coatings

Article
Correlation between Microstructure and Tribological
Properties of Laser Surface Heat-Treated
Stellite Coatings
Chang-Kyoo Park 1 , Jung-Hoon Lee 2 , Nam-Hyun Kang 2 and Eun-Joon Chun 3, *
1 Laser and Electron Beam Application Department, Korea Institute of Machinery and Materials,
Daejeon 34103, Korea; ck0421@kimm.re.kr
2 Department of Materials Science and Engineering, Pusan National University, Busan 46241, Korea;
ljh898989@naver.com (J.-H.L.); nhkang@pusan.ac.kr (N.-H.K.)
3 Department of Nano Materials Science and Engineering, Kyungnam University, Changwon 51767, Korea
* Correspondence: ejchun@kyungnam.ac.kr




Received: 10 April 2020; Accepted: 27 April 2020; Published: 28 April 2020


Abstract: To manufacture superior-performance continuous casting mold components, high-velocity

oxygen fuel spraying of a Stellite-1 coating was followed by its laser heat treatment at 1373–1473 K
using a diode laser. The effects of the laser irradiation conditions on the macro- and microstructural
variations along with the hardness and wear resistance within the Stellite-1 coating were evaluated.
After the heat treatment, micro-voids within the sprayed coating decreased in number slightly with
an increase in the heat treatment temperature. The hardness of the sprayed Stellite-1 coating increased
from that of the as-sprayed coating (680 HV) after the laser heat treatment, with a hardness of 860 HV
obtained at 1473 K. The cause of the increase in hardness could be the formation of nano-sized W- and
Cr-based carbides such as WC, M7 C3 , and M23 C6 , as suggested by transmission electron microscopy
analysis. The tribological properties of as-sprayed and laser heat-treated samples were investigated
by a pin-on-disk tribometer. The laser heat treatment of Stellite-1 coating enhanced wear resistance.
This resulted in a lower coefficient of friction and wear rate for the laser heat-treated sample than
those for the as-sprayed sample.

Keywords: Stellite; thermal spray coating; laser surface heat treatment; microstructure; wear resistance

1. Introduction
High-velocity oxygen fuel (HVOF) spraying is widely employed in the deposition of highly
wear-resistant and corrosion-resistant protective coatings [1]. Stellite alloys are a group of Co-based
superalloys that contain a high level (20–30 wt.%) of Cr, a moderate amount (4–18 wt.%) of W or
Mo, and a specific amount (0.25–3 wt.%) of C; they are strengthened by the precipitation of carbides
embedded in the cobalt solid solution matrix. These carbides provide excellent wear resistance to the
Stellite alloys. In this regard, Stellite alloy powder has been largely employed in the HVOF spraying
process [1] together with arc cladding [2,3], plasma transfer arc hardfacing [4], supersonic laser
deposition [5], laser cladding [6–8], etc.
Throughout the steel production process, the production hardware is exposed to a combination
of high temperatures, corrosive environments, and wear. This demanding and severe environment
produces a broad range of degradation mechanisms and ultimately leads to deterioration in the product
quality, reduced operating efficiencies, and high maintenance costs [9]. From among the available
production hardware, the continuous casting mold is exposed to high-temperature abrasive wear
environments. In other words, the casting mold wherein solidification of the molten steel is initiated
experiences a large amount of high-temperature wear [9–11]. In particular, the continuous casting

Coatings 2020, 10, 433; doi:10.3390/coatings10050433 www.mdpi.com/journal/coatings

Coatings 2020, 10, 433 2 of 14

mold is the core component of the continuous casting system, and the surface quality of the mold
is highly correlated with the surface quality of the slab. It determines the production efficiency of
the continuous casting machine. Therefore, it should be highly durable and undergo minimal mold
surface damage. To this end, Cu molds have been electroplated with a Ni and Ni-B alloy, and in
addition, a HVOF spray coating of a Stellite alloy was examined for further enhancement of the surface
mechanical properties. However, even though several studies have investigated the HVOF spraying of
Stellite alloys [12–16], relevant results concerning high-durability continuous casting molds have not
been reported upon sufficiently.
As a general rule, post-coating heat treatment is usually necessary as HVOF spray coating
results in an inhomogeneous microstructure distribution that creates voids in the coating [1,12,13,17].
Therefore, numerous studies have already examined the influence of the heat treatment itself as well as
the conditions imposed by the treatment, on the mechanical and chemical properties of the HVOF
sprayed coating [17–20]. Gil et al. reported that the hardness and corrosion resistance of a Ni-based
HVOF sprayed coating improved after heat treatment in a furnace, resulting in a densification of the
microstructure as well as reduced porosity compared to that of the as-sprayed coating [17]. Navas et al.
also investigated the effect of the flame melting treatment on the wear properties of a Ni-based sprayed
coating. After the flame melting process, the porosity decreased and the microstructure exhibited a
homogeneous distribution. As a result, the hardness and wear properties of the material improved [18].
Especially in the case of the continuous casting molds investigated in this study (consisting of a Cu
plate with an electroplated Ni alloy layer and a Stellite HVOF coating), the application of classical heat
treatment (i.e., using a furnace) is extremely difficult owing to distortion and desquamation issues
arising from the different thermal expansion coefficients and melting points of the constituent materials.
Thus, a laser heat treatment process is required in the case of HVOF sprayed coating of the continuous
casting mold, as lasers bypass these issues and offer several advantages such as selective and precise
control of the surface properties [21].
In this regard, many researchers have investigated the laser-based surface treatment of several
types of Stellite coating [14,15,21–25]. Ciubotariu et al. undertook the surface remelting of a Stellite-6
coating by a pulsed Nd:YAG laser and optimized the remelting conditions [14]. Houdková et al.
also investigated the surface remelting behavior of a Stellite-6 coating using a diode laser, and they
reported a homogeneously distributed microstructure and an enhanced sliding wear property, despite
decreased hardness [15]. In other words, almost all such studies used the selective melting process
with laser power and scan speed as the main parameters. One of the main possible disadvantages of
this remelting concept of the coating is an inhomogeneous remelted depth (i.e., dilution with substrate)
because of thermal storage during the laser irradiation. On the other hand, when compared to the
results on selective melting, there is a paucity of results on heat treatment within the solid-state
temperature range and on the heat treatment temperature that is maintained constant during the laser
irradiation. This heat treatment temperature does not cause the Stellite coating to melt.
In this study, the HVOF coating of the Stellite alloy was employed to obtain a high-durability
continuous casting mold, and the effects of the temperature-controlled laser heat treatment on the
variations of the surface mechanical properties and the microstructure were investigated.

