very important role in pharmacy, especially in cancer therapy. Most drugs used in the treatment of cancer are characterized by poor solubility in water and lack of selectivity in their toxic effects on normal and cancer cells. Administration of the drug in the form of a complex with an appropriately selected carrier can significantly improve its therapeutic effect and reduce side effects. In this study, the possibility of using the cryptand L1, containing two diazacrown ethers and two saccharide groups, as a potential drug carrier is investigated. In order to determine whether it can form complexes with drugs, the cryptand L1 and its complexes with two anticancer drugs, busulfan (BSF) and lomustine (CCNU), were synthesized. Their selected structural and energetic properties were investigated using both experimental and computational methods. Additionally, water solubility and cytotoxicity tests were performed for all compounds. The measured 1H NMR spectra confirm that L1 forms complexes L1:BSF and L1:CCNU, the solubility of which in water appears to be much higher than that of the pure drugs. The results of DFT calculations made in water described with the implicit solvent model confirm high stability of L1:BSF and L1:CCNU and indicate that L1 forms with the drugs mainly non-inclusion complexes. However, additional tests with 20 H2O molecules explicitly included in the model suggest that both inclusion and non-inclusion forms can occur in a real solution. Cytotoxicity studies show that the macrocycle L1 is non-toxic towards both normal and cancer cells, and its complexes with drugs show greater selectivity towards cancer cells. Interestingly, while the cytotoxicity of the L1:BSF complex is stronger than that of pure BSF, the relationship is opposite in the case of L1:CCNU and CCNU. Therefore, L1 can be considered as a potential drug carrier, especially for those drugs that have weak activity on cancer cells.

Structural and Viscoelastic Properties of Bacterial Cellulose Composites: Implications for Prosthetics

This study investigates the morphological, mechanical, and viscoelastic properties of bacterial cellulose (BC) hydrogels synthesized by the microbial consortium Medusomyces gisevii. BC gel films were produced under static (S) or bioreactor (BioR) conditions. Additionally, an anisotropic sandwich-like composite BC film was developed and tested, consisting of a rehydrated (S-RDH) BC film synthesized under static conditions, placed between two BioR-derived BC layers. Sample characterization was performed using scanning electron microscopy (SEM), atomic force microscopy (AFM), rheometry, and uniaxial stretching tests. To our knowledge, this is the first study to combine uniaxial and rheological tests for BC gels. AFM and SEM revealed that the organization of BC fibrils (80±20 nm in diameter) was similar to that of collagen fibers (96±31 nm) found in human dura mater, suggesting potential implications for neurosurgical practice. Stretching tests demonstrated that the drying and rehydration of BC films resulted in a 2- to 8-fold increase in rigidity compared to other samples. This trend was consistent across both small and large deformations, regardless of direction. Mechanically, the composite (BioR+S-RDH) outperformed BC hydrogels synthesized under static and bioreactor conditions by approx. 26%. The composite material (BioR+S-RDH) exhibited greater anisotropy in the stretching tests compared to S-RDH, but less than the BioR-derived hydrogels, which had anisotropy coefficients ranging from 1.29 to 2.03. BioR+S-RDH also demonstrated the most consistent viscoelastic behavior, indicating its suitability for withstanding shear stress and potential use in prosthetic applications. These findings should provide opportunities for further research and medical applications.

Structural, optical and electrochemical properties of a new phosphate-based compounds Na2Mn2−xNixFe(PO4)3 as negative electrode for sodium-ion batteries

Structural, optical and electrochemical properties of a new phosphate-based compounds Na2Mn2−xNixFe(PO4)3 as negative electrode for sodium-ion batteries

Systematic investigation of structural, magneto-electronic, mechanical, thermophysical, optical and thermoelectric properties of Hf2VZ (Z = Ga, In, Tl) inverse Heusler alloy for spintronics applications

Systematic investigation of structural, magneto-electronic, mechanical, thermophysical, optical and thermoelectric properties of Hf2VZ (Z = Ga, In, Tl) inverse Heusler alloy for spintronics applications

