Film formation on stainless steel in a solution containing chromic and sulphuric acids

The paper discusses the kinetics of the spontaneous reaction occurring during the formation of a coloured interference film on stainless steel in hot CrO₃ + H₂SO₄ aqueous solution. The film behaves as a porous membrane, permitting liquid phase diffusion of the dissolution product of the steel through it. Film growth is by precipitation at the film/solution interface of a spinel oxide to which metal ions formed by both anodic dissolution of the steel and reduction of chromic acid—the accompanying cathodic process—contribute. The kinetics of the reaction follow an exponentially increasing growth law, which is unusual and possibly novel among film-forming reactions.     

Über den Einfluß der Strömungsgeschwindigkeit und der NaCl-Konzentration auf die Sauerstoffkorrosion unlegierten Stahls in Wässern

Influence of flow velocity and sodium chloride concentration on the oxygen corrosion of unalloyed steels in water Corrosion of mild steel in aerated water normally leads to pitting, and to an enrichment of anions within the pits. Even HCO₃^? ions can support localized corrosion. The intensity of this is remarkably increased by chloride ions. In equilibrium water with Ca²⁺ and HCO₃^? ions and about 40 ppm free CO₂ protective rust layers are formed after about 500 hs exposure not depending on flow rate and salt concentration. These layers decrease the mean corrosion rate to about 0.1 mm/a, but do not prevent localized corrosion. Protective passive layers with extremely low corrosion rates are formed in flowing water with Ca²⁺ and HCO₃^? ions and about 40 ppm free CO₂. The minimum flow rate can be estimated for a 3/4 inch pipe to lie between 0.35 and 1.5 m/s. Investigations with water containing 40 ppm free CO₂ without Ca²⁺ at pH 4.7 and with NaHCO₃ (pH 7.2) show at low pH high corrosion rates – as expected –, and at pH 7.2 formation of protective layers with poor reproducibility in comparison with the situation in equilibrium water. Thus, Ca²⁺ ions support the protective properties of rust layers. HCO₃^? ions are necessary for the formation of protective layers because these are not formed in pure NaCl solutions.     

Entstehung und Aufbau farbiger Schichten auf rostfreiem Stahl: II. Verfärbungen unter den Bedingungen in einer Geschirrspülmaschine

Composition and formation of coloured layers on stainless steel: II. Discolorations formed under the conditions in an automatic dish-washer Discolorations can appear on stainless dishes or pots upon cleansing in a dish-washer, also the stainless steel components of the dish-washers can show such discolorations after long use. These discolorations are caused by corrosion of the stainless steel at a high redox potential of the electrolyte and intermediate pH-values. Such corrosive conditions result from a content of organic acid in the cleansing agent. The alloying elements Cr, Ni and Fe are dissolved under formation of complexes and an unsoluble, coloured oxyhydrate is enriched on the surface, which stems from a small Ti-content of the steels. This thin golden yellow or bluish violet passive layer is very corrosion resistant. The process can be avoided if there are no strongly oxidizing components in the cleansing agent.     

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.     

A case of nitridation,carburization and oxidation on a stainless steel

A case of corrosion was studied on stainless steel tubes, exposed to a nitriding, carburizing and oxidizing environment (mainly NH₃ and CO₂) at 390–450°C. Due to the high nitriding potential prior formation of internally nitrided layers occurs, at higher temperatures (> about 425°C) under precipitation of CrN in the layer and at lower temperatures under formation of the γ_N‐phase, i.e. austenite with high N‐content and expanded lattice. The latter process causes more severe corrosion, due to the high expansion, the stresses in the nitrided layers lead to bursting and repeated spalling of the scales. Carburization and oxidation are less important. The carburization is slower than nitridation, Fe₃C formation is observed and carbon deposition. Also the oxidation by CO₂ is slow and converts the nitrides and carbides formed before, to unprotective oxide flakes.     

