Search Results (34)

In this study, the solvent displacement method was used. This is a low-energy technique that generates a spontaneous “oil-in-water” nanoemulsion by diffusing ethanol from the oily phase to the aqueous phase. Subsequently, chitosan, a biocompatible and biodegradable cationic polymer, was incorporated, applying ionic gelation with sodium sulfate (Na₂SO₄) to achieve uniform coatings. Atomic force microscopy (AFM) characterization revealed nanocapsules with defined morphology and regular topography. Analysis with WSxM 4.0 Beta 10 software revealed a partially ordered hexagonal arrangement, which was evidence of controlled synthesis and the potential of chitosan as a polymeric system. Full article

Birnessite has a strong ability to fix rare-earth elements (REEs), but the transformation process of birnessite and its effects on the migration of these elements are not well understood. This study examines how pH and Mn(II) concentrations influence the transformation of cerium-adsorbed hexagonal birnessite (Ce/HB) and the behaviors of Ce and Mn. The results show that the effect of Mn(II) on Ce/HB transformation strongly depended on solution pH. At a pH of 5.0, HB initially underwent transformation into feitknechtite, followed by further disproportionation that resulted in the regeneration of HB and Mn(II). Concurrently, redox reactions occur between Mn(IV) in MnO₂ (a secondary phase of HB) and Ce(III)/Mn(II), creating a local redox gradient that facilitates partial HB transformation. At pH = 7.0, Mn(II) reduces the crystallinity of transformed products while enhancing the thermodynamic stability of feitknechtite, making it the dominant manganese oxide phase. At pH = 9.0, high-concentration Mn(II) causes lattice distortion in original HB; Ce(III) acts as a structural inducer, promoting mineral transition from hexagonal to orthorhombic symmetry, while excess soluble Mn(II) precipitates new feitknechtite. Additionally, surplus Mn(II) could engage in interfacial redox reactions with high-valent manganese oxides to generate secondary feitknechtite. Ce primarily exists as Ce(IV), forming CeO₂ on the mineral surface via oxidation reactions that significantly increase hydroxylation and surface reactivity. This study clarifies the transformation pathways of manganese oxides and the migration and transformation patterns of Ce and Mn in rare-earth-rich mining areas. Full article

This study employs a multi-technique approach to elucidate how graphene incorporation affects phase formation, microstructure, and thermal behavior in PVA-assisted sol–gel synthesized Ca_2.95Eu_0.05Co₄O_x nanomaterials. XRD confirms the preservation of the primary phases (hexagonal CaCO₃ and cubic CoO) alongside a distinct graphene (002) reflection; a systematic low-angle shift of the calcite (104) peak evidences partial relaxation of residual lattice strain with increasing graphene content, while Scherrer analysis indicates tunable crystallite size. Raman spectroscopy corroborates graphene incorporation through pronounced D (~1300 cm⁻¹) and G (~1580 cm⁻¹) bands and supports the XRD-identified phase coexistence via cobalt-oxide and calcite vibrations in the 200–700 cm⁻¹ region, also indicating increased defect/disorder with graphene loading. SEM shows grain refinement, denser/bridged lamellar textures, and reduced porosity at low–moderate graphene contents (1–3 wt.%), contrasted by agglomeration-driven heterogeneity at higher loadings (5–7 wt.%). EDX reveals increasing carbon with Ca/Co redistribution at accessible surfaces, and TG–DSC corroborates the removal of oxygen-containing groups and oxidative combustion of graphene at mid temperatures. Collectively, Raman–XRD-consistent evidence demonstrates that graphene provides a tunable handle over lattice strain, crystallite size, and grain-boundary architecture, establishing a processing–composition basis for optimizing functional (e.g., electrical/thermoelectric) performance. Full article

