Angular distribution of photoelectrons is investigated during the inner photoemissive effect for two variants: quantum of light basically reveals wave and basically corpuscular properties interacting with orbital elec...Angular distribution of photoelectrons is investigated during the inner photoemissive effect for two variants: quantum of light basically reveals wave and basically corpuscular properties interacting with orbital electron. Distinction in angular distribution of photoelectrons for these variants is demonstrated. Angular distribution in the second variant is investigated for the nonrelativistic and relativistic cases.展开更多
The Earth surface is a multiple open system. Semiconducting minerals, including most metal oxides and sulfides, absorb visible light of the solar spectrum. Microorganisms evolve varied pathways to get carbon and energ...The Earth surface is a multiple open system. Semiconducting minerals, including most metal oxides and sulfides, absorb visible light of the solar spectrum. Microorganisms evolve varied pathways to get carbon and energy sources. It is obvious that the interaction among solar light, semiconducting minerals, photoelectron/photohole, organics, inorganics, valence electrons and microorganisms occurs continuously on our planet. In a recent study, Lu et al. (2012) presented evidence demonstrating solar energy mediated by semiconducting mineral photocatalysis, acting as energy source, promoted the growth of some non-photosynthetic bacteria and revealed that the ternary system of microorganisms, minerals and solar light has played a critical role in the history of life on our planet. In simulated system, under simulated solar light semiconducting minerals, such as metal oxides and metal sulfides, generates photoelectrons which could be used by non-phototrophic microorganisms to support their metabolisms. The growth of microorganism was closely related to photon quantity and energy, and the microorganism growth and mineral light absorption spectra were fitted well under different light wavelengths. The overall energy efficiency from photon to biomass was 0.13‰ to 1.9‰. Further studies revealed that in natural soil systems, semiconducting mineral photocatalysis could influence the microbial population. Solar energy utilization pathway by nonphototrophic microorganisms mediated by semiconducting mineral photocatalysis provides a new concept to evaluate the origin and evolution of life. Semiconducting minerals are ubiquitous on Earth’s surface and widely participate in redox reactions following photoelectron-photohole pairs excited by solar light. As photoholes can be easily scavenged by environmental reductive substances and microorganisms possess multiple strategies to utilize extracellular electrons, the highly reductive photoelectrons serve as potential energy source for microbial life. The discovery of this pathway extends our knowledge on the use of solar energy by nonphototrophic microorganisms, and provides important clues to evaluate life on the early Earth. Microorganisms, minerals and solar light constitute a complex but important ternary system through Earth history. The discovery of the novel energy conversion pathway in this system demonstrates how nonphototrophic microorganisms directly or indirectly utilized photoelectrons as the solar energy source. The fully comprehending of nonphototrophic bacteria solar energy utilization conducted by semiconducting minerals in present environment will greatly help us to better understand the energy transform mechanism among interfaces of lithosphere, pedosphere, hydrosphere and biosphere.展开更多
Electron pitch angle distributions similar to bidirectional electron conics(BECs)have been reported at Mars in previous studies based on analyses of Mars Global Surveyor measurements.BEC distribution,also termed“butt...Electron pitch angle distributions similar to bidirectional electron conics(BECs)have been reported at Mars in previous studies based on analyses of Mars Global Surveyor measurements.BEC distribution,also termed“butterfly”distribution,presents a local minimum flux at 90°and a maximum flux before reaching the local loss cone.Previous studies have focused on 115 eV electrons that were produced mainly via solar wind electron impact ionization.Here using Solar Wind Electron Analyzer measurements made onboard the Mars Atmosphere and Volatile Evolution spacecraft,we identify 513 BEC events for 19-55 eV photoelectrons that were generated via photoionization only.Therefore,we are investigating electrons observed in regions well away from their source regions,to be distinguished from 115 eV electrons observed and produced in the same regions.We investigate the spatial distribution of the 19-55 eV BECs,revealing that they are more likely observed on the nightside as well as near strong crustal magnetic anomalies.We propose that the 19-55 eV photoelectron BECs are formed due to day-to-night transport and the magnetic mirror effect of photoelectrons moving along cross-terminator closed magnetic field lines.展开更多
The ZnO and Zn1-xMnxO minicrystal were synthesized by chemical vapor transport (CVT). The electron trap structure (donor level) and process on the temporal behavior of photoelectrons of materials were respectively stu...The ZnO and Zn1-xMnxO minicrystal were synthesized by chemical vapor transport (CVT). The electron trap structure (donor level) and process on the temporal behavior of photoelectrons of materials were respectively studied by thermo-luminescence and microwave absorption dielectric spectrometry. There are two peaks in the thermo-luminescence spectra in pure ZnO, one is -183 ℃ and the other is -127 ℃, which shows two kinds of electron trap energy level produced by the intrinsic defects in ZnO;but obtain very low thermo-luminescence that only equals to ten percent of pure ZnO in Zn1-xMnxO, which shows that its intensity of electron trap is less. The studies of microwave absorption dielectric spectrometry show that conduction band photoelectrons are two-step exponential decay process in ZnO, the lifetime of rapid process is 83 ns, while slow process is 828 ns, the reason of delay is relaxation effects of electron trap to conduction band photoelectrons. The intensity of electron trap is less in Zn1-xMnxO minicrystal, the relaxation effects of conduction band photoelectrons from electron trap is little, so electrons disappeared quickly at conduction band, and the decay process of photoelectrons is only 10~20 ns.展开更多
Non-resonant multiphoton ionization of atomic lead at 1064nm laser field has been studied.Both the angular distribution and the intensity dependence of photoelectrons have been measured.The results show that they are ...Non-resonant multiphoton ionization of atomic lead at 1064nm laser field has been studied.Both the angular distribution and the intensity dependence of photoelectrons have been measured.The results show that they are very sensitive to the process of multiphoton ionization.展开更多
