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
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
Microstructural evolution of the zirconium alloy deformed at a strain rate of about 1000 s-1 was investigated. Four different strain levels of the zirconium alloy subjected to dynamic compression were designed by seve...Microstructural evolution of the zirconium alloy deformed at a strain rate of about 1000 s-1 was investigated. Four different strain levels of the zirconium alloy subjected to dynamic compression were designed by several-times impacting at almost the same strain rate. The results show that abundant low angle boundaries at different strain levels were observed in the deformed microstructures, and the quantity and density of low angle boundary increase dramatically with the strain increasing. Besides low angle boundaries and high angle boundaries observed in grain boundary maps, the twin boundaries including the tensile twins {10 2}, {11 1} and compressive twins {11 2} were distinguished at different strain levels, and most twin boundaries were indexed as {10 2} twins. With the stain increasing, the twin boundary density in the deformed microstructures increases indistinctively. Based on the characterization of the deformed microstructures at the different strain levels, the deformation and evolution processes of the zirconium alloy subjected to dynamic loading were proposed. Microhardness measurements show that the microhardness in the impacted specimens increases gradually with the strain increasing, which should be associated with the strain hardening caused by the tangled dislocation.展开更多
Silica gels with a high specific surface area and high adsorption activity ,which have high selectivity and high adsorption capacity for zirconium in acidic high level radioactive liquid waste (HLLW), have been prepar...Silica gels with a high specific surface area and high adsorption activity ,which have high selectivity and high adsorption capacity for zirconium in acidic high level radioactive liquid waste (HLLW), have been prepared from water-glass and hydrochloric acid through adding surfactants. The surfactant modifies the surface of the primary sol particles, thus suppresses the growth of the primary particle,but accelerates their agglomeration. The action of the surfactant is similar to that of the organic structure-directing agent and makes the sol cluster cross-linkage ring-like network in short order. The specific surface area of the silica gel is 998 m 2/g; the static adsorption capacity and the adsorption distribution coefficient for zirconium in HLLW are 32.6 mg/g and 56.1 mL/g, respectively.展开更多
The effect of surface polishing on the wear behavior of thermally oxidized commercial pure zirconium (CP-Zr) under dry sliding conditions was investigated. Surface ground CP-Zr with a roughness of 0.21 μm (Ra) was th...The effect of surface polishing on the wear behavior of thermally oxidized commercial pure zirconium (CP-Zr) under dry sliding conditions was investigated. Surface ground CP-Zr with a roughness of 0.21 μm (Ra) was thermally oxidized (TO) at 650 °C for 6 h. After TO, some samples were polished to smoothen the surface with a finish of 0.04 μm (Ra). The response of the polished and unpolished TO samples to dry sliding wear was investigated under unidirectional sliding conditions. The results show that surface polishing after TO affects the dry sliding wear behavior of TO CP-Zr in several aspects, including coefficient of friction, wear rate, crack formation and oxide layer breakdown. In particular, it is found that smoothening the TO surface favors the formation of semi-circular cracks in the wear track and accelerates oxide layer breakdown during dry sliding. A slightly rough TO surface helps to reduce the tendency of the oxide layer towards cracking and to increase the wear resistance at high contact loads. The mechanisms involved are discussed in terms of asperity contacts, crack formation, propagation and final fracture.展开更多
