Corrosion properties of plasma nitrided AISI 410 martensitic stainless steel in 3.5% NaCl and 1% HCl aqueous solutions

Samples of an AISI 410 martensitic stainless steel were plasma nitrided at a temperature of 420 °C, 460 °C or 500 °C for 20 h. The composition, microstructure and hardness of the nitrided samples were characterised using a variety of analytical techniques. In particular, the corrosion properties of the untreated and plasma nitrided samples were evaluated using anodic polarisation tests in 3.5% NaCl solution and immersion tests in 1% HCl acidic water solution. The results showed that plasma nitriding produced a relatively thick nitrided case consisting of a compound layer and a nitrogen diffusion layer on the 410 stainless steel surface. Plasma nitriding not only increased the surface hardness but also improved the corrosion resistance of the martensitic stainless steel. In the immersion test, nitrided samples showed lower weight loss and lower corrosion rate than untreated one. In the electrochemical corrosion tests, the nitrided samples showed higher corrosion potentials, higher pitting potentials and greatly reduced current densities. The improved corrosion resistance was believed to be related to the iron nitride compound layer formed on the martensitic stainless steel surface during plasma nitriding, which protected the underlying metal from corrosive attack under the testing conditions.     

Corrosion behaviour of magnetron-sputtered Al1−x-Mnx coatings in neutral saline solution

Al-Mn coatings with different contents (0-41 at.%) were deposited on glass slides by magnetron co-sputtering. These coatings were characterised, before and after immersion tests, by X-ray diffraction, scanning electron microscopy (SEM) and electron probe microanalysis. The electrochemical measurements in a neutral saline solution showed that the pitting corrosion resistance of Al-Mn coatings increased with increasing Mn content as the pitting corrosion potentials are progressively shifted towards positive values. The immersion tests reveal that for all Mn contents, Al-Mn coatings keep a sacrificial character compared with steel. For Mn content above 26 at.%, XRD analysis showed the formation of an amorphous phase. This structure would be responsible for the high increase of the hardness of Al-Mn coatings and of the stabilisation of their open circuit potentials during the 48 h immersion tests.     

Corrosion evaluation of microarc oxidation coatings formed on 2024 aluminium alloy

Dense alumina ceramic coatings of 7 μm thickness were fabricated on 2024 aluminium alloy by microarc oxidation (MAO). The corrosion behaviour of the MAO coated alloys was evaluated using potentiodynamic polarisation and EIS measurements. The results show that the corrosion process of the coated alloy can be divided into three stages: (1) the initial stage (the first 2-6 h of immersion): penetration of corrosion medium into the aluminium alloy was inhibited by coating; (2) the second stage (after 24 h of immersion), corrosion medium penetrated to attack the interface between the substrate and the coating; (3) the final stage (after about 96 h): corrosion process was controlled by the diffusion of corrosion products.     

Passivation oxide film on Nd-Fe-B permanent magnets in borate buffer solution by ellipsometry

The passivation of Nd-Fe-B permanent magnet was investigated in neutral borate solution at pH 8.4. The thickness of the passive oxide film on the magnets was measured by ellipsometry and the composition was estimated by glow discharge optical emission spectroscopy (GD-OES).The passivation of the magnets takes place in the potential range between −0.2 and 1.0 V vs. Ag/AgCl/Sat. KCl. In the potential range, current density decays to the lower than 10⁻⁶ A cm⁻² after potentiostatic oxidation for 1800 s. The passive oxide film growth is assumed to be optically simulated from a model with a homogeneous film with complex refractive index, N = 2.1 − j0.086. The thickness estimated from the refractive index linearly increases with potential from 3.6 nm at −0.2 V to 7.8 nm at 1.0 V. The passive film growth follows the ionic migration model under high electric field, i.e., the Cabrera-Mott growth model. The ionic conductivity estimated from the model is about κ = 1.7 × 10⁻¹⁶ Ω⁻¹ cm⁻¹. The passive oxide film is preferentially composed of iron oxide/hydroxide. Boron and neodymium are, respectively, concentrated at the surface of the oxide film and at the inner layer in the oxide film.     

Corrosion studies of stainless steel protected by a TiO2 thin film deposited on a sulfonate-functionalized self-assembled monolayer

Thioacetate hexadecyltrimethoxysilane was deposited on SiO₂-coated stainless steel to form a thioacetate-functionalized monolayer. In situ oxidation of the thioacetate yielded a sulfonate-functionalized monolayer. Solution deposition of TiO₂ on this monolayer covered the stainless steel with a thin layer of the metal oxide (5-10 nm). Cyclic voltammetry (CV) and potentiostatic current transient demonstrated the efficiency of the corrosion protection in sodium chloride media, including protection against pitting corrosion.     

