coatings
Article
High-Temperature Corrosion of AlCrSiN Film in
Ar-1%SO2 Gas
Poonam Yadav 1 , Dong Bok Lee 1, *, Yue Lin 2 , Shihong Zhang 2 and Sik Chol Kwon 3
1
2
3
*
School of Advanced Materials Science & Engineering, Sungkyunkwan University, Suwon 16419, Korea;
[email protected]
School of Materials Science & Engineering, Anhui University of Technology, Maanshan 243002, China;
[email protected] (Y.L.); [email protected] (S.Z.)
Department of Advanced Materials Engineering, Chungbuk National University, Cheongju 28644, Korea;
[email protected]
Correspondence: [email protected]; Tel.: +82-31-290-7355
Academic Editors: Niteen Jadhav and Andrew J. Vreugdenhil
Received: 26 December 2016; Accepted: 9 March 2017; Published: 13 March 2017
Abstract: AlCrSiN film with a composition of 29.1Al-17.1Cr-2.1Si-51.7N in at. % was deposited on
a steel substrate by cathodic arc ion plating at a thickness of 1.8 µm. It consisted of nanocrystalline
hcp-AlN and fcc-CrN, where a small amount of Si was dissolved. Corrosion tests were carried
out at 800 ◦ C for 5–200 h in Ar-1%SO2 gas. The major corrosion reaction was oxidation owing to
the high oxygen affinity of Al and Cr in the film. The formed oxide scale consisted primarily of
(Al,Cr)2 O3 , within which Fe, Si, and S were dissolved. Even after corrosion for 200 h, the thickness
of the scale was about 0.7–1.2 µm, indicating that the film had good corrosion resistance in the
SO2 -containing atmosphere.
Keywords: AlCrSiN film; oxidation; sulfidation; SO2 gas corrosion
1. Introduction
Aluminum nitride films have good oxidation resistance due to the formation of Al2 O3 scale [1].
Their properties can be enhanced by alloying with the transition metal Cr. AlCrN films have been
applied on dies, molds, and cutting tools [2] for their high hardness [3], thermal stability [4], good
resistance to wear [5], and oxidation [6–9]. AlCrN films were oxidized to Al2 O3 and Cr2 O3 [6], or
(Cr,Al)2 O3 [9], which suppressed oxygen diffusion. The addition of Si to the AlCrN films refines the
grain [10,11], decreases crystallinity [11], increases hardness [12,13], and improves the resistance to
wear [10] and oxidation [13–15]. AlCrSiN films have been deposited on cemented carbides [11,13,16],
Si [11,12,15], and steel [10–12,17] by cathodic arc evaporation [11,16,17], cathodic arc ion plating [10],
and magnetron sputtering [13,15]. The high-temperature oxidation of AlCrSiN films in air results in
the formation of thin, dense oxide layers consisting primarily of Cr2 O3 [17], (Cr2 O3 , Al2 O3 ) [14], and
(Cr2 O3 , Cr2 O5 , Al2 O3 ) [13]. However, the corrosion behavior of AlCrSiN films in various corrosive
environments needs be investigated for broad applications. In this study, the high-temperature
corrosion of AlCrSiN film in a SO2 -containing atmosphere was performed, with an emphasis on
TEM/EDS analyses. Resistance to sulfur-containing atmospheres is vital for utilizing AlCrSiN as
the protective coating in petrochemical plants, coal-gasification units, turbines, and heat exchangers.
Sulfur in SO2 can induce serious corrosion by forming non-protective, highly non-stoichiometric
sulfide scales [18]. In this study, corrosion tests were carried out on AlCrSiN film at 800 ◦ C for 5–200 h
in Ar-1%SO2 gas. The microstructure, corrosion products, and corrosion mechanism of the AlCrSiN
film are discussed.
