Search Results (44)

Levitation techniques reduce the available heterogeneous nucleation sites and provide stable access to deeply undercooled melts. However, some samples have repeatably demonstrated that, in the presence of strong stirring, solidification may be induced at moderate, sub-critical undercoolings. Dynamic nucleation is a mechanism by which solidification may be induced through flow effects within a sub-critically undercooled melt. In this mechanism, collapsing cavities within the melt produce very high-pressure shocks, which shift the local melting temperature. In these regions of locally shifted melt temperatures, thermodynamic conditions enable nuclei to grow and trigger solidification of the full sample. By deepening the local undercooling, dynamic nucleation enables solidification to occur in conditions where classical nucleation does not. Dynamic nucleation has been observed in several zirconium and zirconium-based samples in the Electromagnetic Levitator onboard the International Space Station (ISS-EML). The experiments presented here address conditions in which a zirconium sample alloyed with 2.5 atomic percent niobium spontaneously solidifies during electromagnetic levitation experiments with strong melt stirring. In these experimental conditions, classical nucleation predicts the sample to remain liquid. This solidification behavior is consistent with the solidification behavior observed in prior experiments on pure zirconium. Full article

As one of the most important platform chemicals, furfural (FAL) can be converted into high-value-added products such as furfuryl alcohol (FOL) through multiple pathways. Zirconium-based MOF-801 demonstrates exceptional catalytic potential for FAL conversion via catalytic transfer hydrogenation (CTH), owing to its unique crystal defects generated during growth. In this study, a series of defective MOF-801 samples were efficiently synthesized using an air–liquid segmented microfluidic technique. The characterization results reveal that the air–liquid segmented flow method not only regulates the defect content of MOF-801 to expose more active sites but also adjusts the crystal size and pore structures by precisely controlling the reaction time. The enhanced defects in MOF-801 significantly improved its catalytic performance. A-MOF-801-64 exhibited the highest activity, achieving over 99% FAL conversion and 98% FOL selectivity under mild conditions (130 °C, 12 h) using isopropanol as the hydrogen donor; this performance surpassed that of other reported Zr-based catalysts. This study will facilitate the practical applications of defect-engineered MOF-801 in upgrading biomass-derived chemicals. Full article

Niobium, with its unique properties, plays a key role in high-tech industries, but its recovery from secondary sources remains poorly studied. The kinetics of niobium leaching from niobium-containing middlings obtained via the water treatment of dust chamber sublimations of titanium chlorinators is considered in this study. The leaching process was conducted using a fluoride–sulphuric acid solution. The experiments were performed at 25–90 °C in agitation mode. Kinetic data were analysed using compression-core and mixed-control models, which made it possible to establish the limiting stages of the process. A mixed mechanism, including a chemical reaction on the surface and diffusion through a layer of products with an activation energy of 30.05 kJ/mol, was established. The niobium recovery degree increased from 35.25 to 93.5% as the temperature increased, highlighting its effect on the process. The insoluble residue, rich in titanium, and the liquid phase with niobium and zirconium have the potential for further processing. The results provide the basis to optimise technologies intended to recover niobium from man-made raw materials, contributing to an increase in resource efficiency. Full article

Heterocyclic aromatic amines (HAAs), known for their mutagenic and carcinogenic potential, are formed during the heating of protein-rich food items. Detecting HAAs swiftly and accurately poses challenges due to complex food matrices and low HAA concentrations. In this study, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous isolation and enrichment of three HAAs such as 2-amino-3,4,8-trimethylimidazo [4,5-f]quinoxaline (4,8-DiMeIQx), 2-amino-3,8-dimethylimidazo [4,5-f]quinoxaline (MeIQx), and 2-amino-3-methylimidazo [4,5-f]quinoline (IQ) in processed meats, employing the magnetic covalent organic framework Fe₃O₄@MOF-545-AMSA as an adsorbent. It was synthesized via a solvothermal method, with Fe₃O₄ as the magnetic core. Its building blocks are as follows: zirconium (Zr) as the coordination metal ion, tetrakis(4-carboxyphenyl)porphyrin and benzoic acid as organic ligands, and aminomethanesulfonic acid (AMSA). This composite captures targeted HAAs efficiently by exploiting the unique porous MOF-545-AMSA structure, specific metal–ligand coordination, and AMSA’s amino and sulfonic acid groups. The quantification of HAAs was achieved through the combination of Ultra-Performance Liquid Chromatography–Tandem Mass Spectrometry (UPLC-MS/MS) and MSPE, demonstrating satisfactory linearity (R² ≥ 0.9917), high recovery rates (83.7–111.0%), and low detection limits (0.1–1.0 μg/kg). Moreover, an automated high-throughput detection system was developed using MSPE to assess the presence of HAAs in meat products. Full article

