In: Superalloys: Production, Properties

ISBN: 978-1-61209-536-3
Editor: Jeremy E. Watson, pp. 73-96
2011 Nova Science Publishers, Inc.

Chapter 5

MECHANICAL PROPERTY AND

CHARACTERIZATION OF A NICOCRALY
TYPE METALLIC BOND
COAT USED IN TURBINE BLADE MADE OF
AE-437A NI BASE SUPERALLOY
Ashok Kumar Ray*
National Metallurgical Laboratory,
Council of Scientific & Industrial Research (CSIR), Jamshedpur, India

ABSTRACT
This work highlights some of the results obtained while studying
Ni20Co18Cr12.5Al0.6Y (NiCoCrAlY) type metallic bond-coat properties of a
thermal-barrier coated (TBC), AE-437A Ni base superalloy mostly employed for
manufacturing compressor and stationary stator blades in aero turbines.
Experiments were mainly focused in the area of evaluation of microstructure,
residual stress, shear strength, hardness and with special emphasis in establishing
the ductile to brittle transition temperature (DBTT) of the bond coat by using
acoustic emission technique during room temperature and high temperature tensile
* Corresponding Author: Dr. Ashok Kumar Ray, Email :asokroy@nmlindia.org ;ray.ashok@
rediffmail.com, Telephone: 0091-657-2345197, Fax: : 0091-657-2435213 ;2435153, Postal
Address: Deputy Director, Materials Science and Technology Division, National
Metallurgical Laboratory (CSIR), PO-Burmamines, Jamshedpur-831007, India

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Ashok Kumar Ray

tests. Results reveal that the residual stress was tensile in nature in the TBC layer
and compressive in the bond coat as well as in the substrate. The DBTT of this
bond coat is around 650 C, which is in close proximity to the value reported in
literature for CoCrAlY type of bond coat. Finite element technique was used to
analyze the equivalent stresses in the bond coat, the result of which revealed the
highest order of equivalent stress 800 C, as the bond coat is ductile above 650 C.
Shear strength of the bond coat is in close proximity with that of the bond strength
reported in literature for CoCrAlY and Ni22Co17Cr12.5Al0.6Y types of bond coat

Keywords: Microstructure, Residual stress, Hardness, Tensile, Acoustic

emission, shear, Thermal barrier coated, Superalloy, Bond coat.

1. INTRODUCTION
Ceramic thermal-barrier coatings (TBCs) have received increasing
attention for gas-turbine engine applications. In the global scenario, both
industry and academia are actively pursuing research on evaluating the
lifetime and thermomechanical behaviour of superalloys with ceramic thermal
barrier coatings (TBCs) which are candidate materials for various components
such as turbine blades, vanes, combustors, etc. These components generally
are subjected to high mechanical stresses and aggressive environments [1-28].
The advantages of using TBCs include increased fuel efficiency by allowing
higher gas temperatures and improved durability and reliability from lower
component temperatures. It was established that under conditions simulating
jet engine applications [4,5], one significant contributor to TBC failure is
spalling from the oxidation of the bond coat, and many studies have
concentrated on the time to spalling as a function of heat flux [6-9] and as
functions of surface stresses and crack tip opening [9]. The life of thermal
barrier coating prior to spallation is dominated by micro-cracking in both the
thermally grown oxide and the yttria stabilized zirconia top coat. The damage
generated by this micro-cracking is expected to be a primary life limiting
factor. Analysis of life data indicates that cyclic thermal loading and thermal
exposure play synergistic roles in controlling the spallation life of the coating
[17]. It cannot be ruled out that the TGO (thermally grown oxide ) scale
growth stress, top coat sintering, creep and the thermal expansion mismatch
stress act synergistically as the driving force behind cracking. However, the
damage process occurs during cooling and when the system is cooled. Studies
on effects of yttrium, aluminum and chromium concentrations in bond

Mechanical Property and Characterization

75

coatings on the performance of zirconia--yttria thermal barriers revealed that

without yttrium in the bond coatings, the zirconia coatings failed very rapidly.
Increasing concentrations of chromium and aluminum in the Ni--Cr--Al--Y
bond coatings increased the total coating lifetimes [18]. This effect was not as
great as that due to yttrium. Increased bond coating thickness was also found
to increase the lifetimes [18] and it was found [18] that the thermal fatigue
resistance increased with decrease of the maximum principal residual stress of
the top coat and the thickness of oxidation layer of the bond coat. Ceramic
sintering and creep, bond-coat oxidation, the effects of thermal cycling, and
their relevance to coating-life prediction are some of the critical issues
surrounding TBCs [19]. Experimental testing techniques have been developed
[19] to characterize these TBC properties on CMSX-4 substrate and to
investigate the failure mechanisms of the coatings. Emphasis is placed on the
dynamic changes of the coating thermal conductivity and elastic modulus,
fatigue and creep interactions, and resulting failure mechanisms during
simulated engine tests [19]. In actual practice there are situations when the
surface of the combustor also bulges, due to violation of the operational stress
conditions, which is a clear indication of creep damage [2].
The substrate material AE-437A Ni base superalloy in the present study is
mostly employed for manufacturing compressor and stationary stator blades in
aero turbines. Establishment of the DBTT (Ductile-Brittle-Transition
Temperature) of the bond coat is most significant as it enables us to estimate
the operating temperature of the TBCs in actual practice. Keeping this in mind,
this paper aims at characterizing the bond coat by some non-destructive tests
(NDT) of which acoustic emission technique during tensile testing on the bond
coated substrate at room temperature as well as determination of shear strength
of the bond , is most relevant in this work.
Acoustic emission (AE) technique was adopted to find out the percentage
strain to first cracking in the MCrAlY type of bond coat which is a brittle
material. Also, because it is currently being developed for use in continuous
monitoring of the integrity of structures such as aircrafts, pipelines, nuclear
reactors and composite pressure vessels. It is a non- destructive technique,
which has found considerable application in the past decade for detecting
crack formation and propagation in engineering structures as diverse in nature
as aircraft wings, high pressure vessels, sea oil rigs etc. [29-31]. The principle
of the technique is simple. Any sudden movement within a material results in
the release of acoustic and thermal energy. The resultant acoustic waves
propagate through the material in all directions from the source and may be
detected by sensitive detectors on the material surface as mechanical

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Ashok Kumar Ray

oscillations. In certain cases, e.g. ice on a pond or wood of a stair treads

creaking under a persons weight, they are in the right frequency and intensity
(amplitude) range to be audible by the human car. Such sudden movements
and energy phases may originate from crack initiation and propagation when
the material is mechanically stressed, but they may also originate from phase
separation or phase change [29].

