Solvent diffusion kinetics in the dilute random alloy

In this paper we address the problem of enhancement of the solvent diffusivity by the addition of very small amounts of solute. The random alloy model is employed at the dilute limit. No Monte Carlo calculations have been available for evaluating the available theoretical treatments. In the present study we report on very-high-precision results of the solvent correlation factors as obtained from Monte Carlo calculations with averaging over 6 210 7 atoms and very long runs (2000 jumps per atom). The results are expressed in terms of the usual solvent enhancement factors b 1 and b 2 . There is good agreement with the theory of Holdsworth and Elliott and excellent agreement with the theory of Moleko et al . but not with other available theories.     

Enhancement of solute self-diffusion in fcc alloys

Using a new simulation approach to the calculation of correlation factors in very dilute solutions, the present paper reports on results of the first calculations of the first and second solute enhancement factors for solute self-diffusion in the fourteen-frequency model postulated by Bocquet for describing the diffusion kinetics of paired and unpaired solute atoms in dilute fcc alloys. Bocquet's assumption that correlation effects do not contribute to solute self-diffusion enhancement is shown to have a fairly limited range of validity. Specifically, it is shown that this assumption is reasonable when the solvent–vacancy exchange frequency far from the solute is high compared with the others or when all of the solute–vacancy exchange frequencies are small compared with the others. The assumption is also reasonable when the vacancy is not attracted to the solute atoms and when the vacancy does not often alternate between two solute atoms. The present study would strongly suggest that many of the ratios of exchange frequencies that have been determined from experimental data on the basis of this assumption are likely to be in error.     

Diffusion kinetics of isolated and paired species: a Monte Carlo study

In this paper, we address a four-frequency diffusion model that allows diffusion of paired and unpaired atoms (or small molecular species) in an otherwise empty lattice. The model is useful for describing tracer and collective diffusion of interstitials in dilute interstitial solid solutions and of adsorbed species on surfaces. Diffusion kinetics of this model have been treated analytically by McKee, Le Claire and Okamura and Allnatt. We use Monte Carlo computer simulation to calculate, for the first time, the correlation factors and the linear solute diffusion enhancement factor. Absolute values of the tracer correlation factors and the linear enhancement factors are in excellent agreement with the results of the theory of Okamura and Allnatt, but only in semi-quantitative agreement with results of the other theory. A general argument is also presented to show that the chemical diffusion coefficient does not exhibit correlation effects. This is verified by computer simulation.     

First principles calculations of alloying element diffusion coefficients in Ni using the five-frequency model

The diffusion coefficients of several alloying elements(Al,Mo,Co,Ta,Ru,W,Cr,Re) in Ni are directly calculated using the five-frequency model and the first principles density functional theory.The correlation factors provided by the five-frequency model are explicitly calculated.The calculated diffusion coefficients show their excellent agreement with the available experimental data.Both the diffusion pre-factor(D 0) and the activation energy(Q) of impurity diffusion are obtained.The diffusion coefficients above 700 K are sorted in the following order:DAl>DCr>DCo>DTa>DMo>DRu>DW>D Re.It is found that there is a positive correlation between the atomic radius of the solute and the jump energy of Ni that results in the rotation of the solute-vacancy pair(E 1).The value of E 2-E 1(E 2 is the solute diffusion energy) and the correlation factor each also show a positive correlation.The larger atoms in the same series have lower diffusion activation energies and faster diffusion coefficients.     

Analysis of temperature and concentration dependence of flow stress in KCl–KBr single crystals with special reference to solute distribution

Available data on the temperature and concentration dependence of critical resolved shear stress (CRSS) of KCl–KBr solid-solution crystals containing 9, 17, 27 and 45?mol% KBr in the temperature range 77–230?K have been analyzed within the framework of the kink-pair nucleation model of plastic flow in solid- solution crystals. It is found that CRSS τ decreases with increasing temperature T in accordance with the model relation lnτ?=?A???BT, where A and B are positive constants. The CRSS τ at a given temperature depends on solute concentration c as τ?∝?c^p , where exponent p has a value between 0.33 and 0.57 as temperature T rises from 0 to 230?K. The model parameter W _o, i.e. binding energy between the edge-dislocation segment L _o involved in the unit activation process and the solute atoms close to it (T?→?0?K), which is inversely proportional to B, increases with solute concentration c monotonically as W _o?∝?c ^0.33 up to a critical value c _m?=?35?mol% KBr, which is in reasonable agreement with the model prediction W _o?∝?c ^0.25. However, W _o decreases with an increase in c beyond c _m, which indicates somewhat ordered distribution of solute in the host lattice of concentrated KCl–KBr solid solutions with c?>?c _m.     

