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Chapter

Electrohydrodynamic Processes
and Their Affecting Parameters
Sajjad Haider, Adnan Haider, Abdulaziz A. Alghyamah,
Rawaiz Khan, Waheed A. Almasry and Naeem Khan

Abstract

Electrohydrodynamic processes such as electrospinning and electrospraying

are simple, flexible, and cost-effective. Both processes use electrically charged
jet of polymer solution for the fabrication of micro- or nanofibers and micro- or
nanoparticle. Both of these electrodynamic techniques have been receiving increas-
ing attention not only in the scientific community but also in industry. These fibers
and particles offer several morphological and functional features that are suitable
for tissue engineering in biomedical applications. The main apparatus used for both
of these processes is almost the same. Both need electric voltage to induce charge
on the droplet, which at optimized electric field leads to micro- or nanofibers and
micro- or nanoparticles. Rayleigh in 1882, for the first time, theoretically estimated
the maximum amount of charge that a liquid droplet could carry to change in a jet.
This theory is now known as the “Rayleigh limit.” He predicted that a droplet on
reaching Rayleigh limit would move as fine jets of liquid. More than 100 years later,
Rayleigh limit theory was confirmed experimentally. Beside electric field there are
other operating and solution parameters that need to be optimized before we obtain
a desire product.

Keywords: electrohydrodynamic processes, cost effective, micro and nanofibers,

micro and nanoparticles

1. Electrospinning

Since the late twentieth century, electrospinning, a technology used for the
fabrication of nanofibers, has been receiving increasing attention not only in the
scientific community but also in industry. With this technique fibrous material
was conveniently prepared with fascinating properties such as ultrafine diame-
ters in the range of 10–500 nanometer (nm), high permeability, porosity, surface
area per unit mass, and small inter-fibrous pore size [1–3]. It is, therefore,
considered to be a vital scientific and commercial venture with global economic
benefits. This technology traced its legacy back to 1902 [4, 5] and 1934 [6], when
the very first patents entitled “Apparatus for Electrical Dispersion of Fluids”
and “Process and Apparatus for Preparing Artificial Over and Done Threads
from Electrically Dispersed Fluids” were registered. Since then, this process was
largely ignored until the 1990s. However, with the recent revelations by research-
ers who are associated with the field of nanotechnology mainly nanofibers,

1
Electrospinning and Electrospraying - Techniques and Applications

investigations into the preparation of nanofibers using the aforementioned

technique picked up momentum [7].
In the literature, various techniques are reported for the fabrication of nano-
materials. These include drawing-processing, template-assisted synthesis, self-
assembly, solvent casting, phase separation, and electrospinning [8–10]. With
advancement of research in nanotechnology, particularly associated with nanopar-
ticles, nanostructures, and more explicitly with the preparation of scaffolds,
electrospinning emerged as a highly developed and frequently used technique/
process. This process is favored over other techniques such as solvent casting and
phase separation, since nanofibers have high surface area to volume ratio and inter-/
intra-fibrous pores. In addition to the previously mentioned properties, it has the
advantages of being easy to use and have a low processing cost. The growing litera-
ture on electrospinning has helped this technique to pave the way for advancements
in areas like environmental protection, bioengineering, electronics, and catalysis
[11–13]. The capability of this technique to produce nanomaterials from numerous
raw materials ranging from simple natural polymers to complex materials such
composites has attracted a large number of researchers. For example, scientists have
reported a wide range of applications of electrospun nanofibers in the protection of
the environment, most importantly in water and air filtration. Subramanian et al.
[14] and Feng et al. [15] emphasized the importance of using electrospun nano-
fibers for the removal of contaminants from water, focusing on the application of
electrospun nanofibers in nanofiltration.
Furthermore, polymers with a piezoelectric effect (i.e., polyvinylidene fluoride)
can be subjected to an electrospinning technique for the fabrication of nanofiber scaf-
folds with a piezoelectric effect. Apart from the use of nanofibers in scaffolds with
piezoelectric effect, they can also be used for producing high-surface-area nanosen-
sors. Huang et al. suggested that scaffolds of the copolymer poly(lactide-co-glycolide)
(PLGA) could be used as sensing tools in both chemical and biological fields [16].
Investigators have also highlighted that sensors prepared of nanofibers might dem-
onstrate improved sensing capabilities for chemicals such as 2,4-dinitrotulene DNT,
mercury (Hg), and ferric (Fe+3) ions as compared to orthodox thin film.

Figure 1.
Scopus data showing year-wise publications in the area of electrospinning. The data is taken on February
09, 2019.

