Effect of electric fields on tungsten distribution in Na2WO4-WO3 molten salt.

Tungsten coatings have unique properties such as high melting points and hardness and are widely used in the nuclear fusion and aviation fields. In experiments, compared to pure Na2WO4 molten salt, electrolysis with Na2WO4-WO3 molten salt results in a lower deposition voltage. Herein, an investigation combining experimental and computational approaches was conducted, involving molecular dynamics simulations with deep learning, high-temperature in situ Raman spectroscopy and activation strain model analysis. The results indicated that the molten salt system's behaviour, influenced by migration and polarization effects, led to increased formation of Na2W2O7 in the Na2WO4-WO3 molten salt, which has a lower decomposition voltage and subsequently accelerated the cathodic deposition of tungsten. We analyzed the mechanism of the effect of the electric field on the Na2W2O7 structure based on the bond strength and electron density. This research provides crucial theoretical support for the effect of electric field on tungsten in molten salt and demonstrates the feasibility of using machine learning-based DPMD methods in simulating tungsten-containing molten salt systems.

Trace removal of benzene vapour using double-walled metal-dipyrazolate frameworks.

In principle, porous physisorbents are attractive candidates for the removal of volatile organic compounds such as benzene by virtue of their low energy for the capture and release of this pollutant. Unfortunately, many physisorbents exhibit weak sorbate-sorbent interactions, resulting in poor selectivity and low uptake when volatile organic compounds are present at trace concentrations. Herein, we report that a family of double-walled metal-dipyrazolate frameworks, BUT-53 to BUT-58, exhibit benzene uptakes at 298 K of 2.47-3.28 mmol g-1 at <10 Pa. Breakthrough experiments revealed that BUT-55, a supramolecular isomer of the metal-organic framework Co(BDP) (H2BDP = 1,4-di(1H-pyrazol-4-yl)benzene), captures trace levels of benzene, producing an air stream with benzene content below acceptable limits. Furthermore, BUT-55 can be regenerated with mild heating. Insight into the performance of BUT-55 comes from the crystal structure of the benzene-loaded phase (C6H6@BUT-55) and density functional theory calculations, which reveal that C-H···X interactions drive the tight binding of benzene. Our results demonstrate that BUT-55 is a recyclable physisorbent that exhibits high affinity and adsorption capacity towards benzene, making it a candidate for environmental remediation of benzene-contaminated gas mixtures.

Closed-loop recovery of molybdenum and value-added reuse of tungsten from alloy waste in additive manufacturing.

As metal additive manufacturing (MAM) technology is booming in the aerospace sector, alternatives to the traditional production methods of metals such as mining, processing, and refining with severe emissions are urgently needed. This study proposed a closed-loop route for efficient recovery of molybdenum (Mo) and value-added reuse of tungsten (W) from Cr-Co-Ni-Mo-W alloy waste in MAM. The results showed that the leaching efficiency of Mo and W reached 99.3% and 99.9%, respectively, using the dual chemical-physical means of mixed-alkali roasting and leaching by microwave heating, while the discharge of waste liquor containing Cr6+ was reduced. Leaching kinetic studies revealed that the metal leaching process was controlled by chemical reaction mechanism. Moreover, the 10%N1923 (primary amine)-5%TRPO (tri-alkyl phosphine oxide)-kerosene extraction system exhibited a synergistic extraction effect on Mo and W. After purification, Mo was recovered as Mo powder for MAM. Simultaneously, the recovered product of W, MnWO4, was applied as a photocatalytic material with excellent degradation of methylene blue dye. Ultimately, the proposed method obtained recovery efficiencies of 98.4% and 99.3% for Mo and W, respectively, achieving efficient and environmentally-friendly reuse of these key metals.

Comparison of Electric Vehicle Lithium-Ion Battery Recycling Allocation Methods.

Power lithium-ion batteries (LIBs) are an important component of carbon neutrality in the transportation sector. The rapid growth of the LIB recycling industry is driven by various factors, such as resource scarcity. As a process interacting upstream and downstream, LIB recycling must consider the impact of the application of modeling approaches on the allocation of environmental benefits and burdens, especially at a time when carbon emissions are highly correlated with profit. In this study, seven allocation methods were chosen and applied to the production and multiple recycling process of typical LIB on the same data basis. The application of different allocation methods produced very disparate allocation results, and the conclusions of previous studies comparing the environmental performance of battery types need to be revisited. The life-cycle assessment (LCA) results should be interpreted with caution due to the impact of the allocation methods. Furthermore, a multi-indicator qualitative analysis based on product and process characteristics compares the applicability of the allocation methods to different aspects of LIB recycling. Relevant product standards for batteries should consider the characteristics of different methods and recommend a specific allocation method for the LCA community to employ in time to ensure that relevant studies are representative and comparable.

