Chemical and Structural Characterization of Amorphous and Crystalline Alumina Obtained by Alternative Sol–Gel Preparation Routes

Aluminum oxide is one of the most commonly used materials in the industry. It is used in the field of catalysis, refractories, and optics. Despite the fact that there are many techniques available, there is still a great challenge in obtaining a material with desired and designed properties. Nevertheless, there is a great flexibility in making customized alumina materials with desired physicochemical properties synthesized by sol–gel methods. This work consists in characterizing the physicochemical properties of sol–gel synthesized aluminum oxide using different sol–gel preparation routes. Three different sols were obtained by using organic precursors and underwent thermal treatment. The structure (Middle Infrared Spectroscopy, Diffused Reflectance Infrared Spectroscopy, X-ray Diffraction, Magic Angle Spinning Nuclear Magnetic Resonance) and microstructure (Scanning Electron Microscopy with Electron Dispersive Spectroscopy) tests of the materials were carried out. The specific surface area was determined by using the Brunauer–Emmett–Teller (BET) method. Thermal analysis was performed for all the powders, in order to analyze the specific temperature of materials transformation.     

Characterization of Al2O3 Samples and NiAl–Al2O3 Composite Consolidated by Pulse Plasma Sintering

The paper describes an investigation of Al₂O₃ samples and NiAl–Al₂O₃ composites consolidated by pulse plasma sintering (PPS). In the experiment, several methods were used to determine the properties and microstructure of the raw Al₂O₃ powder, NiAl–Al₂O₃ powder after mechanical alloying, and samples obtained via the PPS. The microstructural investigation of the alumina and composite properties involves scanning electron microscopy (SEM) analysis and X-ray diffraction (XRD). The relative densities were investigated with helium pycnometer and Archimedes method measurements. Microhardness analysis with fracture toughness (K_IC) measures was applied to estimate the mechanical properties of the investigated materials. Using the PPS technique allows the production of bulk Al₂O₃ samples and intermetallic ceramic composites from the NiAl–Al₂O₃ system. To produce by PPS method the NiAl–Al₂O₃ bulk materials initially, the composite powder NiAl–Al₂O₃ was obtained by mechanical alloying. As initial powders, Ni, Al, and Al₂O₃ were used. After the PPS process, the final composite materials consist of two phases: Al₂O₃ located within the NiAl matrix. The intermetallic ceramic composites have relative densities: for composites with 10 wt.% Al₂O₃ 97.9% and samples containing 20 wt.% Al₂O₃ close to 100%. The hardness of both composites is equal to 5.8 GPa. Moreover, after PPS consolidation, NiAl–Al₂O₃ composites were characterized by high plasticity. The presented results are promising for the subsequent study of consolidation composite NiAl–Al₂O₃ powder with various initial contributions of ceramics (Al₂O₃) and a mixture of intermetallic–ceramic composite powders with the addition of ceramics to fabricate composites with complex microstructures and properties. In composites with complex microstructures that belong to the new class of composites, in particular, the synergistic effect of various mechanisms of improving the fracture toughness will be operated.     

Synthesis of Ni/Y2O3 Nanocomposite through USP and Lyophilisation for Possible Use as Coating

The Ni/Y₂O₃ catalyst showed high catalytic activity. Based on this, the aim of this study was to create Ni/Y₂O₃ nanocomposites powder with two innovative technologies, Ultrasonic Spray Pyrolysis (USP) and lyophilisation. In the USP process, thermal decomposition of the generated aerosols in an N₂/H₂ reduction atmosphere caused a complete decomposition of the nickel (II) nitrate to elemental Ni, which became trapped on the formed Y₂O₃ nanoparticles. The Ni/Y₂O₃ nanocomposite particles were captured via gas washing in an aqueous solution of polyvinylpyrrolidone (PVP) in collection bottles. PVP was chosen for its ability to stabilise nano-suspensions and as an effective cryoprotectant. Consequently, there was no loss or agglomeration of Ni/Y₂O₃ nanocomposite material during the lyophilisation process. The Ni/Y₂O₃ nanocomposite powder was analysed using ICP-MS, SEM-EDX, and XPS, which showed the impact of different precursor concentrations on the final Ni/Y₂O₃ nanocomposite particle composition. In a final step, highly concentrated Ni/Y₂O₃ nanocomposite ink (Ni/Y₂O₃ > 0.140 g/mL) and test coatings from this ink were prepared by applying them on a white matte photo paper sheet. The reflection curve of the prepared Ni/Y₂O₃ nanocomposite coating showed a local maximum at 440 nm with a value of 39% reflection. Given that Ni is located on the surface of the Ni/Y₂O₃ nanocomposite in the elemental state and according to the identified properties, tests of the catalytic properties of this coating will be performed in the future.     

