Analysis of composition and growth mechanisms of oxide scales on high temperature alloys by SNMS,SIMS, and RBS

Composition and growth phenomena of alumina scales on a conventional wrought alloy Fe-20Cr-5Al and an yttria containing ODS alloy with the same base composition were investigated. The alloys were oxidized in a twostage oxidation process at 1000 °C in air and air containing¹⁸O-tracer. By using secondary neutrals and secondary ion mass spectrometry in combination with RBS, the in-depth concentration of main and minor alloying elements as well as the oxygen isotope distribution in the alumina scale could be determined. It is shown, that the difficulties in deriving the exact growth processes of the scales from the oxygen tracer profiles can be overcome by using the time dependance of the iron and chromium distribution in the alumina. From these results it could be derived that growth of the oxide scales formed on the ODS and the conventional alloy mainly differ in the relative contribution of aluminium diffusion. The mechanisms which lead to these differences in scale growth phenomena will be discussed.     

Determination of lattice and grain boundary diffusion coefficients in protective alumina scales on high temperature alloys using SEM, TEM and SIMS

Grain and grain boundary diffusion coefficients in alumina scales on FeCrAl-based ODS alloys have been determined. The boundary diffusion-coefficients have been derived by combining gravimetrically determined growth rate data with SEM and TEM analyses of the oxide scale microstructure. The diffusion coefficients determined have been used as input parameters for a computer model describing the oxygen isotope exchange between grain and grain boundary in the alumina scale which forms during a two-stage oxidation using ¹⁸O-tracers. This comparison of the calculated tracer profiles with profiles determined experimentally by SIMS allows the estimation of the lattice diffusion coefficient of oxygen in the alumina scale.     

Determination of lattice and grain boundary diffusion coefficients in protective alumina scales on high temperature alloys using SEM,TEM and SIMS

Grain and grain boundary diffusion coefficients in alumina scales on FeCrAl-based ODS alloys have been determined. The boundary diffusion-coefficients have been derived by combining gravimetrically determined growth rate data with SEM and TEM analyses of the oxide scale microstructure. The diffusion coefficients determined have been used as input parameters for a computer model describing the oxygen isotope exchange between grain and grain boundary in the alumina scale which forms during a two-stage oxidation using (18)O-tracers. This comparison of the calculated tracer profiles with profiles determined experimentally by SIMS allows the estimation of the lattice diffusion coefficient of oxygen in the alumina scale.     

Interfacial phenomena in the oxidation and high temperature corrosion of metals and alloys

Metallic materials for application at high temperatures must form a slowly growing, dense oxide scale for their own protection. Up to about 1000°C, chromia-forming, at higher temperatures, alumina-forming Fe, Ni or Co based materials are used. In the present paper it is demonstrated how intact homogeneous scales on materials can be studied by AES sputter profiling and SNMS, but the main objective is to show phenomena at surfaces and interfaces which occur in complex atmospheres. In complex atmospheres, the formation of a protective scale is aggravated if several aggressive components of the gas atmosphere attack the free metal surface. This was demonstrated by AES for oxidizing and chlorinating atmospheres, in which chlorides and oxides grow simultaneously on the free metal surface. The chlorides are overgrown after some minutes by the stable oxide, but the formation of a dense, protective oxide scale is prevented. Similar effects have been observed by AES in oxidizing and nitriding atmospheres and also in oxidizing and sulfidizing atmospheres. The structure and the composition of the interface oxide/metal is decisive for the adherence of oxide scales. Stresses in the oxide scale can initiate detachment, diffusion processes in the alloy can lead to formation of voids and cavities beneath the oxide layer; both processes are favoured by segregation of sulfur from the alloy to the nascent metal surface as was shown by AES. For the investigation of the interface, this has to be laid bare by in-situ bending of the sample; this causes physical removal of the oxide scale. In addition to the surface of the oxide and the interface oxide/metal, grain boundaries of the alloys are also of interest; at these grain boundaries, dissolved non-metal atoms such as C, O, N, S ... can penetrate into the alloy. The grain boundaries can be analyzed by AES if the samples are fractured inside the UHV system. It can be shown, for example, that oxygen can penetrate into the grain boundaries of the intermetallic compounds NbAl₃ and NiAl; this oxygen penetration leads to grain boundary oxidation or even disintegration of the material into fine oxidized metal particles. These examples should demonstrate that the application of surface analytical methods, especially of AES, can provide valuable information for improved understanding and control of the high temperature corrosion of metallic materials.     

