钨/铜界面处氢原子与空位相互作用的第一性原理计算

钨/铜界面是聚变堆偏滤器的重要连接界面,在高热流密度和强中子辐照下会成为氢同位素渗透滞留的高速通道和捕获陷阱.本文利用第一性原理方法研究了钨/铜界面处氢原子与点缺陷的相互作用,考察了氢原子的滞留行为和空位在界面处的形成行为,分析了氢原子的优先占据位置及氢原子与空位的作用机理.结果表明:在钨/铜界面中,氢原子稳定存在于钨...     

氢氦在钨中的影响的第一性原理研究

采用PBE形式的广义梯度近似(GGA)的第一性原理计算方法研究了氢或氦在钨中产生点缺陷的形成能以及缺陷形成后对钨的弹性的影响;采用同样的方法研究了空位和自间隙原子这两种缺陷。经计算发现:氢氦掺杂在钨的晶体结构中会引起晶体体积的变化,其变化结果跟掺杂的位置有关,在四面体或八面体处的掺杂会使晶体体积增加,替位掺杂会引起晶体体积减小;从形成能来看,氢掺杂在钨中最占优的位置是四面体处,而氦最占优的则是替位掺杂。在几种缺陷中,形成能最小的是氢的四面体掺杂,形成能最大的则是钨的自间隙原子形成;钨中若含有氢或氦的点缺陷,晶体的体弹模量和剪切模量会发生改变,当钨中含有氢替位或自间隙原子时晶体会向塑性改变,含有其他点缺陷时晶体会沿着脆性方向转变。但总体来说带有缺陷的钨仍然具有延展性。值得注意的是,氢或氦在钨中会引起晶体的各向异性,其具体结果与缺陷所处位置相关,只有缺陷属于替位时才不会发生各向异性。本文的研究工作可为第一壁材料的开发提供理论参考。     

基于第一性原理的bcc-Fe/FeCr2O4界面稳定性研究

针对反应堆结构材料铁素体/马氏体钢氧化腐蚀问题,本文采用第一性原理计算方法,研究了辐照环境下bcc-Fe与FeCr₂O₄的界面稳定性。基于优化后的Fe（001）表面的3种高对称性位点（桥位、空心位和顶位）和FeCr₂O₄（001）表面的Fe终止面（Fe^T）与CrO终止面（CrO^T）,构建了6种不同构型的bcc-Fe/FeCr₂O₄界面模型（Fe^T-桥位、Fe^T-空心位、Fe^T-顶位、CrO^T-桥位、CrO^T-空心位和CrO^T-顶位）,并通过界面能和黏附功评价界面稳定性。结果表明,CrO^T-空心位界面具有最低的界面能和最大的黏附功,是最稳定的界面构型。基于最稳定模型,考察了界面区域空位形成能和空位对界面黏附功的影响。研究结果表明,Fe空位更容易形成且分布在bcc-Fe/FeCr₂O₄界面的Fe侧第1层,与实验观测到内氧化区域空隙一致。同时,有空位的界面的最小黏附功降低,且断裂面由bcc-Fe/FeCr₂O₄界面处变为FeCr₂O₄侧第2层。这表明辐照诱导缺陷不仅促进氧化层脱落,还改变了氧化层的脱落行为。     

稀有气体原子与Pu（100）表面相互作用的第一性原理研究

采用第一性原理研究了稀有气体原子在Pu（100）表面上的吸附。计算结果表明：除He原子外,其他稀有气体原子在桥位处的吸附能均为最大;稀有气体原子在Pu（100）表面吸附后,稀有气体原子失去电荷,而Pu原子得到电荷,稀有气体原子中Xe原子的电荷转移数最大。差分电荷密度的计算结果表明,对位于Pu（100）表面穴位和桥位处的Xe原子,可观察到较明显的电荷再分布现象,这表明Xe原子具有一定极化效应,能与Pu（100）表面发生相互作用,从He到Xe,原子的极化效应越来越明显。     

