Oxid Met (2007) 68:3751 DOI 10.

1007/s11085-007-9053-2 ORIGINAL PAPER

Chromium-oxide Growth on FeCrNi Alloy Studied with Grazing-emission X-ray Fluorescence

I. K. Koshelev A. P. Paulikas M. Beno G. Jennings J. Linton M. Grimsditch S. Uran B. W. Veal

Received: 28 October 2005 / Revised: 17 February 2006 / Published online: 4 May 2007 Springer Science+Business Media, LLC 2007

Abstract Using grazing-emission X-ray uorescence (GEXRF), isothermal oxidation of the alloys 55Fe25Cr20Ni and 55Fe25Cr20Ni(+0.3Y) (wt.%) were studied as a function of oxidation time at 750 8C in O2. In addition, the effect of thermal cycling was studied. Using GEXRF, oxide thickness, the Cr-depletion zone in the substrate, and Fe and Ni concentrations in the oxide were monitored as a function of oxidation time. Scanning-electron microscopy was used to independently measure the Cr-depletion zone. Raman spectroscopy was used to measure the concentration of Fe2O3 appearing in the oxides in early oxidation (less than 2 h). Both GEXRF and Raman measurements show that the thermally-grown chromium oxide puries with extended oxidation; initially abundant Fe2O3 became undetectable after 2 h of oxidation. However, the total Fe concentration was still *3% after 2 h but systematically decreased with further oxidation. Thermal cycling had no effect on these results. Keywords Grazing emission X-ray uorescence Chromia scale Scale growth PACS 68.55.-a 61.10,Ht

Introduction Chromium-oxide scales which form naturally on a variety of alloys in hightemperature environments provide essential corrosion protection for those alloys.
I. K. Koshelev A. P. Paulikas M. Beno G. Jennings J. Linton M. Grimsditch S. Uran B. W. Veal (&) Materials Science Division, Argonne National Laboratory, 9700 S. Cass Av., Argonne, IL 60439, USA e-mail: veal@anl.gov

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For in-service use, it is important that these economically vital protective oxides be highly adhesive, slow growing and self healing [14]. The oxide scale forms in a complex process involving the outward diffusion of chromium atoms and the inward diffusion of oxygen atoms. Since Cr atoms are extracted from the substrate as the oxide grows, a chromium-depletion region necessarily develops at the oxidemetal interface. In early-stage growth, transient phases appear in the scale and eventually disappear as the scale matures. For FeCr Ni alloys, transient Fe- and Ni-rich phases appear in early oxidation, but eventually disappear after long-term oxidation [57]. Apparently, after the formation of a continuous chromia scale, Fe and Ni uptake decline; i.e., the chromia scale increases in purity. In this study we measure, as a function of scale growth time, the concentrations of Fe and Ni in the scale. In relatively early-stage growth, the Ni concentration falls to a very low level (<1 at.%). While the concentration of Fe in the scale diminishes somewhat more slowly, we observe that the total amount of Fe in a given area of scale declines as oxidation proceeds. Thus, what is occurring is not a simple dilution process resulting from the addition of new scale. The observed behavior is explained using simple thermodynamic arguments. Scales, grown isothermally on 55Fe25Cr20Ni(Y) (wt.%) alloys, were studied as a function of oxidation time, at 750 8C in O2, using grazing-emission X-ray uorescence (GEXRF). The GEXRF measurements were complemented by Raman spectroscopy, SEM and optical reectivity to obtain independent determinations of scale-characterization parameters. In the GEXRF measurement, the intensity I(h) of X-ray uorescence spectra for Fe, Cr and Ni was measured vs. emission angle h. By simultaneously tting calculated spectral functions [7, 8] to all of the measured data [I(h) emission spectra for Cr, Fe and Ni], and requiring an internally consistent set of materials parameters, the scale thickness, composition, and the substrate Cr-depletion zone were quantitatively measured. Raman spectroscopy was used to measure the ratio of Fe2O3 to Cr2O3 in the early-stage oxidation of the evolving scales. Evolution of the measured parameters was followed as oxidation proceeded.