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2. Experimental Section
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AlCrSiN film was deposited on a steel substrate (AISI M2 high speed steel; Fe-6W-5Mo-4Cr-2V
2. Experimental Section
in wt %) by cathodic arc ion plating using Cr and Al88 Si12 cathodes. It was deposited for 5 h at a
◦ C, a(AISI
AlCrSiN film
on a steel
substrate
high speed
steel;V,Fe-6W-5Mo-4Cr-2V
nitrogen pressure
of 1was
Pa, deposited
a temperature
of 400
bias M2
voltage
of −150
an arc current of 55 A,
in
wt
%)
by
cathodic
arc
ion
plating
using
Cr
and
Al
88Si12 cathodes. It was deposited for 5 h at a
and a cathode-to-substrate distance of 7 cm. The rotation speed of the sample holder was 3 rpm,
nitrogen pressure of 1 Pa, a temperature of 400 °C, a bias voltage of −150 V, an arc current of 55 A,
and an AlCrN interlayer was deposited between the film and the substrate for 20 min. The coated
and a cathode-to-substrate distance
of 7 cm. The rotation speed of the sample holder was 3 rpm, and
samples
were corroded at 800 ◦ C for 5–200 h in the flowing Ar-1%SO gas inside the quartz reaction
an AlCrN interlayer was deposited between the film and the substrate for2 20 min. The coated samples
tube, which
was heated
inside
tube furnace.
Following
corrosion,
the coated samples were inspected
were corroded
at 800
°C fora 5–200
h in the flowing
Ar-1%SO
2 gas inside the quartz reaction tube,
using which
a scanning
electron
microscope
(SEM),
Auger
electron
spectrometer
(AES), X-ray
photoelectron
was heated inside a tube furnace. Following corrosion, the coated samples
were inspected
spectrometer
(XPS), and
transmission
microscope
operated
at 200
keV)
equipped with
using a scanning
electron
microscopeelectron
(SEM), Auger
electron (TEM
spectrometer
(AES),
X-ray
photoelectron
spectrometer
(XPS),
and transmission
electron
at 200
keV) equipped
with
an energy
dispersive
spectrometer
(EDS
with 5microscope
nm spot (TEM
size). operated
The TEM
samples
were prepared
by
an
energy
dispersive
spectrometer
(EDS
with
5
nm
spot
size).
The
TEM
samples
were
prepared
by
milling using a focused ion beam system after carbon coating.
milling using a focused ion beam system after carbon coating.
3. Results and Discussion
3. Results and Discussion
Figure 1 shows the TEM/SAED/EDS results of the as-deposited AlCrSiN film, the composition
Figure 1 shows the TEM/SAED/EDS results of the as-deposited AlCrSiN film, the composition
of which
was 29.1Al-17.1Cr-2.1Si-51.7N
in at.in%at.according
to the
probe
microanalysis
(EPMA).
of which
was 29.1Al-17.1Cr-2.1Si-51.7N
% according
to electron
the electron
probe
microanalysis
The AlCrSiN
film
was
1.8
µm
thick,
single-layered
(Figure
1a),
and
consisted
of
nanocrystalline
(EPMA). The AlCrSiN film was 1.8 μm thick, single-layered (Figure 1a), and consisted hcp-AlN
of
and fcc-CrN
(Figurehcp-AlN
1b). It is
known
that
the crystal
CrAlN
changes
from
B1-fcc to
nanocrystalline
and
fcc-CrN
(Figure
1b). It is structure
known thatofthe
crystalfilms
structure
of CrAlN
films
fromAlN
B1-fcc
to B4-hcp above
AlNat.concentration
of 65–75
at. %of
[6],
the addition
Si
B4-hcpchanges
above the
concentration
of the
65–75
% [6], and the
addition
Siand
to CrAlN
filmsoffacilitates
to CrAlNof
films
facilitates
hcp-AlN
[16]. Inofthis
study,seemed
the nucleation
of hcp-AlN by Si.
the formation
hcp-AlN
[16].the
In formation
this study,ofthe
nucleation
hcp-AlN
to be accelerated
seemed
to beAlN-rich
accelerated
by was
Si. Inbrighter
Figure 1c,
the the
AlN-rich
area was
In Figure
1c, the
area
than
CrN-rich
areabrighter
becausethan
Al the
hasCrN-rich
a lower area
scattering
because Al has a lower scattering factor than Cr. Si dissolved rather uniformly in the film, as shown
factor than Cr. Si dissolved rather uniformly in the film, as shown in Figure 1d. Here, the presence of
in Figure 1d. Here, the presence of nitrogen in the film was ignored, because TEM/EDS could not
nitrogen
in the film
wasthe
ignored,
because TEM/EDS could not accurately quantify the light element.
accurately
quantify
light element.
