Control of the columnar to equiaxed transition(CET)is a major challenge in additively manufacturedβtitanium alloys.In this work,the promotion of CET was successfully achieved through in-situ fabrication of Ti-5Cu(wt....Control of the columnar to equiaxed transition(CET)is a major challenge in additively manufacturedβtitanium alloys.In this work,the promotion of CET was successfully achieved through in-situ fabrication of Ti-5Cu(wt.%)alloys with additions of 5,15,and 25 wt.%Nb using elemental Ti,Cu,and Nb powders by employing laser powder bed fusion(LPBF).The alloy containing 5 wt.%Nb consisted ofαlamellae,Ti2 Cu precipitates,and unmeltedβ-Nb inclusions,whereas the 25 wt.%Nb alloy consisted of equiaxedβgrains,ωprecipitates,and Ti2 Cu precipitates at the grain boundaries.In terms of mechanical proper-ties,despite the presence of Nb inclusions and liquation cracks in the 5 wt.%Nb alloy,it showed a yield strength of 1051±40 MPa and an elongation of 5.2%±1.3%.Both the strength and ductility decreased with increasing Nb content,e.g.,the 25 wt.%Nb alloy exhibited a yield strength of 808±53 MPa and an elongation of 1.6%±0.2%.As the Nb content increased from 5 to 25 wt.%,the Young’s modulus decreased from 110 to 65 GPa.The 25 wt.%Nb alloy showed a high ratio of hardness to Young’s mod-ulus(H/E)and yield pressure(H3/E2).However,due to its brittle nature,the material manifested high wear rates.These findings provide a basis for the future development of novel low-modulus isotropicβ-titanium alloys using LPBF.展开更多
The synthesis method of propargylamines has always been the focus of research in organic synthetic methodology.A method of alkynylation of tertiary aliphatic amines with alkynes in the presence of copper doped zeolite...The synthesis method of propargylamines has always been the focus of research in organic synthetic methodology.A method of alkynylation of tertiary aliphatic amines with alkynes in the presence of copper doped zeolite Y as a catalyst and oxygen in the air as an oxidant has been developed.The most important feature of this reaction is that copper molecular siolite is used as catalyst,which avoids the intermolecular self-coupling of alkynes,and thus realizes the high efficiency propargylization of alkyl tertiary amines.展开更多
The present work provides a facile and efficient method for producing ultrafine copper powders.Ultrafine copper powders were synthesized through a solvothermal method,utilizing ethanol both as a solvent and a reducing...The present work provides a facile and efficient method for producing ultrafine copper powders.Ultrafine copper powders were synthesized through a solvothermal method,utilizing ethanol both as a solvent and a reducing agent.Specifically,by exploiting the weak reducing property of ethanol,the copper precursor is first converted to copper oxide and then further reduced to cuprous oxide and pure copper.Such a method can effectively control the morphology and particle size of the copper powder,reduce particle aggregation,and enhance oxidation resistance.It is cost-effective and produces fewer toxic by-products.Spherical copper particles with an average particle size of about 180 nm were obtained.The initial oxidation temperature is approximately 150℃,and the resulting copper powders can be stored stably under ambient conditions for at least 5 months,demonstrating excellent oxidation resistance and thermal stability.展开更多
To investigate the effect of solution treatment and aging process parameters on the microstructure and mechanical properties of TB18 titanium alloy,process optimization research was conducted based on the mixed-level ...To investigate the effect of solution treatment and aging process parameters on the microstructure and mechanical properties of TB18 titanium alloy,process optimization research was conducted based on the mixed-level orthogonal experiment design of factor levels.Results show that through range analysis,the significance order of process parameters is determined as follows:solution cooling method>solution temperature>aging time>aging temperature>solution time.Considering the strength-ductility matching and engineering application requirements,the benchmark parameters are selected as solution time of 1 h,solution cooling method of air cooling(AC),aging temperature of 525℃,and aging time of 4 h.Furthermore,the effects of solution temperature in the range of 790–870℃ on the impact toughness and micro-fracture characteristics of the alloy were studied.The results reveal that the larger the area of shear lip and fibrous zone,and the smaller the area of radiation zone,the better the toughness of the alloy.With the increase in solution temperature,the length of secondary cracks on the fracture surface increases,the number of dimples increases,and the toughness is enhanced.Based on the collaborative optimization of strength and toughness,the optimal heat treatment process for TB18 alloy is determined as 870℃/1 h,AC+525℃/4 h,AC.展开更多
