Temperature dependence of migration features of self-interstitials in zirconium

Molecular dynamics simulations are conducted to study self-interstitial migration in zirconium. By defining crystal lattice points where more than one atom is present in corresponding Wigner-Seitz cells, as the locations of self-interstitial atoms （LSIAs）, three types of events are identified as LSIA migrations：the jump remaining in one 〈1120〉 direction （ILJ）, the jump from one 〈1120〉 to another 〈1120〉 direction in the same basal plane （OLJ）, and the jump from one basal plane to an adjacent basal plane （OPJ）. The occurrence frequencies of the three types are calculated. ILJ is found to be a dominant event in a temperature range from 300 K to 1200 K, but the occurrence frequencies of OLJ and OPJ increase with temperature increasing. The total occurrence frequency of all jump types has a good linear dependence on temperature. Moreover, the migration trajectories of LSIAs in the hcp basal-plane is not what is observed if only conventional one-or two-dimensional migrations exists; rather, they exhibit the feature that we call fraction-dimensional. Using Monte Carlo simulations, the potential kinetic effects of fraction-dimensional migration, which is measured by the average number of lattice sites visited per jump event （denoted by nSPE）, are analysed. The significant differences between the nSPE value of the fraction-dimensional migration and those of conventional one-and two-dimensional migrations suggest that the conventional diffusion coefficient cannot give an accurate description of the underlying kinetics of SIAs in Zr. This conclusion could be generally meaningful for the cases where the low-dimensional migration of defects are observed.

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).

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.

Stability of concentration-related self-interstitial atoms in fusion material tungsten

Based on the density functional theory, we calculated the structures of the two main possible self-interstitial atoms（SIAs） as well as the migration energy of tungsten（W） atoms. It was found that the difference of the 110 and 111 formation energies is 0.05–0.3 e V. Further analysis indicated that the stability of SIAs is closely related to the concentration of the defect. When the concentration of the point defect is high, 110 SIAs are more likely to exist, 111 SIAs are the opposite. In addition, the vacancy migration probability and self-recovery zones for these SIAs were researched by making a detailed comparison. The calculation provided a new viewpoint about the stability of point defects for selfinterstitial configurations and would benefit the understanding of the control mechanism of defect behavior for this novel fusion material.

Size effect of He clusters on the interactions with self-interstitial tungsten atoms at different temperatures

The behaviors of helium clusters and self-interstitial tungsten atoms at different temperatures are investigated with the molecular dynamics method. The self-interstitial tungsten atoms prefer to form crowdions which can tightly bind the helium cluster at low temperature. The crowdion can change its position around the helium cluster by rotating and slipping at medium temperatures, which leads to formation of combined crowdions or dislocation loop locating at one side of a helium cluster. The combined crowdions or dislocation loop even separates from the helium cluster at high temperature. It is found that a big helium cluster is more stable and its interaction with crowdions or dislocation loop is stronger.

One-step ethylene separation from ternary C_(2) hydrocarbon mixture with a robust zirconium metal-organic framework

One-step separation of high-purity ethylene(C_(2)H_(4))from C_(2) hydrocarbon mixture is critical but challenging because of the very similar molecular sizes and physical properties of C_(2)H_(4),ethane(C_(2)H_(6)),and acetylene(C_(2)H_(2)).Herein,we report a robust zirconium metal-organic framework(MOF)Zr-TCA(H3TCA=4,4',4"-tricarboxytriphenylamine)with suitable pore size(0.6 nm×0.7 nm)and pore environment for direct C_(2)H_(4) purification from C_(2)H_(4)/C_(2)H_(2)/C_(2)H_(6) gas-mixture.Computational studies indicate that the abundant oxygen atoms and non-polar phenyl rings created favorable pore environments for the preferential binding of C_(2)H_(2) and C_(2)H_(6) over C_(2)H_(4).As a result,Zr-TCA exhibits not only high C_(2)H_(6)(2.28 mmol·g^(-1))and C_(2)H_(2)(2.78 mmol·g^(-1))adsorption capacity but also excellent C_(2)H_(6)/C_(2)H_(4)(2.72)and C_(2)H_(2)/C_(2)H_(4)(5.64)selectivity,surpassing most of one-step C_(2)H_(4) purification MOF materials.Dynamic breakthrough experiments confirm that Zr-TCA can produce high-purity C_(2)H_(4)(>99.9%)from a ternary gas mixture(1/9/90 C_(2)H_(2)/C_(2)H_(6)/C_(2)H_(4))in a single step with a high C_(2)H_(4) productivity of 5.61 L·kg^(-1).

