Surface & Coatings Technology 206 (2012) 2316–2324

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Parameter study influencing thermal conductivity of annealed pure copper coatings

deposited by selective cold spray processes
D. Seo a,⁎, K. Ogawa b, K. Sakaguchi b, N. Miyamoto c, Y. Tsuzuki c
a
Dept. of Mechanical Eng., Toyohashi University of Technology, Toyohashi, Aichi 441-8580, Japan
b
Fracture and Reliability Research Institute, Tohoku University, Sendai, Miyagi 980-8579, Japan
c
Metallic Material Dept., Material Eng. Div., Toyota Motor Co., Toyota, Aichi 471-8572, Japan

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

Article history: When two copper splats are in contact, a resistance to heat transfer exists between the splats. In thermal
Received 13 January 2011 spraying, the conductivity of the coating is mainly reduced by non-metallic bonds at internal interfaces
Accepted in revised form 8 October 2011 and trapped oxides. In cold spraying, however, almost no oxidation occurs during spraying. To demonstrate
Available online 14 October 2011
the capabilities and advantages of Cold Spray for the manufacturing of a conductive copper coating, the pre-
sent study is focused at comparing the different processing methods in the as-sprayed and the annealed state.
Keywords:
Copper
As a result, the coatings sprayed with spherical copper particles showed superior thermal conductive charac-
Cold spray teristics than coatings sprayed with non-spherical particles. There was a critical annealing temperature
Thermal conductivity giving the maximum thermal conductivity. Up to a critical temperature, the annealing process enhanced
Annealing the thermal conduction between adjacent splats. But, over that temperature, the voids in the coating rear-
range and concentrate along the grain boundaries.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Copper as spray material offers some essential benefits as com-
pared to other metals. Suitable copper powders in different degrees
of purity are already available as commercial feedstock for thermal
spray processes or metal injection molding. Because of their
sensitivity against oxidation, the microstructures and properties of
cold-sprayed copper coatings are expected to be significantly differ-
ent to those thermally sprayed [1]. With respect to demands from in-
dustry, cold-sprayed copper coatings can cover a broad range of
applications. The low oxygen content and thus the high thermal and
electrical conductivity in combination with the focused spray area
allow spraying narrow conducting lines or contacting segments for
automotive and electrical applications.
Conduction is the transfer of thermal energy from a region of
higher temperature to a region of lower temperature through direct
molecular communication within a medium or between mediums in
physical contact. The transfer of energy could be primarily by elastic
impact as in fluids or by free electron diffusion as predominant in
metals or phonon vibration in insulators [2]. In other words, heat is
transferred by conduction when adjacent atoms vibrate against one
another, or as electrons move from atom to atom. Conduction is
greater in solids, where atoms are in close contact. In liquids (except
liquid metals) and gasses such as air, the molecules are usually fur-
ther apart, giving a lower chance of molecules colliding and passing
on thermal energy.
Metals such as copper and silver are usually the best conductors of
thermal energy. This is due to the way they are chemically bonded,
i.e., metallic bonds (as opposed to covalent or ionic bonds) have
free-moving electrons and form a crystalline structure, greatly aiding
in the transfer of thermal energy [3]. The metallic bond accounts for
many physical characteristics of metals, such as strength, malleability,
ductility, conduction of heat and electricity. To quantify the ease with
which a particular medium conducts, engineers employ the thermal
conductivity, also known as the conductivity constant or conduction
coefficient, k. Thermal conductivity is a material property that is pri-
marily dependent on the medium's phase, temperature, density, and
molecular bonding.
When two splats (solid bodies) are in contact, a resistance to heat
transfer exists between them. The study of heat conduction between
such bodies (splats or grains) is called thermal contact conductance
(or thermal contact resistance). Experimental evidence has shown
that the temperature profile varies along the two bodies, e.g., a tem-
perature drop can be observed at the interface between the two sur-
faces in contact. This phenomenon is said to be a result of a thermal
contact resistance existing between the contacting interfaces [4].
According to Fourier's law, the heat flow between the bodies is
found by the relation:

⁎ Corresponding author. Tel.: + 81 532 44 6695; fax: + 81 532 44 6690.

