This research presents a thorough assessment of the cyclic oxidation characteristics of Y-and Hf-doped NiCoCrAlTaRe superalloy bond coatings in a pure steam atmosphere,emphasizing the distinct influences of reactive e...This research presents a thorough assessment of the cyclic oxidation characteristics of Y-and Hf-doped NiCoCrAlTaRe superalloy bond coatings in a pure steam atmosphere,emphasizing the distinct influences of reactive elements (Y and Hf) and refractory elements (Ta and Re)on the growth mechanisms of thermally grown oxide(TGO).The findings indicate that,in contrast to air conditions,elevated levels of water vapor significantly diminish the oxidation resistance of the bond coatings,leading to considerable porosity defects in both the central and lower regions of the TGO.Furthermore,this environment hinders the development of the"peg"structure at the TGO/metal interface,thereby accelerating the premature delamination of the coating.Additionally,the presence of doped elements such as Hf,Ta,and Y leads to their segregation at the Al_(2)O_(3)grain boundaries within the TGO,creating grain boundary structures characterized by a high density of defects.This defective architecture promotes the inward diffusion of water molecules at elevatedtemperatures,causing hydrogen atoms generated from oxidation and reduction reactions at the TGO/metal interface to become entrapped within the Al_(2)O_(3)lattice at the base of the TGO,rather than escaping efficiently.Ultimately,this phenomenon contributes to the formation of internal porosity defects during the oxidation of TGO in a steam environment.展开更多
Two kinds of NiCrAlY coatings(Ni-25Cr-10Al-0.5Y)were prepared on K417 superalloy using ion plating(AIP)and magnetron sputtering(MS),respectively.The isothermal and cyclic oxidation behaviors of the two NiCrAlY coating...Two kinds of NiCrAlY coatings(Ni-25Cr-10Al-0.5Y)were prepared on K417 superalloy using ion plating(AIP)and magnetron sputtering(MS),respectively.The isothermal and cyclic oxidation behaviors of the two NiCrAlY coatings were evaluated at 1323 K in stair air.The results revealed that the nanocrystalline NiCrAlY coating exhibited better isothermal and cyclic oxidation resistance compared to the conventional NiCrAlY at 1323 K.The mass gain and parabolic rate constant Kp of the nanocrystalline NiCrAlY coating were 45.2%and 44.7%lower than those of the conventional NiCrAlY coating,respectively.During cyclic oxidation,the tendency for spallation of the oxide scale was evidently decreased by nanocrystallization due to the formation of a continuous,compact,adherent,and slow-growing exclusiveα-Al_(2)O_(3)scale.The mechanism responsible for the improvement of the nanocrystalline NiCrAlY coating was discussed.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
The present levels of CO_(2)emission in the atmosphere require the development of technologies to achieve carbon neutrality using inexpensive processes.Conversion of CO_(2)into cyclic carbonates is one of the solution...The present levels of CO_(2)emission in the atmosphere require the development of technologies to achieve carbon neutrality using inexpensive processes.Conversion of CO_(2)into cyclic carbonates is one of the solutions to this problem.Here,we synthesized a ZnV_(2)O_(6)/Bi_(2)WO_(6)nanocomposite and catalyzed the cycloaddition of CO_(2)to epoxides for the green synthesis of cyclic carbonates under visible light irradiation.The present nanocomposite photocatalyst exhibited up to 96%yield of cyclic carbonates.The photocatalyst was found to be efficient for photocatalytic cycloaddition reactions,and the recovered photocatalyst showed stability in up to five consecutive photocatalytic experiments.The current methodology of cyclic carbonate production is a significant step toward the mitigation of atmospheric CO_(2)and can work well with the development of nanocomposite photocatalysts.展开更多
To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretre...To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.展开更多
The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batte...The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).展开更多
Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,...Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.展开更多
