Oxid Met (2007) 68:37–51 DOI 10.

1007/s11085-007-9053-2 ORIGINAL PAPER

Chromium-oxide Growth on Fe–Cr–Ni Alloy Studied with Grazing-emission X-ray Fluorescence
I. K. Koshelev Æ A. P. Paulikas Æ M. Beno Æ G. Jennings Æ J. Linton Æ M. Grimsditch Æ S. Uran Æ B. W. Veal

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

Abstract Using grazing-emission X-ray fluorescence (GEXRF), isothermal oxidation of the alloys 55Fe–25Cr–20Ni and 55Fe–25Cr–20Ni(+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 purifies 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 fluorescence Á Chromia scale Á Scale growth PACS 68.55.-a Á 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 Á A. P. Paulikas Á M. Beno Á G. Jennings Á J. Linton Á M. Grimsditch Á S. Uran Á B. W. Veal (&) Materials Science Division, Argonne National Laboratory, 9700 S. Cass Av., Argonne, IL 60439, USA e-mail: veal@anl.gov


what is occurring is not a simple dilution process resulting from the addition of new scale.3 wt. at 750 8C in O2. Pairs of samples (with and without RE) were concurrently treated isothermally at 750 8C in flowing O2 for 2. using grazing-emission X-ray fluorescence (GEXRF). and rotated between melts.99% pure) were repeatedly arc melted (usually 6 melts) in an Ar/He atmosphere. transient Fe. composition.3Y (wt. 8] to all of the measured data [I(h) emission spectra for Cr. but eventually disappear after long-term oxidation [5–7]. Evolution of the measured parameters was followed as oxidation proceeded. Starting materials (at least 99. Thus. we observe that the total amount of Fe in a given area of scale declines as oxidation proceeds.% of Y. For Fe–Cr– Ni alloys. if needed.. the intensity I(h) of X-ray fluorescence spectra for Fe.and Ni-rich phases appear in early oxidation. with the samples cleaned. emission angle h. Spectroscopic analyses showed approximately 50 ppm levels of O. In early-stage growth. Experimental Procedures The oxidation study was performed on noncommercial bulk samples of composition 55Fe–25Cr–20Ni and 55Fe–25Cr–20Ni–0. the Ni concentration falls to a very low level (<1 at. In the GEXRF measurement. Apparently. Sample pairs were heated in one-hour intervals at 750 8C and 123 . A second set of eight samples (four pairs with and without RE) were given cyclicoxidation treatments. were studied as a function of oxidation time. transient phases appear in the scale and eventually disappear as the scale matures. In relatively early-stage growth. While the concentration of Fe in the scale diminishes somewhat more slowly. Raman spectroscopy was used to measure the ratio of Fe2O3 to Cr2O3 in the early-stage oxidation of the evolving scales. The observed behavior is explained using simple thermodynamic arguments. Fe and Ni]. a total of eight coupons was polished. ground flat and polished with 1 l alumina abrasive.38 Oxid Met (2007) 68:37–51 For in-service use. and the substrate Cr-depletion zone were quantitatively measured. H.%). the chromia scale increases in purity.%) alloys. The GEXRF measurements were complemented by Raman spectroscopy.e. In this study we measure. after the formation of a continuous chromia scale. Scales. Samples were cut from the rolled sheet. and requiring an internally consistent set of materials parameters. it is important that these economically vital protective oxides be highly adhesive. as a function of scale growth time. Cr and Ni was measured vs.%). After the final melt. By simultaneously fitting calculated spectral functions [7. 4. the scale thickness. samples were rolled to 1 mm thickness. 8 and 16 h. Fe and Ni uptake decline. four contained 0. the concentrations of Fe and Ni in the scale. N and C. grown isothermally on 55Fe–25Cr–20Ni(Y) (wt. slow growing and self healing [1–4]. Since Cr atoms are extracted from the substrate as the oxide grows. a ‘‘reactive element’’ (RE) [1–4] and four were RE-free. SEM and optical reflectivity to obtain independent determinations of scale-characterization parameters. i. a chromium-depletion region necessarily develops at the oxide–metal interface. For the GEXRF studies. The oxide scale forms in a complex process involving the outward diffusion of chromium atoms and the inward diffusion of oxygen atoms.

