ESCA-studies of the structure and composition of the passive film formed on stainless steels by various immersion times in 0.1 M NaCl solution

This report deals with the structure of the passive film formed on stainless steels during immersion in a 0.1 M NaCl solution for various immersion times. The film was examined using ion etching and Electron Spectroscopy for Chemical Analysis (ESCA).Through the chemical-composition profiles a three-factor model was developed to describe the structure of the passive films: a hydrated layer in contact with the solution, an oxide layer consisting of iron and chromium oxides having maxima at depths of 3 and 10 Å, respectively, and a metallic layer enriched in nickel. There is a smooth transition between the layers, with the thickness of the outer two layers being about 15 A. The maximum concentration of iron in the oxidized state decreases with increasing immersion time concomitant with an increase in both the maximum concentration of chromium in the oxidized state and the maximum concentration of nickel in the metallic state.It is found that air-formed films have similar structures to films formed by exposure to the solution. Longer air exposure thickens the air-formed film, with the maximum of both oxidized iron and chromium nearly equal in magnitude in comparison with the solution formed films. Films formed by short-time exposure only to the solution are somewhat thinner indicating that the total history is important in determining the structure of these passive films, whereas passive films formed by exposures of 15 h to the solution are no longer strongly dependent on prior air exposure.     

ESCA-Studies of the structure and composition of the passive film formed on stainless steels by various immersion temperatures in 0.1 M NaCl solution

This paper deals with the structure and composition of the passive film formed on the surface of two commercial stainless steels during immersion in 0.1 M NaCl for 0.5 h at 25, 60, and 90°C. The data shows that the passive films formed at 60 and 90°C by short-time solution exposure are very similar to these formed at 25°C, and are consistent with the three-factor model described previously: a hydrated layer in contact with the solution, an oxide layer consisting of iron and chromium oxides having maxima at depths of 3 and 10 Å, respectively, and a metallic layer enriched in nickel. There is a smooth transition between the layers, with the thickness of the outer two layers being about 15 Å.     

ESCA-studies of the surface film formed on stainless steels by exposure to 0.1 M NaCl solution at various controlled potentials

After immersion in a 0.1 M NaCl solution for 1 h at various controlled potentials, the surface films formed on two commercial stainless steels, 18–12 and 29-4-2, have been studied using a surface analysis technique ESCA (Electron Spectroscopy for Chemical Analysis) combined with ion etching. The influence of controlled potential in the lower region, between the OCP and the critical pitting potential, on the structure and chemical composition of the passive film is in limited agreement with the prior work. At higher controlled potentials above the pitting potential, the surface films consist of two components: the passive film and corrosion products. Changes to both oxidized chromium and metallic iron form major differences in the depth profiles in comparison with the previous results with the passive film. At higher controlled potentials oxidized alloying elements tend to the higher oxidation states on the outermost part of surface together with a possibility of enhanced adsorption of chloride ions. There is a great amount of oxidized molybdenum and chloride ions mainly from the corrosion products on the surface at higher applied potential. Their contents increase with the controlled potential.     

Corrosion of stainless steels in chloride solution: An XPS investigation of passive films

Five commercial steels ranging from the martensitic stainless steel containing 12% chromium to the superferrite containing 29% chromium, 4% molybdenum, and 2% nickel have been studied by XPS. In addition, a pure iron-chromium alloy containing 7% chromium has been investigated. Armco iron and pure chromium (99.99%) were included as references. The formation of the passive films (or corrosion) occurred in deoxygenated 0.1 M NaCl solution (pH=5.6), from which the samples were transferred directly to the XPS chamber under controlled atmosphere (Ar). Concentration profiles (at.-%) of the alloy constituents in their oxidized and metallic states have been determined separately from the measured XPS depth profiles. Forc= 12% chromium the passive films have the following structure: there is a depletion of Cr in the inner region, followed by an enrichment (concentration maximum) in the central region of the films. The height of this maximum increases, and its position shifts towards the surface with increasing chromium content in the alloy. The outermost monolayers are rich in water and hydroxyl groups. Various significant properties of the films change drastically at the critical chromium concentration of about 12%. This behaviour is rather independent of the other components (Mo, Ni, Cu) present in the alloys and is discussed in terms of a phase transition in the films which is controlled by the chromium concentration.     