2. Materials and Methods

2.1. Materials
A single type of commercial Stellite-1 (Deloro, Koblenz, Germany) powder was employed in the
HVOF spraying. It was spherical shape (diameter: 30–45 µm) and the chemical composition is listed in
Table 1. The substrate subjected to the thermal spraying consisted of two layers: a pure Cu sheet on
which a pure Ni layer is deposited by electroplating. A schematic cross-sectional view of the substrate
along with its dimensions is shown in Figure 1a.
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Coatings 2020, 10, x FOR PEER REVIEW 3 of 14

Table 1. Chemical compositions of Stellite-1 powder used (wt.%).

Table 1. Chemical compositions of Stellite-1 powder used (wt.%).
Materials Co Cr C W Ni Si Fe Mo
Materials Co Cr C W Ni Si Fe Mo
Stellite-1 Bal. Stellite-1
31 Bal. 2.531 2.5 1212 3.0 3.02.0 3.02.0 1.0 3.0 1.0

Figure
Figure 1.
1. Schematic
Schematicdescription
descriptionof
ofthe
thespecimen
specimenand
andthe
theoverall
overallview
viewof
of the
the experimental
experimental setup
setup for
for
laser
laserheat
heat treatment.
treatment.

2.2. Experimental
2.2. ExperimentalProcedures
Procedures
The pure
The pureCu Cusheet
sheetwas
waselectroplated
electroplated with
with pure
pure Ni.Ni.
Next,Next, thermal
thermal spraying
spraying of theofsubstrate
the substrate
(i.e.,
(i.e., spraying carried out on the surface of the electroplated pure Ni layer)
spraying carried out on the surface of the electroplated pure Ni layer) was performed using the was performed using
HVOFthe
HVOF method. The thermal spraying conditions are summarized in Table
method. The thermal spraying conditions are summarized in Table 2. The specimens were then 2. The specimens were then
subjected to
subjected to heat
heat treatment
treatment using
using aa diode
diode laser
laser system.
system. The
Thekeykeyconditions
conditionsfor forthe
thelaser
laserheat
heattreatment
treatment
are listed in Table 3, while Fig. 1 also shows the laser heat treatment experiment and
are listed in Table 3, while Fig. 1 also shows the laser heat treatment experiment and the arrangement the arrangement of
the specimen. The laser beam dimensions were 6 mm × 4 mm. Laser beam
of the specimen. The laser beam dimensions were 6 mm × 4 mm. Laser beam irradiation was irradiation was performed
with temperature
performed control applied
with temperature in real
control time.in
applied The incident
real laser
time. The power laser
incident was automatically controlled to
power was automatically
regulate the temperature. To this end, in order to monitor the heat treatment
controlled to regulate the temperature. To this end, in order to monitor the heat treatment temperature at the specimen
surface, a pyrometer
temperature was positioned
at the specimen surface, coaxially
a pyrometerwithwas
thepositioned
laser beam.coaxially
The laser head,
with thetogether
laser beam.withThe
the
laser head, together with the pyrometer system, was controlled by a multi-axis robot. The heata
pyrometer system, was controlled by a multi-axis robot. The heat treatment was performed over
temperature
treatment wasrange of 1373–1473
performed over a K, at a laser scan
temperature rangespeed of 0.5 mm/s.
of 1373–1473 K, at a laser scan speed of 0.5 mm/s.

Table 2.
Table Conditions of
2. Conditions of HVOF
HVOF coating.
coating.

Parameter
Parameter ValueValue
Thermal sprayer JP-5000 ®
Thermal sprayer JP-5000 ®
Powder flow rate (g/m) 70–100
Oxygen flow rate
Powder flow(`/m)
rate (g/m) 1000–1200
70–100
Gasoline flow rate (`/m) 3–5
Thickness Oxygen flow
of sprayed rate(mm)
layer (ℓ/m) 1000–12000.3

Gasoline flow rate (ℓ/m) 3–5

The cross-sectional macrostructure of the treated specimen was observed using optical microscopy
Thickness of sprayed layer (mm) 0.3
(OM, BX51M, Olympus, Tokyo, Japan). X-ray diffraction (XRD, Ultima IV, Rigaku, Tokyo, Japan)
with Cu-Kα radiation was used to qualitatively identify the phase variation after the laser heat
treatment of the coating layer. The diffraction data were collected over a 2θ range of 30–80◦ .
The cross-sectional microstructure and the elemental distribution were observed and analyzed using
scanning electron microscopy (SEM, JXA-8530F, JEOL, Tokyo, Japan) and electron probe X-ray micro
Coatings 2020, 10, 433 4 of 14