Manufacturing of Al2O3/Ni/Ti Composites Enhanced by Intermetallic Phases

In this study, ceramic–metal composites in the Al₂O₃/Ti/Ni system were fabricated using the slip casting method. Two series of composites with 15 vol.% metal content and different solid phase contents were obtained and examined. A proper fabrication process allows obtaining composites enhanced by intermetallic phases. The microstructure of the base powders, slurries, and sintered composites was analyzed by scanning electron microscope. Analysis of the sedimentation tendency of slurries was carried out. The phase composition of the sintered samples was examined by X-ray diffraction analysis. A monotonic compression test was used to investigate the mechanical properties of the composites. A fractography investigation was also carried out. The research conducted revealed that the slip casting method allows the obtaining of composites enhanced by intermetallic phases (TiNi, Ni₃Ti). The results show the correlation between solid-phase content, microstructure, and mechanical properties of the composites.     

Effects of Solvent Diols on the Synthesis of ZnFe2O4 Particles and Their Use as Heterogeneous Photo-Fenton Catalysts

A solvothermal method was used to prepare zinc ferrite spinel oxide (ZnFe₂O₄) using ethylene glycol and 1,4 butanediol as solvent diols, and the influence of diols on the physical properties of ZnFe₂O₄ particles was investigated. The produced particles were characterized by X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption isotherms, and the catalytic activity for the organic pollutant decomposition by heterogeneous photo-Fenton reaction was investigated. Both solvents produced particles with cubic spinel structure. Microporous and mesoporous structures were obtained when ethylene glycol and 1,4 butanediol were used as diols, respectively. A higher pore volume and surface area, as well as a higher catalytic activity for the pollutant degradation were found when 1,4 butanediol was used as solvent.     

Characterization of Al2O3 Matrix Composites Fabricated via the Slip Casting Method Using NiAl-Al2O3 Composite Powder

This work aimed to characterize Al₂O₃ matrix composites fabricated by the slip casting method using NiAl-Al₂O₃ composite powder as the initial powder. The composite powder, consisting of NiAl + 30 wt.% Al₂O₃, was obtained by mechanical alloying of Al₂O₃, Al, and Ni powders. The composite powder was added to the Al₂O₃ powder to prepare the final powder for the slip casting method. The stained composite samples presented high density. EDX and XRD analyses showed that the sintering process of the samples in an air atmosphere caused the formation of the NiAl₂O₄ spinel phase. Finally, the phase composition of the composites changed from the initial phases of Al₂O₃ and NiAl to Al₂O₃, Ni, and NiAl₂O₄. However, in the area of Ni, fine Al₂O₃ particles remaining from the initial composite powder were visible. It can be concluded that after slip casting, after starting with Al₂O₃ and the composite powder (NiAl-Al₂O₃) and upon sintering in air, ceramic matrix composites with Ni and NiAl₂O₄ phases, complex structures, high-quality sintered samples, and favorable mechanical properties were obtained.     

Elaboration of Alumina-Zirconia Composites: Role of the Zirconia Content on the Microstructure and Mechanical Properties

Alumina-zirconia (AZ) composites are attractive structural materials, which combine the high hardness and Young’s modulus of the alumina matrix with additional toughening effects, due to the zirconia dispersion. In this study, AZ composites containing different amounts of zirconia (in the range 5–20 vol %) were prepared by a wet chemical method, consisting on the surface coating of alumina powders by mixing them with zirconium salt aqueous solutions. After spray-drying, powders were calcined at 600 °C for 1 h. Green bodies were then prepared by two methods: uniaxial pressing of spray-dried granules and slip casting of slurries, obtained by re-dispersing the spray dried granulates. After pressureless sintering at 1500 °C for 1 h, the slip cast samples gave rise to fully dense materials, characterized by a quite homogeneous distribution of ZrO₂ grains in the alumina matrix. The microstructure, phase composition, tetragonal to monoclinic transformation behavior and mechanical properties were investigated and are here discussed as a function of the ZrO₂ content. The material containing 10 vol % ZrO₂ presented a relevant hardness and exhibited the maximum value of K_I0, mainly imputable to the t → m transformation at the crack tip.     

