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Oxidation of Metals, Vol. 55, Nos.

1/2, 2001

Diffusion Cells and Chemical Failure of MCrAlY Bond Coats in Thermal-Barrier Coating Systems
H. E. Evans* and M. P. Taylor*
Receied February 18, 2000; reised July, 26 2000

It is proposed that bond coats in thermal-barrier coating (TBC) systems, particularly those deposited by plasma spraying, can contain regions which are diffusionally isolated from the bulk of the coating. This can arise through the internal formation of alumina layers as a consequence of the ingress of molecular oxygen into the relatiely porous structure. Such isolated regions, termed diffusion cells, will experience enhanced depletion of aluminum as a result of the continued thickening of the alumina layer at their surface. This process has been demonstrated for a CoNiCrAlY bond coat after oxidation in air at 1100C. A consequence of this enhanced depletion is that chemical failure will occur sooner in diffusion cells and oluminous breakaway oxides will form aboe them at the interface of the bond coat and the ceramic top coat. The associated spatial ariation in oxidation and displacement rates across the surface of the bond coat are expected to aid delamination of the outer ceramic layer.
KEY WORDS: Thermal-barrier coatings; Al depletion; chemical failure; delamination.

INTRODUCTION Thermal-barrier coating (TBC) systems offer an elegant solution to the challenge of operating gas turbines at increasingly higher temperatures. TBCs usually consist of an outer coating of zirconia, partially-stabilized with yttria (YSZ), overlying an oxidation-resistant bond coat deposited onto the component surface. The low thermal conductivity of this outer ceramic layer
*School of Metallurgy and Materials, The University of Birmingham, Birmingham B15 2TT, UK. 17
0030-770X010200-0017$19.500 2001 Plenum Publishing Corporation

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can result in a substantial temperature gradient through its thickness under heat-ux conditions, such that the outer surface of the bond coat will be at substantially lower temperatures, say 200C, than the outer surface of the ceramic top coat. To achieve benets of this order, ceramic layer thicknesses in excess of approximately 200 m are required. Even so, oxidation of the bond coat remains an important issue and compositions based on MCrAlX alloys, where M is typically nickel or cobalt or a combination and X is often a combination of reactive elements such as yttrium, hafnium or silicon is a widely used generic type. In applications that require extended periods of operation at high temperature, e.g., industrial gas turbines, this type of coating tends to offer better oxidation resistance than diffusion variants1 since they provide a greater reservoir of aluminum. MCrAlX-type bond coats can be deposited by a variety of methods, but plasma spraying is frequently used and will be the application method considered principally in this paper. Similarly, a choice of deposition routes exists for the ceramic top coat, but vapor deposition or plasma spraying are generally favored. Failure of the TBC system usually occurs by delamination of the ceramic top coat.25 The fracture path lies either within or close to the thermally grown oxide (TGO) layer that forms on the surface of the bond coat during high-temperature exposure. Delamination models that have been considered in some theoretical depth are those involving edge cracking6 and buckling.7,8 In the latter case, signicant exure of the ceramic layer under the in-plane compressive stress developed during cooling requires the prior formation of an extensive zone of decohesion at the base of the outer layer. The possible origins of such a zone of decohesion is an aspect that has received relatively little study, although the development of such a zone may occupy a large fraction of the lifetime of the coating system. Mechanisms proposed to date involve the growth of interfacial defects by a stress-corrosion process9 or by fatigue.10 However, recent studies by Niranatlumpong11 have suggested that cracks at the base of the ceramic top coat can develop even under isothermal oxidation in the absence of applied stresses. The purpose of this paper is to suggest an alternative route to the development of a zone of decohesion close to the TGO layer. It is envisaged that, as a consequence of the high-temperature exposure, some surface regions of the bond coat will experience chemical failure and eventual breakaway oxidation in advance of the bulk of the bond coat surface. These latter regions will continue to experience protective oxidation and the slow growth of an alumina layer, but the chemically failed regions will be characterized by the relatively rapid growth of voluminous oxides other than alumina, typically chromium- or nickel-rich.11,12 These high growth rates reect the ionic-transport rates within such oxides, but the oxidation rates may also be enhanced by molecular access through porosity within this nonprotective