analysis (EPMA, JXA-8530F, JEOL). The metallographic samples were prepared by polishing until 1 µm.
The characterization of phases was performed by a transmission electron microscope (TEM, JEM-2100F,
JEOL) with an energy-dispersive X-ray spectroscope (EDS, Inca X-sight, Oxford Instrument, Oxford,
UK). TEM samples were prepared using a multi-beam focused-ion beam (FIB) and a scanning electron
microscope (SEM) system (LYRA 1 XMH, Tescan, Kohoutovice, Czech), using an in-situ lift-out method.
To confirm the effect of the heat treatment conditions on the mechanical properties of the thermal
spray coating, Vickers hardness testing (MMT-X, Matsuzawa, Akita, Japan) was performed with a
testing load of 25 gf and a dwell time of 10 s. The hardness was evaluated on three layers within the
cross-sectional coating (top: below 0.05 mm, middle: below 0.15 mm, bottom: below 0.25 mm from the
coating surface), and the measurement width and interval was 5 mm (within the heat-treated region)
and 0.2 mm, respectively. The influence of the laser heat treatment on the tribological properties of
the coating were also evaluated by a pin-on-disk tribometer (CETR UMT-2, Bruker, Billerica, MA,
USA). The 10 mm × 10 mm × 8 mm sized samples were pressed against a rotating cast iron disk
with a diameter of 142 mm. All the samples were burnished before the tribology testing to achieve
an even surface contact with a counter material. The burnishing process was conducted with SiC
abrasive papers (PC221, # 600 mesh size Deerfos Co., Seoul, Korea) attached to the cast iron disk.
The tribological properties of as-sprayed and laser heat-treated samples were measured by sliding
them against SiC abrasive papers (PC221, # 320 mesh size, Deerfos Co.) attached to the cast iron
disk. The new SiC abrasive paper was utilized at every 30 m of sliding distance. The tribotesting was
conducted using 30 N of normal load, 28.8 mm/s of sliding speed, and 120 m of total wear distance.
At every 30 m of wear distance, the worn volume was measured to calculate the wear rate. The average
roughness of the worn surface was measured by laser microscopy (VK-8710, Keyence, Osaka, Japan)
after the tribotesting.

Table 3. Specification of equipment and conditions for laser surface heat treatment.

Parameter Value
Oscillator 4 kW (capable maximum power) diode laser
Wavelength of laser beam (nm) 970
Beam dimensions (mm) 6 × 4 (square type)
Direction of laser beam irradiation Perpendicular to specimen
Focal length (mm) 310
Defocus distance (mm) 0
Scan speed of laser beam (mm/s) 0.5
Homogenization temperature (K) 1373–1473

3. Selection and Control of Laser Heat Treatment Conditions

3.1. Thermodynamic Calculation of Phase Fraction

Figure 2 shows the relationship between the temperature (ranging from 1300 to 1550 K) and the
phase fraction calculated for the Stellite-1 alloy using the Thermo-Calc software (TCNI8 database).
The primary matrix phase within this temperature range comprised FCC-Co with HCP-Co; carbides
were also confirmed to be present in the secondary phase. The temperature range selected for this
study included temperatures at which the material would exist in the solid state (i.e., 1373, 1423, and
1473 K). The treatment temperature is also indicated in Figure 2.
Coatings 2020, 10, x FOR PEER REVIEW 5 of 14
Coatings 2020, 10, x FOR PEER REVIEW 5 of 14
study included temperatures at which the material would exist in the solid state (i.e., 1373, 1423, and
study
1473 K).included temperatures
The treatment
Coatings 2020, 10, 433
at which
temperature the material
is also would
indicated exist2.in the solid state (i.e., 1373, 1423,5 of
in Figure and14
1473 K). The treatment temperature is also indicated in Figure 2.

Figure 2. Relationship between the phase fraction and temperature for Stellite-1.
Figure 2. Relationship between the phase fraction and temperature for Stellite-1.
Figure 2. Relationship between the phase fraction and temperature for Stellite-1.
3.2. History
3.2. History ofof Surface
Surface Temperature
Temperature andand Laser
Laser Power
Powerduring
duringLaser
LaserIrradiation
Irradiation
3.2. History of Surface Temperature and Laser Power during Laser Irradiation
Figure 33 shows
Figure shows the
the representative
representative surface
surface temperature
temperature and and laser
laser power
power trends
trends during
during thethe laser
laser
heat Figure
treatment3 shows
at the
1473 representative
K. The target surface
heat temperature
treatment and
temperature laser power
was trends
consistently
heat treatment at 1473 K. The target heat treatment temperature was consistently maintained by during the
maintained laser
by
heat treatment
adjusting the at
laser 1473
powerK. The
in target
real time.heat
The treatment
laser power temperature
was was
approximately consistently
0.9 kW
adjusting the laser power in real time. The laser power was approximately 0.9 kW at the beginning of maintained
at the beginningby
adjusting
of the
the heat
heat the laser power
treatment,
treatment, andand
wasin
wasreal
latertime.
later The laser
decreased
decreased totoa power
astable was
stablevalueapproximately
value ofof0.6
0.6kW 0.9 kW at the at
kW(approximately)
(approximately) beginning
at the heat
the heat
of the heat
treatment treatment,
temperature and
of was
1473 later
K. decreased
Similar to
temperaturea stable
and value
laser of 0.6
power kW (approximately)
trends were
treatment temperature of 1473 K. Similar temperature and laser power trends were observed for other observed at the
for heat
other
treatment
heat temperature
heat treatment
treatment of 1473 K. Similar temperature and laser power trends were observed for other
conditions.
conditions.
heat treatment conditions.

Figure 3. Trends for the laser power and temperature against time during laser heat treatment
Figure 3. Trends for the laser power and temperature against time during laser heat treatment (set
(set temperature: 1473 K).
temperature:
Figure 1473for
3. Trends K).the laser power and temperature against time during laser heat treatment (set
temperature:
4. Macro- 1473 K).
and Microstructure of the As-Sprayed Coating
4. Macro- and Microstructure of the As-Sprayed Coating
Figure
4. Macro- 4 shows
and the representative
Microstructure cross-sectional
of the As-Sprayed Coating OM and SEM (backscattered electron (BSE)
mode)Figure
images4 shows the representative
for the as-sprayed Stellite-1cross-sectional OM and
coating. As shown SEM 4a,
in Figure (backscattered electron
the HVOF sprayed (BSE)
coating
mode)Figure 4
images shows
for thethe representative
as-sprayed cross-sectional
Stellite-1 coating. AsOM and
shown SEM
in (backscattered
Figure 4(a), the
covered the electroplated Ni layer, and large numbers of voids were present within the coating. electron
HVOF (BSE)
sprayed
mode)
coating
The SEM images
coveredforthe
micrograph the(image
as-sprayed
electroplated Stellite-1
A”)coating.
Ni layer,
of “Enlarged and Asnumbers
large
demonstratesshown inofFigure
that the voids 4(a),
were the
microstructure ofHVOF
present sprayed
within the
the as-sprayed
coating consisted
coating covered the electroplated
of individual Ni layer,
splats. In the and large
splats, numbers structure
the dendritic of voids were
couldpresent within and
be recognized the
the voids were mainly positioned in the intersplat boundaries.
Coatings 2020, 10, x FOR PEER REVIEW 6 of 14

coating. The SEM micrograph (image of “Enlarged A”) demonstrates that the microstructure of the
as-sprayed
Coatings coating
2020, 10, consisted of individual splats. In the splats, the dendritic structure could
433 6 ofbe
14
recognized and the voids were mainly positioned in the intersplat boundaries.

