Passivation of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys in 1 M H2SO4 and 1 M NaOH solutions

The corrosion mechanisms of Al–Cr–Fe and Al–Cu–Fe–Cr complex metallic alloys have been investigated by potentiodynamic and potentiostatic polarization. Very good passivation of the Al–Cr–Fe surface is exhibited from 1 M H₂SO₄ to 1 M NaOH solutions, which was confirmed by ICP-OES analysis over a period of 273 days. Potentiostatically formed passive films analysed by XPS revealed chromium enrichment in the outermost layer of the aluminium oxy-hydroxide film. Although Al–Cu–Fe–Cr showed passivation during potentiodynamic polarization, heavy active corrosion at OCP was revealed by ICP-OES. For the Al–Cu–Fe–Cr alloy, the 10% content of Cr is insufficient to maintain a protective “chemically stable” Cr oxide/hydroxide.     

Interface characteristics and corrosion behaviour of oriented bulk Fe2B alloy in liquid zinc

The interface characteristics and corrosion behaviour of oriented Fe₂B in liquid zinc have been investigated. The results indicate that Fe₂B with preferential growth direction parallel to corrosion interface displays better corrosion resistance to liquid zinc. The Fe₂B/FeB phase transition occurs due to gradient of chemical potential in solid Fe₂B–liuqid zinc system. The liquid zinc corrosion is competition process of dissolution, Fe₂B/FeB transition and fracture–spalling. The fracture–spalling dominates corrosion process when preferred direction of Fe₂B is perpendicular to corrosion interface while Fe₂B/FeB transition plays a role in liquid zinc corrosion as preferred direction of Fe₂B is parallel to corrosion interface.     

Corrosion mechanism of Mo/Nd16Fe71B13/Mo film in a simulated marine atmosphere

This study describes the corrosion mechanism of Mo/Nd₁₆Fe₇₁B₁₃/Mo film induced by sodium chloride particles in 80% relative humidity (RH) environment. The deliquescence of sodium chloride particles on the Mo/Nd₁₆Fe₇₁B₁₃/Mo film caused the step by step attacks. Initial loosening of the Mo layer allows permeation of electrolyte into Nd–Fe–B layer, resulting in cavitations of electrolyte and subsequent film failure. The second failure step involves corrosion of Nd element in the Nd–Fe–B layer, with Fe element remaining beneath the corrosion product. Corrosion of Fe constitutes the third-step failure, forming a mixture of Nd and Fe corrosion product.     

The effects of temperature and hydrodynamics on the CO2 corrosion of 13Cr and 13Cr5Ni2Mo stainless steels in the presence of free acetic acid

This paper describes the effects of temperature and hydrodynamics on the CO₂ corrosion of two stainless steels in the presence of free acetic acid. The experimental set-up developed in this work was able to evaluate the corrosion behavior of 13Cr and 13Cr5Ni2Mo stainless steels in static conditions with a flow velocity of 1 m s⁻¹ at temperatures of 125, 150 and 175 °C. Electrochemical tests of impedance and linear polarization resistance have been carried out, as well as mass loss tests and surface analysis.     

Effect of boron concentration on the corrosion resistance of cast B‐bearing steel in molten zinc

The microstructures, mechanical properties and corrosion resistance in molten zinc of five kinds of cast B‐bearing steels containing X wt% B ‐ 0.8 wt% Si ‐ 1.0 wt% Mn ‐ (1.0～2.0) wt% Cr ‐ (0.3～0.5) wt% C (X = 0.50, 1.00, 1.50, 2.00, 2.50) were studied. The effects of boron concentration on microstructure and mechanical properties of cast B‐bearing steels have been investigated by optical microscopy (OM), X‐ray diffraction (XRD) analysis, hardness and impact tester. The evaluation of corrosion resistance in molten zinc of cast B‐bearing steel is calculated from the slopes of mass loss versus dipping time and surface area of sample at 480 °C. The results showed that boride volume fraction and hardness increased and the impact toughness of cast B‐bearing steel decreased with the increase in boron concentration. The corrosion rate of cast B‐bearing steels decreased and corrosion resistance in molten zinc increased with the increase in boron concentration. Moreover, the corrosion rate of cast B‐bearing steels decreased with the increase in temperature of molten zinc.     

The influence of chromium content on the electrochemical behavior of weathering steels

To investigate the influence of chromium content on corrosion characteristics of weathering steels, the electrochemical measurements were performed on the steels containing 0–9% Cr (wt.%) in NaHSO₃ aqueous solution. The results indicated that the open circuit potential of these steels shifted to the positive direction remarkably, because the additions of Cr improved the passivation capability of the steels. The corrosion current density of the steels containing more than 7% Cr (wt.%) decreased significantly after pre-rusted treatment, implying the corrosion resistance could be enhanced by the formation of protective goethite rust layer.     