TEM and SNMS studies on the oxidation behaviour of NiCrAlY-based coatings

The effect of minor Ti additions content (0% Ti, 0.4% Ti, 1% Ti, 2% Ti) on the oxidation behaviour of Ni-20Cr-10Al-0.4Y (in weight-%) model alloys was investigated in the temperature range 950° C to 1100° C up to 200 h in Ar – 20% O₂. Alloy microstructure, oxide scale morphology and microstructure of the scale were characterized by SEM/EDX and TEM. The growth mechanisms of the alumina scales formed on the model alloys were studied by two-stage oxidation experiments with ¹⁸O₂-tracer and subsequent SNMS-analyses. The microstructural observations were correlated with the oxide scale properties in respect to growth rates and spalling resistance, which was tested during cyclic oxidation. Received: 24 June 1996 / Accepted: 18 November 1996     

Analysis of corrosion layers on protective coatings and high temperature materials in simulated service environments of modern power plants using SNMS,SIMS, SEM,TEM, RBS and X-ray diffraction studies

In three different examples, the effects of the oxidation behaviour as well as the microstructural stability of high temperature materials and protective coatings was determined by combining the results of kinetic studies with extensive analytical investigations using, among other techniques, SNMS, SIMS, SEM, TEM, Rutherford back scattering (RBS) as well as X-ray diffraction. 1). The effect of water vapour on the oxidation behaviour of 9% Cr steels in simulated combustion gases has been determined. The effects of O2 and H2O content on the oxidation behaviour of 9% Cr steel in the temperature range 600-800 degrees C showed that in dry oxygen a protective scale was formed with an oxidation rate controlled by diffusion in the protective scale. In the presence of water vapour, after an incubation period, the scales became non-protective as a result of a change in the oxidation limiting process. The destruction of the protective scale by water vapour does not only depend on H2O content but also on the H2O/O2-ratio. 2). The increase of component surface temperature in modern gas turbines leads to an enhanced oxidation attack of the blade coating. Improvements in corrosion resistance and longer lifetime thermal barrier coatings in gas turbines have been achieved by improvement of the high temperature properties of MCrAlY coatings by additions of minor alloying elements such as yttrium, silicon and titanium. 3). The use of oxide dispersion strengthened (ODS) alloys provides excellent creep resistance up to much higher temperatures than can be achieved with conventional wrought or cast alloys in combination with suitable high temperature oxidation/corrosion resistance. Investigation of the growth mechanisms of protective chromia and alumina scales were examined by a two-stage oxidation method with 18O tracer. The distribution of the oxygen isotopes in the oxide scale was determined by SIMS and SNMS. The results show the positive influence of a Y2O3 dispersion on the oxidation resistance of the ODS alloys and its effect on growth mechanisms.     

Anodic film formation on binary Al?Mg and Al?Ti alloys in nitric acid

Nitric acid is commonly used for surface treatments of aluminium alloys. It is used to clean the surfaces after alkaline etching; it has application in chemical polishing and is also used for electrograining. The majority of these treatments undergo the application of anodic polarisation that results in formation of anodic oxide film. However, little is known about the behaviour of aluminium containing magnesium or titanium in solid solution under such conditions. To reveal the effects of magnesium and titanium alloying additions on anodic film formation in nitric acid, Al‐1800 ppm Mg and Al‐800 ppm Ti alloys were investigated. It was found that porous alumina film developed on the surfaces with reduced efficiency of 40%, due to the reactive nature of nitric acid to alumina. The presence of magnesium and titanium in aluminium had little influence on the efficiency of film growth, as confirmed by the relatively similar thicknesses of oxide formed on binary alloys and aluminium. However, incorporation of magnesium ions into the alumina film led to development of a high‐population density of localised voids near the alloy/film interface. An increased titanium content was found in the film regions close to the alloy/film interface, indicating its oxidation. Copyright © 2009 John Wiley & Sons, Ltd.     

The Use of SIMS, SEM, EPMA, LRS and X-Ray Diffraction Measurements for the Examination of Corrosive Layers and Protective Coatings on Steels and Alloys in Advanced Power Stations