2
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

Furthermore, fluorescent polymer electrospun nanofiber optical sensors also

showed high sensitivity [17]. Ultrafine electrospun nanofiber scaffolds can also
be applied in the preparation of nanotubes, which are of prime importance in
various industries [18]. To prepare nanotubes, electrospun nanofibers are coated
with the raw material of the nanotubes, and upon the evaporation of a solvent via
solvent evaporation or the thermal degradation of the polymers, the nanotubes
are synthesized. Bognitzki et al. adopted a physical and chemical vapor deposition
technique using poly (L-lactide)(PLLA) nanofibers as a template and synthesized
polymer composite nanotubes comprised of poly(p-xylene)/aluminum metal
with a thickness of 0.1–1 mm [19]. Hou et al. prepared nanotubes with an even
smaller diameter by adopting the same technique using poly(L-lactide)(PLA) and
poly(tetramethylene adipamide)(PA) as templates [16, 20].
Electrospun nanofibers have also played a pivotal role in the area of bioma-
terials. The importance of electrospun nanofibers in the biomedical field can
be determined from the fact that numerous articles are being published every

Figure 2.
Showing Scopus data subject wise where electrospinning has been used. The data is taken on February 09, 2019.

Figure 3.
Showing Scopus data of the institutions, which are working in area of electrospinning. The data is taken on
February 09, 2019.

3
Electrospinning and Electrospraying - Techniques and Applications

year on a regular basis in high-quality journals, highlighting their significance

in biomedical engineering. Nanofiber scaffolds were also functionalized with
desired triggering groups. These triggering groups performed a significant role
in providing conducive atmosphere to the cells, which resulted in their enhanced

Figure 4.
Country-wise Scopus data of electrospinning. The data is taken on February 09, 2019.

Figure 5.
Nanofiber market to 2025—Global analysis and forecasts by material (polymer nanofiber, carbon nanofiber,
ceramic nanofiber, composite nanofiber, and glass nanofiber) and application (energy, medical life science and
pharmaceutical, and chemical and environmental and defense and security, consumer, electronics, https://
www.theinsightpartners.com/reports/nanofiber-market). Polymer nanofiber market, research report—Forecast
to 2023 https://www.marketresearchfuture.com/reports/polymer-nanofiber-market-4416.

4
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

anchoring, proliferation, and differentiation. For example, collagen fibril has

been known to enhance the interaction between cells and scaffolds. Similarly,
electrospun nanofiber scaffolds are also used as a drug delivery carrier for carry-
ing drugs to their target sites [21, 22].
Nanofibers, until now, have been produced using electrospinning from nearly
100 diverse polymers of natural and synthetic origins. All polymers have been
electrospun via solvent and melt spinning. Even with the persistent use of this tech-
nique, the understanding of the basics still need to be acquired. Figures 1–5 show
the research interest in the area of electrospinning and the market interest in the
electrospun product. More than 200 universities and research institutes worldwide
(some with high publications are shown in Figure 3) are still studying a variety of
the electrospinning processes, their various aspects, and the nanofibers produced.
The market of electrospun product is expected to increase mostly in filtration and
medical fields by 2025 (Figure 5).

2. Electrospinning and its mechanism

Much research has been done on the electrospinning technique. Based on the
literature, the fundamental setup used for electrospinning (Figure 6a) consists
of mainly four parts: a glass syringe (holding solution), needle (metallic), applied
voltage, and collector (metallic, with a variable morphology). The process com-
mences, when electric charges, produced on the needle due to the applied voltage,
transfer into the polymer solution via the metallic needle [22]. These charges cause
instability within the polymer droplet. The repulsion of charges generates a force
opposite to surface tension. These forces cause the polymer solution to move in the
direction of the electric field (Figure 6b). An increase in the electric field forces the
spherical droplet to distort and adopt a conical shape. At this phase, fine nanofibers
(nano to micro in diameters) appear from the conical droplet called Taylor cone,
which are whippingly collected on the collector and kept at an optimized distance.
A steady charge jet could only form, when the polymer solution possesses adequate
cohesive force. This whipping of the fibers permits the polymer chains to stretch

Figure 6.
Schematic depicting (a) electrospinning setup, and (b) phenomenon of electrospinning.

5
Electrospinning and Electrospraying - Techniques and Applications

and slide past each other in the solution, which leads to the fabrication of fibers
with diameters as mentioned above [23, 24].

3. Effects of parameters on electrospinning

There are various factors that affect the electrospinning process. These factors
are classified as electrospinning parameters and solution parameters. The electros-
pinning parameters include the applied electric field, distance between the needle
and collector, flow rate, and needle diameter. The solution parameters include the
solvent, polymer concentration, and viscosity. All of these parameters directly
affect the generation of smooth and bead-free electrospun fibers. Therefore, to gain
a better understanding of the electrospinning technique and fabrication of poly-
meric nanofibers, it is essential to thoroughly understand the effects of all of these
governing parameters. Detailed information highlighting the role of electrospin-
ning and the effects of the solution parameters on the morphology of electrospun
polymeric nanofibers are summarized below.