The electrochemical reduction of Zr^4＋（complex） ions in NaCl-KCl-K2ZrF6 molten salt on Pt electrode was investigated using cyclic voltammetry and square wave voltammetry at 1023 K.Two cathodic reduction peaks relat...The electrochemical reduction of Zr^4＋（complex） ions in NaCl-KCl-K2ZrF6 molten salt on Pt electrode was investigated using cyclic voltammetry and square wave voltammetry at 1023 K.Two cathodic reduction peaks related to Zr^4＋/Zr^2＋ and Zr^2＋/Zr steps were observed in the cyclic voltammograms.The result was also confirmed by square wave voltammetry.The diffusion coefficient of Zr^4＋（complex） ions at 1023 K in NaCl-KCl-K2ZrF6 melt,measured by cyclic voltammetry,is about 4.22×10^-6 cm^2/s.The characterization of the deposits obtained by potentiostatic electrolysis at different potentials was investigated by XRD,and the results were well consistent with the electrochemical reduction mechanism of Zr^4＋（complex） ions.展开更多
In order to optimize the microstructure and composition of N18 zirconium alloy （Zr-1Sn-0.35Nb-0.35Fe-0.1Cr, in mass fraction, %）, which was developed in China in 1990s, the effect of microstructure and composition v...In order to optimize the microstructure and composition of N18 zirconium alloy （Zr-1Sn-0.35Nb-0.35Fe-0.1Cr, in mass fraction, %）, which was developed in China in 1990s, the effect of microstructure and composition variation on the corrosion resistance of the N18 alloy has been investigated. The autoclave corrosion tests were carried out in super heated steam at 400 ~C/10.3 MPa, in deionized water or lithiated water with 0.01 mol/L LiOH at 360 ~C/18.6 MPa. The exposure time lasted for 300-550 days according to the test temperature. The results show that the microstructure with a fine and uniform distribution of second phase particles （SPPs）, and the decrease of Sn content from 1% （in mass fraction, the same as follows） to 0.8% are of benefit to improving the corrosion resistance; It is detrimental to the corrosion resistance if no Cr addition. The addition of Nb content with upper limit （0.35%） is beneficial to improving the corrosion resistance. The addition of Cu less than 0.1% shows no remarkable influence upon the corrosion resistance for N18 alloy. Comparing the corrosion resistance of the optimized N18 with other commercial zirconium alloys, such as Zircaloy-4, ZIRLO, E635 and Ell0, the former shows superior corrosion resistance in all autoclave testing conditions mentioned above. Although the data of the corrosion resistance as fuel cladding for high burn-up has not been obtained yet, it is believed that the optimized N18 alloy is promising for the candidate of fuel cladding materials as high burn-up fuel assemblies. Based on the theory that the microstructural evolution of oxide layer during corrosion process will affect the corrosion resistance of zirconium alloys, the improvement of corrosion resistance of the N18 alloy by obtaining the microstructure with nano-size and uniform distribution of SPPs, and by decreasing the content of Sn and maintaining the content of Cr is discussed.展开更多
Zirconium-based materials are efficient adsorbent for aqueous phosphate removal.However,current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity.Here,we demonstrate a...Zirconium-based materials are efficient adsorbent for aqueous phosphate removal.However,current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity.Here,we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose(QC-Zr) for the selective phosphate removal.Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional(3D) cross-linked cellulose chains.The maximum P adsorption capacity of QC-Zr was 83.6 mg P/g.Furthermore,the QC-Zr shows high P adsorption performance in a wide pH range,generally due to the electrostatic effects of quaternized cellulose.The enhanced adsorption of P was also achieved in the presence of competing anions(including Cl^-,NO3^-,SO4^2-,SO4^4-) and humic acid(HA) even at a molar ratio up to 20 levels.The column adsorption capacity of QC-Zr reached 4000 bed volumes(BV) at EBCT=0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L.Mechanism study revealed that both-N^+(CH3)3 groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between -N^+(CH3)3 and phosphate,and the formation of zirconium hydrogen phosphate(Zr(HPO4)x).The 31 P nuclear magnetic resonance(NMR) study implied that P surface-precipitated and inner-sphere complexed with zirconium hydroxide at a ratio of 3:1.展开更多
