ARTICLE IN PRESS

Journal of Electrostatics 66 (2008) 197–219

www.elsevier.com/locate/elstat

Electrospraying route to nanotechnology: An overview

A. Jaworek, A.T. Sobczyk
Institute of Fluid Flow Machinery, Polish Academy of Sciences, Fiszera 14, 80-952 Gdansk, Poland
Received 8 June 2007; accepted 12 October 2007
Available online 28 January 2008

Abstract

Electrospraying (electrohydrodynamic spraying) is a method of liquid atomization by means of electrical forces. In electrospraying, the
liquid at the outlet of a nozzle is subjected to an electrical shear stress by maintaining the nozzle at high electric potential. The advantage
of electrospraying is that droplets can be extremely small, in special cases down to nanometers, and the charge and size of the droplets
can be controlled to some extent by electrical means, i.e., by adjusting the flow rate and voltage applied to the nozzle. Due to its
properties, electrospraying is considered as an effective route to nanotechnology. The paper considers the latest achievements in micro-
and nano-thin-film production, including self-assembled nanostructures, in solid nano-particle generation, and in the formation of
micro- and nanocapsules.
r 2008 Elsevier B.V. All rights reserved.

Keywords: Electrospraying; EHD spraying; Nanotechnology; Thin-film deposition; Fine powder production; Electro-encapsulation; Direct writing; Spray
forming; Biotechnology

1. Introduction feature can be advantageous, for example, in surface

Electrospraying (electrohydrodynamic spraying) is a
method of liquid atomization by means of electrical forces.
In electrospraying, the liquid flowing out of a capillary
nozzle, which is maintained at high electric potential, is
forced by the electric field to be dispersed into fine droplets.
Electrospray systems have several advantages over me-
chanical atomisers. The size of electrospray droplets can
range from hundreds micrometers down to several tens of
nanometer. The size distribution of the droplets can be
nearly monodisperse. Droplet generation and droplet size
can be controlled to some extent via the flow rate of the
liquid and the voltage at the capillary nozzle. The fact that
the droplets are electrically charged facilitates control of
their motion (including their deflection and focusing) by
means of an electric field. Charged droplets are self-
dispersing in space, resulting also in the absence of droplet
coagulation. The deposition efficiency of a charged spray
on an object is higher than for an un-charged spray. This
Corresponding author.
E-mail address: jaworek@imp.gda.pl (A. Jaworek).
coating, thin-film production, or electroscrubbing.
Electrospraying can be widely applied to both industrial
processes and scientific instrumentations. The interest in
industrial or laboratory applications has recently prompted
the search for new, more effective techniques which allow
control of the processes in which the droplets are involved.
Electrospraying has opened new routes to nanotechnology.
Electrospray is used for micro- and nano-thin-film deposi-
tion, micro- or nano-particle production, and micro- or
nano-capsule formation. Thin films and fine powders
are (or potentially could be) used in modern material
technologies, microelectronics, and medical technology.
Research in electro-microencapsulation and electro-emul-
sification is aimed at developing new drug delivery systems,
medicine production, and ingredients dosage in the
cosmetic and food industries. Electrohydrodynamic spin-
ning (electrospinning) of viscous liquids facilitates the
production of nanofibers for masks, filters, scaffolds for
biological tissue, and intelligent garment manufacturing.
Recent advancements in nanoelectrospray technologies
have been briefly reviewed by Salata [1].
This paper reviews many aspects of these emerging
applications of electrospray in nanotechnology. In this

0304-3886/$ - see front matter r 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.elstat.2007.10.001
 ARTICLE IN PRESS
198 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219

Nomenclature e0 permittivity of the free space

rl mass density of the liquid
d droplet diameter rq volume charge density
~
D electric flux density Zl liquid viscosity
~
E electric field sl surface tension of the liquid
~e ~
~ Dp
F electrodynamic force P stress tensor acting on the liquid surface due to
~g
F gravitational force hydrostatic pressure difference
~r ~
~Z
F inertial force P stress tensor acting on the liquid surface due to
~Z
F drag force liquid viscosity
~
~l
~
g gravity acceleration L tensor of electromagnetic and polarization
Ll volume density of electromagnetic and polar- stresses on inter-phase surface
~
~
ization forces on the liquid phase Xi tensor of the surface tension
p pressure ~
1n unit vector (perpendicular to the inter-phase
~
q surface charge density surface)
~
~
~
vl liquid jet velocity 1 unit tensor (perpendicular to the inter-phase
Q liquid volume flow rate surface)
gl liquid bulk conductivity

paper, the term nanotechnology refers to the processing,
production, or application of materials and structures
having size scale less than 100 nm. Thus nanotechnology
includes the investigation of physical phenomena at supra-
atomic levels, the creation of atomic clusters/compounds
(e.g. polymers, quantum dots, molecular switches, carbon
nanotubes, fullerenes of the size o10 nm), generation of
nanoparticles (nanograins, nanocapsules of diameter
o100 nm), deposition of nano-thin films (nanocoatings,
self-assembling monolayers, nanowires of thickness
o100 nm), spinning of nanofibers (carbon fibers, polymer
fibers, textiles, nanoyarns of diameter o1000 nm), and
production of nanostructured materials (nanocomposites
which are conjunction all of above). There are two main
approaches to the nanotechnology: ‘‘top-down’’ and
‘‘bottom-up’’. The ‘‘top-down’’ approach refers to physical
or chemical machining of a bulk material down to
nanometer scale by grinding, milling, etching, or litho-
graphing. The ‘‘bottom-up’’ approach involves building a
nanostructure from elementary components via molecule-
by-molecule or grain-by-grain deposition onto a substrate,
epitaxial growth, plating, and intercalation or implanta-
tion. Among these techniques, electrospraying is placed
among the ‘‘bottom-up’’ techniques because the building
blocks are produced from fine droplets after solvent
evaporation.
strong electric filed is build-up at the capillary outlet.
Liquid flowing out from the nozzle forms a meniscus,
which becomes elongated in this electric field, and
disintegrated into droplets due to electrical forces. There
are two groups of forces, which cause deformation and
disruption of the liquid jet (cf. Fig. 2): bulk forces on
the jet, and normal and tangential stresses at the liquid
surface.
The bulk forces on the jet may be described as follows:
1. The electrodynamic force (Fe), proportional to the
electric field.
For a continuous medium, this force can be repre-
sented by the volume density of the electrodynamic
forces (cf. Nomenclature):
h i
~l ¼ rq E
L ~ þ 1 Dr~ TE
~  Er
~ TD
~ . (1)
2
The electrodynamic force occurs due to the electric
field caused by the voltage imposed on the capillary
nozzle, and also from the space charge of any previously
emitted droplets (FQ).

2. Fundamentals

A photograph of a typical electrohydrodynamic atomi-

zer (electroatomizer) is shown in Fig. 1. The device consists
of a capillary nozzle, usually made from a fine, hypodermic
needle, and a ring extractor electrode. Usually, the
capillary nozzle is connected to a high-voltage supply,
while the ring electrode and a substrate are grounded. In
another configuration, the nozzle is grounded, while the
extractor electrode is at high voltage. By this means, a Fig. 1. A photograph of an electroatomizer.
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219 199

2. Stress tensor due to pressure difference on both sides of

the inter-phase surface:

~ Dp ¼ ~
~
P ~
1ðpl  pg Þ. (5)
3. Stress tensor due to liquid dynamic viscosity, which is
important for liquid in motion, and is proportional
to the gradient of liquid velocity perpendicular to the
inter-phase surface:
~
~ Z ¼ Zl r~
P vl . (6)
4. Stress tensor due to liquid inertia, which is proportional
to the dyadic product of local liquid velocity at the
inter-phase surface:
~
~ r ¼ rl~
P vl  ~
vl . (7)
These forces and stresses cause the meniscus to elongate
into a jet, which then disintegrates into droplets. The
symbol  denotes the dyadic product of two vectors.
The balance of bulk forces per unit volume on the jet is
given by the following equation:
qrl~vl  
~St  r P
~l  F ~ ~
~ Dp þ P ~
~Z þ P
~r
¼ rl ~
gþL (8)
qt
and the stress balance by the equation
~ ~ ~ ~ ~
~l .
r~
X¼P ~Z þ P
~ Dp þ P ~r þ L (9)
Fig. 2. Schematic illustration of stresses and forces on the electrohy-
drodynamic liquid jet.