Experimental Procedures The oxidation study was performed on noncommercial bulk samples of composition 55Fe25Cr20Ni and 55Fe25Cr20Ni0.3Y (wt.%). Starting materials (at least 99.99% pure) were repeatedly arc melted (usually 6 melts) in an Ar/He atmosphere, with the samples cleaned, if needed, and rotated between melts. After the nal melt, samples were rolled to 1 mm thickness. Samples were cut from the rolled sheet, ground at and polished with 1 l alumina abrasive. Spectroscopic analyses showed approximately 50 ppm levels of O, H, N and C. For the GEXRF studies, a total of eight coupons was polished; four contained 0.3 wt.% of Y, a reactive element (RE) [14] and four were RE-free. Pairs of samples (with and without RE) were concurrently treated isothermally at 750 8C in owing O2 for 2, 4, 8 and 16 h. A second set of eight samples (four pairs with and without RE) were given cyclicoxidation treatments. Sample pairs were heated in one-hour intervals at 750 8C and

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were then cycled to room temperature. These sample pairs were given 2, 4, 8, and 16 heating cycles. For the Raman studies, pairs of polished samples were isothermally oxidized for periods of 1/4, 1/2, 1 and 2 h. For the heat treatments, samples were placed in an alumina boat which was then inserted into a (horizontal) quartz tube furnace through which oxygen was owing. The boat was inserted upstream, i.e., into the owing gas. After the heat treatment, the samples and boat were cooled by quenching into air. GEXRF measurements were used to monitor the evolution of oxide thickness, Fe and Ni concentrations, and the Cr-depletion zone as a function of isothermaloxidation time, as the scale developed at 750 8C in O2. The GEXRF measurements were performed using X-ray synchrotron radiation generated by a bending magnet at the Advanced Photon Source, Argonne National Laboratory (beamline 12BM). Monochromatized X-rays of *10 eV bandwidth struck the sample at near-normal incidence illuminating an area of about 1 mm 0.5 mm. Fluorescent emission from the sample was simultaneously monitored, at emission angles near grazing, from Fe, Ni and Cr atoms using an energy-dispersing Ge detector. Slits placed in front of the detector were adjusted to provide a 3 milliradian acceptance aperture. The intensities I(h) were recorded as a function of emission angle h, measured relative to the sample surface. Although Fe, Cr and Ni uorescence spectra were simultaneously recorded while the sample was irradiated, an I(h) scan for each of the three elements was also acquired separately, using different excitation energies, in order to avoid complications resulting from secondary uorescence. For each uorescing element, the impinging excitation was tuned to an energy just above the K-edge energy of that element. Thus, 6.8 keV excitation energy was used to study Cr, 8 keV to study Fe, and 9 keV to study Ni atom uorescence. Measured uorescence spectra were always normalized to the X-ray intensity incident on the sample. I(h) spectra were t using a calculated function ([7], Eq. 15). A standard sample (the preoxidized bulk alloy with known composition) was rst measured to determine an overall scale factor for each uorescent element under investigation (accounting, for example, for unknown transition probabilities). These scale factors were then used for analyzing data from the oxidized sample. Scale thickness and elemental concentrations are obtained as tting parameters. Independent determinations of scale thickness were obtained from measurements of Ka/Kb intensity ratios, and from optical-interference measurements [9, 10]. Raman-spectroscopy measurements were performed using the facility and procedures described in [5]. Fe2O3 has a clear Raman signature, quite distinct from Cr2O3 or spinels, and no competing signal is obtained from the substrate. Further, Fe2O3 appears distinctly in early oxidation of the FeCrNi alloy but is replaced by a Cr2O3 signal as oxidation proceeds [5]. The Fe2O3 signal is measured as a fraction of the total of Fe2O3 and Cr2O3. Measured intensity ratios for Fe2O3 and Cr2O3 are calibrated against standard samples consisting of known mixtures of Fe2O3 and Cr2O3. Energy dispersive X-ray measurements were conducted on Hitachi SEM equipment. Concentrations of Cr, Fe and Ni were measured in the substrate, as a function of distance from the scale/metal interface, on cross sections of FeCrNi

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samples, that had been isothermally oxidized for 4 h and for 16 h. The energy of the electron beam was 15 kV, with spatial resolution of approximately 1 micron.