(a)
carbon coating
(b)
CrN(222)
AlN(101)
Film
CrN(220)
AlN(103)
CrN(200)
0.5 μm
(c)
B
200 nm
Concentration (at.%)
substrate
(d)
60
Al
40
Cr
20
Si
0
0
300
100
200
Distance (nm)
400
Figure 1. As-deposited AlCrSiN film. (a) TEM cross-sectional image; (b) selected area electron
Figure 1. As-deposited AlCrSiN film. (a) TEM cross-sectional image; (b) selected area electron
diffraction (SAED) pattern of the film; (c) enlarged TEM image of the film; (d) EDS concentration
diffraction
(SAED) pattern of the film; (c) enlarged TEM image of the film; (d) EDS concentration
profiles along A-B shown in (c).
profiles along A-B shown in (c).
Gold was deposited on the AlCrSiN film using a sputter, and corroded at 800 °C for 5 h in order
◦ C for
to
understand
the corrosion
of the
AlCrSiN
film atand
the corroded
early corrosion
stage.
In Figure
2,
Gold was deposited
on themechanism
AlCrSiN film
using
a sputter,
at 800
5 h in order
to
the highest point of Au indicates the original film surface. During corrosion, nitrogen diffused
understand the corrosion mechanism of the AlCrSiN film at the early corrosion stage. In Figure 2, the
outwardly from the film, while oxygen and sulfur diffused inwardly. Oxygen diffused dominantly
highest point of Au indicates the original film surface. During corrosion, nitrogen diffused outwardly
and deeply, while sulfur was present only at the outermost surface. The ingress of sulfur through
from the
film,oxides
whilecould
oxygen
and sulfur
diffused
inwardly.
Oxygen
diffused
compact
be limited,
because
the solubility
of sulfur
in most
oxides dominantly
is very limitedand
[19].deeply,
while sulfur was present only at the outermost surface. The ingress of sulfur through compact oxides
could be limited, because the solubility of sulfur in most oxides is very limited [19]. It is worth noting
that oxides are thermodynamically more stable than the corresponding sulfides. Since Al is more active
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It is worth noting that oxides are thermodynamically more stable than the corresponding sulfides.
than
Al
predominantly
underneath
the Au
film.stable
Silicon
was
and
non-uniformly
Since
Al
is oxidized
more
than Cr,
oxidized predominantly
underneath
the Au
film.
Silicon
was
It isCr,
worth
notingactive
that
oxides
areAl
thermodynamically
more
than
theweakly
corresponding
sulfides.
present
in
the
film.
weakly
present
inoxidized
the film. predominantly underneath the Au film. Silicon was
Since and
Al isnon-uniformly
more active than
Cr, Al
weakly and non-uniformly present in the film.
◦ C for
Figure
2. 2.
AES
depth
profiles
the
AlCrSiN
film
after
corrosion
at800
800
5h
in
Ar-1%SO
2 gas.
Figure
2.
AES
depth
profiles
ofof
the
AlCrSiN
film
after
corrosion
atat
800
5for
h5 in
Ar-1%SO
The
Figure
AES
depth
profiles
of
the
AlCrSiN
film
after
corrosion
°C°Cfor
h
in
Ar-1%SO
2 gas.
2 gas.
The
penetration
rate
is
19
nm/min
for
the
reference
SiO
2
.
penetration
rate israte
19 nm/min
for the
SiO2SiO
. 2.
