In situ characterization of localized corrosion of stainless steel by scanning electrochemical microscope

Scanning electrochemical microscopy (SECM) area scan measurements have been performed to investigate the localized corrosion of type 304 stainless steel in neutral chloride solution. Variations in the Faradaic current measured at selected tip potential values can be related to changes in the local concentration and electrochemical activities of electroactive species involved in corrosion reactions occurring at the substrate as a function of immersion times of the substrate and polarized currents or potentials applied on the substrate. To further verify the results acquired from cyclic voltammetric experiments, SECM measurements were employed to in situ study the compositions and electrochemical activity distribution profile of the pitting corrosion products of stainless steel. It has been demonstrated that the combination of feedback current mode with generation-collection (G-C) mode of SECM is suitable to elucidate the possible reaction mechanisms and paths involved in the localize corrosion of stainless steel in neutral chloride solution.     

Characterisation of passive films formed on low carbon steel in borate buffer solution (pH 9.2) by electrochemical impedance spectroscopy

The comprehension of passivity and its protective character against corrosion is closely connected with the electronic properties of passive films. Passive films formed anodically on carbon steel in borate/boric acid solution, pH 9.2, have been characterised by electrochemical impedance spectroscopy (EIS). Mott-Schottky plots and impedance measurements were made on films formed at different potentials and times. The investigation allowed the determination of the semiconductive properties of the films. The results of the capacitance response indicate that the passive films behave like highly doped n-type semiconductors, showing that the passive film properties are dominated by iron. The value of donors density (N_D) for the passive film is of the order of 10²¹ cm⁻³ and decreases with increasing formation time and potential, indicating that defects decrease with increasing film thickness. Based on the information about the physical phenomena, an equivalent circuit is proposed to fit the experimental data, leading to determination of anodic film capacitance and film resistance.     

Role of surface reactions in the transpassive dissolution of ferrous alloys in concentrated H3PO4

The transpassive dissolution of a range of ferrous alloys (Fe–12% Cr, Fe–12% Cr–5% Mo, Fe–25% Cr, Fe–25% Cr–10% Mo) in concentrated H₃PO₄ was studied within the frames of an investigation of electropolishing mechanisms. Measurements by the contact electric resistance (CER) technique have demonstrated that in the transpassive region, the resistance of the anodic film first decreases with increasing potential due to enhanced conductivity of that film and then increases at higher potentials, indicating transpassive film growth. The release of soluble Cr(VI) as detected by rotating ring–disc measurements is the higher, the higher the Cr content in the alloy, and further increases upon addition of 10% Mo to the Fe–Cr alloys. Impedance spectra in the transpassive region have been found to include contributions both from the anodic film and a multistep transpassive dissolution reaction at the film/solution interface. The results were interpreted using a generalised model of transpassive dissolution. The kinetic parameters of the process were determined and the influence of alloy composition on their values is discussed in relation to the processes of anodic surface treatment.     

Room and high-temperature scanning tunnelling microscopy and spectroscopy (HT-STM/STS) investigations of surface nanomodifications created on the TiO2(1 1 0) surface

High-temperature scanning tunnelling microscopy, scanning tunnelling spectroscopy and current imaging tunnelling spectroscopy (HT-STM/STS/CITS) were used to study the topographic and electronic structures changes due to surface modifications of the TiO₂(1 1 0) surface caused by the STM tip. In situ high-temperature STM results showed that the created modifications were stable even at elevated temperatures. The STS/CITS results showed the presence of energy gap below the Fermi level on the untreated regions. The disappearance of energy gap below the Fermi level on the modifications created by the tip was observed. It is assumed that the presence of the tip can change the chemical stoichiometry of the surface from TiO_2−x towards Ti₂O₃.     

Scanning tunnelling microscopy and spectroscopy of the reduced TiO2(1 0 0) surface

Scanning tunnelling microscopy and current imaging tunnelling spectroscopy were used to study the topographic and electronic structure of a reduced TiO₂(1 0 0) surface. The STM results showed that the TiO₂(1 0 0) surface is capable to form (1 × 7) reconstruction which can transform to (1 × 3) reconstruction due to reoxidation of the surface. The CITS results showed that the (1 × 7) reconstruction is much more metallic in compared to the (1 × 3) reconstruction showing pronounced surface states at energy 1.3 eV and 0.8 eV below the Fermi level and at energy 1.0-1.2 eV above the Fermi level.     

