Discontinuous oxidation and erosion-oxidation of a CeO2-dispersion-strengthened chromium coating

A CeO₂-dispersion-strengthened chromium coating was developed on a carbon steel using a two-step process: prior electrodeposition of a Ni-CeO₂ nanocomposite film and subsequent chromization using a conventional pack cementation method. Compared to the CeO₂-free coatings prepared on the carbon steel without and with pre-electrodeposition of a pure Ni film, the CeO₂ dispersed chromium coating offered profoundly improved discontinuous oxidation resistance at 900 °C in 5% O₂ + N₂ and in 5% O₂ + 1000 ppm SO₂ + N₂, and erosion-oxidation resistance in a laboratory-scale fluidized-bed combustor (FBC), mainly because of the development of a denser, less wrinkled and more adherent chromia scale.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.     

Hot corrosion behaviour of Yb2Zr2O7 ceramic coated with V2O5 at temperatures of 600-800 °C in air

To better understand the hot corrosion behaviour of Yb₂Zr₂O₇ ceramic in molten V₂O₅, hot corrosion experiments were performed in a temperature range of 600-800 °C in air. Different reaction products of ZrV₂O₇, YbVO₄ and m-ZrO₂ were identified depending upon the hot corrosion conditions, for example, ZrV₂O₇ and YbVO₄ at 600 °C for 2 h and 8 h; ZrV₂O₇, m-ZrO₂ and YbVO₄ at 700 °C for 2 h; m-ZrO₂ and YbVO₄ either at 800 °C for 2 h or at 700-800 °C for 8 h. The hot corrosion reaction mechanisms were further discussed based on the thermal instability of ZrV₂O₇ at elevated temperatures.     

Effect of lamellar microstructure on oxidation kinetics of Fe3Al sintered by hot isostatic pressing

The present paper focuses on the investigation of the relationship between microstructure of Fe₃Al prepared by hot isostatic pressing (HIP) and kinetics of alumina layer formation during oxidation at 900 °C, 1000 °C and 1100 °C. As prepared HIPed Fe₃Al sample reveals lamellar microstructure with inhomogeneous Al distribution which originates from the preliminary mechanical activation of Fe-Al mixture. At 900 °C, Fe₃Al oxidation is characterized by selective growth of very rough alumina layer containing only transient aluminium oxides. In addition to these transient oxides, α-Al₂O₃ stable phase is formed at 1000 °C. At the highest temperature (1100 °C), continuous and relatively smooth alumina layer mainly contains fine crystallites of α-Al₂O₃. The initial lamellar structure and phase inhomogeneity in as-HIPed Fe₃Al samples are supposed to be the main factors that determine observed peculiarities after Fe₃Al oxidation at 900 °C and 1000 °C.     

Temperature and water vapour effects on the cyclic oxidation behaviour of Fe-Cr alloys

Binary Fe-Cr alloys were subjected to cyclic oxidation at 600, 700 and 950 °C in flowing gases of Ar-20O₂ and Ar-20O₂-5H₂O (vol.%). The minimum chromium concentration required to achieve protective scale growth decreased as temperature increased from 600 to 700 °C. This change is attributed to faster chromium diffusion at higher temperature. Conversely, this minimum chromium level increased when the temperature was raised from 700 to 950 °C. This is attributed to faster scale growth, leading to its rapid mechanical failure, along with formation of slow-diffusing austenite. Water vapour accelerated scaling, leading to a need for higher chromium concentrations to resist breakaway oxidation.     

Recession behavior of Yb2Si2O7 phase under high speed steam jet at high temperatures

Recession behavior of Yb₂Si₂O₇ phase was examined under high speed steam jet environment between 1300 °C and 1500 °C. Yb₂SiO₅ phase was formed on the bulk surface by the decomposition of Yb₂Si₂O₇ phase and the elimination of silica component at elevated temperatures. The phase ratio of Yb₂SiO₅/Yb₂Si₂O₇ increased up to 1400 °C and then decreased above 1400 °C. The relative intensity of 2 2 0 peak for Yb₂Si₂O₇ phase increased with increasing the temperatures. Fine grains were generated on the bulk surface at 1300 °C. The phase decomposition caused on the grain interior. A porous structure was formed on the bulk surface during the test at 1400 °C. Surface cracks were generated for 1400 °C test sample. A smooth surface was generated on the surface of 1500 °C test sample. The triple points of the grains were bridged with a glassy phase.     