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oxide layer. The spatial variation in TGO growth rates across the bond coat surface will tend to develop out-of-plane tensile stresses in the vicinity of the TGO interface with the ceramic top coat. These will encourage the growth of a zone of decohesion in these regions, as shown schematically in Fig. 1. Development of these cracking models will not be attempted in this paper, but rather the focus will be on identifying the conditions needed to initiate chemical failure, specically in plasma-sprayed MCrAlX bond coats. As part of this, it will be necessary to introduce the concept of diffusion cells and to demonstrate that aluminum depletion within such cells can be quantitatively predicted. It is anticipated that these cells will correspond to the splat particles comprising the coating and that these may be diffusionally isolated from the remainder of the coating as a consequence of a layer of oxide surrounding the particle. This oxide will form initially during the spraying operation and, as will be shown, can continue to grow in lowdensity coatings during high-temperature exposure. As part of this study, predictions will be made of the oxidation time required to initiate chemical failure in diffusion cells of various sizes as a consequence of local aluminum depletion. Insofar that recent studies13 have suggested a link between the formation of nickel- and chromium-containing oxides late in life (i.e., chemical failure) at the bond coat surface and the imminence of TBC failure, such predictions of the onset of chemical failure may provide a guide to the lifetimes of such coatings. THE ROUTE TO CHEMICAL FAILURE During the early stages of oxidation of MCrAlX coating alloys, transient oxides containing chromium and nickel form, but their growth rate is

Fig. 1. A schematic diagram showing how nonuniform oxidation rates at the bond coattop coat interface can develop out-of-plane tensile stresses and associated delamination cracks.

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much reduced after the formation of a continuous protective alumina layer.12 The continued growth of this layer necessarily results in the selective depletion of aluminum within the coating. This process of depletion, if carried to excess, will lead to chemical failure. Recently, a theoretical framework for chemical failure, and the ensuing stage of breakaway oxidation, has been proposed14 in chromia-forming alloys and these concepts will be translated here to the current bond-coat application. Two routes have been identied14 for the initiation of chemical failure and breakaway oxidation. Under the demanding conditions typical of TBC operation, the protective alumina layer will experience a wide range of tensile and compressive stresses. These are likely to produce a range of throughthickness cracks or partial spalls of the alumina layer which, given the ease of ionic and molecular transport through the ceramic top coat, will permit direct oxygen access to the depleted bond coat. Normally, the transient oxidation that follows will be rapidly healed by the formation of another alumina layer, but this healing process will require a minimum, local concentration of aluminum. This critical-healing concentration, Ch, is not well established, but on the basis of work on other alloy systems,15,16 is likely to be in the range of 4 to 5 at.% Al. Mechanically-induced chemical failure (MICF) is then possible when the concentration of aluminum in the coating, or as will be discussed below, isolated regions of the coatings falls below Ch. Intrinsic chemical failure (InCF) arises14 when depletion has occurred to such an extent that the alumina layer becomes thermodynamically unstable in relation to the adjacent coating. At this stage it will then become favorable to form oxides other than alumina through reactions of the type:12 Al2O3C2Cr 2AlCCr2O3 or
1 O2CNi NiAl2O4 Al2O3C2

(A)

(B)

depending on the detailed composition beneath the alumina layer and the supply of excess oxygen by diffusion through this layer. These examples are not exclusive but demonstrate the concept. In each case, however, they will be favored only when aluminum depletion in the coating is severe and its activity approaches zero, e.g., Pettit17 calculates that, for a chromium activity of 0.15, an aluminum activity lower than approximately 108 will be needed at 1200C to move reaction (A) in the direction shown. Although residual aluminum is not shown explicitly in reaction (B), low levels will permit a rise in oxygen potential beneath the alumina layer and will again favor the reaction as shown. In this case, however, kinetic (through the rate

