47th AIAA Aerospace Sciences Meeting Including The New Horizons Forum and Aerospace Exposition AIAA 2009-1433

5 - 8 January 2009, Orlando, Florida

Degradation of Thermal Barrier Coatings by Molten CMAS

(CaO-MgO-Al2O3-SiO2) Deposits

Prabhakar Mohan1, Travis Patterson2, and Yongho Sohn3

Advanced Materials Processing and Analysis Center (AMPAC) and Department of Mechanical, Materials, and
Aerospace Engineering, University of Central Florida, Orlando, Florida, 32816

and

Vimal H. Desai4
Office of Research, New Mexico State University, Las Cruces, New Mexico, 88003

Thermal barrier coatings (TBCs) are susceptible to degradation by molten CMAS

(calcium-magnesium alumino silicate) deposits, when employed in gas turbine engines
operating in a dust-laden environment. In this study, thermochemical aspects of CMAS
induced degradation of TBCs are thoroughly investigated. Free-standing yttria stabilized
zirconia (8YSZ) coatings and CoNiCrAlY metallic coatings in contact with a model CMAS
deposit were subjected to isothermal heat treatment in air at temperatures ranging from
1200°C to 1350°C. Phase transformations and microstructural development were examined
by using x-ray diffraction, scanning electron microscopy, and transmission electron
microscopy. Starting at 1250°C, CMAS melt readily infiltrated and dissolved the YSZ
coating followed by reprecipitation of zirconia with a different morphology and composition
that depends on the local melt chemistry. The mechanism of dissolution and reprecipitation
due to molten CMAS damage resulted in destabilization of the YSZ with disruptive phase
transformation (t’  f + m). TGO scale of CoNiCrAlY coating was completely consumed by
CMAS melt that was also accompanied by significant spinel oxide formation. Attempts to
mitigate CMAS attack by employing an environmental barrier overlay composed of α-Al2O3
are also introduced.