The development of modern power generation systems with higher thermal efficiency requires the use of constructional materials of higher strength and improved resistance to the aggressive service atmospheres. In this paper the following examples are discussed:1) The oxidation behaviour of 9% (w/w) Cr steels in simulated combustion gases: the effects of O₂ and H₂O content on the oxidation behaviour of 9% (w/w) Cr steels in the temperature range of 600–800°C showed that in dry oxygen a protective scale was formed with an oxidation rate controlled by diffusion. However, in the presence of water vapour, after an incubation period, the scale became non-protective as a result of a change in the oxidation mechanism.Oxidation experiments on 10% (w/w) Cr steel in simulated steam atmosphere at 650°C have shown that a haematite layer is formed. The investigation suggests that several independent processes, such as oxide dissociation and solid state diffusion of iron cations in the scale, significantly contribute to the overall oxide growth process.2) The development of light-weight intermetallics based on TiAl-basis: TiAl-based intermetallics are promising materials for future turbine components because of their combination of high temperature strength and low density. These alloys, however, exhibits poor oxidation resistance at temperatures above 700°C. The experimental results showed that the oxidation behaviour of TiAl-based intermetallics can be significantly improved by minor additions of 1–2 at-% silver.     

Surface analytical investigations on the oxidation behaviour of TiAl-base intermetallics

Summary The oxidation behaviour of TiAl-base intermetallics has been investigated at 800°C in air. The main emphasis was placed on the mechanism by which niobium additions decrease the oxidation rate of titanium aluminides. For this purpose specimens of Ti50Al and Ti45Al10Nb were oxidized in a two-stage oxidation technique using an ¹⁸O-tracer. The scale formed during this oxidation process was analyzed by SNMS. It was found that niobium is mainly incorporated in the titanium dioxide and the nitride scale which forms beneath the initially formed alumina layer. The effect of this behaviour of the niobium on the oxide scale growth rates is discussed.     

Interfacial analyses for elucidation of the intergranular disintegration upon oxidation of intermetallic phases

Summary In a range of intermediate temperatures from 600 to 1000°C and in the presence of oxygen, numerous intermetallic phases show the phenomenon pest, an intergranular disintegration into small pieces. Thermo-gravimetric investigations and annealings in quartz ampoules have been performed, for annealing the oxygen pressures were established in the range 10^–30 to 10^–10 bar O₂ using metal/oxide mixtures. The specimens after annealing were fractured in UHV and the intergranular fracture faces were analyzed by AES. The Auger peaks of Al are markedly different for the intermetallic phase and for Al₂O₃, therefore it can be distinguished if oxygen has diffused into grain boundaries and not yet reacted or if Al₂O₃ was formed. The fracture face of NbAl₃ shows oxide precipitates near the surface and oxygen which had penetrated into the interior. Also in NiAl, Al₂O₃ was detected as well as oxygen penetrated into the grain boundaries. The pest obviously is a complex interplay of the processes: 1) penetration of oxygen through the outer oxide layer on the surface into grain boundaries of the intermetallic phase; 2) inward diffusion of oxygen along the grain boundaries into the interior of the intermetallic phase; 3) precipitation of Al₂O₃, beginning near the surface or (at low oxygen pressure) in the whole cross section, and cracking of the materials by the growth of Al₂O₃ into grain boundaries and cracks. Depending on the range of oxygen pressure different steps can be rate determining.     

SIMS investigations on the growth mechanisms of protective chromia and alumina surface scales

The oxidation behaviour of the oxide-dispersion strengthened (ODS) high-temperature alloys MA 956 (an aluminium oxide former) and MA 754 (a chromium oxide former) has been compared with that of two model alloys, Fe-20Cr-5Al and Ni-25Cr. The morphology and composition of the oxide scales were investigated by metallography, X-ray diffraction analysis and scanning electron microscopy. For analysis of the oxide layer growth mechanisms, twostage oxidation experiments with¹⁸O as tracer were used, the distribution of the oxygen isotopes in the oxide scale being determined by SIMS. The ODS alloys show a more selective oxidation than the two model alloys; moreover, the protective oxides on the ODS alloys have a lower growth rate and better adhesion than those on the two model alloys. From the SIMS investigations it can be deduced that the improved properties of the layers on the ODS alloys result from a change in the transport processes in the protective layer; whereas the aluminium and chromium oxide films on the conventional alloys grow by cation and anion transport, the scales on the ODS alloys grow almost exclusively by anion transport. It is shown that the observed properties of the oxide scales on the ODS alloys can be explained by this change in transport mechanism.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

The oxidation behaviour of niobium containing γ-TiAl based intermetallics in air and argon/oxygen