Ultrafine-grained(UFG)pure titanium was produced by equal channel angular pressing for 4 passes,followed by rotatory swaging at room temperature.The strain-controlled low-cycle fatigue tests of UFG and coarse-grained(...Ultrafine-grained(UFG)pure titanium was produced by equal channel angular pressing for 4 passes,followed by rotatory swaging at room temperature.The strain-controlled low-cycle fatigue tests of UFG and coarse-grained(CG)pure titanium were conducted by Instron electro-hydraulic servo fatigue testing machine in the strain amplitude range of 0.5%—1.1%at room temperature.Transmission electron microscope(TEM)and scanning electron microscope were used to investigate the microstructure and fracture surface of UFG pure titanium after fatigue tests.Results show that UFG pure titanium exhibits a longer low-cycle fatigue life,compared with the CG pure titanium.For example,at a total strain amplitude of 0.5%,UFG and CG pure titanium has fatigue life of 10850 and 4820 cycles,respectively.Significant cyclic softening occurs in UFG pure titanium,except in the case of a total strain amplitude of 0.5%.Hysteresis loop area is increased rapidly with the increase in strain amplitude.The fracture surface shows that the fatigue crack is initiated from the specimen surface.A series of fatigue striations and many microcracks exist in the propagation region.With the increase in strain amplitude,the predominant failure mode is transformed from ductile failure into quasi-cleavage failure.Dislocation slip is the main plastic deformation mechanism of UFG pure titanium during low-cycle fatigue deformation.展开更多
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron tran...The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron transfer at the electrode produces catalysts with more valence states.Among these transition metal catalysts,electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention.This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates,which can be broadly classified into the functionalization of C=C bonds,C-H bond activation,C-C and C-X bond activation,and so on.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
A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates.By optimizing the reaction conditio...A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates.By optimizing the reaction conditions,it was found that when using L3(5 mol%)as the ligand,CuCl(5 mol%)as the catalyst,dichloromethane as the solvent,2,2,6,6-tetramethylpiperidine 1-oxyl(TEMPO)/O2 as the oxidant,and under the reaction condition of 40℃,this method exhibited good substrate tolerance.Under these conditions,a series of chiral 1,1'-bi-2-naphthol(BINOL)derivatives were synthesized with yields of 45%~90%and enantioselectivities ranging from 50∶50 to 97∶3.展开更多
In this study,copper extraction from low-grade oxide-sulfide ores was investigated using a leaching method combined with response surface methodology(RSM)to optimize operational conditions and assess leaching kinetics...In this study,copper extraction from low-grade oxide-sulfide ores was investigated using a leaching method combined with response surface methodology(RSM)to optimize operational conditions and assess leaching kinetics.Given copper's extensive industrial applications,sustainable recovery from low-grade ores is critical.Five key parameters-acid concentration,leaching time,particle size,temperature,and solids percentage-were identified as major influences on copper recovery.The results revealed that leaching time and solids percentage,along with interactions between temperature-time and temperature-solids percentage,had the most significant effects.Optimal conditions for 80% copper recovery while minimizing iron recovery below 3% included an acid concentration of 1.21 mol L^(-1),a leaching time of 108 min,a particle size of 438μm,a temperature of 45℃,and a solids percentage of 18.2%.Leaching kinetics were analyzed using shrinking core models,with the Dickinson model best describing the process,showing an activation energy of 32.63 kJ mol^(-1),indicative of mixed diffusion and chemical reaction control.The final kinetic model effectively predicted the influence of key parameters.These findings highlight the importance of optimizing process variables and selecting suitable kinetic models to enhance extraction efficiency,reduce costs,and improve sustainability in copper recovery.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
A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)...A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)S,metallic copper converts chalcopyrite into bornite(Cu_(5)FeS_(4)).However,the introduction of H_(2)S promotes the formation of chalcocite(Cu_(2)S)by altering the oxidation pathway of copper.Electrochemical analysis demonstrates that the presence of H₂S significantly reduces the corrosion potential of copper from 0.251 to−0.223 V(vs SHE),reaching the threshold necessary for the formation of Cu_(2)S.Nevertheless,excessive H_(2)S triggers sulfate reduction via the reaction of 8Cu+H_(2)SO_(4)+3H_(2)S=4Cu_(2)S+4H_(2)O(ΔG=−519.429 kJ/mol at 50℃),leading to inefficient copper utilization.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
