单轴应变对H在α-Fe中占位及扩散的影响

采用基于密度泛函理论的第一性原理方法,研究了H在不同单轴应变下α-Fe中的间隙占位,计算了H原子的溶解能、态密度、电荷差分密度和电荷布居.结果表明:不同单轴拉压应变作用下,H原子优先占据四面体间隙(Ts)位,且随着压应变减小、拉应变增加,H原子越易溶于α-Fe.压应变使得Ts位的H获得更多的电子,而拉应变减少了这种电荷转移.应用LST/QST过渡态搜索计算垂直应变方向的扩散.八面体间隙位是邻近Ts位H的扩散过渡态.扩散激活能与应变呈线性关系,且随着压应变的增加,扩散激活能降低,扩散更容易.     

LiNH2储氢材料中间隙H与掺杂原子交互作用对其释氢性能影响机理研究

采用基于密度泛函理论的赝势平面波第一性原理方法,研究了LiNH₂缺陷及其掺杂原子交互作用对其释氢影响.通过对其进行优化求得它们的局域最稳定结构并计算了含间隙H原子缺陷的LiNH₂及其掺杂合金的结合能、间隙缺陷形成能、态密度和电荷布居.结果表明: 系统结合能不能反映LiNH₂及其掺杂合金的释氢性质;平衡时,LiNH₂中有一定的间隙氢原子存在,Mg,Ti掺杂使形成能大大降低,大大增大了间隙氢的浓度. 间隙H原子在带隙引入了缺陷能级使带隙大大减小,提高释氢能力.间隙H原子导致[NH₂]^-中N-H原子间相互作用减弱,容易释氢.间隙H与[NH₂]^-中N存在共价作用,可以解释LiNH₂释氢反应中NH₃的放出.当存在掺杂时,N-H键的键强不均衡,部分较弱,部分较强,较弱的N-H键中H容易放出. 关键词： 储氢材料 第一性原理 缺陷 释氢机理     

杂质P对α-Fe中刃型位错上扭折电子结构的影响

利用离散变分方法和DMol方法,研究了P对bcc Fe中［100］(010)刃型位错上扭折电子结构的影响,计算了杂质偏聚能、原子间相互作用能、电荷密度及态密度.计算结果表明：微量P引入体系后,电荷发生了重新分布,P原子得到电子,其周围Fe原子失去电子,由于P原子的3p轨道与近邻Fe原子的3d4s4p轨道之间杂化,使P原子与近邻Fe原子间有较强的相互作用,不利于扭折的迁移,使位错运动受阻,有利于材料强度的提高.同时,杂质P原子与基体原子间的成键主要是d,p轨道起作用,使得它们之间的成键有较强的方向性,有可能 关键词： 电子结构 刃型位错 扭折 杂质元素     

Obstacles for one-dimensional migration of interstitial clusters in iron

Interstitial clusters are known to cause frequent one-dimensional (1D) jumps (stepwise positional changes) under electron irradiation around room temperature. The distance of 1D jumps in iron was examined in detail through in-situ observation using high-voltage electron microscopy. The 1D jump distance was found to be longer for smaller clusters in specimens of higher purity, although the distance did not depend on the irradiation beam intensity and electron energy. The distribution of the 1D jump distance was well described by the distribution of the free path of interstitial clusters migrating through randomly distributed impurity atoms. The 1D jump process is considered as fast 1D diffusion of interstitial clusters at low activation energy from the point where the cluster detrapped from an impurity atom to the point where the cluster was trapped again by another impurity. Electron irradiation provides a trigger for causing 1D migration by detrapping of clusters from impurity atoms.     

The unambiguous identification of vacancy migration stage in resistivity recovery of irradiated metals based on trapping of vacancies at probe impurity atoms

The method of resistivity recovery is a powerful tool for studying point defects in irradiated metals. However, the method is nonspecific with respect to a type (vacancy or interstitial) of investigated defects. To overcome this shortcoming, we made use of opposite signs of excess electric charges of the vacancies and self-interstitial atoms in a lattice. Resistivity loss takes place on trapping of vacancies at impurity atoms if excess charges of the impurity atom and defect are opposite in sign. A way of selecting the impurity atoms with the excess charge opposite in sign to that of vacancies is proposed. The specific evolution of resistivity recovery spectrum induced by vacancy trapping at the selected impurity atoms (probe traps) allows one to unambiguously identify the stage of free long-range vacancy migration.     