Calcium aluminate cement (CAC) offers rapid strength development, chemical durability in harsh environments, and high-temperature resistance, but its long-term performance may be compromised by the conversion of metastable hexagonal hydrates into stable cubic phases. Concurrently, recycling spent fluorescent lamp glass (SFLG) is limited because of its residual mercury content. This study investigates the use of manually (MAN) and mechanically (MEC) processed SFLG as partial CAC replacements (up to 50 wt.%). Both SFLG types had irregular morphologies with mean particle sizes of ~20 µm and mercury concentrations of 3140 ± 61 ppb (MAN) and 2133 ± 119 ppb (MEC). Moreover, the addition of SFLG reduced the initial and final setting times, whilst MEC waste notably extended the plastic state duration from 20 min (reference) to 69 min (50 wt.% MEC). Furthermore, strength development was accelerated, with SFLG/CAC mortars reaching peak strengths at 7–10 days versus 28 days as in the CAC reference. CAC and 15 wt.% SFLG mortars showed strength loss over time by reason of their phase conversion, whereas mortars with 25–50 wt.% SFLG experienced significant long-term strength gains, reaching ~60 MPa (25 wt.%) and ~45 MPa (35 wt.%), respectively, after 365 days, with strength activity indexes (SAI) near 90% and 70%, respectively. These improvements are attributed to the formation of strätlingite (C₂ASH₈), which stabilized hexagonal CAH₁₀ and mitigated conversion to cubic katoite (C₃AH₆). Mercury leaching remained below 0.01 mg/kg dry matter for all mixes and curing ages, classifying the mortars as non-hazardous and inert under Spanish Royal Decree 646/2020. The results suggest that SFLG can be safely reused as a sustainable admixture in CAC systems, enhancing long-term mechanical performance while minimizing environmental impact. Full article

Hydroxyapatite (HAP) is the most widely accepted biomaterial for repairing bone tissue defects, demonstrating excellent biocompatibility and bioactivity that promote new bone formation. Zirconia (ZrO₂), known for its strength and fracture toughness, is commonly used to reinforce ceramics. In this study, magnesium oxide (MgO) served as a stabilizer for zirconia, resulting in magnesia partially stabilized zirconia (Mg-PSZ). Both Mg-PSZ and HAP were synthesized via coprecipitation and mixed in specific ratios to create composites through a ceramic method involving mixing, compaction, and sintering at 1100 °C. The samples were characterized using techniques such as X-ray powder diffraction (XRPD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS). Structural analyses confirmed the presence of both monoclinic and tetragonal zirconia phases. Besides, the increased wt.% HAP in the composites produced distinct peaks for hexagonal HAP. Crystallite sizes ranged from 27.45 nm to 31.5 nm, and surface morphology was homogeneous with small pores. Elements such as calcium, phosphorus, magnesium, zirconium, and oxygen were detected in all samples. This research also examined microhardness changes in the materials. The findings revealed enhancement in microhardness for the biocomposite with higher zirconia content, 90Mg-PSZ/10HAP sample, with the smallest average pore size, highlighting its potential for biomedical applications. Full article

Enhanced hard coatings with exceptional mechanical and thermal qualities have prompted substantial study into multicomponent nitride systems. TiAl(Si)N coatings have emerged as viable possibilities owing to their remarkable hardness, thermal stability, and oxidation resistance. This work involved the fabrication of thickness-varied TiAl(Si)N gradient coatings using reactive magnetron sputtering, employing a controlled modulation of aluminum and silicon content across the film thickness. Three samples, with thicknesses of ~400 nm, ~600 nm, and ~800 nm, were deposited under uniform Ar/N₂ gas flow ratios, and their microstructural, mechanical, and tribological characteristics were rigorously examined. SEM investigation demonstrated a significant change across thicknesses. XRD results validated the emergence of a predominant cubic TiAl(Si)N phase alongside a secondary hexagonal AlN phase, signifying partial phase segregation. The nanoindentation results indicated that Sample 2 exhibited the maximum hardness (~38 GPa) and Young’s modulus (~550 GPa) due to an optimized equilibrium between solid solution strengthening and nanocomposite production. Tribological testing revealed that Sample 1 displayed the lowest and most consistent friction coefficient, corresponding to its superior H/E and H3/E2 ratios, which signify improved elasticity and resistance to plastic deformation. The findings emphasize that the implementation of a compositional gradient, especially in the distribution of Si and Al, markedly affects the microstructure and performance of TiAl(Si)N coatings. Gradient structures enhance the microstructure, optimize hardness, and increase the friction coefficient. Ongoing refinement of gradient profiles and deposition parameters may further improve the characteristics of TiAl(Si)N coatings, facilitating their wider industrial use. Full article