E-mail address: seodw@me.tut.ac.jp (D. Seo). q ¼ −kAdT=dx; ð1Þ

0257-8972/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2011.10.010
 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324
where q is the heat flow, k is the thermal conductivity, A is the cross
sectional area and dT/dx is the temperature gradient in the direction
of flow. From this equation, the heat flow is directly proportional to
the contact area. Thermal contact conductance is a complicated
phenomenon, influenced by many factors. The most important ones
are contact pressure, interstitial materials, surface roughness, surface
deformations and so on [5]. If two splats are impinged by spraying,
surface deformation may occur on both bodies either plastically or
elastically, depending on the material properties and the impinge-
ment pressure. When a surface undergoes plastic deformation,
contact resistance is lowered, since the deformation causes the actual
contact area to increase [6].
In thermal spraying, the conductivity of a coating is mainly reduced
by non-metallic bonds at internal interfaces and trapped oxides. In
Cold Spray, however, almost no oxidation of the coating material oc-
curs during spraying. Cold Spray is a relatively novel deposition tech-
nique in which powder particles (typically 10–50 μm) are accelerated
to a velocity of about 600–1000 m/s by a supersonic jet of expanding
gas and form a coating layer by layer upon impingement onto a target
surface [7]. The Cold Spray process does not melt the feedstocks in
contrast to a conventional thermal spray and thus provides an excel-
lent opportunity to produce high conductivity copper coatings with
low porosity, low oxide content and low-thermal stresses [7,8]. The
deposits form due to the severe plastic deformation and the subse-
quent phenomenon at the deposit-substrate and the interface of splats
such as dynamic recrystallization or partial chemical reaction [4,9,10].
Thus, in combination with low oxygen content of the initial spray
powder, the thermal conductivity is mainly affected by the very high
dislocation density and therefore the low mean free path of electrons
[4].
Apart from investigating as-sprayed coatings, subsequent analysis
of annealed coatings should supply information on the recombination
of defects and so on. However, information concerning the effective pa-
rameters on the thermal conductivity in cold sprayed coatings provid-
ed by prior studies is limited [7], no data on the annealing effect on the
thermal conductivity of copper has been reported so far. If annealing is
allowed to continue once recrystallization has been completed, grain
growth may occur, in which the microstructure starts to coarsen and
may cause the coating to alter its mechanical and physical properties.
To demonstrate the capabilities and advantages of cold spraying for
copper coatings, the present study is also aimed at comparing the dif-
ferent processing methods in the as-sprayed and the annealed state
with those from high velocity air fuel spraying (HVAF).
2. Experimental procedures
Pure copper (Cu) powders manufactured by three different
manufacturing processes were used as feedstocks shown in Table 1,
and five copper coatings were deposited on the 7075 aluminum
alloy plates (50 × 50 × 4t mm) using commercially available cold
spray equipment (with converging–diverging de Laval nozzle) with
air and helium as impellent gas. Three types of commercial CS system
were used; Dymet system (model 403, OCPS, Russia; 5 mm-dia. tubu-
lar metallic nozzle) was applied for sample A, B and C-1, Inovati (KM-
CDS, Inovati, USA; round metallic nozzle) was for sample C-2 and CGT
Table 1
Feedstocks and spray parameters.
Sample Feedstock Particle size of Gas pressure, Gas temperature,
manufacturing feedstock, D50, μm MPa °C
A Electrolysis 20 Air, 0.6 400
B Water 12 Air, 0.6 400
atomization
C-1 Gas atomization 16 Air, 0.6 400
C-2 Gas atomization 16 Helium, 0.6 RT
C-3 Gas atomization 16 Helium, 3.0 RT
2317
(Kinetiks 3000, CGT, Germany; round metallic nozzle) was for sample
C-3. The other process conditions such as traverse speed (20 mm/s),
stand-off distance of nozzle (15 mm), and powder feeding rate
(1.5 g/s) were kept constant for all cold spray samples. HVAF process
was also applied for a comparison, and its working parameters were
kerosene flow rate of 10 l/h, spraying distance of 200 mm, and
powder feeding rate of 5 g/s. The coatings are classified into six
types according to different powder manufacturing and spray condi-
tions. The five coatings deposited by cold spray systems are referred
as; 1) A, 2) B, 3) C-1, 4) C-2, 5) C-3 shown in Table 1 and 6) HVAF
(using powder made by water atomization) is also referred.
To characterize the effect of annealing on the thermal conductivi-
ty, an isothermal heat treatment was carried out in vacuum (about
10 − 2 Pa) for 1 h. up to 600 °C (as-sprayed, 200, 300, 400, 500, and
600 °C). Thermal conductivity measurement was performed using
coupons of ø10 mm with a thickness of 2 mm at room temperature,
which were cut out of thick layers parallel to the substrate interface.
Coating porosity was measured by an image analyzing software
(ImageJ, NIH, USA) using a number of scanning electron microscope
(SEM) images which were taken at different locations in the copper
layer and its mean value was taken with deviation. The Vickers micro-
hardness (Hv) of coating was measured by a computer-controlled
measuring system (Fischerscope HM2000 XYp, Germany) using the
load versus indentation depth method according to ISO 14577–1. A
300 mN load was provided to the needle for penetration and the in-
denter is a diamond Vickers pyramid with 136° plane angle. The
mean Hv values were taken by measuring 7 points on the several
splats in the center of coating (about 1.5 mm from substrate-coating
interface). The elastic modulus (E) was also computed automatically
from the recorded measurement plot, calculated on the basis of the
slope of the tangent on the unloading curve with F = Fmax.
3. Results and discussion
3.1. Thermal conductivity
Fig. 1 shows the distribution of the thermal conductivity of the six
coatings. Thermal conductivities of the five cold-sprayed pure-Cu
coatings (three by air and two by helium gas) increased with increas-
ing annealing temperature on the whole. This, of course, could be due
to the microstructural changes during the heat treatment process [5].
The thermal conductivity of sprayed coating is affected by the poros-
ity, impurity, microcrack, grain size, annealing time and temperature,
spraying methods and etc. [11–14]. The various defects in the inside-
coating microstructure result from the application process, as shown
in Fig. 2. The most significant in reducing thermal conductivity will be
the porosity and microcracks that are oriented perpendicular to the
500
A C-2
B C-3
Thermal conductivity, W/mK
C-1 HVAF
400 Bulk Cu
300
200
100
0
0 100 200 300 400 500 600
Annealing temperature, °C
Fig. 1. Thermal conductivities of copper coatings deposited by various cold spray
systems and HVAF against annealing temperature.
2318 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324

