Hot corrosion characteristics of Ni-20Cr-18W superalloy in molten salt

The hot corrosion behavior of a Ni?20Cr?18W (mass fraction, %) superalloy in the mixture of 75%Na 2 SO 4?25%NaCl melts at 700 and 800 °C was studied. The results demonstrate that the alloy suffers from serious hot corrosion attack in the mixture molten salt. Meanwhile, the degradation of the substrate accelerates with increasing the corrosion temperature. The corrosion layer has an obvious duplex microstructure, and the Cr-depletion zone is detected obviously nearby the inner corrosion layer. The main corrosion products at 700 and 800 °C are almost the same and mainly include NiO, Cr2O3and Ni3S2, but a trace amount of NiCrO2 is detected at 800 °C for 20 h. The hot corrosion mechanism and formation mechanism of corrosion scales of the Ni?20Cr?18W superalloy in the molten salt are proposed.

Electrochemical behaviors of Mg^(2+) and B^(3+) deposition in fluoride molten salts

By using cyclic and linear sweep voltammetry,the electrochemical deposition behaviors of Mg^2＋ and B^3＋ in fluorides molten salts of KF-MgF2 and KF-KBF4 at 880℃ were investigated,respectively.The results show that the electrochemical reduction of Mg^2＋ is a one-step reaction as Mg^2＋＋2e-→Mg in KF-1%MgF2 molten salt,and the electrochemical reduction of B^3＋ is also a one-step reaction as B^3＋＋3e-→B in KF-KBF4 （1%,2% KBF4） molten salts.Both the cathodic reduction reactions of Mg^2＋ and B^3＋ are controlled by diffusion process.The diffusion coefficients of Mg^2＋ in KF-MgF2 molten salts and B^3＋ in KF-KBF4 molten salts are 6.8×10^-7 cm^2/s and 7.85×10^-7 cm^2/s,respectively.Moreover,the electrochemical synthesis of MgB2 by co-deposition of Mg and B was carried out in the KF-MgF2-KBF4 （molar ratio of 6：1：2） molten salt at 750℃.The X-ray diffraction analysis indicates that MgB2 can be deposited on graphite cathode in the KF-MgF2-KBF4 molten salt at 750℃.

Purification of metallurgical grade silicon by electrorefining in molten salts

Electrochemical studies on silicon deposition were performed in molten salt electrolytes. Purification of metallurgical grade silicon by electrorefining was carried out in molten Si-chloride salts at temperatures from 973 K to 1223 K. It was found that the use of a liquid alloy anode of silicon and copper was beneficial in molten CaCl2 with NaCl, CaO and dissolved Si. ICP-AES analysis results showed efficient removal of metal impurities, such as titanium, aluminum and iron, which are present in significant quantities in the feedstock. The contents of boron and phosphorus in the silicon after electrorefining were reduced from 36×10-6 and 25×10-6 to 4.6×10-6 and 2.8 ×10-6, respectively. The energy consumption of electrorefining was estimated to be about 9.3 kW?h/kg.

Electrical conductivity of NaF-AlF_3-CaF_2-Al_2O_3-ZrO_2 molten salts

The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt system decreases with increase of ZrO2 content in an interval of 0-5%. The increase of 1%ZrO2 results in a corresponding electrical conductivity decrease of 0.02 S/cm, and the equivalent conductivity increases with the increase of molar ratio of NaF to AlF3. When the temperature increases by 1 °C, the electrical conductivity increases by 0.004 S/cm. At last, the regression equations of electrical conductivity relative to temperature and ZrO2 are obtained by quadratic regression analysis.

Cerium Oxide Film Prepared from Molten Salts

Cerium oxide film formed on the nickel electrode at 453 K in LiNO3-KNO3 molten salts. The molten salt background and the cathode process of Leeds on the nickel electrode were studied by using cyclic voltammetry. The cathodic reaction mechanism of the molten salt background was: O-2(-)+e <----> O-2(-2); O-2+2NO(3)(-) --> 2NO(2)(-)+2O(2). According to the results of SEM and XPS, cerium oxide film, which is composed of CeO2, can form on the nickel electrode at - 1.850 V vs. Ag/AgNO3 (0.1 mol/L) reference electrode.

Nonmetal-Metal Transition in Solutions of Metals in Molten Salts

Solutions of metals in molten salts present a rich phenomenology: localisatlon of electrons in disordered ionic media, activated electron transport increasing with metal concentration towards a nonmetal-metal (NM-M) transition, and liquid-liquid phase separation. A brief review of progress in the study of these systems is given in this article, with main focus on the NM-M transition. After recalling the known NM-M behaviour of the component elements in the case of expanded fluid alkali metals and mercury and of solid halogens under pressure, the article focuses on liquid metal-molten salt solutions and traces the different NM-M behaviours of the alkalis in their halides and of metals added to polyvalent metal halides.