Coatings 2020, 10, x FOR PEER REVIEW 6 of 14

coating. The SEM micrograph (image of “Enlarged A”) demonstrates that the microstructure of the
as-sprayed coating consisted of individual splats. In the splats, the dendritic structure could be
recognized and the voids were mainly positioned in the intersplat boundaries.

Figure 4. Cross-sectional OM and SEM (backscattered electron mode) micrographs of the as-sprayed
Stellite-1 coating.

Figure 5a shows the BSE images and the distribution maps of the alloying elements for the as-sprayed
coating analyzed by EPMA and Figure 5b also shows the enlarged view and corresponding distribution
at the region “A” marked in Figure 5a. A slight macrosegregation of certain elements such as Si, Mo,
and Figure
W was4.observed in the corresponding distribution maps in Figure 5a. Furthermore, as displayed in
Cross-sectional OM and SEM (backscattered electron mode) micrographs of the as-sprayed
Figure 5b, nocoating.
Stellite-1 carbides (i.e., W- or Cr-based carbides) were present.

Figure 5. (a) Element distribution and BSE images of the as-sprayed Stellite-1 coating obtained by
EPMA, and (b) enlarged view and corresponding element distributions in region “A” in (a).

Figure 5a shows the BSE images and the distribution maps of the alloying elements for the as-
sprayed coating analyzed by EPMA and Figure 5b also shows the enlarged view and corresponding
distribution at the region “A” marked in Figure 5a. A slight macrosegregation of certain elements
Figure
Figure5.5. (a)
(a)Element
Elementdistribution
distributionand
andBSE
BSEimages
imagesofofthe
theas-sprayed
as-sprayedStellite-1
Stellite-1coating
coatingobtained
obtainedby
by
EPMA,
EPMA,andand(b) (b)enlarged
enlargedview
viewand
andcorresponding
corresponding element
element distributions
distributions in
in region
region “A”
“A” in
in (a).
(a).

Figure 5a shows the BSE images and the distribution maps of the alloying elements for the as-
sprayed coating analyzed by EPMA and Figure 5b also shows the enlarged view and corresponding
distribution at the region “A” marked in Figure 5a. A slight macrosegregation of certain elements
Coatings 2020, 10, x FOR PEER REVIEW 7 of 14

Coatings 2020, 10, x FOR PEER REVIEW 7 of 14

such as Si, Mo, and W was observed in the corresponding distribution maps in Figure 5(a).
Furthermore,
such as displayed
as Si, Mo, and W wasin Figure 5b, no
observed incarbides (i.e., W- or Cr-based
the corresponding carbides)
distribution mapswere present.5(a).
in Figure
Coatings 2020, 10, 433 7 of 14
Furthermore, as displayed in Figure 5b, no carbides (i.e., W- or Cr-based carbides) were present.
5. Variation of Macrostructure and Hardness by Laser Heat Treatment
5. Variation
5. Variation of of Macrostructure
Macrostructure and
and Hardness
Hardness by by Laser
Laser Heat
Heat Treatment
Treatment
5.1. Cross-Sectional Macrostructure
5.1. Cross-Sectional
5.1. Cross-SectionalMacrostructure
Macrostructure
Figure 6 shows the variations in the cross-sectional optical macrostructure as a function of the
Figure
heat Figure 66 shows
treatment shows the variations
variations
temperature
the inStellite-1
for thein the cross-sectional
the cross-sectional optical
coating. Itoptical macrostructure
was confirmed that the
macrostructure as number
as aa function
function of
of of the
voids
the
heat
withintreatment
the temperature
as-sprayed for
coating the Stellite-1
decreased coating.
slightly in It was
number confirmed
with an that the
increase number
in
heat treatment temperature for the Stellite-1 coating. It was confirmed that the number of voidsthe of voids
temperature within
from
the as-sprayed
withinmacrostructuralcoating
the as-sprayed decreased
viewpoint.
coating Atslightly
the heat
decreased intreatment
slightlynumber with
in number an increase
temperature
with in the
of 1473
an increase K,temperature
in Stellite-1from
thetemperature
the coating
fromthe
macrostructural
wasmacrostructural
the viewpoint.
almost homogenized. At the
viewpoint. heatheat
At the treatment temperature
treatment temperatureof 1473 K, the
of 1473 K, Stellite-1 coating
the Stellite-1 was
coating
almost homogenized.
was almost homogenized.

Figure 6. Cross-sectional macrostructures as functions of the heat treatment temperatures.

Figure
Figure6.6.Cross-sectional
Cross-sectionalmacrostructures
macrostructuresas
asfunctions
functionsof
ofthe
the heat
heat treatment
treatment temperatures.
temperatures.
5.2. Hardness Variation
5.2. Hardness
5.2. Hardness 7Variation
Figure Variation
shows the hardness variation upon being subjected to laser heat treatment
temperatures.
Figure The
Figure 77shows
showsposition
thethe and interval
hardness ofupon
variation
hardness hardness
variation uponmeasurement
being subjected was heat
to laser
being subjected also schematically
to treatment depicted
temperatures.
laser heat treatment
in
The Figure 7.
position and interval of hardness measurement was also schematically depicted in Figure
temperatures. The position and interval of hardness measurement was also schematically depicted 7.
in Figure 7.

