Materials Science and Engineering A368 (2004) 212221

Microstructural aspects of the sintering of thermal barrier coatings

Vanni Lughi, Vladimir K. Tolpygo, David R. Clarke
Materials Department, College of Engineering, University of California, Santa Barbara, CA 93160-5050, USA Received 6 August 2003; received in revised form 27 October 2003

Abstract Densication of EB-PVD yttria-stabilized zirconia (YSZ) coatings occurs in two stages. Initially, the feathery morphology of the individual columns of the as-deposited coatings smoothens with the concurrent development of surface undulations. Then, some of these undulations on adjacent columns grow in amplitude until impinging to span the gap between the columns and form rows of local necks along the columns. The necks motivate sintering together of adjacent columns. The formation of necks and the overall response of the coating to this sintering process, however, depend on the roughness of the alloy surface. If the surface on which the coating is deposited is at the columns are straight and parallel. Adjacent columns sinter together and the columnar microstructure is preserved with no cracking and the coating can withstand exposure to 1400 C for at least 350 h with no transformation to monoclinic zirconia occurring. If the substrate is not at, or develops roughness on thermal cycling, necks form and clusters of individual columns sinter together to form large-scale dense regions with larger gaps in between. The pattern of the gaps appears to reproduce the roughness of the underlying bond-coat alloy. The origin of this different behavior is attributed to the local undulations in the substrate surface causing individual columns to converge, narrowing the gap between them. 2003 Elsevier B.V. All rights reserved.
Keywords: Thermal barrier coatings; Sintering; Zirconia; Bond-coat; Phase transformation

1. Introduction One of the concerns related to the long-term reliability of yttria-stabilized zirconia (YSZ) thermal barrier coatings is how their key attributes (low through-thickness thermal conductivity, high strain compliance in the plane of the coating, crystallographic phase content and erosion resistance) change over time with high temperature exposure. Observations of coatings, reported in the literature [17], as well as service exposure [8] indicate that densication, cracking and partial transformation to monoclinic zirconia can all occur. However, it is not clear to what extent the observed changes, particularly those in service conditions, are intrinsic to the coating material or whether they are promoted by the presence of contaminants in the engines, for instance due to the ingestation of silicate-based dust. To study the intrinsic behavior of coatings at high-temperatures, one approach has been to separate the TBC coating from the metallic alloy and study its densication as a free-standing piece of ceramic [27]. Such studies indicate that the coating decreases its
Corresponding author. Tel.: +1-805-893-8275; fax: +1-805-893-8486. E-mail address: clarke@engineering.ucsb.edu (D.R. Clarke). 0921-5093/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.msea.2003.11.018

volume and begins to transform from its initial, metastable tetragonal prime form to a mixture of monoclinic, tetragonal and cubic at times and temperatures as low as 200 h at 1200 C [2] and 30 h at 1300 C [3]. From such observations of free-standing coatings, the kinetics of the densication and the transformation to monoclinic phase has been reported. The transformation studies have typically been performed by X-ray diffraction and, in the case of ref. [2], by neutron diffraction. These types of studies, however, do not take into account the possible effects of the underlying alloy and, in particular, differences in thermal expansion coefcient and the effect of surface roughness. For instance, it is known that the densication characteristics of ceramic powders sintering on a dense substrate can be quite different from those in the absence of the substrate. This is commonly referred to as constrained sintering [9] and is likely to also apply to TBC coatings on superalloy components. In use, a temperature gradient exists through the coating thickness and so the outer surface of the coating is exposed to a higher temperature than the inner surface in contact with the bond-coat and underlying superalloy. Whilst it would be desirable to study the densication of coatings under such realistic conditions, carrying out experiments under the large thermal gradients characteristic of turbine