钨中空位及其团簇的能量学和动力学性质参数

在总结前人钨中空位及其团簇的能量学和动力学行为的研究成果基础上,采用第一性原理方法系统计算了钨中空位及其团簇的结合能和扩散能垒。研究发现,交换关联泛函PW91和PBE较PBEsol、AM05和LDA更适合用于计算钨空位的能量学性质。基于第一性原理计算结果对文献中单空位形成能、双空位作用性质等争议性问题进行了讨论,并对钨经验势进行了评估。研究结果表明,钨中孤立单空位间总是相互排斥,而空位团簇（V_n>3）对单空位具有很强的吸引作用,其结合能随着所含空位个数增多呈现波动性增大的趋势。空位团簇稳定结构可通过最小化Wigner-Seitz表面积来确定,其结合能与V_n与V_n-1之间的Wigner-Seitz面积之差呈正比。     

钨中空位及其团簇的 能量学和动力学性质参数

在总结前人钨中空位及其团簇的能量学和动力学行为的研究成果基础上,采用第一性原理方法系统计算了钨中空位及其团簇的结合能和扩散能垒.研究发现,交换关联泛函PW91和PBE较PBEsol、AM05和LDA更适合用于计算钨空位的能量学性质.基于第一性原理计算结果对文献中单空位形成能、双空位作用性质等争议性问题进行了讨论,并对钨...     

铯在钨(110)表面吸附行为的第一性原理研究

通过基于密度泛函理论的第一性原理计算方法,研究了铯原子在钨(110)表面上的吸附行为。计算结果表明,通过原子数之比定义的最大单层铯原子吸附率为0.4,铯原子的吸附位置随吸附率的增加而变化。铯原子吸附率为0.25时,最可能的吸附位置是长桥,而铯原子吸附率达0.4时,铯原子在钨(110)表面形成完整的单原子层,并呈现-ABA′B′-结构形式。随铯原子吸附率的增加,表面功函数先减小后增大,最终稳定在2.134 eV,其中最小值1.524 eV出现在吸附率为0.25时,该最小值低于纯铯(110)表面的功函数。偶极子模型和分态密度计算结果表明,铯原子向钨基体表面的电子转移机制和铯原子电子能量分布的变化是造成表面功函数降低的原因。     

高压下惰性气体晶体的第一性原理研究

利用第一性原理,研究了惰性气体晶体的晶体结构和非金属-金属转变。晶体的焓差显示：氦、氖晶体在高压下未发生结构相变,分别保持六角密堆积结构和面心立方;而氩、氪、氙晶体分别在192、95、40GPa从面心立方结构转变为六角密堆积结构。通过研究惰性气体晶体的能带随压强的变化,发现氦、氖、氩、氪、氙的非金属 金属转变压强分别为22000、319000、578、365、149GPa,这与实验结果接近。     

含单空位纯α-Zr晶体的结构、电子和能量性质的第一性原理研究

采用第一性原理方法,使用Win2k软件对含不同单空位浓度纯α-Zr体系的结构、电子和能量性质开展了研究,获得了含不同单空位浓度的纯α-Zr晶格常数的变化,并计算了其电子密度、态密度和能带结构。结果表明,随着单空位浓度的升高,纯α-Zr的晶格常数减小;当空位作为纯α-Zr晶格中Zr原子的第一近邻原子时,其电子密度在相邻Zr原子的方向上延伸,而不含空位的Zr原子的电子密度呈对称分布;随着体系空位浓度的降低,总态密度主峰升高,能带结构和费米面变得更加复杂。     

Fe掺杂SnO_2稀磁半导体超精细场的第一性原理计算

采用基于密度泛函理论线性缀加平面波方法的WIEN2k程序,计算Fe掺杂SnO2稀磁半导体的电子结构和磁性,计算中性电荷态Fe0和电荷受主态Fe1-或Fe2-。结果表明,Fe掺杂SnO2的基态都是铁磁态,O空位更容易出现在Fe原子周围。中性电荷态Fe0磁矩较小,Fe1-或Fe2-态磁矩变大,并且计算的磁超精细场和磁矩与穆斯堡尔谱测量结果相符合。电子结构分析表明,掺杂Fe-3d轨道与氧八面体O-2p轨道相互作用,造成3d轨道能级分裂。不同电荷态下,能级分裂的程度不同,从而影响电子填充3d轨道的模式。3d轨道中未成对电子数增加,处于高自旋态的Fe原子是产生巨磁矩的原因。     

Atomic scattering potentials for an aluminum surface: Test of ab initio calculations

Atom-surface potentials entering the calculations of fast atom scattering at surfaces are often taken to be purely repulsive and parameterized by variants of the ZBL potential. However, such surface potentials derived from pairwise superpositions of binary potentials fail to reproduce recent rainbow scattering measurements performed for various atomic projectiles above different faces of atomically flat single crystal Al surfaces. It was found that the dependence of the rainbow angle θ_rb on the projectile’s kinetic energy component normal to the surface E_⊥ varies with the electronic structure of the projectile as well as with the crystallographic face of the aluminum surface. We determine static atom-surface potentials by ab initio methods which show fair agreement with the experiment.     

