High-purity titanium powder was prepared by molten salt electrorefining from sponge titanium in NaCl-KCl-TiClx salts. The titanium valence, purity and electrocrystallization during electrolysis process were studied. T...High-purity titanium powder was prepared by molten salt electrorefining from sponge titanium in NaCl-KCl-TiClx salts. The titanium valence, purity and electrocrystallization during electrolysis process were studied. The XPS analysis showed that the titanium valences are mainly ＋4, ＋3 and ＋2 at the earlier, medium and later stages of electrolysis, respectively. During the electrolysis process, the contents of impurities Si, Cr, Mn, Al vary little, and the contents of impurities Fe, Cu, Ni decrease markedly, while the contents of impurities O, N, H increase obviously. The residual impurities are usually distributed in small tunnel of dendritic crystals. Enhancing the electrolysis temperature and prolonging the electrolysis time can increase the titanium particle size. The TEM analysis showed that the electrodeposited titanium is not a single crystal, but contains many nanostructured grains and subgrains, with grain size of 100-500 nm. The electrolysis mechanisms were also discussed.展开更多
It is practically difficult to find titanium sponges with low and stable aluminum impurities on the market even though it is the precondition to prepare high-purity titanium. Analysis indicates that almost all the alu...It is practically difficult to find titanium sponges with low and stable aluminum impurities on the market even though it is the precondition to prepare high-purity titanium. Analysis indicates that almost all the aluminum impurities in the titanium sponge are inherited from the magnesium used to reduce titanium tetrachloride. However, it remains elusive for decades why magnesium produced through the silicothermic reduction method contains a high content of aluminum impurities with large fluctuations. By recourse to thermodynamic calculations and comparative experiments, we demonstrate that fluorite, a material used as a catalyst in the silicothermic reduction method to produce magnesium, is the chief culprit for the pest aluminum and propose a mechanism to rationalize the observed phenomena. Our findings indicate that one practical way to produce qualified magnesium for the production of high-purity titanium is to abandon fluorite during the production of magnesium with the silicothermic reduction method.展开更多
TiClx （x=2.17） was prepared by using titanium sponge to reduce the concentration of TiCl4 in a NaCl-KCl melt under negative pressure. The as-prepared NaCl-KCl-TiClx melt was employed as the electrolyte, and two para...TiClx （x=2.17） was prepared by using titanium sponge to reduce the concentration of TiCl4 in a NaCl-KCl melt under negative pressure. The as-prepared NaCl-KCl-TiClx melt was employed as the electrolyte, and two parallel crude titanium plates and one high-purity titanium plate were used as the anode and cathode, respectively. A series of electrochemical tests were performed to investigate the influence of electrolytic parameters on the current efficiency and quality of cathodic products. The results indicated that the quality of cathodic products was related to the current efficiency, which is significantly dependent on the current density and the initial concentration of titanium ions. The significance of this study is the attainment of high-purity titanium with a low oxygen content of 30× 10^-6.展开更多
A high-purity Ti sheet with dense preexisting twins(introduced by 10%cold rolling)was subjected to isochronal annealing at 500–800°C for 1 h and isothermal annealing at 600°C for 0.17–100 h,respectively.By...A high-purity Ti sheet with dense preexisting twins(introduced by 10%cold rolling)was subjected to isochronal annealing at 500–800°C for 1 h and isothermal annealing at 600°C for 0.17–100 h,respectively.By mainly utilizing electron backscatter diffraction(EBSD)and electron channel contrast(ECC)imaging techniques,the microstructure and texture evolution during the isochronal and isothermal annealing were investigated systematically.Results show that recrystallization nuclei appear in the specimen annealed at 600°C for 1 h.In contrast,recrystallization cannot be initiated for those annealed at lower temperatures or for a shorter time.With the increase in temperature or time,the fraction of the recrystallized structure increases with gradual grain coarsening.Nearly complete recrystallization is reached after 800°C-1 h or 600°C-100 h annealing.Due to the distribution heterogeneity of microstructure and stored energy induced by the dense preexisting twins,recrystallization nucleation preferentially occurs in some specific regions(twin-twin or twin-grain boundary junctions).Then,they selectively consume twin lamellar structures,leading to non-uniform grain growth.It is demonstrated that the recrystallization nucleation is dominated by the strain-induced boundary migration mechanism,allowing scattered texture components corresponding to the twin lamellar structures to be gradually encroached by those untwinned structures with the initial bimodal basal texture(BBT).Eventually,a strong BBT is always obtained after sufficient recrystallization.展开更多
High-purity indium finds extensive application in the aerospace,electronics,medical,energy,and national defense sectors.Its purity and impurity contents significantly influence its performance in these applications.Hi...High-purity indium finds extensive application in the aerospace,electronics,medical,energy,and national defense sectors.Its purity and impurity contents significantly influence its performance in these applications.High-purity indium was prepared by combining zone refining with vacuum distillation.Results show that the average removal efficiency of impurity Sb can approach 95%,while the removal efficiency of impurities Sn and Bi can reach over 95%,and the removal efficiency of Si,Fe,Ni,and Pb can reach over 85%.Ultimately,the amount of Sn and Sb impurities is reduced to 2.0 and 4.1μg/kg,respectively,and that of most impurities,including Fe,Ni,Pb,and Bi,is reduced to levels below the instrumental detection limit.The average impurity removal efficiency is 90.9%,and the indium purity reaches 7N9.展开更多