Valence and coordination form transition of tungsten ions in molten alkali chlorides.

This study examined the possibility of deep significance for the reduction of low-valence tungsten to inhibit disproportionation reactions in various molten alkali chlorides. Electrolysis and electrochemical tests of tungsten carbide were carried out in molten LiCl, LiCl-KCl, NaCl-KCl, NaCl-CsCl, and KCl-CsCl. One finding was that the reduction valence of tungsten ions decreased as the radius of the solvent alkali ion increased. This phenomenon may be viewed from the dissolution of tungsten carbide and the existence and deposition of tungsten ions. The mechanism of tungsten ion reduction and the stable configuration of tungsten ion groups were confirmed via a detailed study of the computational calculation. The increase in the radius of the solvent alkali ion was conducive to the dissolution of tungsten from tungsten carbide in the form of low valence state. Other results also indicated that W(II) ion groups first deposited on the cathode. They had the advantages of smaller coordination numbers and faster diffusion combined. Morphological and composition analysis results of the products are also presented.

A Practice of Reticular Chemistry: Construction of a Robust Mesoporous Palladium Metal-Organic Framework via Metal Metathesis.

Constructing stable palladium(II)-based metal-organic frameworks (MOFs) would unlock more opportunities for MOF chemistry, particularly toward applications in catalysis. However, their availability is limited by synthetic challenges due to the inertness of the Pd-ligand coordination bond, as well as the strong tendency of the Pd(II) source to be reduced under typical solvothermal conditions. Under the guidance of reticular chemistry, herein, we present the first example of an azolate Pd-MOF, BUT-33(Pd), obtained via a deuterated solvent-assisted metal metathesis. BUT-33(Pd) retains the underlying sodalite network and mesoporosity of the template BUT-33(Ni) and shows excellent chemical stability (resistance to an 8 M NaOH aqueous solution). With rich Pd(II) sites in the atomically precise distribution, it also demonstrates good performances as a heterogeneous Pd(II) catalyst in a wide application scope, including Suzuki/Heck coupling reactions and photocatalytic CO2 reduction to CH4. This work highlights a feasible approach to reticularly construct noble metal based MOFs via metal metathesis, in which various merits, including high chemical stability, large pores, and tunable functions, have been integrated for addressing challenging tasks.

Preparation of Silica Aerogels by Ambient Pressure Drying without Causing Equipment Corrosion.

The silica aerogels were prepared via a sol-gel technique and ambient pressure drying by using industrial solid wastes, dislodged sludges, as raw materials. A strategy was put forward to reduce the corrosion of equipment during the drying procedure. The pore structure, hydrophobicity, and thermal insulation property of the obtained samples were investigated in detail. The results show that the corrosion can be effectively avoided by using an equimolar mixture of trimethylchlorosilane (TMCS) and hexamethyldisilazane (HMDS) as silylation agents. At a Si:TMCS:HMDS molar ratio of 1:0.375:0.375, the silica aerogels possess a desirable pore structure with a pore volume of 3.3 ± 0.1 cm³/g and a most probable pore size of 18.5 nm, a high hydrophobicity with a water contact angle of 144.2 ± 1.1°, and a low thermal conductivity of 0.031 ± 0.001 W/(m∙K).

Compression deformation of WC: atomistic description of hard ceramic material.

The deformation characteristics of WC, as a typical hard ceramic material, were studied on the nanoscale using atomistic simulations for both the single-crystal and polycrystalline forms under uniaxial compression. In particular, the effects of crystallographic orientation, grain boundary coordination and grain size on the origin of deformation were investigated. The deformation behavior of the single-crystal and polycrystalline WC both depend strongly on the orientation towards the loading direction. The grain boundaries play a significant role in the deformation coordination and the potential high fracture toughness of the nanocrystalline WC. In contrast to conventional knowledge of ceramics, maximum strength was obtained at a critical grain size corresponding to the turning point from a Hall-Petch to an inverse Hall-Petch relationship. For this the mechanism of the combined effect of dislocation motion within grains and the coordination of stress concentration at the grain boundaries were proposed. The present work has moved forward our understanding of plastic deformability and the possibility of achieving a high strength of nanocrystalline ceramic materials.

The thermal stability of the nanograin structure in a weak solute segregation system.