Detection of breakaway oxidation with Acoustic Emission during titanium oxide scale growth

Extensive in-situ analysis of high temperature breakaway oxidation of titanium metal has been performed using the Acoustic Emission (AE) technique. Depending on temperature and oxidising atmosphere, different model cases were examined: with breakaway (900 °C/O₂), without breakaway (750 °C/O₂ and 900 °C/H₂O). Two specific population of AE hits were observed before and after breakaway. Contrary to the pre-breakaway population, the post-breakaway population exhibited low AE activity characterised by high values of energy. A critical energy value of E = 3 fJ was determined as a frontier between signals resulting from oxide parabolic growth and signals resulting from rapid linear growth.     

Temperature dependence of oxide scale formation on high-Cr ferritic steels in Ar–H2–H2O

Four high chromium ferritic steels were oxidized in Ar/H₂/H₂O at temperatures between 500 and 900 °C. Polished specimens of all steels formed iron-rich oxides at temperatures below 600 °C, whereas increasing the temperature resulted in local formation of protective chromia scales. As the temperature was raised further, the specimens were totally covered with chromia scales. For the higher chromium steels this was also observed at 900 °C but not for the steel with a chromium content of 16%. The temperature dependence of the oxidation rates is governed by the competing diffusion processes in the alloy and the growing scales.     

Oxidation performance of Mo3Si with Al additions

The Mo₃Si alloys with different aluminum contents were fabricated by the arc-melting and drop-casting technique, heat treated and then exposed to air at 700, 800, 900 and 1000 °C in order to assess their oxidation behavior. Line scan studies led to the assumption that the oxide scale thermally grown at 1000 °C was composed of SiO₂ which was located closer to the alloy matrix and Al₂O₃ around the outer surface of the oxidized sample, while the Mo oxide volatilized at this oxidation temperature. The results also showed that the unalloyed sample (Mo₃Si) underwent a pest reaction in a short time of exposure, while the sample with 16 at.% Al exhibited the best oxidation behavior, which could be attributed to the formation of SiO₂ and Al₂O₃ in the oxide scale.     

Baking treatment effect on materials characteristics and electrochemical behavior of anodic film formed on AZ91D magnesium alloy

The composition and microstructure of the anodic films formed on AZ91D Mg alloy, with or without baking, were investigated. The associated corrosion behavior of the anodized alloy in 3.5 wt% NaCl solution was also examined using electrochemical impedance spectroscopy (EIS). The results show that MgO was the main component in the anodic film which also contained some Mg(OH)₂, Al₂O₃, Al(OH)₃, and MgAl₂O₄. Both the amorphous and crystalline forms of anodic film were identified. The degree of crystallinity depended on baking temperature, which increased with increasing temperature in the range of 50-250 °C. The amounts of MgO and Al₂O₃ increased as a result of a dehydration reaction. The polarization resistance of anodized Mg alloy was improved significantly by increasing the oxide content in the anodic film. An optimum value of polarization resistance of anodic film was obtained for the alloy baked at 150 °C for 2 h followed by air cooling.     

Effects of dithionite ion on corrosion of type 304 stainless steel in sulphuric acid solution

Corrosion behaviour of type 304 stainless steel was investigated, with particular attention to additive effects of hydrosulphite (Na₂S₂O₄) on corrosion in 0.1 mol/l H₂SO₄ solution with various amounts of Na₂S₂O₄ up to 60 mmol/l.Corrosion of SUS304 occurred below pH 3.0 at 30 °C in a 0.1 mol/l H₂SO₄ solution in which Na₂S₂O₄ was added to 0.1-20 mmol/l. The maximum corrosion rate at 30 °C was measured as 7.2 g/m² h (7.9 mm/y) in 0.1 mol/l H₂SO₄-10 mmol/l Na₂S₂O₄ at pH 1.2. Microscopic surface observation revealed that active dissolution was accompanied by intergranular corrosion at the metal surface.The SUS304 was easily passivated in 0.1 mol/l H₂SO₄ solution with more than 30 mmol/l Na₂S₂O₄. NiS was detected in the passivated film.     