Effect of heat treatment on anodic activation of aluminium by trace element indium

The presence of trace elements in Group IIIA-VA is known to activate aluminium anodically in chloride environment. The purpose of this paper is to investigate the surface segregation of trace element In by heat treatment and resulting surface activation. Model binary AlIn alloys, containing 20 and 1000 ppm by weight of In, were characterized after heat treatment at various temperatures by use of glow discharge optical emission spectroscopy, electron microscopy and electrochemical polarization. Heat treatment for 1 h at 300 °C gave significant segregation of discrete In particles (thermal segregation), which activated the surface. Indium in solid solution with aluminium, obtained by 1 h heat treatment at 600 °C, also activated by surface segregation of In on alloy containing 1000 ppm In, resulting from the selective dissolution of the aluminium component during anodic oxidation (anodic segregation). The effect of anodic segregation was reduced by decreasing indium concentration in solid solution; it had negligible effect at the 20 ppm level. The segregated particles were thought to form a liquid phase alloy with aluminium during anodic polarization, which in turn, together with the chloride in the solution destabilized the oxide.     

Effects of electrical discharge surface modification of superalloy Haynes 230 with aluminum and molybdenum on oxidation behavior

The effects of the electrical discharge alloying (EDA) process on improving the high temperature oxidation resistance of the Ni-based superalloy Haynes 230 have been investigated. The 85 at.% Al and 15 at.% Mo composite electrode provided the surface alloying materials. An Al-rich layer is produced on the surface of the EDA specimen alloyed with positive electrode polarity, whereas, many discontinuous piled layers are attached to the surface of the EDA superalloy when negative electrode polarity is selected. The oxidation resistance of the specimen alloyed with positive electrode polarity is better than that of the unalloyed superalloy, and the effective temperature of oxidation resistance of the alloyed layer can be achieved to 1100 °C. Conversely, the oxidation resistance of the other EDA specimen alloyed with negative electrode polarity is even worse than that of the unalloyed superalloy.     

Effect of nickel ion from autoclave material on oxidation behaviour of 304 stainless steel in oxygenated high temperature water

Characteristics of the oxide films formed on 304 stainless steel exposed to 290 °C oxygenated water in a nickel-lined autoclave were examined. The oxides evolve from dominating irregularly shaped hematite to faceted spinels with increasing immersion time. The surface layer of oxide film is first Cr-enriched and then Ni-enriched as immersion time increases. The oxides nucleate by solid-state reactions with selective dissolution of Fe and Ni, and then grow up through precipitation of cations from solution. Nickel ions dissolved from the nickel lining could promote the stability of NiFe₂O₄ spinel and influence the oxidation behaviour of 304 stainless steel significantly.     

The effect of atmospheric corona treatment on AA1050 aluminium

The effect of atmospheric corona discharge on AA1050 aluminium surface was investigated using electrochemical polarization, SEM-EDX, FIB-SEM, and XPS. The corona treatment was performed with varying time (1, 5, and 15 min) in atmospheric air. A 200 nm oxide layer was generated on AA1050 after the 15 min air corona treatment. A significant reduction in anodic and cathodic reactivities was observed starting from 1 min exposure, which further decreased with prolonged exposure (15 min) and after delayed testing (after 30 days). The reduction in surface reactivity is due to the formation of thicker and denser oxide film.     

Improving the high-temperature oxidation resistance of a β-γ TiAl alloy by a Cr2AlC coating

A Cr₂AlC coating was deposited on a β-γ TiAl alloy. Isothermal oxidation tests at 700 °C and 800 °C, and thermocyclic oxidation at 800 °C were performed in air. The results indicated that serious oxidation occurred on the bare alloy. Thick non-protective oxide scales consisting of mixed TiO₂ + α-Al₂O₃ layers formed on the alloy surface. The coated specimens exhibited much better oxidation behaviour by forming an Al-rich oxide scale on the coating surface during the initial stages of oxidation. This scale acts as diffusion barrier by effectively blocking the ingress of oxygen, and effectively protects the coated alloys from further oxidation.     