measured relative to the sample surface. A standard sample (the preoxidized bulk alloy with known composition) was first measured to determine an overall scale factor for each fluorescent element under investigation (accounting. Monochromatized X-rays of *10 eV bandwidth struck the sample at near-normal incidence illuminating an area of about 1 mm · 0.Oxid Met (2007) 68:37–51 39 were then cycled to room temperature. in order to avoid complications resulting from secondary fluorescence. 10]. 6. 15). as a function of distance from the scale/metal interface. Although Fe. 8 keV to study Fe. Cr and Ni fluorescence spectra were simultaneously recorded while the sample was irradiated. Measured intensity ratios for Fe2O3 and Cr2O3 are calibrated against standard samples consisting of known mixtures of Fe2O3 and Cr2O3. and the Cr-depletion zone as a function of isothermaloxidation time. pairs of polished samples were isothermally oxidized for periods of 1/4. an I(h) scan for each of the three elements was also acquired separately. quite distinct from Cr2O3 or spinels. using different excitation energies. samples were placed in an alumina boat which was then inserted into a (horizontal) quartz tube furnace through which oxygen was flowing. The intensities I(h) were recorded as a function of emission angle h. Slits placed in front of the detector were adjusted to provide a 3 milliradian acceptance aperture. and 9 keV to study Ni atom fluorescence. For the Raman studies. the samples and boat were cooled by quenching into air. i. The Fe2O3 signal is measured as a fraction of the total of Fe2O3 and Cr2O3. Further.8 keV excitation energy was used to study Cr. Fe and Ni concentrations. 8. into the flowing gas. for unknown transition probabilities). Fluorescent emission from the sample was simultaneously monitored. Raman-spectroscopy measurements were performed using the facility and procedures described in [5]. and from optical-interference measurements [9. 1 and 2 h. 4. The GEXRF measurements were performed using X-ray synchrotron radiation generated by a bending magnet at the Advanced Photon Source. These sample pairs were given 2. The boat was inserted upstream. Fe and Ni were measured in the substrate. and no competing signal is obtained from the substrate. as the scale developed at 750 8C in O2. GEXRF measurements were used to monitor the evolution of oxide thickness.. Measured fluorescence spectra were always normalized to the X-ray intensity incident on the sample. These scale factors were then used for analyzing data from the oxidized sample. Fe2O3 has a clear Raman signature. After the heat treatment. Eq. at emission angles near grazing.5 mm.e. Independent determinations of scale thickness were obtained from measurements of Ka/Kb intensity ratios. Fe2O3 appears distinctly in early oxidation of the Fe–Cr–Ni alloy but is replaced by a Cr2O3 signal as oxidation proceeds [5]. Ni and Cr atoms using an energy-dispersing Ge detector. Thus. 1/2. I(h) spectra were fit using a calculated function ([7]. and 16 heating cycles. Scale thickness and elemental concentrations are obtained as fitting parameters. Argonne National Laboratory (beamline 12BM). on cross sections of Fe–Cr–Ni 123 . from Fe. for example. Energy dispersive X-ray measurements were conducted on Hitachi SEM equipment. For the heat treatments. Concentrations of Cr. the impinging excitation was tuned to an energy just above the K-edge energy of that element. For each fluorescing element.