The above-threshold ionization process of ammonia molecules induced by a femtosecond laser field at 800 nm is studied in the intensity range from 1.6×10^(13) to 5.7×10^(13)W/cm^(2).Channel switching under di...The above-threshold ionization process of ammonia molecules induced by a femtosecond laser field at 800 nm is studied in the intensity range from 1.6×10^(13) to 5.7×10^(13)W/cm^(2).Channel switching under different laser intensities is observed and identified in the photoelectron kinetic energy spectra of ammonia.Based on the photoelectron kinetic energy distributions and the photoelectron angular distributions,the characteristic peaks observed are exclusively assigned to the multiphoton resonance through certain intermediate states,followed by multiphoton above-threshold ionization.展开更多
Energy is the key issue of all life activities.The energy source and energy yielding pathway are the key scientific issues of the origin and early evolution of life on Earth.Current researches indicate that the utiliz...Energy is the key issue of all life activities.The energy source and energy yielding pathway are the key scientific issues of the origin and early evolution of life on Earth.Current researches indicate that the utilization of solar energy in large scale by life was an important breaking point of the early evolution of life on Earth and afterwards life gradually developed and flourished.However,in the widespread biochemical electron transfer of life activities,it is still not clear whether the electron source is sun or how electrons originated from sun.For billions of years,the ubiquitous semiconducting minerals in epigeosphere absorb solar energy,forming photoelectrons and photoholes.In reductive and weak acidic environment of early Earth,when photoholes were easily scavenged by reducing matters,photoelectrons were separated.Photoelectrons could effectively reduce carbon dioxide to organic matters,possibly providing organic matter foundation for the origin of life.Photoelectrons participated in photoelectron transfer chains driven by potential difference and transfer into primitive cells to maintain metabolisms.Semiconducting minerals,by absorbing ultraviolet,also protected primitive cells from being damaged by ultraviolet in the origin of life.Due to the continuous photoelectrons generation in semiconducting minerals and utilization by primitive cells,photoelectrons from semiconducting minerals’photocatalysis played multiple roles in the origin of life on early Earth,such as organic synthesis,cell protection,and energy supply.This mechanism still plays important roles in modern Earth surface systems.展开更多
The dynamic evolution of surface electrochemical potential of the electrolyte plays a key role in the performance of solid-state electrochemical devices,while its real-time characterization remains challenging.Here,we...The dynamic evolution of surface electrochemical potential of the electrolyte plays a key role in the performance of solid-state electrochemical devices,while its real-time characterization remains challenging.Here,we visualize the dynamic evolution of the surface electrochemical potential on yttria-stabilized zirconia(YSZ)in a planar Au|YSZ|Au model cell,using spatially resolved photoelectron-based techniques including photoemission electron microscopy(PEEM)and micro-region X-ray photoelectron spectroscopy(μ-XPS).PEEM reveals two sequential reaction fronts in YSZ under cathodic polarization,corresponding to the evolution of the chemical potential of oxygen ions,with a faster propagation speed on the top surface and a slower one in the near-surface region.XPS measurements quantitatively reveal the time-dependent electric potential distribution across YSZ surface.COMSOL simulations confirm the presence of a stronger electric field at the top surface,particularly at the advancing reaction fronts,compared to the near-surface region.The critical role of the electric field in driving surface reactions is further supported by the enhanced reactions observed at the tips of the zigzag-shaped electrode edges.This work offers mechanistic insights into the coupling between electrochemical potential dynamics and electrolyte reactions.展开更多
It is highly desired to improve the photoelectric property of nanosized BiOBr by promoting the photogenerated charge transfer and separation. Herein, SnO2 and Ag comodified BiOBr nanocomposites(Ag-SO-BOB) have been pr...It is highly desired to improve the photoelectric property of nanosized BiOBr by promoting the photogenerated charge transfer and separation. Herein, SnO2 and Ag comodified BiOBr nanocomposites(Ag-SO-BOB) have been prepared through a simple one-pot hydrothermal method.Surface photovoltage response of BiOBr nanoplates has 4.1-time enhancement after being modified with SnO2 nanoparticles. Transient-state surface photovoltage(TS-SPV) and the atmosphere-controlled steady-state surface photovoltage spectroscopy(AC-SPS) confirmed that this exceptional enhancement of the photovoltage response can be ascribed to the coupled SnO2 acting as platform for accepting the photoelectrons from BiOBr so as to prolong the lifetime and enhance charge separation. Remarkably, the surface photovoltage response can be further enhanced by synchronously introducing Ag nanoparticles, which is up to 15.4-times enhancement compared with bulk BiOBr nanoplates. The enhancement can be attributed to the improved O2 adsorption by introducing Ag to further enhance charge separation. Finally, the synergistic effect of SnO2 and Ag co-modification enhances the surface photovoltage response due to the enhanced charge separation and promoted O2 adsorption, which is also confirmed through photoelectrochemistry and photocatalytic experiment.展开更多
We report a study on the electronic structure and chemical bonding of the PB and AsB diatomic molecules using high-resolution photoelectron imaging of cryogenically-cooled PB^(−)and AsB^(−)anions.The electron affiniti...We report a study on the electronic structure and chemical bonding of the PB and AsB diatomic molecules using high-resolution photoelectron imaging of cryogenically-cooled PB^(−)and AsB^(−)anions.The electron affinities of PB and AsB are measured to be 2.751(1)and 2.600(1)eV,respectively.The ground states of the PB^(−)and AsB−anions are determined to be ^(2)Σ^(+) with a σ^(1)π^(4) valence electron configuration.The ground states of neutral PB and AsB are found to be ^(3)Π_(2) with a σ^(1)π^(3) electron configuration.The spin-orbit excited states(^(3)Π_(1) and ^(3)Π_(0)),as well as two low-lying singlet excited states(^(1)Σ^(+)and ^(1)Π),are observed.Unusual spectroscopic characteristics are observed in the ^(3)Π_(2) ground state of AsB,probably due to state mixing with a higher-lying ^(1)Δ_(2) state.The current work provides extensive electronic and spectroscopic information for the PB and AsB molecules.展开更多
Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ra...Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ray Photoelectron emission spectroscopy(HAXPES)and microscopy(HAXPEEM)as well as microscopic X-ray absorption spectroscopy(μ-XAS)techniques.The results reveal the inhomogeneity in the oxide films on the micron-sized Cr_(2)N-and VN-type particles,while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600℃.The oxide film formed on Cr_(2)N-type particles is rich in Cr_(2)O_(3) compared with that on the martensite matrix and VN-type particles.With the increase of tempering temperature,Cr_(2)O_(3) formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.展开更多
Magnesium alloys as medical implant materials necessitate a lower and adjustable corrosion rate for clinical applications.The microstructure and corrosion behavior of AZ31Mn-xEr(x=0.1,0.5,1.2)alloys were systematicall...Magnesium alloys as medical implant materials necessitate a lower and adjustable corrosion rate for clinical applications.The microstructure and corrosion behavior of AZ31Mn-xEr(x=0.1,0.5,1.2)alloys were systematically investigated using optical microscopy(OM),scanning electron microscopy(SEM),and X-ray photoelectron spectroscopy(XPS),combined with Tafel polarization and electrochemical impedance spectroscopy(EIS)analyses.The findings showed that the alloying element Er refined the grain structure during solidification by increasing the nucleation rate and forming a secondary phase of Al_(3)Er with Al.The Er and Mg in the matrix co-oxidize to form a dense MgO/Er_(2)O_(3)composite oxide,preventing the formation of loose magnesium hydroxide/basic magnesium carbonate.The trace alloying element Mn interacts with impurities Fe in the magnesium matrix to form an AlFeMn second phase,reducing micro-galvanic corrosion driving force.Electrochemical testing in a 3.5%NaCl solution demonstrated a marked reduction in corrosion rate from 10.46 mm/a(AZ 31 Mn alloy)to 0.44 mm/a(AZ31Mn-1.2Er alloy).This research offers a reference for searching for corrosion-resistant magnesium alloy and degradable medical magnesium alloy materials.展开更多
The corrosion behaviors of an as-cast FeCoNiAl_(0.75)Cr_(1.25)high-entropy alloy(HEA)in acidic Na_(2)SO_(4)solution with different pH values were investigated.The results indicate that the as-cast FeCoNiAl_(0.75)Cr_(1...The corrosion behaviors of an as-cast FeCoNiAl_(0.75)Cr_(1.25)high-entropy alloy(HEA)in acidic Na_(2)SO_(4)solution with different pH values were investigated.The results indicate that the as-cast FeCoNiAl_(0.75)Cr_(1.25)HEA is mainly composed of face-centered cubic phase,body-centered cubic(BCC1)phase(Co–Cr–Fe)and ordered BCC(B2)phase(Ni–Al),in which BCC1 phase and B2 phase have a eutectic microstructure.Moreover,the corrosion of B2 phase occurs preferentially in a 0.05 mol/L SO_(4)^(2−)acidic solution.The electrochemical measurement results show that the corrosion resistance of the investigated HEA significantly changes as the solution pH increases from 2 to 2.5.This indicates that there is a critical pH in the range of 2–2.5 that affects the corrosion of HEA.In addition,the results of X-ray photoelectron spectroscopy prove that the surface film of FeCoNiAl_(0.75)Cr_(1.25)in SO_(4)^(2−)solution is formed with Al_(2)O_(3)and Cr_(2)O_(3)as the main components,and The content of Al2O3 and Cr_(2)O_(3)increases with increasing solution pH.展开更多
In the present work,the effects of neodymium(Nd)on micro structure,mechanical performance,and corrosion behavior of powder metallurgy Mg-2Si-xNd(x=0.05 wt%,0.15 wt%,and 0.20 wt%)alloys were investigated.Microstructure...In the present work,the effects of neodymium(Nd)on micro structure,mechanical performance,and corrosion behavior of powder metallurgy Mg-2Si-xNd(x=0.05 wt%,0.15 wt%,and 0.20 wt%)alloys were investigated.Microstructures were examined by optical and scanning electron microscopes combined with an energy-dispersive spectrometer.Hardness and compressive tests were used to study the mechanical properties of alloys.Potentiodynamic polarization,electrochemical impedance spectroscopy(EIS),Mott-Schottky analysis,and the hydrogen evolution test were applied to characterize the corrosion behavior of alloys in Hanks'solution.The microstructure of Mg-2Si-xNd alloys mainly consists ofα-Mg matrix,Mg2Si,and MgNd phases.The increase in Nd content tends to decrease the aspect ratio ofα-Mg grains,which leads to the enhancement of the ultimate-compressive strengths and hardness of the alloys.Potentiodynamic polarization shows that increasing Nd content leads to a lower corrosion current density in the Mg-2Si-xNd alloys.The EIS results confirm that a higher addition of Nd suppresses the dissolution kinetics of the alloys due to the increasing charge transfer resistance.Mott-Schottky analysis reveals the formation of an n-type semiconductive passive film on the alloy surfaces,where the interstitial and oxygen vacancies predominate over the metal vacancies.The X-ray photoelectron spectroscopy(XPS)reveals that a mixture of Mg(OH)_(2),MgO,MgCO_(3),and Nd_(2)O_(3)has formed as the corrosion products on the Mg-2Si-xNd alloy surfaces after a longer immersion time in Hanks'solution.展开更多
High-resolution photoelectron spectra of cryogenically cooled TiO_(2)CH_(3)OH^(−)anions obtained with slow electron velocity-map imaging are reported and used to explore the reactions of TiO_(2)^(−/0)with methanol.The...High-resolution photoelectron spectra of cryogenically cooled TiO_(2)CH_(3)OH^(−)anions obtained with slow electron velocity-map imaging are reported and used to explore the reactions of TiO_(2)^(−/0)with methanol.The highly structured spectra were compared with results from DFT calculations to determine the dominant structure to be cis-CH_(3)OTi(O)OH^(−),a dissociative adduct in which CH3OH is split by TiO_(2)^(−).The experiment yields an electron affinity of 1.2152(7)eV for TiO_(2)CH^(3)OH as well as several vibrational frequencies for the neutral species.Comparison to Franck−Condon(FC)simulations shows that while most experimental features appear in the simulations,several are not and are assigned to FC-forbidden transitions involving non-totally symmetric vibrational modes.The FC-allowed and forbidden transi-tions also exhibit different photoelectron angular distributions.The FC-forbidden transitions are attributed to Herzberg−Teller(HT)coupling with the A^(2)A″excited state of the anion.The results are compared to previous cryogenic slow electron velocity-map imaging(cryo-SE-Ⅵ)studies of bare TiO_(2)^(−)and the water-split adduct TiO_(3)H_(2)^(−).展开更多
The structure and electronic properties of Co_(2)Ge_(10)^(-)anion and its neutral counterpart were investigated by anion photoelectron spectroscopy and theoretical calculations.The experimental vertical detachment ene...The structure and electronic properties of Co_(2)Ge_(10)^(-)anion and its neutral counterpart were investigated by anion photoelectron spectroscopy and theoretical calculations.The experimental vertical detachment energy of Co_(2)Ge_(10)^(-)was measured to be 2.86±0.08 eV.The lowest-energy isomer of Co_(2)Ge_(10)^(-)is in a doublet state and has a cage-like structure with Cs symmetry,which can be constructed by a tetragonal bipyramid on top of a pentagonal bipyramid and these two bipyramid structures share a common Co atom.The most stable structure of neutral Co_(2)Ge_(10)resembles its anionic counterpart and it is in a triplet state.The natural population analysis showed that the inner Co atom of both the anionic and neutral Co_(2)Ge_(10)acquires negative charge from the neighboring Ge atoms.The outer Co atom has a larger spin moment than the inner Co atom,indicating that the magnetic moments of Co_(2)Ge_(10)^(-/0)are mainly contributed by the outer Co atom.Analyses of the density of states and molecular orbitals indicated that there are a few highly delocalized molecular orbitals in Co_(2)Ge_(10)^(-),which are mainly contributed by Ge 4s atomic orbitals.展开更多
