Reaction mechanism of preparation of titanium by electro-deoxidation in molten salt

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.

Dynamic simulation analysis of molten salt reactor-coupled air-steam combined cycle power generation system

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.

Growth kinetics of titanium carbide coating by molten salt synthesis process on graphite sheet surface

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.

Etching Mechanism of Ti_(3)C_(2)Cl_(2) MXene Phases by CuCl_(2)-Lewis Molten Salt Method

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.

A Novel High Temperature Apparatus for in situ Synchrotron X-ray Diffraction Studies of Molten Salt

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.

Preliminary safety analysis for heavy water-moderated molten salt reactor

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.

Plutonium utilization in a small modular molten-salt reactor based on a batch fuel reprocessing scheme

A molten salt reactor(MSR)has outstanding features considering the application of thorium fuel,inherent safety,sustainability,and resistance to proliferation.However,fissile material^(233)U is significantly rare at the current stage,thus it is difficult for MSR to achieve a pure thorium-uranium fuel cycle.Therefore,using plutonium or enriched uranium as the initial fuel for MSR is more practical.In this study,we aim to verify the feasibility of a small modular MSR that utilizes plutonium as the starting fuel(SM-MSR-Pu),and highlight its advantages and disadvantages.First,the structural design and fuel management scheme of the SM-MSR-Pu were presented.Second,the neutronic characteristics,such as the graphite-irradiation lifetime,burn-up performance,and coefficient of temperature reactivity were calculated to analyze the physical characteristics of the SM-MSR-Pu.The results indicate that plutonium is a feasible and advantageous starting fuel for a SM-MSR;however,there are certain shortcomings that need to be solved.In a 250 MWth SM-MSR-Pu,approximately 288.64 kg^(233)U of plutonium with a purity of greater than 90% is produced while 978.00 kg is burned every ten years.The temperature reactivity coefficient decreases from -4.0 to -6.5 pcm K^(-1) over the 50-year operating time,which ensures a long-term safe operation.However,the amount of plutonium and accumulation of minor actinides(MAs)would increase as the burn-up time increases,and the annual production and purity of^(233)U will decrease.To achieve an optimal burn-up performance,setting the entire operation time to 30 years is advisable.Regardless,more than 3600 kg of plutonium eventually accumulate in the core.Further research is required to effectively utilize this accumulated plutonium.

Molten salt construction of core-shell structured S-scheme CuInS_(2)@CoS_(2) heterojunction to boost charge transfer for efficient photocatalytic CO_(2) reduction

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.

Analysis of burnup performance and temperature coefficient for a small modular molten‑salt reactor started with plutonium

In a thorium-based molten salt reactor(TMSR),it is difficult to achieve the pure 232Th–^(233)U fuel cycle without sufficient^(233)U fuel supply.Therefore,the original molten salt reactor was designed to use enriched uranium or plutonium as the starting fuel.By exploiting plutonium as the starting fuel and thorium as the fertile fuel,the high-purity^(233)U produced can be separated from the spent fuel by fluorination volatilization.Therefore,the molten salt reactor started with plutonium can be designed as a^(233)U breeder with the burning plutonium extracted from a pressurized water reactor(PWR).Combining these advantages,the study of the physical properties of plutonium-activated salt reactors is attractive.This study mainly focused on the burnup performance and temperature reactivity coefficient of a small modular molten-salt reactor started with plutonium(SM-MSR-Pu).The neutron spectra,^(233)U production,plutonium incineration,minor actinide(MA)residues,and temperature reactivity coefficients for different fuel salt volume fractions(VF)and hexagon pitch(P)sizes were calculated to analyze the burnup behavior in the SM-SMR-Pu.Based on the comparative analysis results of the burn-up calculation,a lower VF and larger P size are more beneficial for improving the burnup performance.However,from a passive safety perspective,a higher fuel volume fraction and smaller hexagon pitch size are necessary to achieve a deep negative feedback coefficient.Therefore,an excellent burnup performance and a deep negative temperature feedback coefficient are incompatible,and the optimal design range is relatively narrow in the optimized design of an SM-MSR-Pu.In a comprehensive consideration,P=20 cm and VF=20%are considered to be relatively balanced design parameters.Based on the fuel off-line batching scheme,a 250 MWth SM-MSR-Pu can produce approximately 29.83 kg of ^(233)U,incinerate 98.29 kg of plutonium,and accumulate 14.70 kg of MAs per year,and the temperature reactivity coefficient can always be lower than−4.0pcm/K.

Molten Salt-Shielded Synthesis(MS^(3))of MXenes in Air

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.

Study on the effect of thermal deformation on the liquid seal of high-temperature molten salt pump in molten salt reactor

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.

