Vacuum 136 (2017) 203e208

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Alumina and titania films deposition by APS/ASPPS dual mode

thermal spray equipment using Ar added N2 working gas
Yasutaka Ando a, *, Dickson Kindole a, Yoshimasa Noda b, Richard N. Mbiu c,
Bernerd K. Kosgey c, Stephen M. Maranga c, Akira Kobayashi d, e, f
a
Division of Renewable Energy and Environment, Ashikaga Institute of Technology, 268-1 Omae, Ashikaga, Tochigi 326-8558, Japan
b
Collaborative Research Center, Ashikaga Institute of Technology, 268-1 Omae, Ashikaga, Tochigi 326-8558, Japan
c
Department of Mechanical Engineering, Jomo Kenyatta University of Agriculture and Technology, P.O. Box 62,000 e 00200, Nairobi, Kenya
d
Malaysia Japan International Institute of Technology, University of Technology Malaysia, Jalan Semarak 54100, Kuala Lumpur, Malaysia
e
Graduate School of Eng., Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
f
University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

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

Article history: In order to develop a low cost oxide film deposition process with short duration time, a 1 kW class
Received 15 April 2016 Atmospheric thermal plasma spray (APS)/Atmospheric solution precursor plasma spray (ASPPS) dual
Received in revised form mode thermal spray equipment was manufactured and film depositions of alumina (Al2O3) and titania
25 September 2016
(TiO2) by APS and titania film deposition by ASPPS were carried out. Consequently, though intensive
Accepted 14 October 2016
Available online 17 October 2016
fluctuation with intensive abrasion of electrodes occurred during plasma jet generation in case of N2
working gas, the plasma jet was stabilized and the abrasion was dramatically diminished by slight
addition of Ar to N2 working gas. Since the suction type feedstock feeder could be confirmed to be
Keywords:
Aluminum oxide
available not only for powder feedstock but also solution precursor feed stock. In the case of APS, lamellar
Titanium oxide structure alumina and titania films could be deposited. However, in the case of titania films deposited by
Atmospheric thermal plasma spray (APS) APS, a phase transformation from anatase to rutile occurred partially during film deposition. Also in the
Atmospheric solution precursor plasma case of ASPPS, titania films including rutile and anatase were deposited. From these results, the devel-
spray (ASPPS) oped equipment was proved to be available as an APS/ASPPS dual mode thermal spray equipment and
Photo-catalyst this technique was found to have high potential for a low-cost oxide film deposition process.
Surface modification © 2016 Elsevier Ltd. All rights reserved.
Chemical vapor deposition (CVD)

1. Introduction
Oxide films have been used for various applications including
corrosion-resistive, abrasion-resistive and thermal barrier coatings
of bridges [1], semiconductor manufacturing equipment, and en-
gines [2e4]. In addition they start to be utilized as functional film
such as a photo-voltaic device, solid electrolyte, and gas sensor.
Especially, because of its excellent chemical stability, alumina
(Al2O3) film has been used in practice. Recently, because of its
excellent photo-catalytic properties [5], titania (TiO2) film is suc-
cessfully applied as a antimicrobial coating, or, photo-voltaic device
for dye-sensitized solar cells (DSSC) [6].
As the oxide film deposition process, chemical vapor deposition
* Corresponding author. Division of Renewable Energy and Environment,
Ashikaga Institute of Technology, 268-1 Omae, Ashikaga, Tochigi 326-8558, Japan.
E-mail address: yando@ashitech.ac.jp (Y. Ando).
(CVD) [7], physical vapor deposition (PVD) [8] and sol-gel method
[9] have been widely and dominantly used. However, since CVD and
PVD have some disadvantages such as low deposition time, high
initial cost due to requirement of vacuum equipment, limitation of
the sample size due to dimension of the vacuum chamber, a low
cost film deposition process with short duration time is demanded.
As for the sol-gel method, although film deposition can be con-
ducted by use of simple equipment, this process also has some
disadvantages such as low deposition rate, limitation of the sample
size due to dimension of the water bath for hydrolysis, difficulty of
thick film deposition due to factors such as the internal stress
generated by volume variation of the film during crystallization. On
the other hand, in atmospheric thermal plasma spray (APS), since
the high rate (over several hundred microns/min.) film deposition
can be conducted by simple equipment in open air without any
chambers, low cost film deposition with short duration time can be
carried out. Also, solution precursor plasma spray (SPPS) [10e14],
which is one of the plasma spray processes, can create a dense film

