Field-ion atom probe analysis

The atom-probe, introduced by Müller in 1967, is a combination of a field-ion microscope with a time-of-flight mass spectrometer. A specimen is prepared and imaged by field-ion microscopy in the normal manner, and the image of any feature of interest may be constrained to fall over an aperture in the imaging system. By applying a high-voltage pulse to the specimen the feature can be field-desorbed as a positive ion or ions. The desorbed ion travels down a flight-tube to a detector and from the measured flight-time its mass-to-charge ratio may be calculated. In this manner individual atoms on a specimen surface may be both imaged and identified. Using the process of field-evaporation, features in the bulk of the specimen may be brought to the surface and analysed. The atom-probe work at Cambridge has been directed both at the development of the instrumentation associated with this technique of microanalysis and at its application to small-scale segregation problems of metallurgical importance. An electronic timing device and automatic data-handling system has been built so that large numbers of ions may be analysed. The apparatus will be described and some of the experimental results obtained to date will be presented. These experiments include the segregation of carbon to grain-boundaries in iron, the clustering of titanium atoms in a nickel-titanium alloy and the analysis of small precipitates in steels. The processes occurring at the specimen surface during field-evaporation have also been studied.     

烧结β型Ti-Nb合金中由间隙原子引起的Snoek弛豫

用粉末冶金方法制备了不同Nb含量的Ti-Nb合金.用美国TA仪器公司的动力学分析仪Q800以单臂振动模式研究了不同Nb含量和不同热处理以及不同测量参数下的Ti-Nb合金的内耗行为,用X-射线衍射检测了不同样品的微观结构.实验表明,在水淬的和烧结态的Ti-Nb合金的内耗-温度曲线上均发现了弛豫型的内耗峰,这个内耗峰的高度与Nb含量有关,在低Nb含量的Ti-Nb合金样品中不出现,水淬样品内耗峰的最大值出现在Ti-35.4 wt.%Nb (以下称Ti-35.4Nb)的合金中,烧结态样品的内耗峰高度在实验成分范围内单调地随Nb含量而增加.水淬的Ti-35.4Nb合金的弛豫参数分别是激活能H_(wq)=(1.67±0.1) eV和指数前因子τ_(0wq)=1.1×10~(-17±1) s.另外,内耗峰的高度也与热处理有关,水淬的Ti-35.4Nb合金比具有相同成分的烧结态的合金的内耗峰高得多,淬火温度对内耗峰高度也有影响.研究发现,这个内耗峰与Ti-Nb合金中的β相有关,峰高取决于β相的稳定性及其含量,当β相的稳定性降低以及β相的量增加时,峰高增加.水淬Ti-35.4Nb合金中的β相是亚稳状态的β相(β_M),时效时β_M能转变成稳定的α相和稳定β相(β_S),烧结态合金中的β相是β_S.不同热处理状态下Ti-35.4Nb合金样品的微观结构的不同导致了内耗峰高度的差别.从微观结构分析,在淬火的合金中,峰高最大值出现在35 wt.%Nb含量附近的现象是由β相的稳定性和β_M相的量随Nb含量变化引起的.在烧结态的Ti-Nb合金中,峰高单调地随Nb含量的增加而增加的情况是由β_S的量决定的.在循环应力作用下,β_M或β_S相晶格点阵中氧原子的跳动和氧原子与替代原子的相互作用是产生内耗峰的根源.     

Sputtering of ordered nickel-aluminium alloys: I. Introduction and preferential sputtering of Ni3Al

A combination of several surface-sensitive microanalytical techniques have been applied to the study of selective or preferential sputtering by inert gas ion bombardment of aluminium from binary ordered nickel-aluminium alloys. Two discrete intermetallic compounds, Ni₃Al (this paper) and NiAl (the companion paper) have been examined in order to provide information regarding the contribution of surface binding states to sputter mechanisms. The use of atom-probe field-ion microscopy for analysis of ion-sputtered surfaces has permitted the depth of bombardment-induced composition profiles to be estimated and comparisons to be drawn between these depth profiles and those obtained by conventional surface analysis techniques. Studies of preferential sputtering in ordered structures have provided information through atom-probe analysis of fundamental and superlattice oriented specimens about composition profiles and bombardment-induced disordering processes. Consideration of these data have led to conclusions that two distinct “equilibria” may be involved in the formation of super-induced altered layers.     

