Aerobic oxidation by using molecular oxygen(O_(2))as the oxidant is highly attractive,in which activating O_(2)to reactive oxygen species(ROS)is a prerequisite.Although some progress has been achieved in regulating RO...Aerobic oxidation by using molecular oxygen(O_(2))as the oxidant is highly attractive,in which activating O_(2)to reactive oxygen species(ROS)is a prerequisite.Although some progress has been achieved in regulating ROS by heterogeneous catalysts,the strategies to efficiently control ROS in aerobic oxidation are still urgently desired.Herein,grain boundaries(GBs)in metal oxides are discovered to be able to facilely regulate ROS.Impressively,MoO_(3)nanocrystals with high density of GBs(MoO_(3)-600)deliver a mass activity of 83 mmol g^(-1)h^(-1)in aerobic oxidation of benzyl alcohol,7 and 8 times as high as that of MoO_(3)nanoparticles without GBs and Pt/C,respectively.In addition,the selectivity of benzoic acid is 100%during whole reaction process over MoO_(3)-600.Mechanistic studies reveal that the oxygen atoms at GBs in MoO_(3)-600 are highly active to form·OH radicals with the generation of oxygen vacancies,while the oxygen vacancies are replenished by O_(2).The reaction path directly contributes to the excellent catalytic performance.展开更多
Studies on the high temperature creep and fracture behaviours in air or in SO_2 contaminated environment for the Fe-base superalloy GH302 with flat or zigzag grain boundaries(GB) and the Ni-base superalloy Rene 80 wer...Studies on the high temperature creep and fracture behaviours in air or in SO_2 contaminated environment for the Fe-base superalloy GH302 with flat or zigzag grain boundaries(GB) and the Ni-base superalloy Rene 80 were carried out.Although the creep rupture properties of the GH302 with zigzag GB was remarkably superior to that of flat GB in air,the properties of both droped dramatically in 10% SO_2-air environment,the creep rupture properties of the directional solidified Rene 80 were much better than that of the conventionally cast alloy in air,and also kept the same property in SO_2 contaminated environment as in air.Owing to the interaction between creep and sulphidation,the failure mechanism relates to the formation of molten Ni-Ni-3S_2 eutectic along GB,led to the premature failure of the alloy.展开更多
xYb2O3-15（20Ni-Cu）/（85 -x）（NiFe2O4-10NiO） （x = 0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0） cermets for aluminum electrolysis were prepared to investigate the effect ofYb2O3 doping on the grain boundary of the cerm...xYb2O3-15（20Ni-Cu）/（85 -x）（NiFe2O4-10NiO） （x = 0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0） cermets for aluminum electrolysis were prepared to investigate the effect ofYb2O3 doping on the grain boundary of the cermets after sintering. The results showed that each interface was very clear and that with increasing Yb2O3 content, most of the Yb was evenly distributed at the grain boundary. Moreover, according to the phase composition and microstructural analysis by X-ray diffraction （XRD）, scanning electron microscopy with energy dispersive X-ray spectroscopy （SEM/EDX）, and electron probe microanalysis （EPMA）, YbFeO3 was produced along the grain boundary. The YbFeO3 was concluded to not only have formed from the interaction between the NiFe2O4 or Fe2O3 component and Yb2O3 at the grain boundary of the cermets, but also from the decomposition of NiFe2O4 into NiO and Fe2O3 and the subsequent reaction of Fe2O3 with Yb2O3. Thus, the production of YbFeO3 resulted in a cermet with high relative density, good electrical conductivity, and good corrosion resistance.展开更多
The effect of the microstructure of an Al 7050-T7451 substrate on the anodic oxide formation in sulfuric acid was studied in this article. The microstructure of the substrate was assessed by optical microscope （OM） ...The effect of the microstructure of an Al 7050-T7451 substrate on the anodic oxide formation in sulfuric acid was studied in this article. The microstructure of the substrate was assessed by optical microscope （OM） and transmission electron microscope （TEM）. The surface and cross-section morphologies of the oxide films were examined by scanning electron microscope （SEM）. The chemical composition of intermetallic particles in the alloys and films was investigated using energy dispersive spectroscope （EDS）. The roles of intermetallic phases and grain or subgrain boundaries on the oxide film formation were researched using the potentiodynamic and potentiostatic polarization technique in sulfuric acid solution. The results show that the transition of coarse intermetallic particles or grain （subgrain） boundaries at the surface of Al alloys can be characterized by potentiodynamic polarization curves. The surface and cross-section micrographs of the anodic layer seem to preserve the microstructure of the substrate. Large cavities in the anodic films are caused by the preferential dissolution of coarse AItCuMg particles and the entrance of Cu-rich remnants into the electrolyte during anodizing. The Al7Cu2Fe particles tend to be occluded in the oxide layer or lose from the oxide surface because of peripheral trenching. Small pores in the films are induced by the dissolution of precipitates in grain or subgrain boundaries. The film surface of recrystallized grain bodies is smooth and homogeneous.展开更多