Many modes of spraying are distinguished in the

2. Gravitational force (Fg), expressed also as a volume
literature depending on the form of the meniscus, the
density:
pattern of motion of the jet, and a way it disintegrates into
~g ¼ rl~ droplets. Various forms of the modes of electrospraying are
L g. (2)
schematically shown in Fig. 3. These modes can be grouped
into two principal categories:
3. Inertial force (Fr) volume density:
 Dripping modes: These modes are characteristic in that
vl
~r ¼ rl d~
L . (3) only fragments of liquid are ejected directly from the
dt capillary nozzle; these fragments can be in the form of
4. The drag force (FZ). regular large drops (dripping mode), fine droplets
(microdripping mode), elongated spindles (spindle or
The drag force is well known for a moving droplet as the multispindle modes), or sometimes irregular fragments of
Stokes drag. However, to our best knowledge, for a moving liquid. At some distance from the nozzle outlet, however,
free jet, the force on the jet-head has not been presented in these fragments contract into spherical droplets.
general form. Lateral motion of the jet, observed for higher  Jet modes: In this case, the liquid is elongated into a
electric field, imposes additional complications on the force long, fine jet, which can be smooth and stable (cone-jet
description. It can be only stated that the drag force is mode) or can move in any regular way. For example, it
proportional to the surrounding gas viscosity and jet velocity. may rotate around the capillary axis (precession mode)
The stresses on the jet surface, which deform the jet or oscillate in its plane (oscillating mode). Sometimes, a
~
~i of few fine jets on the circumference of the capillary can
shape, are opposed to the tensor of the surface tension X
also be observed. This specific mode is known as the
the liquid. The following stress tensors can be distinguished:
‘‘multi-jet’’ mode. In each case, the jet disintegrates into
1. Electrodynamic stress tensor, resulting from the surface droplets due to electrostatic forces.
charge density (q) and the local electric field E:
The most important mode of spraying is the cone-jet
h i
~
~l ¼ ~ ~þ~
~ ~E~l  E
~g Þ  Eð
~D ~l  D
~g Þ . mode. In this mode, the liquid meniscus assumes the form
L qE 1  12 Dð (4)
of regular, axisymmetric cone with a thin jet (o100 mm in
 ARTICLE IN PRESS
200 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219

Fig. 3. Various modes of electrospraying.

diameter) at its apex, stretching along the capillary axis. Table 1

The end of the jet undergoes instabilities of one of two Constants proposed for Eq. (8) to determine droplet size
types: varicose and kink. Authors aQ ae ar as ag
These modes of spraying are systematically presented by
Hayati et al. [2,3], Cloupeau and Prunet-Foch [4,5], Fernandez de la Mora and Loscertales [20] 1
3
1
3
0 0 1
3
Gañan-Calvo [21] and Gañan-Calvo et al. [22] 1 1 1 1 1
Shiryaeva and Grigor’ev [6], and Jaworek and Krupa 2 6 6 6 6
Hartman et al. [23] 1 1 1 1 1
[7,8]. In recent years a novel approach to the classification 2 6 6 6 6
of the spraying modes has been based on Fourier analysis of
current oscillations correlated with fast jet imaging [9–13].
This analysis opens a new way to quantitative analysis of dry particles by Basak et al. [27], and for pulsed drop
electrospraying, however, an effect of electrical discharge generation by Chen et al. [28].
(corona discharge), which was observed many times during The main conclusion from Eq. (10) is that the droplet
electrospraying [2,3,14–19], on the spray current, and on the size can be decreased via decreasing the liquid flow rate and
spraying modes has not been considered. increasing liquid conductivity or surface tension. This
Eqs. (8) and (9) have never, to our knowledge, been equation does not take liquid viscosity into consideration
solved in the general case. There are, however, considera- because the droplet size only weakly depends on this
tions regarding specific modes of spraying, mainly the parameter [29]. This phenomenon was explained by Paine
cone-jet mode. For the cone-jet mode, the size of the et al. [30]. For liquids of higher viscosity, more energy is
droplets is usually given by the following equation [20–24]: required to drive the liquid from the meniscus, and,
therefore, the droplets are generated with lower frequency
QaQ a ar than for liquids of low viscosity. The size of the capillary
0 rl
d¼a ag . (10) also has an effect on the droplet diameter. In general,
sas
l gl changing liquid physical properties independently of each
The constant a in Eq. (10) depends on the liquid other is not an easy task, hence droplet size control by this
permittivity. The given exponents for the spraying para- method is limited in practice.
meters vary, depending on author (cf. Table 1). This scaling The minimum flow rate at which the cone-jet mode can
law has been confirmed by many experiments for single and operate at steady state was determined by Barrero and
coaxial jet, and recently, for a jet generated within an Loscertales [31]:
insulating liquid. Nowadays this law is commonly accepted
and widely used in the literature [21,25,26]. Recently, the sl 0 r
Qmin  . (11)
scaling laws were modified for strong ionic solutions and rl gl
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
In this case, the size of droplets can be on the order of
1 mm, when the liquid’s electrical conductivity is 103 S/m.
The droplet’s size decreases to about 10 nm when the
conductivity assumes a value of 1 S/m.
The electrospraying has the following advantages over
conventional mechanical atomizers:
1. Droplet size is smaller than that available from
conventional mechanical atomisers, and can be smaller
than 1 mm.
2. The size distribution of the droplets is usually narrow,
with small standard deviation that allows production of
particles of nearly uniform size.
3. Charged droplets are self-dispersing in space (due to
their mutual repulsion), resulting also in the absence of
droplet coagulation.
4. The motion of charged droplets can be easily controlled
(including deflection or focusing) by electric fields.
5. The deposition efficiency of a charged spray on an
object is order of magnitudes higher than for un-charged
droplets.
These characteristics characterize electrospraying as a
versatile tool for micro- and nano-thin-film deposition, or
micro- and nano-particle production.
3. Applications
3.1. Micro- and nano-thin-film deposition
Thin solid films, thinner than 10 mm, are used in
manufacturing micro- and nano- electromechanical sys-
tems (MEMS or NEMS), in microelectronic devices as
semiconducting, insulating or conducting layers, or for
improving surface properties of mechanical elements.
There are several conventional methods available for
thin-film deposition on a substrate. These include:
1. Casting of a solution or colloidal suspension on a
substrate, followed by solvent evaporation;
Fig. 4. Scheme of electrospray deposition of micro- and nano-thin film: (a) from a solution or suspension of particles to be deposited and (b) from a
precursor thermally decomposed on the substrate.
201
2. Cathode spraying, applicable to metal layer preparation;
3. Condensation of vapors of a material on the substrate;
4. Laser ablation for material evaporation;
5. Chemical vapor deposition and plasma assisted/enhanced
chemical vapor deposition;
6. Physical vapor deposition;
7. Electroplating, applicable only to metal film formation.
Recently, many researchers have tested the electrospray
deposition technique of liquid-phase materials on various sub-
strates. Electrospray deposition (Fig. 4a), is a process in which
droplets produced by electrospraying from a solution or sus-
pension of a material to be deposited are targeted to a sub-
strate to form a tight surface layer. A solid layer is obtained
after solvent evaporation. Evaporation can be sped-up by
heating the substrate. To improve mechanical properties, the
layer may be sintered at higher temperatures, if applicable.
Usually, the material to be deposited is sprayed directly
onto the substrate, but the layer can also be formed from a
precursor. The precursor is a compound which is decom-
posed at high temperature or converted to another
substance in chemical reactions with other compound
sprayed simultaneously or delivered in the gaseous phase.
The reactions usually take place on the substrate, and a
new product is obtained (Fig. 4b).
Initially, electrospray was used to produce thin layers of
radioactive materials, such as a- or b-particle sources or
neutron emitters (e.g. obtained from U233, Pu238, Am241 or
Cm242 nitrates) [32–35] or targets prepared for activation in
particle accelerators or nuclear reactors. Nowadays,
electrospray is involved in nanotechnology and nanoelec-
tronics for thin-film deposition. The following applications
have been reported in the literature:
 Solar cells, thin films produced from CdS, CdSe, SnO2,
or TiO2 [36–43];
 Fuel cells, thin films made of La(Sr)MnO3 on Zr
substrate, YOx on Ni–ZrO2, and ZrO2:Y2O3, GdxCe1xO2,
La1xSrxCo1yFeyO3, or ZrO2:Y2O3 deposited on
Ni72Cr16Fe8 substrate [44–58];
 ARTICLE IN PRESS
202 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
 Lithium batteries, thin cathode layers made of LiMn2O4,
LiNiO2, LiCoO2, LiCoxMn2xO4, LiCo0.5Ni0.5O2, LiAl0.25
Ni0.75O2, and V2O5; anodes made of SnO2 [37,59–82];
 Micro- and nanoelectronic devices, metal-oxide layers
used as dielectric: Al2O3 [83–89], CeO2 [90–92], CoO
[83], MgO [93–95], Mn3O4 [73], RuO [96], SnO2
[36,40,65,97–101], Ta2O5 [102], TiO2 [38,103–107], ZnO
[83,108–110], ZrO2 [51,83,103,111–117], WO3 [118],
alumina–zirconia composite [119], or semiconductor
films: CdSe, CdS or ZnS [39,41,42,107,120–122], SiC
[111–115,123,124], SnO2+LaOCl [125] or ZrO2:Y2O3
[51,126];
 MEMS, piezoelectric microactuators made of zirconium
n-propoxide, Zr(C3H7O)4, titanium tetraisopropoxide,
Ti((CH3)2CHO)4, lead acetate, Pb(CH3COO)2, or lead–
zinc–niobate (PZN) [127,128], piezoelectric transducers
of PbTiO3 [129,130], or BaZrO3 [131], or polymer
ferroelectric films on an Si wafer [132];
 Other applications, electrocatalysts made from NiCo2O4
[133], catalyst made of platinum [134], ITO glass-
covered with In2O3:Sn [135], optochemical sensors
with SnO2 layer [136,137], plasma displays with
(Zn,Mn)2SiO2 dielectric film [138].
The precursors used for the formation of these thin films
by electrospray pyrolysis and solvents applied by this
process are summarized in Table 2. For example, metal
nitrates or acetates dissolved in water, methanol, ethanol,
or their mixtures are electrosprayed as precursors for
metal–oxide layer production. The suspensions tested as
source of nanoparticles for thin-film deposition via
electrospraying are listed in Table 3.
All the authors reported that the films produced by
electrospraying were homogeneous and composed of small
agglomerates built of particles smaller than 1 mm, which
were the particles of dry powder used for preparing a
suspension, or crystallites smaller than 1 mm. The crystal-
lites are formed as an effect of solvent evaporation from
the droplet during its flight towards the substrate. In
specific cases the layer exhibit better properties than those
obtained by other methods. For example, in the case of
lithium batteries, the cathode or anode deposited by the
electrospraying method showed very stable charging/
discharging characteristics. The spray systems used usually
operate in the cone-jet mode, but sometimes the multi-jet
mode also is used [93,94]. The multi-jet mode made it
possible to obtain simultaneously a large number of
emission cones and droplets smaller than those obtainable
from a single cone.
Changing the physical properties of the liquid to be
sprayed allows tailoring, to some extent, of the film
morphology. The quality of thin film formed on a substrate
strongly depends on the size of particles or droplets
forming the layer, and their monodispersity. Even layers
of uniform thickness are obtained when the droplets
are uniformly dispersed over the substrate. Smaller
particles of narrow size distribution are required in order
to reduce the number and size of voids, flaws, and cracks
in the film. Thus electrospray is a promising tool for
the production of high quality layers, because it fulfills
all of these requirements. This technique allows generating
fine droplets in micro- and submicron size ranges,
with narrow size distribution. Electrostatic forces dis-
perse the droplets homogeneously in the space between
the nozzle and the substrate. The film thickness, its
crystallinity, texture, and deposition rate can be easily
controlled by varying the voltage, flow rate, concentration
of the material to be deposited, and the substrate
temperature.
Many authors have optimized the electrospray process
with regard to its application to thin-film deposition in
nanotechnology (cf., for example [139–141]). The electro-
spray methods used for thin-film deposition have been
reviewed by Jaworek [142]. Fig. 5 illustrates the progress in
the thinnest films produced by electrospraying over the last
decade. By this method, also organic films thinner than
100 nm have been produced [143]. At the present time, the
thinnest film reported is 15 nm [132].
From analysis of the experimental data from over 20
papers, a general law can be formulated that the deposition
rate of a layer is proportional to the final thickness of the
layer. This trend is illustrated in Fig. 6. The power in the
trend-line equation is close to unity. Large scattering of
the points around the trend line is a result of different
experimental conditions and various properties of the
sprayed liquids. This law means that thinner layers are
deposited with lower rates than those of larger final
thickness. In other words, the reciprocal of the deposition
rate (or the time required for deposition of a unit-thick
film) is inversely proportional to the final film thickness.
This means that the time of deposition of, for example,
1 mm layer takes about half an hour while a 100 mm film
deposition lasts only 10–20 s. This unobvious effect results
from the fact that lower particle suspension or precursor
concentrations have to be used for thinner films to obtain
coatings that are more uniform and have a lower roughness
factor.
From the reviewed literature it can be concluded that
electrospray facilitates the production of extremely thin
layers, which can be crack-free and more homogeneous
than those obtained by other methods. The process is
simple, cheap, flexible, and easy to control. Compared to
other methods such as chemical vapor deposition (CVD) or
physical vapor deposition (PVD), its main advantage is
that the growth rate of the layer is relatively high. For
example, the deposition rate of a 1-mm thin-film layer
produced by electrospray is about 0.1 mm/min [144], while
for PVD it is in the range of 0.006–0.06 mm/min [145], and
for CVD from 0.02 to 0.05 mm/min [144]. The electro-
spraying process can be carried out in an ambient
atmosphere, in air or other gas, and at low temperature,
without the need for complex reactors and high-vacuum
systems. Using the electrospray deposition technique,
highly pure materials can be produced, with structural
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219 203

