Sensitivity of a solid Eu(III) complex towards acetonitrile vapor: Structural and spectroscopic characterization

The Eu(III) nitrate complex of the meso- N,N′-bis(2-pyridylmethylene)-1,2-(R,S)-cyclohexanediamine ligand was synthesized and characterized by single crystal and powder X-ray diffraction. The crystal lattice of the complex is capable of absorbing and desorbing selectively acetonitrile molecules, at 293 K upon an acetonitrile vapor pressure of ∼0.1 × 10⁵ Pa. This process, which is partially reversible, can be easily followed by both powder X-ray diffraction (P-XRD) and Eu(III) luminescence spectroscopy. The acetonitrile molecule, located in the outer coordination sphere of the metal ion, does not affect the radiative transition probability of ⁵D₀ level of Eu(III) and also it does not activate further non-radiative channels from this level. On the other hand, this molecule is capable of affecting the energy position and intensities of the crystal field components of the ⁵D₀→⁷F₂ transition. The complex in solid form can be considered a promising material for the optical sensing of acetonitrile vapors.     

Characterization of superficial modification of ferrous rusted substrates subjected to dechlorination-electrochemical process

Preservation of archaeological artefacts after their removal from saline media is a difficult task due to the chloride content of the oxide layers which are unstable in atmospheric conditions, especially if the relative humidity exceeds 85%. For this reason, removal of chlorides from rust layers is one of the priorities of conservationists or restorers of historical artefacts. However, removal of chloride ions is not an easy procedure because of the many considerations involved in the process. In this research, artificially pre-rusted iron samples and an actual historical cannonball were subject to a dechlorination process in a potassium hydroxide solution to measure constant chloride release in a bulk solution. After the chloride removal process, a commercial protective layer was applied to the rust for stabilization purposes. It was calculated that the kinetics of the dechlorination process is driven by diffusion behaviour following Fick’s second law. When this diffusion process prevails, the dechlorination extraction affects the integrity of rust layers as is demonstrated with scanning electron microscopy and X-ray diffraction analyses. It was proven that the chloride removal procedure causes the studied iron layers to stiffen, provoking superficial modification and, in some cases, fractures of the rust. By means of electrochemical impedance spectroscopy it was calculated that the magnitude of the positive effect of the dechlorinated samples depends on the protective features of the rust. Therefore, this research reveals that an efficient chloride removal procedure depends on the electrochemical properties of the dechlorination process and the initial morphology of the iron rust.     

2219铝合金搅拌摩擦焊和钨极保护焊焊接件残余应力的中子衍射研究

利用中子衍射法对2219铝合金搅拌摩擦焊（FSW）和钨极保护焊（TIG）焊接件开展了三维残余应力测量，并对残余应力分布规律进行了分析。结果表明：焊接件的纵向残余应力数值较大；FSW焊接件残余应力整体较TIG焊接件的小；FSW和TIG焊接件的残余拉应力最大值分别为101 MPa和174 MPa，FSW焊接件残余拉应力最大值较TIG焊接件的小；FSW残余拉应力最大值处于轴肩边缘，且前进侧峰值大于后退侧峰值；TIG焊接件残余拉应力最大值处于焊缝边缘。通过中子衍射实验获得的焊接件残余应力分布，将可用于焊接工艺的优化与焊接件的寿命预测。     

Mg-bearing quartz solid solutions as structural intermediates between low and high quartz

Glass powder samples of cordierite composition (doped with 8 mol% TiO₂) were heat-treated to produce a series of increasingly SiO₂-enriched Mg-bearing quartz solid solutions (Qss). The obtained materials were then analyzed by X-ray diffraction: Rietveld structural refinements revealed that Mg-bearing Qss phases possess trigonal symmetry and a compositionally dependent intermediate structural arrangement between those of low and high quartz. High-temperature diffraction measurements were performed up to 700°C to characterize the thermal expansion behavior of the crystals. At SiO₂-rich compositions, a reversible high-to-intermediate inversion of the quartz structure is observed, which shifts with increasing stuffing to lower temperatures than the conventional 573°C for pure quartz. Similarities and differences to the better-established Li-bearing Qss are discussed in the text.     

