A nonlinear dynamic simulation model based on coordinated control of speed and flow rate for the molten salt reactor and combined cycle systems is proposed here to ensure the coordination and stability between the mol...A nonlinear dynamic simulation model based on coordinated control of speed and flow rate for the molten salt reactor and combined cycle systems is proposed here to ensure the coordination and stability between the molten salt reactor and power system.This model considers the impact of thermal properties of fluid variation on accuracy and has been validated with Simulink.This study reveals the capability of the control system to compensate for anomalous situations and maintain shaft stability in the event of perturbations occurring in high-temperature molten salt tank outlet parameters.Meanwhile,the control system’s impact on the system’s dynamic characteristics under molten salt disturbance is also analyzed.The results reveal that after the disturbance occurs,the controlled system benefits from the action of the control,and the overshoot and disturbance amplitude are positively correlated,while the system power and frequency eventually return to the initial values.This simulation model provides a basis for utilizing molten salt reactors for power generation and maintaining grid stability.展开更多
We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it ...We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it forms an intermediate product Ti_(3)CuC_(2),and then reacts with Ti_(3)CuC_(2)to obtain Ti_(3)C_(2)Cl_(2).The reaction of Ti_(3)AlC_(2)and CuCl_(2)at a temperature of 800℃for 2 h to obtain Ti_(3)C_(2)Cl_(2)with an optimal lamellar structure is shown in SEM results.The pseudopotential plane-wave(PP-PW)method is used to calculate on the electronic structure.The etching mechanism is investigated by the total energies of each substance.The chemical reaction of Ti_(3)AlC_(2)and CuCl_(2)will first become Ti_(3)CuC_(2)and Cu,and then become Ti_(3)C_(2)Cl_(2)during the Lewis acid etching process,which are consistent with the experimental results.展开更多
The synthesis of carbide coatings on graphite substrates using molten salt synthesis(MSS),has garnered significant interest due to its cost-effective nature.This study investigates the reaction process and growth kine...The synthesis of carbide coatings on graphite substrates using molten salt synthesis(MSS),has garnered significant interest due to its cost-effective nature.This study investigates the reaction process and growth kinetics involved in MSS,shedding light on key aspects of the process.The involvement of Ti powder through liquid-phase mass transfer is revealed,where the diffusion distance and quantity of Ti powder play a crucial role in determining the reaction rate by influencing the C content gradient on both sides of the carbide.Furthermore,the growth kinetics of the carbide coating are predominantly governed by the diffusion behavior of C within the carbide layer,rather than the chemical reaction rate.To analyze the kinetics,the thickness of the carbide layer is measured with respect to heat treatment time and temperature,unveiling a parabolic relationship within the temperature range of 700-1300℃.The estimated activation energy for the reaction is determined to be 179283 J·mol^(-1).These findings offer valuable insights into the synthesis of carbide coatings via MSS,facilitating their optimization and enhancing our understanding of their growth mechanisms and properties for various applications.展开更多
The heavy water-moderated molten salt reactor(HWMSR)is a newly proposed reactor concept,in which heavy water is adopted as the moderator and molten salt dissolved with fissile and fertile elements is used as the fuel....The heavy water-moderated molten salt reactor(HWMSR)is a newly proposed reactor concept,in which heavy water is adopted as the moderator and molten salt dissolved with fissile and fertile elements is used as the fuel.Issues arising from graphite in traditional molten salt reactors,including the positive temperature coefficient and management of highly radio-active spent graphite waste,can be addressed using the HWMSR.Until now,research on the HWMSR has been centered on the core design and nuclear fuel cycle to explore the viability of the HWMSR and its advantages in fuel utilization.However,the core safety of the HWMSR has not been extensively studied.Therefore,we evaluate typical accidents in a small modular HWMSR,including fuel salt inlet temperature overcooling and overheating accidents,fuel salt inlet flow rate decrease,heavy water inlet temperature overcooling accidents,and heavy water inlet mass flow rate decrease accidents,based on a neutronics and thermal-hydraulics coupled code.The results demonstrated that the core maintained safety during the investigated accidents.展开更多