In this work,we constructed a three-dimensional electrochemical system(3D-ECO),which included the cathode and anode electrode plates,as well as the screening of three-dimensional particle electrodes and parameter opti...In this work,we constructed a three-dimensional electrochemical system(3D-ECO),which included the cathode and anode electrode plates,as well as the screening of three-dimensional particle electrodes and parameter opti-mization,for the degradation of landfill leachate(LL)containing elevated levels of tetracycline(TC),and explored its mechanism of action.Firstly,titanium-based ruthenium-iridium(Ti/RuO_(2)-IrO_(2)),titanium-based ruthenium-iridium-platinum(Ti/Pt-RuO_(2)-IrO_(2)),and titanium-based tin-antimony(Ti/SnO_(2)-Sb_(2)O_(3))were employed as an-odes in the electrocatalytic oxidation system,with titanium and stainless steel plates serving as cathodes,to construct the optimal two-dimensional electrocatalytic oxidation system(2D-ECO)through cross-comparison ex-periments.Subsequently,using granular activated carbon(GAC),coconut shell biochar(CBC),walnut shell carbon(WBC),and bamboo charcoal(BBC)as particle electrodes,a 3D-ECO system was developed.The influence of var-ious operational parameters on treating TC-containing LL was investigated.The optimal operating parameters obtained from the study was:pH=5,current density of 30 mA/cm^(2),particle dosage of 7 g/L,particle size ranging from 1.70 to 2.00 mm,and electrode spacing of 4 cm.Under these conditions,the COD removal rate of 3D-ECO within three hours was 90.25%,the TC removal rate was 72.41%,and the NH_(3)-N removal rate was 39.52%.The removal of TC followed a pseudo-first-order kinetic model.Additionally,degradation mechanisms were elucidated through electron paramagnetic resonance(EPR)spectrometer and Tert-Butanol(TBA)quenching experiments,indicating that the degradation primarily occurred through a non-radical(1O_(2))pathway.This re-search offers a comprehensive analysis of the simultaneous breakdown of intricate LL matrices and TC,enhancing our comprehension of the degradation processes and underlying mechanisms.展开更多
TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing Ti...TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing TiB_(2)coatings have disadvantages such as high equipment costs,complicated processes,and highly toxic gas emissions.This paper proposes an environmentally friendly method,which requires inexpensive equipment and simple processing,for preparing TiB_(2)coating on molybdenum via electrophoretic deposition within Na3AlF6-based molten salts.The produced TiB_(2)layer had an approximate thickness of 60μm and exhibited high density,outstanding hardness(38.2 GPa)and robust adhesion strength(51 N).Additionally,high-temperature oxidation experiments revealed that,at900℃,the TiB_(2)coating provided effective protection to the molybdenum substrate against oxidation for 3 h.This result indicates that the TiB_(2)coating prepared on molybdenum using molten salt electrophoretic deposition possesses good high-temperature oxidation resistance.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Chromium coatings with and without Al_2O_3 or Y_2O_3 particles were prepared by chromizing the as-deposited Ni-film with and without Al_2O_3 or Y_2O_3 particles using a conventional pack-cementation method at 800 ℃. ...Chromium coatings with and without Al_2O_3 or Y_2O_3 particles were prepared by chromizing the as-deposited Ni-film with and without Al_2O_3 or Y_2O_3 particles using a conventional pack-cementation method at 800 ℃. The cyclic oxidation at 800 ℃ and hot corrosion in molten 75% Na2SO4＋25% NaC1 at 800 ℃ of the three different chromizing coatings were investigated. The effects of Al_2O_3 or Y_2O_3 on the cyclic oxidation and hot corrosion behavior of the chromizing coatings were discussed. Microstructure results show that the codeposited Al_2O_3 or Y_2O_3 particles significantly retard the grain growth of the chromizing coating, which increases the cyclic oxidation and hot corrosion resistance of the chromizing coatings, due to the more rapid formation of purer and denser chromia scnle展开更多
An electrodeposited Ni-Al nanocomposite having a nanocrystalline Ni matrix dispersing Al nanoparticles was annealed in vacuum at 500 ℃ for different time （3, 5 and 8 h, respectively）. The results show that the anne...An electrodeposited Ni-Al nanocomposite having a nanocrystalline Ni matrix dispersing Al nanoparticles was annealed in vacuum at 500 ℃ for different time （3, 5 and 8 h, respectively）. The results show that the annealing treatment leads to the reaction of Ni and Al to form intermetallics and the coarsened Ni grains that are doped with a certain amount of Al atoms diffused from the nanoparticles. Cyclic oxidation in air at 1 000 ℃ indicates that the scale spallation resistance of the annealed Ni-Al nanocomposite increases with the increase of annealing time, due to prevention of the composite intergranular cracking during the cycling, reduction of numerous surface NiO nodules formed on the scale spalled area and prevention of internal oxidation.展开更多