体心立方固溶体合金中的"团簇+连接原子"结构模型

为体现固溶体合金中的溶质原子产生的化学短程序,文章提出了配位数为14的团簇在体心立方(bcc)点阵中的堆垛模式,并建立了基于bcc结构的"团簇+连接原子"结构模型,用团簇成分式[团簇](连接原子)_x表述. 此模型中,与基体组元具有相对大的负混合焓的溶质原子占据团簇心部,其他原子作为连接或者替代团簇壳层基体原子. 1 ∶1结构模型[团簇](连接原子)₁由于最大程度地保证了团簇与连接原子的近邻,构成了连接原子最有效的合金化方式. 在两个实用bcc固溶体合金体系中, 1 ∶1模型指导设计了低V含量的储氢合金 V₁和低弹性模量高强度的 Nb₁合金. 关键词： 体心立方固溶体成分设计 "团簇+连接原子"结构模型 Ti-Cr-V合金 Ti-Zr-Mo-Nb合金     

Solute-diffusion-controlled dislocation creep in pure aluminium containing 0.026 at.% Fe

Pure aluminium containing about 200?at.ppm Fe in solution is shown to creep about 10⁶ times slower at 200°C than the same aluminium containing a negligible amount of iron in solution. The high creep resistance of the Al–200?at.ppm?Fe alloy is attributed to the presence of subgrain boundaries containing iron solute atoms. It is proposed that the opposing stress fields from subgrain boundaries and from the piled-up dislocations during creep are cyclically relaxed, by iron solute diffusion, to allow climb of the lead dislocation in the pile-up. The mechanism is a form of mechanical ratcheting. The model is applied to Al–Fe alloys and correctly predicts that the creep rate is controlled by the rate of iron solute diffusion and by a temperature dependence equal to the activation energy for iron diffusion, namely Q _c?=?221?kJ?mol^?1. Basic creep studies on solid-solution alloying with solute atoms that diffuse slowly in the lattice of aluminium (e.g. manganese, chromium, titanium and vanadium) appear worthy of study as a way of enhancing creep strength and of understanding creep mechanisms involving solute-atom-containing subgrain boundaries.     

Dielectric inserts for sensitivity and RF magnetic field enhancement in NMR volume coils

A method for enhancing the signal to noise ratio (SNR) in NMR volume coils is described. By introducing inserts made of low-loss, high dielectric constant material into specific locations in the coil, the SNR can often be enhanced by up to 20%, while B₁ homogeneity is hardly affected. A model for predicting the limit of the SNR improvement is also presented. The model accurately predicts the SNR gain obtained in both numerical simulations and experiment. An experiment was conducted on a mini-MRI system. Experimental results are in very good agreement with the simulations in regard to both SNR improvement and B₁ enhancement in transmission. Inserts made of ultra high dielectric constant materials can be as thin as few millimeters, thus, conveniently fitting into existing coil-sample gaps in volume coils.     

Dynamic and thermodynamic consequences of adsorbate lateral interactions in surface reaction kinetics

The effects of lateral interactions on the two-dimensional distribution of adspecies on solid surfaces and their consequences for reaction kinetics are demonstrated for the bimolecular reactive systemA+BAB. The discussion concentrates on systems where one reactant,A, is stationary while the other,B, is freely diffusing and instantaneously relaxing. A modified Bethe-Peierls-type lattice gas approximation is formulated in order to account for the rapidly-equilibrating distribution ofB atoms. The approximation takes into account all nearest and next nearest neighbor interactions between the adspecies and the nonuniformity of the lattice available toB implied by the presence of immobileA's on the surface. This model is combined with a Monte Carlo simulation of the reactive events in order to calculate reaction rates, e.g., in temperature-programmed processes. The rates are compared with full Monte Carlo simulations (for all kinetic processes), showing good agreement between the two schemes, except at very high coverages, where very long range correlations in the system which are ignored in the lattice gas approximation must be taken into account.This paper is dedicated to Howard Reiss in celebration of his 66th birthday.     