The penetration
is 19 nm/min
forreference
the reference
Figure
of
the AlCrSiN
AlCrSiNfilm
filmafter
aftercorrosion
corrosionatat
800
°C
10 The
h. The
Figure33 3shows
showsthe
theTEM/EDS
TEM/EDS results
results
of of
the
800
forfor
◦10
Figure
shows
the
TEM/EDS
results
the AlCrSiN
film after
corrosion
at°C800
C h.
for 10 h.
scale
was
0.20.2μm
reflecting
the
corrosion
resistanceofofthe
the AlCrSiN
film
(Figure
3a).
Oxide
scale
was
μmthick,
thick,
reflecting
thegood
good
corrosion
resistance
film
(Figure
Oxide
The
scale
was 0.2
µm
thick,
reflecting
the good
corrosion
resistanceAlCrSiN
of the AlCrSiN
film3a).
(Figure
3a).
whiskers
protruded
(Figure3b).
3b).According
Accordingtotothe
theTEM/EDS
TEM/EDS
spot
analysis,
whiskers
protrudedover
overangular
angularoxide
oxide grains
grains (Figure
spot
analysis,
Oxide whiskers protruded over angular oxide grains (Figure 3b). According to the TEM/EDS spot
scaleconsisted
consistedofof(Al,Cr)
(Al,Cr)2O
2O33 grains
grains with dissolved
Chromia
and
α- αthethe
scale
dissolved Fe
Feand
andSiSiions
ions(Figure
(Figure3c).
3c).
Chromia
and
analysis, the scale consisted of (Al,Cr)2 O3 grains with dissolved Fe and Si ions (Figure 3c). Chromia and
3 are
misciblebecause
becausethey
theyhave
havethe
the same corundum
ofof
Si Si
shown
in Figure
AlAl
2O23O
are
miscible
corundumstructure.
structure.The
Theamount
amount
shown
in Figure
α-Al2 O3 are miscible because they have the same corundum structure. The amount of Si shown in
inaccurate,because
becausethe
thespurious
spurious Si
Si signal can
owing
to to
thethe
3c 3c
is is
inaccurate,
can come
come out
outfrom
fromthe
theEDS
EDSdetector
detector
owing
Figure 3c is inaccurate, because the spurious Si signal can come out from the EDS detector owing to the
internal
fluorescence.
Iron
diffused
outward
from
the
substrate
through
the
nanocrystalline
film
internal fluorescence. Iron diffused outward from the substrate through the nanocrystalline film
internal
fluorescence.
Iron diffused
outward
from the substrateSince
through the nanocrystalline
film toward
toward
thesurface
surfaceaccording
accordingto
tothe
the concentration
concentration gradient.
preferentially
toward
the
gradient. Sinceoxidation
oxidationoccurred
occurred
preferentially
theowing
surface
according
to
the
concentration
gradient.
Since
oxidation
occurred
preferentially
owing to
the
thermodynamicstability
stability of
of the
the oxides,
oxides, sulfur
3c.3c.
The
XPS
analysis,
owing toto
the
thermodynamic
sulfurwas
wasabsent
absentininFigure
Figure
The
XPS
analysis,
thehowever,
thermodynamic
stability
ofatthe
oxides,
sulfur
was
absent
in Figure 3c. The XPS analysis, however,
identified
2.6
at.
%S
the
surface
of
the
(Al,Cr)
2O3 scale. Such a discrepancy in the chemical
however, identified 2.6 at. %S at the surface of the (Al,Cr)2O3 scale. Such a discrepancy in the chemical
identified
2.6 at.of%S
the surface
ofthe
thesurface
(Al,Cr)2was
O3 scale.
Suchto
a discrepancy
the chemicalofcomposition
composition
theatoxide
scale at
attributed
the differentindetectability
XPS and
composition of the oxide scale at the surface was attributed to the different detectability of XPS and
of TEM-EDS.
the oxide scale at the surface was attributed to the different detectability of XPS and TEM-EDS.
TEM-EDS.
