The efficient separation of chalcopyrite(CuFeS2)and galena(PbS)is essential for optimal resource utilization.However,find-ing a selective depressant that is environmentally friendly and cost effective remains a challe...The efficient separation of chalcopyrite(CuFeS2)and galena(PbS)is essential for optimal resource utilization.However,find-ing a selective depressant that is environmentally friendly and cost effective remains a challenge.Through various techniques,such as mi-croflotation tests,Fourier transform infrared spectroscopy,scanning electron microscopy(SEM)observation,X-ray photoelectron spec-troscopy(XPS),and Raman spectroscopy measurements,this study explored the use of ferric ions(Fe^(3+))as a selective depressant for ga-lena.The results of flotation tests revealed the impressive selective inhibition capabilities of Fe^(3+)when used alone.Surface analysis showed that Fe^(3+)significantly reduced the adsorption of isopropyl ethyl thionocarbamate(IPETC)on the galena surface while having a minimal impact on chalcopyrite.Further analysis using SEM,XPS,and Raman spectra revealed that Fe^(3+)can oxidize lead sulfide to form compact lead sulfate nanoparticles on the galena surface,effectively depressing IPETC adsorption and increasing surface hydrophilicity.These findings provide a promising solution for the efficient and environmentally responsible separation of chalcopyrite and galena.展开更多
Epoxy resin-reinforced graphite composites have found extensive application as bipolar plates in fuel cells for stationary power supplies,valued for their lightweight nature and exceptional durability.To enhance the i...Epoxy resin-reinforced graphite composites have found extensive application as bipolar plates in fuel cells for stationary power supplies,valued for their lightweight nature and exceptional durability.To enhance the interfacial properties between graphite and epoxy resin(EP),surface oxidation of graphite was carried out using diverse functional groups.Experimental assessments illustrated that the composites with graphite oxide resulted in heightened mechanical strength and toughness compared to pristine graphite,which could be attributed to the excellent interface connection.Moreover,these composites displayed remarkable conductivity while simultaneously retaining their mechanical attributes.Furthermore,molecular dynamics simulations outcomes unveiled that the inclusion of oxygen-containing functional groups on the graphite surface augmented the interfacial energy with EP,and the interface morphology between graphite and resin exhibited heightened stability throughout the stretching process.This simple and effective technique presents opportunities for improving composites interfaces,enabling high load transfer efficiency,and opens up a potential path for developing strong and tough composite bipolar plates for fuel cells.展开更多
This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were chara...This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were characterized with several different techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and Raman, when they were fresh from sputter chamber and aged after years, respectively, in order to determine their structure and composition. It finds that a small amount of sodium occurred on the surface of vanadium dioxide films, which was probably due to sodium ion diffusion from soda-lime glass when sputtering was performed at high substrate temperature. It also finds that aging for years significantly affected the nonstoichiometry of vanadium dioxide films, thus inducing much change in Raman modes.展开更多
Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and ox...Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol（tBA） with low dosages of AC,while it was hardly affected by tBA when the AC dosage was greater than 0.3 g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05 g/L, but it did not work when the AC dosage was no less than 0.1 g/L. These observations indicate that HOUin bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HOU oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5 g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HOUoxidation in basic bulk solution. A mechanism involving both HOUoxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.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
In this study, chalcopyrite was oxidized in hydrogen peroxide(H_(2)O_(2)) solutions of different concentrations to simulate different degrees of oxidation in real ores, and the effects of H_(2)O_(2) treatment on chalc...In this study, chalcopyrite was oxidized in hydrogen peroxide(H_(2)O_(2)) solutions of different concentrations to simulate different degrees of oxidation in real ores, and the effects of H_(2)O_(2) treatment on chalcopyrite surface properties and flotation performance were investigated by surface analysis techniques and floatation experiments, which implied the reason for the poor grade and recovery of oxidized chalcopyrite concentrate in the production process of the ore. Flotation results showed that when the concentration of H_(2)O_(2) increased from 0%(by weight) to 5%, the flotation recovery of chalcopyrite decreased sharply.However, with increasing H_(2)O_(2) concentration from 5% to 30%, chalcopyrite recovery improved relatively to different degrees with different collector concentrations. Analyses of X-ray photoelectron spectroscopy(XPS) and inductively coupled plasma-atomic optical emission spectrophotometry(ICP-OES) results indicated that the pretreatment with H_(2)O_(2) caused that hydrophilic substance formed on chalcopyrite surface with the dissolution of copper ions, and the dissolution amount of copper increased with the increase of H_(2)O_(2) concentration. UV–visible spectrophotometer and Fourier transform infrared spectrum(FTIR) studies indicated that the pretreatment of chalcopyrite with H_(2)O_(2) had little effect on the adsorption amount of potassium butyl xanthate(PBX) on chalcopyrite surface. However, due to the dissolution of copper ions, PBX interacted with chalcopyrite mainly as buthyl dixanthogen(BX)_(2).展开更多
Many transition metal sulfides and phosphides are susceptible to surface oxidation under ambient conditions.The formed surface oxidation layer,which is likely to further restructure under reaction conditions,alters th...Many transition metal sulfides and phosphides are susceptible to surface oxidation under ambient conditions.The formed surface oxidation layer,which is likely to further restructure under reaction conditions,alters the chemical properties of the pristine material but has not been well studied.In this work,we for the first time use X-ray photoelectron spectroscopy to quantify the natural surface oxidation of transition metal phosphide and sulfide nanoparticles and employ a simplified Deal-Grove model to analyze the kinetics.We show that CoS2 oxidizes faster than CoS whereas CoP_(2) is more difficult to oxidize compared to CoP,and there exists an inverse correlation between the surface oxidation rate and the Co-S/P distance in the pristine structure.More inclusive investigation unveils different types of surface oxidation behavior:CoS,NiS and FeS are limited by their reactivity with oxygen;CoS2 is the most reactive and its oxidation is governed by oxygen diffusion;CoP_(2) is influenced by both reactivity and diffusion;CoP,Ni_(2)P,Cu_(3)P and MoP exhibit high initial oxidation degrees and the kinetics are not well-defined;MoS2 is largely stable against oxidation.展开更多
Recently,the layered transition metal dichalcogenide 1T′-MoTe2 has generated considerable interest due to their superconducting and non-trivial topological properties.Here,we present a systematic study on 1T′-MoTe2 ...Recently,the layered transition metal dichalcogenide 1T′-MoTe2 has generated considerable interest due to their superconducting and non-trivial topological properties.Here,we present a systematic study on 1T′-MoTe2 single-crystal and exfoliated thin-flakes by means of electrical transport,scanning tunnelling microscope(STM)measurements and band structure calculations.For a bulk sample,it exhibits large magneto-resistance(MR)and Shubnikov–de Hass oscillations inρxx and a series of Hall plateaus inρxy at low temperatures.Meanwhile,the MoTe2 thin films were intensively investigated with thickness dependence.For samples,without encapsulation,an apparent transition from the intrinsic metallic to insulating state is observed by reducing thickness.In such thin films,we also observed a suppression of the MR and weak anti-localization(WAL)effects.We attributed these effects to disorders originated from the extrinsic surface chemical reaction,which is consistent with the density functional theory(DFT)calculations and in-situ STM results.In contrast to samples without encapsulated protection,we discovered an interesting superconducting transition for those samples with hexagonal Boron Nitride(h-BN)film protection.Our results indicate that the metallic or superconducting behavior is its intrinsic state,and the insulating behavior is likely caused by surface oxidation in few layer 1T’-MoTe2 flakes.展开更多
The experiment utilized commercial hot-dip Zn-1.2Al-1.2Mg(designated ZM)coated steel sheets,which were heated in a resistance furnace and held for 5 min at temperatures ranging from 600℃to 900℃.The main goal was to ...The experiment utilized commercial hot-dip Zn-1.2Al-1.2Mg(designated ZM)coated steel sheets,which were heated in a resistance furnace and held for 5 min at temperatures ranging from 600℃to 900℃.The main goal was to investigate the effect of heating temperature on the surface oxidation behavior of the ZM coating.The results show that at lower heating temperatures,the surface oxides are mainly composed of an original thin Al_(2)O_(3) layer,which acted as a barrier preventing further oxidation of the coating.By contrast,at higher heating temperatures,intermetallic phase formation caused Al_(2)O_(3) layer fragmentation.As a result,the oxide layer of the coating surface became more complex,featuring thicker Al_(2)O_(3),MgO,and ZnO.展开更多
The effect of surface roughness on the oxidation behavior of a directionally solidified Ni-based superalloy was investigated by surface mapping microscope,scanning electron microscope and X-ray diffraction.It was foun...The effect of surface roughness on the oxidation behavior of a directionally solidified Ni-based superalloy was investigated by surface mapping microscope,scanning electron microscope and X-ray diffraction.It was found that specimens with surface roughness of 0.05 urn exhibit the best oxidation resistance,while specimens with surface roughness of 0.14 μm behave worse than specimens with surface roughness of 0.83 μm.The specimens with surface roughness of 0.05 μm have the best oxidation resistance,which is mainly due to the smallest surface area exposed in air and thinnest work-hardening layer.The AlOlayer alleviates the oxidation process of the specimens with surface roughness of 0.83 μm,and this is the possible reason for the better oxidation resistance of samples with surface roughness of 0.83 μm than samples with surface roughness of 0.14 μm.展开更多
Surface oxidation of polycrystalline nickel foil in air and pure water at different temperatures and the thermal stability of the surface oxides have been investigated by means of XPS.In ad- dition to NiO,Ni_2O_3 is f...Surface oxidation of polycrystalline nickel foil in air and pure water at different temperatures and the thermal stability of the surface oxides have been investigated by means of XPS.In ad- dition to NiO,Ni_2O_3 is formed especially after long periods of air exposure.Nickel surfaces are much less reactive to pure water than to air.The thermal stability of the surface oxides is related to oxidative temperature.The surface species of oxides formed by air exposure at temperatures below 120℃ can be reduced into nickel metal after heating the sample in vacuum at 300℃ for only 10 minutes (in the case of room temperature) to 1 h (in the case of 120℃). This reduction is caused by reaction with surface carbon contaminants.However,the surface species of nickel oxides formed by air exposure with heating at temperatures above 200℃ can not be reduced into metal after heating the sample in vacuum at 300℃ for 1h.展开更多
In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of...In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of ZK60 Mg alloy after single MPO and HCPEB＋MPO compounded treatment were investigated by SEM. The results showed that the density of the ceramic layer of HCPEB＋MPO-treated ZK60 Mg alloy was improved and defects were reduced compared to that under MPO treatment alone. Surface modified layer of ZK60 Mg alloys treated by HCPEB＋MPO was divided into three zones, namely the top loose ceramic zone, middle compact zone and inside HCPEB-induced melted zone. Corrosion resistance of ZK60 Mg alloy before and after the compounded surface modification was measured in a solution of 3.5% NaCl by potentiodynamic polarization curves. It was found that the corrosion current density of ZK60 Mg alloys could be reduced by about three orders of magnitude, from 311μA/cm^2 of the original sample to 0.2μA/cm^2 of the HCPEB＋MPO-treated sample. This indicates the great application potential of the HCPEB＋MPO compounded surface modification technology in improving the corrosion resistance of ZK60 Mg alloys in the future.展开更多
Polyacrylonitrile （PAN） based carbon fibers with different surface morphology were electrochemically treated in 3 wt% NH4HCO3 aqueous solution with current density up to 3.47 A/m 2 at room temperature, and surface s...Polyacrylonitrile （PAN） based carbon fibers with different surface morphology were electrochemically treated in 3 wt% NH4HCO3 aqueous solution with current density up to 3.47 A/m 2 at room temperature, and surface structures, surface morphology and residual mechanical properties were characterized. The crystallite size （La） of carbon fibers would be interrupted due to excessive electrochemical etching, while the crystallite spacing （d（002）） increased as increasing current density. The disordered structures on the surface of carbon fiber with rough surface increased at the initial oxidation stage and then removed by further electrochemical etching, which resulting in continuous increase of the extent of graphitization on the fiber surface. However, the electrochemical etching was beneficial to getting ordered morphology on the surface for carbon fiber with smooth surface, especially when the current density was lower than 1.77 A/m 2 . The tensile strength and tensile modulus could be improved by 17.27% and 5.75%, respectively, and was dependent of surface morphology. The decreasing density of carbon fibers probably resulted from the volume expansion of carbon fibers caused by the abundant oxygen functional groups intercalated between the adjacent graphite layers.展开更多
In order to explore an effective way to shorten treatment time and enhance the quality of treatment coating, AC micro-arc oxidation was conducted to treat the surface of AZ31 B deformation magnesium alloy in KF＋KOH t...In order to explore an effective way to shorten treatment time and enhance the quality of treatment coating, AC micro-arc oxidation was conducted to treat the surface of AZ31 B deformation magnesium alloy in KF＋KOH treatment solution. The infl uences of micro-arc oxidation parameters such as concentration of KF, concentration of KOH, output voltage of booster, temperature of treatment solution, and treatment time on treatment coating thickness were raveled out under different conditions. The structure and composition of treatment coating were determined, the growth mechanism of treatment coating was discussed, and the quick surface treatment technology for compact treatment coating with maximum thickness was developed. The experimental results show that： A maximum 33 μm-thick compact treatment coating, consisting of MgF2 and MgO mainly, can be formed on AZ31 B in 112 s under the conditions of 1 132 g/L KF, 382 g/L KOH, 66 V for output voltage of booster and 34 ℃ of treatment solution which were optimized by a genetic algorithm from the model established by artifi cial neural networks. There are no ＂crater-shaped＂ pores in this treatment coating as the heat shock resulting from the smooth variation of AC sinusoidal voltage is far smaller than that of the rigidly varied DC or pulse current. The treatment time is only one sixth of that adopted in the other surface treatment technology at best, principally for the reason that the coating can always grow irrespective of the electric potential of AZ31 B. This investigation lays a fi rm foundation for the extensive application of magnesium alloy.展开更多
The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy o...The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy of O2 on pyrrhotite surface is the largest, followed by that on marcasite surface and then pyrite surface. O2 molecules adsorbed on pyrite, marcasite and pyrrhotite surfaces are all dissociated. The oxygen atoms and surface atoms of pyrite, marcasite and pyrrhotite surfaces have different bonding structures. Due to more atoms on pyrrhotite and marcasite surfaces interaction with oxygen atoms, the adsorption energies of O2 on pyrrhotite and marcasite surfaces are larger than that on pyrite surface. Larger values of Mulliken populations for O？Fe bond of pyrrhotite surface result in relative larger adsorption energy compared with that on marcasite surface.展开更多
Titanium and its alloys are widely used in the aerospace, marine, and biomedical industry due to their unique bulk properties such as high strength-to-weight ratio and melting temperature, good corrosion resistance, a...Titanium and its alloys are widely used in the aerospace, marine, and biomedical industry due to their unique bulk properties such as high strength-to-weight ratio and melting temperature, good corrosion resistance, and favorable biocom- patibility. However, in some applications, com- ponents made of titanium or titanium alloys exhibit poor wear resistance under stationary or dynamic loading as well as contact corrosion manifested by the relatively negative standard electrode potential （-1.63 V ） . In order to improve the surface properties of titanium and its alloys, several techniques such as PVD （ physical vapor deposition ） /CVD （chemical vapor deposition ） coatings,展开更多
Leached Pt-Fe and Pt-Co catalysts were prepared by acid leaching the reduced catalysts in acid solution. Oxidation treatments of leached catalysts produced the structure o f metal oxides decorat-ing the surface of...Leached Pt-Fe and Pt-Co catalysts were prepared by acid leaching the reduced catalysts in acid solution. Oxidation treatments of leached catalysts produced the structure o f metal oxides decorat-ing the surface of nanoparticles. The fully oxidized Fe2O3 and Co3O4 species on Pt nanoparticle sur-faces result in the low performance of the CO complete oxidation （COOX） reaction. In contrast, un-saturated FeO and CoO surface species can be formed during exposure to the CO preferential oxida-tion （CO-PROX） reaction with an excess of H2, leading to a high O2 activation ability and enhancing the CO-PROX activity. The FeOx surface structures can be transformed between these two states by varying the reactive gas environments, exhibiting oscillating activity in these two reactions. Con-versely, the CoO surface structure formed in the H2 -rich atmosphere is stable when exposed to the COOX reaction and exhibits similar activity in these two reactions. It is hoped that this work may assist in understanding the important role of surface oxides in real reactions.展开更多
Marcasite(FeS2)is widespread in nature,its oxidation plays a vital role in acid mine drainage,mineral resource recovery,and photoelectric material applications.In this paper,the oxidation mechanism of marcasite has be...Marcasite(FeS2)is widespread in nature,its oxidation plays a vital role in acid mine drainage,mineral resource recovery,and photoelectric material applications.In this paper,the oxidation mechanism of marcasite has been studied for the first time using density functional theory(DFT).It is found that,unlike the oxidation of pyrite,the oxidation of marcasite merely occurs at surface S atoms.Under the coexistence of water and oxygen,S atoms around surface Fe atoms are replaced by O atoms.The surface S sites are initially oxidized to form S==O bonds,and continue to adsorb oxygen to gradually generate SO3^2-,SO4^2-species,and eventually FeSO4.In this process,H2O molecules participate in neither oxidation nor dissociation,and they are adsorbed on surface Fe sites in the form of molecules,i.e.,all O atoms in SO4^2-derive from oxygen rather than water molecules.展开更多
As the dominated composition of Si_(3)N_(4)ceramics,α-silicon nitride(α-Si_(3)N_(4))can satisfy the strength and fracture toughness demand in the applications.However,α-Si_(3)N_(4)is oxygen-sensitive at high temper...As the dominated composition of Si_(3)N_(4)ceramics,α-silicon nitride(α-Si_(3)N_(4))can satisfy the strength and fracture toughness demand in the applications.However,α-Si_(3)N_(4)is oxygen-sensitive at high temperatures,which limits its high-temperature performance.To improve the oxidation resistance ofα-Si_(3)N_(4)ceramics,it is necessary to shed light on the oxidation mechanism.Herein,the initial oxidation ofα-Si_(3)N_(4)was systematically studied at the atomic and molecular levels.The density functional theory(DFT)calculation denotes that the(001)surface ofα-Si_(3)N_(4)has the best stability at both room temperature and high temperature.Besides,the oxidation process of theα-Si_(3)N_(4)(001)surface consists of O adsorption and N desorption,and the consequent formation of nitrogen-vacancy(VN)is the key step for further oxidation.Moreover,the molecular dynamics(MD)simulation indicates that the oxidation rate ofα-Si_(3)N_(4)(100)surface is slower than that ofα-Si_(3)N_(4)(001)surface due to the lower N concentration at the outermost layer.Therefore,the oxidation resistance ofα-Si_(3)N_(4)can be improved by regulating the(100)surface as the dominant exposure surface.In addition,reducing the concentration of N on the final exposed surface ofα-Si_(3)N_(4)by mean of constructing the homojunction of the Si-terminal(100)surface and other N-containing surfaces(such as(001)surface)should be also a feasible approach.展开更多
基金the National Natural Science Foundation of China(Nos.52204298 and 52004335)the National Key R&D Program of China(Nos.2022YFC2904502 and 2022YFC2904501)+1 种基金the Major Science and Technology Projects in Yunnan Province(No.202202AB080012)the Science Research Initiation Fund of Central South University(No.202044019).
文摘The efficient separation of chalcopyrite(CuFeS2)and galena(PbS)is essential for optimal resource utilization.However,find-ing a selective depressant that is environmentally friendly and cost effective remains a challenge.Through various techniques,such as mi-croflotation tests,Fourier transform infrared spectroscopy,scanning electron microscopy(SEM)observation,X-ray photoelectron spec-troscopy(XPS),and Raman spectroscopy measurements,this study explored the use of ferric ions(Fe^(3+))as a selective depressant for ga-lena.The results of flotation tests revealed the impressive selective inhibition capabilities of Fe^(3+)when used alone.Surface analysis showed that Fe^(3+)significantly reduced the adsorption of isopropyl ethyl thionocarbamate(IPETC)on the galena surface while having a minimal impact on chalcopyrite.Further analysis using SEM,XPS,and Raman spectra revealed that Fe^(3+)can oxidize lead sulfide to form compact lead sulfate nanoparticles on the galena surface,effectively depressing IPETC adsorption and increasing surface hydrophilicity.These findings provide a promising solution for the efficient and environmentally responsible separation of chalcopyrite and galena.
基金the financial supports from the National Key R&D Program of China(No.2020YFB1505901)。
文摘Epoxy resin-reinforced graphite composites have found extensive application as bipolar plates in fuel cells for stationary power supplies,valued for their lightweight nature and exceptional durability.To enhance the interfacial properties between graphite and epoxy resin(EP),surface oxidation of graphite was carried out using diverse functional groups.Experimental assessments illustrated that the composites with graphite oxide resulted in heightened mechanical strength and toughness compared to pristine graphite,which could be attributed to the excellent interface connection.Moreover,these composites displayed remarkable conductivity while simultaneously retaining their mechanical attributes.Furthermore,molecular dynamics simulations outcomes unveiled that the inclusion of oxygen-containing functional groups on the graphite surface augmented the interfacial energy with EP,and the interface morphology between graphite and resin exhibited heightened stability throughout the stretching process.This simple and effective technique presents opportunities for improving composites interfaces,enabling high load transfer efficiency,and opens up a potential path for developing strong and tough composite bipolar plates for fuel cells.
基金supported by the National Natural Science Foundation of China (Grant No 60776039)China Agricultural University Foundation (Grant No 2007037)
文摘This paper reports that the thermochromic vanadium dioxide films were deposited on various transparent substrates by radio frequency magnetron sputtering, and then aged under circumstance for years. Samples were characterized with several different techniques such as x-ray diffraction, x-ray photoelectron spectroscopy, and Raman, when they were fresh from sputter chamber and aged after years, respectively, in order to determine their structure and composition. It finds that a small amount of sodium occurred on the surface of vanadium dioxide films, which was probably due to sodium ion diffusion from soda-lime glass when sputtering was performed at high substrate temperature. It also finds that aging for years significantly affected the nonstoichiometry of vanadium dioxide films, thus inducing much change in Raman modes.
基金supported by the National Natural Science Foundation of China (No. 21177130)the National Key Technology R&D Program (No. 2011BAC06B09)the Chinese Academy of Sciences Visiting Professorships for Senior International Scientists (No. 2009G2-28)
文摘Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol（tBA） with low dosages of AC,while it was hardly affected by tBA when the AC dosage was greater than 0.3 g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05 g/L, but it did not work when the AC dosage was no less than 0.1 g/L. These observations indicate that HOUin bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HOU oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5 g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HOUoxidation in basic bulk solution. A mechanism involving both HOUoxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.
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the support of the National Natural Science Foundation of China (No. 52174268)the Independent Exploration and Innovation Project of Graduate Students of Central South University (No. 2021zzts0885)。
文摘In this study, chalcopyrite was oxidized in hydrogen peroxide(H_(2)O_(2)) solutions of different concentrations to simulate different degrees of oxidation in real ores, and the effects of H_(2)O_(2) treatment on chalcopyrite surface properties and flotation performance were investigated by surface analysis techniques and floatation experiments, which implied the reason for the poor grade and recovery of oxidized chalcopyrite concentrate in the production process of the ore. Flotation results showed that when the concentration of H_(2)O_(2) increased from 0%(by weight) to 5%, the flotation recovery of chalcopyrite decreased sharply.However, with increasing H_(2)O_(2) concentration from 5% to 30%, chalcopyrite recovery improved relatively to different degrees with different collector concentrations. Analyses of X-ray photoelectron spectroscopy(XPS) and inductively coupled plasma-atomic optical emission spectrophotometry(ICP-OES) results indicated that the pretreatment with H_(2)O_(2) caused that hydrophilic substance formed on chalcopyrite surface with the dissolution of copper ions, and the dissolution amount of copper increased with the increase of H_(2)O_(2) concentration. UV–visible spectrophotometer and Fourier transform infrared spectrum(FTIR) studies indicated that the pretreatment of chalcopyrite with H_(2)O_(2) had little effect on the adsorption amount of potassium butyl xanthate(PBX) on chalcopyrite surface. However, due to the dissolution of copper ions, PBX interacted with chalcopyrite mainly as buthyl dixanthogen(BX)_(2).
基金This work is partially supported by the Sloan Research FellowshipL.H.and H.L.acknowledge graduate student exchange fellowships from the China Scholarship Council.
文摘Many transition metal sulfides and phosphides are susceptible to surface oxidation under ambient conditions.The formed surface oxidation layer,which is likely to further restructure under reaction conditions,alters the chemical properties of the pristine material but has not been well studied.In this work,we for the first time use X-ray photoelectron spectroscopy to quantify the natural surface oxidation of transition metal phosphide and sulfide nanoparticles and employ a simplified Deal-Grove model to analyze the kinetics.We show that CoS2 oxidizes faster than CoS whereas CoP_(2) is more difficult to oxidize compared to CoP,and there exists an inverse correlation between the surface oxidation rate and the Co-S/P distance in the pristine structure.More inclusive investigation unveils different types of surface oxidation behavior:CoS,NiS and FeS are limited by their reactivity with oxygen;CoS2 is the most reactive and its oxidation is governed by oxygen diffusion;CoP_(2) is influenced by both reactivity and diffusion;CoP,Ni_(2)P,Cu_(3)P and MoP exhibit high initial oxidation degrees and the kinetics are not well-defined;MoS2 is largely stable against oxidation.
基金The work was supported by the Guangdong Innovative and Entrepreneurial Research Team Program,China(Grant No.2016ZT06D348)the National Natural Science Foundation of China(Grant No.11874193)the Shenzhen Fundamental Subject Research Program,China(Grant No.JCYJ20170817110751776).K.D.W.acknowledges support from the National Natural Science Foundation of China(Grant No.11574128).X.D.acknowledges support from NSF under award DMR-1808491.
文摘Recently,the layered transition metal dichalcogenide 1T′-MoTe2 has generated considerable interest due to their superconducting and non-trivial topological properties.Here,we present a systematic study on 1T′-MoTe2 single-crystal and exfoliated thin-flakes by means of electrical transport,scanning tunnelling microscope(STM)measurements and band structure calculations.For a bulk sample,it exhibits large magneto-resistance(MR)and Shubnikov–de Hass oscillations inρxx and a series of Hall plateaus inρxy at low temperatures.Meanwhile,the MoTe2 thin films were intensively investigated with thickness dependence.For samples,without encapsulation,an apparent transition from the intrinsic metallic to insulating state is observed by reducing thickness.In such thin films,we also observed a suppression of the MR and weak anti-localization(WAL)effects.We attributed these effects to disorders originated from the extrinsic surface chemical reaction,which is consistent with the density functional theory(DFT)calculations and in-situ STM results.In contrast to samples without encapsulated protection,we discovered an interesting superconducting transition for those samples with hexagonal Boron Nitride(h-BN)film protection.Our results indicate that the metallic or superconducting behavior is its intrinsic state,and the insulating behavior is likely caused by surface oxidation in few layer 1T’-MoTe2 flakes.
基金financial support by the Natural Science Foundation of Shanghai(grant number 24ZR1423300).
文摘The experiment utilized commercial hot-dip Zn-1.2Al-1.2Mg(designated ZM)coated steel sheets,which were heated in a resistance furnace and held for 5 min at temperatures ranging from 600℃to 900℃.The main goal was to investigate the effect of heating temperature on the surface oxidation behavior of the ZM coating.The results show that at lower heating temperatures,the surface oxides are mainly composed of an original thin Al_(2)O_(3) layer,which acted as a barrier preventing further oxidation of the coating.By contrast,at higher heating temperatures,intermetallic phase formation caused Al_(2)O_(3) layer fragmentation.As a result,the oxide layer of the coating surface became more complex,featuring thicker Al_(2)O_(3),MgO,and ZnO.
基金financially supported by the National Natural Science Foundation of China(No.51201164)National High Technology Research and Development Program of China(No.2012AA03A511)
文摘The effect of surface roughness on the oxidation behavior of a directionally solidified Ni-based superalloy was investigated by surface mapping microscope,scanning electron microscope and X-ray diffraction.It was found that specimens with surface roughness of 0.05 urn exhibit the best oxidation resistance,while specimens with surface roughness of 0.14 μm behave worse than specimens with surface roughness of 0.83 μm.The specimens with surface roughness of 0.05 μm have the best oxidation resistance,which is mainly due to the smallest surface area exposed in air and thinnest work-hardening layer.The AlOlayer alleviates the oxidation process of the specimens with surface roughness of 0.83 μm,and this is the possible reason for the better oxidation resistance of samples with surface roughness of 0.83 μm than samples with surface roughness of 0.14 μm.
文摘Surface oxidation of polycrystalline nickel foil in air and pure water at different temperatures and the thermal stability of the surface oxides have been investigated by means of XPS.In ad- dition to NiO,Ni_2O_3 is formed especially after long periods of air exposure.Nickel surfaces are much less reactive to pure water than to air.The thermal stability of the surface oxides is related to oxidative temperature.The surface species of oxides formed by air exposure at temperatures below 120℃ can be reduced into nickel metal after heating the sample in vacuum at 300℃ for only 10 minutes (in the case of room temperature) to 1 h (in the case of 120℃). This reduction is caused by reaction with surface carbon contaminants.However,the surface species of nickel oxides formed by air exposure with heating at temperatures above 200℃ can not be reduced into metal after heating the sample in vacuum at 300℃ for 1h.
基金supported by Liaoning BaiQianWan Talents Program of China (No. 2008921028)Doctoral Fund of Ministry of Education of China (No. 200801451082)
文摘In this study, compounded surface modification technology-high current pulsed electron beam （HCPEB） ＋ micro-plasma oxidation （MPO） was applied to treat ZK60 Mg alloys. The characteristics of the microstructure of ZK60 Mg alloy after single MPO and HCPEB＋MPO compounded treatment were investigated by SEM. The results showed that the density of the ceramic layer of HCPEB＋MPO-treated ZK60 Mg alloy was improved and defects were reduced compared to that under MPO treatment alone. Surface modified layer of ZK60 Mg alloys treated by HCPEB＋MPO was divided into three zones, namely the top loose ceramic zone, middle compact zone and inside HCPEB-induced melted zone. Corrosion resistance of ZK60 Mg alloy before and after the compounded surface modification was measured in a solution of 3.5% NaCl by potentiodynamic polarization curves. It was found that the corrosion current density of ZK60 Mg alloys could be reduced by about three orders of magnitude, from 311μA/cm^2 of the original sample to 0.2μA/cm^2 of the HCPEB＋MPO-treated sample. This indicates the great application potential of the HCPEB＋MPO compounded surface modification technology in improving the corrosion resistance of ZK60 Mg alloys in the future.
基金supported by the National Basic Research Program of China (No. 2011CB605602)
文摘Polyacrylonitrile （PAN） based carbon fibers with different surface morphology were electrochemically treated in 3 wt% NH4HCO3 aqueous solution with current density up to 3.47 A/m 2 at room temperature, and surface structures, surface morphology and residual mechanical properties were characterized. The crystallite size （La） of carbon fibers would be interrupted due to excessive electrochemical etching, while the crystallite spacing （d（002）） increased as increasing current density. The disordered structures on the surface of carbon fiber with rough surface increased at the initial oxidation stage and then removed by further electrochemical etching, which resulting in continuous increase of the extent of graphitization on the fiber surface. However, the electrochemical etching was beneficial to getting ordered morphology on the surface for carbon fiber with smooth surface, especially when the current density was lower than 1.77 A/m 2 . The tensile strength and tensile modulus could be improved by 17.27% and 5.75%, respectively, and was dependent of surface morphology. The decreasing density of carbon fibers probably resulted from the volume expansion of carbon fibers caused by the abundant oxygen functional groups intercalated between the adjacent graphite layers.
基金Funded by the National Natural Science Foundation of China(No.50974010)the Natural Science Foundation of Beijing City,China(No.2102039)
文摘In order to explore an effective way to shorten treatment time and enhance the quality of treatment coating, AC micro-arc oxidation was conducted to treat the surface of AZ31 B deformation magnesium alloy in KF＋KOH treatment solution. The infl uences of micro-arc oxidation parameters such as concentration of KF, concentration of KOH, output voltage of booster, temperature of treatment solution, and treatment time on treatment coating thickness were raveled out under different conditions. The structure and composition of treatment coating were determined, the growth mechanism of treatment coating was discussed, and the quick surface treatment technology for compact treatment coating with maximum thickness was developed. The experimental results show that： A maximum 33 μm-thick compact treatment coating, consisting of MgF2 and MgO mainly, can be formed on AZ31 B in 112 s under the conditions of 1 132 g/L KF, 382 g/L KOH, 66 V for output voltage of booster and 34 ℃ of treatment solution which were optimized by a genetic algorithm from the model established by artifi cial neural networks. There are no ＂crater-shaped＂ pores in this treatment coating as the heat shock resulting from the smooth variation of AC sinusoidal voltage is far smaller than that of the rigidly varied DC or pulse current. The treatment time is only one sixth of that adopted in the other surface treatment technology at best, principally for the reason that the coating can always grow irrespective of the electric potential of AZ31 B. This investigation lays a fi rm foundation for the extensive application of magnesium alloy.
基金Project supported by the High Level Innovation Team and Outstanding Scholar Program in Guangxi Colleges(the second batch),ChinaProjects(51304054+1 种基金51364002)supported by the National Natural Science Foundation of ChinaProject supported by the Open Foundation of Guangxi Colleges and University Key Laboratory of Minerals Engineering in Guangxi University,China
文摘The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy of O2 on pyrrhotite surface is the largest, followed by that on marcasite surface and then pyrite surface. O2 molecules adsorbed on pyrite, marcasite and pyrrhotite surfaces are all dissociated. The oxygen atoms and surface atoms of pyrite, marcasite and pyrrhotite surfaces have different bonding structures. Due to more atoms on pyrrhotite and marcasite surfaces interaction with oxygen atoms, the adsorption energies of O2 on pyrrhotite and marcasite surfaces are larger than that on pyrite surface. Larger values of Mulliken populations for O？Fe bond of pyrrhotite surface result in relative larger adsorption energy compared with that on marcasite surface.
文摘Titanium and its alloys are widely used in the aerospace, marine, and biomedical industry due to their unique bulk properties such as high strength-to-weight ratio and melting temperature, good corrosion resistance, and favorable biocom- patibility. However, in some applications, com- ponents made of titanium or titanium alloys exhibit poor wear resistance under stationary or dynamic loading as well as contact corrosion manifested by the relatively negative standard electrode potential （-1.63 V ） . In order to improve the surface properties of titanium and its alloys, several techniques such as PVD （ physical vapor deposition ） /CVD （chemical vapor deposition ） coatings,
基金supported by the National Natural Science Foundation of China(21403004,21403003)~~
文摘Leached Pt-Fe and Pt-Co catalysts were prepared by acid leaching the reduced catalysts in acid solution. Oxidation treatments of leached catalysts produced the structure o f metal oxides decorat-ing the surface of nanoparticles. The fully oxidized Fe2O3 and Co3O4 species on Pt nanoparticle sur-faces result in the low performance of the CO complete oxidation （COOX） reaction. In contrast, un-saturated FeO and CoO surface species can be formed during exposure to the CO preferential oxida-tion （CO-PROX） reaction with an excess of H2, leading to a high O2 activation ability and enhancing the CO-PROX activity. The FeOx surface structures can be transformed between these two states by varying the reactive gas environments, exhibiting oscillating activity in these two reactions. Con-versely, the CoO surface structure formed in the H2 -rich atmosphere is stable when exposed to the COOX reaction and exhibits similar activity in these two reactions. It is hoped that this work may assist in understanding the important role of surface oxides in real reactions.
基金financial support provided by the National Natural Science Foundation of China(NSFC)(51974094,51874106,and U20A20269).
文摘Marcasite(FeS2)is widespread in nature,its oxidation plays a vital role in acid mine drainage,mineral resource recovery,and photoelectric material applications.In this paper,the oxidation mechanism of marcasite has been studied for the first time using density functional theory(DFT).It is found that,unlike the oxidation of pyrite,the oxidation of marcasite merely occurs at surface S atoms.Under the coexistence of water and oxygen,S atoms around surface Fe atoms are replaced by O atoms.The surface S sites are initially oxidized to form S==O bonds,and continue to adsorb oxygen to gradually generate SO3^2-,SO4^2-species,and eventually FeSO4.In this process,H2O molecules participate in neither oxidation nor dissociation,and they are adsorbed on surface Fe sites in the form of molecules,i.e.,all O atoms in SO4^2-derive from oxygen rather than water molecules.
基金financially supported by the National Science Fund for Distinguished Young Scholars(No.52025041)the National Natural Science Foundation of China(Nos.51904021,51974021,51902020)+1 种基金the Fundamental Research Funds for the Central Universities(No.FRF-TP-19-008A1)the State Key Laboratory of Refractories and Metallurgy,Wuhan University of Science and Technology(No.G202003)。
文摘As the dominated composition of Si_(3)N_(4)ceramics,α-silicon nitride(α-Si_(3)N_(4))can satisfy the strength and fracture toughness demand in the applications.However,α-Si_(3)N_(4)is oxygen-sensitive at high temperatures,which limits its high-temperature performance.To improve the oxidation resistance ofα-Si_(3)N_(4)ceramics,it is necessary to shed light on the oxidation mechanism.Herein,the initial oxidation ofα-Si_(3)N_(4)was systematically studied at the atomic and molecular levels.The density functional theory(DFT)calculation denotes that the(001)surface ofα-Si_(3)N_(4)has the best stability at both room temperature and high temperature.Besides,the oxidation process of theα-Si_(3)N_(4)(001)surface consists of O adsorption and N desorption,and the consequent formation of nitrogen-vacancy(VN)is the key step for further oxidation.Moreover,the molecular dynamics(MD)simulation indicates that the oxidation rate ofα-Si_(3)N_(4)(100)surface is slower than that ofα-Si_(3)N_(4)(001)surface due to the lower N concentration at the outermost layer.Therefore,the oxidation resistance ofα-Si_(3)N_(4)can be improved by regulating the(100)surface as the dominant exposure surface.In addition,reducing the concentration of N on the final exposed surface ofα-Si_(3)N_(4)by mean of constructing the homojunction of the Si-terminal(100)surface and other N-containing surfaces(such as(001)surface)should be also a feasible approach.
