Recent studies have revealed the extraordinary performance of zirconium oxide in propane dehydrogenation,which is attributed to the excellent reactivity of the coordinatively unsaturated zirconium sites(Zr_(cus))aroun...Recent studies have revealed the extraordinary performance of zirconium oxide in propane dehydrogenation,which is attributed to the excellent reactivity of the coordinatively unsaturated zirconium sites(Zr_(cus))around the oxygen vacancies.The origin of the enhanced catalytic activity of ZrO_(2)with defective tetrahedral Zr sites was examined by direct comparison with its pristine counterpart in the current study.Electronic-structure analysis revealed that electrons from oxygen removal were localized within vacancies on the defective surface,which directly attacked the C-H bond in propane.The involvement of localized electrons activates the C-H bond via back-donation to the antibonding orbital on the defective surface;conversely,charge is transferred from propane to the pristine surfaces.The barrier for the first C-H bond activation is clearly significantly reduced on the defective surfaces compared to that on the pristine surfaces,which verifies the superior activity of Zr_(cus).Notably,however,the desorption of both propene and hydrogen molecules from Zr_(cus)is more difficult due to strong binding.The calculated turnover frequency(TOF)for propene formation demonstrates that the pristine surfaces exhibit better catalytic performance at lower temperatures,whereas the defective surfaces have a larger TOF at high temperatures.However,the rate-determining step and reaction order on the defective surface differ from those on the pristine surface,which corroborates that the catalysts follow different mechanisms.A further optimization strategy was proposed to address the remaining bottlenecks in propane dehydrogenation on zirconium oxide.展开更多
Zirconium alloys are critical materials in nuclear engineering due to their exceptional irradiation resistance and corrosion stability.However,prolonged exposure to extreme operational environments,including a high ra...Zirconium alloys are critical materials in nuclear engineering due to their exceptional irradiation resistance and corrosion stability.However,prolonged exposure to extreme operational environments,including a high radiation,mechanical stress,and corrosive media,induces surface degradation mechanisms including stress corrosion cracking and erosion from impurity particle impacts,necessitating advanced surface treatments to improve hardness and corrosion resistance.We explore the application of laser shock peening(LSP)to enhance the surface properties of the Zr4 alloy.Experimental analyses reveal substantial microstructural modifications upon the LSP.The surface grain refinement achieved a maximum reduction of 52.7%in average grain size(from 22.88 to 10.8μm^(2)),accompanied by an increase of 59%in hardness(204 to 326 HV).Additionally,a compressive residual stress layer(approximately-100 MPa)was generated on the treated surface,which reduces the risk of stress corrosion cracking.To elucidate the mechanistic basis of these improvements,a multiscale computational framework was developed,integrating finite-element models for macroscale stress field evolution and molecular dynamics simulations for nanoscale dislocation dynamics.By incorporating the strain rate as a critical variable,this framework bridges microstructure evolution with macroscopic mechanical enhancements.The simulations not only elucidated the dynamic interplay between shockwave-induced plastic deformation and property improvements but also exhibited a good consistency with experimental residual stress profiles.Notably,we propose the application of strain rate-driven multiscale modeling in LSP research for Zr alloys,providing a predictive method to optimize laser parameters for a tailored surface strengthening.This study not only confirms that LSP is a feasible strategy capable of effectively enhancing the comprehensive surface properties of Zr alloys and extending their service life in nuclear environments,but also provides a reliable simulation methodology in the field of laser surface engineering of alloy materials.展开更多
Zirconium,prized for its exceptional corrosion resistance,high melting point,and unique nuclear properties,plays a critical role in multiple industrial sectors globally.Zirconium deposits are categorized into endogene...Zirconium,prized for its exceptional corrosion resistance,high melting point,and unique nuclear properties,plays a critical role in multiple industrial sectors globally.Zirconium deposits are categorized into endogenetic and exogenetic types in China.Endogenetic deposits-including alkaline rock-,alkaline granite-,and pegmatite-type mineralizations-predominantly occur along the Tarim Craton’s northern margin,the North China Craton,the southern Greater Khingan metallogenic belt,and the Yangtze Craton’s western margin.Exogenetic deposits,comprising clastic sedimentary,weathering crust,and fragmentation types,are concentrated in South China’s coastal zones.Endogenetic mineralization formed during Permian-Cretaceous magmatic-hydrothermal events linked to evolved alkaline granitic systems,while exogenetic deposits developed in Quaternary periods through weathering of zirconium-rich protoliths.However,economic extraction of endogenetic deposits remains constrained by rare earth element(REE)associations and radioactive complexities.Currently,China’s most economically significant reserves derive from clastic sedimentary systems,particularly coastal placer deposits.This study systematically synthesizes the spatial distribution and metallogenic mechanisms of Chinese zirconium deposits,offering strategic insights for resource exploration and sustainable utilization.展开更多
NO catalytic oxidation is the key performance of the diesel oxidation catalyst(DOC).We present a facile deposition method for the core-shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite pha...NO catalytic oxidation is the key performance of the diesel oxidation catalyst(DOC).We present a facile deposition method for the core-shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite phase uniform loading on the surface of zirconium-based composite(YMO/CYZO),which demonstrates a superior NO oxidation catalytic performance in simulated diesel combustion conditions and better thermal stability than mullite phase YMn_(2)O_(5)oxide.The NO oxidation at 250℃over YMO/CYZO-a approaches 25.2%in contrast to 13.52%over YMn_(2)O_(5)-a.Then the catalytic performance of YMO/CYZO,YMO and commercial 1 wt%Pt/Al_(2)O_(3)in a NO+O_(2)atmosphere was compared.The maximum conversion rate of YMO/CYZO to NO oxidation is 89.6%at 274℃with a GHSV of 50000 h^(-1),and the performance is superior to that of YMO(82.8%at 293℃)and 1 wt%Pt/Al_(2)O_(3)(68.6%,335℃).The NO-temperature programmed desorption(NO-TPD)and diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)results reveal that YMO/CYZO has multiple NO adsorption sites and high storage capacity.Furthermore,density functional theory(DFT)calculation indicates that YMO/CYZO has lower oxygen vacancy formation energies(E_(v)=0.93 eV)and favorable NO adsorption energies(E_(ads)=2.1 eV).Moreover,in situ X-ray photoelectron spectroscopy(XPS)characterization shows that the core-shell structure of YMO/CYZO has the potential to transmit active oxygen species to help realize Mn3+to Mn4+during the reaction process to enhance the conversion of NO*molecules,while NO oxidation reactions follow the MvK mechanism.展开更多