Materials utilized in extreme environments, such as those necessitating protection and impact resistance at cryogenic temperatures, must exhibit high strength, ductility, and structural stability. However, most alloys fail to maintain adequate toughness at cryogenic temperatures, thereby compromising their safety during cryogenic temperature service. This study investigates the quasi-static mechanical properties of a CoCr₀.₄NiSi₀.₃ medium-entropy alloy (MEA) at room temperature, −75 °C, and −150 °C. The deformation behavior and mechanisms responsible for strengthening and toughening at reduced cryogenic temperatures are analyzed, revealing that decreasing cryogenic temperature enhances the strength of the as-cast MEA. Specifically, both the yield strength (YS) and ultimate tensile strength (UTS) of the MEA increase significantly with decreasing temperature during cryogenic tensile testing. Under tensile testing at −150 °C, the YS reaches 617.5 MPa, the UTS is 1055.0 MPa, and the elongation to fracture remains approximately 21.0% at both −150 °C and −75 °C. After cryogenic temperature tensile deformation, the matrix exhibits a dispersed distribution of nanoscaled tetragonal and orthorhombic phases, a coherent hexagonal close-packed phase, L1₂ phase and layered long-period stacking ordered (LPSO) structures, which are rarely observed in the cryogenic deformation of metals and alloys. The metastable phase evolution path of this MEA at cryogenic temperatures is closely associated with the decomposition of perfect dislocations into a/6<112> Shockley partial dislocations and their subsequent evolution at reduced cryogenic temperatures. At −75 °C, the a/6<112> Shockley partial dislocation interacts with the L1₂ phase to form antiphase boundaries (APBs) approximately 3 nm thick. At −150 °C, two phase transition paths from stacking faults (SFs) to nanotwins and LPSO occur, leading to the formation of layered LPSO structures and deformation-induced nanotwins. The dispersion of these coherent nanophases and nanotwins induced by the reduced stacking fault energy under cryogenic temperatures is the key factor contributing to the excellent balance of strength and plasticity in the as-cast MEA, providing an important basis for research on the cryogenic mechanical properties of CoCrNi-based MEAs. Full article

Melted rocks (clinkers and paralavas) of the Mongolian combustion metamorphic (CM) complexes were formed during modern and ancient (since the Quaternary) wild-fires of brown coal layers in the sedimentary strata of the Early Cretaceous Dzunbain Formation. According to XRD, Raman spectroscopy, and SEM-EDS data, cordierite, sekaninaite, indialite, ferroindialite, silica polymorphs, mullite, Fe-mullite, anhydrous Al-Fe-Mg silicate spinel (presumably new mineral), and other phases were identified. It has been established that isomorphic impurity of potassium in the cordierite-group minerals does not correlate with their crystal structure (hexagonal or orthorhombic). Indialite and ferroindialite retained their hexagonal structure in some fragments of the CM rocks, possibly due to the very fast cooling of local zones of sedimentary strata and the quenching of high-temperature K-rich peraluminous melt. Clinkers, tridymite–sekaninaite, and cristobalite–fayalite ferroan paralavas were produced by partial melting of Fe-enriched pelitic rocks (mudstone, siltstone, and silty sandstone) in a wide temperature range. The formation of mullite, Fe-mullite, and Al-Fe-Mg silicate spinel in clinkers developed from dehydration–dehydroxylation and incongruent partial melting of Fe-enriched pelitic matter (Al-Mg-Fe-rich phyllosilicates, ‘meta-kaolinite’, and ‘meta-illite’). Large-scale crystallization of these minerals in the K-rich peraluminous melts occurred, presumably, in the range of T > 850–900 °C. The subsurface combustion of coal layers heated the overburden pelitic rocks from sedimentary strata to T > 1050 °C (judging by the formation of cordierite-group minerals) or locally till the melting point of detrital quartz grains at T > 1300 °C and, possibly, till the stability field of stable β-cristobalite at T > 1470 °C. Ferroan paralavas were formed during the rapid crystallization of Fe-rich silicate melts under various redox conditions. From the analysis of the liquidus surface in the Al₂O₃–FeO–Fe₂O₃–SiO₂ major-oxide system, it follows that the least high-temperature (<1250 °C) and the most oxidizing conditions occurred during the crystallization of mineral assemblages in the most-enriched iron silicate melts parental for cristobalite–fayalite paralava. Full article