High-purity antimony(Sb)is essential for industries like semiconductors and photovoltaics,driving research on its production.This review summarizes research advances in production and preparation techniques for high-p...High-purity antimony(Sb)is essential for industries like semiconductors and photovoltaics,driving research on its production.This review summarizes research advances in production and preparation techniques for high-purity Sb.Three process flowcharts to produce high-purity Sb are described according to different raw materials.Various process parameters of vacuum distillation,zone refining purification techniques and research progress in the field of high-purity Sb are discussed.Numerical simulation,atomic scale simulation,and research progress of alloying elements in the field of high-purity Sb are highlighted.It is shown that for the difficult removal of As element in Sb,the addition of Al makes the regional refining process more effective in reducing the arsenic content.Finally,the purification of high-purity Sb is summarized,providing insights into achieving efficient and environmentally friendly high-purity Sb production and outlining future directions.展开更多
High-purity silver(Ag)is extensively utilized in electronics,aerospace,and other advanced industries due to its excellent thermal conductivity,electrical conductivity,and machinability.However,the prohibitive material...High-purity silver(Ag)is extensively utilized in electronics,aerospace,and other advanced industries due to its excellent thermal conductivity,electrical conductivity,and machinability.However,the prohibitive material cost poses substantial challenges for optimizing thermal processing parameters through repetitive experimental trials.In this work,hot compression experiments on high-purity silver were conducted using a Gleeble-3800 thermal simulator.The high temperature deformation behaviors,dynamic recovery(DRV)and dynamic recrystallization(DRX)of high-purity silver were studied by constructing an Arrhenius constitutive equation and developing thermal processing maps.The results show that plastic instability of high-purity silver occurs at high strain rates and the optimized hot processing parameters are the strain rate below 0.001 s^(−1) and the temperature of 340−400℃.Microstructural observations exhibit that DRV prefers to occur at lower deformation temperatures(e.g.,250℃).This is attributed to the low stacking fault energy of high-purity silver,which facilitates the decomposition of dislocations into partial dislocations and promotes high-density dislocation accumulation.Furthermore,DRX in high-purity silver becomes increasingly pronounced with increasing deformation temperature and reaches saturation at 350℃.展开更多
The rapid growth of semiconductor,photovoltaic,and other emerging industries has led to a sharp increase in the demand for high-purity quartz in China,particularly 4N5-grade(99.995%pure SiO_(2)).However,heavy reliance...The rapid growth of semiconductor,photovoltaic,and other emerging industries has led to a sharp increase in the demand for high-purity quartz in China,particularly 4N5-grade(99.995%pure SiO_(2)).However,heavy reliance on imported high-purity quartz poses a significant risk to the security of key national strategic industries.To address this challenge,China is focusing on identifying domestic sources of high-purity quartz and developing efficient evaluation methods.This study investigates the inclusion content in three types of quartz:pegmatite,vein quartz,and white granite.A grading system based on the transmittance of quartz grains was established by analyz-ing the number of inclusions.Five quartz ore samples from different regions were purified,and the resulting concentrates were analyzed using inductively coupled plasma mass spectrometry(ICP-MS).The relationships among the inclusion content of raw quartz,impurity composition of purified quartz,and quality of sintered fused quartz products were examined.The findings demonstrate that quartz with fewer inclusions results in lower impurity levels after purification,higher SiO_(2)purity,and more translucent glass,as confirmed by firing tests.Herein,this study establishes a clear connection between quartz inclusions and the overall quality of high-purity quartz.The pro-posed approach enables the rapid assessment of quartz deposit quality by identifying inclusions,offering a practical and efficient method for locating high-quality quartz resources.展开更多
Two-dimensional(2D)nitride MXenes are predicted to exhibit exceptional metallic properties and high polarity;however,their synthesis remains challenging.Research has relied on traditional molten salt etching,highlight...Two-dimensional(2D)nitride MXenes are predicted to exhibit exceptional metallic properties and high polarity;however,their synthesis remains challenging.Research has relied on traditional molten salt etching,highlighting the need for a scalable,high-purity approach.Here,we present the first solution-based synthesis of Ti_(4)N_(3)T_(x)MXene via a novel saturated salt solution(S^(3))etching technique employing alkali metal salts.By optimizing the sintering process for high-purity Ti_(4)AlN_(3)MAX and refining the S^(3)etching route,we significantly reduced the etch pit density to 1.2×10^(6)cm^(-2)and lowered the etch pit formation rate to 4%,yielding high-quality,phasepure Ti_(4)N_(3)T_(x)MXene.Our study highlights the critical role of alkali metal ions in selective A-layer removal and demonstrates the impressive electrical conductivity and electromagnetic interference shielding performance of 2D nitride MXene,setting a new benchmark for this underexplored material.These findings pave the way for advancing 2D nitride MXenes and their diverse applications.展开更多
Titanium exhibits outstanding properties,particularly,high specific strength and resistance to both high and low temperatures,earning it a reputation as the metal of the future.However,because of the highly reactive n...Titanium exhibits outstanding properties,particularly,high specific strength and resistance to both high and low temperatures,earning it a reputation as the metal of the future.However,because of the highly reactive nature of titanium,metallic titanium production involves extensive procedures and high costs.Considering its advantages and limitations,the European Union has classified titanium metal as a critical raw material(CRM)of low category.The Kroll process is predominantly used to produce titanium;however,molten salt electrolysis(MSE)is currently being explored for producing metallic titanium at a low cost.Since 2000,electrolytic titanium production has undergone a wave of technological advancements.However,because of the intermediate and disproportionation reactions in the electrolytic titanium production process,the process efficiency and titanium purity according to industrial standards could not be achieved.Consequently,metallic titanium production has gradually diversified into employing technologies such as thermal reduction,MSE,and titanium alloy preparation.This study provides a comprehensive review of research advances in titanium metal preparation technologies over the past two decades,highlighting the challenges faced by the existing methods and proposing potential solutions.It offers useful insights into the development of low-cost titanium preparation technologies.展开更多