The energy of the electron beam was 15 kV. We assume illumination by a monoenergetic beam of X-rays whose energy is above the absorption edge of the element of interest. a is the angle of incidence of the illuminating radiation. for data fitting. Simultaneously fitting I(h)/I0 spectra from multiple elements substantially reduces errors in the extracted parameters. as is the absorption cross section of the fluorescing atoms for the illuminating radiation (area/atom). cj is the concentration of fluorescing atoms in layer j (atoms/volume). Fe and Ni).e. is IðhÞj ¼ n l lemj o i Dx à Io à cj à as à Ee h ilj þ à 1 À exp À zj à lilj lemj sin a sin h sin a þ sin h ( ) jÀ1 X l lemi  ili þ À exp zi sin a sin h i¼1 ð2Þ Here. Non-redundant information is obtained by simultaneously fitting spectra of all of the major constituents of the sample (i. A standard sample (the preoxidized bulk alloy with known composition) was first measured to determine an overall scale factor Const ¼ Dx à cj à as à Ee ð3Þ 123 .40 Oxid Met (2007) 68:37–51 samples. Cr. Thus. Io is the flux of illuminating radiation. Ee is the probability for the emission of an X-ray of interest after an absorption of an illuminating photon has occurred. Data were fitted to a specialized form of the general model function describing angle-dependent fluorescent emission [7. the emission intensity is given by X IðhÞ ¼ IðhÞj ð1Þ j where I(h)j . that had been isothermally oxidized for 4 h and for 16 h. the incident intensity. 8]. Results and Discussion Scale characterization using GEXRF Characterization parameters for the scales were extracted from fits to measured I(h) normalized by Io . To analyze the oxidized sample. we consider a homogeneous film over a substrate containing a Cr-depleted zone located at the scale–metal interface. Dx is the solid angle of the detector which is subtended by the illuminated area of the specimen. lilj and lemj are absorption coefficients for illuminating and fluorescent radiation in layer j. contributions to the intensity from the film. from the depletion-zone layers and from the (undepleted) substrate are included. h the angle of emission of fluorescing radiation.. with spatial resolution of approximately 1 micron. zj is the thickness of the jth layer (numbered from the topmost layer which is designated j = 1). the contribution from layer j. For multiple-layer films over a substrate.

which becomes increasingly buried as scale growth advances. This characteristic change in the shape of the leading edge occurs when fluorescing atoms on the top surface become buried by an absorbing layer. 1. 1. Cr and Ni data acquired from the alloy prior to oxidation appear in Fig. each with a single adjustable parameter (the scale factor). This occurs because the Fe and Ni signals come predominately from the substrate. Note that simulated spectra (solid lines) provide excellent fits to the measured I(h) after adjustment of a single parameter (overall scale factor). as oxidation proceeds. (b) Simultaneously acquired I(h) measurements of Cr.Oxid Met (2007) 68:37–51 41 for each fluorescent element under investigation. the Cr signal increases since the Cr concentration in the scale exceeds that in the substrate. Panels (b) and (c) show that the Fe and Ni signals become progressively weaker. depletion zone. solid lines are data simulations which provide measurements of scale parameters (thickness. Fig. However. Note also. relative to Cr. The solid line fits to the Fe. Fe and Ni for the 55Fe–25Cr–20Ni alloy after 2 h oxidation and (c) after 16 h oxidation. in Fig. Cr and Ni in the bulk alloy. panel (a). that the shape of I(h) for Fe and Ni spectra near the critical angle changes dramatically as the scale forms. Fe and Ni concentrations) 123 . The fitting functions. very adequately describes the I(h) spectra for Fe. In (b) and (c). 1 (a) Simultaneously acquired I(h) measurements of Cr. Fe and Ni for the unoxidized 55Fe–25Cr– 20Ni 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).

we calculate I(h) for Cr. that was oxidized for 4 h.42 Oxid Met (2007) 68:37–51 With scale factors determined.. the depletion zone is represented by a histogram of three rectangles of equal width w (in microns). e. a rather crude approximation to the actual gradient. and Ni concentration to find those that yield the minimum root-meansquared differences between measured and calculated intensities. Fe concentration. In [8] plots of calculated rms deviations are shown vs. [8]). and systematically changing Cr concentrations [8]. we proceed to analyze I(h) spectra for the oxidized sample. The fitting procedure requires simultaneous fits of I(h) for Cr. Fe and Ni concentrations. is recorded. Scale thickness. the histogram parameter w. in the vicinity of the scale–metal interface. but arguably all that is justified by the multiparameter fitting procedure. That is. Thus we examine the whole four-dimensional parameter space of physically reasonable values of scale thickness. Modeling of I(h) Spectra from GEXRF To fit the measured I(h) spectra. included in this study. This is. This is a very demanding constraint leading to well-defined fitting parameters. Fe and Ni when the set of parameters (scale thickness. since the Cr which makes up the scale is extracted.e.g. For a given set of parameter values. 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. 123 . by oxidation. from the substrate. the deviations of each datum point from the calculated I(h) curves are calculated and the rms of the deviations. 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. The Cr concentration gradient is thus approximated by a (stepped) linear function. the depletion zone is approximated by three homogeneous layers with Cr concentrations of neighboring layers differing by a constant increment [8]. obtained for the three spectral fits. Prior measurements of the Cr-depletion zone [11. for oxidation at 750 8C in O2. Fe and Ni concentrations) for the sample. fitting parameter values (for scale thickness. within a physically reasonable range of values. i. in all of the oxidation treatments. The histogram is determined by specifying a single parameter.. I(h). The deviation plots display minimum values where best fits to the four parameters are obtained. depletion-zone depth. For modeling I(h) obtained from GEXRF. The total number of Cr atoms removed from the zone. the total amount of Cr is conserved. Fe and Ni. Further. 2. a circumstance which effectively removes one of those fit parameters. by chemical diffusion. of course. and depletion-zone depth) is varied to include all possible combinations. Cr depletion must occur in the substrate. 12] in related chromia-forming alloys suggest that. even though four parameters are used. The Cr concentration at the oxide–metal interface is determined from the depletion range (3w) and the total amount of Cr removed by the scale. Cr depletion in the substrate. the Ni concentration in the scale was found to be very low. depletion-zone depth. a Cr-depletion zone will originate at the scale–metal interface and will extend for several microns. as well as Fe and Ni concentrations in the scale are treated as fitting parameters.