Effect of Electroless Cu Plating Ti3AlC2 Particles on Microstructure and Properties of Gd2O3/Cu Composites

Ti₃AlC₂ presents a hexagonal layered crystal structure and bridges the gap between metallic and ceramic properties, and Gadolinia (Gd₂O₃) has excellent thermodynamic stability, which make them potentially attractive as dispersive phases for Cu matrix composites. In this paper, Cu@Ti₃AlC₂-Gd₂O₃/Cu composites, Ti₃AlC₂-Gd₂O₃/Cu composites, and Gd₂O₃/Cu composites were prepared by electroless Cu plating, internal oxidation, and vacuum hot press sintering. The microstructure and the effect of the Cu plating on the properties of the Cu@Ti₃AlC₂-Gd₂O₃/Cu composites were discussed. The results showed that a Cu plating with a thickness of about 0.67 μm was successfully plated onto the surface of Ti₃AlC₂ particles. The ex situ Ti₃AlC₂ particles were distributed at the Cu grain boundary, while the in situ Gd₂O₃ particles with a grain size of 20 nm were dispersed in the Cu grains. The electroless Cu plating onto the surface of the Ti₃AlC₂ particles effectively reduces their surfactivity and improves the surface contacting state between the Cu@Ti₃AlC₂ particles and the Cu matrix, and reduces electron scattering, so that the tensile strength reached 378.9 MPa, meanwhile, the electrical conductivity and elongation of the Cu matrix composites was maintained at 93.6 IACS% and 17.6%.     

Al2O3/ZrO2/Y3Al5O12 Composites: A High-Temperature Mechanical Characterization

An Al₂O₃/5 vol%·ZrO₂/5 vol%·Y₃Al₅O₁₂ (YAG) tri-phase composite was manufactured by surface modification of an alumina powder with inorganic precursors of the second phases. The bulk materials were produced by die-pressing and pressureless sintering at 1500 °C, obtaining fully dense, homogenous samples, with ultra-fine ZrO₂ and YAG grains dispersed in a sub-micronic alumina matrix. The high temperature mechanical properties were investigated by four-point bending tests up to 1500 °C, and the grain size stability was assessed by observing the microstructural evolution of the samples heat treated up to 1700 °C. Dynamic indentation measures were performed on as-sintered and heat-treated Al₂O₃/ZrO₂/YAG samples in order to evaluate the micro-hardness and elastic modulus as a function of re-heating temperature. The high temperature bending tests highlighted a transition from brittle to plastic behavior comprised between 1350 and 1400 °C and a considerable flexural strength reduction at temperatures higher than 1400 °C; moreover, the microstructural investigations carried out on the re-heated samples showed a very limited grain growth up to 1650 °C.     

Initial Processes of Atomic Layer Deposition of Al2O3 on InGaAs: Interface Formation Mechanisms and Impact on Metal-Insulator-Semiconductor Device Performance

Interface-formation processes in atomic layer deposition (ALD) of Al₂O₃ on InGaAs surfaces were investigated using on-line Auger electron spectroscopy. Al₂O₃ ALD was carried out by repeating a cycle of Al(CH₃)₃ (trimethylaluminum, TMA) adsorption and oxidation by H₂O. The first two ALD cycles increased the Al KLL signal, whereas they did not increase the O KLL signal. Al₂O₃ bulk-film growth started from the third cycle. These observations indicated that the Al₂O₃/InGaAs interface was formed by reduction of the surface oxides with TMA. In order to investigate the effect of surface-oxide reduction on metal-insulator-semiconductor (MIS) properties, capacitors and field-effect transistors (FETs) were fabricated by changing the TMA dosage during the interface formation stage. The frequency dispersion of the capacitance-voltage characteristics was reduced by employing a high TMA dosage. The high TMA dosage, however, induced fixed negative charges at the MIS interface and degraded channel mobility.     