Metal halides are an important class of optoelectronic materials combining exceptional optical and electronic properties.An inherent advantage of metal halides is their solution synthesis and processability,which rend...Metal halides are an important class of optoelectronic materials combining exceptional optical and electronic properties.An inherent advantage of metal halides is their solution synthesis and processability,which render them as low-cost and environmentally friendly materials for a range of applications from photovoltaics and photodetection to solid-state lighting(SSL).In this study,we synthesized three previously unreported lead-free organic–inorganic hybrid copper halides:(OA)_(4)CuX_(5)(X=Br,I;OA^(+) =C_(8)H_(17)NH_(3)^(+) ,n-octylammonium cation)and(HA)_(2)CuI_(3)(HA^(+) =C_(6)H_(13)NH_(3)^(+) ,n-hexylammonium cation),all of which exhibit broadband emissions arising from self-trapped excitons(STEs).Among these compounds,(OA)_(4)CuI_(5) demonstrates tunable dual-band white-light emission with a high color rendering index value of 91 at room temperature.Temperature-dependent photoluminescence measurements and first-principles calculations reveal distinct behaviors between the two emission states in(OA)_(4)CuI_(5).These findings highlight the potential of copper halide compounds for optoelectronic applications,particularly in the development of environmentally friendly solid-state lighting technologies.展开更多
Copper ions are essential for cellular function but can induce cytotoxic effects when dysregulated.This review explores the multifaceted role of copper in cancer metabolism with a focus on the novel concept of cupropt...Copper ions are essential for cellular function but can induce cytotoxic effects when dysregulated.This review explores the multifaceted role of copper in cancer metabolism with a focus on the novel concept of cuproptosis,a regulated form of cell death triggered by copper accumulation.The mechanisms underlying copper homeostasis are detailed,including dietary absorption,systemic distribution,and intracellular utilization.Key transporters,such as copper transporter 1(CTR1)and ATPase copper transporting alpha/b(ATP7A/B),are highlighted.Cancer cells often exhibit elevated copper levels,supporting proliferation and metastasis through pro-tumorigenic pathways.Recent studies have shown that disrupting copper homeostasis can induce cuproptosis,which is characterized by the aggregation of lipoylated mitochondrial proteins and disruption of iron-sulfur cluster biogenesis.Advances in copper-based nanotechnology have enabled targeted delivery of copper to tumors,enhancing therapeutic efficacy through synergistic effects with reactive oxygen species(ROS)generation and immunomodulation.However,the hypoxic tumor microenvironment poses significant challenges by upregulating copper-sequestering proteins and downregulating key cuproptosis mediators.Future directions include integrating multi-omics approaches to identify novel therapeutic targets and developing combination therapies to overcome hypoxia-induced resistance.This review provides a comprehensive overview of copper metabolism in cancer,emphasizing the potential of cuproptosis induction as a powerful strategy for oncologic intervention.展开更多
As the speeds of trains increase,higher demands are placed on brake materials.In order to overcome the thermal degradation phenomenon of brake pads during high-speed braking,we prepared copper fiber reinforced alkali-...As the speeds of trains increase,higher demands are placed on brake materials.In order to overcome the thermal degradation phenomenon of brake pads during high-speed braking,we prepared copper fiber reinforced alkali-activated slag composite(AASC)friction materials by hot-pressing method,using slag as matrix,Na_(2)SiO_(3)·9H_(2)O as alkali excitant,copper fiber as reinforcement,and graphite as friction modifier.The results show that the AASC prepared by hot-pressing method has undergone alkali-activated reaction and has geopolymer amorphous characteristics as the conventional cast molding AASC by XRD analysis.The addition of copper fibers can improve the mechanical strength and toughness of the composites substantially,and the AASC has the highest flexural strength,compressive strength and impact toughness when the volume fraction of copper fibers reaches 25 vol%.Toughening mechanisms such as drawing,bridging and crack deflection of copper fibers in composites were analyzed by SEM morphology.Addition of appropriate amount of graphite to AASC can effectively reduce the wear rate and improve the stability of the material friction coefficient.The coefficient of friction also remains stable in the high-speed friction experiments without thermal degradation.Therefore,copper fiber reinforced AASC friction materials prepared by hot-pressing method has good mechanical and friction properties.展开更多
The development of β-titanium alloys with bone-mimicking elastic moduli remains a significant challenge.Although machine learning has the potential to accelerate alloy discovery,traditional methods often face data li...The development of β-titanium alloys with bone-mimicking elastic moduli remains a significant challenge.Although machine learning has the potential to accelerate alloy discovery,traditional methods often face data limitations such as sparsity,compositional discontinuity,and feature heterogeneity,leading to overfitting and restricting the exploration of novel compositional spaces.In this study,we introduce a domain-adversarial neural network framework that balances predictive accuracy with the generalization ability of unexplored composition space through integrated feature alignment and adversarial training.Using this approach,we successfully developed a non-intuitiveβ-Ti alloy with an ultra-low elastic modulus of 28±3 GPa,providing new insights beyond conventionally designed biomedical titanium alloys.This work establishes a screening framework for materials discovery in small-sample data spaces,with broad implications for the design of biomedical and other alloy systems.展开更多