http://dx.doi.org/10.1016/j.vacuum.2016.10.019
0042-207X/© 2016 Elsevier Ltd. All rights reserved.
204 Y. Ando et al. / Vacuum 136 (2017) 203e208

with control of film component and crystal structure as in con-

ventional CVD because the film is created by chemical reaction
among feedstocks, working gas and ambient gas. Although use of
SPPS has so far been mainly conducted under low pressure envi-
ronments in order to avoid oxidation of the film during operation,
atmospheric SPPS (ASPPS) has started to be conducted for oxide
film deposition by various laboratories only recently. Previously,
authors used to deposit titania films using the developed ASPPS
equipment with titanium tetra iso-butoxide (TTIB) as feedstock
[15e18]. Subsequently, it was proved that the anatase film which
had enough photo-catalytic properties to decolor methylene-blue
droplets with 8 h UV irradiation and could generate electric po-
wer as the photo-voltaic devise of the dye-sensitized solar cell,
could be deposited.
Maranga, Ando et al. have been developing electric power
generating systems using renewable energy devices such as small
hydro, Dye-Sensitized Solar Cell (DSSC) and so on for non-
electrified rural areas in the Project for Capacity Development for
Promoting Rural Electrification as part of the Renewable Energy
Fig. 1. Schematic diagram of the APS/ASPPS dual mode thermal plasma spray
(BRIGHT project) [19]. For lifetime elongation of the small hydro
equipment.
and low cost (DSSC) Solar Cell manufacturing in this area, devel-
opment of alumina film and titania film deposition processes using
APS is thought to be effective. However, since solid materials such Table 1
as powder and wires are used as feedstock in the case of thermal APS alumina film deposition conditions.
spray, the flame should have enough thermal energy to melt the Substrate SUS304 stainless steel
feedstock during flight and high power (over 30 kW class) thermal Working gas (Flow rate) Ar (0.5 l/min.)/N2 (0.5e2.5 l/min.)
spray generating equipment is considered necessary. Therefore, it is Spray distance 70 mm
not suitable for the non-electrified rural area because of its high 50 mm
Discharge Current 50 A, 20 V
equipment cost and energy consumption. Therefore, we developed Deposition time 30 s.
a 1 kW class APS equipment [20], which will be able to be driven by Feedstock material Al2O3 powder
electric power from batteries charged by renewable energy devices.
*Conditions for the sample shown in Figs. 4 and 5.
Consequently, it could be confirmed that stainless films could be
deposited using Ar working gas and alumina films also could be
deposited by addition of N2 to the Ar working gas using 20 l/min. Table 2
and 2 l/min. in Ar and N2 working gas flow rates, respectively. APS titania film deposition conditions.
Nevertheless, since Ar is a very expensive gas, a low running cost Substrate SUS304 stainless steel
deposition condition such as using low price N2 dominant working Working gas (Flow rate) Ar (0.5 l/min.)/N2 (0.5e2.5 l/min.)
gas is required. Spray distance 100 mm
In this study, in order to develop a low cost and low power oxide 50 mm
Discharge Current 50 A, 20 V
film deposition process with short duration time for non-electrified
Deposition time 30 s.
rural area, a 1 kW class APS/ASPPS dual mode thermal spray Feedstock material Anatase powder
equipment was manufactured. Using this dual mode alumina and
*Conditions for the sample shown in Figs. 6 and 7.
titania film depositions by APS and titania film deposition by ASPPS
were carried out.
Table 3
2. Experimental procedure ASPPS alumina film deposition conditions*.