Table 2
Precursors and solvents used for thin film deposition or microstructure formation by electrospraying

Layer Precursor Solvent Substrate References

temperature (1C)

CaP Ca(NO3)2  4H2O+H3PO4 Ethanol+butyl carbitol 300 [146,147]

Butyl carbitol (C8H18O3) 325–400 [148]
Ca(OH)2+H3PO4 Ethanol [149]
CdS CdCl2+(NH2)2CS Ethanol+water 200–450 [39–43,120,122]
CdSe CdCl2+(NH2)2CSe Ethanol+water 100–450 [42,120,150]
CeO2 Ce(NO3)2 Ethanol+water 400–600 [91,92]
CeO2:NiO:Gd Ce(NO3)3  6H2O, Gd(NO3)3  6H2O, Ni(NO3)2  6H2O Ethanol 200–450 [47]
CoO Co(NO3)2  6H2O Ethanol or ethanol+butyl carbitol 100–250 [83]
(+acetic acid)
GdxCe1xO2 Gd(NO3)3  6H2O+Ce(NO3)3  6H2O Ethanol+butyl carbitol 230–350 [57]
In2O3:Sn SnCl4+InCl3 Ethanol 200–550 [135]
Sn(CH3COO)+HF Methanol 350–600 [36]
La0.7Ca0.3CrO3d La(NO3)3+Ca(NO3)2+Cr(NO3)3 Ethanol+methyl glycol 180–400 [48]
La1xSrxCo1yFeyO3 La(NO3)3  6H2O+Co(NO3)2  5H2O+SrCl2  6H2O+Fe(NO3)2  9H2O Ethanol+butyl carbitol 230–350 [56]
(La0.85Sr0.15)0.95MnO3d
La(NO3)3  6H2O+Sr(NO3)2+Mn(NO3)2  6H2O+SrCl2  6H2O Ethanol+butyl carbitol 225–500 [53,54]
LiAl0.25Ni0.75O2 Li(CH3COO)  2H2O+Ni(CH3COO)2  4H2O+Al(NO3)3  9H2O Ethanol 450 [79]
LiBPO4 Li(CH3COO)  2H2O+H3BO4+P2O5 Ethanol or ethanol+butyl carbitol 250 [78]
(+acetic acid)
LiCoO2 Li(CH3COO)+Co(NO3)2  6H2O Ethanol or ethanol+butyl carbitol 230–450 [74–77]
LiNO3+Co(NO3)2  6H2O Ethanol 300 [80]
LiCoxMn2xO4 LiNO3+Co(NO3)2+Mn(NO3)2 Ethanol [61,62]
LiCo0.5Ni0.5O2 Li(CH3COO)  2H2O+Ni(CH3COO)2  4H2O+Co(NO3)2  6H2O Ethanol 450 [79]
LiMn2O4 LiCl+Mn(CH3COO)2  4H2O Ethanol [82]
Li(CH3COO)2  2H2O+Mn(CH3COO)2  4H2O Ethanol, or ethanol+butyl carbitol 235–300 [59,72,73,104]
(+acetic acid), or ethanol+glycerol
LiNO3+Mn(NO3)2  6H2O Ethanol 200–400 [64,66–69,81]
Li(CH3COO)2  2H2O+Mn(NO3)2  4H2O Ethanol [59,70,71]
LiNiO2 Li(CH3COO)+Ni(CH3COO)2 Ethanol 700 [79]
MgO Mg(C11H19O2)2 Ethanol+acetic acid; or 400–500 [93,94]
tetrahydrofuran+1-butyl alcohol
Mg(CH3COO)2 Ethanol 265–400 [95]
Mn3O4 Mn(CH3COO)2 Ethylene glycol or butyl carbitol 170–220 [73]
NiCo2O4 Ni(NO3)2  6H2O+Co(NO3)2  6H2O Ethanol)+di(ethylene glycol) butyl 350–400 [133]
ether
PbTiO3 Pb(CH3COO)2  3H2O+[CH3(CH2)3O]4Ti 2-Ethoxy ethanol 150 [129,130]
Pb(Zn1/3Nb2/3)O3 Pb(Zn1/3N2/3)O3+PbTiO3+BaTiO3 water+ethanol+acetic acid 200 [128]
Pb(Zr, Ti)O3 Zr(C3H7O)4+Ti((CH3)2CHO)4+Pb(CH3COO)2 25–100 [127]
Pt Pt(NH3)4(OH)2H2O, or PtCl4, or platinum acetylacetonate Water+ethanol, or water+butyl 343–575 [134]
carbitol
RuO RuCl3  xH2O Ethanol+butyl carbitol 200 [96]
SiC Ter-polysilane Toluene 1300 [123]
SnO2 SnCl4  5H2O Ethanol 300–500 [65,97,98,136,137]
SnO2:Cu SnCl4  5H2O+Cu(NO3)2  2.5H2O Ethanol 150–400 [40]
SnO2:F SnCl4  5H2O+HF Ethanol 500–550 [100,101]
SnO2+LaOCl SnCl4  5H2O+LaCl3  6H2O Ethanol 400 [125]
SnO2:Mn2O3 SnCl4  5H2O+Mn(CH3COO)2  4H2O Ethanol or ethanol+butyl carbitol 400 [97,98]
(+acetic acid)
Ta2O5 Ta(OC2H5)5 Ethanol or ethanol+butyl carbitol 100–210 [102]
TiO2 Ti(i-C3H7O)4 Ethanol or ethanol+butyl carbitol 250 [104]
(+acetic acid)
Ti((CH3)2CHO)4 Ethanol 100–220 [105]
Titanium diisopropoxide bis(2,4-pentamedionate) 2-Propanol 350–550 [38,107]
V2O5 [(CH3)2CHO]3VO Ethanol 200 [63]
WO3 W(C2H5O)6 Ethanol 200–400 [118]
(Zn,Mn)2SiO2 Mn(CH3COO)2+Zn(CH3COO)2+tetraethyl orthosilicate Ethanol or ethanol+butyl carbitol [138]
(+acetic acid)
ZnO SnCl4  5H2O+Zn(CH3COO)2  2H2O Ethanol or ethanol+butyl carbitol 100–250 [83]
(+acetic acid)
Zn(CH3COO)2 Ethanol+hydrochloric acid 350 [108]
Zn(C2F3COO)2 Methanol 340–400 [109]
Zn(NO3)2  2H2O Water+izopropyl alcohol+acetic 350 [110]
acid
ZnS ZnCl2+(NH2)2CS Water 450–550 [106]
ZrO2 Zr(OCH2 CH2CH3)4 Ethanol 100–220 [83]
ZrO(NO3)2  xH2O Ethanol+butyl 200–500 [139,140]
carbitol+water+(0–0.5%) polyvinyl
alcohol (87%) or ethanol
ZrO2:Y2O3 Zr(C5H7O2)4+Y(C5H7O2)3 Ethanol+butyl carbitol+acetic acid 300–400 [51]
Zr(C6H7O2)4+YCl3  6H2O Ethanol+butyl carbitol 285–340 [50]
Zr(C6H7O2)4+YCl3  6H2O Ethanol+diethylene glycol 480–575 [141]
Zr(C5H7O2)4+YCl3  6H2O or Y(NO3)3  6H2O Ethanol+diethylene glycol 300–335 [52]
Zr(C3H7O)4+YCl3  6H2O or Y(NO3)3  6H2O 325 [52]
 ARTICLE IN PRESS
204 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219