MgATP is a stable complex formed by the chelation of Mg^(2+)with deprotonated adenosine-5'-triphosphate(ATP).In the cellular environment,MgATP plays a critical role in ATP hydrolysis,releasing substantial energy t...MgATP is a stable complex formed by the chelation of Mg^(2+)with deprotonated adenosine-5'-triphosphate(ATP).In the cellular environment,MgATP plays a critical role in ATP hydrolysis,releasing substantial energy to support essential biological functions.To understand the structure and stabilization mechanism of MgATP,we conducted a joint negative ion photoelectron spectroscopic and computational study of the[ATP^(4-)·Mg^(2+)]^(2-)complex dianion,using[ATP^(4-)·2H^(+)]^(2-)as a reference.The experimentally determined adiabatic and vertical detachment energies(ADE and VDE)of[ATP^(4-)·Mg^(2+)]^(2-)at 20 K are 3.51±0.05 eV and 3.82±0.05 eV,respectively.The major spectral features of[ATP^(4-)·Mg^(2+)]^(2-)are attributed to two theoretically identified isomers with unfolded geometries,which are stabilized primarily by electrostatic interactions between Mg^(2+)and the triphosphate and ribose groups,with four deprotonated oxygens forming a pseudo-tetrahedral coordination.In contrast,[ATP^(4-)·2H^(+)]^(2-)exhibits a fundamentally different stabilization mechanism.Although most of the fifteen identified[ATP^(4-)·2H^(+)]^(2-)isomers also adopt unfolded geometries,they are primarily stabilized by intramolecular hydrogen bonds within the triphosphate group and between triphosphate and ribose groups.The interaction between ATP^(4-)and two protons is found to be much weaker than that with Mg^(2+),and[ATP^(4-)·2H^(+)]^(2-)exhibits substantial structural flexibility compared to[ATP^(4-)·Mg^(2+)]^(2-)due to the conformational constraint of the triphosphate chain by Mg^(2+).Thirteen[ATP^(4-)·2H^(+)]^(2-)isomers with unfolded geometries likely account for the major high-EBE(electron-binding-energy)spectral features.Notably,for the first time,a low EBE and temperature-dependent spectral feature is observed and attributed to two folded isomers of[ATP^(4-)·2H^(+)]^(2-),which exist at 20 K but disappear at room temperature.This study provides valuable molecular-level insights into cellular MgATP that resides within the hydrophobic pockets of proteins.展开更多
The vibrational resolved spectra of MO_(2)^(-)/MO_(2)(M=Ti,Zr,and Hf)are reported by using photoelectron imaging and theoretical calculations.The results indicate that all the ground states of anionic and neutral MO_(...The vibrational resolved spectra of MO_(2)^(-)/MO_(2)(M=Ti,Zr,and Hf)are reported by using photoelectron imaging and theoretical calculations.The results indicate that all the ground states of anionic and neutral MO_(2)(M=Ti,Zr,and Hf)compounds are formed in bent insertion structures.The observed ground-state adiabatic detachment energy(ADE)is measured to be 1.597±0.003,1.651±0.003,and 2.119±0.003 eV for TiO_(2)^(-),ZrO_(2)^(-),and HfO_(2)^(-),respectively.The vibrational frequencies of the anionic and neutral MO_(2)are also determined from the experimental spectra.The results of theoretical calculations show that the electronic configurations of MO_(2)^(-)are^(2)A_(1)with C_(2v)point group.Bond order analysis indicates that the two M-O bonds are all multiple characters.展开更多
The corrosion behavior of CoCrCu_(0.1)FeMoNi high entropy alloy(HEA)in 0.5 mol/L NaOH solution was investigated using X-ray photoelectron spectroscopy,X-ray diffraction,scanning electron microscopy,potentiodynamic pol...The corrosion behavior of CoCrCu_(0.1)FeMoNi high entropy alloy(HEA)in 0.5 mol/L NaOH solution was investigated using X-ray photoelectron spectroscopy,X-ray diffraction,scanning electron microscopy,potentiodynamic polarization measurement,and electrochemical impedance spectroscopy.The results showed that the microstructure of this HEA displayed a dendritic morphology along with inter-dendritic regions.At the applied potential of–0.3,0,and 0.1 V vs.saturated calomel electrode(SCE),no significant damage to the surface of the alloy was observed.At the applied potentials of 0.15 and 0.2 V vs.SCE,selective detachment and tearing of the microstructure on the alloy surface were observed,attributed to micro-galvanic corrosion.HEA demonstrates typical spontaneous passivation behavior and exhibits capacitance at all five applied potentials.The energy dispersive spectroscopy results indicate significant elemental segregation within HEA,with a decrease in the content of Cr_(2)O_(3)in the passive film as the applied potential increases.Consequently,the protective efficacy of the passive film over the substrate in 0.5 mol/L NaOH solution was compromised.展开更多
Magnesium(Mg)alloys have attracted considerable attention as promising implant materials for biodegradable medical devices.In this study,we focused on investigating the effect of macroscopic environmental heterogeneit...Magnesium(Mg)alloys have attracted considerable attention as promising implant materials for biodegradable medical devices.In this study,we focused on investigating the effect of macroscopic environmental heterogeneity due to the degradation of Mg on its corrosion behavior.The immersion experiments using pure Mg plates,which were placed vertically in a culture medium(Dulbecco’s Modified Eagle’s Medium(DEME)+10%fetal bovine serum(FBS))for 1,5,and 10 days,were conducted.Surface analyses for the corrosion product layers and the measurements of the pH values and concentrations of eluted ions in the immersion medium around the upper and lower areas of the Mg plate were performed.The significant effect of the macroscopic environmental heterogeneity derived from Mg degradation on the corrosion behavior was demonstrated by in vitro tests.Additionally,the in vivo tests were carried out by implanting the pure Mg plates in the femur of rabbits.The in vivo results exhibited macroscopically heterogeneous Mg degradation,with areas of more severe corrosion compared to the in vitro test;it is especially noticeable during the early stage of degradation,even though the average corrosion rate was lower.展开更多
文摘Angular distribution of photoelectrons is investigated during the inner photoemissive effect for two variants: quantum of light basically reveals wave and basically corpuscular properties interacting with orbital electron. Distinction in angular distribution of photoelectrons for these variants is demonstrated. Angular distribution in the second variant is investigated for the nonrelativistic and relativistic cases.
