Compared to traditional superhard materials with high electron density and short,strong covalent bonds,alloy materials mainly composed of metallic bonding structures typically have great toughness and lower hardness.B...Compared to traditional superhard materials with high electron density and short,strong covalent bonds,alloy materials mainly composed of metallic bonding structures typically have great toughness and lower hardness.Breaking through the limits of alloy materials is a preface and long-term topic,which is of great significance and value for improving the comprehensive mechanical properties of alloy materials.Here,we report on the discovery of a cubic alloy semiconducting material Ti_(2)Co with a large Vickers of hardness K_(v)^(exp)∼6.7GPa and low fracture toughness of K_(IC)^(exp)∼1.51MPa·m^(1/2).Unexpectedly,the K_(v)^(exp)∼6.7GPa is nearly triple of the K_(v)^(cal)∼2.66GPa predicted by density functional theory(DFT)calculations and theK_(IC)^(exp)∼1.51MPa·m^(1/2)is about one or two orders of magnitude smaller than that of ordinary titanium alloy materials(K_(IC)^(exp)∼30-120MPa·m^(1/2)).These specifications place Ti_(2)Co far from the phase space of the known alloy materials.Upon incorporation of oxygen into structural void positions,both values were simultaneously improved for Ti_(4)Co_(2)O to∼9.7GPa and∼2.19MPa·m^(1/2),respectively.Further DFT calculations on the electron localization function of Ti_(4)Co_(2)X(X=B,C,N,O)vs.the interstitial elements indicate that these simultaneous improvements originate from the coexistence of Ti-Co metallic bonds,the emergence of newly oriented Ti-X covalent bonds,and the increase of electron concentration.Moreover,the large difference between K_(v)^(exp)and K_(v)^(cal)of Ti_(2)Co suggests underlying mechanism concerning the absence of the O(16d)or Ti_(2)-O bonds in the O-(Ti_(2))_(6) octahedron.This discovery proposes a new pathway to simultaneously improve the comprehensive mechanical performances and illuminates the path of exploring superconducting materials with excellent mechanical performances.展开更多
基金supported by the National Key Research and Development Program of China(Grant Nos.2024YFA1408400,2023YFA1406100,2023YFA1607400,2022YFA1403800,and 2022YFA1403203)the National Natural Science Foundation of China(Grant Nos.12474055,12404067,12025408,52025026,and U23A6003)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB33000000)the Chinese Academy of Sciences President’s International Fellowship Initiative(Grant No.2024PG0003)the Outstanding Member of Youth Promotion Association of Chinese Academy of Sciences(Grant No.Y2022004)supported by the CAC station of Synergetic Extreme Condition User Facility(SECUF,https://cstr.cn/31123.02.SECUF)。
文摘Compared to traditional superhard materials with high electron density and short,strong covalent bonds,alloy materials mainly composed of metallic bonding structures typically have great toughness and lower hardness.Breaking through the limits of alloy materials is a preface and long-term topic,which is of great significance and value for improving the comprehensive mechanical properties of alloy materials.Here,we report on the discovery of a cubic alloy semiconducting material Ti_(2)Co with a large Vickers of hardness K_(v)^(exp)∼6.7GPa and low fracture toughness of K_(IC)^(exp)∼1.51MPa·m^(1/2).Unexpectedly,the K_(v)^(exp)∼6.7GPa is nearly triple of the K_(v)^(cal)∼2.66GPa predicted by density functional theory(DFT)calculations and theK_(IC)^(exp)∼1.51MPa·m^(1/2)is about one or two orders of magnitude smaller than that of ordinary titanium alloy materials(K_(IC)^(exp)∼30-120MPa·m^(1/2)).These specifications place Ti_(2)Co far from the phase space of the known alloy materials.Upon incorporation of oxygen into structural void positions,both values were simultaneously improved for Ti_(4)Co_(2)O to∼9.7GPa and∼2.19MPa·m^(1/2),respectively.Further DFT calculations on the electron localization function of Ti_(4)Co_(2)X(X=B,C,N,O)vs.the interstitial elements indicate that these simultaneous improvements originate from the coexistence of Ti-Co metallic bonds,the emergence of newly oriented Ti-X covalent bonds,and the increase of electron concentration.Moreover,the large difference between K_(v)^(exp)and K_(v)^(cal)of Ti_(2)Co suggests underlying mechanism concerning the absence of the O(16d)or Ti_(2)-O bonds in the O-(Ti_(2))_(6) octahedron.This discovery proposes a new pathway to simultaneously improve the comprehensive mechanical performances and illuminates the path of exploring superconducting materials with excellent mechanical performances.