Figure 7.7.Relationship between

Relationship laser
between heatheat
laser treatment temperatures
treatment and the
temperatures andaverage hardness
the average of Stellite-
hardness of
Stellite-1
1 coating. coating.
Figure 7. Relationship between laser heat treatment temperatures and the average hardness of Stellite-
1 coating.
The
The average
average hardness
hardnessvalue
valuefrom
fromthe
themapping
mappingwas wasused
usedininFigure
Figure7.7.The
Thehardness
hardnessofofthe
theStellite-1
Stellite-
coating increased
1 coating from
increased the level
from the observed
level with
observed the as-sprayed
with the coating (680 HV) to that observed with the
The average hardness value from the mapping wasas-sprayed coating
used in Figure (680
7. The HV) to of
hardness that
theobserved
Stellite-
heat-treated coating at 1473 K (860 HV). In other words, approximately 130% of the hardness increment
1 coating increased from the level observed with the as-sprayed coating (680 HV) to that observed
could be attributed to the laser heat treatment of the Stellite-1 coating. Figure 8 shows the typical XRD
Coatings 2020, 10, x FOR PEER REVIEW 8 of 14

with the heat-treated coating at 1473 K (860 HV). In other words, approximately 130% of the hardness
Coatings 2020, 10, 433 8 of 14
increment could be attributed to the laser heat treatment of the Stellite-1 coating. Figure 8 shows the
typical XRD patterns obtained for the as-sprayed coating and the laser heat-treated coatings. The
patterns
formation obtained
of the Mfor 7C3the as-sprayed
, M23C6, and WC coating
phasesand
wasthe laser heat-treated
attributed to the lasercoatings. The formation
heat treatment of the
by comparing
M
theC
7 XRD
3 , M C , and
23patterns
6 WC phases was attributed to the laser heat treatment by comparing the
obtained for the laser heat treated coatings and those for the plain as-sprayedXRD patterns
obtained
coatings. for
Wethe laser heat
speculate thattreated
130% ofcoatings and those
the hardness for theisplain
increment as-sprayed
highly related tocoatings. We speculate
the formation of these
that 130% of
secondary the hardness
phases. increment
The formation is highly
of the M7C3, related to the
M23C6, and WC formation
phases wasof these secondary
confirmed phases.
for the laser
The formation of the M
heat-treated Stellite-1 coating,C
7 3 , M C , and WC phases was confirmed for the laser heat-treated
and6 these secondary phases induced the increase in hardness after the
23 Stellite-1
coating,
laser heatand these secondary phases induced the increase in hardness after the laser heat treatment.
treatment.

Figure 8. XRD patterns obtained for the as-sprayed Stellite-1 coating and laser heat-treated coating.
Figure 8. XRD patterns obtained for the as-sprayed Stellite-1 coating and laser heat-treated coating.
6. Relationship between Hardness and Microstructural Features
6. Relationship between Hardness and Microstructural Features
Figure 9a shows the backscattered electron (BSE) image and distribution maps of the alloying
Figure
elements 9(a) shows
analyzed the backscattered
by EPMA electron
near the surface of (BSE)
the laserimage and distribution
heat-treated maps
Stellite-1 of theatalloying
coating 1373 K.
elements analyzed by EPMA near the surface of the laser heat-treated
Figure 9b shows the enlarged views and corresponding distribution for the region “A” marked Stellite-1 coating at 1373 K.in
Figure 9a.
Figure 9b shows the9a,
In Figure enlarged
it can beviews andobserved
clearly corresponding
that thedistribution for the region
intersplat boundaries “A” marked
weakened and thein
Figureof
extent 9a.the
Invoid
Figure 9a, it can be clearly
decreased—that observed that the
is, the inhomogeneity intersplat
of the boundaries
as-sprayed weakened
coating was enhancedandnear
the
extent of the void decreased—that is, the inhomogeneity of the as-sprayed coating
the surface because of the laser heat treatment as compared to that of the as-sprayed coating without the was enhanced
near the surface
treatment (Figuresbecause
4 and 5).of This
the laser heat treatment
enhancement occurred as despite
compared the to that ofofthe
presence theas-sprayed coating
macrosegregation
without
of certainthe treatment
alloying (Figures
elements (such4asand 5). This
Co and enhancement
W). Based on the BSE occurred
image, despite
the depth the
of presence of the
the heat-treated
macrosegregation of certain alloying elements (such as Co and W). Based on the
region was approximately 130 µm at 1373 K of heat treatment temperature. In addition, in the enlarged BSE image, the depth
of theinheat-treated
view Figure 9b, the region was of
formation approximately
secondary phases 130 μmsuchatas1373
W- andK of heat treatment
Cr-based carbides temperature.
can be observed In
addition, in the enlarged view in Figure 9b, the formation of secondary phases
that are not seen in the as-sprayed coating without laser heat treatment (Figure 5b). Figure 10 also such as W- and Cr-
based carbides
shows can beand
the BSE images observed that are
distribution maps notforseen in the as-sprayed
the alloying coating without
elements analyzed by EPMA laser
nearheat
the
treatment (Figure 5b). Figure 10 also shows the BSE images and distribution maps
surface of the laser heat-treated Stellite-1 coating at 1473 K (heat treatment condition giving the highest for the alloying
elements analyzed
hardness). The splatby EPMA near
structures, the the surface of
segregation of the laserelements,
certain heat-treated
and Stellite-1
the voids coating at 1473 K
were diminished.
(heat treatment condition giving the highest hardness). The splat structures,
Furthermore, the microstructure of the sprayed coating fully consisted of fine secondary phases the segregation of certain
based
elements, and the voids were diminished. Furthermore,
on the Co matrix. These secondary phases were also W- and Cr-based carbides. the microstructure of the sprayed coating
fullyFigure
consisted of fine secondary
11 displays representativephases based
bright fieldon
(BF)theimage
Co matrix. Thesedispersive
and energy secondary phases
X-Ray were also
spectroscopy
W- and Cr-based carbides.
(EDS) results analyzed by TEM for the laser heat-treated Stellite-1 coating at 1473 K. Similar to the
results obtained by EPMA (Figure 10), the carbides consisted of W and Cr and their size distributions
ranged from 30 to 300 nm. Figure 12 also shows the BF image and elected area diffraction pattern
(SADP) of the carbides. The matrix phase was FCC-structured Co (SADP-A in Figure 12a) and
the carbides could be characterized by M7 C3 (SADP-B in Figure 12a), WC (SADP-C in Figure 12b),
and M23 C6 (SADP-D in Figure 12b). These characterization results coincide well with those obtained
by the XRD pattern mentioned in Figure 8. It has been reported that a high hardness is mainly due to
Coatings 2020, 10, 433 9 of 14