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operation (of the order of 106 C/m) is extremely difcult requiring large scale, high heat ux conditions. Instead, in this work we describe the behavior of coatings under isothermal conditions. This enables an identication of the mechanisms associated with high-temperature exposure but precludes direct quantication of the densication rates under realistic temperature gradients. Another experimental limitation is that incipient melting between aluminide bond coats and the underlying nickel-based superalloy imposes a maximum temperature (1200 C) at which isothermal annealing studies can be performed on actual TBC coatings. To circumvent this limitation, a portion of this work describes the microstructural changes in TBC coatings deposited on sapphire and annealed at much higher temperatures. Moreover, by comparing the microstructural changes of coatings on a bond-coated alloy with those on sapphire, it is possible to investigate the effect of substrates having different thermal expansion coefcients and hence differences in constraint during heating and cooling. To illustrate the possible effect on the coating densication of the differences in thermal expansion coefcient between the coating and the alloy consider a microstructure consisting of parallel columns with gaps in between (Fig. 1(a)). It is assumed that the coating is deposited on the substrate at a temperature, TDeposition , and that it is then exposed for a prolonged period of time at a higher temperature, TE . The columns are assumed to be cylindrical and

at the deposition temperature have a uniform radius, RD , and their centers are spaced a distance, dD , apart. If the coating has a smaller thermal expansion coefcient than the substrate, as is the case for a YSZ zirconia TBC on a superalloy, then at the higher temperature, TE , the center-center distance, d, between columns, which is xed by the thermal expansion of the alloy, increases more than the diameter of the individual columns and so the gap between individual columns also increases (Fig. 1(c)). On the other hand, if the coating has a larger thermal expansion than the substrate, then at the exposure temperature, the difference in thermal expansion will have the effect of narrowing the gap between the columns (Fig. 1(b)) and promoting mechanisms by which columns sinter together. Sapphire has a smaller thermal expansion coefcient than YSZ so a comparison of the densication of YSZ coatings on a superalloy with those on a sapphire substrate provides a means of comparing the intrinsic densication mechanisms of a TBC constrained on a substrate. It is emphasized that the width of the gaps at high temperatures is expected to be different than that at room temperature because of the difference in thermal expansion coefcient between the zirconia coating and the underlying substrate, whether it be a superalloy or sapphire. This difference, typically 1% strain, may be too small to discern except in quantitative microscopy studies but may be signicant for sintering studies.

Fig. 1. Schematic illustration of the effect of thermal expansion mismatch between an EB-PVD coating and the underlying substrate on the gaps between columns. The width of the gaps at high temperatures is expected to be larger than that seen in micrographs recorded at room temperature because of the larger thermal expansion coefcient of the superalloy than that of zirconia. Details in the text.

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2. Experimental details The thermal barrier coatings studied in this work were deposited by electron-beam evaporation and provided by Howmet Corporation. The coatings were standard yttria-stabilized zirconia (7YSZ) coatings, 140 m thick, deposited simultaneously on sapphire substrates and platinum-modied nickel-aluminide coated N5 superalloy substrates placed adjacent to one another in the evaporator. Both types of substrates were generally grit-blasted prior to TBC deposition although a number of coating on as-deposited bond-coated superalloy were also studied. The TBC coated sapphire samples were annealed in air at temperatures of 1200 and 1400 C whereas the coatings on the bond-coated superalloy were typically annealed at 1120 C or 1150 C, also in air, usually under cyclic oxidation conditions. The microstructure of the coatings was characterized using both optical microscopy and scanning electron microscopy prior to, and at various times, after isothermal annealing. Complementary characterization of the crystallographic phases in the coatings was made by X-ray diffraction and Raman spectroscopy, the latter chosen because of its particularly sensitivity to the presence of monoclinic zirconia.

