Thin Solid Films, 119 (1984),301-315 METALLURGICAL AND PROTECTIVE COATINGS

301

THERMAL BARRIER COATINGS FOR JET ENGINE IMPROVEMENT*

G. JOHNER AND K. K. SCI-I1A/EITZER MTU Motoren- und Turbinen-Union Miinchen G.m.b.H., Munich (F.R.G.) (Received March 30, 1984; accepted May 7, 1984)

The aim of these investigations is to develop thermal barrier coatings (TBCs) with improved resistance against thermal cycling to prevent problems of overheating in the hot section of jet engines. Plasma-sprayed TBCs consisting of an Ni-Cr-A1 bond coat and zirconia overlayers stabilized with different materials (CaO, MgO or Y203) were tested in a burner rig under thermocyclic conditions, in a hot gas centrifugal rig and in a modern jet engine. These tests demonstrate good correlation between the failure mode of the coatings in the thermocyclic tests and in engine tests. The best performance in all tests was shown by zirconia partially stabilized with yttria according to microanalytical investigations of the unstressed and stressed TBCs. Furthermore, heat treatments as well as ongoing optimization of the spraying parameters of the TBCs demonstrate potential improvement.

1. INTRODUCTION In the future there will be an ever-increasing demand for improved fuel efficiency of aircraft gas turbine engines, both in the military and civil sectors. An unavoidable concomitant of this demand will be higher gas temperatures. Directionally solidified eutectics, single-crystal materials and oxide-dispersionstrengthened superalloys are costly ways of achieving high gas temperature resistance. A comparatively favourable method lies in the use of ceramic thermal barrier coatings (TBCs) consisting, inter alia, of a metallic bond coat and a top coat constituted mainly of ZrO2. Both coatings are preferably applied by plasma spraying. The purpose of the present investigation is to obtain a TBC on internally cooled turbine blades with best possible insulating properties and high reliability against spalling during operation. 2. THEORETICAL ASPECTS ZrOz is used as the base material of TBCs mainly because of its physical * Paper presentedat the InternationalConferenceon MetallurgicalCoatings,San Diego,CA, U.S.A., April 9-13, 1984. 0040-6090/84/$3.00 ElsevierSequoia/Printedin The Netherlands

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G. J O H N E R , K. K. S C H W E I T Z E R

properties, such as its thermal conductivity (2 ~ 1.7 W m 1 K 1 for the bulk material), thermal expansion coefficient (ct ~ 9 10 -6 mm 1 K 1) and melting point ( ~ = 2710 C)1. The crystal structure of Z r O 2 alters with temperature, changing from monoclinic to tetragonal to cubic as the temperature increases, and vice versa as the temperature decreases again. The rapid diffusionless martensitic change from monoclinic to tetragonal structure in the temperature range 950-1400 C, accompanied by a volume contraction of J/o-J,-/o~"/1-~o/2.3, in particular, leads to material fatigue and consequently means that ZrO2 alone is unsuitable as a TBC. However, by alloying ZrO2 with other oxides such as Y203, MgO or CaO, it is possible to obtain materials with a partly or even entirely stable cubic lattice structure of the fluoride type all the way from room temperature to over 2000 c'C. The stabilization, complete or partial, in which the tetragonal and monoclinic phases also occur in addition to the cubic phase, depends on the amount of added oxide. Complete stability certainly solves the problem of martensitic phase transformation and volume change, but this is offset by poor thermal shock behaviour 4. The thermal shock behaviour, which is one of the most important properties, can be decisively improved by partial stabilization 5. This phenomenon can be explained, for example, with the aid of the model of stress-induced phase transformation, also called phase transformation toughening 2,6 s, as follows. If a crack front meets a tetragonal particle, the particle will undergo transformation into the monoclinic phase. The resulting increase in volume of the particle stops crack growth as a result of compressive stresses, or leads to the formation of microcracks (length, 1 ~m or less) 9 in the vicinity accompanied by energy dissipation of the primary crack. This transformation process can be caused just as easily by thermal stress. The influence of CaO, MgO and Y203 as stabilizers on the thermal shock resistance of ZrO 2 thermal barrier coatings can be illustrated by the earlier experiments by Stecura 1 and Stepka et al. 11, who obtained the following results with MAR-M-200 as substrate and Ni-16Cr-6AI-0.6Y as bond coat, where each hot gas cycle was for 1 h at Mach 0.3 with the temperature varied from 280 to 975 to 280 C: ZrO2'5.4CaO, spalling after 87 cycles; ZrOz.3.4MgO, spalling after 450 cycles; ZrO2" 12Y203, 650 cycles without problems. In these experiments, the Y203stabilized TBC proved to have the best resistance to erosion as well. Complete stabilization of ZrO2 is assumed from about 2 wt.~o Y20312, 13 3.
E X P E R I M E N T A L DETAILS