Table 2 (continued )

Layer Precursor Solvent Substrate References

temperature (1C)

Ethanol+butyl carbitol or
ethanol+1-methoxy-2-propanol
ZrO(NO3)2  xH2O+YCl3  6H2O or Y(NO3)3  6H2O Ethanol+butyl carbitol or 265–325 [52]
ethanol+1-methoxy-2-propanol
Zr(C5H7O2)4+ZrO(NO2)3+YCl3 Ethanol+butyl carbitol or 196–365 [58]
ethanol+1-methoxy-2-propanol
ZrCl4 Ethanol+butyl carbitol or 325 [52]
ethanol+1-methoxy-2-propanol

Table 3
Submicron layers formed from suspensions deposited by electrospraying

Layer Particles size (sintering Solvent Flow rate (spray time) References
temperature)

Alumina (Al2O3) 500 nm Ethanol 0.0036–6 ml/h [84–89]

100 nm (100–250 1C) Ethanol or ethanol+butyl carbitol 0.8 ml/h or 1.5 ml/h [83]
(60 min)
Molybdenite (MoS2) 120  1000 nm (platelets) Isopropanol, acetone, alcohol, or toluene 2.4 ml/h (25 min) [151,152]
Nickel (Ni) 2–3 nm (600 1C) Ethylene glycol monoethyl ether [153]
acetate+alkylnaphthalene+polyamine
Platinum on carbon (Pt//C) 5 nm Isopropanol or isopropanol+Nafion 0.2–1 ml/h [154]
Silica (SiO2) 20 nm Ethylene glycol 36 ml/h [155,156]
5 nm Ethylene glycol 22 ml/h [157]
Silicon (Si) 3 nm 1-Octanol 0.1 ml/h [158]
Zirconia (ZrO2) 410 nm (1450 1C) Ethanol+0.5% dispersant 3.3 ml/h (2 h) [159]
410 nm (1500 1C) Ethanol+0.5% dispersant 0.36 ml/h (153 s for 100 [160]
layers)
200 nm Butyl acetate+ethanol 0.6–45 ml/h (0.2 g/h) [117]
Zirconia+alumina 500 nm (Al2O3), 400 nm Glycerol (for alumina), olive oil (for 0.25–250 ml/h [119]
composite (Al2O3+ZrO2) (ZrO2) (1200 1C) zirconia)+1 wt% dispersant

100 100
y = 0.0023x0.9959
Film thickness in micrometers

10 1 2
Deposition rate, µm/h

10

1 3
6
4 5 7 1
0.1 8

10
9 11
0.01
0.1
1990 1995 2000 2005 2010
10 100 1000 10000 100000
Year
Film thickness, nm
Fig. 5. Thinnest films produced by electrospraying over the last decade:
Fig. 6. Deposition rate vs. final film thickness.
1. Hall and Hemming (1992) [161] (photosensitive resist); 2. Chen et al.
(1996) [45] (ZrO2); 3. Denisyuk (1996) [162] (plastic); 4. Hoyer et al. (1996)
[163] (celulose acetate); 5. Sobota and Sorensen (1997) [151] (MoS2); 6. 3.2. Micro- and nano-particle production
Heine et al. (1998) [150] (CdSe); 7. Rhee et al. (2001) [95] (MgO); 8.
Matsushima et al. (2004) [99] (SnO2); 9. Saf et al. (2004) [143] (organic); Fine particles of size smaller than 10 mm are, for
10. Dam et al. (2005) [164] (MEH-PPV); 11. Rietveld et al. (2006) [132]
(PVDF).
example, applied for ceramic coatings, paints, or emulsion
production, as powder in the cosmetic or pharmaceutical
industries, or as toner in electro-reprographic systems.
control at the nanometer scale. The electrospray method is Nanoparticles may also be deposited to create thin solid
also a very efficient process because at least 80–90% of films. Conventional methods of synthesis of nanoparticles
base material can be deposited onto the substrate. in the gas phase for electronic, optical and magnetic
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
applications were reviewed by Kruis et al. [165] with only
minor attention to electrospraying.
Electrospraying was also successfully tested as a tool for
fine particle production [16,166–185]. A diagram of the
steps involved in micro- and nano-particle production is
shown in Fig. 7. The solvent from the electrosprayed
droplets evaporates, and the remaining solid material
forms a fine powder. The particles are produced from a
solution or suspension of a solid material. For the solution-
based droplets, the remaining substance crystallizes form-
ing solid particles. When a suspension is used for powder
production, the nanosized particles suspended in the
solvent form a tight cluster after the droplets dry. The size
of such particles can be controlled by changing the
concentration of the dissolved or suspended substance.
Electrospraying allows the generation of particles of small
size, down to 10 nm, and of high monodispersity
[27,106,182,184,185]. Fig. 8 illustrates the size of the
smallest particles produced by electrospraying over the
past decade. At the present time, the size of smallest
particle reported is 4 nm [182]. The materials from which
the micro- and nanoparticles were produced via electro-
spraying, the size of the obtained particles, and the
production rate are summarized in Table 4. From this
table we can see that the production rate of the particles is
usually in the range of 105–104 particles/s for particles of
about 10 mm, increasing to 1010–1011 particles/s for parti-
cles smaller than 10 nm.
The cone-jet mode, most frequently used for the
production of powders, operates only over limited voltage
and flow-rate ranges. Any change in physical properties
of the liquid—due, for example, to temperature variation—
may also change this mode to another, or shift the
operating range to other values of voltage and flow
rate. The size and monodispersity of the droplets
and particles can also undergo unacceptable change.
The problem was solved by using pulsed or ac voltage
superimposed on dc-bias voltage (ac/dc excitation)
[188–195]. When the frequency of the ac voltage is pro-
perly tuned, the jet disintegrates into a stream of
droplets of uniform size. The size of the droplets can be
controlled by the dc-bias and ac-voltage magnitudes, ac
frequency, and flow rate of the liquid. The production rate
of particles can be controlled by the flow rate and
excitation frequency.
Fig. 7. Steps of micro- and nanoparticle production via electrospraying.
205
An electrospraying system using ac/dc excitation was
first proposed by Vonnegut and Neubauer [196]. The
process of drop formation was controlled by an ac voltage
at 60 Hz applied to the capillary. Later, ac/dc electrospray
systems were developed by Sample and Bollini [188],
Bollini et al. [189], Sato et al. [190–194], and Balachandran
et al. [195]. The synchronous mode of droplet generation
operates within a limited range of flow rate and ac
frequency. Low viscosity of the liquid to be sprayed is
favorable to synchronous generation over wider frequency
and flow-rate ranges [29,30,197]. An increase in the flow
rate allows droplet generation with higher frequency.
From the reviewed literature it can be concluded that
electrospraying allows production of fine solid particles
over broad size range, from about 100 mm down to a few
nanometers, and of small standard deviation. The produc-
tion of such particles via electrospraying is easier than by
other methods. This technique is particularly useful for the
production of metal oxides or ceramic powders from the
liquid phase (cf. Table 4). The size of the droplets and
particles can be controlled by flow rate of the liquid, the
voltage, or by the frequency of ac excitation. It was
reported by many authors that electrospraying allows fine
powder production without significant change in chemical
100
1
Particle size in micrometers
10
1
0.1 2
0.01 4 7 9
5 6 8 11
10
3
0.001
1990 1995 2000 2005 2010
Year
Fig. 8. Finest particles produced by electrospraying over the last decade.
1. Verma et al. [186] (sodium silicate); 2. Meesters et al. [170] (DOP);
3. Chen et al. [182] (sucrose); 4. Lenggoro and Okuyama [185] (ZnS);
5. Dudout et al. [184] (CaCl2); 6. Choy and Su [39] (CdS); 7. Lenggoro et
al. [173] (PSL); 8. Nakaso et al. [177] (SiO2, TiO2, ZrO2); 9. Erven et al.
[174] (Pt); 10. Suh et al. [187] (HAuCl4); 11. Basak et al. [27] (FeO).
 ARTICLE IN PRESS
206 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219

