Search Results (22)

Vacancy-ordered double-perovskite Cs₂SnI₆ is known to be a good candidate for perovskite photovoltaics, as it is a light harvesting material which has potential both as an individual compound and as a component of a composite material. The compound is interesting due to being free of atom sites in B cationic positions, making the lattice “breathable” and giving it optoelectronic characteristics that vary with dopants. Here, antimony was examined as a possible heterovalent dopant with an ionic radius larger than that of Sn⁴⁺. In practice, it has been found that most of the materials are composites of Cs₂SnI₆ and Cs₃Sb₂I₉ phases. In the CsI–SnI₄–SbI₃ phase triangle, the melt crystallization process produced a layered (111)-oriented microstructure of crystallites with an increasing percentage of antimony. Two-dimensional perovskite materials look more promising in the decomposition of a solid solution to Cs₂SnI₆ and Cs₃Sb₂I₉ phases than in heterophase nucleation. The observed effect of (111)-oriented growth could be translated to other inorganic halides to form new oriented films or single crystals of perovskite materials. Diffuse reflectance spectroscopy showed an additional absorption shoulder in the NIR region for all groups of compounds, most likely induced by point defects in I sublattices of Cs₂SnI₆. Expanding the Cs₂SnI₆ absorption range to the NIR region could lead to new perspectives for its application. Full article

Structural heterogeneity plays a crucial role in enhancing the mechanical properties of metallic glasses (MGs) by impeding the propagation of shear bands (SBs). Metallic glass matrix composites (MGCs) consisting of reinforcements are of great interest as they enhance the mechanical performance of brittle MGs. However, managing the dispersity of hetero-phases within the glassy matrix presents technical challenges due to surface tension and thermal property incompatibility. Binodal phase separation is an effective approach for fabricating MGCs with uniformly dispersed glassy droplets or particles. The species of matrix and characteristics of particle reinforcements significantly influence mechanical properties. This study theoretically examines how the fraction, size, and variety of particle reinforcements influence performance using finite element models based on free volume theory. The synergistic mechanisms for performance tuning involve stress fields generated by particle reinforcements that modify the nucleation and propagation of SBs in the matrix. Additionally, the size effect of particles depends on their interaction with SBs. This comprehensive understanding could substantially enhance the design and optimization for MGCs. Full article

During sulfite delignification of wood, sulfo derivatives of lignin—lignosulfonates (LS)—are formed as a byproduct. Due to their amphiphilic nature, LS are used as plasticizers, dispersants, and stabilizers. The functions and performance characteristics of this surface-active polyelectrolyte are determined by its behavior in aqueous solution, at surfaces and interfaces, which, in turn, is determined by its chemical composition. This study investigated the effect of LS with various molecular weight compositions (M_w 9–50 kDa) on the behavior and aggregation stability of aqueous dispersions of elemental sulfur (S⁰) under conditions simulating hydrothermal leaching of sulfide ores. Using conductometry, potentiometry, tensiometry, and viscometry, a detailed study of the physicochemical properties of aqueous LS solutions (C_LS 0.02–1.28 g/dm³) obtained from a few sources (Krasnokamsk, Solikamsk, and Norwegian Pulp and Paper Mills) was conducted. The composition, molecular weight, and concentration of LS were found to significantly affect their specific electrical conductivity, pH, intrinsic viscosity, and surface activity. LS introduction during the formation of sulfur sols is shown to promote their stabilization through electrostatic and steric mechanisms. Optimum dispersion stability (293 K, pH 4.5–5.5) was observed at moderate LS concentrations (0.02–0.32 g/dm³), when a stable adsorption layer forms on the surface of sulfur particles. High-molecular-weight LS samples provided more effective spatial stabilization of sulfur particles. It has been established that increasing temperature (293–333 K) and changing pH (1–7) significantly affect the aggregative stability of systems; specifically, the sol stability decreases with increasing temperature, and the stabilizing effect of different LS types reverses upon changing pH. The obtained results highlight the potential of using naturally occurring polymeric dispersants to control the aggregation stability of sulfur-containing heterophase systems and can be applied to the design of stable colloidal systems in chemical engineering and hydrometallurgy. Full article