CeO_2 as the Oxygen Carrier for Partial Oxidation of Methane to Synthesis Gas in Molten Salts: Thermodynamic Analysis and Experimental Investigation

A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the reaction process, and the results indicated that direct partial oxidation of methane to synthesis gas using lattice oxygen of cerium oxide is feasible in theory. In a stainless steel reactor, the effects of temperature and varying amounts of γ-Al2O3 supported CeO2 on cn4 conversion, H2 and CO selectivity, were investigated, respectively. The results show that 10% CeO2/γ-Al2O3 has the maximal reaction activity at a temperature of 865 ℃ and above, the H2/CO ratio in the gas that has been produced reaches 2 and the CH4 conversion, H2 and CO selectivity reached the following percentages： i.e. 61%, 89%, and 91% at 870 ℃, respectively. In addition, increase of reaction temperature is favorable for the partial oxidation of methane.

Capture and electro-splitting of CO_2 in molten salts

Due to the serious greenhouse gas effects caused by the increasing concentration of atmospheric CO_2,carbon capture and storage(CCS) has been an important area of research and many technologies are developed within this field. Molten salt CO_2 capture and electrochemical transformation(MSCC-ET) process is a desirable method due to a high CO_2 solubility, a wide potential window of molten salts and easily-controlled electrode reactions. Generally, electro-splitting CO_2 in molten salts begins with CO_2 absorption reactions to form CO_3^(2-), which is then followed by the carbon deposition at the cathode and O_2 evolution at the anode. As a result, CO_2 is electro-converted to O_2 and carbon with different morphologies, compositions, microstructures and functional properties. This report introduces the MSCC-ET process, summarizes the reactions occurring in the molten salts and at the electrode surfaces, as well as the morphological variations of the cathodic products. The inert anode materials, cost estimation and scale-up evaluation of the process are then discussed. It is presumed that with a comprehensive understanding of the electrode reactions during electrolysis and the functional properties of carbon materials obtained during CO_2 electro-splitting can provide a foundation for further developing this environmentally friendly process.

Electrochemical synthesis of ammonia in molten salts

Ammonia is important feedstock for both fertilizer production and carbon-free liquid fuel.Many techniques for ammonia formation have been developed,hoping to replace the industrial energy-intensive Haber-Bosch route.Electrochemical synthesis of ammonia in molten salts is one promising alternative method due to the strong solubility of N3- ions,a wide potential window of molten salt electrolytes and tunable electrode reactions.Generally,electrochemical synthesis of ammonia in molten salts begins with the electro-cleavage of N2/hydrogen sources on electrode surfaces,followed by diffusion of N3^-/H^+-containing ions towards each other for NH3 formation.Therefore,the hydrogen sources and molten salt composition will greatly affect the reactions on electrodes and ions diffusion in electrolytes,being critical factors determining the faradaic efficiency and formation rate for ammonia synthesis.This report summarizes the selection criteria for hydrogen sources,the reaction characteristics in various molten salt systems,and the preliminary explorations on the scaling-up synthesis of ammonia in molten salt.The formation rate and faradaic efficiency for ammonia synthesis are discussed in detail based on different hydrogen sources,various molten salt systems,changed electrolysis conditions as well as diverse catalysts.Electrochemical synthesis of ammonia might be further enhanced by optimizing the molten salt composition,using electrocatalysts with well-defined composition and microstructure,and innovation of novel reaction mechanism.

Application of annexation principle to the study of thermodynamic properties of ternary molten salts CaCl_2-MgC_2-NaCl

Based on the practical basis of measured activities and phase diagrams aswell as in the light of the mass action law. the model of inseparable cations and anions of moltensalts and mattes, and the annexation principle of two kinds of solutions in binary melts, thecalculating model of mass action concentrations of molten salts CaCl_2-MgCl_2-NaCl was formulated.The results of calculation not only agree with experimental values, but also obey the mass actionlaw, testifying that the model formulated can embody the structural characteristics of these ternarysalts, and that the model of inseparable cations and anions as well as the annexation principle oftwo kinds of solutions in binary melts are also applicable to these ternary salts.

