In this study, the reaction characteristics of reduction of calcined dolomite with ferrosilicon under argon flow to produce magnesium were studied by conducting experiments Pidgeon pellets were used to study the effec...In this study, the reaction characteristics of reduction of calcined dolomite with ferrosilicon under argon flow to produce magnesium were studied by conducting experiments Pidgeon pellets were used to study the effect of reduced temperature, argon flow, and reduced time on the conversion of calcined dolomite reduction by ferrosilicon. The results show that the conversion significantly increases with the increase in the reduction temperature and reduction time. The conversion first increases and then decreases with the increase in argon flow. The highest conversion was obtained when the argon flow rate was 3 L·min^(-1), and a nearly spherical shape, nanoscale magnesium powder was obtained. Then the characters of the circulating argon entrainment process were numerically studied by ANSYS Fluent 17. A physical model of multilayer pellet arrangement was established, and a numerical calculation model of chemical reaction, radiation, heat conduction, and convection heat transfer was constructed. This confirms that high-temperature argon can effectively strengthen the heat exchange between pellets, improve the heat transfer efficiency, and facilitate the pellets to react quickly. When the conversion is 80%, the production efficiency increased by about 28.6%. In addition, the magnesium production efficiency showed an increase tendency with the increase of the argon inlet flow rate.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
The macroscopic characteristics of molten salts are governed by their microstructures.Research on the structures of molten salts provides the foundation for a full understanding of the physicochemical properties of mo...The macroscopic characteristics of molten salts are governed by their microstructures.Research on the structures of molten salts provides the foundation for a full understanding of the physicochemical properties of molten salts as well as a deeper analysis of the microscopic electrolysis process in molten salts.Information about the microstructure of matter can be obtained with the help of several speculative and experimental procedures.In this review,the advantages and disadvantages of the various test procedures used to determine the microstructures of molten salts are compared.The typical coordination configurations of metal ions in molten salt systems are also summarized.Furthermore,the impact of temperature,anions,cations,and metal oxides(O2-)on the structures of molten salts is discussed in detail.The accuracy and completeness of the information on molten salt structures need to be investigated by the integration of multiple methods and interdisciplinary fields.Information on the microstructure and coordination of molten salts deepens the understanding of the elementary elements of the microstructure of matter.This paper,which is based on the review of the coordination states of metal ions in molten salts,is hoped to inspire researchers to explore the inter-relationship between the microstructure and macroscopic properties of materials.展开更多
The silicothermic reduction of magnesium was investigated by the non-isothermal thermoanalysis in flowing argon,while the traditional investigations of silicothermic process for magnesium reduction were carried out un...The silicothermic reduction of magnesium was investigated by the non-isothermal thermoanalysis in flowing argon,while the traditional investigations of silicothermic process for magnesium reduction were carried out under vacuum conditions.Firstly,the thermal gravimetric(TG)and derivative thermogravimetric(DTG)characteristic of briquettes prepared with calcined dolomite,ferrosilicon and fluorite were characterized by the thermogravimetric analyzer(TGA)at different heating rates.The intrinsic chemical kinetic mechanism was identified as a formal chemical reaction with the Nth order type which showed apparent activation energy E and reaction order n were 290.168 kJ mol^(-1) and 1.076,respectively.Then,a novel technique of magnesium production without vacuum was put forward and a three-dimensional unsteady numerical model incorporating the chemical reaction,radiation,heat conduction and heat convection was established and simulated,which was verified by Pidgeon process and novel tech no logy.rIhe nu merical results showed that the cycle time of the novel technique could be reduced when the argon temperature was higher than 1343 K and the argon entrance velocity was over 0.05 m s^(-1).And the effect of the argon temperature on reduction degree was much larger than that of entrance velocity.展开更多