The oxidation behaviour of -TiAl based alloys with different Nb contents (2–10 At.%) was investigated in air and in argon-20% oxygen at 900 °C using thermogravimetric analysis. The oxide scales were characterized by a combination of optical microscopy, SEM/EDX and X-ray diffraction analyses. Although in all studied cases the presence of niobium improves the oxidation resistance of -TiAl, the oxidation kinetics, scale morphology and composition in air differed strongly from that in argon-oxygen. In air the oxidation resistance increases with increasing niobium-content. In Ar/O₂ the niobium dependence is far more complex because internal oxidation occurs which is favoured by the presence of niobium. SNMS analysis revealed that the differences in behaviour in the two atmospheres are related to the formation of Ti-rich nitride at the scale/alloy interface during air oxidation. The positive effect of niobium on the oxidation resistance of -TiAl is mainly caused by a decrease of the transport processes in the heterogeneous TiO₂/Al₂O₃-surface scale. Nitride formation and/or niobium enrichment at the scale/alloy interface also affect the oxidation behaviour, however these factors are believed to be the result of the decreased transport processes rather than the main reason for the niobium effect.     

Fe-50Cu纳米涂层的制备及氧化行为

为探讨晶粒尺寸变化对多相合金氧化行为的影响,采用磁控溅射技术制备了Ｆｅ－５０Ｃｕ过饱和固溶体纳米涂层,并利用热重实验对比研究了该涂层与同成分的铸态合金在８００℃空气中的氧化行为。结果表明,铸态合金中形成了包括铁和铜的氧化物及其复合氧化物在内的复杂外氧化膜,同时发生了铁的内氧化。涂层中发生了铁的单一外氧化,但涂层退化后,合金基体中仍出现铁的内氧化。这种氧化模式的转变机制在于涂层尺寸的纳米化显著扩展了     

Materials corrosion in molten LiF-NaF-KF salt

Corrosion tests of high temperature alloys, Hastelloy-N, Hastelloy-X, Haynes-230, Inconel-617, and Incoloy-800H were performed in molten fluoride salt, FLiNaK (LiF-NaF-KF:46.5-11.5-42 mol%) with the goal of understanding the corrosion mechanisms and ranking these alloys for their suitability for molten fluoride salt heat exchanger and thermal storage applications. The tests were performed at 850 °C for 500 h in sealed graphite crucibles under an argon cover gas. Corrosion was noted to occur predominantly by dealloying of Cr from the alloys, an effect that was particularly pronounced at the grain boundaries of these alloys. Weight-loss due to corrosion generally correlated with the initial Cr-content of the alloys, and was consistent with the Cr-content measured in the salts after corrosion tests. Two Cr-free alloys, Ni-201 and Nb-1Zr, were also tested. Ni-201, a nearly pure Ni alloy with minor alloying additions, exhibited good resistance to corrosion, whereas Nb-1Zr alloy exhibited extensive corrosion attack. The graphite crucible may have accelerated the corrosion process by promoting the formation of carbide phases on the walls of the test crucibles, but did not alter the basic corrosion mechanism.     

Quantitative analysis of oxide films on ODS-alloys using MCs+-SIMS and e-beam SNMS

Summary Attempts to obtain a quantitative analysis of depth profiles of oxide films on iron-based ODS-alloys using MCs⁺-SIMS and e-beam SNMS are presented. Since the oxide films of the alloys consist mainly of alumina, implantation standards in Al₂O₃(sapphire) were used for the quantification of the measured depth profiles. The so-called matrix effect, normally present in SIMS analysis, is strongly reduced by recording the MCs⁺-secondary ions. Over a wide concentration range, agreement between SIMS and SNMS data is obtained within a factor 2–3. The evaluated concentration profiles for the main alloying elements in combination with ¹⁸O tracer-experiments have been used to give an interpretation of the growth processes of the oxide films for Fe-based ODS-alloys, with and without the addition of an yttria dispersion. The results show that the addition of yttria dispersion is responsible for the dramatic change observed in the oxide growth mechanism.ODS=Oxide Dispersion strengthenedThis poster was awarded the First Prize in Poster Session A by the Deutscher Arbeitskreis für Spektroskopie (DASp)     

Influence of grain size on the oxygen permeation performance of perovskite-type (Ba0.5Sr0.5)(Fe0.8Zn0.2)O3−δ membranes