3.1 Effect of changes in applied voltage

Generally, it is a known fact that the flow of current from a high-voltage power
supply into a solution via a metallic needle will cause a spherical droplet to deform
into a Taylor cone and form ultrafine nanofibers at a critical voltage (Figure 7a–f).
This critical value of applied voltage varies for different polymers systems. The
creation of nanofibers with smaller diameter as the applied voltage is increased
could be ascribed to the stretching of the polymer solution and charge repulsion
in the polymer jet [25]. An increased applied voltage further than the critical value

Figure 7.
The images showing the droplet deformation and eventual fiber ejection with an increase in electric field on
droplet and effect of charges on polymeric solutions [28].

6
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

while keeping the flow rate constant will lead to the creation of beads or beaded
nanofibers. The creation of beads or beaded nanofibers with an increased applied
voltage is ascribed to the decrease in size of the Taylor cone and increase in the jet
velocity. Deitzel et al. reported bead formation with an increase in the applied volt-
age using poly(ethylene oxide) (PEO)/water. Similar results were also reported by
Meechaisue et al. and Zong et al. [26]. Furthermore, the diameter of the nanofibers
was also reported to increase with an increase in the applied voltage. This increase
in the diameter was attributed to an increase in the jet length with the applied volt-
age (Figure 7) [27].

4. Effect of solution flow rate

The movement of solution through the tip of the needle controls the morphol-
ogy of the nanofibers. Uniform beadless nanofibers could be fabricated via a critical
flow rate. The flow rate varies for different polymers systems. An increase in the
flow rate further than the critical value results in the creation of beads. For instance,
the increase in flow rate of polystyrene (PS) to 0.10 mL/min led to bead creation.
However, when the flow rate was reduced to 0.07 ml/min, bead-free, narrow-
diameter electrospun fibers were formed. Because an increase and the decrease
in the flow rate affect the nanofiber diameter, a minimum flow rate is preferred
to maintain a balance between the leaving polymeric solution and replacement of
that solution with a new one during jet formation [29, 30]. This will also permit
the formation of a steady cone jet and sometimes a receded jet: a jet that appears
from the inside of the needle with no apparent droplet or cone. Receded jets are
not steady jets, and during the process, these jets are unceasingly substituted by
cone jets. This phenomenon results in the formation of nanofibers with wide range
diameters (Figure 8a–h) [31]. Numerous research groups have studied the effect
of the flow rate on the morphology and diameter of nanofibers. For instance, Zong
et al. revealed that smaller diameter nanofibers can be prepared using a low flow
rate, whereas a high flow rate will not only yield high-diameter nanofibers, but the
bead formed will also have a high diameter [32]. Megelski et al. showed an increase
in the pore size and fiber diameter of PS nanofibers by increasing the flow rate of
the polymeric solution. They also concluded that fibers with beads were formed at
a high flow rate as a result of the incomplete drying of the nanofibers jet during its
flight between the needle tip and metallic collector [29]. In addition to bead forma-
tion, in some cases, at an elevated flow rate, ribbonlike defects [29] and unspun
droplets (Figure 8e) have also been reported in the literature [31]. The creation of
beads and ribbonlike structures with an increased flow rate was mainly ascribed to
the low stretching of the solution in the flight between the needle and metallic col-
lector and the non-evaporation of the solvent. Similar effect could also be ascribed
to an increase in diameter of the nanofibers with an increase in the flow rate [29].
The presence of the unspun droplets is attributed to the influence of the gravita-
tional force [31]. Another important factor that may cause defects in the nanofiber
structure is the surface charge density. Any change in the surface charge density
may also affect the morphology of the nanofibers. For example, Theron et al. found
that flow rate and electric current are directly linked to each other. His group inves-
tigated the effects of the flow rate and surface charge density using PEO, polyacrylic
acid (PAA), polyvinyl alcohol (PVA), polyurethane (PU), and polycaprolactone
(PCL). They noted that, in the case of PEO, an increase in the flow rate increased
the electric current and decreased the surface charge density at the same time. A
decreased surface charge density permits the merger of nanofibers in their flight to
the collector. This merger of nanofibers helps in the creation of garlands [33, 34].

7
Electrospinning and Electrospraying - Techniques and Applications

Figure 8.
Formation of various jets with increasing flow rate; here, ( f–h) show images of electrospun fibers on aluminum
foil [31].