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of ingress of oxygen) as well as thermodynamic factors apply and calculation of critical residual aluminum activities are less straightforward. Nevertheless, recent work12 on NiCrAlY overlay coatings (i.e., without a ceramic top coat) clearly shows the development of both nickel- and chromium-containing oxides underneath an apparently continuous and adherent alumina layer. This work shows that aluminum depletion sufcient to initiate InCF can occur in the alloy compositions used for MCrAlX bond coats. The depletion prole, within long rectangular specimens of nite width resulting from the parabolic thickening of an alumina layer on both major faces, can be calculated analytically.18,19 The analysis for this idealized geometry can be applied, however, to the depletion within less regularly shaped splat particles, i.e., diffusion cells, provided that the depletion distance is much less than the local curvature. Some examples will be provided later. Cells of various widths, 2w, will exist within the bond coat, as shown schematically in Fig. 2, where the origin of the x coordinate normal to the surface of the bond coat lies at the oxidebond coat interface. A key aspect of the analysis is that an alumina layer is assumed to grow at the same rate at both the external (i.e., in contact with the top coat) and internal surface of the diffusion cell, but this can occur only if the oxidizing gas has molecular access around the boundaries of the splat particle comprising the cell. It has been recognized for many years that plasma-sprayed coatings, at least those deposited in air or argon-shrouded environments, are of relatively low density and permit gas access sufcient to form layers of oxide at the

Fig. 2. The model used in the analysis showing the sense of the xcoordinate and diffusion cells of varying widths, x G2w.

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internal surfaces of splat particles. An example for the present air plasmasprayed coatings is shown in Fig. 3. What is not clear is whether these gasaccess channels can remain sufciently open over time to continue to provide unconstrained access of the oxidant, even though an alumina layer is being formed within them. One factor that could aid this process of retaining the gas channels open is the volume contraction within the splat particle as a consequence of phase transformation resulting from aluminum depletion, e.g., dissolution of the phase. In any event, the test of the assumption of equal alumina growth rates around the diffusion cell will be the presence of a symmetrical aluminum-depletion prole. Evidence that these do, indeed, occur will be presented later. The rate of alumina growth at each surface of the diffusion cell will be characterized by the rate constant, kp G 2t, where is the oxide thickness and t is the oxidation time. During protective oxidation, the rate of consumption of metal is so low that the recession of the oxidemetal interface may be neglected. It is also assumed that end effects may be neglected. The aluminum concentration across the specimen width, 2w, i.e., along the x coordinate, is then obtained from Ficks second law: C 2C GD 2 t x (1)

where D is the interdiffusion coefcient. This is subject to the boundary conditions: C GCb , for t G0 for all t k0.5 p 2 Alt0.5 , for tH0

x t
C

G0,

x Gw

x G0,2w

(2)

where Cb is the initial aluminum concentration (at.%) and C the current value; the second condition is required to satisfy symmetry; the third reects the parabolic growth kinetics of the alumina layer, where is the Pilling Bedworth ratio (1.28 for alumina) and Al is the volume of an aluminum atom. The solution for C (in at.%) can be derived from previous analyses18,19 as: C GCbA 50 kp D

1/2 S

n G0

erfc

2(Dt) Cerfc
2nwCx
1/2

2(nC1)wAx 2(Dt)1/2

(3)

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Fig. 3. Cross sections of the CoNiCrAlY bond coat: (a) a relatively unrepresentative area in the as-received condition showing spheroidal protuberances from the bond coat and (b) a more representative area after oxidation in air for 4 hr at 1100C showing oxide formation at splat boundaries within the bond coat. The grit particles of (a) are a residue of the surface preparation prior to coating.

