Effects of water vapour on isothermal oxidation of chromia-forming alloys in Ar/O2 and Ar/H2 atmospheres

Fe9Cr, Fe17Cr and Fe25Cr alloys were subjected to isothermal oxidation in Ar/O₂ and Ar/H₂ atmosphere at 700 °C as high temperature corrosion for 48 h. Oxidation weight change measurement showed increasing Cr content reduced the oxidation rate. The oxidized Cr alloys were analysed using SEM, TEM and XRD. The addition of water vapour accelerates the onset of breakaway oxidation kinetics for Fe9Cr. The presence of water vapour promotes internal oxidation of Cr within Fe9Cr. For Fe17Cr and Fe25Cr, the water vapour effect is not significant due to the large Cr reservoir due to continue growth of Cr₂O₃.     

Impact of oxyfuel atmospheres H2O/CO2/O2 and H2O/CO2 on the oxidation of ferritic–martensitic and austenitic steels

In future power plant technologies, oxyfuel, steels are subjected to steam rich and carbon dioxide rich combustion gases. The effect of simulated combustion gases H₂O/CO₂/O₂ (30/69/1 mol%) and H₂O/CO₂ (30/70 mol%) on the corrosion behavior of low alloyed steels, 9–12% chromium steels and an austenitic steel were studied. It was discovered that the formation of protective chromium rich oxides is hampered due to the carburization of the base material and the formation of chromium rich carbides. The kinetics of corrosion and carburization are quantified. The effect of temperature and the effect of gas pressure are analyzed statistically.     

Corrosion behaviour of Y2O3-ZrO2 coatings on IN713LC in a LiCl-Li2O molten salt

Hot corrosion studies were performed on superalloy specimens. The IN713LC superalloy were sprayed with an aluminized NiCrAlY-bond coat and then with an yttria-zirconia top coat. The bare superalloy reveals an obvious weight loss due to spalling of the scales by the rapid scale growth and thermal stress. The top coatings showed a much better hot corrosion resistance in the presence of LiCl-3 wt.% Li₂O molten salt when compared with those of the bare superalloy and the aluminized bond coatings. These coatings have been found to be beneficial for increasing hot corrosion resistance of structural materials for lithium molten salts.     

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 behavior of molten magnesium in atmospheres containing SO2

The microchemistry and morphology of the oxide layer formed on molten magnesium in atmospheres containing SO₂ were examined. Based on the results and the thermodynamic and kinetic calculations of oxide-growth process, a schematic oxidation mechanism is presented. The results showed that the oxide scales with network structure were generally composed of MgO, MgS, and MgSO₄ with different layers, depending on the SO₂ content, the time and the temperature. The formation of MgSO₄ was important for the formation of the protective oxide scales. The growth of the oxide scales followed the parabolic law at 973 K and was controlled by diffusion.     

Oxidation kinetics of high strength low alloy steels at elevated temperatures

High strength low alloy (HSLA) steels are candidate Rockbolt materials for use as underground roof supports at Yucca Mountain nuclear waste repository. Oxidation kinetics of International Rollforms Split Set Friction Rock Stabilizers (SS46), and Swellex Mn24 steels have been determined by temperature modulated thermogravimetry at temperatures ranging between 600 and 900 °C in pure oxygen atmosphere for 100 hr. The imposed sinusoidal temperature modulations (±5 °C for a period of 1 cycle per 200 s) on the isothermal temperature did not have any noticeable effect on the weight gain characteristics during oxidation. Weight gain data on the steels indicate two distinct regions with different oxidation profiles, where a definite change in rates of oxidation is observed: a first oxidation regime where the steels followed a rate law y = kt^0.40-0.63 (changing index of rate law depending upon steel and temperature) and a second stage oxidation regime that follows the parabolic law. The results of characterization of the oxide films using SEM/EDAX, X-ray diffraction and Synchrotron white beam X-ray microdiffraction are presented. The oxidation data of the steels presented here is expected to be useful for characterizing those steels for use in underground rock bolt system and as roof support for the DOE proposed Yucca Mountain Nuclear Waste Repository. To the best of our knowledge this is the first time thermogravimetric studies of this kind have been done on these steels.     

The role of microstructure in the high temperature oxidation mechanism of Cr3C2-NiCr composite coatings

Composites of Cr₃C₂-NiCr provide superior oxidation resistance to WC-Co composites, which has seen them applied extensively to components subjected to combined high temperature erosion and oxidation. This work characterises the variation in oxidation mechanism of thermally sprayed Cr₃C₂-NiCr composites at 700 °C and 850 °C as a function of heat treatment. Carbide dissolution during spraying increased the Ni alloy Cr concentration, minimising the formation of Ni oxides during oxidation. Compressive growth stresses resulted in ballooning of the oxide over the carbide grains. Carbide nucleation with heat treatment reduced the Ni alloy Cr concentration. The oxidation mechanism of the composite coating changed from being Cr based to that observed for NiCr alloys.     

