Characterization of Pure Aluminum and Zinc Sprayed Coatings Produced

by Flame Spraying
*
1
Takeshi Kobayashi, Toru Maruyama and Masatoshi Kano
*
2
Department of Material Science and Engineering, Faculty of Engineering, Kansai University, Suita 564-8680, Japan
We investigate ame spraying of pure aluminum and pure zinc powders on various dierent substrates and study shrinkage properties and
thermal analysis curves of sprayed coatings during the forming process. We also examined eects of the spray distance on the porosity, tensile
strength and hardness of sprayed coatings, and obtained the following results. With an increase in spray distance, shrinkage of the sprayed
coating and the maximum temperature in the thermal analysis curve decrease. When the cooling ability of the substrate is higher, the shrinkage
ratio and the maximum temperature become decrease. The porosity and the hardness of a sprayed coating increase with an increase in spray
distance. This occurs because with the increase in the spray distance, the temperature of the sprayed particles decreases, the amount of air taken
in the spray increases and, as a result, the cooling rate of the coating increases. The tensile strength of a pure aluminum coating decreases with an
increase in spray distance due to the introduction of pores. On the contrary, the tensile strength of a pure zinc coating increases with an increase
in spray distance. This occurs because when the spray distance is short, coating temperature is high and, as a result, a large quantity of zinc oxide
is formed.
(Received September 22, 2003; Accepted October 29, 2003)
Keywords: ame spraying, hardness, pore, porosity, pure aluminum, pure zinc, shrinkage property, spray distance, spray forming, sprayed
coating, surface roughness, tensile strength, thermal analysis curve
1. Introduction
Spray coating is widely used as a means of reforming the
surface of a substrates and it is essential to establish strong
adhesion between the substrate surface and the sprayed
coating. However, in spray forming situations where struc-
tures such as metal molds are made of a sprayed coating, the
above-mentioned adhesion is not required, although shrink-
age of the sprayed coating, which aects the dimensional
accuracy of formed structures, should be considered. Ac-
cordingly, it is important to gain an understanding of the
physical and mechanical properties of the coating formed
during spray processing. To manufacture various types of
metal molds, housings and others with high dimensional
accuracy by spray forming, it is most important to under-
standing shrinkage properties of all the physical properties of
a coating.
In this study, we investigate changes in temperature and
shrinkage of coatings on various types of substrates as a
function of time after spraying under the condition that pure
aluminum and pure zinc coatings do not adhere closely to the
substrate surface in an unrestrained state. Furthermore, we
study relationships between the spray distance and the
porosity, surface roughness, tensile strength, and the hardness
of formed spray coatings.
2. Experimental Procedure
2.1 Spray material, substrate and spraying conditions
A powder ame spraying apparatus using oxygen and
acetylene (Terodyne System 2000) was used. The spray
powders used were pure aluminum and pure zinc, and the