I. Introduction

I ncreasing demand to improve the performance of gas turbine engines in aircraft and marine propulsion as well as
power generation led to various technological developments over the past decades. Development of thermal
barrier coatings (TBCs) has undoubtedly been the most critical advancement in materials technology for gas turbine
engines. TBCs facilitate a tremendous increase in turbine inlet temperature (TIT) by providing thermal insulation to
hot section metallic components and have become the materials system of choice for improved efficiency and
performance of gas turbine engines (Ref. 1-5). Because of the demanding extreme operating conditions, TBCs
possess the most complex structure among the widely available coatings that are used to protect structural materials
from various environments. TBCs are multilayered systems consisting of a ceramic topcoat (YSZ - ZrO2 stabilized
with 7 to 8 wt.% Y2O3) for thermal insulation, a thermally grown oxide (TGO) scale, predominantly alumina, a
metallic bond coat that provides oxidation/corrosion resistance, and a superalloy substrate. TBCs possess their long-
term durability at high temperatures with high strain compliance and the long term stability of YSZ topcoat that is
primarily composed of metastable, tetragonal prime ZrO2 phase (ť-ZrO2). The equilibrium phases for the YSZ
1
Graduate Research Assistant and Doctoral Candidate, Advanced Materials Processing and Analysis Center
(AMPAC), Engineering Building 1, Room 381, Box 162455, Orlando, FL 32816, AIAA Student Member.
2
Graduate Research Assistant and Doctoral Student, Advanced Materials Processing and Analysis Center
(AMPAC), Engineering Building 1, Room 381, Box 162455, Orlando, FL 32816, AIAA Non-Member.
3
Associate Professor, Advanced Materials Processing and Analysis Center (AMPAC), Engineering Building 1,
Room 381, Box 162455, Orlando, FL 32816, AIAA Member.
4
Vice-President for Research, Office of the VP for Research, New Mexico State University, MSC 3RES,
Anderson Hall, Box 30001, Las Cruces, NM 88003, AIAA Non-Member.
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Copyright © 2009 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
topcoat at typical gas turbine temperatures are a mixture of tetragonal (t) and fluorite-cubic (f) phases (Ref. 6).
However, during air plasma spraying of YSZ, a rapid quench promotes the formation of the metastable tetragonal-
prime phase (ť-ZrO2). This ť phase helps prevent the phase transformation to room temperature equilibrium phases
such as monoclinic (m) and fluorite-cubic (f) phases during thermal cycling. It is well known that the transformation
to m phase is accompanied by a large destructive volume change (3 to 5%) that could lead to delamination and
spallation of the ceramic topcoat (Ref. 7). YSZ coatings are often deposited either by air plasma spray (APS) or
electron beam physical vapor deposition (EB-PVD); the choice of the respective deposition process depends on
factors such as coating thickness, aerodynamic requirement, repair-ability and production costs.
The TGO scale that forms between the YSZ topcoat and the metallic bond coat significantly influences the
durability of TBCs (Ref. 8-10). Bond coat is primarily designed as a local Al reservoir for facilitating the formation
of α-Al2O3 as TGO scale in preference to other oxides. Because of its major influence on TBC durability through the
morphology and structure of TGO formed, bond coat has been considered as the most crucial component of TBCs
(Ref. 4). Two different types of widely used bond coats are: MCrAlY (M = Ni and/or Co) and Pt-modified nickel
aluminide (Ni,Pt)Al. MCrAlY bond coats that are typically deposited by low-pressure plasma spraying (LPPS),
consist of two phases: β-NiAl and either γ-Ni solid solution or γ′-Ni3Al. Yttrium acts as a solid state gettering site
for elemental S impurities that diffuse from superalloy substrate and thus Y addition at a lower concentration
improves the adhesion of the TGO (Ref. 11). Pt-modified nickel aluminide coatings, which are primarily a single
phase β-NiAl with Pt in solid solution, are usually fabricated by electroplating a thin layer of platinum onto the
superalloy substrate and then aluminizing by either chemical vapor deposition or pack cementation (Ref. 12). Recent
developments in thermal spray processing techniques of MCrAlY type bond coats identified High Velocity OxyFuel
(HVOF) technique as the effective method to fabricate denser and less oxidized bond coats (Ref. 13). Other
techniques include the conventional Air Plasma Spraying (APS), which is the cost effective technique, often used to
deposit ceramic YSZ topcoat (Ref. 14), and Vacuum Plasma Spraying (VPS) (Ref. 15). More recently High
Frequency Pulse Detonation (HFPD) has been studied as another cost effective alternative for fabricating bond coats
of desired quality (Ref. 16).
Among the several widely known mechanisms that control the durability of TBCs, a critical durability issue that
received much attention in recent years, is their resistance to high temperature degradation by airborne contaminants
that deposit on hot surfaces of gas turbine components. TBCs are increasingly susceptible to degradation by molten
CMAS (calcium-magnesium alumino silicate) deposits in gas turbine engines, especially in aircraft engines, which
operate in a dust-laden environment wherein ingestion of siliceous debris into engines has been commonly reported
(Ref. 17-20). Such airborne deposits like CMAS were reported to melt, adhere and ingress in to TBCs above
1150°C, and subsequently degrade the TBCs via ingression and repeated freeze-thaw action and, to a certain extent,
direct chemical reaction with TBC constituents (Ref. 18-20). With an ever increasing demand to raise the turbine
inlet temperature (TIT), degradation of TBCs by molten CMAS has received a greater attention in recent years.
Thermomechanical damage being the envisaged damage mechanism has been investigated as the result of the
introduction of sufficient stress in the coating during infiltration of molten CMAS followed by solidification upon
cooling during thermal cycling (Ref. 17). Additional damage mechanisms associated with the thermochemical
aspects of molten CMAS interaction with TBCs have also been reported recently (Ref. 18, 19). The
thermomechanical and thermochemical interactions can accelerate the failure of TBCs and underlying components
by various deleterious mechanisms such as destabilization of YSZ topcoat (ť  t  m+f), accelerated oxidation and
hot corrosion of underlying metallic bond coat and superalloy substrate.
Various studies have attempted to mitigate the melt-induced attack of TBCs, in general. These attempts include
surface sealing of YSZ topcoat by laser glazing (Ref. 21), employing environmental barrier layers fabricated by APS
and EBPVD techniques that are composed of inert materials such as mullite, alumina and calcium silicate that are
resistant to molten deposit attack (Ref. 22, 23). Modifying the YSZ topcoat chemistry was also studied to a greater
extent to mitigate CMAS attack, in specific. TBCs with novel topcoat chemistry such as YSZ incorporated with
Al2O3 and TiO2 as solid solution were developed to mitigate CMAS melt ingression via crystallization of CMAS
glass by increasing Al content of CMAS (Ref. 24). Recently, zirconate pyrochlores such as La2Zr2O7 (Ref. 25) and
Gd2Zr2O7 (Ref. 26) received greater attention due to their promising resistance against CMAS attack. Primary
objectives of this study were to investigate the individual degradation mechanisms of free standing air plasma
sprayed (APS) yttria stabilized zirconia (YSZ) coatings and free standing APS CoNiCrAlY coatings by molten
CMAS deposits at elevated temperatures. Temperature gradient in TBCs typically arrests CMAS ingression before
reaching the underlying layers of TBCs such as TGO and metallic bond coat. However, bond coat could be locally
prone to CMAS interaction due to spallation of YSZ topcoat. Hence, the individual interactions of CMAS with pre-
oxidized APS CoNiCrAlY coatings were also studied. Attempts to mitigate the CMAS melt-infiltration attack by