Fig. 2. Cross-sectional micrographs of as-sprayed coating of samples a) A, b) B, c) C-1, d) C-2, e) C-3 and f) HVAF.

direction of heat flow through the coating [5]. Changes in the shape, After annealing, it was released quickly in all coatings excepting a C-2
distribution, and surface area of the defects that occur upon heating sample. A temporary rise in hardness was observed between 300 and
will influence the thermal conductivity. 500 °C. Over this region, the value decreased again up to the same
The effect of the microstructural changes on the thermal conduc- values of other pure-Cu coatings. This final value (at 600 °C) was almost
tivity is evident in Fig. 1. It is apparent that the microstructural the same that of bulk Cu (50 Hv). The values from all coatings converged
changes are occurred during annealing process when the thermal within the range 50–70 Hv. The hardness value of sample C-3 is lower
conductivity begins to increase at 200 °C. Especially the increase of
grain size by recrystallization via annealing together with porosity
improvement might affect the thermal conduction in the coatings. 250
This also revealed a significant reduction in the specific surface of A C-2
the interlamellar cracks beginning near 200 °C. The highest value of B C-3
200 C-1 HVAF
thermal conductivity among the sprayed coatings is approximately
Microhardness, Hv0.3N

340 W/mK at 500 °C annealing temperature of C-2 coating and it is

approximately 88% of that of bulk Cu (385 W/mK at 20 °C, referred 150
to International Annealed Copper Standard IACS). Taking the non-
homogeneous structure of sprayed materials into account, this value
is quite high. 100