Silk Foams with Metallic Nanoparticles as Scaffolds for Soft Tissue Regeneration

Tissue regeneration can be achieved by providing endogenous cells with a biomaterial scaffold that supports their adhesion and proliferation, as well as the synthesis and deposition of an extracellular matrix (ECM). In this work, silk fibroin protein foams were formed by lyophilization to generate tissue engineering scaffolds. Three types of medically relevant nanoparticles (NPs) (iron oxide, gold and silver) were added to this biomaterial to assess the ability of silk foams to be functionalized with these NPs. The structural and mechanical properties of the foams with and without the NPs were suitable for tissue support. The in vitro cytocompatibility of the scaffolds was confirmed according to the ISO 10993 guidelines. The biocompatibility of the scaffolds was investigated by assessing inflammation and endogenous cell colonization in a mouse subcutaneous model These in vivo experiments demonstrated a loss of acute inflammation and the absence of chronic inflammation in the grafted animals. The obtained results show that silk foams are good candidates for supporting soft tissue regeneration with the additional possibility of functionalization with NPs.

Structural evolution and mechanical properties of Cr coatings deposited by magnetron sputtering on PCrNi1MoA steel

Cr coatings were prepared by direct current magnetron sputtering on PCrNi1MoA steel, a substrate that has received limited attention in previous studies. The influence of deposition temperature on the microstructure and mechanical properties of Cr coatings was clarified. A comparative analysis was also performed to assess their performance relative to Cr coatings on the stainless steel substrate. All coatings on PCrNi1MoA steel exhibited densely packed fibrous grains in the cross section and a faceted triangular pyramid shape on the surface. Generally, increasing the deposition temperature led to enhanced mechanical properties, primarily due to the reduction of flaws and microporosity, facilitated by the increased mobility of adatoms at higher temperatures. The maximum values of hardness (H), elastic modulus (E), ratios of H/E and H3/E2, and adhesion strength are 4.1 GPa, 117.8 GPa, 0.43, 0.45 GPa, and 27 N, respectively. Compared to the Cr coatings on stainless steel, those on PCrNi1MoA steel exhibited a higher (110) texture coefficient, more uniform grain structures at high deposition temperatures, smoother surfaces, and better adhesion to the substrate.

Personalized Pricing and Assortment Optimization Under Consumer Choice Models with Local Network Effects

We introduce a consumer choice model where each consumer’s utility is affected by their neighbors’ purchase probabilities in a network. We first characterize the choice probabilities and then consider the associated personalized assortment optimization problem. Although this problem is NP-hard, we show that for star networks, the optimal assortment to the central consumer cannot be strictly larger than that without network effects; and the optimal assortment to each peripheral consumer must be a revenue-ordered assortment. Then, we propose a novel idea in which the sellers are allowed to offer “randomized assortments” to each node in the network by viewing each node as a consumer group. We show that randomized assortments may further increase the revenue, and for general network setting, under certain conditions, the optimal assortment must be a combination of two adjacent revenue-ordered assortments. Finally, we study the associated optimal pricing problem and develop structural properties and efficient algorithms.

Transmission electron microscopic study on rutile-type GeO2 film on TiO2 (001) substrate

Rutile-type GeO2 (r-GeO2) with an ultrawide bandgap of ∼4.7 eV has emerged as a promising material for next-generation power-electronic and optoelectronic devices. We performed transmission electron microscopy (TEM) observation to analyze the structural properties of r-GeO2 film on r-TiO2 (001) substrate at an atomic level. The r-GeO2 film exhibits a threading dislocation density of 3.6 × 109 cm−2 and there exist edge-, screw-, and mixed-type dislocations in the film as demonstrated by two-beam TEM. The edge-type dislocations have Burgers vectors of [100] and/or [110]. The bandgap of the r-GeO2 film is 4.74 ± 0.01 eV as determined by electron energy loss spectroscopy.