Results and Discussion Scale characterization using GEXRF Characterization parameters for the scales were extracted from ts to measured I(h) normalized by Io , the incident intensity. Data were tted to a specialized form of the general model function describing angle-dependent uorescent emission [7, 8]. For multiple-layer lms over a substrate, the emission intensity is given by X Ih Ihj 1
j

where I(h)j , the contribution from layer j, is Ihj n l lemj o i Dx Io cj as Ee h ilj 1 exp zj lilj lemj sin a sin h sin a sin h ( ) j1 X l lemi  ili exp zi sin a sin h i1

Here, zj is the thickness of the jth layer (numbered from the topmost layer which is designated j = 1), Dx is the solid angle of the detector which is subtended by the illuminated area of the specimen, Io is the ux of illuminating radiation, cj is the concentration of uorescing atoms in layer j (atoms/volume), as is the absorption cross section of the uorescing atoms for the illuminating radiation (area/atom), Ee is the probability for the emission of an X-ray of interest after an absorption of an illuminating photon has occurred, a is the angle of incidence of the illuminating radiation, h the angle of emission of uorescing radiation, lilj and lemj are absorption coefcients for illuminating and uorescent radiation in layer j. We assume illumination by a monoenergetic beam of X-rays whose energy is above the absorption edge of the element of interest. To analyze the oxidized sample, we consider a homogeneous lm over a substrate containing a Cr-depleted zone located at the scalemetal interface. Thus, for data tting, contributions to the intensity from the lm, from the depletion-zone layers and from the (undepleted) substrate are included. Non-redundant information is obtained by simultaneously tting spectra of all of the major constituents of the sample (i.e., Cr, Fe and Ni). Simultaneously tting I(h)/I0 spectra from multiple elements substantially reduces errors in the extracted parameters. A standard sample (the preoxidized bulk alloy with known composition) was rst measured to determine an overall scale factor Const Dx cj as Ee 3

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for each uorescent element under investigation. The solid line ts to the Fe, Cr and Ni data acquired from the alloy prior to oxidation appear in Fig. 1, panel (a). The tting functions, each with a single adjustable parameter (the scale factor), very adequately describes the I(h) spectra for Fe, Cr and Ni in the bulk alloy. Figure 1 also shows I(h) spectra after the sample has been oxidized for 2 h (panel b) and for 16 h (panel c). Panels (b) and (c) show that the Fe and Ni signals become progressively weaker, relative to Cr, as oxidation proceeds. This occurs because the Fe and Ni signals come predominately from the substrate, which becomes increasingly buried as scale growth advances. However, the Cr signal increases since the Cr concentration in the scale exceeds that in the substrate. Note also, in Fig. 1, that the shape of I(h) for Fe and Ni spectra near the critical angle changes dramatically as the scale forms. This characteristic change in the shape of the leading edge occurs when uorescing atoms on the top surface become buried by an absorbing layer.

Fig. 1 (a) Simultaneously acquired I(h) measurements of Cr, Fe and Ni for the unoxidized 55Fe25Cr 20Ni alloy. Note that simulated spectra (solid lines) provide excellent ts to the measured I(h) after adjustment of a single parameter (overall scale factor). (b) Simultaneously acquired I(h) measurements of Cr, Fe and Ni for the 55Fe25Cr20Ni alloy after 2 h oxidation and (c) after 16 h oxidation. In (b) and (c), solid lines are data simulations which provide measurements of scale parameters (thickness, depletion zone, Fe and Ni concentrations)