Transparent and conducting zirconium-doped zinc oxide films with high transparency and relatively low resistivity have been successfully prepared by radio frequency （RF） msgnetron sputtering at room temperature, The...Transparent and conducting zirconium-doped zinc oxide films with high transparency and relatively low resistivity have been successfully prepared by radio frequency （RF） msgnetron sputtering at room temperature, The RF power is varied from 75 to 150 W. At first the crystallinity and conductivity of the film are improved and then both of them show deterioration with the increase of the RF power, The lowest resistivity achieved is 2.07 × 10^-3Ωcm at an RF power of 100W with a Hall mobility of 16cm^2V^-1s^-1 and a carrier concentration of 1.95 × 10^20 cm^-3. The films obtained are polycryetalline with a hexagonal structure and a preferred orientation along the c-axis, All the films have a high transmittance of approximately 92% in the visible range. The optical band gap is about 3.33 eV for the films deposited at different RF powers.展开更多
To understand the effect of precipitation pH and coexisting Mg^(2+) on phosphate adsorption onto zirconium oxide(ZrO_2), ZrO_2 particles precipitated at pH 5.3, 7.1 and 10.5, i.e., ZrO_2(5.3), ZrO_2(7.1)and ZrO_2(10.5...To understand the effect of precipitation pH and coexisting Mg^(2+) on phosphate adsorption onto zirconium oxide(ZrO_2), ZrO_2 particles precipitated at pH 5.3, 7.1 and 10.5, i.e., ZrO_2(5.3), ZrO_2(7.1)and ZrO_2(10.5), respectively were prepared and characterized, then their adsorption performance and mechanism in the absence and presence of Mg^(2+) were comparatively investigated in this study. The results showed that the Elovich, pseudo-second-order and Langmuir isotherm models correlated with the experimental data well. The adsorption mechanism involved the complexation between phosphate and zirconium. Coexisting Mg^(2+) slightly inhibited the adsorption of phosphate on ZrO_2(5.3), including the adsorption capacity and rate, but coexisting Mg^(2+) greatly increased the adsorption capacity and rate for ZrO_2(7.1)and ZrO_2(10.5). The enhanced adsorption of phosphate on ZrO_2(7.1) and ZrO_2(10.5) in the presence of Mg^(2+) was mainly due to the formation of Mg^(2+)-HPO_4^(2-) ion pair(MgHPO_4~0) in the solution and then the adsorption of MgHPO_4~0 on the adsorbent surface, forming the phosphatebridged ternary complex Zr(OPO_3H)Mg. In the absence of Mg^(2+) , the maximum phosphate adsorption capacity at pH 7 calculated from the Langmuir isotherm model decreased in the order of ZrO 2(7.1)(67.3 mg/g) > ZrO_2(5.3)(53.6 mg/g) ≈ ZrO_2(10.5)(53.1 mg/g), but it followed the order of Zr O2(7.1)(97.0 mg/g) > ZrO_2(10.5)(79.7 mg/g) > ZrO_2(5.3)(51.3 mg/g) in the presence of Mg^(2+) . The results of this work suggest that ZrO_2(7.1) is more suitable for use as an adsorbent for the effective removal of phosphate from municipal wastewater than ZrO_2(5.3) and ZrO_2(10.5),because Mg^(2+) is generally present in this wastewater.展开更多
Esterification of acrylic acid（AA） to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorptio...Esterification of acrylic acid（AA） to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate（ZS） loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20% （mass fraction） ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions.展开更多
The equilibrium and kinetics of methyl isobutyl ketone(MIBK) extraction resin for adsorption and separation of zirconium and hafnium were studied under the different conditions of acidity,initial total concentrations ...The equilibrium and kinetics of methyl isobutyl ketone(MIBK) extraction resin for adsorption and separation of zirconium and hafnium were studied under the different conditions of acidity,initial total concentrations of zirconium and hafnium and temperature.The equilibrium data of both zirconium and hafnium are found to follow the Freundlich adsorption isotherm,and the Freundlich isotherm constants(KF) are 3.53 and 0.64 mg/g,respectively.The equilibrium data of zirconium also fit the Langmuir adsorption isotherm,and the saturation adsorption capacity(Qmax) and the Langmuir isotherm constant(KL)are 75.93 mg/g and-0.012 7 L/g,respectively.The obtained kinetic data of both zirconium and hafnium are found to fit the HO pseudo-second-order kinetic model,and the rate constants of pseudo-second-order equation(k2) are-0.019 and 0.41 g/(mg·min),respectively.Column tests show that the MIBK extraction resin could be used as efficient adsorbent material for separating hafnium from zirconium.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.