Influence of N2 Partial Pressure on Structure and Mechanical Properties of TiAlN/Al2O3 Multilayers

TiAlN/Al₂O₃ multilayers with different Ar/N₂ ratios were deposited on Sisubstrates in different N₂ partial pressure by magnetron sputtering. The crystalline and multilayer structures of the multilayers were determined by a glancing angle X-ray diffractometer (XRD). A nanoindenter was used to evaluate the hardness, the elastic modulus and scratch scan of the multilayers. The chemical bonding was investigated by a X-ray Photoelectron Spectroscopy (XPS). The maximum hardness (36.3 GPa) and elastic modulus (466 GPa) of the multilayers was obtained when Ar/N₂ ratio was 18:1. The TiAlN/Al₂O₃ multilayers were crystallized with orientation in the (111) and (311) crystallographic planes. The multilayers displayed stably plastic recovery in different Ar/N₂ ratios. The scratch scan and post scan surface profiles of TiAlN/Al₂O₃ multilayers showed the highest critical fracture load (L_c) of 53 mN for the multilayer of Ar/N₂ = 18:1. It indicated that the multilayer had better practical adhesion strength and fracture resistance.     

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.     

Effects of Ni and Cu Residuals on the Magnetic Properties and Microstructure of SmCo5 Magnets

The effect of Ni/Cu-coating residuals on the magnetic properties and microstructures of samarium–cobalt (SmCo₅) magnets was studied. SmCo₅ magnets with 0.0, 0.5, 1.0, 2.0, 3.0 and 4.0 wt.% of added Ni/Cu (85 wt.% Ni/15 wt.% Cu) were prepared using a conventional sintering route. The magnetic properties of the magnets were found to be consistent up to 2 wt.% Ni/Cu. Any further increase in the Ni/Cu content resulted in a significant reduction in the magnetic properties, to lower than values that would be commercially acceptable. SEM/EDS studies showed that two major phases, i.e., the SmCo₅ matrix phase and Sm₂O₃ were present in all the sintered SmCo₅ magnets. The presence of Sm₂Co₇ as a minor phase fraction was detected in the sintered SmCo₅ magnets containing up to 2 wt.% Ni/Cu. A 2 wt.% Ni/Cu addition to magnets resulted in the presence of two new phases with compositions close to SmCo and Sm₂Co₁₇ in addition to SmCo₅ and Sm₂O₃ as major phases in the SEM-observed microstructure. These newly formed phases are present in small fractions and are presumably homogenously distributed at the grain boundaries of the magnets. As they are known to act as nucleation sites for reverse magnetic domains, they effectively reduce the intrinsic grain boundary magnetic strength, leading to a drop in the coercivity. We concluded that the sintered SmCo₅ magnets could be recycled with up to 2 wt.% Ni/Cu as a residual from the coating under our sintering and heat treatment conditions.     

Facile Solvothermal Synthesis and Gas Sensitivity of Graphene/WO3 Nanocomposites

Graphene has attracted enormous attention owing to its extraordinary properties, while graphene-based nanocomposites hold promise for many applications. In this paper, we present a two-step exploitation method for preparation of graphene oxides and a facile solvothermal route for preparation of few-layer graphene nanosheets and graphene/WO₃ nanocomposites in an ethanol-distilled water medium. The as-synthesized samples were characterized by using field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible (UV-vis) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric-differential thermal analysis (TG-DTA) and gas-sensing test. The resistivity of the thick-film gas sensors based on sandwich-like graphene/WO₃ nanocomposites can be controlled by varying the amount of graphene in the composites. Graphene/WO₃ nanocomposites with graphene content higher than 1% show fast response, high selectivity and fine sensitivity to NO_x.     

Effect of Current Density on the Microstructure and Mechanical Properties of 3YSZ/Al2O3 Composites by Flash Sintering

The 3YSZ/40 wt% Al₂O₃ composites were prepared by flash sintering at a low furnace temperature (700 °C). The effects of the current density on the relative density and Vickers hardness of the composites were systematically investigated. The results showed that the relative densities and Vickers hardness of the samples increased gradually with the increasing of the current densities, and the relative density was as high as 94.2%. The Vickers hardness of 11.3 GPa was obtained under a current density of 102 mA/mm². Joule heating and defects generation are suggested to be the main causes of rapid densification in flash sintering. The microstructure of the molten zone showed the formation of eutectic structures in the composite, suggesting that grain boundary overheating may have contributed to the formation of the molten zone.     