4.1 Effects of polymer concentration and solution viscosity

Electrospinning counts on the uniaxial stretching of a charged jet. The stretch-

ing of the charged jet is considerably affected if the solution concentration is
changed. For instance, when the concentration is low, the applied electric field and
surface tension force the entangled polymer chains to rupture into fragments before
reaching the collector [23, 35] . These fragments then lead to the creation of beads
or beaded nanofibers. Increased concentration of the solution, however, leads to
an increase in the viscosity, which subsequently increases the chain entanglement.
These entanglements then overcome the surface tension and eventually result in
uniform and beadless nanofibers. Moreover, increasing the concentration further
than a critical value impedes the flow of the solution through the needle tip. In
simple words viscous solution partially blocks and dries at the needle tip. This
eventually leads to defective and beaded nanofibers [23]. The morphologies of the
beads depict an interesting shape change from a round droplet-like shape (with
low-viscosity solutions) to a stretched droplet or ellipse to smooth fibers (with suf-
ficient viscosity) as the solution viscosity changes (Figure 9a–h). This effect of the
concentration/viscosity on the morphology of the nanofibers was also reported by
Doshi et al. Working with PEO, they concluded that the optimum viscosity for the
generation of electrospun nanofibers is 800–4000 cp [7]. In addition to the work of
Doshi et al., an experiment on a polyacrylonitrile (PAN) polymer solution showed
that smooth electrospun nanofibers could be prepared when the viscosity of the
solution was kept at 1.7–215 cp. Hence, it can be concluded that in addition to the

8
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

Figure 9.
Variation in morphology of electrospun nanofibers with viscosity: (a–d) schematic and (e–h) SEM
micrographs [36, 37].

electrospinning parameters, the determination of the critical value of the concen-

tration/viscosity is also essential to obtain beadless nanofibers [27].

4.2 Role of solvent in electrospinning

The selection of solvent is one of the key factors for the fabrication of smooth
and beadless electrospun nanofibers. Usually two things need to be kept in mind
before selecting the solvent. First, the preferred solvents for electrospinning
process have polymers that are completely soluble. Second, the solvent should have
a moderate boiling point. Its boiling point gives an idea about the volatility of a
solvent. Mostly volatile solvents are desired as their high evaporation rates boost
the fabrication of nanofibers. However, very highly volatile solvents are commonly
avoided since their high evaporation rate forces the drying of jet at the needle tip.
This drying blocks the needle tip and thus hampers the electrospinning process.
Likewise, low-volatile solvents are also avoided since their low evaporation inhibits
their drying in the flight. The deposition of solvent-containing nanofibers on the
collector will cause the formation of beaded nanofibers [25, 38]. Numerous research
groups have studied the effects of the solvent and solvent system on the morphol-
ogy of nanofibers (Figure 10a–f) [39] and concluded that similar to the applied
voltage, solvent also affects the polymer system [40]. Moreover, solvents also play a
vibrant role in the fabrication of highly porous nanofibers. This may happen when
a polymer is dissolved in two solvents, where one act as solvents and the other
as a non-solvent. The difference in the evaporation rates of the solvent and non-
solvent causes phase separation, which results in the creation of pores in nanofibers
(Figure 10f) [25]. Similar results were also reported by Zhang et al. [41]. Megelski
et al. prepared porous nanofibers by varying the ratio of tetrahydrofuran (THF)

9
Electrospinning and Electrospraying - Techniques and Applications

Figure 10.
SEM images of 5% PCL solutions dissolved in different solvents: (a) glacial acetic acid, (b) 90% acetic acid,
(c) methylene chloride/ DMF = 4/1, (d) glacial formic acid, (e) and formic acid/acetone, along with ( f) SEM
images of PVB nanofibers prepared from 10 wt% THF/DMSO (9/1 v/v) [39, 43].

and dimethylformamide (DMF) [29]. The conductivity and dipole moment of

the solvent are also very vital. Jarusuwannapoom et al. from the test of 18 solvents
concluded only five solvents (ethyl acetate, DMF, THF, methyl ethyl ketone, and
1,2-dichloroethane) were feasible to be used in the electrospinning of PS, since
these solvents displayed relatively superior conductivity and dipole moment [42].

4.3 Effects of capillary and collector distance

The distance between the metallic needle tip and collector plays an essential role
in determining the morphology of electrospun nanofibers. Similar to the applied
electric field, viscosity, and flow rate, the distance between the metallic needle tip
and collector also varies with the polymer system. The nanofiber morphology could
be easily affected by the distance because it depends on the deposition time, evapo-
ration rate, and whipping or instability interval [44]. Hence, a critical distance
needs to be maintained to prepare smooth and uniform electrospun nanofibers, and
any changes on either side of the critical distance will affect the morphology of the
nanofibers [45]. Numerous research groups have studied the effect of the distance
between the needle tip and collector and concluded that defective and large-diame-
ter nanofibers are formed when this distance is kept small, whereas the diameter of
the nanofibers decreased as the distance was increased [27, 44, 46]. However, there
are cases where no effect on the morphology of the nanofibers was observed with a
change in the distance between the metallic needle and collector [47].