Mossbauer analysis of deformation dissolution of the products of cellular decomposition in high-nitrogen chromium manganese austenite steel

Methods of Mossbauer spectroscopy and electron microscopy analysis of high-nitrogen chromium manganese steel FeMn₂₂Cr₁₈N_0.8 have been used to investigate the processes of dissolution of the products of cellular decomposition in austenite matrix upon severe deformation under the conditions of dry sliding friction and shear under pressure in Bridgman anvils. Deformation-induced redistribution of nitrogen from the chromium nitrides to interstitial positions of the quenched and preliminary aged steel has been determined. According to the data of Mossbauer analysis the depth of dissolution of chromium nitrides and the increase of content of nitrogen in steel matrix upon friction is 10?μn and more. Aging decreases the amount of nitrogen which transfers to the solid solution under deformation. This is a factor of the enhanced adhesive wear in the aged samples.     

Structural properties of TiN films grown on stainless steel substrates by a reactive radio-frequency sputtering technique at low temperature

TiN thin films were grown on stainless steel substrates by using the reactive radio-frequency magnetron-sputtering technique at relatively low temperature (200°C) using Ti and N₂. The deposition rate of the TiN film increased linearly with increasing applied radio-frequency power, and it decreased with increasing partial-pressure ratio of the N₂ gas to the Ar gas. Scanning electron microscopy (SEM) showed that the surfaces of the TiN films had very smooth morphologies. The TiN thin film had good stoichiometry for a partial-pressure ratio of 0.05. The stoichiometry of the TiN films and the interface qualities of the TiN/stainless steel heterostructures were investigated by Auger electron spectroscopy (AES) measurements. Auger depth profiles indicated that the compositions of the as-grown films consisted of titanium and nitrogen uniformly distributed throughout the films and that the films exhibited smooth interfaces. The interface quality of the TiN films to the stainless steel substrates were improved by annealing. These results indicate that annealed TiN thin films grown on stainless steel substrates hold promise for potential applications in advanced ceramic devices.     

Thickness dependence of the surface plasmon dispersion in ultrathin aluminum films on silicon

The collective excitation in Al films deposited on Si(1 1 1)-7 × 7 surface was investigated by high-resolution electron-energy-loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). At the Al film thickness d < 10 ML, the surface plasmon of Al film has only a small contribution to the observed energy-loss peaks in the long wavelength limit (q_∥≈0), while its contribution becomes significant for q_∥>d^-1. More interestingly, for thin Al films, the initial slope of the surface plasmon dispersion curve is positive at q_∥∼0, in a sharp contrast to bulk Al surface where the energy dispersion is negative. These observations may be explained based on the screening interaction of the space charge region at the Al-Si interface.     

Enhanced transient reactivity of an O-sputtered Au(1 1 1) surface

The interaction of SO₂ with oxygen-sputtered Au(1 1 1) (θ_oxygen  0.35 ML) was studied by monitoring the oxygen and sulfur coverages as a function of SO₂ exposure. The morphology of the sputtered Au is relatively smooth on a long length scale, but rough on a finer scale with islands averaging 15 nm. The rough surface is not stable to scanning with the STM. Two reaction regimes were observed: oxygen depletion followed by sulfur deposition. An enhanced, transient sulfur deposition rate is observed at the oxygen depletion point. This effect is specifically pronounced if the Au surface is continuously exposed to SO₂. The enhanced reactivity towards S deposition seems to be linked to the presence of highly reactive, under-coordinated Au atoms. Adsorbed oxygen appears to stabilize, but also to block these sites. In absence of the stabilization effect of adsorbed oxygen, i.e. at the oxygen depletion point, the enhanced reactivity decays on a timescale of a few minutes. These observations shed a new light on the catalytic reactivity of highly dispersed gold nanoparticles.     

Scanning probe microscopy studies of PbS surfaces oxidized in air and etched in aqueous acid solutions

Natural n-type PbS single crystals have been studied using AFM, STM and STS after long-term oxidation in air at ambient temperatures and extensive etching in aqueous acid solutions, in contrast to previous work devoted to initial corrosion of fresh surfaces. The exposure of PbS to atmosphere at high relative humidity for several days yields widespread loose oxidation products; the process is much slower at low humidity. Surface morphologies diverge after the treatment in 1 M perchloric and hydrochloric acid solutions at room temperature and become widely different at elevated temperatures, displaying commonly etch pits up to several micrometers in size and depth along with rather uniformly distributed 20-100 nm protrusions of PbS phase. The changes both in topography and semiconducting properties of PbS found by tunneling spectroscopy have been explained in terms of the non-uniform distribution of donor- and acceptor-type defects D⁺/D⁻ in the metal depleted surface layer, which are generated by chemical reactions and, in turn, determine the rates of the PbS corrosion. In particular, the D⁻ centers exhibit a self-catalyzing effect on the non-oxidative local dissolution of PbS in HCl media, resulting in the deep etch pits.     