The effect of grain size distribution in perovskite-type (Ba_0.5Sr_0.5)(Fe_0.8Zn_0.2)O_3−δ (BSFZ) ceramics on their oxygen permeation behaviour has been investigated by variation of calcination temperature in powder production and sintering time for the ceramics. The membranes were examined via scanning electron microscopy (SEM), transmission electron microscopy (TEM) and oxygen permeation experiments. We found that the dwell time during sintering has an important influence on the microstructure of the ceramic. The longer the dwell time, the further proceeds the grain coarsening, which affects the oxygen permeation in a positive way and leads to an enhanced permeation. Supplementary, decreasing calcination temperature in perovskite powder synthesis delivers fine powders with grain sizes less than one micrometer and thus smaller grains in the ceramic. Unfortunately, the grain size distribution in sintered membranes is not constant through membrane cross-sections since grains in the bulk are smaller compared to those at the surface which is not favorable for the oxygen permeation of the ceramics. The activation energy was determined to be in the range of 51–53 kJ/mol and its variation does not exhibit a dependence of grain size changes. High-resolution transmission electron microscopy proved that grain boundaries are atomically thin without any interfacial phases. We come to the conclusion that the transport rate of the oxygen permeation is limited predominantly by bulk diffusion and due to the fact that grain boundaries in BSFZ act as barriers for bulk diffusion, this material is a high mobility material.     

Enrichment,incorporation and oxidation of copper during anodising of aluminium–copper alloys

Porous anodic oxides generated on copper‐containing aluminium alloys are less regular than anodic oxides generated on pure aluminium. Specifically, a porous oxide morphology comprising layers of embryo pores, generated by a cyclic process of oxide film growth and oxygen evolution, is generally observed. In this work, the relation between the oxidation behaviour of copper during anodising and the specific porous oxide film morphology was investigated by electrochemical techniques, transmission electron microscopy and Rutherford backscattering spectroscopy (RBS). It was found that the anodising potential determines the oxidation behaviour of copper, and the latter determines the porous oxide morphology. At low voltage, relatively straight pores with continuous cell walls were obtained on Al? Cu alloys, but selective oxidation of aluminium atoms resulted in the occlusion of copper‐containing metallic nanoparticles in the anodic film. At higher potentials, copper oxidation promoted oxygen evolution within the barrier layer, and generation of a less regular film morphology. RBS, performed on Al? Cu alloy specimens, revealed a high volume fraction of copper atoms in the anodic films generated at low potentials and a reduced amount of copper atoms in the anodic oxide films generated at high potentials. Copyright © 2009 John Wiley & Sons, Ltd.     

富钇混合稀土对AM60镁合金显微组织与力学性能的影响

在AM60镁合金的基础上添加不同质量分数的富Y混合稀土(分别为0.5%,1.0%,1.5%,2.0%),研究了富钇混合稀土对AM60镁合金显微组织与力学性能的影响。结果表明:富Y稀土的加入使AM60镁合金的显微组织明显细化,并能显著提高合金的抗拉强度、屈服强度及延伸率。加入混合稀土后,合金中形成块状的铝钇化合物Al2Y,Al6Mn6Y,β-Mg17Al12相数量减少。当稀土加入量为1%时,合金的各方面性能达到最好。     

Thermodynamics of oxygen in dilute liquid silver–tellurium alloys

Abstract  

The activity coefficient of oxygen in liquid Ag and binary Ag–Te dilute alloys were determined between 1,285 and 1,485 K by coulometric titration using the electrochemical cell (Ir, [O] in liquid metal or alloy | yttria stabilized zirconia | air, Pt). The experimental and evaluation procedures described in the literature were adopted. The oxygen activity coefficient was determined in pure liquid silver to be . Next, the oxygen activity coefficient in dilute Ag–(Te)–O alloys for variable X _Te content (from 0.01 to 0.06) was measured. From the obtained results, Wagner’s interaction parameter as a function of temperature was derived in the form . The electrochemical coulometric titration method seems to be very useful to study the thermodynamics of oxygen interaction in liquid silver and its alloys.     

Microstructure and Conduction of Composites Bi<Subscript>2</Subscript>CuO<Subscript>4</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> Near the Eutectic Melting Point

Microstructure and conduction of ceramic composites Bi₂CuO₄ + xBi₂O₃ (x = 5, 10, 15, 20 wt %) near the eutectic melting point (770°C) are studied. Bismuth oxide, initially randomly distributed over the ceramics bulk, after quenching from temperatures exceeding the eutectic melting point, becomes localized at triple junctions and grain boundaries in Bi₂CuO₄, which is caused by wetting grain boundaries and forming a liquid-channel structure. The jumpwise change in the composites’ conductivity near 730 and 770°C caused by polymorphic transformation of Bi₂O₃ and the eutectic melting with simultaneous formation of a liquid-channel structure. Transport numbers of the oxygen ion are measured at 770°C by coulomb-volumetric method. The conduction by oxygen ions increases in the composites with decreasing average size of Bi₂CuO₄ crystallites.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 596–601.Original Russian Text Copyright © 2005 by Lyskov, Metlin, Belousov, Tret’yakov.