The formation of copper deposits is closely related to hydrothermal processes.Understanding the migration of copper in hydrothermal fluids aids in reconstructing mineralization processes and deciphering deposit genesi...The formation of copper deposits is closely related to hydrothermal processes.Understanding the migration of copper in hydrothermal fluids aids in reconstructing mineralization processes and deciphering deposit genesis.Copper primarily exists as Cu^(+)and Cu^(2+)in hydrothermal solutions,with redox conditions governing their interconversion.In chloride-rich geological fluids,Cu-Cl complexes are considered critical for copper transport.However,the specific types and valence transitions of Cu-Cl complexes under varying hydrothermal conditions remain poorly understood.This study employed in situ Raman spectroscopy to systematically analyze Cu+HCl and CuCl_(2)+K_(2)S_(2)O_(3)/H_(2) systems under saturated vapor pressure at 25-300℃,elucidating the effects of temperature,Cl^(-)concentration,and redox conditions on copper speciation.In the Cu^(+)HCl system,copper dissolved as monovalent Cu-Cl complexes.At high temperatures(>200℃),[CuCl_(2)]^(-)is the dominated species,whereas[CuCl_(3)]^(2-)becomes prevalent at lower temperatures and higher HCl concentrations.For the Cu^(2+)-Cl system,the dominant species transitioned from[Cu(H_(2)O)n]^(2+)(<50℃)to[CuCl_(4)]^(2-)(100℃)and further to[CuCl]^(+)and[CuCl_(2)]^(0) at 300℃.The introduction of reducing agents(K_(2)S_(2)O_(3)/H_(2))facilitated Cu^(2+)→Cu^(+)reduction,thereby stabilizing Cu^(+)-Cl complexes and inducing partial copper precipitation.The behavior of copper in chloriderich hydrothermal fluids observed in this study indicates that high-temperature oxidizing fluids facilitate Cu mobilization,while cooling and redox changes promote deposition and ore minerals formation.展开更多
At 82,master craftsman Zhu Bingren,China’s preeminent copper artist,continues to dynamically evolve his ancient heritage,proving that true preservation lies in innovation and bringing tradition into the contemporary ...At 82,master craftsman Zhu Bingren,China’s preeminent copper artist,continues to dynamically evolve his ancient heritage,proving that true preservation lies in innovation and bringing tradition into the contemporary world.THE copper art should not be confined to display cases,believes artist Zhu Bingren.From living rooms to fashion runways,and from the Great Wall in Beijing to the Louvre in Paris,the Chinese master craftsman brings his metal creations to life in diverse settings.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
It is difficult to recover chrysocolla from sulfidation flotation which is closely related to the mineral surface composition.In this study,the effects of fluoride roasting on the surface composition of chrysocolla we...It is difficult to recover chrysocolla from sulfidation flotation which is closely related to the mineral surface composition.In this study,the effects of fluoride roasting on the surface composition of chrysocolla were investigated,its impact on sulfidation flotation was explored,and the mechanisms involved in both fluoride roasting and sulfidation flotation were discussed.With CaF_(2)as the roasting reagent,Na_(2)S·9H_(2)O as the sulfidation reagent,and sodium butyl xanthate(NaBX)as the collector,the results of the flotation experiments showed that fluoride roasting improved the floatability of chrysocolla,and the recovery rate increased from 16.87%to 82.74%.X-ray diffraction analysis revealed that after fluoride roasting,approximately all the Cu on the chrysocolla surface was exposed in the form of CuO,which could provide a basis for subsequent sulfidation flotation.The microscopy and elemental analyses revealed that large quantities of"pagoda-like"grains were observed on the sulfidation surface of the fluoride-roasted chrysocolla,indicating high crystallinity particles of copper sulfide.This suggests that the effect of sulfide formation on the chrysocolla surface was more pronounced.X-ray photoelectron spectroscopy revealed that fluoride roasting increased the relative contents of sulfur and copper on the surface and that both the Cu~+and polysulfide fractions on the surface of the minerals increased.This enhances the effect of sulfidation,which is conducive to flotation recovery.Therefore,fluoride roasting improved the effect of copper species transformation and sulfidation on the surface of chysocolla,promoted the adsorption of collectors,and improved the recovery of chrysocolla from sulfidation flotation.展开更多
基金the National Natural Science Foun-dation of China(Grant Nos.12374022,U23A20540)the Natu-ral Science Foundation of Hunan Province for Distinguished Young Scholars(Grant No.2023JJ10075)+3 种基金the China Postdoctoral Science Foundation(Grant Nos.GZC20241335,2024MD753962)the YueLuShan Center Industrial Innovation(Grant No.2024YCII0106)the Scientific and Technological Project of Yunnan Precious Met-als Laboratory(Grant No.YPML-2023050247)the Central South University Research Programme of Advanced Interdisci-plinary Studies(Grant No.2023QYJC039).