Monolayer nanosheets of zirconium phosphate in aqueous suspension exhibit short-range repulsion and long-range attraction, producing, at overall volume fractions larger than about half a percent, phase separation into higher-concentration liquid crystal and lower-concentration isotropic regions. At high concentrations, this phase separation takes the form of an emulsion of condensed, liquid-crystalline droplets, which anneal to form lens-shaped tactoids. These tactoids provide an opportunity to study the liquid crystal ordering of inorganic nanosheets in the limit of large shape anisotropy (diameter/thickness~400) and high packing fraction (volume fraction $\gtrsim$ 70%). The internal liquid crystal structure of the tactoids remains nematic even under conditions that would usually favor ordering into lamellar smectics. Local lamellar ordering is suggested by short-range, smectic-like layer correlations, but a full transition into a smectic phase appears to be inhibited by the nanosheet edges, which act as a perturbative population of dislocation loops in the system of layers. Under conditions of thermal equilibrium, the nanoplates organize positionally to enable bend deformation of the director, a hallmark of the nematic phase and its principal distinction from the smectic, where bend must be expelled. Full article

Zirconium carbide (ZrC) ceramics have a high melting point, low neutron absorption cross section, and excellent resistance to the impact of fission products and are considered to be one of the best candidate materials for fourth-generation nuclear energy systems. ZrC ceramics with a high relative density of 99.1% were successfully prepared via pressureless sintering using a small amount of MoSi₂ as an additive. The influence of the MoSi₂ content on the densification behavior, microstructure, mechanical properties, and thermal properties of ZrC ceramics was systematically investigated. The results show that the densification of ZrC was significantly enhanced by the introduction of MoSi₂ due to the formation of a liquid phase during sintering. In addition, the ZrC grains were refined due to the pinning effect of the generated silicon carbide. The flexural strength and Vickers hardness of ZrC ceramics with 2.5 vol% MoSi₂ sintered at 1850 °C were 408 ± 12 MPa and 17.1 GPa, respectively, which were approximately 30% and 10% higher compared to the samples without the addition of MoSi₂. The improved mechanical properties were mainly attributed to the high relative density (99.1%) and refined microstructure. Full article

The development of capsules with additives that can be added to polymers during extrusion processing can lead to advances in the manufacturing of textile fabrics with improved and durable properties. In this work, caffeine (CAF), which has anti-cellulite properties, has been encapsulated by liquid-assisted milling in zirconium-based metal–organic frameworks (MOFs) with different textural properties and chemical functionalization: commercial UiO-66, UiO-66 synthesized without solvents, and UiO-66-NH₂ synthesized in ethanol. The CAF@MOF capsules obtained through the grinding procedure have been added during the extrusion process to recycled polyamide 6 (PA6) and to a biopolymer based on polylactic acid (PLA) to obtain a load of approximately 2.5 wt% of caffeine. The materials have been characterized by various techniques (XRD, NMR, TGA, FTIR, nitrogen sorption, UV–vis, SEM, and TEM) that confirm the caffeine encapsulation, the preservation of caffeine during the extrusion process, and the good contact between the polymer and the MOF. Studies of the capsules and PA6 polymer+capsules composites have shown that release is slower when caffeine is encapsulated than when it is free, and the textural properties of UiO-66 influence the release more prominently than the NH₂ group. However, an interaction is established between the biopolymer PLA and caffeine that delays the release of the additive. Full article

The aim of the research was to find a zirconia treatment method that would reduce or minimize the transformation from the tetragonal phase to the monoclinic phase. Background: Yttria-stabilized zirconia is increasingly chosen for the base of permanent prosthetic restorations. To achieve a good bond between the prosthetic cup and the veneer material, the material must be treated to achieve surface development. This is a mechanical process, during which an unfavorable transformation from the tetragonal into the monoclinic phase takes place, which leads to the weakening of the internal structure of zirconium dioxide, and later damages the prosthetic restoration. Methods: The tested material consisted of cylindrical samples of 3Y-TZP CeramillZi zirconium oxide, which were sintered after cutting out from the block. After sintering, the samples were subjected to the following types of processing: laser structuring, chemical etching and plasma etching. After the surface treatments, the samples were subjected to diffraction tests to determine the phase composition. Next, the wettability was tested to determine the surface free energy. Results: On the basis of the conducted tests, it was noticed that the applied treatments caused a phase transformation from the tetragonal to the monoclinic phase. After the process of chemical etching, the range of the monoclinic phase for the sample was 5%; after plasma etching, it was 8%, and after laser structuring, it was 2%. In addition, post-surface free energy studies have shown that zirconia is wetted better with an apolar than a polar liquid. Conclusions: The obtained results indicate that the transformation was minimized with the treatments we applied; that is why they are called non-invasive methods. According to the literature data, depending on the parameters of the sandblasting process, the percentage of the monoclinic phase in the treated surfaces ranges from 22% to 52%, which confirms the above-mentioned conclusion. Full article