shows fits to I(h) for Cr. samples in this study have substantially thicker oxide scales. However. Small unidentified systematic errors in the measurements might also contribute to the discrepancies. Horizontal line represents bulk concentration of Cr in unoxidized alloy 123 . panels (b) and (c). the depletion zone was calculated as a stepped triangle function. also. Thus. or inadequacy of the approximation for the depletion zone [8]. EXAFS oscillations will cause relative absorption coefficients for metal and oxide to vary with energy. such as Fe concentration gradient in the scale. the behavior of the fluorescence signal is determined by the absorption length of X-rays which pass though the film and the penetrated substrate. we show in Fig. Any spectral lineshape variations that could be associated with these oscillations were not considered. for Fe emission. respectively. reported in this study. smoothed triangle functions Fig. 2. the influence of interface roughness on the GEXRF measurements. Here. For Fe emission through chromia scales on Fe–Cr–Ni substrates.Oxid Met (2007) 68:37–51 43 Figure 1. 8 (c) and 16 (d) h of oxidation. For simplicity. A weak sensitivity to roughness occurs at very low emission angles for films with smooth interfaces (rms roughness on ˚ order of X-ray wavelength k. Although differences between measured and calculated spectra are very subtle. With monochromatic excitation radiation (as used in these experiments). We observe that the data are very well described by the model function. Note. those differences might be attributable to additional effects not considered in the fitting. is expected to be negligible. 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. Cr-depletion Zone as Defined from GEXRF In fitting the GERXF data. the GEXRF technique is normally quite insensitive to roughness at these interfaces. a length scale where roughness effects could again become discernible. 2 The evolution of the Crdepletion zone in Fe–Cr–Ni at 750 8C. Fe and Ni for the Y-free alloy oxidized for 2 h and for 16 h. as measured using GEXRF for 2 (a). the absorption length is *5 microns. However. 4 (b). Roughness at the oxide/air and oxide/metal interfaces can change substantially during the course of oxidation. The depletion zone is approximated by a simple triangle function (from smoothed step functions—see text). k * 2 A).