10
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

5. Electrospray

Electrospray is a technique that uses electricity to disperse a liquid and produce

fine aerosol. High voltage is applied to a liquid supply usually a glass or metallic
capillary. The liquid on reaching to the tip of the capillary tube (in ideal conditions)
forms a Taylor cone, which produces a liquid jet through its top. Varicose waves
(twisted and lengthened waves) on the surface of the jet lead to the creation of
small and highly charged liquid droplets, which due to Coulomb repulsion are radi-
ally dispersed. Electrospray deposition technique is very famous among chemical
and medical researchers. This system has several advantages (such as high drug-
loading efficiency and self-dispersion) over conventional methods.

5.1 Evolution history of electrospray

In the late sixteenth century, Gilbert [48] described the behavior of magnetic
and electrostatic phenomena. He noticed that, in the presence of a charged piece
of amber, a drop of water deformed into a cone. This effect was clearly related
to electrospray and considered to be the first such observation. Gilbert did not
record/elaborate the observation. In 1750, a French clergyman and physicist
Jean-Antoine (Abbé) Nollet noticed that water flowing from a vessel aerosol-
ized when the vessel was electrified and placed near electrical ground. He also
observed that if a person is electrified due to a connection to a high-voltage
generator, he would not bleed normally if he were to cut himself. The blood would
only spray from the wound [49]. In 1882, Rayleigh theoretically estimated the
maximum amount of charge a liquid droplet could carry [50]. This theory is now
known as the “Rayleigh limit.” He predicted that a droplet on reaching Rayleigh
limit would move as fine jets of liquid. More than 100 years later, Rayleigh limit
theory was confirmed experimentally [51]. In 1914, Zeleny studied the behavior
of fluid droplets at the end of glass capillaries. The work was later published [52].
The report presented experimental evidence for several electrospray-operating
regimes (dripping, burst, pulsating, and cone jet). A few years later, the first
time-lapse images of the dynamic liquid meniscus were captured [53]. Between
1964 and 1969, Taylor produced the theoretical groundwork of electrospraying
[54–56]. Taylor demonstrated a cone formation by the fluid droplet when an
electric field was applied. This characteristic droplet shape is named as the Taylor
cone. He further worked with Melcher to develop the “leaky dielectric model” for
conducting fluids [57].

6. Mechanism of electrospray

Electrospraying is a technique (Figure 11) used for liquid atomization that

achieves the stretching and breakup of polymeric solution via electrical forces to
obtain micro- or nanoscale particles. Many forces control and direct the electro-
spraying process; the most important are (i) gravity of polymeric solution, (ii)
electrostatic force generated (from external electric field) between nozzle and
collector, (iii) repulsion force (Coulomb forces) among adjacent charged carriers
on the surface of jet, (iv) viscoelastic force of polymeric solution, (v) interfacial
surface tension between air and liquid, and (vi) frictional force between the
charged jet and the surrounding air. Among these forces, electrostatic, repulsion,
viscoelastic forces, and surface tension affect the stretching and atomization of
the droplets during the electrospraying process. When a solution flows out of the
nozzle (needle), the charge distribution and carried charge quantity on the surface

11
Electrospinning and Electrospraying - Techniques and Applications

Figure 11.
(a) Basic electrospraying setup and (b) electrospraying mechanism [59].

of the solution will change in varying degrees, according to its electrical conduc-
tivity and dielectric constant, because of the polarization effect coming from the
external electric field. At the same time, initially, the uncharged liquid becomes
charged jet and is further stretched toward the direction of electrostatic attraction.
However, compared to gravity and electrostatic force that accelerates the movement
and stretching of polymeric solution from the nozzle to the collector, the surface
tension and viscoelastic ones prevent this movement and elongation because of
their opposite behavior on the electrosprayed solution. When these forces reach a
balance at a certain range, the droplets at the tip of the nozzle are stretched from the
spherical surface into conical surface. In 1964, Taylor proposed, for a perfectly con-
ducting liquid, a first explanation of the conical shape formation, corresponding to
a hydrostatic balance between electrostatic forces and surface tension. The presence
of the conical surface at the tip of the nozzle during electrospraying is also called
Taylor cone. According to Rayleigh’s theory, when the charge quantity distributed
on the surface of droplets reaches the value between 50 and 80% of the Rayleigh
limit, the breakup and fission of charged droplets occur due to Coulomb repulsions
among charged droplets [58]. A classical electrospray setup is considered, with the
glass capillary tube situated at a distance (d) from a grounded counter-electrode.
The liquid being sprayed is characterized by its viscosity (μ), surface tension (γ),
conductivity (κ), and relative permittivity (εr).