3.1. Test materia&

Four different types of TBC were applied by plasma spraying, namely ZrO2" 5CaO, ZrOz'24MgO, ZrO2"20Y203 and ZrO/'7Y203. The bond coat was sprayed using an (Ni-16Cr~-6AI composite powder. The surface of the substrate was blasted with aluminium oxide prior to coating. The thicknesses of the bond and top coats were 0.1 mm and 0.4 mm respectively. These coatings were selected because firstly the references show a lack of agreement about their properties and secondly they ought to be readily available since they are made from standard powders.

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3.2. Test methods To ensure that testing of the TBC took place under realistic engine conditions as far as possible, the leading edges of turbine blades were simulated by using hollowed-out round specimens of IN 100 (Figs. 1 and 2). The coated IN 100 specimens were subjected to thermocyclic and thermomechanical stresses in a stream of hot gas using JP4 fuel for combustion (Figs. 1 and 3). Thermal fatigue stresses were applied by the cyclic impingement (every 30 s) of a stream of hot gas with a velocity of Mach 1 and a temperature of 1670 K (heat transfer coefficient at stagnation point % = 8200 W m - 2 K - t), whilst cooling air flowed through the bore of the specimen. Cooling (every 30 s) was effected by free convection in atmospheric
sectionA-A

] comlxtsfion ]
[ cho,,~ I ~'~'~IN ~o

il
2 turn fixture lOmm

Fig. 1. Schematic set-up for the thermal fatigue test.

Fig. 2. Hollow specimen for the hot spin test.

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G. JOHNER, K. K. SCHWEITZER

air (~o ~ 10 W m 2 K 1). Testing was continued until the TBCs started to spall. The thermomechanical stresses were applied by spinning round specimens mounted on a disc driven by a compressed air turbine and housed in a casing supplied with hot JP4 gas from a combustor (Fig. 3). The specimens, cooled internally with compressed air, were each spun in hot gas at a temperature of 1470 K for 5 and 30 min at speeds of 22 500 and 30 000 rev min 1. The specimens were weighed before and after testing.

om

Fig. 3. Spin test disc of M A R - M - 2 4 6 with attached specimen.

For testing the behaviour of the TBC in a jet engine, internally cooled turbine blades of IN 100 were coated in the same manner as the round specimens. To verify the transferability of the test results, ZrOz.5CaO and ZrO2.7YEO 3 TBCs with widely differing thermal fatigue resistance were tested in accordance with the literature 1'11 in a modern military aeroengine.

3.3. Methods of investigation

The round specimens and turbine blades were subjected to metallographic examination to determine the effects of stress on the morphology of the TBCs. The examinations were carried out with the aid of scanning electron microscopy (SEM) in conjunction with energy-dispersive analysis of X-rays (EDAX) and a microprobe analyser. The phase stability was determined with one type of TBC, in the asdeposited condition and after the thermal fatigue test, by means of X-ray fine structure analysis (using a Siemens Kristalloflex 4 instrument). Because, as a result of the rapid solidification, as-deposited TBCs are characterized by a metastable phase structure and uneven distribution of the natural stresses throughout the coating, heat treatment and microhardness tests were carried out. The purpose of the heat treatment was to relieve stresses and to obtain uniform stresses in the coating. Furthermore, heating and quenching were used to improve the segmentation of the TBC. These investigations are continuing in close co-operation with the Technical University of Munich 14. Tests are also being carried out into obtaining uniform properties throughout the TBC by appropriate temperature control. For these tests, the Ni-Cr-A1 bond coat and the Z r O / t o p coat have been plasma sprayed with no interruption in time onto several blades.

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4.