The efficient separation of Zr(IV) ions from strong acidic and radioactive solutions is a significant challenge, especially in the context of the aqueous reprocessing of nuclear fuels. The complexity of such solutions, which are often characterized by high acidity and the presence of radioactive elements, poses formidable challenges for separation processes. Herein, several mesoporous silicas (HMS, MCM-41, KIT-6, and SiO₂-70 Å) with excellent acid and radiation resistance properties were employed as sorbents to remove Zr(IV) ions from simulated high-level liquid waste. The batch experiments were designed to investigate the influence of adsorption time, HNO₃ concentration, initial Zr(IV) concentration, adsorbent dosage, and temperature on the adsorption behavior of Zr(IV). The results indicate that the adsorption equilibrium time of mesoporous silica materials was approximately 8 h, and all the adsorption processes followed the pseudo-second-order kinetics equation. The isotherms of Zr(IV) adsorption by KIT-6 exhibited good agreement with the Langmuir model, while the Freundlich model could be utilized to fit the adsorption on HMS, MCM-41, and SiO₂-70 Å. The adsorption capacity of MCM-41 for Zr(IV) in 3 mol/L HNO₃ was 54.91 mg/g, which is three times the adsorption capacity reported for commercial silica gel (17.91 mg/g). The thermodynamic parameters indicate that the adsorption processes for zirconium are endothermic reactions. Furthermore, the mesoporous silicas exhibited a pronounced selectivity in the adsorption of Zr(IV) within a simulated high-level liquid waste containing 10 co-existing cations (3 mol/L HNO₃). This suggests that mesoporous silicas have great potential for Zr(IV) removal in actual radioactive liquids with high acidity during spent fuel reprocessing. Full article

An inorganic solid electrolyte is the most favorable candidate for replacing flammable liquid electrolytes in lithium batteries. Lithium lanthanum zirconium oxide (LLZO) is considered a promising solid electrolyte due to its safe operating potential window (0–5 V) combined with its good electrochemical stability. In this work, 250 g batches of pre-sintered Ta-doped LLZO (Li₇La₃Zr_1.6Ta_0.4O₁₂, Ta-LLZO) were synthesized for bulk production of a dense LLZO electrolyte. A simple two-step thermal treatment process was developed. The first thermal step at 950 °C initiates nucleation of LLZO, with carefully controlled process parameters such as heating atmosphere, temperature, and dopant concentration. In the second thermal step at 1150 °C, sintered discs were obtained as solid electrolytes, with relative densities of 96%. X-ray diffraction analysis confirmed the phase purity of the sintered Ta-LLZO disc, and refined data were used to calculate the lattice parameter (12.944 Å). Furthermore, the presence of the Ta dopant in the disc was confirmed through X-ray photoelectron spectroscopy (XPS) analysis. The ionic and electronic conductivity values of the Ta-LLZO disc were 10⁻⁴ S cm⁻¹ and 10⁻¹⁰ S cm⁻¹, respectively. These values confirm that the prepared (Ta-LLZO) discs exhibit ionic conductivity while being electronically insulating, being suitable for use as solid electrolytes with the requisite electrical properties. Full article

Modern magnesium-based alloys are broadly used in various industries as well as for biodegradable medical implants due to their exceptional combination of light weight, strength, and plasticity. The studied ZEK100 alloy had a nominal composition of 1 wt.% zinc, 0.1 wt.% zirconium, and 0.1 wt.% rare earth metals (REMs) such as Y, Ce, Nd, and La, with the remainder being Mg. It has been observed that between the solidus (T_s = 529.5 ± 0.5 °C) and liquidus temperature (T_l = 645 ± 5 °C), the Mg/Mg grain boundaries can contain either the droplets of a melt (incomplete or partial wetting) or the continuous liquid layers separating the abutting Mg grains (complete wetting). With the temperature increasing from T_s to T_l, the transformation proceeds from incomplete to complete grain boundary wetting. Below 565 °C, all grain boundaries are partially wetted by the melt. Above 565 °C, the completely wetted Mg/Mg grain boundaries appear. Their portion grows quickly with an increasing temperature until reaching 100% at 622 °C. Above 622 °C, all the solid Mg grains are completely surrounded by the melt. After rapid solidification, the REM-rich melt forms brittle intermetallic compounds. The compression strength as well as the compression yield strength parameter σ₀₂ strongly depend on the morphology of the grain boundary layers. If the hard and brittle intermetallic phase has the shape of separated particles (partial wetting), the overall compression strength is about 341 MPa and σ₀₂ = 101 MPa. If the polycrystal contains the continous intergarnular layers of the brittle intermetallic phase (complete wetting), the overall compression strength drops to 247 Mpa and σ₀₂ to 40 Mpa. We for the first time observed, therefore, that the grain boundary wetting phenomena can strongly influence the mechanical properties of a polycrystal. Therefore, grain boundary wetting can be used for tailoring the behavior of materials. Full article

