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.     

Improved thermal stability of the near-infrared Al-modulated Zn3Ga2GeO8: Cr3+ phosphors for plant growth applications

The exploration of the high thermal stability near-infrared (NIR) phosphors is significantly crucial for the development of plant lighting. However, NIR phosphors suffer from the poor chemical and thermal stability, which severely limits their long-term operation. Here, the successful improvement of luminous intensity (149.5%) and thermal stability at 423 K of Zn₃Ga₂GeO₈ (ZGGO): Cr³⁺ phosphors is achieved for the introduction of Al³⁺ ions into the host. The release of carriers in deep traps inhibits the emission loss for the thermal disturbance. Furthermore, an NIR light emitting diodes (LEDs) lamp is explored by combining the optimized Zn₃Ga_1.1675Al_0.8GeO₈: 0.0325Cr³⁺ phosphors with a commercial 460 nm blue chip, and the emission band can match well with the absorption bands of photosynthetic pigments and the phytochrome (P_R and P_FR) of plants. The explored LEDs lamp further determines the growth and the pheromone content of the involved plants for the participation of the NIR emission originated from Cr³⁺ ions. Our work provides a promising NIR lamp as plant light with improved thermal stability for long-term operation.     

Preparation of a ternary hybrid of P-g-C3N4@PGS-Ti and its enhancement of the flame retardancy of epoxy resins

A novel ternary hybrid flame retardant named P-g-C₃N₄@PGS-Ti was prepared through step-by-step method. First, titanium dioxide was loaded on PGS to make PGS-Ti (where PGS = palygorskite), and then, PGS-Ti was decorated by phosphor-doped g-C₃N₄ (abbreviated as P-g-C₃N₄) to prepare a ternary flame retardant of P-g-C₃N₄@PGS-Ti. It showed that P-g-C₃N₄@PGS-Ti could efficiently improve the flame retardancy of epoxy resins (EP). The structure and the morphology of P-C₃N₄@PGS-Ti were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scaanning electron microscopy and hermogravimetric analysis (TGA). The flame retardancy and the burning behavior of 5 wt% P-g-C₃N₄@PGS-Ti composited EP were well investigated through TGA, limiting oxygen index (LOI), cone calorimeter test (CCT) and vertical burning test (UL-94 standard). It was found that the peak heat releasing (pk-HRR) of the EP/P-g-C₃N₄@PGS-Ti composite reduced 36% (from 1459 to 852 kW/m²) with the addition of 5 wt% of P-g-C₃N₄@PGS-Ti flame retardant to the matrix of EP. The combustion residue analysis showed that the EP/P-g-C₃N₄@PGS-Ti composite gained the most continuous and firmest char yield due to the synergistic effect of PGS, TiO₂ and the introducing of P element. The mechanism proved that the combination of gas phase and condensed phase flame-retardant processes were well coordinated to improve the fire retardancy for EP. We tested and studied the mechanical properties of EP/P-g-C₃N₄@PGS-Ti composites. Only 2.4% decreasing of flexural strength and 23.5% decreasing of impact strength in EP/P-g-C₃N₄@PGS-Ti composites compared to pure EP, respectively. But according to the test results of EP/P-g-C₃N₄@PGS-Ti composite material and the control sample in the system, EP/P-g-C₃N₄@PGS-Ti composite material had the highest flexural modulus and impact strength.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Water vapor volatilization and oxidation induced surface cracking of environmental barrier coating systems: A numerical approach

A numerical model is developed for surface crack propagation in brittle ceramic coatings, aiming at the intrinsic failure of rare-earth silicate environmental barrier coating systems (EBCs) under combustion conditions in advanced gas turbines. The main features of progressive degradation of EBCs in such conditions are captured, including selective silica vaporization in the top coat due to exposure to water vapor, diffusion path-dependent bond coat oxidation, as well as crack propagation during cyclic thermal loading. In light of these features, user-defined subroutines are implemented in finite element analysis, where surface crack growth is simulated by node separation. Numerical results are validated by existing experimental data, in terms of monosilicate layer thickening, thermal oxide growth, and fracture behaviors. The experimentally observed quasi-linear oxidation in the early stage is also elucidated. Furthermore, it is suggested that surface crack undergoes rapid propagation in the late stage of extended thermal cycling in water vapor and leads to catastrophic failure, driven by both thermal mismatch and oxide growth stresses. The latter is identified as the dominant mechanism of penetration. Based on detailed analyses of failure mechanisms, the optimization strategy of EBCs composition is proposed, balancing the trade-off between mechanical compliance and erosion resistance.     

The Effect of Interface Cracks on the Electrical Performance of Solar Cells

Among a variety of solar cell types, thin-film solar cells have been rigorously investigated as cost-effective and efficient solar cells. In many cases, flexible solar cells are also fabricated as thin films and undergo frequent stress due to the rolling and bending modes of applications. These frequent motions result in crack initiation and propagation (including delamination) in the thin-film solar cells, which cause degradation in efficiency. Reliability evaluation of solar cells is essential for developing a new type of solar cell. In this paper, we investigated the effect of layer delamination and grain boundary crack on 3D thin-film solar cells. We used finite element method simulation for modeling of both electrical performance and cracked structure of 3D solar cells. Through simulations, we quantitatively calculated the effect of delamination length on 3D copper indium gallium diselenide (CIGS) solar cell performance. Moreover, it was confirmed that the grain boundary of CIGS could improve the solar cell performance and that grain boundary cracks could decrease cell performance by altering the open circuit voltage. In this paper, the investigated material is a CIGS solar cell, but our method can be applied to general polycrystalline solar cells.     

Variables Applicable to Benchmarking of Tap-Hole Life-Cycle Management Practices in Coke-Bed-Based Ferroalloy Production

Benchmarking is a tool available to furnace operators to evaluate their tap-hole life-cycle management practices against those of their peers. It allows furnace operators to challenge their own practices in order to increase furnace utilization. To facilitate the benchmarking process, it is necessary to define the variables to be considered and how they relate to one another. This article develops, from the literature and industry interviews, a holistic conceptualization of the variables that form part of tap-hole lifecycle management and performance. Specifically, the article focuses on the variables related to coke-bed-based processes (FeCr, SiMn, and HCFeMn) applying SAF technology of circular design.     

Removal of Antimony and Bismuth from Copper Electrorefining Electrolyte: Part II—An Investigation of Two Proprietary Solvent Extraction Extractants

Antimony and bismuth recovery from copper electrorefining electrolyte could reduce the impacts of these problem elements and produce a new primary source for them. Two proprietary phosphonic acid ester extractants were examined (REX-1 and REX-2) for the removal of antimony and bismuth from copper electrorefining electrolytes. Experimentation included shakeout and break tests to determine the basic parameters for the extractants in terms of maximum loading, break times, and extraction and stripping efficiency. Five permutations of extractant mixtures (100 wt.% REX-1 and 25 wt.%, 50 wt.%, 75 wt.% and 100 wt.% REX-2) were studied. It was determined that REX-2 was able to extract Sb and Bi from the electrolyte, but required some mixture with REX-1 to better facilitate stripping with 400 g/L sulfuric acid. The laboratory electrorefining electrolyte containing glue had faster disengagement times than a synthetic solution without glue.