文摘The Earth surface is a multiple open system. Semiconducting minerals, including most metal oxides and sulfides, absorb visible light of the solar spectrum. Microorganisms evolve varied pathways to get carbon and energy sources. It is obvious that the interaction among solar light, semiconducting minerals, photoelectron/photohole, organics, inorganics, valence electrons and microorganisms occurs continuously on our planet. In a recent study, Lu et al. (2012) presented evidence demonstrating solar energy mediated by semiconducting mineral photocatalysis, acting as energy source, promoted the growth of some non-photosynthetic bacteria and revealed that the ternary system of microorganisms, minerals and solar light has played a critical role in the history of life on our planet. In simulated system, under simulated solar light semiconducting minerals, such as metal oxides and metal sulfides, generates photoelectrons which could be used by non-phototrophic microorganisms to support their metabolisms. The growth of microorganism was closely related to photon quantity and energy, and the microorganism growth and mineral light absorption spectra were fitted well under different light wavelengths. The overall energy efficiency from photon to biomass was 0.13‰ to 1.9‰. Further studies revealed that in natural soil systems, semiconducting mineral photocatalysis could influence the microbial population. Solar energy utilization pathway by nonphototrophic microorganisms mediated by semiconducting mineral photocatalysis provides a new concept to evaluate the origin and evolution of life. Semiconducting minerals are ubiquitous on Earth’s surface and widely participate in redox reactions following photoelectron-photohole pairs excited by solar light. As photoholes can be easily scavenged by environmental reductive substances and microorganisms possess multiple strategies to utilize extracellular electrons, the highly reductive photoelectrons serve as potential energy source for microbial life. The discovery of this pathway extends our knowledge on the use of solar energy by nonphototrophic microorganisms, and provides important clues to evaluate life on the early Earth. Microorganisms, minerals and solar light constitute a complex but important ternary system through Earth history. The discovery of the novel energy conversion pathway in this system demonstrates how nonphototrophic microorganisms directly or indirectly utilized photoelectrons as the solar energy source. The fully comprehending of nonphototrophic bacteria solar energy utilization conducted by semiconducting minerals in present environment will greatly help us to better understand the energy transform mechanism among interfaces of lithosphere, pedosphere, hydrosphere and biosphere.
基金supported by the B-type Strategic Priority Program No.XDB4100000funded by the Chinese Academy of Sciences and the pre-research projects on Civil Aerospace Technologies No.D020105 and D020104+1 种基金funded by China’s National Space Administrationthe National Natural Science Foundation of China through grants 41525015,41774186,and 41904154.
文摘Electron pitch angle distributions similar to bidirectional electron conics(BECs)have been reported at Mars in previous studies based on analyses of Mars Global Surveyor measurements.BEC distribution,also termed“butterfly”distribution,presents a local minimum flux at 90°and a maximum flux before reaching the local loss cone.Previous studies have focused on 115 eV electrons that were produced mainly via solar wind electron impact ionization.Here using Solar Wind Electron Analyzer measurements made onboard the Mars Atmosphere and Volatile Evolution spacecraft,we identify 513 BEC events for 19-55 eV photoelectrons that were generated via photoionization only.Therefore,we are investigating electrons observed in regions well away from their source regions,to be distinguished from 115 eV electrons observed and produced in the same regions.We investigate the spatial distribution of the 19-55 eV BECs,revealing that they are more likely observed on the nightside as well as near strong crustal magnetic anomalies.We propose that the 19-55 eV photoelectron BECs are formed due to day-to-night transport and the magnetic mirror effect of photoelectrons moving along cross-terminator closed magnetic field lines.
基金Project supported by the National Natural Science Foundation of China (50472037) the Natural Science Foundation of Hebei Province (E2004000117 and F2004000130) the Science and Technology Research Program from the Bureau of Science and Technology of Hebei Province (2002158)
文摘The ZnO and Zn1-xMnxO minicrystal were synthesized by chemical vapor transport (CVT). The electron trap structure (donor level) and process on the temporal behavior of photoelectrons of materials were respectively studied by thermo-luminescence and microwave absorption dielectric spectrometry. There are two peaks in the thermo-luminescence spectra in pure ZnO, one is -183 ℃ and the other is -127 ℃, which shows two kinds of electron trap energy level produced by the intrinsic defects in ZnO;but obtain very low thermo-luminescence that only equals to ten percent of pure ZnO in Zn1-xMnxO, which shows that its intensity of electron trap is less. The studies of microwave absorption dielectric spectrometry show that conduction band photoelectrons are two-step exponential decay process in ZnO, the lifetime of rapid process is 83 ns, while slow process is 828 ns, the reason of delay is relaxation effects of electron trap to conduction band photoelectrons. The intensity of electron trap is less in Zn1-xMnxO minicrystal, the relaxation effects of conduction band photoelectrons from electron trap is little, so electrons disappeared quickly at conduction band, and the decay process of photoelectrons is only 10~20 ns.
文摘Non-resonant multiphoton ionization of atomic lead at 1064nm laser field has been studied.Both the angular distribution and the intensity dependence of photoelectrons have been measured.The results show that they are very sensitive to the process of multiphoton ionization.
基金supported by the National Natural Science Foundation of China(Grant Nos.11574116,11534004,11704147,and 10704028)。
文摘The above-threshold ionization process of ammonia molecules induced by a femtosecond laser field at 800 nm is studied in the intensity range from 1.6×10^(13) to 5.7×10^(13)W/cm^(2).Channel switching under different laser intensities is observed and identified in the photoelectron kinetic energy spectra of ammonia.Based on the photoelectron kinetic energy distributions and the photoelectron angular distributions,the characteristic peaks observed are exclusively assigned to the multiphoton resonance through certain intermediate states,followed by multiphoton above-threshold ionization.
