Re-examination of phase relations between solid solutions in R4Al2O9-R4Si2N2O7-R4Si2O10 (R=Y,Gd, Yb) systems

Samples in Si–Al-R-O-N (R = Y, Gd, Yb) systems were prepared by solid-state reactions using R₂O₃, Al₂O₃, SiO₂ and Si₃N₄ powders as starting materials. X-ray diffraction was done to investigate RAM-J(R) solid solutions [RAM = R₄Al₂O₉, J(R) = R₄Si₂N₂O₇] formation and their equilibrium with RSO (R₄Si₂O₁₀). Phase relations between RAM, J(R) and RSO at 1700 °C were summarized in a phase diagram. It was determined that a limited solid solution of RAM and RSO could be formed along RAM-RSO tie-line, while RAM and J(R) form a continuous solid solution along RAM-J(R) tie-line. In RAM-J(R)-RSO ternary systems, the RAM-J(R) tie-lines were extended towards the RSO corner to form a continuous solid solution area of JRAMss (R = Y, Gd, Yb). The established phase relations in the Si–Al-R-O-N (R = Y, Gd, Yb) systems may facilitate compositional selections for developing JRAMss as monolithic ceramics or for SiC/Si₃N₄ based composites using the solid-solutions as a second refractory phase.     

Hydrophobic Cross-Linked Poly(dimethylsiloxane)-Based Sorbents for Oil Spill Applications

With the increase of industrialization and urbanization, humankind faces massive oil-based pollution due to tanker accidents, human error, and natural disasters. For this, hydrophobic sorbents are fabricated and their applications for the removal of oil from polluted water sources are investigated. These hydrophobic sorbents are prepared by the condensation reaction of poly(dimethylsiloxane) and tris[3-(trimethoxysilyl)propyl]isocyanurate cross-linker via bulk polymerization. The obtained sorbents exhibit high oil sorption capacity, fast absorption–desorption kinetics, and great reusability. Moreover, they can selectively absorb oil from the water surface, thus making them practical for water clean-up applications.     

Non-Platinum Group Metal Electrocatalysts toward Efficient Hydrogen Oxidation Reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.     

Kinetic analysis of crystallization of zeolite beta synthesized by direct heating

To quantitatively investigate the initial crystallization of zeolite beta synthesized by direct heating, the extent of the reaction was precisely evaluated by X-ray diffraction measurements and Rietveld structural refinement, and a kinetic analysis of crystallization was performed using the Avrami-Erofe'ev equation. The activation energy for crystallization was lower than that for hydrothermal synthesis. Reaction and synthesis time curves revealed that the initial zeolite beta crystallization consisted of three stages. The first was an induction period with nucleation by the generation of building units and the formation of an initial coordinated structure. The second stage was crystal growth by a diffusion-controlled reaction, and the third stage involved slowing down of crystallization by the limitation of dehydrocondensation. These stages could be analyzed by calculation of the rate constant and Avrami exponent for each stage.     

New insights into the mechanisms of carbon dioxide mineralization by portlandite

Portlandite (Ca(OH)₂; also known as calcium hydroxide or hydrated lime), an archetypal alkaline solid, interacts with carbon dioxide (CO₂) via a classic acid–base “carbonation” reaction to produce a salt (calcium carbonate: CaCO₃) that functions as a low-carbon cementation agent, and water. Herein, we revisit the effects of reaction temperature, relative humidity (RH), and CO₂ concentration on the carbonation of portlandite in the form of finely divided particulates and compacted monoliths. Special focus is paid to uncover the influences of the moisture state (i.e., the presence of adsorbed and/or liquid water), moisture content and the surface area-to-volume ratio (s_a/v, mm⁻¹) of reactants on the extent of carbonation. In general, increasing RH more significantly impacts the rate and thermodynamics of carbonation reactions, leading to high(er) conversion regardless of prior exposure history. This mitigated the effects (if any) of allegedly denser, less porous carbonate surface layers formed at lower RH. In monolithic compacts, microstructural (i.e., mass-transfer) constraints particularly hindered the progress of carbonation due to pore blocking by liquid water in compacts with limited surface area to volume ratios. These mechanistic insights into portlandite's carbonation inform processing routes for the production of cementation agents that seek to utilize CO₂ borne in dilute (≤30 mol%) post-combustion flue gas streams.     