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With scale factors determined, we proceed to analyze I(h) spectra for the oxidized sample. Scale thickness, Cr depletion in the substrate, as well as Fe and Ni concentrations in the scale are treated as tting parameters. Modeling of I(h) Spectra from GEXRF To t the measured I(h) spectra, we calculate I(h) for Cr, Fe and Ni when the set of parameters (scale thickness, Fe and Ni concentrations, and depletion-zone depth) is varied to include all possible combinations, within a physically reasonable range of values. For a given set of parameter values, the deviations of each datum point from the calculated I(h) curves are calculated and the rms of the deviations, obtained for the three spectral ts, is recorded. In [8] plots of calculated rms deviations are shown vs. tting parameter values (for scale thickness, depletion-zone depth, Fe and Ni concentrations) for the sample, included in this study, that was oxidized for 4 h. The deviation plots display minimum values where best ts to the four parameters are obtained. Thus we examine the whole four-dimensional parameter space of physically reasonable values of scale thickness, depletion-zone depth, Fe concentration, and Ni concentration to nd those that yield the minimum root-meansquared differences between measured and calculated intensities, I(h). The tting procedure requires simultaneous ts of I(h) for Cr, Fe and Ni. This is a very demanding constraint leading to well-dened tting parameters, even though four parameters are used. Further, in all of the oxidation treatments, the Ni concentration in the scale was found to be very low, a circumstance which effectively removes one of those t parameters. Cr depletion must occur in the substrate, in the vicinity of the scalemetal interface, since the Cr which makes up the scale is extracted, by chemical diffusion, from the substrate. Prior measurements of the Cr-depletion zone [11, 12] in related chromia-forming alloys suggest that, for oxidation at 750 8C in O2, a Cr-depletion zone will originate at the scalemetal interface and will extend for several microns. For modeling I(h) obtained from GEXRF, the depletion zone is approximated by three homogeneous layers with Cr concentrations of neighboring layers differing by a constant increment [8]. That is, the depletion zone is represented by a histogram of three rectangles of equal width w (in microns), and systematically changing Cr concentrations [8]. The Cr concentration gradient is thus approximated by a (stepped) linear function. This is, of course, a rather crude approximation to the actual gradient, but arguably all that is justied by the multiparameter tting procedure. The total number of Cr atoms removed from the zone, by oxidation, is determined by the scale thickness since the quantity of Cr removed from the depletion zone is equal to the quantity of Cr in the scale, i.e., the total amount of Cr is conserved. Thus the depletion zone is represented by a histogram which approximates a triangle (linear) function of varying width and depth depending on scale thickness (Fig. 2, [8]). The histogram is determined by specifying a single parameter, e.g., the histogram parameter w. The Cr concentration at the oxidemetal interface is determined from the depletion range (3w) and the total amount of Cr removed by the scale.

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Figure 1, panels (b) and (c), shows ts to I(h) for Cr, Fe and Ni for the Y-free alloy oxidized for 2 h and for 16 h, respectively. We observe that the data are very well described by the model function. Although differences between measured and calculated spectra are very subtle, those differences might be attributable to additional effects not considered in the tting, such as Fe concentration gradient in the scale, or inadequacy of the approximation for the depletion zone [8]. Note, also, that both metal and oxide spectra (from substrate and scale) are monitored in I(h) with a different weighting of metal and oxide signals as emission angle is changed. With monochromatic excitation radiation (as used in these experiments), EXAFS oscillations will cause relative absorption coefcients for metal and oxide to vary with energy. Any spectral lineshape variations that could be associated with these oscillations were not considered. Small unidentied systematic errors in the measurements might also contribute to the discrepancies. Roughness at the oxide/air and oxide/metal interfaces can change substantially during the course of oxidation. However, the GEXRF technique is normally quite insensitive to roughness at these interfaces. A weak sensitivity to roughness occurs at very low emission angles for lms with smooth interfaces (rms roughness on order of X-ray wavelength k; for Fe emission, k * 2 A). However, samples in this study have substantially thicker oxide scales. Here, the behavior of the uorescence signal is determined by the absorption length of X-rays which pass though the lm and the penetrated substrate. For Fe emission through chromia scales on FeCrNi substrates, the absorption length is *5 microns, a length scale where roughness effects could again become discernible. Thus, the inuence of interface roughness on the GEXRF measurements, reported in this study, is expected to be negligible. Cr-depletion Zone as Dened from GEXRF In tting the GERXF data, the depletion zone was calculated as a stepped triangle function. For simplicity, we show in Fig. 2, smoothed triangle functions

