Influence of Cu Content on Structure,Thermal Stability and Magnetic Properties in Fe72−xNi8Nb4CuxSi2B14 Alloys

The effect of substitution of Fe by Cu on the crystal structure and magnetic properties of Fe_72−xNi₈Nb₄Cu_xSi₂B₁₄ alloys (x = 0.6, 1.1, 1.6 at.%) in the form of ribbons was investigated. The chemical composition of the materials was established on the basis of the calculated minima of thermodynamic parameters: Gibbs free energy of amorphous phase formation ΔG^amorph (minimum at 0.6 at.% of Cu) and Gibbs free energy of mixing ΔG^mix (minimum at 1.6 at.% of Cu). The characteristic crystallization temperatures T_x1onset and T_x1 of the alpha-iron phase together with the activation energy E_a for the as-spun samples were determined by differential scanning calorimetry (DSC) with a heating rate of 10–100 °C/min. In order to determine the optimal soft magnetic properties, the wound cores were subjected to a controlled isothermal annealing process in the temperature range of 340–640 °C for 20 min. Coercivity Hc, saturation induction Bs and core power losses at B = 1 T and frequency f = 50 Hz P_10/50 were determined for all samples. Moreover, for the samples with the lowest Hc and P_10/50, the magnetic losses were determined in a wider frequency range 50 Hz–400 kHz. The real and imaginary parts of the magnetic permeability µ′, µ″ along with the cut-off frequency were determined for the samples annealed at 360, 460, and 560 °C. The best soft magnetic properties (i.e., the lowest value of Hc and P_10/50) were observed for samples annealed at 460 °C, with Hc = 4.88–5.69 A/m, Bs = 1.18–1.24 T, P_10/50 = 0.072–0.084 W/kg, µ′ = 8350–10,630 and cutoff frequency at 8–9.3 × 10⁴ Hz. The structural study of as-spun and annealed ribbons was carried out using X-ray diffraction (XRD) and a transmission electron microscope (TEM).     

Insertion Compounds of 2H-TaS(2).NH(3)

A new method of intercalating metals into layer compounds has been developed using electrolytic generation from the salt solution in ammonia. The results suggest that metals that are soluble in ammonia will form a homogeneous metal-ammonia intercalate layer, NH₃·M_x, when x is less than the limiting solubility of M in NH₃. The superconducting transition temperature (T_c) was found to increase as the c-axis expansion [2δ = c(TaS₂·NH₃·M_x) - c(2H-TaS₂)] decreased when M = lithium, sodium, and potassium. Of all the alkali metals, potassium gave the most stable compounds and the highest T_c, 4.7°K.     