The electrochemical behavior of Mg^(2+)and Al^(3+)in LiCl-KCl(mass 4:1)melt at 973 K was studied on a Mo electrode systematically by cyclic voltammetry,square wave voltammetry and chronopotentiometry.The results showe...The electrochemical behavior of Mg^(2+)and Al^(3+)in LiCl-KCl(mass 4:1)melt at 973 K was studied on a Mo electrode systematically by cyclic voltammetry,square wave voltammetry and chronopotentiometry.The results showed that the reductions of Mg^(2+)and Al^(3+)were reversible processes controlled by the rate of the mass transfer.When Mg^(2+)and Al^(3+)coexisted in LiCl-KCl melt,they had no significant effect on the reduction potential of each other.The equilibrium potentials of Mg^(2+)/Mg and Al^(3+)/Al were obtained by open circuit potential method.Their apparent standard potentials were also calculated in this system and the values were-2.52 V vs Cl_(2)/Cl^(−),-1.66 V vs Cl_(2)/Cl^(−),respectively.Correspondingly,the apparent Gibbs free energies of Mg^(2+)/Mg and Al^(3+)/Al were-485.71 kJ/mol^(-1),-480.78 kJ/mol^(-1).Finally,potentiostatic electrolysis was performed on a Mo electrode in LiCl-KCl-MgCl_(2)-AlCl_(3)(the mass ratio of MgCl_(2) to AlCl_(3) was 10:1)melt at different potentials.The components of the deposits were characterized by scanning electron microscope and energy dispersive spectroscopy.The study revealed that the content of Al in the deposit decreased as the overpotential increased and Al tended to segregate at the grain boundaries.展开更多
The effects of fluoride ions(F^(-)) on the electrochemical behavior and coordination properties of titanium ions(Ti^(n+)) were studied in this work,by combining electrochemical and mathematical analysis as well as spe...The effects of fluoride ions(F^(-)) on the electrochemical behavior and coordination properties of titanium ions(Ti^(n+)) were studied in this work,by combining electrochemical and mathematical analysis as well as spectral techniques.The α was taken as a factor to indicate the molar concentration ratio of F^(-) and Ti^(n+).Cyclic voltammetry(CV),square wave voltammetry(SWV),and open circuit potential method(OCP)were used to study the electrochemical behavior of titanium ions under conditions of various α,and in-situ sampler was used to prepare molten salt samples when α equal to 0.0,1.0,2.0,3.0,4.0,5.0,6.0,and 8.0.And then,samples were analyzed by X-ray photoelectron spectroscopy(XPS) and Raman spectroscopy.The results showed that F^(-) in molten salt can reduce the reduction steps of titanium ions and greatly affects the proportion of valence titanium ions which making the high-valence titanium content increased and more stable.Ti^(2+) cannot be detected in the molten salt when α is higher than 3.0 and finally transferred to titanium ions with higher valence state.Investigation revealed that the mechanism behind those phenomenon is the coordination compounds(TiCl_(j) F_(i)^(m-)) forming.展开更多
Spent catalyst used for denitration by selective catalytic reduction(spent SCR denitration catalysts) is one of the important urban mines due to the high content of TiO_(2)(~85 wt%) and the massive accumulation amount...Spent catalyst used for denitration by selective catalytic reduction(spent SCR denitration catalysts) is one of the important urban mines due to the high content of TiO_(2)(~85 wt%) and the massive accumulation amount(over 100,000 tons),therefore,value-added reutilization of titanium in spent SCR catalysts is considerably meaningful.In this paper,a novel method is proposed for converting the titanium oxide in spent SCR denitration catalysts to metallic titanium.Specifically,titanium dioxide(TiO_(2)) was firstly obtained from spent SCR denitration catalysts after removing the impurities by hydrometallurgy process.Then,TiO_(2) is converted to Ti_(2)CO by carbothermic reduction method,and Ti_(2)CO was further purified by oleic acid capture.Finally,by utilizing the as-prepared Ti_(2)CO as the consumable anode in the NaCl-KCl molten salt,high-purity metallic titanium was deposited at cathode,all confirming the feasibility for the conversion of low-grade TiO_(2) in the spent catalysts,from 60 wt% to high-purity metallic Ti(99.5 wt%), furthermore,the energy consumption of this process is 3950 kWh tonne-1 Ti,which is lower than that of most traditional titanium metallurgy methods.The method herein can provide new insights for the value-added recycling of titanium resources in urban mines.展开更多
High-entropy rare-earth aluminate(Y_(0.2)Yb_(0.2)Lu_(0.2)Eu_(0.2)Er_(0.2))_(3)Al_(5)O_(12)(HE-RE_(3)Al_(5)O_(12))has been considered as a promising thermal protection coating(TPC)material based on its low thermal cond...High-entropy rare-earth aluminate(Y_(0.2)Yb_(0.2)Lu_(0.2)Eu_(0.2)Er_(0.2))_(3)Al_(5)O_(12)(HE-RE_(3)Al_(5)O_(12))has been considered as a promising thermal protection coating(TPC)material based on its low thermal conductivity and close thermal expansion coefficient to that of Al2O3.However,such a coating has not been experimentally prepared,and its thermal protection performance has not been evaluated.To prove the feasibility of utilizing HE-RE_(3)Al_(5)O_(12) as a TPC,HE-RE_(3)Al_(5)O_(12) coating was deposited on a nickelbased superalloy for the first time using the atmospheric plasma spraying technique.The stability,surface,and cross-sectional morphologies,as well as the fracture surface of the HE-RE_(3)Al_(5)O_(12) coating were investigated,and the thermal shock resistance was evaluated using the oxyacetylene flame test.The results show that the HE-RE_(3)Al_(5)O_(12) coating can remain intact after 50 cycles at 1200℃ for 200 s,while the edge peeling phenomenon occurs after 10 cycles at 1400℃ for 200 s.This study clearly demonstrates that HE-RE_(3)Al_(5)O_(12) coating is effective for protecting the nickel-based superalloy,and the atmospheric plasma spraying is a suitable method for preparing this kind of coatings.展开更多