High-Temperature Chemical Stability of Cr(III) Oxide Refractories in the Presence of Calcium Aluminate Cement

Al₂O₃-CaO-Cr₂O₃ castables are used in various furnaces due to excellent corrosion resistance and sufficient early strength, but toxic Cr(VI) generation during service remains a concern. Here, we investigated the relative reactivity of analogous Cr(III) phases such as Cr₂O₃, (Al_1−xCr_x)₂O₃ and in situ Cr(III) solid solution with the calcium aluminate cement under an oxidizing atmosphere at various temperatures. The aim is to comprehend the relative Cr(VI) generation in the low-cement castables (Al₂O₃-CaO-Cr₂O₃-O₂ system) and achieve an environment-friendly application. The solid-state reactions and Cr(VI) formation were investigated using powder XRD, SEM, and leaching tests. Compared to Cr₂O₃, the stability of (Al_1−xCr_x)₂O₃ against CAC was much higher, which improved gradually with the concentration of Al₂O₃ in (Al_1−xCr_x)₂O₃. The substitution of Cr₂O₃ with (Al_1−xCr_x)₂O₃ in the Al₂O₃-CaO-Cr₂O₃ castables could completely inhibit the formation of Cr(VI) compound CaCrO₄ at 500–1100 °C and could drastically suppress Ca₄Al₆CrO₁₆ generation at 900 to 1300 °C. The Cr(VI) reduction amounting up to 98.1% could be achieved by replacing Cr₂O₃ with (Al_1−xCr_x)₂O₃ solid solution. However, in situ stabilized Cr(III) phases as a mixture of (Al_1−xCr_x)₂O₃ and Ca(Al_12−xCr_x)O₁₉ solid solution hardly reveal any reoxidation. Moreover, the CA₆ was much more stable than CA and CA₂, and it did not participate in any chemical reaction with (Al_1−xCr_x)₂O₃ solid solution.     

Microstructure and Mechanical Properties of Alumina Composites with Addition of Structurally Modified 2D Ti3C2 (MXene) Phase

This study presents new findings related to the incorporation of MXene phases into ceramic. Aluminium oxide and synthesised Ti₃C₂ were utilised as starting materials. Knowing the tendency of MXenes to oxidation and degradation, particularly at higher temperatures, structural modifications were proposed. They consisted of creating the metallic layer on the Ti₃C₂, by sputtering the titanium or molybdenum. To prepare the composites, powder metallurgy and spark plasma sintering (SPS) techniques were adopted. In order to evaluate the effectiveness of the applied modifications, the emphasis of the research was placed on microstructural analysis. In addition, the mechanical properties of the obtained sinters were examined. Observations revealed significant changes in the MXenes degradation process, from porous areas with TiC particles (for unmodified Ti₃C₂), to in situ creation of graphitic carbon (in the case of Ti₃C₂-Ti/Mo). Moreover, the fracture changed from purely intergranular to cracking with high participation of transgranular mode, analogously. In addition, the results obtained showed an improvement in the mechanical properties for composites with Ti/Mo modifications (an increase of 10% and 15% in hardness and fracture toughness respectively, for specimens with 0.5 wt.% Ti₃C₂-Mo). For unmodified Ti₃C₂, enormously cracked areas with spatters emerged during tests, making the measurements impossible to perform.     

Remarkable Reduction in IG with an Explicit Investigation of the Leakage Conduction Mechanisms in a Dual Surface-Modified Al2O3/SiO2 Stack Layer AlGaN/GaN MOS-HEMT

We demonstrated the performance of an Al₂O₃/SiO₂ stack layer AlGaN/GaN metal–oxide semiconductor (MOS) high-electron-mobility transistor (HEMT) combined with a dual surface treatment that used tetramethylammonium hydroxide (TMAH) and hydrochloric acid (HCl) with post-gate annealing (PGA) modulation at 400 °C for 10 min. A remarkable reduction in the reverse gate leakage current (I_G) up to 1.5×10−12 A/mm (@ V_G = −12 V) was observed in the stack layer MOS-HEMT due to the combined treatment. The performance of the dual surface-treated MOS–HEMT was significantly improved, particularly in terms of hysteresis, gate leakage, and subthreshold characteristics, with optimized gate annealing treatment. In addition, an organized gate leakage conduction mechanism in the AlGaN/GaN MOS–HEMT with the Al₂O₃/SiO₂ stack gate dielectric layer was investigated before and after gate annealing treatment and compared with the conventional Schottky gate. The conduction mechanism in the reverse gate bias was Poole–Frankel emission for the Schottky-gate HEMT and the MOS–HEMT before annealing. The dominant conduction mechanism was ohmic/Poole-Frankel at low/medium forward bias. Meanwhile, gate leakage was governed by the hopping conduction mechanism in the MOS–HEMT without gate annealing modulation at a higher forward bias. After post-gate annealing (PGA) treatment, however, the leakage conduction mechanism was dominated by trap-assisted tunneling at the low to medium forward bias region and by Fowler–Nordheim tunneling at the higher forward bias region. Moreover, a decent product of maximum oscillation frequency and gate length (f_max × L_G) was found to reach 27.16 GHz∙µm for the stack layer MOS–HEMT with PGA modulation. The dual surface-treated Al₂O₃/SiO₂ stack layer MOS–HEMT with PGA modulation exhibited decent performance with an I_DMAX of 720 mA/mm, a peak extrinsic transconductance (G_MMAX) of 120 mS/mm, a threshold voltage (V_TH) of −4.8 V, a higher I_ON/I_OFF ratio of approximately 1.2×109, a subthreshold swing of 82 mV/dec, and a cutoff frequency(f_t)/maximum frequency of (f_max) of 7.5/13.58 GHz.     