Molecular dynamics simulations of supercooled and amorphous Co(100-x)Zr(x): atomic mobilities and structural properties

Molecular dynamics simulations are reported on Co(100-x)Zrx in the complete range of compositions. The simulations are based on Hausleitner-Hafner potentials. For the glassy states of the alloys, a comparison of simulated pair-correlation functions with experimental data is presented. Diffusivities were evaluated for the liquid and supercooled melt from isothermal simulation runs. Therefrom a strong dependency on alloy composition is found for the critical temperature T(c)(x) of the mode-coupling theory. Lines of constant averaged diffusivity in the supercooled melts scale closely with this temperature. The ratio of the component diffusivities shows a more involved variation with temperature and composition. These variations reflect differences in the amorphous structure of the alloys, which are quantified in terms of the chemical short-range-order at the level of tetrahedral clusters.     

Nearest neighbour diagnostic statistics on the accuracy of APT solute cluster characterisation

Diagnostic statistics and information theory techniques have been developed to investigate the accuracy to which solute clusters characterised in atom probe tomography (APT) data can reflect the true nature of the physical clusters in the original specimen. Simulated atom-probe datasets representing a range of atomic solute clustering within a pseudo-binary alloy upon an fcc aluminium lattice were generated for the study. The effectiveness of partitioning the APT-like simulated data based upon a binary classification defined by a distance threshold d _max upon the kth nearest neighbour distance distribution was investigated. Information theory was also used to optimise the selection of the threshold d _max. Analysis of variation was performed upon a factorial design of data simulations with low and high levels of: solute concentration; short-range order; and background to the mass-to-charge-state-ratio spectrum. This meta-analysis showed that the background levels have a significant compromising effect upon the binary classification in low solute systems with relatively low or random levels of clustering. Although the random clustering of higher solute concentrations is better analysed, significantly non-random clustering in both low and high solute concentrations is analysed well despite the presence of high levels of background. A meta-analysis of the binary classification upon a simulated dispersion of coherent precipitates within a similar matrix was also undertaken. Optimal k and d _max parameters are likely a dependent upon the physical dimensions of precipitate size as well as the precipitate/matrix solute concentrations.     

The structural,elastic,and electronic properties of Zr_x Nb_(1-x)C alloys from first principle calculations

The structural,elastic,electronic,and thermodynamic properties of Zr x Nb1-x C alloys are investigated using the first principles method based on the density functional theory.The results show that the structural properties of Zr x Nb1-x C alloys vary continuously with the increase of Zr composition.The alloy possesses both the highest shear modulus(215 GPa)and a higher bulk modulus(294 GPa),with a Zr composition of 0.21.Meanwhile,the Zr0.21Nb0.79C alloy shows metallic conductivity based on the analysis of the density of states.In addition,the thermodynamic stability of the designed alloys is estimated using the calculated enthalpy of mixing.     

The occurrence of field-induced surface vacancies on iridium field-ion microscope specimens

As part of a study of the field-ion imaging characteristics of some dilute iridium-based alloys, the occurrence of “vacant-site” contrast in micrographs from specimens of two purities of iridium (one nominally oxygen-free) has been investigated. Detailed small field-evaporation sequences have been performed and the resulting helium-ion micrographs analysed by a method which allows the dependence of contrast events on various parameters to be determined. On all the types of poles studied, the surface vacancy concentration was observed to be orders of magnitude above the expected bulk level characteristic of the specimen materials' thermomechanical history. The critical parameters governing the concentrations of these events are discussed and a model introduced to explain the generation of these vacant-sites which are assumed to be field-evaporation-induced surface artefacts. At worst the observed vacancy concentrations are 1–2% of the sites observed in the high-field {420} array of the fcc field-ion image, and vary with several parameters. Such observations imply important limitations on the technique of field-ion microscopy for studying certain point defect distributions.     