基金Project(50890172)supported by the National Natural Science Foundation of ChinaProject(NCET-08-0606)supported by New Century Excellent Talents in University,China
文摘Microstructural evolution of the zirconium alloy deformed at a strain rate of about 1000 s-1 was investigated. Four different strain levels of the zirconium alloy subjected to dynamic compression were designed by several-times impacting at almost the same strain rate. The results show that abundant low angle boundaries at different strain levels were observed in the deformed microstructures, and the quantity and density of low angle boundary increase dramatically with the strain increasing. Besides low angle boundaries and high angle boundaries observed in grain boundary maps, the twin boundaries including the tensile twins {10 2}, {11 1} and compressive twins {11 2} were distinguished at different strain levels, and most twin boundaries were indexed as {10 2} twins. With the stain increasing, the twin boundary density in the deformed microstructures increases indistinctively. Based on the characterization of the deformed microstructures at the different strain levels, the deformation and evolution processes of the zirconium alloy subjected to dynamic loading were proposed. Microhardness measurements show that the microhardness in the impacted specimens increases gradually with the strain increasing, which should be associated with the strain hardening caused by the tangled dislocation.
文摘Silica gels with a high specific surface area and high adsorption activity ,which have high selectivity and high adsorption capacity for zirconium in acidic high level radioactive liquid waste (HLLW), have been prepared from water-glass and hydrochloric acid through adding surfactants. The surfactant modifies the surface of the primary sol particles, thus suppresses the growth of the primary particle,but accelerates their agglomeration. The action of the surfactant is similar to that of the organic structure-directing agent and makes the sol cluster cross-linkage ring-like network in short order. The specific surface area of the silica gel is 998 m 2/g; the static adsorption capacity and the adsorption distribution coefficient for zirconium in HLLW are 32.6 mg/g and 56.1 mL/g, respectively.
文摘The effect of surface polishing on the wear behavior of thermally oxidized commercial pure zirconium (CP-Zr) under dry sliding conditions was investigated. Surface ground CP-Zr with a roughness of 0.21 μm (Ra) was thermally oxidized (TO) at 650 °C for 6 h. After TO, some samples were polished to smoothen the surface with a finish of 0.04 μm (Ra). The response of the polished and unpolished TO samples to dry sliding wear was investigated under unidirectional sliding conditions. The results show that surface polishing after TO affects the dry sliding wear behavior of TO CP-Zr in several aspects, including coefficient of friction, wear rate, crack formation and oxide layer breakdown. In particular, it is found that smoothening the TO surface favors the formation of semi-circular cracks in the wear track and accelerates oxide layer breakdown during dry sliding. A slightly rough TO surface helps to reduce the tendency of the oxide layer towards cracking and to increase the wear resistance at high contact loads. The mechanisms involved are discussed in terms of asperity contacts, crack formation, propagation and final fracture.
文摘The electrochemical reduction of Zr^4＋（complex） ions in NaCl-KCl-K2ZrF6 molten salt on Pt electrode was investigated using cyclic voltammetry and square wave voltammetry at 1023 K.Two cathodic reduction peaks related to Zr^4＋/Zr^2＋ and Zr^2＋/Zr steps were observed in the cyclic voltammograms.The result was also confirmed by square wave voltammetry.The diffusion coefficient of Zr^4＋（complex） ions at 1023 K in NaCl-KCl-K2ZrF6 melt,measured by cyclic voltammetry,is about 4.22×10^-6 cm^2/s.The characterization of the deposits obtained by potentiostatic electrolysis at different potentials was investigated by XRD,and the results were well consistent with the electrochemical reduction mechanism of Zr^4＋（complex） ions.
