Alumina Solubility in Na_3AlF_6-K_3AlF_6-AlF_3 Molten Salt System Prospective for Aluminum Electrolysis at Lower Temperature

The alumina solubility in the title system within the composition range of KR{m（K3AlF6）/[m（K3AlF6）＋ m（Na3AlF6）]} 10%―50%, a ternary Na3AlF6-K3AlF6-AlF3 molten system with 23%―29%（mass fraction） AlF3 was investigated by measuring the mass loss of a rotating sintered corundum disc. And the following empirical equation was derived when superheat degree was no more than 60 °C： w（Al2O3）sat=A×（T/1000）B, where A= –1.85774＋ 26.754234w（AlF3）–0.3683–0.00783KR2.363＋0.010266KR2.3048＋0.7902w（AlF3）0.00652, B=112.4625–53.2567w（AlF3）0.4236＋ 5.1079w（AlF3）0.9241＋0.01542w（AlF3）1.3540. Considering both higher alumina solubility and not too high superheat de gree are required, alumina solubility of different compositions at not the same temperature but the same superheat degree was studied, which will be more industrial helpful for selecting prospective compositions. The results show that the composition deserved to be further tested in lower temperature cells is 10%―30% KR and 23%―26%（mass fraction） AlF3.

A Prediction of the Excess Partial Molar Free Energies of MgCl_2 in the KCI-MgCl_2-LiCl Molten Salt System Containing MgCl_2 below 0.5 from Thermodynamic Properties of Binary Systems

The thermodynamical properties of MgCl_2 in KCI-MgCl_2-LiCl molten electrolytes containing MgCl_2 below 0.5 (mole fraction, the same below) have been determined from the interchange energies of two binary systems KCI-MgCl_2 and LiCI-MgCl_2, by means of a model on the assumptions that the electrolytes in the solution are treated as independent particles instead of their ion forms and the interchange energy between the component pair KCI-LiCl is ignored when compared with those of component pairs KCl-MgCl_2 and MgCl_2-LiCl. The interchange energies, wKCl-MgCl_2 and wMgcCl_2-Licl, are obtained as-70000 and -13800 J.mol-1, from the corresponding binary solutions, respectively.

Preparation and Characterization of Bi_4Ti_3O_(12) Platelets by a Novel Low-temperature Molten Salt System

Bismuth titanate （Bi4Ti3O12） platelets were prepared by molten salt method in a new salt system of CaCl2·NaCl at 650-750℃, using bismuth nitrate pentahydrate （Bi （NO3）3·H2O） and titanium butoxide （Ti （OC4H9）4） as raw materials. The synthesis temperature of Bi4Ti3O12 platelets was decreased to 650℃ from 900-1100℃. The phase compositions and crystalline morphology of Bi4Ti3O12 platelets were investigated by XRD and SEM. The experimental results indicate that Bi4Ti3O12 platelets containing tetragonal and orthorhombic phase with the size of 1-3μm can be synthesized at 650℃ for 2 h, and the orthorhombic phase becomes the dominant phase at 750℃ for 5 h. The size and proportion of Bi4Ti3O12 platelets increase with the increment of the calcining temperature and holding time. The proportion of platelets increases to about ninety percent, and the platelets grow up to about 3-10μm at 750℃ for 5 h from 1-2μm at 650℃ for 2 h. This technical route provides a new low-temperature molten salt system for preparing platelets by molten salt methods.

MOLTEN SALT PHASE DIAGRAMS CALCULATION USING ARTIFICIAL NEURAL NETWORK OR PATTERN RECOGNITION-BOND PARAMETERS Part 2.Prediction of phase diagrams of ternary molten salt systems

ＭＯＬＴＥＮＳＡＬＴＰＨＡＳＥＤＩＡＧＲＡＭＳＣＡＬＣＵＬＡＴＩＯＮＵＳＩＮＧＡＲＴＩＦＩＣＩＡＬＮＥＵＲＡＬＮＥＴＷＯＲＫＯＲＰＡＴＴＥＲＮＲＥＣＯＧＮＩＴＩＯＮＢＯＮＤＰＡＲＡＭＥＴＥＲＳ①Ｐａｒｔ２．Ｐｒｅｄｉｃｔｉｏｎｏｆｐｈａｓｅｄｉａｇ...

Micromorphology and texture of niobium coating electrodeposited in NaCl−KCl−CsCl molten salt system

A low-toxicity and environment-friendly NaCl−KCl−CsCl−K_(2)NbF_(7) system was used to prepare Nb coatings on Mo substrates.The effects of temperature,current density and electrodeposition time on the micromorphologies and textures of the electrodeposited Nb coatings were studied.The results showed that Nb coatings obtained at 30−70 mA/cm^(2) in the temperature range of 700−750℃ were continuous and compact,with a hardness range of 2.16−2.45 GPa.As the columnar crystals grew with time,the preferential growth orientations of the Nb coatings changed from<200>to<211>and then became disordered.With increasing polarization,the morphologies of the Nb coatings changed from hexagonal star-like surface to conical or pyramid-like surface.