Structures and potential energy functions for ground states of PuU and U2 molecules

Pu-Pu,Pu-U and U-U interatomic potentials must be known in molecular dynamics (MD) calculation of the effects of U recoil nucleus produced by self irradiation on physical properties and phase stability in δ-Pu.Because of the lack of experimental data for fitting Pu-U and U-U potentials,electronic states and potential data of PuU and U2 molecules are obtained by ab initio calculations with B3LYP hybrid exchange-correlation functional.The valence electrons of Pu and U atoms are treated with contraction basis sets,and the cores are approximated with relativistic effective core potential.The results show that electronic states for the ground states are X11Σu+ and X9Σg+.The pair potential data are fitted with the Murrell-Sorbie analytical potential function.The LDA+U calculations on the Pu-U intermetallic compound are performed with Perdew and Wang exchange-correlation functional at the spin-polarized level.The material parameters,such as the cohesive energies,elastic constants,and bulk modulus,are used to fit the 0-K universal Rose EOS,so the Pu-U EAM potential model is obtained.     

Manufacturing and testing of W/Cu mono-block small scale mock-up for EAST by HIP and HRP technologies

ITER-like W/Cu mono-block plasma-facing components (PFCs) will be used in vertical target regions of the experimental advanced superconducting tokamak (EAST) divertor. The first W/Cu mono-block small scale mock-up with five W mono-blocks has been manufactured successfully by technological combination of hot isostatic pressing (HIP) and hot radial pressing (HRP). The joining of a W mono-block and a pure copper interlayer was achieved by means of HIP technology and the bonding strength was over 150 MPa. The good bonding between the pure copper interlayer and a CuCrZr cooling tube was obtained by means of HRP technology. In order to understand deeply the process of HRP, the stress distribution of the mock-up during HRP process was simulated using ANSYS code. Ultrasonic Nondestructive Testing (NDT) of the W/Cu and Cu/CuCrZr interfaces was performed, showing that excellent bonding of the W/Cu and Cu/CuCrZr interfaces. The thermal cycle fatigue testing of the mock-up has been carried out by means of an e-beam device in Southwest Institute of Physics, Chengdu (SWIP) and the mock-up withstood 1000 cycles of heat loads up to 8.4 MW/m² with the cooling water of 2 m/s, 20 °C, 0.2 MPa.     

Design and evaluation of an optimized W/Cu interlayer for W monoblock components

Divertor plasma-facing components of future fusion reactors should be able to withstand heat fluxes of 10-20 MW/m² in stationary operation. Tungsten blocks with an inner cooling tube made of CuCr1Zr, so-called monoblocks, are potential candidates for such water-cooled components. To increase the strength and reliability of the interface between the W and the cooling tube of a Cu-based alloy (CuCr1Zr), a novel advanced W-fibre/Cu metal matrix composite (MMC) was developed for operation temperatures up to 550 °C. Based on optimization results to enhance the adhesion between fibre and matrix, W fibres (W_f) were chemically etched, coated by physical vapour deposition with a continuously graded W/Cu_PVD interlayer and then heated to 800 °C. The W_f/Cu MMC was implemented by hot-isostatic pressing and brazing process in monoblock mock-ups reinforcing the interface between the plasma-facing material and the cooling channel. The suitability of the MMC as an efficient heat sink interface for water-cooled divertor components was tested in the high heat flux (HHF) facility GLADIS. Predictions from finite element simulations of the thermal behaviour of the component under loading conditions were confirmed by the HHF tests. The W_f/Cu MMC interlayer of the mock-ups survived cyclic heat loads above 10 MW/m² without any damage. One W block of each tested mock-up showed stable thermal behaviour at heat fluxes of up to 10.5 MW/m².     

