One-Pot Self-Assembly of Dinuclear,Tetranuclear, and H-Bonding-Directed Polynuclear Cobalt(II), Cobalt(III), and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core

The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO₄⁻, CH₃CO₂⁻, Cl⁻, NO₃⁻), sodium azide (NaN₃), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence Co^IICo^III: [Co₂^III(H₂L⁻¹)₂(AP⁻¹)(N₃)](ClO₄)₂ (1), [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]·4CH₃OH (2), [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ₃-OH)₂](NO₃)₂·2CH₃CH₂OH (3), and [Co₂^IICo₂^III (H₂L1²⁻)₂(THMAM⁻¹)₂](NO₃)₄ (4). In 1, two cobalt(III) ions are connected via three single atom bridges; two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and μ₃-1,1,1-N₃ azido bridges, and the two dinuclear units are interconnected by two μ-1,1-N₃ and two μ₃-1,1,1-N₃ azido bridges generating tetranuclear cationic [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]²⁺ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL²⁻ holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, μ-1,3-CH₃CO₂⁻, and μ₃-OH⁻ bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two μ₃-OH⁻ bridges generating cationic tetranuclear [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ_3-OH)₂]²⁺ units with an incomplete double cubane core. In 4, H₂L1⁻² holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (μ-RO⁻) in the side arms of the ligands and two ethanolic O (μ₃-RO⁻) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co₂^IICo₂^III (H₂L1⁻²)₂(THMAM⁻¹)₂]⁴⁺ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions.     

Maghemite (γ-Fe2O3) and γ-Fe2O3-TiO2 Nanoparticles for Magnetic Hyperthermia Applications: Synthesis,Characterization and Heating Efficiency

In this report, the heating efficiencies of γ-Fe₂O₃ and hybrid γ-Fe₂O₃-TiO₂ nanoparticles NPs under an alternating magnetic field (AMF) have been investigated to evaluate their feasible use in magnetic hyperthermia. The NPs were synthesized by a modified sol-gel method and characterized by different techniques. X-ray diffraction (XRD), Mössbauer spectroscopy and electron microscopy analyses confirmed the maghemite (γ-Fe₂O₃) phase, crystallinity, good uniformity and 10 nm core sizes of the as-synthesized composites. SQUID hysteresis loops showed a non-negligible coercive field and remanence suggesting the ferromagnetic behavior of the particles. Heating efficiency measurements showed that both samples display high heating potentials and reached magnetic hyperthermia (42 °C) in relatively short times with shorter time (~3 min) observed for γ-Fe₂O₃ compared to γ-Fe₂O₃-TiO₂. The specific absorption rate (SAR) values calculated for γ-Fe₂O₃ (up to 90 W/g) are higher than that for γ-Fe₂O₃-TiO₂ (~40 W/g)_, confirming better heating efficiency for γ-Fe₂O₃ NPs. The intrinsic loss power (ILP) values of 1.57 nHm²/kg and 0.64 nHm²/kg obtained for both nanocomposites are in the range reported for commercial ferrofluids (0.2–3.1 nHm²/kg). Finally, the heating mechanism responsible for NP heat dissipation is explained concluding that both Neel and Brownian relaxations are contributing to heat production. Overall, the obtained high heating efficiencies suggest that the fabricated nanocomposites hold a great potential to be utilized in a wide spectrum of applications, particularly in magnetic photothermal hyperthermia treatments.     

Preparation and Properties of (YCa)(TiMn)O3?δ Ceramics Interconnect of Solid Oxide Fuel Cells

(YCa)(TiMn)O_3–δ ceramics prepared using a reaction-sintering process were investigated. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. Y₂Ti₂O₇ instead of YTiO₃ formed when a mixture of Y₂O₃ and TiO₂ with Y/Ti ratio 1/1 were sintered in air. Y₂Ti₂O₇, YTiO_2.085 and some unknown phases were detected in Y_0.6Ca_0.4Ti_0.6Mn_0.4O_3–δ. Monophasic Y_0.6Ca_0.4Ti_0.4Mn_0.6O_3–δ ceramics were obtained after 1400–1500 °C sintering. Dense Y_0.6Ca_0.4Ti_0.4Mn_0.6O_3–δ with a density 4.69 g/cm³ was observed after 1500 °C/4 h sintering. Log σ for Y_0.6Ca_0.4Ti_0.6Mn_0.4O_3–δ increased from –3.73 Scm^–1 at 350 °C to –2.14 Scm^–1 at 700 °C. Log σ for Y_0.6Ca_0.4Ti_0.4Mn_0.6O_3–δ increased from –2.1 Scm^–1 at 350 °C to –1.36 Scm^–1 at 700 °C. Increasing Mn content decreased activation energy E_a and increased electrical conductivity. Reaction-sintering process is proved to be a simple and effective method to obtain (YCa)(TiMn)O_3–δ ceramics for interconnects in solid oxide fuel cells.     

