S. Kozhukharov, S.

Tchaoushev
111

Journal of Chemical Technology and Metallurgy, 48, 1, 2013, 111-118
SPRAY PYROLYSIS EQUIPMENT FOR VARIOUS APPLICATIONS
S. Kozhukharov, S. Tchaoushev
University of Chemical Technology and Metallurgy
8 Kl. Ohridski, 1756 Sofa, Bulgaria
E-mail: stephko1980@abv.bg
ABSTRACT
The fabrication of all kinds of industrial products is based on the specifc combination between the applied methods,
and the conditions of syntheses (temperatures, pressures, fow rates and the chemical compositions of gaseous and liquid
fuxes, etc.), resulting on the properties and performance of the obtained products. On the other hand, both the methods and
the conditions for synthesis depend on the available equipment, which is able to supply suitable conditions for synthesis
via Spray Pyrolysis (SP) and further treatments of the desired product. The present work is an attempt to summarize the
basic types of equipment, and conditions for obtaining of products for various applications, via the spray pyrolysis method.
Keywords: Spray pyrolysis, Basic concepts, Synthesis, Deposition, Parameters, Conditions.
Received 02 November 2011
Accepted 20 September 2012
INTRODUCTION

The aim of the present work is to summarize the
basic constructive elements of the equipment for spray
pyrolysis synthesis of powder materials, deposition of
thin flms, or multilayer systems for various applica-
tions. It could be mentioned that basically, the method
applied for synthesis predetermines the form of the
obtained product. Its properties, as a consequence of the
conjunction of its composition, and structure depend on
the conditions used for each particular synthesis. The
composition of the product depends simultaneously on
the composition of the precursors solution, the physical
processes, and the chemical conversion reactions during
the synthesis, as is described in the present work.
METHODS
Synthesis of particles
Systems by direct fame: The performance of this
method requires passing of precursors fux across a
direct fame. By that manner, all chemical (oxidation)
and physical (evaporation and pore formation) pro-
cesses of conversion proceeds in the fame. With a zinc
acrylatemethanolacetic acid solution, the authors
[1] have obtained nano-sized particles with crystalline
structure and particle size between 10 and 20 nm. The
particle size has been controlled by the fow rate and
fuel/oxidant ratio. The method can proceed either by
supplemental burners, mounted near to the spray noz-
zle, or by additional feeding of the nozzle by oxidant
(air or pure oxygen) and the combustibles. If the spray
solution is prepared in an organic solvent, then the latter
can serve as a fame fuel, as well.
2.1.2. Synthesis in a high temperature chamber
The chambers are generally thermally insulated boxes
or tubes, with electric heaters, which contain recipients
for the collection of the powder products, or targets
(substrates) for flm deposition. If atmospheric air is
present in the chamber, and then the thermal decomposi-
tion of the precursors compounds occurs, accompanied
by oxidation of the respective metal. Consequently,
always the products are in the form of metal oxides. By
application of an ultrasonic nebuliser and a horizontal
tubular chamber with three separated temperature zones,
Journal of Chemical Technology and Metallurgy, 48, 1, 2013
112
Kozhukharov et al. [2] have obtained a large variety
of sub-micronic powders of polymetallic oxides with
perovskite structures and even size distribution. Vari-
ous frequencies of ultrasound nebulising are proposed
by different authors, varying from 20 kHz, to 2.5 MHz
[3-8]. Additionally, in [3, 6] the authors propose an
empirical dependence between the frequency applied,
and the droplet size:
(1)
where D (mx10
-6
) is average droplet diameter, is
the liquids surface tension(N m
-1
), is the solution
density(kg m
-3
), and f is the ultrasonic frequency (MHz).
When a nozzle is used instead of an ultrasonic
nebuliser, the diameter of the spray drops depends on
the diameter of the nozzle outlet tip, the surface tension
of the respective precursor solution, its viscosity, and the
pressure difference before and after the spraying (e.g.
inside and outside the nozzle). Alternatively, ultrafne
dispersive powders could be produced by swift rise of
the temperature inside the chamber, as is recommended
in [9]. By this manner, the already formed solid particles
undergo further crumbling and splitting, due to mechani-
cal tensions, or phase transitions, occurring at the high
temperatures.