Polystyrene resins(PS)have been practical ion exchangers for radionuclides removal from water.However,nonspecific effects of ion exchange groups continue to be a major obstacle for emergency treatment with coexisting ...Polystyrene resins(PS)have been practical ion exchangers for radionuclides removal from water.However,nonspecific effects of ion exchange groups continue to be a major obstacle for emergency treatment with coexisting ions of high concentrations.The selectivity for Cs+enables zirconium phosphate(ZrP)to be the most promising inorganic sorbent for radioactive cesium extraction,despite being difficult to synthesize and causing excessive pressure loss in fixed-bed reactors due to fine powder.Herein,through facile confined crystallization in host macropores,we prepared PS confinedα-ZrP nanocrystalline(ZrP-PS).Size-screen sorption of layeredα-ZrP and sulfonic acid group preconcentration of PS synergistically enable a considerably higher Cs+affinity of ZrP-PS than PS,as confirmed by X-ray photoelectron spectroscopy(XPS)analysis.ZrP-PS demonstrated remarkable cesium sequestration performance in both batch and continuous experiments,with a high adsorption capacity of 269.58 mg/g,a rapid equilibrium within 80 min,and a continuous effluent volume of 2300 L/kg sorbents.Given the excellent selectivity for Cs+and flexibility to separate from treated water,ZrP-PS holds great promise as purification packages for the emergency treatment of radioactively contaminated water.展开更多
Previously,the in-plane mechanical anisotropy of Zr hot-rolled plates is ascribed mainly to the different activities of the deformation modes activated when loading along different directions.In this work,a quantitati...Previously,the in-plane mechanical anisotropy of Zr hot-rolled plates is ascribed mainly to the different activities of the deformation modes activated when loading along different directions.In this work,a quantitative study on the deformation behavior of a pure Zr hot-rolled plate under tension along the rolling direction(RD)and transverse direction(TD)reveals that both the activities of deformation modes and the anisotropy of grain boundary strengthening account for a tensile yield strength anisotropy along the TD and RD.Crystal plasticity simulations using viso-plastic self-consistent model show that prismatic slip is the predominant deformation mode for tension along the RD(RD-tension),while prismatic slip and basal slip are co-dominant deformation modes under tension along the TD(TD-tension).A low fraction of■under TD-tension,while hardly activated under RD-tension.The activation of basal slip with a much higher critical resolve shear stress under TD-tension contributes to a higher yield strength along the TD than along the RD.The grain boundary strengthening effect under tension along the TD and RD were compared by calculating the activation stress difference(△Stress)and the geometric compatibility factor(m′)between neighboring grains.The results indicate a higher grain boundary strengthening for TD-tension than that for RD-tension,which will lead to a higher yield strength along the TD.That is,the anisotropy of grain boundary strengthening between TD-tension and RD-tension also plays an important role in the in-plane anisotropy along the RD and TD.Afterward,the reasons for why there is a grain-boundary-strengthening anisotropy along the TD and RD were discussed.展开更多
Hydride precipitation in zirconium cladding materials can damage their integrity and durability.Service temperature and material defects have a significant effect on the dynamic growth of hydrides.In this study,we hav...Hydride precipitation in zirconium cladding materials can damage their integrity and durability.Service temperature and material defects have a significant effect on the dynamic growth of hydrides.In this study,we have developed a phasefield model based on the assumption of elastic behaviour within a specific temperature range(613 K-653 K).This model allows us to study the influence of temperature and interfacial effects on the morphology,stress,and average growth rate of zirconium hydride.The results suggest that changes in temperature and interfacial energy influence the length-to-thickness ratio and average growth rate of the hydride morphology.The ultimate determinant of hydride orientation is the loss of interfacial coherency,primarily induced by interfacial dislocation defects and quantifiable by the mismatch degree q.An escalation in interfacial coherency loss leads to a transition of hydride growth from horizontal to vertical,accompanied by the onset of redirection behaviour.Interestingly,redirection occurs at a critical mismatch level,denoted as qc,and remains unaffected by variations in temperature and interfacial energy.However,this redirection leads to an increase in the maximum stress,which may influence the direction of hydride crack propagation.This research highlights the importance of interfacial coherency and provides valuable insights into the morphology and growth kinetics of hydrides in zirconium alloys.展开更多
The corrosion properties of pure zirconium(Zr)with different grain sizes in acid,alkali,and salt environments were studied.The microstructures of pure Zr were observed by optical microscope,X-ray diffractometer,and el...The corrosion properties of pure zirconium(Zr)with different grain sizes in acid,alkali,and salt environments were studied.The microstructures of pure Zr were observed by optical microscope,X-ray diffractometer,and electron backscattered diffraction probe.The corrosion resistance of pure Zr was analyzed by electrochemical corrosion test and immersion test.Results show that pure Zr with grain size of 4–32μm can be obtained after annealing at 800°C for different durations,and the relationship between grain size and annealing duration is D^(3)−D_(0)^(3)=3.35t.The electrochemical corrosion and immersion corrosion test results show that the pure Zr with grain size of about 24μm(annealing at 800°C for 20 h)possesses the optimal corrosion resistance.展开更多
Introducing minor alloying elements is an effective strategy to improve the corrosion and mechanical properties of zirconium alloys for nuclear applications.During in-reactor service,external environment and stress ca...Introducing minor alloying elements is an effective strategy to improve the corrosion and mechanical properties of zirconium alloys for nuclear applications.During in-reactor service,external environment and stress can affect the distribution of alloying elements,substantially changing the degradation process of zirconium alloys.To date,there is a lack of in-depth understanding of the interaction between creep and microchemistry changes.Here,we conducted systematic transmission electron microscopy(TEM)and atom probe tomography(APT)investigations to address creep-induced redistribution of alloying elements in CZ1(Zr-Sn-Nb-Fe-Cr-Cu)zirconium alloy with different initial microstructures.Nb,Fe,Sn,and Cu are found to co-segregate at grain boundaries.The higher the intermediate annealing temperature,the larger the Gibbsian interfacial excesses of solute elements are.We further demonstrate that creep can reduce the excess value of Fe at grain boundaries due to the coarsening of Zr-Fe-Cr second phase particles via grain boundary and dislocation pipe diffusion.At the same time,the excess value of Sn is increased by diffusing from the matrix to grain boundaries.Moreover,Cu as a minor element in the concentration range of 0.05-0.3 wt.%is found to segregate at dislocations to form the Cottrell atmosphere and develop Cu-rich nanoclusters for suppressing dislocation motion.The new understanding of the segregation and clustering of minor alloying elements provides guidance for developing zirconium alloys with enhanced creep resistance.展开更多
