Double pyrovanadates CaMgV2O7: Formation mechanism,phase structure,and thermodynamic properties

A double pyrovanadate CaMgV₂O₇ sample was synthesized via a facile solid-state route under an air atmosphere. The nonequilibrium formation pathways of the CaMgV₂O₇ were investigated via powder X-ray diffraction. A multistep reactions path (metavanadates–pyrovanadates–double pyrovanadate CaMgV₂O₇) was proposed to describe the formation of the CaMgV₂O₇ considering the thermodynamic and kinetic factors. The cell unit parameters of the CaMgV₂O₇ sample indicated the crystallization according to a monoclinic system with space group P12/c1(14), and the lattice parameters of a = 6.756 Å, b = 14.495 Å, c = 11.253 Å, β = 99.12, and V = 108.806 Å³. X-ray photoelectron spectroscopy also confirmed the +5 oxidation state vanadium in CaMgV₂O₇. The endothermic effects at 1033 and 1143 K were related to the incongruent melting and liquidus temperatures of CaMgV₂O₇, respectively. The comprehensive thermodynamic properties of CaMgV₂O₇ were established in both low- and high-temperature regions, utilizing a physical property measurement system and multi-high-temperature calorimetry (96 lines). The heat capacity (200 J mol K⁻¹) and entropy (198 J mol K⁻¹) at 298.15 K were computed based on the low-temperature heat capacity values, and the enthalpy of formation at 298.15 K was also estimated. The fitted high-temperature capacity can be used to obtain the changes in the enthalpy, entropy, and Gibbs free energy. This study is part of building a reliable thermodynamic database of the CaO–MgO–V₂O₅ system.     

一种可传输轨道角动量的螺旋光子晶体光纤北大核心

设计了一种基于阿基米德螺线的新型螺旋光子晶体光纤,该光纤以二氧化硅为基底材料,包层由24个螺旋臂组成,每个螺旋臂包含11个小空气孔,纤芯设有大空气孔,包层与纤芯中间的环形区域用于传输轨道角动量模式。该结构在1300~1800 nm波段上可支持22种轨道角动量模式稳定传输,在1550 nm波长下,有效折射率差最高可达2.89×10^(-3),色散系数最低可达66.4 ps/(nm·km),非线性系数最低可达2.17 W^(-1)·km^(-1),且1500~1600 nm波段上的色散值变化均小于15.15 ps/(nm·km)。此螺旋光子晶体光纤不仅结构简单,且具有低非线性、色散平坦的性能,为螺旋光子晶体光纤的设计提供了思路。     

Dual functions of three-dimensional hierarchical architecture on improving the rate capability and cycle performance of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion battery

The main obstacles in lithium-ion battery are limited by rate performance and the rapid capacity fading of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811). Herein, a novel three-dimensional (3D) hierarchical coating material has been fabricated by in situ growing carbon nanotubes (CNTs) on the surfaces of Ni–Al double oxide (Ni–Al-LDO) sheets (named as LDO&CNT) with Ni–Al double hydroxide (Ni–Al-LDH) as both the substrate and catalyst precursor. The resultant LDO&CNT nanocomposites are uniformly coated on the surfaces of NCM811 by the physical mixing method. The rate capability of the resultant cathode material retains to 78.80% at a current rate of 3C. Its capacity retention increases by 6.7–14.42% compared with pristine NCM811 after 100 cycles within a potential range of 2.75–4.3 V at 0.5C. The improved rate capability and cycle performance of NCM811 are assigned to the synergistic effects between Ni–Al-LDO and CNTs. The hierarchical LDO&CNT nanocomposites coating on the surface of NCM811 avoids the aggregation of conductive CNTs and the stacking of Ni–Al-LDO nanosheets. Furthermore, it accelerates Li⁺ and electrons shuttle and reduces the reaction of Li₂O with H₂O and CO₂ in air, which results in Li₂CO₃ and LiOH alkali formation on the NCM811 surface.     