文摘Control of the columnar to equiaxed transition(CET)is a major challenge in additively manufacturedβtitanium alloys.In this work,the promotion of CET was successfully achieved through in-situ fabrication of Ti-5Cu(wt.%)alloys with additions of 5,15,and 25 wt.%Nb using elemental Ti,Cu,and Nb powders by employing laser powder bed fusion(LPBF).The alloy containing 5 wt.%Nb consisted ofαlamellae,Ti2 Cu precipitates,and unmeltedβ-Nb inclusions,whereas the 25 wt.%Nb alloy consisted of equiaxedβgrains,ωprecipitates,and Ti2 Cu precipitates at the grain boundaries.In terms of mechanical proper-ties,despite the presence of Nb inclusions and liquation cracks in the 5 wt.%Nb alloy,it showed a yield strength of 1051±40 MPa and an elongation of 5.2%±1.3%.Both the strength and ductility decreased with increasing Nb content,e.g.,the 25 wt.%Nb alloy exhibited a yield strength of 808±53 MPa and an elongation of 1.6%±0.2%.As the Nb content increased from 5 to 25 wt.%,the Young’s modulus decreased from 110 to 65 GPa.The 25 wt.%Nb alloy showed a high ratio of hardness to Young’s mod-ulus(H/E)and yield pressure(H3/E2).However,due to its brittle nature,the material manifested high wear rates.These findings provide a basis for the future development of novel low-modulus isotropicβ-titanium alloys using LPBF.
文摘The synthesis method of propargylamines has always been the focus of research in organic synthetic methodology.A method of alkynylation of tertiary aliphatic amines with alkynes in the presence of copper doped zeolite Y as a catalyst and oxygen in the air as an oxidant has been developed.The most important feature of this reaction is that copper molecular siolite is used as catalyst,which avoids the intermolecular self-coupling of alkynes,and thus realizes the high efficiency propargylization of alkyl tertiary amines.
文摘The present work provides a facile and efficient method for producing ultrafine copper powders.Ultrafine copper powders were synthesized through a solvothermal method,utilizing ethanol both as a solvent and a reducing agent.Specifically,by exploiting the weak reducing property of ethanol,the copper precursor is first converted to copper oxide and then further reduced to cuprous oxide and pure copper.Such a method can effectively control the morphology and particle size of the copper powder,reduce particle aggregation,and enhance oxidation resistance.It is cost-effective and produces fewer toxic by-products.Spherical copper particles with an average particle size of about 180 nm were obtained.The initial oxidation temperature is approximately 150℃,and the resulting copper powders can be stored stably under ambient conditions for at least 5 months,demonstrating excellent oxidation resistance and thermal stability.
基金Key Program of National Natural Science Foundation of China(52431001)。
文摘To investigate the effect of solution treatment and aging process parameters on the microstructure and mechanical properties of TB18 titanium alloy,process optimization research was conducted based on the mixed-level orthogonal experiment design of factor levels.Results show that through range analysis,the significance order of process parameters is determined as follows:solution cooling method>solution temperature>aging time>aging temperature>solution time.Considering the strength-ductility matching and engineering application requirements,the benchmark parameters are selected as solution time of 1 h,solution cooling method of air cooling(AC),aging temperature of 525℃,and aging time of 4 h.Furthermore,the effects of solution temperature in the range of 790–870℃ on the impact toughness and micro-fracture characteristics of the alloy were studied.The results reveal that the larger the area of shear lip and fibrous zone,and the smaller the area of radiation zone,the better the toughness of the alloy.With the increase in solution temperature,the length of secondary cracks on the fracture surface increases,the number of dimples increases,and the toughness is enhanced.Based on the collaborative optimization of strength and toughness,the optimal heat treatment process for TB18 alloy is determined as 870℃/1 h,AC+525℃/4 h,AC.