Electropolishing effects on corrosion behavior of 304 stainless steel in high temperature, hydrogenated water

The corrosion rate of electropolished 304 stainless steel surfaces (UNS S30400) is found to be lower by more than a factor of three relative to that determined previously for machined surfaces in mildly alkaline, hydrogenated water at 260 °C. This favorable result is attributed to significant changes in nanocrystallinity of the corrosion oxide layer caused by the removal of surface microstrain, which had been imparted during the machining process. In the absence of microstrain, a low-porosity, protective, corrosion layer forms that is composed of extremely small and uniformly-sized spinel oxide crystals. Application of scanning electron microscopy (FEG-SEM), X-ray diffraction and X-ray photoelectron spectroscopy (XPS) in conjunction with ion milling and target factor analyses, found the corrosion layer to consist of micrometer-size crystals of a ferrite-based spinel oxide (non-protective) over-laying nanometer-size crystals of a chromite-based spinel oxide (protective). Composition of both phases is unchanged from that previously observed on corroded, machined surfaces and is representative of solvus phases in the immiscible Fe(Fe_1−nCr_n)₂O₄ spinel binary. The smaller size (10 vs. 26 nm) and greater surface density (∼10,000 vs. 835 μm⁻²) of the chromite-based crystals relative to those formed on machined (i.e., cold-worked) surfaces, however, is consistent with the absence of preferred high energy nucleation sites on strain-free surfaces. Therefore, electropolishing, which removes surface microstrain induced by cold-working, represents a preferred reference surface condition.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

Oxidation of 316 stainless steel in supercritical water

The oxide scales of 316 stainless steel (316 SS) have been examined after exposure to supercritical water (SCW) with 2.0% H₂O₂ for up to 250 h. The exposed samples were analyzed using weight measurement, scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). It was found that mass gain of all samples increased with increasing temperature and exposure time. Higher temperature SCW resulted in rougher surfaces and thicker oxide scales. Duplex layer oxide structures with Ni-enrichment at the oxide/metal interface developed on all samples exposed to SCW, which were identified as Fe₂O₃/Fe₃O₄ + spinel/Cr₂O₃/Ni-enrichment/316 SS from the outer to inner layer. The possible oxidation mechanisms are also discussed.     

Corrosion properties of active screen plasma nitrided 316 austenitic stainless steel

AISI 316 austenitic stainless steel has been plasma nitrided using the active screen plasma nitriding (ASPN) technique. Corrosion properties of the untreated and AS plasma nitrided 316 steel have been evaluated using various techniques, including qualitative evaluation after etching in 50%HCl + 25%HNO₃ + 25%H₂O, weight loss measurement after immersion in 10% HCl, and anodic polarisation tests in 3.5% NaCl solution. The results showed that the untreated 316 stainless steel suffered severe localised pitting and crevice corrosion under the testing conditions. AS plasma nitriding at low temperature (420 °C) produced a single phase nitrided layer of nitrogen expanded austenite (S-phase), which considerably improved the corrosion properties of the 316 austenitic stainless steel. In contrast, AS plasma nitriding at a high temperature (500 °C) resulted in chromium nitride precipitation so that the bulk of the nitrided case had very poor corrosion resistance. However, a thin deposition layer on top of the nitrided case, which seems to be unique to AS plasma nitriding, could have alleviated the corrosion attack of the higher temperature nitrided 316 steel.     

Characterization of air-formed surface oxide film on Ti-29Nb-13Ta-4.6Zr alloy surface using XPS and AES

The surface oxide film on a Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) was precisely characterized using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) to understand the composition and chemical state of the surface oxide film of TNTZ. For comparison, the component metals, titanium, niobium, tantalum, and zirconium, were also characterized to consider the effect of those on the formation of the surface oxide film on their alloy. The characterization of the surface oxide films on TNTZ and its component revealed the following issues. The surface oxide film on TNTZ consists of a composite oxide that contains titanium, niobium, tantalum, and zirconium but forms continuous layer and is very thin, ca. 3.7 nm. The oxide film is not completely oxidized because it contains various valences of cations. In particular, the oxidation of tantalum is inhibited in the oxide. Tantalum is enriched in the substrate in TNTZ just under the surface oxide because of this inhibition in the oxidation. The formation of the surface oxide film in TNTZ is predominantly governed by titanium. The preferential oxidation of an element is not always dependent on the initial oxidation potential of that element, the relationship between the oxidation energy from a smaller valence to a larger valence, and the dehydration process. In other words, a complicated competition governs the resultant composition of surface oxide.     