Oxidation, carburisation and metal dusting of 304 stainless steel in CO/CO2 and CO/H2/H2O gas mixtures

The oxidation and carburisation behaviour of 304 stainless steel was studied during thermal cycling in CO/CO₂ at 700 °C, and also in CO/H₂/H₂O at 680 °C. Thermal cycling caused repeated scale separation which accelerated chromium depletion from the alloy subsurface regions. The CO/CO₂ gas, with a_C=7 and , caused internal precipitation of oxides and carbides, some surface damage, but no dusting. In contrast, the CO/H₂/H₂O gas, with a_C = 19 and caused rapid graphite deposition and metal dusting. This was accompanied by internal oxidation and carburisation. The internal oxide was identified as spinel, which forms in the short term, but not at long reaction time. Its formation produced a significant volume expansion, which disrupted the material and resulted in surface damage in both gas atmospheres. In CO/H₂/H₂O, however, direct graphite deposition and metal disintegration into dust was the main reaction. The very different reaction morphologies produced by the two gas mixtures are discussed in terms of competing gas-alloy reaction steps.     

Oxidation properties of self-propagating high temperature synthesized niobium disilicide

NbSi₂ monoliths were prepared by self-propagating high temperature synthesis (SHS) and hot pressing (HP) and their oxidation behavior was investigated at various temperatures (823–1123 K) in air. The combustion mode of SHS reaction was steady state combustion, and the combustion product was single-phase NbSi₂. Oxidation studies show that the highest mass gain was 0.95675 kg m⁻² at 1023 K. In cyclic oxidation, the oxidation rate was reduced and the mass gain was only 0.15507 kg m⁻². A dense protective amorphous SiO₂ scale formed at 823 K and 923 K whereas a porous multilayer SiO₂ and α/β-Nb₂O₅ oxide scales formed at and above 1023 K and spalled off. Pest oxidation of NbSi₂ monoliths was not observed in hot pressed NbSi₂ monoliths.     

Oxidative dissolution of nickel metal in hydrogenated hydrothermal solutions

A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of metallic nickel in hydrogenated ammonia and sodium hydroxide solutions between 175 and 315 °C. The solubility measurements were interpreted by means of an oxidative dissolution reaction followed by a sequence of Ni(II) ion hydrolysis reactions:

Ni(s)+2H⁺(aq)=Ni²⁺(aq)+H₂(g)     

Oxidation of single crystal PWA 1483 at 950 °C in flowing air

The oxidation behaviour of single crystal PWA 1483 at 950 °C was investigated by means of XRD, SEM and EDS. The parabolic oxidation behaviour, as defined by mass gain and the respective oxide layer thicknesses, is characterized by a parabolic rate constant of about 4 × 10⁻⁶ mg²/(cm⁴ × s) and the formation of a multi-layered oxide scale. An outer scale contains a Ti-bearing thin film composed of TiO₂ and NiTiO₃ but mostly Cr in Cr₂O₃ and (Ni/Co)Cr₂O₄ besides NiTaO₄. This outer scale is connected to a discontinuous layer of Al₂O₃ and an area of γ′-depletion within the base material.     

Corrosion of Ti3AlC2 at 800–1100 °C in Ar–0.2% SO2 gas atmosphere

Ti₃AlC₂ was corroded between 800 and 1100 °C in an Ar–0.2% SO₂ gas atmosphere according to the equation: Ti₃AlC₂ + O₂ → rutile-TiO₂ + α-Al₂O₃ + (CO or CO₂). The scales that formed on the Ti₃AlC₂ were thin and rich in α-Al₂O₃, whose growth rate was exceedingly slow. The TiO₂ was present either as the outermost surface scale or a mixture inside the α-Al₂O₃-rich scale. In the Ti₃AlC₂, the activity and diffusivity of Ti were low, whereas those of Al were high. This was the main reason for the superior corrosion resistance of Ti₃AlC₂ over TiAl.     

Testing of high temperature reference electrodes for light water reactor applications

The main objective of the LIRES (light water reactor reference electrodes) project, supported by the EC within the EURATOM FP5, was to develop reference electrodes, which are robust enough to be used inside a light water reactor at temperatures up to 320 °C and pressures up to 120 bar. This contribution summarises the test of three types of reference electrodes developed within LIRES: (i) an external Ag/AgCl reference electrode from the NRI, Rez, Plc, (ii) a PtIr alloy hydrogen electrode from Studsvik Nuclear AB, and (iii) a Pd-hydride reference electrode—Pd(Pt) polarised active electrode pair—from the VTT Technical Research Centre of Finland. Our results are being compared, within a Round Robin test, with similar measurements of a number of laboratories to select the appropriate reference electrodes for long-term tasks, when the potential should be monitored for months under irradiating conditions.     