Perovskite functional ceramics have been widely applied for thermal protection owing to their unique physical properties.However,formation of oxygen vacancies under external stimuli usually limits their performance in...Perovskite functional ceramics have been widely applied for thermal protection owing to their unique physical properties.However,formation of oxygen vacancies under external stimuli usually limits their performance in practical applications.Therefore,the mechanism of the effect of oxygen vacancy on the layer structure of perovskite La_(0.9)Sr_(0.1)TiO_(3+δ)was investigated by experiments and first-principles simulations.The experimental results showed that the lattice distortion occurred in oxygen-deficient environment to give a longer c-axis,along with a significant adjustment in the modes of A/B–O bond vibration,resulting in lower reflectivity.Advanced transmission electron microscopy studies revealed that oxygen vacancies induced localized atomic rearrangements via[TiO_(6)]layer movements to adapt to the lattice distortion.This eventually restructured a part of the layer interfaces by expanding the overlapping projection of atoms in the c-axial direction.The specific transformation process was described as a compendious process,while geometric phase analysis effectively clarified how oxygen vacancies can inhibit reflectivity on the layer structure.Thus,this study provides effective approaches for researching the effects of oxygen vacancy on the physical properties of orthorhombic layer perovskite structures,which may facilitate the development of perovskite-based functional devices.展开更多
基金supported by Key Program of the National Natural Science Foundation of China (Grant No.92062223)the National Natural Science Foundation of China (Grant No.51804277)Anhui University Natural Science Research Project (KJ20190048)。
文摘In this study, the reaction characteristics of reduction of calcined dolomite with ferrosilicon under argon flow to produce magnesium were studied by conducting experiments Pidgeon pellets were used to study the effect of reduced temperature, argon flow, and reduced time on the conversion of calcined dolomite reduction by ferrosilicon. The results show that the conversion significantly increases with the increase in the reduction temperature and reduction time. The conversion first increases and then decreases with the increase in argon flow. The highest conversion was obtained when the argon flow rate was 3 L·min^(-1), and a nearly spherical shape, nanoscale magnesium powder was obtained. Then the characters of the circulating argon entrainment process were numerically studied by ANSYS Fluent 17. A physical model of multilayer pellet arrangement was established, and a numerical calculation model of chemical reaction, radiation, heat conduction, and convection heat transfer was constructed. This confirms that high-temperature argon can effectively strengthen the heat exchange between pellets, improve the heat transfer efficiency, and facilitate the pellets to react quickly. When the conversion is 80%, the production efficiency increased by about 28.6%. In addition, the magnesium production efficiency showed an increase tendency with the increase of the argon inlet flow rate.
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.
基金financially supported by the National Key Research and Development Program of China (Nos.2021YFC2901600 and 2021YFC2902305)the National Natural Science Foundation of China (No.52274356)+2 种基金the Natural Science Foundation of Henan Province,China (No.222300420545)the State Key Laboratory of Special Rare Metal Materials,China (No.SKL2020K004)the Northwest Rare Metal Materials Research Institute,China,and the State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,China (No.CNMRCUKF2008)。
文摘The macroscopic characteristics of molten salts are governed by their microstructures.Research on the structures of molten salts provides the foundation for a full understanding of the physicochemical properties of molten salts as well as a deeper analysis of the microscopic electrolysis process in molten salts.Information about the microstructure of matter can be obtained with the help of several speculative and experimental procedures.In this review,the advantages and disadvantages of the various test procedures used to determine the microstructures of molten salts are compared.The typical coordination configurations of metal ions in molten salt systems are also summarized.Furthermore,the impact of temperature,anions,cations,and metal oxides(O2-)on the structures of molten salts is discussed in detail.The accuracy and completeness of the information on molten salt structures need to be investigated by the integration of multiple methods and interdisciplinary fields.Information on the microstructure and coordination of molten salts deepens the understanding of the elementary elements of the microstructure of matter.This paper,which is based on the review of the coordination states of metal ions in molten salts,is hoped to inspire researchers to explore the inter-relationship between the microstructure and macroscopic properties of materials.