Phase engineering has emerged as a powerful method for manipulating the structural and electrical characteristics of nanomaterials, resulting in significant enhancements in their electrochemical performance. This paper examines the correlation among morphology, crystal phase, and electrochemical performance of nanomaterials engineered for high-performance batteries and supercapacitors. The discourse starts with phase engineering methodologies in metal-based nanomaterials, including the direct synthesis of atypical phases and phase transformation mechanisms that provide metastable or mixed-phase structures. Special emphasis is placed on the impact of these synthetic processes on morphology and surface properties, which subsequently regulate charge transport and ion diffusion during electrochemical reactions. Additionally, the investigation of phase engineering in transition metal dichalcogenide (TMD) nanomaterials highlights how regulated phase transitions and heterophase structures improve active sites and conductivity. The optimized phase-engineered ZnCo₂O₄@Ti₃C₂ composite exhibited a high specific capacitance of 1013.5 F g⁻¹, a reversible capacity of 732.5 mAh g⁻¹, and excellent cycling stability, with over 85% retention after 10,000 cycles. These results confirm that phase and morphological control can substantially enhance charge transport and electrochemical durability, offering promising strategies for next-generation batteries and supercapacitors. The paper concludes by summarizing current advancements in phase-engineered nanomaterials for lithium-ion, sodium-ion, and lithium-sulfur batteries, along with supercapacitors, emphasizing the significant relationship between phase state, morphology, and energy storage efficacy. This study offers a comprehensive understanding of the optimal integration of phase and morphological control in designing enhanced electrode materials for next-generation electrochemical energy storage systems. Full article

Light alloys based on magnesium are widely used in most areas of science and technology. However, magnesium powder alloys are quite difficult to sinter due to the stable film of oxides that counteracts diffusion. Therefore, finding a method to activate magnesium sintering is urgent. This study examines the effect of adding 5 wt. % and 10 wt. % zinc to the sintering pattern of magnesium powders at 430 °C; a dwell of 30 min was used to homogenize at the densification’s temperature. Scanning electron microscopy (SEM) was used to characterize the alloy’s microstructure, while the phase composition was characterized using X-ray diffraction (XRD) and energy dispersion spectroscopy (EDS). The sintering densities of Mg–5Zn and Mg–10Zn were found to be 88% and 92%, respectively. The results show that after sintering, a heterophase structure of the alloy is formed based on a solid solution and phases MgZn and Mg₅₀Zn₂₁. To establish the sintering mechanism, the interaction at the MgO and Zn melt phase interface was analyzed using the sessile drop method. The minimum contact angle—65°—was discovered at 500 °C with a 20 min holding time. It was demonstrated that the sintering process in the Mg–Zn system proceeds through the following stages: (1) penetration of zinc into oxide-free surfaces; (2) crystallization of a solid solution, intermetallics; and (3) the removal of magnesium oxide from the particle surface, with oxide particles deposited on the surface of the sample. Full article

Polymethylmethacrylate (PMMA) is the most commonly used bone void filler in orthopedic surgery. However, the biocompatibility and radiopacity of PMMA are insufficient for such applications. In addition to insufficient biocompatibility, the microbial infection of medical implants is one of the frequent causes of failure in bone reconstruction. In the present work, the preparation of a novel PMMA-based hydroxyapatite/ZnFe₂O₄/ZnO composite with heterophase ZnFe₂O₄/ZnO NPs as an antimicrobial agent was described. ZnFe₂O₄/ZnO nanoparticles were produced using the electrical explosion of zinc and iron twisted wires in an oxygen-containing atmosphere. This simple, highly productive, and inexpensive nanoparticle fabrication approach could be readily adapted to different applications. From the findings, the presented composite material showed significant antibacterial activity (more than 99% reduction) against P. aeruginosa, S. aureus, and MRSA, and 100% antifungal activity against C. albicans, as a result of the combined use of both ZnO and ZnFe₂O₄. The composite showed excellent biocompatibility against the sensitive fibroblast cell line 3T3. The more-than-70% cell viability was observed after 1–3 days incubation of the sample. The developed composite material could be a potential material for the fabrication of 3D-printed implants. Full article