Fe-vacancy order and superconductivity in tetragonal β-Fe1-xSe

Several superconducting transition temperatures in the range of 30–46 K were reported in the recently discovered intercalated FeSe system (A_1-xFe_2-ySe₂, A = K, Rb, Cs, Tl). Although the superconducting phases were not yet conclusively decided, more than one magnetic phase with particular orders of iron vacancy and/or potassium vacancy were identified, and some were argued to be the parent phase. Here we show the discovery of the presence and ordering of iron vacancy in nonintercalated FeSe (PbO-type tetragonal β-Fe_1-xSe). Three types of iron-vacancy order were found through analytical electron microscopy, and one was identified to be nonsuperconducting and magnetic at low temperature. This discovery suggests that the rich-phases found in A_1-xFe_2-ySe₂ are not exclusive in Fe-Se and related superconductors. In addition, the magnetic β-Fe_1-xSe phases with particular iron-vacancy orders are more likely to be the parent phase of the FeSe superconducting system instead of the previously assigned β-Fe_1+δTe.The iron pnictide superconductors have opened the door to a new way to obtain superconductivity at very high temperatures. β-Fe_1+δSe is remarkable among those superconductors in that it contains the essential electronic and structural constituents required for superconductivity without the conceptual complexity seen in other systems (1). Previous studies showed that the superconducting property of β-Fe_1+δSe made under high-temperature thermodynamic conditions is very sensitive to stoichiometry (1, 2). In the Fe-Se binary phase diagram (2–4), the PbO-type tetragonal structure (the β phase) only stabilized at the Fe-rich side (δ = 0.01–0.04), whereas bulk superconductivity was observed in samples with δ close to 0.01 (5). McQueen et al. showed no superconductivity for samples with δ = 0.03 (5). On the other hand, the fact that only one superconducting phase has been reported in FeSe, unlike the other Fe-As–based superconductors that exhibit clear doping dependence of superconductivity and the absence of superconductivity in FeTe, led to the suggestion that FeTe is the nonsuperconducting parent compound of FeSe (6). Thus, the phase diagram derived from this picture shows very different features compared with other Fe-As–based superconductors (6, 7). In this work, we use low-temperature synthesis methods to prepare β-Fe_1-xSe for a wide range of compositions, which allows for the determination for the composition-dependent electronic behavior for this important superconducting system.The recent discovered alkali/alkaline-intercalated iron selenide (A_1-xFe_2-ySe₂) superconductors with rich superconducting phases, where A = K, Rb, Cs, Tl, attracted great attention not only due to its high superconducting transition temperature (T_c, up to 46 K) (8), but also because of their dissimilar characteristics compared with other iron-based superconductors, especially its seemingly intrinsic multiphase nature and the presence of iron vacancies and orders in the nonsuperconducting regime (9–13). The most frequently observed Fe-vacancy order in A_1-xFe_2-ySe₂ is the × × 1 superstructure, which yields a phase of A_0.8Fe_1.6Se₂ (or A₂Fe₄Se₅). Scanning tunneling microscopy (STM) (11, 14, 15) and transport studies (12, 13, 16, 17) showed that A₂Fe₄Se₅ is an antiferromagnetic (AFM) insulator. Neutron scattering measurements (9) revealed a blocked checkerboard AFM with magnetic moments along the c axis for A₂Fe₄Se₅, ordered at a temperature as high as >500 K, with an unexpected large ordered magnetic moment of ∼3.3 μ_B/Fe at 10 K. Experiments have further shown that the type of vacancy and magnetic orders is highly sensitive to the stoichiometry (x and y) of A_1-xFe_2-ySe₂. Reports have shown the existence of other Fe-vacancy order with the forms × × 1 (10), × 2 × 1 (13, 18), and × × 1 (19). However, the magnetic properties such as the type and transition temperature of the magnetic order are far less studied compared with that of the K₂Fe₄Se₅ phase. In addition, there were also results showing in K_1-xFe_2-ySe₂ samples with a typical T_c = 31 K and additional superconducting phase with T_c = 44 K (20), whereas no clear identification of the new phases was available.The complexity of phases and phase separation during crystal preparation in A_1-xFe_2-ySe₂ make it difficult to conclusively verify the phase-property relationship, even for the superconducting phases. β-Fe_1+δSe, on the other hand, has the simplest structure among all iron-based superconductor families. Several surprising results related to the Fe-Se system appeared in the literature during the last few years, including the enhancement of T_c to about 40 K under high pressure (21–23) and the intriguing extremely high T_c (with a superconducting energy gap of ∼20 meV) in molecular beam epitaxy (MBE)-grown single-layer FeSe (24–26). We also demonstrated the presence of a superconducting-like feature with T_c close to 40 K in samples of nano-dimensional form (27). Therefore, it is quite natural to ask whether the presence of the complex phases observed in A_1-xFe_2-ySe₂ compounds and Fe-vacancy order exist in samples without alkaline metals. Here we present the first discovery of iron vacancies and three types of vacancy orders in tetragonal β-Fe_1-xSe, characterized by analytical transmission electron microscopy (TEM). Our observations imply that an unprecedented phase diagram should be considered in the Fe-Se superconductors.     

Investigation of Superconductivity in Ce-Doped (La,Pr)OBiS2 Single Crystals

Single crystals of Ce-doped (La,Pr)OBiS₂ superconductors, the multinary rare-earth elements substituted ROBiS₂, were successfully grown. The grown crystals typically had a size of 1–2 mm and a plate-like shape with a well-developed c-plane. The c-axis lattice constants of the obtained (La,Ce,Pr)OBiS₂ single crystals were approximately 13.6–13.7 Å, and the superconducting transition temperature was 1.23–2.18 K. Valence fluctuations of Ce and Pr were detected through X-ray absorption spectroscopy analysis. In contrast to (Ce,Pr)OBiS₂ and (La,Ce)OBiS₂, the superconducting transition temperature of (La,Ce,Pr)OBiS₂ increased with the increasing concentrations of the tetravalent state at the R-site.     

