METAL 2009 19. – 21. 5.

2009, Hradec nad Moravicí

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MICROSTRUCTURE DEGRADATION OF NICKEL BASE SINGLE

CRYSTAL SUPERALLOY CMSX-4

Juraj Lapina
Marek Geburaa
Tatiana Pelachováa
Oto Bajanaa
a
Institute of Materials and Machine Mechanics, Slovak Academy of Sciences,
Račianska 75, 831 02 Bratislava, Slovak Republic, ummslapi@savba.sk

Abstract
The aim of the present work is to study the effect of microstructure degradation on
mechanical properties of single crystal nickel base superalloy CMSX-4. Three types
of microstructure degradation were observed in the studied alloy: (i) growth of
cuboidal γ’ precipitates during isothermal ageing; (ii) spontaneous rafting formed
preferentially within the dendrites during long-term ageing at high temperatures and
(iii) rafting during creep exposure. It is shown that the microstructure degradation
resulting from the growth and morphological changes of the γ’ precipitates affects
mechanical properties of the alloy and represents a significant contribution to all
degradation processes affecting performance and service life of critical gas turbine
components.

1. INTRODUCTION
Single crystal nickel base superalloys are widely used in first-stage turbine blades
because of their unusual ability to retain excellent combination of mechanical
properties and corrosion resistance at high temperatures. A typical microstructure of
single crystal superalloys usually contains L12-ordered γ’ (Ni3(Al,Ti)) precipitates
coherently embedded in γ (Ni-based solid solution) matrix with face-centered cubic
crystal structure [1-6]. The mechanical properties of these materials depend on the
volume fraction, distribution, size and morphology of the γ’ precipitates. During
service the initial microstructure of single crystal blades is subjected to degradation
processes due to combined effect of temperature, mechanical stresses and
environmental conditions. Three types of microstructure degradation can be
observed in a single crystal superalloy: (i) growth of cuboidal γ’ precipitates during
ageing [4]; (ii) spontaneous rafting formed preferentially within the dendrites during
long-term ageing at high temperatures [7] and (iii) rafting during creep exposure [1-3].
The microstructure degradation resulting from the growth and morphological changes
of the γ’ precipitates represents a significant contribution to all degradation processes
affecting performance and service life of critical gas turbine components such as first-
stage turbine blades. Hence, it is important to study the effect of microstructure
degradation on mechanical properties of single crystal superalloys at temperatures
and stresses corresponding to those of turbine components.
The aim of the present work is to study microstructure degradation of nickel base
single crystal superalloy CMSX-4 during ageing and creep exposure. In additions, the
effect of microstructure degradation on mechanical properties is evaluated and
discussed. The studied nickel base superalloy CMSX-4 is mainly used in
manufacturing single crystal first-stage turbine blades for aircraft engines and
stationary gas turbines for power engineering and such microstructure degradation

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processes affect significantly their service life.

2. EXPERIMENTAL PROCEDURE
Single crystal samples of CMSX-4 alloy with the chemical composition Ni-7.0Cr-
9.0Co-0.6Mo-6.0W-7.0Ta-3.0Re-5.6Al-1.0Ti-0.1Hf (wt.%) were prepared by seeding
using seeds with [001] crystallographic orientation. Both the seed and cylindrical rod
were put into a high-purity (99.95%) alumina mould with a diameter of 11/15 mm
(inside/outside diameter) and directionally solidified (DS) in a modified Bridgman type
apparatus described elsewhere [8]. All samples were directionally solidified at
a constant growth rate of V = 2.78x10-5 ms-1 and constant temperature gradient in
liquid at the solid-liquid interface of GL = 8x103 Km-1 under argon atmosphere.
After directional solidification the single crystal samples were subjected to heat
treatments consisting of solution annealing at 1315 °C for 6 or 120 h, fast gas cooling
to room temperature and precipitation ageing. Two types of precipitation ageing were
used: (i) two steps ageing at 1140 °C for 6 h followed by the second ageing at 870 °C
for 20 h and (ii) single step ageing at 950 °C for various time ranging from 100 to
2000 h to prepare the samples with various size of cuboidal γ’ precipitates.
Microstructure stability of the samples was studied by long-term ageing at
temperatures ranging from 850 to 1000 °C and various time ranging from 100 to
5000 h.
The microstructure degradation during creep was studied at a temperature of
950 °C, applied stresses of 60, 90, 120 and 150 MPa for various time up to 2000 h
using cylindrical creep specimens with multiple gauge sections. In addition, creep
degradation tests were performed at 950 °C, applied stress of 230 MPa for 300 h to
study the effect of microstructure degradation on mechanical properties. The creep
deformation was measured by high-temperature extensometers attached to the
ridges of creep specimens. The tensile axis of creep specimens was parallel or
nearly parallel (maximal deviation of 3°) to [001] crystallographic direction.
Vickers hardness measurements were performed at an applied load of 298 N on
cylindrical specimens with a diameter of 11 mm and a length of 5 mm. Cylindrical
tensile specimens with a gauge diameter of 5 mm and a gauge length of 25 mm were
prepared by lathe-machining and grinding. The longitudinal axis of the tensile
specimens was parallel to [001] crystallographic direction. Tensile tests were
conducted at temperatures ranging from room temperature (RT) to 950 °C at an
initial strain rate of 1x10-4 s-1. The offset tensile yield strength was measured at 0.2%
plastic strain and ductility was evaluated from the total plastic elongation to fracture.
Crystallographic orientation of each single crystal was determined by a Laue
diffraction method. Microstructural analysis was performed by light optical microscopy
(OM), scanning electron microscopy (SEM) and transmission electron microscopy
(TEM). OM and SEM samples were prepared using standard metallographic
techniques and etched in a reagent of 12.5 ml alcohol, 12.5 ml HNO3 and 13.5 ml
HCl. TEM samples (thin carbon replicas) were prepared by deposition of thin carbon
layer on etched surface, which was then removed from the surface by electrolytic
etching in a solution of 9.4 ml H3PO4, 37.5 ml H2SO4 and 35.6 ml HNO3 at a voltage
of 7 V. Quantitative metallography was performed on digitalized micrographs using
a computerized image analyser. Five basic microstructural parameters were
evaluated in the specimens: (i) size of cuboidal γ’ precipitates, (ii) volume fraction of
γ’ precipitates, (iii) width of γ channels, (iv) width of γ’ rafts and (v) length of γ’ rafts on
longitudinal sections of creep specimens. All measured values were evaluated
statistically using appropriate distribution functions.