A hybrid model that combines first principles calculations and thermodynamic evaluation was developed to describe the thermal stability of a nanocrystalline solid solution with weak segregation. The dependence of the solute segregation behavior on the electronic structure, solute concentration, grain size and temperature was demonstrated, using the nanocrystalline Cu-Zn system as an example. The modeling results show that the segregation energy changes with the solute concentration in a form of nonmonotonic function. The change in the total Gibbs free energy indicates that at a constant solute concentration and a given temperature, a nanocrystalline structure can remain stable when the initial grain size is controlled in a critical range. In experiments, dense nanocrystalline Cu-Zn alloy bulk was prepared, and a series of annealing experiments were performed to examine the thermal stability of the nanograins. The experimental measurements confirmed the model predictions that with a certain solute concentration, a state of steady nanograin growth can be achieved at high temperatures when the initial grain size is controlled in a critical range. The present work proposes that in weak solute segregation systems, the nanograin structure can be kept thermally stable by adjusting the solute concentration and initial grain size.

Variation Trend and Driving Factors of Greenhouse Gas Emissions from Chinese Magnesium Production.

As the largest magnesium producer in the world, China is facing a great challenge of greenhouse gas (GHG) emissions reduction. In this paper, the variation trend and driving factors of GHG emissions from Chinese magnesium production were evaluated and the measures of technology and policy for effectively mitigating GHG emissions were provided. First, the energy-related and process-oriented GHG inventory is compiled for magnesium production in China. Then, the driving forces for the changes of the energy-related emission were analyzed by the method of Logarithmic Mean Divisia Index (LMDI) decomposition. Results demonstrated that Chinese magnesium output from 2003 to 2013 increased by 125%, whereas GHG emissions only increased by 16%. The emissions caused by the fuels consumption decline most significantly (from 28.4 to 6.6 t CO2eq/t Mg) among all the emission sources. The energy intensity and the energy structure were the main offsetting factors for the increase of GHG emissions, while the scale of production and the international market demand were the main contributors for the total increase. Considering the improvement of technology application and more stringent policy measures, the annual GHG emissions from Chinese primary magnesium production will be controlled within 22 million tons by 2020.

Efficient purification and high-quality regeneration of graphite from spent lithium-ion batteries by surfactant-assisted methanesulfonic acid.

With the vigorous development of the new energy industry, the use of lithium-ion batteries (LIBs) is growing exponentially, and the recycling of spent LIBs has gradually become a research hotspot. Currently, recycling both cathode and anode materials of LIBs is important to environmental protection and resource recycling. This research reportsa method ofefficient purification and high-quality regeneration of graphite from spent LIBs by surfactant-assisted methanesulfonic acid (MSA). Under the optimal conditions (0.006 mol/L sodium dodecyl sulfonate, 0.25 mol/L MSA, 10 vol% hydrogen peroxide, liquid-solid ratio of 30:1 mL/g, 60 °C, 1.5 h), the purity of the regenerated graphite was 99.7 %, and the recovery efficiency was 98.0 %. The regenerated graphite showed the characteristics of small interplanar spacing, high degree of graphitization, a small number of surface defects, and excellent pore structure, which was closer to commercial graphite. Furthermore, the regenerated graphite electrode exhibited superior rate performance and cycling stability with a high specific capacity of 397.03 mAh/g after 50 cycles at 0.1C and a charge-discharge efficiency of 99.33 %. The recovery of anode graphite beneficial for resource utilization, environmental protection, and cost control throughout the entire production chain.

Simultaneous enhancement of strength and conductivity via self-assembled lamellar architecture.

Simultaneous improvement of strength and conductivity is urgently demanded but challenging for bimetallic materials. Here we show by creating a self-assembled lamellar (SAL) architecture in W-Cu system, enhancement in strength and electrical conductivity is able to be achieved at the same time. The SAL architecture features alternately stacked Cu layers and W lamellae containing high-density dislocations. This unique layout not only enables predominant stress partitioning in the W phase, but also promotes hetero-deformation induced strengthening. In addition, the SAL architecture possesses strong crack-buffering effect and damage tolerance. Meanwhile, it provides continuous conducting channels for electrons and reduces interface scattering. As a result, a yield strength that doubles the value of the counterpart, an increased electrical conductivity, and a large plasticity were achieved simultaneously in the SAL W-Cu composite. This study proposes a flexible strategy of architecture design and an effective method for manufacturing bimetallic composites with excellent integrated properties.

The Influence of Precipitated Particles on the Grain Size in Cold-Rolled Al-Mn Alloy Foils upon Annealing at 100-550 °C.

