NEW ELECTRON BEAM PHYSICAL VAPOUR DEPOSITION (EB-PVD)

THERMAL BARRIER COATINGS

by
Nadège Coignard and Rodney Wing

(Chromalloy United Kingdom Limited)

ABSTRACT

Partially stabilised 8 wt.% yttria zirconia is the current ceramic material of choice for thermal barrier coatings in gas
turbine engines. However, this material is limited in use to a temperature of about 1200°C due to sintering and phase
transformation. Hence, further increase in efficiency of gas turbine engines (by increasing turbine inlet temperature)
can only be achieved if new ceramic materials capable of operation above 1200°C are developed.

Work has been undertaken within a European Union funded research project to investigate new ceramic
compositions that will operate at increased temperatures compared to the standard 8 wt.% yttria zirconia. New
ceramic materials with different composition and crystal structure to that of partially stabilised 8 wt.% yttria zirconia
have been produced and investigated using air plasma-spraying (APS) and electron-beam physical vapour deposition
techniques (EBPVD). As these new ceramics were not commercially available, it was necessary to produce powders
suitable for plasma-spraying and ingots for the electron beam physical vapour deposition process.

This paper investigates the new ceramic composition coatings produced by electron beam physical vapour
deposition and compares them with the standard partially stabilised 8 wt.% yttria zirconia coating. The new
coatings were characterised by microstructure and by physical properties such as density and thermal conductivity.
In addition, the thermal stability was evaluated by analysing microstructure and phase changes after heat-treatment
and by determination of shrinkage rates at elevated temperatures.

INTRODUCTION

The high pressure section of a modern gas turbine engine operates in a very aggressive environment.
Following combustion highly oxidising gases enter the turbine at temperatures more than 200ºC above the
melting point of the turbine blade superalloy material. In the new generation of civil aircraft gas turbine
engine TET’s (turbine entry temperature) on take-off will exceed 1800K.The only reason that turbine
components survive under these conditions is due to the massive amount of cooling air blown through
them to maintain metal temperature below the superalloy melting point.

The continuing demand for increased power, improved specific fuel consumption and reduced levels of
harmful emissions in modern gas turbines has resulted in a progressive increase in TET since introduction
of the gas turbine engine. This trend is expected to continue into the foreseeable future as more powerful,
fuel efficient engines are developed as shown in Figure 1.

Current high performance gas turbine engines already use EBPVD thermal barrier coatings on high
pressure turbine blades and nozzle guide vanes to reduce metal temperature to enable components to
survive at the very high temperatures present in this section of the engine. With time at temperature the
currently used ceramic material, partially stabilised 8 wt.% yttria zirconia, will sinter with a change to
critical properties such as thermal conductivity and fracture toughness as shown in Figures 2 and 3. 1
However, as turbine temperatures increase further then improved thermal barrier coatings are required to
meet this need.

YEAR
 2000

1950

1900

1850

1800
TET (K)
1750

1700

1650

1600

1550

1500
1975 1980 1985 1990 1995 2000 2005

YEAR

Figure 1. TET trend in civil aero-engines

(a) (b) (c)

Figure 2. Showing comparison between standard 8wt.% yttria/zirconia

as new (a) and in sintered condition (b) and (c)

1200oC exposure

250%
thermal conductivity

200%

150%

100%

50%
0 1000 2000
tim e at tem perature (hrs)

Figure 3. Changes in thermal conductivity of standard 8wt.% yttria/zirconia

with time at temperature exposure.

Thermal barrier coatings currently in use in gas turbine engines are 8 wt.% yttria/zirconia ceramic
material. This composition has a high melting point, low thermal conductivity and a relatively high
coefficient of thermal expansion and is ideal for use as a thermal barrier coating on nickel based
superalloy materials. The requirement for new ceramic materials is high toughness, very low thermal
conductivity, high temperature microstructure and phase stability and ability to remain attached to the
bond coat for long times at high temperature 2,3,4. It may also be possible to pursue these aims by utilising
the standard bond coat/ceramic system for the initial coating with an improved ceramic layer deposited on
top.