Space charge solution of Rittner photoconductor equation for a HgCdTe detector

The steady-state charge continuity equations are linearized to derive a space charge field that accompanies the ambipolar diffusion and drift described by the Rittner equation. The space charge field is evaluated for a typical 14.2 μm cutoff wavelength HgCdTe detector operating at 85 K. It is found that the space charge density is ∼10⁻⁵ times the hole and electron population density generated by photon flux. This corroborates that Rittner's equation gives an accurate solution for the hole and electron densities. But, at relatively high photon flux levels that are found in some Geostationary Operational Environment Satellite instrument channels, the small average space charge field can have a noticable effect on the linearity of detector response. Divergence of electric field terms in the continuity equations, which are absent from the Rittner equation, can also contribute a non-linearity to detector response.     

Ab initio thermodynamic characteristics of the formation of oxygen vacancies,and boron,carbon, and nitrogen impurity centers in anatase

Using the ab initio projector augmented wave (PAW) method, calculations are performed for the electronic energy-band structure of titanium dioxide having the structure of anatase doped with boron, nitrogen, and carbon. Thermodynamic characteristics are determined for the formation of impurity centers, such as the preference energy for the interstitial position, the energy of impurity oxidation, and the energy of oxygen vacancy formation. It is shown that under the conditions of thermodynamic equilibrium the interstitial position of boron atoms is stable, whereas carbon atoms, depending on the oxygen pressure, can occupy both interstitial positions and substitutional positions of oxygen atoms, and nitrogen atoms replace oxygen atoms. It is shown that the presence of oxygen vacancies promotes the thermodynamic stability of carbon and nitrogen atoms. The obtained densities of electronic states correspond to ESR spectroscopy data, which indicates the presence of spin-polarized electrons in the states of the oxygen vacancy.     

On the accuracy of the BGK model for ion drift in own gas

The model of collisions of ions with gas atoms, considering resonant charge exchange of ions, polarization and elastic (gas-kinetic) interactions is constructed. Ion drift characteristics in the dc electric field are calculated. The results are compared to calculations based on the Bhatnagar-Gross-Krook model collision integral (BGK integral). It is shown that the use of the BGK collision integral leads to significant errors due to the specificity of ion-atom collisions.     

难熔元素钨在NiAl位错体系中的占位及对键合性质的影响

用第一性原理离散变分方法研究了难熔元素钨(W)在金 属间化合物NiAl<100>(010)刃型位错体系中的占位以及对键合性质的影响, 计算了纯位错体系和掺杂体系的能量参数(结合能、 杂质偏聚能及原子间相互作用能)、 态密度和电荷密度分布. 体系结合能和杂质偏聚能的计算结果表明: 难熔元素W优先占据Al格位. 此外,由于难熔元素W的4d轨道与近邻基体原子Ni的3d轨道和Al的3p轨道的杂化, 使得掺杂体系中难熔元素W与近邻基体原子间的相互作用能加强; 同时难熔元素W与位错芯区近邻基体原子间有较多的电荷聚集, 这表明W与近邻基体原子间形成了较强的化学键. 难熔元素W对NiAl化合物的能量及电子结构有较大的影响, 从而影响位错的运动及NiAl金属间化合物的性能. 关键词： 电子结构 位错 金属间化合物 杂质     

Low density approximation for diffusion annealing

The problem of annealing of Frenkel-pairs in electron irradiated fee metals due to diffusion of interstitials is treated starting from exact equations for single particle densities, pair densities, etc. The mobile interstitials are considered to interact with vacancies (leading to recombination), impurity atoms (leading to interstitial-impurity complexes) and with each other (leading to interstitial clusters).

By using the superposition approximation, i.e. replacing three-particle probabilities by products of two-particle probabilities we obtain generalized Waite equations. For low defect densities the annealing is at different times governed by different processes. For short times the important process is the recombination of an interstitial with the near-by correlated vacancy generated by the same electron impact event, the so-called correlated recovery. For long times the remaining interstitials undergo long range migration and interact with uncorrelated sinks. During this process interstitial impurity complexes and interstitial clusters are formed.