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3. RESULTS AND DISCUSSION

3.1. Coarsening of cuboidal γ’ precipitates

Fig. 1 shows an initial microstructure of the alloy which was subjected to solution
annealing for 6 h and two steps precipitation hardening before ageing. Nearly square
sections of the γ’ precipitates on (001) crystallographic plane as well as similar nearly
square sections on (010) and (100) crystallographic planes confirmed their cuboidal
morphology. Volume fraction Vp of the γ’ precipitates was measured to be
(69 ± 1) vol.% and remained constant within the experimental error of measurements
during ageing. Statistical analysis of measured size of cuboidal γ’ precipitates defined
as their edge length showed log-normal distribution. Mean size of the γ’ precipitates
in the samples before ageing was measured to be a0 = 314 nm. Fig. 2 shows
dependence of mean size of the γ’ precipitates on ageing time. The mean size
increases with increasing ageing time and temperature. Detail analysis of the growth
of cuboidal γ’ precipitates reported recently by Lapin et al. [4] showed that their
coarsening kinetics follows a cube rate law and is controlled by volume diffusion of
alloying elements in the γ matrix with activation energy for coarsening of
272.4 kJ/mol. Fig. 3 shows dependence of normalized mean size of cuboidal
γ’ precipitates a on ageing time. In this figure, region of stability of cuboidal γ’
precipitates and region of formation of spontaneously rafted microstructure are
marked by a bold line.
Fig. 4 shows dependence of Vickers hardness HV on normalized volume fraction
Vp and mean size a of the cuboidal γ’ precipitates in the samples which were solution
annealed for 6 h and precipitation aged at 950 °C. Vickers hardness increases with
increasing volume fraction from 0.62 to 0.71 and decreasing mean size from 523 to
147 nm of the γ’ precipitates according to relationship in the form

Vp
HV = 3.38 + 4.3 x10−4 (1)
a

The correlation coefficient of this fit is r2 = 0.99. Fig. 5 shows dependence of 0.2%
offset yield strength (YS), ultimate tensile strength (UTS) and plastic elongation

800
850 °C
Size of precipitate (10-9 m)

700 900 °C
925 °C
950 °C
600
1000 °C
500

400

300
0 500 1000 1500 2000

Ageing time (h)

Fig. 1. SEM showing the typical cuboidal Fig. 2. Dependence of mean size of
morphology of γ’ precipitates embedded cuboidal γ’ precipitates on ageing time at
in the γ matrix before ageing. five ageing temperatures.