Effect of Plasma Nitriding and Nitrocarburizing on HVOF-Sprayed Stainless Steel Coatings

In this work, the effects of plasma nitriding (PN) and nitrocarburizing on HVOF-sprayed stainless steel nitride layers were investigated. 316 (austenitic), 17-4PH (precipitation hardening), and 410 (martensitic) stainless steels were plasma-nitrided and nitrocarburized using a N₂ + H₂ gas mixture and the gas mixture containing C₂H₂, respectively, at 550 °C. The results showed that the PN and nitrocarburizing produced a relatively thick nitrided layer consisting of a compound layer and an adjacent nitrogen diffusion layer depending on the crystal structures of the HVOF-sprayed stainless steel coatings. Also, the diffusion depth of nitrogen increased when a small amount of C₂H₂ (plasma nitrocarburizing process) was added. The PN and nitrocarburizing resulted in not only an increase of the surface hardness, but also improvement of the load bearing capacity of the HVOF-sprayed stainless steel coatings because of the formation of CrN, Fe₃N, and Fe₄N phases. Also, the plasma-nitrocarburized HVOF-sprayed 410 stainless steel had a superior surface microhardness and load bearing capacity due to the formation of Cr₂₃C₆ on the surface.     

Influence of Irradiation on the Oxide Film Formed on 316 L Stainless Steel in PWR Primary Water

Oxidation of stainless steel in PWR primary water at 325 °C was studied by investigating the influence of defects created at the alloy subsurface by proton irradiation before corrosion exposure. Corrosion experiments were conducted by sequentially exposing samples, with H ₂ ¹⁸ O used for the second exposure. The oxide layer, formed in these conditions was studied by SEM and TEM and could be divided in two parts: an external discontinuous layer composed of crystallites rich in iron and an internal continuous layer richer in chromium. Tracer experiments revealed that the growth of this protective scale was due to oxygen diffusion in the grain boundary of the oxide layer. Defects created by irradiation have an effect on the two oxide layers. They are a preferential nucleation site for the external layer and so increase the density of the crystallites. They also induce a slower diffusion of oxygen in the internal layer.     

The initiation of selective oxidation of a ferritic stainless steel at low temperatures and oxygen pressures

Oxidation of a ferritic stainless steel of type Fe-18Cr-2Mo has been performed in the temperature range 285–495°C and oxygen partial pressure range 10^?9-10^?8 torr. The chemical composition of thin oxide layers formed has been analysed by means of Auger Electron Spectroscopy and interpreted in terms of available chromium, iron and oxygen at the solid/gas interface. The selective oxidation of chromium is considered by different probabilities for the oxidation of available chromium and iron respectively. At oxide thicknesses below 100 Å the supplies of chromium and iron are ruled by diffusion in the steel matrix. The results have been used to predict the chemical compositions of two subsequently growing oxide layers provided the thickness of the first oxide layer is below 50 Å.     

Electrochemische Untersuchungen zur Hochtemperaturkorrosion von Chromstählen in Alkalisulfatschmelzen

Electrochemical investigation into the high temperature corrosion of chromium steels in alkali sulfate melts Electrochemical and corrosion-chemical investigations have been carried out with scaling resistant chromium steels, iron, chromium and platinum in a eutectic (Li, Na, K)₂-SO₄. It has turned out that sufficiently exact data concerning corrosion reactions can be obtained only from mass losses, not, however, from current density. The corrosion behaviour depends from potential. Comparable to the conditions in aqueous solutions potential ranges exist with passive and transpassive corrosion and with a rupture potential which depends from the chromium content of a steel. Protective oxide layers exist in the passive range where the mass loss becomes almost constant after a certain in cubation period. In the transpassive range corrosion follows an almost parabolic law with formation of an inner sulfide layer and a thicker external oxide layer where chromium is enriched. These layers are largely formed by oxidizing media carried to the metal surface via sulfur oxides; during this reaction inert marks in the steel remain unchanged. Sulfur oxides may be formed as secondary consecutive products by reactions between metal ions and sulfates. The solubility of metal ions in the sulfate melt is an important parameter for corrosion rates. Oxide ions (as reduction products of O₂) act as inhibitor on the anodic partial reaction, while SO₃ and ferric ions have a large lating effect, so that the anodic dissolution is autocatalyzed. Chlorides, too, act as stimulators in the transpassive range. Corrosion at the free corrosion potential is largely controlled by ferric ions which act as anodic and cathodic stimulators in acid melts. In neutral melts under oxygen an 18% chromium steel is passive.     