Reinforced 3D Composite Structures of γ-, α-Al2O3 with Carbon Nanotubes and Reduced GO Ribbons Printed from Boehmite Gels

The ability of boehmite to form printable inks has sparked interest in the manufacturing of 3D alumina (Al₂O₃) and composite structures by enabling direct ink writing methods while avoiding the use of printing additives. These materials may exhibit high porosity due to the printing and sintering procedures, depending on the intended application. The 3D-printed porous composite structures of γ-Al₂O₃ and α-Al₂O₃ containing 2 wt.% of carbon nanotubes or reduced graphene oxide ribbons were fabricated from boehmite gels, followed by different heat treatments. The reinforcing effect of these carbon nanostructures was evidenced by compression tests carried out on the different alumina structures. A maximum relative increase of 50% in compressive strength was achieved for the γ-Al₂O₃ composite structure reinforced with reduced graphene oxide ribbons, which was also accompanied by an increase in the specific surface area.     

Green Synthesis of Hexagonal Hematite (α-Fe2O3) Flakes Using Pluronic F127-Gelatin Template for Adsorption and Photodegradation of Ibuprofen

Hematite (α-Fe₂O₃) with uniform hexagonal flake morphology has been successfully synthesized using a combination of gelatin as natural template with F127 via hydrothermal method. The resulting hematite was investigated as adsorbent and photocatalyst for removal of ibuprofen as pharmaceutical waste. Hexagonal flake-like hematite was obtained following calcination at 500 °C with the average size was measured at 1–3 µm. Increasing the calcination temperature to 700 °C transformed the uniform hexagonal structure into cubic shape morphology. Hematite also showed high thermal stability with increasing the calcination temperatures; however, the surface area was reduced from 47 m²/g to 9 m²/g. FTIR analysis further confirmed the formation Fe-O-Fe bonds, and the main constituent elements of Fe and O were observed in EDX analysis for all samples. α-Fe₂O₃ samples have an average adsorption capacity of 55–25.5 mg/g at 12–22% of removal efficiency when used as adsorbent for ibuprofen. The adsorption capacity was reduced as the calcination temperatures increased due to the reduction of available surface area of the hexagonal flakes after transforming into cubes. Photocatalytic degradation of ibuprofen using hematite flakes achieved 50% removal efficiency; meanwhile, combination of adsorption and photocatalytic degradation further removed 80% of ibuprofen in water/hexane mixtures.     

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C₂O₄)]·1.5H₂O}_n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu₃(bpy)₃(CH₃OH)(H₂O)(C₂O₄)₄][Cu(bpy)Cr(C₂O₄)₃]·CH₂Cl₂·CH₃OH·H₂O}_n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C₂O₄)]_n of 1, with intra-chain super-exchange interaction 𝐽 = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C₂O₄)₃]_nⁿ⁻ (Cr2–Cu4) with alternating [Cr(C₂O₄)₃]³⁻ and [Cu(bpy)]²⁺ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H₂O)(µ-C₂O₄)Cu(bpy)(CH₃OH)]²⁺ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) comprising three different metal centers (Ca²⁺, Cr³⁺ and Cu²⁺) oxalate-bridged, contains Ca²⁺ atoms as nodes connected with four Cr³⁺ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (6⁶) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [Cu^IICr^III], whose mutual interaction could possibly originate through the spin polarization of Ca²⁺ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.     

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%).     

