Morphological characteristics of oxide scales grown on H11 steel oxidised in dry or wet air

Abstract

The oxidation behaviour in dry and wet air of H11 steel was studied at 600 and 700°C by Thermo Gravimetric Analysis (TGA) and in situ oxidation in the specimen chamber of an Environmental Scanning Electron Microscope (ESEM) equipped with a hot stage specimen holder. The oxidation kinetics of H11 steels are quite sensitive to the presence of water vapour and, although the final mass gains show a good overall reproducibility, they are locally rather irregular. The morphology and microstructure of oxide scale are complex and often heterogeneous, particularly at 700°C. In situ oxidation tests permit to follow the evolution of oxide scales and to observe several growth modes of oxide scales. The diversity of the observed scale growth modes can explain the complexity and irregularity of scale growth mechanisms. Some additional in situ oxidation tests were performed in wet nitrogen. Morphology and growth modes of oxide scale grown in wet air and wet nitrogen differ strongly.     

Simulation of road salt corrosion in austenitic alloys for automotive exhaust systems

Abstract

Cyclic oxidation tests in air with intermittent salt spraying have been performed to simulate the conditions of road salt (NaCl–CaCl₂) enhanced corrosion in automotive exhaust systems.

Tests were carried out at 600 and 700°C on three austenitic alloys, including two stainless steels currently employed for exhaust components (AISI 316 Ti and AISI 302B) and a higher nickel heat resisting alloy.

The presence of salt causes internal corrosion, both along a regular front beneath an outer oxide scale and down alloy grain boundaries. An increase in temperature accelerates the corrosion rate and particularly enhances intergranular penetration.

The results of micrographic and microanalytical investigations are in general agreement with an active oxidation mechanism in which Na_xCl_x vapour species, and not only chlorine, appear to play an important role. The regions directly affected are depleted in chromium and iron and enriched in nickel.

Although internal oxidation of silicon is observed, a high silicon content (2%) does not necessarily ensure effective protection against this type of attack.     

Mechanisms of chromia scale failure during the course of 15–18Cr ferritic stainless steel oxidation in water vapour

Abstract

Breakaway oxidation of 15–18 % Cr ferritic stainless steels occurring in water vapour is described in the temperature range 800–1000°C. The failure of the protective chromia scale leads to iron oxide(s) nodule formation with accelerated kinetics. Characterisation of the (Fe,Cr)₂O₃ initial oxide scale by Raman spectroscopy and photoelectrochemistry shows chemical evolution with oxidation time, with increasing Cr/Fe ratio before haematite suddenly appears at the steel-oxide interface. The mechanisms for such a phenomenon are discussed, first on a thermodynamic point of view, where it is shown that chromium (VI) volatilisation or chromia destabilisation by stresses are not operating. It is rather concluded that mechanical cracking or internal interface decohesion provide conditions for haematite stabilisation. From a kinetic point of view, rapid haematite growth in water vapour compared to chromia is thought to be the result of surface acidity difference of these two oxides.     

Transient oxidation of alumina forming Ti–Al–Ag-based alloys and coatings studied by SEM,AFM, XPS and LRS

Abstract

γ-TiAl based intermetallics possess poor oxidation properties at temperatures above approximately 700°C. Previous studies showed that protective alumina scale formation on γ-TiAl can be obtained by small additions (around 2 at.%) of Ag. Recently, this type of materials has therefore been proposed as oxidation resistant coatings for high strength TiAl alloys. In the present study, a number of cast Ti–Al–Ag alloys and magnetron sputtered Ti–Al–Ag coatings were investigated in relation to transient oxide formation in air at 800°C. After various oxidation times the oxide composition, microstructure and morphology were studied by combining a number of analysis techniques, such as SEM, ESCA, AFM and LIOS-RS. The γ-TiAl–Ag alloys and coatings appear to form an α-Al₂O₃ oxide scale from the beginning of the oxidation process, in spite of the relatively low oxidation temperature of 800°C. The formation of metastable alumina oxides seems to be related to the presence of Ag-rich precipitates in the alloy matrix.     

