J. Am. Ceram. Soc.
, 1–9 (2015)
Journal
Multilayer, Multimaterial Thermal Barrier Coating Systems: Design,
Synthesis, and Performance Assessment
Vaishak Viswanathan, Gopal Dwivedi, and Sanjay Sampath†
Center for Thermal Spray Research, Department of Materials Science and Engineering, Stony Brook University, Stony Brook,
Thermal barrier coatings (TBCs) are increasingly playing a
vital role in enhancing efficiency and performance of gas tur-
bine engines. As engine operating temperatures rise, yttria-sta-
bilized zirconia (YSZ), the currently principal TBC material,
reaches its operational limits. Gadolinium Zirconate (GDZ)-
based pyrochlore oxides are now emerging contenders, not only
due to their lower thermal conductivity, but also their ability to
resist attack by silicate deposits. However, GDZ cannot be
directly substituted for YSZ due to its incompatibility with the
thermally grown alumina layer, therefore requiring to be a
component of multilayer system. Although industry has already
adopted these materials in various applications, a number of
fundamental issues arise with respect to layered-coating design,
their properties and processing dependence. In this study sev-
eral multilayer architectures, based on the YSZ–GDZ system,
have been developed and tested for durability under furnace
thermal cycling conditions. Coating designs considered optimi-
zation of microstructure and properties of individual layers
based on their location within the top-coat thickness to address
competing interests of thermal conductivity, compliance, and
resistance to silicates. A large variance in durability was
observed in coatings made with different multilayer designs.
The results and the associated failure mechanisms are rational-
ized through preliminary evaluation of elastic energies at the
failure locations and corresponding energy release rates. The
results point to new strategies in the design and manufacturing
of optimal multilayer coatings.
I. Introduction
T HERMAL barrier coatings (TBCs) are critical materials in
modern propulsion and energy-generating gas turbines.
They provide protection to the superalloy structure, enhance
efficiency by enabling higher temperature operations, and
allow life extension of expensive components.1,2 Partially
stabilized zirconia-yttria (YSZ) has been the workhorse of
the TBC industry.1,3 These coatings are now applied either
by plasma spray or electron beam physical vapor deposition
technology, on a variety of stationary components such as,
combustors, afterburners and stator vanes, and rotating com-
ponents, such as turbine blades, both by original equipment
manufacturers and during engine overhaul.4
Even in its simplest form TBCs are multilayer structures
comprised of an oxidation-resistant metallic bond-coat with
adequate roughness, which then allows anchoring of a por-
ous low-conductivity ceramic layer. These layers change
dynamically during service through bond-coat oxidation,
thus introducing a thermally grown oxide (TGO) between
K. Faber—contributing editor
Manuscript No. 35717. Received October 1, 2014; approved February 16, 2015.
†
Author to whom correspondence should be addressed. e-mail: sanjay.sampath@
stonybrook.edu
1
DOI: 10.1111/jace.13563
© 2015 The American Ceramic Society
New York 11794-2275
the bond-coat and top-coat. The ceramic itself undergoes sin-
tering during sustained thermal exposure, resulting in
changes in mechanical and thermal properties, which affect
performance and durability.5–10 In recent years, the failure
scenarios have greatly expanded, particularly for situations
involving contaminants entering the engines.11 These include
solid particle (dust) erosion, foreign object damage, and
deposition of high-silicate containing sand particles which is
termed CMAS, for calcium magnesium aluminosilicate, par-
ticularly for engines operating in dusty environments.11
Although YSZ continues to be an important TBC, it has
reached its limits in terms of potential capability. Newer
engines use higher gas-inlet temperatures and require greater
flexibility in terms of operational envelopes and fuels. YSZ–
TBCs generally can operate up to about 1200°C, above
which occur phase instabilities and sintering. At these ele-
vated temperatures, the YSZ–TBC experiences increase in
thermal conductivity and, due to sintering, loss of compli-
ance.12 Above 1200°C, the issue of ingested sand/ash deposits
(CMAS, volcanic/coal ash), is significant. Porous or vertically
cracked YSZ coatings offer no resistance to the CMAS
liquid, allowing the contaminant to penetrate into the bond-
coat interface, solidifying during cooling cycle and causing
spallation of the top-coat.13,14 These deficiencies have pre-
vented the engine community from fully utilizing the TBC
vis-
a-vis enhanced efficiencies.
Over the last decade there has been a worldwide search for a
replacement of YSZ.15,16 A number of ceramic chemistries
have been investigated from zirconate compounds to multi-
component perovskites with limited success.16 This is in part
due to the several unique attributes of YSZ for TBCs, which
has good high-temperature compatibility with the TGO, and
higher toughness. In addition, YSZ is relatively easy to process
(similarities in vapor pressures for yttria and zirconia), has a
relatively high thermal expansion coefficient and low cost.
A majority of the new compositions cannot meet all the above
attributes, thus suggesting multilayer solutions.
Zirconates, particularly those based on gadolinium (Gd)
and lanthanum (La) offer promise as high-temperature TBCs
and have already been implemented by industry.11 Gadolinium
zirconate (Gd2Zr2O7) offers excellent high-temperature stabil-
ity, low thermal conductivity, a moderate expansion coeffi-
cient, and the potential to operate in a CMAS/ash
environment.17,18 However, zirconates have poor toughness
and react with TGOs requiring a YSZ transition layer at the
bond-coat interface.9,19,20 Although, industrial tests indicate
promise for CMAS mitigation, concerns exist regarding their
suitability against particulate erosion. These engineering devel-
opments have suggested opportunities for scientific enquiry into
the design, synthesis, and performance assessment of multima-
terial coatings, which is the focus of this work.
(1) Objectives and Approach
The examination of multilayer reported here will be APS–
TBC system based on YSZ and GDZ. APS coatings offer
2 Journal of the American Ceramic Society—Viswanathan et al.