Zirconium hydride(ZrH_(2)) is an ideal neutron moderator material. However, radiation effect significantly changes its properties, which affect its behavior and the lifespan of the reactor. The threshold energy of dis...Zirconium hydride(ZrH_(2)) is an ideal neutron moderator material. However, radiation effect significantly changes its properties, which affect its behavior and the lifespan of the reactor. The threshold energy of displacement is an important quantity of the number of radiation defects produced, which helps us to predict the evolution of radiation defects in ZrH_(2).Molecular dynamics(MD) and ab initio molecular dynamics(AIMD) are two main methods of calculating the threshold energy of displacement. The MD simulations with empirical potentials often cannot accurately depict the transitional states that lattice atoms must surpass to reach an interstitial state. Additionally, the AIMD method is unable to perform largescale calculation, which poses a computational challenge beyond the simulation range of density functional theory. Machine learning potentials are renowned for their high accuracy and efficiency, making them an increasingly preferred choice for molecular dynamics simulations. In this work, we develop an accurate potential energy model for the ZrH_(2) system by using the deep-potential(DP) method. The DP model has a high degree of agreement with first-principles calculations for the typical defect energy and mechanical properties of the ZrH_(2) system, including the basic bulk properties, formation energy of point defects, as well as diffusion behavior of hydrogen and zirconium. By integrating the DP model with Ziegler–Biersack–Littmark(ZBL) potential, we can predict the threshold energy of displacement of zirconium and hydrogen in ε-ZrH_(2).展开更多
Two-dimensional diagnosis of laser-induced zirconium(Zr)plasma has been experimentally performed using the time-of-flight method by employing Faraday cups in addition to electric and magnetic probes.The characteristic...Two-dimensional diagnosis of laser-induced zirconium(Zr)plasma has been experimentally performed using the time-of-flight method by employing Faraday cups in addition to electric and magnetic probes.The characteristic parameters of laser-induced Zr plasma have been evaluated as a function of different laser irradiances ranging from 4.5 to 11.7 GW cm-2 at different axial positions of 1–4 cm with a fixed radial distance of 2 cm.A well-supporting correlation between the plume parameters and the laser-plasma-produced spontaneous electric and magnetic(E and B)fields was established.The measurements of the characteristic parameters and spontaneously induced fields were observed to have an increasing trend with the increasing laser irradiance.However,when increasing the spatial distance in both the axial and radial directions,the plasma parameters(electron/ion number density,temperature and kinetic energy)did not show either continuously increasing or decreasing trends due to various kinetic and dynamic processes during the spatial evolution of the plume.However,the E and B fields were observed to be always diffusing away from the target.The radial component of electron number densities remained higher than the axial number density component,whereas the axial ion number density at all laser irradiances and axial distances remained higher than the radial ion number density.The higher axial self-generated electric field(SGEF)values than radial SGEF values are correlated with the effective charge-separation mechanism of electrons and ions.The generation of a self-generated magnetic field is observed dominantly in the radial direction at increasing laser irradiance as compared to the axial one due to the deflection of fast-moving electrons and the persistence of two-electron temperature on the radial axis.展开更多
For the challenging nature of the zirconium environment analysis, this study consists to analyze the electrochemical behavior of Zirconium in both aqueous and organic media. To that end first the electrolytic media wa...For the challenging nature of the zirconium environment analysis, this study consists to analyze the electrochemical behavior of Zirconium in both aqueous and organic media. To that end first the electrolytic media was selected on the basis of the Pourbaix potential-pH diagram, which provides informations on the predominance of Zr<sup>(IV) </sup> ion and Zr in aqueous media. In aqueous media, analyzes were first carried out in acidic media then in basic media. Studies have thus revealed that the acidic environment is not favourable for the electrochemical analysis of zirconium. Voltammograms obtained in an acidic environment show no zirconium detection signal;this is due to the strong presence of H<sup>+</sup> ions in the solution. We have also observed in acidic media the phenomenon of passivation of the electrode surface. In aqueous alkaline media (pH = 13), we have drawn in reduction several Intensity-Potential curves by fixingsome technical parameterslike scanning speed, rotation speed of the electrode. The obtained voltammograms show cathodic waves, starting from -1.5 V/DHW and attributed to the reduction of Zr<sup> (IV) </sup> to Zr (0). The last phase of this study focused on the electrochemical analysis of zirconium in an organic media. In this media, several intensity-potential curves were plotted in reduction and in cyclic voltammetry with various parameters. Through several reduction analysis, the Zr<sup> (IV) </sup> was reduced to Zr (0) to the potential of -1.5 V/DHW. The electrochemical analysis of zirconium in organic media seems globally easier to achieve thanks to its large solvent window (i.e. dimethylformamide (DMF) solvent window > 6 V).展开更多
This article focuses on the electrorefining process in molten fluorides to selectively recover zirconium from one Zr-based metallic alloy involved in the field of nuclear energy: Zircaloy-4. Firstly, zirconium electro...This article focuses on the electrorefining process in molten fluorides to selectively recover zirconium from one Zr-based metallic alloy involved in the field of nuclear energy: Zircaloy-4. Firstly, zirconium electrodeposition was investigated in molten LiF-NaF at 750˚C in order to determine appropriate operating conditions to ensure Zr metal recovery: concentration and applied current density. Then, anodic behaviour of Zircaloy-4 was studied and compared to its composing elements. These results allowed us to define an adapted electrorefining strategy. Electrorefining progress, anodic and cathodic faradic efficiencies were evaluated by materials characterization obtained after galvanostatic electrolyses.展开更多
The aim of this research was to develop an intrarradicular dental post based on epoxy resin/nano zirconium phosphate composite with potential appli-cation in prosthetic dentistry. Zirconium phosphate (ZrP) nanoparticl...The aim of this research was to develop an intrarradicular dental post based on epoxy resin/nano zirconium phosphate composite with potential appli-cation in prosthetic dentistry. Zirconium phosphate (ZrP) nanoparticle was synthesized by a reaction between phosphoric acid (H3PO4) and zirconium (IV) oxide chloride 8-hydrate (ZrOCl2·8H2O) and applied as filler. Commer-cial epoxy resin and hardener were used as polymer matrix. The composites were prepared at different proportions of epoxy resin/hardener, filler amount, reaction time and temperature. Infrared revealed that degree of conversion decreased with amount of ZrP. Insoluble matter was upper than 97%. Thermogravimetry indicated two steps of degradation. The best values of flexural modulus and flexural strength were achieved for the post desig-nated as 1:0.25:0.25. Laser scanning confocal microscopy suggested that the morphology of the posts fractured surface varied according to epoxy-resin:hardener ratio and the ZrP amount. From atomic force micros-copy, the topographic view exposed the shape and size of ZrP particles. Field emission scanning electron microscopy and energy dispersive spectroscopy indicated good adhesion between epoxy resin matrix-ZrP and that the pres-ence of phosphate rendered brittle the fracture surface.展开更多
