Journal of Materials Science & Technology 35 (2019) 344–350

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Journal of Materials Science & Technology

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Research article

Epitaxial growth and oxidation behavior of an overlay coating on a

Ni-base single-crystal superalloy by laser cladding
Jingjing Liang a,c , Yongsheng Liu b , Jinguo Li a,∗ , Yizhou Zhou a,∗ , Xiaofeng Sun a
a
Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China
b
State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China
c
Space Manufacturing Technology (CAS Key Lab), Beijing, 100094, China

a r t i c l e i n f o a b s t r a c t

Article history: An overlay coating material was deposited on a single crystal superalloy SRR99 by laser cladding.
Received 30 July 2018 The microstructure and oxidation behavior of this coating was investigated through scanning electron
Received in revised form 28 August 2018 microscopy (SEM) and X-ray diffraction (XRD). The results indicated that although the composition of the
Accepted 29 August 2018
coating was chosen based on the ␥’ composition in René N5 superalloy, the primary solidification phase of
Available online 13 October 2018
this coating during laser cladding was ␥-Ni. Furthermore, under the laser cladding condition, fine parallel
dendrites grew epitaxially in the coating from the substrate, indicating the single crystal structure of the
Keywords:
substrate was reproduced. When the single crystal MCrAlY coating was oxidized at 1000◦ , both ␪-Al2 O3
Laser cladding
Single crystal growth
and ␣-Al2 O3 formed during initial oxidation process. As the oxidation time proceeded, the presence of
Epitaxy ␪-Al2 O3 facilitated the formation of NiAl2 O4 spinel oxide. Once the spinel was observed, it flourished and
Overlay coating induced some porosity in the scale. When the scale thickness increased to 6–7 ␮m, large area spallation
of the scale began.
© 2018 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science &
Technology.

1. Introduction In order to decrease the influence of the property mismatch

Nowadays, Ni-base single-crystal superalloys are the first choice
for high temperature and high pressure gas turbine blades. The
mechanical properties of the single crystal superalloy are out-
standing, but their resistance to oxidation and corrosion is usually
insufficient in many service conditions. To overcome this problem,
many kinds of protective coatings are applied to the surface of the
superalloy substrate; an important one of these coatings is MCrAlY
(with M = Co, Ni or combination thereof) coating. MCrAlY coatings
can be applied by a wide range of techniques, such as low pressure
plasma spray (LPPS) [1,2], high velocity oxygen fuel (HVOF) spray
[3], and arc ion plating (AIP) [4]. These current processes produce
polycrystalline coating layers which have different phase consti-
tutes, crystalline orientations and mechanical properties with the
single-crystal superalloy substrate. In such a case, incompatibility
stresses may develop near the interface between the coating and
the substrate during thermal cycling, leading to reduced thermo-
mechanical fatigue strength of the superalloy component.
∗ Corresponding authors.
E-mail addresses: jgli@imr.ac.cn (J. Li), yzzhou@imr.ac.cn (Y. Zhou).
between polycrystalline MCrAlY coatings and single-crystal super-
alloys, one potential way is to develop single crystal MCrAlY
coatings that have the same crystalline orientation with the super-
alloy substrate. It is reported that laser cladding technique can
allow epitaxial build-up of protective coatings to match the ori-
ented substrate [5,6], so it is a promising method to produce single
crystal coatings.
In this laser cladding process, metallic powder is injected into
a molten pool produced by a laser beam of high energy intensity.
If the composition of the cladding powder is the same as the sub-
strate, solidification will begin by epitaxial growth of dendrites.
This means no nucleation will occur and the cladded layer will have
the same crystallographic orientation as the substrate when den-
drite growth remains columnar during the solidification process. If
the composition of the metallic powder has a different composition
to the substrate, such as MCrAlY coatings and single crystal super-
alloy substrates, epitaxial growth can also occur when the primary
solidification phase of the coating is ␥ with ␥’ as a solid state precip-
itation. In this case, the crystallographic structure and orientation
of the ␥/␥’ substrate can also be reproduced in the cladded MCrAlY
coating. However, when the primary solidification phase changes
to be ␤ or ␥/␤ eutectic, non single crystal solidification will occur
due to the nucleation of ␤ which has an ordered body-centered