Passive films on stainless steels in aqueous media

The purpose of this paper is to provide a syntheses of experimental results regarding films formed on the surface of stainless steels. Such syntheses are attempted for the environments most studied. In each case the overview is presented with reference to the most important papers. Conflicting data are also presented and discussed. Based on the results of the prior studies, a four region model is proposed to describe the surface passive film and its breakdown.     

ESCA studies of nitrogen-containing stainless steels

ESCA examination of films formed on nitrogen-containing stainless steels after immersion in 0.1 M NaCl revealed that nitrogen was enriched in the outer 0.5 nm of the film at a concentration a few times higher than in the substrate. The N(1s) binding energy varied from 399.6–399.7 eV at the outermost surface of the film to 398.3–398.8 eV in the film at a depth of about 0.5 nm. This indicates a change in the chemical state of nitrogen upon exposure of the nitrogen-containing stainless steels to the solution, and furthermore, that the surface nitrogen enrichment could be of significance in the improved pitting resistance.     

ESCA studies of Ni-Cr alloys

ESCA examination on Ni-Cr alloys has shown that a thin passive film was formed after 24 h immersion in 0.1 M NaCl. The film contained only chromium oxide in the form of Cr₂O₃. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Both Ni-10 wt. % Cr and Ni-20 wt. % Cr alloys showed a slightly higher corrosion rate than the Ni-40 wt. % Cr alloy.The present ESCA study of the Ni-Cr system is part of our programme which involves an examination of the four binary alloy systems Fe-Si, Cr-Co, Ni-Cr, and Mo-Ni [1]. The aim is to correlate the structure and composition of the passive films formed in 0.1 M NaCl to the corrosion behaviour in the same solution.     

ESCA studies of Fe-Ti alloys

Fe-Ti alloys containing 5 to 47% Ti have been studied by ESCA. The alloys were exposed to 0.1 M NaCl for 24 h under open-circuit potential (OCP) during which passive films were formed. The passive film consisted of FeO and TiO₂ in the inner layer while Fe₂O₃, water, and hydroxyl groups were present in the outermost monolayers, irrespective of composition. The thickness of the passive layer was reduced from 4.4 nm to 1.0 nm with increasing Ti content. The amount of iron oxide in the passive layer also decreased with increasing Ti. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Alloys with 5–28% Ti showed a relatively high corrosion rate but that with 47 wt.% Ti had a much lower corrosion rates.     

A study of the compounds which are induced on the metallic target surface under the action of a pulsed laser plasmatron

The compounds induced on the surface of titanium and copper targets by a breakdown plasma produced by focused TEA-CO₂ high-repetition frequency laser pulses was studied by transmission electron microscopy and selected area diffraction in correlation with absorptivity data determined before and after laser irradiation. The possibility of using TEA-CO₂ lasers to produce complex thermal treatments was demonstrated for metallic surfaces by the modification of the physico-chemical properties at the sites of plasma action on these surfaces.     

Laser nitriding of iron: Influence of the laser parameters on the nitriding efficiency

Laser nitriding of Armco iron in nitrogen was studied for KrF-excimer-laser irradiation. The influence of the energy density and number of pulses on the nitrogen take-up and the nitride phases formed was investigated using Resonant Nuclear Reaction Analysis (RNRA) and Mössbauer spectroscopy. Besides the original a-iron, austenite-Fe(N), martensite-Fe(N),-Fe₂₊N, and-Fe₁₆N₂ were identified. The fraction of the e-phase was found to increase with the number of pulses and the energy density. A threshold energy density of 1.8(2) J/cm² for the laser nitriding process was found.     

Dependence of photoemission efficiency on the pulsed laser cleaning of Tungsten photocathodes, part 1: Experimental

3+ :YAG laser with 5^th harmonic generator, generating 16 ps duration pulses at 213 nm, with energies up to 0.5 mJ. Experimental results concerning the action of laser pulses, as well as the effects of residual pressure on the cleanliness of the photocathodes surface are presented and discussed. Influence of laser pulses and residual pressure on the work function of the metal are also investigated. Received: 15 April 1996/Accepted: 5 November 1996     

Influence of passive potential on the electronic property of the passive film formed on Ti in 0.1 M HCl solution during ultrasonic cavitation

The influence of the applied passive potential on the electronic property of the passive film formed on Ti at different potentials in 0.1 M HCl solution during ultrasonic cavitation, was investigated by electrochemical impedance spectra (EIS) and Mott–Schottky plot. The influence of the applied passive potential on the structure and composition of the passive film was studied by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The results showed that the applied passive potential can obviously affect the electronic property of the passive film formed on Ti during ultrasonic cavitation. The resistance of the passive film increased, and the donor density of the passive film decreased with increasing the potential. The flat band potential moved to positive direction and the band gap of the passive film moved to negative direction with increasing potential. AES and XPS results indicated that the thickness of the passive film increased evidently with applying passive potential. The passive film was mainly composed of the mixture of TiO and TiO₂. While the TiO₂ content increased with increasing the applied passive potential, and the crystallization of the passive film increased with the increased potential.     