particle size of the powders used was 5-150 mm. Steel plates,
shell molds for casting, mullite wool boards, and plaster
molds for casting were used as substrates each with
dimension of 110 mm 100 mm 10 mm. Table 1 gives
the spraying conditions for the powder ame spraying in this
study. For the purpose of this study, a sprayed coating formed
on the surface of a substrate should not adhere to the surface
but solidify and shrink freely. To meet this requirement, the
surfaces of the steel plates and plaster molds were lined with
a ne powder of boron nitride as parting powder. After
spraying, the sprayed coatings were removed from the
substrate surfaces and their physical and mechanical proper-
ties were examined.
2.2 Method for measuring shrinkage of sprayed coat-
ings
To manufacture metal molds with high dimensional
accuracy by sprayed coatings and to use them practically, it
is necessary to gain clear understanding of the shrinkage
behavior of sprayed coatings. The eects of spray distance
and type of substrate on the shrinkage of sprayed coatings
Table 1 Spraying conditions for powder ame spraying.
Gas pressure, Gas ow rate, Carrier gas Coating
Powder P
COM
/kPa FR/m
3
h
1
pressure, rate,
Acet. Oxygen Acet. Oxygen P
CAR
/kPa CR/kgh
1
Al 78 343 1.0 1.8 27 3.6
Zn 78 343 0.6 1.8 137 9.0
Spray distance, D/mm Spray time, t/s Substrate
250 Steel plate (SS400)
300 10
Shell mold
Mullite wool board
350 Plaster mold
*
1
This Paper was Presented at the Spring meeting of the Japan Thermal
Spraying Society, held in Osaka, on June 6, 1997
*
2
Graduate Student, Kansai University. Present address: Aishin Takaoka
Co. Ltd., Aichi 473-8501, Japan
Materials Transactions, Vol. 44, No. 12 (2003) pp. 2711 to 2717
#2003 The Japan Institute of Metals
EXPRESS REGULAR ARTICLE
were investigated. Figure 1 shows the apparatus for measur-
ing the shrinkage of sprayed coatings. Two hooks, separated
by about 30 mm, made of silica tubing are set on the surface
of the substrate: the left-side hook in the gure is xed, while
the right-side hook is connected to a gauge sensor. To prevent
interference by spraying on the gauge sensor, an insulating
cover is used. The region between the two hooks is sprayed
for 10 s. Shrinkage length is measured continuously after
nishing spraying until the temperature of sprayed coatings
cooled to 323 K, and a K (JIS standard) thermocouple is
inserted at the center of the coating layer. The shrinkage ratio
(known hereafter as shrinkage), r
S
(%), is the value in
which the shrinkage is divided by the distance between the
two hooks.
A specimen measuring 10 mm 20 mm was taken out
from the center of each sprayed coating after measuring its
shrinkage length. The specimen was used for measurement of
porosity, microstructure observation, measurement of rough-
ness on the contact surface with the substrate, and hardness
measurement (Hv, 0.49 N). Tensile specimens were taken
from sprayed coatings obtained by spraying onto plaster
molds under the same spraying conditions.
2.3 Measuring method for the porosity, surface rough-
ness and tensile strength of sprayed coatings
Vaseline was applied thinly to the surfaces of specimens
(10 mm 20 mm) for measuring porosity, and porosity was
measured with the buoyancy method.
1)
The porosity was
calculated according to the following equation:
r
P
(%) = {1 (M
c
=
c