（TiB2＋TiC）/Ni3Al composites were prepared by mechanical alloying of elemental powders and subsequently spark plasma sintering.Microstructure of（TiB2＋TiC）/Ni3Al composite sintered at 950°C was finer than tha...（TiB2＋TiC）/Ni3Al composites were prepared by mechanical alloying of elemental powders and subsequently spark plasma sintering.Microstructure of（TiB2＋TiC）/Ni3Al composite sintered at 950°C was finer than that of composite sintered at 1050°C.The influence of grain size on cyclic oxidation behavior was investigated.Cyclic oxidation results showed that the composite sintered at 950°C had smaller mass gains than the composite sintered at 1050°C.XRD and EDS results indicate that finer grain size is beneficial for increasing the oxidation resistance by improving the formation of a continuous TiO2 outer layer and a continuous Al2O3 inner layer on the surface of the composites sintered at 950°C.展开更多
Cyclic oxidation test is a fundamental method to assess lifetime of materials in high temperature environment.Cycle length or cyclic frequency is one important variable in cyclic oxidation testing.In present work,cycl...Cyclic oxidation test is a fundamental method to assess lifetime of materials in high temperature environment.Cycle length or cyclic frequency is one important variable in cyclic oxidation testing.In present work,cyclic oxidation tests were performed on cast K38 alloys with 0 wt.%,0.1 wt.%,and 0.5 wt.% yttrium additions at 1 273 K respectively.Two cyclic frequencies were used to investigate the influence of cycle length （1 h vs.20 h） on the high temperature oxidation behavior of superalloy.The results showed that the degradation of cast K38 alloy critically was dependent on the cyclic frequency.The yttrium addition was beneficial to reducing scale-growth rate,improving the scale adhesion and stress releasing,thereby increased the spallation resistance.It could be drawn that the effect of cyclic frequency was highly dependent on the scale adherence to the substrate.展开更多
A low-diffusion Ni Re Pt Al coating((Ni,Pt)Al outer layer in addition to a Re-rich diffusion barrier layer)was prepared on a Ni_(3)Al-base single crystal(SC)superalloy via electroplating and gaseous aluminizing treatm...A low-diffusion Ni Re Pt Al coating((Ni,Pt)Al outer layer in addition to a Re-rich diffusion barrier layer)was prepared on a Ni_(3)Al-base single crystal(SC)superalloy via electroplating and gaseous aluminizing treatments,wherein the electroplating procedures consisted of the composite deposition of Ni-Re followed by electroplating of Pt.In order to perform a comparison with conventional Ni Al and(Ni,Pt)Al coatings,the cyclic oxidation performance of the Ni Re Pt Al coating was evaluated at 1100 and 1150℃.We observed that the oxidation resistance of the Ni Re Pt Al coating was significantly improved by the greater presence of the residualβ-Ni Al phase in the outer layer and the lesser outward-diffusion of Mo from the substrate.In addition,the coating with the Re-rich diffusion barrier demonstrated a lower extent of interdiffusion into the substrate,where the thickness of the second reaction zone(SRZ)in the substrate alloy decreased by 25%.The mechanisms responsible for improving the oxidation resistance and decreasing the extent of SRZ formation are discussed,in which a particular attention is paid to the inhibition of the outward diffusion of Mo by the Re-based diffusion barrier.展开更多
Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catal...Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.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
The cyclic oxidation behavior of Fe-9Cr-1Mo steel (9Cr-1Mo) in 10%H2O+90%Ar (volume fraction) atmosphere at 600, 650 and 700 ℃ for various time was studied. The oxidation mechanism of 9Cr-1Mo steel in 10%H2O+90%Ar at...The cyclic oxidation behavior of Fe-9Cr-1Mo steel (9Cr-1Mo) in 10%H2O+90%Ar (volume fraction) atmosphere at 600, 650 and 700 ℃ for various time was studied. The oxidation mechanism of 9Cr-1Mo steel in 10%H2O+90%Ar atmosphere was discussed. The thermal stress was evaluated in two oxide layers to illustrate the spallation of the oxide layer. The experimental results indicate that there exists a duplex oxide scale with an outer layer of Fe2O3 and an inner layer of mixed (Fe, Cr)3O4 formed on 9Cr-1Mo steel during cyclic oxidation. Some cracks generated in both inner and outer oxide layers. Parts of oxide scales spalled from substrate during the cyclic oxidation. A higher tensile stress in the oxide layer is formed at the early oxidation stage than at the later oxidation stage during heating. This tensile stress results in the formation of cracks in the oxide layer.展开更多