The formation processes of a composite ceramic coating on AM50 magnesium alloy prepared by plasma electrolytic oxidation （PEO） in a K 2 ZrF 6 electrolyte solution were studied by scanning electron microscope （SEM）...The formation processes of a composite ceramic coating on AM50 magnesium alloy prepared by plasma electrolytic oxidation （PEO） in a K 2 ZrF 6 electrolyte solution were studied by scanning electron microscope （SEM） and energy dispersive X-ray spectroscope （EDX）. Electrochemical impedance spectroscopy （EIS） tests were used to study the variation of the corrosion resistance of the coating during the PEO treatment. The results show that the coating formed on Mg alloy is mainly composed of MgO and MgF 2 when the applied voltage is lower than the sparking voltage, and zirconium oxides start to be deposited on Mg substrate after the potential exceeding the sparking voltage. The corrosion resistance of the coating increases with increasing the applied voltage.展开更多
The effects of zirconium addition on the microstructure and mechanical properties of Mg97Y2Zn1 alloy were investigated.The microstructure of as-cast Mg97Y2Zn1 alloy is refined by the addition of zirconium.During the e...The effects of zirconium addition on the microstructure and mechanical properties of Mg97Y2Zn1 alloy were investigated.The microstructure of as-cast Mg97Y2Zn1 alloy is refined by the addition of zirconium.During the extrusion,the initial nucleation sites of the alloy are mainly original grain boundaries and secondary phase.The addition of zirconium could stimulate the DRX process because more grain boundaries are formed,which increases the dynamic recrystallization rate.Both the strength and elongation of the alloy are increased by the addition of zirconium.展开更多
Industry pure zirconium sheets with a strong c-axis fiber texture were rolled to different strains at 77 K to investigate the twinning behavior and deformation mechanism. The microstructure and texture of the rolled s...Industry pure zirconium sheets with a strong c-axis fiber texture were rolled to different strains at 77 K to investigate the twinning behavior and deformation mechanism. The microstructure and texture of the rolled specimens were characterized by scanning electron microscopy （SEM） together with electron backscatter diffraction （EBSD） techniques. The results show that the {1022} （1123） compression twinning mode is the dominant deformation twin at low strains loaded along the c-axis, and the {1012} （ 10]- 1 ） tensile twinning generates as the second twin in {1022} （ 1123 ） twins. The selection of twinning modes is governed by Schmid factor （SF） due to the calculating of SF and the EBSD simulating of twinning distribution. The evolution of texture during rolling affected by twins with increase of the strain was explained.展开更多
The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H...The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H- and Zr3O7H- are observed after the reaction. Den-sity functional theory calculations indicate that the hydrogen abstraction is favorable in the reaction of Zr2O5- with C2H6, which supports that the observed Zr2O5H- and Zr3O7H- are due to hydrogen atom abstraction from the alkane molecules. This work shows a newpossible pathway in the reaction of zirconium oxide cluster anions with alkane molecules.展开更多
In order to understand the dnve-in target in a D-D type neutron generator,it is essential to study the mechanism of the interaction between hydrogen ion beams and the hydrogenabsorbing metal film.The present research ...In order to understand the dnve-in target in a D-D type neutron generator,it is essential to study the mechanism of the interaction between hydrogen ion beams and the hydrogenabsorbing metal film.The present research concerns the nucleation of hydride within zirconium film implanted with hydrogen ions.Doses of 30 keV hydrogen ions ranging from 4.30×10^（17） to1.43×10^（18） ions cm^（-2） were loaded into the zirconium film through the ion beam implantation technique.Features of the surface morphology and transformation of phase structures were investigated with scanning electron microscopy,atomic force microscopy and x-ray diffraction.Confirmation of the formation of 5 phase zirconium hydride in the implanted samples was first made by x-ray diffraction,and the different stages in the gradual nucleation and growth of zirconium hydride were then observed by atomic force microscope and scanning electron microscopy.展开更多
Anodic dissolutionbehaviorof zirconium inBu^n 4NBr-contaningisopropanol solution was investigated using cyclic voltammetry, linear sweep voltammetry and chronoamperometry, complemented with a scanning electron microsc...Anodic dissolutionbehaviorof zirconium inBu^n 4NBr-contaningisopropanol solution was investigated using cyclic voltammetry, linear sweep voltammetry and chronoamperometry, complemented with a scanning electron microscope （SEM）.The voltammograms did not exhibit active dissolutionuntil the breakdown of passive layer induced by aggressive bromide anions.SEM images confirmed the existence of pits on zirconium surface.The depth and breadth of pits were intensified with increasing potential. The pitting potentialshifted negatively as either temperature orBu^n 4NBr concentration was increased, while it increased with increasing scan rate.The corrosion current density increased with increasing temperature. The apparent activation energyof anodic dissolutionofzirconiumwas 21.88kJ/mol. The chronoamperometry revealed that increasingBu^n 4NBrconcentration shortened the incubation time for passivity breakdown and accelerated the pit nucleation and growth. The experimental results were helpfulto obtain the optimum conditions for electrosynthesis of zirconium isopropoxide.展开更多
文摘Recent studies have revealed the extraordinary performance of zirconium oxide in propane dehydrogenation,which is attributed to the excellent reactivity of the coordinatively unsaturated zirconium sites(Zr_(cus))around the oxygen vacancies.The origin of the enhanced catalytic activity of ZrO_(2)with defective tetrahedral Zr sites was examined by direct comparison with its pristine counterpart in the current study.Electronic-structure analysis revealed that electrons from oxygen removal were localized within vacancies on the defective surface,which directly attacked the C-H bond in propane.The involvement of localized electrons activates the C-H bond via back-donation to the antibonding orbital on the defective surface;conversely,charge is transferred from propane to the pristine surfaces.The barrier for the first C-H bond activation is clearly significantly reduced on the defective surfaces compared to that on the pristine surfaces,which verifies the superior activity of Zr_(cus).Notably,however,the desorption of both propene and hydrogen molecules from Zr_(cus)is more difficult due to strong binding.The calculated turnover frequency(TOF)for propene formation demonstrates that the pristine surfaces exhibit better catalytic performance at lower temperatures,whereas the defective surfaces have a larger TOF at high temperatures.However,the rate-determining step and reaction order on the defective surface differ from those on the pristine surface,which corroborates that the catalysts follow different mechanisms.A further optimization strategy was proposed to address the remaining bottlenecks in propane dehydrogenation on zirconium oxide.