3. Observations The columnar microstructure of the as-deposited coatings was supercially similar on both the sapphire and superalloy substrates. The columns had the characteristic feathery structure, illustrated in the upper micrograph of Fig. 2, with well-dened facets at the tops of the columns as has previously been described by many authors. The individual columns also had a similar diameter on both substrates. Although it was not possible to quantify, the individual columns on the sapphire substrates were generally straighter and more parallel than those formed on the superalloy, presumably because the bond-coated superalloy was somewhat rougher after grit-blasting than the sapphire substrates. The microstructural evolution of the coatings at relatively short times, less than 50 h at 1200 C, was also similar with the feathery features on the sides of the columns transforming to a smooth surface, almost rippled in appearance as illustrated in the lower micrograph of Fig. 2 and in Fig. 3. Examination of columns fractured after these short times revealed that the smoothing was restricted to the column surface and that discrete, faceted pores lay just beneath the surface as shown in Fig. 3. With longer times at high temperature, the columns developed pronounced surface undulations over their surfaces, as shown in Figs. 2 and 3 and observations suggest that the amplitude of these undulations increases with time. Concurrently, along adjacent, closely-spaced columns, particularly on the superalloy, rows of necks (features F in Fig. 4)

Fig. 2. The surface morphology of the TBC columns in (a) their as-deposited condition and (b) after 50 h at 1200 C. The initial feathery microstructure evolves to a smoother surface.

between columns formed. Neck formation occurred in all the coatings irrespective of whether on sapphire or superalloy substrates but only between the most closely spaced columns. Where the columns are most densely packed, close to the substrate, closely spaced columns near the substrate are observed to sinter together after long times to form nearly dense regions of zirconia with vertical strings of pores along the prior boundaries between columns. The majority of coatings on the PtNiAl bond-coated superalloy failed upon thermal cycling before microstructural changes other than inter-columnar necking and sintering could be observed. However, in a number of cases, the coatings did last for a sufciently long time that changes could be observed. Thus, in Fig. 5 is a comparison of a coating after 100 1 h cycles and after 815 1 h cycles at 1150 C on a non-grit-blasted alloy substrate. In the latter, distinct mud-cracking of the coating is seen to have developed. Interestingly, at higher magnication, such as in Fig. 6 recorded from a sample at 1200 C, it can be seen that there is no discernable difference between the mud-cracks and other gaps between columns except that the opening of the

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Fig. 3. Faceted pores beneath the smooth surface of a column revealed by fracturing a coating after exposure for 50 h at 1200 C.

former is larger. In this and other examples, the spacing of the mud-cracks was about 80 m, the approximate size of the grains in the underlying bond-coat. Raman spectroscopy of the coatings on the superalloy indicated that, even after 815 h at 1150 C, they remained in their tetragonal-prime crystallographic phase. The behavior of the coatings deposited on sapphire was quite different. No mud-cracking patterns of gaps formed

on these coatings even after 350 h at 1400 C. The principal difference was that individual groups of two or three columns sintered together rather than clumps of a large number of columns as must have occurred to create the mud-cracking on the super-alloy. The contrasting sintering behavior on sapphire is illustrated by the micrographs in Fig. 7 of a coating after 150 h at 1400 C. The images in the gures were recorded from the identical area of the coating on the

Fig. 4. Necks between columns revealed in this fracture cross-section after exposure for 50 h at 1150 C. Both intact necks, such as at locations N, and fractured necks, F, are indicated.

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Fig. 5. Surface of a TBC on a PtNiAl bond-coated N5 superalloy after (a) 100 1 h cycles and (b) 815 1 h cycles to 1150 C. A mud-cracking pattern of gaps and cracks develops in the coating.