Table 4
Electrosprayed materials used for micro- and nanoparticle production

Material (precursor) Solvent Particle size (droplet size) Production rate (flow rate, capillary i.d.) References

C12H22O11 (sucrose) Water 1–20 mm (20–600 mm) 4  105 particles/s [166]

Water (10 ppm-10%)+nitric acid 4 nm–0.18 mm 2.5  1010 particles/sa (3–18 ml/h, 81 mm) [182]
(0.04–1.8 mm)
CaCl2 Ethanol 8 nm (5 ml/h, 100 mm) [184]
CdS (CdCl+CH4N2S) Water 10 nm (10–30 ml/h) [106]
CeO2 Ethanol+diethylene glycol butyl 10–100 nm (1.45 mm) 3.5–8.7  107 particles/sa (0.2–0.5 ml/h, [90]
(Ce(NO3)3  6H2O) ether 460 mm)
Dextrin Water 100–150 mm (14.5 l/h for 100 nozzles, 53 mm) [167,169]
DOP Ethanol 80–300 nm (1.3–1.5 mm) 108–1010 particles/s (0.1–30 ml/h, 200 mm) [16,170,171]
ethylene glycol 80–300 nm (1.3–1.5 mm) 108–1010 particles/s (0.1–30 ml/h, 200 mm) [16,170,171]
FeO [Fe(NO3)3] Ethanol or water 6–40 nm (0.6–5.4 ml/h—water, 12–144 ml/h—ethanol, [27]
160 mm)
NaCl Water 1–20 mm (20–600 mm) 4  105 particles/s [166]
PSL Water+methanol+surfactants, or 21 nm (o0.1 mm) 5.3  1010 particles/sa (0.1 ml/h, 100 mm) [173]
methanol+surfactants+ammonium
acetate (0.2–20 mM)
Pt (0.2 wt% Ethanol 8-12 nm (0.42 mm) 6  107 particles/s (8 ml/h, 60 mm) [174]
H2PtCl6  6H2O
SiO2 Water+methanol+surfactants, 109 nm (o0.1 mm) 5.3  1010 particles/sa (0.1 ml/h, 100 mm) [173]
methanol+surfactants+ammonium
acetate (0.2–20 mM)
Ethanol+water mixture 50 nm (1 mm) 3.2  108 particles/sa (0.6 ml/h) [175]
Ethylene glycol 20 nm (0.11 ml/h, 200 mm) [176]
SiO2 (Si(OC2H5)4) 1-Butanol 10–40 nm (0.02 ml/h, 300 mm) [177]
SnO2 (Sn(OC4H9)4) Ethanol 2.4–5 mm (5–20 mm) (5–20 ml/h) [179]
TiO2 (Ti(OC3H7)4) 1-Butanol 10–40 nm (0.02 ml/h, 300 mm) [177]
TiO2 (Ti(OC4H9)4) Ethanol 2.4–5 mm (5–20 mm) (5–20 ml/h) [179]
1-Butanol 100 nm-4 mm (5.7 mm) 2.9  107 particles/sa (1–9 ml/h) [178]
Water glass Water 65 mm 5  102 particles/s (3.6–5.16 ml/h, 170 mm) [168]
ZnS Ethanol (0.0025–0.2 mol/l) 20 nm (0.125–0.64 mm) 3.2  108–1.3  1010 particles/sa [172,185]
(Zn(NO3)2+SC(NH2)2) (0.05–0.16 ml/h, 400 mm or 900 mm)
ZrO2 (Zr(OC4H9)4) 1-Butanol 100 nm–4 mm (5.7 mm) 2.9  107 particles/sa (1–9 ml/h) [178]
1-Butanol 10–40 nm (0.02 ml/h, 300 mm) [177]
a
Production rate estimated from the flow rate and mean diameter of the droplet.