Substrate SUS 304 stainless steel

Fig. 1 shows the schematic diagram of the thermal spray
equipment used in this study. This equipment consists of plasma
torch, DC power source, feed-stock supplying system and working
gas supply system. Except the feedstock supplying system, the
constitution of this equipment was the same as for the APS and the
ASPPS equipment used in our previous studies and for conventional
high power thermal plasma spray equipment. In the case of the
conventional thermal spray equipment, the mechanically and
electrically driven type powder feeder is generally used. Because
the powder feeder is very expensive, a suction type powder feeder,
which can feed the powder into the plasma jet by negative pressure
generated by the thermal plasma jet, was developed in this study.
Tables 1e3 show film deposition conditions for alumina film
deposition by APS, titania film deposition by APS and titania film
deposition by ASPPS, respectively. As the feedstock, alumina pow-
der (PRAXAIR Al-1010-HP) and titania (anatase) powder were used
in case of APS and TTIB (Ti(OC4H9)4) was used for ASPPS. A
15 mm
15 mm x 1 mm SUS304 stainless steel plate with grit
Working gas (Flow rate) Ar (0.5e1 l/min)/N2 (0.5e2.5 l/min.)
Spray distance 50 mm
Discharge Current 50 A, 20 V
Deposition time 1 min.
Feedstock material Ethanol diluted TTIB**
*Conditions for the sample shown in Figs. 9 and 10.
** Titanium tetra iso butoxide (Ti(C4H9)4)(Volume ratio of TTIB/Ethanol ¼ 1/1).
blasted surface was used as the substrate. Fig. 2 shows the X-ray
diffraction patterns of the Al2O3 powder, TiO2 powder and SUS304
stainless steel substrate used in this study. The substrate was hor-
izontally set on the substrate holder and the central area of the
sample was placed perpendicular to the axial center of the plasma
jet. The input power for the discharge was fixed at 20 V, 50 A. After
oxide film deposition, the microstructures of the films were
investigated using an optical microscope and X-ray diffraction with
CuKa at 40 kV and 100 mA. For confirming the hardness and
adhesion strength of the deposited films, pencil scratch testing (ISO
 Y. Ando et al. / Vacuum 136 (2017) 203e208
Fig. 2. XRD patterns of the feedstock powders and substrates used in this study. a)
Feedstock Al2O3 powder. b) Feedstock TiO2 powder. c) SUS304 stainless steel substrate.
15184:2012) was carried out.
3. Results and discussion
3.1. Effect of Ar addition on stabilization of N2 plasma jet
From the experimental results in our previous study, addition of
N2 was proved to be effective for increase of thermal energy of the
Ar plasma jet. However, there are the following disadvantages on
using Ar working gas as well as its cost.
* In the case of an Ar plasma jet, the thermal energy of the
plasma jet increased with increasing Ar working gas flow rate. On
the other hand, the thermal energy of the plasma jet decreased
with increasing Ar working gas flow rate under the conditions of N2
working gas flow rate fixed Ar/N2 plasma jets because the thermal
energy of the Ar plasma jet is much lower than that of the N2
plasma jet.
* In addition, since feedstock powder feed rate was increased
with increasing working gas flow rate when using the suction type
feedstock feeder, non-melted particle content in the deposited film
was increased with increasing Ar working gas flow rate under the
conditions of the N2 flow rate fixed Ar/N2 plasma jets.
205
Table 4
State of N2 plasma jets and Ar added N2 plasma jets.
Working gas N2 flow rate (1/min.)
<1 1.5 2 2.5 3
N2 D D D X X
Ar added N2 B B B B X
B: Continuous discharge without abrasion of electrodes.
D: Continuous discharge with abrasion of electrodes.
X: Discharge was extinguished within 10 s.
In this study, the states of the plasma jets under the conditions
of N2 working gas and Ar added N2 working gas were investigated.
Table 4 shows the states of the plasma jets. In case of N2 working
