Solute segregation to grain boundaries and free surfaces in an Fe---Si multicomponent alloy

Solute segregation was measured at both the {310} symmetrical tilt grain boundary and the (310) free surface of a sample of an Fe-6at%Si alloy containing traces of P, S, N and C at 873 K. Large phosphorus enrichment and silicon depletion characterize the grain boundary segregation in spite of a different bulk concentration of nitrogen. The surface segregation in nitrogen-containing samples is controlled by strong cosegregation of Si and N, resulting in the formation of a stable Si_xN_y 2D surface compound, whereas pronounced surface segregation of sulphur dominates in denitridized samples. The differences of grain boundary and surface segregation are discussed as a kind of “anisotropy of interfacial segregation” on the basis of Guttmann's theory with different values of free energies of segregation to grain boundary and free surface. They also suggest that the measurements of surface segregation cannot be unambiguously used for predicting the grain boundary segregation. In some non-brittle multicomponent systems, a better way of predicting segregation behavior at grain boundaries would be the measurement of grain boundary segregation in a related system with solute concentrations that cause embrittlement. The findings can then be applied to the required alloy composition on the basis of Guttmann's theory.     

Surface Segregation in Miscible Blends of Polystyrene and Poly(vinylmethyl ether): Comparison of Theory and Experiment

The effect of the interplay between bulk and surface free energy terms on surface segregation in miscible blends is probed by comparing angle-dependent x-ray photoelectron spectroscopy (ADXPS) measurements for polystyrene/polyvinylmethylether (PS/PVME) blends of with those for perdeuteropolystyrene/polyvinylmethylether (dPS/PVME) blends. The magnitudes of the bulk interaction parameters for the two systems differ markedly while the surface interactions are essentially identical. Experimental concentration depth profiles are almost identical for the two systems indicating that their surface properties are little affected by bulk interactions and dominated by surface energy effects.These data and previous data from our group are compared to the predictions of the square gradient theory developed by Schmidt and Binder in order to gain a more quantitative understanding of the factors that control surface segregation in miscible blends. While there is general qualitative agreement between theory and experiment, predicted surface compositions fall significantly below experimental values and predicted composition depth profiles decay more gradually than what is observed experimentally, especially for low PVME contents. The use of the more appropriate Sanchez-Lacombe-Balazs equation of state does not yield any significant improvement over the use of the Flory-Huggins lattice model for representing the bulk free energy terms. Careful analysis of the experimental behavior suggests that configurational effects associated with the flattening of surface adsorbed chains and differences in mer-mer interaction parameters in the bulk and near surface regions are possible origins for the discrepancies between theory and experiment.     

Thermal structure of the evaporation front in laser drilling processes

Dynamic measurements of velocity and temperature yield information on the temperature distribution and the thermal thickness of the evaporation front caused by focused laser irradiation on metals. The thermal thickness of the evaporation front is inversly proportional to the steady-state velocity of the front. Direct temperature values are obtained by measuring the thermoelectric signals from thermocouple junctions of 10 μm average dimensions, located at the back side of the drilled sample. Experimental results are compared to thermal models theory and the implications concerning the drilled efficiency are considered.     

Segregation of dissolved Li to the surface of Si: A new activation process

Photoemission measurements have been performed on Li covered Si samples. The Li layer is formed: (i) by adsorption, (ii) by segregation of dissolved Li to the Si surface.These two methods of activation give comparable results: the photoemissive quantum yield is about 10 per cent at 5 eV and the threshold is 2.5 eV for p type Si. Moreover, the surface layer obtained by segregation seems highly pure and uniform. The segregation kinetics are analyzed using a simple theoretic model.     

Spatial distribution of impurities in delta-doped n-type GaAs

Capacitance-voltage (CV) profiling measurements on delta-doped n-type GaAs reveal extremely narrow peaks with a full-width at half-maximum of 40 Å. Comparison of experimental with self-consistently calculated CV profiles demonstrates that Si impurities are localized on a length scale of a lattice constant in delta-doped GaAs. Diffusion and segregation are of minor importance. The basic theory of CV measurements on quantummechanical systems such as delta-doped semiconductors is developed and presented.     

Orientation dependence of the solid/liquid interfacial free energy in binary systems

A first-order theory of compositional segregation at solid/liquid interfaces, based on a pair-bonded, lattice-liquid interfacial model, has been applied to predict the effect of segregation on the orientation dependence of the interfacial free energy in binary metallic systems. The results show that the sharpness of the cusps in the gamma plot is reduced due to preferential segregation at layer edges as compared to layer faces, and cusps may be eliminated under certain conditions. The reduction in cusp sharpness is the greatest when the composition difference of the solid and liquid phases is large and the solutions are appreciably non-ideal. The relative reduction of sharpness due to segregation is less pronounced for cusps which are sharper in the unsegregated condition, so segregation tends to smooth the form of the gamma plot. Graphical results are presented for calculation of segregational anisotropy effects in general systems.     