This study demonstrates the design and application of a novel high temperature rotatory apparatus for insitu synchrotron X-ray diffraction studies of molten salts,facilitating investigation into the interaction betwee...This study demonstrates the design and application of a novel high temperature rotatory apparatus for insitu synchrotron X-ray diffraction studies of molten salts,facilitating investigation into the interaction between various structural materials and molten salts.The apparatus enables accurate detection of every phase change during hightemperature experiments,including strong reaction processes like corrosion.Molten salts,such as chlorides or fluo⁃rides,together with the structure materials,are inserted into either quartz or boron nitride capillaries,where X-ray diffraction pattern can be continuously collected,as the samples are heated to high temperature.The replacement re⁃action,when molten ZnCl2 are etching Ti3AlC2,can be clearly observed through changes in diffraction peak intensity as well as expansion in c-axis lattice parameter of the hexagonal matrix,due to the larger atomic number and ionic ra⁃dius of Zn2+.Furthermore,we investigated the high-temperature corrosion process when GH3535 alloy is in FLiNaK molten salt,and can help to optimize its stability for potential applications in molten salt reactor.Additionally,this high temperature apparatus is fully compatible with the combined usage of X-ray diffraction and Raman technique,providing both bulk and surface structural information.This high temperature apparatus has been open to users and is extensively used at BL14B1 beamline of the Shanghai Synchrotron Radiation Facility.展开更多
Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-mat...Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.展开更多
The high-temperature molten salt pump is the core equipment in a molten salt reactor that drives the flow of the molten salt coolant.Rotor stability is key to the continuous and reliable operation of the molten salt p...The high-temperature molten salt pump is the core equipment in a molten salt reactor that drives the flow of the molten salt coolant.Rotor stability is key to the continuous and reliable operation of the molten salt pump,and the liquid seal at the wear ring can affect the dynamic characteristics of the rotor system.When the molten salt pump is operated in the hightemperature molten salt medium,thermal deformation of the submerged parts inevitably occurs,changing clearance between the stator and rotor,affecting the leakage and dynamic characteristics of the seal.In this study,the seal leakage,seal dynamic characteristics,and rotor system dynamic characteristics are simulated and analyzed using finite element simulation software based on two cases of considering the effect of seal thermal deformation effect or not.The results show a significant difference in the leakage characteristics and dynamic characteristics of the seal obtained by considering the effect of seal thermal deformation and neglecting the effect of thermal deformation.The leakage flow rate decreases,and the first-order critical speed of the seal-bearing-rotor system decrease after considering the seal’s thermal deformation.展开更多
MXenes are two-dimensional transition metal carbides and/or nitrides with unique physiochemical properties and have attracted extensive interest in numerous fields.However,current MXene synthesis methods are limited b...MXenes are two-dimensional transition metal carbides and/or nitrides with unique physiochemical properties and have attracted extensive interest in numerous fields.However,current MXene synthesis methods are limited by hazardous synthesis conditions,high production costs,or difficulty in largescale production.Therefore,a general,safe,cost-effective,and scalable synthesis method for MXenes is crucial.Here,we report the fast synthesis of MXenes in the open air using a molten salt-shielded synthesis(MS^(3))method,which uses Lewis-acid salts as etchants and a low-melting-point eutectic salt mixture as the reaction medium and shield to prevent MXene oxidation at high temperatures.Carbide and nitride MXenes,including Ti_(3)C_(2)T_(x),Ti_(2)CT_(x),Ti_(3)CNT_(x),and Ti_(4)N_(3)T_(x),were successfully synthesized using the MS^(3) method.We also present the flexibility of the MS^(3) method by scaling the etching process to large batches of 20 and 60 g of Ti_(3)AlC_(2) MAX precursor in one pot.When used as negative electrodes,the prepared MS^(3)-MXenes delivered excellent electrochemical properties for high-rate Li-ion storage.展开更多