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employing a dense, continuous environmental barrier overlay, applied by electropherotic deposition (EPD) are also
introduced.

II. Experimental Details

A. Free Standing Air Plasma Sprayed YSZ and CoNiCrAlY Coatings

Free standing APS YSZ and CoNiCrAlY coatings for this study were prepared in an in-house thermal spray
facility. Free standing APS YSZ coatings were processed by depositing ZrO2-8 wt.% Y2O3; 8 YSZ powders (Praxair
Inc, Danbury, CT) on grit-blasted surfaces of graphite disks of 1” diameter, which were subsequently burnt off. 8
YSZ powders of average particle size of 106 µm were sprayed on graphite using a Sulzer-Metco F4 MB plasma gun
(Westbury, NY) under a spraying current of 675 A with a primary gas Ar flow of 100 SCFH, a secondary gas H 2
flow of 20 SCFH and a carrier gas Ar flow of 8 SCFH. Similarly, APS CoNiCrAlY coatings were also processed by
depositing CoNiCrAlY powders (CO-159, Praxair Inc, Danbury, CT) of composition 38.5 wt.% Co, 32 wt.% Ni, 21
wt.% Cr, 8 wt.% Al, and 0.5 wt.% Y, on graphite substrates that were subsequently burnt off. APS of CoNiCrAlY
powders (average particle size of 75 µm) utilized Sulzer-Metco F4 MB plasma gun under a spraying current of 675
A with a primary gas Ar flow of 120 SCFH, a secondary gas H2 flow of 18 SCFH and a carrier gas Ar flow of 8
SCFH. Both free-standing APS 8YSZ coating and APS CoNiCrAlY coating specimens were 300 µm in thickness
for all experiments. Free-standing CoNiCrAlY coatings were initially pre-oxidized at 1100°C for 50 h to have
coating microstructure with internal oxidation and appreciably thick TGO on surface that is likely to be exposed to
molten deposits in a real engine operation.

B. CMAS Testing at Elevated Temperatures

Based on the average composition of deposits on aircraft turboshaft shrouds operated in a desert environment, as
reported earlier [18], the in-laboratory synthesized model CMAS sand used in this study had a chemical composition
of 33 CaO – 9 MgO – 13 AlO1.5 – 45 SiO2 that can be referred as C33M9A13S45 (composition is in mole percent of
single cation oxide formula units). This was prepared by mechanically milling the individual oxides of high purity in
a SPEX shaker mill (SPEX CretPrep, Metuchen, NJ) for 1 hour at room temperature. APS YSZ and CoNiCrAlY
coating specimens of dimensions 1 cm x 1 cm were sectioned from the as-sprayed free-standing coatings for CMAS
testing. The as-milled CMAS powders were subsequently spread uniformly over the as-sprayed free standing
coating specimens at a concentration of 20 mg/cm2. YSZ and CoNiCrAlY specimens in contact with CMAS were
subjected to isothermal heat-treatment at temperature ranging from 1200° to 1350°C for various durations up to 4
hours.