It is widely accepted that helium(He) bubbles can prevent dislocations from moving and causing hardening and embrittlement of the material. However, He can affect the mechanical properties of materials in various ways...It is widely accepted that helium(He) bubbles can prevent dislocations from moving and causing hardening and embrittlement of the material. However, He can affect the mechanical properties of materials in various ways. In this work,ultrafine nanocrystal high entropy oxide(HEO) films with He implantation are prepared by using a radio frequency(RF)reactive magnetron sputtering system to investigate the effects of He bubbles located at grain boundary on the mechanical properties of the films. The mechanical properties of the HEO films are investigated systematically via nanoindentation measurements. The results indicate that the grain boundary cavities induced by He implantation can degrade the hardness,the elastic modulus, and the creep resistance of the HEO films. The mechanical properties of the HEO films are sensitive to the interaction between the He bubbles and the dominating defects.展开更多
Oxidation behaviour of undopedβ-NiAl andβ-NiAl-0.05Hf single crystals were investigated at 1100℃in 20 vol%O_(2)+Ar and 15 vol%H2O+Ar,respectively.On contrary to the well-known beneficial effect of Hf additions on t...Oxidation behaviour of undopedβ-NiAl andβ-NiAl-0.05Hf single crystals were investigated at 1100℃in 20 vol%O_(2)+Ar and 15 vol%H2O+Ar,respectively.On contrary to the well-known beneficial effect of Hf additions on the oxidation behaviour of polycrystallineβ-NiAl,severe-scale spallation is observed forβ-NiAl-0.05Hf single-crystal alloy,especially in dry atmosphere.It is proposed that the presence of the grain boundaries in the polycrystalline substrate enables proper content of Hf segregating at the grain boundaries of the oxide scale and at the scale-substrate interface,which promotes the conditions required for reactive element effect.Once the reactive element effect of Hf does not work,its strong affinity with oxygen will accelerate the process of high-temperature oxidation.However,the absence of the grain boundaries as fast diffusion paths partially compromises the adverse influence of water vapour on cyclic oxidation resistance ofβ-NiAl single crystal,resulting in considerable suppression of the oxidation rate and less loss of protection compared with that in dry atmosphere.In addition,interfacial cavities are observed in dry and humid atmospheres,which may eventually result in the spallation of the oxide scale.展开更多
Iron‐based superconductors(IBSCs)are a class of material under investigation for the development of superconducting wires in the low‐temperature‐high magnetic fields power application.Among the various families of ...Iron‐based superconductors(IBSCs)are a class of material under investigation for the development of superconducting wires in the low‐temperature‐high magnetic fields power application.Among the various families of IBSCs,the 1144 CaKFe_(4)As_(4) compound is a promising material able to achieve outstanding superconducting properties with a cheap and simple chemical composition.Oxidation,in these compounds,is considered an obstacle for high intergranular critical current density,J_(c,GB).A study devoted to the evaluation of oxidation phenomena and their effects on the superconducting properties is thus needed in order to fully understand the involved mechanisms.From the evaluation of polycrystalline samples obtained by a mechanochemically assisted synthesis route,a degradation of the critical temperature and critical currents has been observed concurrently with oxygen accumulation at grain boundaries in open porosities.However,the crystalline structure at an atomic level seems not affected,as well as intragranular superconducting properties assessed by means of calorimetric methods.These results suggest that loss of superconducting properties in Ca/K‐1144 compounds following oxidation is significantly associated with the worsening of grain connectivity.展开更多
Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-sit...Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-situ ambient-pressure X-ray photoemission spectroscopy(APXPS)to experimentally determine the role of grain boundary in the thermal stability of platinum doped cerium oxide(Pt/CeO_(2)).The grain boundaries were introduced in Pt/CeO_(2)thin films by pulsed laser deposition without significantly change of the surface microstructure.The defect level was tuned by the strain field obtained using a highly/low mismatched substrate.The Pt/CeO_(2)thin film models having well defined crystallographic properties but different grain boundary structural defect levels provide an ideal platform for exploring the evolution of Pt–O–Ce bond with changing the temperature in reducing conditions.We have direct demonstration and explanation of the role of Ce^(3+)induced by grain boundaries in enhancing Pt2+stability.We observe that the Pt^(2+)–O–Ce^(3+)bond provides an ideal coordinated site for anchoring of Pt^(2+)ions and limits the further formation of oxygen vacancies during the reduction with H_(2).Our findings demonstrate the importance of grain boundary in the atomic-scale design of thermally stable catalytic active sites.展开更多
基金supported by National Natural Science Foundation of China(Grant no.51801235,11875258,11505187,51374255,51802356,and 51572299)Innovation-Driven Project of Central South University(No.2018CX004)+3 种基金the Start-up Funding of Central South University(No.502045005)the Fundamental Research Funds for the Central Universities(Nos.WK2310000066,WK2060190081)Posdoctoral Science Foundation of China(No.2019M652797)Central South University Postdoctoral Research Opening Fund