The direct transformation of dinitrogen(N_(2)) into nitrogen-containing organic compounds holds substantial importance.In this work,we report a titanium-promoted method for the conversion of N_(2) to N-methylimides.In...The direct transformation of dinitrogen(N_(2)) into nitrogen-containing organic compounds holds substantial importance.In this work,we report a titanium-promoted method for the conversion of N_(2) to N-methylimides.Initially,the N_(2)-bridging end-on dititanium side-on dipotassium complex[{(Tren^(TMS))Ti}_(2)(μ-η^(1):η^(1):η^(2):η^(2)-N_(2)K_(2))] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate(Me OTf),yielding [{(N^(Me,TMS)NN^(TMS)_(2))Ti}(μ-NMe)]_(2) with complete cleavage of the N≡N bond.The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane(TMSCl) to form heptamethyldisilazane,or with acyl chlorides to generate N-methylimides.Moreover,nitrogen-15(^(15)N) labeled experiments provided a novel approach to synthesizing ^(15)N-labeled methylimides.展开更多
Ti-5Al-5Mo-5Cr-2Zr-xNb with different Nb(abbreviated as Ti-5552-xNb,x=3,6,9,12,wt.%)contents were stretched at 923 K to study their superplastic behavior and mechanical properties below recrystallization temperature.T...Ti-5Al-5Mo-5Cr-2Zr-xNb with different Nb(abbreviated as Ti-5552-xNb,x=3,6,9,12,wt.%)contents were stretched at 923 K to study their superplastic behavior and mechanical properties below recrystallization temperature.The microstructure of as-cast Ti-5552-xNb alloy is consisted of a singleβphase,and theβgrain size increases slightly with the increase of Nb content.The thermal effect in the process of high temperature drawing leads to the precipitation ofαphase.The addition of Nb in Ti-5552 titanium alloys reduces theα/βphase transformation temperature,which causes a decrease in the volume fraction ofαphase.Reducing theαphase content reduces incompatibility,but too low a proportion ofαphase will lead to premature fracture,so tensile strength and plasticity firstly increase and then decrease.The results show that Ti-5552-9Nb titanium alloy shows the best tensile strength(307.2 MPa)and superplasticity(106%).The superplastic mechanism of Ti-5552-9Nb alloy is mainly caused by relative sliding ofβgrain boundaries and dislocation movement.展开更多
During electrochemical machining(ECM),the passivation film formed on the surface of titanium alloy can lead to uneven dissolution and pitting.Solid particle erosion can effectively remove this passivation film.In this...During electrochemical machining(ECM),the passivation film formed on the surface of titanium alloy can lead to uneven dissolution and pitting.Solid particle erosion can effectively remove this passivation film.In this paper,the electrochemical dissolution behavior of Ti-6.5Al-2Zr-1Mo-1V(TA15)titanium alloy at without particle impact,low(15°)and high(90°)angle particle impact was investigated,and the influence of Al_(2)O_(3)particles on ECM was systematically expounded.It was found that under the condition of no particle erosion,the surface of electrochemically processed titanium alloy had serious pitting corrosion due to the influence of the passivation film,and the surface roughness(Sa)of the local area reached 10.088μm.Under the condition of a high-impact angle(90°),due to the existence of strain hardening and particle embedding,only the edge of the surface is dissolved,while the central area is almost insoluble,with the surface roughness(S_(a))reaching 16.086μm.On the contrary,under the condition of a low-impact angle(15°),the machining efficiency and surface quality of the material were significantly improved due to the ploughing effect and galvanic corrosion,and the surface roughness(S_(a))reached 2.823μm.Based on these findings,the electrochemical dissolution model of TA15 titanium alloy under different particle erosion conditions was established.展开更多
Titanium plates with a Ti−O solid solution surface-hardened layer were cold roll-bonded with 304 stainless steel plates with high work hardening rates.The evolution and mechanisms affecting the interfacial bonding str...Titanium plates with a Ti−O solid solution surface-hardened layer were cold roll-bonded with 304 stainless steel plates with high work hardening rates.The evolution and mechanisms affecting the interfacial bonding strength in titanium/stainless steel laminated composites were investigated.Results indicate that the hardened layer reduces the interfacial bonding strength from over 261 MPa to less than 204 MPa.During the cold roll-bonding process,the hardened layer fractures,leading to the formation of multi-scale cracks that are difficult for the stainless steel to fill.This not only hinders the development of an interlocking interface but also leads to the presence of numerous microcracks and hardened blocks along the nearly straight interface,consequently weakening the interfacial bonding strength.In metals with high work hardening rates,the conventional approach of enhancing interface interlocking and improving interfacial bonding strength by using a surface-hardened layer becomes less effective.展开更多
A novel purification process based on mixer-settlers for high-purity NdClwas developed. Acidic solution and pure NdClsolution were compared to scrub the less-extractable rare earths(REs)(La, Ce, and Pr)from loaded org...A novel purification process based on mixer-settlers for high-purity NdClwas developed. Acidic solution and pure NdClsolution were compared to scrub the less-extractable rare earths(REs)(La, Ce, and Pr)from loaded organic phase. The extractant with low-degree saponification was evaluated to remove the more-extractable element(Sm). Then the RE impurities(La, Ce, Pr, and Sm) in Nd were purified by an integrated process. Furthermore, effect of smuggling behavior on the purification of NdClin mixersettlers was studied. Based on the investigation mentioned above, the pilot-scale purification process for NdClwith a purity of 99.999% was developed, and the total recovery was about 99%.展开更多
