X-ray photoelectron spectroscopic studies on oxidation behavior of nickel and iron aluminides under oxygen atmosphere at low pressures

Oxidation behaviors of NiAl, Ni₃Al, and FeAl under oxygen atmosphere at low pressures were studied by X-ray photoelectron spectroscopy (XPS). Clean surfaces of these aluminides were prepared by fracturing in an ultra high vacuum, and then the fractured surfaces were oxidized by exposing to high-purity oxygen at pressures up to 1.3 Pa without exposing to air. The oxides formed on NiAl and FeAl surfaces were Al₂O₃, whereas the oxide on Ni₃Al was NiAl₂O₄. Aluminum, nickel, and iron on clean surfaces were oxidized even at a pressure of 1.3 × 10⁻⁶ Pa. The oxidation evolves with an increase in the pressure of oxygen, and further oxidation of aluminum occurs prior to that of nickel or iron. The oxidation behaviors under such oxygen atmosphere were similar to those of the aluminides oxidized in air, and these behaviors could be predicted from thermodynamic consideration.     

Photoabsorption of alloys of Al with transition metals V,Fe, Ni and Cu and Pr near the AlL2,3-edge

The onset of Al 2p transitions of VAl₃, FeAl, NiAl, NiAl₃, CuAl₂, PrAl₂ and the disordered alloys VAl (16 at % Al, 28%, 41%), FeAl (11%) is shifted up to 1.1 eV. New pronounced structure develops close to the onset which for NiAl agrees with a density of states calculation by Connolly and Johnson.     

Optical properties of ternary β electronphases based on NiAl

Optical constants of several ternary β Hume-Rothery phases have been investigated as a function of the valence electron concentration and defect structure. The composition of the alloys was based on the β phase NiAl, the absorption spectrum of which is dominated by two maxima at 2·5 and 4 eV. The intensity of the 2·5 eV-ε₂ peak is considerably increased with increasing valence-electron concentration, whereas that of the other peak is decreased. The valence electron concentration is varied by substituting Cu for Ni in Ni_1?yCu_yAl or Si for Al in NiAl_1?ySi_y. The 2·5 eV absorption peak disappears when Co is substituted for Ni in Ni_1?yCo_yAl. The absorption peaks are attributed to interband transitions of electrons and are discussed according to the rigid band model. The absorption in the infrared is explained by the scattering of electrons from lattice defects and phonons. The position of the d-band relative to the Fermi level is discussed in connection with s-d band scattering.     

Growth of thin, crystalline oxide, nitride and oxynitride films on metal and metal alloy surfaces

This paper reviews the current knowledge of the properties of ultrathin, well-ordered oxide, nitride and oxynitride films grown on metal and metal alloy surfaces. Different modes of preparation are discussed and the vibrational and structural properties are summarized. The focus will be put onto Al-oxides grown on surfaces of the intermetallic alloys NiAl, Ni₃Al and FeAl. The properties of Ga₂O₃ grown on surfaces of the intermetallic alloy CoGa are also described. In these cases Al- and Ga-atoms, respectively, segregate from the substrate and react with adsorbed oxygen. The grown Al- and Ga-oxide films, respectively, order at elevated temperatures. Systems are also discussed where Al-oxide is grown by oxidation of Al-atoms which are evaporated on surfaces of the transition metals Re and Ru. The growth of transition metal oxides CoO (1 1 1)/Co (0 0 0 1), CoO (1 0 0)/Co (1 1 2 0), NiO (1 0 0)/Ni (1 0 0), NiO/Ni (1 1 1) and Cr₂O₃/Cr (1 1 0) are also presented. Thin films of Al- and Ga-nitride, respectively, can be grown on the base of the intermetallic alloy NiAl and CoGa by low-temperature adsorption of ammonia. These nitride films order at elevated temperatures. Al- and Ga-oxynitride, respectively, can be grown on surfaces of NiAl and CoGa substrates by adsorption on nitric oxide. An ordering of these ultrathin oxynitride layers is observed at elevated temperatures.     