基金Supported by National Key Research and Development Program of China(Grant No.2023YFB4603803)National Natural Science Foundation of China(Grant No.12374295).
文摘Zirconium alloys are critical materials in nuclear engineering due to their exceptional irradiation resistance and corrosion stability.However,prolonged exposure to extreme operational environments,including a high radiation,mechanical stress,and corrosive media,induces surface degradation mechanisms including stress corrosion cracking and erosion from impurity particle impacts,necessitating advanced surface treatments to improve hardness and corrosion resistance.We explore the application of laser shock peening(LSP)to enhance the surface properties of the Zr4 alloy.Experimental analyses reveal substantial microstructural modifications upon the LSP.The surface grain refinement achieved a maximum reduction of 52.7%in average grain size(from 22.88 to 10.8μm^(2)),accompanied by an increase of 59%in hardness(204 to 326 HV).Additionally,a compressive residual stress layer(approximately-100 MPa)was generated on the treated surface,which reduces the risk of stress corrosion cracking.To elucidate the mechanistic basis of these improvements,a multiscale computational framework was developed,integrating finite-element models for macroscale stress field evolution and molecular dynamics simulations for nanoscale dislocation dynamics.By incorporating the strain rate as a critical variable,this framework bridges microstructure evolution with macroscopic mechanical enhancements.The simulations not only elucidated the dynamic interplay between shockwave-induced plastic deformation and property improvements but also exhibited a good consistency with experimental residual stress profiles.Notably,we propose the application of strain rate-driven multiscale modeling in LSP research for Zr alloys,providing a predictive method to optimize laser parameters for a tailored surface strengthening.This study not only confirms that LSP is a feasible strategy capable of effectively enhancing the comprehensive surface properties of Zr alloys and extending their service life in nuclear environments,but also provides a reliable simulation methodology in the field of laser surface engineering of alloy materials.
基金supported by Science and technology basic resources survey special project(2022FY101701)China Geological Survey Project(DD2023350).
文摘Zirconium,prized for its exceptional corrosion resistance,high melting point,and unique nuclear properties,plays a critical role in multiple industrial sectors globally.Zirconium deposits are categorized into endogenetic and exogenetic types in China.Endogenetic deposits-including alkaline rock-,alkaline granite-,and pegmatite-type mineralizations-predominantly occur along the Tarim Craton’s northern margin,the North China Craton,the southern Greater Khingan metallogenic belt,and the Yangtze Craton’s western margin.Exogenetic deposits,comprising clastic sedimentary,weathering crust,and fragmentation types,are concentrated in South China’s coastal zones.Endogenetic mineralization formed during Permian-Cretaceous magmatic-hydrothermal events linked to evolved alkaline granitic systems,while exogenetic deposits developed in Quaternary periods through weathering of zirconium-rich protoliths.However,economic extraction of endogenetic deposits remains constrained by rare earth element(REE)associations and radioactive complexities.Currently,China’s most economically significant reserves derive from clastic sedimentary systems,particularly coastal placer deposits.This study systematically synthesizes the spatial distribution and metallogenic mechanisms of Chinese zirconium deposits,offering strategic insights for resource exploration and sustainable utilization.
基金supported by National Natural Science Foundation of China(52204376)Open Project of Yunnan Precious Metals Laboratory Co.(YPML-2023050266)Youth Foundation of Hebei Province(E2022103007)。
文摘NO catalytic oxidation is the key performance of the diesel oxidation catalyst(DOC).We present a facile deposition method for the core-shell rare-earth manganese-zirconium composite oxide that shows the Mn mullite phase uniform loading on the surface of zirconium-based composite(YMO/CYZO),which demonstrates a superior NO oxidation catalytic performance in simulated diesel combustion conditions and better thermal stability than mullite phase YMn_(2)O_(5)oxide.The NO oxidation at 250℃over YMO/CYZO-a approaches 25.2%in contrast to 13.52%over YMn_(2)O_(5)-a.Then the catalytic performance of YMO/CYZO,YMO and commercial 1 wt%Pt/Al_(2)O_(3)in a NO+O_(2)atmosphere was compared.The maximum conversion rate of YMO/CYZO to NO oxidation is 89.6%at 274℃with a GHSV of 50000 h^(-1),and the performance is superior to that of YMO(82.8%at 293℃)and 1 wt%Pt/Al_(2)O_(3)(68.6%,335℃).The NO-temperature programmed desorption(NO-TPD)and diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)results reveal that YMO/CYZO has multiple NO adsorption sites and high storage capacity.Furthermore,density functional theory(DFT)calculation indicates that YMO/CYZO has lower oxygen vacancy formation energies(E_(v)=0.93 eV)and favorable NO adsorption energies(E_(ads)=2.1 eV).Moreover,in situ X-ray photoelectron spectroscopy(XPS)characterization shows that the core-shell structure of YMO/CYZO has the potential to transmit active oxygen species to help realize Mn3+to Mn4+during the reaction process to enhance the conversion of NO*molecules,while NO oxidation reactions follow the MvK mechanism.