Eastern Qinling,China is one of the important rare metal metallogenic provinces with extensively distributed granite pegmatite dikes.The No.5 granite pegmatite intruded into the granitic gneiss of the Qinling Group,an...Eastern Qinling,China is one of the important rare metal metallogenic provinces with extensively distributed granite pegmatite dikes.The No.5 granite pegmatite intruded into the granitic gneiss of the Qinling Group,and the major minerals are quartz(39.8%),K-feldspar(18.8%),albite(36.3%),muscovite(3.4%),and garnet(1.1%).Monazite U–Pb isotopic dating indicates that the No.5 pegmatite from the Eastern Qinling was emplaced at ca.420.2±2.2 Ma,which confirms that highpurity quartz mineralization probably formed during the Early Devonian.In-situ laser ablation inductively coupled plasma mass spectrometry analysis of quartz show that quartz samples from Eastern Qinling have total trace element concentrations(Al,Ti,Sc,Li,B,Cr,Mn,and Fe)ranging from 23.2 to 52.8 ppm,slightly higher than the quartz(impurity element content from 13.4 to 25.9 ppm)of the Spruce Pine high-purity quartz deposit in western North Carolina.The No.5 pegmatite of Eastern Qinling could be defined as one high-purity quartz deposit of China.展开更多
A new process for preparing high-purity iron(HPI)was proposed,and it was investigated by laboratory experiments and pilot tests.The results show that under conditions of a reduced temperature of 1075°C,reduced ti...A new process for preparing high-purity iron(HPI)was proposed,and it was investigated by laboratory experiments and pilot tests.The results show that under conditions of a reduced temperature of 1075°C,reduced time of 5 h,and CaO content of 2.5wt%,a DRI with a metallization rate of 96.5%was obtained through coal-based direct reduction of ultra-high-grade iron concentrate.Then,an HPI with a Fe purity of 99.95%and C,Si,Mn,and P contents as low as 0.0008wt%,0.0006wt%,0.0014wt%,and 0.0015wt%,respectively,was prepared by smelting separation of the DRI using a smelting temperature of 1625°C,smelting time of 45 min,and CaO content of 9.3wt%.The product of the pilot test with a scale of 0.01 Mt/a had a lower impurity content than the Chinese industry standard.An HPI with a Fe purity of 99.98wt%can be produced through the direct reduction?smelting separation of ultra-high-grade iron concentrate at relatively low cost.The proposed process shows a promising prospect for application in the future.展开更多
High-purity magnesium(HP Mg)and Mg-1Ca,as representations of Mg-matrix implants produced by purifying and alloying,are employed in biomedical applications primarily because of their bioactivity and degradability.The s...High-purity magnesium(HP Mg)and Mg-1Ca,as representations of Mg-matrix implants produced by purifying and alloying,are employed in biomedical applications primarily because of their bioactivity and degradability.The superiority of both degradation properties,the match between degradation and osteo-genesis in vivo,and biosafety are critical problems that will decide future purifying or alloying to construct Mg-based implants and promote clinical translation.The present study investigated the benefits and limitations of degradation behavior and biosafety of HP Mg and Mg-1Ca according to the electro-chemical experiment,hydrogen evolution test,immersion test,and in vivo bone implantation assay.The results indicated that due to its Mg 2 Ca phase,Mg-1Ca exhibited a considerably higher corrosion current density and hydrogen production than HP Mg in vitro.Furthermore,HP Mg and Mg-1Ca display a favorable match between their degradation and the surrounding osteogenesis,resulting in no significant variation in degradation in vivo during 26 weeks.Additionally,the implantation and degradation of HP Mg and Mg-1Ca do not result in major organ dysfunction or pathological abnormalities.This work is expected to lay the foundation for future clinical translation of Mg and Mg alloy orthopedic implants.展开更多
The effects of various contaminants in the electrolytic refinement of indium were investigated using a glow discharge mass spectrometer(GDMS).The effects of several factors such as the indium ion(In3+)concentration,th...The effects of various contaminants in the electrolytic refinement of indium were investigated using a glow discharge mass spectrometer(GDMS).The effects of several factors such as the indium ion(In3+)concentration,the sodium chloride(NaCl)concentration,the current density,the gelatin concentration,the pH,and the electrode distance,were examined.Significant variations in impurity levels concerning gelatin concentration were observed.Both the gelatin and In3+concentration were moderately positively correlated with the Pb content.The Sb concentration was associated positively with the NaCl concentration,while the Ti concentration had an adverse correlation with the NaCl concentration.The Bi element content was positively linked to the electrode distance.As the current density increased,Cu,Pb,and Bi impurities initially rose and then eventually declined.Notably,a critical current density of 45 A·m^(-2) was identified in this behavior.展开更多
A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted u...A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.展开更多
基金Project(20110942K)supported by Open Fund of State Key Laboratory of Powder Metallurgy,ChinaProject(51021063)supported by the National Natural Science Foundation of China
文摘High-purity titanium powder was prepared by molten salt electrorefining from sponge titanium in NaCl-KCl-TiClx salts. The titanium valence, purity and electrocrystallization during electrolysis process were studied. The XPS analysis showed that the titanium valences are mainly ＋4, ＋3 and ＋2 at the earlier, medium and later stages of electrolysis, respectively. During the electrolysis process, the contents of impurities Si, Cr, Mn, Al vary little, and the contents of impurities Fe, Cu, Ni decrease markedly, while the contents of impurities O, N, H increase obviously. The residual impurities are usually distributed in small tunnel of dendritic crystals. Enhancing the electrolysis temperature and prolonging the electrolysis time can increase the titanium particle size. The TEM analysis showed that the electrodeposited titanium is not a single crystal, but contains many nanostructured grains and subgrains, with grain size of 100-500 nm. The electrolysis mechanisms were also discussed.