https://doi.org/10.1016/j.jmst.2018.10.011
1005-0302/© 2018 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.
 J. Liang et al. / Journal of Materials Science & Technology 35 (2019) 344–350
Table 1
Chemical compositions of the substrate and the coating powder.
Cr Co W Mo Ta
TMBC-1 4.06 6.13 4.62 1.02 9.91
SRR99 8.50 5.01 9.52 – 2.81
cubic structure different from the face-centered cubic substrate of
the ␥/␥’ substrate.
In the present study, an innovative overlay coating material
was deposited on a single crystal superalloy by laser cladding. This
coating is termed TMBC-1, a kind of EQ (equilibrium) coating and
developed by National Institute for Materials Science (NIMS), Japan
[7–9]. More information of this coating can be found in ref. [10].
The microstructure and epitaxial growth behavior of this TMBC-1
coating deposited by laser cladding was investigated. The oxidation
behavior of this coating was also concerned.
2. Experimental
The substrate samples were cut from SRR99, a commercial first
generation Ni-base single crystal superalloy, in solid solution heat-
treatment condition. Its chemical composition is shown in Table 1.
The SRR99 substrate had a longitudinal direction approximately
parallel to the [001] crystallographic direction, and was cross-
sectioned perpendicularly to its axis in order to obtain a substrate
with its surface nominally parallel to the (001) plane. Prior to the
laser cladding process, the substrates were grounded through 400#
SiC grit paper.
Laser cladding was performed using a 4 kW continuous CO2 laser
of about 1.0 mm beam diameter. The TMBC-1 coating powder of a
mesh size of -100/+300 was transported by an argon jet and injected
into the melt pool through a coaxial nozzle. The samples were
moved under the stationary laser beam at constant speed using
a numerically controlled X–Y stable. Epitaxial dendrite growth of
the coating was achieved during the solidification of the melt pool
by a careful selection of the processing parameters. The processing
Fig. 1. Optical microstructure of the one-layer coating deposited on a SRR99 substrate by laser cladding: (a) whole coating; (b) bottom part; (c) top part.
345
Al Hf Ti C Y Ni
8.10 0.30 – – 0.031 Bal.
5.50 – 2.17 0.015 Bal.
parameters of this laser cladding were: laser beam power 800 W,
laser spot size 1 mm, powder feed rate 10 g/min, scanning velocity
10 mm/s and overlap rate 45%. In order to avoid dilution contami-
nation in the coating caused by remelting of superalloy substrates
during deposition, a second layer was deposited on the first layer.
Isothermal oxidation performance of the single-crystal EQ
coating was evaluated. Before oxidation test, the surface of the
double-layer samples were ground to 1000-mesh and then ultra-
sonically cleaned in acetone. The isothermal oxidation tests at
1000 ◦ C were conducted in static air in muffle furnaces. All the
samples were put into the furnace at the same time after the
test temperature was reached. During oxidation, the samples were
taken out of the furnace and freely cooled to room temperature
according to a preplanned schedule for microstructure observation
and oxidized product analysis. Standard polishing procedure was
applied to prepare samples for SEM (scanning electron microscopy,
JEOL JSM 6500 F, Japan) observation. The samples were also exam-
ined using X-ray diffraction (XRD, D8 Discover, Bruker, Germany).
3. Results and discussion
3.1. Epitaxial growth of the as-clad coating
The microstructure of the single layer EQ coating deposited by
laser cladding is shown in Fig. 1. Fine parallel dendrites in the
deposited coating were clearly visible and perpendicularly arrayed
on the substrate, and no heterogeneous nucleation was discovered
(Fig. 1(a) and (b)). These microstructure features suggested that
these dendrites grew epitaxially from the single crystal substrate
and the single crystal structure of the substrate was reproduced
346 J. Liang et al. / Journal of Materials Science & Technology 35 (2019) 344–350
Fig. 2. Optical microstructure of the two-layer coating deposited on a SRR99 substrate by laser cladding: (a) periphery part; (b) middle part.
[11–14]. These dendrites in the coating did not present well-
developed secondary or higher-order arms. The mean primary arm
interdendritic distance was about 5 ␮m.
Some dendrites with different orientations (marked by a red
circle Fig. 1(b)) were observed in the coating near the coat-
ing/substrate interface. It was reported that this misoriented grain
formation and resulting epitaxy loss at the substrate was gener-
ally attributed to (1) the difference of crystallographic structures
between the coating and the substrate [15] and (2) the composi-
tion segregation at the substrate interdendritic region [16]. After a
