Thermal Barrier Coatings Technology: Critical Review, Progress Update, Remaining Challenges and Prospects

International Materials Reviews
ISSN: 0950-6608 (Print) 1743-2804 (Online) Journal homepage: http://www.tandfonline.com/loi/yimr20
Thermal barrier coatings technology: critical

review, progress update, remaining challenges and
prospects
R Darolia
To cite this article: R Darolia (2013) Thermal barrier coatings technology: critical review,
progress update, remaining challenges and prospects, International Materials Reviews, 58:6,
315-348, DOI: 10.1179/1743280413Y.0000000019
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Published online: 18 Nov 2013.
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Thermal barrier coatings technology: critical
review, progress update, remaining
challenges and prospects
R. Darolia*
A comprehensive and integrated review of thermal barrier coatings (TBCs) applied to turbine
components is provided. Materials systems, processes, applications, durability issues, technical
approaches and progress for improved TBC, and our understanding of the science and
technology are discussed. Thermal barrier coating prime reliance and further advances have
been hampered by TBC loss by particle impact and erosion in certain locations of the turbine
blades. Accumulation of low melting eutectic containing calcia, magnesia, alumina and silica
resulting in TBC spallation limits maximum surface temperature. Design methodologies to
address durability and data scatter issues are discussed. Compositions, morphology,
characteristics and performance data for new bonds to achieve longer TBC life are described.
Further reduction in the thermal conductivity of the top layer to minimise the parasitic mass of the
coating on the component is being sought via top layer composition and processing
modifications as well as by alternate ceramic compositions. The progress in these areas is
critically reviewed including processing, stability and durability limitations. The paper also
describes effort to understand various failure mechanisms including modelling and simulation.
Keywords: Thermal barrier coatings, Bond coat, Yttria stabilised zirconia, Low thermal conductivity, EB-PVD, CMAS, Erosion, Impact, Design
methodology
Introduction surpass other material technologies advances including

single crystal Ni based superalloys (Fig. 2) achieved
Application of thermal barrier coatings (TBCs) on over a 30 year period. The initial applications were
cooled turbine engine components such as combustors, driven by the need to suppress component degradation
high pressure turbine (HPT) blades and HPT nozzles is due to excessive surface temperatures in combustors and
increasing in commercial and military jet engines. This some selected turbine aerofoils experiencing oxidation
trend will certainly continue because the insulating damage. In spite of significant improvements, TBCs are
capability of TBC enables higher operating temperatures yet considered ‘prime reliant’ because of local spalls and
and/or permits a reduction in the required amount of reduction in thickness, and full utilisation has eluded
cooling air, thereby improving efficiency, reducing turbine designers. Research and technology develop-
emission and increasing thrust/weight ratio. Power
ments have been carried out for the last two decades to
generation turbine engines are also increasingly using
address performance and reliability while extensive
TBC. Thermal barrier coatings are also slated to be used
research is being carried out for higher temperature
on components made out of ceramic–matrix composites
applications beyond the baseline system, and for TBC
(CMCs).
with lower thermal conductivity.
A schematic of a TBC system on an HPT blade is
Thermal barrier coatings are complex, multilayered
shown in Fig. 1. Thermal barrier coatings are currently
and multimaterial systems with many variants related to
used to provide metal temperature reductions of up to
composition, processing and microstructure. There are
y100uC (Fig. 1b), while potential benefits are estimated
to be greater than y200uC. Factors that determine over 400 publications on this subject. This review paper
temperature reductions include part geometry and will describe the currently used TBC materials systems
location, heat flux, heat transfer coefficients, backside and summarise our current understanding of the science,
cooling air, TBC thickness and thermal conductivity. technology and failure mechanisms. Emphasis will be
The temperature benefits are highly significant and placed on engineering application aspects to draw on
the author’s vast experience directing TBC research at
a major aerospace company in collaboration with many
(Retired) GE Aviation, 7377 Overland Park Court, West Chester, OH universities and national laboratories. References select-
45069, USA ed based on relevance and scientific value are provided.
*Corresponding author, email [email protected] Recent review papers1–10 capture various aspects of the
ß 2013 Institute of Materials, Minerals and Mining and ASM International

Published by Maney for the Institute and ASM International
DOI 10.1179/1743280413Y.0000000019 International Materials Reviews 2013 VOL 58 NO 6 315
Darolia Thermal barrier coatings technology
1 a An HPT blade coated with TBC. TBC components (bond coat and top coat) are shown with temperature drop though
the thickness of TBC. b An example of temperature drop in an HPT by TBC application
TBC technology and provide excellent additional back- Thermal barrier coating application
ground. The author has also relied heavily for insight for
his research on papers in five conference proceedings Thermal barrier coatings are applied to components
‘Science and technology of zirconia, Volumes I–V’11–13 which are internally cooled by directing air though
that are excellent sources for fundamental information channels. Designs with TBC coated parts consider part
on sintered or hot pressed ‘bulk’ zirconia based ma- configuration and thickness, heat flux, heat transfer
terials. The author has found that the properties and coefficients, combustion and turbine inlet temperatures
behaviour in the coating form are quite similar to those and total cooling air allowed by the system engineers. To
of the bulk materials. minimise adding excessive mass and cooling hole
closure, thinner coatings are preferred.
Main components in propulsion turbine engines where
TBC is applied are shown in Fig. 3. The combustor liners
were the first components to routinely use TBC applied
by an air plasma spray (APS) process. Thermal barrier
coatings on aeroturbine blades are applied by an electron
beam physical vapour deposition (EB-PVD) process. The
larger components of the power generation turbines
(combustor, several stages of nozzles and blades, referr-
ed to as buckets) predominantly use the APS process
because of their larger size. Thermal barrier coating
thickness on aerorotating parts is typically 100–250 mm
compared to 250–500 mm on the stationary components
such as shrouds, nozzles and combustor parts. In these
parts, both EB-PVD and APS processes are consider-
ed. The rationale for the process choices will be describ-
ed in the section on ‘Processing methods for top coat’.
Component designs with TBC have evolved from simply
applying a thin layer of TBC on existing components to
2 Turbine temperature advancement with TBC compared sophisticated design practices based on laboratory
with Ni based superalloys test data and observations from the field returned
316 International Materials Reviews 2013 VOL 58 NO 6

3 Examples of TBC application in propulsion engines. Combustor liners, HPT blades and vanes are coated with TBC
hardware. It is also planned to use TBC on components fabrication and most notably during use, these compo-
made out of CMCs. nents interact chemically and mechanically. Dynamic
relationships between these layers control the durability
of TBC. It must be pointed out that the composition
Constituents of TBC system and the microstructures of these layers are continually
changing during service. Properties measured in the as
Thermal barrier coatings are primarily a two layer fabricated condition could lead to misleading con-
system consisting of a porous (porosities generally in the clusions. Interfaces between the layers also play a
range of 10–25%) ceramic top coat layer comprising significant role. An additional layer, about 0?05–0?1 mm
zirconia (ZrO2) ‘partially stabilised’ with about 6–8 thick, referred to as ‘mixed zone’ (Fig. 6),14 forms
wt-% (y3?4 to 4?5 mol.-%) yttria (Y2O3) generally between the TGO and YSZ lop layer during preheating
referred to as 7YSZ or YSZ, and an alumina forming and top layer deposition by the EB-PVD process. This
bond coat layer, primarily of NiCoCrAlY or NiAlPt layer consists of zirconia and yttria particles dispersed
based compositions. Expanded views of an EB-PVD in the TGO matrix.14 It is likely that this layer
TBC microstructure can be seen in Fig. 4a and b. There influences TGO/TBC adhesion, though further studies
are four main components with unique functions that are warranted.
influence TBC life as shown in Fig. 5:
(i) top coat layer: provides thermal insulation Yttria stabilised zirconia top coat
(ii) thermally grown oxide (TGO) layer: provides Yttria stabilised zirconia has high melting point (not of
bonding of TBC to bond coat and slows much significance to current usage), low thermal
subsequent oxidation conductivity, high oxygen permeability and relatively
(iii) bond coat layer: contains the source of elements high coefficient of thermal expansion compared to other
to create TGO in oxidising environment and oxides and the 6–8 wt-%Y2O3 composition is relatively
provides oxidation protection stable during high temperature exposure. An important
(iv) superalloy substrate: carries mechanical load. attribute of YSZ for turbine design is that thermal
Each of these components has markedly different conductivity is essentially temperature invariant. Another
physical, thermal and mechanical properties that are important attribute of YSZ is that ZrO2 and Y2O3 have
strongly affected by processing conditions. During similar vapour pressures allowing deposition of YSZ with
International Materials Reviews 2013 VOL 58 NO 6 317

In addition to enhancing oxidation resistance, TGO

serves to bond the ceramic top coat to the substrate/
bond coat system. Thickening and buckling of the TGO
scale and subsequent cracking is one of the several
failure mechanisms of TBC. The adhesion and mechan-
ical integrity of the TGO scale is dependent on the
composition and impurity levels of the bond coat.
A pseudobinary ZrO2–Y2O3 phase diagram modified
by Levi1 is shown in Fig. 8. In this figure, the Y2O3
content in the x axis is labelled as mole fraction YO1?5
since wt-%Y2O3 roughly translates to 0?5 mol.-%Y2O3
in ZrO2–Y2O3 compositions. Numerous modifica-
tions to precisely define phase boundaries have been
proposed.15 As opposed to the equilibrium tetrago-
nal phase t (t-ZrO2), a closely related non-equilibrium,
metastable phase t (t’-ZrO2) is obtained in the as
deposited TBC due to high rate deposition by either
APS or EB-PVD. This phenomenon is highly desirable
for achieving optimised lives. Though thermodynami-
cally driven to partition into equilibrium tzc, the t’
phase does not transform easily to tetragonal and
monoclinic phases under normal circumstances until at
least y1200uC,16,17 which is adequate in current use.
Stability will become an issue for higher temperature
operations. Transformation to monoclinic phase at
lower Y2O3 contents is undesirable due to significant
volume change (y3 to 4%) causing cracks and TBC
spallation. Higher Y2O3 contents have been shown to
have lower fracture toughness, a possible cause of
lower erosion and impact resistance to be discussed
later.
During the initial TBC development originating at
NASA during the 1970s, it was demonstrated by
Stecura18–20 in APS TBC that about 6–8 wt-% (y3 to
4?5 mol.-%) Y2O3 addition to ZrO2 provided the longest
TBC thermal cycle life in burner rig tests, even though
ZrO2 was not fully stabilised. This conclusion was
drawn with different test temperatures and various bond
coat compositions. Time to first crack related to
4 a TBC microstructure with four components (Ni based subsequent TBC spallation in thermal cycle tests as a
superalloy, bond coat, TGO and YSZ top coat). Note function of Y2O3 content and four composition varia-
the columnar microstructure of the zirconia coating. tions of NiCrAlY bond coat is shown in Fig. 9. Later,
The white band is an interdiffusion layer between the Stecura evaluated Yb2O3 containing ZrO2 and con-
Al rich bond coat above and the Ni rich superalloy. b cluded that maximum life is obtained between 12?4 and
Expanded view of zirconia top coat 14?7 wt-%Yb2O3. Thermal barrier coating life decreased
very rapidly at concentrations exceeding these optimum
uniform composition by the EB-PVD process. This is values. It must be pointed out that, after extensive
unlike alternate TBC materials containing oxides of research for the last two decades to identify better top
different vapour pressures yielding undesirable, non- coat compositions, 6–8 wt-%Y2O3 content in ZrO2
uniform and layered structures. Yttria stabilised zirco- continues to be optimum. Alternate oxide stabilisers
nia is applied either by APS or EB-PVD techniques. evaluated primarily to reduce thermal conductivity have
These processes make YSZ ‘strain tolerant’ by deposit- shown TBC lives to be inferior to YSZ to be discussed in
ing a structure that contains numerous pores, gaps, a later section. To date, YSZ continues to be a material
microcracks and interfaces (Fig. 7). Strain tolerant system of choice. It is interesting to note that Engel
structures are necessary to accommodate thermal et al.21 observed on ‘single-crystal’ ZrO2 that maximum
expansion misfit between the substrate and top layer. fracture toughness and fracture strength are obtained
The high oxygen permeability of the YSZ requires that around 4–5 wt-%Y2O3 (Fig. 10).
the bond coats be highly resistant to oxidation and hot It has been proposed by Virkar22,23 and Baither et al.24
corrosion attack. The bond coat compositions are rich based on experiments on sintered ZrO2–3 mol.-%Y2O3
in aluminium to form a protective, TGO scale of a- specimens that the t’ phase microstructure consists of
Al2O3, typically 1–6 mm. The NiCoCrAl (Y, Hf, Si and large grains on the order of 100 mm or greater. These
Re) type overlay bond coats, typically 100–200 mm, are grains contain very small domains (y0?1 mm) arranged
mainly based on the c-Ni and b-NiAl phases. The Pt in three mutually orthogonal orientations in each grain
platinum modified diffusion aluminide bond coats, making t’ phase extremely non-transformable. How-
typically 50 mm, mainly consist of a b-NiAl–Pt phase. ever, these domains reorient under stress that provides