sapphire substrate so that the changes in column shape, position and the local sintering of individual columns can be directly compared. There are several notable changes. Firstly, although adjacent columns have sintered and, in some cases, merged together, there is no long range sintering together of columns. Secondly, there has been a smoothing of the columns giving the appearance of an opening up of a gap in between the clumps of columns. Thirdly, the high magnication images reveal that the crystallographic facet structure of the tops of the individual columns, so distinctive in the as-deposited coatings and after annealing at 1150 C, has been replaced by a surface smoothing at 1400 C. Despite these pronounced morphological changes, Raman spectroscopy reveals that even at this stage, after 150 h

at 1400 C, the coating remains principally metastable tetragonal-prime with some cubic phase but with no indications of the formation of any monoclinic phase. Subsequent heating for a further 200 h at 1400 C resulted in further smoothing of the columns and the coalescence of adjacent columns but again no mud-cracking. As assessed by Raman spectroscopy the coating still did not contain any monoclinic zirconia even after this additional annealing time. Fig. 8 illustrates the Raman spectra of the coatings in their as-deposited state, after 300 h at 1200 C and 350 h at 1400 C. In all cases, the spectra are characteristic of tetragonal-prime zirconia with the notable differences being in the width of the principal Raman bands. A subsequent contribution will describe the changes in the Raman spectra

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Fig. 6. The surface of the TBC on a PtNiAl bond-coated N5 superalloy after 50 h at 1200 C. At this magnication a portion of one of the mud cracks is seen together with smaller gaps between individual columns.

and X-ray diffraction patterns with high-temperature exposure [10].

4. Sintering mechanism The micrographs presented here and in previous studies [11,12] all indicate that the feathery morphology of the individual columns rather quickly smoothes out. This is presumably by surface diffusion since there was little coarsening of the porosity within the columns, even immediately below their surface, over the same period of time. (Vapor transport can also be ruled out since zirconia ceramics usually do not sinter through the vapor at these temperatures except in the presence of HCl containing moist atmospheres [13]). The time to smooth the feathery surface depends on the temperature but appears to be reasonably complete within 50 h at 1150 C. Subsequently, the observations show that undulations form over the surfaces of the columns and some grow in amplitude. As they grow it is likely that there is a certain probability that ones on adjacent columns become sufciently large to span the gap between the columns. Where they do, necks of material form between the columns as shown schematically in Fig. 9. Necks can also form between touching, misaligned columns. We attribute the growth of the surface undulations to diffusional-driven surface perturbations akin to those causing Rayleigh instability in initially planar surfaces and

smooth cylinders. As Herring rst described, diffusional mass transport will ow from regions of net positive curvature to regions of net negative curvature driven by the differences in chemical potential caused by the difference in net curvature [14]. As the spacing of the necks is observed to be less than the column diameter, this precludes the undulations from being formed by the standard Rayleigh instability of smooth cylindrical surfaces since the characteristic wavelengths of perturbations on a smooth cylinder are of the order of cylinder diameter.1 Rather, the distance between necks appears to be determined by the spacing of the feathers, the successively deposited layers of material as the columns are built up as the coating passes through the evaporative ux. The formation of necks suggests that, by analogy with the densication of powders, there is a force that tends to pull the columns together. The magnitude of the sintering force depends on the number of necks along the length of each column as well as on the zirconia surface tension, , and the radius of the necks, r. If the average coordination of the columns in the plane of the coating is n, then the lateral sintering stress, sintering , is sintering = nFN 2nNr = dh d

1 According to linear stability analysis [15] of the Rayleigh instability, the minimum wavelength of perturbations that grows with time is given by min = 2R and the fastest growing wavelength corresponds to max = 2 2R 9R.

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Fig. 7. Side by side comparison of the identical area of a coating on a sapphire substrate, at successively higher magnication, in its as-deposited condition (left column) and after 150 h at 1400 C (right column).

where h is the coating thickness, N the number of necks per unit length along an individual column, F the capillary force due to a single neck, and d is the inter-column distance. Of all the parameters, the number of necks per unit length has the greatest variability. If the number of necks does not change appreciably with time at temperature, then the sintering force will monotonically increase with the square root of time as the growth of a neck will be controlled by diffusional ow to the neck.