基金Natural Science Foundation of Shaanxi Province (2023-JC-YB-312)。
文摘Ultrafine-grained(UFG)pure titanium was produced by equal channel angular pressing for 4 passes,followed by rotatory swaging at room temperature.The strain-controlled low-cycle fatigue tests of UFG and coarse-grained(CG)pure titanium were conducted by Instron electro-hydraulic servo fatigue testing machine in the strain amplitude range of 0.5%—1.1%at room temperature.Transmission electron microscope(TEM)and scanning electron microscope were used to investigate the microstructure and fracture surface of UFG pure titanium after fatigue tests.Results show that UFG pure titanium exhibits a longer low-cycle fatigue life,compared with the CG pure titanium.For example,at a total strain amplitude of 0.5%,UFG and CG pure titanium has fatigue life of 10850 and 4820 cycles,respectively.Significant cyclic softening occurs in UFG pure titanium,except in the case of a total strain amplitude of 0.5%.Hysteresis loop area is increased rapidly with the increase in strain amplitude.The fracture surface shows that the fatigue crack is initiated from the specimen surface.A series of fatigue striations and many microcracks exist in the propagation region.With the increase in strain amplitude,the predominant failure mode is transformed from ductile failure into quasi-cleavage failure.Dislocation slip is the main plastic deformation mechanism of UFG pure titanium during low-cycle fatigue deformation.
基金supported by the National Natural Science Foundation of China (No.22271166)the Frontiers Science Center for New Organic Matter,Nankai University (No.63181206) for generous financial support for our programs。
文摘The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron transfer at the electrode produces catalysts with more valence states.Among these transition metal catalysts,electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention.This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates,which can be broadly classified into the functionalization of C=C bonds,C-H bond activation,C-C and C-X bond activation,and so on.
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.
文摘A series of new chiral amide ligands were prepared from natural amino acids and applied to the copper-catalyzed asymmetric oxidative homocoupling reaction of 3-hydroxy-2-naphthoates.By optimizing the reaction conditions,it was found that when using L3(5 mol%)as the ligand,CuCl(5 mol%)as the catalyst,dichloromethane as the solvent,2,2,6,6-tetramethylpiperidine 1-oxyl(TEMPO)/O2 as the oxidant,and under the reaction condition of 40℃,this method exhibited good substrate tolerance.Under these conditions,a series of chiral 1,1'-bi-2-naphthol(BINOL)derivatives were synthesized with yields of 45%~90%and enantioselectivities ranging from 50∶50 to 97∶3.
基金Open Access funding enabled and organized by Projekt DEAL.
文摘In this study,copper extraction from low-grade oxide-sulfide ores was investigated using a leaching method combined with response surface methodology(RSM)to optimize operational conditions and assess leaching kinetics.Given copper's extensive industrial applications,sustainable recovery from low-grade ores is critical.Five key parameters-acid concentration,leaching time,particle size,temperature,and solids percentage-were identified as major influences on copper recovery.The results revealed that leaching time and solids percentage,along with interactions between temperature-time and temperature-solids percentage,had the most significant effects.Optimal conditions for 80% copper recovery while minimizing iron recovery below 3% included an acid concentration of 1.21 mol L^(-1),a leaching time of 108 min,a particle size of 438μm,a temperature of 45℃,and a solids percentage of 18.2%.Leaching kinetics were analyzed using shrinking core models,with the Dickinson model best describing the process,showing an activation energy of 32.63 kJ mol^(-1),indicative of mixed diffusion and chemical reaction control.The final kinetic model effectively predicted the influence of key parameters.These findings highlight the importance of optimizing process variables and selecting suitable kinetic models to enhance extraction efficiency,reduce costs,and improve sustainability in copper recovery.
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financially supported by the National Key Research and Development Program of China (No. 2022YFC2105300)。
文摘A series of leaching and electrochemical experiments were conducted to elucidate the critical role of hydrogen sulfide(H_(2)S)in copper-driven reduction of chalcopyrite.Results demonstrate that in the absence of H_(2)S,metallic copper converts chalcopyrite into bornite(Cu_(5)FeS_(4)).However,the introduction of H_(2)S promotes the formation of chalcocite(Cu_(2)S)by altering the oxidation pathway of copper.Electrochemical analysis demonstrates that the presence of H₂S significantly reduces the corrosion potential of copper from 0.251 to−0.223 V(vs SHE),reaching the threshold necessary for the formation of Cu_(2)S.Nevertheless,excessive H_(2)S triggers sulfate reduction via the reaction of 8Cu+H_(2)SO_(4)+3H_(2)S=4Cu_(2)S+4H_(2)O(ΔG=−519.429 kJ/mol at 50℃),leading to inefficient copper utilization.