The time dependence of the defect densities, the remaining fraction of defects after completion of diffusion annealing and the size distribution of interstitial clusters are calculated. Detailed comparison with experiments in Cu and Pt will be made.     

Evolution of the concentration of point defects at the tip of a crack

The evolution of the distribution of interstitial impurity atoms in the plastic zone around the tip of a tension crack is analyzed. The transport of point defects is determined by: 1) the hydrostatic component of the elastic stress at the crack tip, created by the superposition of the elastic fields of the crack and dislocations; 2) the elastic field of moving dislocations (“sweeping out” of interstitial impurity atoms); 3) the dislocation-driven transport of point defects present in the dislocation cores. The contributions of each mechanism of transport of point defects to the crack tip are calculated over the entire time from the start of loading of a sample containing a crack until an equilibrium distribution of plastic deformation is established after the cessation of loading. Numerical calculations are carried out for interstitial hydrogen atoms dissolved in an α-Fe crystal. Fiz. Tverd. Tela (St. Petersburg) 39, 1580–1585 (September 1997)     

Effect of P impurity on NiAlΣ5 grain boundary from first-principles study

First-principles calculations based on the density functional theory(DFT) and ultra-soft pseudopotential are employed to study the atomic configuration and charge density of impurity P in Ni Al Σ5 grain boundary(GB). The negative segregation energy of a P atom proves that a P atom can easily segregate in the Ni Al GB. The atomic configuration and formation energy of the P atom in the Ni Al GB demonstrate that the P atom tends to occupy an interstitial site or substitute a Al atom depending on the Ni/Al atoms ratio. The P atom is preferable to staying in the Ni-rich environment in the Ni Al GB forming P–Ni bonds. Both of the charge density and the deformation charge imply that a P atom is more likely to bond with Ni atoms rather than with Al atoms. The density of states further exhibits the interactions between P atom and Ni atom, and the orbital electrons of P, Ni and Al atoms all contribute to P–Ni bonds in the Ni Al GB. It is worth noting that the P–Ni covalent bonds might embrittle the Ni Al GB and weakens the plasticity of the Ni Al intermetallics.     

On the theory of fluctuations around non-equilibrium steady states: A generalized time-convolutionless projector formalism

A new method of finding nonlinear Langevin type equations of motion for relevant macrovariables and the corresponding master equation for systems far from thermal equilibrium is presented by generalizing the time-convolutionless formalism proposed previously for equilibrium hamiltoian systems by Tokuyama and Mori. The Langevin type equation consists of a fluctuating force, and the nonlinear drift coefficients which are always identical to those of the master equation. A simple formula which relates the drift coefficients to the time correlation of the fluctuating forces is derived. This is a generalization of the fluctuation-dissipation theorem of the second kind in equilibrium systems and is valid not only for transport phenomena due to internal fluctuations but also for transport phenomena due to externally-driven fluctuations. A new cumulant expansion of the master equation is also obtained. The conditions under which a Langevin and a Fokker-Planck equation of a generalized type for non-equilibrium open systems can be derived are clarified.The theory is illustrated by studying hydrodynamic fluctuations near the Rayleigh-Bénard instability. The effects of two kinds of fluctuations, internal fluctuations of irrelevant macrovariables and external (thermal) noises, on the convective instability are investigated. A stochastic Ginzburg-Landau type equation for the order parameter and the corresponding nonlinear Fokker-Planck equation are derived.     

Dynamics of oxygen atoms in the Ta-O interstitial system

The dynamics of oxygen atoms in a Ta-O solid solution is studied. The vibrational energies of interstitial O impurities are determined, and the metal-impurity interaction constants are calculated. The experimental data obtained suggest that an oxygen atom is displaced from the center of the octahedral interstice of the crystal lattice. The oxygen vibrational energy in tantalum is shown to satisfy the relation between the localmode energy and the transition metal-interstitial impurity distance that is common for all M-O systems.     