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25 4.4
850 °C
Spontaneous rafts 900 °C 4.3

Vickers hardness (GPa)

20
925 °C
a3 - ao3 (20-20 m3)
950 °C 4.2
15 1000 °C
4.1
10
4.0
5
3.9
Cuboidal precipitates
0 3.8
0 1000 2000 3000 4000 5000 6000 900 1200 1500 1800 2100 2400

Ageing time (h) (Vp/a)0.5 (m-0.5)

Fig. 3. Dependence of normalized size of Fig. 4. Dependence of Vickers hardness

cuboidal γ’ precipitates on ageing time. on normalized volume fraction and size
Ageing temperatures are indicated in the of cuboidal γ’ precipitates.
figure.

to fracture on normalized volume fraction and size of the cuboidal γ’ precipitates. YS

increases with increasing volume fraction and decreasing size of the γ’ precipitates.
On the other hand, no clear dependence of UTS and elongation on normalized
volume fraction and size of the γ’ precipitates can be defined. The reason of selecting
normalized volume fraction and size in the form shown in Eq. (1) results from the fact
that the studied CMSX-4 superalloy behaves as the typical overaged material
strengthened by ordered precipitates. As showed by Ardell [9] the overaged alloys
are characterized by a continuous decrease of the YS with increasing size and
decreasing volume fraction of the γ’ precipitates. Fig. 6 shows a linear dependence of
0.2% offset tensile yield strength YS measured at 950 °C on room temperature
Vickers hardness HV. Using linear regression analysis yields an equation in the form

YS = −607.4 + 346.7HV (2)

1000 50 900
YS
950 UTS 870
Yield strength (MPa)

Elongation 40
Elongation (%)

900
Stress (MPa)

840

850 30 810

800 780
20
750 750

700 10 720
1000 1200 1400 1600 1800 2000 2200 3.8 3.9 4.0 4.1 4.2 4.3
(Vp/a)0.5 (m-0.5) Vickers hardness (GPa)

Fig. 5. Dependence of yield strength Fig. 6. Dependence of tensile yield

(YS), ultimate tensile strength (UTS) and strength measured at 950 °C on room
elongation on normalized volume fraction temperature Vickers hardness.
and size of γ’ precipitates at 950 °C.

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Fig. 7. Development of spontaneously rafted microstructure during ageing at

1000 °C for 2000 h of a sample subjected to solution annealing for 6 h: (a) OM
micrograph showing spontaneous rafts within the dendrites; (b) SEM micrograph
showing details of spontaneous rafts.

The correlation coefficient of this fit is r2 = 0.97. Eq. (2) can be considered as
a simple tool to estimate high temperature yield strength from simple RT
measurements of Vickers hardness.

3.2. Spontaneous rafting of γ’ precipitates

Fig. 3 indicates morphological instabilities of cuboidal γ’ precipitates during long-
term ageing experiments leading to formation of spontaneously rafted microstructure.
Fig. 7 shows development of spontaneously rafted microstructure during ageing at
1000 °C of the samples subjected to 6 h solution annealing. Such spontaneously
rafted microstructure develops in all <001> crystallographic directions. As shown by
Gebura and Lapin [7] the spontaneous rafts are formed preferentially within the
dendrites while cuboidal γ’ precipitates are preserved in the interdendritic region for
relatively long time. The development of spontaneous rafts can be attributed to local
chemical heterogeneity between the dendrites and the interdendritic region resulting

120
1000
100
800
Elongation (%)

80
Stress (MPa)

600 YS - 6 h
YS - 120 h 60
UTS - 6 h
UTS - 120 h
400 Elongation - 6 h 40
Elongation - 120 h
200 20

0 0
0 200 400 600 800 1000

Fig. 8. OM micrograph showing homoge-
nous distribution of spontaneously rafted
microstructure after ageing at 1000 °C
for 2000 h in a sample subjected to
solution annealing for 120 h.
Temperature (°C)
Fig. 9. Temperature dependence of yield
strength (YS), ultimate tensile strength
(UTS) and elongation to fracture of the
specimens with spontaneously rafted
microstructure.

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from microsegregation of alloying elements during directional solidification and to
internal stresses present in the material. In order to minimize the effect of chemical
heterogeneity affecting the lattice misfit between γ’ precipitates and γ matrix within
the samples, the solution annealing time was increased to 120 h. Fig. 8 shows that
longer solution annealing at 1315 °C for 120 h leads to development of
homogenously distributed spontaneous rafts within the material. Hence, it is clear
that such heat treatments cannot avoid problems with morphological instabilities of
cuboidal γ’ precipitates leading to spontaneous rafting. Fig. 9 shows temperature
dependence of 0.2% offset yield strength (YS), ultimate tensile strength (UTS) and
plastic elongation to fracture for both types of tensile specimens solution annealed at
1315 °C for 6 and 120 h and finally aged at 1000 °C for 2000 h. The specimens
annealed for 6 h show improved YS and UTS when compared to those of specimens
solution annealed for 120 h at all studied temperatures.