An ESCA and Mössbauer study of the oxide layer formed on steel in water containing chromate and chloride ions

The formation of oxidic layers on steel in chromate solutions was studied by photo-electron and Mössbauer spectroscopy. To simulate more aggressive realistic systems, some chloride ions were added to the solution. The layers formed under these conditions were found to be thicker by an order of magnitude than those formed in the absence of chloride ions. They probably consist of ferric and chromic oxides of the corundum type (Fe_1?2Cr_x)₂O₃, with the Cr : Fe ratio being depth dependent. The oxide layer is subdivided into small regions behaving superparamagnetically. This heterogeneity of the layer is ascribed to the attack by the chloride ions. The structure of the oxides found differs from the spinel structure reported by other authors who used chloride-free solutions.     

Effects of different inorganic anions on equipment material corrosion behaviour in subcritical water oxidation

In this work, possible corrosion mechanisms of Fe- and Ni-based alloys are discussed which are protected by Cr₂O₃, NiO and MoO₂ surface layers. But chloride ions can dissolve these oxide films and there is a strong synergistic effect between hydronium ions and oxygen, leading to severe local alloy corrosion. On the other hand, titanium and Zr-3 alloys show good corrosion resistance in acidic oxidising subcritical water containing different inorganic salts. A double-layer oxide film (TiO and TiO₂) is formed on the surface of TA2 and TA9 alloys, while a triple oxide layer (TiO, Ti₂O₃ and TiO₂) is formed on TA10 surfaces in such aqueous solutions containing chloride and sulphate ions. In addition to the two oxide layers, Ti₃(PO₄)₄ deposits are also formed on the surface of TA2 and TA9 alloys when the subcritical water contains phosphates. Moreover, (TiO)₂P₂O₇ deposits form besides Ti₃(PO₄)₄ layers on the surface when the TA10 alloy is oxidised under the latter conditions.     

Microstructure of aluminized stainless steel 310 after annealing

The aluminized coating on type 310 stainless steel prepared by high-activity Al pack cementation method has been annealed at 900 °C for 12 h to transform the brittle δ-Fe₂Al₅ phase into the more ductile β-FeAl phase. The microstructure is studied in detail with transmission electron microscopy. The thick outer layer has β-(Fe, Ni)Al as matrix with cube-like Cr₂Al precipitates. The interfacial layer has a thin layer of metastable FCC phase (layer I) and then mixed β-(Fe, Ni)Al grains and α-(Fe, Cr) grains (layers II and III). The Cr₂Al precipitates are present in the β-(Fe, Ni)Al grains in layer II but not in those in layer III, while β-FeAl precipitates are present in the α-(Fe, Cr) grains in both layers. The orientation relationships between various phases, the formation of the layers, and the precipitation of Cr₂Al in β-(Fe, Ni)Al are discussed.     

Interfacial features of TiAl alloy/316L stainless steel joint brazed with Zr−Cu−Ni−Al amorphous filler metal

TiAl alloy and 316L stainless steel were vacuum-brazed with Zr?50.0Cu?7.1Ni?7.1Al (at.%) amorphous filler metal. The influence of brazing time and temperature on the interfacial microstructure and shear strength of the resultant joints was investigated. The brazed seam consisted of three layers, including two diffusion layers and one residual filler metal layer. The typical microstructure of brazed TiAl alloy/316L stainless steel joint was TiAl alloy substrate/α₂-(Ti₃Al)/AlCuTi/residual filler metal/Cu₉Zr₁₁+Fe₂₃Zr₆/Laves-Fe₂Zr/α-(Fe,Cr)/316L stainless steel substrate. Discontinuous brittle Fe₂Zr layer formed near the interface between the residual filler metal layer and α-(Fe,Cr) layer. The maximum shear strength of brazed joints reached 129 MPa when brazed at 1020 °C for 10 min. The diffusion activation energies of α₂-(Ti₃Al) and α-(Fe,Cr) phases were ?195.769 and ?112.420 kJ/mol, respectively, the diffusion constants for these two phases were 3.639×10^?6 and 7.502×10^?10 μm²/s, respectively. Cracks initiated at Fe₂Zr layer and propagated into the residual filler metal layer during the shear test. The Laves-Fe₂Zr phase existing on the fracture surface suggested the brittle fracture mode of the brazed joints.     