Ar ion laser assisted chemical etching of via holes in tungsten sheets in air

Ar ion laser assisted chemical etching of 150 m thick annealed tungsten sheets in air is reported. The material removal mechanism involves local heating by the laser to temperatures in the range of 1000–1500 °C that causes rapid oxidation of the W to WO₃ which volatilizes readily. Holes with straight walls and slightly enlarged entrances near the surface were drilled with etch rates as high as 11.5 m/s at 13.8 W, and a minimum hole diameter of 21 m at 8.1 W. The diameters of the holes and the etch rates were measured and found to increase as a function of the laser power. It was found that by increasing the laser power above 11–12 W, no change was observed in the hole diameters which remained constant at about 31 m, whereas the etch rates continued to increase even faster than at low powers. Distinct adjacent holes of 25 m diameter could be drilled with their centers separated by as little as 60 m. This is therefore also the etching resolution in the present study.     

Growth of thin, crystalline oxide, nitride, and oxynitride films on NiAl and CoGa surfaces

At 300 K, an amorphous Al-oxide film is formed on NiAl(001) upon oxygen adsorption. Annealing of the oxygen-saturated NiAl(001) surface to 1200 K leads to the formation of thin well-ordered θ-Al₂O₃ films. At 300 K, and low-exposure oxygen atoms are chemisorbed on CoGa(001) on defects and on step edges of the terraces. For higher exposure up to saturation, the adsorption of oxygen leads to the formation of an amorphous Ga-oxide film. The EEL spectrum of the amorphous film exhibits two losses at ≈400 and 690 cm^-1. After annealing the amorphous Ga-oxide films to 550 K thin, well-ordered β-Ga₂O₃ films are formed on top of the CoGa(001) surface. The EEL spectrum of the β-Ga₂O₃ films show strong Fuchs-Kliewer (FK) modes at 305, 455, 645, and 785 cm^-1. The β-Ga₂O₃ films are well ordered and show (2×1) LEED pattern with two domains, oriented perpendicular to each other. The STM study confirms the two domains structure and allows the determination of the two-dimensional lattice parameters of β-Ga₂O₃. The vibrational properties and the structure of β-Ga₂O₃ on CoGa(001) and θ-Al₂O₃ on NiAl(001) are very similar. Ammonia adsorption at 80 K on NiAl(111) and NiAl(001) and subsequent thermal decomposition at elevated temperatures leads to the formation of AlN. Well-ordered and homogeneous AlN thin films can be prepared by several cycles of ammonia adsorption and annealing to 1250 K. The films render a distinct LEED pattern with hexagonal [AlN/NiAl(111)] or pseudo-twelve-fold [AlN/NiAl(001)] symmetry. The lattice constant of the grown AlN film is determined to be a_AlN= 3.11 Å. EEL spectra of AlN films show a FK phonon at 865 cm^-1. The electronic gap is determined to be E_g= 6.1±0.2 eV. GaN films are prepared by using the same procedure on the (001) and (111) surfaces of CoGa. The films are characterized by a FK phonon at 695 cm^-1 and an electronic band gap E_g= 3.5±0.2 eV. NO adsorption at 75 K on NiAl(001) and subsequent annealing to 1200 K leads to the formation of aluminium oxynitride (AlON). An oxygen to nitrogen atomic ratio of ≈2:1 was estimated from the analysis of AES spectra. The AlON films shows a distinct (2×1) LEED pattern and the EEL spectrum exhibits characteristic Fuchs-Kliewer modes. The energy gap is determined to be E_g= 6.6±0.2 eV. The structure of the AlON film is derived from that of θ-Al₂O₃ formed on NiAl(001). Received: 21 March 1997/Accepted: 12 August 1997     