C. Characterization
X-ray diffraction studies were performed on CMAS tested specimens to examine the development of constituent
phases. This was performed using Rigaku D-Max B Diffractometer (Tokyo, Japan) with Cu Kα radiation. It is worth
mentioning that the XRD patterns were obtained on both the top and bottom surfaces (surface on which CMAS was
applied is referred as top surface) of CMAS infiltrated YSZ. For microstructural characterization, specimens were
embedded in epoxy resin and metallographically prepared down to 0.25 µm using diamond paste. Surface
morphological and cross-sectional microstructural analyses were carried out to examine deposit penetration and
degradation mechanisms by using JEOL 6400F field-emission scanning electron microscope (FE-SEM) (Tokyo,
Japan) equipped with X-ray energy dispersive spectrometer (XEDS). A Philips/FEI Tecnai F30 300KeV
transmission electron microscope (TEM) (Hillsboro, OR, USA), equipped with high angle annular dark field
(HAADF) and XEDS was also employed to examine the detailed chemical aspects of degradation mechanisms and
the phase transformations of YSZ due to CMAS infiltration. The sample preparation for TEM was performed by
focused ion beam (FIB) in-situ lift-out (INLO) using a FEI 200 TEM FIB (Hillsboro, OR, USA) through a
procedure discussed elsewhere [27].

D. Environmental Barrier Overlay by Electrophoretic Deposition

In order to protect TBCs from CMAS, a crack-free continuous Al2O3 overlay coating on APS YSZ was processed
by electrophoretic deposition (EPD) technique. For EPD of Al2O3 coatings, a colloidal suspension of α-Al2O3
powders (0.3 µm α-Al2O3 powder, Metlab Corporation, NY) was prepared by dispersing powders in an acetone-
ethanol organic solvent mixture of volume ratio 1:1 at a solid loading concentration of 10 g/l. Iodine at a
concentration of 0.4 g/l was used as an additive. This colloidal suspension was mechanically stirred for 10 minutes
and subsequently subjected to ultrasonication for 1 h to break down the particle agglomerates for a stable colloidal

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suspension of individually dispersed Al2O3 particles. YSZ coated with Pt was used as cathode and an inert graphite
disk of same surface area and geometry as of YSZ disk was used as anode. EPD cell was simply assembled by
completely immersing the electrodes in Al2O3 colloidal suspension that was constantly stirred. A DC voltage of 25
V was applied between the cathode and anode for 10 minutes using a Protek 3032B DC power supply. During EPD,
positively charged α-Al2O3 powders in colloidal suspension were drifted and deposited on Pt coated APS YSZ
cathode. The deposited powder compact by EPD was carefully dried at ambient atmosphere for 2 hours and
subjected to densification by sintering. It should be noted that a controlled slow ramping rate during sintering is
required in order to densify the EPD powder compact to fabricate a fully dense adherent coating. Sintering was
performed at 1400°C for 4 h with a carefully controlled ramp up and ramp down rates of 1°C/min. Free standing
APS YSZ with Al2O3 overlay coating was also subjected to CMAS testing at 1300°C.

III. Results and Discussion

A. Characterization of Free Standing APS Coatings

As-sprayed free-standing APS YSZ and CoNiCrAlY coating specimens were characterized for initial
microstructure and phase constituents. X-ray diffraction study was used to characterize the initial phases present in
the as-sprayed coatings. The as-sprayed YSZ was found to exist as metastable tetragonal prime zirconia phase (ť –
ZrO2), which is the most desirable phase for TBC applications. Fig. 1(a) and (b) illustrate the cross-section of APS
YSZ with typical splat-quenched microstructure, and Fig. 1(c) and (d) show the typical cross-sectional and surface
splat microstructure of APS bond coat respectively.