RESULTS AND DISCUSSION

4.1. Test results

The thermal fatigue and spin tests in hot JP4 gas demonstrate the superior characteristics of the ZrO2.7Y20 3 TBC, as shown in Table I. The ZrO2.5CaO and ZrO2"20Y203 TBCs are characterized by poor resistance to thermal fatigue. In comparison, the ZrO2.24MgO coating is considerably more resistant to fatigue and also to spinning, but still does not attain the fatigue resistance of the ZrO2"7Y203 coating.
TABLE I CHARACTERISTICSOF VARIOUSTHERMAL BARRIER COATINGS

TBC

Number of cycles to start of spalling

,~ 80 ~ 2000 ~ 60

Material removal after spinning (g)

ZrO 2.5CAO ZrO 2.24MGO ZrO2.20Y20 3

0.46-0.54, nearly completely spalled 0.14-0.19 Not established because of poor thermal

ZrO2-7Y203

,~ 4700

resistance 0.0-0.02

The spin test specimens without any outward signs of damage to the coating (see Table I) were spun again (see Section 3), this time with the addition of 5 g of IN 100 powder with a grain size of less than 45 ~tm, to obtain information about the resistance of ZrO2"7Y203 coatings to particle erosion. Of three specimens tested, a material loss of 0.18 g was found on one specimen only. The fact that two specimens exhibited no loss of mass, despite spinning prior to the erosion test, indicates conformity with Stecura 1 and Stepka et al. 1~ concerning the high resistance of ZrO2"7Y203 coatings to particle erosion. Turbine blades with TBCs (see Section 3.2) show signs of damage to the coating after operation in the engine (duration, 60 h) similar to that of the round specimens after the thermal fatigue test. Whereas only one of ten blades coated with ZrO2.7Y203 exhibited appreciable loss of material in the area of the leading edge to the convex side, all 11 blades coated with ZrO2"5CaO suffered extensive damage (Fig. 4).
4.2. Microscope examination

The damage to the blade coated with ZrO2.5CaO in the leading edge area is in the nature of localized spalling (Fig. 5). Separation has apparently occurred within the TBC and not between the TBC and the bond coat. In addition, there is hardly any blackening of these areas by the residues of combustion, in contrast with the adjacent coating surface, indicating that this spalling presumably occurred towards the end of the engine run. The ZrO2.5CaO coating in the neighbouring convex area has been gas eroded down to the bond coat, and this phenomenon is borne out by the poor resistance to erosion of this type of TBC observed in the spin test. In contrast, the ZrO2.7Y203 coating shows only distinct, partially expanded, segmentation cracking in the

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2 cm

(a) (b) Fig. 4. Turbine blades coated with (a) ZrO2-7Y203 and (b) ZrO2-5CaOafter 60 h in an engine.

Fig. 5. A ZrO 2-5CAOcoating after a 60 h engine run; leading edge peeling has occurred. Fig. 6. A ZrO 2.7Y203 coating after a 60 h engine run; the leading edge shows segmentation. leading edge area (Fig. 6). Peeling or pitting of the coating was n o t found in the convex area o n nine of the ten blades tested. T o clarify the reason for the spalling of the Z r O 2 - 7 Y 2 0 3 coating of one blade, microsections were prepared (Fig. 7). It was revealed that the poor quality of the b o n d coat, n a m e l y insufficient thickness a n d incompleteness, in the leading edge area was to blame.

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Fig. 7. A ZrO 2.7Y203 coating after a 60 h engine run; leading edge peeling has occurred. The bond coat is too thin and is incomplete.

Fig. 8. ZrOz-5CaO coating after one thermal cycle. Cracking between the TBC and the bond coat has occurred, and there is high porosity.

The low thermal fatigue resistance of the ZrO2.5CaO coating can be explained by the fact that clear separation of the TBC parallel to the surface near the bond coat occurs after just one thermal cycle (see Section 3.2 and Fig. 8). Furthermore, microfractography (Fig. 9) shows the expected separation within the TBC parallel to the surface owing to the small contact surfaces between the individual ceramic splats. Because of excessive stressing at pore edges and the notch effect of small cracks, thermal stresses quickly lead to serious separation parallel to the surface, with the result that complete areas of the coating are removed by gas forces. These findings are supported by ongoing investigations into extremely dense poreless ZrO2-5CaO coatings which show first signs of spalling after more than 2000 thermal cycles for the same deposit thickness and test conditions. TBCs of ZrO2'24MgO have essentially better resistance to thermal fatigue than the ZrO2"5CaO coatings. The unstressed coating is characterized by a comparatively good union between the bond coat and the top coat and by moderate porosity (Fig. I 0). Under greater magnification, the multiphase character of the TBC

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G. JOHNER, K. K. SCHWEITZER

Fig. 9. A ZrO 2.5CAO coating after 70 thermal cycles. The contact surface between the ceramic clusters is small, and the expected separation parallel to the surface has occurred.