Figure 3. AlCrSiN film after corrosion at 800 °C for 10 h in Ar-1%SO2 gas. (a) TEM cross-sectional
Figure 3. AlCrSiN film after corrosion at 800 ◦ C for 10 h in Ar-1%SO2 gas. (a) TEM cross-sectional
image, (b) enlarged image of rectangular area shown in (a), (c) EDS concentration profiles along the
image,
enlargedfilm
image
of corrosion
rectangular
shown
in h
(a),
EDS concentration
profiles
along the
Figure (b)
3. AlCrSiN
after
at area
800 °C
for 10
in(c)
Ar-1%SO
2 gas. (a) TEM
cross-sectional
spots 1–14.
spots
image,1–14.
(b) enlarged image of rectangular area shown in (a), (c) EDS concentration profiles along the
spots 1–14.
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Figure 4 shows the TEM/EDS results of the AlCrSiN film after corrosion at 800 °C for 50 h. The
◦ C for 50 h.
4 shows
the TEM/EDS
results of the
the slowly
AlCrSiN
film after
corrosion
at 8004a).
scaleFigure
was still
thin because
of the formation
growing
oxide
scale (Figure
Spots 1–3
The
scale
was
still
thin
because
of
the
formation
of
the
slowly
growing
oxide
scale
(Figure
4a).
Spots 1–3
and 4–9 corresponded to the (Fe, Si, S)-dissolved (Al,Cr)2O3 scale and the S-free, (Fe, O)-dissolved
and
4–9 corresponded
to the (Fe,
Si, S)-dissolved
(Al,Cr)
scale and
the S-free,
(Fe, O)-dissolved
AlCrSiN
film, respectively
(Figure
4b). Nitrogen
was
around
the oxide
scale. The
2 O3absent
AlCrSiN
film, respectively
(Figure4b4b).
was
absent around
the of
oxide
The concentrations
concentrations
shown in Figure
are,Nitrogen
however,
suspicious,
because
the scale.
difficulty
in quantifying
shown
in Figure
are,Si.
however,
suspicious,
of the difficulty
in quantifying
nitrogen,
nitrogen,
oxygen,4band
Nonetheless,
sulfurbecause
was detected
at the outer
part of the scale.
The oxygen,
inward
and
Si. Nonetheless,
sulfur was
at the outer
The inward
diffusion
ofamount
oxygen
diffusion
of oxygen through
thedetected
nanocrystalline
filmpart
led of
tothe
thescale.
dissolution
of rather
a large
through
theinnanocrystalline
film led
to theshown
dissolution
of rather
a large
of oxygen
the film.
of oxygen
the film. The oxide
grains
in Figure
4a were
tensamount
of nanometers
inindiameter.
The
oxide grains
shown
in such
Figure
nanometers
in diameter.
Dissolution
foreign
Dissolution
of foreign
ions
as 4a
Fe were
and Sitens
canoffacilitate
the rapid
establishment
of the of
protective
ions
such
Fe and
Si can facilitate
the rapid
establishment
of the
(Al,Cr)
(Al,Cr)
2O3 as
scale
by increasing
the defect
concentration
through
the protective
doping effect.
The
2 Oprotruded
3 scale by
increasing
the defect
through
the
effect. diffusion
The protruded
oxides
at spots
1 and
oxides at spots
1 and concentration
2 were evidently
formed
bydoping
the outward
of Cr, Al,
Fe, and
Si. Hence,
2it were
evidently
formed byproceeded
the outward
diffusion
ofinward
Cr, Al, transport
Fe, and Si.
is seen
that
the
is seen
that the corrosion
not only
by the
of Hence,
oxygen it
(see
Figure
2) but
corrosion
proceeded
only by
inward
transport
oxygen
(see Figure
2) Figures
but also 3byand
the4).
outward
also by the
outward not
diffusion
ofthe
cations
from
the filmofand
the substrate
(see
At the
diffusion
of of
cations
from the
the substrate
Figures
3 and 4). Atthat
the outer
part oftothe
scale,
outer part
the scale,
Cr film
was and
frequently
richer(see
than
Al, suggesting
Cr tended
diffuse
Cr
was frequently
richer
outwardly
faster than
Al.than Al, suggesting that Cr tended to diffuse outwardly faster than Al.