Study on the corrosion behavior of 316H stainless steel in molten NaCl–KCl–MgCl_(2) salts with and without purification

The corrosion behavior of 316H stainless steel(SS)in the impure and purified Na Cl–KCl–Mg Cl_(2) salt was investigated at700°C.Results indicate that the main deleterious impurity induced corrosion in the impure salt was the absorbed moisture,present in the form of Mg Cl_(2)·6H_(2)O.316H SS occurred severe intergranular corrosion with a corrosion depth of 130μm for1000 h in the impure Na Cl–KCl–Mg Cl_(2) salt.In contrast,the purification treatment of molten chloride salt by the dissolved Mg metal can remove the absorbed moisture,and the corresponding reactions were also discussed.As a result,the corrosiveness of Na Cl–KCl–Mg Cl_(2) salt is reduced significantly.316H SS occurred slight uniform corrosion with a depth of less than 5μm for 3000 h in the purified Na Cl–KCl–Mg Cl_(2) salt.

Preparation of RE-containing magnesium alloys via molten-salt-mediated magnesiothermic reduction

RE-containing magnesium alloys were prepared via molten-salt-mediated magnesiothermic reduction by using RE_(2)O_(3)(RE=Y,Nd and Gd)and Mg metal as raw materials.The thermomechanical analysis of the magnesiothermic reduction reactions in molten salt was investigated.Then the molten-salt-mediated magnesiothermic reduction process was studied from three different perspectives.After that,the RE-containing magnesium alloy was characterized by using chemical analysis,XRD analysis and SEM analysis.The magnesiothermic reduction was a liquid-liquid reaction with relatively weak driving force.During the melting process and the magnesiothermic reduction process,magnesium metal and the obtained alloy went up and down as a whole in molten salt,which improved the process safety without introducing chloride inclusions.Meanwhile,the hydrolysis of the RECl_(3^(-))containing molten salt occurred at elevated temperature,which severely impeded the magnesiothermic reduction process.After the magnesiothermic reduction at 750°C for 2.0 h,the content of RE and the common impurity elements in the obtained RE-containing alloy met the both requirements of the commercial WE43A and WE43B.

Effect of reprocessing on neutrons of a molten chloride salt fast reactor

Due to their unique features,such as the inherent safety,simplified fuel cycle,and continuous on-line reprocessing,molten salt reactors(MSRs)are regarded as one of the six reference reactors in the Generation IV International Forum(GEN-IV).Molten chloride salt fast reactors(MCFRs)are a type of MSR.Compared to molten fluoride salt reactors(MFSRs),MCFRs have a higher solubility of heavy metal atoms,a harder neutron spectrum,lower accumulation of fission products(FPs),and better breeding and transmutation performance.Thus,MCFRs have been recognized as a type of MSR with great prospects for future development.However,as the most important feature for MSRs,the effect of different reprocessing modes on MCFRs must be researched in depth.As such,this study investigated the effect of different isotopes,especially FPs,on the neutronic performance of an MCFR,such as its breeding performance.Furthermore,the characteristics of the different reprocessing modes and MCFR rates were analyzed in terms of safety,radioactivity level,neutron economy,and breeding capacity.In the end,a reprocessing method suitable for MCFRs was determined through calculation and analysis,which provides a reference for the further research of MCFRs.

Electro-deoxidation of V_2O_3 in molten CaCl_2-NaCl-CaO

The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.

Preparation of Zr-Cu Coatings on Copper Substrate Using a Molten Salt Method

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.

Advances in Molten Salt Synthesis of Non-oxide Materials

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.

Molten salt synthesis,morphology modulation,and lithiation mechanism of high entropy oxide for robust lithium storage

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.

Preparation of Periclase-forsterite Lightweight Heat-insulating Refractories by Molten Salt Method

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.

Research progress on protective coatings against molten nitrate salts for thermal energy storage in concentrating solar power plants

Concentrating solar power(CSP) has garnered considerable global attention as a reliable means of generating bulk electricity, effectively addressing the intermittent nature of solar resources.The integration of molten salt technology for thermal energy storage(TES) has further contributed to the growth of CSP plants;however, the corrosive nature of molten salts poses challenges to the durability of container materials, necessitating innovative corrosion mitigation strategies.This review summarizes scientific advancements in high-temperature anticorrosion coatings for molten nitrate salts, highlighting the key challenges and future trends.It also explores various coating types, including metallic, ceramic, and carbon-based coatings, and compares different coating deposition methods.This review emphasizes the need for durable coatings that meet long-term performance requirements and regulatory limitations, with an emphasis on carbon-based coatings and emerging nanomaterials.A combination of multiple coatings is required to achieve desirable anticorrosion properties while addressing material compatibility and cost considerations.The overall goal is to advance the manufacturing, assembly, and performance of CSP systems for increased efficiency, reliability, and durability in various applications.