Eect of Spray Condition and Heat Treatment on the Structure

and Adhesive Wear Properties of WC Cermet Coatings

Yasunari Ishikawa, Jin Kawakita and Seiji Kuroda
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0045, Japan
An improved HVOF spray process called Gas-shrouded HVOF (GS-HVOF) has been developed over the past several years. By using an
extension nozzle at the exit of a commercial HVOF spray gun, GS-HVOF is capable of controlling the oxidation of sprayed materials during
ight as well as achieving higher velocity of sprayed particles. These features result in extremely dense and clean microstructure of the sprayed
coatings. The process has been successfully applied to corrosion resistant alloys such as SUS316L, HastelloyC, and alloy 625 as well as cermets
such as WC-Cr
3
C
2
-Ni. Wear properties of WC cermet coatings were measured by using a pin-on-disk wear tester. The specic wear rates of the
coatings prepared by the GS-HVOF with a reducing (fuel rich) ame were close to that of chrome plating. The wear amount of the heat-treated
GS-HVOF coatings could not be detected after testing. It is believed that transition to mild wear appeared early because of the increased surface
oxidation due to the heat treatment.
(Received March 25, 2005; Accepted May 9, 2005; Published July 15, 2005)
Keywords: high velocity oxygen fuel, gas-shroud, tungsten carbide cermet, wear property, heat treatment
1. Introduction
Hard chrome plating is widely used to deposit a lm for
wear resistance. The eect of hexavalent chromium to the
environment and the operators health is a big problem.
Therefore, research for alternatives of chrome plating is
widely carried out in the world.
1,2)
HVOF-sprayed cermet
coating is one of such alternative candidates. HVOF process
owes both its heat source and acceleration force to a
supersonic jet ame made from a high-pressured mixture of
oxygen and fuel. This technique enables us to obtain sprayed
particles with a speed over 500 m/s and with a temperature
up to around 2000

C. Such particles impinge onto a target

substrate often in the semi-molten state and pile up to form
coatings.
However, for some cermet powders, it is dicult to make a
dense coating. When one intends to decrease the coating
porosity by usual HVOF equipment, such spray conditions
tend to increase the degree of oxidation of the sprayed
coating. The increase of oxidation can be reasons of lowering
abrasive wear resistance of the sprayed coating. Therefore,
we have developed a gas-shroud attached HVOF (GS-
HVOF), which can introduce an inert gas at the exit of the
barrel into the shroud attachment (Fig. 1). With this
modication, it is possible to suppress the oxidation of
sprayed particles while raising the velocity of sprayed
particles.
3,4)
In our previous work,
5)
by using the gas-shroud attach-
ment, corrosion resistance of sprayed coatings increased with
increase of density. Wear resistance of the coatings against
abrasion increased with increase of the hardness of the
coating. These classes of coatings are widely used as wear
resistant coating for the steel making rolls and the paper-
making rolls in Japan. The coatings used in such applications
are rubbed repeatedly against steel or paper. In this case, the
wear mode is dominated by the adhesive wear.
When metals slide against each other, it is generally
accepted that severe-mild wear transition occurs. In other
words, adhesive wear changes from the high wear rate
condition (severe wear) to the low wear rate condition (mild
wear).
6)
In the early stage of adhesive wear, an oxide layer on the
surface is destroyed and the exposed fresh surfaces adhere
with each other and are worn apart repeatedly. The surface is
worn severely and the large metallic wear debris is generated
(0.10.2 mm). The specic wear rate lies in the range from
10
5
to 10
6
mm
2
/N. This is called the severe wear. Once
the worn surface is covered with the oxidized wear debris,
specic wear rate decreases by a factor of 1/100 and small
dark wear debris is generated. The specic wear rate becomes
below 10
8
mm
2
/N. This is called the mild wear. The wear
rate transition like this phenomenon is called the severe-mild
wear transition.
7)
A number of papers have been published about the wear
properties of thermal spray coatings, mostly about the
abrasive wear and erosion wear.
8,9)
In some researches of
adhesive wear, the wear property of thermal spray coatings is
only evaluated for the relationship between the specic wear
rate (volume wear loss) and the mechanical properties such as
hardness, which depend on the porosity and the micro-
structure of the coatings.
1012)
In this study, we investigate the adhesive wear property of
HVOF sprayed cermet coatings by using a pin-on-disk wear
tester. The eect of spray condition and heat treatment on the
structure and wear properties such as the specic wear rate
and the severe-mild wear transition are discussed in detail.
2. Method
Coatings were prepared with a commercial HVOF
(JP5000, Praxair TAFA) and the GS-HVOF thermal spray Fig. 1 Schematic representation of HVOF with the gas shroud attachment.
Materials Transactions, Vol. 46, No. 7 (2005) pp. 1671 to 1676
#2005 The Japan Institute of Metals
equipment, which use kerosene and oxygen to generate a
supersonic combustion ame. A commercially available
cermet powder (SURPREX W2007L, WC/20Cr
3
C
2
/7Ni,
FUJIMI Inc.) with size distribution from 15 to 53 mm was
used as the feedstock. The substrate was JIS SS400 low
carbon steel and its surface was blasted by alumina grit and
degreased by ultrasonic cleaning in acetone. Thickness of all
the coatings was aimed at about 300 mm. The basic operating
conditions are listed in Table 1. Table 2 shows detailed
spraying conditions used for spraying, i.e., fuel ow rate,
oxygen ow rate, the fuel to oxygen ratio and combustion
pressure Pc. F/O is the fuel to oxygen ratio, where F/O 1
corresponds to the stoichiometoric mixture ratio for complete
combustion. Coatings were prepared by the oxidizing ame,
the reducing ame and with the gas shroud, which operates
with the reducing ame.
We measured the in-ight velocity and temperature of
sprayed particles by an instrument called the in-ight thermal
sprayed particle analyzer (DPV-2000, TECNAR Co.) at the
substrate position. Its principle and mechanism were describ-
ed in detail elsewhere.
13)
This equipment utilizes the thermal
radiation from the in-ight sprayed particles. The image of a
hot particle is formed on a pair of vertical slits by means of a
lens. Temperature is determined by the two-color pyrometry.
Velocity is determined by dividing the interval (160 mm) of
the two slits by the time between two radiation signals
detected when the image of one particle passes in front of the
slits.
Wear property of the coatings was evaluated by using a
pin-on-disk type wear tester (Fig. 2). Coated disk surfaces
were polished with diamond grinding, and nished with
bung so that their surface roughness had a Ra 0.01
0.02 mm. Furthermore, some GS-HVOF coatings were heat
treated in air atmosphere before wear testing. The samples
were heated at a rate of 20