High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimensi...High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimension and morphology remains a major challenge.Here,scalable HEO morphology modulation is implemented through a salt-assisted strategy,which is achieved by regulating the solubility of reactants and the selective adsorption of salt ions on specific crystal planes.The electrochemical properties,lithiation mechanism,and structure evolution of composition-and morphology-dependent HEO anode are examined in detail.More importantly,the potential advantages of HEOs as electrode materials are evaluated from both theoretical and experimental aspects.Benefiting from the high oxygen vacancy concentration,narrow band gap,and structure durability induced by the multi-element synergy,HEO anode delivers desirable reversible capacity and reaction kinetics.In particular,Mg is evidenced to serve as a structural sustainer that significantly inhibits the volume expansion and retains the rock salt lattice.These new perspectives are expected to open a window of opportunity to compositionally/morphologi cally engineer high-performance HEO electrodes.展开更多
Dense zirconium coatings on copper substrates were obtained in an alumina crucible and a stainless steel crucible from FLiNaK-K_(2)ZrF_(6)molten salt at 1023 K.Due to the potential difierences between copper and zirco...Dense zirconium coatings on copper substrates were obtained in an alumina crucible and a stainless steel crucible from FLiNaK-K_(2)ZrF_(6)molten salt at 1023 K.Due to the potential difierences between copper and zirconium,zirconium can difiuse into the copper substrate to form zirconium alloys on the surface of copper substrates in the course of deposition.The coating deposited in a stainless steel crucible has a gray surface.The components of the coating are mainly CuZr2alloy and Cu_(10)Zr_(7)alloy,and,the outermost layer of the coating is a layer of amorphous pure zirconium.The coating deposited in an alumina crucible has a silvery white metallic luster.The components of the coating are mainly Cu-Zr-Al intermetallic compounds,AlCu_(2)Zr,ZrAl,AlCu and CuZr.Furthermore,two types of zirconium coatings can greatly increase the hardness of the substrate.展开更多
The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MA...The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MAX phases,the preparation methods,which are environmentally friendly,efficient,economical,and easy to scale-up,have always been the focus of attention.Molten salt synthesis has demonstrated unparalleled advantages in achieving non-oxide materials.In addition,with the development of the process in molten salt synthesis,it also shows great potential in scale-up production.In this review,the recent progress of molten salt synthesis in the preparation of binary non-oxide and MAX phase is reviewed,as well as some novel processes.The reaction mechanisms and the influence of synthetic conditions for certain materials are discussed in detail.The paper is finalized with the discussion of the application prospect and future research trends of molten salt synthesis in non-oxide materials.展开更多
Low grade magnesite is one of the main research directions in the future as the raw material for the preparation of magnesia based insulating refractories.Periclase-forsterite(MgO-Mg_(2)SiO_(4)) lightweight insulating...Low grade magnesite is one of the main research directions in the future as the raw material for the preparation of magnesia based insulating refractories.Periclase-forsterite(MgO-Mg_(2)SiO_(4)) lightweight insulating refractories were prepared by the molten salt method with high silica magnesite and tertiary talc ore as raw materials by pretreating them to get light burnt magnesia and talc,and NaCl molten salt as the reaction medium.The effects of the NaCl addition,the sintering temperature,the holding time and the raw material ratio on the sample preparation were studied.The results show that when the NaCl addition is 20% of the mass of light burnt magnesia and talc mixture,the sintering temperature is 1 200 ℃,the holding time is 6 h,and m(light burnt magnesia):m(talc)=5:5,the sample has the optimal comprehensive properties:the bulk density of 1.46 g·cm^(-3) and the apparent porosity of 55.0%.In addition,it is found that self-decomposition of talc and the formation of forsterite can form pores inside the sample.展开更多
The reduction mechanism of Ir in the NaCl-KCl-IrCl3 molten salt was investigated by cyclic voltammetry and chronopotentiometry, and Ir film was deposited effectively on platinum in potentiostatic mode. The morphology ...The reduction mechanism of Ir in the NaCl-KCl-IrCl3 molten salt was investigated by cyclic voltammetry and chronopotentiometry, and Ir film was deposited effectively on platinum in potentiostatic mode. The morphology and constitution of Ir film were examined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). It is found that the reduction mechanism of Ir(III) is a three-electron step and electro reaction is a reversible diffusion controlled process; the diffusion coefficients of Ir(III) at 1083, 1113, 1143 and 1183 K are 1.56×10-4, 2.23×10-4, 2.77×10-4 and 4.40×10-4 cm2/s, respectively, while the activation energy of the electrode reaction is 102.95 kJ/mol. The compacted Ir film reveals that the applied potential greatly affects the deposition of Ir, the thickness of Ir film deposited at the potential of reduction peak is the highest, the temperature of the molten salt also exerts an influence on deposition, the film formed at a lower temperature is thinner, but more micropores would occur on film when the temperature went too high.展开更多
