Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Nanoarchitectonics of CdS/ZnSnO3 heterostructures for Z-Scheme mediated directional transfer of photo-generated charges with enhanced photocatalytic performance

The construction of heterostructure is an effective strategy to synergetically couple wide-band-gap with the narrow-band-gap semiconductor with a mediate optical property and charge transfer capability. Herein, the Z-Scheme CdS/ZnSnO₃ (CdS/ZSO) heterostructures were constructed by anchoring CdS nanoparticles on the surface of double-shell hollow cubic ZnSnO₃ via the hydrothermal method. The direct recombination of excited electrons in the conduction band (CB) of ZSO and holes in the valence band (VB) of CdS via d-p conjugation at the interface greatly accelerated the internal electric field (IEF). The transfer mode follows the Z-Scheme mechanism, where CdS/ZSO synergistically facilitates the efficient charges transfer from CdS to ZnSnO₃ through the intimate interface. Here, ZnSnO₃ and CdS serve as an oxidation photocatalyst (OP) and reduction photocatalyst (RP), respectively. Thus, it can promote synergistically the oxidation half-reaction and reduction half-reaction of H₂ evolution. The density-functional theory (DFT) calculation further confirms the charges transfer from CdS to ZnSnO₃. The hydrogen evolution of 5% CdS/ZSO heterostructure reached 1167.3 μmol g^?1, which was about 8 and 3 folds high compared to pristine ZSO (141.9 μmol g^?1) and CdS (315.5 μmol g^?1), during 3 h of reaction respectively. Furthermore, the CdS/ZSO heterostructures could suppress the photo corrosion of CdS, resulting in its high stability. This work is expected to enlighten the rational design of heterostructure for OP and RP to promote the hybrid heterostructures photocatalytic H₂ evolution.     

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.     

Evaluation of Scale and Corrosion Inhibition of Modified Polyaspartic Acid

Amino acid modified polyaspartic acids were evaluated as calcium-scale inhibitors. Feasibility of scale inhibition experiments was analyzed by molecular dynamics simulation and Gaussian optimization, and the scale inhibition mechanism was theoretically analyzed. Scale inhibition performance was studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, static scale inhibition experiments, and electrochemical performance testing, which provided an experimental basis for the molecular dynamics simulation. The experimental results showed that Arg-SA-PASP has better scale inhibition and corrosion inhibition performance than His-SA-PASP. The scale inhibition effect increased with increasing concentration. Electrochemical tests indicated that Arg-SA-PASP is an excellent scale and corrosion inhibitor.     

高温氢工质热物理性质计算分析

氢工质在新能源与动力、航天推进、化工材料等领域有着广泛应用。通过开展高温氢工质热力学与输运性质研究，建立了原子态氢、分子态氢、热解平衡态氢的热物理性质计算模型，开发了热物性计算程序Prop_H_H2，适用范围为温度100~3 500 K、压力104~5×107 Pa 。验证表明，Prop_H_H2在适用范围内计算氢工质的物性参数合理可靠，在温度200~3 000 K、压力104~107 Pa范围内，程序预测值更加准确，相对偏差在±5%左右。本研究可为氢工质相关的航天推进、应用物理学、能源动力等行业的科研和应用提供支持借鉴。     

Deposition of UF5 on the surface of steel material having oxide coating in contact with gaseous UF6

When UF6 is handled in leak tight system, the amount of uranium compound formed on the surface of containers, valves, and others in UF6 handling facilities is not so significant for a short term that special attention has not been given to this problem. The present work was done to throw some more light on this problem based on the recent experiment. We discuss the possibility that the intermolecular transfer of a fluorine atom from UF6 to UF5 may participate in the formation of uranium compound. The discussion includes also the unique features contained in the experimental result, the reaction processes assumed in this problem, and the derivation of a rate equation for expressing the deposition of uranium compound. Furthermore, we propose a new method for determining nonlinear parameters included in a governing differential equation having two variables for expressing the deposition of uranium compound from experimental raw data.     

Ab initio calculations of the NO2 fission for CL-20 conformers

NO₂ fission is regarded to be the most important initial decomposition process of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20). In this study, four CL-20 conformers based on the ε-CL-20 were obtained after the optimization at m062x/cc-pvtz level, and the bond length, bond order and bond dissociation energy of the N-N bonds were examined to investigate the stability of these bonds. In addition, the rate constants and activation energy of the NO₂ fission were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that N-N bonds in the case of pseudo-equatorial and axial of nitro groups are the most stable and the least stable, respectively, by evaluating the bond length, bond order and minimum energy path (MEP). The NO₂ fission rate constants are affected by not only the stability of N-N bonds but also the repulsion forces from the other nitro groups, and the fission process for pseudo-equatorial positioning of nitro groups is easier to be accelerated due to the increase of the repulsion forces. The decomposition of CL-20 conformer may mainly originate from the fission of the pseudo-equatorial positioning of nitro groups, especially for CL-20 III conformer because of the significant low activation energy.     

Experimental and numerical study on compressive performance of perforated brick masonry after fire exposure

This paper discusses the compressive performance of perforated brick masonry after fire exposure. Compressive strength tests of the mortar, clay perforated brick, and perforated brick masonry specimens were performed in accordance with ISO834 fire tests of different durations. The temperature distribution of the masonry materials and specimens was simulated using the finite element software ABAQUS, with the thermal parameters of masonry materials recommended by European standard Eurocode 6 and related literature. The compressive strength reduction factors of mortar and clay perforated brick exposed to different fire durations were calculated via the layered method suggested by European standard Eurocode 1. In addition, the compressive strength reduction factors after cooldown were obtained from the experimental data of the masonry materials, and by considering further reductions in the compressive strength after cooling from high temperatures. Experimental data of the masonry specimens were compared with the numerical results obtained using the reduction factors proposed in this work. The comparison revealed an overall acceptable approximation. Thus, the method presented in this paper can be used to evaluate the residual capacity of masonry structures after fire.     

Role of Co in formation of Ni-Ti clusters in maraging stainless steel

The effect of Co addition on the formation of Ni-Ti clusters in maraging stainless steel was studied by three dimensional atom probe (3DAP) and first-principles calculation. The cluster analysis based on the maximum separation approach showed an increase in size but a decrease in density of Ni-Ti clusters with increasing the Co content. The first-principles calculation indicated weaker Co-Ni (Co-Ti) interactions than Co-Ti (Fe-Ti) interactions, which should be the essential reason for the change of distribution characteristics of Ni-Ti clusters in bcc Fe caused by Co addition.     

Single-Crystalline TiO2(B) Nanobelts with Unusual Large Exposed {100} Facets and Enhanced Li-Storage Capacity

The {100} facet of single-crystalline TiO₂(B) is an ideal platform for inserting Li ions, but it is hard to be obtained due to its high surface energy. Here, the single-crystalline TiO₂(B) nanobelts from H₂Ti₃O₇ with nearly 70% {100} facets exposed are synthesized, which significantly enhances Li-storage capacity. The first-principle calculations demonstrate an ab in-plane 2D diffusion through the exposed {100} facets. As a consequence, the nanobelts can significantly accommodate Li ions in LiTiO₂ formula with specific capacity up to 335 mAh g⁻¹, which is in good agreement with the electrochemical characterizations. Coating with conductive and protective poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), the cut-off discharge voltage is as low as 0.5 V, leading to a capacity of 160.7 mAh g⁻¹ after 1500 cycles with a retention rate of 66% at 1C. This work provides a practical strategy to increase the Li-ion capacity and cycle stability by tailoring the crystal orientation and nanostructures.