Structure and properties of Ti(IV)-doped zinc hydroxychloride rusts formed at various temperatures

To simulate the atmospheric corrosion of steels galvanized with Ti–Zn alloys under different atmospheric temperatures, Ti(IV)-doped zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O: ZHC) was prepared at various aging temperatures of 6–120 °C. Adding the Ti(IV) inhibited the crystallization and particle growth of ZHC, showing a minimum at 50 °C. Higher aging temperature promoted the formation of TiO₂ nano-particles. Elevating the aging temperature suppressed the adsorption of H₂O and CO₂ on Ti(IV)-doped ZHC. These results suggest that the alloying Ti in galvanized steel forms compact zinc rust layer at various atmospheric temperatures in marine environment, which would lead to the enhancement of corrosion resistance.     

Corrosion of austenitic and ferritic-martensitic steels exposed to supercritical carbon dioxide

Supercritical carbon dioxide (S-CO₂) is a potential coolant for advanced nuclear reactors. The corrosion behavior of austenitic steels (alloys 800H and AL-6XN) and ferritic-martensitic (FM) steels (F91 and HCM12A) exposed to S-CO₂ at 650 °C and 20.7 MPa is presented in this work. Oxidation was identified as the primary corrosion phenomenon. Alloy 800H had oxidation resistance superior to AL-6XN. The FM steels were less corrosion resistant than the austenitic steels, which developed thick oxide scales that tended to exfoliate. Detailed microstructure characterization suggests the effect of alloying elements such as Al, Mo, Cr, and Ni on the oxidation of the steels.     

Accelerated corrosion of five commercial steels under a ZnCl2-KCl deposit in a reducing environment typical of waste gasification at 673-773 K

The corrosion of five Fe-Cr commercial steels containing 0-18 wt.% Cr at 673-773 K has been studied in a reducing H₂-HCl-CO₂ atmosphere under a ZnCl₂-KCl deposit typical of waste gasification environments. In comparison with the behavior of the same steels in a similar gas mixture without salt deposit, all steels suffered from accelerated corrosion induced by the salt and formed porous scales with poor adherence to the underlying steels. Some Cl was detected close to the steels/scale interface, indicating that Cl-containing species were able to go through the scale down to the metal matrix. Even though the corrosion rates generally decreased with increasing Cr content, the high-Cr stainless steel SS304 was still unable to provide a good corrosion resistance against the ZnCl₂-KCl deposit. The reaction mechanisms are discussed on the basis of thermodynamic considerations and of the “active oxidation” model.     

Hot corrosion of a novel (Ni,Co)O/(Ni,Co)Fe2O4 composite coating thermally converted from an electrodeposited Ni–Co–Fe2O3 composite coating

Ni–Co–Fe₂O₃ composite coatings were successfully developed by sediment co-deposition. In order to improve their hot corrosion resistance, a pre-oxidation treatment was conducted at 1000 °C for 6 h. The corrosion behaviour of the oxidised composite coating was investigated at 960 °C in an atmosphere consisting of a mixture of Na₃AlF₆–AlF₃–CaF molten salts and air. They exhibited good hot corrosion resistance due to not only the pre-formed oxide scale with (Ni,Co)O and (Ni,Co)Fe₂O₄ phases after pre-oxidation, but also the formation of (Ni,Co,Fe)Al₂O₄ phases in the outer layer and a well-distributed NiFe₂O₄-enriched phase along the grain boundaries in the subscale area during the corrosion process.     

Internal oxidation and phase transformations of multi-phase Fe–Ni–Al and Fe–Ni–Al–Cr alloys induced by KCl corrosion

The corrosion of two multiphase Fe–Ni–Al and Fe–Ni–Al–Cr alloys is studied at 650 °C in KCl-contaminated air. The oxidation rate of the alloys in air alone is low. When KCl is introduced, the corrosion is accelerated, producing a thick external scale of iron oxides, an intermediate layer of spinel, and a region of internal oxidation of Al. Potassium chromate is detected on Fe–Ni–Al–Cr surface that accounts for the degradation of protective chromia. An Al-depleted single phase region is observed in the front of the internal oxidation, due to the selective consumption of Al via an “active oxidation” process.     