Direct Electrochemistry and Electrocatalysis of Horseradish Peroxidase Immobilized in a DNA/Chitosan-Fe3O4 Magnetic Nanoparticle Bio-Complex Film

A DNA/chitosan-Fe₃O₄ magnetic nanoparticle bio-complex film was constructed for the immobilization of horseradish peroxidase (HRP) on a glassy carbon electrode. HRP was simply mixed with DNA, chitosan and Fe₃O₄ nanoparticles, and then applied to the electrode surface to form an enzyme-incorporated polyion complex film. Scanning electron microscopy (SEM) was used to study the surface features of DNA/chitosan/Fe₃O₄/HRP layer. The results of electrochemical impedance spectroscopy (EIS) show that Fe₃O₄ and enzyme were successfully immobilized on the electrode surface by the DNA/chitosan bio-polyion complex membrane. Direct electron transfer (DET) and bioelectrocatalysis of HRP in the DNA/chitosan/Fe₃O₄ film were investigated by cyclic voltammetry (CV) and constant potential amperometry. The HRP-immobilized electrode was found to undergo DET and exhibited a fast electron transfer rate constant of 3.7 s⁻¹. The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP(Fe^(III)) and HRP(Fe^(II)). The obtained electrode also displayed an electrocatalytic reduction behavior towards H₂O₂. The resulting DNA/chitosan/Fe₃O₄/HRP/glassy carbon electrode (GCE) shows a high sensitivity (20.8 A·cm⁻²·M⁻¹) toward H₂O₂. A linear response to H₂O₂ measurement was obtained over the range from 2 μM to 100 μM (R² = 0.99) and an amperometric detection limit of 1 μM (S/N = 3). The apparent Michaelis-Menten constant of HRP immobilized on the electrode was 0.28 mM. Furthermore, the electrode exhibits both good operational stability and storage stability.     

Vacancy Defects in Ga2O3: First-Principles Calculations of Electronic Structure

First-principles density functional theory (DFT) is employed to study the electronic structure of oxygen and gallium vacancies in monoclinic bulk β-Ga₂O₃ crystals. Hybrid exchange–correlation functional B3LYP within the density functional theory and supercell approach were successfully used to simulate isolated point defects in β-Ga₂O₃. Based on the results of our calculations, we predict that an oxygen vacancy in β-Ga₂O₃ is a deep donor defect which cannot be an effective source of electrons and, thus, is not responsible for n-type conductivity in β-Ga₂O₃. On the other hand, all types of charge states of gallium vacancies are sufficiently deep acceptors with transition levels more than 1.5 eV above the valence band of the crystal. Due to high formation energy of above 10 eV, they cannot be considered as a source of p-type conductivity in β-Ga₂O₃.     

Detailed Inspection of γ-ray,Fast and Thermal Neutrons Shielding Competence of Calcium Oxide or Strontium Oxide Comprising Bismuth Borate Glasses

For both the B₂O₃-Bi₂O₃-CaO and B₂O₃-Bi₂O₃-SrO glass systems, γ-ray and neutron attenuation qualities were evaluated. Utilizing the Phy-X/PSD program, within the 0.015–15 MeV energy range, linear attenuation coefficients (µ) and mass attenuation coefficients (μ/ρ) were calculated, and the attained μ/ρ quantities match well with respective simulation results computed by MCNPX, Geant4, and Penelope codes. Instead of B₂O₃/CaO or B₂O₃/SrO, the Bi₂O₃ addition causes improved γ-ray shielding competence, i.e., rise in effective atomic number (Z_eff) and a fall in half-value layer (HVL), tenth-value layer (TVL), and mean free path (MFP). Exposure buildup factors (EBFs) and energy absorption buildup factors (EABFs) were derived using a geometric progression (G–P) fitting approach at 1–40 mfp penetration depths (PDs), within the 0.015–15 MeV range. Computed radiation protection efficiency (RPE) values confirm their excellent capacity for lower energy photons shielding. Comparably greater density (7.59 g/cm³), larger μ, μ/ρ, Z_eff, equivalent atomic number (Z_eq), and RPE, with the lowest HVL, TVL, MFP, EBFs, and EABFs derived for 30B₂O₃-60Bi₂O₃-10SrO (mol%) glass suggest it as an excellent γ-ray attenuator. Additionally, 30B₂O₃-60Bi₂O₃-10SrO (mol%) glass holds a commensurably bigger macroscopic removal cross-section for fast neutrons (Σ_R) (=0.1199 cm⁻¹), obtained by applying Phy-X/PSD for fast neutrons shielding, owing to the presence of larger wt% of ‘Bi’ (80.6813 wt%) and moderate ‘B’ (2.0869 wt%) elements in it. 70B₂O₃-5Bi₂O₃-25CaO (mol%) sample (B: 17.5887 wt%, Bi: 24.2855 wt%, Ca: 11.6436 wt%, and O: 46.4821 wt%) shows high potentiality for thermal or slow neutrons and intermediate energy neutrons capture or absorption due to comprised high wt% of ‘B’ element in it.     