基金the support from the National Natural Science Foundation of China (No.52031011)funding from the Science and Technology Departments of Shaanxi and Xi’an,China (Nos.2021GXLH-Z-015,2016KTZDGY-04-04 and 201805064ZD15CG48)。
文摘It is practically difficult to find titanium sponges with low and stable aluminum impurities on the market even though it is the precondition to prepare high-purity titanium. Analysis indicates that almost all the aluminum impurities in the titanium sponge are inherited from the magnesium used to reduce titanium tetrachloride. However, it remains elusive for decades why magnesium produced through the silicothermic reduction method contains a high content of aluminum impurities with large fluctuations. By recourse to thermodynamic calculations and comparative experiments, we demonstrate that fluorite, a material used as a catalyst in the silicothermic reduction method to produce magnesium, is the chief culprit for the pest aluminum and propose a mechanism to rationalize the observed phenomena. Our findings indicate that one practical way to produce qualified magnesium for the production of high-purity titanium is to abandon fluorite during the production of magnesium with the silicothermic reduction method.
基金the National Science Foundation of China(Nos.50934001 and 51322402)the National High-Tech Research and Development Program of China (No.2012AA062302)+2 种基金the Program of the Co-construction with Beijing Municipal Commission of Education of China (Nos.00012047 and 00012085)the Program for New Century Excellent Talents in Universities(NCET-11-0577)the Fundamental Research Funds for the Central Universities(No.FRF-AS-11-003A)
文摘TiClx （x=2.17） was prepared by using titanium sponge to reduce the concentration of TiCl4 in a NaCl-KCl melt under negative pressure. The as-prepared NaCl-KCl-TiClx melt was employed as the electrolyte, and two parallel crude titanium plates and one high-purity titanium plate were used as the anode and cathode, respectively. A series of electrochemical tests were performed to investigate the influence of electrolytic parameters on the current efficiency and quality of cathodic products. The results indicated that the quality of cathodic products was related to the current efficiency, which is significantly dependent on the current density and the initial concentration of titanium ions. The significance of this study is the attainment of high-purity titanium with a low oxygen content of 30× 10^-6.
基金financially supported by the Cultivation Project of CQUT for Research and Innovation Group(No.2023TDZ006)the Graduate Student Innovation Program of CQUT(No.CYS23648)the Postdoctoral Science Foundation of China(No.2021M690174)。
文摘A high-purity Ti sheet with dense preexisting twins(introduced by 10%cold rolling)was subjected to isochronal annealing at 500–800°C for 1 h and isothermal annealing at 600°C for 0.17–100 h,respectively.By mainly utilizing electron backscatter diffraction(EBSD)and electron channel contrast(ECC)imaging techniques,the microstructure and texture evolution during the isochronal and isothermal annealing were investigated systematically.Results show that recrystallization nuclei appear in the specimen annealed at 600°C for 1 h.In contrast,recrystallization cannot be initiated for those annealed at lower temperatures or for a shorter time.With the increase in temperature or time,the fraction of the recrystallized structure increases with gradual grain coarsening.Nearly complete recrystallization is reached after 800°C-1 h or 600°C-100 h annealing.Due to the distribution heterogeneity of microstructure and stored energy induced by the dense preexisting twins,recrystallization nucleation preferentially occurs in some specific regions(twin-twin or twin-grain boundary junctions).Then,they selectively consume twin lamellar structures,leading to non-uniform grain growth.It is demonstrated that the recrystallization nucleation is dominated by the strain-induced boundary migration mechanism,allowing scattered texture components corresponding to the twin lamellar structures to be gradually encroached by those untwinned structures with the initial bimodal basal texture(BBT).Eventually,a strong BBT is always obtained after sufficient recrystallization.
基金National Key Research and Development Program of China(2023YFC2907904)National Natural Science Foundation of China(52374364)。
文摘High-purity indium finds extensive application in the aerospace,electronics,medical,energy,and national defense sectors.Its purity and impurity contents significantly influence its performance in these applications.High-purity indium was prepared by combining zone refining with vacuum distillation.Results show that the average removal efficiency of impurity Sb can approach 95%,while the removal efficiency of impurities Sn and Bi can reach over 95%,and the removal efficiency of Si,Fe,Ni,and Pb can reach over 85%.Ultimately,the amount of Sn and Sb impurities is reduced to 2.0 and 4.1μg/kg,respectively,and that of most impurities,including Fe,Ni,Pb,and Bi,is reduced to levels below the instrumental detection limit.The average impurity removal efficiency is 90.9%,and the indium purity reaches 7N9.
文摘High-purity antimony(Sb)is essential for industries like semiconductors and photovoltaics,driving research on its production.This review summarizes research advances in production and preparation techniques for high-purity Sb.Three process flowcharts to produce high-purity Sb are described according to different raw materials.Various process parameters of vacuum distillation,zone refining purification techniques and research progress in the field of high-purity Sb are discussed.Numerical simulation,atomic scale simulation,and research progress of alloying elements in the field of high-purity Sb are highlighted.It is shown that for the difficult removal of As element in Sb,the addition of Al makes the regional refining process more effective in reducing the arsenic content.Finally,the purification of high-purity Sb is summarized,providing insights into achieving efficient and environmentally friendly high-purity Sb production and outlining future directions.
基金Project(52274369)supported by the National Natural Science Foundation of China。
文摘High-purity silver(Ag)is extensively utilized in electronics,aerospace,and other advanced industries due to its excellent thermal conductivity,electrical conductivity,and machinability.However,the prohibitive material cost poses substantial challenges for optimizing thermal processing parameters through repetitive experimental trials.In this work,hot compression experiments on high-purity silver were conducted using a Gleeble-3800 thermal simulator.The high temperature deformation behaviors,dynamic recovery(DRV)and dynamic recrystallization(DRX)of high-purity silver were studied by constructing an Arrhenius constitutive equation and developing thermal processing maps.The results show that plastic instability of high-purity silver occurs at high strain rates and the optimized hot processing parameters are the strain rate below 0.001 s^(−1) and the temperature of 340−400℃.Microstructural observations exhibit that DRV prefers to occur at lower deformation temperatures(e.g.,250℃).This is attributed to the low stacking fault energy of high-purity silver,which facilitates the decomposition of dislocations into partial dislocations and promotes high-density dislocation accumulation.Furthermore,DRX in high-purity silver becomes increasingly pronounced with increasing deformation temperature and reaches saturation at 350℃.