Figure 4.
4. AlCrSiN
after corrosion
corrosion at
at 800
800 ◦°C
for 50
50 h.
h. (a)
(a) TEM
TEM cross-sectional
cross-sectional image;
image; (b)
(b) EDS
EDS
Figure
AlCrSiN film
film after
C for
concentration profiles
profiles along
along the
the spots
spots 1–10.
1–10.
concentration
The SEM/TEM/EDS results of the AlCrSiN film at the later stage of corrosion are shown in
The SEM/TEM/EDS results of the AlCrSiN film at the later stage of corrosion are shown in
Figure 5. The surface of the scale was covered with angled, round, and rod-shaped oxide grains
Figure 5. The surface of the scale was covered with angled, round, and rod-shaped oxide grains
(Figure 5a). Spots 1–4 shown in Figure 5b show a rod-shaped (Al,Cr)2O3 grain dissolved with Fe, Si,
(Figure 5a). Spots 1–4 shown in Figure 5b show a rod-shaped (Al,Cr)2 O3 grain dissolved with Fe,
and S (Figure 5c). Al, Cr, Fe, and Si clearly diffused outwards to spots 1–4. The ratio of Al/Cr in the
Si, and S (Figure 5c). Al, Cr, Fe, and Si clearly diffused outwards to spots 1–4. The ratio of Al/Cr
oxide scale fluctuated depending on the location, as shown in Figure 5c. For example, spots 1–4 are
in the oxide scale fluctuated depending on the location, as shown in Figure 5c. For example, spots
Al-rich, while spots 5 and 6 are Cr-rich. More frequently, Cr-rich oxide scale formed on the Al-rich
1–4 are Al-rich, while spots 5 and 6 are Cr-rich. More frequently, Cr-rich oxide scale formed on the
oxide scale. Spot 7 indicates that the (Al,Cr)2O3 oxide contained some Si, S, and N. At spot 8, the
Al-rich oxide scale. Spot 7 indicates that the (Al,Cr)2 O3 oxide contained some Si, S, and N. At spot 8,
nitride film began to oxidize. Spots 9–14 corresponded to the (Fe, O, S)-dissolved AlCrSiN film.
the nitride film began to oxidize. Spots 9–14 corresponded to the (Fe, O, S)-dissolved AlCrSiN film.
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Figure 5.
corrosion at
at 800
800 ◦°C
for 200
200 h
h in
in Ar-1%SO
Ar-1%SO22 gas.
Figure
5. AlCrSiN
AlCrSiN film
film after
after corrosion
C for
gas. (a)
(a) SEM
SEM top
top view;
view; (b)
(b) TEM
TEM
cross-sectional
image;
(c)
EDS
concentration
profiles
along
the
spots
1–14.
cross-sectional image; (c) EDS concentration profiles along the spots 1–14.
4. Conclusions
4.
Conclusions
The AlCrSiN
AlCrSiN film
was single-layered,
single-layered, and
nanocrystalline hcp-AlN
The
film was
and consisted
consisted of
of nanocrystalline
hcp-AlN and
and fcc-CrN,
fcc-CrN,
which
had
a
small
amount
of
dissolved
Si.
Its
corrosion
behavior
was
studied
at
800
°C
for
5–200
h
◦
which had a small amount of dissolved Si. Its corrosion behavior was studied at 800 C for 5–200
h in
in
Ar-1%
SO
2 gas. At the early corrosion stage, Al oxidized preferentially at the surface. As the
Ar-1% SO2 gas. At the early corrosion stage, Al oxidized preferentially at the surface. As the corrosion
corrosion proceeded,
the competitive
and
to the formation
(Al,Cr)
2O3 grains
proceeded,
the competitive
oxidationoxidation
of Al andof
CrAl
led
to Cr
theled
formation
of (Al,Cr)of2 O
3 grains with or
with or without
dissolved
ions
Fe,S.Si,
and
S. TheO(Al,Cr)
2O3 scale effectively protected the film. The
without
dissolved
ions of Fe,
Si, of
and
The
(Al,Cr)
2 3 scale effectively protected the film. The corrosion
corrosion
proceeded
not
only
by
the
inward
transport
of
oxygen
sulfur,
but outward
also by the
outward
proceeded not only by the inward transport of oxygen and sulfur, and
but also
by the
diffusion
of
diffusion
of
Al,
Cr,
Si,
and
N
from
the
film
as
well
as
Fe
from
the
substrate.