Oxidation behaviour of molten magnesium and AZ91D magnesium alloy in 1,1,1,2-tetrafluoroethane/air atmospheres

The oxidation rates, the morphologies and compositions of the surface films on molten magnesium and AZ91D alloy in covering gas of 1,1,1,2-tetrafluoroethane/air at 760 °C were investigated using thermogravimetric techniques, SEM, XRD and XPS. The oxidation rates of the two melts followed parabolic law in the atmosphere of high concentrate 1,1,1,2-tetrafluoroethane, and obeyed linear law in the atmosphere of low concentrate 1,1,1,2-tetrafluoroethane. But the oxidation rates of molten magnesium and AZ91D alloy presented a certain difference. The oxidation products on its surface films were composed of MgF₂ which played an import role to prevent the molten oxidation and other compounds.     

Oxidation and interfacial fracture behaviour of NiCrAlY/Al2O3 coatings on an orthorhombic-Ti2AlNb alloy

Al₂O₃ diffusion barriers of various thicknesses have been fabricated by filtered arc ion plating between the NiCrAlY coating and the O-Ti₂AlNb alloy. Isothermal oxidation tests and three-point bend tests have been conducted to investigate the influence of the Al₂O₃ diffusion barriers on the oxidation and interfacial fracture behaviour of the coatings. The results indicate that the Al₂O₃ diffusion barrier defers interdiffusion and gives oxidation resistance of the NiCrAlY coatings. The thickness of the Al₂O₃ interlayer not only influences the oxidation behaviour but also affects the interfacial fracture properties. Additionally, thermal exposure affects the critical load in three-point bend tests.     

Unusual oxidation behaviour of Zr50Cu50 alloy at high temperatures

The oxidation of Zr₅₀Cu₅₀ alloy at 500-700 °C is characterized by preferential oxidation of zirconium, while the excess of copper is accumulated at the alloy-oxide interface forming the Zr₁₄Cu₅₁ phase. The strong reaction at 800 and 850 °C resulted in the total corrosion of the specimens in 21 and 15 h, respectively. The oxidation at elevated temperatures showed an anomalous decrease of the oxygen consumption rate in the temperature range 930-1000 °C, corresponding to the preferentially oriented crystallites of ZrO₂ in the oxide scale at 900 and 1000 °C. The oxide layer consists of ZrO₂ and CuO in the whole temperature interval of the oxidation. The reaction kinetics obeys a parabolic rate law. An activation energy of 92.0 ± 0.3 kJ/mol has been estimated.     

Quantification of growth kinetics and adherence of oxide scales formed on Ni-based superalloys at high temperature

Cyclic and isothermal oxidation behaviors of first and fourth-generation superalloys AM1 and MCNG were investigated to evaluate the ability of the scratch test to quantify the adhesion of multi-layered oxide scales. Effects of sulfur content and of scale thickness were studied independently. Available models lead to large discrepancies in the calculated work of adhesion values with the evaluation of the residual stress being the largest source of error. Nevertheless, models can assess the effect of sulfur content and the scratch test can be used to correlate the long-term cyclic oxidation behavior and the adhesion of oxide scales.     

Platinum-catalyzed high temperature oxidation of metals

Samples of Al, Cr, Ni, and Zr were sputter-coated with porous Pt-films with a particle size of 20-30 nm. Thermal oxidation of these samples was studied by gas phase analysis (GPA) and secondary ion mass spectrometry (SIMS). SIMS analysis on partly Pt-coated samples of Al, Cr, Ni, and Zr at different oxide depths in areas with Pt and in areas away from Pt indicates an enhanced inward oxide growth in the Pt area and mm-ranged distance from Pt-area. Weight gain measurements on Pt-coated Ni samples show a reduced or increased oxidation rate depending on the amount of porous Pt-coating. Pt has two effects on the thermal oxidation of metals and the overall effect of Pt on the oxidation of metals depends on the mechanism of oxide growth in the absence of Pt.     

The isothermal and cyclic oxidation behaviour of two Co modified aluminide coatings at high temperature

The isothermal and cyclic oxidation behaviour of two Co modified aluminide coatings together with the simple aluminide coating were performed at 1000 °C and 1100 °C. All the three coatings show a much lower oxidation rate compared with the bare alloy. Results also indicate the addition of Co to the aluminide coating decreases the oxidation resistance slightly. It can be ascribed to that Co is easier to be oxidized than Ni at high temperature, and the Cr(W) rich phases which could act as a diffusion barrier are less in the coating with higher Co content.     

Corrosion of metals and alloys in molten glasses. Part 2: nickel and cobalt high chromium superalloys behaviour and protection

Electrochemical methods have been used for the characterisation of high chromium alloys corrosion in molten glasses (cobalt and nickel base alloys in a borosilicate glass at 1050 °C, with rotating working electrodes). All the tested alloys are active but passivable materials. The active state is characterised by a rapid dissolution of the constitutive elements of the alloy in the glass melt. The passive state can be obtained by an air oxidation of the alloys (called preoxidation) or with a temporary anodic polarisation of the alloy. The obtained passive state is due to the presence of a thin protective chromia scale.