3.2. Microhardness 50
Bulk Cu

Microhardness values of all coatings gradually decreased with in-

0
crease of annealing temperature as shown in Fig. 3. This may be due 0 100 200 300 400 500 600
to the microstructural transformation of the spray deposits after
Annealing temperature, °C
annealing process. Comparing with bulk Cu, all values of as-sprayed
samples are higher than that of bulk. This may be resulted from the Fig. 3. Hardness variation of copper coatings deposited various cold spray systems and
strain hardening (or work hardening) phenomenon during deposition. HVAF against annealing temperature.
 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324 2319

200 20
A C-2
A C-2 B C-3 (a)
B C-3 C-1 HVAF
C-1 HVAF 15
Elastic modulus, GPa

Porosity, area%
150
10

Bulk Cu 5
100

50 -5
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Annealing temperature, °C Annealing temperature, °C

Fig. 4. Elastic modulus variation of copper coatings deposited by various cold spray 10.0
systems and HVAF against annealing temperature. (b) A C-2
B C-3
9.5
C-1

Bulk density, kg/m3

than sample C-2 at the as-sprayed state. It might result from the wide BULK Cu
9.0
error gap, and it can be additionally considered that both samples
were made by two different commercial systems (manufactured by
8.5
different companies). Therefore it might depend on not only the gas
pressure but also the nozzle geometry, heating region, powder carrier
8.0
system and so on.

7.5

7.0
0 100 200 300 400 500 600
Annealing temperature, °C

Fig. 6. a) Cross-sectional porosity and b) bulk density of copper coatings deposited by

various cold spray systems against annealing temperature.

3.3. Elastic modulus

Elastic moduli of coatings changed slowly with increasing anneal-

ing temperature relatively comparing with the microhardness plot, as

Fig. 5. Particle morphologies of a) A and b) B feedstocks and c) a wide view of B having Fig. 7. Cross-sectional morphologies of C-1 coating after a) as-spraying and b) annealing
irregular surfaces. at 600 °C.
2320 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324

shown in Fig. 4. Coatings deposited by gas atomized powders (C-1, and drag. It is also possible to improve the elastic modulus via alternat-
C-2 and C-3) exhibited a tendency for elastic moduli to decrease with ing the main gas to more fast gas, helium in order to elevate the pow-
increasing annealing temperature. But in the case of A and B samples, der flight speed such as the sample C-2 and C-3.
elastic moduli increased slightly with increasing annealing tempera- In general, thermal sprayed coatings have the reduced elastic
ture. This is due to the irregular morphology of powder shown in modulus values, compared to the bulk materials [15]. It is attributed
Fig. 5. These two starting powders have the concavo–convex surfaces, to the unique microstructure of thermal spray deposits; i.e., the
and this morphology makes coating more porous than the other spher- shape of lamella, weak interlamellar boundaries, interlamellar pores,
ical powders. The closure of micro- or sub-micropores may lead the and vertical cracks (translamellar cracks). In this case of study,
elastic modulus to increase via proper annealing process. The elastic cold-sprayed coatings showed increased elastic moduli compared to
modulus could be also affected by the particle impact velocity more the bulk Cu except two non-spherical powder deposited coatings.
than the particle morphology. The particle velocities of sample A and This phenomenon may be due to the relatively dense structure of
B having non-spherical shape may be slow than the spherical powder cold-sprayed coatings than thermal sprayed coatings, and due to the
such as sample C-1, because of their relatively big wind resistance work-hardening effect of the splats deformed by sequent collisions.