2
PROCESSING

Both standard and new ceramic thermal barrier coatings were deposited using both development and
production EBPVD coaters. Initial coating trials and coating of test pieces was undertaken using the von
Ardenne pilot plant coater at the German Aerospace Centre (DLR). Production trials were undertaken at
Chromalloy United Kingdom Ltd using the ALD manufactured production coater.

The ceramic coatings deposited by electron beam physical vapour deposition for evaluation were as
follows;

EB – PSYZ : standard 8wt.% yttria/zirconia

EB – PYR : pyrochlore
EB – PDZ : pentavalent doped zirconia

The pentavalent doped zirconia (PDZ) was included in the programme as these types of materials exhibit
high phase stability, high fracture toughness, low thermal conductivity and low thermal expansion
compared with the standard 8wt.% yttria/zirconia material. Pyrochlore materials also show these types of
improvements and an example (PYR) was also included for evaluation.

Development Deposition Trials

The initial coating trials on the new ceramic materials (PYR and PDZ) were undertaken using pilot plant
equipment (Espri von Ardenne) with a maximum EB power of 150KW at the Institute for Materials
Research, German Aerospace Centre (DLR). Dense alumina plates and disks were used as the test pieces
and these were rotated at 12 revolutions per minute during coating. It was noted that material PDZ was
more difficult to evaporate.

Examination of the coatings following deposition revealed microstructures and surface morphologies as
shown in Figures 4 and 5 respectively.

(b) PYR
(a) PSYZ (c) PDZ

Figure 4. a, b and c showing cross section of PSYZ, PYR and PDZ ceramic materials

(a) PSYZ (b) PYR (c) PDZ

Figure 5. a, b and c showing surface (column tips) of PSYZ, PYR and PDZ ceramic materials

3
Production Deposition Trials

Deposition parameters obtained from the development coating trials using the DLR EBPVD coater were
used in the C-UK production coater to establish the deposition characteristics of the PYR and PDZ
materials.

The PDZ material was difficult to evaporate in a homogenous manner even using advanced beam control
techniques. A lot of “spitting” occurred during melting and was reflected in the coated surface produced;
Figure 6 compares the surfaces produced following deposition of PYR and PDZ materials. In addition,
evaporation of the PDZ ingot could only be made to happen at a very slow rate being a factor of about 5
times less than standard PSYZ material.

Evaporation of the PYR material was much easier and the evaporation rate was about the same as the
standard material. There were no problems of “spitting” and the coated surface produced was similar to
the standard material.

(a) (b)
)
Figure 6. a and b, showing as deposited surface condition for PYR and PDZ materials.

(a) PSYZ (b) PYR

(c) PDZ

Figure7. a, b and c, showing cross section microstructures for PSYZ, PYR and PDZ materials.

COATING PROPERTIES

Phase Stability

XRD analysis of the PYR as deposited ceramic material revealed it to be fine grained and weakly
crystalline; sharpening of XRD peaks after thermal exposure indicates that crystallisation and grain
growth occurs during ageing but phase stability is maintained. XRD analysis of PDZ material shows
some crystallisation on ageing but tetragonal phase remains stable. Phase stability is increased for both
new compositions compared with the standard PSYZ ceramic.

4
Composition

Analysis of the PDZ ceramic at DLR following deposition in the C-UK production coater confirmed it to
contain different amounts of constituents compared with the original ingot composition; one of the major
constituents was seen to have reduced by between 10-13 wt.%. This confirmed the uneven melting as
seen during evaporation in the C-UK coater

Microstructure

The microstructures of the as deposited PYR and PDZ materials from DLR development coater and the
C-UK production coater are shown in Figures 4, 5, 6 and 7. Both new ceramic coatings exhibit typical
EBPVD columnar morphology but column width and inter-columnar structure differs from that of
standard PSYZ; the PYR ceramic appears more branched and PDZ shows larger columns.

Following thermal exposure the feather arm structure is lost for the PSYZ and PDZ ceramic coatings but
is retained in the PYR variant as shown in Figures 8 and 9. The PDZ aged coatings also show fully
recrystallised grains with considerable grain growth.