基于数值模拟的挤压参数对AZ91镁合金管转角焊合室分流挤压焊合压力的影响规律研究

提出了一种镁合金管材转角焊合室分流挤压新工艺，该工艺可在有效延长焊合室长度和焊合时间前提下保证舌针刚度，从而保证管材尺寸精度，并且可通过转角剪切变形机制增加预焊合金属变形量和动态再结晶程度，从而有利于提高管材性能和焊缝焊合性能。利用有限元法揭示了转角焊合室分流挤压成形过程中金属的流动特征，应变分布特征和焊合室内的静水压力分布特征。结果表明，整个挤压过程无金属折叠，从而保证管材的表面质量；流经转角后预焊合金属变形量明显增加，有利于提高管材质量和焊缝质量。最后，研究揭示了坯料初始温度，挤压速度和模具转角对焊合室内静水压力的影响规律。结果表明，随着挤压速度的增加和模具转角的增大，转角焊合室内静水压力增大；随着坯料预热温度的增加，转角焊合室内静水压力呈先增大后减小的趋势。     

Form selection of concomitant polymorphs: A case study informed by crystallization kinetics modeling

Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation and concomitant crystallization are difficult to be distinguished in practice, as multiple forms can be detected at the same time. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid. Our kinetic modeling aims to understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the composition of form I in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.     

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.     

Multiple material domain‐based computational tools for ease assessment of modal parameter in photonic crystal fibers

We report here the development of two computational tools PCFPS (Photonic Crystal Fiber Parameter Study) and PCFPA (Photonic Crystal Fiber Parameter Analysis), equipped with graphical user interface (GUI) for modeling of photonic crystal fiber. The tools are based on different structural parameters, and they provide characteristic analysis of the modal parameters from the structural parameters. The main feature of PCFPS is that it enables the user to find out the values of each defining modal parameter that has an immense contribution towards the manufacture of photonic crystal fiber. Additionally, PCFPA allows the user to observe the variation in the modal parameters with respect to the changes in structural parameters (such as d, Λ, d/Λ, and λ/>Λ). Besides their ease of use, these two schemes have high computational precision and adaptability, giving a novel platform to optical engineers to modulate the microstructured fibers according to their requirement.     

Optical properties of gadolinia-doped cubic yttria stabilized zirconia single crystals

Cubic zirconia single crystals stabilized with yttria and doped with Gd₂O₃ (0.10–5.00 mol%) were prepared by the optical floating zone method, and characterized by a combination of X-ray diffraction (XRD), and Raman, electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis), photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopic techniques. XRD and Raman spectroscopy showed that the crystal samples were all in the cubic phase, whereas the ceramic sample consisted of a mixture of monoclinic and cubic phases. The absorption spectrum showed four peaks at 245, 273, 308, and 314 nm in the ultraviolet region, and the optical band gap differed between samples with ≤3.00 mol% and those with >3.00 mol% Gd₂O₃. The emission spectrum showed a weak peak at 308 nm and a strong peak at 314 nm, which are attributed to the ⁶P_5/2 → ⁸S_7/2 and ⁶P_7/2 → ⁸S_7/2 transitions of Gd³⁺, respectively. The intensities of the peaks in the excitation and emission spectra increased with Gd³⁺ concentration, reached a maximum at 2.00 mol%, then decreased with higher concentrations. This quenching is considered to be the result of the electric dipole-dipole interactions, and this interpretation is supported by the Gd³⁺ EPR spectra, which showed progressive broadening with increasing Gd³⁺ concentration throughout the concentration range investigated.     

Effect of electric field intensity on domain kinetics of Pb(Mg1/3Nb2/3)O3–0.38PbTiO3 single crystal

As one of the outstanding piezoelectric materials, relaxor-PbTiO₃ single crystal also exhibits promising electro-optic and nonlinear-optic properties. Therefore, it is vital to understand the domain switching kinetics not only for optimizing strain-mediated devices performance but also for fabricating optical waveguides and periodic domain structures in optical applications. In this work, domain switching kinetics in annealed and pre-poled PMN-0.38PT single crystal under different external electric field were studied. Polarization reversal can be accomplished only by c-domain nucleation and growth in the annealed sample where the formation of the ferroelastic domains is hindered. In pre-poled sample, 90° domain switching happened by 90° domain wall reorientation under low electric field while 180° domain switching is accomplished by two-step 90° domain switching and c-domain growth under high electric field. The results are important for modulating domain structure for strain mediated and optical devices.