and by Evans and Donaldson [11] from analysis of Cr-depletion measurements following lengthy oxidations at 900 8C. 4. In applying this Crconservation criterion. we use scale-thickness measurements appropriate to the 2. Also shown in Fig. the condition was imposed. Further. were obtained using D = 3.5 · 10À16 m2/s in Eq. 3 are calculated diffusion profiles obtained by considering the diffusion of Cr from a homogeneous semi-infinite substrate to a surface sink (the oxide layer).8 · 10À16 m2/s) in a sample of 19Cr– 25Ni–bal Fe that was oxidized for 500 h at 800 8C in steam [12]. 3 plotted with the depletion zone obtained from GEXRF. We compare this measured value (D = 3. (4).5 · 10À16 m2/s) to that obtained from an analysis of the Cr-depletion profile (D = 0. 8. cb is the concentration in the substrate before oxidation and ci is the Cr concentration at the metal–oxide interface. 8 and 16 h oxidation times [10]. Results obtained using the two techniques are in reasonable agreement. 3. which can change as a function of time as the oxide grows. The depletion zone extends several microns into the substrate. For Y-free samples oxidized for 4 h and for 16 h. For these alloys.44 Oxid Met (2007) 68:37–51 representing the extracted depletion zones for the 2. the 123 . using energy-dispersive X-rays (EDX). D is the diffusion coefficient and t is the oxidation time. The Table 1 indicates that. with somewhat different compositions. Si and Nb.%). but containing additions of Mn. The calculated profiles shown in Fig. the Cr concentration at the oxide–metal interface is independent of oxidation time for these treatments. 4. on a polished sample cross section. for the 2. For a fixed D. as a function of depth in the vicinity of the scale–metal interface. Results are shown in Fig. Within experimental uncertainty. 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. the range and composition of the depletion zone was independently measured using scanning-electron microscopy (SEM). Similar behavior is observed for the Y-containing sample. SEM measurements were obtained with a spatial resolution of 1–2 microns. which reasonably represent the experimental concentration profiles. 8 h and 16 h oxidations. and 16 h oxidations of the Fe–Cr–Ni sample (Y-free). were also reported by Smith and Gibbs [13] using tracer techniques. The calculated concentrations of Cr at the scale– metal interface as function of oxidation time are shown in Table 1. concentration of Cr on the oxide–metal interface is nearly independent of oxidation time. the total amount of depletion increases with oxidation. reported values at 900 8C vary between 4 · 10À17 and 6 · 10À16 m2/s. The concentration is given by [11] ! x c ¼ ci þ ðcb À ci Þ Ã erf ð4Þ 2ðDtÞ1=2 where x is the distance into the sample from the scale–metal interface. consistent with scale thickening. The Cr concentration in the substrate was measured. 4. Equation (4) assumes that the recession rate of the oxide-interface is slow. Cr-diffusion measurements in alloys of approximate composition 20Cr–25Ni–bal Fe (wt.

35 0.52 0. distance into the metal from the scale–metal interface.49 0. The dashed lines are calculated diffusion profiles (see text) relatively high value of Cr concentration at the scale–metal interface confirms that oxide growth is limited by diffusion through the oxide.5 3.97 D (m2/s*10À16) 3.198 Thickness (mm) 0. rather than the substrate. 3 Measurements of the Cr-depletion zone in proximity to the scale–metal interface for the Y-free alloy after 4 h and 16 h oxidation treatments at 750 8C in O2. Table 1 Concentration of Cr at the scale–metal interface calculated from diffusion profiles and scale thicknesses obtained from GEXRF measurements for depletion zones of Fe–Cr–Ni(Y) alloys as function of the isothermal oxidation time at 750 8C in O2 Time (h) 2 4 8 16 ci (at.18 0. The step function was obtained from GEXRF.15 0.%) 0.2 0.5 3.5 3. consistent with previous results [11]. the dots were obtained from EDX of a cross section.5 123 .Oxid Met (2007) 68:37–51 45 Fig. Cr concentration is plotted vs.