Ni3Al coatings with and without Y2O3 particles were developed by annealing the electrodeposited Ni-Al composite coatings with and without Y2O3 particles at 800°C for 3 h.The microstructures and cyclic oxidation p...Ni3Al coatings with and without Y2O3 particles were developed by annealing the electrodeposited Ni-Al composite coatings with and without Y2O3 particles at 800°C for 3 h.The microstructures and cyclic oxidation performances of the produced Ni3Al coatings were comparatively investigated,with the emphasis on the effect of Y2O3.SEM/EDAX and TEM characterizations showed that the dispersion of Y2O3 refines the grains.Oxidation at 900°C for 100 h showed that the addition of Y2O3 significantly improved the cyclic oxidation resistance of Ni3Al coating.The effect of Y2O3 on the microstructure and the oxidation of the Ni3Al coating were discussed in detail.展开更多
基金financially supported by the National Key R&D Program of China(No.2023YFB3711200)the National Natural Science Foundation of China(No.U21A2044)the Science Center for Gas Turbine Project(No.P2022-B-IV-008-001)
文摘This research presents a thorough assessment of the cyclic oxidation characteristics of Y-and Hf-doped NiCoCrAlTaRe superalloy bond coatings in a pure steam atmosphere,emphasizing the distinct influences of reactive elements (Y and Hf) and refractory elements (Ta and Re)on the growth mechanisms of thermally grown oxide(TGO).The findings indicate that,in contrast to air conditions,elevated levels of water vapor significantly diminish the oxidation resistance of the bond coatings,leading to considerable porosity defects in both the central and lower regions of the TGO.Furthermore,this environment hinders the development of the"peg"structure at the TGO/metal interface,thereby accelerating the premature delamination of the coating.Additionally,the presence of doped elements such as Hf,Ta,and Y leads to their segregation at the Al_(2)O_(3)grain boundaries within the TGO,creating grain boundary structures characterized by a high density of defects.This defective architecture promotes the inward diffusion of water molecules at elevatedtemperatures,causing hydrogen atoms generated from oxidation and reduction reactions at the TGO/metal interface to become entrapped within the Al_(2)O_(3)lattice at the base of the TGO,rather than escaping efficiently.Ultimately,this phenomenon contributes to the formation of internal porosity defects during the oxidation of TGO in a steam environment.
基金financially supported by the National Natural Science Foundation of China(No.52101075)China Postdoctoral Science Foundation(Nos.2021M700557,2022M723272)+1 种基金Postdoctoral Scienceof Chongqing Natural Science Foundation(Nos.cstc2021jcyj-bshX0053,cstc2021jcyj-bshX0039)Scientific Research Foundation of Chongqing University of Technology(No.2020ZDZ004)。
文摘Two kinds of NiCrAlY coatings(Ni-25Cr-10Al-0.5Y)were prepared on K417 superalloy using ion plating(AIP)and magnetron sputtering(MS),respectively.The isothermal and cyclic oxidation behaviors of the two NiCrAlY coatings were evaluated at 1323 K in stair air.The results revealed that the nanocrystalline NiCrAlY coating exhibited better isothermal and cyclic oxidation resistance compared to the conventional NiCrAlY at 1323 K.The mass gain and parabolic rate constant Kp of the nanocrystalline NiCrAlY coating were 45.2%and 44.7%lower than those of the conventional NiCrAlY coating,respectively.During cyclic oxidation,the tendency for spallation of the oxide scale was evidently decreased by nanocrystallization due to the formation of a continuous,compact,adherent,and slow-growing exclusiveα-Al_(2)O_(3)scale.The mechanism responsible for the improvement of the nanocrystalline NiCrAlY coating was discussed.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金sponsored in part by the National Natural Science Foundation of China(No.21477167)the Science and Technology Research Plan Program of Henan Province(Nos.222102320328,232102210075,232102320137)the Key Science Research Program Foundation of High Education Schools of Henan Province(No.23B610010).