5 Thermal barrier coating consists of four main components with unique functions that influence TBC life
high toughness, a phenomenon called ferroelastic domain Processing methods for top coat
switching. Mercer et al.25 and co-workers have argued Thermal barrier coatings are porous with overall
based on indentation and TEM studies that the nuclea- porosities generally in the range of 10–25%. In the EB-
tion of domains contributes to the toughness of YSZ PVD process, an ingot (or ingots) of a YSZ composition
TBC, and not the switching. This assertion was drawn by is vapourised in a vacuum chamber using a focused
examining the material in the wake of an indentation electron beam. Before deposition, the samples are pre-
induced crack by using TEM and by interferometry. heated to y1000uC in a low oxygen partial pressure
Yttria stabilised zirconia compositions are thermally environment resulting in the growth of a thin (y0?05 to
stable up to the current use temperatures of TBC which is 0?1 mm) TGO layer. The parts are coated by manipula-
y1200uC. Yttria stabilised zirconia has shown minimum tion within the vapour cloud on the preheated substrate
partition to the cubicztetragonal phases which in turn surface. The EB-PVD process is especially effective in
transform to tetragonalzmonoclinic phases respective- tailoring microstructures and inplane modulus. For
ly, upon cooling. It is another desirable attribute since example, EB-PVD can yield a very desirable columnar
destabilisation and subsequent monoclinic formation can microstructure (Figs. 7 and 11) to result in a low inplane
lead to TBC spallation. Investigation on the thermal modulus that provides strain accommodation for the
stability of YSZ and ZrO2 containing various stabilisers coefficient of thermal expansion mismatch between the
has been conducted more recently by Rebollo et al.16 metallic substrate and the ceramic top coat. The air
At higher temperatures, in addition to destabilisation, plasma spray process yields a microstructure with
sintering can modify pore structure influencing thermal horizontal splats of YSZ (Fig. 11). The interfaces/gaps
conductivity as well as strain tolerance. between the splats provide additional reduction in
6 a TGO microstructure, predominantly a-Al2O3 and b mixed zone of a-Al2O3zZrO2

8 The zirconia rich corner of the ZrO2–YO1?5 binary phase

diagram. Yttria stabilised zirconia composition and
operating temperature range are shown by the hatched
region. The tetragonal prime phase is metastable within
the To bounds shown as dashed lines superimposed
on the phase diagram (courtesy: Professor Carlos Levi,
UCSB)
roughness requirement, line of sight versus non-line of

sight characteristics and degree of cooling hole closure.
The EB-PVD process provides longer TBC life,
smoother coating with excellent composition and thick-
ness control, and causes minimum cooling hole closure.
This process is preferred for blades and vanes in spite of
much higher cost compared to the APS processes.
a column gaps; b feathers on columns; c porosity in Air plasma spray processes are used for combustor
columns due to rotation parts, HPT shrouds and on most power generation
7 Types of TBC porosity components due to lower cost and requirement for
thicker coatings. A variation of the APS process that is
thermal conductivity and thermal expansion compliance increasingly being used is ‘dense vertically cracked’
with the substrate. The pore structure characteristics of (DVC) TBC coating process.29 Vertical cracks are
EB-PVD and APS are schematically shown in Fig. 12 introduced to provide strain tolerance and serve similar
(reproduced from Ref. 26). Various versions of the function as intercolumnar gaps in the EB-PVD coatings
plasma spray processes are used as an alternative to at much lower cost. However, the performance is
the expensive EB-PVD process. Excellent reviews of the compromised in this lower cost version of the EB-PVD
APS process and processing parameters, and the control process.
of coating characteristics and properties are provided by Promising newer processing methods that are attemp-
Sampath.26,27 During preheating and top coat depositing to compete with EB-PVD and APS include directed
tion, and during subsequent heat treatments, the bond vapour deposition, a variation of the EB-PVD process
coat generates an adherent a-alumina layer (TGO) be- where a supersonic gas jet is used to direct vapours onto
tween the bond coat and the YSZ top coat. Forma- components being coated to increase process efficiency
tion of this a-alumina of optimal thickness and and deposition rate. The process acts as a non-line of
crystallography is critical to achieve reproducible TBC sight process, and is able to coat multiple components
life and prevent premature spallation of the TBC. A with complex geometry.30–32 Composition uniformity
TGO thickness of about 0?3–1?0 mm is considered and microstructural flexibility are other beneficial
optimum right after deposition.28 The TGO thickens attributes. Suspension plasma spray or liquid solution
during the TBC use, eventually contributing to TBC precursor plasma spray33–35 creates microstructures with
spallation. Thermal barrier coating failure mechanisms high segmented crack density and finer pores for
are discussed in the section on ‘Temperature and ther- reduced thermal conductivity and improved thermal
mal cycle dependent failure’. cycle performance. The process employs suspensions of
Process selection considers performance, capital cost, submicrometre particles as feedstock. This circumvents
per-part process cost, thickness requirements and con- flow issues with finer particles in a powder feedstock,
trol, composition requirements and control, surface thereby, improving process efficiency. Microstructure

9 Time to first crack and subsequent TBC spallation in a thermal cycle test as a function of Y2O3 content for APS TBC
(Stecura18–20)
and composition flexibility are two other advantages. A experience, design philosophy, performance and cost.
recent review of the developments in this technology is Although designed originally for environmental resis-
provided by Killinger et al.36 tance, these coatings have been used as bond coats for
TBC applications without any specific composition
Bond coat modifications and process development.
Before introduction of TBC, turbine blades and vanes The MCrAlX type bond coats usually contain (in
were protected from oxidative and corrosive environ- wt-%) 15–25%Cr, 10–15%Al and 0?2–0?5%Y, and con-
ments with either diffusion coatings such as single phase, sist of a b-NiAl phase in a c-Ni matrix. These coatings,
simple, b-NiAl or Pt modified b-NiAl or two phase typically 100–150 mm thick, are applied using a variety
overlay czb MCrAlX coatings (where M represents Ni of overlay processes: APS, high velocity oxyfuel, low
or Co and X represents Y, Hf, Si, or other minor pressure plasma spray, cathodic arc/ion plasma deposi-
additives such as Re). The choice between these coating tion or EB-PVD. The overlay coating processes are
types by turbine engine manufacturers was based on about 2–4 times more expensive than the diffusion
10 Flexure strength and fracture toughness of ZrO2 single crystals as a function of Y2O3 content (Engel et al.21)

a EB-PVD; b APS; c DVC

11 Thermal barrier coating top coat microstructures
processes, but offer much greater control of the coating between the alloy and the b-NiAl layer. A typical
composition since the coating composition is dictated microstructure of TBC with a b-NiAl type bond coat
essentially by the composition of the coating source. and a TGO layer between the bond coat and the YSZ
This attribute provides flexibility in depositing bond top layer is shown in Fig. 4a.
coat layers of various different chemical compositions. It must be strongly emphasised that environmental
In actual practice, a knowledge of the vapour pressure, coatings form and reform the TGO layer as the coating
deposition efficiency and spatial distribution of all the is thermally cycled. In TBC applications, TGO spalla-
chemical elements of the coating is required. The b-NiAl tion leads to TBC spallation. A significant level of
bond coats contain (in wt-%) 20–30%Al, and are understanding has been developed over the last two
generally applied by a diffusion process. Electroplating decades on various stages of TGO formation, growth
of Pt on the surface of the alloy precedes the diffusion and adhesion. The effects of major elements (aluminium,
cycle in the Pt modified b-NiAl bond coats. The chromium and platinum) and minor elements additions
diffusion processes enrich the component surface with (Y, Hf, Zr, Si, Pt and Re) have been studied extensively
Al. The composition of a diffusion coating is dictated by in bulk alloys and coatings. Of these, additions of small
thermodynamic and kinetic constraints, and there are amounts of Hf, Y, Zr, Si and the elements (e.g. Ti, S, Hf
limitations on what multicomponent compositions can and W) diffusing into the coating from the substrate
be deposited in reproducible and cost effective manner. play a critical role.6,37–59 A thin layer of Pt over a grit
The thickness is typically limited to about 40–60 mm. blasted NiCoCrAlHfSi coating surface has demon-
The b-NiAl coatings consist of an interdiffusion zone strated a beneficial effect,44 though, this observation
typically about the thickness of the top layer sandwiched would have limited industrial application due to high
12 An illustrative description of microstructures of TBCs across length scales. The defect architectures of plasma
sprayed coatings are differentiated from those of EB-PVD coatings26