Scale formation mechanisms of martensitic steels in high CO2/H2O-containing gases simulating oxyfuel environments

Abstract

In oxyfuel power plants, metallic components will be exposed to service environments containing high amounts of CO₂ and water vapour. Therefore, the oxidation behaviour of a number of martensitic 9–12%Cr steels in a model gas mixture containing 70% CO₂–30% H₂O was studied in the temperature range 550–700°C. The results were compared with the behaviour in air, Ar–CO₂ and Ar–H₂O. It was found that in the CO₂- and/or H₂O-rich gases, the mentioned steels tended to form iron-rich oxide scales with significantly higher growth rates than the Cr-rich surface scales formed during air exposure. The iron-rich scales were formed as a result of a decreased flux of chromium in the bulk alloy toward the surface because of enhanced internal oxidation of chromium in the H₂O-containing gases and carbide formation in the CO₂-rich gases. Additionally, the presence of water vapour in the exposure atmosphere led to buckling of the outer haematite layer, apparently as a result of compressive oxide growth stresses. The Fe-base oxide scales formed in CO₂(–H₂O)-rich gases appeared to be permeable to CO₂ molecules resulting in substantial carburization of the steel.     

Kinetics of Carbon Multi‐wall Nanotube Synthesis by Catalytic Pyrolysis of Methane

Abstract

By method of isothermal gravimetry at 600–700°C, CH₄ concentration 32–100% in Ar and 91–100% in H₂ under atmospheric pressure the kinetics of CH₄ pyrolysis under Ni/La₂O₃ catalysts is studied. Estimated apparent activation energy of reaction is 73 kJ/mol for fresh catalyst and 71 kJ/mol for aged one. The reaction order on CH₄ changes from 1.05 at 600°C to 1.3 at 700°C. The influence of H₂ concentration on the reaction rate is more complicated. On the basis of kinetics measurements continuously working laboratory‐scale reactor with gas and catalyst counter‐flow is constructed and tested.     

Oxidation behavior of aluminide coatings on carbon steel with and without electrodeposited Ni–CeO2 film by low-temperature pack cementation

A CeO₂-dispersed aluminide coating was fabricated through aluminizing the electrodeposited Ni–CeO₂ nanocomposite film on carbon steel using pack cementation method at 700 °C for 4 h. The isothermal and cyclic oxidation behavior of the CeO₂-dispersed aluminide coating at 900 °C, including the growth of oxide scale and the microstructure of the coatings, have been investigated comparing with the aluminide coating on carbon steel. The results show enhanced oxidation performance of the CeO₂-dispersed aluminide coating, which is concerned with not only CeO₂ effect on the microstructure and oxidation, but also decreased interdiffusion between the aluminide and the Ni film. The CeO₂ benefit effects and interdiffusion are discussed in detail.     

Oxidation and fatigue crack propagation in the range of low stress intensity factor in relation to the microstructure in P122 Cr–Mo steel

Fatigue strength and life of weldment at high temperatures are important for the materials in power plants. The fatigue crack growth rate is accelerated by oxidation. Similarly, the high-temperature fatigue life is influenced by oxidation. The base metal, the weld metal and the heat-affected zone (HAZ) of the P122 (Cr–Mo steel) weldment were oxidized between 600 °C and 700 °C for up to 500 h in air, and their oxidation behavior was examined. The oxidation resistance increased in the order of HAZ, base metal and weld metal. The scales were mainly Fe₂O₃. Fatigue tests were performed to measure the fatigue crack growth rate in the range of low stress intensity factor, and the results are discussed from the viewpoint of different microstructures and oxidation.     

Effect of aging treatments and microstructural evolution on corrosion resistance of tungsten substituted 2205 duplex stainless steel

Abstract

The effect of partial substitution of tungsten for molybdenum on the microstructure and corrosion resistance in 22Cr–5Ni–3Mo duplex stainless steel (DSS) has been investigated following aging heat treatments in a temperature range of 600-1000°C. Electrochemical tests were carried out for the evaluation of corrosion resistance. Aging treatment had hardly influenced the general corrosion resistance. With the increase of aging time, the pitting corrosion resistance of the DSSs had decreased. After aging for 2 min at 700–900°C, the pitting potential of the 3Mo steel decreased remarkably, while that of the W substituted steel hardly changed. During aging, the intermetallic σ and secondary austenite (γ₂) phases were precipitated, and the pitting corrosion and intergranular corrosion resistance were significantly decreased after aging at 700–750°C for 10 h, which could be caused by the γ₂ formation. The γ₂ phase could effect the depletion of molybdenum and chromium in the γ₂ /α and γ₂/σ boundaries.     

