A kinetic model involving oxidation and volatilization in SiC-B4C-xAl2O3 ceramics system

In this paper, a new kinetic model considering both oxidation and volatilization kinetics is established and applied to analyze the oxidation of SiC-B₄C-xAl₂O₃ ceramics and other systems in various oxidation conditions. The effects of diffusion area and volume changes during the oxidation process are considered in this model. The physical meaning of each parameter in this model is explicit and simple. According to this model, the diffusion coefficient of species and the corresponding diffusion activation energy are easily available. The practicability of this model is well verified by the experimental data of SiC-B₄C-xAl₂O₃ and other systems oxidized under different conditions. In addition, the practice shows that the model is applicable not only to the systems where oxidation and volatilization coexist, but also to the system where only oxidation plays a major role. We hope the model proposed in this work can be used in other materials with more complex environments.     

Silica-based ceramics toward electromagnetic microwave absorption

Silica-based ceramics have been explored extensively as a class of versatile materials for various applications in architecture, catalysis, energy, machinery, and biomedical engineering. Nevertheless, comprehensive information on silica-based ceramic and electromagnetic microwave (EMW) absorption is scarce, although excellent progress has been made in this field. Here, recent progress in the investigation of silica-based ceramics toward EMW absorption is reviewed. We first introduced the basis of ceramics (characteristics, classification, synthetic methods, potential applications). Subsequently, the silica-based ceramics, including Si-based oxides and alloys, SiOC/SiC/Si₃N₄/SiCN-based composite, Ti₃SiC₂ and composite for EMW absorption were systematically summarized. Notably, the fabrication strategies, absorption properties, and mechanisms of silica-based ceramics are described in detail, with a focus on structure and component design. Lastly, the prospects and ongoing challenges of this field in the future are presented. This review is expected to learn from the past and achieve progress toward the future of silica-based ceramic for EMW absorption.     

Ultra-high temperature ceramics based on ZrB2 obtained by pressureless sintering with addition of Cr3C2, Mo2C,and WC

ZrB₂-MeC and ZrB₂-19 vol% SiC-Me_xC_y where Me=Cr, Mo, W were obtained by pressureless sintering. The capability to promote densification of ZrB₂ and ZrB₂-SiC matrices is the highest for WC and lowest for Cr₃C₂. The interaction between the components results in the formation of new phases, such as MeB (MoB, CrB, WB), a solid solution based on ZrC, and a solid solution based on ZrB₂. The addition of Cr₃C₂ decreases the mechanical properties. On the other hand, the addition of Mo₂C or WC to ZrB₂-19 vol% SiC composite ceramics leads increased mechanical properties. Long-term oxidation of ceramics at 1500 °C for 50 h showed that, in binary ZrB₂-Me_xC_y, a protective oxide scale does not form on the surface thus leading to the destruction of the composite. On the contrary, triple composites showed high oxidation resistance, due to the formation of dense oxide scale on the surface, with ZrB₂-SiC-Mo₂C displaying the best performance.     

Highly efficient chemical mechanical polishing method for SiC substrates using enhanced slurry containing bubbles of ozone gas

In this study, a highly efficient method for chemical mechanical polishing (CMP) of silicon carbide (SiC) substrates using enhanced slurry was proposed and developed. The enhanced slurry contains bubbles of ozone gas generated by ozone gas generator in pure water mixed with a conventional commercially available slurry. Therefore, the enhanced slurry has an oxidizing effect on the Si-face of SiC substrates. To confirm the effectiveness of bubbles enclosing ozone gas, both nano-indentation test and X-ray photoelectron spectroscopy (XPS) analysis were conducted. As a result, the hardness decrease of the Si-face of the SiC substrate was confirmed through the nano-indentation test, and the generation of reaction products was confirmed on Si-face of SiC substrate in the XPS analysis. According to a series of experimental results of our proposed highly efficient CMP method for SiC substrates, the removal rate can be increased when the enhanced slurry was applied, comparing with that for the not only conventional commercially available slurry but also commercially available dedicated slurry.     

Physicochemical structure characteristics and intrinsic reactivity of demineralized coal char rapidly pyrolyzed at elevated pressure

This study aims to investigate the effect of pyrolysis pressure on the physical and chemical structure characteristics and reactivity of subbituminous demineralized coal char. The pyrolysis experiments were studied under different pressures using a pressurized drop tube reactor (PDTR). Structural properties of coal chars were investigated by the application of scanning electron microscopy (SEM), nitrogen adsorption analyzer, automatic mercury porosimeter, and Raman spectroscopy, respectively. The Random Pore Model was used to determine kinetic parameters and intrinsic reactivity of chars. The specific pore volume of chars pyrolyzed at 900–1000 °C increased first and then decreased with pyrolysis pressure increasing, and the maximum value of the specific pore volume of chars occurred at 1.0 MPa. The degree of graphitization of chars deepened with the increase of temperature or pressure. Intrinsic activation energy of char-O₂ was within the range of 126–134 kJ/mol. The intrinsic reactivity of char-O₂ reaction showed strong correlation the Raman parameters with the change of pyrolysis conditions, and it suggested that the intrinsic reactivity of char-O₂ reaction was mainly affected by aromatic ring structures rather than pore structures.     