Layer growth kinetics and wear resistance of martensitic precipitation hardening stainless steel plasma nitrocarburized at 460°C with rare earth addition

To study the effect of rare earth (RE) addition on low temperature plasma nitrocarburizing of martensitic precipitation hardening stainless steel, 17-4PH stainless steel was plasma nitrocarburized at 460 °C for different times with RE addition. The modified layers were tested by optical microscope, scanning electron microscope, X-ray diffraction, microhardness tester and pin-on-disc tribometer. The experimental results show that the layer depth of plasma RE nitrocarburized layer can be increased up to 56% compared with plasma nitrocarburizing without RE addition. Incorporation of RE element is beneficial to the formation of nitrogen and carbon expanded martensite (α′_N). The surface microhardness of plasma RE nitrocarburized layer can be increased to 1286 HV and higher up to 80 HV than that obtained from the conventional treated one. The friction coefficient of martensitic stainless steel can be dramatically decreased by low temperature plasma nitrocarburizing with RE addition, and the friction coefficient of the modified specimens decrease gradually with increasing process time in the present test condition.     

The oxidation behaviour of 304 stainless steel in oxygenated high temperature water

Characteristics of the oxide films formed on 304 stainless steel immersed in 290 °C oxygenated water for different duration time were examined. The results show that the oxide film is mainly composed of outer irregularly shaped α-(Fe, Cr)₂O₃ and minor spinel in the inner layer. The morphology and chemical composition of the oxide film evolve with increasing immersion time. The surface layer is first enriched in Cr and then enriched in Fe. It is proposed that the oxide nucleated by solid-state reactions with the selective dissolution of Fe and Ni, and grew up through precipitation of extraneous metallic ions from solution.     

Depth profile analysis of thin passive films on stainless steel by glow discharge optical emission spectroscopy

Thin passive films formed on highly corrosion-resistant type-312L stainless steel, containing 20 mass% chromium and 6 mass% molybdenum, in 2 mol dm⁻³ HCl solution at 293 K have been analyzed by glow discharge optical emission spectroscopy (GDOES). The stainless steel does not suffer pitting corrosion even in this aggressive solution, showing a wide passive potential region. The depth profiles obtained clearly show a two-layer structure of the air-formed and passive films: an outer iron-rich layer and an inner layer highly enriched in chromium. Alloy-constituting molybdenum is deficient in the inner layer of the passive films and is enriched in the outer layer, particularly at the active dissolution potential. The molybdenum species in the outer layer may retard the active dissolution of stainless steel, promoting the formation of stable passive films highly enriched in chromium. Chloride ions are present only at the outermost part of the passive films, not penetrating into the interior part.     

Bildungsgeschwindigkeit kathodisch erzeugter Hydroxid-Deckschichten

Rate of formation of cathodically produced hydroxide surface layers The cathodic hydrogen evolution shifts the pH values in the vicinity of the electrode to ward higher values. If a metal ion is present in the solution and if the pH shift results in a condition where the solubility product of the metal oxide or hydroxide respectively is attained at the electrode surface a further current density increase may give rise to the precipitation of the metal hydroxide which then forms a suface layer on the electrode. The rate of formation of such layers is assessed whereby it is presumed that the rate controlling step is exclusively the transport of the ions taking part in the reactions. Tracing current density overtension curves and weighing the surface layers formed enables the rate of formation to be measured as a function of current density, pH value, metal ion concentration and diffusion layer thickness. The results obtained for layers of Ni(OH)₂, Cd(OH)₂, Co(OH)₂, Zn(OH)₂, Mg(OH)₂, Ce(OH)₃ and La(OH)₃ are in good agreement with theoretical considerations. In the case of the formation of Al(OH)₃ layers it is necessary to take account of the contribution to charge transport by aluminium ions dissolved in the form of hydroxo-complexes.     