6.1 Effect of small electric fields on liquid menisci

The liquid meniscus adopts a semispherical shape at the needle tip under the
influence of surface tension. Application of the voltage (V) will bring into effect the
electric field [60]:

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Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

where (r) is the liquid radius of curvature. The electric field causes the polar-
ization of the liquid into negative and positive charges. At low voltage, the liquid
assumes an equilibrium geometry with a small radius of curvature.

6.2 Taylor cone

A Taylor cone is formed at the applied electric field above the threshold value.
Theoretically the shape of the cone depends on two assumptions: first the cone has
equipotential surface, and second the cone is in steady-state equilibrium [54]. To
meet both of these conditions, the electric field must have (R1/2) dependence and
azimuthal symmetry to counter the surface tension. The answer to this problem is
given as below:

where ((V=Vo) equipotential surface) occurs at a value of (θo) (regardless of R)

leading to an equipotential cone. The angle necessary for (V=Vo) for all R is a zero of
the Legendre polynomial of order 1/2, P1/2 (cosθo). There is only one zero between 0
and Π at 130.7099°, which is the complement of the Taylor’s now famous 49.3° angle.

6.3 Singularity development

The top of the conical meniscus cannot turn into substantially small. A singular-
ity develops when the hydrodynamic relaxation time becomes larger than the
charge relaxation time [61]. The undefined symbols stand for characteristic
length (r) and vacuum permittivity (εo). Due to intrinsic varicose unsteadiness, the
charged jet that eject from the cone ruptures into small charged droplets, which are
dispersed radially by the space charge.

6.4 Closing the electrical circuit

The charged liquid ejects through the cone top and is collected as charged
droplets on the collector which act as electrode. To balance the loss charge, the

Figure 12.
Scopus data showing year-wise publication in the area of electrospraying. The data is taken on February 09,
2019.

13
Electrospinning and Electrospraying - Techniques and Applications

negative charge (which is in excess) is neutralized electrochemically at the nozzle

tip. A disproportion between the amount of charge produced electrochemi-
cally and that of the lost at the cone top could result in numerous electrospray
regimes. For a stable electrosprays, the potential at interface (metal/liquid)
self-regulates to produce the equal amount of charges that are lost through the
cone tip [62].
Various institution and disciplines around the world are working on electrospray
technique to prepare nano- and microparticles for a number of applications rang-
ing from food to biomedical. Figures 12–15 show the research interest in the area
of electrospraying. However, even with the widespread use of the electrospraying
technique, the understanding of this method is still very limited.

Figure 13.
Country-wise Scopus data of electrospraying. The data is taken on February 09, 2019.

Figure 14.
Showing Scopus data subject wise where electrospraying has been used. The data is taken on February 09, 2019.

14
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

Figure 15.
Showing Scopus data of the institutions, which are working in area of electrospraying. The data is taken on
February 09, 2019.

7. Effects of parameters on electrospraying

Similar to electrospinning, there are various factors that affect the electrospray-
ing process. These factors are classified as operating and solution parameters.
The operating parameters include (i) applied voltage, (ii) working distance, (iii)
liquid flow rate, and (iv) nozzle type. The solution parameters include (i) electri-
cal conductivity, (ii) surface tension, (iii) viscosity, (iv) vapor pressure, and (v)
dielectric constant. All these parameters directly affect the formation of the Taylor
cone, which leads to the production of particles having a low mean diameter and
narrow particle size distribution. Therefore, to gain a better understanding of the
electrospraying technique and achieve low mean diameter and narrow particle
size distribution, it is essential to thoroughly understand the effects of all of these
governing parameters [58].

7.1 Applied voltage

Applied voltage is one of the essential parameters, which needs to be optimized

to get low diameter and narrow particle distribution. Voltage applied between
the nozzle and collector not only influences the stretching of the jet but also the
formation of the Taylor cone at the end of the nozzle. Increase in the applied volt-
age increases the electrostatic forces that are acting on the surface of the charged
droplets. This causes the spray mode to gradually take its route from dripping to
multi-jet and then to a stable cone jet (Figure 16 and Table 1). When the electro-
static forces acting on the surface of the spray droplets are not sufficiently strong
to overcome surface and viscoelastic tensions (low applied voltage causes drop-to-
drop mode), film formation occurs on the collector. In the dripping area, electrified
liquid form drops at the capillary end till the gravitational and electrical forces
overcome their surface tension. The droplets emerge at the end of the capillary
at low frequency and maintain spherical morphologies due to gravitational force
and surface tension. As the voltage is increased, the shape of the ejected droplet
is affected by its wetting properties, which allows the formation of particles with
high average diameter and wide size distribution. At higher voltages, the jet mode
changes to stable conical jet mode (Figure 17). At this point the electrostatic forces

15
Electrospinning and Electrospraying - Techniques and Applications

Figure 16.
Schematic showing various possible jet modes during electrospraying process adopted from [63].

