Thermal & Environmental Barrier Coatings

Rachel Guarriello*
Materials Science & Engineering, the Pennsylvania State University, University Park, PA, 16802

†
Dr. Dongming Zhu
NASA John H. Glenn Research Center, Brook Park, OH, 44142

Turbine engine components capable of withstanding higher operating temperatures will help
achieve more efficient engines. SiC/SiC ceramic matrix composites (CMCs) are lightweight,
high strength composite materials, but require the use of an environmental barrier coating
(EBC) to protect against degradation and oxidation. Silicon-carbon nanotubes (SiCNT’s)
were successfully doped with rare-earth silicates and oxides to improve oxidation stability
and strength at high temperatures. A zirconium-silicide system was examined and its
processing was optimized for high temperature stability in air when applied to a CMC as a
bond coat. Various ratios of ytterbium silicates were studied for their strength and high
temperature stability, showing promise for possible applications in coatings.

Nomenclature
BOR = Ball-on-ring
CMC = Ceramic matrix composite
EBC = Environmental barrier coating
HHFLR = High heat flux laser rig
SEM = Scanning electron microscopy
SiC = Silicon Carbide
TBC = Thermal barrier coating
XRD = X-ray diffraction

I. Introduction

Achieving high temperatures is essential for increasing the efficiency of gas turbine engines. The range of
temperatures of a heat engine limits its efficiency, and because the cold temperature limit cannot be lowered (the
ambient air), the only option to increase efficiency is to raise the hot temperature limit. Higher engine temperatures
allow less input energy (fuel and compressed air) to do more work to generating power or run the engine. Currently,
the materials used in engine components are limiting factors for operating temperatures. Current hot section
components super alloy materials which have insufficient temperature capabilities for ultra-efficient engines. The
optimal operating temperatures for these engines often exceed the melting points of current materials. Thermal
barrier coatings (TBCs) have been developed to insulate super alloy components from high gas temperatures, but
many systems still reach temperature limits around 2500F(about 1370ºC)1. Silicon carbide (SiC/SiC) ceramic
matrix composites (CMCs) are a lightweight, high strength alternative material to super alloys with higher
temperature capabilities. However, SiC/SiC ceramic matrix composites (CMCs) are susceptible to environmental

*
Undergraduate student researcher, RXD, NASA GRC, The Pennsylvania State University
†
Materials research engineer, RXD, 106-2, NASA GRC
1
 NASA USRP – Internship Final Report

attack from harsh combustion and general engine operation. This makes it necessary to apply layers of
environmental barrier coatings (EBCs) to protect SiC/SiC CMCs from degradation.

EBC’s are necessary to seal out water vapor, while maintaining slow diffusion of oxygen to the underlying
CMC engine component tin order to ensure a long lifetime and suitable performance. Furthermore, a layer between
the EBC and the substrate, called a bond coat, is essential for good adherence to the underlying CMC . EBC
materials have to withstand the extremely high temperature and the corrosive environment of gas turbine engines
and integrate well with the CMCs to ensure maximum durability. Advanced multi component oxide and silicate
composites are being developed to improve mechanical integrity and environmental stability for CMC coatings.
SiC/SiC CMC gas turbine components generally require a layered environmental barrier coating system for ideal
performance, stability, and durability. EBC top coats and intermediate coatings are typically made of rare-earth
doped oxides and silicates to optimize their thermal, mechanical, and physical properties at high temperatures

II. Materials & Experimental Procedures

The systems I studied centered on a group of rare-earth silicates. I studied various ytterbium (Yb) silicate based
systems for their oxidation and heat stability, as well as strength properties. There were four different Yb-silicates
studied. There were one silica-rich and one stoichiometric system (AE9913C and AE9914C respectively) and two
silica-lean systems that were studied (AE9762 and AE9915C). The difference between these silicates was the ratios
of Yb2O3 to the SiO2 present in the powders. In addition, combinations of the silicates and rare earth oxides (Yb and
Gd) were studied when combined as well as with the oxide applied as a top coat. I doped SiC nanotubes with Yb
and Gd (gadolinium) silicates or oxides as a way to improve the stability of the nanotubes, which are known for their
high mechanical strength, but oxidize quickly at high temperatures. In addition, a Zr-Si (zirconium silicide) system
was studied for its high temperature stability when applied as a bond coating to a SiC/SiC CMC.