is highlighted by the various shades of grey (Fig. l 1). The dark phase, extending in the direction of striation and running roughly parallel to the surface, is enriched near the bond coat. Judging by the phase system ZrOz-MgO 15, this phase is probably free MgO. This assumption is confirmed by the microprobe element maps in the transition between the TBC and the bond coat in the immediate vicinity of the spalled spots (Fig. 12). The stressed ZrOz.24MgO coating is characterized by distinct cracks in the vicinity of the bond coat or in the area of MgO enrichment (Fig. 13), indicating that there is a recognizable cause. Optimal thermal fatigue resistance of ZrOz'24MgO TBCs calls for as uniform as possible distribution of the free MgO. Of the TBC investigated, ZrO2-7Y20 3 shows the highest thermal fatigue resistance. The unstressed coating exhibits numerous segmentation cracks and comparatively few pores (Fig. 14). The multiphase structure of the coating is

Fig. 10. A ZrO2.24MgO coat in the unstressed condition; there is good union between the bond and the top coats. Fig. 11. A ZrO 2"24MGO coating in the unstressed condition, showing dark striations with enrichment near the bond coat.

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(a) (b) Fig. 12. ZrOz.24MgOelementmapsfor(a)magnesiumand (b)zirconium;see Fig. ll.

Fig. 13. A ZrO2"24MgO coating after 2000 thermal cycles, showing clear signs of damage to the TBC in unpeeled areas.

Fig. 14. A ZrO2.7Y203 coating in the unstressed condition, showing numerous segmentation cracks.

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G, JOHNER, K. K. SCHWEITZER

revealed under greater magnification (Fig. 15). Dark, and in some cases striated, precipitations are shown to be rich in yttrium by the microprobe element maps. Judging by the phase system ZrO2-YzO316, this is probably yttrium-rich ZraY4012, present in addition to the monoclinic phase at room temperature. In addition to the above elements, scattered silicon enrichments, sometimes in the immediate vicinity of the yttrium enrichments, were found. According to the manufacturer of the spray powder, this is due to almost unavoidable impurities (SiO2 content of the powder, 0.24 wt.'%). After thermal fatigue stressing the coating is characterized by an increase in segmentation, which is also visible macroscopically (Fig. 16). Horizontal separations occur only near the surface and not between the bond coat and the TBC, with the result that the coating appears still to be functionable. Numerous areas of the coating indicate very compact good segmentation and an intact TBC (Fig. 17). The noticeable resistance of this coating is confirmed by X-ray fine-structure analysis, which has not yet been completed and which permits only qualitative statements to be made at present ~4. X-ray diffraction analysis of the ZrOz-7Y203 spray powder reveals that, in addition to the predominant tetragonal phase, in this

(a)

(b)

9?

20 ~tm

Cc)
Fig. 15. (a) M i c r o g r a p h and (b), (c) electron s c a n n i n g microprobe analyser pictures of Z r O 2" 7Y 203 for (b) zirconium and (c) yttrium.

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f~ Fig. 16. A ZrOz.7YzO3coatingafter 4000thermalcycles,showingonlyslightdamage.

Fig. 17. A ZrO2.7Y20a coating after 4000 thermal cycles, showingalmost complete freedom from defects. condition the monoclinic phase is also present. In the as-deposited condition on flat IN 718 specimens, only the tetragonal phase is present, without the occurrence of the X-ray peaks of the monoclinic phase. After 10 000 thermal fatigue cycles (see Section 3.3) the monoclinic phase is again present in addition to the predominant tetragonal phase. These findings agree well with those of Boch and Rogeaux ~7. The manufacturing process (crushing of solidified melt after 700 h of cooling) leads to the expectation that the spray powder is in phase equilibrium and a cubic phase is thus also present, but cannot be recognized because of linear overlapping with the tetragonal phase. The fact that the monoclinic phase becomes recognizable in this type of coating only after a large number of thermal cycles indicates that the mechanism of