the formation of Cr- and W-rich carbides and the solid solution hardening of W in the FCC-Co phase
for Stellite-1 alloys [26]. Thus, the main reason for the increase in the hardness after the laser heat
treatment as shown in Figure 7, could be the formation of these nano-sized WC, M7 C3 , and M23 C6 .
Coatings
Coatings2020,
2020,10,
10,x xFOR
FORPEER
PEERREVIEW
REVIEW 9 9ofof1414

Figure
Figure9.9.(a)
Figure (a)Element
Elementdistribution and(b)
distributionand (b)BSE
BSEimages
imagesofofStellite-1 coatingafter
Stellite-1coating afterlaser
laserheat
heattreatment
treatmentatat
1373
1373 K.
K.
1373 K.

Figure
Figure10.
Figure 10.Element
10. Elementdistribution
Element distributionand
distribution andBSE
and BSEimages
BSE imagesofof
images ofthe
theStellite-1
the Stellite-1coating
Stellite-1 coatingafter
coating afterlaser
after laserheat
laser heattreatment
heat treatmentatat
treatment at
1473
1473K.
K.
1473 K.

Figure
Figure 11 11 displays
displays representative
representative bright
bright field
field (BF)
(BF) image
image and
and energy
energy dispersive
dispersive X-Ray
X-Ray
spectroscopy
spectroscopy(EDS)
(EDS)results
resultsanalyzed
analyzedby byTEM
TEMforforthe
thelaser
laserheat-treated
heat-treatedStellite-1
Stellite-1coating
coatingatat1473
1473K.K.
Similar
Similartotothe
theresults
resultsobtained
obtainedby
byEPMA
EPMA(Figure
(Figure10),
10),the
thecarbides
carbidesconsisted
consistedofofW Wand
andCrCrand
andtheir
their
size
sizedistributions
distributionsranged
rangedfrom
from3030toto300
300nm.
nm.Figure
Figure12 12also
alsoshows
showsthe
theBF
BFimage
imageandandelected
electedarea
area
diffraction
diffractionpattern
pattern(SADP)
(SADP)ofofthe
thecarbides.
carbides.The
Thematrix
matrixphase
phasewas wasFCC-structured
FCC-structuredCo Co(SADP-A
(SADP-Ainin
Figure
Figure12a)
12a)and
andthethecarbides
carbidescould
couldbe becharacterized
characterizedbybyMM7C 3 3(SADP-B
7C (SADP-BininFigure
Figure12a),
12a),WC
WC(SADP-C
(SADP-C
those
those obtained
obtained by by the
the XRD
XRD pattern
pattern mentioned
mentioned in in Figure
Figure 8.
8. ItIt has
has been
been reported
reported that
that aa high
high hardness
hardness
is
is mainly due to the formation of Cr- and W-rich carbides and the solid solution hardening of
mainly due to the formation of Cr- and W-rich carbides and the solid solution hardening of W
W inin
the
the FCC-Co
FCC-Co phase phase for
for Stellite-1
Stellite-1 alloys
alloys [26].
[26]. Thus,
Thus, the
the main
main reason
reason for for the
the increase
increase in
in the
the hardness
hardness after
after
the
the laser
laser heat
heat treatment
treatment as as shown
shown in in Figure
Figure 7,7, could
could be
be the
the formation
formation of of these
these nano-sized
nano-sized WC,WC, M M77CC33,,
and
and M M2323C
Coatings C66..
2020, 10, 433 10 of 14

Figure
Figure
Figure 11.
11.
11. (a,b)
(a),
(a), (b)
(b) BF
BF images
images and
and EDS
EDS results
results of laser heat
of laser heat treated
treatedStellite-1
Stellite-1coating
coatingat
at1473
1473K.
K.

Figure 12. Cont.

Coatings 2020, 10, x FOR PEER REVIEW 11 of 14
Coatings 2020, 10, x FOR PEER REVIEW 11 of 14
Coatings 2020, 10, 433 Figure 12. Cont. 11 of 14
Figure 12. Cont.

Figure 12. BF image and corresponding SADP for laser heat treated Stellite-1 coating at 1473 K: (a) Co
Figure
Figure
and M12.12. BF
7C3,BF
image
(b)image and
and
WC and M corresponding
corresponding
23C6.
SADPfor
SADP forlaser
laserheat
heattreated
treatedStellite-1
Stellite-1coating
coatingat
at1473
1473K:
K:(a)
(a)Co
Co
and M
and M77CC3,3 ,(b)
(b)WCWCand
andMM2323
CC 6. 6 .