C/min up to 500

C and held at the

temperature for 30 h.
The diameter of the iron pin (Fe, >99:5%) used in the
experiment was 4 mm. After applying ultrasonic cleaning to
the pin and the disk in acetone for 1 h, they were xed to the
test apparatus. The pitch circle diameter (P.C.D.) was 20 mm.
In this experiment, the sliding velocity was xed at 0.25 m/s
for the entire test. The load between the pin and the disk was
10 N in the tests. The wear amount of coatings was measured
after 3000 m sliding. The specic wear rates are the averages
of three measurements on each sample. The displacement of
the top surface of the pin was measured by using a gap sensor
during the wear test. Wear rate was dened as the volume
loss per unit load and per unit sliding distance. For
comparison, the wear amount of chrome plating was also
measured. Coatings, sliding surfaces and wear debris were
observed by optical microscope and were analyzed by SEM
(EDX), XRD techniques.
3. Results and Discussion
Figure 3 shows spray particles in-ight average velocity
and temperature measured by the in-ight thermal sprayed
particle analyzer. Spray particles in-ight velocity increased
from 680 to 820 m/s as it went from the oxidizing ame to
the gas shroud condition. By using the gas shroud equipment,
the particle temperature fell by 150 degree, whereas the
particles velocity increased. Each error bar shows the
maximum value and minimum value obtained by all data.
The hardness on the cross section of coatings was
measured by a Vickers hardness tester at a 3 N load. Figure 4
shows the relationship between the hardness of coatings and
the ight velocity of spray particles. The hardness values are
the averages of ten measurements on each sample. Coatings
hardened with the increase of spray particles in-ight
velocity. The coating hardness did not depend on the spray
Table 1 Basic operating conditions.
Barrel length mm 150
Powder feed rate g/min 70
Torch velocity mm/s 700
Spray distance mm 300
Powder feed gas Nitrogen
Coating thickness mm 300
Table 2 Spraying conditions.
Fuel Oxygen F/O Pc
Unit dm
3
/min dm
3
/min MPa
Oxidizing ame 0.32 897 0.73 0.63
Reducing ame 0.44 826 1.09 0.67
Gas shroud 0.44 826 1.09 0.67
Load
Pin
Substrate
Gap
sensor
Coating
d
Disk:30 30mm(Ra0.01)
Pin :4(Fe, Hv 138)
Load: 10N
Velocity:0.25m/s
P.C.D.: 20mm
Distance:3000m
Fig. 2 Pin-on-disk type wear tester.
600
650
700
750
800
850
Oxidizing flame Reducing flame Gas shroud
I
n
-
f
l
i
g
h
t