Energetics and electronic structure of refractory elements in the dislocation of NiAl

Using DMol and the discrete variational method within the framework of the density functional theory,we study the alloying effects of Nb,Ti,and V in the [100](010) edge dislocation core of NiAl.We find that when Nb(Ti,V) is substituted for Al in the center-Al,the binding energy of the system reduces 3.00 eV(2.98 eV,2.66 eV).When Nb(Ti,V) is substituted for Ni in the center-Ni,the binding energy of the system reduces only 0.47 eV(0.16 eV,0.09 eV).This shows that Nb(Ti,V) exhibits a strong Al site preference,which agrees with the experimental and other theoretical results.The analyses of the charge distribution,the interatomic energy and the partial density of states show that some charge accumulations appear between the impurity atom and Ni atoms,and the strong bonding states are formed between impurity atom and neighbouring host atoms due mainly to the hybridization of 4d5s(3d4s) orbitals of impurity atoms and 3d4s4p orbitals of host Ni atoms.The impurity induces a strong pinning effect on the [100](010) edge dislocation motion in NiAl,which is related to the mechanical properties of the NiAl alloy.     

STM tunneling through a quantum wire with a side-attached impurity

The STM tunneling through a quantum wire (QW) with a side-attached impurity (atom, island) is investigated using a tight-binding model and the non-equilibrium Keldysh Green function method. The impurity can be coupled to one or more QW atoms. The presence of the impurity strongly modifies the local density of states of the wire atoms, thus influences the STM tunneling through all the wire atoms. The transport properties of the impurity itself are also investigated mainly as a function of the wire length and the way it is coupled to the wire. It is shown that the properties of the impurity itself and the way it is coupled to the wire strongly influence the STM tunneling, the density of states and differential conductance.     

Screening due to non-equilibrium carriers in presence of deep repulsive traps

The characteristics of screening length due to non-equilibrium electrons at low lattice temperatures are investigated theoretically, when the lifetime of the carriers is controlled by deep repulsive traps. The calculations have been made covering a wide range of the electric field, starting from a weakly heated carrier ensemble up to the onset of impurity breakdown. Apart from becoming field dependent, the screening length now shows a rather complicated dependence upon the lattice temperature. The numerical results for high-purity covalent semiconductors like Ge and Si show that the characteristics of the screening length are now significantly different from what one obtains for an ensemble of carriers that is in thermodynamic equilibrium with the lattice atoms.     

基于第一性原理的含空位a-Fe和H原子相互作用研究

氢致裂纹是制约超高强度钢应用的关键问题,掌握扩散氢的分布行为有助于弄清氢致裂纹的形成机理.本文采用第一性原理方法计算了H原子占据α-Fe晶格间隙和空位时的情况,得到了晶体的稳定构型及能量,并据此分析了H原子在晶格间隙和空位中的溶解倾向;从Mulliken布居、电子密度分布、态密度分布等角度分析了H原子与α-Fe晶体间隙和空位之间的相互作用.结果表明:间隙H原子倾向占据α-Fe四面体间隙位,其1s轨道电子与Fe的4s轨道电子呈微弱共轭杂化;空位是强氢陷阱, H原子倾向占据空位内壁附近的等电荷面.在真空0 K条件下单空位最多稳定溶解3个H原子,且H原子之间未表现出自发形成H2的倾向;间隙和空位中的H原子溶入改变了Fe晶格内电子分布导致原子结合力弱化,并在局部区域形成反键.基于第一性原理能量计算结果开展热力学分析,分析结果表明大多数情况下间隙H原子都是H主要的固溶形式, H平衡溶解度计算结果与实际符合良好.     

Mass transfer in nonuniform media

The lattice model was used to derive equations describing diffusion in a nonuniform medium in the absence of local equilibrium at nonzero temperature gradients. Equations are obtained that extend a diffusion equation with fractional derivative in time and a nonlinear diffusion equation, which was previously obtained within the framework of a generalized thermodynamic approach, to cover diffusion in a medium with a nonuniform temperature field.     

Diffusion and solubility of some interstitial impurities in deformed metals

Summary The problem of impurity diffusion accompanying segregation phase nucleation on dislocations has been studied using the approximation of the local equilibrium with respect to the impurity distribution between the volume solution and dislocation regions. It has been shown that the known experimental data on diffusion and solubility of some interstitial impurities in cold-worked b.c.c. and f.c.c. metals and alloys can be described in the framework of the dislocation trap model. The characteristics of the impurity segregation regions near dislocations have been obtained from the treatment of the diffusion and solubility data for the systems. On the basis of the crystallographic and thermodynamic considerations the possibility of the existence of such segregation phase regions along dislocations in the systems in question has been shown.