This study showed that for the oxidation at 750 8C the parabolic constant is 1. there is a measurable Ni-rich residue on the oxide surface that persists throughout the ˚ oxidation treatment. shows that the Fe is declining as the thickness increases. Raman spectroscopy provides an estimate of the approximate amount of Fe3+ in the early-stage scale. after 2 h of treatment.5 at.46 Oxid Met (2007) 68:37–51 This result is in agreement with previously measured [10] constants for parabolic oxidation of Fe–Cr–Ni(Y). demonstrating that the scale purifies as growth progresses. is very low at all stages of oxidation between 2 and 16 h. obtained from GEXRF measurements. relative to Cr2O3.. 5. however. However. The ratio of kp =D is *3 · 10À3. all valence states) contained in the scale.%). 14. The GEXRF results. 1 h (panel b) and 2 h (panel c) of oxidation at 750 8C in O2. The intensity of the Fe2O3 peak at 230 cmÀ1 measured relative to the Cr2O3 peak at 550 cmÀ1 provides fractional amounts of Fe2O3 and Cr2O3 in a transient scale forming on the Fe–Cr–Ni alloy. Figure 5 shows Fe concentrations obtained from GEXRF and Raman measurements.25 h of oxidation but that it declines rapidly. in very early stages of oxidation. from which an approximate value of the Cr-diffusion rate in the substrate can be extracted. and 1. 12. Figure 4 shows Raman spectra obtained from the Y-free alloy after 0. The Fe2O3 measurements obtained from Raman spectroscopy probe only one crystal structure and thus provide a lower limit on the Fe concentration. Fe and Ni Concentrations in Scale The Ni concentration in the scale. Ni is essentially undetectable in the scale (always less than 0. Note that Fe2O3 is a dominant peak after 0.3 · 10À18 m2/s for Fe–Cr–Ni alloy. 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. reveals the total Fe concentration in the scale as it evolves with oxidation time. There is no discernible difference in Fe concentration for the Y-free and Y-containing alloy scales. The very rapid 123 . which measure the total Fe (i. More typically. the dashed line in Fig.%. with further oxidation.25 h (panel a). The contribution of Fe to this high-energy-peak structure cannot be readily obtained [5]. Raman measurements should provide a reasonably accurate determination of the total Fe concentration near time = 0. containing GEXRF and early stage Raman data. equivalent to *7 A of NiO [10]. For the Fe–Cr–Ni–Y sample. the Fe concentration in the scale is substantially higher. The maximum value is about 3 at. Structures between 600 and 700 cmÀ1 can be attributed to (FeCr)3O4 spinels with Fe2+/3+ valence states and/ or to (FeCr)2O3 solid solution [16].1 · 10À18 m2/s for Fe–Cr–Ni(Y). Thus the oxidation process is limited by diffusion within the oxide layer. and falls systematically with further oxidation. 15]. However. It is shown that the GEXRF measurements provide a rough determination of the Cr-depletion zone. For Fe–Cr–Ni. at all oxidation times up to 16 h. Fe is expected to appear predominately as Fe2O3. Thus. even with relatively short oxidation times and relatively low oxidation temperatures. consequently.e. the depletion zone is studied after much longer oxidation times and higher oxidation temperatures [11.

e. However. They indicate that. 123 . 6. it would constitute about 23% of the atoms in the early scale (assuming a mix of Fe2O3. all of the metal atoms will be oxidized without significant segregation. In the early stages of oxidation. the Fe2O3 peak declines relative to the Cr2O3 peak. we can determine the total amount of Fe in a given area of scale (product of concentration times thickness).25.2 microns thick). the total amount of Fe in the scale decreases with further oxidation. Since Fe constitutes 55% of the metal atoms. the scale purifies rapidly with increasing thickness. Cr2O3 and NiO). it does not determine if the total amount of Fe in the scale might be declining as growth proceeds. 4 Raman-spectroscopy measurements from the oxide scale on Fe–Cr–Ni after 0.. after an initial rise (lasting until the scale is approximately 0. Since we have measurements of both Fe concentration and scale thickness. and 2 h of oxidation at 750 8C in O2. 1. we expect oxidized Fe. 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. In this range. These results are shown in Fig.1–0. i. Ni and Cr atoms to appear in the scale in ratios comparable to their ratios in the unoxidized alloy.Oxid Met (2007) 68:37–51 47 Fig. Figure 5 indicates that Fe dilution occurs as a result of a reduced rate of Fe uptake as the scale thickens. Note that. with oxidation.

circles) of scale for Fe–Cr–Ni(Y) alloys isothermally oxidized at 750 8C in O2. the total amount of Fe in the scales decreases. 6 The number of Fe atoms per cm2 (total.35 (assuming the Ni concentration is negligible). the ratio Fe2O3/(Cr2O3 + Fe2O3) in the scale is about 0. Thus. as oxidation proceeds. squares and 3+ ions. circles) and Fe2O3 (wt. 5 Measured total Fe concentration (wt. the Fe concentration in the scales decreases The Raman measurements indicate that.%. A lower limit for the ratio of Fe/(Fe+Cr) can thus be estimated to be Fig. Dotted line represents model calculations of Fe quantity in the scale. more Fe moves out of the scale than is taken up 123 . triangles) in the scales grown on the Fe–Cr–Ni(Y) alloys plotted vs. With increased oxidation. isothermal oxidation time at 750 8C in O2.48 Oxid Met (2007) 68:37–51 Fig.%. As scales thicken. after 15 min of oxidation.