Compared
to
sulfur,
Al, Cr, Si, and N from the film as well as Fe from the substrate. Compared to sulfur, oxygen diffused
oxygen diffused
dominantly
andfilm.
deeply
the of
film.
of the with
scaleangled,
was covered
dominantly
and deeply
into the
The into
surface
the The
scalesurface
was covered
round,with
and
angled,
round,
and
rod-shaped
oxide
grains.
rod-shaped oxide grains.
Acknowledgments: This work was supported under the framework of the international cooperation program
Acknowledgments:
This work
wasFoundation
supported under
the(2016K2A9A1A01952060).
framework of the international cooperation program
managed by the National
Research
of Korea
managed by the National Research Foundation of Korea (2016K2A9A1A01952060).
Author Contributions:
Contributions: Yue
YueLin,
Lin,Shihong
ShihongZhang
Zhangand
andSik
Sik
Chol
Kwon
synthesized
coatings
by cathodic
arc
Author
Chol
Kwon
synthesized
thethe
coatings
by cathodic
arc ion
ion
plating.
Poonam
Yadav
did
the
corrosion
test
and
analyzed
the
results.
Dong
Bok
Lee
supervised
the
work.
plating. Poonam Yadav did the corrosion test and analyzed the results. Dong Bok Lee supervised the work.
Conflicts
Conflicts of
of Interest:
Interest: The
The authors
authors declare
declare no
no conflict
conflict of
of interest.
interest.
References
1.
2.
3.
4.
behavior
of AlN
films
at high
temperature
underunder
controlled
atmosphere.
J. Eur.
Lin, C.Y.;
C.Y.;Lu,
Lu,F.H.
F.H.Oxidation
Oxidation
behavior
of AlN
films
at high
temperature
controlled
atmosphere.
Ceram.
Soc. 2008,
691–698.
[CrossRef]
J. Eur. Ceram.
Soc.28,
2008,
28, 691–698.
B.D.; Endrino,
Endrino, J.L.;
J.L.;Veldhuis,
Veldhuis, S.C.;
S.C.; Parkinson,
Parkinson,R.;
R.;Shuster,
Shuster,L.S.;
L.S.;Migranov,
Migranov, M.S.
M.S.
Fox-Rabinovich, G.S.; Beake, B.D.;
Effect of mechanical properties measured at room and elevated temperatures on the wear resistance of
cutting tools with TiAlN and AlCrN coatings.
coatings. Surf. Coat. Technol. 2006, 200, 5738–5742. [CrossRef]
Bourhis, E.L.; Goudeau, P.; Staia, M.H.; Carrasquero, E.; Puchi-Cabrera, E.S. Mechanical properties of hard
AlCrN-based coated substrates. Surf. Coat. Technol. 2009, 203, 2961–2968. [CrossRef]
Willmann, H.; Mayrhofer, P.H.; Persson, P.O.A.; Reiter, A.E.; Hultman, L.; Mitterer, C. Thermal stability of
Al–Cr–N hard coatings. Scr. Mater. 2006, 54, 1847–1851.
Coatings 2017, 7, 44
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
6 of 6
Willmann, H.; Mayrhofer, P.H.; Persson, P.O.A.; Reiter, A.E.; Hultman, L.; Mitterer, C. Thermal stability of
Al–Cr–N hard coatings. Scr. Mater. 2006, 54, 1847–1851. [CrossRef]
Ding, X.Z.; Zeng, X.T. Structural, mechanical and tribological properties of CrAlN coatings deposited by
reactive unbalanced magnetron sputtering. Surf. Coat. Technol. 2005, 200, 1372–1376. [CrossRef]
Reiter, A.E.; Derflinger, V.H.; Hanselmann, B.; Bachmann, T.; Sartory, B. Investigation of the properties
of Al1−x Crx N coatings prepared by cathodic arc evaporation. Surf. Coat. Technol. 2005, 200, 2114–2122.