Structure and Phase State of Ti49.4Ni50.6 (at%) Hydrogenated in Normal Saline

The paper analyzes the surface structure and phase state of Ti_49.4Ni_50.6 (at%) hydrogenated at 295 K in normal saline (0.9% NaCl aqueous solution with pH = 5.7) at 20 A/m² for 0.5–6 h. The analysis shows that the average hydrogen concentration in the alloy increases with the hydrogenation time t_H as follows: slowly to 50 ppm at t_H = 0.5–1.5 h, steeply to 150 ppm at t_H = 1.2–2 h, and linearly to 300 ppm at t_H = 2–6 h. According to Bragg–Brentano X-ray diffraction data (θ–2 θ, 2 θ ≤ 50°, CoKα radiation), the alloy in its scanned surface layer of thickness ~5.6 µm reveals a TiNiH_x phase with x = 0.64 and x = 0.54 after hydrogenation for 4 and 6 h, respectively. The structure of this phase is identifiable as an orthorhombic hydride similar to β₁–TiFeH_0.94 (space group Pmcm), rather than as a tetragonal TiNiH_x hydride with x = 0.30–1.0 (space group I4/mmm). Time curves are presented to trace the lattice parameters and volume change during the formation of such an orthorhombic phase from the initial cubic B2 phase in Ti_49.4Ni_50.6 (at%).     

In vitro unfolding of yeast multicopper oxidase Fet3p variants reveals unique role of each metal site

Fet3p from Saccharomyces cerevisiae is a multicopper oxidase (MCO) that contains 3 cupredoxin-like β-barrel domains and 4 copper ions located in 3 distinct metal sites (T1 in domain 3, T2, and the binuclear T3 at the interface between domains 1 and 3). To better understand how protein structure and stability is defined by cofactor coordination in MCO proteins, we assessed thermal unfolding of apo and metallated forms of Fet3p by using spectroscopic and calorimetric methods in vitro (pH 7). We find that unfolding reactions of apo and different holo forms of Fet3p are irreversible reactions that depend on the scan rate. The domains in apo-Fet3p unfold sequentially [thermal midpoint (T_m) of 45 °C, 62 °C, and 72 °C; 1 K/min]. Addition of T3 imposes strain in the apo structure that results in coupled domain unfolding and low stability (T_m of 50 °C; 1 K/min). Further inclusion of T2 (i.e., only T1 absent) increases overall stability by ≈5 °C but unfolding remains coupled in 1 step. Introduction of T1, producing fully-loaded holo-Fet3p (or in the absence of T2), results in stabilization of domain 3, which uncouples unfolding of the domains; unfolding of domain 2 occurs first along with Cu-site perturbations (T_m 50–55 °C; 1 K/min), followed by unfolding of domains 1 and 3 (≈65–70 °C; 1 K/min). Our results suggest that there is a metal-induced tradeoff between overall protein stability and metal coordination in members of the MCO family.     

Crystal and molecular structure of n,n'-diethyl-n,n'-diphenylurea

N,N′-diphenyl-N,N′-diethylurea (C₁₇H₂₀N₂O) crystallizes in the space group P2₁/c. The unit cell constants are: a = 10.42 ± 0.01 Å, b = 16.86 ± 0.02 Å, c = 10.66 ± 0.001 Å, β = 125°16′ ± 5′; Z = 4, D_x = 1.16 g·cm^-3, D_meas = 1.16 ± 0.01 g·cm^-3. Data for 1392 reflections were collected at room temperature on a Picker automated diffractometer. The crystal structure was solved by direct methods and refined by bloc-diagonalized matrix least-squares calculations. The molecule is characterized by a pseudo C₂ symmetry; both phenyl groups are trans with respect to the oxygen atom. The hybridization of the two nitrogen atoms is intermediate between trigonal and tetrahedral; the nonplanar distortion of the amide groups is about 30°. The amide C-N bond lengths are 1.37 Å.     