基金the National Key R&D Program of China(Grant No.2016YFB0301100)Anhui Provincial Natural Science Foundation of China(Grant No.1808085QE152).
文摘The silicothermic reduction of magnesium was investigated by the non-isothermal thermoanalysis in flowing argon,while the traditional investigations of silicothermic process for magnesium reduction were carried out under vacuum conditions.Firstly,the thermal gravimetric(TG)and derivative thermogravimetric(DTG)characteristic of briquettes prepared with calcined dolomite,ferrosilicon and fluorite were characterized by the thermogravimetric analyzer(TGA)at different heating rates.The intrinsic chemical kinetic mechanism was identified as a formal chemical reaction with the Nth order type which showed apparent activation energy E and reaction order n were 290.168 kJ mol^(-1) and 1.076,respectively.Then,a novel technique of magnesium production without vacuum was put forward and a three-dimensional unsteady numerical model incorporating the chemical reaction,radiation,heat conduction and heat convection was established and simulated,which was verified by Pidgeon process and novel tech no logy.rIhe nu merical results showed that the cycle time of the novel technique could be reduced when the argon temperature was higher than 1343 K and the argon entrance velocity was over 0.05 m s^(-1).And the effect of the argon temperature on reduction degree was much larger than that of entrance velocity.
基金the National Natural Science Foundation of China(Grant No.51804277).
文摘The electrochemical behavior of Mg^(2+)and Al^(3+)in LiCl-KCl(mass 4:1)melt at 973 K was studied on a Mo electrode systematically by cyclic voltammetry,square wave voltammetry and chronopotentiometry.The results showed that the reductions of Mg^(2+)and Al^(3+)were reversible processes controlled by the rate of the mass transfer.When Mg^(2+)and Al^(3+)coexisted in LiCl-KCl melt,they had no significant effect on the reduction potential of each other.The equilibrium potentials of Mg^(2+)/Mg and Al^(3+)/Al were obtained by open circuit potential method.Their apparent standard potentials were also calculated in this system and the values were-2.52 V vs Cl_(2)/Cl^(−),-1.66 V vs Cl_(2)/Cl^(−),respectively.Correspondingly,the apparent Gibbs free energies of Mg^(2+)/Mg and Al^(3+)/Al were-485.71 kJ/mol^(-1),-480.78 kJ/mol^(-1).Finally,potentiostatic electrolysis was performed on a Mo electrode in LiCl-KCl-MgCl_(2)-AlCl_(3)(the mass ratio of MgCl_(2) to AlCl_(3) was 10:1)melt at different potentials.The components of the deposits were characterized by scanning electron microscope and energy dispersive spectroscopy.The study revealed that the content of Al in the deposit decreased as the overpotential increased and Al tended to segregate at the grain boundaries.
基金financially supported by the National Natural Science Foundation of China(No.51804277)the State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,China(No.CNMRCUKF2008)+1 种基金the State Key Laboratory of Special Rare Metal Materials,China(No.SKL2020K004)the Northwest Rare Metal Materials Research Institute,China。
文摘The effects of fluoride ions(F^(-)) on the electrochemical behavior and coordination properties of titanium ions(Ti^(n+)) were studied in this work,by combining electrochemical and mathematical analysis as well as spectral techniques.The α was taken as a factor to indicate the molar concentration ratio of F^(-) and Ti^(n+).Cyclic voltammetry(CV),square wave voltammetry(SWV),and open circuit potential method(OCP)were used to study the electrochemical behavior of titanium ions under conditions of various α,and in-situ sampler was used to prepare molten salt samples when α equal to 0.0,1.0,2.0,3.0,4.0,5.0,6.0,and 8.0.And then,samples were analyzed by X-ray photoelectron spectroscopy(XPS) and Raman spectroscopy.The results showed that F^(-) in molten salt can reduce the reduction steps of titanium ions and greatly affects the proportion of valence titanium ions which making the high-valence titanium content increased and more stable.Ti^(2+) cannot be detected in the molten salt when α is higher than 3.0 and finally transferred to titanium ions with higher valence state.Investigation revealed that the mechanism behind those phenomenon is the coordination compounds(TiCl_(j) F_(i)^(m-)) forming.