文摘The present levels of CO_(2)emission in the atmosphere require the development of technologies to achieve carbon neutrality using inexpensive processes.Conversion of CO_(2)into cyclic carbonates is one of the solutions to this problem.Here,we synthesized a ZnV_(2)O_(6)/Bi_(2)WO_(6)nanocomposite and catalyzed the cycloaddition of CO_(2)to epoxides for the green synthesis of cyclic carbonates under visible light irradiation.The present nanocomposite photocatalyst exhibited up to 96%yield of cyclic carbonates.The photocatalyst was found to be efficient for photocatalytic cycloaddition reactions,and the recovered photocatalyst showed stability in up to five consecutive photocatalytic experiments.The current methodology of cyclic carbonate production is a significant step toward the mitigation of atmospheric CO_(2)and can work well with the development of nanocomposite photocatalysts.
基金National Natural Science Foundation of China(52071274)Key Research and Development Projects of Shaanxi Province(2023-YBGY-442)Science and Technology Nova Project-Innovative Talent Promotion Program of Shaanxi Province(2020KJXX-062)。
文摘To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.
基金supported by the Low-Cost Long-Life Batteries program,China(No.WL-24-08-01)the National Natural Science Foundation of China(No.22279007)。
文摘The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).
基金supported by the National Key Research and Development Program of China(2024YFA1612900)the National Natural Science Foundation of China(Grant No.52103365 and No.12375270)the Guangdong Innovative and Entrepreneurial Research Team Program,China(Grant No.2021ZT09L227).
文摘Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.
基金supported by the National Natural Science Foundation of China(Nos.42477406 and 51878617)the Horizontal Scientific Research Project(No.KYY-HX-20220803)the Engineering Research Center of Ministry of Education for Renewable Energy Infrastructure Construction Technology.
文摘In this work,we constructed a three-dimensional electrochemical system(3D-ECO),which included the cathode and anode electrode plates,as well as the screening of three-dimensional particle electrodes and parameter opti-mization,for the degradation of landfill leachate(LL)containing elevated levels of tetracycline(TC),and explored its mechanism of action.Firstly,titanium-based ruthenium-iridium(Ti/RuO_(2)-IrO_(2)),titanium-based ruthenium-iridium-platinum(Ti/Pt-RuO_(2)-IrO_(2)),and titanium-based tin-antimony(Ti/SnO_(2)-Sb_(2)O_(3))were employed as an-odes in the electrocatalytic oxidation system,with titanium and stainless steel plates serving as cathodes,to construct the optimal two-dimensional electrocatalytic oxidation system(2D-ECO)through cross-comparison ex-periments.Subsequently,using granular activated carbon(GAC),coconut shell biochar(CBC),walnut shell carbon(WBC),and bamboo charcoal(BBC)as particle electrodes,a 3D-ECO system was developed.The influence of var-ious operational parameters on treating TC-containing LL was investigated.The optimal operating parameters obtained from the study was:pH=5,current density of 30 mA/cm^(2),particle dosage of 7 g/L,particle size ranging from 1.70 to 2.00 mm,and electrode spacing of 4 cm.Under these conditions,the COD removal rate of 3D-ECO within three hours was 90.25%,the TC removal rate was 72.41%,and the NH_(3)-N removal rate was 39.52%.The removal of TC followed a pseudo-first-order kinetic model.Additionally,degradation mechanisms were elucidated through electron paramagnetic resonance(EPR)spectrometer and Tert-Butanol(TBA)quenching experiments,indicating that the degradation primarily occurred through a non-radical(1O_(2))pathway.This re-search offers a comprehensive analysis of the simultaneous breakdown of intricate LL matrices and TC,enhancing our comprehension of the degradation processes and underlying mechanisms.