A. Sample processing
The samples that required the most processing were the nanotubes. I started with pure carbon nanotubes, which
were then processed with 55% Si in a furnace at 1400ºC for 4 hours in a reducing environment of Ar + 5% H 2 gas.
They were then mixed up and put in the furnace again for the same conditions to ensure that all of the Si bonded to
the carbon nanotube while keeping the cylindrical structure. The SiCNTs were then purified in air at 700ºC for 8
hours. Once purified, the nanotubes were doped with AE9762 Yb2Si2O7, AE10044 Gd2O3, and AE10045 Yb2O3 in a
weight ratio of 5:1 dopants to SiCNTs. Each doped batch of SiCNT’s was processed under one of 3 sets of
conditions; 1300ºC for 8 hours, 1400ºC for 4 hours, or 1500ºC for 4 hours in a graph-foil lined crucible, again in the
reducing environment of Ar + 5% H2 gas. The first two batches were doped with only AE9762 Yb2Si2O7 or
AE10045 Yb2O3. The third batch was doped with a 2.5: 2.5: 1 ratio of AE10044 Gd 2O3: AE9762 Yb2Si2O7:
SiCNTs. All of the doped nanotubes were then tested using XRD for phase analysis before being prepared for
mechanical testing. Some samples were also examined using SEM to determine how successful the doping was.

B. Mechanical Testing
Samples from both the SiCNT systems and the Yb-silicate systems
were tested for their mechanical strength properties. Powders were
pressed into 1-inch discs using a small hot-press rig. The raw powders
are placed into a graph-foil lined die mold and placed in the press. The
chamber of the press is evacuated and the powders are placed under 15
ksi of pressure and heated to 1500ºC. The high pressure and temperature
sinter the powders together into a solid 1 inch disc. The discs all undergo

Figure 1: The Ball-on-Ring Strength test rig

Glenn Research Center 2 16 December, 2011

 NASA USRP – Internship Final Report

phase analysis using XRD before the mechanical stress tests. To gauge the mechanical strength, the samples are
tested in a BOR force rig. The sample is placed between a support ring and a spherical loading tip driven by
hydraulics. The force on the sample is increased while the sample displacement is measured until the sample
fractures. The mechanical strength of the sample, was then calculated according to Eq. (1)2 where t is the sample
thickness, a is the support radius, b is the radius of constant stress (t/3), R is the specimen radius,  is the Poisson’s
ratio (~0.3), and P is the load.

(1)

C. Environmental Stability Testing

The Yb-silicate systems and the ZrSi bond coats were all tested for environmental stability to simulate the
conditions that would be found inside turbine engines where these coatings might be applied. The ZrSi system was
tested in a furnace with air at a variety of temperatures ranging from 800ºC to 1500ºC. These furnace tests were
done in air to see how the bond coat on its own would react to high temperatures over time. XRD phase analysis
was then done after each furnace test to see how the phases in the bond coat were developing and changing
compared to the original phases of the coating.

The Yb-silicates underwent a variety of tests. The silica-lean (AE9915C) and stiochiometric (AE9914C)
samples were hot-pressed and the pieces from the mechanical testing were then used for stability tests. Each sample
was tested in air at 1500ºC for 50 hours or 100 hours in a furnace. XRD phase analysis and SEM imaging were
then used to examine microstructure and determine the phase changes that occurred during the heat treatments. In
addition to these uniform samples, the hot press was used to make 2 samples of AE9762 Yb 2Si2O7 each with an
oxide top coat of either AE10044 Gd 2O3 or AE10045 Yb2O3. These samples were then tested in the HHFLR with
the steam attatchment (Figure 2a). The samples were heated to 1400ºC on the surface using a laser, while the back
side was cooled by an air stream (Figure 2b). Water lines blast steam over the coated surface of the sample. The
steam test runs for 20 hours,
simulating the effects of water vapor
products of the combustion reactions
in an engine. The sample’s surface
and backside temperatures were
measured with pyrometers which
a. b.
recorded real-time data throughout
Figure 2: a. HHFLR test apparatus with laser heat from above,
the test. The temperature data in cooling air from below, and water lines protected with aluminum foil.
tandem with SEM and XRD analysis b. Close up of a sample during a water vapor test under laser heating.
shows the phase stability of the
samples.

Glenn Research Center 3 16 December, 2011

 NASA USRP – Internship Final Report

III. Experimental Results

A. Silicate Stability
Furnace tests on the Stiociometric (AE9914C) and silica-lean (AE9915C) Yb-silicates resulted in definite
changes in the phases and structure of the samples. After 50 hours in the furnace, AE9914C showed a separation of
Silica from the already-formed Silicate. This can also be seen in the SEM images by the presence of two distinct
phases (Figure 3a.). The darker areas are the silica while the lighter clusters are Yb 2Si2O7. A close up of the
clutsers (Figure 3b.) shows many individual grains of Yb2Si2O7 that seem to hace clumped together during the
furnace tests. In addition, after 100 hours in the furnace, the AE9914C shows no more free silica, only the Yb-
silicate and some Yb-silicide. In contrast, the AE9915C had formed a monosilicate and a dislicate phase after 50
hours in the furnace, and there were the same phases that were present after the 100 hour test as well. This shows
that the extra silica in the AE9914C, as compared to the AE9915C, separated out during the testing and eventually
burned off, leaving only what silica was already bonded to the Ytterbium.