文摘Aerobic oxidation by using molecular oxygen(O_(2))as the oxidant is highly attractive,in which activating O_(2)to reactive oxygen species(ROS)is a prerequisite.Although some progress has been achieved in regulating ROS by heterogeneous catalysts,the strategies to efficiently control ROS in aerobic oxidation are still urgently desired.Herein,grain boundaries(GBs)in metal oxides are discovered to be able to facilely regulate ROS.Impressively,MoO_(3)nanocrystals with high density of GBs(MoO_(3)-600)deliver a mass activity of 83 mmol g^(-1)h^(-1)in aerobic oxidation of benzyl alcohol,7 and 8 times as high as that of MoO_(3)nanoparticles without GBs and Pt/C,respectively.In addition,the selectivity of benzoic acid is 100%during whole reaction process over MoO_(3)-600.Mechanistic studies reveal that the oxygen atoms at GBs in MoO_(3)-600 are highly active to form·OH radicals with the generation of oxygen vacancies,while the oxygen vacancies are replenished by O_(2).The reaction path directly contributes to the excellent catalytic performance.
文摘Studies on the high temperature creep and fracture behaviours in air or in SO_2 contaminated environment for the Fe-base superalloy GH302 with flat or zigzag grain boundaries(GB) and the Ni-base superalloy Rene 80 were carried out.Although the creep rupture properties of the GH302 with zigzag GB was remarkably superior to that of flat GB in air,the properties of both droped dramatically in 10% SO_2-air environment,the creep rupture properties of the directional solidified Rene 80 were much better than that of the conventionally cast alloy in air,and also kept the same property in SO_2 contaminated environment as in air.Owing to the interaction between creep and sulphidation,the failure mechanism relates to the formation of molten Ni-Ni-3S_2 eutectic along GB,led to the premature failure of the alloy.
基金financially supported by the National Natural Science Foundation of China (No. 51404298)the Key Project of Science and Technology of Hunan Province, China (No. 2014FJ2002)the Project of Post-doctoral Foundation of Central South University and the China Scholarship
文摘xYb2O3-15（20Ni-Cu）/（85 -x）（NiFe2O4-10NiO） （x = 0, 0.25, 0.5, 0.75, 1.0, 2.0, and 10.0） cermets for aluminum electrolysis were prepared to investigate the effect ofYb2O3 doping on the grain boundary of the cermets after sintering. The results showed that each interface was very clear and that with increasing Yb2O3 content, most of the Yb was evenly distributed at the grain boundary. Moreover, according to the phase composition and microstructural analysis by X-ray diffraction （XRD）, scanning electron microscopy with energy dispersive X-ray spectroscopy （SEM/EDX）, and electron probe microanalysis （EPMA）, YbFeO3 was produced along the grain boundary. The YbFeO3 was concluded to not only have formed from the interaction between the NiFe2O4 or Fe2O3 component and Yb2O3 at the grain boundary of the cermets, but also from the decomposition of NiFe2O4 into NiO and Fe2O3 and the subsequent reaction of Fe2O3 with Yb2O3. Thus, the production of YbFeO3 resulted in a cermet with high relative density, good electrical conductivity, and good corrosion resistance.
文摘The effect of the microstructure of an Al 7050-T7451 substrate on the anodic oxide formation in sulfuric acid was studied in this article. The microstructure of the substrate was assessed by optical microscope （OM） and transmission electron microscope （TEM）. The surface and cross-section morphologies of the oxide films were examined by scanning electron microscope （SEM）. The chemical composition of intermetallic particles in the alloys and films was investigated using energy dispersive spectroscope （EDS）. The roles of intermetallic phases and grain or subgrain boundaries on the oxide film formation were researched using the potentiodynamic and potentiostatic polarization technique in sulfuric acid solution. The results show that the transition of coarse intermetallic particles or grain （subgrain） boundaries at the surface of Al alloys can be characterized by potentiodynamic polarization curves. The surface and cross-section micrographs of the anodic layer seem to preserve the microstructure of the substrate. Large cavities in the anodic films are caused by the preferential dissolution of coarse AItCuMg particles and the entrance of Cu-rich remnants into the electrolyte during anodizing. The Al7Cu2Fe particles tend to be occluded in the oxide layer or lose from the oxide surface because of peripheral trenching. Small pores in the films are induced by the dissolution of precipitates in grain or subgrain boundaries. The film surface of recrystallized grain bodies is smooth and homogeneous.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11775150 and 11505121)
文摘It is widely accepted that helium(He) bubbles can prevent dislocations from moving and causing hardening and embrittlement of the material. However, He can affect the mechanical properties of materials in various ways. In this work,ultrafine nanocrystal high entropy oxide(HEO) films with He implantation are prepared by using a radio frequency(RF)reactive magnetron sputtering system to investigate the effects of He bubbles located at grain boundary on the mechanical properties of the films. The mechanical properties of the HEO films are investigated systematically via nanoindentation measurements. The results indicate that the grain boundary cavities induced by He implantation can degrade the hardness,the elastic modulus, and the creep resistance of the HEO films. The mechanical properties of the HEO films are sensitive to the interaction between the He bubbles and the dominating defects.