The Al-Mn alloy heat exchanger fin production process includes a brazing treatment at s high temperature of 600 °C, in which coarse grains are preferred for their high resistance to deformation at elevated temperatures by decreasing the grain boundary sliding. In this study, Al-1.57Mn-1.57Zn-0.58Si-0.17Fe alloy foils cold rolled by 81.7% (1.1 mm in thickness) and 96.5% (0.21 mm in thickness) were annealed at 100-550 °C for 1 h to investigate their recrystallization behavior, grain sizes, and precipitates by increasing the annealing temperature, using micro-hardness measurement, electron back-scattered diffraction (EBSD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. The micro-hardness results showed that the recrystallization finishing temperatures for the two samples were almost the same, 323 ± 2 °C. The EBSD results showed that when the annealing temperature decreased from 550 to 400 °C, the recrystallized grain sizes of the two samples were nearly identical-both increased slightly. Further decreasing the annealing temperature from 400 to 330 °C caused the grain sizes to increase more, with the thinner foil sample having a more significant increase. The SEM and TEM observations showed that the micron-sized primary-phase remained unchanged during the annealing process. The nano-sized secondary phase precipitates formed during the hot-rolling process experienced a coarsening and dissolving process upon annealing. The particle size of the secondary phase increased from 32 nm to 44 nm and the area fraction decreased from 4.2% to 3.8%. The nucleation analysis confirmed that the large primary-phase could act as a nucleation site through particle stimulated nucleation (PSN) mode. The relatively dense secondary phase precipitates with small sizes at lower temperatures could provide higher Zener drag to the grain boundaries, leading to fewer nuclei and thereafter coarser grains. The coarsening of the recrystallized grains in the foils could be implemented through thickness reduction and/or precipitation processes to form densely distributed nano-sized precipitates.

[Determination of film thickness, component and content based on glass surface by using XRF spectrometry].

Film thickness, component and content based on glass surface were determined by using XRF technic, measure condition and instrument work condition in every layer were set and adjusted for the best measure effect for every element. Background fundamental parameter (BG-FP) method was built up. Measure results with this method were consistent with the actual preparation course and the method could fit to production application.

In Situ SEM, TEM, EBSD Characterization of Nucleation and Early Growth of Pure Fe/Pure Al Intermetallic Compounds.

The nucleation and growth processes of pure Fe/pure Al intermetallic compounds (IMCs) during heat treatment at 380 °C and 520 °C were observed through in situ scanning electron microscopy (SEM). The size of the IMCs were statistically analyzed using image analysis software. The types and distribution of IMCs were characterized using transmission electron microscopy (TEM) and electron backscattering diffraction (EBSD). The results showed that: at 380 °C, the primary phase of the Fe/Al composite intermetallic compounds was Fe4Al13, formed on the Fe side and habituated with Fe. The IMC was completely transformed from the initial Fe4Al13 to the most stable Fe2Al5, and the Fe2Al5 was the habitus with Fe during the process of holding at 380 °C for 15 min to 60 min. At 380 °C, the initial growth rate of the IMC was controlled by reaction, and the growth rate of the thickness and horizontal dimensions was basically the same as 0.02-0.17 µm/min. When the IMC layer thickness reached 4.5 µm, the growth rate of the thickness changed from reaction control to diffusion control and decreased to 0.007 µm/min. After heat treatment at 520 °C (≤20 min), the growth of IMC was still controlled by the reaction, the horizontal growth rate was 0.53 µm/min, the thickness growth rate was 0.23 µm/min, and the main phase of the IMC was the Fe2Al5 phase at 520 °C/20 min.

Effect of Zr and Er Addition on the Microstructural Evolution of a Novel Al-Mg-Zn-Er-Zr Alloy during Hot Compression.

The hot compression experiment of homogenized Al-5.2Mg-0.6Mn-0.29Zn-0.16Er-0.12Zr alloy was carried out by the Gleeble-3500 thermal simulation testing system. The deformation behavior in temperatures of 350~500 ℃ and deformation rates of 0.01~10 s-1 was studied. The relationship between stress and strain rate and deformation temperature was analyzed. The constitutive equation of alloy high-temperature deformation was constructed by the Zener-Hollomon method, and the hot working diagram with the true strain of 0.2 and 0.5 was constructed according to the dynamic material model. The research results show that flow stress has a positive correlation with strain rate and a negative correlation with temperature. The steady flow stress during deformation can be described by a hyperbolic sinusoidal constitutive equation. Adding Er and Zr into Al-Mg alloy can not only refine grains and strengthen precipitation but also form a core-shell Al3(Er, Zr) phase. In the deformation process, Al3(Er, Zr) precipitates can pin dislocations and inhibit dynamic recrystallization (DRX). Dynamic recovery (DRV) is dominant during hot deformation. The mechanism of dynamic recovery is dislocation motion. At high temperatures, Al3(Er, Zr) can also inhibit grain coarsening. The average hot deformation activation energy of the alloy is 203.7 kJ/mol. This high activation energy can be due to the pinning effect of Er and Zr precipitates. The processing map of the alloy was analyzed and combined with the observation of microstructure, the hot deformation instability zone of the alloy was determined, and the suitable process parameters for hot deformation were obtained, which were 450~480 °C, and the strain rate is 0.01~0.09 s-1.