Kinetics of phase transformations in a dispersed nickel-aluminum system

We have studied the kinetics of phase transformations in a dispersed nickel—aluminum system. By the use of quantitative metallography and x-ray diffraction we have studied the succession of phase transformations and the growth properties of the intermetallic phases at a temperature of 693 K, over anneal times up to 500 h. We have shown that in the powders the solid phase interaction first leads to formation of aluminum-rich phases NiAl₃ and Ni₂Al₃. This reaction proceeds most vigorously in the first 50 to 100 h, after which it shows down as the NiAl₃ phase dissolved and refractory phases appear which are enriched in nickel: NiAl and Ni₃Al. We have established the kinetic laws for the formation of NiAl₃ and Ni₂Al₃ in powder mixtures and for the growth of the Ni₂Al₃ phase in mixtures with nickel granules. Institute of Structural Macrokinetics, Russian Academy of Sciences Tomsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 31–36, July, 1996.     

ELS study on initial oxidation of Ni(100) surfaces

Electron energy loss spectra of clean and oxygen-covered Ni(100) surfaces were observed with concomitant measurements of LEED, work function change, and Auger peak height ratio O(KL_{2, 3}L_{2, 3})/Ni(L_{2, 3}VV). The observed electronic transitions are interpreted on the basis of primary election energy dependence, and of comparison with the loss spectrum for a UHV-cleaved NiO(100) surface and optical data of Ni. The observed loss peaks at 9.1, 14, and 19 eV in the clean surface spectrum are ascribed to the bulk plasmon of the 4s electrons, the surface plasmon, and the bulk plasmon of the coupled 3d + 4s electrons, respectively, and the weak but sharp peak at 33 eV is tentatively attributed to the localized many-body effect in the final state. Three oxygen-derived peaks at 6.0, 8.0, and 10.3 eV in the low oxygen exposure region (?4 L) are ascribed to the O 2p(e) → Ni 3d, O 2p(a₁) → Ni 3d, and O 2p → Ni 4s transitions, respectively. In the high oxygen exposure region (?50 L), the spectra become quite similar to that of the UHV-cleaved NiO(100) surface. The oxidation process consistent with LEED, Auger peak height ratio and work function change measurements is discussed.     

A study on the orientation inheritance in laminated NiAl produced by in situ reaction annealing

In order to promote the performance of B2 NiAl by texture control of orientation during in situ processing, phase transformation in laminated NiAl with bimodal grain size distribution manufactured by reaction annealing of Ni and Al foils has been studied. It turned out that there existed a Kurdjumov–Sachs orientation relationship (K–S OR) between parent Ni and product NiAl by crystallography analysis according to the electron backscatter diffraction (EBSD) results. The parent Ni did not transform to the product NiAl directly but via the formation of Ni₃Al firstly according to the transmission electron microscope (TEM) observation of the interface. This led to a new K–S OR between Ni₃Al and NiAl with a small atomic misfit, which made less residual stress generated through the formation of Ni₃Al than directly from the parent Ni.     

Epitaxial alloyed films out of the bulk stability domain: Surface structure and composition of Ni3Al and NiAl films on a stepped Ni(1 1 1) surface

We have studied by Spot Profile Analysis Low Energy Electron Diffraction (SPA-LEED) and Auger Electron Spectroscopy (AES) Ni–Al alloyed layers formed by annealing, around 780 K, Al deposits on a stepped Ni(1 1 1) surface. The surface structure and composition of the thin epitaxial Ni₃Al and NiAl films, obtained respectively below and above a critical Al initial coverage θ_c, differ markedly from those of corresponding bulk alloys.The Ni₃Al ordered films form in a concentration range larger than the stability domain of the L1₂ Ni₃Al phase. The NiAl films present a marked distortion with respect to the lattice unit cell of the B2 NiAl phase, which slowly decreases when the film thickness increases.It also appears that the value of θ_c depends on the morphology of the Ni(1 1 1) substrate, increasing from θ_c = 4.5 ML for a flat surface to θ_c = 10 ML for a surface with a miscut of 0.4°. This could be directly related to the presence of steps, which favour Ni–Al interdiffusion.     