Zinc–tungsten coatings have been considered as environmentally friendly, and corrosion- and wear-resistant coatings. Here, Zn–W coatings were successfully electrodeposited from an aqueous solution. Citrate-based electrolytes with pH in the range of 3.0 to 5.7 were used as plating baths. The kinetics of co-reduction in the Zn(II)–W(VI)–Cit system was studied on the basis of partial polarization curves. The effects of applied potential, electrolyte composition, pH, hydrodynamic conditions and passed charge on the electrodeposition of Zn–W layers were determined. X-ray photoelectron spectroscopy confirmed the presence of metallic tungsten co-deposited with zinc. X-ray diffraction analysis revealed the formation of hexagonal Zn–W phase resulting from a substitution of Zn atoms by W atoms in the Zn crystal lattice. The formation of the proper stable and electroactive W(VI) and Zn(II) complexes is the first crucial factor enabling the induced codeposition of Zn–W alloys. The tungsten content in the Zn–W deposit is closely related to the concentration of electroactive tungstate–citrate species and its ratio relative to the zinc–citrate electroactive species in the electrolytic bath. The oxidation state of tungsten in the electrodeposited Zn–W layers can be controlled mainly by the applied deposition potential and by the bath pH, which determines the type of W(VI)–Cit species that can be reduced. Full article

Magnesium-based alloys are highly sought after in the industry due to their lightweight and reliable strength. However, the hexagonal crystal structure of magnesium results in the mechanical properties’ anisotropy. This anisotropy is effectively addressed by alloying magnesium with elements like zirconium, zinc, and rare earth metals (REM). The addition of these elements promotes rapid seed formation, yielding small grains with a uniform orientation distribution, thereby reducing anisotropy. Despite these benefits, the formation of intermetallic phases (IP) containing Zn, Zr, and REM within the microstructure can be a concern. Some of these IP phases can be exceedingly hard and brittle, thus weakening the material by providing easy pathways for crack propagation along grain boundaries (GBs). This issue becomes particularly significant if intermetallic phases form continuous layers along the entire GB between two neighboring GB triple junctions, a phenomenon known as complete GB wetting. To mitigate the risks associated with complete GB wetting and prevent the weakening of the alloy’s structure, understanding the potential occurrence of a GB wetting phase transition and how to control continuous GB layers of IP phases becomes crucial. In the investigation of a commercial magnesium alloy, ZEK100, the GB wetting phase transition (i.e., between complete and partial GB wetting) was successfully studied and confirmed. Notably, complete GB wetting was observed at temperatures near the liquidus point of the alloy. However, at lower temperatures, a coexistence of a nano-scaled precipitate film and bulk particles with nonzero contact angles within the same GB was observed. This insight into the wetting transition characteristics holds potential to expand the range of applications for the present alloy in the industry. By understanding and controlling GB wetting phenomena, the alloy’s mechanical properties and structural integrity can be enhanced, paving the way for its wider utilization in various industrial applications. Full article

In the present paper, the influence of partial substitution of Mn by Pd on structure, thermomagnetic properties, and phase transitions in the MnCoGe alloys was investigated. The studies of phase constitution revealed an occurrence of the orthorhombic TiNiSi-type and hexagonal Ni₂Ti- type phases. Deep analysis of the XRD pattern supported by the Rietveld analysis allowed us to notice the changes in lattice parameters and quantity of recognized phases depending on the Pd content. An increase of palladium in alloy composition at the expense of manganese induced a rise in the Curie temperature. The values of ΔS_M measured for the variation of external magnetic field ~5 T equaled 8.88, 23.99, 15.63, and 11.09 for Mn_0.97Pd_0.03CoGe, Mn_0.95Pd_0.05CoGe, Mn_0.93Pd_0.07CoGe, and Mn_0.9Pd_0.1CoGe alloy, respectively. The highest magnetic entropy change ΔS_M was observed for samples with Pd content x = 0.05 induced by magnetostructural transformation. The analysis of the n vs. T curves allowed confirmation of the XRD and DSC results of an occurrence of the first-order magnetostructural transition in Mn_0.95Pd_0.05CoGe and Mn_0.93Pd_0.07CoGe alloys samples. Full article