(a) PSYZ (b) PYR (c) PDZ

Figure 8. a, b and c, cross sections PSYZ, PYR and PDZ ceramic materials, thermal
exposure 100 hours at 1300ºC or 1400ºC.

(a) PSYZ (b) PYR (c) PDZ

Figure 9. a, b and c, tips of columns of PSYZ, PYR and PDZ ceramic materials, thermal
exposure 100 hours at 1300ºC or 1400ºC.

Density

The density of the standard and new ceramic materials was measured using a water immersion
(Archimedes) method; measurements were made in the as deposited condition and after thermal exposure
at 1300ºC and 1400ºC for 100 hours.

Little difference was seen in the density after 1300ºC exposure but a significant increase in density
occurred after 1400ºC exposure as shown in Figure 10. Porosity decreases to almost zero following
1400ºC exposure.

5
Thermal Conductivity

Thermal conductivity was calculated using experimental results obtained from thermal diffusivity
measurements. The method used a 10.6 µm wavelength laser which was directed at the front face of the
test specimen inside a furnace; the increase in temperature was measured at the rear of the test piece with
an infra-red detector. Thermal conductivity values for the as deposited coatings are 0.8 (PYR) and 1.0
(PDZ) W.m-1.K-1 and are considerably lower than the standard coating (PSYZ) value of 1.7 W.m -1.K-1 as
shown in Figure 10. With thermal soaking for 100 hours at 1300ºC both PYR and PDZ showed an
increase in thermal conductivity but were still below the standard material; with soaking at 1400ºC the
PDZ material had slightly increased thermal conductivity of 1.2 W.m -1.K-1 compared with its original
value but was significantly lower than the standard material at the same test condition; no value was
available for PYR at 1400ºC.

SAMPLE AGED CONDITION THERMAL CONDUCTIVITY DENSITY

W.m-1K-1 g/cm3
virgin 1.7 5.06
PSYZ 1300C 1.7 5.11
1400C 2.4 5.67
virgin 0.8 4.85
PYR 1300C 1.4 4.90
1400C - -
virgin 1.0 5.84
PDZ 1300C 1.2 5.92
1400C 1.2 6.36

Figure 10. Thermal conductivity and density measurements in as deposited and thermally exposed
conditions.

SUMMARY

1. Deposition trials in both development and production EBPVD coaters revealed that the PYR
pyrochlore ceramic material was much easier to evaporate and deposit than the PDZ pentavalent
doped zirconia material.

2. The microstructure of the as deposited PYR coating is closer to the standard PSYZ material with the
PDZ coating having a much larger column width. Following thermal exposure the PYR ceramic
structure still retained its feather arm structure although it had been lost on the PSYZ and PDZ
materials.

3. Thermal conductivity measurements following thermal exposure revealed that although the PYR and
PDZ materials showed an increase, both were still below the value for the standard PSYZ material.

4. The phase stability of both new ceramic coatings is superior to that of the currently used partially
stabilised 8 weight percent yttria zirconia material.

6
5. It is evident from the work undertaken to date in the EU funded research programme that the PYR
ceramic material has more potential for productionising and applying to turbine components due to its
much better evaporation characteristics and columnar microstructure. However, no data is yet
available on spallation resistance of the PYR ceramic and this needs to be obtained as soon as
possible to complete the understanding prior to any commitment to engine testing.

REFERENCES

1. “High Temperature Ageing EBPVD Thermal Barrier Coating”, U.Schultz, K.Fritscher, C.Leyens,
M.Peters, CESP 12, 4 Part B, 2001

2. “Thermal Barrier Coatings with High Phase Stability”, R.Subramanian, US Patent 6,258,467 B1,
2001

3. “Zirconates as New Materials for Thermal Barrier Coatings”, R.Vassen, X.Cao, F.Tietz, D.Basu,
D.Stover, Journal American Ceramic Society, Volume 83, 2000

4. Thermal Properties of Zirconia Co-Doped with Trivalent and Pentavalent Oxides, S.Raghavan,
H.Wang, W.D.Porter, R.B.Dinwiddie, M.J.Mayo, Acta Materialica, 49, 2001