2. EXPERIMENTAL
2.1. Generation of TBCs
Hot rolled Ni base superalloy grade AE 437 A (see Table.1) was the
substrate material for the TBCs. The alloy had been solution treated (heated
o
to1080 C for 8 hours followed by air cooling and then subsequently ageing at
o
700 C for 16 hours followed by air cooling ) which lead to non-textured '
(18.98 mean volume %) strengthened polycrystalline alloy with ~60 m
diameter grains containing intragranular as well as intergranular carbides. A
Ni 20Co18Cr12.5Al0.6Y type metallic undercoat/bond coat was first applied
by plasma spraying to ensure the bonding and adherence of TBC (ceramic
layer) on the substrate and also to improve the corrosion resistance of the
TBC. Thereafter, zirconia (stabilized with 8 wt% yttria) based TBC was
plasma sprayed on the bond coat. The plasma gas for the TBC as well as for
the bond coat was Metco 7 MB (mixture of Ar/H2). The plasma spraying
parameters are collated in Table 2. The bond coat as well as the ceramic layer
were deposited by plasma spraying on all the four sides of the flat, solution
aged and machined specimens. Specimens were machined by electrical
discharged machining
Table.1 Chemical analysis of the substrate (AE437 A super alloy).
Material

Elements (mass %)
Cr
Si
Mn Ti Al C
Fe Ce P
S
Pb
Ni
AE 437A 19.82 0.06 0.19 2.50 0.81 0.039 0.07 0.01 0.003 0.001 0.001 Balance
super alloy

Mechanical Property and Characterization

77

Table. 2. Spray parameters for top coat (TBC) and bond Coat
I. Plasma spray parameters for top coat (TBC) on the bond coat
Plasma gas: 9MB
Gas mixture (Argon and
Pressure,
Gas flow rate
Hydrogen)
MPa
SCFM
Argon
0.689
80
Hydrogen
0.552
13
Arc current: 800 Amps
Arc voltage: 100 Volts
Spray distance:102 mm
II. Plasma spray parameters for bond coat (Ni20Co18Cr12.5Al0.6Ytype) on substrate
(AE-437A Ni base superalloy)
Plasma gas::SG 100
Gas mixture (Argon and Helium) Pressure,
Gas flow rate
MPa
SCFM
Argon
0.296
10
Helium
0.827
50
Arc current: 609 Amps
Arc voltage: 115 Volts
Spray distance:63 mm

2.2. Metallography
The TBC -substrate material was polished and the thickness of the TBC
(ceramic layer) as well as that of the bond coat were measured by optical
microscopy. All the samples were polished by standard metallographic
technique and by using a final polishing step with 0.1m diamond paste.
Etchant used was 20% HNO3, 10% HCl, 20% distilled water and 50% fresh
glacial acetic acid. To reveal the ' precipitates in the matrix of the substrate,
the substrate material after the final polishing step, was etched with glycergia
(10 ml conc. HNO3 , 15 ml conc. HCl , 10 ml glacial acetic acid, & three
drops of glycerol). The mean volume % and the mean aspect ratio of the of the
' precipitates were calculated by image analysis technique. A few of the TBC
specimens were oxidized at 1000oC for 200 hours in an Argon/20 volume%
oxygen atmosphere. The precipitates in the substrate, at the bond
coat/substrate interface and in the Al depleted zone after the bond coat were
analyzed using EDS (Energy Dispersive Spectroscopy) facility attached to
JSM 840A SEM (Scanning Electron Microscope).

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Ashok Kumar Ray

2.3. Measurement of Residual Stress

Residual stresses were measured using an AST portable stress analyzer
from the peak shift in the Sin2method. Data collected for x-ray stress work
and XRD pattern on each layer of the composite sample over a range of 2
range 132 to 135o using CrK (30kV/5mA) radiation showed the order of
residual stresses in the TBC layer, bond coat and in the substrate. Each
measurement was taken using four tilt angles ( = 0 to 45o). The measuring
parameters during residual stress measurements were as follows:
A. Measuring parameters: For the TBC layer
Equipment
Method
Radiation
Diff. Plane
Voltage/Current
E
v

: AST Portable X-ray stress analyzer

: Sin2method
: CrK
: (313) ZrO2
: 30kV/5mA
: 110GPa [1,8,9]
: 0.3

B. Measuring parameters: For bond coat and substrate

Equipment
Radiation
Method
Diff. Plane
Voltage/Current
E
v

: AST Portable X-ray stress analyzer (USA)

: CrK
: Sin2method
: (220) Ni
: 30kV/5mA
: 206GPa for bond coat & 210 for substrate
: 0.28 for bond coat & 0.29 for substrate

Due to the presence of residual stress, , there would be a peak shift d

in the x-ray diffraction curve. This can be used for calculation of , from the
following equation.
= E d//[d(1 ) Sin2 ]

(1)

Mechanical Property and Characterization

79

2.4. Hardness Measurement on Bond Coat

Nano indentation was performed on the bond coat, for enabling estimation
of the hardness of the bond coat . Several of these tests were carried out on a
Nano Indenter XP machine. Indentations were made with Berkovich indenter
having a tip diameter of 40 nanometers (0.040 m), under continuous stiffness
measurement (CSM) mode up to 2000 nanometers (2m) with a harmonic
displacement target of 3 nanometers (0.003 m).

2.5. Tensile Test

Since the material used in practice is in the solution-aged condition, all the
o
tensile specimens of the substrate were solution aged (heated to1080 C for 8
o
hours followed by air cooling and then subsequently ageing at 700 C for 16
hours followed by air cooling) prior to final machining and then finally
cleaned with ethanol to remove the scales and to degrease the final test
specimen. Specimens were machined by electrical discharged machining.
Tensile tests at room temperature (25oC), 200oC, 400oC, 600oC and 800oC
of the TBC specimens were performed using a digitally controlled 8562
Instron Servo-Electric Testing System, equipped with a 3-zone split furnace
with PID control. Standard tensile specimens were made as per ASTM E8-79
specification. The specimen geometry was maintained as flat specimen (dog
bone shape) with nominal dimensions of a thickness of 3mm and width of 4
mm from the longitudinal direction of the bars of AE 437A Ni base superalloy.
The bond coat was deposited by plasma spraying on all four sides of the
solution aged and machined flat tensile specimens on the gauge length portion.
So the coating thickness was 10% (bond coat only) of the thickness of the
substrate. Tensile tests were carried out on the bond coat samples and also on
samples without the bond coat. During tensile testing, temperature was
maintained constant to within 2oC and a constant displacement rate of 0.2
mm/min was maintained. An acoustic emission technique was employed for
monitoring the initiation of first cracking phenomenon in the bond coat. This
is a sensitive technique for monitoring any dynamic substructural change
occurring within a material such as plastic deformation, crack initiation and
crack growth. For monitoring the acoustic emission generated during testing, a
70 kHz resonant high temperature sensor was placed on the pull rod. Signals
were amplified by a 40dB amplifier and were then fed into a Spartan AT

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Ashok Kumar Ray

system (PAC, USA) for analysis. The threshold setting was kept at 45dB to
eliminate the background noise. A typical representative of the AE signals
generated during the test showing the AE activity with respect to load vs time
and counts vs time for the 800oC test, is shown in Fig.1.

Figure 1. Acoustic emission activity recorded for a specimen with Ni20Co18Cr12.5Al

0.6Y type bond coat during tensile test at 800oC.