certain growth distance, the misoriented dendrite was suppressed
and overgrown, and the main parallel dendrites with a preferred
crystal direction clearly predominated. This phenomenon agreed
well with the classic theory of competitive grain growth during
directional solidification process [17–19].
The interface between the deposited coating and the substrate
was marked by a featureless layer of about 3 ␮m which was prob-
ably formed by planar solid-liquid interface solidification [13,20]
(Fig. 1(b)). No grain boundaries had been detected at the interface.
This interface showed continuous, adherent and metallurgically
sound. At the top of the coating, there was a systematic change
in the dendrite morphology (Fig. 1(a) and (c)). This transition in the
dendrite morphology had been proofed to be caused by a change
in the heat flux direction [21].
It was reported that some remelting of superalloy substrates
occurred during deposition, and dilution contamination of the coat-
ing by the substrate material could not be avoided [22]. So the
composition of the deposited coating was probably different from
Fig. 3. (a) Isopleth and (b) Scheil-Gulliver solidification process map in the coating system calculated with Thermo-Calc software and TTNi8 database.
the original composition of the coating powder. In order to avoid
the influence of the substrate and make sure whether this EQ coat-
ing can epitaxially grow on the superalloy substrate, a second layer
of the EQ coating was added to the previously deposited layer. Fig. 2
shows the microstructure of the two-layer sample. It can be seen
that columnar dendrites grew throughout the layers, and fine den-
dritic morphology was preserved in the second layer (Fig. 2). This
suggested that epitaxial growth was obtained by columnar growth
of dendrites in the EQ coating.
A condition for epitaxial growth of a MCrAlY coating on a Ni-base
single crystal superalloy has been defined by Bezençon et al. [15]:
the primary solidification phase under laser treatment condition
must be ␥, a face-centered cubic (FCC) solid solution. In this case, the
crystallographic structure can be reproduced in the laser cladded
coating whether the coating composition is the same as that of the
substrate or not. This is because under this condition the coating has
the same crystallographic structure as the ␥/␥’ superalloy substrate.
It was known that the composition of TMBC-1 coating was cho-
sen based on the composition of ␥’ in René N5 superalloy. In order to
make sure whether the primary solidification phase of this coating
was ␥’ or not, isoplethal section and Scheil-Gulliver solidification
process map of this coating alloy were calculated by commercially-
available thermodynamic software Thermo-Calc and Ni-database
TTNi8. The calculated results are shown in Fig. 3. The isopleth
(Fig. 3(a)) was plotted as a function of Al fraction from 0 to 20 wt%
whereas Ni was adapted to give a total fraction of 100 wt%. The
fractions of other alloy elements were kept constant to the respec-
tive TMBC-1 composition. The nominal Al content for TMBC-1 alloy
 J. Liang et al. / Journal of Materials Science & Technology 35 (2019) 344–350
Fig. 4. XRD patterns of (a) TMBC-1 powder and (b) its as-deposited coating by laser
cladding.
was highlighted with a black dash line. From the isopleth and the
solidification process map (Fig. 3), it was suggested that the first
solidified phase of this coating was ␥’, but the largest amount of
phases in the coating was ␥.
Besides the thermodynamic calculation, XRD analysis of both
the coating powder and the as-deposited sample were conducted.
The results were presented in Fig. 4. The XRD pattern (Fig. 4(b))
of the as-deposited sample had ␥ (200) as the strongest diffrac-
tion peak, indicating a strong preference of the dendritic growth
direction along <100> crystallographic direction. This was in coin-
cidence with the microstructure observation (Fig. 1). According to
the intensity and the number of the XRD peaks in Fig. 4, the phase
of TMBC-1 coating in the present study was ␥ only. This meaned
the primary solidification phase of this coating material was ␥, not
␥’. This result agreed well with Bezençon’s conclusion mentioned
above [15]. The reason responsible for the disagreement between
thermodynamic calculation (Fig. 3) and XRD results (Fig. 4) was
probably attributed to quick solidification during powder prepa-
ration and laser cladding. Quick solidification would lead to phase
constituent of the investigated alloy far differ from that in totally
thermodynamic equilibrium state obtained through Thermo-calc
calculation. So it brought in some deviation to confirm primary
solidification phase during laser cladding through thermodynamic