Fig. 2 The evolution of the Crdepletion zone in FeCrNi at 750 8C, as measured using GEXRF for 2 (a), 4 (b), 8 (c) and 16 (d) h of oxidation. The depletion zone is approximated by a simple triangle function (from smoothed step functionssee text). Horizontal line represents bulk concentration of Cr in unoxidized alloy

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representing the extracted depletion zones for the 2, 4, 8, and 16 h oxidations of the FeCrNi sample (Y-free). The depletion zone extends several microns into the substrate; the total amount of depletion increases with oxidation, consistent with scale thickening. Within experimental uncertainty, the Cr concentration at the oxidemetal interface is independent of oxidation time for these treatments. Similar behavior is observed for the Y-containing sample. For Y-free samples oxidized for 4 h and for 16 h, the range and composition of the depletion zone was independently measured using scanning-electron microscopy (SEM). The Cr concentration in the substrate was measured, on a polished sample cross section, using energy-dispersive X-rays (EDX), as a function of depth in the vicinity of the scalemetal interface. SEM measurements were obtained with a spatial resolution of 12 microns. Results are shown in Fig. 3 plotted with the depletion zone obtained from GEXRF. Results obtained using the two techniques are in reasonable agreement. Also shown in Fig. 3 are calculated diffusion proles obtained by considering the diffusion of Cr from a homogeneous semi-innite substrate to a surface sink (the oxide layer). The concentration is given by [11] ! x c ci cb ci erf 4 2Dt1=2 where x is the distance into the sample from the scalemetal interface, D is the diffusion coefcient and t is the oxidation time. cb is the concentration in the substrate before oxidation and ci is the Cr concentration at the metaloxide interface, which can change as a function of time as the oxide grows. Equation (4) assumes that the recession rate of the oxide-interface is slow. The calculated proles shown in Fig. 3, which reasonably represent the experimental concentration proles, were obtained using D = 3.5 1016 m2/s in Eq. (4). For a xed D, the condition was imposed, by appropriately adjusting the interface Cr concentration ci that the amount of Cr removed from the depletion zone was equal to the amount of Cr appearing in the scale. In applying this Crconservation criterion, we use scale-thickness measurements appropriate to the 2, 4, 8 and 16 h oxidation times [10]. The calculated concentrations of Cr at the scale metal interface as function of oxidation time are shown in Table 1. We compare this measured value (D = 3.5 1016 m2/s) to that obtained from an analysis of the Cr-depletion prole (D = 0.8 1016 m2/s) in a sample of 19Cr 25Nibal Fe that was oxidized for 500 h at 800 8C in steam [12]. Cr-diffusion measurements in alloys of approximate composition 20Cr25Nibal Fe (wt.%), but containing additions of Mn, Si and Nb, were also reported by Smith and Gibbs [13] using tracer techniques, and by Evans and Donaldson [11] from analysis of Cr-depletion measurements following lengthy oxidations at 900 8C. For these alloys, with somewhat different compositions, reported values at 900 8C vary between 4 1017 and 6 1016 m2/s. The Table 1 indicates that, for the 2, 4, 8 h and 16 h oxidations, concentration of Cr on the oxidemetal interface is nearly independent of oxidation time. Further, the

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Fig. 3 Measurements of the Cr-depletion zone in proximity to the scalemetal interface for the Y-free alloy after 4 h and 16 h oxidation treatments at 750 8C in O2. Cr concentration is plotted vs. distance into the metal from the scalemetal interface. The step function was obtained from GEXRF, the dots were obtained from EDX of a cross section. The dashed lines are calculated diffusion proles (see text)

relatively high value of Cr concentration at the scalemetal interface conrms that oxide growth is limited by diffusion through the oxide, rather than the substrate, consistent with previous results [11].