Effect of Zr addition on the interfacial reaction of the SiC joint brazed by Inconel 625 powder filler

Ni-based alloys are believed to be the most suitable brazing fillers for SiC ceramic application in a nuclear environment. However, graphite, which severely deteriorates the mechanical property of the joint, is inevitable when Ni reacts with SiC. In this paper, Different amounts of Zr powders are mixed with Inconel 625 powders to braze SiC at 1400 °C. When Zr addition reaches 40 wt%, the brazed seam confirms the absence of graphite. This research proves that Zr can avoid the graphite’s formation by suppressing Ni’s activity. The room-temperature shear strength of the joint with graphite’s absence is tested to be 81.97 MPa, which is almost three times higher than that of the joint with graphite. The interfacial reaction process and mechanism of the SiC joint are investigated and explained in this paper using thermodynamic calculations.     

Re-Looking into the Active Moieties of Metal X-ides (X- = Phosph-, Sulf-, Nitr-, and Carb-) Toward Oxygen Evolution Reaction

Non-precious metal-based catalysts for oxygen evolution reaction (OER) have been extensively studied, among which the transition metal X-ides (including phosph-ides, sulf-ides, nitr-ides, and carb-ides) materials are emerging as promising candidates to replace the benchmark Ir/Ru-based materials in alkaline media. However, it is controversial whether the metal Xides host the real active sites since these metal Xides are thermodynamically unstable under a harsh OER environment—it has been reported that the initial metal Xides can be electrochemically oxidized and transformed into corresponding oxides and (oxy)hydroxides. Therefore, the metal Xides are argued as “pre-catalysts”; the electrochemically formed oxides and (oxy)hydroxides are believed as the real active moieties for OER. Herein, the recent advances in understanding the transformation behavior of metal Xides during OER are re-looked; importantly, hypotheses are provided to understand why the electrochemically formed oxides and (oxy)hydroxides catalysts derived from metal Xides are superior for OER to the as-prepared metal oxides and (oxy)hydroxides catalysts.     

Taylor Bubble Study of the Influence of Fluid Dynamics on Yield and Selectivity in Fast Gas-Liquid Reactions

A consecutive competitive gas-liquid reaction is investigated using a Taylor bubble setup regarding the influence of fluid mixing in the bubble wake on yield and selectivity. The concentration fields behind a Taylor bubble are visualized and measured quantitatively with a novel time-resolved absorption imaging technique based on Beer Lamberts law and an integral selectivity is derived. In addition, the calculation of the local selectivity, often used in numerical approaches, is discussed and the existing experimental limits for its derivation are pointed out. Finally, an increase in selectivity of a competitive consecutive reaction for enhanced mixing is experimentally confirmed.     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

Fabrication and properties of the superhydrophobic ceria-based composite coating on magnesium alloy

A superhydrophobic ceria-based composite coating is developed to improve anticorrosion properties of AZ61 magnesium alloy, fabricating via chemical conversion method followed by hydrothermal treatment. The cerium conversion coating has a block structure with microcracks. After the hydrothermal treatment, a dense CeO₂ layer, porous CeO₂ nanorods, and stearic absorbing layers are grown stepwise on the conversion coating. And the composite coating is hydrophobic or even superhydrophobic and has almost no microcracks. As the hydrothermal reaction time increases, the water contact angle of the composite coating first increases and then decreases, and it reaches the maximum value of 152° after hydrothermal treatment for 4 h. Both the dense CeO₂ layer and the superhydrophobic stearic absorbing layer can effectively prevent the electrolyte from contacting the substrate; the corrosion current density of the superhydrophobic composite coating is lower than that of the hydrophilic composite coating and the cerium conversion coating, and has the best corrosion resistance.