Transformation strains in martensitic phase transitions of Co alloys

The thermally induced fcc → dhcp martensitic phase transformation was investigated in two different CoFe alloys (Co-5.75 and 6.0at.% Fe). Analysis by transmission electron microscopy methods yields that in both alloys the transformation proceeds by the movement of transformation dislocations (partials) that are correlated on an atomic scale; partials on adjacent close packed planes interact and combine to a paired partial. Two different and competitive modes of the transformation were observed. In Co-6.0 at. % Fe all the paired partials have the same Shockley partial Burgers vector adding up their long-range strain fields (transformation mode A). Contrary to this, in Co-5.75 at.%Fe paired partials of different Burgers vectors are compensating their long-range strain fields on an atomic scale (transformation mode B). The mode of the transformation seems to depend on both the parameters of the material and the experimental conditions.     

Phase characterization in the Fe−Co−V and Fe−Co−Nb systems

Two distinct phases of the Fe?Co?Nb and three of the Fe?Co?V systems have been studied by means of X-ray diffraction and Mössbauer spectroscopy. The dependence of the lattice parameter of the alpha phase on the nominal solute content in equiatomic FeCo together with the alterations of the Mössbauer spectra have shown a very limited solubility of niobium in alpha FeCo. There are indications that the solubility of vanadium in alpha FeCo increases with increasing nominal content of solute in the alloy. A mechanism involving the withdrawal of cobalt from the alpha matrix to form a phase rich in Co and V (gamma) is proposed to explain such a varying solubility. The vanadium content of the sigma phase in equiatomic FeCo alloys with 22 wt% V is proposed to be less than 50 at%.     

Interaction between interstitial hydrogen and substitutional solute atoms in solid solutions of niobium-base ternary alloys

The interaction between interstitial hydrogen and substitutional solute atoms has been investigated by the measurements of the hydrogen solubility and the influence of hydrogen charging on the half-width of the X-ray reflection lines in pure Nb, Nb-5%V, Nb-5%Mo and Nb-5%Ta alloys. In Nb-5%V and Nb-5%Mo alloys, the solubility considerably increases with respect to pure Nb. On the other hand, the solubility hardly changes in Nb-5%Ta alloy. With addition of hydrogen, the half-widths in pure Nb and Nb-5%Ta alloy show a monotonic increase, but in Nb-5%V and Nb-5%Mo alloys they show a minimum. The results are explained by the interaction of hydrogen with substitutional solute atoms. The interaction is considered to be caused by the internal strain induced by the difference in atomic radii between substitutional and solvent (Nb) atoms.     

Atom-probe field-ion microscopy of GaAs and GaP

The atom-probe field-ion microscope (atom-probe FIM) was applied for the first time to GaAs and GaP which belong to the III–V compound semiconductors. The general character of the pulsed field-evaporation of GaAs and GaP was quite similar. Ga field-evaporated predominantly in the form of singly charged ions. As and P also field-evaporated mainly as singly charged ions, but their abundances were small compared with Ga⁺. It appears that As (or P) atoms can field-evaporate more easily in the form of AsO⁺ (or PO⁺) in the presence of oxygen on the surface. In all experiments, GaAsⁿ⁺ and GaPⁿ⁺ were rarely detected. After chemical etching the surfaces were covered with oxide films and various oxide ions were detected. The abundance of oxide ions dramatically decreased after field evaporation in hydrogen. No distinct difference between the 〈111〉 orientations of these materials which have zinc-blende structure could be observed. Most of the experimental results obtained were explained in terms of the existing theory of field evaporation. It was concluded that field penetration effects have a considerable influence on the field evaporation processes of these materials as well as on the field ionization processes.     