基金supported by National Natural Science Foundation of China(Grant No.41230103)National Basic Research Program of China(Grant No.2014CB846001)
文摘Energy is the key issue of all life activities.The energy source and energy yielding pathway are the key scientific issues of the origin and early evolution of life on Earth.Current researches indicate that the utilization of solar energy in large scale by life was an important breaking point of the early evolution of life on Earth and afterwards life gradually developed and flourished.However,in the widespread biochemical electron transfer of life activities,it is still not clear whether the electron source is sun or how electrons originated from sun.For billions of years,the ubiquitous semiconducting minerals in epigeosphere absorb solar energy,forming photoelectrons and photoholes.In reductive and weak acidic environment of early Earth,when photoholes were easily scavenged by reducing matters,photoelectrons were separated.Photoelectrons could effectively reduce carbon dioxide to organic matters,possibly providing organic matter foundation for the origin of life.Photoelectrons participated in photoelectron transfer chains driven by potential difference and transfer into primitive cells to maintain metabolisms.Semiconducting minerals,by absorbing ultraviolet,also protected primitive cells from being damaged by ultraviolet in the origin of life.Due to the continuous photoelectrons generation in semiconducting minerals and utilization by primitive cells,photoelectrons from semiconducting minerals’photocatalysis played multiple roles in the origin of life on early Earth,such as organic synthesis,cell protection,and energy supply.This mechanism still plays important roles in modern Earth surface systems.
基金financially supported by the National Key R&D Program of China(Nos.2022YFA1504500 and 2021YFA1502800)the National Natural Science Foundation of China(Nos.22372158,22332006,and 22288201)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0600300)iChEM and Photon Science Center for Carbon Neutrality.
文摘The dynamic evolution of surface electrochemical potential of the electrolyte plays a key role in the performance of solid-state electrochemical devices,while its real-time characterization remains challenging.Here,we visualize the dynamic evolution of the surface electrochemical potential on yttria-stabilized zirconia(YSZ)in a planar Au|YSZ|Au model cell,using spatially resolved photoelectron-based techniques including photoemission electron microscopy(PEEM)and micro-region X-ray photoelectron spectroscopy(μ-XPS).PEEM reveals two sequential reaction fronts in YSZ under cathodic polarization,corresponding to the evolution of the chemical potential of oxygen ions,with a faster propagation speed on the top surface and a slower one in the near-surface region.XPS measurements quantitatively reveal the time-dependent electric potential distribution across YSZ surface.COMSOL simulations confirm the presence of a stronger electric field at the top surface,particularly at the advancing reaction fronts,compared to the near-surface region.The critical role of the electric field in driving surface reactions is further supported by the enhanced reactions observed at the tips of the zigzag-shaped electrode edges.This work offers mechanistic insights into the coupling between electrochemical potential dynamics and electrolyte reactions.
基金financial support from the National Natural Science Foundation of China (U1401245, 21501052 and 91622119)the Program for Innovative Research Team in Chinese Universities (IRT1237)+2 种基金China Postdoctoral Science Foundation (2015M570304)the Special Funding for Postdoctoral of Heilongjiang Province (LBH-TZ06019)UNPYSCT-2016173
文摘It is highly desired to improve the photoelectric property of nanosized BiOBr by promoting the photogenerated charge transfer and separation. Herein, SnO2 and Ag comodified BiOBr nanocomposites(Ag-SO-BOB) have been prepared through a simple one-pot hydrothermal method.Surface photovoltage response of BiOBr nanoplates has 4.1-time enhancement after being modified with SnO2 nanoparticles. Transient-state surface photovoltage(TS-SPV) and the atmosphere-controlled steady-state surface photovoltage spectroscopy(AC-SPS) confirmed that this exceptional enhancement of the photovoltage response can be ascribed to the coupled SnO2 acting as platform for accepting the photoelectrons from BiOBr so as to prolong the lifetime and enhance charge separation. Remarkably, the surface photovoltage response can be further enhanced by synchronously introducing Ag nanoparticles, which is up to 15.4-times enhancement compared with bulk BiOBr nanoplates. The enhancement can be attributed to the improved O2 adsorption by introducing Ag to further enhance charge separation. Finally, the synergistic effect of SnO2 and Ag co-modification enhances the surface photovoltage response due to the enhanced charge separation and promoted O2 adsorption, which is also confirmed through photoelectrochemistry and photocatalytic experiment.
基金supported by the National Science Foundation (Grant No.CHE-2403841)。
文摘We report a study on the electronic structure and chemical bonding of the PB and AsB diatomic molecules using high-resolution photoelectron imaging of cryogenically-cooled PB^(−)and AsB^(−)anions.The electron affinities of PB and AsB are measured to be 2.751(1)and 2.600(1)eV,respectively.The ground states of the PB^(−)and AsB−anions are determined to be ^(2)Σ^(+) with a σ^(1)π^(4) valence electron configuration.The ground states of neutral PB and AsB are found to be ^(3)Π_(2) with a σ^(1)π^(3) electron configuration.The spin-orbit excited states(^(3)Π_(1) and ^(3)Π_(0)),as well as two low-lying singlet excited states(^(1)Σ^(+)and ^(1)Π),are observed.Unusual spectroscopic characteristics are observed in the ^(3)Π_(2) ground state of AsB,probably due to state mixing with a higher-lying ^(1)Δ_(2) state.The current work provides extensive electronic and spectroscopic information for the PB and AsB molecules.
基金supported by the Vinnova(project number 2020-03778)supported by the Swedish Research Council(Vetenskapsradet,project number 2021-04157).
文摘Nano-scale chemical inhomogeneity in surface oxide films formed on a V-and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron-based hard X-ray Photoelectron emission spectroscopy(HAXPES)and microscopy(HAXPEEM)as well as microscopic X-ray absorption spectroscopy(μ-XAS)techniques.The results reveal the inhomogeneity in the oxide films on the micron-sized Cr_(2)N-and VN-type particles,while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600℃.The oxide film formed on Cr_(2)N-type particles is rich in Cr_(2)O_(3) compared with that on the martensite matrix and VN-type particles.With the increase of tempering temperature,Cr_(2)O_(3) formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.