Equilibrium segregation in a ternary solution: A model for temper embrittlement

Whereas experimental evidence has established that temper embrittlement is due to the simultaneous intergranular segregation of some impurities I (Sb, P, As Sn, ...) and of metallic alloying elements M (Ni, Cr, Mn, ...), all the theories of this phenomenon have failed so far to rationalize the role of the alloying elements, i.e. essentially to explain why they are necessary for the segregation of the impurities to occur. The thermodynamical formalism of equilibrium segregation, when taking into account the interaction of M and I atoms in an iron base solid solution can explain this behaviour. The simplest analytical treatment of such interaction based on the regular solution model is developed. The values of the interaction coefficients between the various atoms, as evaluated from the enthalpies of mixing of the intermetallic compounds, appear consistent with the value deduced from segregation measurements. The model is shown to allow a comprehensive interpretation of the segregation behaviour of various binary and ternary solutions, in particular the iron base systems. Eventually the role of bi-dimensional compound formation in the segregation process is considered.     

质子与裂变核238U反应的理论计算

利用球型光学模型、耦合道理论、核内级联、激子模型、蒸发模型、带宽度涨落修正的Hauser-Feshbach模型,Bohr-Wheeler裂变理论,对入射能量从阈能到200 MeV的p+²³⁸U各种反应进行了计算,计算结果和实验符合较好.     

Surface segregation in liquid GaSn alloys by AES

The surface segregation of Sn in liquid GaSn alloys has been studied by Auger electron spectroscopy as a function of bulk concentration at 350° C. The Sn was found to be strongly adsorbed at the surface. The surface concentrations of Sn and Ga were calculated from the Auger measurements using inelastic mean free paths and backscattering factors estimated in recent theoretical work. The values found for the surface concentrations are essentially in agreement with those deduced from surface tension measurements using Gibbs adsorption theory. This result supports a monolayer adsorption distribution in the GaSn system.     

基于雷达海杂波的区域性非均匀蒸发波导反演方法

由于不同海域上空气象条件的不同, 海上蒸发波导在大尺度海面上空发生时通常是区域性非均匀的, 这一特性使得该环境中的电波传播特性相对于水平均匀的蒸发波导环境情况而明显不同, 因此, 进行区域性非均匀的蒸发波导探测反演对正确预测电波传播特性及提高雷达系统的工作性能具有重要的意义. 考虑到实际应用中蒸发波导信息获取手段的多样性, 将中尺度数值气象模式MM5预报的区域性蒸发波导修正折射率剖面作为先验信息, 提出了一种含该先验信息的区域性非均匀蒸发波导的雷达海杂波后验概率估计模型. 该模型使用主分量分析法对蒸发波导的水平非均匀性进行参数化建模, 然后通过贝叶斯理论将修正折射率剖面参数的先验概率分布、后验概率分布和似然函数联系起来, 利用雷达海杂波实现蒸发波导剖面参数的最大后验概率估计反演. 通过我国东海海域的实际区域性非均匀蒸发波导反演测试, 表明该模型能够以更高的精度实现区域性非均匀蒸发波导的反演.     

Atomistic theory of insulator surfaces and interfaces

Surface and interfaces play an important role in many processes including catalysis, corrosion and conductivity. However, they present special problems to their study by either experiment or calculation. Because of this, their properties are generally still poorly understood. This paper describes some recent calculations on the simulation of two-dimensional periodic boundaries where theory and experiment are interacting in a particularly useful way. Surface segregation of impurities or dopants is considered first and the calculations can predict a segregation energy and the Arrhenius behaviour for large crystals. Modification of this behaviour for high surface area materials is also considered. The surface vibrational modes provide a possible way of probing the surface and may give details of defective structures such as over-layers or segregation. The atom-scattering experiments also provide a valuable test of the potentials used in atomistic calculations. Finally, the structure of oxide grain boundaries is considered. In this case, calculation provides a way of interpreting experimental measurements on diffusion or conductivity in terms of atomic processes and boundary structure.     