Figure 1. Microstructure of as-sprayed free standing APS YSZ and CoNiCrAlY coatings: (a) uniformly thick
YSZ coating consists of (b) splat-quenched microstructure, (c) uniformly thick CoNiCrAlY coating and (d) its
surface splat microstructure.

B. Degradation of APS YSZ Coatings by CMAS: Microstructural Analysis

The interaction between YSZ and CMAS was observed to occur only for elevated temperatures starting at
1250°C, where CMAS was found to completely melt and infiltrate the YSZ coating specimen (Ref. 19). Cross-
sectional microstructural analysis revealed a similar microstructure for all samples that suffered CMAS attack at
temperatures above 1250°C for all durations studied in this work (2 - 4 hours). Cross-sectional backscattered
electron micrographs of YSZ coating subjected to molten CMAS infiltration at 1250°C for 4h is shown in Fig. 2.

Figure 2. Cross-sectional backscattered electron micrographs near the (a) top and (b) bottom surface of the
APS YSZ coating subjected to molten CMAS infiltration at 1250°C for 4 h. Regions 1 and 2 correspond to
solidified CMAS and bulk YSZ (Ref. 19).
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 CMAS melt readily infiltrated the 300 µm thick YSZ coating and the solidified CMAS islands were observed
near the top and bottom surfaces of the YSZ coating. Infiltration is complete in isothermal exposures, however it
will vary in a real engine operation dictated by viscosity of the melt and thermal gradient across TBCs. The
accumulation of CMAS melt in the interconnected pores and cracks of the YSZ coatings resulted in a gradual
dissolution of the YSZ in CMAS melt followed by reprecipitation of ZrO2 grains with a different microstructure and
composition based on the local melt chemistry (Ref. 19). Morphological changes are presented in the backscattered
electron micrographs as shown in Fig. 3. The typical microstructure revealing the solidified CMAS islands and bulk
YSZ is illustrated in Fig. 3(a). The reprecipitation of spherical ZrO2 grains from the CMAS melt is clearly presented
in Fig. 3(b) and 3(c).

Figure 3. Backscattered electron micrographs obtained from the YSZ coating infiltrated by molten CMAS at
1300°C for 4 h: (a) and (b) - Cross-sections at lower and higher magnifications showing solidified CMAS
(region 1), unaffected YSZ (region 2) and reprecipitated ZrO2 (region 3), (c) - micrograph showing the
surface morphology of CMAS infiltrated coating with coarse and fine reprecipitated ZrO2 grains (Ref. 19).

C. Degradation of APS YSZ Coatings by CMAS: Phase Transformations

XRD patterns obtained from CMAS infiltrated APS YSZ (1300°C for 4h) specimens are presented in Fig. 4.
Similar XRD patterns were obtained for all specimens when CMAS infiltration had occurred. The disruptive phase
transformation of metastable tetragonal zirconia (ť-ZrO2) to monoclinic+cubic zirconia (ťtm+f) is evident. The
transition of two adjacent Bragg reflections from planes (103) and (211) of tetragonal zirconia to one single peak
that corresponds to the reflection from (311) plane of cubic ZrO2 is clearly presented in Fig. 4(b).

Figure 4. X-ray diffraction patterns illustrating the phase transformation of YSZ due to CMAS infiltration:
(a) Collected patterns from (i) as sprayed YSZ coating – top surface, (ii) Top surface and (iii) bottom surface
of the YSZ infiltrated by molten CMAS at 1300°C for 4 h. (b) Magnified representation of the shaded region
in (a) at a narrow 2θ range of 57° to 62° (Ref. 19).