基金financially supported by the Consulting Research Project of the Chinese Academy of Engineering,China(Nos.2024-XBZD-10 and 2024-XZ-20).
文摘The rapid growth of semiconductor,photovoltaic,and other emerging industries has led to a sharp increase in the demand for high-purity quartz in China,particularly 4N5-grade(99.995%pure SiO_(2)).However,heavy reliance on imported high-purity quartz poses a significant risk to the security of key national strategic industries.To address this challenge,China is focusing on identifying domestic sources of high-purity quartz and developing efficient evaluation methods.This study investigates the inclusion content in three types of quartz:pegmatite,vein quartz,and white granite.A grading system based on the transmittance of quartz grains was established by analyz-ing the number of inclusions.Five quartz ore samples from different regions were purified,and the resulting concentrates were analyzed using inductively coupled plasma mass spectrometry(ICP-MS).The relationships among the inclusion content of raw quartz,impurity composition of purified quartz,and quality of sintered fused quartz products were examined.The findings demonstrate that quartz with fewer inclusions results in lower impurity levels after purification,higher SiO_(2)purity,and more translucent glass,as confirmed by firing tests.Herein,this study establishes a clear connection between quartz inclusions and the overall quality of high-purity quartz.The pro-posed approach enables the rapid assessment of quartz deposit quality by identifying inclusions,offering a practical and efficient method for locating high-quality quartz resources.
基金supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(Grant No.RS-2024-00408180)by Institute for Basic Science(No.IBS-R019-G1).
文摘Two-dimensional(2D)nitride MXenes are predicted to exhibit exceptional metallic properties and high polarity;however,their synthesis remains challenging.Research has relied on traditional molten salt etching,highlighting the need for a scalable,high-purity approach.Here,we present the first solution-based synthesis of Ti_(4)N_(3)T_(x)MXene via a novel saturated salt solution(S^(3))etching technique employing alkali metal salts.By optimizing the sintering process for high-purity Ti_(4)AlN_(3)MAX and refining the S^(3)etching route,we significantly reduced the etch pit density to 1.2×10^(6)cm^(-2)and lowered the etch pit formation rate to 4%,yielding high-quality,phasepure Ti_(4)N_(3)T_(x)MXene.Our study highlights the critical role of alkali metal ions in selective A-layer removal and demonstrates the impressive electrical conductivity and electromagnetic interference shielding performance of 2D nitride MXene,setting a new benchmark for this underexplored material.These findings pave the way for advancing 2D nitride MXenes and their diverse applications.
基金financial support from the Yunnan Province Key Industries Science and Technology Special Project for Colleges and UniversitiesChina(No.FWCY-QYCT2024006)+6 种基金National Natural Science Foundation of China(Nos.52104351 and 52364051)Science and Technology Major Project of Yunnan Province,China(No.202202AG050007)the Yunnan Fundamental Research ProjectsChina(No.202401AT070314)the Key Technology Research and Development Program of Shandong Province,China(No.2023CXGC010903)Central Guidance Local Scientific and Technological Development Funds,China(No.202407AB110022)Yunnan Province Xingdian Talent Support Plan Project,China。
文摘Titanium exhibits outstanding properties,particularly,high specific strength and resistance to both high and low temperatures,earning it a reputation as the metal of the future.However,because of the highly reactive nature of titanium,metallic titanium production involves extensive procedures and high costs.Considering its advantages and limitations,the European Union has classified titanium metal as a critical raw material(CRM)of low category.The Kroll process is predominantly used to produce titanium;however,molten salt electrolysis(MSE)is currently being explored for producing metallic titanium at a low cost.Since 2000,electrolytic titanium production has undergone a wave of technological advancements.However,because of the intermediate and disproportionation reactions in the electrolytic titanium production process,the process efficiency and titanium purity according to industrial standards could not be achieved.Consequently,metallic titanium production has gradually diversified into employing technologies such as thermal reduction,MSE,and titanium alloy preparation.This study provides a comprehensive review of research advances in titanium metal preparation technologies over the past two decades,highlighting the challenges faced by the existing methods and proposing potential solutions.It offers useful insights into the development of low-cost titanium preparation technologies.
基金Financial supports from the National Natural Science Foundation of China (Nos.22025109,22371283)the National Key R&D Program of China (No.2023YFA1507902)+1 种基金CAS Project for Young Scientists in Basic Research (No.YSBR-050)the State Key Laboratory of Fine Chemicals,Dalian University of Technology (No.KF2102) are gratefully acknowledged。
文摘The direct transformation of dinitrogen(N_(2)) into nitrogen-containing organic compounds holds substantial importance.In this work,we report a titanium-promoted method for the conversion of N_(2) to N-methylimides.Initially,the N_(2)-bridging end-on dititanium side-on dipotassium complex[{(Tren^(TMS))Ti}_(2)(μ-η^(1):η^(1):η^(2):η^(2)-N_(2)K_(2))] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate(Me OTf),yielding [{(N^(Me,TMS)NN^(TMS)_(2))Ti}(μ-NMe)]_(2) with complete cleavage of the N≡N bond.The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane(TMSCl) to form heptamethyldisilazane,or with acyl chlorides to generate N-methylimides.Moreover,nitrogen-15(^(15)N) labeled experiments provided a novel approach to synthesizing ^(15)N-labeled methylimides.