基金Projects(82171030,81870678)supported by the National Natural Science Foundation of China。
文摘Magnesium alloys as medical implant materials necessitate a lower and adjustable corrosion rate for clinical applications.The microstructure and corrosion behavior of AZ31Mn-xEr(x=0.1,0.5,1.2)alloys were systematically investigated using optical microscopy(OM),scanning electron microscopy(SEM),and X-ray photoelectron spectroscopy(XPS),combined with Tafel polarization and electrochemical impedance spectroscopy(EIS)analyses.The findings showed that the alloying element Er refined the grain structure during solidification by increasing the nucleation rate and forming a secondary phase of Al_(3)Er with Al.The Er and Mg in the matrix co-oxidize to form a dense MgO/Er_(2)O_(3)composite oxide,preventing the formation of loose magnesium hydroxide/basic magnesium carbonate.The trace alloying element Mn interacts with impurities Fe in the magnesium matrix to form an AlFeMn second phase,reducing micro-galvanic corrosion driving force.Electrochemical testing in a 3.5%NaCl solution demonstrated a marked reduction in corrosion rate from 10.46 mm/a(AZ 31 Mn alloy)to 0.44 mm/a(AZ31Mn-1.2Er alloy).This research offers a reference for searching for corrosion-resistant magnesium alloy and degradable medical magnesium alloy materials.
基金supported by Key Laboratory of Research on Hydraulic and Hydro-Power Equipment Surface Engineering Technology of Zhejiang Province(20240304).
文摘The corrosion behaviors of an as-cast FeCoNiAl_(0.75)Cr_(1.25)high-entropy alloy(HEA)in acidic Na_(2)SO_(4)solution with different pH values were investigated.The results indicate that the as-cast FeCoNiAl_(0.75)Cr_(1.25)HEA is mainly composed of face-centered cubic phase,body-centered cubic(BCC1)phase(Co–Cr–Fe)and ordered BCC(B2)phase(Ni–Al),in which BCC1 phase and B2 phase have a eutectic microstructure.Moreover,the corrosion of B2 phase occurs preferentially in a 0.05 mol/L SO_(4)^(2−)acidic solution.The electrochemical measurement results show that the corrosion resistance of the investigated HEA significantly changes as the solution pH increases from 2 to 2.5.This indicates that there is a critical pH in the range of 2–2.5 that affects the corrosion of HEA.In addition,the results of X-ray photoelectron spectroscopy prove that the surface film of FeCoNiAl_(0.75)Cr_(1.25)in SO_(4)^(2−)solution is formed with Al_(2)O_(3)and Cr_(2)O_(3)as the main components,and The content of Al2O3 and Cr_(2)O_(3)increases with increasing solution pH.
基金Project supported by National Research and Innovation Agency of the Republic of Indonesia(Badan Riset dan Inovasi Nasional-BRIN)through the Grant of Rumah Program Organisasi Riset Nanoteknologi dan Material(RP-ORNM)No.20/Ⅲ.10/HK/2024。
文摘In the present work,the effects of neodymium(Nd)on micro structure,mechanical performance,and corrosion behavior of powder metallurgy Mg-2Si-xNd(x=0.05 wt%,0.15 wt%,and 0.20 wt%)alloys were investigated.Microstructures were examined by optical and scanning electron microscopes combined with an energy-dispersive spectrometer.Hardness and compressive tests were used to study the mechanical properties of alloys.Potentiodynamic polarization,electrochemical impedance spectroscopy(EIS),Mott-Schottky analysis,and the hydrogen evolution test were applied to characterize the corrosion behavior of alloys in Hanks'solution.The microstructure of Mg-2Si-xNd alloys mainly consists ofα-Mg matrix,Mg2Si,and MgNd phases.The increase in Nd content tends to decrease the aspect ratio ofα-Mg grains,which leads to the enhancement of the ultimate-compressive strengths and hardness of the alloys.Potentiodynamic polarization shows that increasing Nd content leads to a lower corrosion current density in the Mg-2Si-xNd alloys.The EIS results confirm that a higher addition of Nd suppresses the dissolution kinetics of the alloys due to the increasing charge transfer resistance.Mott-Schottky analysis reveals the formation of an n-type semiconductive passive film on the alloy surfaces,where the interstitial and oxygen vacancies predominate over the metal vacancies.The X-ray photoelectron spectroscopy(XPS)reveals that a mixture of Mg(OH)_(2),MgO,MgCO_(3),and Nd_(2)O_(3)has formed as the corrosion products on the Mg-2Si-xNd alloy surfaces after a longer immersion time in Hanks'solution.
基金funded by the Air Force Office of Scientific Research (AFOSR) under Grant (No.FA955023-1-0545)。
文摘High-resolution photoelectron spectra of cryogenically cooled TiO_(2)CH_(3)OH^(−)anions obtained with slow electron velocity-map imaging are reported and used to explore the reactions of TiO_(2)^(−/0)with methanol.The highly structured spectra were compared with results from DFT calculations to determine the dominant structure to be cis-CH_(3)OTi(O)OH^(−),a dissociative adduct in which CH3OH is split by TiO_(2)^(−).The experiment yields an electron affinity of 1.2152(7)eV for TiO_(2)CH^(3)OH as well as several vibrational frequencies for the neutral species.Comparison to Franck−Condon(FC)simulations shows that while most experimental features appear in the simulations,several are not and are assigned to FC-forbidden transitions involving non-totally symmetric vibrational modes.The FC-allowed and forbidden transi-tions also exhibit different photoelectron angular distributions.The FC-forbidden transitions are attributed to Herzberg−Teller(HT)coupling with the A^(2)A″excited state of the anion.The results are compared to previous cryogenic slow electron velocity-map imaging(cryo-SE-Ⅵ)studies of bare TiO_(2)^(−)and the water-split adduct TiO_(3)H_(2)^(−).
基金supported by the National Natural Science Foundation of China(Nos.92461313,12074387,and 92161114)the Innovation Capability Support Program of Shaanxi Province(No.2023-CX-TD-49).
文摘The structure and electronic properties of Co_(2)Ge_(10)^(-)anion and its neutral counterpart were investigated by anion photoelectron spectroscopy and theoretical calculations.The experimental vertical detachment energy of Co_(2)Ge_(10)^(-)was measured to be 2.86±0.08 eV.The lowest-energy isomer of Co_(2)Ge_(10)^(-)is in a doublet state and has a cage-like structure with Cs symmetry,which can be constructed by a tetragonal bipyramid on top of a pentagonal bipyramid and these two bipyramid structures share a common Co atom.The most stable structure of neutral Co_(2)Ge_(10)resembles its anionic counterpart and it is in a triplet state.The natural population analysis showed that the inner Co atom of both the anionic and neutral Co_(2)Ge_(10)acquires negative charge from the neighboring Ge atoms.The outer Co atom has a larger spin moment than the inner Co atom,indicating that the magnetic moments of Co_(2)Ge_(10)^(-/0)are mainly contributed by the outer Co atom.Analyses of the density of states and molecular orbitals indicated that there are a few highly delocalized molecular orbitals in Co_(2)Ge_(10)^(-),which are mainly contributed by Ge 4s atomic orbitals.
基金was supported by the U.S.Department of Energy(DOE),Office of Science,Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,and Biosciences,Condensed Phase and Interfacial Molecular Science program,FWP 16248.
文摘MgATP is a stable complex formed by the chelation of Mg^(2+)with deprotonated adenosine-5'-triphosphate(ATP).In the cellular environment,MgATP plays a critical role in ATP hydrolysis,releasing substantial energy to support essential biological functions.To understand the structure and stabilization mechanism of MgATP,we conducted a joint negative ion photoelectron spectroscopic and computational study of the[ATP^(4-)·Mg^(2+)]^(2-)complex dianion,using[ATP^(4-)·2H^(+)]^(2-)as a reference.The experimentally determined adiabatic and vertical detachment energies(ADE and VDE)of[ATP^(4-)·Mg^(2+)]^(2-)at 20 K are 3.51±0.05 eV and 3.82±0.05 eV,respectively.The major spectral features of[ATP^(4-)·Mg^(2+)]^(2-)are attributed to two theoretically identified isomers with unfolded geometries,which are stabilized primarily by electrostatic interactions between Mg^(2+)and the triphosphate and ribose groups,with four deprotonated oxygens forming a pseudo-tetrahedral coordination.In contrast,[ATP^(4-)·2H^(+)]^(2-)exhibits a fundamentally different stabilization mechanism.Although most of the fifteen identified[ATP^(4-)·2H^(+)]^(2-)isomers also adopt unfolded geometries,they are primarily stabilized by intramolecular hydrogen bonds within the triphosphate group and between triphosphate and ribose groups.The interaction between ATP^(4-)and two protons is found to be much weaker than that with Mg^(2+),and[ATP^(4-)·2H^(+)]^(2-)exhibits substantial structural flexibility compared to[ATP^(4-)·Mg^(2+)]^(2-)due to the conformational constraint of the triphosphate chain by Mg^(2+).Thirteen[ATP^(4-)·2H^(+)]^(2-)isomers with unfolded geometries likely account for the major high-EBE(electron-binding-energy)spectral features.Notably,for the first time,a low EBE and temperature-dependent spectral feature is observed and attributed to two folded isomers of[ATP^(4-)·2H^(+)]^(2-),which exist at 20 K but disappear at room temperature.This study provides valuable molecular-level insights into cellular MgATP that resides within the hydrophobic pockets of proteins.
基金supported by the National Natural Science Foundation of China(No.22273065)Shandong Energy institute(SEI U202312)"Strategic Priority Research Program"of the Chinese Academy of Sciences(No.XDA02020000).
文摘The vibrational resolved spectra of MO_(2)^(-)/MO_(2)(M=Ti,Zr,and Hf)are reported by using photoelectron imaging and theoretical calculations.The results indicate that all the ground states of anionic and neutral MO_(2)(M=Ti,Zr,and Hf)compounds are formed in bent insertion structures.The observed ground-state adiabatic detachment energy(ADE)is measured to be 1.597±0.003,1.651±0.003,and 2.119±0.003 eV for TiO_(2)^(-),ZrO_(2)^(-),and HfO_(2)^(-),respectively.The vibrational frequencies of the anionic and neutral MO_(2)are also determined from the experimental spectra.The results of theoretical calculations show that the electronic configurations of MO_(2)^(-)are^(2)A_(1)with C_(2v)point group.Bond order analysis indicates that the two M-O bonds are all multiple characters.
基金funded by National Key Research and Development Program of China(No.2021YFB3401100)Evaluation Project of Guangdong Provincial Key Laboratory(No.2023B1212060043)+1 种基金Young Elite Scientists Sponsorship Program by CAST(No.2022QNRC001)GDAS'Project of Science and Technology Development(Nos.2023GDASQNRC-0205 and 2024GDASZH-2024010102).
文摘The corrosion behavior of CoCrCu_(0.1)FeMoNi high entropy alloy(HEA)in 0.5 mol/L NaOH solution was investigated using X-ray photoelectron spectroscopy,X-ray diffraction,scanning electron microscopy,potentiodynamic polarization measurement,and electrochemical impedance spectroscopy.The results showed that the microstructure of this HEA displayed a dendritic morphology along with inter-dendritic regions.At the applied potential of–0.3,0,and 0.1 V vs.saturated calomel electrode(SCE),no significant damage to the surface of the alloy was observed.At the applied potentials of 0.15 and 0.2 V vs.SCE,selective detachment and tearing of the microstructure on the alloy surface were observed,attributed to micro-galvanic corrosion.HEA demonstrates typical spontaneous passivation behavior and exhibits capacitance at all five applied potentials.The energy dispersive spectroscopy results indicate significant elemental segregation within HEA,with a decrease in the content of Cr_(2)O_(3)in the passive film as the applied potential increases.Consequently,the protective efficacy of the passive film over the substrate in 0.5 mol/L NaOH solution was compromised.
基金supported by JSPS KAKENHI Grant Number 22K12903.
文摘Magnesium(Mg)alloys have attracted considerable attention as promising implant materials for biodegradable medical devices.In this study,we focused on investigating the effect of macroscopic environmental heterogeneity due to the degradation of Mg on its corrosion behavior.The immersion experiments using pure Mg plates,which were placed vertically in a culture medium(Dulbecco’s Modified Eagle’s Medium(DEME)+10%fetal bovine serum(FBS))for 1,5,and 10 days,were conducted.Surface analyses for the corrosion product layers and the measurements of the pH values and concentrations of eluted ions in the immersion medium around the upper and lower areas of the Mg plate were performed.The significant effect of the macroscopic environmental heterogeneity derived from Mg degradation on the corrosion behavior was demonstrated by in vitro tests.Additionally,the in vivo tests were carried out by implanting the pure Mg plates in the femur of rabbits.The in vivo results exhibited macroscopically heterogeneous Mg degradation,with areas of more severe corrosion compared to the in vitro test;it is especially noticeable during the early stage of degradation,even though the average corrosion rate was lower.