lower in-plane compliance compared with EB-PVD, which is

a key factor driving thermal cycle durability in laboratory
furnace cycle tests.
Although the fabrication of a two-layered coating with
APS is straight forward, there is no well-established strategy
of microstructure design and optimization. This is particu-
larly true for such a multilayer assembly to meet the dispa-
rate and sometimes competing performance requirements of
thermal durability, erosion, and CMAS. A great deal is
understood of the YSZ process–property relationships, which
translate reasonably well for the GDZ system. However, inte-
grating the two materials introduces new challenges due to
differences in toughness and sintering rates.21,22 We here
present a comprehensive study of multilayer coating architec-
ture, its fabrication and performance to impart both multi-
functionality (CMAS and erosion) and durability.
APS TBCs can broadly be classified into two types: low-
density coatings with the porosity ranging from 10% to
20%, applied on stationary components (combustors, vanes)
where the porosity imparts compliance. An alternative is a
denser TBC with segmentation cracks (dense vertically
cracked or DVC), which provides in-plane compliance at the
expense of conductivity. Recent work has critically examined
a third APS variant, a bilayer TBC with a thin, dense, high
toughness ceramic layer in the interfacial region, followed by
standard porous TBC. Here, the goal is to impart higher Fig. 1. Two YSZ–GDZ coating architectures (S1 and S2) with
toughness at the bond-coat top-coat interfacial region (which different porosity levels and their FCT performance benchmarked
is the location prone to delamination failure) while reducing against conventional porous YSZ. The two bilayer coatings show
the overall stiffness of the coating with porosity.23 Such bi- reduced cyclic life resultant from cohesive delamination at the
layers have shown considerable promise in furnace cycling interface between the two ceramics.
tests, hence the multilayer architectures considered in this
study are inspired by these bilayer designs.

(2) Multimaterial Coating Design Considerations

The APS process provides considerable flexibility in terms of
layer assembly with which to meet multifunctional require-
ments. However, to ensure adequate performance and dura-
bility, the layer characteristics require careful optimization in
terms of microstructure and properties. For instance, a sim-
ple extension to a standard porous APS–YSZ–TBC incorpo-
rating the GDZ as the top-coat would be a logical strategy.
A preliminary study on the furnace cycle durability of such
equithickness two-layer YSZ–GDZ coatings show a substan-
tial furnace cycle performance debit compared to standard
porous single-layer YSZ coating (1100°C/24 h cycle). Fig-
ure 1 summarizes the results of two variants of equithickness
YSZ–GDZ systems with varying levels of porosity of their
constituent layers—S1 has higher porosity (more compliant)
than S2. This variation in porosity levels was obtained by
changing the plasma power from 24 kW (S1) to 47 kW (S2).
Although, both these coatings performed poorly in terms of
FCT life than a standard YSZ–TBC, the results showed coat-
ing microstructure to be a key factor. It should also be noted Fig. 2. Schematic of the proposed multilayered TBC architecture
that both S1 and S2 coatings failed prematurely within the comprised of YSZ and GDZ layers with the desired characteristics
GDZ layer near the YSZ and GDZ interface (Fig. 1). Similar of through-thickness layer microstructures to simultaneously meet
results on the failure locations of YSZ–GDZ system have the requirements of cyclic durability, erosion, and environmental
been reported in the literature: Bolcavage et al. reported attack.
cohesive failure of a proprietary dual-layer TBC under both
thermal gradient condition and for isothermal cycling.24 They 1. A high toughness, TGO-compatible, interfacial layer,
attributed this to a density mismatch between the two layers. preferably made with a thin YSZ layer of high den-
In a study by Vassen et al. on a YSZ–GDZ bilayer tested sity.23 Prior studies have shown that a
60 lm thick
under gradient conditions, partial failure was observed within and dense APS–YSZ layer at the interface provides
the GDZ.20 In a more recent study by the Vassen’s group, both the requisite toughness and durability.
the failure location was sensitive to the microstructure, and 2. Following this, a porous, low-conductivity layer serves
strongly affected by preferential Gadolinia evaporation the function of a thermal barrier. This layer can be
within the process.22 made of YSZ or GDZ with the goal to retain the
Based on these observations, a framework for a new porosity during thermal aging.
YSZ–GDZ-based multilayer coating, with which to meet the 3. The top-layer would primarily be made of GDZ to sat-
coating systems durability and functionality requirements, is isfy the CMAS/Ash requirements. Given the low frac-
illustrated in Fig. 2 and is rationalized as follows: ture toughness of GDZ,9 a denser layer is preferred to
 Multilayer Multimaterial TBCs 3