Usually, the products of spray pyrolysis synthesis
techniques are various metallic oxides, because of the
oxidation processes, due either to the simultaneous pres-
ence of air and high temperatures, or as consequence of
direct combustion of the spray. The latter method for
providing high temperatures is described in [1, 10, 11].
Alternatively, the use of chambers with controlled
gaseous atmosphere is also reported [12]. Pingali et al.
[4] proposed production of metallic silver particles from
ultrasonically atomized spray of a silver nitrate solution
in water at temperatures above 650C and below the
melting point of silver in a chamber, flled with argon.
The particle size achieved was from 20 to 300 nm of
diameter.
An alternative approach for modifcation of the
gaseous composition is the usage of volatile anions in
the precursors solutions, for instance NO
3
-
or SO
4
2-
.
During the pyrolysis, they decompose to metal oxides,
and NO
2
or SO
3
. An interesting example for application
of this method is the obtaining of TiO
2
coupled by its
partial fuorination for production of photocatalysts [13].
The authors report successful synthesis of F-doped TiO
2

by spray pyrolysis from an aqueous solution of H
2
TiF
6
,
obtaining either TiOF
2
, or TiO
2
with substitutive fuorine
atoms inside the titania crystalline lattice. As a result,
they obtain a photocatalyst with improved activity.
Kang et al. [14] have used a vertical chamber with an
operating temperature from 700C up to 1200C, aiming
to obtain NaTaO
3
as a photocatalyst, by spraying of a
liquid mixture of NaNO
3
and Ta(OC
2
H
5
)
4
. Afterwards,
they have put the obtained NaTaO
3
-powder into the so-
lution of Ni(NO
3
)
2
. After evaporation of the water and
posterior sintering at 250C, the authors have obtained
a powder consisting of NaTaO
3
, impregnated by NiO.
A vertical chamber was used by other researchers for
obtaining of water splitting ferrites for solar hydrogen
production [15]. The authors have obtained the desired
product by spraying of solution of nitrates of Mn, Zn and
Fe by an atomizer, mounted at the bottom of the oven.
In this case, the obtained M
n-x
Zn
x
Fe
2
O
4
was collected in
a flter at the upper part of the oven.
While the above mentioned chambers are verti-
cal (Fig. 1(a)), Hirunlabh et al. [12] noticed that the
horizontal thermal chambers enable separation of larger
and smaller particles fractions (Fig. 1(b)). Industrially
available horizontal chambers for preparation of oxides
as La
0.7
Sr
0,3
CoO
3
for solid oxide fuel cells (SOFC) ap-
plications, is described in detail [16].
The precursor mixtures for spraying can be also col-
loidal systems, as is proposed by Suh and Suslik [17].
They report successful elaboration of magnetic porous
nano-particles spray pyrolysis of a colloidal suspension
of Co(CO)
8
. The precursors mixture has been obtained
by stirring of the silica colloid LUDOX SH 40 - 1 ml,
styrene-2 ml, ethylene glycol dimethacrylate - 1.6 ml,
Azobisisobutyronitrile - 16.4 mg, Co
2
(CO)
8
- 0.15 g and
1,4-dioxane - 30 ml, in 75 ml of aqueous 0.01 M sodium
dodecylsufonate in purifed water. The ingredients have
been mixed and nebulized at 1.7 MHz with N
2
or Ar
carrier gas. The obtained product has been collected in
bubblers and separated by centrifugation. As a result,
the authors have obtained either consolidated spherical
submicron particles (at 200C), or porous nanoparticles
(at 700C). This approach allows further modifcation of
the obtained particles by selective dissolving of the silica
cores, resulting in the formation of spherical hollow
particles, which can be used as catalyst or drug carriers.
In that means, the solubility of SiO
2
powders in diluted
S. Kozhukharov, S. Tchaoushev
113
hydrolytic acids and even hot water is investigated at
the beginning of XX century [18].