Els investigations of the beginning oxidation on aluminum thin films

ELS and simultaneous quartz microbalance investigations have been carried out on clean aluminum and its surface oxide layer. The loss spectrum of clean Al is interpreted by the collective features of the conduction electrons: volume and surface plasmons, the latter being extremely sensitive to a small oxygen uptake. In the very beginning the oxidation is characterized by a loss peak at 7.3 eV which is attributed to a single electron transition from the O(2p) level to an unfilled state near the Fermi level of the metal. The decreasing intensity of the 7.3 eV loss and the increasing of a second loss at 19.2 eV with further oxygen uptake are tentatively explained by the formation of Al₂O₃ and interband transitions of amorphous Al oxide. The formation of A1₂O₃ is supported by the gravimetric measurements of oxygen mass gain.     

Surface studies of 2,4-pentanedione on γ-Al2O3/NiAl (1 0 0) and NiAl (1 0 0)

The chemical compound 2,4-pentanedione (Hacac) has been shown to etch the oxidized metal surfaces metals such as copper and nickel, but not their unoxidized surfaces. Here it is shown that on the γ-Al₂O₃/NiAl (1 0 0) surface (oxidized NiAl (1 0 0)) etching of aluminum occurs at 170 K and 750 K. Reflection-absorption infrared spectroscopy (RAIRS) is used to show that Hacac binds to both the clean, metallic and oxidized surfaces, but decomposition and combustion products dominate on the metallic surface and no etching occurs. The binding process that involves a deprotonation reaction of the enol species was identified by redshift in the carbonyl peaks and the appearance of an Al-H peak observed in the IR spectrum. The implication of these results is that there is both an unusual low temperature and high temperature etching of the alumina by bound acac.     

Adsorption of methanol on Ni3Al(1 1 1) and NiAl(1 1 0): A high resolution PES study

The adsorption of methanol on Ni₃Al(1 1 1) and NiAl(1 1 0) has been studied using high resolution photoemission spectroscopy (HR-PES) and density functional theory (DFT). Both methanol and methoxy are formed on these surfaces after the initial methanol exposure at low temperatures. Heating to 200 K leads to further formation of methoxy. On NiAl(1 1 0) two different methoxy species are observed where the first is formed upon methanol adsorption, and the other results from methanol decomposition during heating. The DFT calculations show that methanol and methoxy interacts with the Al atoms on both surfaces. Methanol is found to bond through the oxygen atom to the Al on-top site on Ni₃Al(1 1 1) and NiAl(1 1 0) with the C–O axis tilted with respect to the surface normal. On Ni₃Al(1 1 1) methoxy is situated in a 2Ni+Al hollow site, whereas on NiAl(1 1 0) the Al–Al bridge site is preferred.     

A phase-field study of the aluminizing of nickel

A quantitative phase-field approach for multiphase systems that is based upon CALPHAD free energies is used to model the aluminization of nickel wires, wherein vapour-phase alloying is used to deposit Al on the surface of the Ni wire and then the wire is annealed so that to remove all Al gradients and achieve a homogenous Ni-Al alloy. Both processes are modelled and numerical results are compared with experiments. It is found that the kinetics of both processes is controlled by bulk diffusion. During aluminization at 1273 K, formation and growth of intermetallics, Ni₂Al₃ NiAl and Ni₃Al, are strongly dependent on the Al content in the vapour phase. Ni₂Al₃ growth is very fast compared with NiAl and Ni₃Al. It is also found that an intermediate Al content in the vapour phase is preferable for aluminization, since the Ni₂Al₃ coating thickness is difficult to control. Ni₂Al₃ is found to disappear in a few minutes during homogenization at 1373 K. Thereafter, the NiAl phase, in which the composition is highly non-uniform after aluminization, continues growing until the supersaturation in this phase vanishes. Then, NiAl coating disappears concomitantly with the growth of Ni₃Al, which disappears thereafter. Finally, the Al concentration profile in Ni(Al) homogenizes.     