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Previously,18,19 the rate constant was dened in terms of the interface recession, x, as kx G(x)2(2t), but this has now been converted in Eq. (3) to kp G22kx so that the more readily measured parameter of oxide thickness may be used. This analysis will be used to dene the onset of the two principal forms of chemical failure as discussed earlier. Specically, the oxidation time will be calculated for the diffusion cell to become susceptible to both MICF and InCF. For the former, this will arise when the aluminum concentration at the mid-plane falls below the critical value, Ch , taken here to be 5 at.%. InCF will be assumed to arise when the aluminum concentration in the alloy at the oxidemetal interface becomes zero. DIFFUSION CELLS: DEMONSTRATION OF THE CONCEPT Plasma-sprayed coatings are produced by the deposition of semimolten alloy particles onto the superalloy substrate. The temperature of these particles and the velocity with which they reach the surface of the alloy depend on factors such as their size and their location within the plasma stream. There is sufcient intrinsic variability within the process to ensure that bonding between adjacent splat particles comprising the coating is often incomplete. The particles will also develop a surface oxide layer within the plasma stream and this also will contribute to a lack of bonding within the coating. Although coating density can be improved by subsequent peening operations or by spraying in low-pressure or inert atmospheres, gas-access paths are likely to remain a feature of plasma-sprayed bond coats. As discussed earlier, a consequence of these paths is that oxide layers will form around the original splats during high-temperature exposure. Figure 3 provides a comparison of bond-coat microstructure prior to and after oxidation. It is clear that the splat boundaries are more clearly delineated after high-temperature exposure and this is the result of the formation of networks of internal oxides. In cross-sectional microprobe scans these internal oxides can be detected readily by the presence of periodic peaks in aluminum concentration, as shown for a CoNiCrAlY coating in Fig. 4, and are, presumably, alumina. These alumina layers provide the diffusion barriers preventing the replenishment of aluminum from the reservoir in the bulk of the coating. Within these diffusion cells, aluminum will be depleted at a far higher rate than would be expected if the coating were homogenous. These regions of the coating will experience chemical failure in advance of the bulk and an example of a TBC system undergoing such partial breakdown is given in Fig. 5. The enhanced localized depletion of aluminum in the diffusion cells can now be quantied through the use of Eq. (3), i.e., by considering the cell as

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Fig. 4. Compositional prole for aluminum (using EDX) and oxygen (using WDX) across the CoNiCrAlY bond coat after oxidation in air for 4 hr at 1100C. The internal-oxide boundaries correspond to the peaks in aluminum and oxygen.

an isolated specimen, which is growing an alumina layer at all its surfaces at the same parabolic rate. In the present work, depletion proles were obtained from regions for which the cell widths were much less than the local surface curvature and also were appreciably smaller than the cell lengths. These are the conditions necessary for the application of Eq. (3), but are not as restrictive as might be thought. For typical regions of bond coat (an example is shown in Fig. 3b), some 30% of the outermost layer of splat particles satised these conditions. Less-typical areas (Fig. 3a is representative) contained regions where spheroidal protuberances had formed during spraying and, for such cases, the present analysis would not be expected to apply. The aluminum depletion prole across a given cell width, i.e., along the x coordinate normal to the TGObondcoat interface, was measured using a JEOL 840A SEM at discrete locations, typically 3- to 10-m apart. The work was undertaken on a plasma-sprayed 35Co27Ni23Cr15AlY (at.%) bond coat, some 150 m in total thickness, between an IN738 substrate and a 250-m thick, plasma-sprayed ZrO28 wt.% Y2O3 top coat after oxidation in owing air at 1100C. Results after 4 hr oxidation, shown as the solid circles in Fig. 6, refer to a diffusion cell some 56 m wide, corresponding to the separation between the interface with the outer TGO and that with the

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Fig. 5. The early stages of chemical failure of the CoNiCrAlY bond coat after oxidation in air for 4 hr at 1100C. In the affected area shown, the breakaway oxides are chromium- and nickelrich and are thought to derive from the partial conversion of a cell (shown as the dotted line) of approximately 15 20 m wide.