7. Effect of Nano-Sized Carbides Formation and Surface Hardening on Tribological Properties

7. Effect of Nano-Sized Carbides Formation and Surface Hardening on Tribological Properties
7. Effect of Nano-Sized Carbides Formation and Surface Hardening on Tribological Properties
Figure 13 shows the coefficient of friction (COF) as a function of wear distance for the as-sprayed
Figure 13 shows the coefficient of friction (COF) as a function of wear distance for the as-sprayed
Figure
coating and13laser
shows the coefficient
heat-treated of friction
coating (COF)
at 1473 as a function
K. The COF of of thewear
laserdistance for thecoating
heat-treated as-sprayed
was
coating and laser heat-treated coating at 1473 K. The COF of the laser heat-treated coating was relatively
coating and
relatively laserthan
lower heat-treated
that of thecoating at 1473
as-sprayed K. The
coating. TheCOF of the
average COFlaser
washeat-treated
found to be coating
0.419 forwas
the
lower than that of the as-sprayed coating. The average COF was found to be 0.419 for the as-sprayed
relatively lower than that of the as-sprayed coating. The average COF was found to be
as-sprayed coating and 0.296 for the laser heat-treated coating. The small COF of the laser heat-treated0.419 for the
coating and 0.296 for the laser heat-treated coating. The small COF of the laser heat-treated coating was
as-sprayed
coating was coating and 0.296
attributed to thefor the laser
increase heat-treated
in hardness coating.
because Theformation
of the small COFofofnano-sized
the laser heat-treated
Cr- and W-
attributed to the increase in hardness because of the formation of nano-sized Cr- and W-rich carbides
coating was attributed
rich carbides after the to theheat
laser increase in hardness
treatment becausein
as mentioned ofFigures
the formation
10 and of
11.nano-sized Cr- and W-
after the laser heat treatment as mentioned in Figures 10 and 11.
rich carbides after the laser heat treatment as mentioned in Figures 10 and 11.

Figure
Figure 13. COF as
13. COF as aa function
function of
of wear
wear distance
distance for
for the
the as-sprayed
as-sprayed coating
coating and
and laser
laser heat-treated
heat-treated coating
coating
at
at 1473
Figure K.
147313.
K.COF as a function of wear distance for the as-sprayed coating and laser heat-treated coating
at 1473 K.
In addition, the variation in the COF of the laser heat-treated coating was relatively smaller in
In addition, the variation in the COF of the laser heat-treated coating was relatively smaller in
comparison to that
thein the as-sprayed coating. The difference between the maximum COFsmaller
(COF in )
In addition,
comparison to that variation
in in the COF
the as-sprayed of the
coating. Thelaser heat-treated
difference betweencoating
the was relatively
maximum COF (COFmax max)
value
comparisonand theto minimum
that in COF
the (COF
as-sprayed ) value was found to be 0.044 for the
min coating. The difference between the maximum COF (COF as-sprayed coating (COFmaxmax):
value and the minimum COF (COFmin) value was found to be 0.044 for the as-sprayed coating
0.436 and
value and COF
the min : 0.392). On
minimum the(COF
otherminhand, the wasdifference between COFmax for and COFmin was 0.034 for
(COFmax : 0.436 and COFminCOF : 0.392). On the ) value
other hand, found to be 0.044
the difference between the
COFas-sprayed
max and COF coating
min was
the
(COF laser heat-treated
: 0.436 coating
and heat-treated
COFmin: 0.392).(COF max : 0.314
On the(COF other and COF min : 0.28). Small variations in COF for the laser
0.034max for the laser coating maxhand,
: 0.314theanddifference between
COFmin: 0.28). COF
Small max and COF
variations in COFmin was
for
heat-treated
0.034 for the coating
laser were attributed
heat-treated to microstructural
coating (COF : 0.314 homogeneity;
and COF : that is,
0.28). the laser
Small heat treatment
variations in COF on
for
the laser heat-treated coating were attributed to microstructural homogeneity; that is, the laser heat
max min
the laser
the Stellite-1 coating reduced
heat-treated coating the number
were attributed of macrosegregations and voids, resulting in the
uniform wear
treatment on the Stellite-1 coating reduced thetonumber
microstructural homogeneity;
of macrosegregations thatvoids,
and is, laser heat
resulting in
behavior.
treatment Figure
on the 14 demonstrates
Stellite-1 coating the wear
reduced rate
the of
number as-sprayed
of and laser
macrosegregations heat-treated
and coatings
voids, resultingat every
in
uniform wear behavior. Figure 14 demonstrates the wear rate of as-sprayed and laser heat-treated
30 m of wear
uniform distance. The wear rate at 120 m of wear distance wasas-sprayed
found to be 17.93 × 103 mm3 /Nm
coatingswear at everybehavior.
30 m of Figure
wear14 demonstrates
distance. The wear the rate
wear atrate120 ofm of wear distanceand laser
washeat-treated
found to be
for the as-sprayed
coatings at3 every 30coating
mfor and 15.09
of the
wear distance.
3
× 10 The mmwear 3 /Nmratefor at
the120 laser3 heat-treated coating.wasThe wear torate
17.93 × 10 mm3/Nm as-sprayed coating and 15.09 × 10m of wear
mm 3/Nmdistance
for the laser found
heat-treated be
of the
17.93 × laser
10 heat-treated sample was 15.8% smaller than that of
3 mm3/Nm for the as-sprayed coating and 15.09 × 103 mm3/Nm for the laser heat-treatedthe as-sprayed sample. This result
coating. The wear rate of the laser heat-treated sample was 15.8% smaller than that of the as-sprayed
suggested
coating. that theratewear of resistance of the Stellite-1 coating was enhanced by the lasertheheat treatment.
sample.The Thiswear the laser
result suggested thatheat-treated sample
the wear resistance was
of the 15.8% smaller
Stellite-1 than
coating that
wasofenhanced as-sprayedby the
The
sample.SEM images
This in Figure
result suggested 15 show the surface morphology of the as-sprayed and laser heat-treated
laser heat treatment. The SEMthat the wear
images resistance
in Figure 15 showof the theStellite-1 coating was of
surface morphology enhanced by the
the as-sprayed
coatings
laser heatafter the tribotesting.
treatment. The SEM images A relatively
in Figure smoother15 show surface morphology
the surface was detected
morphology in the laser
of the as-sprayed
Coatings 2020, 10, x FOR PEER REVIEW 12 of 14
Coatings 2020, 10, x FOR PEER REVIEW 12 of 14
Coatings 2020, 10, 433 12 of 14
and laser heat-treated coatings after the tribotesting. A relatively smoother surface morphology was
and laser heat-treated coatings after the tribotesting. A relatively smoother surface morphology was
detected in the laser heat-treated sample than in the as-sprayed sample. In the case of the as-sprayed
detected in the laser heat-treated sample than in the as-sprayed sample. In the case of the as-sprayed
sample, deepsample
heat-treated and thick
than abrasion grooves, sample.
in the as-sprayed wear debris,
In theand
casespalling were detected
of the as-sprayed sample,at the
deepworn
and
sample, deep and thick abrasion grooves, wear debris, and spalling were detected at the worn
surface.
thick The presented
abrasion grooves, voids at the Stellite-1
wear debris, coating
and spalling weremay cause at
detected thethe
surface damage The
worn surface. in the form of
presented
surface. The presented voids at the Stellite-1 coating may cause the surface damage in the form of
spalling.
voids at theOnStellite-1
the other hand,
coating may thin and
cause theshallow abrasioningrooves
surface damage the formwith small-sized
of spalling. On thedebris were
other hand,
spalling. On the other hand, thin and shallow abrasion grooves with small-sized debris were
observed
thin for the laser
and shallow heat-treated
abrasion groovessample. The measured
with small-sized average
debris roughnessfor
were observed (Rthe
a) oflaser
the worn surface
heat-treated
observed for the laser heat-treated sample. The measured average roughness (Ra) of the worn surface
after theThe
sample. tribotesting
measured was 3.79 μm
average for the as-sprayed
roughness sample
(Ra ) of the worn and 2.83
surface afterμm
thefor the laser was
tribotesting heat-treated
3.79 µm
after the tribotesting was 3.79 μm for the as-sprayed sample and 2.83 μm for the laser heat-treated
sample.
for The lasersample
the as-sprayed heat treatment
and 2.83 µmon for
thethe
Stellite-1 coating increased
laser heat-treated the laser
sample. The surfaceheathardness
treatmentand
on
sample. The laser heat treatment on the Stellite-1 coating increased the surface hardness and
microstructural
the homogeneity,
Stellite-1 coating increased resulting
the surfaceinhardness
an enhancement of wear resistance.
and microstructural homogeneity, resulting in an
microstructural homogeneity, resulting in an enhancement of wear resistance.
enhancement of wear resistance.