2.6. Shear Test

Shear test of the TBC samples were conducted at ambient temperature on
a table top Universal Mechanical Testing (UTS) machine (Honsfield H-10KS,
10 kN capacity), at a cross head speed of 0.1mm S-1. An indigenously
designed fixture was used for this purpose. Reproducibility of the data was
checked by performing the test with three samples. The TBC coated
(substrate+ bond coat + top coat) samples were placed in the
fixture and the fixture was mounted on the table top UTS machine with
proper clamping device. In case of shear test of the bond coat/substrate
interface, interaction between the specimen and the test fixture may lead to the
following problems,
(i) The fixture may not load the specimen asymmetrically.
(ii) The specimen may twist during the test.
(iii) The two-fixture portion may misalign during the test

Mechanical Property and Characterization

81

During the design of the fixture, special consideration have been made to
minimize the above-mentioned problems. In this case the mould (M) and the
plunger (P) are made large enough to accommodate the small bending force so
that words the effective bending force on the sample is minimized (Fig.2)..

P
H1
M

H2

Metal

Bond Coat + TBC

BASE PLATE

Figure 2. Schematic of the indigenously designed and fabricated shear test fixture used
in the present investigation [33].

The thickness of bond coat/substrate interface was narrow, so it was

difficult to differentiate (through a lens) the interface from the substrate .
Therefore shear tests were carried out for all the samples keeping the plunger
close to the bond coat/ substrate interface, as it was expected to be the weakest
zone to fail. In all practical purposes lowest strength has been considered as
the strength of the bond coat/substrate interface.

3. FINITE ELEMENT ANALYSIS

To evaluate the stress distribution within the bond coat, a finite element
(FE) model was developed using ANSYS 6 (Swanson Analysis Inc.).
PLANE82 (eight-noded quadrilateral structural element) was selected for the
analysis [10,11]. The model geometry used in the analysis represented a
rectangular shape AE 437A Ni base super alloy substrate of 2.5 mm in

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Ashok Kumar Ray

thickness; the bond coat layer of 0.1 mm in thickness and the width of the
specimen is 3.5 mm. A half model was used since the specimen is axi symmetric. Material properties [8,9] used in the finite element calculation are
shown in Table.3. During the tensile tests, a particular load of 400 N, which is
well within the elastic limit of the composite specimens comprising of
substrate + bond coat, was selected at different temperatures. This enabled
calculation of the equivalent stresses in the bond coat at a particular load (see
Table.4).
Table. 3 Material properties /8,9/ used in the finite element calculation
Material

Temperature
0
C
Ni base super alloy 25
(substrate)
200
400
600
800
NiCoCrAlY
25
(Bond coat )
200
400
600
800

E(Young's Modulus)
GPa
210
208
206
204
200
209
206
200
190
183

(Poisson's ratio)
0.29

0.28

Table. 4 Stresses in bond calculated from Finite Element Analysis

Temperature
0
C
25
200
400
600
800

Equivalent Stress, Pa
max
287345
287608
307081
307492
307610

min
176103
175712
175123
174631
174726

Table.5 Polynomial constants from regression analysis.

Type of material

Order of polynomial

AE 437A superally
m=1, C = 15
(substrate)
TBC coated substrate m=1, C = 15

Standard
deviation
98.454

ao

a1

7.5436

-2.85034 X 10-4

99.779

9.22364

-3.66597 X 10-4

Mechanical Property and Characterization

83

4. RESULTS AND DISCUSSION

Optical metallograpby of the TBC composite revealed that the ceramic
layer and the bond coat were 290 m and ~100 m thick respectively ( Fig.3
(a)). The TBC or top coat layer had ~ 15% porosity which is normally desired
[1] and the bond coat also had pores that offer attractive sinks for stress
relaxation. The substrate in solution aged condition showed precipitation of
carbides within the grains , (Fig.3(b)) and the carbides within the grains were
MC (M=Ti) type and those at the grain boundary were mainly M23C6 (M = Cr,
Mo), which has been found in EDS analysis [15]. The morphology of the '
precipitates (18.96 mean volume%), revealed in Fig.3 (c) clearly shows that
they were more or less cuboidal in the substrate , with a mean aspect ratio of
1.94. X ray line profile depicted in Fig,3b, reveals the elemental distribution
along a particular direction from TBC to bond coat.. Only a part of the TBC
layer is shown. Arrows in the top coat or TBC layer and in the bond coat show
the presence of micro-pores. Fig. (e) X ray dot mapping of different elements,
along the direction of the large arrow in the micrograph (from TBC to bond
coat).

Figure 3(a). Typical optical metallograph of the thermal barrier coated AE 437A super alloy
(in unetched condition). The width of the TBC (ceramic coating- 8wt% yttria stabilized
zirconia) is 290 m. The width of the bond coat is around 100 m. Arrow indicates
presence of micri pores.

The EDS analyses of the precipitates at the bond coat/substrate interface

and in the diffused zone in the substrate after the bond coat are revealed in Fig
. 4 . In the diffused zone the Al peak intensity was least which justifies the fact
that a part of the Al from the bond coat has diffused out of the depleted zone

84

Ashok Kumar Ray

into substrate after the bond coat. This phenomenon was also observed by
previous investigators, on TBC coated Ni base superalloys used for turbine
blades and vanes [1,4,5,8,9]. The Al depleted zone is observed when the TBC
specimens were oxidized at 1000oC for 200 hours in an Argon/20 volume%
oxygen atmosphere.

Figure 3 (b ). SEM micrograph of the substrate revealing M23C6 carbides on the grain
boundaries and MC6 carbides within the grains . Prior austenitic grain boundary and EDS
analysis of the precipitates within the grains have been shown.

Figure 3 (c). SEM micrograph of the substrate clearly revealing that the ' precipitates in
the matrix are cuboidal shaped.

Mechanical Property and Characterization

85

Bond Coat
TBC

(d) X ray of
linedifferent
profile of different
elements,
along the
of the large
arrow
in thearrow
Figure 3 (d). X rayFigure.3
line profile
elements,
along
thedirection
direction
of the
large
micrograph (from TBC to bond coat). Only a part of the TBC layer is
in the micrograph (from TBC to bond coat). Only a part of the TBC layer is shown. Arrows
in the TBC layer and in the bond coat show the presence of micro-pores.

Figure 3(e). X ray dot mapping of different elements, along the direction of the large arrow
in the micrograph (from TBC to bond coat).

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Ashok Kumar Ray

Al2O3

Figure 4 SEM micrograph of the cross section of heat treated TBC sample revealing oxidation of bond
Fig.4 SEM micrograph of the cross section of heat treated TBC sample revealing oxidation of bond coat and
coat and formation of Al2O3 layer of thickness 3 m at the TBC/bond coat interface, Al depleted
zones (confirmed from EDS analysis) are seen at the TBC/bond coat and bond coat/substrate interfaces.
Substrate reveals coarsening of grains with rich ' precipitation within the grains in the substrate
(confirmed from EDS analysis).

Mechanical Property and Characterization

Material
TBC layer
Bond Coat
Substrate

Stress (MPa)
Centre
15
-314
-411

Edge 1
37
-321
-425

87

Edge 2
19
-304
-436

Figure 5. Schematic of the TBC coated substrate indicating the locations and nature of
residual stresses.

Figure 6a. Typical variation of load with displacement for plasma sprayed bond coat
layer. The arrows indicate pop-in or discontinuities (pores) in the bond coat.