s
p
r
a
y

p
a
r
t
i
c
l
e
s

v
e
l
o
c
i
t
y
,

V
/

m
s
-
1
1750
1800
1850
1900
1950
2000
I
n
-
f
l
i
g
h
t

s
p
r
a
y

p
a
r
t
i
c
l
e
s

t
e
m
p
e
r
a
t
u
r
e
,

T

/

C
Velocity
Temperature
Fig. 3 In-ight particles velocity and temperature. Each error bar shows
the maximum value and minimum value obtained by all data.
1672 Y. Ishikawa, J. Kawakita and S. Kuroda
particles in-ight temperature. Lidong et al. investigated the
inuence of the spray particles in-ight velocity and the
spray particles in-ight temperature exerted on hardness of
WC-CoCr coating on mild steel St 37 made by HVOF. The
coatings hardness increased with increasing the spray
particles in-ight velocity and the spray particles in-ight
temperature.
14)
From these results, we consider that the
coating hardness was increased with increasing of the work
hardening or the residual stress that were increased by the
increase of the spray particles in-ight velocity.
The coating made by the GS-HVOF process was heat-
treated at 500

C for 30 h. Its hardness was not changed by the

heat-treatment. This result appears to be contrary to the report
by Okada et al.
15)
They investigated the eect of heat
treatment on the hardness of WC-27NiCr coating on SUS403
made by HVOF. Coatings were heated to either 300, 400,
500

C and held at those temperature between 1 h and 45 h.

The hardness of all coatings was increased by heat treatment.
The hardness of the coating heat treated at 500

C showed the
greatest increase, i.e. the hardness was increased from Hv750
to HV1100. The amount of voids in the coatings was
calculated by the image processing of SEM image. The
increase of the hardness was attributed to the decrease of
voids in the coatings. Since the coating by GS-HVOF in the
present study has essentially no voids and pores in the as
spray condition. Therefore, the coating hardness was not
increased by the heat-treatment.
We observed the cross section of the coatings by using
SEM (Fig. 5). Boundaries among the particles were observed
in the coating prepared with the oxidizing ame. Pores and
voids are also visible on the cross section. Lamellar structure
was slightly revealed in the cross section of the coating
prepared by the reducing ame. The spray particles boundary
(lamellar structure) decrease gradually as it goes from the
oxidizing ame to the reducing ame. By using the gas
shroud equipment, boundaries are hardly observed and the
lamellar structure cannot be identied. This result indicates
the improvement in density of coatings by the gas shroud
attachment.
The crystal structures of the coating were characterized
from the surface by XRD (Fig. 6). We conrmed the
existence of Cr
3
C
2
and Cr
2
O
3
peak. The ratio of Cr
2
O
3

Cr
3
C
2
was calculated by using the intensity of the main peak
of each material (Fig. 7). The heat-treated coating showed
the highest oxidation degree in all the specimens. During heat
treatment (at high enough temperature) oxygen combines
with Cr in the coating to form Cr
2
O
3
.
16)
The XRD diraction
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
600 650 700 750 800 850 900
In-flight velocity of particles, V/m?s
-1
V
i
c
k
e
r
s