Table 1: Phases present in Yb-silicate samples after Furnace Testing

Figure 3: AE9914C after 50 hours of furnace testing at 1500ºC

a b
a. Two distinct phases are shown silica (darker) and Yb-
silicate (lighter)
b. A close-up of a Yb-silicate cluster showing the
microstructure

B. Nanotube Doping and Mechanical strength

All of the solid disc sample from the hot press were tested for their biaxial strength (Graph 1). The most
important of these results were the doped nanotubes. The goal of these strength tests wass to optimize the nanotube
doping process. The sample with the highest strength was purified SiCNTs with an additional 20% (weight) of Si
powder, just mixed before being placed in the hot press. Although this sample had very good strength test results,
the Silicon is volatile at high temperature without being bonded to something else. If put to use in an engine, the
sample would most likely just burn up. To minimize the amount of sree silicon in the samples, the nanotubes were

Glenn Research Center 4 16 December, 2011

 NASA USRP – Internship Final Report

doped with Yb2Si2O7 (AE9762), Yb2O3 (AE10045) , and Gd2O3 (AE10044). The silicates consistently had better
strength resuls than the oxides. In addition, the mixed oxide and silicates had higher strength than the pure oxides
did. The samples that were processed at 1400ºC also had consistently higher results than those processed at higher
or lower temperatures. AE9762 is silica-lean mixture, and had a lower strength when compared to the
stoichiometric and silica-rich mixtues. Future testing might include doping nanotubes with stoichiometric or silica
rich mixtures since more silica seems to result in higher strength.

Graph 1: The results of the biaxial strength tests

C. Bond Coat heat Stability

ZrSi coated CMC’s were treated in the furnace over a range of temperatures to observe the thermal stability of
the coating (Table 2). XRD phase analysis was done on all the samples after the furnace treatments. The sample
that was tested at 800ºC showed terrible degradationof both the coating and the CMC substrate. This was
determined to be a result of the Pesting effect. 800ºC was too low a temperature for the formation of any silica.

Glenn Research Center 5 16 December, 2011

 NASA USRP – Internship Final Report

The formation of a silica phase creates a protective coating that prevents excessive oxidation and degradation. The
absence of this phase resulted in the immediate formation of a zirconium oxide and pure silica. These are very weak
compounds, causing the coating to flake off of the substrate, and the surbstrate easily chipped apart. When treated at
higher temperatures (900ºC - 1200ºC) the coating showed much more stability. There was uniform formation of
zirconium silicates, oxides, and silicides. The coatings were uniform in color, and there was no degradation to be
found in the coatings or CMC substrates. When tested at higher temperatures (1400ºC +), the coatings showed the
formation of mostly zirconium oxides and Silicates. Though these prevented CMC degradation, the coatings
themselves were brittle and spalled off of the CMC substrate.

Table 2: Phase and physical analysis of the furnace treated ZrSi coated CMCs

Glenn Research Center 6 16 December, 2011

 NASA USRP – Internship Final Report

D. Top Coat Stability

EBC systems often have many layers. The CMC substrate is the base layer followed by a bond coat that helps to
fasten the top coat to the substrate. The ZrSi system was a bond coat system that was studied, but different top coat
systems were also tested as a part of my research. The first system that I studied was AE9762 with an oxide top
coat. Two different top coats, Yb2O3 and Gd2O3, were studied for this system. The samples were made in the hot
press and then tested on the HHFLR with the steam attatchment. Both samples had XRD phase analysis before and
after the steam testing (Table 3) as well as SEM imaging of the samples’ cross-sections(Figures 4 & 5). Combined
with the temperature data from the test (Graphs 2 & 3), we were able to determine the stability of these coatings.
Both coatings became very porous after the steam test. The Yb2O3 spalled off of the 9762 sub-layer in most areas.
Despite the spalling, there seemed to be a lot of inter-diffusion with the Yb2O3 top coat(Figures 4&5 a), implying
very fast silicate formation. In addition to the interdiffusion, the Yb2O3 seemed to be much more porous and have a
lot more contamination(Figures 4&5 b) than the Gd2O3top coat did. The Gd2O3 also had better phase stability
according to the XRD scans.