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The phase transformation to Y2O3-depleted monoclinic ZrO2 and Y2O3-rich cubic ZrO2 phases are attributed to a
deviation in the content of Y2O3 stabilizer from the original YSZ solid solution during reprecipitation. This
argument is in agreement with the earlier reported literature (Ref. 18). This disruptive phase transformation is
accompanied by a large volume change of 3% to 5% that could lead to delamination and spallation of the ceramic
topcoat. It should be noted that the Y2O3-rich cubic ZrO2 phase was found to be the predominant phase at the bottom
surface. This could be due to the enrichment of Y2O3 content in the CMAS melt accumulated at the bottom surface
that could have resulted in precipitation of ZrO2 with higher Y2O3 content (Ref. 19). Bright field TEM micrographs
obtained from the YSZ specimen subjected to molten CMAS degradation at 1350°C for 2 h revealed the presence of
various phases as shown in Fig. 5. Both metastable tetragonal zirconia (ť-ZrO2) and monoclinic zirconia (m-ZrO2)
were present in the CMAS infiltrated specimens, which is consistent with the XRD results. The electron diffraction
patterns obtained from the three primary regions were indexed as ť-ZrO2 with a zone axis of [113], m-ZrO2 with a
zone axis of [302] and the completely amorphous CMAS glass. EDS analysis performed by XEDS equipped with
both TEM and SEM revealed presence of Y and Zr. Solidified CMAS glass was found to have higher Y:Zr content
(atomic ratio) compared to the desired ratio of 1:12 in the bulk YSZ of 7-8 YSZ coatings (Ref. 19). Few localized
spots were identified to be extremely richer in Y content compared to Zr content. During the dissolution of the YSZ
coating in CMAS melt, a preferential dissolution of Y may occur based on thermodynamic aspects. These results
also support the observation of reprecipitated monoclinic ZrO2.

Figure 5. (a) and (b) Bright-field TEM micrographs obtained from the APS YSZ coating subjected to molten
CMAS attack at 1350°C for 2 h. The corresponding electron diffraction patterns obtained from the three
primary phases present, which are indexed as (c) metastable tetragonal (ť) ZrO2, (d) monoclinic ZrO2 and (e)
amorphous CMAS glass (Ref. 19).

D. Degradation of APS CoNiCrAlY Coatings by CMAS Melt

Pre-oxidized APS CoNiCrAlY coatings were exposed to CMAS melt at 1250°C for 5 h. Secondary electron
micrographs obtained from coating surface after interaction with CMAS revealing the crystallization of applied
CMAS are evident from Fig. 6(a) and (b). CMAS crystallization consumed the TGO, α-Al2O3 that was also
accompanied by extensive spinel oxide [(Ni,Co)(Al,Cr)2O4] formation. Reaction products as thin platelets are visible
in the cross-sectional backscattered electron micrograph as shown in Fig. 6(c). These platelets were found to be rich
in Al content compared to the elemental composition of applied CMAS, which confirmed the extensive
consumption of TGO, α-Al2O3. Crystallization of CMAS glass through enrichment of Al content has been reported

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earlier (Ref. 24), where Anorthite [CaAl2Si2O8] crystals were found to be the predominant reaction product. Hence,
α-Al2O3 as an environmental barrier overlay for TBCs has also been studied in this work.

Figure 6. (a) and (b) - Secondary electron micrographs obtained from surface of CoNiCrAlY coating exposed
to CMAS melt at 1250°C for 5 h revealing the crystallization of CMAS (region 1) and spinel oxide formation
(region 2), (c) – Cross-sectional backscattered electron micrograph revealing the interaction layer composed
of reaction product (region 1), spinel oxide (region 2) and unreacted CMAS (region 3) and (d) - their
corresponding EDS spectra.

E. Al2O3 Overlay to Mitigate CMAS Attack

Electrophoretic deposition (EPD) technique followed by controlled sintering has the potential to deposit a
continuous crack-free ceramic layer with controlled thickness and porosity (Ref. 28-30). EPD was chosen to deposit
α-Al2O3 as an environmental barrier overlay for TBCs to protect against CMAS attack. A crack-free, continuous
Al2O3 layer of 25 µm was deposited on APS YSZ by EPD technique followed by controlled sintering at 1400°C for
4 h (Ref. 28). As-processed surface and cross-sectional microstructure of EPD Al2O3 overlay are presented in Fig.
7(a) and (b).