基金NSFC(Nos.U22A20403,21301151 and 52070115)Natural Science Foundation of Hebei Province(Nos.B2021203036 and E2022203011)Key Project of the Hebei Education Department(No.ZD2021103).
文摘Polystyrene resins(PS)have been practical ion exchangers for radionuclides removal from water.However,nonspecific effects of ion exchange groups continue to be a major obstacle for emergency treatment with coexisting ions of high concentrations.The selectivity for Cs+enables zirconium phosphate(ZrP)to be the most promising inorganic sorbent for radioactive cesium extraction,despite being difficult to synthesize and causing excessive pressure loss in fixed-bed reactors due to fine powder.Herein,through facile confined crystallization in host macropores,we prepared PS confinedα-ZrP nanocrystalline(ZrP-PS).Size-screen sorption of layeredα-ZrP and sulfonic acid group preconcentration of PS synergistically enable a considerably higher Cs+affinity of ZrP-PS than PS,as confirmed by X-ray photoelectron spectroscopy(XPS)analysis.ZrP-PS demonstrated remarkable cesium sequestration performance in both batch and continuous experiments,with a high adsorption capacity of 269.58 mg/g,a rapid equilibrium within 80 min,and a continuous effluent volume of 2300 L/kg sorbents.Given the excellent selectivity for Cs+and flexibility to separate from treated water,ZrP-PS holds great promise as purification packages for the emergency treatment of radioactively contaminated water.
基金supported by the National Natural Science Foundation of China(No.52275161)the Ministry of Science and Technology High-End Intelligence Plan Team Project(No.G2022040015L)+2 种基金the Shaanxi Science and Technology Innovation Team(No.2023-CX-TD-50)the Shaanxi Qin Chuangyuan scientists and engineers’team(No.2022KXJ-145)the International Joint Research Center for Value-added Metallurgy and Processing of Non-ferrous Metals(No.2019SD0010).
文摘Previously,the in-plane mechanical anisotropy of Zr hot-rolled plates is ascribed mainly to the different activities of the deformation modes activated when loading along different directions.In this work,a quantitative study on the deformation behavior of a pure Zr hot-rolled plate under tension along the rolling direction(RD)and transverse direction(TD)reveals that both the activities of deformation modes and the anisotropy of grain boundary strengthening account for a tensile yield strength anisotropy along the TD and RD.Crystal plasticity simulations using viso-plastic self-consistent model show that prismatic slip is the predominant deformation mode for tension along the RD(RD-tension),while prismatic slip and basal slip are co-dominant deformation modes under tension along the TD(TD-tension).A low fraction of■under TD-tension,while hardly activated under RD-tension.The activation of basal slip with a much higher critical resolve shear stress under TD-tension contributes to a higher yield strength along the TD than along the RD.The grain boundary strengthening effect under tension along the TD and RD were compared by calculating the activation stress difference(△Stress)and the geometric compatibility factor(m′)between neighboring grains.The results indicate a higher grain boundary strengthening for TD-tension than that for RD-tension,which will lead to a higher yield strength along the TD.That is,the anisotropy of grain boundary strengthening between TD-tension and RD-tension also plays an important role in the in-plane anisotropy along the RD and TD.Afterward,the reasons for why there is a grain-boundary-strengthening anisotropy along the TD and RD were discussed.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.U2230401,U1930401,and 12004048)the National Key Research and Development Program of China (Grant No.2021YFB3501503)+1 种基金the Science Challenge Project (Grant No.TZ2018002)the Foundation of LCP。
文摘Hydride precipitation in zirconium cladding materials can damage their integrity and durability.Service temperature and material defects have a significant effect on the dynamic growth of hydrides.In this study,we have developed a phasefield model based on the assumption of elastic behaviour within a specific temperature range(613 K-653 K).This model allows us to study the influence of temperature and interfacial effects on the morphology,stress,and average growth rate of zirconium hydride.The results suggest that changes in temperature and interfacial energy influence the length-to-thickness ratio and average growth rate of the hydride morphology.The ultimate determinant of hydride orientation is the loss of interfacial coherency,primarily induced by interfacial dislocation defects and quantifiable by the mismatch degree q.An escalation in interfacial coherency loss leads to a transition of hydride growth from horizontal to vertical,accompanied by the onset of redirection behaviour.Interestingly,redirection occurs at a critical mismatch level,denoted as qc,and remains unaffected by variations in temperature and interfacial energy.However,this redirection leads to an increase in the maximum stress,which may influence the direction of hydride crack propagation.This research highlights the importance of interfacial coherency and provides valuable insights into the morphology and growth kinetics of hydrides in zirconium alloys.
基金National Natural Science Foundation of China(52071126)Natural Science Foundation of Tianjin City,China(22JCQNJC01240)+2 种基金Central Guidance on Local Science and Technology Development Fund of Hebei Province(226Z1009G)Special Funds for Science and Technology Innovation in Hebei(2022X19)Foundation Strengthening Program(2019-JCJQ-00)。
文摘The corrosion properties of pure zirconium(Zr)with different grain sizes in acid,alkali,and salt environments were studied.The microstructures of pure Zr were observed by optical microscope,X-ray diffractometer,and electron backscattered diffraction probe.The corrosion resistance of pure Zr was analyzed by electrochemical corrosion test and immersion test.Results show that pure Zr with grain size of 4–32μm can be obtained after annealing at 800°C for different durations,and the relationship between grain size and annealing duration is D^(3)−D_(0)^(3)=3.35t.The electrochemical corrosion and immersion corrosion test results show that the pure Zr with grain size of about 24μm(annealing at 800°C for 20 h)possesses the optimal corrosion resistance.
基金the funding support from the Young Elite Scientists Sponsorship Program by CSEE.