Electrical conductivity optimization of the Na3AlF6–Al2O3–Sm2O3 molten salts system for Al–Sm intermediate binary alloy production

Metal Sm has been widely used in making Al–Sm magnet alloy materials. Conventional distillation technology to produce Sm has the disadvantages of low productivity, high costs, and pollution generation. The objective of this study was to develop a molten salt electrolyte system to produce Al–Sm alloy directly, with focus on the electrical conductivity and optimal operating conditions to minimize the energy consumption. The continuously varying cell constant(CVCC) technique was used to measure the conductivity for the Na3AlF6–AlF3–LiF–MgF2–Al2O3–Sm2O3electrolysis medium in the temperature range from 905 to 1055°C. The temperature(t) and the addition of Al2O3(W(Al2O3)), Sm2O3(W(Sm2O3)), and a combination of Al2O3and Sm2O3into the basic fluoride system were examined with respect to their effects on the conductivity(κ) and activation energy. The experimental results showed that the molten electrolyte conductivity increases with increasing temperature(t) and decreases with the addition of Al2O3or Sm2O3or both. We concluded that the optimal operation conditions for Al–Sm intermediate alloy production in the Na3AlF6–AlF3–LiF–MgF2–Al2O3–Sm2O3system are W(Al2O3) + W(Sm2O3) = 3wt%, W(Al2O3):W(Sm2O3) = 7:3, and a temperature of 965 to 995°C, which results in satisfactory conductivity, low fluoride evaporation losses, and low energy consumption.

The Synthesis of TiNi and Composite Particles in Molten Salts

A novel process for synthesizing TiNi and TiNi/TiC particles, called the high-temperature salt-melting method, is discussed in this paper. So far as this method is concerned, the molten salts are a reaction medium that does not take part in the chemical reaction but can be easily dissolved by water washing. With this method, TiNi shape memory alloy and TiNi/TiC composite particles were prepared in molten salts at 680-850℃. TiNi particles, ranging from 100 nm to several microns in diameter, are obtained and the reverse martensitic transformation is confirmed in these particles by the differential scanning calorimetry （DSC）. The reaction temperature and the holding time have no significant influence on the particle size, morphology or the reverse martensitic transformation characteristics. In the molten salts, the released heat of the chemical reaction causes the local temperature to rise quickly, which is the key to obtaining the desired particulate composite.

Silicon prepared by electro-reduction in molten salts as new energy materials

Silicon has a large impact on the energy supply and economy in the modern world. In industry, high purity silicon is firstly prepared by carbothermic reduction of silica with the produced raw silicon being further refined by a modified Siemens method. This process suffers from the disadvantages of high cost and contaminant release and emission. As an alternative, the molten salt electrolysis approach, particularly the FFC Cambridge Process(FFC: Fray-Farthing-Chen), could realize high purity silicon products with morphology-controllable nanostructures at low or mild temperatures(generally 650–900 ℃). In this article, we review the development, reaction mechanisms, and electrolysis conditions of silicon production by the FFC Cambridge Process. Applications of the silicon products from electrolysis in molten salts are also discussed in terms of energy applications, including using them as the photovoltaic element in solar cells and as the charge storage phase in the negative electrode(negatrode) of lithium ion batteries.

Interfacial confinement of Ni-V2O3 in molten salts for enhanced electrocatalytic hydrogen evolution

Implementation of non-precious electrocatalysts is key-enabling for water electrolysis to relieve challenges in energy and environmental sustainability. Self-supporting Ni-V2O3 electrodes consisting of nanostrip-like V2O3 perpendicularly anchored on Ni meshes are herein constructed via the electrochemical reduction of soluble NaVO3 in molten salts for enhanced electrocatalytic hydrogen evolution. Such a special configuration in morphology and composition creates a well confined interface between Ni and V2O3. Experimental and Density-Functional-Theory results confirm that the synergy between Ni and V2O3 accelerates the dissociation of H2O for forming hydrogen intermediates and enhances the combination of H*for generating H2.

Interactions of molten salts with cathode products in the FFC Cambridge Process

Molten salts play multiple important roles in the electrolysis of solid metal compounds,particularly oxides and sulfides,for the extraction of metals or alloys.Some of these roles are positive in assisting the extraction of metals,such as dissolving the oxide or sulfide anions,and transporting them to the anode for discharging,and offering the high temperature to lower the kinetic barrier to break the metal-oxygen or metal-sulfur bond.However,molten salts also have unfavorable effects,including electronic conductivity and significant capability of dissolving oxygen and carbon dioxide gases.In addition,although molten salts are relatively simple in terms of composition,physical properties,and decomposition reactions at inert electrodes,in comparison with aqueous electrolytes,the high temperatures of molten salts may promote unwanted electrode-electrolyte interactions.This article reviews briefly and selectively the research and development of the F ray-F arthing-Chen(FFC)Cambridge Process in the past two decades,focusing on observations,understanding,and solutions of various interactions between molten salts and cathodes at different reduction states,including perovskitization,non-wetting of molten salts on pure metals,carbon contamination of products,formation of oxychlorides and calcium intermetallic compounds,and oxygen transfer from the air to the cathode product mediated by oxide anions in the molten salt.