enhance erosion resistance.25 As this layer requires zation and particle diagnostics were carried out to ensure
compliance to survive thermal cycling, a DVC-type consistency and repeatability in microstructure and proper-
coating is proposed. ties.27,29,30 In Table I and II are summarized the details of
feedstock and optimized processing conditions developed for
This study critically examines the feasibility of such a mul-
each layer, respectively. Three different types of YSZ coat-
tilayer TBC design to meet the demands of fabrication, func-
ings were used for the multilayers: porous, dense, and DVC
tionality (conductivity), and durability (furnace cycling).
referred to as Y1, Y2, and Y3. Similarly for GDZ porous,
There are several options within this generic multilayer
dense, and DVC, structures (G1, G2, and G3) were devel-
framework which requires consideration. In this study, an
oped.28
experimental investigation of a range of proposed multilayer
The properties of the coating were monitored during and
TBC coatings with preliminary explanation of their durabil-
after spraying by employing beam curvature monitoring.30–32
ity is presented.
The measurements were made only on one specimen for each
case. This enabled an assessment of process-induced stresses
II. Experimental Details and overall elastic moduli of both single layer and multilayer
coatings. Details of these methodologies are available in the
Five variants of multilayer GDZ–YSZ coatings with an
literature.32 These diagnostics capabilities ensure high degree
equivalent total thickness (~300 lm) were investigated
of process and coating repeatability, which is crucial for reli-
(Fig. 3). All the coatings follow the general guidelines out-
able performance assessment.23 Note that, the CTE of coat-
lined in Fig. 2 but incorporate deliberate variations to assess
ing materials/layers are required to extract the coating elastic
critical microstructural attributes on performance. First, to
modulus from the curvature measurements. The actual CTE
introduce high fracture toughness at bond-coat and top-coat
values are somewhat different (~9 9 106/°C for GDZ and
interface, a dense YSZ coating layer was employed. Two
~10 9 106/°C for YSZ), but not considered here. The
variants of the high toughness YSZ layers were considered: a
“effective overall modulus” of the coating reported here was
DVC coating (A and E) and dense without vertical cracks
calculated assuming a single value of CTE for both YSZ and
(B, C and D). These microstructures were built from prior
GDZ. Calculations (not discussed here) suggested that
knowledge of the microstructure-toughness relations for
impact of this assumption on the effective overall modulus
plasma sprayed YSZ.9,26 The thickness of this interfacial
was less than 5%; although, the elastic energy calculations
layer of dense coating, was maintained close to 60 lm, which
reported in the appendix used material specific individual
was found to offer optimal performance in terms of enhanced
values.
furnace cycle durability.23 The DVC coatings were generally
During fabrication of the multilayered coatings, the
thicker ~150 lm as it is difficult to form vertical cracks in
plasma torch was stopped at the end of deposition of each
thin coatings. Although this variation in thickness is not
layer and the specimens were allowed to cool to ambient
ideal, as will be noted in this study, they do provide insights
temperatures. Before deposition of the subsequent layers, the
into coating failure mechanisms.
predeposited coating layers were preheated to a temperature
A similar approach of dense GDZ coatings with and with-
of around 250°C to ensure good adhesion between the suc-
out vertical cracks was considered for the top layers of all
cessive layers. For individual layer, the number of passes was
the tested variants. All coatings except A had a DVC GDZ
calibrated to achieve desired layer thicknesses.
microstructure. These dense layers provide enhanced resis-
The thermal conductivities of both single and multilayer
tance to erosion compared to porous counterparts, with the
coatings were measured on one specimen for each case, in
DVC architecture providing the requisite compliance. The
their free-standing forms by the Xenon-flash technique
thickness of this top layer was selected to maintain a total
(Anter Corp. -Flash Line, Pittsburgh, PA). Details of the
thickness of ~300 lm among the five architectures.
measurement procedures are reported elsewhere.33,34
Dense and DVC coatings generally have high thermal con-
For the FCT, coatings were deposited on Rene 80 sub-
ductivity. To reduce the overall thermal conductivity, coat-
strate, (25.4 mm diameter, 3.4 mm thick).Three samples were
ings A, B, and C included porous ceramic layers. Coatings B
tested for each architecture. The substrates were grit blasted
and C have identical architectures except for the porous lay-
at 5.5 bar with alumina grit following which a two-layer
ers. Coating B incorporates GDZ, whereas coating C
NiCoCrAlYHfSi (AMDRY-386; Oerlikon Metco, Westbury,
replaces this layer with YSZ. The implications of these coat-
NY) bond-coat was deposited using the WokaJetTM HVOF
ing architectures on both conductivity and durability are
thermal spray system (Oerlikon Metco). The two-layered
evaluated in this study.
bond-coat deposition schedule was adopted to meet the dual
needs of high-density and high surface roughness. Using a
fine powder (AMDRY 386-2, D50 = 32 lm), the first layer of
(1) Coating Fabrication
bond-coat was deposited on to the substrates to a thickness
For each layer of the coating, the thickness and coating char-
of 100 lm. This provided a dense microstructure. This was
acteristics were independently optimized using extensive prior
followed by a coarse powder (AMDRY 386-4, D50 = 63 lm)
processing knowledge established at Stony Brook.27–29
to a thickness of 50 lm, which results in a higher roughness.
Advanced process control strategies, such as injection optimi-