文摘Introducing minor alloying elements is an effective strategy to improve the corrosion and mechanical properties of zirconium alloys for nuclear applications.During in-reactor service,external environment and stress can affect the distribution of alloying elements,substantially changing the degradation process of zirconium alloys.To date,there is a lack of in-depth understanding of the interaction between creep and microchemistry changes.Here,we conducted systematic transmission electron microscopy(TEM)and atom probe tomography(APT)investigations to address creep-induced redistribution of alloying elements in CZ1(Zr-Sn-Nb-Fe-Cr-Cu)zirconium alloy with different initial microstructures.Nb,Fe,Sn,and Cu are found to co-segregate at grain boundaries.The higher the intermediate annealing temperature,the larger the Gibbsian interfacial excesses of solute elements are.We further demonstrate that creep can reduce the excess value of Fe at grain boundaries due to the coarsening of Zr-Fe-Cr second phase particles via grain boundary and dislocation pipe diffusion.At the same time,the excess value of Sn is increased by diffusing from the matrix to grain boundaries.Moreover,Cu as a minor element in the concentration range of 0.05-0.3 wt.%is found to segregate at dislocations to form the Cottrell atmosphere and develop Cu-rich nanoclusters for suppressing dislocation motion.The new understanding of the segregation and clustering of minor alloying elements provides guidance for developing zirconium alloys with enhanced creep resistance.
基金Project supported by the Joint Fund of the National Natural Science Foundation of China–“Ye Qisun”Science Fund(Grant No.U2341251)。
文摘Zirconium hydride(ZrH_(2)) is an ideal neutron moderator material. However, radiation effect significantly changes its properties, which affect its behavior and the lifespan of the reactor. The threshold energy of displacement is an important quantity of the number of radiation defects produced, which helps us to predict the evolution of radiation defects in ZrH_(2).Molecular dynamics(MD) and ab initio molecular dynamics(AIMD) are two main methods of calculating the threshold energy of displacement. The MD simulations with empirical potentials often cannot accurately depict the transitional states that lattice atoms must surpass to reach an interstitial state. Additionally, the AIMD method is unable to perform largescale calculation, which poses a computational challenge beyond the simulation range of density functional theory. Machine learning potentials are renowned for their high accuracy and efficiency, making them an increasingly preferred choice for molecular dynamics simulations. In this work, we develop an accurate potential energy model for the ZrH_(2) system by using the deep-potential(DP) method. The DP model has a high degree of agreement with first-principles calculations for the typical defect energy and mechanical properties of the ZrH_(2) system, including the basic bulk properties, formation energy of point defects, as well as diffusion behavior of hydrogen and zirconium. By integrating the DP model with Ziegler–Biersack–Littmark(ZBL) potential, we can predict the threshold energy of displacement of zirconium and hydrogen in ε-ZrH_(2).
文摘Two-dimensional diagnosis of laser-induced zirconium(Zr)plasma has been experimentally performed using the time-of-flight method by employing Faraday cups in addition to electric and magnetic probes.The characteristic parameters of laser-induced Zr plasma have been evaluated as a function of different laser irradiances ranging from 4.5 to 11.7 GW cm-2 at different axial positions of 1–4 cm with a fixed radial distance of 2 cm.A well-supporting correlation between the plume parameters and the laser-plasma-produced spontaneous electric and magnetic(E and B)fields was established.The measurements of the characteristic parameters and spontaneously induced fields were observed to have an increasing trend with the increasing laser irradiance.However,when increasing the spatial distance in both the axial and radial directions,the plasma parameters(electron/ion number density,temperature and kinetic energy)did not show either continuously increasing or decreasing trends due to various kinetic and dynamic processes during the spatial evolution of the plume.However,the E and B fields were observed to be always diffusing away from the target.The radial component of electron number densities remained higher than the axial number density component,whereas the axial ion number density at all laser irradiances and axial distances remained higher than the radial ion number density.The higher axial self-generated electric field(SGEF)values than radial SGEF values are correlated with the effective charge-separation mechanism of electrons and ions.The generation of a self-generated magnetic field is observed dominantly in the radial direction at increasing laser irradiance as compared to the axial one due to the deflection of fast-moving electrons and the persistence of two-electron temperature on the radial axis.
文摘For the challenging nature of the zirconium environment analysis, this study consists to analyze the electrochemical behavior of Zirconium in both aqueous and organic media. To that end first the electrolytic media was selected on the basis of the Pourbaix potential-pH diagram, which provides informations on the predominance of Zr<sup>(IV) </sup> ion and Zr in aqueous media. In aqueous media, analyzes were first carried out in acidic media then in basic media. Studies have thus revealed that the acidic environment is not favourable for the electrochemical analysis of zirconium. Voltammograms obtained in an acidic environment show no zirconium detection signal;this is due to the strong presence of H<sup>+</sup> ions in the solution. We have also observed in acidic media the phenomenon of passivation of the electrode surface. In aqueous alkaline media (pH = 13), we have drawn in reduction several Intensity-Potential curves by fixingsome technical parameterslike scanning speed, rotation speed of the electrode. The obtained voltammograms show cathodic waves, starting from -1.5 V/DHW and attributed to the reduction of Zr<sup> (IV) </sup> to Zr (0). The last phase of this study focused on the electrochemical analysis of zirconium in an organic media. In this media, several intensity-potential curves were plotted in reduction and in cyclic voltammetry with various parameters. Through several reduction analysis, the Zr<sup> (IV) </sup> was reduced to Zr (0) to the potential of -1.5 V/DHW. The electrochemical analysis of zirconium in organic media seems globally easier to achieve thanks to its large solvent window (i.e. dimethylformamide (DMF) solvent window > 6 V).
文摘This article focuses on the electrorefining process in molten fluorides to selectively recover zirconium from one Zr-based metallic alloy involved in the field of nuclear energy: Zircaloy-4. Firstly, zirconium electrodeposition was investigated in molten LiF-NaF at 750˚C in order to determine appropriate operating conditions to ensure Zr metal recovery: concentration and applied current density. Then, anodic behaviour of Zircaloy-4 was studied and compared to its composing elements. These results allowed us to define an adapted electrorefining strategy. Electrorefining progress, anodic and cathodic faradic efficiencies were evaluated by materials characterization obtained after galvanostatic electrolyses.