基金financially supported by the China Postdoctoral Science Foundation(Nos.2016M600028,2017T100023)。
文摘Oxidation behaviour of undopedβ-NiAl andβ-NiAl-0.05Hf single crystals were investigated at 1100℃in 20 vol%O_(2)+Ar and 15 vol%H2O+Ar,respectively.On contrary to the well-known beneficial effect of Hf additions on the oxidation behaviour of polycrystallineβ-NiAl,severe-scale spallation is observed forβ-NiAl-0.05Hf single-crystal alloy,especially in dry atmosphere.It is proposed that the presence of the grain boundaries in the polycrystalline substrate enables proper content of Hf segregating at the grain boundaries of the oxide scale and at the scale-substrate interface,which promotes the conditions required for reactive element effect.Once the reactive element effect of Hf does not work,its strong affinity with oxygen will accelerate the process of high-temperature oxidation.However,the absence of the grain boundaries as fast diffusion paths partially compromises the adverse influence of water vapour on cyclic oxidation resistance ofβ-NiAl single crystal,resulting in considerable suppression of the oxidation rate and less loss of protection compared with that in dry atmosphere.In addition,interfacial cavities are observed in dry and humid atmospheres,which may eventually result in the spallation of the oxide scale.
基金Part of the work was carried out in the framework of the Cooperative Research And Development Agreement CRADA FRA‐2022‐0041Northwestern University’s NUANCE Center,which has received support from the SHyNE Resource(NSF ECCS‐2025633)the IIN,and Northwestern's MRSEC program(NSF DMR‐1720139).
文摘Iron‐based superconductors(IBSCs)are a class of material under investigation for the development of superconducting wires in the low‐temperature‐high magnetic fields power application.Among the various families of IBSCs,the 1144 CaKFe_(4)As_(4) compound is a promising material able to achieve outstanding superconducting properties with a cheap and simple chemical composition.Oxidation,in these compounds,is considered an obstacle for high intergranular critical current density,J_(c,GB).A study devoted to the evaluation of oxidation phenomena and their effects on the superconducting properties is thus needed in order to fully understand the involved mechanisms.From the evaluation of polycrystalline samples obtained by a mechanochemically assisted synthesis route,a degradation of the critical temperature and critical currents has been observed concurrently with oxygen accumulation at grain boundaries in open porosities.However,the crystalline structure at an atomic level seems not affected,as well as intragranular superconducting properties assessed by means of calorimetric methods.These results suggest that loss of superconducting properties in Ca/K‐1144 compounds following oxidation is significantly associated with the worsening of grain connectivity.
基金The APXPS experiments were performed at BL02B01 of SSRF with the approval of the Proposal Assessing Committee of SiP.ME2 platform project(Proposal No.2019-SSRF-PT-011613)the Natural Science Foundation of China(No.11227902)the Shanghai Key Research Program(No.20ZR1436700).
文摘Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-situ ambient-pressure X-ray photoemission spectroscopy(APXPS)to experimentally determine the role of grain boundary in the thermal stability of platinum doped cerium oxide(Pt/CeO_(2)).The grain boundaries were introduced in Pt/CeO_(2)thin films by pulsed laser deposition without significantly change of the surface microstructure.The defect level was tuned by the strain field obtained using a highly/low mismatched substrate.The Pt/CeO_(2)thin film models having well defined crystallographic properties but different grain boundary structural defect levels provide an ideal platform for exploring the evolution of Pt–O–Ce bond with changing the temperature in reducing conditions.We have direct demonstration and explanation of the role of Ce^(3+)induced by grain boundaries in enhancing Pt2+stability.We observe that the Pt^(2+)–O–Ce^(3+)bond provides an ideal coordinated site for anchoring of Pt^(2+)ions and limits the further formation of oxygen vacancies during the reduction with H_(2).Our findings demonstrate the importance of grain boundary in the atomic-scale design of thermally stable catalytic active sites.