Intercalation assisted liquid phase production of disulfide zirconium nanosheets for efficient electrocatalytic dinitrogen reduction to ammonia

Disulfide zirconium(ZrS_(2)) is a two-dimensional(2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties.However,mass production of high quality of ZrS_(2)nanosheets to realize their practical application remains a challenge.Here,we have successfully exfoliated the bulk ZrS_(2)powder with the thickness of micron into single and few-layer nanosheets through liquid-phase exfoliation in N-methylpyrrolidone(NMP) assisted via aliphatic amines as intercalators.It is found that the exfoliation yield is as high as 27.3%,which is the record value for the exfoliation of ZrS_(2)nanosheets from bulk ZrS_(2)powder,and 77.1% of ZrS_(2)nanosheets are 2-3 layers.The molecular geometric size and aliphatic amine basicity have important impact on the exfoliation.Furthermore,the ZrS_(2)nanosheets have been used as catalyst in the electrocatalytic dinitrogen reduction with the NH3yield of 57.75 μg h^(-1)mg_(cat.)^(-1),which is twice that by ZrS_(2)nanofibers reported in literature and three times that by the bulk ZrS_(2)powder.Therefore,the liquid phase exfoliation strategy reported here has great potential in mass production of ZrS_(2)nanosheets for high activity electrocatalysis.

Biomimetic amelioration of zirconium nanoparticles on a rigid substrate over viscous slime--a physiological approach

In this article,an investigation is conducted to study the precise role of zirconium nanoparticles that exist in a slime-like fluid subject to specific adjustments.Since gliding is a technique of mobility used by bacteria that lack motility components,bacteria travel on their own strength in gliding locomotion by secreting a layer of slime on the substrate.A model of an undulating sheet over a layer of slime of a Rabinowitsch fluid is investigated as a potential model of bacteria’s gliding motility.With the aid of long wavelength approximation,the equations governing the circulation of slime underneath the cells are established and analytically solved.The effects of pseudoplasticity,dilatation and non-Newtonian parameter on the behavior of zirconium concentration,speed of microorganism(bacteria),streamline patterns,and pressure rise for non-Newtonian and Newtonian fluids are compared.The power required for propulsion is also investigated.Physical interpretation for the pertinent variables has been graphically discussed against the parameters under consideration.It is found that with the increase in the concentration of zirconium nanoparticles,the bacterial flow is accelerated and attains its maximum near the rigid substrate wall while an opposite behavior is noticed in the rest region.

Relations of Microstructural Attributes and Strength-Ductility of Zirconium Alloys with Hydrides

As the first safety barrier of nuclear reactors,zirconium alloy cladding tubes have attracted extensive attention because of its good mechanical properties.The strength and ductility of zirconium alloy are of great significance to the service process of cladding tubes,while brittle hydrides precipitate and thus deteriorate the overall performance.Based on the cohesive finite element method,the effects of cohesive strength,interfacial characteristics,and hydrides geometric characteristics on the strength and ductility of two-phase material(zirconium alloy with hydrides)are numerically simulated.The results show that the fracture behavior is significantly affected by the cohesive strength and that the overall strength and ductility are sensitive to the cohesive strength of the zirconium alloy.Furthermore,the interface is revealed to have prominent effects on the overall fracture behavior.When the cohesive strength and fracture energy of the interface are higher than those of the hydride phase,fracture initiates in the hydrides,which is consistent with the experimental phenomena.In addition,it is found that the number density and arrangement of hydrides play important roles in the overall strength and ductility.Our simulation provides theoretical support for the performance analysis of hydrogenated zirconium alloys during nuclear reactor operation.