88

Ashok Kumar Ray

Plasma spraying induces an extremely large thermal gradient onto the

surface of the specimen that is being coated. Under many instances, residual
stresses might form within the deposited coating and substrate. As the nature
of the residual stresses might influence the fatigue behavior of TBC specimens
[25], measurement of residual stresses in each layer of the composite was
essential. The nature of residual stress () present in the TBC (top coat) is
tensile, which was introduced during plasma spraying. However, the
magnitude of is of the order of 15 to 37 MPa and is negligible. The TBC
layer, however, is very brittle and its strength is negligible. Following the TBC
(top coat) layer, is the bond coat and it had compressive residual stresses. (
Fig.5) The bond coat was first deposited on the substrate by plasma spraying
and on its top, the TBC was generated by plasma spraying. So, whatever
tensile residual stresses would have been introduced in the bond coat due to
the plasma spraying technique, they would have been relieved (stress
relieving) due to the deposition of the ceramic layer (TBC or top coat) on the
top of the bond coat. Therefore, finally after the coating of TBC was
generated, the TBC showed tensile residual stresses and the bond coat revealed
compressive stress, which is due to the deposition of ceramic layer (TBC) on
the bond coat. The substrate revealed compressive residual stresses (Fig.5).
Compressive residual stresses are beneficial, as they would increase the
fatigue life of the entire composite specimens comprising of three layers. It
should be noted that the term compressive in the present case is used only in a
relative sense from the negative sign (Fig.5) in order to delineate from the
tensile residual stresses present in the ceramic layer.
Fig.6 typically represents the variation of load (Fig.6(a)) and hardness
(Fig.(6b)) with displacement, in the plasma sprayed bond coat layer from nano
indentation tests. It is noteworthy that nano indentions performed on the bond
coat were till a depth of 2000 nanometers only, which corresponded to 2 % of
the total coating thickness of the bond coat . Therefore, there is negligible
influence of the substrate on the hardness of the bond coat. Several readings
were taken and only a typical representation of variation of load and that of
hardness with displacement is revealed in Fig.6. It is clear from Fig.6(a) that
there are plenty of discontinuities in the load-displacement curve, indicated by
arrows. The arrows indicate pop-in or discontinuities (pores) in the bond
coat. The anisotropy in the bond coat was due to the presence of pores, which
offer as attractive sinks for stress relaxation. Therefore, the hardness values
reported in Fig.6(b) are all qualitative because of the presence of porosity and
its influence on the hardness of the bond coat.

Mechanical Property and Characterization

89

Figure 6b. Typical variation of hardness with displacement for plasma sprayed bond
coat layer.

The ceramic layers provide an increase in the thermal inertia of the parts
and therefore a reduction of the severe thermal temperature gradients during
heating and cooling [ 1,2,8 ] of the gas turbine components (i.e. improvement
in thermal fatigue behavior). It also reduces the substrate temperature and so
there is a possibility of increasing the turbine inlet temperature or cooling air
mass flow. This means efficiency gain in both cases [1]. Thermo graphic
studies [14] carried out on the TBC composite, across the substrate to the
ceramic layer (top coat), revealed that at 800oC, there was no temperature
gradient between the ceramic layer, bond coat and the substrate as the TBC
composite is thermodynamically in a steady state condition.
The mechanical integrity of the bond coat is related to its ductility.
Ductility is generally quantified by the strain necessary for the initiation of the
first crack in a coated material in a bending or tension test [1]. The load at
which the first AE signal to cracking of the bond coat appeared was noted
along with the corresponding displacement value recorded in the machine.

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Ashok Kumar Ray

Knowing the Youngs Modulus of the bond coat at the particular test
temperature from literature [8,9], the % strain to cracking was calculated , thus
enabling the plot of % strain to cracking vs test temperature (Fig.7).The
elevated temperature tests reveal that, above a certain temperature, the strain to
cracking increases rapidly, which means that the material behaves in a ductile
way [1]. It is then possible to define a ductile -to -brittle transition temperature
(DBTT). In the case of samples without bond coat no AE activity was
observed within the elastic limit of load-displacement plots, so this justifies
that it is the bond coat which cracks first well within the elastic limit of the
bond coated composite samples and the acoustic signals observed were due to
the cracking in the bond coat only. In the case of aluminide coatings [1], the
DBTT ranges from 600 to 750oC. The transition temperature depends on the
thickness of the coating as well as the Al content. As far as the MCrAlY bond
coat is concerned, a somewhat less brittle behavior is reported than that of
aluminides [1], but the ductility depends on the Al content. The transition
temperature, is dependent on the Al content in the bond coat. When the
components are subjected to severe thermo-mechanical cycles, MCrAlY is
chosen because of its favorable ductility and thermal expansion coefficient.
There is no acceptable approach available to date [1], for use in making
quantitative judgments of sufficient combinations of properties for design. In
the present investigation, the type of bond coat applied was Ni20Co18Cr2.5Al
0.6Y and it is clear from Fig. 7, that the DBTT of this bond coat is around
650oC, which is in close proximity to the value reported for CoCrAlY [1] and
for Ni 22 Co 17 Cr 12.5 Al 0.6 Y type of bond coats [ 25 ]. However, since the
coating composition may noticeably change as a function of time and service
environment, in this instance, information drawn from service experience is
ultimately needed.
Finite element technique used for analyzing the equivalent stresses in the
bond coat, well within the elastic limit of the composite specimens (see
Table.3), during tensile tests, revealed highest order of equivalent stress at
800oC as the bond coat is ductile above 650oC. It is observed from Fig.8 that
although the maximum equivalent stress in the bond coat did reveal standard
deviation values, the minimum equivalent stress in the bond coat has hardly
shown any standard deviation value.
Experimental raw data variation of load vs displacement plot of the as
received and heat treated TBC coated (substrate+ bond coat + top coat)
samples during shear tests and their respective shear strengths are depicted in
Fig.9. The values of the shear strength of the bond coat are in close proximity
with those of the bond strengths reported in [8,9] for MCrAlY coatings.

Mechanical Property and Characterization

Figure 7. Ductile to brittle transition temperature of Ni20Co18Cr12.5Al0.6Y bond

coat.

Figure 8. Variation of equivalent stress in the bond coat with test temperature.

91

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Ashok Kumar Ray

The NiCoCrAlY bond coat generally consists of Ni- rich - NiAl phase that
gradually transform to -Ni3Al phase due to oxidation or interdiffusion [1].
Precipitation of Al-rich -Ni3(AlTi) phase in the substrate (see Fig.4) probably
led to overall strengthening of the metal matrix of the heat treated TBC
composite specimens in shear test compared to the as received TBC specimen,
although the bond coat/substrate interface was relatively weak [1,8-9,13]. The
Al depleted zones of the precipitates in the bond coat/substrate as well as in
the TBC/bond coat interface, were confirmed from EDS analysis ( Fig.4). Not
only Al diffuses from the bond coat to the substrate, other elements (Mo, Ti
and Co ) may also diffuse into the bond coat from the substrate. Therefore, the
interdiffusion between the bond coat and the substrate [26] involves a variety
of elements contained in the coating and the superalloy,

Figure 9. Experimental raw data obtained in shear tests of the TBC coated samples
revealing a typical variation of load with displacement and shear strength of the bond
coat in as received and heat treated conditions.