The effect of support on the performance of Pd₁Ag₁₀/Al₂O₃ and Pd₁Ag₁₀/CeO₂–ZrO₂ catalysts in the selective hydrogenation of diphenylacetylene (DPA) was studied. Characterization of the catalyst by DRIFTS-CO and HRTEM revealed the formation of a PdAg single-atom alloy (SAA) structure on the surface of PdAg nanoparticles, with Pd₁ sites isolated by Ag atoms. It was found that the use of CeO₂–ZrO₂ as a carrier makes it possible to increase the activity of the Pd₁Ag₁₀ catalyst by a factor of three without loss of selectivity compared to the reference Pd₁Ag₁₀/Al₂O₃. According to the HRTEM data, this catalytic behavior can be explained by an increase in the dispersion of Pd₁Ag₁₀/CeO₂–ZrO₂ compared to its Pd₁Ag₁₀/Al₂O₃ counterpart. As evidenced by DRIFTS-CO data, the high selectivity of the Pd₁Ag₁₀/CeO₂–ZrO₂ sample presumably stems from the stability of the structure of isolated Pd₁ sites on the surface of SAA Pd₁Ag₁₀/CeO₂–ZrO₂. Full article

A metal–organic framework (MOF) is a three-dimensional crystalline compound made from organic ligands and metals. The cross-linkage between organic ligands and metals creates a network of coordination polymers containing adjustable voids with a high total surface area. This special feature of MOF made it possible to form a host–guest interaction with small molecules, such as ionic liquid (IL), which can alter the phase behavior and improve the performance in battery applications. The molecular interactions of MOF and IL are, however, hard to understand due to the limited number of computational studies. In this study, the structural parameters of a zirconium-based metal–organic framework (UiO-66) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][TFSI] were investigated via a combined experimental and computational approach using the linker model approach. When IL was loaded, the bond length and bond angle of organic linkers were distorted due to the increased electron density surrounding the framework. The increase in molecular orbital energy after confining IL stabilized the structure of this hybrid system. The molecular interactions study revealed that the combination of UiO-66 and [EMIM][TFSI] could be a promising candidate as an electrolyte material in an energy storage system. Full article

Different amounts of sodium-alendronate (ALN) were loaded into layered zirconium phosphates of alpha and gamma type (αZP and γZP) by means of topotactic exchange reactions of phosphate with ALN. In order to extend the exchange process to the less accessible interlayer regions, ALN solutions were contacted with colloidal dispersions of the layered solids previously exfoliated in single sheets by means of intercalation reaction of propylamine (for αZP) or acetone (for γZP). The ALN loading degree was determined by liquid P-nuclear magnetic resonance (NMR) and inductively coupled plasma (ICP), and it was reported as ALN/Zr molar ratios (Rs). The maximum R obtained for γZP was 0.34, while αZP was able to load a higher amount of ALN, reaching Rs equal to 1. The synthesized compounds were characterized by X-ray powder diffractometry, scanning electron microscopy (SEM), solid-state NMR, and infrared spectroscopy. The way the grafted organo-phosphonate groups were bonded to the layers of the host structure was suggested. The effect of ZP derivatives was assessed on cell proliferation, and the results showed that after 7 days of incubation, none of the samples showed a decrease in cell proliferation. Full article

Bismuth–lithium alloys are considered primary candidates for the reductive extraction step in the on-line reprocessing of molten salt reactor fuel. The corrosion behavior of molybdenum-based alloys and Hastelloy^® B-3 alloy (taken for comparison) was examined here in a liquid Bi–Li (5 mol.%) alloy at 650 °C. MoW10, MoW30, and TZM corrosion-resistant alloys were studied as prospective construction materials for holding liquid bismuth–lithium alloy. Rates of corrosion were determined by the gravimetric method as well as by chemical analysis of corrosion products formed in liquid-phase Bi–Li alloy. The microstructure and chemical composition of samples of the materials and Bi–Li alloys containing the corrosion products after the tests were determined using inductively coupled plasma–atomic emission spectroscopy, X-ray fluorescence analysis, scanning electron microscopy, and energy dispersive spectroscopy. TZM molybdenum-based alloy corrodes in the bismuth-lithium alloy due to the formation of a zirconium–bismuth intermetallic compound, which passes into the liquid phase. The corrosion rates of MoW10, MoW30, and TZM alloys at 650 °C were 16, 16, and 23 µm/year, respectively. Hastelloy^® B-3 alloy, despite its high molybdenum content, was subjected to severe corrosion in liquid Bi–Li alloys due to dissolution of nickel in liquid bismuth. The corrosion rate of this alloy was 14 mm/year. Full article