Functional zirconium phosphate nanosheets enabled transfer hydrogenolysis of aromatic ether bonds over a low usage of Ru nanocatalysts

Catalytic hydrogenolysis of aromatic ether bonds is a highly promising strategy for upgrading lignin into small-molecule chemicals,which relies on developing innovative heterogeneous catalysts with high activity.Herein,we designed porous zirconium phosphate nanosheet-supported Ru nanocatalysts(Ru/ZrPsheet)as the heterogeneous catalyst by a process combining ball milling and molten-salt(KNO_(3)).Very interestingly,the fabricated Ru/ZrPsheetshowed good catalytic performance on the transfer hydrogenolysis of various types of aromatic ether bonds contained in lignin,i.e.,4-O-5,a-O-4,β-O-4,and aryl-O-CH3,over a low Ru usage(<0.5 mol%)without using any acidic/basic additive.Detailed investigations indicated that the properties of Ru and the support were indispensable.The excellent activity of Ru/ZZrPsheetoriginated from the strong acidity and basicity of ZrPsheetand the higher electron density of metallic Ru0as well as the nanosheet structure of ZrPsheet.

Incorporation of Nano-Zinc Oxide in Lamellar Zirconium Phosphate: Synthesis and Characterization

In order to provide ultraviolet barrier, antifungal and antibacterial properties, nano-zinc oxide (ZnO) was added to lamellar zirconium phosphate (ZrP). The phosphate was synthesized via reaction of zirconium oxychloride octahydrate and phosphoric acid following its chemical modification with Jeffamine and nano-ZnO. Diffractometric, morphological, thermal, structural and relaxometric evaluations were conducted. Fourier transform infrared spectroscopy (FTIR) revealed increase of the area between 4000 - 3000 cm-1 due to the formation of ionic specie PO? +NH3-[C-(H)(CH3)-CH2-O-(C-(H)(CH3)-CH2-O)8-(CH2-CH2-O-CH3)] and nano-ZnO particles. Wide-angle X-ray diffraction indicated that intercalation of Jeffamine was successful. Thermogravimetry confirmed that nano-ZnO particle forced the expulsion of Jeffamine outside ZrP galleries. Scanning electron microscopy evidenced the Jeffamine intercalation and sample heterogeneity. Hydrogen molecular relaxation indicated the increase of molecular rigidity owing to the formation of ionic specie and the addition of nano-ZnO particles. It was postulated that a multifunctional and miscellaneous material constituted by as prepared ZrP, some delaminated ZrP platelets and nano-ZnO particles was achieved. The material has potential for usage as filler in polymeric composites.

氢含量对锆合金蠕变-疲劳行为的影响及机理研究

针对反应堆用锆合金渗氢后易发生蠕变-疲劳失效问题,采用频率修正应变寿命法和频率修正滞回能法研究了再结晶状态的锆合金在320oC、不同渗氢含量下的蠕变-疲劳行为。结果表明:随保持时间增加,无渗氢试样的抗蠕变-疲劳性能降低,但保持时间30 s以上时无明显影响;保持时间对渗氢试样的抗蠕变-疲劳性能无影响。不同保持时间下,未渗氢试样的抗蠕变-疲劳性能最好,0.04%氢含量试样的性能最差,0.005%氢含量在高应变水平(高滞回能)下的抗蠕变-疲劳性能弱于0.02%氢含量试样,而在低应变水平区域优于0.02%氢含量试样。氢含量的影响机理为:固溶氢可提高蠕变-疲劳寿命,氢化物可降低蠕变-疲劳寿命;0.04%氢含量试样中氢化物起主导作用,导致其蠕变-疲劳性能最差。