Processing of Waste from Enrichment with the Production of Cement Clinker and the Extraction of Zinc

This paper presents studies on the processing of enrichment tailings as a component of a raw mixture in order to obtain cement clinker, with simultaneous distillation of zinc. Thermodynamic studies were carried out in the temperature range of 600–1600 °C using the software application “HSC Chemistry 6” developed by the metallurgical company Outokumpu (Finland). As a result of the conducted studies, we found that zinc contributes to the intensification of mineral formation of cement clinker. In particular, it was found that the formation of belite is possible in the temperature range from 990.7 to 1500 °C with Gibbs energy values of −0.01 and −323.8 kJ (which is better than the standard process by −11.4 kJ), respectively; the formation of alite is possible in the temperature range from 982.9 to 1500 °C with Gibbs energy values of −0.05 and −402.1 kJ (better than the standard process by −11.4 kJ), respectively; the formation of tricalcium aluminate is thermodynamically possible in the temperature range from 600 °C at ΔG_T^o = −893.8 kJ to 1500 °C at ΔG_T^o = −1899.3 kJ (better than the standard process by −1570.1 kJ), respectively; and the formation of four calcium aluminoferrite is possible in the temperature range from 600 °C at ΔG_T^o = −898.9 kJ to 1500 °C at ΔG_T^o = −1959.3 kJ (better than the standard process by −1570.2 kJ), respectively, with simultaneous distillation of zinc into a gaseous state for its further capture.     

Development of Ni-Sr(V,Ti)O3-δ Fuel Electrodes for Solid Oxide Fuel Cells

A series of strontium titanates-vanadates (STVN) with nominal cation composition Sr_1-xTi_1-y-zV_yNi_zO_3-δ (x = 0–0.04, y = 0.20–0.40 and z = 0.02–0.12) were prepared by a solid-state reaction route in 10% H₂–N₂ atmosphere and characterized under reducing conditions as potential fuel electrode materials for solid oxide fuel cells. Detailed phase evolution studies using XRD and SEM/EDS demonstrated that firing at temperatures as high as 1200 °C is required to eliminate undesirable secondary phases. Under such conditions, nickel tends to segregate as a metallic phase and is unlikely to incorporate into the perovskite lattice. Ceramic samples sintered at 1500 °C exhibited temperature-activated electrical conductivity that showed a weak p(O₂) dependence and increased with vanadium content, reaching a maximum of ~17 S/cm at 1000 °C. STVN ceramics showed moderate thermal expansion coefficients (12.5–14.3 ppm/K at 25–1100 °C) compatible with that of yttria-stabilized zirconia (8YSZ). Porous STVN electrodes on 8YSZ solid electrolytes were fabricated at 1100 °C and studied using electrochemical impedance spectroscopy at 700–900 °C in an atmosphere of diluted humidified H₂ under zero DC conditions. As-prepared STVN electrodes demonstrated comparatively poor electrochemical performance, which was attributed to insufficient intrinsic electrocatalytic activity and agglomeration of metallic nickel during the high-temperature synthetic procedure. Incorporation of an oxygen-ion-conducting Ce_0.9Gd_0.1O_2-δ phase (20–30 wt.%) and nano-sized Ni as electrocatalyst (≥1 wt.%) into the porous electrode structure via infiltration resulted in a substantial improvement in electrochemical activity and reduction of electrode polarization resistance by 6–8 times at 900 °C and ≥ one order of magnitude at 800 °C.     

The Influence of Service Temperature and Thickness on the Tensile Properties of Thin T2 Copper Sheets

Thin T2 copper sheets with nine different thicknesses were employed in uniaxial tensile tests to investigate the influence of service temperature and thickness on their tensile properties. A total of 33 groups of tensile samples were separately tested at 20 °C, 100 °C, 150 °C, 200 °C, and 250 °C to obtain their elongation and their tensile and yield strengths. The change laws of the tensile properties of the investigated T2 copper were analyzed using different fitting functions. The main results show that both sheet thickness and temperature have an important influence on the tensile properties of T2 copper. As the sheet thickness increased, the tensile and yield strengths of the tested materials first increased rapidly, then decreased sharply, and finally stabilized. As the temperature increased, the tensile strength increased linearly while the yield strength decreased linearly. The relationships between the elongation and the sheet thickness and temperature were exponential and polynomial functions, respectively. T–t–Rm, T–t–Rel, and T–t–δ empirical formulas were proposed and established to predict the tensile properties of the investigated T2 copper sheet, and the predictive models exhibited solid accuracy.     