Electrochemical behavior of Al2O3/Al composite coated Al electrodes through surface mechanical alloying in alkaline media

The behavior of $A{l}_2{O}_3/Al$ composite coated Al electrodes fabricated by surface mechanical alloying ‘SMA’ was studied. The work was accomplished using Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) techniques in alkaline media $2MKOH$ were done at room temperature. Results show hydroxyl ions accumulate on the surface due to Al deformation micro cavities filling with $A{l}_2{O}_3$ until full charge blockage reached. A barrier cover layer development causing an increase of both resistance and capacitance as it becomes more stable and thinner with exposure time increase. Migrating hydroxyl ion inside micro cavity changed its composition from Al₂O₃ to stable tetrahedral $Al{\left(OH\right)}_4^{?}$ aluminate ions. Therefore future benefits could be reached by developing such surfaces having charge accumulation that enables environmental interaction.     

Selective oxidation of dual phase steel after annealing at different dew points

Hot galvanized steels have been extensively used in the automotive industry. Selective oxidation on the steel surface affects the wettability of zinc on steel and the grain orientation of inhibition layer (Fe-Al-Zn alloy) and reduces the iron diffusion to the zinc layer. The aim of this work is to identify and quantify selective oxidation on the surface of a dual phase steel, and an experimental steel with a lower content of manganese, annealed at different dew points. The techniques employed were atomic force microscopy, X-ray photoelectron spectroscopy, and glow discharge optical emission spectroscopy. External selective oxidation was observed for phosphorus on steel surface annealed at 0 °C dp, and for manganese, silicon, and aluminum at a lower dew point. The concentration of manganese was higher on the dual phase steel surface than on the surface of the experimental steel. The concentration of molybdenum on the surface of both steels increased as the depth increased.     

Investigation of STM tip influence on the recorded position of the Shockley surface state on Au(1 1 1)

Current imaging tunneling spectroscopy (CITS) carried out in UHV at room temperature was used to study the electronic structure of the Au(1 1 1) surface in the range of −1.0-1.0 eV. The CITS experiment showed the existence of the Shockley surface state (SS) located in range 0.3-0.7 eV below the Fermi level. A wide range of SS locations is explained by the influence of the electronic structure of the tip on the measurement of the tunneling current. This hypothesis is supported by a simple theoretical model. Finally, a new method of CITS analysis is suggested. The method is related to counting local maxima locations on each tunneling spectroscopy curve and building a histogram. This method of data analysis allows finding statistically the most frequently appearing maxima. Using the histogram method the location of the SS is estimated to 0.47 eV below the Fermi level.     

Influence of CrN surface compound on the initial stages of high temperature oxidation of ferritic stainless steel

Segregation phenomena and formation of surface compounds on Fe-17Cr (ferritic stainless steel) were studied at temperatures up to 800 °C upon annealing and kinetically controlled oxidation by photoelectron spectroscopy and inelastic electron background analysis. The results revealed the formation of a chromium nitride surface compound during annealing in ultrahigh vacuum at temperatures exceeding 527 °C. Surface enrichment of P, As, and other trace elements became more prominent at higher temperatures approaching 800 °C. It was found that nitrogen was buried below the surface oxide layer during oxygen exposure, yet it had little effect on the rate of oxidation. However, the formation of CrN surface compound promoted the selective oxidation of Cr initially, which is of great importance in processing and application environments involving high temperature and controlled atmosphere conditions.     

Surface characterisation and electrochemical behaviour of porous titanium dioxide coated 316L stainless steel for orthopaedic applications

Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise the surface morphology and also to understand the structure of the as synthesised coating on the substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface.     