The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were...The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were carried out for solving the puzzle of reduction mechanism.The results showed that the reduction process proceeded step by step.TiO2 was first reduced to Ti3O5 or Ti2O3,and then further reduced to Ti3O,Ti2O,TiO and Ti.In addition,direct electrochemical reduction of titanium dioxide was the primary cathodic reaction;meanwhile,some calciothermic reduction reactions also happened at the cathode.Cyclic voltammograms of solid titanium dioxide and molybdenum wire in molten salts with different compositions were also studied.展开更多
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...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.展开更多
Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluor...Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluoride addition on the electrolysis was investigated comprehensively. X-ray diffraction (XRD) was used to characterize some of the Mg-La alloy products and the sludges. As the content of MgO or La203 in the electrolyte increased, both the current efficiency and the mass of alloy product decreased, indicating that both MgO and La203 may take part in the reactions in the electrolyte. When the same mass of the oxide was added, compared with La203, MgO had a more pronounced effect on both the current efficiency and the mass of alloy product. XRD studies confirmed the formation of LaOC1 when MgO or LazO3 was added into the electrolyte. The formation of LaOCl sludge would be the main reason for the negative effect of the oxide addition on both the current efficiency and the mass of alloy. In the electrolytic system, the addition of CaF2 was not helpful to suppress the negative effect of MgO on the electrolysis, probably due to the complex reactions of the La compounds in the electrolyte.展开更多
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 ho...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.展开更多
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 sy...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.展开更多
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 ...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℃.展开更多
The electrochemical process of Mg-Sr codeposition was studied in MgCl2-SrCl2-KCl melts containing different MgCl2 concentrations at 700 ℃ by cyclic voltammetry, chronopotentiometry and chronoamperometry. The results ...The electrochemical process of Mg-Sr codeposition was studied in MgCl2-SrCl2-KCl melts containing different MgCl2 concentrations at 700 ℃ by cyclic voltammetry, chronopotentiometry and chronoamperometry. The results show that the actual precipitation potential of Sr reduces by nearly 0.5 V because of the depolarization effects of Sr activity reduced by forming Mg-Sr alloy. The codeposition potential condition of Mg and Sr to form Mg-Sr alloy is as follows: When electrode potential is more negative than -1.5 V, the magnesium will precipitate; when electrode potential is more negative than -2.0 V, the magnesium and strontium will both deposit. The control step of codeposition process of Mg and Sr is not diffusion control step. The codeposition current condition of Mg and Sr to form Mg-Sr alloy by chronoptentiometry is as follows: cathode current densities are higher than 0.71, 1.57 and 2.83 A/cm^2 in MgCl2-SrCl2-KCl melts with MgCl2 concentrations of 2%, 5% and 10% (mass fraction), respectively. Key words:展开更多
基金This work was supported by the Chinese TMSR Strategic Pioneer Science and Technology Project(No.XDA02010300).
文摘A nonlinear dynamic simulation model based on coordinated control of speed and flow rate for the molten salt reactor and combined cycle systems is proposed here to ensure the coordination and stability between the molten salt reactor and power system.This model considers the impact of thermal properties of fluid variation on accuracy and has been validated with Simulink.This study reveals the capability of the control system to compensate for anomalous situations and maintain shaft stability in the event of perturbations occurring in high-temperature molten salt tank outlet parameters.Meanwhile,the control system’s impact on the system’s dynamic characteristics under molten salt disturbance is also analyzed.The results reveal that after the disturbance occurs,the controlled system benefits from the action of the control,and the overshoot and disturbance amplitude are positively correlated,while the system power and frequency eventually return to the initial values.This simulation model provides a basis for utilizing molten salt reactors for power generation and maintaining grid stability.