gas, although the plasma jet could not be generated continuously
on the conditions of over 2.5 l/min. in a N2 flow rate, plasma jets
could be generated continuously for conditions of under 2.5 l/min.
However, even under 2 l/min., intensive fluctuation with intensive
abrasion of electrodes occurred. On the other hand, for Ar (flow
rate: 0.5 l/min.) and added N2 working gas, although the plasma jet
could not be generated continuously in the conditions of over 3 l/
min., plasma jets could be generated without electrodes abrasion
and intensive fluctuation of the plasma jets using under 2.5 l/min.
3.2. Alumina film deposition by APS
Fig. 3 shows the appearances of the Ar added N2 plasma jets
without and with powder injection, respectively. As shown in this
figure, the length and width of the plasma jet was dramatically
increased with increasing N2 working gas flow rate. Since thermal
energy was increased with increasing N2 flow rate, there was no
non-melted particle in the deposited film on the condition of 2.5 l/
min. even though feedstock powder feed rate was increased with
increasing working gas flow rate. Fig. 4 shows the appearance and
cross-sectional optical micrograph of the alumina film coated
sample and Fig. 5 shows the XRD pattern of the alumina film
deposited sample for the condition of QAr ¼ 0.5 l/min., QN2 ¼ 0.6 l/
min. and d ¼ 70 mm (d: deposition distance). Since alumina films
were deposited on the conditions of fixed plasma torch and sub-
strates, a white colored alumina spot was deposited on the sub-
strate in each case. As shown in Fig. 5 b), the lamellar structure
Fig. 3. Appearances of the Ar (0.5 l/min.) added N2 plasma jets. (QN2: N2 flow rate).
206 Y. Ando et al. / Vacuum 136 (2017) 203e208
Fig. 4. Appearance and cross-sectional optical micrograph of the alumina film coated
sample on the condition of QAr ¼ 0.5 l/min., QN2 ¼ 0.6 l/min. and d ¼ 70 mm (QAr: Ar
flow rate, QN2: N2 flow rate, d: deposition distance). a) Appearance b) Cross-section.
Fig. 5. XRD pattern of the alumina film deposited sample on the condition of
QAr ¼ 0.5 l/min., QN2 ¼ 0.6 l/min. and d ¼ 70 mm (QAr: Ar flow rate, QN2: N2 flow rate,
d: deposition distance). (B: Al2O3, :: Fe-Cr (Substrate)).
alumina film with almost the same structure as that for conven-
tional high power APS was deposited. Although the film was
deposited under N2 rich working gas, alumina films without ni-
trides could be deposited. From these results, it was proved that an
alumina film without nitrides could be obtained, even using low
power and simple thermal plasma spray equipment using Ar/N2
working gas that is N2 dominant. As for the pencil scratch testing,
Fig. 6. Appearance and cross-sectional optical micrograph of the titania film coated
sample on the condition of QAr ¼ 0.5 l/min., QN2 ¼ 0.6 l/min. and d ¼ 100 mm (QAr: Ar
flow rate, QN2: N2 flow rate, d: deposition distance). a) Appearance b) Cross-section.
the deposited alumina film could stand 9H pencil scratch.
3.3. Titania film deposition by APS
Fig. 6 shows the appearance and cross-sectional optical micro-
graph of the titainia film coated sample and Fig. 7 shows the XRD
patterns of the titania film deposited samples on the condition of
QAr ¼ 0.5 l/min., QN2 ¼ 0.6 l/min. and d ¼ 100 mm. Although the
color of the feedstock (anatase) powder was white, the color of the
particles turned into gray during flight in the plasma jet and the
gray colored film was deposited. Concerning the micro structure of
the film, also in this case, a lamellar structure film which is almost
the same as that in the conventional APS equipment was shown to
be deposited. However, as shown in Fig. 7, though the feedstock
powder was anatase, a rutile-dominant film was deposited. As for
the pencil scratch testing, since the deposited alumina film could
stand the 9H pencil scratch, it was proved that a practically useful
 Y. Ando et al. / Vacuum 136 (2017) 203e208 207