composition and physical properties of the material to be
sprayed. This process seems to be useful for industries
requiring fine powders of material that must remain
unaffected during the production process.
3.3. Electroencapsulation
Encapsulation is a process for capturing solid particles,
liquid droplets, or a gaseous bubble as a core material in a
solid or liquid envelope (shell) made of another material.
Encapsulation can be regarded as the conversion of liquid
phase to powder particles having the physical and chemical
properties of the shell for easier transport and processing of
the core material. Under certain conditions (heating,
diffusion, or shell dissolution), the core material can be
released from the shell.
Conventional techniques of micro- and nano-encapsula-
tion include: sol–gel encapsulation [198], polymerization
or atomization of an emulsion of core in shell material
for shell hardening [199], coextrusion, a process of
simultaneous spraying of two liquids using two coaxial
nozzles [200], fluidized-bed mixing of core material (larger
particles) with dispersed particles of a size of about 1 mm
which cover the core and are subsequently stabilized by
spraying a coating formulation [201], coacervation, which
is a process of two immiscible soles separation after
addition of an electrolyte [202], and rapid expansion of a
solution of a core and shell materials in a supercritical fluid
(CO2) [203–205]. Solid envelopes are obtained by subse-
quent solidification of the shell material, for example, by
solvent evaporation or chemical reactions.
Regardless of the method of encapsulation, the process
can be effective when the two materials forming a capsule
are immiscible but are mutually wettable, the core material
has higher surface tension, and the two droplets are about
of the same size [206].
Employing electrical forces can increase the effectiveness
of micro- and nano- encapsulation. This process is called
electro-encapsulation. The following electro-encapsulation
techniques may be found in the literature:
 Impacting of two oppositely charged droplets (Fig. 9a)
[206]: Both of the droplet’s streams are emitted from two
separated capillary nozzles maintained at opposite
potentials, one of the capillaries at positive, and the
other at negative. The droplets collide due to Coulomb
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
Fig. 9. Schematics of various electro-encapsulation processes: (a) impacting of two oppositely charged droplets; (b) electrospraying/evaporation of
colloidal suspension; (c) electrospraying/gelatinization of colloidal suspension; (d) electro-coextrusion; and (e) structure of microcapsule.
attraction, forming a capsule via submerging the droplet
of higher surface tension within that of smaller surface
tension.
 Electrospraying/evaporation of colloidal suspension
(Fig. 9b) [207,208]: The suspension is electrosprayed
and next the shell is solidified by solvent evaporation.
The surplus solvent of the solution evaporates,
forming a hardened envelope. Electro-encapsulation
via spraying of colloidal suspension requires low
concentration of the particles in order to generate
droplets with only one particle inside. Usually a
surfactant is added to the colloidal suspension prepared
for electrospraying to prevent particle coagulation,
aggregation, or flocculation.
 Electrospraying/gelatinization of colloidal suspension
(Fig. 9c) [191,209]: A suspension of core material is
electrosprayed into a bath with gelatinizing or poly-
merizing agent. The agent forms a hard envelope on the
core material. Ultraviolet light has also been tested for
surface polymerization in order to form hardened
envelope.
 Electro-coextrusion (Fig. 9d) [25,210–216]: The process
is a simultaneous spraying of two different liquids from
two coaxial capillaries. In this case, the capillaries are at
the same potential. The core liquid flows from the
central capillary, and the envelope liquid flows through
the annular nozzle between the capillaries. Electro-
coextrusion allows spraying of core liquid of high
207
resistivity, but only if the envelope has sufficiently
high conductivity. The opposite arrangement, i.e., a
conducting core liquid and dielectric envelope, is also
feasible [210].
Electro-encapsulation was also used for micro- and
nano-composite materials production. For example, the
core material (acrylic powder) was charged with an
electrostatic gun, while envelope powder was suspended
in an ethanol+water mixture, and electrosprayed [201].
The droplets were deposited onto acrylic particles due to
Coulomb attraction and, after drying, composite particles
built from core acrylic powder and dry envelope were
formed.
Encapsulation permits the protection of environment-
sensitive core materials, such as cultures, vitamins,
flavours, dyes, enzymes, salts, sweeteners, acidulates,
nutrients, or preservatives. Oil-in-water or water-in-oil
emulsions are most frequently used as a carrier for such
ingredients [210,217,218]. The shell may consist of starch,
gums, fats, waxes, oils, dextran, polysaccharides, proteins,
or glucoses. For their properties, micro- and nano-capsules
are applied in pharmaceutical, cosmetic, or food industries.
For example, by encapsulation, a drug used as a core
material can be targeted and released in a controlled
manner.
The electro-encapsulation process was used in biotech-
nology, for example, for the capturing of living cells
 ARTICLE IN PRESS
208 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
in polymer beads (for example, sodium alginate)
[209,216,219–224]. It has been reported by the authors
that the viability of the living cells was over 80–90%. In
pharmaceuticals production, various drugs or antibodies
have been encapsulated in polyethylenoxide, dextrose,
starch, sucrose, lactose, poly-lactic-co-glycolic acid, or
poly-lactic acid [31,225–227]. Poly(lactide) and poly-
lactic-co-glycolic acid are used most frequently due to their
biocompatibility and biodegradable properties, solubility
in many organic solvents, and ease of manipulation of their
physical properties.
In the literature, there are also reports on applications of
microcapsules in agrochemistry used to control insecticides
or pesticides with higher efficiency and a smaller amount of
an active agent, thereby reducing the environmental
pollution [228]. In the textile industry, durable fragrances
added to textile and skin softeners using microcapsules
have been demonstrated by Nelson [229].
Capsules can also be generated synchronously by pulsed
or ac-voltage excitation [191,209,230]. The capsules can be
smaller than 1 mm and uniform. Application of alternating
current [230] allowed the production of capsules of zero net
charge with a frequency of 20 kHz. An advantage of ac
excitation is that it does not require two capillaries of
opposite potentials for capsule production. In contrast to
dc electro-encapsulation, by which only polar liquids
having free electric charge can be dispersed, the ac
encapsulation technique also allows the use of dielectric
liquids based on organic solvents.
Various types of capsules (core and shell materials)
produced via electro-encapsulation are summarized in
Table 5. Fig. 10 illustrates progress in the electro-
encapsulation technology leading to a decrease in the
size of microcapsules produced over the past decade. At
the present time, the smallest microcapsules reported are
150 nm. Such capsules were produced by Loscertales et al.
[211] using two coaxial nozzles.
Many authors have shown experimentally that electro-
encapsulation offers several advantages over conventional
methods used for capsule production. Most of the authors
claim that this process does not disturb physical and
chemical stability of the core material. Electro-encapsula-
tion thus appears to be promising in the pharmaceutical,
cosmetics, and food industries. In biotechnology, where
low-temperature processes that preserve heat-sensitive
materials are needed, electro-encapsulation also has been
found to be very useful [215,230,231]. The shortcoming of
this method is its low throughput, but for effective and
rapid mass production of microcapsules, simultaneously
operated capillary nozzles can be used.
3.4. Electrospray forming and direct writing
Spray forming is a process by which fine, semi-solid
droplets of a material to be deposited are placed layer-by-
layer onto a substrate to form a bulk product or thick
coating. During this process, the droplets impacting a
surface mix with previously deposited layer, penetrating its
pores to form a tight product. The result is similar to a
sintering process [233]. A comparison between spray
forming technology and conventional casting was per-
formed by Chaudhury et al. [234], Mesquita and Barbosa
[235], Srivastava et al. [236], and Yu et al. [233]. The
authors concluded that the spray-formed materials can be
less porous, and their microstructure can be more uniform
that those obtained via other methods, for example,
casting. A bulk product is cooled faster without shrinkage,
and strength within the material is relatively low. Spray
forming from nanometer droplets additionally offers the
possibility of production of alloys of controlled composi-
tion and microstructure down to molecular layers. Simul-
taneous spraying of metal droplets and ceramics can be
used for micro- or nano-composite material production. It
was noticed that the particles in the matrix are distributed
uniformly, and the hardness of the spray-formed composite
or alloy can be relatively great [234–236]. An advantage of
spray-formed products is that the composition can be
changed on demand during the course of production.
Spray formed composites were, for example, produced
from alumina and titania [234,237] components. Drop-by-
drop, bulk materials were produced, for example, by Wang
et al. [176] who applied non-electrified ink-jet printing
using a suspension of micrometer ceramic particles. The
height of the prism formed by this method was 10 mm.
Electrospray forming is a process of layer-by-layer
deposition of electrosprayed droplets of a solution or a
colloidal suspension which are continuously dried or
solidified to form a thick coating or bulk product. In
conventional spray forming systems, 40–50% of the
material is oversprayed [238], but in the electrospray
forming process the efficiency can exceed 80%.
Electrospray forming was proposed by Chen et al. [239].
The authors produced a SnPb coating by agitating an
electrified jet with a piezoelectric transducer tuned to
10 kHz. The droplets were charged by induction at the
instant they detached from the cone.
The electrospray production of composite layers from
crystallites of different materials was demonstrated by
Diagne and Lumbreras [125] (SnO2+LaOCl for CO2 gas
sensors), Nguyen and Djurado [51] (ZrO2:Y2O3 for fuel
cells), and Choy [106,126] (Y2O3:Eu) (cf. Table 2). Multi-
layer films from different materials were deposited on a
substrate by Choy et al. [46] and Choy [126] for fuel cell
production, Wei and Choy [92] as a buffer layer for
superconducting YBa2Cu3O7x film, Yoon et al. [81] for
deposition a double-layer cathode of LiMn2O4-coated
LiCoO2 for lithium batteries, and Miao et al. [114]
(ZrO2+SiC) as a ceramic coating. Such films were
deposited in consecutive processes by changing the pre-
cursor solution. Recently, the electrospray method was
utilized by Balasubramanian et al. [119] using two coaxial
capillaries for the production of composite ceramics
from an alumina–zirconia mixture (cf. Table 3). Deotare
and Kameoka [175] have fabricated nano-composite
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219 209

Table 5
Microcapsules produced by electrospraying

Core material Shell material Capsule size Method References

Astrocytoma cells Poly-dimethylsiloxane (PDMS) 10–40 mm Electro-coextrusion [216]

(1321N1) (33 mm mean)
Bacteria in poly(vinyl 0.25–0.4 mm Spraying a suspension [223]
alcohol)+water fibers, 1–2 mm
capsules
Bovine serum albumin 1–4% Poly(lactide) in 1,2-dichloroethane or 4.77 mm Spraying an emulsion [227]
dichloromethane+acetone
Poly (D,L-glycolide-co-lactide) (PLGA) 20 mm Spraying an emulsion [231]
Cells Sodium alginate 160–180 mm Spraying into a bath [219]
Enzymes Sodium alginate 100 mm Spraying into a bath, nozzle-to- [224]
extractor system
Ethanol Olive oil 1 mm Electro-coextrusion [215]
Ethylene glycol Photopolymer (Somos 6120-DuPont) 0.15–10 mm Electro-coextrusion [211]
Olive oil 8 mm Electro-coextrusion [215]
Somos oil 25–60 mm Electro-coextrusion [25]
Gas Water 70 mm Electro-coextrusion [213]
Glycerol Butyl phthalate 2–20 mm Impacting of oppositely charged [206]
droplets
Hepatocytes HepG2, Sodium alginate (1.5%) +NaCl 440–830 mm Spraying into gelling bath CaCl2 [209]
C3A (2  106 or 4  106 (0.9%)+water (solvent) (1.67%)+NaCl (0.9%)+HEPES
cells/ml) (0.26%)+water
Kerosene Water 500 mm Electro-coextrusion [212]
Water 100 mm Spraying within a bath (nozzle at the [212]
bottom of vessel)
Polyurehane 100 mm Spraying within a bath (nozzle at the [191]
bottom of vessel)
Medicine Bovine serum albumin (5, 20 and 50/ml) in 10–20 mm Surface polymerization [232]
10vol% ethanol/water mixture
Oil (66%)+water Cocoa butter 9–21 mm Electro-coextrusion [210]
(33%)+emulsifier
Paclitaxel (a drug) (up to Poly-lactic-co-glycolic acid 1–5 mm Spraying an emulsion and drying [208]
10%) (2–16 wt%)+surfactant (0–16%)+organic 0.2 mm
salts (0–2 mM)+acetonitrile (@0.1 ml/h)
Silicone oil Glycerol Microns Electro-coextrusion [214]
Tributyl phosphate Olive oil 4 mm Electro-coextrusion [215]
Triethylene glycol Olive oil 1–8 mm Electro-coextrusion [215]
Water Olive oil 0.15–10 mm Electro-coextrusion [211]
Sunflower oil 25–60 mm Electro-coextrusion [25]
Water (50%)+sugar Cocoa butter 12.4–22.5 mm Electro-coextrusion [210]
(49.5%)+colorant
(0.5%)