h
a
r
d
n
e
s
s
,

H
v
0
.
3
Fig. 4 The relationship between the coating hardness and In-ight
particles velocity. The hardness values are the averages of ten measure-
ments on each sample. Each error bar shows the maximum value and
minimum value obtained by all data.
5m
Void
WC
CrC
Ni
Boundary
5m
Reducing
Flame
Oxidizing
Flame
5m
5m
Gas
Shroud
Heat
Treatment
CrC
WC
CrC
Boundary
WC
Ni
Ni
CrC
WC
Ni
Fig. 5 Cross section SEM image of coatings. White: WC, Light gray: Ni, Black: Cr
3
C
2
.
Eect of Spray Condition and Heat Treatment on the Structure and Adhesive Wear Properties of WC Cermet Coatings 1673
spectrum of the heat-treated coating shows peaks indexed to
NiWO
4
. However, after polishing 50 mm by an abrasive
paper, the oxidation degree was decreased and XRD peaks of
inside of coating was similar to that of gas-shroud coatings.
The coating by the reducing ame showed the highest
oxidation degree among the untreated specimens.
This result was in agreement with Kreyes research, which
showed the eect of F/O ratio on the oxide content of the
coatings.
17)
The formation of oxide during the thermal spray
process can be categorized into three regions.
18)
Region 1 is
in the jet core, region 2 is in the atmosphere from the outside
of jet ame to the substrate and region 3 is on the substrate.
The spray particles in-ight temperature with the reducing
ame was little higher than that by the other ames. The
oxygen content of the coatings depends not only by the heat
of jet ame, but also by the substrate temperature. Since the
reducing ame burns further at the outside of the nozzle exit,
the substrate temperature should be higher than other
combustion ames. Therefore, the coating by the reducing
ame showed the highest oxidation degree among the
untreated specimens.
Figures 8 and 9 show the specic wear rates of the coatings
and the iron pin. Each error bar shows the maximum value
and minimum value of the specic wear rate obtained by 3
runs. The specic wear rate of the coating prepared by the
oxidizing ame was greater than the other coatings. The
specic wear rate of the coating prepared by the reducing
ame and GS-HVOF ame was in the order of 10
9
mm
2
/N
and was close to that of chrome plating. The specic wear
rate of the heat-treated coating is shown as zero, because the
wear amount of the heat-treated coating could not be detected
after the wear testing. Even though hardness is not dierent
between the heat-treated GS coating and the untreated GS
coating, the specic wear rate of the heat-treated GS coating
is much lower than that of the untreated GS coating. From the
result of Fig. 7, we consider that the adhesive wear property
was inuenced by the existence of oxides.
The specic wear rate of the iron pin was in the order of
10
8
mm
2
/N except for the combination of the iron pin and
the coating prepared with the oxidizing ame. Although the
wear amount of the heat-treated coating could not be detected
after the wear testing, the specic wear rate of the pin showed
a value in the order of 10
8
mm
2
/N, which is little higher
than that of the iron pin against the coatings prepared by the
GS-HVOF.
With the comparison of these wear behaviour, it is obvious
that the specic wear rate of the combination of the oxidizing
ame coating was the highest among the tested combinations.
However, even in this case the specic wear rate of the pin
was just above 10
7
mm
2
/N. From such low wear rates of
both the pin and the coatings, it is likely that the wear of all
the combinations was in the mild wear mode after 3000 m
WC, W
2
C, WO
3
, Cr
3
C
2
, Cr
2
O
3
, NiO, NiWO
4
30 40 50 60 70 80 90
30 40 50 60 70 80 90
-Heat treatment
-Heat treatment
(50mm inside)
30 40 50 60 70 80 90
-Oxidizing flame
-Reducing flame
-Gas shroud
2
Fig. 6 XRD patterns of coatings.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Oxydizing flame Reducing flame GS Heat treatment
T
h
e

r
e
l
a
t
i
v
e

i
n
t
e
n
s
i
t
y

o
f

C
r
2
O
3
/
C
r
3
C
2
Fig. 7 Oxidation degree during spraying in terms of the XRD intensity
ratio of Cr
2
O
3
/Cr
3
C
2
.
0
0.5
1
1.5
2
2.5
Oxidizing
flame
Reducing
flame
Gas shroud Chrome
plating
Heat treated
S
p
e
c
i
f
i
c

w
e
a
r

r
a
t
e
,

W
/

1
0
-
8

m
m
2

N
-
1
Fig. 8 Specic wear rate of coatings.
0
5
10
15
20
25
Oxidizing
flame
Reducing flame Gas shroud Chrome plating Heat treated
S
p
e
c
i
f
i
c