cost of Pt. The effect of grit blasting,57 preoxidation58

and post-oxidation60 has been studied. Some of these
modifications alter transformation kinetics of transient
alumina such as h-Al2O3 to a-Al2O3, faster establish-
ment of a-Al2O3 being desirable.59 A remarkable effect
on initial stages of oxide formation, transformation and
growth kinetics has been demonstrated by Gleeson when
Y, Hf and Si are added synergistically (codoping) at very
low levels (Fig. 13).61 An excellent summary of research
on the oxidation mechanism and bond coat composi-
tions is provided by Gleeson.5 Impurities such as S and
C in the starting materials and introduced during
processing have a critical role on TGO scale adhesion,
sometimes leading to infant mortality. The impurity
effect will be discussed in section TBC scatter. A recent
review on alumina scale formation is given by Heuer
et al.10
Thermal barrier coating operating at higher tempera-
tures will require improved bond coats capable of 13 Synergistic beneficial effect of Hf, Si and Y in a b-
operating at higher temperatures. This is especially true NiAl coating composition61
if TBCs are used as a prime reliant coating. Localised
TBC loss due to foreign object impact will probably be issue, Rickerby et al.63,64 and Gleeson et al.65 have
difficult to avoid. In this case, TBC loss will expose and developed lower aluminium containing bond coats
rapidly oxidise the bond coat, causing rapid degradation chemically compatible with the Ni based superalloy
of underlying substrate. However, it must be recognised substrate. Rickerby applies a thin layer of Pt followed by
that bond coat materials and the underlying substrate a diffusion heat treat to create a Pt modified czc9
have similar thermal conductivities, and, therefore, coating layer. With investigation of phase equilibria at
improvement in bond coat temperature capability will 1100 and 1150uC in the Ni–Al–Pt system, Hayashi
be limited by the creep strength of the substrate. It et al.66 have identified czc9 bond coat compositions that
should be pointed out that the extent of coating/ have demonstrated oxidation performance matching the
substrate interdiffusion will increase as the operating conventional MCrAlX and a b-NiAl coating. To address
temperature of the turbine increases. An ideal bond coat the high cost of Pt, Gleeson61 has developed coating
should have the following attributes: compositions with lower Pt levels in combination with
(i) oxidation resistance by forming a slow growing, low level additions of Hf, Y and Si.
non-porous, continuous and adherent a-Al2O3 A modified version of a b-NiAl bond coat has been
scale layer (TGO) developed by Darolia et al.67–71 at GE Aviation using
(ii) minimal interdiffusion with the substrate to overlay processes such as ion plasma deposition, APS
minimise Al depletion and upward diffusion of and EB-PVD. The bond coat is predominantly a b
refractory elements and impurities such as S, phase, and contains (in wt-%) about 20–25Al, 5Cr, 0?25–
and avoid formation of ‘secondary reaction 0?5Zr and/or 0?25–0?5Hf. The bond coat was designed
zone’ (SRZ) below the bond coat on the newer based on the author’s extensive knowledge gained
generation of Ni based superalloys during the development of NiAl based intermetallic
(iii) minimal strain misfit with the substrate result- alloys for turbine applications.72–74 A large library of
ing from thermal expansion differences NiAl compositions is available in single crystal form
(iv) high creep strength to suppress plasticity/rum- to evaluate oxidation resistance and TBC coated life.
pling effect (to be discussed in the section on Compositions were selected based on the knowledge
‘Thermal barrier coating damage and degrada- of strengthening behaviour in single crystal NiAl to
tion mechanisms’) develop an oxidation resistant and ‘strong’, creep re-
(v) compatibility with the processes to coat internal sistant bond coat. Thermal expansion data were used
cooling passages of the blade to match thermal expansion of the coating with the
(vi) minimum use of Pt and other expensive underlying substrate. Reactive element doped NiAl
elements such as Ru, Re and Pd coupons coated with TBC and tested to spallation
(vii) minimally affected by impurities such as S, C, failure showed that minor additions of Hf or Zr to NiAl
etc. provided substantial increases in the TBC spallation life
The newer generation Ni based superalloys contain high as seen in Fig. 15. The improvement was linked, in part,
levels of rhenium (Re) and relatively higher levels of Al. to increase in the room and high temperature strengths
The higher levels of alloying elements tend to cause provided by solid solution strengthening by Cr in
microstructural instability. Specifically, Re has been solution within the b phase matrix of the coating and
identified as a key alloying element promoting an SRZ dispersions of a-Cr particles, and by the b9-Heusler
layer beneath the coating layer (Fig. 14). The SRZ layer phase Ni2Al(Hf, Zr) precipitates within the b phase
consists of a c’ matrix containing c and P phase (TCP) matrix of the coating (Figs. 16–18). In addition, TGO
needles (as opposed to a c matrix containing c’ of a scale adherence was provided, in part, by Zr or Hf oxide
typical Ni based superalloy). The SRZ formation has pegging.
been demonstrated to be detrimental to the creep and A programme was initiated to translate the improved
rupture properties of the alloys.62 To address the SRZ performance of the TBC coated NiAl single crystal

14 An SRZ is created between the coating and a high Re

15 Thermal barrier coating spallation life for TBC coated
containing Ni based superalloy
single crystal NiAl compositions containing small
amounts of Zr, Hf and Ti (compositions in at-%) com-
alloys into bond coat compositions. The result was pared with stoichiometric NiAl (50/50)
development of an overlay b phase NiAlCrZr bond coat
strengthened to prevent rumpling. As an example, rotating parts such as turbine blades. For higher gas
dependence of TBC life in a NiAlCrZr bond coating path temperatures, thicker coatings required to maintain
as a function of Zr content is shown in Fig. 19. Thermal constant metal temperatures are undesirable. Hence,
expansion match with the substrate is demonstrated as considerable effort has been directed for the last two
shown in Fig. 20. In addition to increased oxidation decades towards reducing thermal conductivity by one-
resistance and TBC life in laboratory and engine tests, third to one-half. Thermal conductivity k (W m21 K21)
the bond coat has demonstrated reduced wall consump- is often calculated from measurements according to the
tion of the turbine blade. Reduced rumpling resulted in formula k5arCp, where k is the thermal conductivity, a
underlying substrate running cooler by maintaining a is the thermal diffusivity measured by a flash diffusivity
smooth air flow boundary layer on the surface (Fig. 21). measurement technique, r is the density of the coatings
The NiAlCrZr bond coat has been introduced in GE and Cp is the specific heat.
Aviation’s new engines such as GEnx for the Boeing 787 In addition to the composition of the starting
Dreamliner airplane. material, thermal conductivity is highly influenced by
Diffusion barriers the density and microstructure (e.g. defect structure,
Owing to increased interdiffusion expected in higher porosity, grain boundaries/interfaces, splat boundaries
temperature applications, and to avoid SRZ formation, in APS TBC and second phases) of the coating. It is also
extensive development effort has been made to identify important that the deposited microstructure, with the
diffusion barrier layers applied between the bond coat optimal porosity level, defect structure and interfaces, be
and the substrate to block interdiffusion. Multilayer stable during high temperature exposures during the
bond coats incorporating a combination of diffusion and engine operation. Some of the highest thermal con-
overlay processes have been evaluated. Diffusion barrier ductivity reductions have been achieved with highly
materials have included metallic (i.e. Re and Ru), in- porous microstructures. Thermodynamically unstable
termetallic (i.e. sigma and laves phases) and oxides.75–78 structures experience a loss or redistribution in vacancy
Majority of the work has been on Ru containing layers. concentration, and coarsening of micropores as well as
Ru and Re are demonstrated to be effective barriers, but sintering during exposure. Such changes cause increase
possess poor oxidation resistance. Alloying to adequately in thermal conductivity by reducing the number of
impart oxidation resistance to Ru and Re has not been microstructural sites available to scatter the thermal
demonstrated. Oxide barriers have durability issues wave (phonons). Approaches to lower the thermal
during thermal cycling. So far, a diffusion barrier layer conductivity have included the following: YSZ composi-
that meets all of the critical requirements, namely, good tion modifications including partial or total substitution
adhesion (due to thermal expansion difference), oxidation of Y2O3 by codoping with rare earth oxides to increase
resistance (or does not oxidise such as an oxide layer), crystalline lattice disorder and oxygen vacancies by
TBC durability during thermal cycling and practical and varying the type and amount (i.e. ionic radius or mass)
cost effective processing is yet to be developed, and of stabilisers; process modifications for microstructure
continues to challenge materials scientists. changes including porosity increase; and alternate
ceramic systems: the efforts have been mainly focused
Thermal conductivity lower than YSZ with plasma spray processing since most alternate
ceramic compositions are difficult to deposit uniformly
(low k TBC) by EB-PVD. Excellent reviews of the scientific basis for
There is a significant design benefit in lowering the approaches for reduced conductivity are provided by
thermal conductivity and density of the top coat to Klemens and Gell,79 Clarke80 and Mévrel et al.81 Before
reduce parasitic mass of the coating especially on the we discuss the progress made with these approaches, the

16 Effects of small amount of alloying additions on the

,100. room temperature fracture strength of single 18 Microstructure of a NiAlCrZr bond coat composition
crystal NiAl compositions showing Cr particle dispersions and b’ precipitates
that contribute to strengthening of the bond coat
author would like to point out the lessons learned
directing this effort over 20 years. APS TBC can be as low as 0?8 W m21 K21, the
(i) Different top coat ceramic compositions result splat boundaries being major contributor for
in different as deposited microstructures and reduction.
density, and it is difficult to separate composi- (ii) The alternative oxide stabilisers to ZrO2 have,
tion and microstructure effects. Therefore, in most cases, vast vapour pressure differences
claims for lower thermal conductivity with a as shown in Fig. 22 (reproduced from Schulz
given composition should be analysed carefully. et al.87). The vapour pressure difference yields
The theoretical/intrinsic thermal conductivity of undesirable layered and non-uniform micro-
YSZ is approximately 2?2 W m21 K21 and is structures, at least in the case of EB-PVD
linked to its composition and phase structure. It processing. Dual source processing and other
is the processing induced microstructure, por- processing advancements can overcome this
osity being a major contributor, that causes a issue, in turn, adding to complexity and cost.
25–50% reduction in conductivity from the (iii) It has been demonstrated that the ‘low k TBC’
theoretical value. In case of EB-PVD, proces- compositions, unlike YSZ, do not ‘bond’ to
sing parameters such as surface preparation, TGO. Lower interface toughness is considered
substrate temperature, processing temperature to be the cause, though, further studies are
and chamber pressure including oxygen partial warranted. This lack of bonding requires a YSZ
pressure, and deposition rate, angles and rota- ‘bonding’ underlayer below the new ceramic top
tion significantly affect microstructure (e.g. coat. This requirement adds to processing steps
volume fraction, geometry and distribution of and associated process reliability, and cost. This
the pores, column gaps and interfaces).82–86 It is certainly an undesirable requirement.
should be mentioned that the conductivity of
17 Improvement in rupture strength (life) at 982uC/

124 MPa in the ,110. orientation with alloying addi- 19 Thermal barrier coating spallation life results from fur-
tions such as Hf, Ti and Ta to a NiAl (50Ni–49?3Al– nace thermal cycle testing of NiAlCrZr coatings pro-
0?5Hf–0?2Ga) single crystal composition. The composi- duced by EB-PVD method as a function of Zr
tions are shown in at-% content68

engine operating temperatures. Phase stability

of new TBC compositions has been studied by
Rebollo et al.,16 Cairney et al.88 and Kakuda
et al.89 During use at the operating tempera-
tures of y1200uC, the feather-like features of
EB-PVD coatings progressively disappear and
transform into a microstructure of dispersed
pores. Additionally, the columns join together
to form blocks separated by cracks perpendi-
cular to the interface. These so called ‘aging’
effects have been shown to increase thermal
conductivity.90,91 Loss of strain compliance
leading to TBC spallation is also a critical issue.
(vii) Radiative heat transfer from the gas, currently a
minor contributor to the blades, could signifi-
cantly increase in higher temperature turbines.
Development of erosion and impact resistant
20 Coefficient of Thermal Expansion match between a reflective layers will become an area of future
second generation single crystal Ni based superalloy development.
(Rene9 N5) and NiAlCrZr bond coat (courtesy
Professor Kevin Hemker, JHU, unpublished work) Yttria stabilised zirconia composition
modifications including codoping with other
(iv) The particle erosion and impact resistance stabilisers
of baseline YSZ, discussed in the section on Incorporation of Y2O3 to the ZrO2 fluorite crystal
‘Erosion and impact damage’, need improve- structure creates a defect structure (solute Y atoms and
ment based on field observations. Unfor- oxygen vacancies). In baseline YSZ, one oxygen vacancy
tunately, the ‘low k TBC’ compositions have is created for every two yttrium cations. The amount
demonstrated, in most cases, inferior resistance and stability of this defect structure and the porosity
assumed due to their reduced fracture tough- created during deposition control the as deposited and
ness. Understanding the relationship between exposed thermal conductivity acting as phonon scatter-
impact resistance, composition and processing ing centres. In baseline YSZ, the easiest approach would
will be key to developing a well balanced, next be to vary the Y2O3 content.
generation ‘low k TBC’. Substitution and addition of ternary and high order
(v) There is significant scatter and error in the laser dopants of metal (M) oxides of the form MO, MO2 or
flash diffusivity measurements primarily due to M2O3 with varying ionic radius or atomic mass have
errors in thickness and density measurements. been evaluated while maintaining the t’ phase. There are
Therefore, reported thermal conductivity values over 50 issued patents related to low conductivity with
are sometimes suspect. subtle differences in compositions and processing.
(vi) Microstructural and phase stability will become Developments with the most relevance, uniqueness and
important issues when TBCs are used at higher impact are discussed next.
21 Engine test results with NiAlCrZr bond coat compared with NiAlPt bond coat. a NiAlPt bond coat and b NiAlCrZr
bond coat. Bond coat rumpling seen in the NiAlPt bond coat c is absent in the NiAlCrZr bond coat d. Lower oxida-
tion in the NiAlCrZr bond coat and retention of czc’ structure in the underlying superalloy was also observed