Kinetics of atoms in an elliptically polarized standing wave

We examine the kinetics of atoms with their ground and excited states being degenerate in the projection of angular momentum. The atoms are located in a standing wave with uniform elliptical polarization. Using the j _g =1/2→j _e =1/2 transition as an example, we show that the friction and diffusion of atoms strongly depend on the ellipticity of the field. For instance, in the low saturation limit the frictional force contains, in addition to the ordinary Doppler friction term, a term that can be interpreted as Sisyphean friction. Under certain conditions, the contributions reflecting the degeneracy of the ground state are dominant, with the result that the values of the friction and diffusion coefficients (and hence the rate of kinetic processes) may differ from the values predicted by the two-level atomic model by several orders of magnitude. Zh. éksp. Teor. Fiz. 115, 791–804 (March 1999)     

Scattering of acoustic phonons by rare earth substitutional atoms in yttrium aluminum garnets

The diffusive maxima of phonon signals, and in particular their arrival timest _m are examined for a number of solid solutions of rare earth atoms in yttrium aluminum garnets. The phonon pulses are generated by metallic films of the characteristic lengthl _h heated by current pulses to the temperatureT _h slightly higher than the ambient temperatureT. The injected phonons travel in wafers of the thicknessL _z. They are scattered by substitutional atoms of rare earth occupying the yttrium dodecahedral sites, rare earth and yttrium atoms occupying the aluminum octahedral sites and by another lattice imperfections generated in the process of sample growing. The qualitative analysis based on our exact formula for the diffusion coefficientD allows us to extract the contribution of rare earth atoms substituting the Y atoms toD. Considering the dependence oft _m/L _z ² on the temperature and the ratiol _h/L_z we conclude thatD∼T _h ⁻⁴ and that the energy of phonons forming the diffusive maxima ranges from 3.2k _BT_H to 4.2k _BT_H, which is in reasonable agreement with the existing estimates.     

Electronic structure and magnetic properties of Gd3Co11B4 compound

The electronic structure of hexagonal Gd₃Co₁₁B₄ compound has been studied by X-ray photoemission spectroscopy (XPS) and ab initio self-consistent tight binding linear muffin tin orbital (TB LMTO) method. We have found a good agreement between the experimental XPS valence band spectra and theoretical LMTO calculations. Results showed that the Gd₃Co₁₁B₄ compound is ferrimagnetic with the calculated total magnetic moment M=14.29 μ_B/f.u. The values of the magnetic moments on Co atoms strongly depend on the local environment. We have also compared the electronic structure and magnetic properties of Gd₃Co₁₁B₄ compound with those of Nd₃Co₁₁B₄ compound.     

Correlated tracer diffusion in an ordered interface structure

In this paper, we postulate a simple two-dimensional structure that attempts to capture the character of many of the qualitative findings from computer simulations of diffusion paths in grain boundaries. We postulate two types of mechanism: those where single atom jumps occur and those where multiple atom jumps occur. We derive analytical expressions for the tracer correlation factors, including those correlation factors that appear in the analysis of the diffusion isotope effect. We also carry out Monte Carlo simulations of these correlation factors. We find very good agreement between the derived expressions for the correlation factors and the simulation results. We are able to show that, in the absence of knowledge about the kinetic energy factor ΔK, isotope effect experiments cannot differentiate between a simple atom-jump mechanism and multiple-atom-jump mechanism.     

Structures and autocorrelation functions of liquid Al and Mg modelled via Lennard-Jones potential from molecular dynamics simulation

The structures and autocorrelation functions of Al and Mg in the liquid state are investigated through the pair distribution functiong(r), the diffusion coefficients as well as the shear viscosity via the Green-Kubo and Einstein relations. From the structure and the Enskog relation we determined the frequency of collisions of atoms in the first shell ofg(r) in the systems. We also discovered that the packing fraction of Lennard-Jones liquids should be approximately half the reduced density value. This approximation is accurate to within 99%. The temperature dependence of the pair distribution function and the atomic mean square displacement are investigated by performing simulations at various experimental temperatures and corresponding densities. The structures of the systems are affected by temperature via movements of atoms in the first minimum ofg(r). The Lennard-Jones model shows that density dependence of the shear viscosity is in agreement with what is expected of simple liquids in the range of investigated temperatures and densities. In the gas limit, the Stoke-Einstein relationDη =K _BT /2πσ is grossly overestimated by Lennard-Jones model. This could not be attributed to deficiencies in the model, as other investigators using first principle method could not obtain the gas limit of the Stoke-Einstein relation.     