Taking into consideration the mechanical properties of the superalloy and

the coating, the later has a low strength due to the numerous defects and a
lower elastic modulus, and the system alloy + coating can be considered as a
composite in which the load bearing contribution of the coating is negligible
[27]. If the coating process involves consumption of alloys as in the case of
aluminides and induces a reduction of alloy section, it is necessary to consider

Mechanical Property and Characterization

93

the residual section of super alloy for the determination of the effective
mechanical stress[27]. This is a particular importance in the case of cooled
blades with thin walled sections. On the other hand, for overlay coatings as in
the present case, there is no reduction in the load bearing section (eventually a
very small reduction, due to interdiffusion effects during the heat treatment
applied). These coatings introduce just an additional mass subjected to
centrifugal stresses for the blades. As a point of interest, it was found [27], that
for both the types of coatings the ratios of the total section of the component
accounting for the stress due to centrifugal loads to the actual load bearing
section [alloy] were found to be quite comparable. Therefore in the present
investigation it was assumed that the load is borne by the super alloy substrate
+ bond coat and not by the top coat (TBC layer)[28].
The interdiffusion between the bond coat and the substrate is beneficial
considering the bond strength, especially in the case of arc ion plated MCrAlY
coatings. The Al diffuses to the top coat/bond coat interface to be oxidized at
the interface. The oxidation at the top coat/bond coat interface invariably has
an adverse effect on the intactness of the TBCs. The major consequence of
TBC oxidation is detachment of the top coat from the bond coat due to a
thermally grown oxide scale (Al2O3 layer of thickness 3 m) at the top coat
/bond coat interface [26] during high temperature fatigue, thermomechanical
fatigue and accelerated creep loading. The life of thermal barrier coating prior
to spallation is dominated by micro-cracking in both the thermally grown
oxide and the yttria stabilized zirconia top coat. The damage generated by this
micro-cracking is expected to be a primary life limiting factor. Previous study
has shown [22], that due to the selective oxidation of Al in the NiCoCrAlY
bond coat and a Ni3 Al film on the surface of the bond coat, an Al2O3 layer
develops between the bond coat and the transition layer [22]. Although the
alumina layer is essential for better adherence of the top coat onto the bond
coat , but if the thickness of the alumina layer is 3 m then the top coat never
remains intact , leading to spallation of the top coat from the bond and hence
the TBC composite would fail [26,32]. The 15% porosity in the topcoat is
normally favourable. However, the pores in the bond coat are in general not
desirable because the porous structure of the bond coat is detrimental to the
oxidation resistance of the bond coat in case that a continuous alumina scale is
formed on the surface of the bond coat or at the top coat/bond coat interface.
Previous bend tests [1,8,9,13] on TBC coated substrates (Inconel 617 and
CMSX-4 alloys) with Ni-18Cr-12Al-0.5Y type of bond coat at 800oC, high
cycle high temperature fatigue and creep behaviour of TBC coated superni
C263 alloy [14-16,2,26] with Ni22Co17Cr12.5Al0.6 Y type of bond coat have

94

Ashok Kumar Ray

indicated similar phenomenon., where failure of the TBCs was mainly due to
cracks that initiated at the bond coat/thermally grown oxide (TGO) interface
and propagated through the bond coat to the substrate.
Thermomechanical fatigue and accelerated creep tests on TBC coated AE
437A Ni base super alloy in the present investigation , are reported in [34,35],
keeping in mind that durability issues for TBCs under high-temperature, cyclic
conditions are still of major concern, especially as future engine temperatures
increase

CONCLUSION
The aforesaid study leads to the following conclusions:
[1] The nature of residual stress present in the plasma sprayed TBC (top
coat) was tensile, whereas that in the bond coat as well as in the
substrate was compressive. The magnitude of the residual stress in the
TBC was of the order of 15 to 37 MPa which is negligible. Finite
element technique used for analyzing the equivalent stresses in the
bond coat, at a particular load well within the elastic limit of the
composite specimens, revealed highest order of equivalent stress at
800oC, as the bond coat is ductile above 650oC.
[2] Discontinuities in the hardness vs displacement plot for the plasma
sprayed bond coat layer were due to the presence of porosity and
therefore the hardness values reported are all qualitative.
[3] The DBTT (ductile to brittle transition temperature) of this bond coat
was around 650oC. Shear strength of the bond coat in as received and
heat treated conditions, is in close proximity with that of the bond
strength reported in literature for MCrAlY coatings .

ACKNOWLEDGMENT
The authors are grateful to DST(Department of Science and Technology,
New Delhi , India) for sanctioning and funding this project and to Director,
NML Jamshedpur for his permission to publish this manuscript.

Mechanical Property and Characterization

95

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Goswami, S. .K. Sahay, D.Sanyal and R .N. Ghosh, High Temp Mater
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A.K. Ray, E.S. Dwarakadasa, , D.K. Das ,V.R. Ranganath, B. Goswami,
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Materialla. 48 (18-19) (2000) 4699.
A. Peichl, T .Beck, and O .Vohringer, Surf.coat.Technol. 162 (2/3)
(2003)113.

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[22] H. Guo, S . Gong, C. Zhou and H. Xu, Surf.coat.Technol. 148 (2-3)

(2001) 110.
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Rupa , S.B.Kumar and A.K. Ray , High Temperature Materials and
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[27] C Duret-Thual, R Morbioli. and P Steinmetz, A guide to the control of
high temperature corrosion and protection of gas turbine materials. In
CEC (commission of the European communities) COST Energy, ed. O.
Morocutti EUR 10682 EN, 1986. Commission of the European
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[28] A. K. Ray and R. W. Steinbrech, J.European ceramic Society,19 (12)
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[29] S McK Cousland and C M Scala , Mater Sci Eng A, 57 (1)(1983) 23.
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[33] Abhijit Kar and Ajoy Kumar Ray; Materials Letters 61 (2007)2985.
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In: Superalloys: Production, Properties

ISBN: 978-1-61209-536-3
Editor: Jeremy E. Watson, pp. 97-113 2011 Nova Science Publishers, Inc.

Chapter 6

CONTROL OF MICROSTRUCTURES BY HEAT

TREATMENTS AND HIGH-TEMPERATURE
PROPERTIES IN HIGH-TUNGSTEN COBALTBASE SUPERALLOYS*
Manabu Tanaka1 and Ryuichi Kato2
1

Research Institute of Materials and Resources, Department of Mechanical

Engineering, Faculty of Engineering and Resource Science,
Akita University, Akita, Japan.
2
Department of Mechanical Engineering, Faculty of Engineering and
Resource Science, Akita University, Akita, Japan.

ABSTRACT
Cobalt-base HS-21 (L-605) alloy has high strength and good oxidation
resistance at high temperatures, and is widely used for high-temperature
components including blades, vanes and combustor parts in the hot sections of jet
engines. In this study, effects of microstructures on the creep-rupture properties
were investigated on the heat-treated specimens of the HS-25 (L-605) type heatresistant alloys containing about 14 to 20% (mass %) tungsten (W) at 1089 and
1311 K. Serrated grain boundaries which were formed by precipitation of W-rich
*

Version of this chapter was also published in Handbook of Material Science Research,
published by Nova Science Publications, Inc. They were submitted for appropriate
modifications in an effort to encourage wider dissemination of research.