文摘The aim of this research was to develop an intrarradicular dental post based on epoxy resin/nano zirconium phosphate composite with potential appli-cation in prosthetic dentistry. Zirconium phosphate (ZrP) nanoparticle was synthesized by a reaction between phosphoric acid (H3PO4) and zirconium (IV) oxide chloride 8-hydrate (ZrOCl2·8H2O) and applied as filler. Commer-cial epoxy resin and hardener were used as polymer matrix. The composites were prepared at different proportions of epoxy resin/hardener, filler amount, reaction time and temperature. Infrared revealed that degree of conversion decreased with amount of ZrP. Insoluble matter was upper than 97%. Thermogravimetry indicated two steps of degradation. The best values of flexural modulus and flexural strength were achieved for the post desig-nated as 1:0.25:0.25. Laser scanning confocal microscopy suggested that the morphology of the posts fractured surface varied according to epoxy-resin:hardener ratio and the ZrP amount. From atomic force micros-copy, the topographic view exposed the shape and size of ZrP particles. Field emission scanning electron microscopy and energy dispersive spectroscopy indicated good adhesion between epoxy resin matrix-ZrP and that the pres-ence of phosphate rendered brittle the fracture surface.
基金Project(2007CB613705)supported by the National Basic Research Program of ChinaProject(50901082)supported by the NationalNatural Science Foundation of China
文摘The formation processes of a composite ceramic coating on AM50 magnesium alloy prepared by plasma electrolytic oxidation （PEO） in a K 2 ZrF 6 electrolyte solution were studied by scanning electron microscope （SEM） and energy dispersive X-ray spectroscope （EDX）. Electrochemical impedance spectroscopy （EIS） tests were used to study the variation of the corrosion resistance of the coating during the PEO treatment. The results show that the coating formed on Mg alloy is mainly composed of MgO and MgF 2 when the applied voltage is lower than the sparking voltage, and zirconium oxides start to be deposited on Mg substrate after the potential exceeding the sparking voltage. The corrosion resistance of the coating increases with increasing the applied voltage.
基金Project (51001072) supported by the National Natural Science Foundation of China
文摘The effects of zirconium addition on the microstructure and mechanical properties of Mg97Y2Zn1 alloy were investigated.The microstructure of as-cast Mg97Y2Zn1 alloy is refined by the addition of zirconium.During the extrusion,the initial nucleation sites of the alloy are mainly original grain boundaries and secondary phase.The addition of zirconium could stimulate the DRX process because more grain boundaries are formed,which increases the dynamic recrystallization rate.Both the strength and elongation of the alloy are increased by the addition of zirconium.
基金Project(51171213)supported by the National Natural Science Foundation of ChinaProject(NCET-08-0606)supported by New Century Excellent Talents in University,China
文摘Industry pure zirconium sheets with a strong c-axis fiber texture were rolled to different strains at 77 K to investigate the twinning behavior and deformation mechanism. The microstructure and texture of the rolled specimens were characterized by scanning electron microscopy （SEM） together with electron backscatter diffraction （EBSD） techniques. The results show that the {1022} （1123） compression twinning mode is the dominant deformation twin at low strains loaded along the c-axis, and the {1012} （ 10]- 1 ） tensile twinning generates as the second twin in {1022} （ 1123 ） twins. The selection of twinning modes is governed by Schmid factor （SF） due to the calculating of SF and the EBSD simulating of twinning distribution. The evolution of texture during rolling affected by twins with increase of the strain was explained.
基金This work was supported by the Chinese Academy of Sciences （Hundred Talents Fund）, the National Natural Science Foundation of China （No.20703048 and No.20803083）, and the Center of Molecular Science Foundation of Institute of Chemistry, Chinese Academy of Sciences （No.CMS-LX200902）.
文摘The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H- and Zr3O7H- are observed after the reaction. Den-sity functional theory calculations indicate that the hydrogen abstraction is favorable in the reaction of Zr2O5- with C2H6, which supports that the observed Zr2O5H- and Zr3O7H- are due to hydrogen atom abstraction from the alkane molecules. This work shows a newpossible pathway in the reaction of zirconium oxide cluster anions with alkane molecules.
基金Financial support from National Natural Science Foundation of China(nos 11205136 and 11505145)the Research Fund for Doctoral Program of Southwest University of Science and Technology(no.l4zx7166)
文摘In order to understand the dnve-in target in a D-D type neutron generator,it is essential to study the mechanism of the interaction between hydrogen ion beams and the hydrogenabsorbing metal film.The present research concerns the nucleation of hydride within zirconium film implanted with hydrogen ions.Doses of 30 keV hydrogen ions ranging from 4.30×10^（17） to1.43×10^（18） ions cm^（-2） were loaded into the zirconium film through the ion beam implantation technique.Features of the surface morphology and transformation of phase structures were investigated with scanning electron microscopy,atomic force microscopy and x-ray diffraction.Confirmation of the formation of 5 phase zirconium hydride in the implanted samples was first made by x-ray diffraction,and the different stages in the gradual nucleation and growth of zirconium hydride were then observed by atomic force microscope and scanning electron microscopy.
基金Project(51374254)supported by the National Natural Science Foundation of ChinaProject(2013JSJJ026)supported by the Teacher Research Foundation of Central South University,China
文摘Anodic dissolutionbehaviorof zirconium inBu^n 4NBr-contaningisopropanol solution was investigated using cyclic voltammetry, linear sweep voltammetry and chronoamperometry, complemented with a scanning electron microscope （SEM）.The voltammograms did not exhibit active dissolutionuntil the breakdown of passive layer induced by aggressive bromide anions.SEM images confirmed the existence of pits on zirconium surface.The depth and breadth of pits were intensified with increasing potential. The pitting potentialshifted negatively as either temperature orBu^n 4NBr concentration was increased, while it increased with increasing scan rate.The corrosion current density increased with increasing temperature. The apparent activation energyof anodic dissolutionofzirconiumwas 21.88kJ/mol. The chronoamperometry revealed that increasingBu^n 4NBrconcentration shortened the incubation time for passivity breakdown and accelerated the pit nucleation and growth. The experimental results were helpfulto obtain the optimum conditions for electrosynthesis of zirconium isopropoxide.