Characterization of a unique [FeS] cluster in the electron transfer chain of the oxygen tolerant [NiFe] hydrogenase from Aquifex aeolicus

Iron-sulfur clusters are versatile electron transfer cofactors, ubiquitous in metalloenzymes such as hydrogenases. In the oxygen-tolerant Hydrogenase I from Aquifex aeolicus such electron “wires” form a relay to a diheme cytb, an integral part of a respiration pathway for the reduction of O₂ to water. Amino acid sequence comparison with oxygen-sensitive hydrogenases showed conserved binding motifs for three iron-sulfur clusters, the nature and properties of which were unknown so far. Electron paramagnetic resonance spectra exhibited complex signals that disclose interesting features and spin-coupling patterns; by redox titrations three iron-sulfur clusters were identified in their usual redox states, a [3Fe4S] and two [4Fe4S], but also a unique high-potential (HP) state was found. On the basis of ⁵⁷Fe Mössbauer spectroscopy we attribute this HP form to a superoxidized state of the [4Fe4S] center proximal to the [NiFe] site. The unique environment of this cluster, characterized by a surplus cysteine coordination, is able to tune the redox potentials and make it compliant with the [4Fe4S]³⁺ state. It is actually the first example of a biological [4Fe4S] center that physiologically switches between 3+, 2+, and 1+ oxidation states within a very small potential range. We suggest that the (1 + /2+) redox couple serves the classical electron transfer reaction, whereas the superoxidation step is associated with a redox switch against oxidative stress.     

The Reaction Products of the Al–Nb–B2O3–CuO System in an Al 6063 Alloy Melt and Their Influence on the Alloy’s Structure and Characteristics

To meet aero-engine aluminum skirt requirements, an experiment was carried out using Al–Nb–B₂O₃–CuO as the reaction system and a 6063 aluminum alloy melt as the reaction medium for a contact reaction, and 6063 aluminum matrix composites containing in situ particles were prepared with the near-liquid-phase line-casting method after the reaction was completed. The effects of the reactant molar ratio and the preheating temperature on the in situ reaction process and products were explored in order to determine the influence of in situ-reaction-product features on the organization and the qualities of the composites. Thermodynamic calculations, DSC analysis, and experiments revealed that the reaction could continue when the molar ratio of the reactants of Al–Nb–B₂O₃–CuO was 6:1:1:1.5. A kinetic study revealed that the Al thermal reaction in the system produced Al₂O₃ and [B], and the [B] atoms interacted with Nb to generate NbB₂. With increasing temperature, the interaction between the Nb and the AlB₂ produced hexagonal NbB₂ particles with an average longitudinal size of 1 μm and subspherical Al₂O₃ particles with an average longitudinal size of 0.2 μm. The microstructure of the composites was reasonably fine, with an estimated equiaxed crystal size of around 22 μm, a tensile strength of 170 MPa, a yield strength of 135 MPa, an elongation of 13.4%, and a fracture energy of 17.05 × 10⁵ KJ/m³, with a content of 2.3 wt% complex-phase particles. When compared to the matrix alloy without addition, the NbB₂ and Al₂O₃ particles produced by the in situ reaction had a significant refinement effect on the microstructure of the alloy, and the plasticity of the composite in the as-cast state was improved while maintaining higher strength and better overall mechanical properties, allowing for industrial mass production.