Synthesis/deposition of layers on various substrates
Successful elaboration of Yttria Stabilzed Zirconia
(YSZ) and YSZ Pt composite flms for SOFC and gas
sensors was reported in [19]. The flms were produced
by multiple spraying of solutions of Y(NO
3
)
3
.6H
2
O,
ZrCl
4
and H
2
[PtCl
6
] in mixtures of citric acid (CA) and
ethylene glycol (EG) on various substrates. The authors
have successfully obtained dense and uniform layers, as
a result of appropriated thermal cycles of subsequent rep-
etition of spraying and annealing procedures. Nakaruk
et al. [20] remark the point out crucial importance of the
annealing temperature. Thus, they report that after the
spray pyrolysis deposition of 0.5 M Titanium butoxide
solution, on quartz substrates at 400C, the flms were
composed by a single-phase anatase (with 50nm grains),
whereas after annealing at 600C the crystals grow to
100 nm, changing entirely the optical properties of the
respective flms. Furthermore, it is underlined in the
same paper that the annealing at 800 or 1000C leads
even to phase transition, either to anatase phase (with 100
nm grains), accompanied by rutile agglomerates (700 nm
size), or pure rutile flms (700 nm grains), respectively.
Consequently, the annealing infuences both the crystal
growth, and the crystal-phase transitions.
In addition, the high temperature posterior treat-
ment can cause a partial fusion of the substrates result-
ing generally in a remarkable improvement of the flm
adherence due to diffusion of the flm and substrates
ingredients. This phenomenon was registered by Peshev
et al. [21]. After deposition of zirconium oxychloride
on silica substrates, followed by annealing at 1100C,
the authors have established formation of ZrSiO
4
by
X-ray Photoelectron Spectroscopy (XPS). Obviously,
the penetration of Zr into the SiO
2
is the consequence
of the partial superfcial fusion of the silica substrates
during the annealing. Detrimental effects caused by the
posterior annealing procedure, are also reported in the
literature [22]. If it proceeds for prolonged periods, then
the extended crystal/grain growth provokes mechanical
tension in the deposited layer, resulting in its cracking
and detachment from the substrate.
Okuya et al. have deposited a multilayer CuO/
TiO
2
/SnO
2
system in order to develop UV-sensors with
Fig. 1. Basic constructions of equipment for spray pyrolysis a- vertical chambers; b- horizontal chambers; c- chambers
for flm deposition; 1- vessel for precursor solution; 2- gas bottle for carrier gas; 3- spray nozzle; 4- spray burner;
5- gas bottle for combustible; 6- gas bottle for oxidizer; 7- vertical chamber; 8- horizontal chamber; 9- chamber for
spray deposition; 10- electric heaters; 11- powder collectors; 12- substrates for flm deposition; 13- flters
Journal of Chemical Technology and Metallurgy, 48, 1, 2013
114
maximum intensity at 354 nm [23]. The entire multilayer
system has been achieved by the subsequent deposition
approach. The process was performed in a chamber for
deposition, as shown in Fig. 1(c). The researchers have
deposited subsequently fve different functional layers,
as follows: (1) transparent conductive SnO
2
; (2) second-
ary denser layer of SnO
2
; (3) the photoactive TiO
2
layer,
(4) layer of CuO; (5) fnal layer of pure metallic Au.
Sensors for humidity have been developed by spray
pyrolysis deposition of Zn
2
SnO
4
[24] and ethanol detec-
tors - by La doped Zn and Sn oxides [25], respectively.
In the former article, the authors have established that
the composition of the obtained stannate flms differs
from that of the initial solution sprayed, and also that
the simultaneous presence of secondary ZnO or SnO
2

phase suppresses the humidity sensing properties of the
obtained flms. As the main result of the latter study,
the authors note that the La doped ZnO flms possess
superior sensitivity, and the optimal presence of Lan-
thanum is 3 % at.
An interesting example for usage of a combined
system, where horizontal and vertical chambers are
simultaneously represented, also can be found in the
literature [26]. The authors have successfully depos-
ited SrTiO3 flms from Sr and Ti citrates, determining
the optimal parameters of deposition process, and the
posterior annealing. The authors propose the obtained
product to be used in optical recording devices.
Layers of La or Gd doped TiO
2
as photocatalysts
for environmental applications are proposed, as well
[27]. The authors report successful elaboration of La/Gd
modifed TiO
2
on various substrates, like: microscope
glass, graphite, metallic Ti, or stainless steel as catalyst
carriers. The flms were obtained by fame-assisted
spray pyrolysis deposition of an initial solution of Ti-
isopropoxide and the respective lanthanide nitrates in a
medium with CA and EG, nebulised with O
2
as a carrier
gas. The combustion of the organic substances in the
oxygen enriched atmosphere was provided the fame
for the pyrolysis process. Again the authors underline
that by multiple repetitions of the deposition procedures
with appropriated annealing after each cycle, they have
achieved easily control of the density, uniformity and
thickness of the respective films. The obtaining of
La
2
Ti
2
O
7
layers, by application of similar approach is
reported, as well [28].