Table 1.
A summary of the main spraying jet modes (adopted from [63]).

are strong enough to overcome surface and viscoelastic tension, which leads to a
balance between different forces and fabrication of low mean diameter particles of
narrow size distribution [63, 64].

16
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

Figure 17.
Showing the switching of a liquid meniscus (subjected to increasing applied voltage) into a conical shape and a
stable jet, adopted from [62, 65].

7.2 Flow rate

The flow rate of the electrospray solution is also an essential factor in the forma-
tion of the Taylor cone. The optimization of this parameter depends on two intrinsic
characteristics of the solutions: (i) vapor pressure of the solvent (ii) and electrical
conductivity of the solutions. A stable Taylor cone prefers low flow rates because
the uncharged drop at the tip of the nozzle needs sufficient time polarization. This
polarization generates charges on the droplet surface, which in turn promote Taylor
cone formation. At higher flows, the decrease in the polarization/partial polariza-
tion of the droplets result in continuous dripping of droplets due to gravity. Having
said this, for different materials the flow rate to form a stable jet varies. The use of
a solvent with a high-saturation vapor pressure needs a higher flow rate to avoid
nozzle blocking, when the solvent evaporates. A lower flow rate is recommended for
solutions prepared from solvents having low saturated vapor pressure. This is done
to ensure complete removal (evaporation) of the solvent during solidification pro-
cess. Another factor that might affect the optimization of flow rate is the conductiv-
ity of the solutions. It is a known fact that conductivity of a solution influences the
droplet polarization time. This means, it will also influence the adjustment of an
adequate flow rate. Since low conductivity solution will need more time to polarize
and generate charges on the droplet, hence in such case low flow rate is recom-
mended. Reverse is the case with high-conductivity solutions [66].

7.3 Working distance

The working distance between the metallic nozzle tip and collector also plays
an essential role in determining the formation of a table Taylor cone. Similar to the
applied electric field, viscosity, and flow rate, the distance between the metallic
needle tip and collector also varies for different polymer systems. Smeets et al.
achieved the formation of a stable Taylor cone using a lager tip-to-collector distance
and low flow rate. The working distance between the tip and the collector is con-
trolled to achieve a critical electric field (at constant applied field) and ensure the
formation of the Taylor cone. At shorter distance, the electric field is higher. This
leads to the formation of small particles. However, this is only possible when the

17
Electrospinning and Electrospraying - Techniques and Applications

solvent is more volatile; otherwise swelled particles are collected on the collector.
Long working distance may cause lower yield. This is attributed mainly to the loss
of material to the surrounding due to the turbulent droplet flight. Having said this,
long working distance is needed when denser polymer particles are required. The
particles do not swell on the collectors because of the availability of sufficient time
for the droplet’s solvent to evaporate in the flight from nozzle tip to the collector. For
low conductive solution with more volatility, nozzle to collector distance is smaller
and vice versa for the high-conductivity and low-volatility solution [64].

7.4 Electrical conductivity

In the process of electrospraying, a solution is stretched and converted into a jet

at the tip of the nozzle due to the electrostatic force, when an electric field is applied
between the nozzle tip and collector. A balance between gravity, electrostatic force,
Coulomb repulsions, viscoelastic and frictional forces, and surface tension leads to the
formation of a Taylor cone at the tip of the nozzle (Figures 11 and 17). The strength of
the electrostatic force and Coulomb repulsions that are acting on the electrosprayed
droplets depends on the amount of polarization charge on the droplets, which in turn
depends on the strength of the applied electric field. These electrostatic attractions
counteract the surface tension and viscoelastic forces, which then leads to the forma-
tion of Taylor cone. When the electrical conductivity of the solution is too high, this
high conductivity causes increased Coulomb repulsions among charged droplets and
breakup of the charged droplets. This phenomenon leads to the modification of the
balance between gravity, electrostatic force, Coulomb repulsions, viscoelastic and fric-
tional forces, and surface tension and a change from a stable cone jet to an unstable jet.
Similarly, a too low electrical conductivity causes decreased electrostatic attractions
on the droplets, which leads to the same unbalance among the abovementioned forces
and results neither in the Taylor cone formation at the nozzle tip nor the formation of
particle. Hence, a critical conductivity of the solution is needed, which results in the
formation of a stable Taylor cone. Jaworek and Xie et al. suggested that a electrohydro-
dynamic process is carried out under cone-jet mode, when the electrical conductivity
of the solution is in the range of 10−11 to 10−1 S/m [67].