Towards expansion of the MATTS data bank with heavier elements: the influence of the wavefunction basis set on the multipole model derived from the wavefunction

The MATTS (multipolar atom types from theory and statistical clustering) data bank is an advanced tool for crystal structure refinement and properties analysis. It applies a multipole model (MM), which describes the asphericity of the atomic electron density and helps to interpret X-ray or electron diffraction data better than approaches based on the spherical atoms approximation. The generation of MATTS data involves density functional theory calculations, and until recently we used the B3LYP/6-31G** level of theory for this stage. However, it was not so clear how the wavefunction level of theory, especially the basis set used, influenced the resulting MM. This study investigates the influence of the wavefunction basis set on the resulting MM from a charge density point of view. For this purpose, we used charge density related properties, such as correlation of electrostatic potentials, atomic electron populations and average electrostatic potential values. The complex analysis reveals that, within the framework of MATTS data generation, the size of the basis set used has the most significant impact on the MM's charge density quality, and switching from double- to triple-zeta basis sets helps notably improve the charge density related properties. This research sets the foundation for the creation of a new version of the MATTS data bank, which will be expanded to include atom types for elements heavier than Kr and selected metal complexes important for biological systems.

Sustainable rigid polyurethane foam composites based on used palm oil and turkey feather fiber: structural, morphological, thermal, insulation and mechanical properties

Sustainable rigid polyurethane foam composites based on used palm oil and turkey feather fiber: structural, morphological, thermal, insulation and mechanical properties

Probing the Interplay of Protein Self-Assembly and Covalent Bond Formation in Photo-Crosslinked Silk Fibroin Hydrogels.

Covalent crosslinking of silk fibroin via native tyrosine residues has been extensively explored; however, while these materials are very promising for biomedical, optical, soft robotics, and sensor applications, their structure and mechanical properties are unstable over time. This instability results in spontaneous silk self-assembly and stiffening over time, a process that is poorly understood. This study investigates the interplay between self-assembly and di-tyrosine bond formation in silk hydrogels photo-crosslinked using ruthenium (Ru) and sodium persulfate (SPS) with visible light. The effects of silk concentration, molecular weight, Ru/SPS concentration, and solvent conditions are examined. The Ru/SPS system enables rapid crosslinking, achieving gelation within seconds and incorporating over 90% of silk into the network, even at very low protein concentrations (≥0.75%wt/v). A model emerges where silk self-assembly both before and after crosslinking affects protein phase separation, mesoscale structure, and dynamic changes in the hydrogel network over time. Silk concentration has the greatest impact on hydrogel properties, with higher silk concentration hydrogels experiencing two orders of magnitude increase in stiffness within 1 week. This new understanding and ability to tune hydrogel properties and dynamic stiffening aids in developing advanced materials for 4D biofabrication, sensing, 3D cancer models, drug delivery, and soft robotics.

A Facile Method to Incorporate Di-Dopant Elements (F and Sb) into Crystalline Mesoporous Tin Dioxide Nano Powder at Ambient Temperature and Pressure.

A simple two step synthetic method for di-doped crystalline mesoporous tin dioxide powder containing antimony and fluoride at ambient pressure and temperature has been developed. This approach produced materials with high surface areas and improved electrical and optoelectrical conductance. The two dopant elements; antimony and fluoride were introduced to tin dioxide by two approaches. Both approaches produced mesoporous tin dioxide with antimony and fluoride that are integrated in the framework. The structures of these materials are analyzed by powder X-ray diffraction, N2 sorption analysis, transmission electron microscopy, energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The conductance of the materials improved by factor of 13-34 compared to undoped mesoporous tin dioxide. The effect of the di-doped elements on structure, conductance and optoelectronic properties of these materials are discussed in this paper.

Fabrication of novel PVA loaded ZnO nanoparticles for anti-renal failure.