20 400 20 400
Porosity (a) Porosity (b)

Thermal conductivity, W/mK

Thermal conductivity, W/mK
Thermal conductivity Thermal conductivity

15 15

Porosity, area%
Porosity, area%

300 300

10 10

200 200
5 5

0 100 0 100
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Annealing temperature, °C Annealing temperature, °C
20 400 20 400
Porosity (c) Porosity (d)
Thermal conductivity, W/mK

Thermal conductivity, W/mK

Thermal conductivity Thermal conductivity
15 15
Porosity, area%
Porosity, area%

300 300

10 10

200 200
5 5

0 100 0 100
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Annealing temperature, °C Annealing temperature, °C
20 400
Porosity (e)
Thermal conductivity, W/mK

Thermal conductivity
15
Porosity, area%

300

10

200
5

0 100
0 100 200 300 400 500 600
Annealing temperature, °C

Fig. 8. Porosity and thermal conductivity against annealing temperature for a) A, b) B, c) C-1, d) C-2 and e) C-3 samples.
 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324 2321

On the other hand, the A and B coatings showed the reduced elastic impurities of starting materials, for example, trace elements in the
modulus values than bulk Cu, like thermal sprayed coatings. chemical composition.
From Fig. 9b, the grain growth of B at 300 °C was considered insuffi-
cient, because the structure was not dense and abnormal in size com-
3.4. Porosity
paring with the 600 °C-annealing condition. This insufficient growth
results mainly from the un-optimized temperature or duration time of
Fig. 6 shows the distribution of the cross-sectional porosity in the
annealing. The abnormal grain growth may lead to suppress the de-
coating and the bulk density as a function of annealing temperature.
crease of interfaces and voids between splats. It may become the one
It was observed that a tendency was divided into two groups. The
of the major reasons for the insufficient improvement of thermal
amount of porosity increased normally with increasing annealing
conductivity.
temperature in the case of coatings deposited with spherical powders
(C-1, C-2, and C-3). This may be due to the assemblage of internal
micro and submicro-scale pores by diffusion via annealing process. 3.6. Coatings deposited with spherical powders
And these pores rearranged along the splat boundaries as shown in
Fig. 7. This phenomenon led the bulk density of coating to decrease In the case of coatings deposited with spherical powders (C-1, C-2
without the emission of pores outward the bulk. and C-3), thermal conductivities increased up to critical annealing
But in the case of A and B coatings deposited with non-spherical pow- temperatures (300 °C of C-1; 400 °C of C-2; 500 °C of C-3) with slight
ders, the porosity decreased with increasing annealing temperature.
These coatings had a relatively high porosity in the as-spraying state.
Such structure makes the extraction of pores possible. Therefore, the
bulk density values can increase with annealing temperature. The
amount of pores decreased over 200 °C gradually. It could be expected
that exposure to relatively low temperatures (200 °C) is sufficient to
heal cracks or pores, and bind splats together, leading to decrease of coat-
ing porosity.
Fig. 8 shows the relation between porosity and thermal conductiv-
ity against annealing temperature. Results can be divided into two
groups according to their tendencies, i.e., 1) the coatings deposited
with non-spherical powders such as A and B with an increasing ther-
mal conductivity in proportion to the drop in porosity, and 2) the
coatings deposited with spherical powders such as C-1, C-2, and C-3
where thermal conductivities increase in proportion to the rise in
porosity.

3.5. Coatings deposited with non-spherical powders

In the case of coatings deposited with non-spherical powders

(A and B), thermal conductivity increased with enhancing the bulk
density (Fig. 6b) and porosity (decreases after 400 °C) shown in
Fig. 8a and b. It is a general tendency in porous metallic materials.
These coatings had the relatively higher porosities (7–10%) in as-
sprayed state than other coatings deposited with spherical powders.
It is due to the morphology of feedstock which has irregular surface
shown in Fig. 5a and b. They can make many interfacial voids between
splats inside coatings when deposited. These voids or spaced pores be-
tween splats can be led to be close by annealing process, and then the
bulk density and porosity enhanced. With such a macro or microscopic
enhancement, sub-microscopic densification was also developed with
increasing annealing temperature at the same time. Deep contact be-
tween adjacent splats would lead to enhance the thermal conductivity.
Grains grew with increasing annealing temperature as shown in
Fig. 9, i.e., the average grain sizes were b100 and >500 nm at as-
sprayed (Fig. 9a) and 300 °C-annealed (Fig. 9b) states, respectively.
The growth in grain size also plays a major part in the increase of
thermal conductivity. The interface between neighboring grains
acts as an interceptive gap in the thermal conductive flow. Neighbor-
ing grains combine into one grain with interface reduction by
recrystallization during annealing process. During recrystallization,
thin oxide layers (mainly, copper oxides) inside as-sprayed coating
shown in Fig. 10, disappeared from the splat or grain interfaces. This
oxide-removal phenomenon would enhance the thermal conductivi-
ty undoubtedly, because the oxide layer also acts as a barrier against
thermal conduction. Such oxides can often transform to another pre-
cipitate like phosphorus oxides (PxOy-oxides) at the relatively high
annealing temperature (Fig. 9c, 600 °C in the case of B), as shown in Fig. 9. TEM morphology of B coating after a) as-spraying, b) annealing at 300 °C and
Fig. 11. Of course, these precipitated elements came from the c) annealing at 600 °C.
2322 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324