Hydrogen is an ideal alternative energy for fossil fuels to solve aggravating environmental and energy problems. Electrocatalytic hydrogen evolution reaction (HER) driven by renewable electricity (sunlight, wind, tide, etc.) is considered to be one of the most promising approaches for hydrogen production. However, its large-scale applications are greatly limited by the use of noble platinum (Pt) group electrocatalysts. As an earth-abundant/non-noble HER catalyst, molybdenum carbide (Mo_xC: MoC or Mo₂C) has attracted extensive attention in the field of sustainable hydrogen production due to its excellent Pt-like catalytic activity, low cost, high chemical stability, and natural abundance. In this review, the progress on the strategies for optimizing the catalytic activity of Mo_xC is summarized, including optimization of synthesis methods, composites with carbon material, non-precious metal doping, transition metal doping, construction of the heterogeneous structure, etc. Among them, the importance of sulphur-doping, Ni-doping, and heterophase structure on molybdenum carbide-based catalysts for enhancement of HER activity has been highlighted. In addition, molybdenum carbide-based bi-functional catalysts are presented for the application in full water splitting. Finally, several effective strategies for molybdenum carbide-based catalyst design are concluded, and challenges remained in electrocatalytic water splitting are raised. Future development trends and perspectives for this promising material are also discussed. Full article

Direct ink writing (DIW) requires careful selection of ink composition with specific rheological properties, and it has limitations, such as the inability to create overhanging parts or branched geometries. This study presents an investigation into enhancing the 3D printing process through the use of a heterophase system, aiming to overcome these limitations. A modification was carried out in the 3D printer construction, involving adjustments to the structural elements responsible for the extrusion device’s movement. Additionally, a method for obtaining a heterophase system based on gelatin microparticles was developed to enable the 3D printing process with the upgraded printer. The structure and rheological properties of the heterophase system, varying in gelatin concentration, were thoroughly examined. The material’s viscosity ranged from 5.4 to 32.8 kPa·s, exhibiting thixotropic properties, pseudoplastic behavior, and long-term stability at 20 °C. The developed 3D printing technology was successfully implemented using a heterophase system based on different gelatin concentrations. The highest product quality was achieved with a heterophase system consisting of 4.5 wt.% gelatin, which exhibited a viscosity of 22.4 kPa·s, enabling the production of products without spreading or compromising geometrical integrity. Full article

Heterophases, such as precipitates, inclusions, second phases, or reinforcement particles, often drive void nucleation due to local incompatibilities in stresses/strains. This results in a significant life-limiting condition, as voids or their coalescence can lead to microcracks that reduce the ductility and fatigue life of engineering components. Continuum-mechanics-based analytical models have historically gained momentum due to their relative ease in predicting failure strain. The momentum of such treatment has far outpaced the development of theories at the atomic and micron scales, resulting in an insufficient understanding of the physical processes of void nucleation and growth. Evidence from the recent developments in void growth theories indicates that the evolution of voids is intrinsically linked to dislocation activity at the void–matrix interface. This physical growth mechanism opens up a new methodology for improving mechanical properties using hydrostatic pressurization. According to the limited literature, with a hydrostatic pressure close to 1 GPa, aluminium matrix composites can be made 70 times more ductile. This significant ductility enhancement arises from the formation of dislocation shells that encapsulate the heterophases and inhibit the void growth and coalescence. With further investigations into the underlying theories and developments of methods for industrial implementations, hydrostatic pressurization has the potential to evolve into an effective new method for improving the ductility and fatigue life of engineering components with further development. Full article

The electrochemical reduction of pelleted heterophase powder Pd-Nd₂O₃-CeO₂ mixtures was studied in molten LiCl-Li₂O (1–1.5 wt%) at 650 °C. The influence of the composition of the mixture, as well as electrochemical factors—i.e., the amount of electricity passed and the cathode potential during electrolysis—were considered. It was found that in the presence of metallic palladium, neodymium and cerium oxides are reduced by lithium released at the cathode and form intermetallic compounds of different compositions. At potentials more positive than the formation of a phase based on liquid lithium at 0.5–0.8 V, CePd₃ and NdPd₃ intermetallic compounds are present in the reduced product. At potentials close to the formation of liquid lithium, a whole spectrum of intermetallic compounds is synthesized: CePd, NdPd, Ce₃Pd₄, and Nd₃Pd₄. The mechanisms of formation of palladium alloys with neodymium and cerium are proposed and considered. The degree of the reduction of lanthanide oxides was calculated from the data on the concentration of residual oxygen in the reduced product. Full article