核用锆合金管氧化过程中光谱发射率特性研究

发射率在锆合金管非接触测温的准确性和失水事故情况下的传热分析上具有重要意义。本文采集了SZA4、SZA6和ZIRLO 3种锆合金在400,500,600℃下氧化100min过程中4~12μm内的光谱发射率数据,分析了温度、氧化膜厚度和合金组分对材料光谱发射率特性的影响规律。结果表明,3种锆合金在氧化过程中发射率变化趋势基本相同,但组分差异导致在发射率的数值和振荡特性上略有差别。通过建立薄膜干涉模型,解释了光谱发射率在波长方向上的振荡现象,并结合振荡极值与干涉效应原理计算了合金表面氧化膜厚度,在0.6~8μm范围内测量精度达到±0.3μm。

内压法锆合金薄壁管弹性模量试验研究

薄壁管内压加载下的弹性模量测量具有较大难度,通常采用拉伸法测得的弹性模量来近似代替。该研究基于弹性力学理论,推导薄壁管受内压时的应力和应变公式,进而建立薄壁管受内压时的弹性模量分析模型。完成某型锆合金薄壁管在20~400℃下的内压试验和拉伸试验,对比分析两种方法得到的弹性模量差异。研究结果表明,该锆合金薄壁管20~400℃的弹性模量在67~96 GPa之间,且弹性模量随温度的增加而减小;基于内压法和拉伸法得到的锆合金薄壁管弹性模量趋势一致,且该变化趋势符合指数函数规律。两种方法所得锆合金薄壁管的弹性模量存在3%的差异,该差异在核电等精密领域不可忽视。因此,该研究建立的基于内压法的弹性模量试验方法具有良好的可行性,可更准确地描述薄壁管在内压状态下的力学性能。

喷雾热解法加热壁温对铈锆固溶体生产过程的影响

【目的】为了探究喷雾热解过程中加热壁温对铈锆固溶体生产过程的影响,分析热解炉内的流量场和浓度场的变化情况,实现对热解炉的设计优化。【方法】采用数值模拟的方法,建立喷雾热解炉的物理模型,分别探讨加热壁温对铈锆固溶体在热解炉的不同阶段及热解炉中水蒸气分布和HCl分布的影响。【结果】当热解温度为850℃时,液滴的反应主要分2个阶段,在炉膛高度为0~0.05 m处,为加热蒸发阶段,在炉膛高度为0.05~0.6 m处,为稳态热解阶段。当炉壁温度为550~650℃时,在炉膛高度为0.9 m处温度变化放缓,喷雾处于稳定热解阶段;而壁温在750~850℃时,在炉膛高度为0.6 m处温度变化放缓;当壁温为850℃时,在炉膛高度为0.1~0.6 m处的温度曲线斜率最大,液滴达到稳定蒸发阶段的时间缩短,水分蒸发变快,热解时间变短。【结论】炉壁加热区的温度越高,HCl生成的速度越快,速度的最大值越小,在炉膛高度为0.4 m处速度变化最大,达到1.6 m/s左右;并且整体HCl生成的量随温度的升高而增大,平均速度变化随着热空气温度的升高而减小。

基于内压法的锆合金薄壁管泊松比试验研究

锆合金包壳管在核电应用中存在变形及破裂等问题,严重影响核电运行安全。为了更好地评价锆合金包壳管等薄壁管材受内压时的变形性能,给燃料组件的设计、计算、验证提供参考,设计基于内压法的泊松比测试方法。根据薄壁圆筒受均匀内压时的应力解,推导出基于内压加载的薄壁管泊松比理论公式。按照该理论公式设计合理的内压试验方法,采用该方法对N36锆合金薄壁管开展20~400℃下的泊松比试验,同时通过拉伸法进行相应温度下的对比试验。结果表明,内压试验方法可以有效获得不同温度下锆合金薄壁管的泊松比,且内压试验方法得到的锆合金薄壁管泊松比与拉伸法结果较为一致,相对误差均在2%以内。试验结果同时表明:N36锆合金薄壁管的泊松比随试验温度的增加呈增大趋势。