基金supported by the Original Exploratory Program of the National Natural Science Foundation of China(No.52450012)。
文摘TiB_(2)coatings can significantly enhance the high-temperature oxidation resistance of molybdenum,which would broaden the application range of molybdenum and alloys thereof.However,traditional methods for preparing TiB_(2)coatings have disadvantages such as high equipment costs,complicated processes,and highly toxic gas emissions.This paper proposes an environmentally friendly method,which requires inexpensive equipment and simple processing,for preparing TiB_(2)coating on molybdenum via electrophoretic deposition within Na3AlF6-based molten salts.The produced TiB_(2)layer had an approximate thickness of 60μm and exhibited high density,outstanding hardness(38.2 GPa)and robust adhesion strength(51 N).Additionally,high-temperature oxidation experiments revealed that,at900℃,the TiB_(2)coating provided effective protection to the molybdenum substrate against oxidation for 3 h.This result indicates that the TiB_(2)coating prepared on molybdenum using molten salt electrophoretic deposition possesses good high-temperature oxidation resistance.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金Project(11531319)supported by Scientific Research Fund of Heilongjiang Provincial Education Department,China
文摘Chromium coatings with and without Al_2O_3 or Y_2O_3 particles were prepared by chromizing the as-deposited Ni-film with and without Al_2O_3 or Y_2O_3 particles using a conventional pack-cementation method at 800 ℃. The cyclic oxidation at 800 ℃ and hot corrosion in molten 75% Na2SO4＋25% NaC1 at 800 ℃ of the three different chromizing coatings were investigated. The effects of Al_2O_3 or Y_2O_3 on the cyclic oxidation and hot corrosion behavior of the chromizing coatings were discussed. Microstructure results show that the codeposited Al_2O_3 or Y_2O_3 particles significantly retard the grain growth of the chromizing coating, which increases the cyclic oxidation and hot corrosion resistance of the chromizing coatings, due to the more rapid formation of purer and denser chromia scnle
基金Project (11531319) supported by Scientific Research Fund of Heilongjiang Provincial Education Department, ChinaProject (06-13) supported by the Scientific Research Startup Foundation of Heilongjiang Institute of Science and Technology, China
文摘An electrodeposited Ni-Al nanocomposite having a nanocrystalline Ni matrix dispersing Al nanoparticles was annealed in vacuum at 500 ℃ for different time （3, 5 and 8 h, respectively）. The results show that the annealing treatment leads to the reaction of Ni and Al to form intermetallics and the coarsened Ni grains that are doped with a certain amount of Al atoms diffused from the nanoparticles. Cyclic oxidation in air at 1 000 ℃ indicates that the scale spallation resistance of the annealed Ni-Al nanocomposite increases with the increase of annealing time, due to prevention of the composite intergranular cracking during the cycling, reduction of numerous surface NiO nodules formed on the scale spalled area and prevention of internal oxidation.
基金Project(QC2010110)supported by Heilongjiang Province Natural Science Foundation,China
文摘（TiB2＋TiC）/Ni3Al composites were prepared by mechanical alloying of elemental powders and subsequently spark plasma sintering.Microstructure of（TiB2＋TiC）/Ni3Al composite sintered at 950°C was finer than that of composite sintered at 1050°C.The influence of grain size on cyclic oxidation behavior was investigated.Cyclic oxidation results showed that the composite sintered at 950°C had smaller mass gains than the composite sintered at 1050°C.XRD and EDS results indicate that finer grain size is beneficial for increasing the oxidation resistance by improving the formation of a continuous TiO2 outer layer and a continuous Al2O3 inner layer on the surface of the composites sintered at 950°C.