incorporated Fe must increase to a maximum of about 2. as observed. For the Y-free alloy. within experimental uncertainty. It will not be energetically favorable for these reduced Fe atoms to remain in the extreme low PO2 region of the scale. this value is about 10À30 atm O2 [17]. a residue of oxidized Ni is readily observed on the top surface of the scale [10]. As new scale growth slowly proceeds. the extremely low solubility acts as a diffusion barrier. the Ni concentration within the scale is sufficiently low to escape detection with GEXRF. in the vicinity of the scale–metal interface.e. it follows that the total amount of Fe in the scale should decline. 6 shows the total amount of Fe that would be incorporated in the scale. should indeed decline at some time after a continuous chromia scale has developed.. 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. If this initial value is the upper limit on Fe concentration in the scale. This suggests that a scale of mixed oxide about 1. However. 6 suggests that.500 A thickness. The Fe2O3 (Raman) signal falls rapidly. a substantially higher pressure than needed to reduce chromium oxides. for the Y-containing alloy. and eventually the total amount of Fe in the scale. as the scale thickens. Effectively. here the scale is about 2. approaching the detection limit after about 1. The dotted line in Fig. near the buried interface. The oxygen partial pressure will rise rapidly with distance away from the scale–metal interface. the oxygen activity will fall to a value sufficiently low to decompose any iron oxides [18].69 for the unoxidized alloy. Figures 5 and 6 show that Fe purification rates in scales thermally grown on Fe–Cr–Ni and Fe–Cr–Ni (Y) alloys are the same. new scale forms at the scale–metal interface (or at least internal to the scale) and the early stage oxidized Ni simply floats on the growing scale. The presence of the Ni residue on the Y-containing alloy and its absence on the Y-free alloy is taken as evidence that. to a value of approximately 1 atm at the outer surface of the scale. the iron solubility in this portion of the scale falls to a very low value.5 · 1017 atoms/cm2 in a scale of approximately 0. A simple thermodynamic argument suggests that the Fe concentration. 17].500 A thick is needed to establish a PO2 sufficiently low at the scale–metal interface to reduce the Fe solubility enough to prevent Fe uptake and to cause previously incorporated Fe to begin migrating out of the scale.15 micron thickness. For the Y-free alloy. At 750 8C. by 2. With additional oxidation.1–0. 16.5 h of ˚ ˚ oxidation. iron oxides will decompose to neutral Fe at a PO2 * 10À19 atm [5. This can be compared to 0. i. Thus. At 750 8C. within the scale. Cr and Ni ratios remained the same as in the substrate metal.35. Consequently.500 A thick. for the Y-containing alloy. Fe uptake is soon halted and the total Fe loading in the scale begins a ˚ rapid decline. 3+ 2+ essentially all of the Fe in the scale has been reduced (to Fe and/or neutral Fe). Further. some new chromia growth occurs 123 .Oxid Met (2007) 68:37–51 49 about 0. as the scale thickens. then Fig. after less than 2 h of oxidation. A driving force will exist promoting Fe diffusion out of this region of the scale. blocking the uptake of new Fe atoms into the scale. the average Fe concentration is the same for the two scales after a given heat treatment. if the Fe. Since Fe uptake is blocked and a driving force has been established for inward diffusion of Fe.