Table 1 Concentration of Cr at the scalemetal interface calculated from diffusion proles and scale thicknesses obtained from GEXRF measurements for depletion zones of FeCrNi(Y) alloys as function of the isothermal oxidation time at 750 8C in O2 Time (h) 2 4 8 16 ci (at.%) 0.15 0.18 0.2 0.198 Thickness (mm) 0.35 0.49 0.52 0.97 D (m2/s*1016) 3.5 3.5 3.5 3.5

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This result is in agreement with previously measured [10] constants for parabolic oxidation of FeCrNi(Y). This study showed that for the oxidation at 750 8C the parabolic constant is 1.1 1018 m2/s for FeCrNi(Y), and 1.3 1018 m2/s for FeCrNi alloy. The ratio of kp =D is *3 103. This means that the potential rate of supply of the metal ions from the bulk to the interface is much higher than the rate at which these ions can be oxidized. Thus the oxidation process is limited by diffusion within the oxide layer. It is shown that the GEXRF measurements provide a rough determination of the Cr-depletion zone, from which an approximate value of the Cr-diffusion rate in the substrate can be extracted, even with relatively short oxidation times and relatively low oxidation temperatures. More typically, the depletion zone is studied after much longer oxidation times and higher oxidation temperatures [11, 12, 14, 15].

Fe and Ni Concentrations in Scale The Ni concentration in the scale, obtained from GEXRF measurements, is very low at all stages of oxidation between 2 and 16 h. For the FeCrNiY sample, there is a measurable Ni-rich residue on the oxide surface that persists throughout the oxidation treatment, equivalent to *7 A of NiO [10]. For FeCrNi, however, Ni is essentially undetectable in the scale (always less than 0.5 at.%). However, the Fe concentration in the scale is substantially higher, at all oxidation times up to 16 h. The maximum value is about 3 at.%, after 2 h of treatment, and falls systematically with further oxidation. Figure 4 shows Raman spectra obtained from the Y-free alloy after 0.25 h (panel a), 1 h (panel b) and 2 h (panel c) of oxidation at 750 8C in O2. The intensity of the Fe2O3 peak at 230 cm1 measured relative to the Cr2O3 peak at 550 cm1 provides fractional amounts of Fe2O3 and Cr2O3 in a transient scale forming on the FeCrNi alloy. Note that Fe2O3 is a dominant peak after 0.25 h of oxidation but that it declines rapidly, relative to Cr2O3, with further oxidation. Structures between 600 and 700 cm1 can be attributed to (FeCr)3O4 spinels with Fe2+/3+ valence states and/ or to (FeCr)2O3 solid solution [16]. The contribution of Fe to this high-energy-peak structure cannot be readily obtained [5]. Figure 5 shows Fe concentrations obtained from GEXRF and Raman measurements. The GEXRF results, which measure the total Fe (i.e., all valence states) contained in the scale, shows that the Fe is declining as the thickness increases, demonstrating that the scale puries as growth progresses. There is no discernible difference in Fe concentration for the Y-free and Y-containing alloy scales. Raman spectroscopy provides an estimate of the approximate amount of Fe3+ in the early-stage scale. The Fe2O3 measurements obtained from Raman spectroscopy probe only one crystal structure and thus provide a lower limit on the Fe concentration. However, in very early stages of oxidation, Fe is expected to appear predominately as Fe2O3, consequently, Raman measurements should provide a reasonably accurate determination of the total Fe concentration near time = 0. Thus, the dashed line in Fig. 5, containing GEXRF and early stage Raman data, reveals the total Fe concentration in the scale as it evolves with oxidation time. The very rapid