乏燃料棒M5锆合金包壳的透射电镜分析

压水堆燃料元件的锆合金包壳,在服役期间会经受高中子注量辐照,其微观组织将发生很大变化,从而影响其宏观性能,因此锆合金包壳的中子辐照行为研究一直是核领域的研究重点。但由于材料经中子辐照后具有较强的放射性,相关的实验必须在热室内进行,因此针对辐照后燃料包壳微观组织的研究也一直是工作的难点。本文在中国原子能科学研究院热室设施上,通过透射电镜分析手段,研究了M5锆合金包壳材料中子辐照后的微观组织。样品来源于国内商业压水堆AFA3G型乏燃料棒,其燃耗分别为14 GW·d/tU和41 GW·d/tU。从燃料棒上截取长度约10 mm的包壳样品,在热室内完成去芯块与化学清洗,获得空包壳样品,然后通过机械制样方法,制备出?3 mm薄片状包壳基体样品,最后采用电解双喷减薄方法,制备出包壳透射电镜观察分析样品。另外,为对比锆包壳辐照后的组织变化,采用同样方法制备了相同材料的冷态观察分析样品。冷态样品与辐照样品的观察分析结果表明:冷态Zr合金包壳基体组织内部存在原生的第二相粒子,基体内部整体较为干净,纳米析出相稀少,未观察到明显的位错结构;辐照后,基体内原生的第二相粒子尺寸和分布与冷态样品差异不明显,但出现了明显的纳米析出相和高密度位错组织;随着燃耗的增加,纳米析出相尺寸有增加的现象;低燃耗与高燃耗样品位错组织具有相似性,表明在14 GW·d/tU燃耗下,锆合金包壳内由辐照产生的位错组织已基本趋于饱和状态;电子选取衍射结果表明,辐照后,基体内原生的第二相粒子虽存在一些非晶组织,但仍以bcc晶体结构为主,表明在41 GW·d/tU燃耗下,第二相粒子保持了一定的辐照稳定性;另外,第二相的EDS结果表明,随着燃耗的增加,Nb元素的含量有贫化趋势;分析认为,Zr合金经中子辐照,第二相粒子中的Nb原子扩展至Zr基体内,将促进Nb元素以纳米富Nb相形式在Zr基体中析出。

环硅酸锆钠散治疗慢性心力衰竭患者高钾血症的临床效果观察

目的观察环硅酸锆钠散对慢性心力衰竭患者高钾血症的治疗效果及安全性。方法选择2021年11月至2022年11月在湖州市中心医院接受环硅酸锆钠散治疗高钾血症的慢性心力衰竭患者42例,其中男24例,女18例,年龄45~85(65.0±8.9)岁。所有患者均接受10g、3次/d的硅酸锆钠散治疗,分析药物降钾效果及不良反应。结果环硅酸锆钠散治疗2 h后,血钾水平由5.68(5.46,5.85)mmol/L降至5.11(4.97,5.24)mmol/L,下降0.60(0.49,0.72)mmol/L。用药24h后血钾水平为4.34(4.03,4.50)mmol/L,下降1.35(1.24,1.62)mmol/L。与治疗前相比,治疗2、24h后血钾水平均明显降低(均P<0.05)。用药24h后发生低钾血症8例(19.0%),根据治疗后血钾水平分为低钾血症组、非低钾血症组,两组患者治疗前血钾水平[5.47(5.35,5.62)mmol/L比5.78(5.50,5.90)mmol/L]比较差异有统计学意义(Z=2.499,P=0.011)。所有患者未见其他药物相关不良反应。结论环硅酸锆钠散可在短时间内有效降低慢性心力衰竭合并的高血钾。轻度高钾血症患者治疗时有发生低钾血症风险。