基金Project supported by the Science and Technology Funds from Liaoning Education Department (2008564)the National Natural Science Foundation of China (50771100)
文摘Cyclic oxidation test is a fundamental method to assess lifetime of materials in high temperature environment.Cycle length or cyclic frequency is one important variable in cyclic oxidation testing.In present work,cyclic oxidation tests were performed on cast K38 alloys with 0 wt.%,0.1 wt.%,and 0.5 wt.% yttrium additions at 1 273 K respectively.Two cyclic frequencies were used to investigate the influence of cycle length （1 h vs.20 h） on the high temperature oxidation behavior of superalloy.The results showed that the degradation of cast K38 alloy critically was dependent on the cyclic frequency.The yttrium addition was beneficial to reducing scale-growth rate,improving the scale adhesion and stress releasing,thereby increased the spallation resistance.It could be drawn that the effect of cyclic frequency was highly dependent on the scale adherence to the substrate.
基金the Key-Area Research and Development Program of Guangdong Province(2019B010936001)financially supported by the National Natural Science Foundation of China(Grant Nos.51671202 and 51301184)。
文摘A low-diffusion Ni Re Pt Al coating((Ni,Pt)Al outer layer in addition to a Re-rich diffusion barrier layer)was prepared on a Ni_(3)Al-base single crystal(SC)superalloy via electroplating and gaseous aluminizing treatments,wherein the electroplating procedures consisted of the composite deposition of Ni-Re followed by electroplating of Pt.In order to perform a comparison with conventional Ni Al and(Ni,Pt)Al coatings,the cyclic oxidation performance of the Ni Re Pt Al coating was evaluated at 1100 and 1150℃.We observed that the oxidation resistance of the Ni Re Pt Al coating was significantly improved by the greater presence of the residualβ-Ni Al phase in the outer layer and the lesser outward-diffusion of Mo from the substrate.In addition,the coating with the Re-rich diffusion barrier demonstrated a lower extent of interdiffusion into the substrate,where the thickness of the second reaction zone(SRZ)in the substrate alloy decreased by 25%.The mechanisms responsible for improving the oxidation resistance and decreasing the extent of SRZ formation are discussed,in which a particular attention is paid to the inhibition of the outward diffusion of Mo by the Re-based diffusion barrier.
基金supported by the National Basic research Program of China (973 Program,2009CB623505)the National Natural Science Foundation of China (21273225)~~
文摘Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.
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Project(2006-8) supported by the Huadian International Corporation Limited
文摘The cyclic oxidation behavior of Fe-9Cr-1Mo steel (9Cr-1Mo) in 10%H2O+90%Ar (volume fraction) atmosphere at 600, 650 and 700 ℃ for various time was studied. The oxidation mechanism of 9Cr-1Mo steel in 10%H2O+90%Ar atmosphere was discussed. The thermal stress was evaluated in two oxide layers to illustrate the spallation of the oxide layer. The experimental results indicate that there exists a duplex oxide scale with an outer layer of Fe2O3 and an inner layer of mixed (Fe, Cr)3O4 formed on 9Cr-1Mo steel during cyclic oxidation. Some cracks generated in both inner and outer oxide layers. Parts of oxide scales spalled from substrate during the cyclic oxidation. A higher tensile stress in the oxide layer is formed at the early oxidation stage than at the later oxidation stage during heating. This tensile stress results in the formation of cracks in the oxide layer.
基金Project(11531319)supported by Scientific Research Fund of Heilongjiang Provincial Education Department,China
文摘Ni3Al coatings with and without Y2O3 particles were developed by annealing the electrodeposited Ni-Al composite coatings with and without Y2O3 particles at 800°C for 3 h.The microstructures and cyclic oxidation performances of the produced Ni3Al coatings were comparatively investigated,with the emphasis on the effect of Y2O3.SEM/EDAX and TEM characterizations showed that the dispersion of Y2O3 refines the grains.Oxidation at 900°C for 100 h showed that the addition of Y2O3 significantly improved the cyclic oxidation resistance of Ni3Al coating.The effect of Y2O3 on the microstructure and the oxidation of the Ni3Al coating were discussed in detail.