X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to investigate the structural, surface and particles properties of a series of zinc oxides (ZnO) doped with polyvinyl alcohol (PVA) that were prepared using the sol-gel method. The results demonstrated that the crystallinity of the catalysts decreased as the PVA content increased beyond 5 PVA/ZnO. However, on raising the calcination temperature up to 500°C, the average crystal size of the PVA/ZnO nanoparticles increased. Next Pyridine adsorption was used to measure the surface acidity of the catalysts, and the results showed that doping ZnO with PVA and raising the calcination temperature to 500°C increased the catalyst's surface acidity. Furthermore, the data indicates that raising the ratio of the Brønsted to Lewis acid sites enhanced the catalytic activity for the synthesis of coumarin derivatives. We concluded that the structural and acidity characteristics of the catalysts under study had a significant impact on the catalytic activity. Furthermore, a study examining the biological activity of ZnO/PVA and pure ZnO revealed that 5PVA/ZnO performed the best in terms of improving the kidney functions of diabetic rats.

First-principles calculations to investigate structural, electronic, elastic, and optical properties of orthorhombic LiBH2 for hydrogen storage and optoelectronic devices

First-principles calculations to investigate structural, electronic, elastic, and optical properties of orthorhombic LiBH2 for hydrogen storage and optoelectronic devices

The effect of humidity on the enhanced CO2 adsorption of amine-functionalized microporous activated carbon.

Cost-effective and environmentally friendly sorbents were created for capturing CO2 by incorporating monoethanolamine (MEA) and tetraethylenepentamine (TEPA) onto a microporous activated carbon (AC) material. The application of a KOH reagent enhanced the surface area and pore volume of the carbon material. The BET, SEM, EDX, and FTIR techniques were employed to analyze the structural and surface properties of the developed samples. Raw AC possessed the highest surface area and largest micropore volume equal to 786 m2/g and 0.33 cm3/g, respectively. The amine impregnation increased the nitrogen content of the carbon material, but it also significantly reduced the BET surface area and total pore volume, which are primarily responsible for physically adsorbing CO2 towards ACs. The CO2 adsorption performance of the raw and impregnated ACs was experimentally evaluated using thermogravimetric analysis (TGA) at different adsorption temperatures (25 and 50 °C) and CO2 concentrations (10 and 90 vol.%). The findings demonstrated that the raw AC exhibited the highest capacity for CO2 adsorption. Specifically, at a temperature of 25 °C and pressure of 1 bar (10 vol.% CO2, N2 balance), the raw AC achieved an uptake of 1.2 mmol/g, which was 60.3% and 79.3% higher compared to the CO2 uptake of MEA-AC (0.5 mmol/g) and TEPA-AC (0.3 mmol/g), respectively. It is surprising that the combined uptake of CO2 + H2O increased by 12.5 and 23.4 wt.% (equivalent to 7 and 13 mmol/g) for MEA-AC and TEPA-AC, respectively, when humid flue gas was taken into account under the conditions of 50 °C, with 10 vol.% CO2, 4 vol.% H2O, and N2 balance. These results indicate that the presence of H2O facilitates the chemisorption of CO2 by the novel and highly promising carbon-based sorbent prepared in this study, leading to an increased capacity for adsorbing CO2 under water vapor containing flue gases.

Enhanced Quantum Efficiency via Co‐Substitution in Red‐Emitting Phosphor Sr2[MgAl5N7] : Eu2+ for Advanced Spectroscopic Applications Including Laser Displays with Ultra‐High Luminescence Saturation Threshold