7.5 Surface tension and viscosity

As discussed earlier, unbalance between the forces affects the formation of a

Taylor cone at the tip of the nozzle during the electrospraying. One of these forces
is surface tension. Cloupeau and Smith suggested that the surface tension value of
the solution used in electrospraying must not exceed 50 mN/m, though some studies
reported more value for glycerine (63 mN/m) and water (72.8 mN/m) [68–71].
A high surface tension of a solution will result in a corona discharge at the tip of the
nozzle, which will cause a stable cone jet to change into an irregular spraying and
an asymmetrical mode. Similar to surface tension, viscosity of the solutions also
affects the formation of a stable Taylor cone. Since the direction of the viscoelastic
force is opposite to the direction of the gravity and electrostatic attraction, when the
viscosity of the solution is low, the combined viscoelastic force and surface tension
are sufficiently strong to counteract the gravity and electrostatic attraction forces.
This leads to dripping instead of cone jet. A high-viscosity solution does not allow
the formation of a stable Taylor cone due to the drying of the polymeric particles,
which block the tip of the capillary and therefore restricting the formation of a stable
Taylor cone. Thus, in order to achieve a stable con jet during electrospraying process,
a critical range of viscosity is needed. This range will be different for different for
polymeric systems. For some the range may be from 1.5 to 5500 mPa·s [52, 53].

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Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

7.6 Vapor pressure and dielectric constant

Boiling point of the solution in electrospraying also affects the formation of

Taylor cone. Since the evaporation of solvent and the formation of Taylor cone at
the tip of the nozzle occur simultaneously in jetting, thus a too low boiling point
(high vapor pressure) changes the shape of the stable cone jet into an unstable one.
Furthermore, a low boiling point of solution will result in the drying of the poly-
meric particles at the tip of the nozzle and will block the tip and stop the process.
The effect of the dielectric constant on the cone-jet formation is similar to the
electrical conductivity. A very high and too low dielectric constant is not favorable
to obtain a stable cone jet during electrospraying process (e.g., polycaprolactone
(PCL)). Some research published on the electrospinning of PS correlated to the
dipole moment and the dielectric constant of the solutions. To date, very few
articles have studied the effect of dielectric constant on the outcomes of electro-
spraying; much work is needed to completely understand its effects [42, 72].

8. Conclusion

Electrospinning is a technique used for the fabrication of nanofibers, whereas

electrospray is a technique used for the preparation of micro- or nanoscale size,
mono-dispersed particles. Both of these electrodynamic techniques have been
receiving increasing attention not only in the scientific community but also in the
food, environmental, and biomedical industries. The main apparatus used for both
of these processes is almost the same. Both need electric voltage to induce charges
on the droplet, which at optimized electric filed leads to micro- or nanofibers and
micro- or nanoparticles. Rayleigh in 1882, for the first time, theoretically estimated
the maximum amount of charge a liquid droplet could carry to change in a jet.
This theory is now known as the “Rayleigh limit.” His predicted that a droplet on
reaching Rayleigh limit would move as fine jets of liquid. More than 100 years later,
Rayleigh limit theory was confirmed experimentally. Beside electric filed there are
other operating and solution parameters that need to be optimized before we obtain
our desired products. The particle and fiber formation mechanisms and principles
of electrospraying and electrospinning are still complicated, and more studies are
needed understand both of these processes.

19
Electrospinning and Electrospraying - Techniques and Applications

Author details

Sajjad Haider1*†, Adnan Haider2†, Abdulaziz A. Alghyamah1†, Rawaiz Khan3†,

Waheed A. Almasry1† and Naeem Khan2†

1 Department of Chemical Engineering, College of Engineering,

King Saud University, Riyadh, KSA, Saudi Arabia

2 Department of Chemistry, Kohat University of Science and Technology,

Kohat, KP, Pakistan

3 Engineer Abdullah Bugshan Research Chair for Dental and Oral Rehabilitation,
College of Dentistry, King Saud University, Riyadh, Saudi Arabia

*Address all correspondence to: shaider@ksu.edu.sa

†
All authors have equal contribution.

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

20
Electrohydrodynamic Processes and Their Affecting Parameters
DOI: http://dx.doi.org/10.5772/intechopen.89929

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