Sol-Gel Processed Cobalt-Doped Methylated Silica Membranes Calcined under N2 Atmosphere: Microstructure and Hydrogen Perm-Selectivity

Methyl-modified, cobalt-doped silica (Co/MSiO₂) materials were synthesized by sol-gel technique calcined in N₂ atmospheres, and membranes were made thereof by coating method. The effects of Co/Si molar ratio (n_Co) on the physical-chemical constructions of Co/MSiO₂ materials and microstructures of Co/MSiO₂ membranes were systematically investigated. The gas permeance performance and hydrothermal stability of Co/MSiO₂ membranes were also tested. The results show that the cobalt element in Co/MSiO₂ material calcined at 400 °C exists not only as Si–O–Co bond but also as Co₃O₄ and CoO crystals. The introduction of metallic cobalt and methyl can enlarge the total pore volume and average pore size of the SiO₂ membrane. The activation energy (E_a) values of H₂, CO₂, and N₂ for Co/MSiO₂ membranes are less than those for MSiO₂ membranes. When operating at a pressure difference of 0.2 MPa and 200 °C compared with MSiO₂ membrane, the permeances of H₂, CO₂, and N₂ for Co/MSiO₂ membrane with n_Co = 0.08 increased by 1.17, 0.70, and 0.83 times, respectively, and the perm-selectivities of H₂/CO₂ and H₂/N₂ increased by 27.66% and 18.53%, respectively. After being steamed and thermally regenerated, the change of H₂ permeance and H₂ perm-selectivities for Co/MSiO₂ membrane is much smaller than those for MSiO₂ membrane.     

Effect of Heating Modes on Reactive Sintering of Ca3Co4O9 Ceramics

The traditional solid-state reaction method was employed to synthesize bulk calcium cobaltite (Ca349/Ca₃Co₄O₉) ceramics via ball milling the precursor mixture. The samples were compacted using conventional sintering (CS) and spark plasma sintering (SPS) at 850, 900, and 950 °C. The X-ray diffraction (XRD) pattern indicates the presence of the Ca349 phase for samples sintered at 850 and 900 °C. In addition, SPS fosters higher densification (81.18%) than conventional sintering (50.76%) at elevated sintering temperatures. The thermo-gravimetric analysis (TGA) and differential thermal analysis (DTA) performed on the precursor mixture reported a weight loss of ~25.23% at a temperature range of 600–820 °C. This current work aims to analyze the electrical properties (Seebeck coefficient (s), electrical resistivity (ρ), and power factor) of sintered samples as a function of temperature (35–500 °C). It demonstrates that the change in sintering temperature (conventional sintering) did not evince any significant change in the Seebeck coefficient (113–142 μV/K). However, it reported a low resistivity of 153–132 μΩ-m and a better power factor (82–146.4 μW/mK²) at 900 °C. On the contrary, the SPS sintered samples recorded a higher Seebeck coefficient of 121–181 μV/K at 900 °C. Correspondingly, the samples sintered at 950 °C delineated a low resistivity of 145–158 μΩ-m and a better power factor (97–152 μW/mK²).     

The Formation of Cr-Al Spinel under a Reductive Atmosphere

In the present work, for the first time, the possibility of formation of CrAl₂O₄ was shown from the equimolar mixture of co-precipitated Al₂O₃ and Cr₂O₃ oxides under a reductive environment. The crystallographic properties of the formed compound were calculated using the DICVOL procedure. It was determined that it has a cubic crystal structure with space group Fd-3m and a unit cell parameter equal to 8.22(3) Å. The formed CrAl₂O₄ is not stable under ambient conditions and easily undergoes oxidation to α-Al₂O₃ and α-Cr₂O₃. The overall sequence of the phase transformations of co-precipitated oxides leading to the formation of spinel structure is proposed.     

Precipitation Hardening at Elevated Temperatures above 400 °C and Subsequent Natural Age Hardening of Commercial Al–Si–Cu Alloy