The role of nitrogen in the preferential chromium segregation on the ferritic stainless steel (1 1 1) surface

The temperature dependence on the segregation behavior of the ferritic stainless steel single crystal (1 1 1) surface morphology has been examined by scanning tunneling microscopy (STM), Auger electron spectroscopy (AES), and low energy electron diffraction (LEED). AES clearly showed the surface segregations of chromium and nitrogen upon annealing. Nanoscale triangular chromium nitride clusters were formed around 650 °C and were regularly aligned in a hexagonal configuration. In contrast, for the ferritic stainless steel (1 1 1) surface with low-nitrogen content, chromium and carbon were found to segregate on the surface upon annealing and Auger spectra of carbon displayed the characteristic carbide peak. For the low-nitrogen surface, LEED identified a facetted surface with (2 × 2) superstructure at 650 °C. High-resolution STM identified a chromium carbide film with segregated carbon atoms randomly located on the surface. The facetted (2 × 2) superstructure changed into a (3 × 3) superstructure with no faceting upon annealing at 750 °C. Also, segregated sulfur seems to contribute to the reconstruction or interfacial relaxation between the ferritic stainless steel (1 1 1) substrate and chromium carbide film.     

Effect of laser-remelting of surface cracks on microstructure and residual stresses in 12Ni maraging steel

The paper presents the results of a study on possible application of laser-remelting to repair of narrow and comparatively deep cracks at the surface of highly thermo-mechanically loaded parts made of 12% Ni hot-working maraging tool steel. Laser-remelting of maraging steel is, due to very good weldability and flexibility of the process, very prospective for repair of fatigued surfaces of parts made of this steel at which the presence of surface microcracks may be observed. In addition to the efficiency of crack remelting, the influence of laser-remelting on the heat-affected zone in terms of its microstructure and residual stresses was also studied. The microstructure in the laser-remelted track is cellular/dendritic. In the heat-affected zone surrounding the laser-remelted track, the microstructure varies considerably. A microstructure analysis revealed, in the heat-affected zone, five microstructural zones and sub-zones. Residual stresses measured after laser-remelting are with reference to gradual through-depth changing of the stresses favourable.     

The effect of nanostructured surface layer on the fatigue behaviors of a carbon steel

A nanostructured surface layer was formed on a carbon steel by means of surface mechanical attrition treatment (SMAT). The microstructure of the surface layer of the SMATed sample was characterized by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Microhardness and residual stress distribution along the depth from the SMATed surface layer were measured at the same time. Fatigue behaviors of the carbon steel subjected to the SMAT process were investigated. A nanostructured layer with average grains size of ∼12.7 nm was formed, of which microhardness is more than twice as high as that in matrix and residual compressive stress can reach about −400 MPa with maximum depth of ∼600 μm. The fatigue strength of as-received sample is 267 MPa and that of SMATed sample is 302 MPa based on fatigue life 5 × 10⁶ cycles. The SMAT process has improved the fatigue strength by as much as 13.1% for the carbon steel. It is shown that the SMAT is an effective method to render the material with the features, such as a nanostructured and work-hardened surface layer as well as compressive residual stresses, which can pronouncedly improve the fatigue strength of the carbon steel.     

Deformation-induced dissolution of the intermetallics Ni3Ti and Ni3Al in austenitic steels at cryogenic temperatures

An anomalous deformation-induced dissolution of the intermetallics Ni₃Al and Ni₃Ti in the matrix of austenitic Fe–Ni–Al(Ti) alloys has been revealed in experiment at cryogenic temperatures (down to 77 K) under rolling and high pressure torsion. The observed phenomenon is explained as the result of migration of deformation-stipulated interstitial atoms from a particle into the matrix in the stress field of moving dislocations. With increasing the temperature of deformation, the dissolution is replaced by the deformation-induced precipitation of the intermetallics, which is accelerated due to a sufficient amount of point defects in the matrix, gained as well in the course of deformation at lower temperatures.     

Absorption of sound at a surface exposed to flow and temperature gradients

In noise abatement using porous or fibrous materials, accurate determination of the surface impedance representing the absorber is decisive for simulation quality. The presence of grazing flow and non-homogeneous ambient temperature influence the reaction of the absorber and may suitably be included in a modified “effective” surface impedance. In this paper, this approach is applied to a generic case representative for the engine bay of a heavy truck, where porous shields suppress the radiated noise, e.g. during a pass-by noise test. The change in the absorption is determined numerically by solving the wave propagation through a layer of varying temperature and flow adjacent to the impedance surface for different angles of incidence. The study shows significant impact of both flow and temperature, especially for materials with low absorption. The diffuse field absorption coefficient is also derived and although the effect is less pronounced in this case, it is still important in lower frequencies and in the frequency range typical for IC engine noise. The proposed numerical method is shown to be accurate and efficient for determination of the effective impedance and moreover not limited to thin boundary layers.