[CrossRef]
Kawate, M.; Hashimoto, A.K.; Suzuki, T. Oxidation resistance of CrAlN and TiAlN films. Surf. Coat. Technol.
2003, 165, 163–167. [CrossRef]
Hirai, M.; Ueno, Y.; Suzuki, T.; Jiang, W.; Grigoriu, C.; Yatsui, K. Characteristics of (Cr1−x , Alx )N films
prepared by pulsed laser deposition. Jpn. J. Appl. Phys. 2001, 40, 1056–1060. [CrossRef]
Banakh, O.; Schmid, P.E.; Sanjinés, R.; Lévy, F. High-temperature oxidation resistance of Cr1−x Alx N thin
films deposited by reactive magnetron sputtering. Surf. Coat. Technol. 2003, 163, 57–61. [CrossRef]
Wu, W.; Chen, W.; Yang, S.; Lin, Y.; Zhang, S.; Cho, T.Y.; Lee, G.H.; Kwon, S.C. Design of AlCrSiN multilayer
and nanocomposite coating for HSS cutting tools. Appl. Surf. Sci. 2015, 351, 803–810. [CrossRef]
Soldán, J.; Neidhardt, J.; Sartory, B.; Kaindl, R.; Čerstvý, R.; Mayrhofer, P.H.; Tessadri, R.; Polcik, P.; Lechthaler, M.;
Mitterer, C. Structure–property relations of arc-evaporated Al–Cr–Si–N coatings. Surf. Coat. Technol. 2008, 202,
3555–3562. [CrossRef]
Tritremmel, C.; Daniel, R.; Lechthaler, M.; Polcik, P.; Mitterer, C. Influence of Al and Si content on structure
and mechanical properties of arc evaporated Al–Cr–Si–N thin films. Thin Solid Films 2013, 534, 403–409.
[CrossRef]
Bobzin, K.; Bagcivan, N.; Immich, P.; Bolz, S.; Cremer, R.; Leyendecker, T. Mechanical properties and oxidation
behaviour of (Al, Cr)N and (Al, Cr, Si)N coatings for cutting tools deposited by HPPMS. Thin Solid Films
2008, 517, 1251–1256. [CrossRef]
Endrino, J.L.; Fox-Rabinovich, G.S.; Reiter, A.; Veldhuis, S.V.; Galindo, R.E.; Albella, J.M.; Marco, J.F.
Oxidation tuning in AlCrN coatings. Surf. Coat. Technol. 2005, 201, 4505–4511. [CrossRef]
Chen, H.W.; Chan, Y.C.; Lee, J.W.; Duh, J.G. Oxidation behavior of Si-doped nanocomposite CrAlSiN coatings.
Surf. Coat. Technol. 2010, 205, 1189–1194. [CrossRef]
Endrino, J.L.; Palacín, S.; Aguirre, M.H.; Gutiérrez, A.; Schäfers, F. Determination of the local environment of
silicon and the microstructure of quaternary CrAl(Si)N films. Acta Mater. 2007, 55, 2129–2135. [CrossRef]
Polcar, T.; Cavaleiro, A. High temperature properties of CrAlN, CrAlSiN and AlCrSiN coatings—Structure
and oxidation. Mater. Chem. Phys. 2011, 129, 195–201. [CrossRef]
Birks, N.; Meier, G.H.; Pettit, F.S. Introduction to the High-Temperature Oxidation of Metals, 2nd ed.;
Cambridge University Press: Cambridge, UK, 2006.
Grabke, H.J. High temperature corrosion in complex, multi-reactant gaseous environments. In High Temperature
Materials Corrosion in Coal Gasification Atmospheres; Norton, J.F., Ed.; Elsevier Applied Science Publishers: London,
UK, 1984; pp. 59–82.
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