Evolution of Grain Structure and Dynamic Precipitation during Hot Deformation in a Medium-Strength Al-Zn-Mg-Er-Zr Aluminum Alloy.

The hot deformation behavior of Al-Zn-Mg-Er-Zr alloy was investigated through an isothermal compression experiment at a strain rate ranging from 0.01 to 10 s-1 and temperature ranging from 350 to 500 °C. The constitutive equation of thermal deformation characteristics based on strain was established, and the microstructure (including grain, substructure and dynamic precipitation) under different deformation conditions was analyzed. It is shown that the steady-state flow stress can be described using the hyperbolic sinusoidal constitutive equation with a deformation activation energy of 160.03 kJ/mol. Two kinds of second phases exist in the deformed alloy; one is the η phase, whose size and quantity changes according to the deformation parameters, and the other is spherical Al3(Er, Zr) particles with good thermal stability. Both kinds of particles pin the dislocation. However, with a decrease in strain rate or increase in temperature, η phases coarsen and their density decreases, and their dislocation locking ability is weakened. However, the size of Al3(Er, Zr) particles does not change with the variation in deformation conditions. So, at higher deformation temperatures, Al3(Er, Zr) particles still pin dislocations and thus refine the subgrain and enhance the strength. Compared with the η phase, Al3(Er, Zr) particles are superior for dislocation locking during hot deformation. A strain rate ranging from 0.1 to 1 s-1 and a deformation temperature ranging from 450 to 500 °C form the safest hot working domain in the processing map.

Effect of the Solid Solution and Aging Treatment on the Mechanical Properties and Microstructure of a Novel Al-Mg-Si Alloy.

A novel Al-Mg-Si aluminum alloy with the addition of the micro-alloying element Er and Zr that was promptly quenched after extrusion has been studied. The solid solution and aging treatment of the novel alloy are studied by observing the microstructure, mechanical properties, and strengthening mechanism. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques are employed to examine the changes in the microstructure resulting from various solid solution treatments and aging treatments. The best strengthening effect can be achieved when the solubility of the MgSi phase and precipitate ß″ (Mg2Si phase) is at their maximum. The addition of Er and Zr elements promotes the precipitation of the ß″ phase and makes the b″ phase more finely dispersed. The aging strengthening of alloys is a comprehensive effect of the dislocation cutting mechanism and bypass mechanism, the joint effect of diffusion strengthening of Al3(Er,Zr) particles and the addition of Er and Zr elements promoting the precipitation strengthening of ß″ phases. In this paper, by adding Er and Zr elements and exploring the optimal heat treatment system, the yield strength of the alloy reaches 437 MPa and the tensile strength reaches 453 MPa after solid solution treatment at 565 °C/30 min and aging at 175 °C/10 h.

[The element determination of six samples of petal powders by using XRF spectrometry].

Elements and contents in three kinds of petal powders of white and red rose, carnation, and butterfly orchis were determined by using XRF technic, and the data for every group were compared and analysed. The results indicated that all powders contain no toxic elements determined but have lots of normal elements and trace elements, such as Fe, Cu, Zn, Mn, Ni, Si, Sr, and Rb. The same sort of powder had approximately equivalent elements but their contents are different, and the element content of the white sort. was higher than the red one.

Novel Styrene-Based Polyamine Sorbent for Efficient Selective Separation of Molybdenum.

Tungsten (W) and molybdenum (Mo) are important strategic resources but the two coexist in both primary ore and waste. Before a single metal product is obtained, it is often necessary to separate the two. In this work, we reported two new polyamine resins (D301@PA and D301@TA), which can be obtained by an assembled amine (primary amine or tertiary amine) and traditional D301 resin by the dipping method. Then, the sorption experiments with the amine resins were carried out, and the selectivity and sorption capacity of the two new polyamine resins for MoS4 2- have been significantly improved. Among them, D301@TA showed the highest sorption capacity of 414 mg·g-1 and a separation factor of 108. Finally, the sorption mechanism can be inferred through scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) analysis, and X-ray photoemission spectroscopy (XPS); the Cl- ions in the amine resin and the MoS4 2- ions were subjected to ion exchange. This work provides a green and efficient approach for separating tungsten and molybdenum.