Low temperature magnetic and magnetostrictive properties in Pr(Fe_(1-x)Co_x)_(1.9) cubic Laves alloys

The structures,spin reorientations,magnetic,and magnetostrictive properties of the polycrystalline Pr(Fe_(1-x)Co_x)_(1.9)(x=0–1.0)cubic laves phase alloys between 5 K and 300 K are investigated.Large low-field magnetostrictions are observed at 5 K in the alloys with x=0.2 and 0.4 due to the low magnetic anisotropies of these two alloys.A large negative magnetostriction of about-1130 ppm is found in PrCo_(1.9) alloy at 5 K.The magnetizations of the alloys with 0≤x≤0.6decrease abnormally at the spin reorientation temperature T_(sr),and an abnormity is detected in the alloy with x=1.0 at its Curie temperature T_c(45 K).The substitution of Fe by Co increases the value of T_(sr) in the alloy with x value increasing from 0.0 to 0.4,and then reduces the value of Tsr with x value further increasing to 0.6.     

ESCA studies of Cr-Co alloys

ESCA examination of films formed on Cr-Co alloys after immersion in 0.1M NaCl for 24 h has shown that the thickness of passive films decreased with an increase in chromium content. Surface films consisted of chromium and cobalt oxides as Cr₂O₃ and CoO. The amount of CoO in the surface film of the alloy was decreased with an increase in chromium but Cr₂O₃ was found at a greater depth in the passive film at any composition. Cr₂O₃ was a major component of the surface film when the chromium content in the alloy was 10% or higher. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate. Both Co-10 wt.% Cr and Co-30 wt.% Cr alloys investigated showed a lower corrosion rate than the Co-5 wt.% Cr alloy. Corrosion rate measured could be correlated to the surface film composition and structure as determined by ESCA.     

On the formation of the nanostructure in Fe80M7B12Cu1 (M: Ti, Ta, Nb, Mo) alloys

The dependence of the formation of the nanocrystalline bcc-Fe phase on the alloy composition is studied for Fe₈₀M₇B₁₂Cu₁ (M: Ti, Ta, Nb, Mo) alloys. The rf-Mössbauer technique is used to determine the optimal soft magnetic properties. This technique allowed us to compare anisotropy fields in each phase present in the composite alloys. The smallest anisotropy field was found in the bcc-Fe nanograins formed in Nb- and Mo-containing alloys.     

Atomic Scale Chemistry of α2/γ Interfaces in a Multi-Component TiAl Alloy

We report on the distribution of micro-alloying elements in a multi-component TiAl-based alloy. The specimen contains 3 at.% Nb, 1.5 at.% Cr, 0.5 at.% Mn, 0.6 at.% (W + Hf + Zr), and 0.2 at.% each of B, C, and O. The distributions of all micro-alloying elements with respect to the heterophase interface between α₂ and γ lamellae are analyzed with a three-dimensional atom-probe (3DAP) microscope. All the elements partition except boron, which resides primarily in boride precipitates. Oxygen, C, Mn, and Cr partition to the α₂-phase, whereas Nb and Zr partition to the γ-phase. Both W and Hf exhibit excess concentration values within ca. 7 nm of the lamellar interface in the α ₂-phase, and their near interfacial excesses are 0.26 and 0.35 atoms nm^?2, respectively.     

Near surface composition of some alloys by X-ray photoelectron spectroscopy

Chemical compositions of the alloys of CuNi (Cu_0.10Ni_0.90, Cu_0.30Ni_0.70, Cu_0.70Ni_0.30) and BiSb (Bi_0.80Sb_0.20, Bi_0.64Sb_0.34, Bi_0.55Sb_0.45) are determined by X-ray photoelectron spectroscopy. The stoichiometries are determined and are compared with the bulk compositions. Possible sources of systematic errors contributing to the results are discussed. Errors arising out of preferential etching in these alloys have been investigated. It has been inferred from such studies that the preferential etching does not enrich the surface composition with a particular component for the two systems reported here. Quantitative results of CuNi system indicate that the surface regions of the Cu_0.70Ni_0.30 alloy is Cu-rich, although no such evidence is observed in case of BiSb system.     