(a) (b) (c) (d) (e)

Fig. 3. Schematic illustrations of different multilayer variants fabricated and tested in this study.
4 Journal of the American Ceramic Society—Viswanathan et al.

The resultant coating had a surface roughness of around
7–8 lm measured by a Mitutoyo SJ 201P profilometer
(Mitutoyo America, IL).
FCT with a 24 h cycle was conducted in a box-furnace
(Carbolite CWF 1300, Hope Valley, UK) at 1100°C in air.
A criterion of 20% or more spallation of top-coat was used
to identify coating failure. For reference and benchmarking,
a single-layered YSZ coating on a similar bond-coat was also
tested along with the multilayered coatings. This step allows
comparison of various single and bilayer YSZ variants as
reported in earlier papers. Scanning electron microscopy was
used to characterize the coating cross sections of both
as-sprayed and failed microstructures.
by depositing a thin and dense YSZ layer on samples B
through D or by a thicker DVC variant for samples A and
E. In samples B and C, porous YSZ or GDZ layers follow
to provide low-conductivity thermal barrier properties.
Finally, in all the samples, except for sample A which has
dense GDZ layer, the top layer is made of DVC GDZ
(B–E). All the DVC layers displayed regularly spaced vertical
cracks, but some lateral cracking is noted in the thicker
GDZ coatings (D).
The microstructures shown in Fig. 4 demonstrate the effec-
tiveness of the processing parameters to meet the layer design
targets outlined in Fig. 3.

(2) Properties of Multilayered Coatings

III. Results
(1) Microstructure and Properties of Multilayered YSZ–
GDZ Coatings
As microstructures of APS TBCs are sensitive to their pro-
cessing conditions, there is a need for process control to
obtain the desirable properties. Evaluating the microstruc-
ture, thermal, and mechanical properties of these APS-multi-
layered coatings thus formed the first step at providing a
basis for assessment as well as design relevant properties
quantification. Figure 4 shows the microstructures of the dif-
ferent YSZ–GDZ multilayer variants.
As mentioned in the Section II, the high fracture tough-
ness and TGO-compatible near-interface layer was achieved
The effective thermal conductivity and overall elastic modu-
lus of the consolidated multilayers as well as their corre-
sponding single layers are provided in Table III and are
representatively depicted as a regime map in Fig. 5. An
assumption relative to the overall modulus of multilayers
obtained from beam curvature measurements is made here as
different layers may have different effective contributions.
The elastic energy calculations described later in the study
addresses these issues. As in the case of conventional APS
coatings, the thermal and mechanical properties of these
YSZ–GDZ multilayers exhibit a strong correlation with mi-
crostructures. Substantial benefits were observed in lowering
thermal conductivities through effective substitution by the

Table I. Feed Stock Morphology and the Corresponding Mean Particle Size
Material Powder designation Morphology Particle size range (lm) Average particle SIZE (lm)

YSZ HOSP-A Hollow Spherical 15–105 55

HOSP-B Hollow Spherical 10–45 22
FC-A Fused & Crushed 10–45 20
GDZ HOSP-C Hollow Spherical 45–105 65
HOSP-D Hollow Spherical 10–45 30

Table II. Processing Parameters Used for the Deposition of the Various Constituent Layers in the Multilayered Coatings Using
F4MB Plasma Spray Torch
Cond no. Feed stock Ar (slpm) H2 (slpm) Current (A) Spray distance (mm) Raster speed (mm/s)