5. Discussion Our observations indicate that several, sometimes competing, mechanisms occur during the exposure of EB-PVD coatings to high temperatures in air. The microscopic mechanisms are independent of the surface on which the coatings are deposited with the overriding mechanisms being the surface diffusional smoothing of the individual columns and the growth of surface undulations, both presumably driven by the overall reduction in the surface energy of the zirconia

Fig. 8. Raman spectra of the as-deposited coating, after 300 h at 1200 C and after 350 h at 1400 C. The spectral lines are characteristic of tetragonal zirconia but become sharper with annealing indicating a decrease in site disorder, probably due to yttrium and oxygen vacancy ordering.

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Fig. 9. Schematic of the microstructural evolution of columns due to the growth of surface undulations leading to the formation of necks between adjoining columns.

coating. Where the undulations on adjacent columns grow and touch, necks of material form between the columns. As in the sintering of powder compacts, the effect of the surface tension along the periphery of the necks is to provide a sintering force that acts to draw the columns together. It can be envisaged that the growth of the necks also provides structural rigidity between columns and presumably is the underlying reason why the in-plane elastic modulus of EB-PVD coatings increase over time at temperature, with consequent reductions in their in-plane compliance [16]. At the macroscopic scale, at lengths much greater than the column diameter, the local sintering together of columns resulting from the formation of necks would be expected to cause the coating to shrink. Since such lateral shrinkage of the coating is constrained by the underlying bond-coat and superalloy, one might expect behavior between two extremes. One is that the shrinkage is accommodated entirely by a reduction in thickness of the TBC. The other is inhomogeneous lateral shrinkage of the coating with local densication of column clusters and opening up of gaps between the clusters so that the overall lateral extent of the TBC remains unchanged. The overall lateral shrinkage strain and the random distribution of initially larger gaps between columns would then lead to a mud-cracking formation of gaps with the shrinkage strain playing an analogous role to the drying shrinkage in mud-cracking. As mentioned in the Introduction, the original purpose for comparing the sintering behavior of TBCs on sapphire with those on a bond-coated alloy was not just to facilitate studies at much higher temperatures but also to compare the effect of the lateral constraint afforded by the two different substrates. Before making observations of the sintering of the TBCs on sapphire, we had anticipated that the smaller ther-

mal expansion coefcient of the sapphire would cause a net compressive strain in the EB-PVD coatings, decreasing the gap between columns and thereby promoting neck growth and consequently, greater mud-cracking than on superalloy substrates. Instead, as illustrated by the micrographs in the gures, the coatings on sapphire, even at the considerably higher temperatures (1400 C) to which we were able to expose them, showed no such cracking. Indeed, the observation that mud-cracking can occur in EB-PVD coatings on the superalloy substrates but not on sapphire appears to discount the effect of thermal expansion mismatch in being the dominant factor in determining the densication behavior of these coatings. This unexpected behavior has led us to a different conclusion, namely that the long-range densication of the coating, and the occurrence of mud-cracking, is related to the morphological stability of the material on which the coating is deposited. When the surface on that material remains at, as sapphire does, then individual, adjacent, closely-spaced columns sinter together forming local gaps between clusters of columns but no large-length scale densication occurs and consequently no mud-cracking. Typically, when the substrate remains at, the individual clusters consist of only a few columns each. These sinter together and pull away from their neighbors. In contrast, TBCs on PtNiAl bond-coated superalloys rumple on thermal cycling [17] because the PtNiAl bond-coat alloy does not, generally, stay at on thermal cycling [1820]. If it is assumed that the columns remain rigidly attached to the bond-coat underneath, then the effect of such bond-coat rumpling is to cant local columns that brings them together in some places and separates them in other places, as shown schematically in Fig. 10. Where the columns are tilted together, the column spacing is decreased and neck growth

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Fig. 10. Diagram illustrating the effect of bond-coat rumpling on the local tilting, (b) of individual columns that were originally parallel to one another when deposited on a at bond-coat, (a).