98

Manabu Tanaka and Ryuichi Kato

phase and M6C carbide by heat treatment, improved rupture strength without
significant loss of creep ductility. Ageing for 1080 ks (300 h) at 1273 K (1000)
caused similar precipitates on grain boundaries and in grains, and also increased
rupture strength in the specimens with normal straight grain boundaries.
Improvement of the rupture properties by heat treatments was remarkable in the
alloys with the higher W content at 1089 K, while such heat treatments were
effective in relatively short-term creep at 1311 K. In the non-aged specimens with
straight grain boundaries, the rupture strength increased with increasing W content
at 1311 K, although the rupture strength was not improved largely with increasing
W content at 1089 K. The principal strengthening mechanism in these alloys was
attributed to the strengthening of grain boundaries and grains by precipitates of Wrich phase and carbide phases in addition to solid-solution strengthening by W
atoms. Fracture surfaces of specimens with serrated grain boundaries and those of
aged specimens were ductile grain-boundary fracture surfaces with small dimples
and ledges, while the non-aged specimens with straight grain boundaries exhibited
brittle grain-boundary facets at 1089 K.

INTRODUCTION
Austenitic cobalt-base HS-21 (L-605) alloy has good formability, high
strength up to 1089 K (816), and good oxidation resistance up to 1366 K
(1093). This alloy is widely used for blades, vanes, combustor parts and
afterburners in the hot sections of aircraft engines, and is also used in the hot
sections of land based gas turbines. In the HS-25 (L-605) type heat-resistant
alloys, the increase of tungsten (W) content may raise the high-temperature
strength [1], but may also increase the tendency to form topologically closepacked phases (tcp) such as the Laves phase (Co2W) which is believed to be
harmful to ductility [2]. Therefore, it is necessary to prevent such phases by
heat treatments in order to utilize beneficial effects of tungsten (W).
Initiation and growth of grain-boundary cracks in polycrystalline
materials are governed by grain-boundary sliding at high temperatures, and
relative contribution of grain-boundary sliding to total creep strain
increases with decreasing creep stress [3, 4]. High-temperature strength can
be considerably improved by serrated grain boundaries in the nickel-base
superalloys [5-7] and the austenitic heat-resisting steels [8, 9], because grainboundary sliding which controls the initiation [5, 10] and growth [11] of grainboundary cracks is inhibited by serrated grain-boundaries.

Control of Microstructures by Heat Treatments

99

In cobalt-base heat-resistant alloys, serrated grain boundaries are formed

by precipitation of M23C6 carbide [12] or a W-rich phase (tungsten solid
solution, bcc) and M6C carbide [13], and improve the creep rupture strength.
R. Tanaka et al. [14] previously found the same W-rich phase in the Ni-20Cr20W alloy. High-temperature ageing at 1273 K also causes precipitates of the
W-rich and carbide phases on grain boundaries and in the grains, and leads to
an improved rupture life without decreasing creep ductility in the HS-25 alloys
[15]. It was found that in high-tungsten HS-25 type cobalt-base superalloys the
rupture life increased with increasing W content at 1311 K [16]. In this study,
effects of microstructures produced by heat treatments on the creep-rupture
properties were investigated using the HS-25 type superalloys containing
about 14 to 20 mass % W at 1089 and 1311 K. Precipitated phases,
microstructures and fracture mechanisms were also examined in the ruptured
specimens of the alloys.

EXPERIMENTAL PROCEDURE
Table 1 lists the chemical composition, typical heat treatments, matrix
hardness, grain size and grain-boundary configuration of HS-25 (L-605) type
cobalt-base alloys used in this study. The alloy bars of 20 mm in diameter
were supplied by Mitsubishi Material Company.
Table 1. Chemical composition, typical heat treatments, matrix hardness,
grain size and grain-boundary configuration of HS-25 type cobalt-base
alloys
Alloys

14W

17W

Chemical
composition
(mass %)
Co-0.07%C19.82%Cr-9.83%Ni14.37%W-2.22%Fe1.46%Mn
Co-0.06%C19.40%Cr9.89%Ni-17.20%W2.37%Fe-0.76%Mn

Typical heat treatments

1473 K, 7.2 ksW.Q.
1473 K, 7.2 ksW.Q. +
1273 K, 1080 ks A.C.
1473 K, 3.6 ksF.C.
1323 K, 72 ks W.Q.
1503 K, 7.2 ksW.Q.
1503 K, 7.2 ksW.Q. +
1273 K, 1080 ks A.C.
1503 K, 7.2 ksF.C.
1323 K, 10.8 ksW.Q.

Matrix
hardness
(Hv)*
253

Grain
size
(m)
255

Grainboundary
configuration
straight
straight (plus
ageing)

326

255

249

260

serrated

264

246

344

246

straight
straight (plus
ageing)

255

249

serrated

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Manabu Tanaka and Ryuichi Kato

Table 1. (Continued)

Alloys

20W

Chemical
composition
(mass %)
Co-0.06%C19.05%Cr9.54%Ni-19.74%W2.28%Fe-0.77%Mn

Typical heat treatments

1573 K, 7.2 ksW.Q.

1573 K, 7.2 ksW.Q. +
1273 K, 1080 ks A.C.
1573 K, 7.2 ksF.C.
1323 K, 3.6 ksW.Q.

Matrix
hardness
(Hv)*
269

Grain
size
(m)
273

379

273

256

280

Grainboundary
configuration
straight
straight (plus
ageing)
serrated

*: Vickers harness number (load 4.9 N); W.Q.: water-quenched; F.C.: furnace-cooled;
A.C.: air-cooled.

Figure 1. Examples of microstructures in the heat-treated specimens of the cobalt-base

alloys. a. 14W (straight grain boundaries) b. 14W (serrated grain boundaries). c. 14W
(straight grain boundaries plus ageing) d. 20W (straight grain boundaries plus ageing).

These alloys containing about 14 to 20 mass % are designated by

approximate tungsten (W) content, such as 14W alloy. Specimens with
straight grain boundaries were produced by simple solution treatment.
Serrated grain boundaries were formed by precipitation of tungsten (W) rich phase (tungsten solid solution, bcc) and carbide phases [13] which were
caused by solution treatment followed by furnace cooling in these alloys.
Some specimens with straight grain boundaries were further aged for 1080 ks
at 1273K to cause similar precipitation of W-rich and carbide phases on grain
boundaries and in the grains. Heat-treated specimens were machined into
creep-rupture test pieces of 30 mm in gauge length and 5 mm in diameter.

Control of Microstructures by Heat Treatments

101

Figure 2. Electron transmission micrographs of the specimen with serrated grain boundaries
of the 14W alloy [13]. a. bright field image, b. selected area electron diffraction pattern of a.

Creep-rupture experiments were carried out using these specimens at 1089 and
1311 K. All specimens were aged for 10.8 ks (3 h) at each test temperature
before loading. Microstructures and fracture patterns were examined with
optical microscope and scanning electron microscope. Precipitated phases
were identified by dint of X-ray diffraction, electron probe microanalysis
(EPMA) or transmission electron microscopy on heat-treated specimens or
ruptured test pieces.