spray equipment, titania film deposition by ASPPS using the

developed APS/ASPPS dual mode thermal spray equipment was
carried out. Fig. 8 shows the appearances of the Ar/N2 plasma jets.
As shown in this figure, it was proved that the suction type feed-
stock feeder had enough potential to deliver the feedstock solution
precursor into the plasma jet and this equipment is available as an
APS/ASPPS dual mode thermal spray equipment. Fig. 9 shows the
appearance of the titainia film deposited sample and Fig. 10 shows
the XRD pattern of the titania film on the condition of QAr ¼ 1 l/
min., QN2 ¼ 0.5 l/min. and d ¼ 100 mm. Rutile dominant titania film
could be deposited. However, as for the film strength, the film was
Fig. 7. XRD pattern of the titania film deposited sample on the condition of QAr ¼ 0.5 l/
min., QN2 ¼ 0.6 l/min. and d ¼ 100 mm (QAr: Ar flow rate, QN2: N2 flow rate, d:
deposition distance). (,: Anatase, -: Rutile).

film could be deposited by using this technique also in case of

titania film deposition.

3.4. Titania film deposition by ASPPS

In the case of APS, it is thought to be difficult to deposit anatase-

rich titania films because of melting of the feed stock particles
during flight in the plasma jet. In a thermal spray process except for
cold spray and gas deposition methods, film deposition with
molten feedstock particles is inevitable. However, in ASPPS, since
the oxide film was deposited by chemical reaction, the crystal
structure and micro-structure of the film can be controlled by
controlling the substrate temperature (that is the deposition tem-
perature). In our previous study using micro-tube pump as feed-
stock feeder, it was revealed that the crystal structure of the anatase
film varied from rutile to anatase and finally became amorphous
with decreasing deposition temperature. If the APS/ASPPS dual
mode thermal spray equipment is developed, the new function can Fig. 9. Appearance of the ASPPS titainia film deposited on the condition of QAr ¼ 1 l/
be easily added to the APS film by using ASPPS. So, in this study, as a min., QN2 ¼ 0.5 l/min. and d ¼ 50 mm (QAr: Ar flow rate, QN2: N2 flow rate, d: depo-
basic study for development of APS/ASPPS dual mode thermal sition distance).