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)+1 种基金Northwest Rare Metal Materials Research Institutesupported by the State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization(No.CNMRCUKF2008)。
文摘Spent catalyst used for denitration by selective catalytic reduction(spent SCR denitration catalysts) is one of the important urban mines due to the high content of TiO_(2)(~85 wt%) and the massive accumulation amount(over 100,000 tons),therefore,value-added reutilization of titanium in spent SCR catalysts is considerably meaningful.In this paper,a novel method is proposed for converting the titanium oxide in spent SCR denitration catalysts to metallic titanium.Specifically,titanium dioxide(TiO_(2)) was firstly obtained from spent SCR denitration catalysts after removing the impurities by hydrometallurgy process.Then,TiO_(2) is converted to Ti_(2)CO by carbothermic reduction method,and Ti_(2)CO was further purified by oleic acid capture.Finally,by utilizing the as-prepared Ti_(2)CO as the consumable anode in the NaCl-KCl molten salt,high-purity metallic titanium was deposited at cathode,all confirming the feasibility for the conversion of low-grade TiO_(2) in the spent catalysts,from 60 wt% to high-purity metallic Ti(99.5 wt%), furthermore,the energy consumption of this process is 3950 kWh tonne-1 Ti,which is lower than that of most traditional titanium metallurgy methods.The method herein can provide new insights for the value-added recycling of titanium resources in urban mines.
基金the National Key Laboratory Foundation of Science and Technology on Materials under Shock and Impact(No.6142902200202)the National Natural Science Foundation of China(No.52002355)+1 种基金the Outstanding Youth Foundation of Henan Province(No.202300410355)Young Talent Lifting Project of the China Association for Science and Technology(No.YESS20200241).
文摘High-entropy rare-earth aluminate(Y_(0.2)Yb_(0.2)Lu_(0.2)Eu_(0.2)Er_(0.2))_(3)Al_(5)O_(12)(HE-RE_(3)Al_(5)O_(12))has been considered as a promising thermal protection coating(TPC)material based on its low thermal conductivity and close thermal expansion coefficient to that of Al2O3.However,such a coating has not been experimentally prepared,and its thermal protection performance has not been evaluated.To prove the feasibility of utilizing HE-RE_(3)Al_(5)O_(12) as a TPC,HE-RE_(3)Al_(5)O_(12) coating was deposited on a nickelbased superalloy for the first time using the atmospheric plasma spraying technique.The stability,surface,and cross-sectional morphologies,as well as the fracture surface of the HE-RE_(3)Al_(5)O_(12) coating were investigated,and the thermal shock resistance was evaluated using the oxyacetylene flame test.The results show that the HE-RE_(3)Al_(5)O_(12) coating can remain intact after 50 cycles at 1200℃ for 200 s,while the edge peeling phenomenon occurs after 10 cycles at 1400℃ for 200 s.This study clearly demonstrates that HE-RE_(3)Al_(5)O_(12) coating is effective for protecting the nickel-based superalloy,and the atmospheric plasma spraying is a suitable method for preparing this kind of coatings.
基金support received from National Natural Science Foundation of China(Grant No.52002355)National Key Laboratory Foundation of Science and Technology on Materials under Shock and Impact(Grant No.6142902200202)+2 种基金China Postdoctoral Science Foundation(Grant No.2019M652569)Key Scientific Research Project of Colleges and Universities in Henan Province(Grant No.20A430025)Henan Province Association for Science and Technology Young Talents Lifting Project(Grant No.2020HYTP021)。
文摘Perovskite functional ceramics have been widely applied for thermal protection owing to their unique physical properties.However,formation of oxygen vacancies under external stimuli usually limits their performance in practical applications.Therefore,the mechanism of the effect of oxygen vacancy on the layer structure of perovskite La_(0.9)Sr_(0.1)TiO_(3+δ)was investigated by experiments and first-principles simulations.The experimental results showed that the lattice distortion occurred in oxygen-deficient environment to give a longer c-axis,along with a significant adjustment in the modes of A/B–O bond vibration,resulting in lower reflectivity.Advanced transmission electron microscopy studies revealed that oxygen vacancies induced localized atomic rearrangements via[TiO_(6)]layer movements to adapt to the lattice distortion.This eventually restructured a part of the layer interfaces by expanding the overlapping projection of atoms in the c-axial direction.The specific transformation process was described as a compendious process,while geometric phase analysis effectively clarified how oxygen vacancies can inhibit reflectivity on the layer structure.Thus,this study provides effective approaches for researching the effects of oxygen vacancy on the physical properties of orthorhombic layer perovskite structures,which may facilitate the development of perovskite-based functional devices.