Process study of chemically vapour-deposited SnOx (x≈2) films

The physical characteristics of SnO_x(x≈2) films deposited onto Pyrex glass substrates by chemical vapour deposition are studied. The temperature dependence indicates that films deposited at 600 °C have good polycrystallinity. The electrical conductivity of the 600 °C films is mainly controlled by the variation in the SnCl₄ vapour flow rate. A subsequent thermal annealing process can even reduce the sheet resistance to 400ω/□. In addition, the visible absorption shows that the 600 °C films tend to lose their transparency in the short wavelength range of the visible spectrum.     

Direct observation and analysis of the oxide scale formed on Y-treated austenitic stainless steels at high temperature

Abstract

We have studied the oxidation behavior of conventional austenitic stainless steels using same small amounts of Y as is added for deoxygenation and desulphurisaton in steel making.

The direct observation and analysis of the oxide scale formed on 19Cr–10Ni–l .5Si steels with and without small amounts of Y at high temperature have been carried out using several types of equipment. The following results were found: (1) Steel with 0.03Y showed good resistance to oxidation at l,000°C.

(2) Oxide scale was composed mainly of Cr oxide, and Si oxide was also detected at the oxide scale–metal interface and in the internal oxides. The Si oxide formed a network cell structure in the inner oxide scale with deeper internal penetrations. The steel with Y formed a uniform oxide scale in every oxide layer.

(3) Small amounts of Y and Si were detected at the grain boundaries of the inner oxide scale, but no Y was detected in the oxide grains.

The beneficial effect of Y addition was more notable in the Si containing austenitic stainless steels, as the existence of Y or Si prevents the diffusion of cations and anions through the oxide grain boundaries. As consequence, the steel treated with Y showed good resistance to oxidation.     

Characterization of chromia scales formed in supercritical carbon dioxide

Abstract

Initial experimental work at 700°–800 °C is in progress to develop a lifetime model for supercritical CO₂ (sCO₂) compatibility for a 30-year lifetime of a >700 °C concentrated solar power system. Nickel-based alloys 282, 740H and 625 and Fe-based alloy 25 are being evaluated in 500-h cycles at 1 and 300 bar, and 10-h cycles in 1 bar industrial grade CO₂. The alloys showed similar low rates of oxidation in 1 and 300 bar CO₂ in 500-h cycles at 750 °C. However, in 10-h cycles, alloy 25 showed accelerated attack at 700° and 750 °C. Transmission electron microscopy scale cross-sections on alloy 25 after 1000 h at 700 °C in sCO₂ and in air only showed a small row of carbides beneath the scale in the former environment. Similar characterisation was performed on alloys 625 and 282 after sCO₂ exposure at 750 °C.     

Effect of substrate type, dopant and thermal treatment on physicochemical properties of TiO2–SnO2 sol–gel films

Thin nanocrystalline TiO₂–SnO₂ films (0–50 mol% SnO₂) were prepared on quartz and stainless steel substrates by sol–gel coating method. The obtained films were investigated by XRD, Raman spectroscopy and XPS. The size of the nanocrystallites was determined by XRD–LB measurements. We ascertained that the increase of treatment temperature and concentration of SnO₂ in the films favour the crystallization of rutile phase. The substrate type influences more substantially the phase composition of the TiO₂–SnO₂ films. It was established that a penetration of elements took place from the substrate into the films. TiO₂ films deposited on quartz substrate include a Si which stabilizes anatase phase up to 600 °C. The films which are deposited on stainless steel substrate and treated at 700 °C show the presence of significant quantity of rutile phase. This phenomenon could be explained by the combined effect of Sn dopant as well as Fe and Cr, which also are penetrated in the films from the steel substrate. The titania films doped up to 10 mol% SnO₂ on stainless steel possess only 12–17 nm anatase crystallites, whereas the TiO₂–(10–50 mol%) SnO₂ films contain very fine grain rutile phase (4 nm).     