3.3. Creep rafting of γ’ precipitates

During creep at 950 °C and applied stresses ranging from 60 to 150 MPa
directional coarsening (rafting) of cuboidal γ’ precipitates was observed. The well
developed γ’ rafts separated by γ channels are oriented nearly perpendicularly to the
loading direction which was parallel to [001] crystallographic direction of the creep
specimens, as seen in Fig. 10. Nabarro et al. [10] showed that the driving force for
development and orientation of γ’ rafts is the lattice misfit, elastic mismatch between
the γ’ precipitates and γ matrix and applied external stresses. Three microstructural
parameters were measured for the rafted microstructure: (i) width of γ’ rafts, (ii)
length of γ’ rafts and (iii) width of γ channels. Fig. 11 shows dependence of width of
γ’ rafts on creep time at four applied stresses. It should be noted that measured
values of the width of the γ’ rafts in specimens tested at 60 and 90 MPa for 100 h are
affected by a transient type of microstructure between cuboidal and rafted one. For
the degraded microstructure with well developed rafts, the width of γ’ rafts decrease
and their length increase with increasing applied stress. Fig. 12 shows dependence
of width of γ channels on creep time at four applied stresses. The γ channel

420
400 60MPa
90MPa
Width of γ' rafts (nm)

380
120MPa
360 150MPa
340
320
300
280
260
240
0 500 1000 1500 2000
Time (h)

Fig. 10. SEM micrograph showing Fig. 11. Dependence of width of γ’ rafts on
rafted microstructure after creep creep time. The applied stresses are
degradation at 950 °C, applied stress indicated in the figure.
of 150 MPa for 2000 h.

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200 1200 140

180 1000 120

Width of γ channels (nm)
160 100

Elongation (%)
800

Stress (MPa)
140 YS - cuboidal 80
600 YS - rafted
120 UTS - cuboidal 60
UTS - rafted
100 400 Elongation - cuboidal
40
60MPa
Elongation - rafted
80 90MPa
200 20
120MPa
60
150MPa 0
40 0
0 500 1000 1500 2000 0 200 400 600 800 1000

Time (h) Temperature (°C)

Fig. 12. Dependence of width of Fig. 13. Dependence of YS, UTS and
γ channels on creep time. The applied elongation on temperature for the
stresses are indicated in the figure. specimens with cuboidal and rafted
microstructure.

widening is an important process because it affects the dislocation mobility in the γ

channels which is one key element of the overall creep process in single crystal
superalloys. As shown by Kamaraj et. al. [11], the γ channel widening is controlled by
a multi-atom diffusion process through the γ channels and multiaxial loading by the
normal stress components perpendicular to the γ/γ’-interfaces during creep. As
reported by Serin et al. [1], the γ channel widening rates increase with increasing
stress level which is in agreement with the experimental results of the present work.
Fig. 13 shows temperature dependence of 0.2% offset YS, UTS and plastic
elongation for the specimens with cuboidal and rafted microstructure. While 0.2%
offset YS and UTS are lower, plastic elongation to fracture is higher in creep
degraded specimens than those measured in the specimens with cuboidal
microstructure. Nazmy et al. [12] attributed change of mechanical properties to
topological inversion of microstructure caused by the rafting process, e.g. γ’ phase
becomes the matrix with embedded particles of the γ phase. Such microstructure
inversion can lead to a severe room temperature embrittlement of nickel base
superalloys exposed to air humidity.

4. CONCLUSIONS
The investigation of microstructure degradation of nickel base single crystal
superalloy CMSX-4 suggests following conclusions:
1. The γ’ precipitates preserve their cuboidal morphology during ageing at
a temperature of 850 °C up to 6000 h and at 1000 °C up to 500 h. Longer ageing
time leads to directional coarsening of the precipitates and formation of
spontaneously rafted microstructure. Both the Vickers hardness HV and YS
linearly decrease with decreasing normalized volume fraction and increasing
normalized mean size of the γ’ precipitates. A linear relationship between the YS
and HV is determined which allows high-temperature yield strength to be
predicted from simple Vickers hardness measurements at room temperature.
2. Short solution annealing time leads to a preferential formation of spontaneous γ’
rafts within the dendrites while cuboidal γ’ precipitates are preserved within the
interdendritic region. Longer solution annealing time leads to development of
more homogenous spontaneously rafted microstructure during ageing. Critical

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parameters, e.g. ageing temperature and time for morphological stability of
cuboidal γ’ precipitates and formation of spontaneously rafted microstructure were
determined. Formation of spontaneously rafted microstructure affects tensile
properties at room and high temperatures. Longer solution annealing time results
in a decrease of YS, UTS and elongation when compared to those of specimens
solution annealed for shorter time.
3. Creep exposure leads to a directional coarsening (rafting) of cuboidal
γ’ precipitates. The width of γ’ rafts decreases and widths of γ channels and
length of γ’ rafts increase with increasing applied stress and creep time. YS and
UTS of creep degraded specimens decrease and elongation increase when
compared to those of non-degraded specimens with cuboidal γ’ precipitates.

ACKNOWLEDGEMENTS
This work was financially supported by the Slovak Grant Agency for Science
under the contract VEGA 2/7085/27.

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