RESULTS AND DISCUSSION

Effects of Tungsten Content on Creep-rupture
Properties at 1089 K
Figure 1 shows examples of microstructures in the heat-treated specimens
of the cobalt-base alloys. In the 14W alloy, grain-boundary precipitates are
visible in specimen with serrated grain boundaries (Figure 1b), while
precipitates are not observed in simply solution-treated specimen with straight
grain boundaries (Figure1a). Figure 2 shows the electron transmission
micrographs of the specimen with serrated grain boundaries of the 14W alloy

102

Manabu Tanaka and Ryuichi Kato

[13]. Large grain-boundary precipitates of W-rich phase can be observed in the

bright field image (Figure 2a). According to the selected area electron
diffraction pattern (Figure 2b), there is a crystallographic orientation
relationship between the W-rich phase (bcc) and -Co matrix (fcc) that (011)W
// (111)-Co and [11]W // [10]-Co. Grain-boundary precipitates of M6C
carbide were also detected by the line analysis using EPMA in addition to Wrich phase [13]. Ageing for 1080 ks at 1273K caused similar precipitates in
grains in the 14W and 20W alloys (Figs. 1c and 1d).
Figure 3 shows some examples of creep curves of the cobalt-base alloys at
1089 K. The creep curve exhibits primary (transient) creep and tertiary
(accelerated) creep terms with very short secondary creep term. The rupture
life is relatively longer in the specimens with serrated grain boundaries and in
the aged specimens with straight grain boundaries. Figure 4 shows the creeprupture properties of the 14W and 20W alloys at 1089 K. Serrated grain
boundaries and the ageing lead to the increase in rupture life without
significantly decreasing ductility, although the creep ductility decreases a little
with increasing W content. The aged specimen with straight grain boundaries
exhibits the longest rupture life (7946.89 ks) and good creep ductility (0.1499)
under the stress of 118 MPa. In non-aged condition, the specimen with
serrated grain boundaries has the longer rupture life than the one with straight
grain boundaries in the 20W alloy. Similar results were obtained in the 17W
alloy. Strengthening by ageing or by serrated grain boundaries was larger in
the specimens of the higher W content.

Figure 3. Creep curves of the 14W and 20W alloys at 1089 K.

Control of Microstructures by Heat Treatments

103

Figure 4. Creep-rupture properties of the 14W and 20W alloys at 1089 K.

Figure 5 shows effects of W content on rupture strength of cobalt-base

alloys at 1089K. The rupture strength increases with increasing W content in
the specimens with serrated grain boundaries and in the aged specimens with
straight grain boundaries except short-term creep. In the non-aged specimens
with straight grain boundaries, the rupture strength does not increase largely
with increasing W content. The strengthening effect of the ageing seems to be

104

Manabu Tanaka and Ryuichi Kato

a little larger than that of serrated grain boundaries. Improvement of the

rupture properties by heat treatments is remarkable in the alloys with the
higher W contents except short-term creep. Precipitation of W-rich phase and
carbide phase on grain boundaries contribute to the strengthening of grain
boundaries and may retard precipitation of Laves phase (Co2W) on grain
boundaries, which is believed to be harmful to ductility in heat-resistant alloys
[11]. Fine precipitates of Laves phase and carbide phases such as M6C and
Cr23C6 were detected by X-ray diffraction on the non-aged specimens ruptured
at 1089 K [16]. The precipitates of carbide phases may contribute to the
strengthening of the matrix in specimens with serrated grain boundaries. The
Laves phase may not decrease the rupture strength in the cobalt-base heatresistant alloys if it is finely dispersed in the matrix [17].

Figure 5. Effects of W content on the rupture strength of cobalt-base alloys at 1089 K.

Figure 6 shows the examples of microstructures and fracture surfaces of

the ruptured specimens at 1089 K. The tensile direction is horizontal in the
optical micrographs. Grain-boundary cracks are visible near the fracture
surface (Figs. 6a, 6c, 6e and 6g). Coarse precipitates of W-rich and carbide

Control of Microstructures by Heat Treatments

105

phases are formed on grain boundaries in the specimen with serrated grain
boundaries (Figure 6c), and on grain boundaries and in the grains in the aged
specimens with straight grain boundaries (Figs. 6e and 6g). Very fine
precipitates which were formed during creep at 1089 K, can be seen on the
grain boundaries and in the grains of the ageing seems to be a little larger than
that of serrated grain boundaries. Improvement of the rupture properties by
heat treatments is remarkable in the alloys with the higher W contents nonaged specimen with straight grain boundaries (Figure 6a) and in the grains of
the specimen with serrated grain boundaries (Figure 6c). These precipitates
may be Laves phase and carbide phases such as M6C and Cr23C6. In the 14W
alloy, small dimples and ledges which are associated with grain-boundary
precipitates can be observed in both specimen with serrated grain boundaries
(Figure 6d) and aged specimen with straight grain boundaries (Figure 6f),
while the non-aged specimen with straight grain boundaries exhibits a brittle
grain-boundary fracture surface (Figure 6b). Similar fracture surfaces were
observed in the ruptured specimens of the 17W and 20W alloys. In the aged
specimen with straight grain boundaries of the 20W alloy that exhibited the
longest rupture life at 118 MPa, small steps and dimples associated with grainboundary precipitates are visible on the fracture surface (Figure 6h). Thus, the
improvement of the rupture life by grain-boundary precipitates may be related
to occurrence of ductile grain-boundary fracture with small dimples, steps and
ledges.
Kobayashi et al. [9] reported that in the austenitic heat-resisting steels the
rupture lives of specimens increase with increasing strength of grains.
However, it is still unknown whether the strengthening of grains works
additive to the strengthening by serrated grain boundaries in cobalt-base
heat-resistant alloys. Some specimen with serrated grain boundaries were aged
ageing seems to be a little larger than that of serrated grain boundaries.
Improvement of the rupture properties by heat treatments is remarkable in the
alloys with the higher W contents for 1080 ks at 1273 K. Figure 7 shows the
creep-rupture properties of the 20W alloy at 1089 K. The aged specimen with
serrated grain boundaries has the longest rupture life and favorable ductility,
although the difference in the rupture life is very small between two aged
specimens with serrated grain boundaries and with straight grain boundaries.
This may be attributed to that grain boundaries were strengthened by the
precipitation of W-rich and carbide phases in the aged specimen with straight
grain boundaries as well as in the aged specimen with serrated grain
boundaries. Similar results were obtained in the 14W alloy and in the 17W
alloy.

106

Manabu Tanaka and Ryuichi Kato

(: stress; tr: rupture life; r: elongation).

Figure 6. Examples of microstructures and fracture surfaces of the ruptured specimens at
1089 K. a, b. straight grain boundaries (14W, =137 MPa, tr=459.8 ks, r=0.3337) c, d.
serrated grain boundaries (14W, =137 MPa, tr=493.60 ks, r=0.2590) e, f. straight grain
boundaries plus ageing (14W, =137 MPa, tr=1437.70 ks, r=0.5278 ) g, h. straight grain
boundaries plus ageing (20W, =118 MPa, tr=7946.89 ks, r=0.1499).

Control of Microstructures by Heat Treatments

Figure 7. Creep-rupture properties of the 20W alloy at 1089 K.