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Fig. 6. The measured (solid points) aluminum concentration, after 4 hr oxidation at 1100C, within a diffusion cell of 56 m width in the Co NiCrAlY bond coat. The solid line is the theoretical t using the values shown for kp and D but excluding the high points from the isolated particles. The broken line is the expected depletion prole, for the same values of the parameters, for a 150-m thick homogeneous bond coat.

nearest internal plane of alumina. Discounting the two high points, which were associated with isolated oxide particles, a feature of these results is their symmetry around the midplane of the cell. This shows that the rate of alumina growth at the interior surface is the same as that at the surface with the ceramic top coat. Not only does this conrm that oxygen ingress does indeed occur readily, but it also means that a sensible value of the parabolic rate constant, kp , can be obtained from measurements only of the TGO thickness. The uncertainties associated with the contribution to internaloxide thickness from aluminum supplied by the remainder of the bond coat need not then be addressed. Measurements of alumina thicknesses at the interface of the bond coat with the top coat in the specimens were then used to obtain values of the parabolic rate constant, kp . These were found to vary within the range 0.3B1016 m2 s1 to 1.6B1016 m2 s1 with an average value of 0.9B1016 m2 s1. This falls within the range of typical values20 for alumina-forming alloys.

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The line shown in Fig. 6 corresponds to the solution of Eq. (3) and represents a by-eye best t to the measurements of aluminum concentration ignoring the two high points. The values of D and kp given in the gure were those found from the curve-tting exercise to give the encouragingly good t shown. The values found for these parameters are also reasonable. Thus, the value of kp falls within the range found experimentally and the value of interdiffusion coefcient, 2.40B1014 m2 s1, is consistent with direct measurements on both NiCrAlY (Ref. 21) and CoCrAlY (Ref. 22) systems (no measurements seem to have been reported on CoNiCrAlY alloys). Similarly, although the initial aluminum concentration of 14.2 at.% used in this t is less than the 15.0 at.% measured in the CoNiCrAlY powder before spraying, the lower value can be explained plausibly by partial oxidation in the plasma stream. For the coatings studied, it was not possible to nd areas in which diffusion cells did not exist, but the expected aluminum concentration prole in their absence can be demonstrated through the use of Eq. (3). The calculation was performed using the same values of kp , D, and Cb as used for the data of Fig. 6, but with an effective value of w equal to the coating thickness of 150 m, i.e., it was assumed that there was no ux of aluminum across the coatingsubstrate interface and that the second of the conditions (2) was valid. The results are shown as the broken line in Fig. 6 and their comparison with the solid line provides a clear demonstration of the deleterious inuence of diffusion cells. The inuence of such diffusion cells on the variation in local aluminum concentration can be appreciated from Fig. 7. This gives further measurements (the solid points) of aluminum concentration for the same specimen, but across a region where a surface diffusion cell existed of only 25 m wide. Again, the depletion prole appears reasonably symmetric, but the overall level of aluminum is appreciably less than that in the 56-m wide cell (Fig. 6). Also shown in Fig. 7, as the solid line, is the prediction of Eq. (3) using the parameters shown. This agreement was obtained with the same values of Cb and D as used in Fig. 6, but with a somewhat smaller value of kp of approximately 0.8B1016 m2 s1 but, again, within the experimental range found in this work. Again, a comparison is made (broken line), using the same values of the parameters, of the anticipated depletion prole if the coating had been homogenous. With continued exposure, the depletion of aluminum increases as is shown in Fig. 8 for a 55-m diffusion cell in a specimen oxidized for 100 hr at 1100C. In this case, the measured aluminum concentrations have fallen close to zero and are probably as low as can sensibly be measured with the EDX technique (0.5 at.% Al). The solid line is the tted curve using Eq. (3) and the parameter values shown. These are the same as used previously

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Fig. 7. The aluminum concentration (solid points) within a 25-m diffusion cell in the CoNiCrAlY bond coat after 4 hr oxidation in air at 1100C. The solid line is the theoretical t using the parameters shown. The broken line is the expected depletion prole, for the same values of the parameters, for a 150-m thick homogeneous bond coat.