Diffusion of Au and Cu in amorphous Fe80B20 and Fe82B18 alloys

Diffusion rates (D) of Au in two amorphous alloys, Fe₈₀B₂₀ and Fe₈₂B₁₈, and of Cu in amorphous Fe₈₂B₁₈ alloy were measured in the temperature range 546–645 K by using the technique of Rutherford backscattering spectrometry (RBS) and Auger electron spectroscopy (AES), respectively. The diffusion of Au was found to be 3 to 6 times faster in Fe₈₀B₂₀ than in Fe₈₂B₁₈, though both the alloys had almost similar crystallization temperatures. The observed differences in the diffusion rates corroborate the fact that Fe₈₀B₂₀ has a more open structure than Fe₈₂B₁₈ as revealed from the reported values of the metal packing fractions of these two alloys. Also, the diffusivities of smaller sized Cu atoms (radius: 0.128 nm) were found to be higher by more than an order of magnitude than those of larger sized Au atoms (radius: 0.146 nm), suggesting a dependence ofD on the size of the diffusing species.     

Magnetic properties of stable structures of small binary clusters

We have studied the optimum geometries and the magnetic behavior of small binary Fe_nGe_m (n+m≤4) clusters usingab initio spin-polarized density functional calculations. Our results reveal that the optimized clusters present high values in the HOMO–LUMO gap and generally prefer structures with high geometries, the local magnetic moments at Fe atoms present an enhancement with respect to Fe bulk magnetization, whereas the Ge atoms present local magnetic moments whose modulus take significative values. The magnetic coupling between Fe and Ge atoms is mainly antiferromagnetic-like. All the clusters studied here present a charge transference from Fe atoms to Ge atoms.     

Importance of solute–solute interactions on glass formability

Microalloying experiments on amorphous Al₈₄La₄Er₂Ni₈TM₂ alloys were performed with the substitution of all 3d TM (transition metal) elements and one 4d TM element. The critical thickness of the amorphous alloys was used as a criterion for glass formability in this system. The results show that, other than atomic size differences and the negative heats of mixing among the solvent and solute atoms, the atomic interactions among the solute atoms play an important role on glass formation. When the solute–solute interaction becomes repulsive (positive heat of mixing), glass formability suffers. Similarly, when the solute–solute interaction becomes highly attractive, exceeding that between the solvent and solute atoms, glass formability is also degraded. Evaluation of a large number of known multicomponent bulk metallic glasses provides additional support to these conjectures. This study shows that the solute–solute interaction plays an important role in glass formation, which has not been recognized previously.     

Aluminium diffusion in titanium nitride films. Efficiency of TiN barrier layers

Two kinds of reactively evaporated titanium nitride films with columnar (B ₀ films) and fine-grained (B ₊ films) film structures, respectively, have been examined as diffusion barriers for preventing aluminium diffusion. The aluminium diffusion profiles have been investigated by 2 MeV ⁴He⁺ Rutherford backscattering spectrometry (RBS) at temperatures up to 550° C. The diffusivity from 300° C to 550° C is: D[m²s^–1]=3×10^–18 exp[–30/(RT)] in B ₀ layers and D[m²s^–1]=1.4×10^–16 exp[–48/(RT)] in B ₊ TiN layers. The activation-energy values determined indicate a grain boundary diffusion mechanism. The difference between the diffusion values is determined implicitly by the microstructure of the layers. Thus, the porous B ₀ layers contain a considerable amount of oxygen absorbed in the intercolumnar voids and distributed throughout the film thickness. As found by AES depth profiling, this oxygen supply allows the formation of Al₂O₃ during annealing the latter preventing the subsequent diffusion of the aluminium atoms.     

Kinetic Monte Carlo simulation of thin film growth

A three-dimensional kinetic Monte Carlo technique has been developed for simulating growth of thin Cu films. The model involves incident atom attachment, diffusion of the atoms on the growing surface, and detachment of the atoms from the growing surface. The related effect by surface atom diffusion was taken into account. A great improvement was made on calculation of the activation energy for atom diffusion based on a reasonable assumtion of interaction potential between atoms. The surface roughness and the relative density of the films were simulated as the functions of growth substrate temperature and film thickness. The results showed that there exists an optimum growth temperatureT _opt at a given deposition rate. When the substrate temperature approaches toT _opt, the growing surface becomes smoothing and the relative density of the films increases. The surface roughness minimizes and the relative density saturates atT _opt. The surface roughness increases with an increment of substrate, temperature when the temperature is higher thanT _opt.T _opt is a function of the deposition rate and the influence of the deposition rate on the surface roughness depends on the substrate temperatures. The simulation results also showed that the relative density decreases with the increasing of the deposition rate and the average thickness of the film.