The precipitation of intermetallic phases and the associated hardening by artificial aging treatments at elevated temperatures above 400 °C were systematically investigated in the commercially available AC2B alloy with a nominal composition of Al–6Si–3Cu (mass%). The natural age hardening of the artificially aged samples at various temperatures was also examined. A slight increase in hardness (approximately 5 HV) of the AC2B alloy was observed at an elevated temperature of 480 °C. The hardness change is attributed to the precipitation of metastable phases associated with the α-Al₁₅(Fe, Mn)₃Si₂ phase containing a large amount of impurity elements (Fe and Mn). At a lower temperature of 400 °C, a slight artificial-age hardening appeared. Subsequently, the hardness decreased moderately. This phenomenon was attributed to the precipitation of stable θ-Al₂Cu and Q-Al₄Cu₂Mg₈Si₆ phases and their coarsening after a long duration. The precipitation sequence was rationalized by thermodynamic calculations for the Al–Si–Cu–Fe–Mn–Mg system. The natural age-hardening behavior significantly varied depending on the prior artificial aging temperatures ranging from 400 °C to 500 °C. The natural age-hardening was found to strongly depend on the solute contents of Cu and Si in the Al matrix. This study provides fundamental insights into controlling the strength level of commercial Al–Si–Cu cast alloys with impurity elements using the cooling process after solution treatment at elevated temperatures above 400 °C.     

Mechanical Properties of Titanium Nitride Nanocomposites Produced by Chemical Precursor Synthesis Followed by High-P,T Treatment

We investigated the high-P,T annealing and mechanical properties of nanocomposite materials with a highly nitrided bulk composition close to Ti₃N₄. Amorphous solids were precipitated from solution by ammonolysis of metal dialkylamide precursors followed by heating at 400–700 °C in flowing NH₃ to produce reddish-brown amorphous/nanocrystalline materials. The precursors were then densified at 2 GPa and 200–700 °C to form monolithic ceramics. There was no evidence for N₂ loss during the high-P,T treatment. Micro- and nanoindentation experiments indicate hardness values between 4–20 GPa for loads ranging between 0.005–3 N. Young''s modulus values were measured to lie in the range 200–650 GPa. Palmqvist cracks determined from microindentation experiments indicate fracture toughness values between 2–4 MPa·m^1/2 similar to Si₃N₄, SiC and Al₂O₃. Significant variations in the hardness may be associated with the distribution of amorphous/crystalline regions and the very fine grained nature (~3 nm grain sizes) of the crystalline component in these materials.     

Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor

Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), and N₂ physisorption isotherms were also determined. The Ni/Al₂O₃ sample reveled agglomerated (1 μm) of nanoparticles of Ni (30–80 nm) however, NiO particles were also identified, probably for the low temperature during the H₂ reduction treatment (350 °C), the Cu/Al₂O₃ sample presented agglomerates (1–1.5 μm) of nanoparticles (70–150 nm), but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH₃ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption.     

Low Temperature Synthesis and Characterization of AlScMo3O12

Recent interest in low and negative thermal expansion materials has led to significant research on compounds that exhibit this property, much of which has targeted the A₂M₃O₁₂ family (A = trivalent cation, M = Mo, W). The expansion and phase transition behavior in this family can be tuned through the choice of the metals incorporated into the structure. An undesired phase transition to a monoclinic structure with large positive expansion can be suppressed in some solid solutions by substituting the A-site by a mixture of two cations. One such material, AlScMo₃O₁₂, was successfully synthesized using non-hydrolytic sol-gel chemistry. Depending on the reaction conditions, phase separation into Al₂Mo₃O₁₂ and Sc₂Mo₃O₁₂ or single-phase AlScMo₃O₁₂ could be obtained. Optimized conditions for the reproducible synthesis of stoichiometric, homogeneous AlScMo₃O₁₂ were established. High resolution synchrotron diffraction experiments were carried out to confirm whether samples were homogeneous and to estimate the Al:Sc ratio through Rietveld refinement and Vegard’s law. Single-phase samples were found to adopt the orthorhombic Sc₂W₃O₁₂ structure at 100 to 460 K. In contrast to all previously-reported A₂M₃O₁₂ compositions, AlScMo₃O₁₂ exhibited positive thermal expansion along all unit cell axes instead of contraction along one or two axes, with expansion coefficients (200–460 K) of α_a = 1.7 × 10⁻⁶ K⁻¹, α_b = 6.2 × 10⁻⁶ K⁻¹, α_c = 2.9 × 10⁻⁶ K⁻¹ and α_V = 10.8 × 10⁻⁶ K⁻¹, respectively.     

