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。     

Stability assessment of 3D reinforced soil structures under steady unsaturated infiltration

Internal stability assessment of geosynthetic-reinforced soil structures (GRSSs) has been commonly carried out assuming plane-strain conditions and dry backfills. However, failures of GRSSs usually show three-dimensional (3D) features and occur under unsaturated conditions. A procedure based on the kinematic limit-analysis method is proposed herein to assess 3D effects and the role of steady unsaturated infiltration on the required geosynthetic strength for GRSSs. A suction stress-based framework is used to describe the soil stress behavior under steady unsaturated infiltration. Based on the principle of energy-work balance, the required geosynthetic strength is determined. A comparison analysis with the prior research is conducted to verify the developed method. Two kinds of backfills, i.e., high-quality backfill and marginal backfill, are considered for comparison in this work. It is shown that accounting for 3D effects and the role of unsaturated infiltration considerably reduces the required geosynthetic strength. The 3D effects are primarily affected by the width-to-height ratio of GRSSs, and the contribution of unsaturated infiltration is mainly influenced by the soil type, flow rate, GRSS's height, and location of the water table.     

Sustainable phenolic thermosets coatings derived from urushiol

The over-exploitation of finite fossil resources and/or the increased environmental and sustainable awareness inspire scientists and technologists to search for inexpensive alternatives from renewable chemicals. Phenol formaldehyde (PF) resins, the oldest type of synthetic polymers with good mechanical properties and heat resistance, are widely used in the production of coatings, laminates, molding compositions, and glues. Here, biobased urushiol-derived PF resins were synthesized from the alkali-catalyzed reaction between urushiol and formaldehyde. The chemical compositions and molecular structures of resole resins were characterized by carbon-13 nuclear magnetic resonance and Fourier transform infrared spectroscopy, and their curing behaviors were studied by differential scanning calorimetry. The as-prepared urushiol-derived resole resins had methylol (Ph−CH₂OH), ortho- and para-hemiformal groups (Ph−CH₂OCH₂OH), and the para−para/ortho−para/ortho−ortho links of methylene groups (Ph−CH₂−Ph), whereas the resole resins had low curing temperatures at about 100–113°C. Additionally, given the long side alkyl group moiety on the aromatic rings of urushiol, the films of cured urushiol-derived resole resins had low glass transition temperatures of 132 ± 2°C. Furthermore, the as-prepared urushiol-derived coatings exhibited excellent physical and mechanical properties.     

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.     

Toward High-Performance Dihydrophenazine-Based Conjugated Microporous Polymer Cathodes for Dual-Ion Batteries through Donor–Acceptor Structural Design

Recent studies have demonstrated that dihydrophenazine (Pz) with high redox-reversibility and high theoretical capacity is an attractive building block to construct p-type polymer cathodes for dual-ion batteries. However, most reported Pz-based polymer cathodes to date still suffer from low redox activity, slow kinetics, and short cycling life. Herein, a donor–acceptor (D–A) Pz-based conjugated microporous polymer (TzPz) cathode is constructed by integrating the electron-donating Pz unit and the electron-withdrawing 2,4,6-triphenyl-1,3,5-triazine (Tz) unit into a polymer chain. The D–A type structure enhances the polymer conjugation degree and decreases the band gap of TzPz, facilitating electron transportation along the polymer skeletons. Therefore the TzPz cathode for dual-ion battery shows a high reversible capacity of 192 mAh g⁻¹ at 0.2 A g⁻¹ with excellent rate performance (108 mAh g⁻¹ at 30 A g⁻¹), which is much higher than that of its counterpart polymer BzPz produced from 1,3,5-triphenylbenzene (Bz) and Pz (148 and 44 mAh g⁻¹ at 0.2 and 10 A g⁻¹, respectively). More importantly, the TzPz cathode also shows a long and stable cyclability of more than 10 000 cycles. These results demonstrate that the D–A structural design is an efficient strategy for developing high-performance polymer cathodes for dual-ion batteries.     

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.