Growth of Ni-Al alloys on Ni(1 1 1), from Al deposits of various thicknesses: (II) Formation of NiAl over a Ni3Al interfacial layer

This paper describes the second part of a study devoted to the growth of thin Ni-Al alloys after deposition of Al on Ni(1 1 1). In the previous paper [S. Le Pévédic, D. Schmaus, C. Cohen, Surf. Sci. 600 (2006) 565] we have described the results obtained for ultra-thin Al deposits, leading, after annealing at 750 K, to an epitaxial layer of Ni₃Al(1 1 1). In the present paper we show that this regime is only observed for Al deposits smaller than 8 × 10¹⁵ Al/cm² and we describe the results obtained for Al deposits exceeding this critical thickness, up to 200 × 10¹⁵ Al/cm². Al deposition was performed at low temperature (around 130 K) and the alloying process was followed in situ during subsequent annealing, by Auger electron spectroscopy, low energy electron diffraction and ion beam analysis-channeling measurements, in an ultra-high vacuum chamber connected to a Van de Graaff accelerator. We evidence the formation, after annealing at 750 K, of a crystallographically and chemically well-ordered NiAl(1 1 0) layer (whose thickness depends on the deposited Al amount), over a Ni₃Al “interfacial” layer (whose thickness—about 18 (1 1 1) planes—is independent of the deposited Al amount). The NiAl overlayer is composed of three variants, at 120° from each other in the surface plane, in relation with the respective symmetries of NiAl(1 1 0) and Ni₃Al(1 1 1). The NiAl layer is relaxed (the lattice parameters of cc-B2 NiAl and fcc-L1₂ Ni₃Al differ markedly), and we have determined its epitaxial relationship. In the case of the thickest alloyed layer formed the results concerning the structure of the NiAl layer have been confirmed and refined by ex situ X-ray diffraction and information on its grain size has been obtained by ex situ Atomic Force Microscopy. The kinetics of the alloying process is complex. It corresponds to an heterogeneous growth leading, above the thin Ni₃Al interfacial layer, to a mixture of Al and NiAl over the whole Al film, up to the surface. The atomic diffusion is very limited in the NiAl phase that forms, and thus the progressive enrichment in Ni of the Al film, i.e. of the mean Ni concentration, becomes slower and slower. As a consequence, alloying is observed to take place in a very broad temperature range between 300 K and 700 K. For annealing temperatures above 800 K, the alloyed layer is decomposed, Al atoms diffusing in the bulk of the substrate.     

Investigation by X-ray photoelectron spectroscopy of the transient oxidation of NiAl

X-ray photoelectron spectroscopy (XPS) has been used to study the oxidation of NiAl in oxygen at atmospheric pressure. Prior to oxidation, the native oxide scale on the specimen was removed by ion sputtering and the specimens were (pre-)heated in vacuum before exposure to oxygen. At low oxidation temperatures (<750 K) scales consisted of Al₂O₃ and NiAl₂O₄, with a thin surface layer of NiO, but at higher temperatures were of Al₂O₃, apart from about 0.5 at % Ni. The Ni content in the latter case was constant throughout the scale and did not increase dramatically near the alloy/oxide interface. In the experimental conditions used in this study, initial formation of NiO and NiAl₂O₄ seems to be avoided at the higher oxidation temperatures ( > 750 K).     

铬和镍的添加对Fe3Al合金力学性能影响的DFT研究

利用第一原理研究了过渡金属元素 Cr 或 Ni 在 Fe₃Al合金中的优先占位行为及其合金化效应. 计算结果表明: Cr 或 Ni 的取代有助于Fe₃Al 合金体系更稳定, Cr 优先占据 Fe_I 位, Ni 优先占据 Fe_II位. Fe₂NiAl-II 具有最小的剪切模量G, 杨氏模量E和G/B值, 因此Fe₂NiAl-II合金的韧性、延展性最佳. 态密度和电荷密度图表明, 过渡金属元素的取代提高了它们与近邻基体原子之间的相互作用, 削弱了Al和Fe的相互作用.     