Nucleation and growth of selective oxide particles on ferritic steel

In the continuous annealing process, steel sheets are annealed at 800 °C in an atmosphere of nitrogen and hydrogen (5 vol.%) containing low partial water pressure (20-50 Pa). Under these conditions, the most oxidizable alloying elements in the steel segregate towards the surface where they form oxide particles. The nucleation and growth of those oxides were examined. Oxide nucleation mainly occurs between 650 and 750 °C. During their growth, the oxides take the form of a spherical cap and are composed of MnO, Mn₂SiO₄ (or MnSiO₃), MnAl₂O₄, SiO₂, Al₂O₃ and B₂O₃. Particle nucleation and growth are favored on grain boundaries.     

Dense La0.9Sr0.1Ga0.8Mg0.2O2.85 electrolyte for IT-SOFC's: Sintering study and electrochemical characterization

This paper presents the sintering behaviour of a La_0.9Sr_0.1Ga_0.8Mg_0.2O_2.85 coral-like microstructure powder. This is prepared by a successive freeze-drying and self-ignition process followed by calcination at 1200 °C during 1 h. This synthesis method gives great uniformity of the powder and allows shaping into compacts without requiring a grinding step. The grain size distribution (between 0.5 and 4 μm) favours a good sintering behaviour: open porosity disappear at 1400 °C and relative densities over 99% can be achieved after 6 h at 1450 °C. The same powder can also be sintered into a thin disc of ∼100 μm thickness. The characterization of the dense material by impedance spectroscopy shows that the activation energies below and above 600 °C are 1.0 eV and 0.7 eV, respectively. The conductivity at 800 °C is ∼0.11 S cm⁻¹. Special attention is devoted to the temperature range between 200 °C and 400 °C, where the intragrain and intergrain contributions can be distinguished. The analysis of the parameters describing the intragrain constant phase element in the equivalent circuit suggests that, above 325 °C, the system evolves from a distribution of relaxation time to only one relaxation time. The analysis of the data by the complexes permittivity show that ionic oxide conduction mechanism would occur in two steps. In the first, an oxygen vacancy would be released and, in the second, the migration of the ionic oxide would take place in the material.     

Transient oxidation in Fe-Cr-Ni alloys: A Raman-scattering study

Using Raman scattering we have investigated the oxidation, in air, of the Fe-Cr-Ni stainless steels Fe-25Cr-20Ni, Fe-25Cr-20Ni-3Zr, and Fe-24Cr-3Zr (wt.%) as a function of temperature in the range 300 to 1000°C. The Raman technique is very sensitive to, and provides a clear identification of, the oxides Fe₂O₃ and Cr₂O₃. However, the technique is insensitive to NiO, FeO, and does not give a clear identification of spinels. The Fe–Cr–Ni alloys form chromia scales at temperatures greater than 800°C. At lower oxidation temperatures, transient phases are observed. With a 1-h heat treatment at 300°C, we observe the formation of an unidentified scale; we speculate that it is either amorphous or consists of disordered spinel(s). Near 400°C we begin to observe hematite (Fe₂O₃). The intensity of the Fe₂O₃ signal increases with temperature to 600°C and then decreases, being largely replaced by the signal from Cr₂O₃. The thickness of the Cr₂O₃ scale increases with temperature up to 1000°C above which spallation becomes apparent. Spinel phases also apparently persist in the scale to 1000°C.     

Early high temperature oxidation behaviour of Ti(C,N)-based cermets in air

Isothermal oxidation behaviour of two Ti(C,N)-based cermets (TiC-10TiN-16Mo-6.5WC-0.8C-0.6Cr₃C₂-(32-x)Ni-xCr, x = 0 and 6.4 wt%) was investigated in air at 800-1100 °C up to 2 h. Mass gains exhibited neither linear nor parabolic law during isothermal oxidation. The oxide scales formed at 800-1100 °C were multi-layered, consisting of NiO outerlayer, NiTiO₃ interlayer and TiO₂-based innerlayer. The internal oxidation zones formed at 1000-1100 °C consisted of Ti-based, Ni-based and Mo-based complex oxides. Cermet with 6.4 wt% Cr exhibited superior oxidation resistance, due to the presences of Cr_0.17Mo_0.83O₂ in TiO₂-based innerlayer of the oxide scale and Cr-rich Ti-based complex oxide in the internal oxidation zone.     