Poly(ortho-ethoxyaniline) in corrosion protection of stainless steel

Corrosion protection of stainless steel (13% Cr) coated with poly(ortho-ethoxyaniline) (POEA) has been investigated. The layers of POEA were synthesised from sulphuric and phosphoric acid solutions by means of cyclic voltammetry. The protecting properties of the layers in supporting electrolytes were investigated by monitoring the open circuit potential (E_oc) vs. time, and by electrochemical impedance spectroscopy (EIS). It was found that polymer layers provide corrosion protection, i.e. they help to stabilise the potential of the metal in the passive potential region. The protective properties of POEA layers have shown to be superior to polyaniline (PANI) layers, which is explained by a denser morphology of POEA. The behaviour of POEA obtained on stainless steel, examined by EIS, is different from the one obtained for POEA on Pt electrode. The registered resistance in the case of POEA on stainless steel represents the charge transfer resistance at polymer/solution interface, i.e. the polymer resistance. These measurements show that a part of the layer is reduced, i.e. that there is an interaction between polymer layer and stainless steel. EIS measurements prove the influence of monomer on stainless steel oxide formation and suggest that polymer is partly incorporated into the oxide film.     

TiO2-Bioactive Glass Nanostructure Composite Films Produced by a Sol-Gel Method: In Vitro Behavior and UV-Enhanced Bioactivity

The aim of this study is to develop TiO₂, titania, -based composite films for 316 stainless steel substrate and to improve their apatite-forming activity. A series of sol-gel derived bioactive glass (49S) and bioactive glass (49S)-TiO₂ films were deposited on the 316L stainless steel substrates by the spin-coating method. Amorphous bioactive glass (49S) film and polycrystalline titania-bioactive glass composite films were obtained after annealing the deposited layers at 600 °C. The microstructure and in vitro bioactivity of the composite films as well as the effect of titania nanopowder content and ultra violet (UV) irradiation on the in vitro bioactivity were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). While bioactivity tests are often carried out within 28-day periods, SEM and EDS data show that, after soaking in SBF for just 7 days, the prepared composite surfaces are covered with an apatite layer. The grown apatite layer consists of spherulites formed by nanosized needle-like aggregates. Fourier transform infrared spectroscopy investigations confirm apatite formation and suggest that the formed apatite is carbonated.     

Proton-conducting sorption-active cyclam-based layers on chemically modified PVC surfaces of cellulose fabric

At different concentrations of hydrochloric, sulfuric, and phosphoric acids, the conductivity of the following electrochemical cell was measured: anode-acid solution-in-air bridge-acid solution-cathode. Cellulose fabric, the fibers of which are encapsulated in polyvinyl chloride, the surface of which is chemically modified with porous layers of aggregates formed by acid molecules and salt groups of ethanol and acetate cyclams, served as the bridge. The range where the logarithmic conductivity is proportional to the acid concentration is found. In this range, the molar contents of acids and water in the layers are estimated, the presence of aggregates composed of acid hydrates and cyclam salt groups is determined, the structure of layer is studied, and the similarity between the H⁺ conductivity of the layers on fabric and the conductivity of membranes based on polymers involving the skeleton ammonia salt groups is followed. For the aggregate layers, the specific surface; the limiting volume of pores; and the adsorption capacities for water, alcohol, benzene, and hexane vapors are measured. The formation of aggregates is shown to produce an insubstantial effect on the adsorption characteristics of the surface. During migration of H⁺ ions in the fabric and on its surface, the following process was carried out in the electrochemical cell: adsorption of NH₃, formation of NH ₄ ⁺ ions, and transfer of NH ₄ ⁺ ions to the catholyte. The migration velocity of H⁺ ions is shown to correspond to the measured current in the circuit, and NH ₄ ⁺ ions formed are found to be accumulated in the catholyte.