Controllable conversion of rice husks to Si/C and SiC/C composites in molten salts

Direct conversion of biomass to functional materials is an ideal solution to relieve challenges in environmental and energy sustainability.We herein demonstrate a molten salt thermoelectrolysis of rice husks(RHs)mainly consisting of organic mass and biosilica to achieve high-efficiency and upgraded utilization of both Si and C in RHs.By coupling pyrolysis of organic mass with electrochemical reduction of silica in molten salts,the thermoelectrolysis of RHs in molten CaCl_(2)-NaCl at 800℃ refines the RHs and acidleached RHs to SiC nanowire/C(SiC-NW/C)and Si nanoparticle/C(Si-NP/C),respectively.The present study highlights the molten salt thermoelectrolysis for reclamation of biomass wastes in an affordable and controllable manner.

Controllable nitridation of Ta_(2)_(O5) in molten salts for enhanced photocatalysis

Pyrolysis of the Ta_(2)_(O5)/melamine mixture in molten chlorides is herein demonstrated as a facile and controllable method to nitridize and functionalize Ta_(2)_(O5).The influence of the stoichiometry and composition of Ta_(2)_(O5)/melamine in molten salts on the nitridation process is rationalized to ensure the controllable preparation of Ta_(3)N_(5) and Ta_(3)N_(5)/TaON.The characterization results,including scanning electron microscopy,transmission electron microscopy,elemental mapping,X-ray photoelectron spectroscopy,and photoluminescence spectroscopy,all confirm the existence of the Ta_(3)N_(5)/TaON heterojunction,in which the TaON nanoparticles are closely anchored to the Ta_(3)N_(5) nanorods.Benefiting from its composition and structure,the Ta_(3)N_(5)/TaON composites show enhanced photocatalytic activity for the degradation of methylene blue.The present study highlights that the molten salt method using a solid nitrogen source can be a new technique for rationalizing the design of nitrides and oxynitrides.

Preparation of niobium nanoparticles by sodiothermic reduction of Nb_2O_5 in molten salts

Niobium nanoparticles with high purity were prepared by a sodiothermic reduction process using Nb2O5 as the raw material, LiCl, NaCl, KCl and CaCl2 as the diluents and sodium as the reducing reagent. The effects of the different molten salt systems, CaCl2 content, reaction time, excessive sodium and reaction temperature on the characteristics of the obtained niobium powder were discussed. The as-prepared niobium nanoparticles under the optimum experimental conditions were obtained by sodiothermic reduction with 20% excessive sodium in the NaCl-52mol%CaCl2- 2mol%Nb2O5 molten salts at 650 ℃for 6 h, and the molar ratio of the oxygen element in Nb2O5 and the CaCl2 of the molten salts is less than 19.23% at 750 ℃. Moreover, the particle size of niobium nanoparticles is ranged about 40~240 nm with increasing of reaction temperature from 650 to 800 ℃.

Characteristics and Nature of Metal Fog in Molten Salts

In this paper are reported the characteristics and nature of metal fog in molten cryolite-alumina mixtures on the basis of laboratory experiments and quantum chemistry studies.The metal fog is the finely divided metal particles in the molten salts, and it dissolves partly in the molten cryolite to form atomic clusters,such as(Al_nNa_m)^(x+) type.

Electrodeposition of aluminum on needle cathode using AlCl3/urea molten salts at low-temperature and its application to hydrogen generation

The electrodeposition of aluminum(Al)was studied using two electrolyte solutions,such as anhydrous AlCl3-urea and hydrated AlCl3·6 H2 O-urea.A systematic examination using cell voltages 1.0–2.0 V was carried out at temperatures((50–100)±2)°C.A needle-shaped cathode was employed for the deposition of aluminum.A dendrite and particulate microstructure of Al were observed on the needle-shaped cathode.An improved condition for the manufacturing of small sizes and high purity of aluminum deposits was obtained.Pure Al with a current efficiency(yield)of 84%–99%was obtained from those of non-aqueous electrolytes and only of 8.6%–9.3%from those of hydrated electrolytes.The electrical conductivities of electrolytes remained considerable at((50–100)±2)°C.The improved aluminum powders were used for the reaction with water.The aluminum reacts with water at room temperature,producing pure H2 with 100%yield.The electrodeposited aluminum metal can be used as an excellent energy carrier.