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primarily supported by Grant 2022066 from the U.S.-Israel Binational Science Foundation(BSF)support by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,under Award Number DESC0025485(material synthesis and structural characterization)+1 种基金supported by the U.S.DOE,Office of Basic Energy Sciences,under Contract No.DE-AC02-06CH11357the support from the US National Science Foundation through awards DMR-2317008。
文摘Metal halides are an important class of optoelectronic materials combining exceptional optical and electronic properties.An inherent advantage of metal halides is their solution synthesis and processability,which render them as low-cost and environmentally friendly materials for a range of applications from photovoltaics and photodetection to solid-state lighting(SSL).In this study,we synthesized three previously unreported lead-free organic–inorganic hybrid copper halides:(OA)_(4)CuX_(5)(X=Br,I;OA^(+) =C_(8)H_(17)NH_(3)^(+) ,n-octylammonium cation)and(HA)_(2)CuI_(3)(HA^(+) =C_(6)H_(13)NH_(3)^(+) ,n-hexylammonium cation),all of which exhibit broadband emissions arising from self-trapped excitons(STEs).Among these compounds,(OA)_(4)CuI_(5) demonstrates tunable dual-band white-light emission with a high color rendering index value of 91 at room temperature.Temperature-dependent photoluminescence measurements and first-principles calculations reveal distinct behaviors between the two emission states in(OA)_(4)CuI_(5).These findings highlight the potential of copper halide compounds for optoelectronic applications,particularly in the development of environmentally friendly solid-state lighting technologies.
基金supported by the National Natural Science Foundation of China(Grant Nos.82303206,82372749,and 82072951)Science and Technology Commission of Shanghai Municipality(Grant Nos.20Y11914300 and 22Y21900100)+2 种基金Shanghai Anticancer Association(Grant No.SACAAX202213)Major Research Projects of Taizhou Clinical Medical College(Grant No.TZKY20230308)Natural Science Foundation in University of Jiangsu Province(Grant No.BK20231261).
文摘Copper ions are essential for cellular function but can induce cytotoxic effects when dysregulated.This review explores the multifaceted role of copper in cancer metabolism with a focus on the novel concept of cuproptosis,a regulated form of cell death triggered by copper accumulation.The mechanisms underlying copper homeostasis are detailed,including dietary absorption,systemic distribution,and intracellular utilization.Key transporters,such as copper transporter 1(CTR1)and ATPase copper transporting alpha/b(ATP7A/B),are highlighted.Cancer cells often exhibit elevated copper levels,supporting proliferation and metastasis through pro-tumorigenic pathways.Recent studies have shown that disrupting copper homeostasis can induce cuproptosis,which is characterized by the aggregation of lipoylated mitochondrial proteins and disruption of iron-sulfur cluster biogenesis.Advances in copper-based nanotechnology have enabled targeted delivery of copper to tumors,enhancing therapeutic efficacy through synergistic effects with reactive oxygen species(ROS)generation and immunomodulation.However,the hypoxic tumor microenvironment poses significant challenges by upregulating copper-sequestering proteins and downregulating key cuproptosis mediators.Future directions include integrating multi-omics approaches to identify novel therapeutic targets and developing combination therapies to overcome hypoxia-induced resistance.This review provides a comprehensive overview of copper metabolism in cancer,emphasizing the potential of cuproptosis induction as a powerful strategy for oncologic intervention.
基金Funded by the National Natural Science Foundation of China(No.51236003)the Natural Science Foundation of Gansu Province(No.1506RJZA076)。
文摘As the speeds of trains increase,higher demands are placed on brake materials.In order to overcome the thermal degradation phenomenon of brake pads during high-speed braking,we prepared copper fiber reinforced alkali-activated slag composite(AASC)friction materials by hot-pressing method,using slag as matrix,Na_(2)SiO_(3)·9H_(2)O as alkali excitant,copper fiber as reinforcement,and graphite as friction modifier.The results show that the AASC prepared by hot-pressing method has undergone alkali-activated reaction and has geopolymer amorphous characteristics as the conventional cast molding AASC by XRD analysis.The addition of copper fibers can improve the mechanical strength and toughness of the composites substantially,and the AASC has the highest flexural strength,compressive strength and impact toughness when the volume fraction of copper fibers reaches 25 vol%.Toughening mechanisms such as drawing,bridging and crack deflection of copper fibers in composites were analyzed by SEM morphology.Addition of appropriate amount of graphite to AASC can effectively reduce the wear rate and improve the stability of the material friction coefficient.The coefficient of friction also remains stable in the high-speed friction experiments without thermal degradation.Therefore,copper fiber reinforced AASC friction materials prepared by hot-pressing method has good mechanical and friction properties.
基金supported by the Guangdong S&T Program(Grant No.2025B1111130003).