calculation.
3.2. Oxidation behavior
Oxidation test of the single-crystal coating were conducted in air
at 1000 ◦ C. In order to identify the oxidized products on the surface
of the coating, XRD analysis was carried out. Table 2 summarizes the
indentified phases of the oxidized products through XRD analysis.
It can be seen that ␣-Al2 O3 has formed on the surface of the sam-
ple oxidized for 20 min. When the exposure time increase to 10 h,
the amount of ␣-Al2 O3 increased, and NiAl2 O4 spinel formed. On
the samples oxidized at 155 h and 355 h, complex spinel (including
NiAl2 O4 , NiCr2 O4 and CoCr2 O4 ) and NiO have been firstly detected,
respectively. After being detected, their amounts increased quickly.
After 355 h, NiO began to be the predominant oxidized product
instead of ␣-Al2 O3 .
347
Table 2
Phase constituents of oxide products on the oxidized coatings at 1000 ◦ C.
Time Oxide products
20 min ␣-Al2 O3 (vw)
5h ␣-Al2 O3 (m)
10 h ␣-Al2 O3 (s), NiAl2 O4 (vw)
155 h ␣-Al2 O3 (vs), Spinel (NiAl2 O4 (m), NiCr2 O4 (s), CoCr2 O4 (w))
355 h ␣-Al2 O3 (vs), NiO (s), Spinel (NiAl2 O4 (s), NiCr2 O4 (s), CoCr2 O4 (w))
506 h NiO (vs), ␣-Al2 O3 (s), Spinel (NiAl2 O4 (s) CoAl2 O4 (m) NiCr2 O4 (m)
CoCr2 O4 (w))
Note:vs = very strong; s = strong; m, medium; w = weak; vw = very weak.
In order to reveal the microstructural evolution of the oxidized
products on the surface of the investigated coating, samples pre-
pared by the same laser cladding parameter were oxidized under
the same condition. At this time the morphologies of the top sur-
face and the cross section of the oxidized samples were checked
and observed.
Fig. 5 shows sets of the surface morphologies of the samples
after being oxidized at 1000 ◦ C for different times. For the present
single crystal coating, after being oxidized for 20 min, a complete
layer of blocky oxidized grains of about 0.2-0.3 ␮m size covered the
whole surface (Fig. 5(a)). Fig. 6 shows the EDS result of the oxidized
scale marked by red rectangle in Fig. 5a. Based on the EDS results
(Fig. 6) and the XRD analysis results (Table 2), it was deduced that
the tiny blocky products should be ␣-Al2 O3 . Besides the blocky
␣-Al2 O3 grains, a needle-like oxide product had also formed at
some regions (Fig. 5(a)). Both the size and the amount of these
needle-like oxides were very small, so it was difficult to identify
their phase composition. According to oxide morphology descrip-
tion on oxidation-protective coatings from reference [23], ␪-Al2 O3
showed a typical needle-like morphology. In addition, Rybicki et.
al. [24] had identified the co-existence of ␪-Al2 O3 and ␣-Al2 O3
on ␤-NiAl coating during isothermal oxidation at 1000 ◦ C for 5 h.
So it was speculated that the needle-like oxidized product in this
study was ␪-Al2 O3 . Based on XRD analysis (Table 2), no diffraction
peak of ␪-Al2 O3 oxide had been detected by XRD. The disagreement
between the XRD result (Table 2) and the microstructure observa-
tion (Fig. 5) was probably attributed to the small amount of ␪-Al2 O3
which could not be detected by XRD.
After oxidation for 1 h (Fig. 5(b)), the surface morphology of
the oxidized scale was the same as that of the samples oxidized
for 20 min. So it was deduced that the oxidized products were
still blocky ␣-Al2 O3 and needle-like ␪-Al2 O3 . As oxidation time
increased to 10 h (Fig. 5(c)), the needle-like oxide product disap-
peared, and a bigger amount of plate-like product was observable.
Generally speaking, the amount of the plate-like oxidized prod-
uct was large enough to be detected by XRD. XRD results (Table 2)
showed there was no ␪-Al2 O3 existing, but NiAl2 O4 spinel existed.
So it is deduced that the plate-like oxide was NiAl2 O4 spinel. Prob-
ably the presence of ␪-Al2 O3 which had large amount of defects
(twin boundaries and screw dislocations) provided a fast diffusion
path for Ni atoms from the coating to the scale and facilitated the
growth of the spinel.
When the oxidation time increased to 155 h (Fig. 5(d)), well-
developed plate-like spinel and blocky ␣-Al2 O3 was present
everywhere. At this time, the spinel included not only NiAl2 O4 but
also NiCr2 O4 and CoCr2 O4 . On the surface of the sample oxidized
for 355 h (Fig. 5(e)), the plate-like spinel became much more flour-
ishing. As the exposure time increased to 506 h (Fig. 5(f)), large area
spallation of the scale happened. On the post-spallation surface, a
new scale layer was shown. EDS results indicated the new scale
was rich in Al and O, indicating that this scale was ␣-Al2 O3 . It was
difficult from the surface morphology to identify this ␣-Al2 O3 scale
was newly formed or already existed underneath the spalled scale.
348 J. Liang et al. / Journal of Materials Science & Technology 35 (2019) 344–350

