Phase-field simulations of the effect of temperature and interface for zirconiumδ-hydrides

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.

Properties of radiation defects and threshold energy of displacement in zirconium hydride obtained by new deep-learning potential

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).

Two-dimensional investigation of characteristic parameters and their gradients for the self-generated electric and magnetic fields of laser-induced zirconium plasma

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.

Electrochemical Analysis of Zirconiumin Aqueous and Organic Media

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(IV) 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+ 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 (IV) 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 (IV) 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).

Formation process of composite plasma electrolytic oxidation coating containing zirconium oxides on AM50 magnesium alloy

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.

Effect of zirconium addition on microstructure and mechanical properties of Mg_(97)Y_2Zn_1 alloy

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.

Deformation twinning and textural evolution of pure zirconium during rolling at low temperature

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.

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

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.

Hydrogenation of zirconium film by implantation of hydrogen ions

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.

Anodic dissolution behavior of zirconium in Bu_4~nNBr-containing isopropanol solution

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.

Microstructural evolution of zirconium alloy under dynamic compression at strain rate of 1000s^(-1)

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.

Effects of Ag-carrying Zirconium Phosphate on the Kinetics of Growth of the Roots of Culture Artemisia annua

在植物组织和细胞培养过程中 ,尤其是在生物反应器培养中的染菌问题 ,一直是制约植物细胞培养工业化的难题。通过比较各种防腐剂的抑菌效果 ,确定银型磷酸锆盐抗菌粉为青蒿根培养的最佳防腐剂。银型磷酸锆盐抗菌粉在浓度为 30mg/L时 ,既能降低培养液的染菌几率 ,又不明显抑制青蒿根的生长及青蒿素的生物合成。在添加 30mg/L抗菌粉的培养液中进行的青蒿根生长、pH值变化以及残糖、铵离子和硝酸根离子消耗的动力学研究表明 ,在 4 0d内青蒿根在培养液中生长良好 ,营养成分的消耗和对照呈相似的趋势。

Preparation of Silica Gels with High Adsorption Activity for Extraction of Zirconium

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.

Surface finish effect on dry sliding wear behavior of thermally oxidized commercially pure zirconium

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.

Electrochemical behavior of zirconium in molten NaCl-KCl-K_2ZrF_6 system

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.

Effect of RF power on the properties of transparent conducting zirconium-doped zinc oxide films prepared by RF magnetron sputtering

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.

Preparation and Catalytic Application of Novel Water Tolerant Solid Acid Catalysts of Zirconium Sulfate/HZSM-5

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.

Equilibrium and kinetic data of adsorption and separation for zirconium and hafnium onto MIBK extraction resin

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.

Properties of hydrogen permeation barrier on the surface of zirconium hydride

A hydrogen permeation barrier was manufactured by the in situ reaction of zirconium hydride with oxygen. A reduction in the hydrogen permeation of the oxide films was detected by measuring the mass difference of the zirconium hydride samples after the dehydrogenation experiment. The reaction of zirconium hydride with oxygen occurs only under the condition that the temperature is higher than 673 K in the oxygen partial pressure of 0.1 MPa. The oxide film is composed of two layers, a permeable oxide layer and a dense oxide layer, and the main phase of the oxide film is ZrO2 with baddeleyite structure. The XPS analysis shows that O-H bonds exist in the oxide film, which are helpful for resisting hydrogen diffusion through the oxide film.

Preparation of Nano-sized Zirconium Carbide Powders through a Novel Active Dilution Self-propagating High Temperature Synthesis Method

High quality nano-sized zirconium carbide （ZrC） powders were successfully fabricated via a developed chemical active dilution self-propagating high-temperature synthesis （SHS） method assisted by ball milling pretreatment process using traditional cheap zirconium dioxide powder （ZrO2）, magnesium powder （Mg） and sucrose （C12H22Oll） as raw materials. FSEM, TEM, HRTEM, SAED, XRD, FTIR and Raman, ICP- AES, laser particle size analyzer, oxygen and nitrogen analyzer, carbon/sulfur determinator and TG-DSC were employed for the characterization of the morphology, structure, chemical composition and thermal stability of the as-synthesized ZrC samples. The as-synthesized samples demonstrated high purity, low oxygen content and evenly distributed ZrC nano-powders with an average particle size of 50nm. In addition, the effects of endothermic rate and the possible chemical reaction mechanism were also discussed.