Characterisation of oxide films formed on Co–29Cr–6Mo alloy used in die-casting moulds for aluminium

Oxide films formed at 700 °C on Co–29Cr–6Mo alloy were characterised extensively to improve the corrosion resistance of the alloy to liquid Al, enabling its use in Al die-casting moulds. Film of duplex layer consisting of an outer CoO-rich layer and an inner Cr₂O₃-rich layer was observed in samples subjected to oxidation for 4 h. With an increase in duration of oxidation, CoO was gradually replaced by Cr₂O₃, resulting in a single-layered oxide film dominantly composed of Cr₂O₃. The oxide film evolved with duration of oxidation treatment indicating the possibility of optimising films for Al die-casting moulds.     

The enhanced passivation of 316L stainless steel in a simulated fuel cell environment by surface plating with palladium

A thin layer of Pd deposition on the surface significantly improves the corrosion resistance of 316L stainless steel in 0.5 mol L⁻¹ H₂SO₄ + 2 ppm F⁻ solution at 80 °C. Compared with the air-formed passive film, the passive film formed in the stainless steel/Pd couple contains more Cr, Cr(OH)₃ and Fe₃O₄ and less point defects, which provides better protection to the stainless steel substrate. The interfacial contact resistance of the stainless steel surface is also decreased. The Pd plated stainless steel is a potential material for bipolar plates in proton exchange membrane (PEM) fuel cells.     

In situ X-ray diffraction of surface oxide on type 430 stainless steel in breakaway condition using synchrotron radiation

Changes in the crystal structure of type 430 stainless steel and the oxides on its surface were studied in situ at 1373 K using a high-intensity synchrotron X-ray source provided by SPring-8 in Japan. The surface of the steel was initially covered with Cr₂O₃, which was then converted to FeCr₂O₄, and finally Fe₃O₄ and Fe₂O₃ formed on it. These results indicated that the reason for the breakaway oxidation in type 430 stainless steel is Cr depletion beneath Cr₂O₃ layer and the subsequent ionisation of Fe, not the simple mechanical failure of Cr₂O₃.     

Corrosion behavior of an alumina forming austenitic steel exposed to supercritical carbon dioxide

Microstructure characterization of corrosion behavior of an alumina forming austenitic (AFA) steel exposed to supercritical carbon dioxide was conducted at 450–650 °C and 20 MPa. At low temperature and short exposure times, the oxidation kinetics were parabolic and the oxide scales were mainly composed of protective and continuous Al₂O₃ and (Cr, Mn)-rich oxide layers. As the temperature and exposure time increased, the AFA steel gradually suffered breakaway oxidation and its oxide scales showed a multilayer structure mainly composed of Fe₃O₄, (Cr, Fe)₃O₄, NiFe/FeCr₂O₄/Cr₂O₃/Al₂O₃, FeCr₂O₄/Al₂O₃, and NiFe/Cr₂O₃/Al₂O₃, in sequence. The corrosion mechanism based on the microstructure evolution is discussed in detail.     

Glass coatings on stainless steels for high-temperature oxidation protection: Mechanisms

The oxidation behavior of a martensitic stainless steel with or without glass coating was investigated at 600–800 °C. The glass coating provided effective protection for the stainless steel against high-temperature oxidation. However, it follows different protection mechanisms depending on oxidation temperature. At 800 °C, glass coating acts as a barrier for oxygen diffusion, and oxidation of the glass coated steel follows linear law. At 700 or 600 °C, glass coating induces the formation of a (Cr, Fe)₂O₃/glass composite interlayer, through which the diffusion of Cr³⁺ or Fe³⁺ is dramatically limited. Oxidation follows parabolic law.     