hemispherical cups from a blended polymer–sol–gel solu-
tion of SiO2 and polyvinylpyrrolidine (PVP) in ethanol/
water (0.5/0.5) mixture. The SiO2 nanocups were 50 nm in
size. An example of the production of composite material
via layer-by-layer electrospray deposition of two materials
is shown in Fig. 11.
In electrospray forming, the particles are of the same
size, and have similar thermodynamic states. This feature
offers significant advantages in reduction of the number
and size of voids and cracks in the bulk product.
Simultaneous, layer-by-layer or drop-by-drop deposition
of solutions of materials of different properties allows
composite bulk materials having novel and unique proper-
ties to be formed.
Direct writing is a maskless process of drop-by-drop
deposition of a material in a liquid or semi-solid phase to
draw a pattern on a substrate. The pattern can be directly
printed under computer control by moving the substrate on
an x–y table. The electrospray technique seems to be ideal
tool for this goal, because it is a low-cost, flexible, and
high-speed process which, additionally, can trace patterns
of higher resolution compared to ink-jet printing or
conventional lithography. In contrast to traditional ink-
jet printing techniques, in which the droplet size is about
twice of the nozzle diameter, the electrospray process can
produce droplets at least an order of magnitude smaller
than the nozzle size. Thus, using coarser nozzles prevents
them from clogging, but at the same time, the droplets can
be of micrometer size. A schematic of direct writing using
electrospray droplets is shown in Fig. 12a.
Experiments with electrospray direct writing on solid
surfaces were carried out by Jayasinghe et al. [155,240]
 ARTICLE IN PRESS
210 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219

using silica suspension in ethylene glycol and alumina
suspension in ethanol. The silica layer was deposited onto a
quartz glass, and alumina on a polymer substrate. The
mean diameter of the deposited relics was between 4 and
8 mm. Wang et al. [160], composed a 5 mm long and 100 mm
thick wall by depositing 100 layers build from 0.41 mm
zirconia particles. The smoothness of the surface was better
than 10 mm. The lines produced by Wang et al. [156] from
SiO2 suspension in ethylene glycol were 80 mm in width.
Recently, Lee et al. [241] applied a direct writing technique
for the production of miniature spiral-type inductors by
depositing silver nanoparticles suspended in ethylene glycol
onto a polyimide substrate. The line width was about
100 mm, and its thickness 100–300 nm. The printing velocity
was 10 mm/s. Nanometer-thin trace was produced by Park
et al. [158] using 3 nm Si particles suspended in 1-octanol.
The line width traced with a speed of 10–20 mm/s on a SiO2
layer was about 700 nm. A lattice of individual Ni dots of
the size of 1 mm was deposited by Ishida et al. [153]. These
1000
1 Fig. 12b. The authors deposited Au or SiO2 particles of
Capsule size in micrometers
examples demonstrate feasibility of deposition of various
structures on a substrate using electrospraying.
The printing quality was improved via placing a particle
concentrator in the form of a sharp needle under the
dielectric substrate co-axially with the capillary nozzle.
This method was developed by Jayasinghe and Edirisinghe
[87,89]. The concentrator was grounded or maintained at
high potential of polarity opposite that of the droplets. In
such a configuration, the electrode attracts the droplets and
helps to converge their trajectories onto a target point on
the substrate.
Another method of direct writing was developed by
Krinke et al. [242]. The authors deposited charged particles
on an oxidized silicon substrate directly from the gaseous
phase. The pattern to be deposited was drawn via contact
charging with a sharp needle maintained at high potential.
The charge remaining on the non-conducting surface
attracted oppositely charged ions from the surrounding
gas. Single charged indium particles of diameter of 30 nm
were deposited by this way to form lines of about 100 nm in
width on the substrate. Lenggoro et al. [243] have modified
this method by using electrospraying as a source of
particles to be deposited. This process is illustrated in

100 about 10–30 nm in size on a silicon/silicon oxide substrate.

2 4
3 11
5 7
10
8 12
9 The line width was about 100 nm. An ‘‘inverse pattern’’
1 10
13
6 particles was the same as that of the pattern on the
0.1
1990 1995 2000 2005
Year
Fig. 10. Smallest microcapsules produced by electro-encapsulation over
the last decade: 1. Sakai et al. [212] (kerosene/water); 2. Sato et al. [191]
(kerosene/polyurethane); 3. Ganan-Calvo [21] (gas/water); 4. Watanabe et
al. [224] (enzymes/sodium alginate); 5. De et al. [201] (acrylic powder/
fluorescent particles); 6. Loscertales et al. [211] (ethylene glycol/oil); 7.
Lopez-Herrera et al. [25] (ethylene glycol/oil); 8. Bocanegra et al. [210]
(oil+water/cocoa butter); 9. Yeo et al. [230] (water/PLA polymer); 10. Xu
et al. [227] (bovine serum albumin/poly-lactide); 11. Xie and Wang [231]
(bovine serum albumin/PLGA); 12. Marin et al. [214] (silicone oil/
glycerol); and 13. Mei and Chen [215] (ethylene glycol/olive oil).
The pattern was drawn with a stainless steel needle at high-
potential gliding over the substrate with zero force
imposed. The substrate was next subjected to electro-
sprayed droplets of polarity opposite that of the pattern.
was also produced by the authors. When the polarity of the
substrate, and additionally an opposite potential was
2010 applied to the substrate, the particles were preferentially
deposited off the pattern, leaving a particle-free surface in
the location where the pattern was drawn.
Although the achievements of electrospraying using
spray forming and direct writing are less spectacular than
those in fine particle and thin-film production, these few
reports have opened a new route of electrospraying to
nanotechnology, because the process is cheap, and more
environmentally friendly than conventional techniques
which use toxic substances to draw a pattern by removing
unwanted material from the surface.

Fig. 11. Schematic of the production of composite material using layer-by-layer electrospray deposition.
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
Fig. 12. Schematic of direct writing: (a) one-step process using electrospray droplets and (b) two-step process: ion deposition with a sharp needle followed
by nanoelectrospray.
3.5. Biotechnology
Biotechnology refers to the application of biological
processes on molecular level for the fabrication of new
materials for medicine, the food industry, the cosmetic
industry, or for the improvement of conventional techno-
logies. These processes require new technical, physical, and
chemical tools for their manipulation. New such tools
based on electrospraying have been developed in recent
years. The experimental work concerning electrospray
applications in medicine and biotechnology are summari-
zed in Table 6.
In the 1990s, electrospraying was tested as a means for
generating on-demand particles. Initially, electrospray
nebulisers were developed for testing the efficiency of
medicine inhalation [244–246]. The authors emphasised
that the electrospraying technique is very simple to operate
and can produce particles in the ‘‘respirable’’ size range
without disturbing the physical and chemical stability of
the drug. The ‘‘respirable size range’’ refers to particles of
aerodynamic size between 2 and 5 mm. Such particles are
effectively transported to lower airways in adults [247–251].
Smaller particles have been produced in recent years.
Submicron drug particles (smaller than 400 nm) have the
advantage that they are not detected by the human immune
system and can be effectively transported via the blood
211
vessels to a target human organ [31]. Electrospraying has
also been tested for the production of biodegradable drug-
carrying agents, for example, as nanoparticles and micro-
capsules from poly-lactic-co-glycolic acid (PLGA) [208].
For investigation purposes or for medical diagnostics,
biologically active substances, such as enzymes and
antibodies have also been electrosprayed. For example,
antibodies electrosprayed by Moerman et al. [252–254]
formed spots of diameter of 130–350 mm and remained
biologically active after this process. The authors noticed
that electrospraying in the stable cone-jet mode allowed for
an accurate and reproducible dispersion of liquid without
splashing, contrary to other deposition techniques such as
piezodispensing or contact-printing. Biologically active
proteins (a-lactalbumina) produced by Uematsu et al.
[255] for protein-based biomaterials, biosensors, and
biochips were also unaffected by the high potential used
for electrospraying. A fine porous (reticular) structure
having pores in the size range 40–600 nm was obtained.
Pareta et al. [232] and Xu et al. [227] also have confirmed
that the high voltage used for electrospraying a suspension
of bovine serum albumin molecules for the encapsulation
of drugs does not degrade the molecules. Thundat et al.
[256] applied electrospray to the deposition of DNA
molecules onto a gold substrate for investigation under a
scanning tunnelling microscope. The sample was uniformly
 ARTICLE IN PRESS
212 A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219