Y1 HOSP-A 47.5 6 550 150 500

Y2 HOSP-B 47.5 6 550 100 500
Y3 FC-A 60 11 650 60 350
G1 HOSP-C 35.2 2.6 450 100 500
G2 HOSP-D 60 11 650 60 350
G3 HOSP-D 47.5 6 550 60 500

(a) (b) (c) (d) (e)

Fig. 4. As-sprayed microstructures of the multilayer variants illustrated in Fig. 3. Two types of YSZ microstructures (dense and DVC) were
examined to offer high toughness at the bond-coat interface. With the exception of coating A, all the coatings had a surface layer of a DVC
GDZ to offer erosion and CMAS resistance. The micrometer bar represents 50 lm.
 Multilayer Multimaterial TBCs
low-conductivity porous layers, either of GDZ (coating B) or
YSZ (coating C) in place of their DVC architectures. These
coatings expectedly displayed lower values of conductivity
than those with the ones with larger thicknesses of DVC
architectures. The coating architecture with DVC variants of
both the YSZ and GDZ exhibited the highest thermal con-
ductivity among this group of coatings, which is attributed
to the overall high density of the coating.
Figure 5 shows clusters of the data into four zones. The
DVC variants, display higher elastic modulus and thermal
conductivity, whereas the porous coatings show significantly
lower modulus and conductivity. They occupy extreme ends
of the conductivity-modulus map. The multilayer data fall in
between again affected by the microstructure (DVC versus
porous) and material (YSZ versus GDZ). The results confirm
that GDZ is an effective substitute for YSZ in lowering over-
all conductivity. This regime map provides a tool for both
engine designers and process engineers as it allows material,
process, and thickness selection to target specific properties.
Notable features are multifunctional, multilayer samples that
incorporate the porous interlayers (B and C), offering a ther-
mal conductivity range 0.8–1.0 W(mK)1, which is consis-
tent with contemporary industrial YSZ coatings.
The modulus of DVC multilayers (e.g., E) is higher than
expected. Detailed microstructural analysis (not included
here) revealed that crack opening in these samples were smal-
Table III. Measured As-Sprayed Elastic Modulus and
Thermal Conductivity of Single-Layer and Multilayer coatings
Thermal
conductivity
Coating ID [W(mK)1]
Porous YSZ Single 1.04
DVC YSZ layer 1.60
Porous GDZ 0.78
DVC GDZ 1.06
Dense YSZ 1.22
A Multilayered 1.07
B coatings 0.93
C 0.83
D 1.09
E 1.55
Fig. 5. A regime map indicating the data clusters for as-sprayed
thermal conductivity and elastic modulus of the single and multilayer
coatings. The thermal conductivity and elastic modulus
measurements were made on coatings without and with substrate,
respectively. SL: single layer, ML: multilayer, P-Y: porous YSZ and
P-G: porous GDZ. S1 and S2 are the coatings discussed in the
Introduction section and are shown in Fig. 1.
5
ler than traditional DVCs attributable to the low overall
layer thickness.
(3) Furnace Cycle Durability of Multilayer TBCs
Figure 6 shows the results for the FCT of the five multilayer
coatings (A–E). All the data were benchmarked against stan-
dard porous APS TBCs, and the recently reported bilayer
YSZ variant with a toughness optimized interface for
enhanced durability.23 Several initial observations can be
made:
1. A substantial variance in durability was observed
among the tested multilayers (from 96 to 1468 h of
cumulative hot time).
2. Samples that contain porous GDZ layers generally
showed lower FCT life.
3. The DVC YSZ–GDZ variant (E) did not show a sig-
nificant improvement over the benchmark porous
YSZ. This is attributed to the somewhat higher stiff-
ness of the coating E (Fig. 5). This is further addressed
in the Discussion section.
(4) Failure Locations of Multilayered Coatings Under
FCT Conditions
Under isothermal cycling conditions the APS TBCs typically
fail due to the prolonged oxidation of the bond-coat. The
loci of failure are usually near the bond-coat and top-coat
interface (differentiated here as adhesive failure). The major-
ity of multilayered TBCs tested in this study exhibited a sig-
Elastic nificant departure from this convention as illustrated through
modulus
representative schematics and SEM observations of the failed
(GPa)
cross sections in Fig. 7. On the other hand, cohesive failure
26 (within the top-coat away from TGO and top-coat interface)
50 was observed in several cases (A, B, and D), pointing to dif-
19 ferences in the failure modes. Notably, samples that showed
40 these cohesive failures also displayed a lower FCT life. Fig-
46 ure 7 shows through-thickness elastic energy curves, which
85 will be further developed in the Discussion section.
51 Samples A and B showed failure within the GDZ layer
61 near the YSZ–GDZ interface. Sample D showed cohesive
90 failure within the DVC–GDZ layer. Samples C and E
87 showed classic APS TBC adhesive failures near the TGO and
top-coat regions. In these samples the top DVC GDZ layer
is generally intact in the coating. Interpretations of the fail-
ure mechanisms are discussed in the next section.
Fig. 6. Furnace cycle test (FCT) durability of the different
multilayer variants illustrated in Fig. 3. The results are benchmarked
against standard porous YSZ single layers and YSZ bilayers
developed in Ref. [23]. All the three specimens with coatings A and
B failed at the same number of FCT hours.
6 Journal of the American Ceramic Society—Viswanathan et al.