基金the financial support by the Major Science and Technology Achievement Transformation Project in Heilongjiang Province(ZC2023SH0075)the National Natural Science Foundation of China(52425401,U2441255,52474377,and 52371015)+1 种基金the Young Elite Scientists Sponsorship Program by·CAST(2021QNRC001)the Henan Provincial Key Research and Development&Promotion Special Program(251111231400)。
文摘Ti-5Al-5Mo-5Cr-2Zr-xNb with different Nb(abbreviated as Ti-5552-xNb,x=3,6,9,12,wt.%)contents were stretched at 923 K to study their superplastic behavior and mechanical properties below recrystallization temperature.The microstructure of as-cast Ti-5552-xNb alloy is consisted of a singleβphase,and theβgrain size increases slightly with the increase of Nb content.The thermal effect in the process of high temperature drawing leads to the precipitation ofαphase.The addition of Nb in Ti-5552 titanium alloys reduces theα/βphase transformation temperature,which causes a decrease in the volume fraction ofαphase.Reducing theαphase content reduces incompatibility,but too low a proportion ofαphase will lead to premature fracture,so tensile strength and plasticity firstly increase and then decrease.The results show that Ti-5552-9Nb titanium alloy shows the best tensile strength(307.2 MPa)and superplasticity(106%).The superplastic mechanism of Ti-5552-9Nb alloy is mainly caused by relative sliding ofβgrain boundaries and dislocation movement.
基金supported by the National Natural Science Foundation of China(No.52175414)the Natural Science Foundation of Jiangsu Province of China(No.BK20220134)+1 种基金the Fundamental Research Funds for the Central Universities,China(No.NE2023002)the Postgraduate Research&Practice Innovation Program of Jiangsu Province,China(No.KYCX24_0559)。
文摘During electrochemical machining(ECM),the passivation film formed on the surface of titanium alloy can lead to uneven dissolution and pitting.Solid particle erosion can effectively remove this passivation film.In this paper,the electrochemical dissolution behavior of Ti-6.5Al-2Zr-1Mo-1V(TA15)titanium alloy at without particle impact,low(15°)and high(90°)angle particle impact was investigated,and the influence of Al_(2)O_(3)particles on ECM was systematically expounded.It was found that under the condition of no particle erosion,the surface of electrochemically processed titanium alloy had serious pitting corrosion due to the influence of the passivation film,and the surface roughness(Sa)of the local area reached 10.088μm.Under the condition of a high-impact angle(90°),due to the existence of strain hardening and particle embedding,only the edge of the surface is dissolved,while the central area is almost insoluble,with the surface roughness(S_(a))reaching 16.086μm.On the contrary,under the condition of a low-impact angle(15°),the machining efficiency and surface quality of the material were significantly improved due to the ploughing effect and galvanic corrosion,and the surface roughness(S_(a))reached 2.823μm.Based on these findings,the electrochemical dissolution model of TA15 titanium alloy under different particle erosion conditions was established.
基金supported by the National Key R&D Program of China (No. 2018YFA0707300)the National Natural Science Foundation of China (No. 52374376)the Introduction Plan for High end Foreign Experts, China (No. G2023105001L)。
文摘Titanium plates with a Ti−O solid solution surface-hardened layer were cold roll-bonded with 304 stainless steel plates with high work hardening rates.The evolution and mechanisms affecting the interfacial bonding strength in titanium/stainless steel laminated composites were investigated.Results indicate that the hardened layer reduces the interfacial bonding strength from over 261 MPa to less than 204 MPa.During the cold roll-bonding process,the hardened layer fractures,leading to the formation of multi-scale cracks that are difficult for the stainless steel to fill.This not only hinders the development of an interlocking interface but also leads to the presence of numerous microcracks and hardened blocks along the nearly straight interface,consequently weakening the interfacial bonding strength.In metals with high work hardening rates,the conventional approach of enhancing interface interlocking and improving interfacial bonding strength by using a surface-hardened layer becomes less effective.
基金Project supported by'Hundreds Talents Program' from Chinese Academy of Sciences,Science and Technology Major Project of Fujian Province(2015HZ0001-3)National Natural Science Foundation of China(21571179)Science and Technology Major Project of Ganzhou(2017-8)
文摘A novel purification process based on mixer-settlers for high-purity NdClwas developed. Acidic solution and pure NdClsolution were compared to scrub the less-extractable rare earths(REs)(La, Ce, and Pr)from loaded organic phase. The extractant with low-degree saponification was evaluated to remove the more-extractable element(Sm). Then the RE impurities(La, Ce, Pr, and Sm) in Nd were purified by an integrated process. Furthermore, effect of smuggling behavior on the purification of NdClin mixersettlers was studied. Based on the investigation mentioned above, the pilot-scale purification process for NdClwith a purity of 99.999% was developed, and the total recovery was about 99%.
基金the National Natural Science Foundation of China(42062006 and 41962007)the National Key Research and Development Program of China(2016YFC0600207)+1 种基金the Project of China Geological Survey(DD20190186 and 12120114034501)the science and technology research project of Jiangxi Provincial Department of Education(GJJ190379)。
文摘Eastern Qinling,China is one of the important rare metal metallogenic provinces with extensively distributed granite pegmatite dikes.The No.5 granite pegmatite intruded into the granitic gneiss of the Qinling Group,and the major minerals are quartz(39.8%),K-feldspar(18.8%),albite(36.3%),muscovite(3.4%),and garnet(1.1%).Monazite U–Pb isotopic dating indicates that the No.5 pegmatite from the Eastern Qinling was emplaced at ca.420.2±2.2 Ma,which confirms that highpurity quartz mineralization probably formed during the Early Devonian.In-situ laser ablation inductively coupled plasma mass spectrometry analysis of quartz show that quartz samples from Eastern Qinling have total trace element concentrations(Al,Ti,Sc,Li,B,Cr,Mn,and Fe)ranging from 23.2 to 52.8 ppm,slightly higher than the quartz(impurity element content from 13.4 to 25.9 ppm)of the Spruce Pine high-purity quartz deposit in western North Carolina.The No.5 pegmatite of Eastern Qinling could be defined as one high-purity quartz deposit of China.