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G. JOHNER, K. K. SCHWEITZER

transformation toughening z applies. The superior resistance to thermal fatigue of the ZrO2.7Y20 3 is thus understandable, especially in view of the anomalous behaviour of the ZrOz'Y203 alloy with regard to sintering, as observed by Ammann is. Whilst the volume of Y203-stabilized ZrO 2 increases under thermocyclic stress, other oxide stabilizers cause a reduction in volume. Consequently, it is easily imaginable that shrinkage cracks, caused by the manufacturing process, do not reach the critical length owing to the generation of light compressive stresses. Another advantageous characteristic of the ZrO2-7Y20 3 coating is its very constant thermal conductivity (2 = 0.95 W m 1 K - 1 in the as-deposited condition; 2 = 1.05 W m 1 K-~ after 100 h of annealing at 1273 K), whereas the other two types o f T B C (ZrO2.5CaO and ZrO2"24MgO) are characterized by a clear increase in this important property (e.g. for ZrO2.5CaO as deposited 2 = 0.6 W m - ~ K and after 100 h annealing at 1273 K 2 = 1.6 W m ~ K - 1).
4.3. Heat treatment Heat treatment including quenching tests are carried out on TBCs with the objective of influencing the segmentation and natural stress condition 14. Initial experiments with ZrO/.5CaO coatings on flat IN 718 specimens exhibited unsatisfactory behaviour with regard to artificially induced segmentation cracking by heating briefly to 970 C, followed by cooling of the coating surface in water (Fig. 18). The crack first runs perpendicular to the surface, then at about half of the coating thickness it changes direction by 45 to continue parallel to the surface near the bond coat. It is assumed that during plasma spraying the first layers are subjected to sharper cooling conditions than are the surface layers. Consequently, it is impossible

Fig. 18. A ZrO2-5CaO coating with a segmentation crack TM.

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for the natural stresses to be distributed evenly throughout the coating; this is borne out by microhardness measurements (Vickers' hardness under a load of 0.2 N; Fig. 19). The non-uniform residual stress distribution may be the cause of the change in direction of the crack propagation. This hypothesis is borne out to a certain extent by the results of heat treatment at 900 C for 20 min followed by quenching in water (Fig. 20), since the segmentation cracks propagate perpendicular to the surface almost without exception and a reduction of the microhardness throughout the coating occurs (Fig. 19).

.90o

:~I
I I

I I L~F ''
'

I
I

~ 9oo~
~ 600~oo-

,ooo!

280o1

~_8oo-

~l ~ooTl
E

~oo1
3001

I I
TBC

H-+

'1o
(a)

':]
%)

I i.;/i 1 I
iN, cr/Ai

[s~,b~t~2i~

Fig. 19. Microhardness of a ZrOz.5CaO coating (a) before and (b) after heat treatment (20 min at 900 C; water quench).

(:i,~:,T~~

~iiii~

............

....... ~ . . . . ~ ...........~

iiiil iil ii! ~ ~ii~~ .~ill ~ ~iliii

Fig. 20. A ZrO2.5CaO coating after heat treatment (20 min at 900 C; water quencM4).

314
5. CONCLUSIONS

G. JOHNER, K. K. SCHWEITZER

To improve the high temperature resistance of internally cooled 1N 100 substrates, four different types of TBC were applied by plasma spraying, namely ZrO2"5aO, ZrO2.24MgO, ZrO2'20Y203 and ZrOE.7Y203. In all cases the bond coat was sprayed using an (Ni-16Cr)-6AI composite powder. To ensure that testing of the TBC took place under realistic engine conditions as far as possible, the leading edges of turbine blades were simulated by using hollowed-out round specimens of IN 100. The coated IN 100 specimens were subjected to thermocyclic and thermomechanical stresses in a stream of hot gas using JP4 fuel for combustion (see Figs. 1-3). To verify the transferability of the test results, ZrO2"5CaO and ZrO2.7Y203 TBCs with widely differing thermal fatigue resistance were tested in a modern military jet engine. To determine the effects of stress on the morphology of the TBCs the specimens and turbine blades were subjected to metallographic examination. The phase stability was determined with one type of TBC in the as-deposited condition and after the thermal fatigue test, by means of X-ray diffraction analyses. Furthermore some heat treatment and microhardness tests were carried out to reduce the residual stresses and to improve the segmentation of the unstressed TBCs. The main result was that the thermal fatigue and spin tests in hot JP4 gas demonstrate the superior characteristics of ZrO 2"7Y203 TBC. The ZrO2' 5CaO and ZrO2.20Y203 TBCs were characterized by poor resistance to thermal fatigue. In comparison the ZrO2.24MgO coating was considerably more resistant to fatigue and also to spinning, but still did not attain the fatigue resistance of the ZrOz'7Y/O3 coating. Turbine blades with TBCs (see Section 3.2) show signs of damage to the coating after 60 h of operation in the engine similar to that of the round specimens after the thermal fatigue test. Whereas only one of ten blades coated with ZrOz.7Y203 exhibited loss of material in the area of the leading edge, all 11 blades coated with ZrO2.5CaO suffered extensive damage. The results of the microscopic investigations show good conformance in the failure mode of the TBCs tested on the specimens and the turbine blades. This means that the results obtained with the rig tests show high transferability to engines. From the results of the microscopic investigations the widely differing behaviour of the four different types of TBC in the rig tests becomes understandable. Apart from the chemical composition of the TBC, these investigations show clearly that only a dense sprayed coating with very few pores and many perpendicular propagated segmentation cracks will have superior resistance against thermal fatigue stress and particle erosion attack. Furthermore, the ongoing research in post-treatment of the TBCs demonstrate how to achieve many well-propagated segmentation cracks by annealing and quenching these coatings.
REFERENCES 1 2 W. Dienst, Hochtemperaturwerkstoffk, Werkstofftechnishche Verlagsgesellschaft, Karlsruhe, 1978, p. 94. N. Claussen, Umwandlungsverst~irkte keramische Werkstoffe, Z. Werksto.JJ?ech., 13 (4) (1982) 138 147.