Transition metal nanoparticle catalysts in releasing hydrogen from the methanolysis of ammonia borane

Ammonia borane (H₃N·BH₃, AB) is one of the promising hydrogen storage materials due to high hydrogen storage capacity (19.6% wt), high stability in solid state as well as in solution and nontoxicity. The methanolysis of AB is an alternative way of releasing H₂ due to many advantages over the hydrolysis such as having high stability against self releasing hydrogen gas. Here we review the reports on using various noble or non-noble metal(0) catalysts for H₂ release from the methanolysis of AB. Ni(0), Pd(0), and Ru(0) nanoparticles (NPs), stabilized as colloidal dispersion in methanol, are highly active and long lived catalysts in the methanolysis of AB. The catalytic activity, lifetime and reusability of transition metal(0) NPs show significant improvement when supported on the surface of solid materials. The supported cobalt, nickel, copper, palladium, and ruthenium based catalysts are quite active in H₂ release from the methanolysis of AB. Rh(0) NPs are highly active catalysts in releasing H₂ from the methanolysis of AB when confined within the void spaces of zeolite or supported on oxide nanopowders such as nanosilica, nanohydroxyapatite, nanoalumina or nanoceria. The oxide supported Rh(0) NPs can provide high activity with turnover frequency values as high as 218 min⁻¹ and long lifetime with total turnover values up to 26,000 in generation of H₂ from the methanolysis of AB at 25 °C. When deposited on carbon the bimetallic AgPd alloy nanoparticles have the highest activity in releasing H₂ through the methanolysis of AB.     

Self-supported Ni2P nanotubes coated with FeP nanoparticles electrocatalyst (FeP@Ni2P/NF) for oxygen evolution reaction

Bimetallic phosphides have been widely investigated as electrocatalysts for oxygen evolution reaction (OER) due to their efficient activity and environmental friendliness. While the reasonable design and controllable synthesis of bimetallic phosphide with typical nanostructure is still a great challenge. Hence, we put forward a novel and straightforward way for constructing FeP nanoparticles coated Ni₂P ultrathin nanotube arrays on the surface of Ni foil (FeP@Ni₂P/NF), which is synthesized through two steps of electrodeposition and subsequent in-situ phosphorization process. The obtained FeP@Ni₂P/NF shows excellent electrochemical activity for OER, and it only needs potential of 1.52 V vs. RHE to reach the current density of 50 mA cm⁻² in an alkaline media. The excellent electrocatalytic activity of FeP@Ni₂P/NF mainly benefits from: (i) the synergistic effect between FeP and Ni₂P promoting electron transfer; (ii) the formation of the unique 3D ultrathin nanotube arrays increasing the quantity of active sites and avoiding the agglomeration of catalysts during testing. In addition, the influence of reaction condition on the electrochemical activity for OER has also been investigated through altering the phosphorization temperature of precursor.     

One-step potentiostatic electrodeposition of Ni–Se–Mo film on Ni foam for alkaline hydrogen evolution reaction

Exploring efficient, abundant, low-cost and stable materials for hydrogen evolution reaction (HER) is highly desired but still a challenging task. Herein, Ni–Se–Mo electrocatalysts supported on nickel foam (NF) substrate were synthesized by a facile one-step electrodeposition method. The Ni–Se–Mo film presents high electrocatalytic activity and stability toward HER, with a low overpotential of 101 mV to afford a current density of 10 mA cm⁻² in 1.0 M KOH medium. Such excellent HER performance of Ni–Se–Mo film induced by the synergistic effects from Mo-doped Ni–Se film leads to the fast electron transfer. This work provides the validity of interface engineering strategy in preparing highly efficient transition metal chalcogenides based HER electrocatalysts.     

Effect of microbial hydrogen consumption on the hydrogen permeation behaviour of AISI 4135 steel under cathodic protection

The feasibility of microbial hydrogen consumption to mitigate the hydrogen embrittlement (HE) under different cathodic potentials was evaluated using the Devanathan-Stachurski electrochemical test and the hydrogen permeation efficiency η. The hydrogen permeation efficiency η in the presence of strain GA-1 was lower than that in sterile medium. The cathodic potential inhibited the adherence of strain GA-1 to AISI 4135 steel surface, thereby reducing the hydrogen consumption of strain GA-1. The adherent GA-1 cells were capable of consuming ‘cathodic hydrogen’ and reducing the proportions of absorbed hydrogen, indicating that it is theoretically possible to control HE by hydrogen-consuming microbes.     

Ceria-Co-Cu-based SOFC anode for direct utilisation of methane or ethanol as fuels

Nickel-free solid oxide fuel cell anodes are an object of study for applications that aim at utilising primary carbonaceous fuels to generate power. In this study, a ceria-Co-Cu anode is produced and tested with hydrogen, methane and ethanol fuels at various temperatures.The produced catalysts were characterised by X-ray analysis and H₂ temperature-programmed reduction (TPR). Catalytic tests were performed and compared with the material under electrochemical operation. The cells were electrochemically characterised by recording i-V plots. The samples were assessed post-test for eventual carbon deposits by Raman spectroscopy investigations and temperature-programmed oxidation (TPO) analysis.The cells were able to operate with hydrogen, methane as well as ethanol, directly fed to the anode, with maximum power densities ranging from 400 to 540 mW.cm⁻², depending on the fuel stream utilised. The cells also kept their integrity demonstrating coking resistance for over 24 h of continuous operation. Important discussions and conclusions are drawn about carbon formation and the role of each compound in the anode composition. The bimetallic cell (ceria-Co-Cu) is herein compared to monometallic ones (ceria-Co and ceria-Cu) that served as baselines. The advantages of the bimetallic composition are listed and evaluated throughout the discussions.