Microstructure and Piezoelectric Properties of Lead Zirconate Titanate Nanocomposites Reinforced with In-Situ Formed ZrO2 Nanoparticles

Lead zirconate titanate (PZT)-based ceramics are used in numerous advanced applications, including sensors, displays, actuators, resonators, chips; however, the poor mechanical characteristics of these materials severely limits their utility in composite materials. To address this issue, we herein fabricate transgranular type PZT ceramic nanocomposites by a novel method. Thermodynamically metastable single perovskite-type Pb_0.99(Zr_0.52+xTi_0.48)_0.98Nb_0.02O_3+1.96x powders are prepared from a citrate precursor before both monoclinic and tetragonal ZrO₂ nanoparticles ranging from 20 to 80 nm are precipitated in situ at a sintering temperature of 1260 °C. The effects of ZrO₂ content on the microstructure, dielectric, and piezoelectric properties are investigated and the mechanism, by which ZrO₂ toughened PZT is analyzed in detail. The ZrO₂ nanoparticles underwent a tetragonal to monoclinic phase transition upon cooling. The fracture mode changed from intergranular to transgranular with increasing ZrO₂ content. The incorporation of ZrO₂ nanoparticles improved the mechanical and piezoelectric properties. The optimized piezoelectric properties (ε^T₃₃/ε₀ = 1398, tan δ = 0.024 d₃₃ = 354 pC N⁻¹, k_p = 0.66 Q_m = 78) are obtained when x = 0.02. T_c initially increased and subsequently decreased with increasing ZrO₂ content. The highest T_c = (387 °C) and lowest ε^T₃₃/ε₀ was obtained at x = 0.01.     

Structural Properties of Thin ZnO Films Deposited by ALD under O-Rich and Zn-Rich Growth Conditions and Their Relationship with Electrical Parameters

The structural, optical, and electrical properties of ZnO are intimately intertwined. In the present work, the structural and transport properties of 100 nm thick polycrystalline ZnO films obtained by atomic layer deposition (ALD) at a growth temperature (T_g) of 100–300 °C were investigated. The electrical properties of the films showed a dependence on the substrate (a-Al₂O₃ or Si (100)) and a high sensitivity to T_g, related to the deviation of the film stoichiometry as demonstrated by the RT-Hall effect. The average crystallite size increased from 20–30 nm for as grown samples to 80–100 nm after rapid thermal annealing, which affects carrier scattering. The ZnO layers deposited on silicon showed lower strain and dislocation density than on sapphire at the same T_g. The calculated half crystallite size (D/2) was higher than the Debye length (L_D) for all as grown and annealed ZnO films, except for annealed ZnO/Si films grown within the ALD window (100–200 °C), indicating different homogeneity of charge carrier distribution for annealed ZnO/Si and ZnO/a-Al₂O₃ layers. For as grown films the hydrogen impurity concentration detected via secondary ion mass spectrometry (SIMS) was 10²¹ cm⁻³ and was decreased by two orders of magnitude after annealing, accompanied by a decrease in Urbach energy in the ZnO/a-Al₂O₃ layers.     

Structural and Luminescence Behavior of Nanocrystalline Orthophosphate KMeY(PO4)2: Eu3+ (Me = Ca,Sr) Synthesized by Hydrothermal Method

KMeY(PO₄)₂:5% Eu³⁺ phosphates have been synthesized by a novel hydrothermal method. Spectroscopic, structural, and morphological properties of the obtained samples were investigated by X-ray, TEM, Raman, infrared, absorption, and luminescence studies. The microscopic analysis of the obtained samples showed that the mean diameter of synthesized crystals was about 15 nm. The KCaY(PO₄)₂ and KSrY(PO₄)₂ compounds were isostructural and they crystallized in a rhabdophane-type hexagonal structure with the unit-cell parameters a = b ≈ 6.90 Å, c ≈ 6.34 Å, and a = b ≈ 7.00 Å, c ≈ 6.42 Å for the Ca and Sr compound, respectively. Spectroscopic investigations showed intense ⁵D₀ → ⁷F₄ transitions connected with D₂ site symmetry of Eu³⁺ ions. Furthermore, for the sample annealed at 500 °C, europium ions were located in two optical sites, on the surface of grains and in the bulk. Thermal treatment of powders at high temperature provided better grain crystallinity and only one position of dopant in the crystalline structure. The most intense emission was possessed by the KSrY(PO₄)₂:5% Eu³⁺ sample calcinated at 500 °C.     