Corrosion inhibition during synthesis of Cu2O nanoparticles by 1,3-diaminopropylene in solution

Corrosion inhibition for Cu₂O nanoparticles in solution using the regulators of 1,3-dimorpholinpropylene and 1,3-diethylaminopropylene was studied by experimental and theoretical calculation methods. The inhibition mechanism of regulators was related to the arrangement of cetyltrimethylammonium (CTAB) molecules on the surface of Cu₂O nanoparticles. Control of the type and amount of regulators has been demonstrated to produce well-dispersed and active Cu₂O nanoparticles (∼100 nm). The oxidation temperature of Cu₂O nanoparticles decreased from 297.9-404.4 °C (blank) to 232.3-334.3 °C (containing regulator). For 1,3-dimorpholinpropylene, its arc structure and active sites (C_4C_5, N_2 and O_2) facilitate the formation of stable protective film over Cu₂O surface.     

Atmospheric pressure chemical vapour deposition and characterisation of crystalline InTaO4, InNbO4 and InVO4 coatings

The possibilities to grow crystalline complex InTaO₄, InNbO₄ and InVO₄ coatings as well as single oxide layers In₂O₃, Ta₂O₅, Nb₂O₅, and VO_x were investigated using aerosol assisted atmospheric pressure chemical vapour deposition technique. Indium(III) and niobium(IV) tetramethylheptanedionates, tantalum(V) tetraethoxyacethylacetonate and vanadium(III) acethylacetonate were used as precursors, monoglyme and toluene as solvents. The influence of deposition conditions and solution composition on elemental and phase compositions of layers was studied. Indium tantalate layers containing pure monoclinic InTaO₄ phase were obtained ex-situ, i.e., after high-temperature (800 °C) annealing of layers grown at lower temperature (500 °C). Films containing pure orthorhombic indium vanadate or monoclinic indium niobate phase may be prepared using both in-situ (600 °C) or ex-situ (deposition at 400 °C, annealing at 800 °C) approaches. Under optimised deposition conditions and solution compositions, Ni-doped InVO₄ and InTaO₄ films were also deposited and their photocatalytic activity was tested.     

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.     

Hot corrosion behaviour of Ni3Al in sulphate-chloride mixtures in the atmosphere

Hot corrosion of Ni₃Al intermetallic compound in the presence of sulphate-chloride mixtures was studied. A comminuted Ni₃Al mixed with NaCl-Na₂SO₄, NaCl-Li₂SO₄, LiCl-Na₂SO₄, LiCl-Li₂SO₄ additions was oxidized in the air up to 1000 °C with linearly increasing temperature and isothermally within the temperature range of 500-700 °C. The corrosion process was observed by thermogravimetric method using Mettler thermoanalyzer.The experiments indicated that LiCl (∼10 wt.%)-Li₂SO₄ mixture was the most corrosive agent. It was also found that by addition of MgO the corrosion of Ni₃Al was reduced. Phase composition of the corrosion products was established by X-ray diffraction analysis; there were detected Al₂O₃, Al₂S₃, NaAlO₂ (or LiAlO₂) as intermediate products, nickel sulphides, NiO and NiAl₂O₄. NiAl₂O₄ spinel was formed only at the highest temperatures, while at lower temperatures alumina was present instead of spinel.Hot corrosion behaviour of Ni₃Al in sulphate-chloride mixtures in air atmosphere.     

Structure and high-temperature oxidation behaviour of Cu-Ni-Fe alloys prepared by high-energy ball milling for application as inert anodes in aluminium electrolysis

Cu_xNi_85−xFe₁₅ (0 ? x ? 85 wt.%) compounds were prepared by mechanical alloying. Monophased face centered cubic (fcc) Cu-Ni-Fe alloys were obtained after 10 h of milling for x varying from 0 to 50, whereas bi-phased compounds fcc Cu-Ni-Fe + body centered cubic (bcc) Fe were formed with richer-Cu compounds. Their oxidation kinetics in air at 750 °C is parabolic for all compositions and increases drastically for x > ∼30. A stable anode for aluminium electrolysis in low-temperature (700 °C) KF-AlF₃ electrolyte was obtained for 65 ? x ? 85. However, a substantial increase of the Cu contamination in produced aluminium was observed for x > 70.