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3 J . F . Lynch, C. G. Ruderer and H. W. Duckworth, Engineering Properties of Selected Ceramic Materials, American Ceramic Society, 1966. 4 P.G. Valentine and R. D. Maier, Microstructure and mechanical properties of bulk and plasmasprayed Y203 partially stabilized zirconia, NASA Contract. Rep. 165126, 1980 (National Aeronautics and Space Administration). 5 R.C. Garvie and P. S. Nicholson, Structure and thermomechanical properties of partially stabilized zirconia in the CaO-ZrO 2 system, J. Am. Ceram. Soc., 55 (1972) 152-157. 6 G.K. Bansal and A. H. Heuer, Precipitation in partially stabilized zirconia, J. Am. Ceram. Soc., 58 (1975) 235-238. 7 R.F. Pabst, I. Bognar and J. B. Zwissler, Ergebnisse zur statischen, dynamischen und zyklischen Ermiidung bei ke ramischen, Werkstoffen, Ber. Dtsch. Keram. Ges., 57 (1980) 13-16. 8 T.K. Gupta, F. F. Lange and J. H. Bechtold, Effects of stress-induced phase transformations on the properties of polycrystalline zirconia containing metastable tetragonal phase, J. Mater. Sci., 13 (1978) 1464-1470. 9 N. Claussen, Microstructural designs of ZrOz-toughened ceramics, Conf. on Zirconia, Stuttgart, June 21-23, 1983, to be published. 10 S. Stecura, Effects of compositional changes of the performance of a thermal barrier coating system, NASA Tech. Memo. TM-78976, 1979 (National Aeronautics and Space Administration). 11 F.S. Stepka, C. H. Liebert and S. Stecura, Summary of NASA research on thermal barrier coatings, Int. Automotive Engineering Congr., Detroit, 1977, in SAE Paper 770343, 1977. 12 R.E. Benner and A. S. Nagelberg, Characterization of ZrO2-YzO 3 thermal barrier coatings by raman spectroscopy, Thin Solid Films, 84 (1981 ) 89-94. 13 R.J. Bratton, S. K. Lau, C. A. Andersson and S. Y. Lee, Ceramic thermal barrier coatings for gas turbine engines, A S M E Paper 82-GT-265, 1980. 14 S. Kunz, W~irmebehandlung yon Wiirmediimmschichten, Project E4.9/1 (Bundesministerium fiir Forschung und Technologie gef6rdertes Projekt der Dechema/Gruppe 4, Technische Universit/it Miinchen). 15 D. Viechniki and V. S. Stubican, Mechanism of decomposition of cubic solid solutions in the system ZrO2-MgO, J. Am. Ceram. Soc., 48 (1965) 292-297. 16 V.S. Stubican R. C. Hink and S. P. Ray, Phase equilibrium and ordering in the system ZrO2-YzO3, J. Am. Ceram. Soc., 61 (1978) 17-21. 17 P. Boch and B. Rogeaux, plasma-sprayed zirconia coatings, Part II, The properties of the deposits, Conf. on Zirconia, Stuttgart, June 21-23, 1983, to be published. 18 C.L. Ammann, Phase stability ofzirconia and other candidate refractory thermal barrier coating materials, P WA Rep., 1976 (Pratt and Whitney Aircraft).