w
)=(M M
/
M
m
=
m

w
M
v
=
v

w
)] 100:
(1)
The temperature was 297 K (24

C) during measurement. The

parameters used are dened as follows.

c
: density of coating (gcm
3
)

w
: density of pure water (gcm
3
)

m
: density of specic gravity pan (gcm
3
)

v
: density of Vaseline (gcm
3
)
M
c
: Weight of coating in air (g)
M: Total weight of coating, specic gravity pan and
Vaseline in air (g)
M
/
: Total weight of coating, specic gravity pan and
Vaseline in pure water (g)
M
m
: Weight of specic gravity pan in pure water (g)
M
v
: weight of Vaseline applied to coating (g)
After porosity was measured the specimens were washed
with petroleum benzine to remove the vaseline from the
surface and cut through the center for microscopic observa-
tion. Using a surface roughness tester (Surftest 201), the
centerline average roughness (R
a
) was measured for the
surface of the cut specimens that had been in contact with the
substrate.
Tensile test specimens with dimensions of 20 90
(0:6 1:03) mm were taken from sprayed coatings sprayed
on the shell mold, and smaller size specimens with
dimensions of 20 mm 20 mm were also taken from the
same sprayed coatings and attached to both grips of the
tensile specimens with an adhesive agent to reinforce the
gripping strength. To obtain uniform thickness of the sprayed
coatings, the thermal spraying torch was slightly agitated
relative to the specimen position. The relationship between
spray distance and thickness of the sprayed coating is shown
in Fig. 2. The spray time was constant at 10 s, and it is clear
that the thickness of the sprayed coating decreases with
increasing spray distance. The thicknesses of tensile test
specimens were 0.75-0.60 mm for pure aluminum and 1.03-
0.73 mm for pure zinc. Tensile strength was measured using a
tensile testing machine (Instron type, Shimazu Autograph
DCS-2000). The crosshead speed was xed to 1:67
10
2
mms
1
.
3. Experimental Results and Discussion
3.1 Shrinkage and thermal analysis curves for the
sprayed coatings of pure aluminum and pure zinc
Figure 3 shows some examples of shrinkage curves and
thermal analysis curves for the sprayed coatings obtained by
spraying pure aluminum and pure zinc powders onto the
surfaces of plaster molds. The temperature of the sprayed
coatings rises dramatically with the start of spraying. During
this initial period, minute uctuations in temperature repeat-
edly occur repeated. This phenomenon is caused by inter-
mittent adhesion of spray particles to the sprayed coating and
intermittent exfoliation of sprayed coating from the substrate.
After spraying for 10 s, the coating temperature begins to
drop, and as can be seen in the gure, the maximum
temperature of the sprayed coatings is higher when the spray
distance is shorter.
During the period from the start of spraying to the
formation of a sprayed coating, the sprayed coating exhibits
Fig. 1 Schematic illustration of experimental apparatus for measurement
of shrinkage.
240 260 280 300 320 340 360
0.6
0.8
1.0
1.2
C
o
a
t
i
n
g

T
h
i
c
k
n
e
s
s
,

T
h
/
m
m
Spray Distance, D/mm
Substrate: Plaster mold
Al
Zn
Fig. 2 Relation between spray distance and coating thickness of pure
aluminum and zinc sprayed coating.
2712 T. Kobayashi, T. Maruyama and M. Kano
complicated shrinkage behavior. Due to the repeated adhe-
sion of spray particles to the coating and partial exfoliation of
the sprayed coating from the substrate, sprayed coatings
repeat cycles of expansion and shrinkage. This phenomenon
is caused by the fact that the sprayed coating does not behave
as a solid until about 60% of the sprayed coating is
solidied.
24)
3.2 Eect of spray distance on the shrinkage and
maximum temperature of pure aluminum and pure
zinc coatings
Figure 4 shows the relationship between the spray distance
and the maximum temperature of pure aluminum and zinc
sprayed coatings. With an increase in spray distance, the
maximum temperature of the sprayed coatings decreases, and
when the spray distance is increased, the ight time of the
spray particles increases and the temperature of the molten
particles drops. As a result, the maximum temperature of the
sprayed coatings decreases. At a spray distance of 250 mm,
both the pure aluminum and pure zinc sprayed coatings show
their maximum temperatures, which are high above or near
the melting point of each respective metal. As for the eect of
each type of substrates, the maximum temperature was the
lowest when sprayed on the steel plate. In contrast, it was
highest when sprayed on the mullite wool board, which is
highly porous and is a highly eective insulator. The shell
mold and plaster mold have almost the same apparent
thermal diusivity, which is a measure of the cooling ability
of the mold.
5)
Consequently, the maximum temperatures for
both are almost the same in this study.
Figure 5 shows the eect of the spray distance on the
shrinkage of pure aluminum and pure zinc sprayed coatings;
with an increase in spray distance, the shrinkage decreases.
This is supposedly because with the increase in spray
distance, the number of molten particles that arrive and
adhere to the sprayed coating decreases and the ratio of solid
Fig. 3 Eects of time on temperature and shrinkage of pure aluminum and
zinc sprayed coating.
600
700
800
900
1000
1100
Mullite wool board
Steel (SS400)
Shell mold
Plaster mold
Melting point
of Al: 933K
240 260 280 300 320 340 360
500
550
600
650
700
750
800
Spray Distance, D/mm
M
a
x
.