基金supported by the National Natural Science Foundation of China (Nos.50871064 and 50971084)Shanghai Leading Academic Discipline Project (No.S30107)
文摘In order to optimize the microstructure and composition of N18 zirconium alloy （Zr-1Sn-0.35Nb-0.35Fe-0.1Cr, in mass fraction, %）, which was developed in China in 1990s, the effect of microstructure and composition variation on the corrosion resistance of the N18 alloy has been investigated. The autoclave corrosion tests were carried out in super heated steam at 400 ~C/10.3 MPa, in deionized water or lithiated water with 0.01 mol/L LiOH at 360 ~C/18.6 MPa. The exposure time lasted for 300-550 days according to the test temperature. The results show that the microstructure with a fine and uniform distribution of second phase particles （SPPs）, and the decrease of Sn content from 1% （in mass fraction, the same as follows） to 0.8% are of benefit to improving the corrosion resistance; It is detrimental to the corrosion resistance if no Cr addition. The addition of Nb content with upper limit （0.35%） is beneficial to improving the corrosion resistance. The addition of Cu less than 0.1% shows no remarkable influence upon the corrosion resistance for N18 alloy. Comparing the corrosion resistance of the optimized N18 with other commercial zirconium alloys, such as Zircaloy-4, ZIRLO, E635 and Ell0, the former shows superior corrosion resistance in all autoclave testing conditions mentioned above. Although the data of the corrosion resistance as fuel cladding for high burn-up has not been obtained yet, it is believed that the optimized N18 alloy is promising for the candidate of fuel cladding materials as high burn-up fuel assemblies. Based on the theory that the microstructural evolution of oxide layer during corrosion process will affect the corrosion resistance of zirconium alloys, the improvement of corrosion resistance of the N18 alloy by obtaining the microstructure with nano-size and uniform distribution of SPPs, and by decreasing the content of Sn and maintaining the content of Cr is discussed.
基金supported by the National Natural Science Foundation of China (Nos.51738013 and 51438011)the National Science and Technology Major Project of China (No. 2017ZX07202003)the Chinese Postdoctoral Science Foundation (No.043211001).
文摘Zirconium-based materials are efficient adsorbent for aqueous phosphate removal.However,current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity.Here,we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose(QC-Zr) for the selective phosphate removal.Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional(3D) cross-linked cellulose chains.The maximum P adsorption capacity of QC-Zr was 83.6 mg P/g.Furthermore,the QC-Zr shows high P adsorption performance in a wide pH range,generally due to the electrostatic effects of quaternized cellulose.The enhanced adsorption of P was also achieved in the presence of competing anions(including Cl^-,NO3^-,SO4^2-,SO4^4-) and humic acid(HA) even at a molar ratio up to 20 levels.The column adsorption capacity of QC-Zr reached 4000 bed volumes(BV) at EBCT=0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L.Mechanism study revealed that both-N^+(CH3)3 groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between -N^+(CH3)3 and phosphate,and the formation of zirconium hydrogen phosphate(Zr(HPO4)x).The 31 P nuclear magnetic resonance(NMR) study implied that P surface-precipitated and inner-sphere complexed with zirconium hydroxide at a ratio of 3:1.
基金Project supported by the National Key Basic Research and Development Programme of China （Grant No 2001CB610504） and the National Natural Science Foundation of China （Grant Nos 60576039 and 10374060）.Acknowledgments We thank Dr Wang Zhuo and Dr Yang ChangHong for their assistance in the experiment.
文摘Transparent and conducting zirconium-doped zinc oxide films with high transparency and relatively low resistivity have been successfully prepared by radio frequency （RF） msgnetron sputtering at room temperature, The RF power is varied from 75 to 150 W. At first the crystallinity and conductivity of the film are improved and then both of them show deterioration with the increase of the RF power, The lowest resistivity achieved is 2.07 × 10^-3Ωcm at an RF power of 100W with a Hall mobility of 16cm^2V^-1s^-1 and a carrier concentration of 1.95 × 10^20 cm^-3. The films obtained are polycryetalline with a hexagonal structure and a preferred orientation along the c-axis, All the films have a high transmittance of approximately 92% in the visible range. The optical band gap is about 3.33 eV for the films deposited at different RF powers.