文摘The development of β-titanium alloys with bone-mimicking elastic moduli remains a significant challenge.Although machine learning has the potential to accelerate alloy discovery,traditional methods often face data limitations such as sparsity,compositional discontinuity,and feature heterogeneity,leading to overfitting and restricting the exploration of novel compositional spaces.In this study,we introduce a domain-adversarial neural network framework that balances predictive accuracy with the generalization ability of unexplored composition space through integrated feature alignment and adversarial training.Using this approach,we successfully developed a non-intuitiveβ-Ti alloy with an ultra-low elastic modulus of 28±3 GPa,providing new insights beyond conventionally designed biomedical titanium alloys.This work establishes a screening framework for materials discovery in small-sample data spaces,with broad implications for the design of biomedical and other alloy systems.
基金jointly funded by the Strategic Priority Research Program of the Chinese Academy of Sciences(grant No.XDA0430301)the National Natural Science Foundation of China(grant Nos.42130109,41973059)。
文摘The formation of copper deposits is closely related to hydrothermal processes.Understanding the migration of copper in hydrothermal fluids aids in reconstructing mineralization processes and deciphering deposit genesis.Copper primarily exists as Cu^(+)and Cu^(2+)in hydrothermal solutions,with redox conditions governing their interconversion.In chloride-rich geological fluids,Cu-Cl complexes are considered critical for copper transport.However,the specific types and valence transitions of Cu-Cl complexes under varying hydrothermal conditions remain poorly understood.This study employed in situ Raman spectroscopy to systematically analyze Cu+HCl and CuCl_(2)+K_(2)S_(2)O_(3)/H_(2) systems under saturated vapor pressure at 25-300℃,elucidating the effects of temperature,Cl^(-)concentration,and redox conditions on copper speciation.In the Cu^(+)HCl system,copper dissolved as monovalent Cu-Cl complexes.At high temperatures(>200℃),[CuCl_(2)]^(-)is the dominated species,whereas[CuCl_(3)]^(2-)becomes prevalent at lower temperatures and higher HCl concentrations.For the Cu^(2+)-Cl system,the dominant species transitioned from[Cu(H_(2)O)n]^(2+)(<50℃)to[CuCl_(4)]^(2-)(100℃)and further to[CuCl]^(+)and[CuCl_(2)]^(0) at 300℃.The introduction of reducing agents(K_(2)S_(2)O_(3)/H_(2))facilitated Cu^(2+)→Cu^(+)reduction,thereby stabilizing Cu^(+)-Cl complexes and inducing partial copper precipitation.The behavior of copper in chloriderich hydrothermal fluids observed in this study indicates that high-temperature oxidizing fluids facilitate Cu mobilization,while cooling and redox changes promote deposition and ore minerals formation.
文摘At 82,master craftsman Zhu Bingren,China’s preeminent copper artist,continues to dynamically evolve his ancient heritage,proving that true preservation lies in innovation and bringing tradition into the contemporary world.THE copper art should not be confined to display cases,believes artist Zhu Bingren.From living rooms to fashion runways,and from the Great Wall in Beijing to the Louvre in Paris,the Chinese master craftsman brings his metal creations to life in diverse settings.
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financially supported by the National Natural Science Foundation of China(No.52374259)the Open Fund of the State Key Laboratory of Mineral Processing Science and Technology,China(No.BGRIMM-KJSKL-2023-11)the Major Science and Technology Projects in Yunnan Province,China(No.202302 AF080004)。
文摘It is difficult to recover chrysocolla from sulfidation flotation which is closely related to the mineral surface composition.In this study,the effects of fluoride roasting on the surface composition of chrysocolla were investigated,its impact on sulfidation flotation was explored,and the mechanisms involved in both fluoride roasting and sulfidation flotation were discussed.With CaF_(2)as the roasting reagent,Na_(2)S·9H_(2)O as the sulfidation reagent,and sodium butyl xanthate(NaBX)as the collector,the results of the flotation experiments showed that fluoride roasting improved the floatability of chrysocolla,and the recovery rate increased from 16.87%to 82.74%.X-ray diffraction analysis revealed that after fluoride roasting,approximately all the Cu on the chrysocolla surface was exposed in the form of CuO,which could provide a basis for subsequent sulfidation flotation.The microscopy and elemental analyses revealed that large quantities of"pagoda-like"grains were observed on the sulfidation surface of the fluoride-roasted chrysocolla,indicating high crystallinity particles of copper sulfide.This suggests that the effect of sulfide formation on the chrysocolla surface was more pronounced.X-ray photoelectron spectroscopy revealed that fluoride roasting increased the relative contents of sulfur and copper on the surface and that both the Cu~+and polysulfide fractions on the surface of the minerals increased.This enhances the effect of sulfidation,which is conducive to flotation recovery.Therefore,fluoride roasting improved the effect of copper species transformation and sulfidation on the surface of chysocolla,promoted the adsorption of collectors,and improved the recovery of chrysocolla from sulfidation flotation.