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

T
M
a
x

/
K
Steel(SS400)
Melting point
of Zn: 693K
Mullite wool board
Shell mold
Plaster mold
(a) Al coating
(b) Zn coating
Fig. 4 Relation between spray distance and maximum temperature of pure
aluminum and zinc sprayed coating.
0
0.4
0.8
1.2
1.6
Mullite wool board
Plaster mold
Shell mold
Steel(SS400)
at 323K
(b) Zn coating
240 260 280 300 320 340 360
0
0.2
0.4
0.6
0.8
1.0
1.2
Spray Distance, D/mm
S
h
r
i
n
k
a
g
e
,

r
S

(
%
)
Steel(SS400)
at 323K
Shell mold
Mullite wool board
Plaster
mold
(a) Al coating
Fig. 5 Relation between spray distance and shrinkage ratio of aluminum
and zinc sprayed coating.
Characterization of Pure Aluminum and Zinc Sprayed Coatings Produced by Flame Spraying 2713
to liquid particles increases. When sprayed on the steel plate
with high cooling ability, molten particles rapidly solidied
immediately after they adhere to the substrate, thus the
shrinkage of the sprayed coating is small. In contrast, when
sprayed on the poorly conducting mullite wool board, the
molten particles solidied slowly and the shrinkage of the
sprayed coating was much more pronounced. Since the
results of the shrinkage shown in Fig. 5 also include
shrinkage by solidication, the values are fairy large
compared with the absolute values of the coecients of
linear thermal expansion for solid aluminum and solid
zinc.
69)
3.3 Microstructure, porosity and surface roughness of
sprayed coatings
Figure 6 shows the relationship between the spray distance
and the microstructures on the cross sections of coatings
sprayed onto the shell mold. The microstructures of alumi-
num and zinc sprayed coatings are sedimentary structures, in
which grain boundaries can be observed. The black parts in
the structures are pores. The images of the pure aluminum
sprayed coatings indicate that with an increase in spray
distance, the number of pores increases. Figure 7 shows
microstructures of the cross-sections of pure aluminum and
zinc coatings sprayed onto various substrates. In the cases of
aluminum and zinc coatings sprayed onto the mullite wool
board, which has the lowest cooling ability, many pores are
observed in the microstructure. This is considered to be
caused by gas generation from the mullite wool board. In the
case of the steel plate, which has the highest cooling ability,
many pores are also observed, and the eect can be explained
as follows: The cooling rate of the coating on the steel plate is
A
l

c
o
a
t
i
n
g
Z
n

c
o
a
t
i
n
g
50m
Substrate: Shell mold
Spray distance: 350mm Spray distance: 300mm Spray distance: 250mm
Fig. 6 Microstructure on cross section of pure aluminum and zinc sprayed coating.
A
l

c
o
a
t
i
n
g
Z
n

c
o
a
t
i
n
g
50m
Spray distance: 300mm
Mullite wool board Plaster mold Shell mold Steel plate
Fig. 7 Microstructure on cross section of pure aluminum and zinc sprayed coating at various substrates.
2714 T. Kobayashi, T. Maruyama and M. Kano
high and, consequently, when molten particles crash against
the steel plate, they are immediately solidied before being
attened completely. Moreover, there is insucient mutual
fusion between particles, resulting many pores being gen-
erated.
Figure 8 shows the relationship between the spray distance
and the porosity of pure aluminum and zinc sprayed coatings.
The gure shows that with an increase in spray distance, the
porosity tends to increase. It has been reported that when zinc
is sprayed with various types of ame spraying methods,
porosity increases with an increase in spray distance,
1)
which
is consistent with our results.
Porosity depends upon the type of substrate. For the
mullite wool board, which has the lowest cooling ability, the
porosity is high. Mullite wool board includes an organic
binding agent to bond mullite bers together, but the binding
agent is thermally decomposed by molten particles, and
decomposition gas is generated. It is supposed that the
decomposition gas is trapped in the coating, leading to an
increase in porosity. For the case of the steel plate, which has
the highest cooling ability, it is supposed that when the spray
distance is increased, some of the ying molten particles start
solidifying and mutual fusion between particles becomes
insucient. As a result, the porosity is increased. The
porosity of both the aluminum and zinc coatings sprayed onto
the plaster molds was the lowest in this experiment.
Regarding the surface roughness of the substrates used in
this study, the shell mold featured the roughest surface with a
roughness value of 26-34 mm (R
a
). On the other hand, the
steel plate had the smoothest surface, with a roughness value
of was 2-3 mm (R
a
). Figure 9 shows roughness proles of the
surfaces of a shell mold and pure aluminum and zinc sprayed
coatings in contact with the shell mold surface. The surface
roughness of the aluminum and zinc sprayed coatings is
smoother than that of the shell mold, implying that the molten
particles in ame spraying do not perfectly trace the contour
of the mold surface. Figure 10 shows the relationship
240 260 280 300 320 340 360
8
16
24
32
40
Spray Distance, D/mm
P
o
r
o
s
i
t
y
,