Clarification of chemical state for alloying elements in iron rust using a binary-phase potential-pH diagram and physical analyses

A binary-phase potential-pH diagram has been investigated to evaluate the chemical stability of various kinds of double oxide rusts (Fe-X) to get a principle for alloy design enhancing the corrosion resistance of steels. It was found that there are the following types of alloying elements enhancing the corrosion resistance of steels in the rust: (1) iron substitution type (Ni), (2) oxide formation type (Al), (3) metallic type (Ru), and (4) oxygen-acid salt type (WO₄). X-ray photoelectron spectroscopy and transmission electron microscopy analyses have been conducted on the rust formed on the low alloy steel in a saline environment. The analytical results were discussed using potential-pH diagrams. The iron substitution type and the oxide formation type elements make spinel double oxides with iron. In the corrosion tests, steels added with Ni or Al had high corrosion resistance. Thus it is possible to obtain high corrosion resistance by the creation of spinel double oxide such as Fe₂NiO₄ and FeAl₂O₄ in an inner layer.On the other hand it was found that the metallic type and the oxygen-acid salt type elements were not contained into the iron rust. In particular the oxygen-acid salt elements were excluded from the iron rust and concentrated into the defects of the rust. It is suggested that insoluble salts like FeWO₄ are formed on the base metal in the defects to act as an anodic inhibitor. Thus, the addition of a small quantity of W gives high corrosion resistance.The penetration of Cl ions can be prevented by the spinel double oxide in an inner layer and the oxygen-acid salt in the defects. In this way, the high corrosion resistance by the addition of these elements can be understood from the potential-pH diagram and the physical analyses.     

The corrosion of Fe3Al alloy in liquid zinc

A systematic study of the isothermal corrosion testing and microscopic examination of Fe₃Al alloy in liquid zinc containing small amounts of aluminum (less than 0.2 wt.%) at 450 °C was carried out in this work. The results showed the corrosion of Fe₃Al alloy in molten zinc was controlled by the dissolution mechanism. The alloy exhibited a regular corrosion layer, constituted of small metallic particles (diameter: 2-5 μm) separated by channels filled with liquid zinc, which represented a porosity of about 29%. The XRD result of the corrosion layer formed at the interface confirmed the presence of Zn and FeZn_6.67. The corrosion rate of Fe₃Al alloy in molten zinc was calculated to be approximately 1.5 × 10⁻⁷ g cm⁻² s⁻¹. Three steps could occur in the whole process: the superficial dissolution of metallic Cr in the corrosion layer, the new phase formation of FeZn_6.67 and the diffusion of the dissolved species in the channels of the corrosion layer.     

Corrosion of low-temperature nitrided molybdenum-bearing stainless steels

Austenitic stainless steels with up to 6.1 wt.% Mo were nitrided at 425 °C and examined in 0.1 M Na₂SO₄ without and with chlorides at pH 3.0 and 6.5. Nitrided steels exhibited an increased resistance to pitting, but at pH 3.0 they had a decreased resistance to general corrosion. After corrosion at pH 3.0 surface films contained chromium nitrides and oxides of Mo, Cr and Fe. It is proposed that the improved pitting resistance of nitrided steels is associated with the initially accelerated dissolution which leads to the accumulation of corrosion resistant CrN and of oxidised steel components.     

Grain size effects on the oxidation of two ternary Cu-Ni-20wt.% Cr alloys at 700-800 °C in 1 atm O2

Two nanocrystalline two-phase Cu-Ni-Cr alloys, both prepared by mechanical alloying and containing about 20 at.% Cr but with different Ni contents (40 and 20 wt.%, respectively), have been oxidized in 1 atm O₂ at 700-800 °C. Their oxidation behavior has been compared with that of two cast alloys of the same composition, already studied previously, to examine the effects of a large reduction of the size of the individual phase grains and particles. The nanophase alloy with 40 wt.% Ni formed a flat external layer of chromia of regular thickness, while the corresponding cast alloy produced a very irregular chromia layer, often protruding deeply into the alloy, only after an initial stage of rather fast corrosion involving also copper and nickel, associated with some degree of internal oxidation. By oxidation at 700 °C the nanophase alloy with 20 wt.% Ni formed an irregular chromia layer associated with low corrosion rates. The corresponding cast alloy formed complex scales containing Cu, Ni and Cr oxides, extending into the alloy in the form of large pegs, even though a very irregular and discontinuous innermost chromia layer was still able to produce low corrosion rates. On the contrary, at 800 °C both alloys formed complex scales containing mixtures of the oxides of the three metal components. However, the scales grown on the cast alloy were much more irregular in thickness and formed large protrusions into the alloy. In spite of this, the corrosion kinetics of the nanophase 20 wt.% Ni alloy at 800 °C were more irregular and, except for an initial stage, less protective than that of the cast alloy with the same composition.     