is promoted, whereas where they are tilted apart the probability of forming necks is decreased. Thus, as rumpling of the bond-coat occurs as a result of thermal cycling, the distance between columns changes, promoting neck formation and local densication where columns are canted together. To test this conjecture, a thin TBC, much thinner than that generally used in aero-engine turbines, was deposited on a PtNiAl bond-coated N5 superalloy and then thermal cycled. The rationale being that the thinner TBC would be more compliant than a standard thickness (140 m) coating and so would more likely follow the behavior of the underlying bond-coat as it deforms on thermal cycling. Observations, such as the micrographs in Fig. 11, revealed severe rumpling of both the TBC and the bond-coat after thermal cycling. As can be seen, the periodicity of the rumpling and the cracking of the TBC corresponds to the lateral grain size of the bond-coat. The micrographs also show that columns along the cracks are tilted away from each other whereas the coating has sintered together in-between. This is clearly an exaggerated response because the TBC was so thin but illustrates both the local tilting of columns and the spatial correlation of cracking of the TBC with the underlying grain boundary morphology of the bond-coat. The observations are pertinent to practical coatings for two reasons. The rst is that ridges do exist along the grain boundaries of bond-coats as a re-

Fig. 11. Top view of a 10 m thick EB-PVD coating, deposited on a at PtNiAl bond-coat, after thermal cycling for 100 1 h cycles to 1150 C. The crack pattern is correlated to the grain boundaries in the underlying bond-coat that has rumpled on thermal cycling. At higher magnication (the lower image) the tilting of the columns along the cracks can be discerned together with separation of clusters of columns, having an appearance of tensile tearing, in between.

sult of the aluminizing process. Although these are largely removed, in best practice by grit-blasting prior to TBC deposition, any remnant surface morphology in the bond-coat is reproduced in the orientation of the columnar structure of the TBC. Secondly, even with an initially at bond-coat there is a propensity for the bond-coat rumpling to occur on a length scale commensurate with the lateral size of the grains in the bond-coat [1720]. It is also worth emphasizing that it is only when the bond-coat/TGO interface remains at that TBCs on bond-coated superalloys exhibit a long cycle life. As the orientation of the as-deposited columns is dictated by the curvature of the surface on which the coatings is deposited, then the effect of the bond-coat morphology changes on the TBC sintering behavior suggests very different response on the concave and convex areas of a blade or vane. Thus, one might expect that sintering will be more pronounced on the high-pressure side of blades than on

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the leading edges and low-pressure sides because the surface curvature will tend to cant columns together on the high-pressure side. In practice, the high-pressure side of a blade also tends to be hotter. Thus, it can be expected that the sintering behavior will vary over the surfaces of blades and vanes. Another unexpected observation, at least based on previous reports, is that even after 350 h at 1400 C, the EB-PVD coatings have not partially, or completely, transformed to monoclinic zirconia. It is always possible that the previously reported transformation of the as-deposited structure of metastable tetragonal prime phase to a mixture of cubic and monoclinic phases is related to the presence of minor impurities. However, further studies are underway to determine the longer time stability of 7YSZ coatings at these high temperatures since they will provide information concerning the kinetics of partitioning of yttrium in the tetragonal phase and hence the transformation to monoclinic zirconia [21]. Also, although the reason for the narrowing of the peaks in the Raman spectrum with time at temperature is not known, it probably indicates a decrease in the disorder of the yttrium ions and oxygen vacancies with time and may well presage the formation of monoclinic zirconia. Finally, one of the striking features revealed by the micrographs is that the tops of the columns in the coatings exposed to 1400 C (but not at 1200 C) are rounded and have lost the highly crystallographic facet structure characteristic of as-deposited EB-PVD coatings and illustrated in Fig. 7. This suggests that 1400 C is above the surface roughening temperature of YSZ in air, the temperature at which the entropic contribution to the free energy of steps exceeds the crystallographic stepstep interaction [22,23]. In marked contrast, the pores within individual columns, exposed by fracture, are generally smooth and spherical after about 100 h at 1120 C indicating that the roughening temperature of internal surfaces of 7YSZ may be signicantly lower. This warrants further study since it suggests that the surface of the internal pores is different, possibly due to segregation, than that of the free surface.

the appearance of mud-cracking. In contrast, when the same coating is deposited on a surface that remains at, no mud-cracking is observed even up to 350 h at 1400 C. While local clusters of adjacent columns sinter together there is no long-range sintering at this temperature. The coatings do not transform to monoclinic zirconia under any of the conditions investigated, even after 350 h at 1400 C in air.