A comparison of the oxidation behaviours of Al2O3 formers and Cr2O3 formers at 700 °C – Oxide solid solutions acting as a template for nucleation

The oxidation behaviour of a number of ferritic iron based commercial steels and model alloys containing 6 and 9 wt% Cr and 0–2.5 wt% Al have been studied at 700 °C. The oxidation time ranged from 5 min to 500 h and the atmosphere consisted of flowing dry synthetic air. The oxide layers formed were analysed by SEM, GI-XRD and ToF-SIMS. The material without Al formed a (Cr,Fe)₂O₃ film with an Fe enrichment in the outer part of the layer. The Al containing alloys showed more complex oxidation behaviour. The oxidation started initially by formation of (Cr,Fe)₂O₃ with an Cr enriched inner part. With time Al was oxidized and dissolved in the inner Cr rich part of the oxide. This process continued until it eventually was transformed into α-Al₂O₃ with minute amount of Fe in the outer and Cr in the inner part of the oxide. The thickness of all oxide films ranged from 20 to 400 nm apart from the material that contained 9% Cr and no Al, which experienced breakaway oxidation after 500 h at 700 °C. This means that materials alloyed with small amounts of Al must also be considered to be protective at 700 °C, as the thicknesses of the Al₂O₃ oxides was comparable with the ones not containing Al, and as they do not experience breakaway corrosion.     

High-temperature oxidation and hot corrosion of Cr2AlC

High-temperature oxidation and hot corrosion behaviors of Cr₂AlC were investigated at 800–1300 °C in air. Thermogravimetric–differential scanning calorimetric test revealed that the starting oxidation temperature for Cr₂AlC is about 800 °C, which is 400 °C higher than other ternary transition metal aluminum carbides. Thermogravimetric analyses demonstrated that Cr₂AlC displayed excellent high-temperature oxidation resistance with parabolic rate constants of 1.08 × 10⁻¹² and 2.96 × 10⁻⁹ kg² m⁻⁴ s⁻¹ at 800 and 1300 °C, respectively. Moreover, Cr₂AlC exhibited exceptionally good hot corrosion resistance against molten Na₂SO₄ salt. The mechanism of the excellent high-temperature corrosion resistance for Cr₂AlC can be attributed to the formation of a protective Al₂O₃-rich scale during both the high-temperature oxidation and hot corrosion processes.     

Corrosion resistance of duplex stainless steel subjected to long-term annealing in the spinodal decomposition temperature range

The effect of thermal annealing up to 15,000 h between 300 °C and 500 °C on the corrosion resistance of the duplex stainless steel (DSS) 7MoPLUS has been investigated by using the DLEPR test. Spinodal decomposition in 7MoPLUS is unabated even after annealing for 15,000 h and no healing has been observed. The possible healing mechanisms in this temperature range (back diffusion of Cr atoms from the Cr-rich ferrite (α_Cr) and diffusion of Cr atoms from the austenite) and its absence in the present steel have been discussed.     

Influence of Cr and Ni content in stainless steel on the degradation mechanisms in PbO–CaO–SiO2 slag

Degradation of stainless steel in contact with PbO–CaO–SiO₂ slag at 1200 °C is experimentally investigated. The contact between steel and slag leads to the reduction of PbO from the slag to liquid Pb, and concurrent oxidation of the steel. The degradation mechanisms can be divided into liquid slag and liquid metal corrosion and oxidation. High Cr content is beneficial as it promotes the formation of a Cr₂O₃ scale which shields the steel from the slag and liquid Pb. The high solubility of Ni in liquid Pb is responsible for the increasing dissolution rate with increasing Ni content of the steel.     

High Temperature Oxidation Behavior of Alloy 617 and Haynes 230 in Impurity-Controlled Helium Environments

The high temperature oxidation behavior of alloy 617 and Haynes 230 have been investigated for VHTR intermediate heat exchanger applications. Oxidation tests were carried out for up to 500 h at 900 °C and 1000 °C in impure helium environments containing H₂, H₂O, CO, CO₂, and CH₄. The oxidation kinetics of the alloys followed a parabolic rate law in all cases. In the impure helium environments with very low oxygen, the external oxides of alloy 617 were composed of a Cr₂O₃ layer, TiO₂ ridges on the grain boundaries, and isolated MnCr₂O₄ grains on top of the Cr₂O₃ layer. On the other hand, those of Haynes 230 consisted of a Cr₂O₃ inner layer and a protective MnCr₂O₄ outer layer, which increased the oxidation resistance. The effect of small amounts of CH₄ and H₂ on the oxidation kinetics of the alloys was insignificant. Irregular oxide morphology, such as cellular Cr₂O₃ oxides for alloy 617 and MnCr₂O₄ platelets for Haynes 230, was formed in the impure helium environment at 900 °C. For Haynes 230, along with platelets, whiskers were frequently found at the tip of the MnCr₂O₄ oxide crystals.     