In this study, composites based on a heterophasic polypropylene (PP) copolymer containing different loadings of micro-sized (i.e., talc, calcium carbonate, and silica) and nano-sized (i.e., a nanoclay) fillers were formulated via melt compounding to obtain PP-based materials suitable for Material Extrusion (MEX) additive manufacturing processing. The assessment of the thermal properties and the rheological behavior of the produced materials allowed us to disclose the relationships between the influence of the embedded fillers and the fundamental characteristics of the materials affecting their MEX processability. In particular, composites containing 30 wt% of talc or calcium carbonate and 3 wt% of nanoclay showed the best combination of thermal and rheological properties and were selected for 3D printing processing. The evaluation of the morphology of the filaments and the 3D-printed samples demonstrated that the introduction of different fillers affects their surface quality as well as the adhesion between subsequently deposited layers. Finally, the tensile properties of 3D-printed specimens were assessed; the obtained results showed that modulable mechanical properties can be achieved depending on the type of the embedded filler, opening new perspectives towards the full exploitation of MEX processing in the production of printed parts endowed with desirable characteristics and functionalities. Full article

Abatement of pharmaceutical pollutants from aquatic systems is crucial but remains a challenge. Semiconductor photocatalysis has emerged as an eco-friendly technique that utilizes renewable solar energy to address environmental issues. Naturally occurring and earth abundant hematite (Fe₂O₃) ores can be incorporated as a suitable component of a photocatalyst. Herein, Brazilian hematite was partially phase transformed into heterophase (consisting of α/γ-Fe₂O₃) by a simple single-stage heat treatment procedure. The method of synthesis was simple and economical, requiring neither solvents nor concentrated acids. The existence of α/γ-phases in the produced Fe₂O₃ (FO) was confirmed by X-ray diffraction analysis. After the phase transformation process, the local structure surrounding the Fe atoms was varied as evidenced from X-ray absorption spectroscopy. Given its low toxicity, narrow bandgap, and chemical stability, FO was further combined with g-C₃N₄ (CN) to form composites. The optical properties of the synthesized CNFO composites confirmed that the visible light harvesting ability of CN was enhanced after combining with FO. The CN sheets were grown uniformly over the surface of FO as evidenced from scanning electron microscopy. The prepared composites could degrade an aqueous solution of ofloxacin (OFX, 10 ppm) under visible light with remarkable efficacy. The performance of CNFO-5% was 4.8 times higher when compared to pure CN. The initial rate constant value for the photocatalytic degradation of OFX by CNFO-5% was 0.1271 min⁻¹. The catalyst was stable even after five repeated cycles of photodegradation. The photoluminescence spectra and electrochemical measurements confirmed the efficient separation and transfer of the photogenerated charges across their interface. The investigations on different scavengers demonstrated that superoxide anion radicals and holes played a significant role in the degradation of OFX. The mechanism for the charge transfer was proposed to be a Z-scheme heterojunction. These results point to the potential of using inexpensive, abundant, and recyclable natural hematite ores as state-of-the-art photocatalysts for the elimination of pharmaceuticals in wastewater. Full article

Ceramic materials in Na₂O-CaO-P₂O₅ system were obtained by firing cement-salt stone made from pastes based on powder mixtures including calcium citrate tetrahydrate Ca₃(C₆H₅O₇)₂∙4H₂O, monocalcium phosphate monohydrate (MCPM) Ca(H₂PO₄)₂∙H₂O and/or sodium dihydrogen phosphate NaH₂PO₄. The phase composition of the obtained samples of cement-salt stone after adding water, hardening and drying included brushite CaHPO₄∙2H₂O, monetite CaHPO₄ and also unreacted Ca₃(C₆H₅O₇)₂∙4H₂O, Ca(H₂PO₄)₂∙H₂O and/or NaH₂PO₄. The phase composition of ceramics in Na₂O-CaO-P₂O₅ system obtained by firing cement-salt stone was formed due to thermal conversion of hydrated salt and heterophase reactions between components presented in samples during firing. The phase composition of ceramic samples based on powder mixture of Ca₃(C₆H₅O₇)₂∙4H₂O and Ca(H₂PO₄)₂∙H₂O after firing at 900 °C included β-calcium pyrophosphate (CPP) β-Ca₂P₂O₇. The phase composition of ceramic samples based on powder mixture of Ca₃(C₆H₅O₇)₂∙4H₂O, and NaH₂PO₄ after firing at 900 °C included β-sodium rhenanite β-CaNaPO_4. The phase composition of ceramic samples based on powder mixture of Ca₃(C₆H₅O₇)₂∙4H₂O, Ca(H₂PO₄)₂∙H₂O and NaH₂PO₄ after firing at 900 °C included β-Ca₂P₂O₇, β-CaNaPO_4, double calcium-sodium pyrophosphate Na₂CaP₂O₇, and Na-substituted tricalcium phosphate Сa₁₀Na(PO₄)₇. Obtained ceramic materials in Na₂O-CaO-P₂O₅ system including biocompatible and biodegradable phases could be important for treatments of bone tissue defects by means of approaches of regenerative medicine. Full article