Electron spectroscopic studies of the oxidation of Fe/Ni alloys

The oxidation of polycrystalline samples of Fe/Ni alloys at 500° C has been studied by means of Auger electron spectroscopy (AES) and soft X-ray appearance potential spectroscopy (APS). Whereas the clean surfaces are always enriched with nickel, oxidation of samples with less than about 70% Ni causes a complete segregation of iron oxide (Fe₃O₄). Alloys containing more than 70% Ni are covered after oxidation with a mixed oxide layer which is identified (in accordance with general experience) with a spinel structure. In the latter case the “chemical shift” of the binding energies of the Ni 2p-electrons decreases from 1.5 to 0.7 eV with decreasing Ni content whereas the corresponding quantities of Fe remain essentially constant over the whole range of concentrations.     

Electronic and magnetic states in metallic compound—II: Electron transport and magnetic susceptibility in NiAl and FeAl

Electron transport and magnetic properties were investigated in NiAl and FeAl alloys in the vicinity of exact stoichiometry. The results as well as those of other workers were compared with recent augmented-plane-wave band calculations for NiAl, and semiquantitative agreement was found. With respect to impurity states in NiAl, it was concluded that transport anomalies, though definitely magnetic in origin, were not due to localized-magnetic moments on excess Ni atoms on Al sites. It was suggested that the anomalies may be due to subtle structural defects or such defects in combination with one of several intrinsic (non-impurity or defect) mechanisms. In the FeAl alloys, it was concluded that excess Fe atoms on Al sites (Fe_x atoms) carry a moment in the paramagnetic state of 7·8 μ_B. Negative magneto-resistance but no resistance minima effects were observed. The data, similar in several respects to those for dilute Rh(Fe) alloys, were interpreted in terms of antiferromagnetically coupled Fe_x atoms which lead to magnetic transitions of a spin-glass or mictomagnetic nature, that is, having no long-range order.     

Phases and reactive-diffusion kinetics for mixed Al-Ni powders

Reactive diffusion has been examined for mixtures of nickel and aluminum powders and also Ni-Al bimetal. An intermediate layer is formed at the boundary between particles, and the phase sequence in this in the direction from nickel to aluminum is NiAl-Ni₂Al₃-NiAl₃. The growth of this intermediate layer under isothermal conditions obeys the law xⁿ=gk(t–t₀), with n=3 for a mixture of the powders and n=2 for the bimetal. The energies of formation for the compounds NiAl, Ni₂Al₃, NiAl₃ are large, so the reactive diffusion in the powder mixtures is accompanied by considerable exothermic effects.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 34–40, November, 1973.     

Adsorption of methanol and methoxy on NiAl(1 1 0) and Ni3Al(1 1 1): A DFT study

The adsorption of methanol and methoxy on NiAl(1 1 0) and Ni₃Al(1 1 1) has been investigated using density functional theory (DFT). Optimised adsorption geometries and core level shifts are presented. On both surfaces we find that methanol binds to the Al on-top site via its oxygen atom and with the C–O axis tilted away from the surface normal. Methoxy also shows a preference for Al-dominated sites. On NiAl(1 1 0), we predict that methoxy adsorbs with its oxygen atom in the Al–Al bridge site, while it is determined to be adsorbed with its oxygen atom in a 2Ni + Al hollow site on Ni₃Al(1 1 1), closer to Al than Ni. Surface and adsorbate induced binding energy shifts in the Al 2p states are calculated and found to be in good agreement with experimental high resolution photoelectron spectroscopy results.     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术,分别沉积Ti和Ti/Al膜,经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序,分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27 关键词： 2薄膜')" href="#">多孔TiO₂薄膜 阳极氧化 紫外光吸收