22 Vapour pressures of various oxides for potential additions to zirconia (Schulz et al.87)
Numerous codoped YSZ compositions have shown larger reductions in conductivity than those found with
lower thermal conductivity. One of first research to Y alone or codoped with only one of the cations at
lower thermal conductivity conducted with ceria stabi- comparable total dopant concentration. Higher thermal
lised zirconia (CeSZ) as an alternate to YSZ or added to stability and TBC thermal cycle life comparable to that
YSZ demonstrated lower thermal conductivity.92 Pro- obtained with YSZ TBC have been shown.
cessing due to vapour pressure differences and inferior
erosion resistance has been major issue on the ceria Yttria stabilised zirconia with HfO2 additions
containing TBC. In spite of this limitation, development Yttria stabilised zirconia compositions containing haf-
in this area is continuing.87 Rickerby and Tamarin,93 nia have also been evaluated by Peters et al.,4 Zhu
Nicholls et al.,94,95 Rigney and Darolia96 and Schulz and Miller,102 Gorman et al.,103 Singh et al.104 and
et al.97 have investigated dopants such as NiO, MgO, Matsumoto et al.,105 since the crystal lattice of zirconia
CaO, Nd2O3, Gd2O3, Er2O3,Yb2O3, Dy2O3, CeO2, SrO, and hafnia is isomor phous, and a complete solubility
Sc2O3, Eu2O3, Fe2O3, In2O, Sm2O3, Ho2O3, HfO2 and exists. Yttria stabilised zirconia ingots generally contain
Ta2O5 with various combinations and levels. Majority of about 1–2 wt-% hafnia. Larger additions of hafnia (e.g.
these dopants have shown to reduce thermal conductiv- 40 wt-% zirconiaz40 wt-% hafniaz20 wt-% yttria) fur-
ity from about 25 up to 40%. A clear trend, however, of ther reduce thermal conductivity but the largest effect of
the effects of ionic radius and/or mass of the dopants is 30% reduction at high temperature was reported for
difficult to establish due to scatter in data, mainly due to zirconia free 27 wt-% yttria stabilised hafnia.104 The
processing difficulties, microstructural differences in latter showed a much denser and fine columnar mic-
the as deposited coatings and errors associated with rostructure and was less susceptible to sintering. Similar
conductivity measurement techniques. favourable lower shrinkage rates have been found for
An interesting ‘multicomponent defect cluster’ con- EB-PVD 7?5 wt-% yttria–hafnia samples that were not
cept investigated by Zhu and Miller98–101 has also shown rotated during deposition. Peters et al.4 have demon-
to lower thermal conductivity. Thermal barrier coatings strated similar results with 32 wt-% yttria–hafnia with-
with oxides clusters of ZrO2–Y2O3–Nd2O3–Yb2O3 out notable processing problems with nearly the same
(Gd2O3, Sm2O3 and Sc2O3) have been investigated on composition in both ingot and coating.
both plasma sprayed and EB-PVD coatings. In one
study, the effect of the cluster dopant type with Pyrochlore type (A2B2O7) structures
compositions ranging from YSZ only, YSZ plus a single Unlike the t’ YSZ based compositions, a new class of
Nd2O3 or Yb2O3 dopant, YSZ plus both the Nd2O3 and low conductivity compositions based on the pyrochlore
Yb2O3 in varying relative concentrations was investi- type zirconate structure [(Gd, Eu, Sm, Nd, La)2Zr2O7]
gated. It was observed that ZrO2–Y2O3 with paired have emerged, of which Gd2Zr2O7, La2Zr2O7 and
dopant additions (Nd2O3zYb2O3) had lower thermal Sm2Zr2O7 have been studied the most.106–110 Con-
conductivity than those of YSZ, or YSZ with a single ductivity reductions up to 50% have been reported. In
cluster dopant, Nd or Yb. The coatings with equal addition to lower conductivity, Gd2Zr2O7 TBC has been
amount of cluster dopants (Yb2O3/Nd2O351) often claimed to provide calcium–magnesium–alumino-sili-
showed the lowest conductivity at a given total dopant cate (CMAS) attack mitigation,111 though, independent
concentration. Optimum dopant concentration was verification and understanding of this benefit is yet to be
established at y10 mol.-%. The results of their findings conducted. Several other beneficial attributes include
are summarised in Fig. 23. The TEM observations phase stability up to at least 1500uC,16 and sluggish
indicated nanoscale clustering of the smaller and larger sintering kinetics.109,112 Some of these compositions
cations in different regions, with Y being uniformly are rather difficult to deposit, especially by EB-PVD,
distributed. It has been postulated that the clusters uniformity of composition and microstructure being the
contribution to the phonon scattering is responsible for major issue.109 Owing to chemical incompatibility with

23 Thermal conductivity of various oxide cluster TBCs as a function of total dopant concentration after 5 or 20 h laser
high heat flux tests at 1316uC (Zhu and Miller98–101)
TGO, a thin, about y25 to 50 mm, underlayer of YSZ is Y3AlxFe52xO12, Y3Fe5O12, W3Nb12O44, mullite, TiO2,
necessary113 to negate reduced TBC life times observed ZrSiO4, ZrTiO4, perovskite structures such as SrZrO3,
with a just a pyrochlore type zirconate top coat layer. BaZrO3 and rare earth aluminates such as RE2SrAl2O7.122
Such underlayers have been reported for majority of Of these compounds, CaxMg1–xZr4(PO4)6 (abbreviated
‘low k TBC’ compositions.4,114 Thermochemical com- as CMZP) has been reported with a conductivity of
patibility issues between alumina and ZrO2–Gd2O3 are 0?7 W m21 K21 at 1000uC.123 Perovskites (ABO3) can
discussed by Leckie et al.115 and an assessment of the accommodate a wide variety of different ions in solid
thermodynamic parameters in the ZrO2–Y2O3–Al2O3 solution including ions with large atomic mass. Some of
system is provided by Fabrichnaya and Aldinger.116 these compounds are stable to very high temperatures,
Significant conductivity reductions have been report- and have the potential to be developed as future low
ed by Vassen et al.109 on zirconate variations such as conductivity materials. Processing as a coating with
La1?7Dy0?3Zr2O7, La1?4Gd0?6Zr2O7, La1?4Eu0?6Zr2O7 and controlled uniform composition, however, will be a
La1?4Nd0?6Zr2O7 applied by APS. serious challenge.
To negate conductivity increase during service, An excellent summary of reported thermal conductiv-
Darolia et al.117,118 have evaluated combinations of ity data is provided by Levi,1 and reproduced in Fig. 24.
one or more dopant oxides for conductivity reduction There appears to be a minimum value obtainable around
along with carbides such as YbC2, NdC2 and LaC2 of 610 wt-% of the total stabiliser additions. Thermal barrier
the dopant metals which are either evaporated from a coating life as determined in furnace thermal cycle tests
carbide ingot source or formed by reaction during or superimposed in the ZrO2–Y2O3 phase diagram by Levi is
after the EB-PVD processing. In another approach, shown in Fig. 25. It is interesting to note that the TBC life
insoluble alumina by Rigney and Darolia,119 or alumina has a maximum value around 6–10 wt-% of the total
combined with lanthanum oxide, chromium oxide and/ stabiliser additions (irrespective of the type of stabiliser)
or yttrium chromate by Ackerman et al.120 have been to ZrO2. Non-transformable tetragonal (t’) phase is the
evaluated. Insoluble particles or dispersions in the TBC predominant phase in this composition range.
structure provide additional sites for phonon scattering
as well as stabilise the structure during subsequent Processing modifications
exposure. Processing modifications to incorporate porosity is the
easiest approach to reduce the thermal conductivity of
New ceramic compositions YSZ. However, the porosity reduction is only effective if
Other suggested compounds121,122 with very limited con- the porosity is retained via improved sintering resis-
ductivity data as a coating are: hafnates such as La2Hf2O7, tance. For EB-PVD, in addition to porosity within the
monazites such as LaPO4, magnetoplumbite structures columns, their feathery structure and gaps between
such as LaMgAl11O19 and LaLiAl11O18?5, garnets such as the columns play a significant role. For APS, splat

24 Comparative summary of thermal conductivity values for EB-PVD coatings reported in the literature for a variety of
zirconia based materials (Levi1)
boundaries which are essentially perpendicular to the Temperature and thermal cycle dependent
heat flow cause conductivity reductions as low as 50% of failure
fully dense YSZ in contrast to y30% for EB-PVD YSZ. Not surprisingly, engine thermal cycles (e.g. tempera-
The EB-PVD processing parameters that have been ture, dwell time, rates of excursions, gradients and
demonstrated for microstructure modifications include cycling frequency) play a significant part in TBC
the following: failures. The oxidation of the bond coat results in the
(i) pressure during processing formation and growth of the TGO that induces stresses
(ii) oxygen partial pressure and displacements at the TGO/TBC/bond coat inter-
(iii) part temperature during preheat faces eventually leading to TBC spallation. Extensive
(iv) part temperature during coating research has been carried out to establish the various
(v) alternate part motions mechanisms and factors that control TBC spallation in
(vi) bond coat roughness/texture. both EB-PVD and APS TBC.124–144 In spite of over 50
It must be pointed out that high temperature exposure publications on this subject, arguments still persist. The
during service will densify the coating structure via pore relative roles of plasticity of TGO and the bond coat as
coarsening and sintering, negating the porosity effect. well as phase transformations in the bond coat due to Al
Thermal barrier coating durability for majority of new depletion are still being debated. During engine opera-
TBC compositions under thermal cycling is reduced and tion, several interrelated thermal cycle dependent
the erosion rate is increased. The decreased performance phenomena take place. The wide variation of engine
has been attributed to lower toughness rendering the operating conditions is one of the reasons why TBC
system susceptible to delamination internally in the TBC failure mechanisms are not completely understood and
upon thermal cycling.8 Non-compatibility with TGO is agreed upon. Additionally, TBC in service is a very
also a major contributor. dynamic system with continuously changing composi-
tion, crystalline phases and microstructures. These changes
Thermal barrier coating damage and lead to changes in physical and mechanical properties, so
creating models becomes rather difficult. The other
degradation mechanisms complicating factor is that current TBC systems show a
Thermal barrier coating failures are generally classified wide distribution in life, with a significant proportion
into two categories: thermal cycle dependent failure, failing at much earlier times primarily due to process-
termed ‘intrinsic failure’ and temperature independent ing variations, and sometimes lack of adequate process
failures, termed ‘extrinsic’ failure which is caused by control. Additionally, the bond coat surface gets con-
particulates in the gas turbine environment leading to taminated with a minute amount of impurities such as S,
top layer thinning, densification, cracking and complete originating from the raw materials or by diffusion from the
loss/spallation. At temperatures .1200uC, CMAS par- underlying substrate. The incidence of lower life TBC is
ticles can deposit onto the TBC surface, melt and avoidable with better raw material control and cleaner heat
penetrate the TBC structure, changing the near surface treat furnaces. Laboratory furnace and rig tests used as
mechanical properties and enhancing the TBC spallation screening tests, unfortunately, are not generally simulative
tendency. A schematic of various degradation modes of engine operating conditions that are difficult to
proposed by Evans et al.8 is shown in Fig. 26. The duplicate in laboratory settings.
various degradation modes are described in the follow- A brief summary of our understanding of the factors
ing sections. that control thermal cycle dependent TBC spall in