Other examples for production of lanthanide flms by
spray pyrolysis can be also found [29, 30]. This method
is applicable for hi-tech materials, such as superconduc-
tors [31-34], or semiconductors [35, 36].
Fig. 1 represents the basic types of constructions of
the equipment for spray pyrolysis.
As can be seen from the fgure, the spray nozzle
or nebulizer, heat source, and product collector (or
substrate for deposition) are the basic operation units
of each SP installation, regardless of its construction.
Additionally, the pressure necessary for spraying
could be provided either by pumping of the precursor
solution, or by compressing of the respective carrier
gas. The SP systems can be supported by optional gas
sources, or even vacuum pumps for control of the gas
medium inside the SP chambers. Another possibility is
to assemble more than one nozzle. By this manner, the
respective nozzles can implant different ingredients in
the depositing flms when they work simultaneously, or
to deposit diffusive functional interlayers with extremal
adherence when they work subsequently. In conditions
of large scale production, when the respective substrates
possess large surface areas, the respective nozzles can be
moved by plotter mechanisms, providing scan-printing
SP deposition.
Application of alternative heat sources
Beside direct fame or heating by electric heaters,
application of microwaves or laser beams is also pos-
sible. Todorovsky et al. [37] have produced a large
variety of metal oxides, such as: Fe
2
O
3
, Y
2
O
3
, CeO
2
,
La
2
Ti
2
O
7
, Y
3
Fe
5
O
12
, LaMnO
3
, LaTiO
3
, etc., using spray
pyrolysis, combined with Nd:YAG solid laser radiation
and a magnetic feld.
Other investigations using laser beam are described
by Starbov et al. [38]. They have also used an excimer
laser, for posterior annealing of ZnO layers, deposited
on lime soda glass substrates. The authors reported that
the posterior procedure had improved signifcantly the
properties of the obtained products as gas sensors.
Other authors [39-43] propose spray pyrolysis as-
sisted by plasma, as a high temperature source. In that
case, cooling systems are required for the respective in-
stallations, in order to prevent their thermal breakdown.
Nevertheless, the temperature distribution inside the
chambers is easily controllable, because the plasma arc
is composed by ionised particles, and consequently - it
can be driven by electric and/or high frequency mag-
S. Kozhukharov, S. Tchaoushev
115
netic felds. Another advantage of the employment of
high voltage between the sprayer and the substrate for
deposition is that the electrostatic charge on the substrate
surface enhances the uniformity of the deposited flm.
A schematic image of plasma assisted SP equipment
is presented in Fig. 2.
The additional needle, illustrated in position b of
Fig. 2 enables supplemental diminishing of the spray-
droplet size, by both rendering of the higher pressure dif-
ference, and decreasing the outlet aperture. The designs
of the spray nozzles/nebulizers are the object of patents
[44-48], as well.
Another advantage of the plasma heating is the
possibility to obtain directly the high temperature crys-
talline phases, without supplemental annealing. Indeed,
Gitzhofer et al. [39] report integrated fabrication of entire
solid oxide fuel cells, by subsequent deposition of each
functional layer, inside the same SP-chamber, assisted
by plasma. Furtermore, in the same article the authors
distinguish several basic types of plasma spray pyrolysis,
according to the plasma ignition: (i) Hybrid Plasma
Spraying (HyPS) in combination of a direct current
and radio frequency; (ii) Induction Plasma Spraying
(IPS); (iii) Triple Torch Plasma Spraying (TTPS), and
(iv) High-Velocity LowPressure Plasma Spraying
(HVLPPS) ignited by a direct current.
Concept summary
It can be concluded from the literature review done
that the spray pyrolysis enables production of a large
variety of products in the form of fne dispersive porous
or dense powders or thin mono/multi layer flms. With
rather simple equipment a large number of parameters of
the pyrolysis process, like the size of the spray droplets,
chemical composition of the obtained products, their
crystal phases, density, etc. can be controlled. Some
authors even propose a device which they call home
made for synthesis and deposition of thin flms of CdS
and NiO on metallic substrates [49]. The capability
for large scale production of ultrafne monofractional
powder-like products by relatively simple equipment
imposes the SP, as a basic high temperature method
for synthesis in the feld of the nano-technologies.