r
p
(
%
)
Mullite wool
board
Shell mold
Plaster mold
Steel(SS400)
(a) Al coating
(b) Zn coating
8
12
16
20
24
28
Mullite wool board
Steel(SS400)
Shell mold
Plaster mold
Fig. 8 Relation between spray distance and porosity ratio of pure
aluminum and zinc sprayed coating.
-50
0
50
100
(a) shell mold surface
-50
0
50
100
(b) Al coating surface in contact
with shell mold
Spray distance: 250mm
0 0.8 1.6 2.4 3.2
-50
0
50
100
L
e
v
e
l
,

L

/

m
Distance, D
R
/mm
(c) Zn coating surface in contact
with shell mold
Spray distance: 250mm
Fig. 9 Prole of roughness curve on shell mold surface and contacted
surface on shell mold of pure aluminum and zinc sprayed coating.
4
8
12
16
20
24
S
u
r
f
a
c
e

R
o
u
g
h
n
e
s
s
,

R
a

/

m
Shell mold
Mullite wool board
Steel(SS400)
Plaster mold
240 260 280 300 320 340 360
4
8
12
16
20
24
28
Spray Distance, D/mm
Shell mold
Mullite wool board
Steel(SS400)
Plaster mold
(a) Al coating surface in contact
with substrate
(b) Zn coating surface in contact
with substrate
Fig. 10 Relation between spray distance and surface roughness on pure
aluminum and zinc sprayed coating surface in contact with substrate.
Characterization of Pure Aluminum and Zinc Sprayed Coatings Produced by Flame Spraying 2715
between the spray distance and the surface roughness of pure
aluminum and zinc sprayed coatings for various substrates.
The gure shows that the surface roughness of the sprayed
coatings tends to increase with an increase in spray distance.
This increased roughness is thought to result from the
insucient adhesion between molten particles and substrate,
which is caused by the increase in spray distance. The surface
roughness of sprayed coatings also depends upon the
substrate surface. For the steel substrate, however, the
surface of the sprayed coatings is rougher than that of the
steel substrate due to insucient mutual fusion between
adhered particles. Furthermore, the surface of the sprayed
coating on the steel substrate is rougher than that on the
plaster substrate.
3.4 Tensile strength and hardness of sprayed coatings
Figure 11(a) shows the relationship between the spray
distance and the tensile strength of sprayed coatings.
Figure 12 shows the tensile test specimens after testing and
the microstructures of the longitudinal sections in the fracture
surface vicinity. Figure 12(a) shows that the fracture
positions are almost all in center of the specimens. The
aluminum sprayed coatings showed a decrease in tensile
strength with an increase in spray distance. The micro-
structures of the longitudinal sections show that when the
spray distance is increased up to 350 mm, fracture occurs at
the boundaries between sprayed particles, implying that with
an increase in spray distance, tensile strength decreases
because of the insucient fusion between particles. On the
contrary, the tensile strength of zinc sprayed coatings
increases with an increase in spray distance. The micro-
structures of the longitudinal sections show that when the
spray distance is short, many oxides exist between the
sprayed particles. This implies that with a decrease in spray
distance, the temperature of the sprayed coatings increases
and, as a result, many oxides are formed. Furthermore, the
microstructure is similar to that of cast material because
when the spray distance is short, the coating exists in a liquid
state on the substrate surface for a long time. Thus, tensile
strength may be aected by the oxide formation and the
microstructural evolution. It has been reported that the tensile
strength of a zinc alloy sprayed coating deposited by electric
arc spraying is as low as about 6 MPa.
10)
Figures 11(b) and (c) show the eects of the spray distance
on the Vickers hardness of pure aluminum and zinc sprayed
coatings. With an increase in spray distance, the hardness of
pure aluminum and zinc sprayed coatings increases. This can
be explained as follows: When the spray distance is
increased, molten particles cool rapidly during ight, and
the strain due to rapid cooling in the coating is increased,
resulting in the increased hardness. This explanation is
consistent with the fact that the increase in hardness is more
remarkable for substrates having a higher cooling ability.
240 260 280 300 320 340 360
20
24
28
32
36
40
Spray Distance, D/mm
H
a
r
d
n
e
s
s
,