基金Funded by the National Natural Science Foundation for Young Scholars of China(No.51302073)the Hubei Provincial Key Laboratory of Green Materials for Light IndustryHubei University of Technology(No.202307B07)。
文摘We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it forms an intermediate product Ti_(3)CuC_(2),and then reacts with Ti_(3)CuC_(2)to obtain Ti_(3)C_(2)Cl_(2).The reaction of Ti_(3)AlC_(2)and CuCl_(2)at a temperature of 800℃for 2 h to obtain Ti_(3)C_(2)Cl_(2)with an optimal lamellar structure is shown in SEM results.The pseudopotential plane-wave(PP-PW)method is used to calculate on the electronic structure.The etching mechanism is investigated by the total energies of each substance.The chemical reaction of Ti_(3)AlC_(2)and CuCl_(2)will first become Ti_(3)CuC_(2)and Cu,and then become Ti_(3)C_(2)Cl_(2)during the Lewis acid etching process,which are consistent with the experimental results.
基金This work was financially supported by the National Natural Science Foundation of China(No.52171144)the Fundamental Research Special Zone Program of Shanghai Jiao Tong University(No.21TQ1400215).
文摘The synthesis of carbide coatings on graphite substrates using molten salt synthesis(MSS),has garnered significant interest due to its cost-effective nature.This study investigates the reaction process and growth kinetics involved in MSS,shedding light on key aspects of the process.The involvement of Ti powder through liquid-phase mass transfer is revealed,where the diffusion distance and quantity of Ti powder play a crucial role in determining the reaction rate by influencing the C content gradient on both sides of the carbide.Furthermore,the growth kinetics of the carbide coating are predominantly governed by the diffusion behavior of C within the carbide layer,rather than the chemical reaction rate.To analyze the kinetics,the thickness of the carbide layer is measured with respect to heat treatment time and temperature,unveiling a parabolic relationship within the temperature range of 700-1300℃.The estimated activation energy for the reaction is determined to be 179283 J·mol^(-1).These findings offer valuable insights into the synthesis of carbide coatings via MSS,facilitating their optimization and enhancing our understanding of their growth mechanisms and properties for various applications.
基金the National Natural Science Foundation of China(No.11905285)the Shanghai Natural Science Foundation(No.20ZR1468700)the Youth Innovation Promotion Association CAS(No.2022258).
文摘The heavy water-moderated molten salt reactor(HWMSR)is a newly proposed reactor concept,in which heavy water is adopted as the moderator and molten salt dissolved with fissile and fertile elements is used as the fuel.Issues arising from graphite in traditional molten salt reactors,including the positive temperature coefficient and management of highly radio-active spent graphite waste,can be addressed using the HWMSR.Until now,research on the HWMSR has been centered on the core design and nuclear fuel cycle to explore the viability of the HWMSR and its advantages in fuel utilization.However,the core safety of the HWMSR has not been extensively studied.Therefore,we evaluate typical accidents in a small modular HWMSR,including fuel salt inlet temperature overcooling and overheating accidents,fuel salt inlet flow rate decrease,heavy water inlet temperature overcooling accidents,and heavy water inlet mass flow rate decrease accidents,based on a neutronics and thermal-hydraulics coupled code.The results demonstrated that the core maintained safety during the investigated accidents.