Fig. 10. EDS mapping of as-sprayed B coating showing oxide layer; (a) TEM image and (b) oxygen mapping.

increase of porosity shown in Fig. 8b. The reason of why C-1, C-2 and
C-3 gave different best thermal conductivity values even though they
used the same spherical powders, is that they used the different spray
system and different working conditions such as different nozzle
geometry, gas pressure, powder feeding and so on, to explore the
optimal working condition for the copper coatings including the
effective spray system. Bulk densities (Fig. 6b) were nearly constant
value or decreased slightly up to their critical points. These coatings
had the relatively lower porosities (0.5–1.5%), therefore higher bulk
densities (8.6–8.8%) than other type powder coatings in as-sprayed
state. That is, they are relatively dense than others especially in the
as-sprayed state. It may be due to the morphology of feedstock
which has spherical shape, if the same impact velocity is applied on
all type of feedstocks. The impact velocity of particles, of cause, can
be more related to the density of as-sprayed coating. The more is
the velocity, the higher the plastic strain induced on the particle
upon impact. According to Phani et al. [3], at a porosity level of 0.8%
cold work is responsible for 1/3 rd of the decrease in electrical con-
ductivity, and it becomes even more important at lower porosity
levels.
The spherical-shaped particles lead to a higher density than other
shaped particles [16]. Less voids and oxides were found inside coat-
ings. During annealing, the voids in as-sprayed state (Fig. 12a) can
be interconnected to each other and exhausted outward by chemical
diffusion, and a deep contact between adjacent splats can also occur
as shown in Fig. 12b. The grains grew normally in size after annealing.