IV. Discussion coatings offer higher toughness than porous vari-

The results presented here point to promise as well as issues
in developing multifunctional and multilayer coatings. For
these strategies to be viable, one needs to address the issue of
durability and understand relevant failure mechanisms. Sev-
eral observations can be made from Fig. 7.
1. The standard failure mode of delamination near the
TGO and top-coat interface as seen for the APS–YSZ
system is not generally applicable for all the multilayer
specimens. This is consistent with some of the previous
results on bilayer YSZ–TBCs.22,24,35
2. Samples A and B with porous GDZ microstructures
near the TGO location, result in premature delamina-
tion within this layer. This is attributed to the lower
toughness of GDZ.9,22
3. Sample D with DVC, instead of porous GDZ layer
near the TGO location, is also prone to premature fail-
ure within the GDZ, although these samples show
improved FCT performance. This is very likely also
related to the toughness of GDZ. (DVC and denser
ants.9,36
4. Samples that do not contain GDZ layers near
(
150 lm of a 300 lm coating thickness) the bond-
coat and top-coat interface generally show enhanced
durability with failure following the classic delamina-
tion at the TGO and top-coat interface.
While the durability of the TBCs under cyclic conditions
is governed by numerous thermochemical and thermome-
chanical changes occurring throughout the dynamic process,
the work by Levi et al. has identified the critical role of the
available elastic energy (U) in the system at the bond-coat
and top-coat interface as a major factor determining the
durability of coating.11 Delamination will occur at a location
when the available elastic energy (driving force) reaches the
value of the critical energy release rate Gc, or toughness of
the material at that location. This U is dependent on the
coating thickness, elastic modulus, and thermal expansion
mismatch with the substrate. The stiffness and thus U can
also evolve through microstructural changes with aging

(a)

(b)

(c)

(d)

(e)

Fig. 7. Representation of the observed FCT failure modes/locations for the tested multilayer variants and their associated cross-sectional SEM
images (black arrows indicate loci of failure in each case). The panel on the right depicts the calculated available elastic energy profiles (U) values
of coating based on the formulation provided in appendix. Vertical line points to the value of available elastic energy at the observed failure
location (Ufail).
 Multilayer Multimaterial TBCs 7