基金CAS Photon Science Research Center for Carbon DioxideCAS President’s International Fellowship Initiative(2024PVA0097)+1 种基金National Key Research and Development Program of China(2017YFA0403000,2017YFA0402800)National Natural Science Foundation of China(U1932201,U1732121)。
文摘This study demonstrates the design and application of a novel high temperature rotatory apparatus for insitu synchrotron X-ray diffraction studies of molten salts,facilitating investigation into the interaction between various structural materials and molten salts.The apparatus enables accurate detection of every phase change during hightemperature experiments,including strong reaction processes like corrosion.Molten salts,such as chlorides or fluo⁃rides,together with the structure materials,are inserted into either quartz or boron nitride capillaries,where X-ray diffraction pattern can be continuously collected,as the samples are heated to high temperature.The replacement re⁃action,when molten ZnCl2 are etching Ti3AlC2,can be clearly observed through changes in diffraction peak intensity as well as expansion in c-axis lattice parameter of the hexagonal matrix,due to the larger atomic number and ionic ra⁃dius of Zn2+.Furthermore,we investigated the high-temperature corrosion process when GH3535 alloy is in FLiNaK molten salt,and can help to optimize its stability for potential applications in molten salt reactor.Additionally,this high temperature apparatus is fully compatible with the combined usage of X-ray diffraction and Raman technique,providing both bulk and surface structural information.This high temperature apparatus has been open to users and is extensively used at BL14B1 beamline of the Shanghai Synchrotron Radiation Facility.
文摘Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.
基金the Strategic Pilot Technology Chinese Academy of Sciences(No.XDA02010500).
文摘The high-temperature molten salt pump is the core equipment in a molten salt reactor that drives the flow of the molten salt coolant.Rotor stability is key to the continuous and reliable operation of the molten salt pump,and the liquid seal at the wear ring can affect the dynamic characteristics of the rotor system.When the molten salt pump is operated in the hightemperature molten salt medium,thermal deformation of the submerged parts inevitably occurs,changing clearance between the stator and rotor,affecting the leakage and dynamic characteristics of the seal.In this study,the seal leakage,seal dynamic characteristics,and rotor system dynamic characteristics are simulated and analyzed using finite element simulation software based on two cases of considering the effect of seal thermal deformation effect or not.The results show a significant difference in the leakage characteristics and dynamic characteristics of the seal obtained by considering the effect of seal thermal deformation and neglecting the effect of thermal deformation.The leakage flow rate decreases,and the first-order critical speed of the seal-bearing-rotor system decrease after considering the seal’s thermal deformation.
基金supported by the National Natural Science Foundation of China(Grant No.52072252,No.51902215)Sichuan Science and Technology Program(No.2020ZDZX0005)+4 种基金the Fundamental Research Funds for the Central Universities(YJ201886)the Agence Nationale de la Recherche(Labex STORE-EX)for financial supportsupported by the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(Grant No.2019R01003)Ningbo Top-talent Team Program,Ningbo Municipal Bureau of Science and Technology(Grant No.2018A610005)President’s International Fellowship Initiative of CAS(No.2021DE0002).
文摘MXenes are two-dimensional transition metal carbides and/or nitrides with unique physiochemical properties and have attracted extensive interest in numerous fields.However,current MXene synthesis methods are limited by hazardous synthesis conditions,high production costs,or difficulty in largescale production.Therefore,a general,safe,cost-effective,and scalable synthesis method for MXenes is crucial.Here,we report the fast synthesis of MXenes in the open air using a molten salt-shielded synthesis(MS^(3))method,which uses Lewis-acid salts as etchants and a low-melting-point eutectic salt mixture as the reaction medium and shield to prevent MXene oxidation at high temperatures.Carbide and nitride MXenes,including Ti_(3)C_(2)T_(x),Ti_(2)CT_(x),Ti_(3)CNT_(x),and Ti_(4)N_(3)T_(x),were successfully synthesized using the MS^(3) method.We also present the flexibility of the MS^(3) method by scaling the etching process to large batches of 20 and 60 g of Ti_(3)AlC_(2) MAX precursor in one pot.When used as negative electrodes,the prepared MS^(3)-MXenes delivered excellent electrochemical properties for high-rate Li-ion storage.