AbstractIn order to obtain novel and more efficient red light‐emitting materials, a series of Sr2[Mg1−xLixAl5−xSixN7] : 0.01Eu2+ (SMAN‐xLS, 0≤x≤0.5) red phosphors were devised and successfully synthesized via the high temperature solid state reaction and the effects of the co‐substitution of [Mg−Al]5+ by [Li−Si]5+ on structural and luminescence properties is investigated in detail. A series of powder XRD data and Rietveld refinement indicate that [Li−Si]5+ co‐substitution can successfully enter the Sr2[MgAl5N7] : 0.01Eu2+ (SMAN) lattice. With the entry of [Li−Si]5+ into the lattice, the substitution of Al3+ by Si4+ leads to the weakening of the nephelauxetic effect of the 5d level of Eu2+, which shifts the emission peak from 657 nm to 647 nm and reduces the excitation in the green region, i.e., lowers the absorption of green light. When the amount of [Li−Si]5+ co‐substitution is x=0.1, the luminescence intensity and thermal stability of the sample are enhanced, in which the external quantum efficiency (EQE), reflecting the luminescence intensity, is elevated by 49.6 %. The increase in lattice rigidity gives rise to higher luminescence intensity, and the introduced trap levels for the compensation of luminescence enhances the thermal stability. Under blue laser excitation, the SMAN‐0.1LS can achieve an ultra‐high luminescence saturation threshold of 52.22 W/mm2, which is remarkably superior to other existing red phosphors, a breakthrough performance that has enormous potential for application in high‐power laser display light sources. Cathodoluminescence (CL) characterization and measurements attest to the favorable CL properties of SMAN‐0.1LS. By measuring the pressure‐dependent luminescence of SMAN‐0.1LS, the emission peak can be shifted from 650 nm to 702 nm with the increase of pressure, and the sensitivity dλ/dP is 5.07 nm/GPa, which is indicative of the potential application of this system as an optical pressure sensor.

Under cover: the nuanced influence of functional properties of cover on resource selection by pygmy rabbits (Brachylagus idahoensis)

Abstract Animals at risk of predation select habitat that enhances security from predators. Two properties of cover related to security are concealment (i.e., habitat structure that blocks an individual from detection by others) and visibility (i.e., visual information accessible relative to habitat structure). Although these properties are often negatively correlated, they are not always inverse; animals in habitat with heterogeneous structure may be able to select for both. We investigated habitat use by pygmy rabbits (Brachylagus idahoensis) at 2 scales (patch and microsite) to evaluate the influence of both structural properties of cover and visual properties (concealment and visibility) on habitat use by prey. We contrasted vegetation structure at paired used and unused patches. At each patch, we measured concealment and viewshed (i.e., visibility) in 3 orientations (i.e., aerial, terrestrial, and overall) and structural density using lidar. We also measured heights of the 3 tallest shrubs. Additionally, within used patches, we assessed the density of fecal pellets as an index of intensity of use and also measured distance to nearest burrow. At the patch scale, rabbits selected for structural properties of cover (dense vegetation and tall shrubs), but not visual properties of cover. Pygmy rabbits more intensively used microsites associated with high terrestrial concealment and in proximity to burrows. Our results suggest that pygmy rabbits may perceive greater threat from terrestrial as opposed to aerial predators at both scales, and they also indicate a nuanced relationship between properties of cover and habitat use.

Effect of Doped Carbon Atoms on Electronic Structure and Optical Properties of Monolayer 1T-ZrS2

In this paper, a method based on density functional theory is used to replace varying numbers of sulfur atoms with carbon atoms in the original monolayer ZrS2 system, resulting in a new doped system. The theory is based on the First Principle. The photovoltaic properties of the new carbon-atom doping systems have been calculated and investigated. The pristine system and the carbon-atom doped systems were structurally optimized using the automatic optimization method. It was found that the stability of the structure decreases as the number of carbon atoms increases. Pristine monolayer 1T-ZrS2 is an indirect bandgap material. The results show that after doping carbon atoms in monolayer 1T-ZrS2, the p-type conductivity of the system increases and exhibits metallicity. The density of states analysis shows that the conduction band consists mainly of S-3p, Zr-4d, Zr-4p, Zr-5s and C-2p orbitals, while the valence band consists mainly of S-3p, S-3s, Zr-4d, C-2p and C-2s orbitals. It is concluded that strong hybridization between Zr-d and S-p orbitals is exhibited by both the pristine and doped systems. The analysis of the optical properties shows that the peak absorption coefficient and reflectivity peaks are blue-shifted in the doped system, and these peaks are lower than in the pristine system. The peaks of the real and imaginary parts of the dielectric function are also blue shifted. With the increase of doping concentration, the system’s energy loss decreases, indicating that proper doping can effectively reduce the system’s energy loss. The above studies provide theoretical support for applying ZrS2 in nano-optoelectronics.