Figure 14.
Figure 14. Measured
Measured wear
wear rate
rate of
of the
the as-sprayed
as-sprayed coating
coating and
and laser
laser heat-treated
heat-treated coating
coating at 1473 K
at 1473 K at
at
Figure 14. Measured wear rate of the as-sprayed coating and laser heat-treated coating at 1473 K at
every 30
every 30 m
m of
of wear
wear distance.
distance.
every 30 m of wear distance.

Figure 15.
15. SEM image
image of
of the
theworn
wornsurface
surfaceofofan
anas-sprayed
as-sprayedsample
sampleand
and the
the laser
laser heat-treated
heat-treated sample
sample at
Figure 15. SEM image of the worn surface of an as-sprayed sample and the laser heat-treated sample
at 1473
1473 K after
K after thethe tribotesting.
tribotesting.
at 1473 K after the tribotesting.
8. Conclusions
8. Conclusions
8. Conclusions
To
To develop high-durabilitycontinuous
develop high-durability continuouscasting
castingmold
moldcomponents,
components, a Stellite-1
a Stellite-1 coating
coating sprayed
sprayed by
by ToHVOF
develop high-durability continuous casting mold components, alaser
Stellite-1 coating sprayed by
the HVOF technique was subjected to the temperature-controlled laser heat treatment usingusing
the technique was subjected to the temperature-controlled heat treatment a high- a
the HVOF
high-power technique was subjected to the temperature-controlled laser heat treatment using a high-
power diodediodelaser. laser. The effects
The effects of theof thetreatment
heat heat treatment on macro-
on macro- and microstructural
and microstructural variations
variations in the
power
in the diode laser.
coating along The effects
with the of the heatdistribution
hardness treatment on macro-
within and
the microstructural
coating were variationsIn
investigated. in the
the
coating along with the hardness distribution within the coating were investigated. In the as-sprayed
coating along
as-sprayed with the
Stellite-1 hardness
coating, distribution
large numbers within
of the coating
micro-voids and were investigated.ofIncertain
macrosegregation the as-sprayed
alloying
Stellite-1 coating, large numbers of micro-voids and macrosegregation of certain alloying elements
Stellite-1 coating, large numbers of micro-voids and macrosegregation of certain alloying elements
Coatings 2020, 10, 433 13 of 14

elements existed. Furthermore, homogeneously distributed carbides could not be detected. After the
laser heat treatment, voids within the sprayed coating decreased slightly with an increase in the
macrostructural temperature. At the heat treatment temperature of 1473 K, the Stellite-1 coating was
almost homogenized. The hardness of the sprayed Stellite-1 coating increased after the laser heat
treatment from that of the as-sprayed coating (680 HV) to 860 HV at 1473 K. The hardness increment
could be attributed to the formation of nano-sized W- and Cr-based carbides such as WC, M7 C3 ,
and M23 C6 , as suggested by TEM analysis. The effect of the laser heat treatment on the tribological
properties of Stellite-1 coating was analyzed by a pin-on-disk tribotest. The laser heat-treated sample
at 1473 K showed a smaller COF and wear rate than those of the as-sprayed sample. This result was
attributed to the formation of nano-sized carbides on the Stellite-1 coating because of the laser heat
treatment that caused surface hardening, resulting in an increment of wear resistance.

Author Contributions: Investigation, C.-K.P. and J.-H.L.; Writing—original draft, C.-K.P. and E.-J.C.;
Writing—review & editing, N.-H.K. and E.-J.C.; Supervision, E.-J.C. All authors have read and agreed to
the published version of the manuscript.
Funding: This work was supported by National Research Foundation, Korea (Project No. 2019R1G1A1099607)
and the National Research Council of Science and Technology, Korea (Project No. NK227C, 2020).
Conflicts of Interest: The authors declare no conflict of interest.

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