基金supported by the National Natural Science Foundation of China(52104309,52272021)the Natural Science Foundation of Hubei Province(2021CFB010)。
文摘High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimension and morphology remains a major challenge.Here,scalable HEO morphology modulation is implemented through a salt-assisted strategy,which is achieved by regulating the solubility of reactants and the selective adsorption of salt ions on specific crystal planes.The electrochemical properties,lithiation mechanism,and structure evolution of composition-and morphology-dependent HEO anode are examined in detail.More importantly,the potential advantages of HEOs as electrode materials are evaluated from both theoretical and experimental aspects.Benefiting from the high oxygen vacancy concentration,narrow band gap,and structure durability induced by the multi-element synergy,HEO anode delivers desirable reversible capacity and reaction kinetics.In particular,Mg is evidenced to serve as a structural sustainer that significantly inhibits the volume expansion and retains the rock salt lattice.These new perspectives are expected to open a window of opportunity to compositionally/morphologi cally engineer high-performance HEO electrodes.
基金Funded by National MCF Energy R&D Program(No.2019YFE03130002)。
文摘Dense zirconium coatings on copper substrates were obtained in an alumina crucible and a stainless steel crucible from FLiNaK-K_(2)ZrF_(6)molten salt at 1023 K.Due to the potential difierences between copper and zirconium,zirconium can difiuse into the copper substrate to form zirconium alloys on the surface of copper substrates in the course of deposition.The coating deposited in a stainless steel crucible has a gray surface.The components of the coating are mainly CuZr2alloy and Cu_(10)Zr_(7)alloy,and,the outermost layer of the coating is a layer of amorphous pure zirconium.The coating deposited in an alumina crucible has a silvery white metallic luster.The components of the coating are mainly Cu-Zr-Al intermetallic compounds,AlCu_(2)Zr,ZrAl,AlCu and CuZr.Furthermore,two types of zirconium coatings can greatly increase the hardness of the substrate.
基金the National Natural Science Foundation of China(Grant No.51804277)supported by the State Key Laboratory of Special Rare Metal Materials(No.SKL2020K004)Northwest Rare Metal Materials Research Institute.
文摘The properties of non-oxide materials are continuously revealed,and their applications in the fields of ceramics,energy,and catalysis are increasingly extensive.Regardless of the traditional binary materials or the MAX phases,the preparation methods,which are environmentally friendly,efficient,economical,and easy to scale-up,have always been the focus of attention.Molten salt synthesis has demonstrated unparalleled advantages in achieving non-oxide materials.In addition,with the development of the process in molten salt synthesis,it also shows great potential in scale-up production.In this review,the recent progress of molten salt synthesis in the preparation of binary non-oxide and MAX phase is reviewed,as well as some novel processes.The reaction mechanisms and the influence of synthetic conditions for certain materials are discussed in detail.The paper is finalized with the discussion of the application prospect and future research trends of molten salt synthesis in non-oxide materials.
文摘Low grade magnesite is one of the main research directions in the future as the raw material for the preparation of magnesia based insulating refractories.Periclase-forsterite(MgO-Mg_(2)SiO_(4)) lightweight insulating refractories were prepared by the molten salt method with high silica magnesite and tertiary talc ore as raw materials by pretreating them to get light burnt magnesia and talc,and NaCl molten salt as the reaction medium.The effects of the NaCl addition,the sintering temperature,the holding time and the raw material ratio on the sample preparation were studied.The results show that when the NaCl addition is 20% of the mass of light burnt magnesia and talc mixture,the sintering temperature is 1 200 ℃,the holding time is 6 h,and m(light burnt magnesia):m(talc)=5:5,the sample has the optimal comprehensive properties:the bulk density of 1.46 g·cm^(-3) and the apparent porosity of 55.0%.In addition,it is found that self-decomposition of talc and the formation of forsterite can form pores inside the sample.
文摘The reduction mechanism of Ir in the NaCl-KCl-IrCl3 molten salt was investigated by cyclic voltammetry and chronopotentiometry, and Ir film was deposited effectively on platinum in potentiostatic mode. The morphology and constitution of Ir film were examined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). It is found that the reduction mechanism of Ir(III) is a three-electron step and electro reaction is a reversible diffusion controlled process; the diffusion coefficients of Ir(III) at 1083, 1113, 1143 and 1183 K are 1.56×10-4, 2.23×10-4, 2.77×10-4 and 4.40×10-4 cm2/s, respectively, while the activation energy of the electrode reaction is 102.95 kJ/mol. The compacted Ir film reveals that the applied potential greatly affects the deposition of Ir, the thickness of Ir film deposited at the potential of reduction peak is the highest, the temperature of the molten salt also exerts an influence on deposition, the film formed at a lower temperature is thinner, but more micropores would occur on film when the temperature went too high.