w
e
a
r

r
a
t
e
,

W
/
1
0
-
8

m
m
2

N
-
1
Fig. 9 Specic wear rate of iron pin.
1674 Y. Ishikawa, J. Kawakita and S. Kuroda
sliding.
To examine the severe to mild wear transition, we recorded
the displacement of the pin head as shown in Fig. 2.
Figure 10 shows the obtained typical displacement curves.
The inclination of specic wear rate slightly changes by each
measurement. Since the wear amount of coatings is very low,
the displacement curve of d may be regarded as the wear
behaviour of iron pin.
In our experiments, only the coating made by the oxidizing
ame showed the severe-mild wear transition at 50 m,
whereas the other coatings did not show the severe-mild
wear transition. Since the coating made by the oxidizing
ame has the highest porosity and the particles boundary is
more obvious larger wear debris might be generated easily at
early wear stage, because of detachment of loosely bonded
sprayed particles. Since small oxide wear debris is generated
by crushing such larger wear debris, the wear behaviour of a
coatings changes from severe wear to mild wear. Therefore,
we consider that only the coating made by the oxidizing
ame showed the severe-mild wear transition.
Furthermore, we observed the wear debris of the latter
coatings without severe-mild wear transition during wear
testing. Dark-colored and small (15 mm) wear debris was
generated on the surface at an early wear stage. Wear tracks
and the iron oxide existed on the surface of the coating after
wear testing. As latter coatings showed the low specic wear
rate (10
8
mm
2
/N), these results indicated that the latter
coatings realized the mild wear condition at a very early stage
of testing.
In previous work,
19)
we found that the abrasive wear
resistance of the coatings depended on the hardness of the
coatings. However, in the adhesive wear mode such as the
pin-on-disk type wear test in this study, the wear rate does not
simply depend on the hardness of coatings but also on the
chemical composition of the coating surface. XRD analysis
of the heat-treated coating from surface indicated the peaks
of NiWO
4
, WO
3
. It seems that the adhesive wear property
was inuenced by the existence of these oxides.
Kato investigated the inuences of oxide particles supplied
to the rubbing surface during sliding on the severemild
wear transition by using a pin-on-disc wear tester.
20)
As a
result, oxide particles were found to play an important role in
reducing the amount of wear. The sever-mild wear transition
distance was decreased by decreasing the size of the supplied
oxide particles.
He surmised that this eect is caused by the formation of
the oxide layers on the rubbing surfaces.
In addition, Picas et al. reported that the specic wear rate
of thermal sprayed nanocrystalline CrC-NiCr coatings was
decreased by the decrease of the spray powder size by using a
pin-on-disk wear tester.
21)
Since the original particle size of our WC cermet powder
feedstock is very small (about 12 mm) and these small
particles are partially oxidized from surface by the spray
ame, it is expected that ne oxide particles were dispersed
in the coatings by thermal spray technique. The thermal spray
coatings might easily generate the small oxide wear debris by
wear than coatings made by other processes. It is well known
that the amount of oxide in the thermal spray coatings is
increased by the decrease of the spray powder size.
22)
As the oxidation of such thermal spray coating is promoted
by the heat treatment in air especially on the coating surface,
the small oxide wear debris could be obtained from an early
wear stage. We consider that this behaviour is similar to the
eect of shortening the severe-mild wear transition distance
by supplying the oxide particles to the rubbing surface during
sliding. This is one explanation why the severe-mild wear
transition was accelerated by heat treatment but more
detailed study is needed.
4. Conclusion
WC/20Cr
3
C
2
/7Ni cermet powder was HVOF sprayed
with combustion ames with dierent fuel-oxygen mixture
ratio. GS-HVOF was also employed to obtain dense coatings
with minimum oxidation. The results show that the coating
obtained by the fuel-rich ame was oxidized most. Heat
treatment in air increased the oxidation on the coating surface
signicantly.
Adhesive wear resistance of the coatings was evaluated by
the pin-on-disk wear tester. The result has demonstrated the
following.
(1) The specic wear rates of the cermet coatings were in
the order of 10
9
mm
2
/N, an order of magnitude
smaller than that of the iron pin. Only the coating
sprayed with the oxidizing ame exhibited the severe-
mild wear transition and the specic wear rate of the pin
was slightly above 10
7
mm
2
/N.
(2) Although the hardness of the coatings was not dierent
between the heat-treated GS coating and the untreated
GS coating, the specic wear rate of the heat-treated GS
coating was much lower to the extent that it could not be
measured. This was attributed to the eect of oxides
formed by the heat treatment, which should promote the
severe-mild wear transition by forming ne oxide
particles in between the sliding surfaces.
This might have a practical signicance it is important
for high wear resistance materials that mild wear
appears early.
Acknowledgement
We would like to thank Dr. T. Itsukaichi and Mr. S. Osawa
of Fujimi Inc. for supplying the cermet powder. Careful
preparation of the coating samples by Mr. M. Komatsu and
Mr. N. Kakeya of NIMS are also appreciated.
0
50
100
0 100 200 300 400 500
0
50
100
150
200
250
300
0 500 1000 1500 2000 2500 3000
Sliding distance, l /m
D
i
s
p
l
a
c
e
m
e
n
t