(sintering, TGO growth, CMAS penetration) but this is not Although no toughness data were available for DVC
considered here. GDZ, it is expected from past work by Donohue et al. and
Levi et al. have formulated equations for U for YSZ– that of Dwivedi et al. that these dense samples can have
TBCs under both isothermal and gradient cycling conditions. higher toughness than that of porous GDZ.9,36
In this study, these general equations were modified to incor-
porate multiple coating layers as well as their characteristics
(e.g., thickness, modulus). Details of this formulation are (1) Challenges and Future Work
provided in the Appendix, and the resultant calculated The interpretation of data and failure mechanisms presented
energy profiles as a function of thickness are shown in Fig. 7 in this study provide critical insights toward multilayer coat-
(right panel) for the representative microstructures (A–E). In ing design. These preliminary results will require analytical
each of these graphs the failure location and thus, the calcu- and numerical modeling of representative microstructures.
lated U at the failure location (Ufail) are highlighted. The key For instance, the interpretations only consider in-plane
coating properties of interest here are toughness, modulus, strains and toughness, whereas the regions near the rough
and thickness (the latter two captured through the elastic interface will experience out-of-plane strains. This may
energy parameter) of the overall coating and subassembly. explain why the coating E shows lower life as compared to
As a preliminary effort, an attempt was made to reconcile C, despite the high fracture toughness interfacial layer in E,
the above results through this Ufail parameter and further as there is very little through-thickness compliance of the
through an estimation of the energy release rate, Gc.11 This is DVCs. Micromechanical modeling and additional experi-
captured in Fig. 8 through a plot of FCT life versus Ufail ments are needed for enhanced descriptions.
obtained from the above-mentioned formulation. For com- Durability of the coatings was assessed only through FCT
pleteness, this data set also includes FCT results from our testing at one temperature–time cycle. At higher temperatures,
previous work on standard single-layer APS–YSZ, single- sintering may be a more significant factor in coatings that con-
layer DVC–YSZ and the bilayer YSZ–TBCs variant with tain porosity. Additional failure modes will occur during accel-
enhanced toughness at the TGO interface.23 One close vari- erated cycling or gradient testing, as well as through extrinsic
ant of architecture E, marked as E0 , which has a 30 lm mechanisms (erosion, CMAS, etc.). Similarly, past work has
thickness of dense YSZ (condition B) between the YSZ– shown that porous APS–GDZ layers are effective against
GDZ coatings, is also included in the figure. The results indi- CMAS/volcanic and coal ash penetration.17,18 These results
cate that the data clusters into two zones. The central points should be reexamined for multilayers both in isothermal and
are as follows: under gradient conditions. Preliminary burner rig studies on
coating E survived many more cycles than conventional YSZ
1. A general trend of increasing FCT durability is noted
coatings indicating promise for these microstructures. Further
as we move the failure location from within the coat-
quantitative studies are needed.
ing (cohesive) to the TGO–TBC interface (adhesive).
This corresponds to increasing values of Ufail as noted
in Fig. 7 for more durable coatings. V. Summary and Conclusions
2. The higher the toughness of the coating at the failure
Several variants of multilayer ceramic TBCs, based on the
location, the greater the durability. Dense YSZ coat-
YSZ–GDZ system were investigated as potential coatings to
ings generally provide higher toughness than porous
meet emerging TBC requirements, such as increasing turbine
layers or GDZ layers.9,26
3. The YSZ–GDZ bilayer DVC microstructures do not
show improved durability despite their failure within
the high toughness YSZ region near the bond-coat
interface (Ufail
120 J/m2). Similar results were also
noted in our earlier study on the single-layer YSZ sys-
tem, where DVC coatings did not perform as well as
dense-porous bilayer coatings.23 Although a detailed
explanation for this behavior is not available, several
potential explanations are noted: (a) The DVC coat-
ings examined in this study have high modulus
(> 60 GPa), which may contribute to a shorter life. It
may be feasible to improve this performance through
further optimization of DVC crack architecture.36,37
(b) Coatings comprised only of DVC microstructures
may not be able to accommodate out-of-plane strains
which are likely to also participate in the failure pro-
cess (due to the undulating, growing TGO layer).
Coatings with some degree of through-thickness poros-
ity may allow accommodation of out-of-plane strains
associated with TGO growth.
Figure 8 can also be reconciled through Gc estimates for
the various materials and microstructures which to some
extent validate the observations and Ufail calculations. Gc
estimates for the samples that showed failure within the por-
ous GDZ point to values of 25–40 J/m2. These numbers are
in the range of recently reported Gc values 45–50 J/m2 by
Donohue et al. for equivalent porous GDZ.26 Donohue et al.
also reported values of 80–120 J/m2 for APS–YSZ micro-
structures with different levels of porosity. Both YSZ and Fig. 8. Plot of FCT life and Ufail obtained from Fig. 7 for the
multilayer variants tested in this study. Data are also included from
GDZ coatings used in those studies were produced by the
past work on YSZ single layer (porous (PY) and DVC (DY)) and
Stony Brook group.36 The differences could arise due to the bilayer (BY) coatings.23 Suggested values of critical energy release
assumptions made in the Ufail calculations. rates of GDZ coating layers are identified on the graph.
8 Journal of the American Ceramic Society—Viswanathan et al.

temperatures and silicate particulate attack. APS–YSZ–GDZ The mismatch strain between the coating and substrate is
coatings have been designed, fabricated, and tested. A multi- therefore;
layer design achieved through layered manufacturing seeks
durability at an equivalent or greater level of the benchmark eðyÞ ¼ ec  es ¼ ac ðyÞDT  as DT ¼ Dac ðyÞDT
YSZ while meeting new requirements imposed by the harsher
environments. The approach incorporates location-specific
where, Dac (y) = as  ac(y) the relative CTE mismatch
property optimization to simultaneously meet both intrinsic
between the coating layer and substrate.
(oxidation induced delamination, sintering) and extrinsic
The in-plane equibiaxial stress in the coating can be
(erosion/silicate ash attack) failure modes.
expressed as:
FCT results and their interpretation, based on the available
elastic energy formulation, shed light on the durability and
associated failure mechanisms of these complex multilayer Ec ðyÞ Ec ðyÞ
rðyÞ ¼ eðyÞ Dac ðyÞDT
coatings. The results indicate that the porous GDZ layer ð1  mc ðyÞÞ ð1  mc ðyÞÞ
within the coating is prone to premature cohesive delamina-
tion due to its lower toughness compared to equivalent YSZ Therefore, the elastic energy/area (U) in the coating will
microstructures. This failure mode can be suppressed by either be as follows
enhancing the density (toughness) of the GDZ layer or by
moving the GDZ layer away from the bond-coat-top-coat Zy
interface. The results also suggest potential limitation of 1 ðr211 þ r222 Þ
DVCs due to lack of out-of-plane compliance. UðyÞ ¼ dy
2 Ec ðyÞ
Initial design maps are proposed as a guideline for coating 0
fabrication and assessment of functionality. Future experi-
mental and modeling work seeks to clarify the failure mecha- where r11 and r22 are the principal stresses.
nisms and further optimize multifunctional TBCs to meet the Under the plane-strain conditions, as the strain component
conflicting operational demands of gas turbine engines. parallel to the crack front is not released, that is, the U associ-
ated with this strain component is not released. Therefore, the
Appendix U contributing to the crack propagation can be written as,