This article describes spark plasma sintering of ceramics based on silicon carbide with nanoadditives, as follows: MnO_nano 5.5 wt. % + Al₂O_3nano 2.0 wt. % + SiC_nm (37–57 wt. %) + SiC_µm (31–51 wt. %) + SiO_2µm 4.5 wt. %. Sintering was carried out at 2000 °C. The diffraction pattern of the analyzed sample showed the presence of silicon carbide with a hexagonal crystal lattice. Residual amounts of rhombohedral SiC, α-Fe, and a solid solution of silicon in iron were also found. The method of thermogravimetric analysis established the change in mass, heat flow, temperature of the samples, and the change in the partial pressures of gases during the experiment. Samples obtained by SPS show a higher density of the material at the level of 3.3 g/cm³, average mechanical strength of 454 MPa, and microhardness of 35 GPa, compared with samples obtained by liquid-phase sintering. The SPS method also made it possible to obtain materials with a higher density (by 8%) and practically no significant crystal growth compared to samples obtained by liquid phase sintering. The results of the study facilitate the achievement of a combination of new approaches to the design of compositions and the technology of manufacturing SiC ceramics, which significantly expands their areas of application. Full article

To investigate changes in the physical and chemical properties of high-density polyethylene (HDPE) upon the rapid release of hydrogen gas at a pressure of 90 MPa, several characterization techniques have been employed, including optical microscopy, scanning electron microscopy, X-ray diffraction, differential scanning thermal analysis, and attenuated total reflectance Fourier-transform infrared spectroscopy. The results showed that both physical and chemical changes occurred in HDPE upon a rapid release of hydrogen gas. Physically, a partial hexagonal phase was formed within the amorphous region, and the overall crystallinity of HDPE decreased. Chemically, hydrogenation occurred, leading to the addition of hydrogen atoms to the polymer chains. Oxidation also occurred, for example, the formation of ester -C=O groups. Crosslinking and an increase in -CH₃ end termination were also observed. These changes suggest that structural transformation and chemical modification of HDPE occurred upon the rapid release of hydrogen gas. Full article

The development of solid oxide fuel cells operating at medium temperatures (500–700 °C and even lower) requires the search for proton conductors based on complex oxides that would have a wide range of required properties. This task stimulates the search for new promising phases with proton conductivity. The new hexagonal perovskite-related compound Ba₇In₆Al₂O₁₉ was synthesized by the solid-state method. The phase was characterized by powder X-ray diffraction, thermogravimetric analysis, FT-IR spectroscopy, and impedance spectroscopy (in a wide range of temperatures, and partial pressures of oxygen at various atmospheric humidities). The investigated phase had a hexagonal structure with a space group of P6₃/mmc; the lattice parameters for Ba₇In₆Al₂O₁₉ are a = 5.921(2) Å, c = 37.717(4) Å. The phase is capable of reversible hydration and incorporates up to 0.15 mol H₂O. IR-data confirmed that protons in the hydrated compound are presented in the form of OH^–-groups. Electrical conductivity data showed that the sample exhibited dominant oxygen-ion conductivity below 500 °C in dry air and dominant proton conductivity below 600 °C in wet air. Full article

We report on crystal structure and thermal stability of epitaxial ε/κ-Ga₂O₃ thin films grown by liquid-injection metal–organic chemical vapor deposition (LI-MOCVD). Si-doped Ga₂O₃ films with a thickness of 120 nm and root mean square surface roughness of ~1 nm were grown using gallium-tetramethylheptanedionate (Ga(thd)₃) and tetraethyl orthosilicate (TEOS) as Ga and Si precursor, respectively, on c-plane sapphire substrates at 600 °C. In particular, the possibility to discriminate between ε and κ-phase Ga₂O₃ using X-ray diffraction (XRD) φ-scan analysis or electron diffraction analysis using conventional TEM was investigated. It is shown that the hexagonal ε-phase can be unambiguously identified by XRD or TEM only in the case that the orthorhombic κ-phase is completely suppressed. Additionally, thermal stability of prepared ε/κ-Ga₂O₃ films was studied by in situ and ex situ XRD analysis and atomic force microscopy. The films were found to preserve their crystal structure at temperatures as high as 1100 °C for 5 min or annealing at 900 °C for 10 min in vacuum ambient (<1 mBar). Prolonged annealing at these temperatures led to partial transformation to β-phase Ga₂O₃ and possible amorphization of the films. Full article