Table 6
Applications of electrospraying in biotechnology

Material to be sprayed Application Solvent Flow rate References

(deposition time)

Antibodies Biologically active micrometer Water, or ethylene glycol+water mixture 0.36–4 ml/h [253,254]
spots
Aspirin Medicine production 300 nm–20 mm 0.36 ml/h [251]
Biomolecules Analytical chemistry 3 nm 3.6 ml/h [180]
Calcium phosphate Implants Ethanol or butyl carbitol 0.5–2 ml/h (60 min) [146–148]
DNA Samples for scanning tunnelling (2–6 s) [256]
microscopy
Enzymes Biologically active micrometer Water, or ethylene glycol+water mixture 0.36–4 ml/h [253,254]
spots
Hydroxyapatite Implants for bone repair Ethanol or methanol 6–10 ml/h [149,259]
Insulin Medicine delivery Ethanol+water (4 vol%) 0.23 mg/h (150 mm [244]
thickness)
Methylparahydroxy- Medicine delivery Ethanol 1–3 ml/h [250]
benzoate (0.5–3%)
Paracetamol Medicine delivery Ethanol (7.5 or 10 wt%) 1.2–4.2 ml [245]
Poly-lactic-co-glycolic Drug-carrying agent Acetonitrile+surfactant+drug+organic salts 0.1 ml/h [208]
acid
Poly(D,L-lactide- Tissue repair Chloroform, ethyl acetate, methylene chloride, 0.01–10 ml/h [266]
coglycolide acetone, trifluoroethanol, or acetonitrile
Siloxane Bio-compatible self-supporting Ethanol+HCl 3.6 ml/h [258]
scaffold structure
Starch Food industry De-ionized water or ethanol 0.2–0.29 ml/h [268]
(2–4 h)
Zirconia Scaffold for bone regeneration Ethanol+0.5% dispersant 3.3 ml/h (2 h) [159]
a-Lactalbumina Protein-based biomaterials Water (10 min) [255]
(0.4–1.8 mg/ml) (a-lactalbumina//Al//
poly(ethylene terephthalate))
a-Lactose monohydrate Drug production Polyvinylpyrrolidone+de-ionised water 10, 15, or 20 ml/h [181]
(6, 8 or 10 wt%)

distributed with isolated strands, and the number of
molecular aggregates was lower than for standard electro-
deposition or drop evaporation techniques.
In recent years, electrospraying and electrospinning were
tested as tools for the production of scaffolds for tissue
regeneration and for bone repairing. For example, calcium
phosphate coatings on endosseous titanium implants were
produced by Siebers et al. [146], and Leeuwenburgh et al.
[147,148,257]. The properties of the coating were similar to
those produced by ESD and RF magnetron sputtering,
although the two coatings differed in roughness, Ca/P
ratio, and molecular composition. The coatings were
amorphous, irrespective of the initial Ca/P solution ratio,
but they crystallized into different crystalline phases after
annealing at 650 1C. Self-supporting scaffold structures
with high macroporosity free of micro- or mesopores
produced by Jayasinghe and Sullivan [258] using electro-
spraying were similar to natural structures. From NMR
investigations it was determined that electrospray-pro-
duced structures had a degree of network condensation of
79% that was higher than for those obtained by the sol–gel
method (66–70%). Bioceramic scaffolds based on zirconia
for host tissue regeneration with reduced number and size
of microcracks and micropores in struts (as compared to
the slurry-dip coating technique) were produced by Chen
et al. [159]. The mechanical strength and Young’s modulus
of the scaffold were higher. Huang et al. [149] produced
hydroxyapatite relics on glass from 50 to 80 nm nanopar-
ticles suspended in ethanol for the formation of implants
for bone repair. The relics produced by electrospraying
were able to support the growth of primary human
osteoblast cells. Hydroxyapatite film was also prepared
by Kim et al. [259] using sol–gel assisted electrostatic spray
deposition with subsequent annealing at a temperature of
500 1C for 30 min. The method is potentially applicable to
orthopedic and dental implants manufacturing, production
of scaffolds for bone growth, or the creation of micro- and
nano-scale surface morphology for a favorable cell
response. Electrospun fibers were tested also for nerve
regeneration by Bini et al. [260], and Yang et al. [261],
blood vessel reconstruction by Ma et al. [262], Xu et al.
[263,264], and muscle cells proliferation by Mo et al. [265].
Electrospray experiments in medicine and biotechnology
often use poly-lactic-co-glycolic acid (PLGA) or poly
(D,L-lactide-coglycolide) (PLG) due to their high biocom-
patibility, low toxicity and immunogenicity, solubility in
many organic solvents, and ease of manipulation of their
physical properties such as permeability, porosity, and
crystallinity and biodegradability [208,266]. PLG is also
used for drug encapsulation, because the drug can be easily
released due to diffusion and erosion of the polymer.
Water, water–methanol, or water–ethanol mixtures are
 ARTICLE IN PRESS
A. Jaworek, A.T. Sobczyk / Journal of Electrostatics 66 (2008) 197–219
the most frequently used solvents for biotechnological
applications. In tissue engineering the poly(3-hydroxybu-
tyrate-co-3-hydroxyvalerate) (PHBV) is used because it is
biodegradable, biocompatible, inexpensive, and its chara-
cteristics are similar to conventional thermoplastics [267].
In the food industry and in pharmaceutical applications,
starch is frequently used because products based on it are
tasteless, odorless, colorless, and are non-toxic. Tradition-
ally, starch dissolution was deposited by casting or
extrusion, but Pareta and Edirisinghe [268] applied an
electrospraying technique for starch film deposition.
4. Conclusions
This review provides a summary of current achievements
in electrospraying in its route to nanotechnology. Electro-
spraying is a versatile tool for liquid atomization that has
the advantage of uniform droplet generation from in-
expensive equipment. Electrospray devices can operate
under atmospheric conditions, and the rate of particle
production is easy to control via voltage and flow rate.
Electrospraying is a single-step, low-energy, and low-cost
material processing technology, which can deliver products
having unique properties. It has been shown in this paper
that electrospraying can be effectively used for micro- and
nano-thin-film deposition, micro- and nano-particle pro-
duction, and micro-and nano-capsule fabrication.
Our brief review shows that interest in industrial and
laboratory applications of electrospraying, which allows
droplets smaller than 1 mm to be generated, has grown over
the last decade. It has been prompted by the need for new,
more effective techniques which will allow automatic
control of droplet size and charge, as well as generation
on-demand particles, especially in nanotechnology. In
recent years, many companies have sought versatile
methods for direct writing of electrically conducting ink,
containing nanosized particles of silver or carbon to
pattern thin, electrically conducting circuits. This process
should be cheap, and more environmentally friendly than
conventional techniques [269]. It seems plausible that
electrospraying will be an ideal tool for this goal. It is
expected that this technique will find many new applica-
tions in various industries due to its low investment, low
operating costs, and high versatility.
Electrospray operation at atmospheric conditions has
the advantage that uniform micro- and nano-thin-film
deposition of large areas is easily controlled with respect to
deposition rate and film thickness. In micro- and nano-
particle production, electrospray allows particles of uni-
form size over a wide size range to be produced.
Electrostatic micro- and nano-encapsulation utilizing
electrospray will provide capsules smaller than a micron
from a wide spectrum of core and shell materials. It can be
envisioned that this technique will increasingly be applied
in materials technology for the production of nano-
composite materials or materials having on-demand
properties, as well as in biotechnology as a new research
213
tool for the production of medicine. In recent years,
electrospraying has been successfully tested as a low-cost
tool for composing small and complex structures via spray
forming and direct writing.
Although there are still a number of challenges to be
faced before commercialization will be possible, advances
in electrospray applications in nanotechnology and bio-
technology will certainly continue in near future, and new
achievements in this field can be expected.
We have attempted to consider a wide spectrum of
relevant refereed papers, but the Authors feel that the
literature cited in this paper is by no means complete.
However, we believe that it should provide the reader
with the development and application of electrospraying,
particularly in nanotechnology.
Acknowledgments
The paper is supported by Polish Ministry of Science and
Higher Education within the Project no. 4078/T02/2007/32.
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