High temperature oxidation of AlCrFe complex metallic alloys

Isothermal oxidation of Al₆₅Cr₂₇Fe₈ and Al₈₀Cr₁₅Fe₅ was studied in the 600–1080 °C range. Formation of transient alumina layers is obtained up to 900 °C. On Al₆₅Cr₂₇Fe₈ transient to α-phase transformations occur when performing oxidation at 1000 °C, together with the possible appearance of (Al_0.9Cr_0.1)₂O₃. At 1080 °C, direct formation of α-alumina is obtained. On Al₈₀Cr₁₅Fe₅, spallation of the oxide layer during the cooling stage is observed following oxidation at 800 and 900 °C, revealing thermal etching of the underneath alloy surface. At 1050 °C the α-Al₂O₃ scale is directly formed but plastic deformation and recrystallization of the underneath alloy into several intermetallic phases is observed.     

Hot corrosion properties of composite coatings in the presence of NaCl at 700 and 900 °C

Cyclic hot corrosion tests have been carried out on three coatings (one NiCoCrAlY and two composite coatings) at 700 and 900 °C. The kinetic curves and evolution of microstructure show that the composite coating with a Cr-base interlayer performs best. The Cr₂O₃ scale is more effective to protect the coating at 700 °C than that at 900 °C. The corrosion process is accelerated by NaCl via forming volatile MCl_x and inducing the formation of molten voids in the coating or extra oxidation at the interface of fusant/oxide scale, determined by the temperature and the compositions of the coating.     

Oxidation of Fe–Si,Fe–Al and Fe–Si–Al alloys in CO2–H2O gas at 800 °C

Binary Fe–(1, 2, 3)Si and Fe–(2, 4, 6)Al, and ternary Fe–(2, 3)Si–(4, 6)Al alloys (all in wt%) were oxidised in Ar–20% CO₂, with and without H₂O, at 800 °C. All binary alloys except Fe–6Al, in all gases, formed a thin outer layer of Fe₃O₄, an intermediate Fe₃O₄ + FeO layer, an inner FeO + Fe₂SiO₄ (or FeAl₂O₄) layer and internally precipitated SiO₂ (or FeAl₂O₄). Ternary alloys and Fe–6Al developed a protective Al₂O₃ layer beneath Fe₂O₃ in Ar–20% CO₂. Water vapour affected ternary alloy oxidation only slightly, but Fe–6Al oxidized internally in high H₂O-content gas, and its scale was non-protective.     

Synthesis of chromium carbide nanopowders via a microwave heating method

Chromium carbide nanopowders were firstly synthesized via a simple microwave heating technique using nanometer chromic oxide (Cr₂O₃) and nanometer carbon black as raw materials in argon gas atmosphere. The samples were characterized by X-ray diffractometry (XRD), thermogravimetric and differential scanning calorimetry (TG–DSC), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The results show that chromium carbide nanopowders with an average crystallite size of 24 nm can be synthesized at 1000 °C for 1 h. The synthesis temperature required by the method is 400 °C lower than those required by the conventional approaches for preparing chromium carbide. SEM and TEM results show that the powders show good dispersion and are mainly composed of spherical or nearly spherical particles with a mean diameter of about 30 nm. The phase transformation sequence during the heat treatment is: Cr₂O₃ → CrO → Cr₇C₃ → Cr₂C → Cr₃C₂.     