spinels, that accelerates localised oxidation by provid-

ing fast oxygen diffusion paths. Al depletion also leads
to phase transformations such as b to c’ and/or
martensite formation (for a b NiAlPt bond coat).
Large stresses generated due to transformations in the
bond coat have been suggested as contributing factors in
promoting undulation growth. Thus, thermal cycl-
ing combined with TGO stresses, strain misfit (due to
thermal expansion and phase transformations), bond
coat creep deformation and initial imperfections leads
to TBC failure. Loss of Al by oxidation and by
interdiffusion between the bond coat and the substrate
also plays a significant role by changing the bond coat
properties, and sometimes, creating voids at the bond
coat/substrate interface. Several of the concurrent
mechanisms operating related to use temperature and
thermal cycling during engine service are schematically
depicted in Fig. 28 (reproduced from Clarke and Levi2).
During the early days of TBC application, TGO
thickness of y6 mm was considered in industry to be
maximum allowable thickness to avoid TBC spallation.
Thermally grown oxide thickness up to 17 mm has been
observed before failure in the b-NiAl bond coat by
Darolia et al.67–71 at GE Aviation. The concept of
25 A line representative of the cyclic durability of TBC is critical TGO thickness is definitely not a very useful
superimposed on a binary phase diagram for the guide since the critical TGO thickness strongly depends
ZrO2–YO1?5 showing phases expected (courtesy of on bond coat composition, impurities, microstructure
Levi, UCSB) and thermal cycling history.
The above scenario suggests the following guidelines
for longer TBC life:
case of EB-PVD TBC with a b phase NiAlPt bond (i) Slow growing TGO: Unfortunately this attribute
coat follows. The failure mechanisms for the EB-PVD cannot be independently controlled. Thermally
TBC with MCrAlX bond coat and APS TBC differ grown oxide formation and growth depends on
somewhat,132 and will not be elaborated in this paper. the bond coat composition.
The TGO thickens with time at operating temperature (ii) Create and maintain a strong adherence of TGO:
resulting in a constrained volume expansion that leads It is universally agreed that impurities such as S
to inplane compressive ‘growth’ stresses. Additionally, diffuse to the TGO/bond coat interface and
upon cooling, the thermal expansion mismatch with the weaken it. Also, rapid conversion to a-Al2O3,
substrate leads to very high ‘thermal’ compressive and minimisation of other faster growing oxides
residual stresses in the TGO reaching about 3–6 GPa (e.g. spinels) is essential.
at ambient temperature. During thermal cycling, TGO (iii) Minimise strain mismatch between the bond
seeks to relieve compression, by means of out of plane coat and the substrate.
displacements, preferentially into the bond coat since it (iv) Higher yield strength and creep resistant bond
is relatively soft at high temperature, and prone to coat to avoid rumpling.
creep deformation. During repeated thermal cycling, (v) Minimal surface imperfections, meaning flat
progressive roughening of the bond coat/TGO/top coat and smooth surfaces.
interfaces occurs due to cyclic creep of the bond coat (vi) Bond coat compositions with slow growing
as shown in Fig. 27. Such roughening/undulations TGO and/or can tolerate thicker TGO.
are often termed ‘ratcheting’, ‘rumpling’ or ‘bucking’, The other temperature dependent TBC degradation is
though, arguments have persisted on the exact terminol- sintering and densification of the porous structure of the
top coat resulting in increased thermal conductivity and
ogy. Once the stored energies at the TGO/TBC/bond
decreased stain tolerance. Phase destabilisation or changes
coat interfaces exceed a threshold value, cracks and
are not currently limiting issues since TBC operating
separation occur. Initial surface imperfections and
temperatures are below the threshold of transformation,
rough bond coat surfaces are considered to be con-
though, it is becoming an issue for the power generation
tributing to the out of plane stresses, and are the origins
turbines that run for extended periods of time (e.g.
of initial displacements and cracks. Large scale buckling
20 000z h), metastable phase t’ being transformed to
of TBC and spallation is preceded by smaller cracks that
the monoclinic phase.
extend and grow either at the TGO/bond coat or TGO/
TBC interface, though, separation within the TGO, and Erosion and impact damage
within the TBC at the TGO/TBC interface is often Thermal barrier coating compaction, plastic deforma-
observed. tion, spallation or gradual thinning by particulates in the
The growth of the TGO and interdiffusion between gas turbine environments generally termed ‘extrinsic
the bond coat and the substrate results in the depletion failures’ have limited full TBC utilisation. The damage is
of Al in the bond coat. The Al depletion can promote assumed to be primarily dependent on the microstruc-
the formation of other oxides, such as Ni containing ture and properties of the top coat. It is quite likely that

26 A schematic of various degradation modes proposed by Evans et al.8
the TBC/TGO and TGO/bond coat interface properties EB-PVD TBC is generally 7–10 times more erosion
also play a significant role. For a given TBC system, resistant than the APS TBC in majority of the particle
impinging particle size, mass, velocity, temperature, impingement conditions.145 A typical particle size dis-
rotation speed of the component, impact location and tribution in a dust collected from a high pressure turbine
incidence angles relative to the specific locations in the blade is shown in Fig. 29. Particle size ranges from 10 to
component are deciding factors to differentiate between 100 mm. Sand, ash and dirt ingested are typically smaller
the impact or erosion damage. Particles of various sizes in size whereas debris from upstream engine components
impinge turbine blades at a variety of angles. The such as combustor can be of much larger size, and their
leading edge of the blade could experience a 90u frequency, fortunately, is low. Different size particles
impingement whereas the other locations are subjected have definite trajectory in the hot flow path rendering
to particle impingement at lower angles. The impinge- impact and erosion damage combined with particle size
ment angles to the TBC coated turbine combustor liners location specific. Turbine blade locations that are prone
are about 20u or lower. It has been demonstrated in to either impact or erosion damage are shown in Fig. 30.
the laboratory tests as well as during service that the Impacts from ‘large’ particles can cause plastic de-
formation, kink bands, compaction and brittle fracture
of the columns and complete spallation of TBC.
Examples of impact damage are given in Figs. 31 and
32. Areas of impact, as noted by compressed and
fractured PVD TBC columns, can be seen in Fig. 32,
and in some areas shear fractures propagating from the
impact site to the bond coat/alumina interface are
evident. This fracture, upon reaching the interface, can
then propagate along the interface and result in a local
spall with an appearance similar to typical thermal cycle
spallation. Terminology for this type of damage as
‘foreign object damage’ is misleading since debris from
27 Thermally grown oxide undulations referred to as TBC spalled from combustor liners often lands on the
rumpling or ratcheting in a thermally cycled TBC (YSZ blades. An example is shown in Fig. 33. The impact
top coat and NiAlPt bond coat) event is unpredictable; however, from field experience,

28 Schematic summary of the several of the concurrent processes occurring in the bond coat, TGO and TBC during use
at high temperatures (Clarke and Levi2)
the leading edges on high pressure blades have been temperatures (typically 1100uC) and high impact velo-
found to be susceptible to impact related TBC spallation cities (up to 300 m s21), as well as the relatively small
because of high rotation speed, sharp curvature, particles involved (y20 to 500 mm) and their com-
relatively higher thermal stresses and their exposure to positions (usually calcium–alumino-silicate: CMAS).
high velocity particulates. In certain applications, Currently, there are no tests capable of single particle
experience has shown that impact related spallation or impacts that can reasonably reproduce engine operating
erosion extends further onto the convex side of the environments.
blades. Thermal barrier coating loss at these locations Evans et al.153–155 have analysed the erosion and
must be accounted for in the design of blades to avoid impact events on field returned blades and laboratory
local hotspots that can accelerate degradation of the tested specimens. The effort was to establish trends of the
underlying bond coat and the superalloy blade. material removal rates with the properties of the
Additional cooling air is required in such locations columnar microstructure EB-PVD TBC. A limitation
negatively affecting engine efficiency. for creating such models is that the size and velocity of the
Typical examples of TBC erosion indicated by gradual impacting particles responsible for specific damage sites
thinning of TBC are shown in Fig. 34. Erosion/thinning are unknown. The exact temperature of the component
of TBC generally occurs on the pressure side pocket, and surface during particle impingement is also unknown
on the suction side near the leading edge of the blade. The whenever engine hardware is used for analysis. Other
design of the blade can account for TBC thinning (e.g. complication arises from the fact that it is unknown
thicker TBC) on blade locations susceptible to erosion on whether the damage comprises a single event or an
the basis of field experience. accumulation of multiple events of various energies,
Development of particle impact resistant TBC con- though, erosion involves a sequence of nanosecond
tinues to be a major development activity for a ‘prime impingement and TBC thinning.
reliant’ TBC. The activities have focused on: capability The analysis has postulated two major damage
to reproduce the damage modes observed in service in modes, erosion mode and impact mode, with an
controlled laboratory tests; understanding of the intermediate mode in between as described in next
mechanisms of various forms of TBC damage caused sections on ‘Erosion mode’ and on ‘Impact mode’. The
by the impinging particles; and improvements in impact transition between the two modes depends on impact
and erosion resistance by TBC composition and micro- velocity, part rotation speed, impact angle, particle size,
structure modifications. temperature, contact area relative to the column
In order to assess impact resistance under conditions diameter as well as the TBC constituent properties and
simulative of turbine blades in service, tests develop- microstructure.
ed by Bruce146 at GE Aviation and Wellman et al.147–152
at Cranfied University have evaluated erosion rates Erosion mode
and impact events with different sizes and types of For low kinetic energy mainly with small particles,
particles introduced into the gas stream of a combustor during initial impact, to accommodate the projectile as it
burner rig at high temperatures and high velocities. penetrates, elastic stress waves that are transmitted
Progress towards a mechanistic understanding has been down the columns, can give fracture at tops of columns,
limited by the absence of well controlled experiments at mid-depth and at TBC/TGO interface. For example,
capable of duplicating the conditions expected in turbine induced elastic bending waves can cause preexisting
engines. The challenges are associated with the high flaws at the column perimeter (e.g. column feathers) to

29 Particle size distribution in a turbine environment
form cracks that extend across the columns, beneath the transition from elastic to plastic response superposed
surface, resulting in an array of column sized cracks are shown in Fig. 36. Evans et al.153 analysis for
(Fig. 35). Once the cracks link, small amounts of initiation and threshold has concluded that increasing
material are removed. Elastic waves also reflect off the TBC toughness should have the most pervasive
the bottom of the columns becoming tensile waves that influence, through its role in elevating the threshold and,
propagate back to the surface. These waves could in some cases, decreasing the removal rate (Fig. 35).
also cause cracks to form and extend across the However, increased toughness may not provide the
columns.153,154 desired benefit since TBC is quite ductile at temperatures
.900uC.156 In fact, doped YSZ with increased tough-
Impact mode ness, to be discussed next, have not proven to be more
With larger particles, combinations of high kinetic resistant relative to baseline compositions in laboratory
energy and high temperature cause YSZ to be susceptible testing.157 The models also imply that softer materials
to large scale plastic deformation and densification (at high temperature) should have a substantially higher
around the contact site (Fig. 32a). Outside the densified threshold as well as a slightly lower erosion rate above
zone, kink bands form and extend diagonally down- the threshold. A systematic assessment of the deforma-
ward, toward the TGO interface. Such bands have been tion mechanisms and of trends in yield strength with
identified at a variety of different angles to the interface composition and temperature would be beneficial.
(Fig. 32b). Within the bands, the columns are plastically Additionally, reducing the diameter of the columns
bent, causing the boundaries to crack, weakening the should be beneficial in affecting material removal in the
material (Fig. 32c). In some cases, the bands reach the elastic range. Designed experiments, preferably using
TGO interface. When this happens, they nucleate a single particle impacts, and further analysis of field
delamination that extends outward from the impact site, returned hardware are required to further aid our
along a trajectory within the TBC, just above the TGO. understanding.
Such delaminations provide a mechanism for creating
Approaches for improved impact and erosion
large scale spalls (Fig. 32d).
resistant TBC
Mechanism maps153 for the onset of material removal
by particle impact with the plane indicating the Composition modifications and composite toughening
Low k compositions
Though lacking in ‘desired’ erosion and impact resis-
tance, YSZ has demonstrated, at least in the laboratory
tests with the newer ‘low k’ TBC compositions, sup-
erior particle erosion and impact resistance. Over 200
combinations of compositions and microstructural vari-
ations have been tested at GE Aviation under various
test conditions to find a low conductivity TBC com-
position or microstructure with erosion and impact
resistance equal to or better than that of baseline YSZ.
This effort has generally been unsuccessful except in a
couple of cases (composite/layered and modulated
structured TBC, discussed later). Wellman et al.149 have
erosion tested ten different TBC compositions under
various test conditions including at room temperature
and high temperatures. The erosion behaviour of several
of the tested low conductivity compositions of doped
30 Locations in an HPT blade prone to impact (locations and codoped YSZ was compared with that of baseline
1 and 2), erosion (locations 2 and 4) and CMAS (loca- YSZ. Their findings are: all the EB-PVD TBC had an
tion 5). No TBC degradation at location 3 erosion rate lower than that of the APS TBC; aging