基金the National Natural Science Foundation of China(No.51904063)the Fundamental Research Funds for the Central Universities,China(Nos.N172503016,N172502005,and N172506011)the China Postdoctoral Science Foundation(No.2018M640259).
文摘A new process for preparing high-purity iron(HPI)was proposed,and it was investigated by laboratory experiments and pilot tests.The results show that under conditions of a reduced temperature of 1075°C,reduced time of 5 h,and CaO content of 2.5wt%,a DRI with a metallization rate of 96.5%was obtained through coal-based direct reduction of ultra-high-grade iron concentrate.Then,an HPI with a Fe purity of 99.95%and C,Si,Mn,and P contents as low as 0.0008wt%,0.0006wt%,0.0014wt%,and 0.0015wt%,respectively,was prepared by smelting separation of the DRI using a smelting temperature of 1625°C,smelting time of 45 min,and CaO content of 9.3wt%.The product of the pilot test with a scale of 0.01 Mt/a had a lower impurity content than the Chinese industry standard.An HPI with a Fe purity of 99.98wt%can be produced through the direct reduction?smelting separation of ultra-high-grade iron concentrate at relatively low cost.The proposed process shows a promising prospect for application in the future.
基金the Science and Technology Commission of Shanghai Municipality(18DZ2201500,19DZ2203900)Innovative Research Team of High-level Local Universities in Shanghai(SHSMU-ZLCX20212400)Research Disci-pline Fund(KQXJXK2021)from Ninth People’s Hospital,Shanghai Jiao Tong University School of Medicine,and College of Stomatology,Shanghai Jiao Tong University.
文摘High-purity magnesium(HP Mg)and Mg-1Ca,as representations of Mg-matrix implants produced by purifying and alloying,are employed in biomedical applications primarily because of their bioactivity and degradability.The superiority of both degradation properties,the match between degradation and osteo-genesis in vivo,and biosafety are critical problems that will decide future purifying or alloying to construct Mg-based implants and promote clinical translation.The present study investigated the benefits and limitations of degradation behavior and biosafety of HP Mg and Mg-1Ca according to the electro-chemical experiment,hydrogen evolution test,immersion test,and in vivo bone implantation assay.The results indicated that due to its Mg 2 Ca phase,Mg-1Ca exhibited a considerably higher corrosion current density and hydrogen production than HP Mg in vitro.Furthermore,HP Mg and Mg-1Ca display a favorable match between their degradation and the surrounding osteogenesis,resulting in no significant variation in degradation in vivo during 26 weeks.Additionally,the implantation and degradation of HP Mg and Mg-1Ca do not result in major organ dysfunction or pathological abnormalities.This work is expected to lay the foundation for future clinical translation of Mg and Mg alloy orthopedic implants.
基金supported by the National Natural Science Foundation of China(52074180)the Science and Technology Major Project of Yunnan Province(202302AB080020)+2 种基金the Independent Research Project of State Key Laboratory of Advanced Special Steel,Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(SKLASS 2023-Z07)the Science and Technology Commission of Shanghai Municipality(19DZ2270200)the Program for Professor of Special Appointment(Eastern Scholar)at SIHL,Shanghai Sailing Program(19YF1416500).
文摘The effects of various contaminants in the electrolytic refinement of indium were investigated using a glow discharge mass spectrometer(GDMS).The effects of several factors such as the indium ion(In3+)concentration,the sodium chloride(NaCl)concentration,the current density,the gelatin concentration,the pH,and the electrode distance,were examined.Significant variations in impurity levels concerning gelatin concentration were observed.Both the gelatin and In3+concentration were moderately positively correlated with the Pb content.The Sb concentration was associated positively with the NaCl concentration,while the Ti concentration had an adverse correlation with the NaCl concentration.The Bi element content was positively linked to the electrode distance.As the current density increased,Cu,Pb,and Bi impurities initially rose and then eventually declined.Notably,a critical current density of 45 A·m^(-2) was identified in this behavior.
基金supported by the Korea Evaluation Institute of Industrial Technology funded by the Korean Ministry of Industry in Korea (Project No.:20000970, 20–9805)Basic Research Project (22–3803) of the Korea Institute of Geoscience and Mineral Resources (KIGAM) funded by the Ministry of Science and ICT of Korea。
文摘A green and effective electrolytic process was developed to produce high-purity Mg metal using primary and secondary resources containing Mg O as a feedstock. The electrolysis of various Mg O resources was conducted using a Cu cathode in MgF2– LiF – KCl molten salt at 1043 K by applying an average current of 1.44 A for 12.5 h. The electrolysis of calcined North Korean magnesite and seawater Mg O clinker yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 89.6–92.4%. The electrolysis of oxidized Mg O-C refractory brick, aged ferronickel slag, and ferronickel slag yielded Mg alloys of MgCu2and(Cu) phases with current efficiencies of 59.3–92.3%. The vacuum distillation of Mg alloys obtained was conducted at 1300 K for 10 h to produce high-purity Mg metal. After vacuum distillation, Mg metal with a purity of above 99.994% was obtained. Therefore, this study demonstrates the feasibility of the production of high-purity Mg metal from various Mg O resources using a novel electrolytic process with a Cu cathode, followed by vacuum distillation.