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Fig. 4 Raman-spectroscopy measurements from the oxide scale on FeCrNi after 0.25, 1, and 2 h of oxidation at 750 8C in O2. Note that, with oxidation, the Fe2O3 peak declines relative to the Cr2O3 peak. Here, star represents a peak from the illuminating laser line

falloff of the Raman Fe2O3 signal suggests that Fe3+ ions are being rapidly reduced as oxidation proceeds. Figure 5 indicates that Fe dilution occurs as a result of a reduced rate of Fe uptake as the scale thickens. However, it does not determine if the total amount of Fe in the scale might be declining as growth proceeds. Since we have measurements of both Fe concentration and scale thickness, we can determine the total amount of Fe in a given area of scale (product of concentration times thickness). These results are shown in Fig. 6. They indicate that, after an initial rise (lasting until the scale is approximately 0.10.2 microns thick), the total amount of Fe in the scale decreases with further oxidation. In this range, the scale puries rapidly with increasing thickness. In the early stages of oxidation, we expect oxidized Fe, Ni and Cr atoms to appear in the scale in ratios comparable to their ratios in the unoxidized alloy, i.e., all of the metal atoms will be oxidized without signicant segregation. Since Fe constitutes 55% of the metal atoms, it would constitute about 23% of the atoms in the early scale (assuming a mix of Fe2O3, Cr2O3 and NiO).

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Fig. 5 Measured total Fe concentration (wt.%, circles) and Fe2O3 (wt.%, triangles) in the scales grown on the FeCrNi(Y) alloys plotted vs. isothermal oxidation time at 750 8C in O2. With increased oxidation, the Fe concentration in the scales decreases

The Raman measurements indicate that, after 15 min of oxidation, the ratio Fe2O3/(Cr2O3 + Fe2O3) in the scale is about 0.35 (assuming the Ni concentration is negligible). A lower limit for the ratio of Fe/(Fe+Cr) can thus be estimated to be

Fig. 6 The number of Fe atoms per cm2 (total, squares and 3+ ions, circles) of scale for FeCrNi(Y) alloys isothermally oxidized at 750 8C in O2. Dotted line represents model calculations of Fe quantity in the scale. As scales thicken, the total amount of Fe in the scales decreases. Thus, as oxidation proceeds, more Fe moves out of the scale than is taken up

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about 0.35. This can be compared to 0.69 for the unoxidized alloy. The Fe2O3 (Raman) signal falls rapidly, approaching the detection limit after about 1.5 h of oxidation; here the scale is about 2,500 A thick. Thus, by 2,500 A thickness, 3+ 2+ essentially all of the Fe in the scale has been reduced (to Fe and/or neutral Fe). The dotted line in Fig. 6 shows the total amount of Fe that would be incorporated in the scale, as the scale thickens, if the Fe, Cr and Ni ratios remained the same as in the substrate metal. If this initial value is the upper limit on Fe concentration in the scale, then Fig. 6 suggests that, as the scale thickens, incorporated Fe must increase to a maximum of about 2.5 1017 atoms/cm2 in a scale of approximately 0.10.15 micron thickness, after less than 2 h of oxidation. With additional oxidation, Fe uptake is soon halted and the total Fe loading in the scale begins a rapid decline. This suggests that a scale of mixed oxide about 1,500 A thick is needed to establish a PO2 sufciently low at the scalemetal interface to reduce the Fe solubility enough to prevent Fe uptake and to cause previously incorporated Fe to begin migrating out of the scale. A simple thermodynamic argument suggests that the Fe concentration, and eventually the total amount of Fe in the scale, should indeed decline at some time after a continuous chromia scale has developed. As new scale growth slowly proceeds, the oxygen activity (essentially the oxygen partial pressure) at the scale metal interface will adjust to that value where the metal and Cr2O3 are in thermodynamic equilibrium. At 750 8C, this value is about 1030 atm O2 [17]. The oxygen partial pressure will rise rapidly with distance away from the scalemetal interface, to a value of approximately 1 atm at the outer surface of the scale. At 750 8C, iron oxides will decompose to neutral Fe at a PO2 * 1019 atm [5, 16, 17], a substantially higher pressure than needed to reduce chromium oxides. Consequently, within the scale, in the vicinity of the scalemetal interface, the oxygen activity will fall to a value sufciently low to decompose any iron oxides [18]. It will not be energetically favorable for these reduced Fe atoms to remain in the extreme low PO2 region of the scale, near the buried interface. Effectively, the iron solubility in this portion of the scale falls to a very low value. A driving force will exist promoting Fe diffusion out of this region of the scale. Further, the extremely low solubility acts as a diffusion barrier, blocking the uptake of new Fe atoms into the scale. Since Fe uptake is blocked and a driving force has been established for inward diffusion of Fe, it follows that the total amount of Fe in the scale should decline, as observed. Figures 5 and 6 show that Fe purication rates in scales thermally grown on FeCrNi and FeCrNi (Y) alloys are the same, within experimental uncertainty; i.e., the average Fe concentration is the same for the two scales after a given heat treatment. For the Y-free alloy, the Ni concentration within the scale is sufciently low to escape detection with GEXRF. However, for the Y-containing alloy, a residue of oxidized Ni is readily observed on the top surface of the scale [10]. The presence of the Ni residue on the Y-containing alloy and its absence on the Y-free alloy is taken as evidence that, for the Y-containing alloy, new scale forms at the scalemetal interface (or at least internal to the scale) and the early stage oxidized Ni simply oats on the growing scale. For the Y-free alloy, some new chromia growth occurs