Fig. 8. Appearances of the Ar and Ar/N2 plasma jets (QAr: Ar flow rate, QN2: N2 flow rate). a) Ar plasma jet b) Ar/N2 plasma jet.
208 Y. Ando et al. / Vacuum 136 (2017) 203e208
Fig. 10. XRD pattern of the ASPPS titania film deposited on the condition of QAr ¼ 1 l/
min. and QN2 ¼ 0.5 l/min. and d ¼ 50 mm (QAr: Ar flow rate, QN2: N2 flow rate, d:
deposition distance). (-: Rutile, :: Fe-Cr (Substrate), +: Cu and Cu2O (derived from
the anode of the plasma torch)).
broken by scratching using a B pencil butt could stand the softer 2B
pencil scratch. In addition, in case of ASPPS, erosion of the anode of
the plasma torch occurred since thermal energy of the plasma jet
was increased due to TTIB injection even under the condition of an
Ar-rich working gas.
4. Conclusions
In order to develop a low cost oxide film deposition process
using thermal spray equipment, a 1 kW class APS/ASPPS dual mode
thermal spray equipment was manufactured and oxide film depo-
sition was carried out. Consequently, the following conclusions
were obtained.
1) Although abrasion of electrodes occurred in case of a N2 plasma
jet, alumina films could be deposited without abrasion of elec-
trodes when using Ar added to the N2 plasma jet. In addition, it
was proved that lamellar structured alumina films with practical
strength could be deposited even using a 1 kW class APS
equipment.
2) Although phase transformation from anatase to rutile occurred
during film deposition, lamellar structure titania films with
practical strength could be obtained.
3) Also in case of ASPPS, the suction type feedstock feeder is
available for continuous feedstock feed without droplet crea-
tion. Also a rutile-rich titania film could be deposited.
Acknowledgements
The authors acknowledge the supports from Ashikaga Institute
of Technology, Jomo Kenyatta University of Agriculture and Tech-
nology (JKUAT) and The Project for Capacity Development for
Promoting Rural Electrification Using Renewable Energy (BRIGHT
Project) of JICA.
References
[1] S. Kuroda, J. Kawakita, Marine exposure tests of thermal sprayed coatings in
Japan, Proc. Therm. Spray 2003 (2003) 343e352.
[2] K. Sridhar, R. Reji Kumar, M. Narasimha, Int. J. Mod. Eng. Res. 3 (3) (2013)
1435e1441.
[3] N. Curry, K. VanEvery, T. Snyder, N. Markocsan, Thermal conductivity analysis
and lifetime testing of suspension plasma-sprayed thermal barrier coatings,
Coatings 4 (2014) 630e650.
[4] D.R. Clarke, M. Oechsner, N.P. Padture, Thermal-barrier coatings for more
efficient gas-turbine engines, MRS Bull. 37 (10) (2012) 891e897.
[5] K. Hashimoto, H. Irie, A. Fujishima, TiO2 photocatalytics: a historical
overview and future prospects, Jpn. J. Appl. Phys. 44 (12) (2005) 8269e8285
[Part1].
[6] B. O'Reagan, M. Gratzel, A low-cost, high-efficiency solar cell base on dye
sensitized colloidal TiO2 films, Nature 353 (1991) 737e739.
[7] M.V. Baryshnikova, L.A. Filatov, A.S. Petrov, Sergey E. Alexandrov, CVD
deposited titania thin films for gas sensors with improved operating charac-
teristics, Chem. Vap. Depos. 21 (2015) 327e333, 10-11-12.
[8] S.E. Cordes, PVD-alumina coatings on cemented carbide cutting tools: a study
about the effect on friction and adhesion mechanism”, Tribol. Industry 34 (1)
(2012) 24e28.
[9] X. Wang, G. Wu, B. Zhou, J.Shen “optical constants of crystallized TiO2 coatings
prepared by sol-gel process, Materials 6 (2013) 2819e2830.
[10] N. Sanpo, C.C. Berndt, A.S.M. Ang, J. Wang, Effect of the chelating agent con-
tents on the topography, composition and phase of SPPS-deposited cobalt
ferrite splats, Surf. Coatings Technol. 232 (15) (2013) 247e253.
[11] L. Pawlowski, Suspension and solution thermal spray coatings, Surf. Coatings
Technol. 203 (19) (2009) 2807e2829.
[12] P. Michaux, G. Montavon, A. Grimaud, A. Denoirjean, P. Fauchais, Elaboration
of porous NiO/8YSZ layers by several SPS and SPPS routes, J. Therm. Spray
Technol. 19 (1) (2010) 317e327.
[13] S.V. Joshi, G. Sivakumar, T. Raghuveer, R.O. Dusane, Hybrid plasma-sprayed
thermal barrier coatings using powder and solution precursor feedstock,
J. Therm. Spray Technol. 23 (4) (2014) 616e624.
[14] H. Murakami, H. Nagai, T. Irokawa, T. Yoshida, K. Akashi, Super high rate
thermal plasma CVD of ceramics, J. Ceram. Soc. Jpn. 97 (1121) (1989) 49e55.
[15] Y. Ando, S. Tobe, H. Tahara, Photo-catalytic TiO2 film deposition by atmo-
spheric TPCVD, Vacuum 80 (2006) 1278e1283.
[16] Y. Ando, S. Tobe, H. Tahara, Rapid deposition of photo-catalytic oxide film by
liquid feedstock injection TPCVD in open air, IEEE Trans. Plasma Sci. 34 (2006)
1229e1234.
[17] Y. Ando, S.-Y. Chen, Y. Noda, Photocatalytic titanium oxide film deposition by
atmospheric TPCVD using air as the working gas, IEEE Trans. Plasma Sci. 41
(2013) 1850e1855.
[18] Y. Ando, Rapid deposition of titanium oxide and zinc oxide films by solution
precursor plasma spray, IEEJ Trans. FM 130-A (2010) 935e940.
[19] JICA's website, URL, http://www.jica.go.jp/kenya/english/office/topics/topics
131115.html.
[20] Y. Ando, N. Noda, A. Kobayashi, “Al2O3 Film Deposition by Atmospheric
Thermal Plasma Spray Using 1kW Class Electric Power Source”, Front. Appl.
Plasma Technol. 7 (2) (2014) 55e60.