Fabrication and Optical Characterization of VO2-Based Thin Films Deposited on Practical Float Glass by Magnetron Sputtering and Professional Annealing

In this paper, VO₂ thin films with good optical properties are fabricated on practical float glass by magnetron sputtering and a professional annealing method. The near-infrared switching efficiency (NIRSE) of the prepared film reaches 39% (@2000 nm), and its near-infrared energy modulation ability (ΔT_ir) reaches 10.9% (780–2500 nm). Further, the highest integral visible transmittance T_lum is 63%. The proposed method exhibits good reproducibility and does not cause any heat damage to the magnetron sputtering machine. The crystalline structure of the VO₂ film is characterized by X-ray diffraction (XRD). The lattice planes (011) and (−211) grow preferentially (JCPDS 65-2358), and a large number of NaV₂O₅ crystals are detected simultaneously. The microstructures are characterized by scanning electron microscopy (SEM), and a large number of long sheet crystals are identified. The phase transition temperature is significantly reduced by an appropriate W doping concentration (T_c = 29 °C), whereas excessive W doping causes distortion of the thermal hysteresis loop and a reduction in the NIRSE. Oxygen vacancies are created by low pressure annealing, due to which the phase transition temperature of VO₂ film decreases by 8 °C. The addition of an intermediate SiO₂ layer can prevent the diffusion of Na⁺ ions and affect the preparation process of the VO₂ thin film.     

The Effect of Heat Treatment on the Corrosion Resistance of Fe-Based Amorphous Alloy Coating Prepared by High Velocity Oxygen Fuel Method

In this study, Fe₄₀Cr₁₉Mo₁₈C₁₅B₈ amorphous coatings were prepared using high velocity oxygen fuel (HVOF) technology. Different temperatures were used in the heat treatment (600 °C, 650 °C, and 700 °C) and the annealed coatings were analyzed by DSC, SEM, TEM, and XRD. XRD and DSC results showed that the coating started to form a crystalline structure after annealing at 650 °C. From the SEM observation, it can be found that when the annealing temperature of the Fe-based amorphous alloy coating reached 700 °C, the surface morphology of the coating became relatively flat. TEM observation showed that when the annealing temperature of the Fe-based amorphous alloy coating was 700 °C, crystal grains in the coating recrystallized with a grain size of 5–20 nm. SAED analysis showed that the precipitated carbide phase was M₂₃C₆ phase with different crystal orientations (M = Fe, Cr, Mo). Finally, the corrosion polarization curve showed that the corrosion current density of the coating after annealing only increased by 9.13 μA/cm², which indicated that the coating after annealing treatment still had excellent corrosion resistance. It also proved that the Fe-based amorphous alloy coating can be used in high-temperature environments. XPS analysis showed that after annealing FeO and Fe₂O₃ oxide components increased, and the formation of a large number of crystals in the coating resulted in a decrease in corrosion resistance.     

Research on the Hot Deformation Behavior of the Casting NiTi Alloy

The hot deformation behavior and processing maps of the casting NiTi alloy were studied at the deformation temperature of 650–1050 °C and the strain rate of 5 × 10⁻³–1 s⁻¹ by Gleeble-3800 thermal simulating tester. The variation of the strain rate sensitivity exponent m and the activation energy Q under different deformation conditions (T = 650–1050 °C, ε˙ = 0.005–1 s⁻¹) were obtained. The formability of the NiTi alloy was the best from 800 °C to 950 °C. The constitutive equation of the casting NiTi alloy was constructed by the Arrhenius model. The processing map of the casting NiTi alloy was plotted according to the dynamic material model (DMM) based on the Prasad instability criterion. The optimal processing areas were at 800–950 °C and 0.005–0.05 s⁻¹. The microstructure of the casting NiTi alloy was analyzed by TEM, SEM and EBSD. The softening mechanisms of the casting NiTi alloy were mainly dynamic recrystallization of the Ti₂Ni phase and the nucleation and growth of fine martensite.     