except for the slightly lower value of kp , but this falls well within the experimental range. Again, the broken line shown in this gure represents the calculated depletion prole for a 150-m thick bond coat without diffusion cells. This provides an even more striking demonstration than in Figs. 6 and 7 of the deleterious inuence of diffusion cells on aluminum depletion within such bond coats. Their presence means that the performance of these coatings falls short of their potential, as implied by their high aluminum content. THE INITIATION OF CHEMICAL FAILURE A consequence of the enhanced depletion of aluminum within diffusion cells is that chemical failure will occur sooner than in a homogeneous bond coat. This can be readily demonstrated, for MICF, by using Eq. (3) to calculate the time to reach, at the midplane within cells of various widths, 2w, the critical aluminum concentration to reform an alumina layer, Ch . No direct measurements of Ch seem to have been reported for this bond-coat

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Fig. 8. The aluminum concentration (solid points) within a 55-m diffusional cell in the CoNiCrAlY bond coat after 100 h oxidation in air at 1100C. The solid line is the theoretical t using the parameters shown whereas the broken line is the expected depletion prole for a 150-m thick homogeneous bond coat.

composition but, based on results on other alumina-forming systems,14,15 a value of 5 at.% was used as the critical condition. Calculations were performed for a temperature of 1100C with Cb G15 at.% and, to be consistent with the present results, values of kpG 0.9B1016 m2 s1 and D G2.40B1014 m2 s1. The dependence of the time to reach the MICF boundary with cell thickness is shown as the lower diagonal line in the chemical-failure diagram of Fig. 9. In addition, similar calculations were performed in order to estimate the time to reach the InCF boundary using the same values of oxidation rate constant and diffusion coefcient and, in this case, a critical aluminum concentration at the oxide metal interface of zero. These additional results are shown as the upper diagonal line in Fig. 9. In both cases, the time to reach the chemical-failure boundary increases as the square of the cell dimension. It is clear from this gure that the MICF boundary is met rst during the exposure at 1100C. This contrasts with the behavior at this temperature of the chromia-forming steel studied earlier13 for which chemical failure was

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Fig. 9. The oxidation time at 1100C needed to initiate chemical failure in the bond coat as a function of diffusion cell width.

initiated by InCF. This difference reects the current lower value of approximately 0.004 for the ratio kpD compared with 0.2 found for the chromiaforming alloy. A consequence of the higher value in the chromia-forming steel is that the supply of solute from the specimen interior to the growing oxide layer cannot readily be met and, as a consequence, the alloy interfacial concentration approaches zero and triggers the InCF condition. In contrast, in the present application the diffusion of aluminum is sufciently fast to ensure that its rate of supply to the growing oxide layer is easily met. Aluminum concentrations at the oxidemetal interface are then only a little less than those at the midplane of the diffusion cells. Similarly at depletion proles have been observed in alumina-forming ferritic steels.23 Below the MICF boundary of Fig. 9, no chemical failure will occur and, after the initial stage of transient oxidation, the protective oxide formed on the bond coat will be slow-growing alumina.12 Above this boundary line, MICF is possible but will occur only if the protective alumina layer cracks or delaminates sufciently to permit gas access to the aluminum-depleted bond coat. Under typical TBC applications involving thermomechanical cycling, it seems likely that such mechanical damage will occur and that the MICF boundary should be taken as the initiating condition for chemical failure. For less-onerous exposure conditions, the integrity of the protective