Fig. 5. Surface morphologies of the coating after oxidation at 1000 ◦ C in air for (a) 20 min, (b) 1 h, (c) 10 h, (d) 155 h, (e) 355 h, (f) 506 h.

Fig. 6. EDS result of the oxidized scale marked by red rectangle in Fig. 5(a).
 J. Liang et al. / Journal of Materials Science & Technology 35 (2019) 344–350
Fig. 7. Cross-section morphologies of the coating after oxidation at 1000 ◦ C in air for (a) 10 h, (b) 155 h, (c) 355 h, (d) 506 h.
Fig. 7 shows the cross-sectional morphology of the coating after
oxidation at 1000 ◦ C in air for different time. It can be seen that
continuous and dense ␣-Al2 O3 oxide scales formed on this coat-
ing. As oxidation time increased, the scale became thicker and a
little unsounding. Some irregular porosities marked by red arrows
existed (Fig. 7(c)). According to the XRD results (Table 2) and the
surface morphology (Fig. 5(e)), it was suggested that the formation
of the large amount of plate-like spinel induced these porosities. As
the thickness of the scale increased to 6–7 ␮m, large area spallation
of the scale began. On the surface of the sample oxidized at 1000 ◦ C
for 506 h, only a thin layer of scale left (Fig. 7(d)).
4. Conclusions
In this work, single crystal overlay coating samples have been
successfully fabricated by laser cladding. The microstructure and
oxidation behavior of this single crystal coating was investigated.
Conclusions can be summarized as follows.
(1) Fine parallel dendrites grew epitaxially from the single crys-
tal substrate and the dendrites did not present well-developed
secondary or higher-order arms. The mean primary arm inter-
dendritic distance was about 5 ␮m. The interface between the
deposited coating and the substrate was marked by a feature-
less layer of about 3 ␮m which was probably formed by planar
solid-liquid interface solidification.
(2) The composition of the investigated coating was chosen based
on the ␥’ composition in René N5 superalloy, and thermody-
349
namic calculation showed the primary solidification phase of
the coating was ␥’. However, XRD results indicated that the pri-
mary solidification phase of the studied coating was ␥-Ni. This
formation of ␥-Ni was probably due to the fast solidification
rate during laser cladding.
(3) During oxidation at 1000 ◦ C, tiny blocky ␣-Al2 O3 and needle-
like ␪-Al2 O3 both formed on the coating surface when oxidized
for 20 min; as oxidation time increased to 10 h, the needle-like
␪-Al2 O3 disappeared and a bigger amount of plate-like spinel
was observable. Once formed, the spinel grew very fast and
induced much porosity in the scale, which was mainly respon-
sible for the spallation of the scale.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (NSFC) under grant Nos. 51771190,
51401210, U1508213, 51701210, 51871221, the National High
Technology Research and Development Program (863 Program, No.
2014AA041701), the fund of the State Key Laboratory of Solidifica-
tion Processing in NWPU (SKLSP201834) and the Theme Special
Project of Shenyang Key Science and Technology Research and
Development Programs (17-85-0-00). The authors are grateful for
those supports.
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