107

108

Manabu Tanaka and Ryuichi Kato

Figure 8. Creep-rupture properties of the 14W and 20W alloys at 1311 K.

Figure 9. Effects of W content on the rupture strength of cobalt-base alloys at 1311 K.

Control of Microstructures by Heat Treatments

(: stress; tr: rupture life; r: elongation)

Figure 10. Examples of microstructures and fracture surfaces of the specimens ruptured
under a stress of 29.4 MPa at 1311 K. a, b. straight grain boundaries (14W, tr=541.26,
r=0.1127) c, d. serrated grain boundaries (14W, tr=682.99 ks, r=0.1945) e, f. straight
grain boundaries plus ageing (14W, tr=1218.96 ks, r=0.1996) g, h. straight grain
boundaries plus ageing (20W, tr=1354.44 ks, r=0.0806).

109

110

Manabu Tanaka and Ryuichi Kato

Effects of Tungsten Content on Creep-rupture Properties

at 1311 K
Figure 8 shows the creep rupture properties of the 14W and 20W alloys at
1311 K. High-temperature ageing increases the rupture life without decreasing
creep ductility in both alloys. Strengthening by serrated grain boundaries has
similar effects on the creep-rupture properties, although the strengthening by
ageing seems to be more effective than the strengthening by serrated grain
boundaries at this temperature. Further, effects of ageing or serrated grain
boundaries on the rupture properties was relatively large in the short-term
creep, especially in the 20W alloy, because precipitation of W-rich and carbide
phases occurred on grain boundaries and in the grains of the non-aged
specimens during creep at 1311 K. Similar results were obtained in the 17W
alloy. The rupture life is longer in the specimens with the higher W content.
Figure 9 shows the effects of W content on the rupture strength of cobalt-base
alloys at 1311 K. The rupture strength tends to increase with increasing W
content in the non-aged specimens with straight grain boundaries. In relatively
short-term creep, the rupture strength also increases with increasing W content
of the aged specimens with straight grain boundaries or the specimens with
serrated grain boundaries. The W-rich phase, M6C and Cr23C6 carbides were
detected by X-ray diffraction on the non-aged specimens ruptured under a
stress of 29.4 MPa at 1311 K [16]. Strengthening of grain boundaries and
grains by these precipitates may also have occurred in the non-aged specimens
during creep at 1311 K. The amount of the precipitates increased with
increasing rupture life of the specimens and with increasing W content in the
alloys. These may be the principal reason that there is almost no difference in
the rupture strength between the non-aged specimens and the aged specimens
or the specimens with serrated grain boundaries.
Figure 10 shows the examples of microstructures and fracture surfaces of
the specimens ruptured under a stress of 29.4 MPa at 1311 K. The tensile
direction is horizontal and grain-boundary cracks can be seen in the optical
micrographs (Figs. 10a, 10c, 10e and 10g). Coarse grain-boundary and matrix
precipitates of W-rich and carbide phases are observed in the specimen with
serrated grain boundaries (Figure 10c) and the aged specimens with straight
grain boundaries (Figs. 10e and 10g) of the 14W alloy. These precipitates can
also be seen in the non-aged specimen with straight grain boundaries of the
14W alloy (Figure 10a). Strengthening of grain boundaries and grains may
occur in the non-aged specimens with straight grain boundaries during creep at
1311 K. Further, the matrix of the specimen with serrated grain boundaries

Control of Microstructures by Heat Treatments

111

may also be strengthened by the precipitation of W-rich and carbide phases

during creep. These strengthening mechanisms may also have worked in the
17W and 20W alloys. Small dimples and ledges which were associated with
coarse grain-boundary precipitates, were observed not only in the specimen
with serrated grain boundaries (Figure 10d) and the aged specimen (Figure
10f) of the 14W alloy but also in non-aged specimens with straight grain
boundaries of the 14W alloy (Figure 10b) and the 20W alloy (Figure 10h).
Such features of the fracture surfaces were common in the alloys with different
W contents.
From the experimental results described above, it is considered that in the
cobalt-base heat-resistant alloys with high W content the principal
strengthening mechanism is the strengthening of grain boundaries and grains
by precipitates of W-rich and carbide phases in addition to solid-solution
strengthening by W atoms. Improved rupture strength and creep ductility may
be associated with occurrence of ductile fracture associated with coarse grainboundary precipitates. Thus, the control of microstructures by heat treatments
is important to utilize favorable effects of W for the improved performance of
the cobalt-base HS-25 type alloys with high W content at high temperatures,
while it is also necessary to evaluate the resistance to high-temperature
oxidation and corrosion in these alloys.

CONCLUSIONS
Effects of microstructures on the creep-rupture properties were
investigated on the cobalt-base superalloys containing about 14 to 20 mass %
tungsten (W) at 1089 and 1311 K. The results obtained were summarized as
follows.
(1) The rupture strength of the alloys was improved by serrated grain
boundaries which were produced by heat treatments, and by ageing
for 1080 ks at 1273 K without serious loss of creep ductility.
Improvement of the rupture properties by heat treatments was
remarkable in the alloys with the higher W content at 1089 K, while
such heat treatments were effective in improving rupture properties of
the alloys in the relatively short-term creep at 1311 K. In the non-aged
specimens with straight grain boundaries, rupture strength increased
with increasing W content at 1311 K, although the rupture strength
was not improved largely with increasing W content at 1089 K. There

112

Manabu Tanaka and Ryuichi Kato

was only a small difference in the rupture life between the aged
specimens with serrated grain boundaries and those with straight grain
boundaries in the cobalt-base alloys containing about 14 to 20 mass%
W at 1089 K.
(2) The principal strengthening mechanism in these alloys was attributed
to the strengthening of grain boundaries and grains by precipitates of
W-rich and carbide phases in addition to solid-solution strengthening
by W atoms. In the specimen with serrated grain boundaries and the
aged specimen with straight grain boundaries, precipitation of the Wrich and carbide phases on grain boundaries probably retarded
precipitation of the Laves phase (Co2W) on grain boundaries. The
Laves phase did not lower the strength of the cobalt-base heatresistant alloys, if it was finely dispersed in the matrix. Precipitation
of the W-rich phase and carbides on the grain boundaries and in the
grains also occurred and contributed to the strengthening in the nonaged specimens with straight grain boundaries during creep at 1311 K.
(3) Fracture surfaces of non-aged specimens with serrated grain
boundaries and those of aged specimens were ductile grain-boundary
fracture surfaces with small dimples and ledges at 1089 K, while
those of non-aged specimens with straight grain boundaries exhibited
brittle grain-boundary facets. Small steps, dimples and ledges were
also observed in non-aged specimens with straight grain boundaries
ruptured at 1311 K. Occurrence of ductile grain-boundary fracture
was associated with the strengthening of grain boundaries by
precipitates of W-rich and carbide phases, and led to the improvement
of rupture properties at high temperatures. The control of
microstructures by heat treatments is important to utilize favorable
effects of W for improvement in performance of components of the
cobalt-base HS-25 type alloys with high W content at high
temperatures.

ACKNOWLEDGMENTS
The authors thank Mitsubishi Material Company for supplying the cobaltbase alloys used in this study.

Control of Microstructures by Heat Treatments

113

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