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at the top surface burying early-stage oxidized Ni, eventually reducing and expelling the Ni from the scale. This shift in the location of new scale growth resulting from the addition of a reactive element has also been reported in independent studies [1820]. The top-surface residue of Ni oxides contains about 4 1015 Ni atoms/cm2, a layer of perhaps 7 A average thickness. The residue persists, relatively unchanged, with further oxidation [10]. These results suggest that, very early after the formation of a continuous scale, the solubility of Ni in the oxide becomes very low so that Ni atoms are rapidly excluded. Thermal Cycling As noted previously, eight samples were given cyclic-oxidation treatments. Sample pairs (samples with and without RE) were heated in one-hour intervals at 750 8C and were then cycled to room temperature (air quench to room temperature followed by insertion into a hot furnace). These four sample pairs were given 2, 4, 8, and 16 heating cycles. Thus the total oxidation times for these pairs were equivalent to the oxidation times for corresponding (noncycled) isothermallytreated specimen pairs discussed above. We nd no discernable effect in any of the scale-characterization parameters that we can attribute to the thermal cycling. Thus, for oxidation at 750 8C in O2, the cyclical compression of the scale that occurs during cooldown to room temperature, apparently does not cause sufcient damage to the scale to alter its growth properties. A substantial room temperature compressive stress results from thermal expansion mismatch between scale and substrate.

Conclusions Using grazing emission X-ray uorescence (GEXRF), isothermal oxidation of 55Fe25Cr20Ni (wt.%) alloys was studied as a function of oxidation time after treatments at 750 8C in O2. Samples were treated for 2, 4, 8 and 16 h. Alloys with and without the reactive element Y were examined. Also, the effect of thermal cycling, after 1 h heating intervals, was studied. Scale thickness, the Cr-depletion zone, as well as Fe and Ni concentrations in the chromia scale were monitored as a function of oxidation time. No effect of thermal cycling was observed in the scalecharacterization parameters. To supplement the GEXRF measurements, the concentration of trivalent Fe in the scale was measured in early oxidation using Raman spectroscopy. It was observed that Ni concentrations in the thermally-grown oxide were consistently very low. Initial Fe concentrations were substantially higher but showed a systematic decrease with oxidation time. It is argued that this scale purication process is a consequence of the very low PO2 in the vicinity of the scalemetal interface.
Acknowledgments This research is supported by the US Department of Energy, Basic Energy Science, Materials Science under Contract No. W-31-109-ENG-38.

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