Influence of anions on the formation and structure of artificial zinc rusts

To simulate the atmospheric corrosion of steels galvanized with Zn under different conditions, artificial zinc rusts of basic zinc salt (BZS) were prepared by hydrolyzing ZnO particles in aqueous solutions including ZnCl₂, ZnSO₄ and Zn(NO₃)₂. In ZnCl₂–ZnSO₄, ZnSO₄–Zn(NO₃)₂ and ZnCl₂–Zn(NO₃)₂–ZnSO₄ systems, zinc hydroxysulfate (Zn₄(OH)₆(SO₄)·nH₂O) was formed while zinc hydroxychloride (Zn₅(OH)₈Cl₂·H₂O) was generated in ZnCl₂–Zn(NO₃)₂ system. Zinc hydroxynitrate (Zn₅(OH)₈(NO₃)₂·2H₂O) was yielded in only Zn(NO₃)₂ system. All the formed artificial zinc rusts were hexagonal plate particles. These results suggest that SO_x is the most effective corrosive gas on the formation of BZS rusts on galvanized steel.     

Hydrogen uptake in austenitic stainless steels by exposure to gaseous hydrogen and its effect on tensile deformation

Hydrogen solubility and diffusivity of Fe–Cr–Ni austenitic stainless steels were measured through exposure to gaseous hydrogen at a pressure of 10 MPa over the temperature range 110–235 °C. The hydrogen solubility depended on the alloy compositions, whereas the diffusion coefficients were nearly identical at a given temperature. Hydrogen uptake in the stable austenitic steels by exposure to high-pressure gaseous hydrogen led to some loss of ductility, while their fracture surfaces showed evidence of plastic deformation. This was attributed to the enhanced inhomogeneity of plastic deformation in the presence of hydrogen and the increased stress for plastic instability with increasing hydrogen concentration.     

Chromium–palladium films on 316L stainless steel by pulse electrodeposition and their corrosion resistance in hot sulfuric acid solutions

Chromium–palladium alloy films with good adhesive strength and higher micro-hardness have been deposited on 316L stainless steel by pulse electroplating. The films are composed mainly of chromium and palladium crystallites in the metallic state, with grain sizes less than 100 nm. On the film surface Cr(OH)₃ and Cr₂O₃ are present. The co-deposited Cr and Pd in the films show a synergetic effect on passivation. In boiling 20 wt.% H₂SO₄ solution, boiling acetic–formic acid mixture, and simulated PEM fuel cells environment, the Cr–Pd-plated 316L steel shows excellent corrosion resistance.     

Electrodeposition of Zn–Ni coatings as Cd replacement for corrosion protection of high strength steel

Electrodeposition of Zn–Ni coatings performed in acidic baths are not suitable for high strength steels due to their high susceptibility to hydrogen embrittlement.In this work, Zn–Ni coatings were deposited on a high strength steel (4340) upon stirring conditions from an alkaline bath. A complete characterisation of the coatings (corrosion, morphology and composition) has been accomplished, correlating the electrodeposition conditions with these features. The best protective properties of the grown coatings were achieved for the alloys with a single phase structure of γ-Ni₅Zn₂₁ and a denser morphology. Additionally, the hydrogen content incorporated is lower than even cadmium-coated 4340 steel which has undergone a postbaking dehydrogenation treatment.     

Effects of cerium and manganese on corrosion of Fe–Cr and Fe–Cr–Ni alloys in Ar–20CO2 gas at 818 °C

Model alloys Fe–9Cr, Fe–20Cr and Fe–20Cr–20Ni (wt.%) with Ce (0.05%, 0.1%) or Mn (1%, 2%) were exposed to Ar–20CO₂ gas at 818 °C. Scales on Fe–9Cr alloys consisted of FeO and FeCr₂O₄, Fe–20Cr–(Ce) alloys formed only Cr₂O₃, and Fe–20Cr–(Mn) alloys formed Cr₂O₃ and MnCr₂O₄. All Fe–20Cr–20Ni alloys formed Fe₃O₄, FeCr₂O₄ and FeNi₃. Cerium additions had little effects, but additions of 2% Mn significantly improved oxidation resistance of Fe–20Cr and Fe–20Cr–20Ni alloys. Most alloys also carburized. All alloys developed protective chromium-rich oxide scales in air. Different behavior in the two gases is attributed to faster Cr₂O₃ scaling rates induced by CO₂.