Figure 7. (a) Secondary electron micrograph revealing the surface morphology of EPD Al2O3 after sintering
at 1400°C for 4 h, (b) Cross-sectional backscattered electron micrograph showing the as-processed EPD
Al2O3 overlay coating (Ref. 28).
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 APS YSZ coating with EPD Al2O3 overlay was exposed to CMAS melt at 1300°C for 1 h. In agreement with
available literature (Ref. 24), CMAS readily consumed α-Al2O3 and crystallized out products such as Anorthite
[CaAl2Si2O8] and Diopside [CaMgSi2O6] that were confirmed by secondary electron surface micrograph and XRD
as presented in figure 8. Enrichment of Al content in CMAS resulted in Anorthite [CaAl2Si2O8] crystallization,
which is similar to the aforementioned mechanism of TGO dissolution by CMAS, when CoNiCrAlY coatings were
exposed to CMAS melt. Consequently, local enrichment of Mg in CMAS could have resulted in crystallization of
Diopside [CaMgSi2O6].

Figure 8. Reaction products crystallized from CMAS melt – EPD Al2O3 interaction at 1300°C for 1 h: (a)
Secondary electron micrograph showing the surface morphology of Al2O3 interacted with CMAS, (b) XRD
patterns confirming the phase constituents of reaction layer as Anorthite and Diopside.

Suppression of CMAS melt ingression into the YSZ coatings is clearly evident from cross-sectional
backscattered electron micrograph presented in Fig. 9. A reaction scale of 10 µm in thickness resulted from
interaction of EPD α-Al2O3 and applied CMAS, which is composed of reaction products such as Anorthite, Diopside
that have higher melting temperatures compared to typical engine operating conditions. Such reaction layer can
further act as an environmental / thermal barrier overlay coating. It is worth mentioning that post-EPD processing
such as sintering at a higher temperature might not be possible on a real TBC system because of the possible
deleterious effects to metallic components of TBC system when exposed to such elevated temperatures. However,
use of smaller (e.g., nano) powders and innovative sintering techniques can help reduce the temperature and time of
sintering and avoid any degradation of TBCs during post-EPD processing.

Figure 9. (a) Al2O3 as environmental barrier overlay coating for APS YSZ fabricated by electrophoretic
deposition (EPD), (b) EPD Al2O3 suppressed CMAS melt ingression in to YSZ by formation of a reaction
scale at the surface, when exposed to CMAS melt at 1300°C for 1 h (Ref. 28).

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 IV. Summary
CMAS melt was found to readily infiltrate free-standing APS YSZ coatings within durations that are negligible
compared to the typical engine operation cycle durations. All samples were observed to be completely infiltrated by
molten CMAS at temperatures starting at 1250°C for all time durations investigated in this study (2 to 4 h).
Infiltrated microstructures and phase transformations were found to be independent of exposure temperature, once
the CMAS melt penetrates into the porous YSZ coating through the cracks and interlamellar gaps. Significant
amount of Y2O3 depleted monoclinic ZrO2 phase evolved from CMAS melt that dissolved ť-ZrO2 was observed. Re-
precipitated grains have a spherical morphology in general. TEM results were consistent with XRD analysis, where
both monoclinic and metastable tetragonal ZrO2 phases were identified. CMAS melt readily dissolved YSZ followed
by reprecipitation of ZrO2 with a composition based on local melt chemistry that deviates in the content of Y2O3
stabilizer from the original YSZ coating. Extensive dissolution of TGO α-Al2O3 of CoNiCrAlY coatings by CMAS
melt and significant spinel oxide formation were identified as degradation mechanisms of APS CoNiCrAlY
coatings, when exposed to CMAS melt. For mitigation of CMAS melt ingression, α-Al2O3 as an environmental
barrier overlay coating for TBCs was also developed by electrophoretic deposition technique followed by controlled
sintering. Continuous, crack-free Al2O3 overlay coating was found to be effective in suppressing CMAS melt
ingression through reactions that crystallize applied CMAS as reaction products such as Anorthite and Diopside.

Acknowledgments
This work was financially supported by the U.S. Department of Energy through University Turbine Systems
Research program under the subcontract No. 02-01-SR118, State of Florida Turbine Initiative (SFTI) from National
Aeronautics and Space Administration (NASA), and Florida Center for Advanced Aeronautics Propulsion
(FCAAP).

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