Characterisation of passive films on 300 series stainless steels

The formation and breakdown of the passive films on stainless steels are mainly controlled by ionic and electronic transport processes. Both these processes are in part controlled by the electronic properties of the oxide film. Consequently, it is vital to gain a detailed perception of the electronic properties of the passive films together with structural and compositional information for a comprehensive understanding of mechanisms behind passivity and localised corrosion. As a step towards this goal the passive films formed on two main austenitic stainless steels AISI 316L and AISI 304L in borate solution were characterised by in situ Raman spectroscopy and photocurrent spectroscopy coupled with electrochemical measurements. This revealed the formation of an Fe-Cr spinel as the dominant constituent in the passive films with more Cr enrichment in the oxide film on 316L than that of 304L. Bandgap readings and semiconductivities of the two stainless steels suggested that three different applied potential regions existed; 800 mV(SCE) to 300 mV(SCE), 200 mV(SCE) to −300 mV(SCE) and below −500 mV(SCE).     

Observation of magnetic-field-enhanced excitation and ionization in the plume of KrF-laser-ablated magnesium

The influence of a magnetic field on the plume produced by KrF-laser ablation of magnesium in vacuum has been investigated using time-integrated photography, streak photography, spectroscopy and charge probes. Line emission spectra in the 200–600 nm interval and effective stream velocities for the plume obtained from the spatiotemporal emission from specific neutral and ion lines are reported. Time of flight velocities are also deduced from measurements using simple charge-collector probes. Changes in the plume structure and dynamics, and enhanced emission and ionization are observed in the presence of the field. A qualitative explanation of the results is given in terms of a magnetohydrodynamic model.     

Laser-induced etching of polycrystalline Al2O3TiC in KOH aqueous solution

Laser-induced etching of polycrystalline Al₂–O₃TiC material by a tightly-focused cw Ar ion laser has been investigated in a KOH solution with different concentrations. It is found that the KOH concentration can strongly affect the etching quality where low KOH concentration can result in rough and irregular patterns. Laser-induced etching of polycrystalline Al₂O₃TiC in a KOH solution is found to be a photothermal reaction in which a threshold laser power exists. With an appropriate set of etching parameters, well-defined grooves can be obtained with clean side walls and with an etching rate up to several hundred micrometers per second. The etching behavior is also found to depend on laser scanning direction. It is also found that the grains in the polycrystalline Al₂O₃TiC material play an important role in the etching dynamics and etching quality. This etching process is believed to be applicable to the formation of a slider surface of magnetic heads in the future.     

Low-nickel stainless steel passive film in simulated concrete pore solution: A SIMS study

Low-nickel and AISI 304 austenitic stainless steel (SS) passive films were studied using secondary ion mass spectrometry (SIMS). An alkaline Ca(OH)₂ saturated test solution containing different chloride additions was used at room temperature. The passive film formed consists mainly of an inner chromium-rich oxide layer and an outer iron-rich oxide layer. The chemistry of the passive film depends strongly on the chloride content in the alkaline solution. Under these exposure conditions nickel was detected in the outer part of the oxide, whereas chloride ions were not found in the passive film for either the low-nickel or AISI 304 SS alloys.     

Kinetics of a rough crystal face: Temperature dependence of the growth rate

We present measurements of the linear growth rate of the (110)-face of naphthalene growing from toluene solution at various equilibrium temperatures. Above a critical supersaturation the growth rate depends linear on the supersaturation and the (110)-face becomes round, which both indicates kinetic roughening. Within a temperature interval of 50° C the growth rate changes by nearly two orders of magnitude. The slope of the linear part of the growth curve can be described by an activated process, the activation energy turns out to be of the order of the evaporation enthalpy of naphthalene.     

Mechanism of and method to avoid discoloration of stainless steel surfaces in laser cleaning

2 O₃. Based on Auger Electron Spectroscopy analyses and optical microscopic observations, γ-Fe₂O₃ and Fe₃O₄ are formed on the stainless steel surface in laser cleaning in the air. Since laser can induce high temperature rise in stainless steel surfaces, the above phenomenon can be explained by a thermochemical reaction between oxygen in the air and the stainless steel. With increasing laser fluences, the temperature rise in the irradiated area of stainless steel surface increases, which enhances oxygen diffusion into the surface and oxidation reaction within the irradiated area. In order to avoid discoloration of stainless steel surfaces, a vacuum system was used to reduce the oxidation reaction between oxygen and stainless steel. Received: 7 June 1996/Accepted: 30 September 1996