31 Electron beam physical vapour deposition TBC delamination at a leading edge of an HPT blade by particle impact
32 Electron beam physical vapour deposition TBC deformation, fracture and delamination in an HPT blade by particle
impact

(circa 1983) of YSZ in the single crystal and polycrys-

talline forms. Fracture toughness was found to be
maximum around 6 wt-%Y2O3 as shown in Fig. 10.21
Impact and erosion test data shown in Fig. 39 obtained
at GE Aviation158 on TBC coatings show a remarkable
resemblance to the fracture toughness plot in Fig. 10.
Research activities, therefore, have sought to identify
TBC compositions with fracture toughness higher than
that of YSZ. A limited number of oxide dopants,
generally with tetravalent (Ti4z) and pentavalent (Ta5z)
cations can increase tetragonality of zirconia and
significantly increase fracture toughness as reported by
Kim159,160 by incorporating small amounts of Ta2O5.
Greater than twofold increase in toughness at room
temperature with substitution of Ti4z for the larger
Zr4z cation into single phase tetragonal (t9) YSZ in-
creasing the tetragonality of the unit cell has been
33 Air plasma spray TBC spalled from combustor can demonstrated by Schaedler et al.161,162 Ferroelastic
cause impact and erosion damage in EB-PVD TBC toughening is postulated to be the underlying mechan-
applied to a turbine blade ism for the increase. As mentioned earlier, laboratory
testing with these new compositions has not demon-
during high temperature exposure decreases impact and strated any improvement. Fracture toughness measure-
erosion resistance, and becomes more pronounced as the ments at elevated temperatures (about 1100–1200uC) are
time and/or temperature of aging increases; YSZ is essential to further elucidate the role of fracture
superior to all the ‘low k compositions’ investigated; and toughness.
thinner inclined columns are more erosion resistant.
Dopant additions to YSZ increase the erosion rate of Composite toughening
EB-PVD YSZ significantly as shown in Fig. 37 (repro- By incorporating dispersion of ceramic particles such as
duced from Ref. 147); this increase is then further alumina or chromia in the YSZ microstructure to explore
magnified when the samples are aged before erosion composite toughening, Darolia and Rigney163,164 have
testing. Engine experiences with the doped YSZ, if any, demonstrated a 50% improvement in impact and erosion
are considered proprietary, and not available in the open resistance with alumina dispersion. In another approach
literature. by Rigney and Darolia,165 the top layer consists of layers
of particle free YSZ alternating with layers of YSZ with
Fracture toughness improvement dispersions of alumina particles.
The superior erosion and impact behaviour of YSZ is
likely related to its higher fracture toughness as shown in TGO/bond coat interface toughening
Fig. 38 (reproduced from Ref. 8) that compares fracture Analytical models have suggested that toughening the
toughness of zirconia coatings containing different Y2O3 bond with the TGO (i.e. interface) should provide
levels. It is interesting to look at fracture toughness data benefit in preventing interfacial delamination and
34 Typical EB-PVD TBC erosion locations and microstructural details of TBC thinning in blade locations indicated by circles

35 Particle erosion mechanism of crack initiation and propagation with small kinetic energy mainly with small particles
complete loss of TBC. Interface strength/toughness S as high as 11 at-% was measured after 50 h at 1100uC
cannot be independently controlled. Bond coat compo- as shown in Fig. 40. Hou and Priimak53 have measured
sition dependent interfacial chemistry, in particular interface fracture strength reduction shown in Fig. 41
segregation of impurities such as S, bond has a strong from y80 to y10 MPa with 2?5 at-%S at the inter-
role. Eberl et al.166 have initiated a difficult task of the face. Experimentally, a large body of literature data
measurement of the interfacial properties while Smith exists46,47,51,53 on the detrimental effect of S, and the
et al.167–169 have conducted first principles computations beneficial effects of reactive elements such as Hf and
of the interfacial adhesion and the role of S and Hf on Y. A fairly recent review of the segregation phenomenon
the interfacial strength: S was calculated to be detri- is given by Hou.171 Improved TBC life has been demon-
mental and Hf was calculated to be beneficial. Hf strated by Darolia and Walston172 in Hf containing Ni
was also shown to negate S effect. If S escapes Hf based superalloys and bond coat compositions.
bulk pinning, Hf can mitigate detrimental S effects at
Microstructure modifications
the interface. Experimentally, Hou and Priimak53 and
Molins et al.170 have measured S segregation at the Porosity effect
TGO/bond coat interface as well as at voids in a NiAl Porosity effects on performance are not clearly under-
based bond coat composition (44Al–11Pt–37Ni in at-%). stood due to the fact that porosity levels cannot be

36 Mechanism maps proposed by Evans et al.153 for the onset of TBC removal by particle impact with the plane indicat-
ing the transition from elastic to plastic response superposed
independently controlled without changing other subtle coatings. On the other hand, increased porosity/softness
microstructural features of porosity such as pore dia- could have inferior erosion performance. Rapid removal
meter and TBC column characteristics such as column and/or compaction leading to impact mode of damage
diameter, gaps and the feathery structure. Additionally, are the issues. For example, ceria doped YSZ deposits as
these features vary through the thickness of the top an extremely soft, friable coating with poor room
coat. Coating chamber pressure, deposition rate, deposi- temperature erosion resistance.92
tion temperature, deposition angle, substrate tempera- Other approaches such as smoother TBC surface and
ture, surface roughness and rotation speed are some dense top layers including metallic layers such as Pt
of the EB-PVD parameters that influence porosity. would have limited, short term value in actual engine
Microstructural modifications have to ensure strain operating environment, roughening of the surface and
compliance of the top coat; maintain a ‘desired’ thermal spallation of dense layers being the underlying issues.
conductivity; and minimum susceptibility to micros-
tructural changes during high temperature exposure.
Experimentally, denser microstructures have demon-
strated inferior erosion resistance.147 Porous coatings
absorb the impact much more effectively than dense
38 Fracture toughness of 7 wt-%YSZ and 20 wt-%YSZ

37 Erosion rates of YSZ modified with Dy2O3 and Gd2O3 coating.8 Also shown data for parially stabilised zirco-
(reproduced from Wellman and Nicholls147) nia in the sintered ‘bulk’ form (TZP)

39 Impact resistance of YSZ coatings containing various

levels of Y2O3.158 The fracture toughness data super- 41 Effect of S on interface fracture strength53
imposed from Ref. 21
melt constituents are calcium–magnesium–alumino-
Modulated/wavy TBC structures silicates referred to as CMAS. A typical chemical composi-
A recent breakthrough observation by Darolia et al.173 tion is 35 mol.-%CaO, 10 mol.-%MgO, 7 mol.-%Al2O3,
from the evaluation of field returned blades showed that 48 mol.-%SiO2, y3 mol.-%Fe2O3 and y1?5 mol.-%NiO.
a ‘modulated’ (as compared to straight TBC columns) This composition melts (TM CMAS
) at y1240uC, and small
TBC structure can better withstand impact damage as amounts of other oxides such as TiO2 can vary the melt
shown in Fig. 42. Evaluation of these blades has shown temperature. When the TBC surface exceeds the CMAS
CMAS
that the layers between each zone of orientation act as melt temperature TM , due to the excellent wetting
sites for deflection of the impact stress, resulting in characteristics of CMAS, it penetrates rapidly to a depth
CMAS
removal of only the outer layer(s) rather than the entire where Ttbc ~TM . Fortunately, the depth of the
coating. In this way, a single layer (perhaps less than penetration is dictated by the thermal gradient across the
25 mm depending on wave design) is sacrificed rather coating and the viscosity of the melt limited in an actual
than the entire coating thickness. engine operation. Upon cooling, it solidifies as a fully dense
layer decreasing the compliance of TBC, and consequently
increasing susceptibility to TBC spallation. The CMAS
Deposition, infiltration and reaction with infiltration induced TBC loss is seen both in EB-PVD and
CMAS particles APS TBC. Examples of CMAS infiltration induced TBC
loss are shown in Fig. 43 for HPT blades and shrouds.
Under certain engine operating conditions (such as in
Thermal gradients though the TBC play a significant role.
coastal or Middle East regions), debris of siliceous
The CMAS (once molten) penetration stiffens the pene-
materials such as airborne dust, sand, fly ash, volcanic
trated layer and generates tensile stress upon cooling leading
dust, concrete dust and fuel residue ingested into the
to mode I delamination within the TBC. Metallographic
engine accumulate on certain hotter surfaces, generally
evaluations have revealed subsurface delaminations within
on the concave side, of the blade, and melt when
infiltrated regions of the TBC shown in Fig. 44, as well as
sufficiently hot. The melt penetrates rather rapidly into
large areas in which the TBC has been entirely removed: all
the top layer densifying the layer and rendering it
covered with yellowish CMAS. Low magnification back-
susceptible to cracking and delamination. The primary
scattered electron image of a region with delamination
cracks is shown in Fig. 45. The intercolumnar gaps on both
sides of the crack have remained aligned, indicating that the
delamination is strictly mode I.
Thermomechanical effect: Mercer et al.174 have
analysed CMAS infiltration caused delamination on
field and laboratory tested hardware, and have proposed
a cold shock degradation mechanism. A schematic of
one of the degradation modes caused by CMAS
infiltration coupled with cooling is shown in Fig. 46.
The inplane modulus of the CMAS penetrated top coat
layer increases by about a factor of 5–10. Such a
relatively high modulus of this layer, in conjunction with
its relatively low toughness, increases its susceptibility to
cold shock during engine shutdown. A shock analysis

has identified a critical infiltration thickness Hpenetrate ,
above which the penetrated layer is susceptible to
40 S segregation at the TGO/bond coat interface in a delamination. For a rapid shock, the model predicts a
NiAl based bond coat composition: 44Al–11Pt–37Ni in
critical thickness, Hpenetrate ~11 mm, with delamination
at-%170 expected at depth b~Hpenetrate =2. This analysis is highly

42 Observations on field returned HPT blades from the same engine service show that modulated TBC structure is resis-
tant to particle impact damage
a HPT blade; b HPT shroud