Acknowledgements The authors are grateful to Dr. Ken Murphy of Howmet Research Center for kindly providing the TBC coated samples studied in this work. The work was supported by the Department of Energys Advanced Gas Turbine Systems Research program through a sub-contract through Clemson University under grant DE-FC21-92MC29061.

References
[1] R.A. Miller, Surf. Coat. Technol. 30 (1987) 111. [2] J. Llavsky, J.K. Stalick, J. Wallace, J. Therm. Spray Technol. 10 (2001) 497501. [3] U. Schulz, J. Am. Ceram. Soc. 83 (2000) 904910. [4] J. Moon, H. Choi, H. Kim, C. Lee, Surf. Coat. Technol. 155 (2002) 110. [5] D. Zhu, R.A. Miller, Surf. Coat. Technol. 108109 (1998) 114120. [6] U. Schulz, K. Fritscher, M. Peters, J. Eng. Gas Turbine Power 119 (1997) 917921. [7] L. Lelait, S. Alperine, C. Diot, R. Mevrel, Mater. Sci. Eng. A 121 (1989) 475482. [8] Private communications from Siemens-Westinghouse, General Electric and Pratt and Whitney. [9] R.K. Bordia, A. Jagota, J. Am. Ceram. Soc. 76 (1993) 2475. [10] V. Lughi, Ph.D. thesis work to be published. [11] S.G. Terry, J. Litty, C. Levi, in: J. Hampkian, N.B. Dahotre (Eds.), Elevated Temperature Coatings: Science and Technology III, The Minerals, Metals and Materials Society, Warrendale, 1999, pp. 1325. [12] A. Azzopardi, R. Mevrel, B. Saint-Ramond, E. Olson, K. Stiller, Surf. Coating Technol., 2003, in press. [13] M.J. Readey, D.W. Readey, J. Am. Ceram. Soc. 69 (1986) 580582. [14] C. Herring, in: W.E. Kingston (Ed.), Physics of Powder Metallurgy, McGraw Hill, New York, 1951. [15] F.A. Nichols, W.W. Mullins, J. Appl. Phys. 36 (1965) 1826. [16] C.A. Johnson, Private communication. [17] V.K. Tolpygo, D.R. Clarke, Surf. Coat. Technol. 163164 (2003) 8186. [18] V.K. Tolpygo, D.R. Clarke, Acta Mater. 48 (2000) 32833293. [19] D.R. Mumm, A.G. Evans, I.T. Spitsberg, Acta Mater. 49 (2001) 23292340. [20] J.A. Ruud, A. Bartz, M.P. Borom, C.A. Johnson, J. Am. Ceram. Soc. 84 (2001) 15451552. [21] N.R. Rebollo, O. Fabrichnaya, C.G. Levi, Z. Metallkd. 94 (2003) 3. [22] W.K. Burton, N. Cabrera, F.C. Frank, Philos. Trans. R. Soc. London A243 (1951) 299358. [23] C. Rottman, M. Wortis, Phys. Rep. 103 (1984) 5979.

6. Conclusions Although individual columns sinter together during prolonged high-temperature exposure, observations indicate that the long-term stability of 7YSZ EB-PVD coatings is determined by morphological instability of the underlying bond-coat rather than the thermodynamic stability of the metastable tetragonal-prime phase per-se. Thermal cycling induced rumpling of the bond-coat causes individual columns to tilt into one another and promote local sintering. This leads to the formation of large gaps that have