Effect of high heating rate on thermal decomposition behaviour of titanium hydride (TiH2) powder in air

DTA and TGA curves of titanium hydride powder were determined in air at different heating rates. Also the thermal decomposition behaviour of the aforementioned powder at high heating rates was taken into consideration. A great breakthrough of the practical interest in the research was the depiction of the P _H2-time curves of TiH ₂ powder at various temperatures in air. In accordance with the results, an increase in heating rate to higher degrees does not change the process of releasing hydrogen from titanium hydride powder, while switching it from internal diffusion to chemical reaction. At temperatures lower than 600 °C, following the diffusion of hydrogen and oxygen atoms in titanium lattice, thin layers TiH _x phase and oxides form on the powder surface, controlling the process. On the contrary, from 700 °C later on, the process is controlled by oxidation of titanium hydride powder. In fact, the powder oxidation starts around 650 °C and may escalate following an increase in the heating rate too.     

Oxidation of nickel-based alloys in dry and water vapour containing air

Abstract

Ni-based alloys are widely used in power generation and their oxidation behaviour in the uncoated state is of interest, especially the impact of water vapour in the air on the formation of a protective underlying alumina scale. High-temperature X-ray diffraction was applied to investigate in situ the oxide scale formation in the initial state on the alumina formers CM247DS and CMSX4 in comparison to the chromia formers IN792 and SCA425+. Post-oxidation analysis was performed by field emission scanning electron microscopy. The samples were oxidised for 100 h at 950°C in dry air and in air with 20% relative moisture in the high temperature device on the X-ray diffractometer. In dry air, CM247 and CMSX-4 form α-Al₂O₃ from the beginning simultaneously with spinels and nickel oxide. The alumina scale underlies the spinels which spall partially on cooling. When adding water vapour, the same oxides were formed simultaneously resulting in a comparable oxide scale. IN792 forms in dry air mainly NiAl₂O₄ and transitionally CrO₂ under laid by an alumina scale. With water vapour, Cr₂O₃ forms and the underlying alumina scale shows a non coherent dendritic structure. SCA425+ forms in dry air Cr₂O₃ and Cr containing mixed oxides and with water vapour a more coherent alumina scale than IN792.     

Formation of chromium rich oxide scales for protection against metal dusting

Abstract

Metal dusting is a disintegration of metals and alloys into graphite and metal particles, caused by strongly carburizing gas mixtures mainly in the temperature range 400–700°C. Protection of steels against metal dusting is possible through the formation of dense chromium rich oxide scales but it is not guaranteed that such scales are formed at low temperatures, even on high Cr-steels.

Surface analytical studies have been conducted on the formation and composition of the oxide scales on 9–20%Cr steels. The growth of oxide films was followed by AES for 3 hours at 10^–7 mbar O₂ great differences were observed in dependence on surface finish. On ground samples, Mn and Si appeared early and Cr-rich oxide was formed, whereas on chemically etched samples Fe-rich oxides grew.

After long term exposures (240 h) under metal dusting conditions, i.e. in CO–H₂–H₂O mixtures at 600°C, thin Cr-rich scales were observed on ground steels which were impermeable to carbon whereas on chemically etched steels thick Fe-rich scales had grown and carbon penetration was detectable. Accordingly, the oxide formation on Cr-steels at relatively low temperatures strongly depends on the surface treatment. Any surface working such as grinding and sand-blasting etc. introduces dislocations and causes a fine-grained microstructure near the surface, and the dislocations and grain boundaries act as rapid diffusion paths for supply of Cr to the surface in the first minutes of exposure, which leads to the formation of a protective oxide scale.     