Native defect properties in β-SiC: Ab initio and empirical potential calculations

There is considerable ambiguity regarding the formation of native defects and their clusters in silicon carbide (SiC), since different empirical potentials give different results, particular for the stability of interstitial configurations. Density functional theory (DFT) is used to study the formation and properties of native defects in β-SiC. The DFT results are compared with those calculated by molecular dynamics (MD) simulations using the Tersoff potentials, with modified cut-off distances and parameters obtained from the literature. The formation energy of vacancies and antisite defects obtained by DFT calculations are in good agreement with those given by the Tersoff potential, regardless of the cut-off distances, but for interstitials there is a disparity between the two methods, depending on the cut-off distances used in the Tersoff potential. The present results provide guidelines for evaluating the quality and fit of empirical potentials for large-scale simulations of irradiation damage (displacement cascades) and point defect migration (recombination or annealing) in SiC.     

珍贵三环核苷衍生物的理论计算与实验研究

N-4-desmethylwyosine (dYt), a derivative of rare tricyclic nucleosides is probably a new member of Y-nucleosides found in tRNA [1]. The structure of dYt has tricyclic ring with rigid conformation and high electron delocalization. Both the absorption and emission bands of dYt are well separated from normal bases, so it could probably be used as an effective natural fluorescent probe to study RNA structure and sequence[2].Fig.1 The secondary structure of yeast tRNAPbe anticodon loop and molecular structures ofguanosine and N-4-desmethylwyosine An ab initio study was performed to evaluate stability of three isomers of this compound. Ionization potential (IP) of dYt was calculated. It was found that the value was lower than that of guanosine and guanine. This shows that dYt loses electron more easily than guanine.In addition, the result has been verified by experimental studies performed by nanosecond laser photolysis.The reactions of dYt and a series of transient species such as reduction radicals eaq-, H· and oxidation radicals ·OH,SO4·-, CO3·- and N3· have been carried out by nanosecond pulse radiolysis. Rate constants of these reactions have been determined and related mechanisms were discussed.     

The Effects of Nonuniform Thermal Boundary Condition on Thermal Stress Calculation of Water-Cooled W/Cu Divertors

The thermal boundary condition has very important effects on the accuracy of thermal stress calculation of a water-cooled W/Cu divertor. In this paper, phase-change heat transfer was simulated based on the Euler homogeneous phase model, and local differences of liquid physical properties were considered under one-sided high heating conditions. The steady-state temperature field and thermal stress field under nonuniform thermal boundary conditions were obtained through numerical calculation. By comparison with the case of traditional uniform thermal boundary conditions, the results show that the distribution of thermal stress under nonuniform thermal boundary conditions exhibits tbe same trend as that under uniform thermal boundary conditions, but is larger in value. The maximum difference of maximum von Mises stress is up to 42% under the highest heating conditions. These results provide a valuable reference for the thermal stress caleulat.ion of water-cooled W/Cu divertors.     

W/Cu和W/C涂层的循环热负荷实验

用等离子体喷涂和热压方法制作了W /Cu梯度功能材料和W /C涂层 ,其中W/C涂层具有多层的钨 (W )、铼 (Re)扩散阻挡势垒。为了试验这些复合材料能否经受聚变等离子体破裂时的高热负荷 ,用大功率ND :YAG激光进行了模拟实验。结果表明 :在 1 0 0～ 4 0 0MW /m2 的瞬时 (脉冲宽度为 4ms)热负荷作用下 ,经过 2 0 0～ 70 0次热循环 ,未发现W /Cu复合体的开裂。其中在 1 2 3MW /m2 的功率密度下作用70 0次后 ,发现等离子体喷涂试样表面的再结晶现象和严重的晶界腐蚀 ,由于激光的冷效应 ,晶粒生长的趋势并不明显 ,再结晶层的晶粒呈垂直于表面的柱状结构。W/C试样的退火实验表明 ,钨涂层的再结晶温度稍高于 1 4 0 0℃。在更高的功率密度下 (3 98MW /m2 )出现了明显的腐蚀坑 ,坑内呈疏松的蜂窝结构 ,坑的边缘形成了沉积区 ,能谱分析表明沉积区集聚了大量的金属杂质。等离子体喷涂试样比热压试样更易产生晶界的断裂和裂纹。在同等的热负荷条件下 ,W /CuFGM的质量损失低于石墨材料