43 Thermal barrier coating loss caused by CMAS
dependent on several variables, heat transfer coefficient shroud with relatively thick APS TBC, after removal
being a major variable. Repeated shock of infiltrated from service. During service, the CMAS melted, pene-
regions could cause large area spalls by sequential trated to a depth about half the coating thickness and
material removal. Chemical reaction of TBC with molten infiltrated all the open areas. Consequently, TBC devel-
CMAS also alters top coat properties. Additionally, oped channel cracks and subsurface delaminations as
thermal misfit between the superposed CMAS and the shown in Fig. 47. Complete TBC spall is also observed in
substrate can be responsible for large spalls because of nearby areas. Estimates of the residual stress gradients
the bending of the underlying TBC columns and mode made on cross-sections (by using the Raman peak shift)
II delamination from through thickness vertical separ- indicated tension at the surface, becoming compressive
ations. Interestingly, the CMAS modified dense layer at below. A fracture mechanics approach relevant to the
the surface of TBC has demonstrated a slightly superior thermoelastic stresses upon cooling was used to rationa-
resistance to particle erosion by Wellman and Nicholls.147 lise the propagation of channel cracks and delaminations.
Krämer et al.175 and Evans and Hutchinson176 have Thermochemical effect: Substantial thermochemical
characterised the susceptibility to delamination when attack of YSZ by CMAS occurs at y1240uC within
penetrated by CMAS on a stationary component, HPT minutes. Krämer et al.177 have observed breakdown of
44 Calcium–magnesium–alumino-silicate penetrated TBC reveals mode I subsurface delamination within infiltrated

regions of the TBC, as well as large areas in which the TBC has been entirely removed: covered with yellowish
CMAS

45 a low magnification backscattered electron image of region with delamination cracks, b backscattered electron image
showing phase contrast at interface TBC/CMAS, c backscattered electron image showing phase contrast in CMAS
infiltrated crack and d backscattered electron image showing CMAS infiltrated crack. Note that the intercolumnar
gaps on both sides of the crack remain aligned, indicating that the delamination is strictly mode I
the columnar structure, coarsening, densification and t’ the strain compliant spaces of the coatings. The sacrificial
phase destabilisation. As seen in Fig. 48, columns have coating reacts with CMAS to increase the melting
lost their identity in the upper portion of TBC, and are temperature or viscosity of the contaminants thereby
replaced by a conglomerate of much smaller globular inhibiting infiltration. One of the examples is alumina
particles embedded in CMAS. The reaction zone depth either as a top layer or codeposited with YSZ.178–181 The
increases with temperature. The chemical interaction other approach is to deposit a dense, non-cracked and
involves dissolution of the metastable t’ phase and non-porous ceramic or metal impermeable or non-
reprecipitation of YSZ that is sufficiently depleted in Y wetting outer layer to inhibit the infiltration of molten
in some locations and susceptible to monoclinic CMAS. Examples include Pd, Pt, Pd–Ag and ceramics
transformation upon cooling, potentially leading to such AlN and BN.
TBC spallation due to volume change associated with Kramer et al.182 have shown that dissolution of
the transformation. gadolinium zirconate, Gd2Zr2O7, into the CMAS melt
In isolated cases, reaction with the TGO has been results in a mixture of crystalline phases, an apatite
observed in field returned hardware, leading to TBC phase based on Gd8Ca2(SiO4)6O2 and the fluorite ZrO2
spallation (Fig. 49). Near the TGO/TBC interface, the phase with Gd and Ca in a solid solution, that fills the
dissolution of the underlying alumina by the CMAS can flow channels, and essentially creates a dense, imper-
cause precipitation of a crystalline aluminosilicate phase vious layer/zone that prevents or significantly slows
and globules of a Y enriched cubic YSZ. down further penetration and reaction as shown in
Fig. 50. The extent of penetration depends on the
Strategy to mitigate CMAS damage relative competitiveness of the infiltration, dissolution
The engine components have been designed with TBC and crystallisation kinetics, all of which are dependent
surface temperatures not exceeding 1240uC until a on the temperature and the compositions of the melt and
materials solution to mitigate CMAS damage is available. the TBC top coat. After an early sealing of the flow
To address this critical issue that limits maximum use channels, reaction continues slowly. The progressive
temperature, the CMAS mitigation strategy has consisted slowing of the attack should be beneficial to the
of depositing a protective coating on the surface of TBC survivability of the reaction layer under thermal cycling
or incorporating sacrificial materials, mostly oxides, in conditions. These promising results with gadolinium

46 A schematic of a CMAS layer that forms on the TBC and penetrates once it melts. This layer develops a large compressive
stress upon cooling to ambient because of the expansion misfit with the substrate. A delamination may be induced near
the base of the TBC if the energy release rate associated with the stress in the CMAS layer is high enough
zirconate have led to evaluation of other rare earth APS results in resistance to CMAS attack while
zirconates such as Nd2Zr2O7 and YSZ containing conventional APS YSZ was fully penetrated and
various amounts of Nd2O3. The results have shown destroyed by molten CMAS (at 1200uC), under the
their effectiveness in mitigating CMAS penetration by same conditions. The molten CMAS was found to
the rapid formation of a dense reaction layer in the penetrate only about a third of the YSZz20Alz5Ti
intercolumnar gaps and the intracolumnar porosity of TBC thickness before it was arrested due to the
an EB-PVD TBC.183 As a further improvement of this formation of crystalline anorthite. It was also demon-
approach, Darolia et al.184 have proposed a two layer strated that the APS Gd2Zr2O7 TBC is resistant to
system consisting of an innerlayer of YSZ and an outer attack by molten lignite fly ash which penetrated only
layer of a pyrochlore structure rare earth zirconate. y25% of the TBC thickness due to the formation of an
Yttria stabilised zirconia doped with rare earth oxides of impervious, stable crystalline structure that arrested the
Gd, La, Eu, Sm and Nd have also been proposed as the penetrating molten fly ash.
outer layer. Darolia and Fu187 have demonstrated that a top layer
Aygun et al.185 and Drexler et al.186 have demon- of Y2O3 or mixtures of YSZ and Y2O3 over a YSZ
strated that incorporation of 20 mol.-%Al2O3 and underlayer reacts with CMAS to produce a yttrium–
5 mol.-%TiO2 in the form of a solid solution into YSZ calcium–silicate phase having a needle-like geometry
(referred to as YSZz20Alz5Ti) coatings deposited by that is very dense and resistant to infiltration of molten
47 Micrographs of cross-sections through the TBC of a CMAS damaged HPT shroud. Delaminations at three different
levels are apparent. In each case, the delaminations originate from channel cracks with separation

48 Thermal barrier coating columns have lost their iden-

tity in the upper portion of TBC, and are replaced by
a conglomerate of much smaller globular particles 49 Voiding at base of wedge shaped segmentation crack
embedded in CMAS177 in a NiAlPt bond coat. Calcium–magnesium–alumino-
silicate has penetrated through 50% of TBC thickness
CMAS. These coatings were deposited by EB-PVD

without any difficulty due to vapour pressure similarity processing at the risk of added cost. The contaminants
between ZrO2 and Y2O3. such as S and C at ppm levels can vastly affect TGO
growth and, therefore, TBC life. Unfortunately, these
impurities are difficult to measure and accurately control
Scatter in TBC performance at the ppm level in a production environment. To inhibit
Scatter in TBC test data and engine performance such degradation, there has been a long history in the
continues to be a major issue as observed in laboratory industry of systematically lowering the S level in
furnace cycle tests data and in infant mortality (e.g. TBC superalloys, as well as using alloy additions such as Y,
spall right after coating deposition, occasional TBC Hf and Pt to tie up remnant S. Continued surface science
failure during rotor grind or during engine qualification research to fully understand role of various contami-
test before shipment). Thermal barrier coating life has a nants, and their synergistic effects would help alleviate
wide variation as shown schematically in Fig. 51. this problem.
Consequently, blade design incorporates only the lower
end of the TBC life distribution curve. Weibull statistical Thermal barrier coating lifetime
distribution curves are also used. Scatter in TBC life
data has been attributed to: processing variables; defects
prediction
(e.g. grits) introduced during manufacture; impurities The major challenge in TBC life-time prediction has
introduced during coating processing and the from the been to identify laboratory and component tests that can
raw materials; segregation of S and other impurities to accurately simulate conditions in an operating turbine.
the TGO/bond coat interface; surface contamination Key variables such as temperature, thermal cycle,
from the heat treat furnaces; and lapse in process pressure and thermal gradients are difficult to reproduce
instructions and equipment maintenance. S segregation in a single test specimen and laboratory set-up. Also,
and resultant reduction in TGO/bond coat interface TBC service life is subject to scatter due to differences in
fracture strength was described in an earlier section. An operating conditions. Modelling of various failure
extreme example of TBC data scatter (tenfold variation mechanisms in TBC involves numerous thermomecha-
in TBC life) is shown in Fig. 52, plotted from a study by nical phenomenon with complexities and nuances not
Darolia188 to pinpoint various sources of TBC data found in other materials. At best, the models have
scatter. Thermal barrier coating specimens having incorporated data on bond coat oxidation and TGO
identical substrate, bond coat and top coat composi- growth, and have relied heavily on the vast body of
tions, processing, thickness, and deposited as a single existing knowledge of environmental coatings and their
batch were heat treated after the bond coat deposition in failure mechanisms. Understanding of the TBC damage
several different furnaces at two slightly different by particles (e.g. erosion, impact and CMAS penetra-
temperatures. Another example of variation is shown tion) is still evolving. Design of the components has been
in Fig. 53. Variation in surface colour in test specimens dependent on physical evidence of damages and their
(with NiAlCrZr bond coat only) arises from varying location on the field hardware. This approach has been
specimen locations in the deposition chamber using the successful, but under utilises TBC capability.
same evaporation target. The coating depositions The current testing protocol for screening candidate
were aimed to have identical NiAlCrZr bond coat materials at GE Aviation typically consists of: furnace
composition. cycle test on simple, flat coupons (no gradient); burner
Coating process improvements need to focus on rig test with cylindrical specimens without gradient;
variability, not just average performance. An opportu- burner rig test with tubular specimens with gradient;
nity exists for utilisation of inline sensors during component test with actual parts/geometry; factory

50 Dissolution of gadolinium zirconate (Gd2Zr2O7) into the CMAS melt results creates a dense, impervious layer/zone
that prevents or significantly slows down further penetration and reaction178
engine test; and flight test. Numerous variations of degree in cases where the failure is bond coat oxidation
specimen designs and test conditions exist to simulate driven.
TBC surface temperature, temperatures at various Since the TBC surface temperature is designed not to
interfaces, thermal gradients, cycle effect and curvature. exceed 1200uC to prevent CMAS melting and penetra-
Without the gradient in the laboratory tests, test tion, TBC sintering and t’ phase transformation is not
temperatures are limited by the bond coat temperature considered life limiting.
capability, and thus provide information on the bond A typical particle erosion and impact test as described
coat oxidation driven TBC failures only. Several earlier by Bruce146 simulates only a few of the damage modes
lifing methodologies were incorrectly derived on the observed in an engine, and therefore, not used for lifing
concept of ‘critical TGO thickness’ to TBC spallation purpose. It is used only as a screening test. There is not
with the temperature dependence following Arrhenius much available engine experience data on erosion and
kinetics.132 This approach is no longer used because the impact behaviour of new top coat compositions since
‘critical TGO thickness’ is dependent on bond coat YSZ has been used exclusively as a top coat. Additional
composition and on a variety of test conditions such as test development including single particle impact is
thermal cycling frequency and specimen geometry. The required. Measurement of properties such as hardness
current models are incorporating TGO growth rate with and fracture toughness at elevated temperatures will
the stored strain energy to predict failure. Only a limited further aid our understanding in this area. A high
number of thermomechanical tests to represent tem- temperature probe to measure deformation at elevated
perature gradients and strains in the coating have temperatures has been developed by Watanabe et al.189
been conducted due to complexity and cost of the test and Bacos et al.190 at ONERA have developed high
set-up. Test development activities to simulate engine temperature microindentation tests that would be useful
conditions and service observations have continued. in this critical area.
Fortunately, TBC life extrapolated from the laboratory There are currently no effective non-destructive eva-
data have matched engine experience to a reasonable luation methods used in industry that can act as quality
control and/or to monitor remaining life. Progress in this
area is being made by Chambers and Clarke,191 Feist
et al.192 and Eldridge et al.193 In situ measurements of
temperature by introducing a minor concentration of a
rare earth oxide into YSZ for recording luminescence
lifetime have been proposed. Clarke and Gentleman194
have proposed coating layers with a different luminescent
ion in each to monitor the wear of the coating by the
changes in luminescence as successive layers are eroded
away.
Design considerations with TBC