Regularities of formability of intermediate compounds in binary molten salt systems

The formability of intermediate compounds for thirteen kinds of binary molten salt systems, including 1 179 phase diagrams was discussed by pattern recognition method with bond parameters as features. These systems were MeX Me′X, MeX Me′X 2, MeX Me′X 3, MeX Me′X 4, MeX 2 Me′X 2, MeX 2 Me′X 3, MeX 2 Me′X 4, MeX 3 Me′X 3, MeNO 3 Me′(NO 3) 2, Me 2SO 4 Me′SO 4 (Me, Me′ denote metallic elements, X denotes halogen), Me AX B Me′ CX D (X is CrO 2- 4, WO 2- 4 or MoO 2- 4), and common cation systems MeX MeX′, MeX Me 2X′ (Me, Me′ denote metallic elements, X, X′ denote anion forming elements or radicals). It had been found that molten salt systems forming intermediate compounds and ones without intermediate compound distribute in different regions. Moreover, six general regularities for the formation of intermediate compounds in binary molten salt systems had been summarized on the basis of thirteen semi empirical models, which was obtained from the known phase diagrams.[

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.

Deep Potential Molecular Dynamics Systematic Study of Microstructure and Thermophysical Properties of NaCl-CaCl_(2) Molten Salt System across Phase Transition Temperature

Understanding the microscopic ionic structure and thermal properties of the NaCl-CaCl_(2) mixture is of great importance for improving its photothermal energy conversion efficiency.However,the measured values of thermophysical parameters are affected by the processes near the phase transition temperature,and the measured values often change abruptly.Classical and first-principles molecular dynamics studies have recently been performed to determine the thermal properties of molten salts,but such simulations for binary molten salts including NaCl-CaCl_(2) are still rare and limited to a range above the phase transition temperature(786.0 K),and the deviations from the measurements are still large.In this study,the molecular dynamics method based on the trained deep potential is used to systematically predict the variations of the ionic structure,phonon density of state,density and thermophysical properties including heat capacity,thermal conductivity,and diffusivity,and Prandtl number of the binary chloride system of NaCl-CaCl_(2) in a wide temperature range(600-1000 K)above the phase transition temperature.The variations and correlations of the properties(especially thermal diffusivity and Prandtl number)with temperature are deduced.It is found that an increase in temperature enhances ionic vibration,thus increasing the specific heat capacity.An increase in temperature weakens the interaction and vibrational transfer between ions,and hence the thermal conductivity tends to decrease.As the temperature increases,the heat capacity increases,while the density,thermal conductivity,thermal diffusion coefficient,and Prandtl number of the system all decrease.In general,the properties obtained by applying the deep potential trained in this work reflect the experimental values more accurately than the classical and first-principles molecular dynamics simulations.

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.

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.

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.

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.

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.

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.

Raman spectroscopy and quantum chemical calculation on YCl_(3)-KCl molten salt system

The knowledge on the ionic structure of YCl_(3)-KCl molten system is of guiding significance for the practical production of yttrium metals and yttrium alloys via molten salt electrolysis using this system as electrolyte.In this paper,the theoretical Raman spectra of the ionic groups which may exist in YCl_(3)-KCl molten system are simulated by quantum chemical calculation using Gaussian09 and Gauss View 5.0 programs based on density functional theory(DFT).Then the ionic structures of 20 mol%-60 mol%YCl_(3)-KCl molten salt systems are studied by comparing the Raman shift values of the bands in the theoretical Raman spectra of different ionic groups with the experimental spectra of this system.YCl_(6)^(3-),Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)are thought to exist in the molten system.With the increase of temperature,the relative content of YCl_(6)^(3-)ionic groups increases while those of Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)ionic groups decrease.Moreover,the"lifetime"of all ionic groups decreases within the temperature range of 692-730℃.Meanwhile,the relative contents of Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-)and Y_(2)Cl_(9)^(3-)increase with the increase of YCl_(3)content,while that of YCl_(6)^(3-)decreases.The wave function analysis of the four ionic groups(YCl_(6)^(3-),Y_(2)Cl_(7)^(-),Y_(2)Cl_(8)^(2-),and Y_(2)Cl_(9)^(3-))is carried out by Multiwfn program.The net charge in each group,the direction of electron migration during the formation of each group,the sites where electrophilic and nucleophilic reactions are most likely to occur in each ionic group,and the order of bond breaking during chemical reactions for the four groups are obtained.

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.

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.

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 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.