Improved Cr2O3 adhesion by Ce ion implantation in the presence of interfacial sulfur segregation

As-polished and preoxidized Ni–20Cr alloys were Ce-implanted with a dosage of 1 × 10¹⁷ ions/cm², then subsequently oxidized at 1050 °C in air. The oxide adhesion and the extent of sulfur segregation at the oxide–alloy interface were determined, respectively, using tensile pull testing and scanning Auger microscopy with an in situ scratch device. The critical load for oxide failure was the lowest on the unimplanted Ni–20Cr, and was slightly higher on those with implantation made into a preformed oxide. Oxides that formed directly on Ce-implanted Ni–20Cr never failed under the pull test, which showed the strongest scale adhesion; however, similar amounts of interfacial sulfur, which segregated from the alloy during oxidation, were found at all interfaces. Ce additions were also found to reduce the oxidation rate and affect the extent of voids at the scale–alloy interface. It is suggested that the change in the oxide growth mechanism reduces the number of interfacial voids and, unlike Al₂O₃, these factors are more important for Cr₂O₃ scale adhesion than sulfur segregation to the scale–alloy interface.     

Nanoscale characterization of the transfer layer formed during dry sliding of Cu–15 wt.% Ni–8 wt.% Sn bronze alloy

The microstructure of the transfer layer, and the underlying severely plastically deformed layer (SPDL), formed during the dry sliding of a spinodally hardened Cu–15 wt.% Ni–8 wt.% Sn bronze against a stainless steel, is characterized at the nanoscale by conventional and analytical transmission electron microscopy, including energy-dispersive spectroscopy and electron energy loss spectroscopy. The SPDL consists of a Cu–Ni–Sn solid solution with elongated nanograins, due to extensive dislocation glide and twinning. In contrast, the transfer layer, 2–3 μm thick, is an equiaxed nanocomposite comprised of a Cu-rich metallic phase with a (Fe,Cr)₂O₃-based oxide precipitates, and forms as a result of the mechanical mixing and compaction of wear debris. The bronze in this layer has undergone dealloying, indicative of the importance of thermal effects. The dispersion of oxide in the transfer layer suggests a different type of forced mixing, possibly turbulent mixing. The transfer layer is observed to improve significantly the wear resistance of the bronze.     

Electrochemical synthesis of a biomedically important Co–Cr alloy

Co–30 wt.% Cr alloy was prepared by electro-deoxidation in molten calcium chloride at 1123 K. A preliminary study was conducted into the preparation of the mixture of the Co₃O₄ and Cr₂O₃ and the formation of the non-stoichiometric, spinel structured, mixed oxide nominally labeled Co_xCr_yO₄. Constant voltage chronoamperometry was used both to prepare the alloy and to investigate its mechanism of formation. Electro-deoxidation proceeds by the simultaneous rapid reduction of CoO to Co and the slower reduction/substitution of Co_xCr_yO₄ to CaCr₂O₄ and Co metal. The final step of the electro-deoxidation is the reduction of CaCr₂O₄ to Cr metal, which alloys with the Co metal, and release of Ca²⁺ back into the electrolyte.     

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.     

The effects of Cr and Al concentrations on the oxidation behavior of oxide dispersion strengthened ferritic alloys

The oxidation of six oxide dispersion strengthened (ODS) ferritic alloys was investigated at 1050 °C in air up to 200 h. Al plays the dominant role in improving the oxidation resistance of the ODS alloys. Cr and Y are of importance in forming the stable Al₂O₃ scale. To produce the dense alumina layer with enhanced adherence to the metal substrate, the concentrations of Al and Cr should be larger than 2 and 14 wt.%, respectively.     

Mechanism of (Mg, Al, Ca)-oxide inclusion-induced pitting corrosion in 316L stainless steel exposed to sulphur environments containing chloride ion

The mechanism of oxide inclusion-induced pitting corrosion in 316L stainless steel exposed to sulphur environments containing chloride ions was investigated by scanning electron microscope analysis, electrochemical measurements and scanning Kelvin probe force microscopy (SKPFM). Two inclusion types were observed. The (Mg, Al, Ca)-oxide inclusions play an important role in pitting formation. SKPFM measurement results show that the inclusion sites exhibited a lower surface potential than the matrix. Finally, the schematic representation of the initiation and propagation process of the (Mg, Al, Ca)-oxide inclusion-induced pitting corrosion in 316L stainless steel exposed to sulphur environments containing chloride ions was established.