Spark plasma sintering of B4C and B4C-TiB2 composites: Deformation and failure mechanisms under quasistatic and dynamic loading

Spark plasma sintering (SPS) was employed to consolidate powder specimens consisting of B₄C and various B₄C-TiB₂ compositions. SPS allowed for consolidation of pure B₄C, B₄C-13 vol.%TiB₂, and B₄C-23 vol.%TiB₂ composites achieving ≥99 % theoretical density without sintering additives, residual phases (e.g., graphite), and excessive grain growth due to long sintering times. Electron and x-ray microscopies determined homogeneous microstructures along with excellent distribution of TiB₂ phase in both small and larger-scaled composites. An optimized B₄C-23 vol.%TiB₂ composite with a targeted low density of ～3.0 g/cm³ exhibited 30–35 % increased hardness, fracture toughness, and flexural bend strength compared to several commercial armor-grade ceramics, with the flexural strength being strain rate insensitive under quasistatic and dynamic loading. Mechanistic studies determined that the improvements are a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B₄C matrix in compression and TiB₂ phase in tension, and c) TiB₂ phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB₂ serves as a toughening and strengthening phase, and scaling of SPS samples show promise for the manufacture of ceramic composites for body armor.     

Coexistence of antiferro- and ferrimagnetism in the spinel ZnFe2O4 with an inversion degree δ lower than 0.3

Samples with inversion parameter values (δ) ranging from 0.27 to 0.14 while maintaining the crystallite size value have been successfully fabricated from commercially available powders by mechanical grinding and thermal annealing treatments at temperatures ranging between 400 and 600 °C. Detailed characterization studies of these samples using X-ray, neutron diffraction and magnetic measurements have confirmed for the first time the simultaneous coexistence at 2 K of short range antiferromagnetic and ferrimagnetic ordering for a wide range of the inversion parameter. The magnetic phase diagram obtained is different from the one previously reported, which shows at 2 K the coexistence of long range antiferromagnetic order and short range order for values of inversion parameters less than 0.1 and the presence of a ferrimagnetic order only for values of δ > 0.2. At room temperature, the Rietveld analysis of NPD patterns and the magnetization curves showed a paramagnetic behavior in the samples with δ ≤ 0.1. For the samples with higher cationic inversion, typical hysteresis curves of ferrimagnetic materials were observed and the saturation magnetization values obtained agree quite well with the net magnetic moment obtained from the Rietveld refinement of the neutron diffraction patterns.     

Anchoring single Pt atoms on hollow Ag3VO4 spheres for improved activity towards photocatalytic H2 evolution reaction

The high cost of noble metal catalysts has been a great bottleneck for the catalyst industry. Using the noble metal at a single-atom level for catalytic applications could dramatically decrease the cost. The impacts of single Pt atoms on the photocatalytic performance of Ag₃VO₄ have been investigated and reported. In this report, single Pt atoms were anchored on the surface of Ag₃VO₄ (AVO) as a cocatalyst, and the resultant composite photocatalyst has been studied for photocatalytic H₂ production from water driven by visible light. The as-prepared AVO particles are hollow nanospheres in the monoclinic phase with a bandgap of 2.20 eV. The light absorption edge of AVO/Pt is slightly red-shifted compared to that of the pristine AVO, indicating more visible light absorption of AVO/Pt. The XPS peaks of Ag, V, and Pt exhibit a significant shift after AVO and Pt get into contact, suggesting the strong interaction between the surface Ag and V atoms, and single Pt atoms. After 3-h illumination, the photocatalytic H₂ evolution amount from AVO/Pt is improved up to 1400 μmol, which is 2.8 times that on the bare AVO. Such efficient photocatalytic H₂ evolution on AVO/Pt is still maintained after five reaction cycles. The better photocatalytic performance of AVO/Pt has been attributed to the more efficient visible light utilization and the lower interfacial charge transfer resistance, as demonstrated in the DRS and EIS spectra. The presence of the surface Pt atoms also leads to a higher amount of reactive radicals, which could efficiently promote the surface redox reactions.     

Validating the efficiency of γ-Al2O3/La0.6Sr0.4Co0.2Fe0.8O3-δ double-layer electrolyte for low temperature solid oxide fuel cell

Perovskite La_0.6Sr_0.4Co_0.2Fe_0.8O_3+δ (LSCF) as a promising cathode material possessed overwhelming electronic conduction along with certain ionic conductivity. Its strong electron conduction capability hinder the application of pure-phase LSCF as electrolyte in semiconductor membrane fuel cell (SMFC). In order to constrain the electron transport and take advantage of the decent ion conduction of LSCF, a thin layer of γ-Al₂O₃ with insulating property was added as an electron barrier layer and combine with LSCF to form a two-layer structure electrolyte. Through adjusting the weight ratio of LSCF/γ-Al₂O₃ to optimize the thickness of double layers, an open circuit voltage of 0.98 V and a maximum power density of 690 mW/cm² was received at 550 °C. At the same time, SEM, EIS and other characterization technology had proven that the LSCF/γ-Al₂O₃ bi-layer electrolyte can work efficiently at low temperature. The advantage of this work is the application of double-layer (γ-Al₂O₃/LSCF) structure electrolyte to instead of mixed material electrolyte in low-temperature solid oxide fuel cells. Structural innovation and the using of insulating materials provided clues for the further development of SMFC.