Fig. 11. EDS mapping for the precipitation of a phosphorus oxide (PxOy-oxide) in B coating annealed at 600 °C; (a) TEM image, (b) copper, (c) oxygen and (d) phosphorus mapping.
 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324
Fig. 12. TEM morphology of C-1 coating after a) as-spraying, b) annealing at 300 °C and
c) annealing at 600 °C.
Neighboring grains combined into one grain with interface reduction
by recrystallization during annealing. Oxide layers were reduced. Pre-
cipitates which came from impurities were observed, as expected.
However, over critical temperature, thermal conductivities of
these coatings decreased together with the decrease of bulk density.
Sub-microscopic densification was developed with deep contact
between adjacent splats or grains which would lead to enhance the
thermal conduction. But the abnormal grain growth in size was
observed with the rarely over-grown grains (approximately 1.5 μm)
at 600 °C annealing as shown in Fig. 12c. Such an abnormal growth
in grain size and increase in the number of grains lead to increase of
interfaces between grains which cause the reduction of thermal
conduction and other mechanical properties. During annealing at
this region, the voids were rearranged and concentrated along the
interfaces of grains by chemical diffusion as shown in Fig. 7b. It can
be estimated that a portion of these voids come from the initial sub-
micron pores along the grain boundaries inside feedstock powders
2323
Fig. 13. Cross-sectional morphology of a C-1 feedstock having submicron voids inside
particle.
shown in Fig. 13. This phenomenon leads to a decrease in thermal
conduction. Precipitates were also observed as shown in Fig. 12b
and c.
Cold sprayed copper contains large numbers of dislocations and
other crystalline defects as a result of heavy cold working during
particle deformation. It can act as scattering centers for conduction
electrons. They also provide a large driving force for recrystallization,
which is the fundamental reason for the difference in annealing be-
havior compared with the material made by HVAF (following Section
3.7). Upon heat treatment, the large, defect-free grains form with an
associated improvement in conductivity.
3.7. HVAF coating
In the case of the HVAF coatings with impurities such as the oxide
layers, thermal conductivities were measured to be nearly constant,
regardless of the annealing process and porosity change shown in
Fig. 6a. It may be due to an impurity inclusion which is unavoidable
in thermal spraying even though a vacuum process is applied [17].
This impurity acts as an interceptive gap in the thermal conductive
flow together with voids inside coating. During annealing, impurity
can interrupt the rearrangement of voids, and structural develop-
ment. For these reasons, thermal conductivity was not enhanced. No
serious change in micro-structure was observed during the annealing
process.
3.8. Mechanism of enhancing thermal conduction
In the case of as-sprayed state, many interfaces and voids are
formed between splats or grains during deposition. Heat flow passes
through these interfaces directly. The interfaces between neighboring
grains and voids act as an interceptive gap in the thermal conductive
flow. Thin oxide layers also form around splats, resulting in low
thermal conductivity.
After annealing up to an optimal temperature, the voids are inter-
connected to each other and exhausted outward by chemical diffusion,
and deep contacts between adjacent splats form. Grain size also in-
creases and becomes homogeneous after annealing. Neighboring
grains combine into one grain with reduction of interface boundary
by recrystallization during annealing. Increase of thermal conductivity
is directly caused by such reduction of grain or splat interfaces. Oxide
layer also reduces. Some precipitated oxides from impurities inside
feedstock powders can also form around interface boundaries.
However they do not have an influence on thermal conduction, as
the heat flux passes from grain to grain in the contacted region by
detouring the precipitates.
If annealing is applied over an optimal annealing temperature (re-
ferred from the spherical type coatings), development of sub-
microscopic densification is kept up with deep contact between adjacent
splats or grains. The grains grow abnormally in size. Such abnormality
2324 D. Seo et al. / Surface & Coatings Technology 206 (2012) 2316–2324
Fig. 14. Schematic description on optimization of annealing process; a) grains in as-
sprayed copper coating, b) uniformly grown grains after optimal annealing, and
c) abnormally grown grains over optimal annealing temperature.
leads to an increase of interfaces between grains. The voids are
rearranged and concentrated along the grain boundaries. A series of
these phenomena causes the insufficient improvement or the reduction
of thermal conductivity comparing the optimal condition. Fig. 14 gives a
summary of the relation between the annealing condition and the
thermal conduction.
4. Conclusions
There was the optimal annealing temperature making the maxi-
mum thermal conductivity. Up to optimal temperature, the annealing
process enhanced the thermal conduction with the deep contact
between adjacent splats and the reduction of interfacial voids. Anneal-
ing over this optimal temperature, however, caused the reduction of
thermal conductivity with the abnormal grain growth in size, and
increase in the number of grain interfaces and voids comparing the
optimal condition. From above mechanism, the process of the C-2
coating with 400 °C annealing or the C-1 coating with 300 °C annealing
shows the best performance for thermal conduction. At 500 °C anneal-
ing, C-2 coating showed the highest thermal conductivity, but it is not
recommended because voids rearrange and concentrate along the
grain boundaries. It can generate drawbacks in mechanical, physical,
or other characteristics.
Microhardness values of all coatings were gradually decreased
with increase of annealing temperature, due to the microstructural
transformation after annealing. In the case of the coatings deposited
by spherical powders (C-1, C-2 and C-3), the elastic moduli de-
creased, but the porosity increased with increasing annealing tem-
perature. It may be due to the assemblage of internal micro and
submicro-scale pores by diffusion via annealing process. In the case
of the non-spherical types (A and B), the elastic moduli increased
slightly, but the porosity decreased with increasing annealing tem-
perature. It could be due to the irregular morphology of powders
and the relatively lower impact velocity.
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