Direct observation of the surface segregation of Cu in Pd by time-resolved positron-annihilation-induced Auger electron spectroscopy

Density functional theory calculations predict the surface segregation of Cu in the second atomic layer of Pd which has not been unambiguously confirmed by experiment so far. We report measurements on Pd surfaces covered with three and six monolayers of Cu using element selective positron-annihilation-induced Auger electron spectroscopy (PAES) which is sensitive to the topmost atomic layer. Moreover, time-resolved PAES, which was applied for the first time, enables the investigation of the dynamics of surface atoms and hence the observation of the segregation process. The time constant for segregation was experimentally determined to τ=1.38(0.21) h, and the final segregated configuration was found to be consistent with calculations. Time-dependent PAES is demonstrated to be a novel element selective technique applicable for the investigation of, e.g., heterogeneous catalysis, corrosion, or surface alloying.     

Optische Untersuchungen des Aufbaus von Kryolith-Aufdampfschichten

Non-homogenities in the structure of cryolite films (produced by evaporation in vacuo) are analysed, applying a previously described theory on measurements of spectral reflectivity near the Brewster angle and also with normal incidence. Thus some quantitative information is obtained about the variation of the refractive index within the layers; it seems that the absorption of water molecules plays an important part.     

Equilibrium segregation to terraces and steps

A method based on empirical interatomic potentials has been developed to calculate energies of segregation to low index (001) surfaces as well as to [110] and [100] steps on a (001) surface in simple (AB) binary alloys. The Baskes and Melius potentials have been used to model the A-A and B-B atomic interactions and a procedure has been outlined to derive an A-B interaction from the pure metal potentials. This approach has been used to compute the energy of segregation of gold, in an infinitely dilute nickel-gold alloy, to both terraces and steps. The results obtained are consistent with previous measurements of the anisotropy of surface segregation in that alloy.     

用分析型嵌入原子方法计算Pd-Au合金的热力学性质

用修正的分析型嵌入原子方法计算了PdAu二元合金系的稀溶解热、形成焓、表面能和表面聚集能,并将计算的热力学性质与实验结果或第一性原理计算结果进行了比较.     

Measurement of the charge state distribution of field evaporated ions: Evidence for post-ionization

Charge state distributions of field evaporated Si, Ni, Mo, Rh, W, Re, Ir and Pt ions have been measured as a function of electric field strength using the pulsed laser atom-probe. The results are compared to previously published theoretical calculations based on the post-ionization model of field evaporation. The agreement between theory and experiment is sufficient to establish the general validity of the post-ionization model. Measurements of the charge state distributions as a function of evaporation rate at constant temperature (increasing field) and constant field (increasing temperature) are also presented for W, Mo and Si. The observation that the fractional abundances of different charge states for the same material do not change with changing temperature indicates that the activation energies of desorption are the same for the different charge states and provides further support for the post-ionization model. The anomalous field evaporation behavior observed at high temperatures (e.g., desorption from localized areas on the surface and the occurrence of ionic clusters) is also discussed.     

Ion bombardment-induced subsurface composition modifications in alloys at elevated temperatures

Modifications of subsurface alloy composition during high-temperature sputtering were studied using a comprehensive kinetic model that Includes Gibbsian adsorption, preferential sputtering, displacement mixing, radiation-enhanced diffusion, and radiation-induced segregation. Numerical solutions were obtained for a Cu-40 at.% Ni alloy under 5-keV Ar⁺ ion bombardment as functions of time and temperature. The model predictions are in good qualitative agreement with recent experimental measurements.     

Electrical and pyrometric measurements of the decay of the anodetemperature after interruption of high-current vacuum arcs andcomparison with computations

Vacuum arcs of up to 20-kA peak current were investigated. The surface temperature of the anode area melted during the anode spot mode was determined by pyrometry and the evaluation of thermionic currents. The measurements confirm the computations of heating and cooling of the anode, taking into account heat conduction melting/solidification, and evaporation. Pyrometrically obtained temperatures agree well with theory. This gives confidence in the heat conduction model and also shows that the boiling temperature was reached during arcing. Another method evaluates currents of a milliampere value after arcs of several kiloamperes and postarc currents of amperes. Experimental observation (e.g., loading of the shield surrounding the contacts) and theoretical analysis of the interfering effects support the idea that the currents measured are due to thermionic emission     

Determination of surface roughness from light scattering measurements

We have measured the angular dependence of the p- and s-pollarized light scattered on films, which are supported by fine polished Suprasil substrates. To study the roughness of the surface we have varied the evaporation process and the thickness of the silver film. We quantitatively determine the roughness structure by using a non scalar scattering theory. The roughness structure is found in good agreement with measurements on the same films using ATR-techniques.