基金supported by the Shanghai Natural Science Foundation (No.15ZR1420700)the National Science Foundation of China (Nos.51408354 and 50908142)the Scientific Research Project of Shanghai Science and Technology Committee (No.10230502900)
文摘To understand the effect of precipitation pH and coexisting Mg^(2+) on phosphate adsorption onto zirconium oxide(ZrO_2), ZrO_2 particles precipitated at pH 5.3, 7.1 and 10.5, i.e., ZrO_2(5.3), ZrO_2(7.1)and ZrO_2(10.5), respectively were prepared and characterized, then their adsorption performance and mechanism in the absence and presence of Mg^(2+) were comparatively investigated in this study. The results showed that the Elovich, pseudo-second-order and Langmuir isotherm models correlated with the experimental data well. The adsorption mechanism involved the complexation between phosphate and zirconium. Coexisting Mg^(2+) slightly inhibited the adsorption of phosphate on ZrO_2(5.3), including the adsorption capacity and rate, but coexisting Mg^(2+) greatly increased the adsorption capacity and rate for ZrO_2(7.1)and ZrO_2(10.5). The enhanced adsorption of phosphate on ZrO_2(7.1) and ZrO_2(10.5) in the presence of Mg^(2+) was mainly due to the formation of Mg^(2+)-HPO_4^(2-) ion pair(MgHPO_4~0) in the solution and then the adsorption of MgHPO_4~0 on the adsorbent surface, forming the phosphatebridged ternary complex Zr(OPO_3H)Mg. In the absence of Mg^(2+) , the maximum phosphate adsorption capacity at pH 7 calculated from the Langmuir isotherm model decreased in the order of ZrO 2(7.1)(67.3 mg/g) > ZrO_2(5.3)(53.6 mg/g) ≈ ZrO_2(10.5)(53.1 mg/g), but it followed the order of Zr O2(7.1)(97.0 mg/g) > ZrO_2(10.5)(79.7 mg/g) > ZrO_2(5.3)(51.3 mg/g) in the presence of Mg^(2+) . The results of this work suggest that ZrO_2(7.1) is more suitable for use as an adsorbent for the effective removal of phosphate from municipal wastewater than ZrO_2(5.3) and ZrO_2(10.5),because Mg^(2+) is generally present in this wastewater.
基金Supported by the Research Fund for the Doctoral Program of Higher Education(No20050010014)the China Petroleum &Chemical Corporation ( No X503015 )the Key Discipline Construction Foundation of Beijing Education Committee ( NoXK100100643)
文摘Esterification of acrylic acid（AA） to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate（ZS） loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20% （mass fraction） ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions.
文摘The equilibrium and kinetics of methyl isobutyl ketone(MIBK) extraction resin for adsorption and separation of zirconium and hafnium were studied under the different conditions of acidity,initial total concentrations of zirconium and hafnium and temperature.The equilibrium data of both zirconium and hafnium are found to follow the Freundlich adsorption isotherm,and the Freundlich isotherm constants(KF) are 3.53 and 0.64 mg/g,respectively.The equilibrium data of zirconium also fit the Langmuir adsorption isotherm,and the saturation adsorption capacity(Qmax) and the Langmuir isotherm constant(KL)are 75.93 mg/g and-0.012 7 L/g,respectively.The obtained kinetic data of both zirconium and hafnium are found to fit the HO pseudo-second-order kinetic model,and the rate constants of pseudo-second-order equation(k2) are-0.019 and 0.41 g/(mg·min),respectively.Column tests show that the MIBK extraction resin could be used as efficient adsorbent material for separating hafnium from zirconium.