Fine powders of brushite CaHPO₄·2H₂O, ardealite Ca(HPO₄)_x(SO₄)_1−x·2H₂O (Ca(HPO₄)_0.5(SO₄)_0.5·2H₂O), and calcium sulfate dihydrate CaSO₄·2H₂O—all containing sodium chloride NaCl as a reaction by-product—were synthesized from 0.5 M aqueous solution of calcium chloride CaCl₂, sodium hydrophosphate Na₂HPO₄ and/or sodium sulfate Na₂SO₄. Powder of ardealite Ca(HPO₄)_x(SO₄)_1−x·2H₂O (Ca(HPO₄)_0.5(SO₄)_0.5·2H₂O) was synthesized by precipitation from aqueous solution of calcium chloride CaCl₂ and mixed-anionic solution simultaneously containing the hydrogen phosphate anion HPO₄²⁻ (Na₂HPO₄) and sulfate anion SO₄²⁻ (Na₂SO₄). Sodium chloride NaCl, presenting in compacts based on synthesized powders of brushite CaHPO₄·2H₂O, ardealite Ca(HPO₄)_x(SO₄)_1−x·2H₂O (Ca(HPO₄)_0.5(SO₄)_0.5·2H₂O) and calcium sulfate dihydrate CaSO₄·2H₂O, was responsible for both low-temperature melt formation and the creation of phase composition of ceramics. Heterophase interaction of components led to the resulting phase composition of the ceramic samples during heating, including the formation of chlorapatite Ca₅(PO₄)₃Cl in powders of brushite and ardealite. The phase composition of the ceramics based on the powder of brushite CaHPO₄·2H₂O containing NaCl as a by-product after firing at 800–1000 °C included β-Ca₂P₂O₇, and Ca₅(PO₄)₃Cl. The phase composition of ceramics based on the powder of ardealite Ca(HPO₄)_x(SO₄)_1−x·2H₂O (Ca(HPO₄)_0.5(SO₄)_0.5·2H₂O) containing NaCl as a by-product after firing at 800 and 900 °C included β-Ca₂P₂O_7, CaSO₄, and Ca₅(PO₄)₃Cl; after firing at 1000 °C, it includedCaSO_4, Ca₅(PO₄)₃Cl and Ca₃(PO₄)₂/Ca₁₀Na(PO₄)₇, and after firing at 1100 °C, it included CaSO₄ and Ca₅(PO₄)₃Cl. The phase composition of ceramics based on powder of calcium sulfate dihydrate CaSO₄·2H₂O containing NaCl as a by-product after firing at 800–1100 °C included CaSO₄ as the predominant phase. The phase composition of all ceramic samples under investigation consisted of biocompatible crystalline phases with different abilities to biodegrade. For this reason, the created ceramics can be recommended for testing as materials for treatment of bone defects using regenerative medicine methods. Full article

Poly(dimethyl siloxane)-MQ rubber molecular composites are easy to prepare, as it does not require a heterophase mixing of ingredients. They are characterized by perfect homogeneity, so they are very promising as rubber materials with controllable functional characteristics. The manuscript reveals that MQ resin particles can significantly, more than by two orders of magnitude, enhance the mechanical properties of poly(dimethyl siloxane), and, as fillers, they are not inferior to aerosils. In the produced materials, MQ particles play a role of the molecular entanglements, so rubber molecular weight and MQ filler concentration are the parameters determining the structure and properties of such composites. Moreover, a need for a saturation of the reactive groups and minimization of the surface energy of MQ particles also determine the size and distribution of the filler at different filler rates. An unusual correlation of the concentration of MQ component and the interparticle spacing was revealed. Based on the extraordinary mechanical properties and structure features, a model of the structure poly(dimethyl siloxane)-rubber molecular composites and of its evolution in the process of stretching, was proposed. Full article