H
v
Steel(SS400)
Mullite wool board
Shell mold
Plaster mold
(b) Al coating hardness
(c) Zn coating hardness
16
20
24
28
32
Steel(SS400)
Mullite wool board
Shell mold
Plaster mold
10
15
20
25
30
35
40
45
T
e
n
s
i
l
e

S
t
r
e
n
g
t
h
,

/
M
P
a
Al
Zn
Substrate: Plaster mold
Spray time: 10 s
(a) Tensile strength of coating
Fig. 11 Eects of spray distance on tensile strength and hardness of pure
aluminum and zinc sprayed coating.
A
l

c
o
a
t
i
n
g
Z
n

c
o
a
t
i
n
g
200m
Substrate: Plaster mold No etching
Spray distance: 350mm Spray distance: 250mm
20mm
(a)
(b)
Al coating Zn coating
250 300 350 250 300 350
Spray distance (mm)
Substrate: Plaster mold
Fig. 12 Appearance of tensile test pieces after testing and microstructure
of longitudinal sections at the fracture zone.
2716 T. Kobayashi, T. Maruyama and M. Kano
4. Conclusion
Flame spraying of pure aluminum and pure zinc powders
on various substrates was conducted, and the shrinkage
properties, porosity, microstructure, surface roughness and
mechanical properties of the sprayed coatings were inves-
tigated. The following results were obtained.
(1) The shrinkage ratio and maximum temperature of the
coatings decrease with an increase in the spray distance.
When the cooling ability of the substrate is high, the
shrinkage ratio and maximum temperature of the coatings
decrease.
(2) The microstructures of sprayed coatings are sedimentary
structures. With an increase in the spray distance, the number
of pores tends to increase. When the cooling ability of the
substrate is low, the microstructure of the sprayed coating
becomes similar to a cast microstructure and the porosity
increases.
(3) The surface roughness of sprayed coatings generally
reects the substrate surface. However, for the steel plate,
which has a higher cooling ability, the surface becomes
rougher due to insucient fusion between molten particles.
(4) The tensile strength of the aluminum sprayed coating
tends to decrease with an increase in spray distance due to the
insucient fusion between sprayed particles. The tensile
strength of the zinc sprayed coating decreases with decrease
in spray distance because many oxides form in the coating
with a cast microstructure. An increase in the spray distance
leads to increased hardness of the coating due to rapid
cooling of the coating.
This is a product of research which was nancially
supported in part by the Kansai University Research Grants:
Grant-in-Aid for Encouragement of Scientists, 2002.
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Characterization of Pure Aluminum and Zinc Sprayed Coatings Produced by Flame Spraying 2717