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alumina layer may be maintained and, as a consequence, MICF will not be initiated. In this case, chemical failure will occur by InCF, but as shown in Fig. 9, this will result in only a factor-2 improvement in exposure time for this particular bond coat. In either event, exposure within the region of the diagram above the InCF boundary line will ensure chemical failure by either or both routes. The importance of the dimensions of the diffusion cell to the oxidation endurance of the bond coat is clear from Fig. 9 and demonstrates how lifetimes can be drastically reduced in their presence. As example, for the smallest cell width of 2wG26 m examined in this work, the time to MICF is only some 9 hr at 1100C, whereas for a homogeneous bond coat 150-m thick (i.e., 2w G300 m), a lifetime approaching 1200 hr would be expected. The implication is that a substantial improvement in bond-coat endurance can be obtained from increasing the dimensions of the diffusion cells or, of course, from eliminating them. Chemical failure will result in the formation of nickel-, chromium- and, possibly, cobalt-rich oxides at the bond coatceramic interface. These oxides grow at an intrinsically higher rate than the original alumina layer and will form rst above narrow diffusion cells at the surface of the bond coat. Since there will be a range of cell widths within the coating, it follows that some will have triggered chemical failure before others and that there will be a spatial distribution of oxide growth rates at the bond coatceramic interface. In fact, the situation will be that shown schematically in Fig. 1 where any localized upward displacement of the outer ceramic layer will develop out-of-plane tensile stresses across the intervening interface where protective oxidation continues. Establishing this displacement rate is beyond the scope of this paper, but will not be a trivial task. One factor is that the growth rates of the nonprotective oxides may be limited by oxygen supply through the ceramic top coat, although this is likely to be more of an issue for plasma-sprayed top coats rather than for those produced by EBPVD. In the former case, there is evidence24 that the early transient stages of bond coat oxidation can be affected by limited oxygen supply. A second factor is that, since the cracking process can occur isothermally at high temperature, the potential for creep accommodation of the displacement by the bond coat needs also to be considered. In advance of this further work, however, the chemical failure diagram of Fig. 9 can provide an estimate of TBC endurance (at least, by the mechanism being considered here) by establishing the exposure time at which the coating system becomes at risk of delamination failure. CONCLUSIONS It is suggested that bond coats in TBC systems, particularly those deposited by plasma spraying, can contain regions which are diffusionally

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isolated from the bulk of the coating. This can arise through the formation of alumina layers at splat boundaries within the bond coat as a consequence of the ingress of molecular oxygen into the relatively porous structure. Such isolated regions, termed diffusion cells, will experience enhanced depletion of aluminum as a result of the continued thickening of the alumina layer at both their external and internal surfaces. This process has been demonstrated for a CoNiCrAlY bond coat after oxidation in air at 1100C. The measured depletion proles agree well with theory provided that the volume being analyzed has no access to the aluminum reservoir in the remainder of the coating, i.e., it is diffusionally isolated. A consequence of the rapid depletion of aluminum within the diffusion cell is that chemical failure of this volume of the coating will occur early. Routes by which this could occur have been described. A consequence is that the protective capacity of the alumina layer will be impaired, gas access to the underlying depleted bond coat will occur, and voluminous breakaway oxides, containing chromium, nickel and, possibly, cobalt will form at the interface of bond coat and top coat. It is anticipated that the associated upward displacement of the top coat above such faster-growing oxides will result in out-of-plane tensile stresses being developed across the interface between these regions where chemical failure has occurred. The implications for TBC endurance are discussed. ACKNOWLEDGEMENTS The authors are grateful to Alstom Power for the supply of specimens and to Mr. Mick Whitehurst for his encouragement and continued interest. The work was funded by the Engineering and Physical Sciences Research Council through Grant GRL91610. REFERENCES
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Evans and Taylor H. E. Evans, A. T. Donaldson, and T. C. Gilmour, Oxid. Met. 52, 379 (1999). C. S. Giggins and F. S. Pettit, J. Electrochem. Soc. 118, 1782 (1971). J. P. Wilber, M. J. Bennett, and J. R. Nicholls, Mater. High Temp. 17, 125 (2000). F. S. Pettit, private communication (1999). D. P. Whittle, Corros. Sci. 12, 869 (1972). H. C. Cowen and S. J. Webster, Corrosion of Steels in CO2 (British Nuclear Energy Society, London, 1974), p. 349. H. Hindum and D. P. Whittle, Oxid. Met. 18, 245 (1983). J. A. Nesbitt and R. W. Heckel, Metall. Trans. 18A, 2075 (1987). G. W. Roper and D. P. Whittle, Met. Sci. 15, 148 (1981). W. J. Quadakkers, J. Jedlinski, K. Schmidt, M. Krasovec, G. Borchardt, and H. Nickel, Appl. Surf. Sci. 47, 261 (1991). M. P. Taylor, P. Niranatlumpong, H. E. Evans, and C. B. Ponton, Mater. High Temp. 17, 219 (2000).