Effect of long term aging on mechanical properties and microstructure of nickel base weld

Abstract

The mechanical properties of a Ni base weld have been examined after long term aging in the temperature range 600–900°C. Impact testing revealed a substantial decrease in toughness after heat treatment at 600 and 700°C. In particular, after aging at 700°C there was a marked loss of ductility, which was associated with elongated particles appearing in the fracture surfaces. The concomitant microstructural changes occurring have been investigated using analytical electron microscopy. In material heat treated at 600°C for 10000 h, seven phases were identified: M₂₃C₆, MC, η, γ′, γ″, G, and δ. At 700°C, the following phases were distinguished after 3000 h: M₂₃C₆, MC, and η. After longer testing times G, γ′, and γ″, were formed. Whereas G, γ′, and γ″ formed intragranular needles, η formed intragranular laths or plates at 700°C. The minimum in ductility observed in material aged at 700°C can be explained in terms of copious intragranular precipitation of γ′, γ″, and η.

MST/1131     

Effect of temperature on the interaction of ÉP823 steel with lead melts saturated with oxygen

We study the corrosion behavior of ferritic-martensitic éP823 steel in a static lead melt, saturated with oxygen, at 550 and 650°C. At these temperatures, a complex magnetite-base scale is formed on the surface of steel, but the mechanisms of its growth are different. At 550°C, corrosion has a cyclic character. On the surface of steel, a Fe_1+x Pb_2−x O₄−Fe_1+x Cr_2−x O₄ two-layer scale is formed periodically. Reaching the critical thickness (18 μm), it exfoliates along the interface with the matrix, to which oxygen-containing lead penetrates, whereupon this process is repeated. The corrosion rate is ∼0.08 mm/year. At 650°C, the intensification of reactions of formation of chromium spinel and plumboferrite induces the growth of a porous scale, where lead is accumulated. This scale has good adherence to the matrix and is formed as a compact conglomerate owing to the efficient mass transfer at all interfaces, which leads to a catastrophic rate of thinning of the specimen (3.82 mm/yr) in a lead melt. On the basis of experimental data, we propose schemes of the oxidation of chromium steels in a lead melt with a high oxygen activity at different temperatures. __________ Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 43, No. 2, pp. 77–84, March–April, 2007.     

Agglomeration of magnesium oxide particles formed by the decomposition of magnesium hydroxide

The agglomeration process of MgO powder derived from Mg (OH)₂ was investigated at fixed temperatures of 600, 800, 900 and 1200° C; these temperatures were chosen as representative of four regions, i.e. below 600° C, 650 to 850° C, 850 to 1050°C and 1050 to 1200° C previously reported. At 600° C, coherent crystallites coalesced within the heating time of 60 min; on further heating till 300 min, the primary particles which consisted of crystallites grew rapidly. The original Mg (OH)₂ framework or pseudomorphs, composed of minute crystallites and primary particles, still remained in the powder. At 800° C, the pseudomorphs had disintegrated into fragments. The crystallite growth and primary particle growth were accelerated with increasing the heating times beyond 60 min. At 900° C, a further fragmentation of agglomerates occurred with increasing the heating times; the crystallite and primary particle growth in fragments brought about the pore coalescence. At 1200° C, the crystallite and primary particle growth proceeded with the coarsening of pores; on heating beyond 240 min, the crystallites and primary particles grew rapidly due to the entrapment of pores within them.     

Oxidation behavior and effect of oxidation on tensile properties of Ti60 alloy

Oxidation behavior of a near-alpha Ti60 titanium alloy was investigated in the temperature range of 600–750 °C for up to 100 h exposure. The results showed that the oxidation kinetics of Ti60 alloy followed parabolic kinetics below 700 °C but parabolic-linear kinetics above 700 °C. The total activation energy was calculated to be 256 kJ/mol over the whole temperature range. The oxidation products were TiO₂ after thermal exposure at 700 °C for 100 h, but a mixture of TiO₂ and a small amount of Al₂O₃ for the specimens oxidized at 750 °C for 50 h. The grain boundaries were preferred sites for oxidation products formation during the oxidation. The tensile tests were performed at room temperature for specimens before and after oxidation. Both of the strength and ductility decreased for the specimens with oxide scale. However, both of them increased when the oxide scale was removed before testing.