The residue persists. These results suggest that. These four sample pairs were given 2. with further oxidation [10]. the Cr-depletion zone. It is argued that this scale purification process is a consequence of the very low PO2 in the vicinity of the scale–metal interface. To supplement the GEXRF measurements. No effect of thermal cycling was observed in the scalecharacterization parameters. isothermal oxidation of 55Fe–25Cr–20Ni (wt. Materials Science under Contract No. 4. 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). the concentration of trivalent Fe in the scale was measured in early oxidation using Raman spectroscopy. Acknowledgments This research is supported by the US Department of Energy. W-31-109-ENG-38. 8 and 16 h. eventually reducing and expelling the Ni from the scale. Thermal Cycling As noted previously. We find no discernable effect in any of the scale-characterization parameters that we can attribute to the thermal cycling.%) alloys was studied as a function of oxidation time after treatments at 750 8C in O2.50 Oxid Met (2007) 68:37–51 at the top surface burying early-stage oxidized Ni. relatively unchanged. It was observed that Ni concentrations in the thermally-grown oxide were consistently very low. was studied. Samples were treated for 2. 8. Thus. Initial Fe concentrations were substantially higher but showed a systematic decrease with oxidation time. The top-surface residue of Ni oxides contains about ˚ 4 · 1015 Ni atoms/cm2. Thus the total oxidation times for these pairs were equivalent to the oxidation times for corresponding (noncycled) isothermallytreated specimen pairs discussed above. the solubility of Ni in the oxide becomes very low so that Ni atoms are rapidly excluded. This shift in the location of new scale growth resulting from the addition of a reactive element has also been reported in independent studies [18–20]. the effect of thermal cycling. and 16 heating cycles. the cyclical compression of the scale that occurs during cooldown to room temperature. as well as Fe and Ni concentrations in the chromia scale were monitored as a function of oxidation time. after 1 h heating intervals. Alloys with and without the reactive element Y were examined. apparently does not cause sufficient damage to the scale to alter its growth properties. 123 . Also. eight samples were given cyclic-oxidation treatments. 4. a layer of perhaps 7 A average thickness. very early after the formation of a continuous scale. Basic Energy Science. Conclusions Using grazing emission X-ray fluorescence (GEXRF). for oxidation at 750 8C in O2. A substantial room temperature compressive stress results from thermal expansion mismatch between scale and substrate. Scale thickness.

Oxidation of Metals 50. Uran. B. Srkiguchi. 73 (2000). 475 (1998). Kofstad. A. 6. P. 4. and B. Jennings. 903 (2001). Bureau of Mines. 3. 93 (1969). McCarty. Linton. Pankrats. Oxidation of Metals 12. Veal. J. J. Gibbs. USA. p. B. Y. A. Renusch. P. 558. London. 413 (1978). F. Materials Science Forum 43. 79 (1989). Hou. Veal. S. 15. B. Journal of Solid State Chemistry 79. E. Boehme. Oxidation of Metals 54. Natesan. and H. Yurek. Wood. 7. Paulikas. Y. H. S. B. Smith. 2. K. F.Oxid Met (2007) 68:37–51 51 References 1. T. and D. Y. 13. and G. 469 (2003). Beno. Baba. and J. 9. 17. Corrosion Science 43. Materials Science and Technology 4. and A. Metal Science Journal 3. Li. Veal. M. Paulikas. P. G. Berger. I. Hou. 8. A. 1982). 401 (1970). D. Przybylski. and B. Bennett. V. Koshelev. Y. Materials at High Temperatures 12. H. Paulikas. P. Physica B 304. 23 (1999). and B. 20. 14. and P. A. Ericsson. K. Linton. 67 (1989). High Temperature Corrosion (Elsevier Applied Science. I. 177 (1994). 1 (1989). 1 (1995). M. M. Materials Science and Engineering A 116. 16. and G. L. Veal. Evans. J. Tuson. 123 . Koshelev. T. D. I. Jennings. 11. Beskr. Materials Science and Engineering A 202. and A. 256 (2001). 19. and G. Donaldson. H. Strawbridge. T. Ramathan. Corrosion Science 35. Evans. 10. Koshelev. G. M. Briefs. 19 (1989). P. J. Stringer. W. 12. 1988). Thermodynamic Properties of Elements and Oxides (United States Department of Interior. Bastow. Uran. and T. L. K. Grimsditch. B. Holzbrecher. Pearson. 1089 (1988). W. A. E. D. C. 18. New York. Oxidation of Metals 46(5/6). and A. Quadakkers. Oxidation of Metals 32. J. G. Oxidation of Metals 51. 5. 871 (1993). Grimsditch. L. Oxidation of Metals 2. Uran. 365 (1996). Veal. B. Beno. and M. M. R. Oxidation of Metals 59. P. S. Whittle.

Sign up to vote on this title
UsefulNot useful