Microstructural evolution during containerless rapid solidification of Co-Si alloys

The Co-12%Si hypoeutectic, Co-12.52%Si eutectic and Co-13%Si hypereutectic alloys are rapidly solidified in a containerless environment in a drop tube. Undercoolings up to 207K (0.14T_E) are obtained, which play a dominant role in dendritic and eutectic growth. The coupled zone around Co-12.52%Si eutectic alloy has been calculated, which covers a composition range from 11.6 to 12.7%Si. A microstructural transition from lamellar eutectic to divorced eutectic occurs to Co-12.52%Si eutectic droplets with increasing undercooling. The lamellar eutectic structure of the Co-12.52%Si alloy consists of εCo and Co_3Si phases at small undercooling. The Co_3Si phase cannot decompose completely into εCo and αCo_2Si phases. As undercooling becomes larger, the Co_3Si phase grows very rapidly from the highly undercooled alloy melt to form a divorced eutectic. The structural morphology of the Co-12%Si alloy droplets transforms from εCo primary phase plus lamellar eutectic to anomalous eutectic, whereas the microstructure of Co-13%Si alloy droplets experiences a `dendritic to equiaxed' structural transition. No matter how large the undercooling is, the εCo solid solution is the primary nucleation phase. In the highly undercooled alloy melts, the growth of εCo and Co_3Si phases is controlled by solutal diffusion.     

Effect of solidification temperature range on the dendritic growth mode

Electromagnetic levitation technique was used to undercool bulk samples of Co-20% Cu and Co-60% Cu alloys and high undercoolings up to 303 and 110 K were achieved,respectively.The dendritic growth velocities were measured as a function of undercooling.The dendrite growth velocity of the Co-20% Cu alloy was much higher than that of the Co-60% Cu alloy.The experimental data were analyzed on the basis of the LKT/BCT dendritic growth model by taking into account non-equilibrium interface kinetics.It has been re...     

Quantitative auger electron analysis of homogeneous binary alloys: Chromium in gold

Quantitative Auger electron analysis of Cr/Au alloys with up to 20% Cr has been accomplished. The surface composition of scribed areas were compared to bulk compositions and it was shown that corrections for variation of density, escape depth, and electron backscattering must be included; these corrections change the measured surface Cr concentrations by approximately 15%. Alloy sputter yield ratios have been calculated from surface concentrations after sputtering with Ar or Ne (0.5, 1.0, 1.5, and 2.0 keV). The sputter yield ratio of Cr to Au was 0.5 at 1% Cr (significant preferred sputtering) but was near unity at 20% Cr (no preferred sputtering). The sputter yield ratio was nearly independent of ion species and ion energy. The 2 keV argon ion sputter yields for pure Cr and Au were determined to be 2.0 and 7.9 atoms/ion, respectively. However, the 2 keV argon ion sputter yield for Au in the alloys drops rapidly from 7.9 atoms/ion for pure Au, to 5 atoms/ion at 10–20% Cr. The sputter yield for Cr in alloys (5 atoms/ion) is relatively independent of composition and is 2.5 times higher than the yield of pure Cr. No simple model is known by which pure elements sputter yields could be used to predict alloy sputtering behavior.     

Backscattering correction for quantitative Auger analysis: II. Verifications of the backscattering factors through quantification by AES

The validity and utility of the backscattering correction factors obtained from Monte Carlo calculations for quantitative analysis by Auger electron spectroscopy (AES) were examined through practical quantification of surface concentrations of binary alloys. Quantifications were attempted, first, to access the surface composition of a sputter-deposited NiPt layer, which is probably the most appropriate test-sample with known surface composition for surface analysis. The quantification by AES has led to the result that the surface composition of the layer agrees well with the bulk composition of the sputtered NiPt alloy, as expected. The composition of a sputtered AuCu alloy surface was, then, examined according to the same correction procedure as for the NiPt layer, leading to the confirmation that no preferential sputtering is observed for AuCu alloys by AES as Färber et al. reported.