To elucidate the microstructural contribution to the failure Zy

process, an approach using the elastic energy (U) has been 1 ð1  m2c ðyÞÞr211
UðyÞ ¼ dy
used. The methodology is based on the recent work of Levi 2 Ec
et al. who have developed the basic equations to calculate 0
stored energy for delamination of TBCs.11 This study builds Zy
1 Ec ðyÞ
off this foundation, incorporating strategies to accommodate ¼ ðDac ðyÞDTÞ2 dy
multilayer coatings with differences in layer chemistry and
2 ð1  mc ðyÞÞ2
0
properties. The schematic below illustrates the key variables
considered for the computation of these elastic energy profiles. For simplicity, the Poisson’s ratio of YSZ and GDZ layers
are kept constant, that is, mc(y) = mc. In addition, DT is main-
y=0
tained constant in these calculations. Therefore, the above
Coating
[αc(y), Ec(y), νc(y)] equation can be reduced to:
y=h
To = cycling temp. (1100oC) Zy 
Substrate Trm = room temp. (30 oC) 1 ðDTÞ2 
[αs , Es , νs ]
ΔT = To – Trm (1070 oC) UðyÞ ¼ Ec ðyÞðDac ðyÞÞ2 dy
h = Overall coating thickness 2 ð1  mc Þ2
0

Here, ac (y), Ec (y), and mc (y) are coefficient of thermal expan-

sion, in-plane elastic modulus, and poisson’s ratio, respectively,
of the coating layer at a location y from the coating surface.
Under FCT conditions, the through-thickness thermal gra-
dient is zero. Assuming that the coated specimen is under
stress-free state at the cycling temperature (1100°C), the
strain [ec(y)] accumulated in the coating layer due to a tem-
perature (DT) drop to room temperature (25°C) at a location
“y” from the surface would be as follows:
ec ðyÞ ¼ ac ðyÞDT
The strain in the substrate:
es ¼ as DT
Here, ac and as are the coefficients of thermal expansion
(CTE) of the coating and substrate, respectively.
For simplicity, the temperature dependence of the CTE of
both substrate and coatings and the elastic modulus of coat-
ings can be ignored.11
As for a given layer in the multilayer coating, the parame-
ters Ec (y) and Dac(y) will remain constant, the integral in
the above equation can be expressed in the following discrete
linear equations, and has been used to estimate the elastic
energy profiles for three-layered coatings shown in Fig. 7,
The elastic modulus (Ei) of individual layer in their as-
sprayed form, used for the elastic energy calculations for the
multilayer coatings, was obtained using beam curvature
method and is provided in Table III. Da1, Da2, and Da3 are
the relative CTE mismatch between the coating layer 1, 2,
and 3 and the substrate. The CTE values for GDZ and YSZ
used in the calculation were 9 9 106 and 10 9 106/°C,
respectively. For these considerations, the temperature-
dependent coating and substrate properties, CTE, and elastic

h i2  
DT For layer 3- thickness h3
UðyÞ ¼ 12 E3 Da23 y
hð1m c Þi2     0 ≤ y ≤ h3
DT
UðyÞ ¼ 1
2 ð1mc Þ E3 Da23 h3 þ E2 Da22 ðy  h3 Þ For layer 2- thickness h2h3  y  ðh2 þ h3 Þ
h i2      
DT
UðyÞ ¼ 12 ð1mc Þ E3 Da23 h3 þ E2 Da22 h2 þ E1 Da21 ðy  ðh3 þ h2 Þ For layer 1- thickness h1
(h2 + h3) ≤ y ≤ (h1 + h2 + h3)
 Multilayer Multimaterial TBCs
modulii, are ignored. These assumptions are similar to those
considered by Levi et al.11 Furthermore, the energy/area der-
ivation does not include any energy term associated with the
bending of coating caused by delamination. However, given
that the bending is generally small, the contribution of bend-
ing strain to the elastic energy/area can be considered to be
negligible.
Acknowledgments
This study was supported by the National Energy Technology Laboratory of
US Department-of-Energy under University Turbine Systems Research pro-
gram award DE-FE0004771. We are grateful to Dr.Anand Kulkarni, Siemens
Energy, for providing superalloy substrates and Howard Waller, Saint-Gobain,
for providing powders. We are also grateful to Professors Curtis Johnson,
John Hutchinson Toshio Nakamura, and Herbert Herman for their insightful
comments on the results and critique of the manuscript. Financial support
through the Industrial Consortium for Thermal Spray Technology is acknowl-
edged.
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