Synthesis of MgB2 at Low Temperature and Autogenous Pressure

High quality, micron-sized interpenetrating grains of MgB₂, with high density, are produced at low temperatures (~420 °C < T < ~500 °C) under autogenous pressure by pre-mixing Mg powder and NaBH₄ and heating in an Inconel 601 alloy reactor for 5–15 h. Optimum production of MgB₂, with yields greater than 75%, occurs for autogenous pressure in the range 1.0 MPa to 2.0 MPa, with the reactor at ~500 °C. Autogenous pressure is induced by the decomposition of NaBH₄ in the presence of Mg and/or other Mg-based compounds. The morphology, transition temperature and magnetic properties of MgB₂ are dependent on the heating regime. Significant improvement in physical properties accrues when the reactor temperature is held at 250 °C for >20 min prior to a hold at 500 °C.     

High-pressure crystal structures and superconductivity of Stannane (SnH4)

There is great interest in the exploration of hydrogen-rich compounds upon strong compression where they can become superconductors. Stannane (SnH₄) has been proposed to be a potential high-temperature superconductor under pressure, but its high-pressure crystal structures, fundamental for the understanding of superconductivity, remain unsolved. Using an ab initio evolutionary algorithm for crystal structure prediction, we propose the existence of two unique high-pressure metallic phases having space groups Ama2 and P6₃/mmc, which both contain hexagonal layers of Sn atoms and semimolecular (perhydride) H₂ units. Enthalpy calculations reveal that the Ama2 and P6₃/mmc structures are stable at 96–180 GPa and above 180 GPa, respectively, while below 96 GPa SnH₄ is unstable with respect to elemental decomposition. The application of the Allen-Dynes modified McMillan equation reveals high superconducting temperatures of 15–22 K for the Ama2 phase at 120 GPa and 52–62 K for the P6₃/mmc phase at 200 GPa.     

Revisiting the Hydrogen Storage Behavior of the Na-O-H System

Solid-state reactions between sodium hydride and sodium hydroxide are unusual among hydride-hydroxide systems since hydrogen can be stored reversibly. In order to understand the relationship between hydrogen uptake/release properties and phase/structure evolution, the dehydrogenation and hydrogenation behavior of the Na-O-H system has been investigated in detail both ex- and in-situ. Simultaneous thermogravimetric-differential thermal analysis coupled to mass spectrometry (TG-DTA-MS) experiments of NaH-NaOH composites reveal two principal features: Firstly, an H₂ desorption event occurring between 240 and 380 °C and secondly an additional endothermic process at around 170 °C with no associated weight change. In-situ high-resolution synchrotron powder X-ray diffraction showed that NaOH appears to form a solid solution with NaH yielding a new cubic complex hydride phase below 200 °C. The Na-H-OH phase persists up to the maximum temperature of the in-situ diffraction experiment shortly before dehydrogenation occurs. The present work suggests that not only is the inter-phase synergic interaction of protic hydrogen (in NaOH) and hydridic hydrogen (in NaH) important in the dehydrogenation mechanism, but that also an intra-phase H^δ+… H^δ– interaction may be a crucial step in the desorption process.     

Degradation Monitoring of HDPE Material in CO2-Saturated NaCl Environment through Electrochemical Impedance Spectroscopy Technique

Extensive damage due to saturated seawater and CO₂ exposure under high temperature and pressure in high-density polyethylene (HDPE) has been studied by Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Field Emission Scanning Electron Microscope (FESEM), and Electrochemical Impedance Spectroscopy (EIS). The degradation of square-shaped HDPE samples having 1 mm thickness was investigated at 70 bars with 60, 75, and 90 °C separately for three weeks in an autoclave chamber. A clear indication of aging was observed in terms of chain scission by the formation of the methyl group (1262 cm⁻¹), and the appearance of degradation products, including the alcohol and hydroxyl groups. The decline in glass transition temperature (T_g), melting point (T_m), and crystallinity (X_c) result from branching and formation of degradation products in the aged samples. TGA results reveal that the degradation shifts the characteristic temperatures (T_5% and T_10%) to lower values compared to virgin HDPE. FESEM images show clear surface cracks and rough patches after 3 weeks. The X_c value increased due to chain mobility at higher temperatures (90 °C). The impedance is relatively high 10¹¹ ohms.cm⁻² for a virgin sample, but it drops down to 10⁹ and 10⁶ after degradation. Impedance and dielectric loss were correlated, and the significance of dielectric loss was observed at lower frequencies. These characterizations will contribute to more efficient and detailed evaluation criteria for degradation monitoring.