Hf1−xSixO2 Nanocomposite Coatings Prepared by Ion-Assisted Co-Evaporation Process for Low-Loss and High-LIDT Optics

Hf_1−xSi_xO₂ nanocomposites with different SiO₂ doping ratios were synthesized using an ion-assisted co-evaporation process to achieve dense amorphous Hf_1−xSi_xO₂ coatings with low loss and a high laser-induced damage threshold (LIDT). The results showed that the Hf_1−xSi_xO₂ nanocomposites (x ≥ 0.20) exhibited excellent comprehensive performance with a wide band gap and a dense amorphous microstructure. High-temperature annealing was carried out to ensure better stoichiometry and lower absorption. Precipitation and regrowth of HfO₂ grains were observed from 400 °C to 600 °C during annealing of the Hf_0.80Si_0.20O₂ nanocomposites, resulting in excessive surface roughness. A phenomenological model was proposed to explain the phenomenon. The Hf_1−xSi_xO₂ nanocomposites (x = 0.3 and 0.4) maintained a dense amorphous structure with low absorption after annealing. Finally, a 1064-nm Hf_0.70Si_0.30O₂/SiO₂ high-performance reflector was prepared and achieved low optical loss (15.1 ppm) and a high LIDT (67 J/cm²).     

Hydrothermal Co-Processing of Coal Fly Ash Cenospheres and Soluble Sr(II) as Environmentally Sustainable Approach to Sr-90 Immobilization in a Mineral-like Form

Co-processing of radioactive effluents with coal fly ash-derived materials is recognized as a resource-saving approach for efficient stabilization/solidification of radioactive components of wastewater. In this context, the paper is focused on the hydrothermal synthesis of Sr²⁺-bearing aluminosilicate/silicate phases as analogs of a mineral-like ⁹⁰Sr waste form using hollow glass-crystalline aluminosilicate microspheres from coal fly ash (cenospheres) as a glassy source of Si and Al (SiO₂-Al₂O₃)_glass) and Sr(NO₃)₂ solutions as ⁹⁰Sr simulant wastewater. The direct conversion of cenosphere glass in the Sr(NO₃)₂-NaOH-H₂O-(SiO₂-Al₂O₃)_glass system as well as Sr²⁺ sorption on cenosphere-derived analcime (ANA) in the Sr(NO₃)₂-H₂O-ANA system were studied at 150–200 °C and autogenous pressure. The solid and liquid reaction products were characterized by SEM-EDS, PXRD, AAS and STA. In the Sr(NO₃)₂-NaOH-H₂O-(SiO₂-Al₂O₃)_glass system, the hydrothermal processing at 150–200 °C removes 99.99% of the added Sr²⁺ from the solution by forming Sr-tobermorite and Sr-plagioclase phases. In the Sr(NO₃)₂-H₂O-ANA system, Sr²⁺ sorption on analcime results in the formation of solid solutions (Na_1−nSr_n/2)AlSi₂O₆·H₂O of the Na-analcime–Sr-wairakite series. The results can be considered as a basis for the development of environmentally sustainable technology for ⁹⁰Sr removal from wastewater and immobilization in a mineral-like form by co-processing waste from coal-fired and nuclear power plants.     

Impact of Li3BO3 Addition on Solid Electrode-Solid Electrolyte Interface in All-Solid-State Batteries

All-solid-state lithium-ion batteries raise the issue of high resistance at the interface between solid electrolyte and electrode materials that needs to be addressed. The article investigates the effect of a low-melting Li₃BO₃ additive introduced into LiCoO₂- and Li₄Ti₅O₁₂-based composite electrodes on the interface resistance with a Li₇La₃Zr₂O₁₂ solid electrolyte. According to DSC analysis, interaction in the studied mixtures with Li₃BO₃ begins at 768 and 725 °C for LiCoO₂ and Li₄Ti₅O₁₂, respectively. The resistance of half-cells with different contents of Li₃BO₃ additive after heating at 700 and 720 °C was studied by impedance spectroscopy in the temperature range of 25–340 °C. It was established that the introduction of 5 wt% Li₃BO₃ into LiCoO₂ and heat treatment at 720 °C led to the greatest decrease in the interface resistance from 260 to 40 Ω cm² at 300 °C in comparison with pure LiCoO₂. An SEM study demonstrated that the addition of the low-melting component to electrode mass gave better contact with ceramics. It was shown that an increase in the annealing temperature of unmodified cells with Li₄Ti₅O₁₂ led to a decrease in the interface resistance. It was found that the interface resistance between composite anodes and solid electrolyte had lower values compared to Li₄Ti₅O₁₂|Li₇La₃Zr₂O₁₂ half-cells. It was established that the resistance of cells with the Li₄Ti₅O₁₂/Li₃BO₃ composite anode annealed at 720 °C decreased from 97.2 (x = 0) to 7.0 kΩ cm² (x = 5 wt% Li₃BO₃) at 150 °C.