o
f

i
r
o
n

p
i
n
,

d

/

m
Gas shroud
Reducing flame
Oxidizing flame
Heat treatment
Chrome plating
Fig. 10 The displacement of iron pin.
Eect of Spray Condition and Heat Treatment on the Structure and Adhesive Wear Properties of WC Cermet Coatings 1675
REFERENCES
1) B. Sartwell, K. Legg and J. Sauer: Joint Test Report, (Validation of
WC/Co HVOF Thermal Spray Coatings as a Replacement for Hard
Chrome Plating On Aircraft Landing Gear, PART I: MATERIALS
TESTING, U.S. DEPARTMENT OF DEFENSE, 2002).
2) J. G. Legoux: Proc. 7th Workshop on the Ultra-Steel, (NIMS, 2003)
pp. 124133.
3) J. Kawakita, S. Kuroda, T. Fukushima and T. Kodama: Sci. Technol.
Advance Mater. 4 (2003) 281289.
4) J. Kawakita and S. Kuroda: Rust Prevention & Corrosion Control 48
(2004) 287294.
5) Y. Ishikawa, J. Kawakita and S. Kuroda: Proc. 1st Tsukuba Interna-
tional Coating Symposium, (NIMS, 2004) pp. 4041.
6) W. Hirst and J. K. Lancaster: Journal of Applied Physics 27 (1956)
10571065.
7) T. Sasada, Y. Tsukamoto and K. Mabuchi: Biotribology, (Tokyo, 1990)
pp. 20.
8) D. A. Stewart, P. H. Shipway and D. G. McCartney: Wear 225229
(1999) 789798.
9) D. Toma, W. Brandl and G. Marginean: Surf. Coatings Technol. 138
(2001) 149158.
10) L. Jacobs, M. M. Hyland and M. De Bonte: J. Thermal Spray Technol.
8 (1999) 125132.
11) L. Zhao, M. Maurer, F. Fischer, R. Dicks and E. Lugscheider: Wear 257
(2004) 4146.
12) J. Wang, K. Li, D. Shu, X. He, B. Sun, Q. Guo, M. Nishio and
H. Ogawa: Mater. Sci. Eng. A 371 (2004) 187192.
13) H. Yamada, S. Kuroda, T. Fukushima and H. Yumoto: Proc. ITSC2001,
ed. by C. C. Berndt, (ASM International, Singapore, 2001) pp. 797
803.
14) L. Zhao, M. Maurer, F. Fischer, R. Dicks and E. Lugscheider: Wear 257
(2003) 4146.
15) R. Okada and M. Yamada: J. Japan Inst. Metals 58 (1994) 763767.
16) J. M. Guilemany, J. M. Miguel, S. Vizcaino, C. Lorenzana, J. Delgado
and J. Sanchez: Surf. Coatings Technol. 157 (2002) 207213.
17) K. Dobler, H. Kreye and R. Schwetzke: J. Thermal Spray Technol. 9
(2000) 407413.
18) C. M. Hackett and G. S. Settles: Proc. 8th NTSC, ed. by C. Berndt and
S. Sampath (ASM International, Texas, 1995) pp. 2129.
19) Y. Ishikawa, J. Kawakita and S. Kuroda: J. Thermal Spray Technol., in
print.
20) H. Kato: Wear 255 (2003) 426429.
21) J. A. Picas, A. Forna, A. Igartua and G. Mendoza: Surf. Coatings
Technol. 174175 (2003) 10951100.
22) C.-J. Li and W.-Y. Li: Surf. Coatings Technol. 162 (2003) 3141.
1676 Y. Ishikawa, J. Kawakita and S. Kuroda