基金Project(2006AA068128)supported by the Hi-tech Research and Development Program of China
文摘The electro-deoxidation of TiO2 was investigated in molten CaCl2.Back electromotive force measurements,constant voltage electrolytic experiments,contrast experiments of different cathodes,and cyclic voltammograms were carried out for solving the puzzle of reduction mechanism.The results showed that the reduction process proceeded step by step.TiO2 was first reduced to Ti3O5 or Ti2O3,and then further reduced to Ti3O,Ti2O,TiO and Ti.In addition,direct electrochemical reduction of titanium dioxide was the primary cathodic reaction;meanwhile,some calciothermic reduction reactions also happened at the cathode.Cyclic voltammograms of solid titanium dioxide and molybdenum wire in molten salts with different compositions were also studied.
基金Project (2007J0012) supported by the Natural Science Foundation of Fujian Province, ChinaProject (019811) supported by Foxy in the 6th Framework Program, European Commission
文摘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.
基金Projects(2012BAE01B04)supported by the National Key and Technology R&D Program of ChinaProject(KZCX2-XB3-06)supported by Western Action Program,Chinese Academy of Sciences
文摘Mg-La alloys were prepared by constant voltage electrolysis in the molten salt system of MgC12-LaC13-KC1 at 750℃, with a graphite crucible as the anode and a tungsten rod as the cathode. The effect of oxide and fluoride addition on the electrolysis was investigated comprehensively. X-ray diffraction (XRD) was used to characterize some of the Mg-La alloy products and the sludges. As the content of MgO or La203 in the electrolyte increased, both the current efficiency and the mass of alloy product decreased, indicating that both MgO and La203 may take part in the reactions in the electrolyte. When the same mass of the oxide was added, compared with La203, MgO had a more pronounced effect on both the current efficiency and the mass of alloy product. XRD studies confirmed the formation of LaOC1 when MgO or LazO3 was added into the electrolyte. The formation of LaOCl sludge would be the main reason for the negative effect of the oxide addition on both the current efficiency and the mass of alloy. In the electrolytic system, the addition of CaF2 was not helpful to suppress the negative effect of MgO on the electrolysis, probably due to the complex reactions of the La compounds in the electrolyte.
基金Project(51171150)supported by the National Natural Science Foundation of China
文摘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.
基金Project (2007CB210305) supported by the National Basic Research Program of ChinaProject (51074045) supported by the National Natural Science Foundation of China
文摘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.
基金Project(50804010) supported by the National Natural Science Foundation of ChinaProject(2007CB210305) supported by the National Basic Research Program of China
文摘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℃.
文摘The electrochemical process of Mg-Sr codeposition was studied in MgCl2-SrCl2-KCl melts containing different MgCl2 concentrations at 700 ℃ by cyclic voltammetry, chronopotentiometry and chronoamperometry. The results show that the actual precipitation potential of Sr reduces by nearly 0.5 V because of the depolarization effects of Sr activity reduced by forming Mg-Sr alloy. The codeposition potential condition of Mg and Sr to form Mg-Sr alloy is as follows: When electrode potential is more negative than -1.5 V, the magnesium will precipitate; when electrode potential is more negative than -2.0 V, the magnesium and strontium will both deposit. The control step of codeposition process of Mg and Sr is not diffusion control step. The codeposition current condition of Mg and Sr to form Mg-Sr alloy by chronoptentiometry is as follows: cathode current densities are higher than 0.71, 1.57 and 2.83 A/cm^2 in MgCl2-SrCl2-KCl melts with MgCl2 concentrations of 2%, 5% and 10% (mass fraction), respectively. Key words: