The rapid advancement of modern science and technology,coupled with the recent surge in new-energy electric vehicles,has significantly boosted the demand for lithium.This has promoted the development and efficient uti...The rapid advancement of modern science and technology,coupled with the recent surge in new-energy electric vehicles,has significantly boosted the demand for lithium.This has promoted the development and efficient utilization of lepidolite as a lithium source.Therefore,the processes for the flotation of lepidolite have been studied in depth,particularly the development and use of lepidolite flotation collectors and the action mechanism of the collectors on the lepidolite surface.Based on the crystal-structure characteristics of lepidolite minerals,this review focuses on the application of anionic collectors,amine cationic collectors(primary amines,quaternary ammonium salts,ether amines,and Gemini amines),and combined collectors to the flotation behavior of lepidolite as well as the adsorption mechanisms.New directions and technologies for the controllable flotation of lepidolite are proposed,including process improvement,reagent synthesis,and mechanistic research.This analysis demonstrates the need for the further study of the complex environment inside lepidolite and pulp.By using modern analytical detection methods and quantum chemical calculations,research on reagents for the flotation of lepidolite has expanded,providing new concepts and references for the efficient flotation recovery and utilization of lepidolite.展开更多
A novel NiAlTa blade tip protective coating is designed and its oxidation,hot corrosion,and interdiffusion with DD5 single-crystal superalloys are investigated.NiAlTa coatings exhibit low oxidation rates.The dragging ...A novel NiAlTa blade tip protective coating is designed and its oxidation,hot corrosion,and interdiffusion with DD5 single-crystal superalloys are investigated.NiAlTa coatings exhibit low oxidation rates.The dragging effect of Ta on Al hinders the external diffusion of Al.Ta that accumulates at the Al_(2)O_(3)grain boundaries reduces the internal diffusion of O by combining or reacting with it.NaCl aggravates the hot corrosion through self ustaining cycles of chlorination/oxidation.β-NiAl phase fails first as a diffusion channel for the corrosive medium.Significant element interdiffusion occurs.An interdiffusion zone and a secondary reaction zone are formed.Interdiffusion changes the percentage of elements,causing a phase transition of the coating.The volume change caused by the phase transition induces bulging and cracking of the oxide film.Furthermore,the oxidation,hot corrosion,and interdiffusion mechanisms are discussed.展开更多
Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchan...Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.展开更多
Layered double hydroxides(LDHs)are promising electrocatalysts for the oxygen evolution reaction(OER),yet their practical application remains limited by poor electrical conductivity and sluggish reaction kinetics.In th...Layered double hydroxides(LDHs)are promising electrocatalysts for the oxygen evolution reaction(OER),yet their practical application remains limited by poor electrical conductivity and sluggish reaction kinetics.In this work,we synthesize three high-entropy LDHs(HELDHs)featuring a hierarchical architecture of microspheres assembled from ultrathin nanosheets,via a simple hydrothermal method using a combination of low-cost,catalytically active transition metals(Fe,Co,Ni,Mn,Zn,Cu,and Cr).Among them,the FeCoNiMnZn HELDH exhibits outstanding OER performance,requiring an overpotential of only 306 mV to reach a current density of 100 mA cm^(-2).Notably,during 200 h of continuous operation,the device exhibits a stable and,in some cases,increasing current output.This exceptional activity is attributed to the formation of abundant cation vacancies,induced by Zn leaching,which enhance the intrinsic catalytic properties by optimizing the adsorption energies of key OER intermediates.Density functional theory calculations further validate that these vacancies modulate the electronic structure and lower reaction barriers,underscoring the effectiveness of cation-vacancy engineering in high-entropy systems for efficient and durable water oxidation catalysis.The optimized catalyst was further evaluated as the air cathode in a zinc-air battery,demonstrating practical electrochemical performance.展开更多
The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative...The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.展开更多
Aqueous zinc-ion batteries(AZIBs) have advantages including low economic cost and high safety.Nevertheless,the serious hydrogen evolution reactions(HER) and rampant growth of Zn dendrite hinder their further developme...Aqueous zinc-ion batteries(AZIBs) have advantages including low economic cost and high safety.Nevertheless,the serious hydrogen evolution reactions(HER) and rampant growth of Zn dendrite hinder their further development.Herein,potassium acetate(KAc) additive with cation/anion synergy effect is added into the ZnSO_(4) electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions.According to density functional theory calculation and experimental results,CH_(3)COO^(-)(Ac^(-))anions are capable of forming stronger hydrogen bonds with H_(2)O molecules,leading to an expanded electrochemical stability window,reduced the reactivity of H_(2)O,and hence suppressing HER.Meanwhile,Ac-anions can also preferentially adsorb onto the Zn anode,promoting dense deposition towards the(100) crystal plane.Besides,dissociated K^(+) ions serve as electrostatic shielding cations,which significantly promote uniform Zn deposition and prevent dendrite formation.Thus,the Zn||Zn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 m A/cm^(2).Furthermore,the Zn||MnO_(2) full battery exhibits superior stability with a capacity retention of 86.95 % at 2.0 A/g after 4000 cycles.Therefore,the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.展开更多
Pure metal Fe films with thickness of about 100nm were deposited on Si （100） substrates by DC magnetron sputtering. Annealing was subsequently performed in a vacuum furnace in the temperature range of 600-1000℃ for...Pure metal Fe films with thickness of about 100nm were deposited on Si （100） substrates by DC magnetron sputtering. Annealing was subsequently performed in a vacuum furnace in the temperature range of 600-1000℃ for 2h. The samples were characterized by means of Rutherford backscattering （RBS） with 3MeV carbon ions. The RBS data were fitted with SIMNRA 6.0, and the results show the atomic interdiffusion in Fe/Si systems. The microstructures and crystal structures were characterized by scanning electron microscope and X-ray diffrac- tion. The effects of annealing on atomic interdiffusion, silicide formation, and microstructures in Fe/Si systems were analyzed.展开更多
The effect of high magnetic field on the atomic interdiffusion in Ni-Cu system was studied using the Cu/Ni/Cu diffusion couples. During the atomic interdiffusion in Ni-Cu system, it was found that the interdiffusion c...The effect of high magnetic field on the atomic interdiffusion in Ni-Cu system was studied using the Cu/Ni/Cu diffusion couples. During the atomic interdiffusion in Ni-Cu system, it was found that the interdiffusion coefficients increased with the increase of molar fraction of Ni atoms in the interdiffusion zones when the couples were annealed with or without the magnetic field. It was noted that all corresponding interdiffusion coefficients under the magnetic field are smaller than those without the magnetic field. The results demonstrate that the magnetic field retards the atomic interdiffusion in Ni-Cu system. This retardation is achieved through reducing the frequency factors but not changing the interdiffusion activation energies.展开更多
To refrain the interdiffusion of elements while holding good oxidation resistance,a(Ni,Pt)Al/Ni composite coating was prepared by sequential treatments of electroplating Ni and Pt and successive gaseous aluminization....To refrain the interdiffusion of elements while holding good oxidation resistance,a(Ni,Pt)Al/Ni composite coating was prepared by sequential treatments of electroplating Ni and Pt and successive gaseous aluminization.In comparison with normal(Ni,Pt)Al coating,high-temperature performance of the composite coating was evaluated in isothermal oxidation test at 1100℃.Both the two coatings exhibited good resistance against high-temperature oxidation,but the interdiffusion of elements between composite coating and single-crystal(SC)superalloy substrate was greatly relieved,in which the thickness of secondary reaction zone(SRZ)and the amount of precipitated topologically close-packed phase in the SC alloy matrix were significantly decreased.Mechanisms responsible for delaying rate of coating degradation and SRZ growth/propagation are discussed.展开更多
To reveal the influence of substrate/coating interdiffusion on the cyclic oxidation property of a metallic coating, cyclic oxida- tion behavior of an EB-PVD CoCrAIY coating on directionally solidified Ni-based superal...To reveal the influence of substrate/coating interdiffusion on the cyclic oxidation property of a metallic coating, cyclic oxida- tion behavior of an EB-PVD CoCrAIY coating on directionally solidified Ni-based superalloy DZ125 at 1 050℃ is investigated. The 40 μm thick CoCrA1Y coating has a cyclic oxidation life of around 160 h, and the oxidation constant is 1.915× 10^-7 mg4.cm^-8.s-1. However, severe spallation of the oxides containing Co, Cr, Ni, Ta and Ti occurs with longer cyclic oxidation. The degradation in oxidation resistance for the coating is related to the depletion of A1 due to the oxide spallation and interdiffu- sion. Severe interdiffusion between the coating and underlying substrate occurs at 1 050 ℃. The composition of the substrate has an important effect on the thermal cycling lifetime of the coating. The influencing mechanism is discussed.展开更多
To investigate the interdiffusion behavior of Ge-modified silicide coatings on an Nb–Si-based alloy substrate,the coating was oxidized at 1250°C for 5,10,20,50,or 100 h.The interfacial diffusion between the(Nb,X...To investigate the interdiffusion behavior of Ge-modified silicide coatings on an Nb–Si-based alloy substrate,the coating was oxidized at 1250°C for 5,10,20,50,or 100 h.The interfacial diffusion between the(Nb,X)(Si,Ge)_2(X = Ti,Cr,Hf) coating and the Nb–Si based alloy was also examined.The transitional layer is composed of(Ti,Nb)_5(Si,Ge)_4 and a small amount of(Nb,X)_5(Si,Ge)_3.With increasing oxidation time,the thickness of the transitional layer increases because of the diffusion of Si from the outer layer to the substrate,which obeys a parabolic rate law.The parabolic growth rate constant of the transitional layer under oxidation conditions is 2.018 μm×h^(-1/2).Moreover,the interdiffusion coefficients of Si in the transitional layer were determined from the interdiffusion fluxes calculated directly from experimental concentration profiles.展开更多
Interdiffusion in the Fe203-TiO2 system was investigated by the diffusion couple method in the temperature range of 1323 to 1473 K. The diffusion concentration curves of Ti4＋ cations were obtained by electron probe m...Interdiffusion in the Fe203-TiO2 system was investigated by the diffusion couple method in the temperature range of 1323 to 1473 K. The diffusion concentration curves of Ti4＋ cations were obtained by electron probe microanalysis, according to which the Boltzmann-Matano method optimized by Broeder was used to calculate the interdiffusion coeffi- cients. The interdiffusion coefficients almost increased linearly with the mole fraction of Ti4＋ cations increasing, and they were in the range of 10-12-10-11cm2-s-1. The increase of temperature could also lead to the increase of the interdiffusion coefficients at a constant concentration of Ti4＋ cations. It was also found that the thickness growth of the diffusion layer obeyed the parabolic rate law.展开更多
MCrAlY(M=Ni and/or Co)overlay coating is widely used as a protective coating against high temperature oxidation and corrosion.However,due to its big difference in chemical composition with the underlying superalloy,el...MCrAlY(M=Ni and/or Co)overlay coating is widely used as a protective coating against high temperature oxidation and corrosion.However,due to its big difference in chemical composition with the underlying superalloy,elements interdiffusion occurs inevitably.One of the direct results is the formation of interdiffusion zone(IDZ)and secondary reaction zone(SRZ)with a high density of fine topological closed-packed phases(TCPs),weakening dramatically the mechanical properties of the alloy substrate.It is by now the main problem of modern high-temperature metallic coatings,but there are still hardly any reports studying the formation,growth and transformation of IDZ and SRZ in deep,as well as the precipitation of TCPs.In this work,a typical NiCrAlY coating is deposited by arc ion plating on a single-crystal superalloy N5.Elements interdiffusion between them and its relationship on microstructure were clarified.Cr rather than Al from the coating diffuses into the alloy at high temperatures and segregates immediately beneath their interface,contributing largely to the formation of IDZ.Simultaneously,diffusion of Ni from the deep alloy to IDZ leads to the formation and continuous expansion of SRZ.展开更多
High-temperature chromium(Cr)-zirconium(Zr)interdiffusion commonly occurs in Cr-coated zircaloys applied for enhanced accident-tolerant fuel(ATF)claddings.Such interdiffusion changes the interfacial microstructure and...High-temperature chromium(Cr)-zirconium(Zr)interdiffusion commonly occurs in Cr-coated zircaloys applied for enhanced accident-tolerant fuel(ATF)claddings.Such interdiffusion changes the interfacial microstructure and thus the fracture mechanism of the coating under external loading.In this study,the interdiffusion behavior in a magnetron sputtered Cr coating deposited on a Zr-4 alloy was studied in a vacuum environment at 1160C.In addition,the effect of interdiffusion on the microcracking behavior of the Cr coating was determined by in situ three-point bending tests.The experimental results show that the interdiffusion behavior resulted in the formation of a ZrCr2 layer,accompanied by the consumption of Cr coating and interfacial roughening.The growth of the diffusion layer followed a nearly parabolic law with respect to annealing time,and the residual stress of the annealed coating decreased with increasing annealing time.Under external loading,a large number of cracks were generated in the brittle interlayer,and some interfacial cracks were formed and grew at the ZrCr2/Zr-4 interface.Despite the remarkable microcracks in the ZrCr2 layer,the vacuum-annealed Cr coating has significantly fewer cracks than the original coating,mainly because of the recrystallization of the coating during annealing.展开更多
NiCrAlY coatings are widely applied on various alloy components to enhance oxidation and/or corrosion resistance at high temperatures.However,elements interdiffusion occurs between them due to composition difference.A...NiCrAlY coatings are widely applied on various alloy components to enhance oxidation and/or corrosion resistance at high temperatures.However,elements interdiffusion occurs between them due to composition difference.Although various diffusion barriers(DBs)are reported,this problem is still far from completely solved as most ceramic barriers suffer from poor adherence,while the metallic barriers play a limited role.In this study,NiCrAlY coating was deposited onto a second-generation single-crystal superalloy by arc ion plating.A novel simple method is provided to address elements interdiffusion.By pre-oxidation at a moderate temperature,a thin scale of Ni(Co)O forms at the alloy surface.It transforms to be an alumina/NiCoCr alloy/alumina sandwich by an in-situ reaction with the overlaying NiCrAlY coating and the alloy substrate at high service temperatures,which offers good barrier ability in conjunction with strong adhesion.In the presence of such an alumina/alloy/alumina DB,the NiCrAlY coating provides high resistance to oxidation and scale spallation for the alloy substrate.展开更多
Interdiffusion coefficients at 950℃ and 1050℃ are calculated by Wagner analysis method as a function of composition of β-NiAI phase. The β-NiAI phase is formed by pack cementation on surface of superalloy. Results...Interdiffusion coefficients at 950℃ and 1050℃ are calculated by Wagner analysis method as a function of composition of β-NiAI phase. The β-NiAI phase is formed by pack cementation on surface of superalloy. Results of the calculation show that interdiffusion coefficients in β-NiAI phase strongly depend on the compositions and vary over several orders of magnitude. Compared with the interdiffusion coefficients in the stoichiometric β-NiAI phase, the interdiffusion coefficients in β-NiAI phase formed on superalloy is obviously small, probably due to the composition, complicated microstructure and precipitates. However, it could be seen clearly that the shapes of the diffusivity curves are very similar to each other. The similarity of the diffusion curves and the difference between interdiffusion coefficients imply that the compositions, microstructures and precipitates of superalloy have a distinctly adverse effect on the interdiffusion of Ni and Al atoms during aluminization, but do not change the essential characteristics of β-NiAI phase.展开更多
Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limi...Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limit its PEC activity for water reduction.Here,we developed a heterostructure photocathode consisting of the Cu-doped NiO(Cu:NiO)hole selective layer(HSL)and Ni-doped CuFeO_(2)(Ni:CuFeO_(2))active layer by simply annealing a homogeneous Cu-Fe oxalate layer grown on the Ni film deposited on the fluorine doped tin oxide(FTO)substrate.The obtained heterostructure of Cu:NiO/Ni:CuFeO_(2) with enhanced charge carrier transportability and high-quality interface greatly promotes the separation of photogenerated carriers.Accordingly,the Cu:NiO/Ni:CuFeO_(2) photocathode exhibits a high photocurrent density of~0.9 mA·cm^(-2 )at 0.2 V(vs.reversible hydrogen electrode,RHE),outperforming most of the reported bare CuFeO_(2) photocathodes in the literature.And the photocurrent density can be further improved to 1.2 mA·cm^(-2) after decorating NiSx cocatalyst.展开更多
The interdiffusion interface microstructures and composition evolution of Ni-Al-Cr/Ni-Al-Cr layered alloys under different temperature gradients were studied using phase-field simulation.A precipitate-free zone forms ...The interdiffusion interface microstructures and composition evolution of Ni-Al-Cr/Ni-Al-Cr layered alloys under different temperature gradients were studied using phase-field simulation.A precipitate-free zone forms near the interface of the layered alloys,and the interface does not move with time under temperature gradients.When Cr concentrations in the alloy layers are different,Al diffuses from a low-to high-temperature region,whereas Cr from a high-to low-temperature region.The width of the precipitate-free zone changes from 0.5 to 2.5μm as the temperature gradient changes fromΔT=0.625 K·μm^(−1) to 1.250 K·μm^(−1);the width of the interdiffusion zone is also enlarged.Additionally,the temperature gradient promotes the interdiffusion of elements through the interface.In contrast,when the initial Al concentration is different in the alloy layers,an uphill diffusion of Al occurs,which is driven by the chemical potential of Al.展开更多
A repeated interdiffusion method is described for phase-stable and high-quality （FA,MA）PbI3 film. The crys- tallization and growth of the perovskite films can be well controlled by adjusting the reactant concentrati...A repeated interdiffusion method is described for phase-stable and high-quality （FA,MA）PbI3 film. The crys- tallization and growth of the perovskite films can be well controlled by adjusting the reactant concentrations. With this method, dense, smooth perovskite films with large crystals have been obtained. Finally, a PCE of 16.5% as well as a steady-state efficiency of 16.3% is achieved in the planar perovskite solar cell.展开更多
The miscibility of poly（vinyl chloride）/poly（n-butyl methacrylate） （PVC/PnBMA） blend and the interdiffusion kinetics of PVC/PnBMA laminates have been investigated by differential scanning calorimetry （DSC） and...The miscibility of poly（vinyl chloride）/poly（n-butyl methacrylate） （PVC/PnBMA） blend and the interdiffusion kinetics of PVC/PnBMA laminates have been investigated by differential scanning calorimetry （DSC） and atomic force microscopy （AFM）, respectively. This blend exhibited a lower critical solution temperature behavior. Below 120 ℃, DSC results showed each blend with different PVC contents exhibited only a single glass transition temperature which increased with PVC content, indicating that PVC and PnBMA were miscible. After PVC/PnBMA laminates were annealed at different temperature for different time, a smooth cross-section across interface was prepared by ultramicrotoming. Combined with topography and phase images of tapping mode AFM, the relative concentration profile, interface width and the relationship between interface width and annealing time could be obtained. In a regime of rubbery/rubbery interdiffusion, the diffusion obeyed a typical Fickian Case-I behavior where the interface width was proportional to the square root of annealing time. The mutual diffusion coefficient was in good agreement with that obtained from DSC and positron annihilation lifetime spectroscopy. However, in the regime of glassy/rubbery interdiffusion, the diffusion followed a typical Case-II behavior where the interface width was proportional to annealing time. These results imply that AFM is a reliable and powerful tool for the investigation of polymer/polymer interdiffusion at a level of polymer chain size.展开更多
基金financially supported by the Excellent Youth Scholars Program of State Key Laboratory of Complex Nonferrous Metal Resource Clean Utilization,Kunming University of Science and Technology,China(No.YXQN-2024003)the Central Government-Guided Local Science and Technology Development Fund Project,China(No.202407AB110022)。
文摘The rapid advancement of modern science and technology,coupled with the recent surge in new-energy electric vehicles,has significantly boosted the demand for lithium.This has promoted the development and efficient utilization of lepidolite as a lithium source.Therefore,the processes for the flotation of lepidolite have been studied in depth,particularly the development and use of lepidolite flotation collectors and the action mechanism of the collectors on the lepidolite surface.Based on the crystal-structure characteristics of lepidolite minerals,this review focuses on the application of anionic collectors,amine cationic collectors(primary amines,quaternary ammonium salts,ether amines,and Gemini amines),and combined collectors to the flotation behavior of lepidolite as well as the adsorption mechanisms.New directions and technologies for the controllable flotation of lepidolite are proposed,including process improvement,reagent synthesis,and mechanistic research.This analysis demonstrates the need for the further study of the complex environment inside lepidolite and pulp.By using modern analytical detection methods and quantum chemical calculations,research on reagents for the flotation of lepidolite has expanded,providing new concepts and references for the efficient flotation recovery and utilization of lepidolite.
基金financially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences,Grant(No.XDB 047010204)Liaoning Key Laboratory of Aero-engine Material Tribology for both financial and facility support
文摘A novel NiAlTa blade tip protective coating is designed and its oxidation,hot corrosion,and interdiffusion with DD5 single-crystal superalloys are investigated.NiAlTa coatings exhibit low oxidation rates.The dragging effect of Ta on Al hinders the external diffusion of Al.Ta that accumulates at the Al_(2)O_(3)grain boundaries reduces the internal diffusion of O by combining or reacting with it.NaCl aggravates the hot corrosion through self ustaining cycles of chlorination/oxidation.β-NiAl phase fails first as a diffusion channel for the corrosive medium.Significant element interdiffusion occurs.An interdiffusion zone and a secondary reaction zone are formed.Interdiffusion changes the percentage of elements,causing a phase transition of the coating.The volume change caused by the phase transition induces bulging and cracking of the oxide film.Furthermore,the oxidation,hot corrosion,and interdiffusion mechanisms are discussed.
基金financially supported the National Key R&D Program of China (No.2022YFA1502902)the National Natural Science Foundation of China (NSFC,Nos.22475152 and U21A20286)the 111 Project of China (No.D17003)。
文摘Converting CO_(2) into methanol(CH_(3)OH),a high-value-added liquid-phase product,through efficient and highly selective photocatalysis remains a significant challenge.Herein,we present a straightforward cation exchange strategy for the in-situ growth of BiVO_(4) on an InVO_(4) substrate to generate a Z-scheme heterojunction of InVO_(4)/BiVO_(4) .This in-situ partial transformation approach endows the InVO_(4)/BiVO_(4) heterojunction with a tightly connected interface,resulting in a significant improvement in charge separation efficiency between InVO_(4) and BiVO_(4).Moreover,the construction of the heterojunction reduces the formation energy barrier of the ^(*)COOH intermediate during the photoreduction of CO_(2) and increases the desorption energy barrier of the ^(*)CO intermediate,facilitating the deep reduction of ^(*)CO.Consequently,the InVO_(4)/BiVO_(4) heterojunction is capable of photocatalytic CO_(2) reduction to CH_(3)OH with high efficiency and selectivity.Under conditions where water serves as the electron source and a light intensity of 100 m W/cm^(2),the yield of CH_(3)OH reaches 130.5 μmol g^(-1)h^(-1) with a selectivity of 92 %,outperforming photocatalysts reported under similar conditions.
基金supported by the National Natural Science Foundation of China(NSFC)(22302151,52502312)Natural Science Foundation of Hubei Province(2024AFB755,2024AFB267)+1 种基金Key Project of Hubei Provincial Department of Education Scientific Research Plan(F2023007)Wuhan Institute of Technology Graduate Education Innovation Fund(CX2024285)。
文摘Layered double hydroxides(LDHs)are promising electrocatalysts for the oxygen evolution reaction(OER),yet their practical application remains limited by poor electrical conductivity and sluggish reaction kinetics.In this work,we synthesize three high-entropy LDHs(HELDHs)featuring a hierarchical architecture of microspheres assembled from ultrathin nanosheets,via a simple hydrothermal method using a combination of low-cost,catalytically active transition metals(Fe,Co,Ni,Mn,Zn,Cu,and Cr).Among them,the FeCoNiMnZn HELDH exhibits outstanding OER performance,requiring an overpotential of only 306 mV to reach a current density of 100 mA cm^(-2).Notably,during 200 h of continuous operation,the device exhibits a stable and,in some cases,increasing current output.This exceptional activity is attributed to the formation of abundant cation vacancies,induced by Zn leaching,which enhance the intrinsic catalytic properties by optimizing the adsorption energies of key OER intermediates.Density functional theory calculations further validate that these vacancies modulate the electronic structure and lower reaction barriers,underscoring the effectiveness of cation-vacancy engineering in high-entropy systems for efficient and durable water oxidation catalysis.The optimized catalyst was further evaluated as the air cathode in a zinc-air battery,demonstrating practical electrochemical performance.
基金financial support of the National Natural Science Foundation of China(NSFC)(52394202,52021004,52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.
基金financially supported by the National Natural Science Foundation of China (No.52372188)the 111 Project (No.D17007)2023 Introduction of studying abroad talent program。
文摘Aqueous zinc-ion batteries(AZIBs) have advantages including low economic cost and high safety.Nevertheless,the serious hydrogen evolution reactions(HER) and rampant growth of Zn dendrite hinder their further development.Herein,potassium acetate(KAc) additive with cation/anion synergy effect is added into the ZnSO_(4) electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions.According to density functional theory calculation and experimental results,CH_(3)COO^(-)(Ac^(-))anions are capable of forming stronger hydrogen bonds with H_(2)O molecules,leading to an expanded electrochemical stability window,reduced the reactivity of H_(2)O,and hence suppressing HER.Meanwhile,Ac-anions can also preferentially adsorb onto the Zn anode,promoting dense deposition towards the(100) crystal plane.Besides,dissociated K^(+) ions serve as electrostatic shielding cations,which significantly promote uniform Zn deposition and prevent dendrite formation.Thus,the Zn||Zn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 m A/cm^(2).Furthermore,the Zn||MnO_(2) full battery exhibits superior stability with a capacity retention of 86.95 % at 2.0 A/g after 4000 cycles.Therefore,the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
文摘Pure metal Fe films with thickness of about 100nm were deposited on Si （100） substrates by DC magnetron sputtering. Annealing was subsequently performed in a vacuum furnace in the temperature range of 600-1000℃ for 2h. The samples were characterized by means of Rutherford backscattering （RBS） with 3MeV carbon ions. The RBS data were fitted with SIMNRA 6.0, and the results show the atomic interdiffusion in Fe/Si systems. The microstructures and crystal structures were characterized by scanning electron microscope and X-ray diffrac- tion. The effects of annealing on atomic interdiffusion, silicide formation, and microstructures in Fe/Si systems were analyzed.
基金Project(2011CB012803) supported by the National Basic Research Program of ChinaProject(NCET-10-0278) supported by Program for New Century Excellent Talents in University,China
文摘The effect of high magnetic field on the atomic interdiffusion in Ni-Cu system was studied using the Cu/Ni/Cu diffusion couples. During the atomic interdiffusion in Ni-Cu system, it was found that the interdiffusion coefficients increased with the increase of molar fraction of Ni atoms in the interdiffusion zones when the couples were annealed with or without the magnetic field. It was noted that all corresponding interdiffusion coefficients under the magnetic field are smaller than those without the magnetic field. The results demonstrate that the magnetic field retards the atomic interdiffusion in Ni-Cu system. This retardation is achieved through reducing the frequency factors but not changing the interdiffusion activation energies.
基金financially supported by the National Natural Science Foundation of China (Nos.51671202 and 51301184)the "Liaoning BaiQianWan Talents" Program
文摘To refrain the interdiffusion of elements while holding good oxidation resistance,a(Ni,Pt)Al/Ni composite coating was prepared by sequential treatments of electroplating Ni and Pt and successive gaseous aluminization.In comparison with normal(Ni,Pt)Al coating,high-temperature performance of the composite coating was evaluated in isothermal oxidation test at 1100℃.Both the two coatings exhibited good resistance against high-temperature oxidation,but the interdiffusion of elements between composite coating and single-crystal(SC)superalloy substrate was greatly relieved,in which the thickness of secondary reaction zone(SRZ)and the amount of precipitated topologically close-packed phase in the SC alloy matrix were significantly decreased.Mechanisms responsible for delaying rate of coating degradation and SRZ growth/propagation are discussed.
基金National Natural Science Foundation of China (50731001, 51071013, 51001032)National Basic Research Program of China (2010CB631200)
文摘To reveal the influence of substrate/coating interdiffusion on the cyclic oxidation property of a metallic coating, cyclic oxida- tion behavior of an EB-PVD CoCrAIY coating on directionally solidified Ni-based superalloy DZ125 at 1 050℃ is investigated. The 40 μm thick CoCrA1Y coating has a cyclic oxidation life of around 160 h, and the oxidation constant is 1.915× 10^-7 mg4.cm^-8.s-1. However, severe spallation of the oxides containing Co, Cr, Ni, Ta and Ti occurs with longer cyclic oxidation. The degradation in oxidation resistance for the coating is related to the depletion of A1 due to the oxide spallation and interdiffu- sion. Severe interdiffusion between the coating and underlying substrate occurs at 1 050 ℃. The composition of the substrate has an important effect on the thermal cycling lifetime of the coating. The influencing mechanism is discussed.
基金financially supported by the National Natural Science Foundation of China(No.51431003)the Joint Funds of the National Natural Science Foundation of China(No.U1435201)
文摘To investigate the interdiffusion behavior of Ge-modified silicide coatings on an Nb–Si-based alloy substrate,the coating was oxidized at 1250°C for 5,10,20,50,or 100 h.The interfacial diffusion between the(Nb,X)(Si,Ge)_2(X = Ti,Cr,Hf) coating and the Nb–Si based alloy was also examined.The transitional layer is composed of(Ti,Nb)_5(Si,Ge)_4 and a small amount of(Nb,X)_5(Si,Ge)_3.With increasing oxidation time,the thickness of the transitional layer increases because of the diffusion of Si from the outer layer to the substrate,which obeys a parabolic rate law.The parabolic growth rate constant of the transitional layer under oxidation conditions is 2.018 μm×h^(-1/2).Moreover,the interdiffusion coefficients of Si in the transitional layer were determined from the interdiffusion fluxes calculated directly from experimental concentration profiles.
基金financially supported by the National Natural Science Foundation of China (No. 51090384)
文摘Interdiffusion in the Fe203-TiO2 system was investigated by the diffusion couple method in the temperature range of 1323 to 1473 K. The diffusion concentration curves of Ti4＋ cations were obtained by electron probe microanalysis, according to which the Boltzmann-Matano method optimized by Broeder was used to calculate the interdiffusion coeffi- cients. The interdiffusion coefficients almost increased linearly with the mole fraction of Ti4＋ cations increasing, and they were in the range of 10-12-10-11cm2-s-1. The increase of temperature could also lead to the increase of the interdiffusion coefficients at a constant concentration of Ti4＋ cations. It was also found that the thickness growth of the diffusion layer obeyed the parabolic rate law.
基金the National Natural Science Foundation of China Nos.51671053 and 51801021the Ministry of Industry and Information Technology Project No.MJ-2017-J-99)。
文摘MCrAlY(M=Ni and/or Co)overlay coating is widely used as a protective coating against high temperature oxidation and corrosion.However,due to its big difference in chemical composition with the underlying superalloy,elements interdiffusion occurs inevitably.One of the direct results is the formation of interdiffusion zone(IDZ)and secondary reaction zone(SRZ)with a high density of fine topological closed-packed phases(TCPs),weakening dramatically the mechanical properties of the alloy substrate.It is by now the main problem of modern high-temperature metallic coatings,but there are still hardly any reports studying the formation,growth and transformation of IDZ and SRZ in deep,as well as the precipitation of TCPs.In this work,a typical NiCrAlY coating is deposited by arc ion plating on a single-crystal superalloy N5.Elements interdiffusion between them and its relationship on microstructure were clarified.Cr rather than Al from the coating diffuses into the alloy at high temperatures and segregates immediately beneath their interface,contributing largely to the formation of IDZ.Simultaneously,diffusion of Ni from the deep alloy to IDZ leads to the formation and continuous expansion of SRZ.
基金the Guangdong Major Project of Basic and Applied Basic Research(No.2019B030302011)National Natural Science Foundation of China(Nos.52005523,U2032143,11902370)+3 种基金International Sci&Tech Cooperation Program of GuangDong Province(No.2019A050510022)Key Research Project of GuangDong Province(Nos.2019B010943001 and 2017B020235001)China Postdoctoral Science Foundation(Nos.2019M653173 and 2019TQ0374)the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.2021qntd12).
文摘High-temperature chromium(Cr)-zirconium(Zr)interdiffusion commonly occurs in Cr-coated zircaloys applied for enhanced accident-tolerant fuel(ATF)claddings.Such interdiffusion changes the interfacial microstructure and thus the fracture mechanism of the coating under external loading.In this study,the interdiffusion behavior in a magnetron sputtered Cr coating deposited on a Zr-4 alloy was studied in a vacuum environment at 1160C.In addition,the effect of interdiffusion on the microcracking behavior of the Cr coating was determined by in situ three-point bending tests.The experimental results show that the interdiffusion behavior resulted in the formation of a ZrCr2 layer,accompanied by the consumption of Cr coating and interfacial roughening.The growth of the diffusion layer followed a nearly parabolic law with respect to annealing time,and the residual stress of the annealed coating decreased with increasing annealing time.Under external loading,a large number of cracks were generated in the brittle interlayer,and some interfacial cracks were formed and grew at the ZrCr2/Zr-4 interface.Despite the remarkable microcracks in the ZrCr2 layer,the vacuum-annealed Cr coating has significantly fewer cracks than the original coating,mainly because of the recrystallization of the coating during annealing.
基金financially supported by the National Natural Science Foundation of China(No.51671053)the Natural Science Foundation of Liaoning Province of China(No.2019-ZD-0264)the Ministry of Industry and Information Technology Project(No.MJ-2017-J-99)。
文摘NiCrAlY coatings are widely applied on various alloy components to enhance oxidation and/or corrosion resistance at high temperatures.However,elements interdiffusion occurs between them due to composition difference.Although various diffusion barriers(DBs)are reported,this problem is still far from completely solved as most ceramic barriers suffer from poor adherence,while the metallic barriers play a limited role.In this study,NiCrAlY coating was deposited onto a second-generation single-crystal superalloy by arc ion plating.A novel simple method is provided to address elements interdiffusion.By pre-oxidation at a moderate temperature,a thin scale of Ni(Co)O forms at the alloy surface.It transforms to be an alumina/NiCoCr alloy/alumina sandwich by an in-situ reaction with the overlaying NiCrAlY coating and the alloy substrate at high service temperatures,which offers good barrier ability in conjunction with strong adhesion.In the presence of such an alumina/alloy/alumina DB,the NiCrAlY coating provides high resistance to oxidation and scale spallation for the alloy substrate.
文摘Interdiffusion coefficients at 950℃ and 1050℃ are calculated by Wagner analysis method as a function of composition of β-NiAI phase. The β-NiAI phase is formed by pack cementation on surface of superalloy. Results of the calculation show that interdiffusion coefficients in β-NiAI phase strongly depend on the compositions and vary over several orders of magnitude. Compared with the interdiffusion coefficients in the stoichiometric β-NiAI phase, the interdiffusion coefficients in β-NiAI phase formed on superalloy is obviously small, probably due to the composition, complicated microstructure and precipitates. However, it could be seen clearly that the shapes of the diffusivity curves are very similar to each other. The similarity of the diffusion curves and the difference between interdiffusion coefficients imply that the compositions, microstructures and precipitates of superalloy have a distinctly adverse effect on the interdiffusion of Ni and Al atoms during aluminization, but do not change the essential characteristics of β-NiAI phase.
基金financially supported by the National Key Research and Development Program of China(No.2021YFA1500800)the National Natural Science Foundation of China(Nos.51825204,52072377,521888101 and 51402199)+6 种基金the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2020192)the International Partnership Program of Chinese Academy of Sciences(No.174321KYSB20200005)China Postdoctoral Science Foundation(No.2017M621137)Liaoning Revitalization Talents Program(No.XLYC2007193)the Natural Science Foundation of Liaoning Province(Nos.2021-MS-014 and 2021NLTS1210)the University Innovation Talent Foundation of Liaoning Province(No.LR2018074)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(No.KF1708)。
文摘Delafossite CuFeO_(2) is a promising photocathode material for cost-efficiently photoelectrochemical(PEC)water splitting,but the unfavorable conductivity and fast recombination dynamics of photogenerated carriers limit its PEC activity for water reduction.Here,we developed a heterostructure photocathode consisting of the Cu-doped NiO(Cu:NiO)hole selective layer(HSL)and Ni-doped CuFeO_(2)(Ni:CuFeO_(2))active layer by simply annealing a homogeneous Cu-Fe oxalate layer grown on the Ni film deposited on the fluorine doped tin oxide(FTO)substrate.The obtained heterostructure of Cu:NiO/Ni:CuFeO_(2) with enhanced charge carrier transportability and high-quality interface greatly promotes the separation of photogenerated carriers.Accordingly,the Cu:NiO/Ni:CuFeO_(2) photocathode exhibits a high photocurrent density of~0.9 mA·cm^(-2 )at 0.2 V(vs.reversible hydrogen electrode,RHE),outperforming most of the reported bare CuFeO_(2) photocathodes in the literature.And the photocurrent density can be further improved to 1.2 mA·cm^(-2) after decorating NiSx cocatalyst.
基金financially supported by the National Natural Science Foundation of China(No.51571122)the Fundamental Research Funds for the Central Universities(No.30921013107)。
文摘The interdiffusion interface microstructures and composition evolution of Ni-Al-Cr/Ni-Al-Cr layered alloys under different temperature gradients were studied using phase-field simulation.A precipitate-free zone forms near the interface of the layered alloys,and the interface does not move with time under temperature gradients.When Cr concentrations in the alloy layers are different,Al diffuses from a low-to high-temperature region,whereas Cr from a high-to low-temperature region.The width of the precipitate-free zone changes from 0.5 to 2.5μm as the temperature gradient changes fromΔT=0.625 K·μm^(−1) to 1.250 K·μm^(−1);the width of the interdiffusion zone is also enlarged.Additionally,the temperature gradient promotes the interdiffusion of elements through the interface.In contrast,when the initial Al concentration is different in the alloy layers,an uphill diffusion of Al occurs,which is driven by the chemical potential of Al.
基金supported by the National Key Basic Research Program (No.2012CB932903)Natural Science Foundation of China (Nos. 51402348,51421002,91433205,21173260,11474333 and 91233202)
文摘A repeated interdiffusion method is described for phase-stable and high-quality （FA,MA）PbI3 film. The crys- tallization and growth of the perovskite films can be well controlled by adjusting the reactant concentrations. With this method, dense, smooth perovskite films with large crystals have been obtained. Finally, a PCE of 16.5% as well as a steady-state efficiency of 16.3% is achieved in the planar perovskite solar cell.
基金supported by the Major International (Regional) Joint Research Project of the National Natural Science Foundation of China (No. 51210004)the National Natural Science Foundation of China (No. 50903035)Chinese Ministry of Education (NCET-11-0174)
文摘The miscibility of poly（vinyl chloride）/poly（n-butyl methacrylate） （PVC/PnBMA） blend and the interdiffusion kinetics of PVC/PnBMA laminates have been investigated by differential scanning calorimetry （DSC） and atomic force microscopy （AFM）, respectively. This blend exhibited a lower critical solution temperature behavior. Below 120 ℃, DSC results showed each blend with different PVC contents exhibited only a single glass transition temperature which increased with PVC content, indicating that PVC and PnBMA were miscible. After PVC/PnBMA laminates were annealed at different temperature for different time, a smooth cross-section across interface was prepared by ultramicrotoming. Combined with topography and phase images of tapping mode AFM, the relative concentration profile, interface width and the relationship between interface width and annealing time could be obtained. In a regime of rubbery/rubbery interdiffusion, the diffusion obeyed a typical Fickian Case-I behavior where the interface width was proportional to the square root of annealing time. The mutual diffusion coefficient was in good agreement with that obtained from DSC and positron annihilation lifetime spectroscopy. However, in the regime of glassy/rubbery interdiffusion, the diffusion followed a typical Case-II behavior where the interface width was proportional to annealing time. These results imply that AFM is a reliable and powerful tool for the investigation of polymer/polymer interdiffusion at a level of polymer chain size.