Table 3: Phase analysis of the 9762 with oxide top coats

a b a b

Figure 4: Gd2O3 coated 9762 Figure 5: Yb2O3 coated 9762

a. Distinct layers show a lack of inter-diffusion a. Inter-diffusion between the oxide top coat
between the top coat and sub-layer (lighter) and the sub-layer (darker)
b. Porosity in the Gd2O3 top coat b. Porosity & Contamination in the Yb2O3 top coat

Graph 2: Temperature data from the Gd2O3 Graph 3: Temperature data from the Yb2O3
HHFLR steam test HHFLR steam test

Glenn Research Center 16 December, 2011

7
 NASA USRP – Internship Final Report

The second top coat system that I studied was an ND system. These samples were CMCs with top coats that
were Hafnia-based with dopants. These samples were also tested
on the HHFLR, but in a regular heat test rather than the steam test.
The samples ranged in composition. ND-0 was HfO2 + 20%
(weight) dopants. The Nd-2 sample was HfO2 + 5% dopants. Nd-3
was HfO2 + 12% dopants, and ND-7 was 20% dopants with 30%
silica. The dopants that were used for these coats were Yttrium,
Gadolinium, and Ytterbium in different ratios. The samples were
tested for 20 hours. In addition to the temperature measurements
taken on these samples during the test, calculations were also made
to find the temperature of the interface between the top coat and the
CMC. With this data, the conductivity of the top coat was
calculated and compared at the beginning and the end of the 20
hour test (Graph 4).
Graph 4: Conductivity changes from the
testing of the ND samples

IV. Conclusions

After strength testing on the BOR rig, we found that Stoichiometric Yb2Si2O7 has higher biaxial strength and
stability than non-stoichiometric compositions or oxide-doped Yb-silicates. When processed in a furnace at 1500˚C,
stoichiometric Yb2Si2O7 (AE9914C) showed silica formation after 50 hours, and silicide formation after 100 hours.
Non-stoichiometric Yb2Si2O7 (AE9915C) showed mono-silicate and di-silicate silicate formation after both 50 and
100 hours. This shows that in the AE9915C sample, all the silica was absorbed into the silicates, while in the
AE9914C sample some of the silica became volatile and burned off during the heat treatment.

The sample with the highest biaxial strength was found to be SiCNT +25% Si due to decreased porosity.
However, Si becomes less stable, and melts quickly at high temperatures. To minimize the amount of silica while
keeping the highest strength possible, nanotube doping was optimized for strength when using AE9762 (silica lean)
Yb2Si2O7, processed in a furnace at 1400˚C. Future experimentation may look at using stoichiometric or silica-rich
Yb2Si2O7 powders instead of the silica-lean powder.

The Zr-Si coatings were found to have the best stability when processed between 900˚C and1200˚C. Processing
at lower temperatures showed the “Pesting Effect”; degradation of both the coating and CMC due to the lack of
continuous SiO2 formation within the coating. Processing at higher temperatures showed fast, non-protective
zirconium oxide formations that resulted in spalling of the coating.

When applied as a top coat, both Gd2O3 and Yb2O3 show porosity after the steam tests, however, there were many
more pores in the Yb2O3 top layer. The Yb2O3 top layer also spalled off the main sample body, although there
seemed to be more inter-diffusion between from the Yb2O3 top coat than there was with the Gd2O3 top coat showing
a quick formation of silicates in the Yb2O3 coated sample and that the Gd2O3 had better phase stability as a top coat.

V. Acknowledgments

I would like to thank my mentor, Dr. Dongming Zhu, for all his guidance with this project, as well as Terry
McCue (SEM/EDS), Rick Rogers (XRD), Bob Angus (Hot Press), Don Humphreys (TGA), Joyce Dever, and the
rest of the RXD branch at NASA Glenn. I would also like to thank the Undergraduate Student Research Program
(USRP) for giving me the opportunity and support to carry out this research at NASA John H. Glenn Research
Center.

Glenn Research Center 8 16 December, 2011

 NASA USRP – Internship Final Report

References

1
Zhu, D., “Advanced Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites: A
Development and Life Prediction Perspective,” RX EBC Mini-Work Shop, 2 Feb 2011.
2
Simpatico, A., Cannon, W. R., Mattewson, M. J., “Comparison of Hydraulic-Burst and Ball-on-Ring
Tests for Measuring Biaxial Strength,” Journal of the American Ceramic Society, Vol. 82, No. 10,
1999, pp. 2737-2744.

Glenn Research Center 9 16 December, 2011