Nowadays, this capability is the object of intensive R&D
activities [1-4, 6-11, 17, 22, 49, 50].
Besides the electric heaters, or the direct combus-
tion of the spray organic ingredients in an air/oxygen
environment, the high temperatures necessary for the
pyrolysis process could be provided by lasers, arc or
induction plasma, etc. This method is basically used
for production of ceramic materials, but it enables also
production of fne metallic powders [4], and carbon
nanotubes [7, 50] with desirable structure and proper-
ties. Another important advantage of this method is the
possibility to produce uniform and dense flms with de-
sirable crystallinity by multiple repetitions of spraying/
annealing cycles. Among the most important advantages
Fig. 2. Installation for plasma assisted SP deposition (a), and cross-section of SP atomizer (b).
1, 4 gas bottles, 2 container for precursor solution, 3 SP atomizer, 5 top ftting, 6 ceramic chambers body, 7 h.f.
inductive coil, 8 external cooler, 9 sample holder, 10 substrate for deposition, 11 internal cooler, 12 vacuum pump
Journal of Chemical Technology and Metallurgy, 48, 1, 2013
116
of the spray pyrolysis deposition method is the ability to
fabricate entire multilayer devices by subsequent deposi-
tion of different functional layers, in the same chamber,
as is proposed in [23, 39]. Finally, some limitations exist,
in relation to the need for temperature control, and the
diffculty to obtain low temperature allotropic forms of
the respective products. In that instance, the installations
for large scale production by SP method need always
cooling systems, and precise temperature control.
Nevertheless, the combination between the re-
markable simplicity of the equipment required, and the
large variety of possible applications of the respective
products, as catalysts [1, 13, 14, 22, 27, 28], electronic
components [26, 31-36], alternative energy sources, [15,
19, 39, 41, 43], sensors for the industrial automation
[19, 24, 25, 38], provides the signifcant versatility of
this method for obtaining of various functional materials
and even entire multilayer devices.
CONCLUSIONS
There are several basic types of constructions of
equipments for spray pyrolysis:
l According the position of the chamber - hori-
zontal or vertical. The horizontal construction permits
size separation of the drops/particles.
l The basic operation units of each SP installation,
regardless of its construction, are the spray nozzle or
nebulizer, heat source, and product collector or substrate
for deposition. Pumps or compressors are also necessary
for reaching of the appropriate pressure for spraying.
l The employment of an ultrasonic nebulizer
instead of a conventional nozzle enables production of
nanomaterials in the form of monodispersive fne pow-
ders, with remarkably ease control of the particle size,
by variation of the US frequency applied.
l Other possible approaches for diminishing of the
particle size of the respective powders are the decrease
of the aperture of the nozzle tip and the increase of the
pressure difference. Alternatively, the sharp rise of the
temperature inside the chamber allows for further split-
ting of the already formed solid particles.
l According to the heating source, they could be
either with electric heaters or by direct fame. The latter
approach requires alimentation of the nozzle, simultane-
ously by the combustible, the precursors and the oxidant.
Alternatively, an additional burner should be mounted
to the chamber. In the cases of flm depositions, the cor-
responding substrates should be heated. That approach
permits cold spraying with posterior heating and drying
of the obtained flm. It permits a much better control over
the structure formation during the course of deposition.
The subsequent repetition of the method allows the for-
mation of multilayer systems, which possess combina-
tions of properties. Further improvement of the obtained
flms could be achieved by posterior annealing. This
approach enables even fabrication of multilayer devices
by deposition of different functional layers in the same
SP chamber. It is the most important advantage of the
Spray pyrolysis as a technological method.
The application of alternative high temperature
sources, as lasers, or plasma has been investigated, as
well.
The combination of the simplicity of the required
equipment and the variety of possible applications
of the SP products, predetermine its versatility and
characterize it as a basic high temperature method of
synthesis, reliable for large scale production. Finally,
the possibility to perform several processes in the same
SP device predetermines the availability for remarkable
rise of the production effciency, and decrease of the
technological time.
Acknowledgements
The authors kindly acknowledge the fnancial sup-
port from the Scientifc Research Center of the Univer-
sity of Chemical Technologies and Metallurgy Sofa;
Contract No. 10 902.
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