Localized coating failure of epoxy-coated aluminium alloy 2024-T3 in 0.5 M NaCl solutions: Correlation between coating degradation, blister formation and local chemistry within blisters

The role of pH on the nature and rate of the degradation of epoxy coatings on AA2024-T3 panels and subsequent corrosion of the substrate during immersion in NaCl solutions was investigated. In acidic solutions both blister formation and growth are rapid. Blisters become very large (≈1 cm) and new blisters appear to form for a certain time after exposure. Often very small (∼0.1 mm) clear blisters surround these large blisters. Enhanced blister formation is due to irreversibly increased permeability of the coating for chloride ions and protons, the formation of more defect sites within the coating, and the weakening/dissolution of the oxide layer in low pH environments. In neutral pH solutions, coatings fail by forming one, or at most two, active blisters (red in color) within a few days of immersion with the time-to-failure dependent upon coating quality and thickness. Blister growth is a very slow process, and blister diameters rarely exceed a few millimeters even after several weeks. The accumulation of corrosion product within the blister slows down the corrosion rate and blister growth. The chloride concentration in the occluded solutions within the blister is significantly increased over the bulk concentration, and the pH is often in the acidic range. From electrochemical measurements it can be concluded that the anodic and cathodic reactions are confined to the blister and its immediate surroundings, rather than involving more of the surface over which the coating is intact. Based on corrosion morphology it is concluded that replated copper contributes to the overall cathodic reaction.     

Cyclic oxidation behaviour of Ti3Al-based alloy with Ni-Cr protective layer

The influence of a thin 80Ni-20Cr (at.%) protective coating on the cyclic oxidation of a Ti-24Al-11Nb (at.%) alloy based on Ti₃Al at 600 and 900 °C in air was investigated using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The results of the oxidation tests showed that deposited Ni-Cr layer provides an improved oxidation resistance due to the formation of protective oxide scale which barriers the outward Ti diffusion into the scale. In some extent surface formation of the nitride layer also prevents diffusion of alloying elements from the matrix. Although oxidation at 900 °C is faster than that at 600 °C, a remarkable reduction in mass gain of the alloy with protective coating was observed. The thickness of oxide scale on the coated samples is approximately two times less than that formed on the uncoated samples treated under the same exposure conditions (120 h).     

Early stages of the oxidation of a FeCrAlRE alloy (Kanthal AF) at 900 °C: A detailed microstructural investigation

Early stages of the evolution of Al₂O₃ scales formed on a FeCrAlRE alloy (Kanthal AF) have been investigated by analytical TEM. The samples were oxidized isothermally at 900 °C in dry O₂ or O₂ + 40% H₂O for 1 h or 24 h. All oxide scales exhibited a two-layered structure, with a continuous inward growing α-Al₂O₃ inner layer and an outward growing outer layer. After 1 h, the outer oxide layer consisted of γ-Al₂O₃ in both environments. After 24 h exposure in dry O₂, the γ-Al₂O₃ in the outer oxide layer was partly transformed to α-Al₂O₃ and spinel oxide (Mg_1−xFe_xAl₂O₄). In contrast, the γ-Al₂O₃ in the outer layer was not transformed after 24 h in O₂ + 40% H₂O, showing that water vapour stabilizes γ-Al₂O₃. All oxide scales contained a Cr-rich band, a product of the initial oxidation. The inner α-Al₂O₃ layer is suggested to nucleate on Cr₂O₃ or Cr_2−xFe_xO₃ in the initial oxide.     

Influence of hydrothermal treatment temperature on oxidation modification of C/C composites with aluminum phosphates solution by a microwave hydrothermal process

Carbon/carbon (C/C) composites were modified with an aluminum phosphates solution by a novel microwave hydrothermal (MH) process in order to improve their low temperature oxidation resistance. Results show that a H₃PO₄ or HPO₃ continuous molten layer with some regular, white cubic Al(PO₃)₃ crystallites are obtained on the surface of the modified composites. The anti-oxidation property of the composites after modification improves with the increase of the MH temperature from 393 to 473 K. The oxidation rate is almost constant after oxidation at 873 K for 6 h. The formation of annular structure of Al(PO₃)₃ is helpful to improve the oxidation resistance of the composites.     

Characterization of microstructure and corrosion properties of cold worked Alloy 800

X-ray diffraction studies indicated that cold worked (∼50%) Alloy 800 was austenitic and transmission electron microscopy revealed the presence of a small volume fraction of hexagonal ε-martensite along with deformation bands, high dislocation density and primary TiN particle with a few dislocations within it. The passivity of cold worked alloy was very stable in H₂SO₄ solution but unstable in HCl solution at room temperature. The exposure of cold worked alloy in 673 K steam (initial pH of water was 10.1) for a period of 264 h showed almost nil corrosion rate. Scanning electron microscopy revealed a number of small oxide particles on the surface exposed in steam indicating initiation of oxide formation. Energy dispersive X-ray analyses of the surface containing small oxide particles indicated that the surface composition was similar to bulk composition of the alloy. X-ray photoelectron spectroscopy revealed that the alloy surface exposed in steam contained mixed oxides of iron and chromium as well as elemental form of iron, nickel and chromium.