The low thermal conductivity of TBC top coat reduces
the temperature of the turbine component metal only
when the surface of the component is cooled with
backside cooling in a high heat flux environment. Also,
because the top coat provides an insulating layer
between the combustion gas and the component, the
component transient response is slowed down which
reduces thermal gradients.
51 A wide variation is seen in TBC thermal cycle test life A fairly conservative design is practiced since TBC is
in laboratory testing. The component is designed to considered not ‘prime reliant’ due to the various
the low end of the life data. New TBC compositions performance issues discussed in the paper. Heat transfer
need to reduce variability as opposed to aiming for conditions and temperature profiles with and without
higher average life TBC at and near the critical and non-critical locations of

52 Scatter in TBC life with identical specimens (substrate, bond coat, top coat, processing and tests are identical).
Variation comes potentially from post-deposition heat treatment conditions (furnace type, contamination from furnace
walls, temperature and vacuum level)
the component dictate specific locations where TBC is Maximum allowable bond coat temperature based on
applied and its thickness. To utilise TBC to a greater bond coat capability for a specific engine mission cycle
extent, TBC performance in the field is being analysed and life requirements and overhaul interval is the first
and related to laboratory data. design consideration. Calcium–magnesium–alumino-
silicate melting temperature of y1240uC sets the upper
temperature limit for the top coat. In areas, prone to
impact, design has considered the maximum allowable
bond coat temperature as the limit to avoid rapid
oxidation of the coating and the underlying substrate. In
rotating components such as blades, TBC thickness that
ranges between 100 and 250 mm is kept to a minimum
sufficient to meet mission requirements to avoid
excessive inertial loads due to the extra mass. On
stationary components, such as shrouds and combus-
tors, the mass is less critical and much thicker layers can
be used. Thermal barrier coating thickness on these
components can range from 250 to 1000 mm.
Based on the field observations and laboratory
experiments, it has been assumed that TBC will
eventually fail. Thermal barrier coatings do not provide
self-renewing protection. When TBC spalls, the thermal
protection is lost unlike environmental coatings used in
turbines where a protective scale such as alumina
reforms. Thermal barrier coating is stripped off the field
returned blades and reapplied if the blade is serviceable.
The design practice has considered the following factors:
when and at what location of the blade TBC spalls, type
of TBC failure mode (thermal/engine cycle related,
particle erosion, impact damage or CMAS induced)
determined by visual and microstructural failure analy-
53 Thermal cycle furnace test buttons (with NiAlCrZr sis, and estimated temperature profiles at the damaged
bond coat only) show variation in surface colour aris- locations.
ing from specimen locations in the deposition cham- Fortunately, the majority of the failure modes and
ber using the same evaporation target. The coating their specific locations have been reasonably predictable.
depositions were aimed to have identical NiAlCrZr Temperature rise in the component is calculated at the
bond coat composition locations where TBC is missing or thinned out. Design

iterations involve TBC spall size or remaining TBC elements such as Pt, Re, Ta and Ru. Long term
thickness, altered heat transfer and heat flux character- availability of the rare earth elements is also a concern
istics. Certain specific locations of the blades (e.g. in the industry. Bond coat development effort will
leading edge) are designed without taking into account continue for further optimisation of TGO and reduced
the benefit of the insulating properties of TBC, since it is interdiffusion with the newer generation of Ni based
difficult to predict and avoid TBC loss due to large superalloys. The maximum bond coat temperature will
impacting particles. In some cases, the leading edge still be limited by the temperature capability of the
curvature of the blade has been redesigned to minimise underlying alloy since there is minimal thermal gradient
impact damage. between the bond coat and the substrate. Life predic-
tion, validation, and oxidation and hot corrosion tests
Conclusions and future directions that simulate engine behaviour will continue to be
pursued. Development efforts for effective diffusion
Application of TBC is one of the major developments in barriers will continue. This area could prove to be a holy
turbine industry that has revolutionised how turbine
grail.
components are designed. The surface temperatures of
The ‘low k TBC’ compositions will most likely require
the components can potentially be increased by as high
an under layer of YSZ because of the chemical
as 200uC. The temperature benefit surpasses other
incompatibility with TGO. This will add to process
material technologies advances including single crystal
complexity and cost. The erosion and impact resistance
Ni based superalloys achieved over a 30 year period.
of the ‘low k TBC’ compositions is inferior to YSZ TBC
Thermal barrier coatings have become an integral
as demonstrated in laboratory and component tests.
part of turbine designs requiring higher efficiency,
Validation of laboratory data with engine tests is
performance and reduced emissions and noise. Ther-
required. Currently, limited engine experience exists.
mal barrier coating applications continue to increase on
components in the propulsion and power generation Development efforts have continued to make TBC
turbines. In future, CMC components will also depend ‘prime reliant’. Prime reliance will require elimination of
on TBC. Thermal barrier coatings have evolved from coating process variability, consistency in quality and
just simple insulating layers for temperature reduction to performance over time and a long and predictable life.
complex designs. However, the turbine designers have a Calcium–magnesium–alumino-silicate caused damage
love and hate relationship with TBC because of modes have limited TBC surface temperature to
unacceptable scatter in laboratory and engine perfor- y1200uC. Calcium–magnesium–alumino-silicate miti-
mance, even with the baseline YSZ TBC due to a variety gation solutions are the most critical development needs,
of reasons mostly related to processing, and issues and will continue to challenge materials scientists. In
related to damage by the particulates in the turbine author’s opinion, CMAS can become TBC’s Achilles’
operating environment. The scatter in performance heel. Mitigation results with rare earth zirconates are
dictates that turbine components should be designed to very promising. Validation with engine tests needs to
the lowest spectrum of the scatter band. Enhanced continue. Thermal barrier coating thinning by particle
reliability should lead to deriving greater TBC benefits. erosion can perhaps be addressed by experience based
While our understanding of mechanisms governing design practices but impact events are unpredictable,
TBC performance has improved significantly after and fail safe designs need to be developed. Further
extensive research and development over the past two development of tailored TBC microstructures involving
decades, no clear top coat composition superior to YSZ multi- or modulated layers should play an important
has been developed; balance of properties being an issue. role in combating impact damage caused by impinging
The baseline top coat composition developed at NASA particles. Additional test development including single
continues to be used. It was essentially a mother nature’s particle impact is required. Measurement of properties
gift after a short development effort mainly at NASA such as hardness and fracture toughness at elevated
based on the knowledge of bulk oxides used in industrial temperatures will further aid our understanding in this
applications. area. Embedded thermographic phosphors for tempera-
Modifications to existing EB-PVD and APS processes ture and wear sensing will be used for specialised mission
such as DVC, directed vapour deposition and suspension critical applications.
plasma spray have been developed for process efficiency, The scientific understanding of TBC systems has
cost reduction, and composition and microstructural benefited from collaboration between industry, govern-
uniformity, control and flexibility. These processes are ment laboratories and universities for the last decade.
increasingly being used. Critical need still exists for better Unfortunately, such collaborations have slowed, at least
process controls with online sensors to avoid infant in United States. The collaborations need to continue
mortality, reduce scatter and improve TBC reliability. because the future TBC systems for higher temperature
Higher temperature applications requiring CMAS related applications will most likely be highly complex incor-
damage mitigation as well as microstructure and phase porating multifunctional multilayers requiring multi-
stability will add to composition and process complexity disciplinary efforts. The challenge will be to develop cost
with added costs that will need to be balanced with TBC effective TBC systems with balanced properties. As the
performance requirements for a specific application. TBC surface temperature is increased, issues such as
New bond coat compositions have been developed for phase stability, densification and microstructural
slow TGO growth, higher temperature and/or longer changes will affect TBC performance particularly,
service life capabilities, reduced interdiffusion and spallation behaviour. Future TBC research will involve,
reduction/elimination of platinum group metals. These in addition to composition and process development, a
newly developed bond coats are being introduced into better understanding of failure mechanisms, life predic-
service. There is still a need to minimise use of expensive tion modelling, more effective use of sensors, perhaps

imbedded, and non-destructive evaluation methods for 15. J. A. Krogstad, S. Krämer, D. M. Lipkin, C. A. Johnson, D. R.
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This review has attempted to capture contributions of a Ceramic Society.
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Thermal Barrier Coatings Technology: Critical Review, Progress Update, Remaining Challenges and Prospects

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International Materials Reviews

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Thermal barrier coatings technology: critical

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Introduction surpass other material technologies advances including

ß 2013 Institute of Materials, Minerals and Mining and ASM International

316 International Materials Reviews 2013 VOL 58 NO 6

International Materials Reviews 2013 VOL 58 NO 6 317

In addition to enhancing oxidation resistance, TGO

318 International Materials Reviews 2013 VOL 58 NO 6

6 a TGO microstructure, predominantly a-Al2O3 and b mixed zone of a-Al2O3zZrO2

International Materials Reviews 2013 VOL 58 NO 6 319

8 The zirconia rich corner of the ZrO2–YO1?5 binary phase

roughness requirement, line of sight versus non-line of

320 International Materials Reviews 2013 VOL 58 NO 6

International Materials Reviews 2013 VOL 58 NO 6 321

a EB-PVD; b APS; c DVC

322 International Materials Reviews 2013 VOL 58 NO 6

cost of Pt. The effect of grit blasting,57 preoxidation58

International Materials Reviews 2013 VOL 58 NO 6 323

14 An SRZ is created between the coating and a high Re

324 International Materials Reviews 2013 VOL 58 NO 6

16 Effects of small amount of alloying additions on the

17 Improvement in rupture strength (life) at 982uC/

International Materials Reviews 2013 VOL 58 NO 6 325

engine operating temperatures. Phase stability

326 International Materials Reviews 2013 VOL 58 NO 6

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328 International Materials Reviews 2013 VOL 58 NO 6

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spinels, that accelerates localised oxidation by provid-

330 International Materials Reviews 2013 VOL 58 NO 6

26 A schematic of various degradation modes proposed by Evans et al.8

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332 International Materials Reviews 2013 VOL 58 NO 6

29 Particle size distribution in a turbine environment

International Materials Reviews 2013 VOL 58 NO 6 333

334 International Materials Reviews 2013 VOL 58 NO 6

(circa 1983) of YSZ in the single crystal and polycrys-

International Materials Reviews 2013 VOL 58 NO 6 335

336 International Materials Reviews 2013 VOL 58 NO 6

38 Fracture toughness of 7 wt-%YSZ and 20 wt-%YSZ

International Materials Reviews 2013 VOL 58 NO 6 337

39 Impact resistance of YSZ coatings containing various

338 International Materials Reviews 2013 VOL 58 NO 6

a HPT blade; b HPT shroud

44 Calcium–magnesium–alumino-silicate penetrated TBC reveals mode I subsurface delamination within inﬁltrated

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340 International Materials Reviews 2013 VOL 58 NO 6

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48 Thermal barrier coating columns have lost their iden-

CMAS. These coatings were deposited by EB-PVD