Journal of Electrostatics 71 (2013) 189e198

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Journal of Electrostatics
journal homepage: www.elsevier.com/locate/elstat

Fiber diameter in electrospinning process

Bogdan Cramariuc a, Radu Cramariuc b, *, Roxana Scarlet c, Liliana Rozemarie Manea c, Iuliana G. Lupu c,
Oana Cramariuc a, d
a
IT Center for Science and Technology, Av. Radu Beller 25, Bucharest, Romania
b
Centre of Competence in Electrostatics and Electrotechnologies, Av. Radu Beller 25, Bucharest, Romania
c
Faculty of Textile, Leather Engineering and Industrial Management, Gh.Asachi Technical University of Iasi, Dimitrie Mangeron 29, 700050 Iasi, Romania
d
Department of Physics, Tampere University of Technology, P.O. Box 692, FI-33101 Tampere, Finland

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

Article history: In order to increase the control on the fiber diameter we propose in this paper a methodology to
Received 10 September 2012 determine stability domains of the process in which the electrospun fiber diameter can be pre-
Received in revised form determined and also controlled by means of the polymer solution flow and the applied voltage. To define
17 December 2012
these stability domains we employ a combination of analytical expressions depending on the location
Accepted 17 December 2012
along the traveling jet. In the vicinity of the nozzle we employ the expression which links the fiber
Available online 8 January 2013
diameter with the kinematic viscosity of the polymer solution, nozzle-collector distance, solution den-
sity, liquid flow, electric current and intensity of the electrostatic field. At larger distances from the
Keywords:
Electrospinning
nozzle, the fiber diameter can be expressed as a function of solution density, liquid flow, intensity of the
Nanofibers applied electrostatic field and distance from the nozzle. Close to the collector the fiber diameter can be
Fiber diameter control expressed with respect to the superficial tension of the polymer solution, dielectric permittivity, liquid
flow and intensity of the electric current. Under specific constrains, the superposition of the plots
obtained from these mathematical expressions will be used to determine the stability domain for the
fiber diameter in which the diameter can be controlled by two process parameters, namely applied
voltage and polymer solution flow. Through this approach the present paper can contribute to increased
control of the electrospinning process and thus enhanced applicability.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction fibers electrospun from polymers can serve as carbon nano-

Electrospinning [1e15] is a method of producing superfine fi-
bers with diameters ranging from 10 mm down to 10 nm by forcing
a polymer melt or a solution through a spinnerette by electric field
and subsequently drawing the resulting filaments as they solidify
or coagulate. The technology has attracted much attention recently
due to the ease with which nanometer diameter fibers can be
produced from a range of natural and synthetic polymers. The list of
electrospun materials includes synthetic polymers with a broad
range of conducting properties from nonconducting polyurethane
to highly conducting polyaniline, and natural polymers such as
collagen and silkworm silk. The potential applications of such small
fibers are numerous and diverse. Their small diameter offers ad-
vantages for filtration and composite materials. Their high surface
area makes them attractive as catalyst supports and for targeted
drug delivery. Electrospinning polymer solution with added carbon
nanotubes results in super strong composite nanofiber. In addition,
* Corresponding author.
E-mail address: raducramariuc@yahoo.com (R. Cramariuc).
materials after pyrolysis. Non-woven fabrics electrospun from
biocompatible materials are being developed for biomedical uses
such as wound dressings and artificial tissue scaffolds. Conducting
polymers can be used to fabricate nanowires. Due to the impor-
tance of the electrospinning process in many potential applications
an increasing amount of work is put into the theoretical modeling
of the process by analytical equations linking the electrospun fiber
diameter with the process parameters and the characteristics of the
polymer solution.
Over the years, Rutledge and co-workers developed a theoretical
framework for understanding the physical mechanisms of electro-
spinning and proposed a method of quantitatively predicting the
parameter regimes where the electrospinning occurs [1e6]. The
group modeled the behavior of the jet in terms of three instabilities:
the classical Rayleigh instability and two “conducting” modes. Feng
et al. proposed a simplified model in which they eliminated the bal-
looning instability of the electric field calculation [5]. The simplified
model was tested against experimental data for a variety of boundary
conditions and parameter values. Consequently non-Newtonian
rheology was introduced into the proposed theoretical model of

0304-3886/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.elstat.2012.12.018
190 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198
electrospinning in order to examine the effects of extension thinning
and extension thickening of the polymer [7]. Reneker et al. and Yarin
et al. contributed significantly to the modeling of electrospinning by
developing a discrete three-dimensional model to describe the dy-
namics of electrospinning [8,9]. In Ref. [13], a brief review of mathe-
matical models of electrospinning is given and in Ref. [14], the
theoretical aspects of the electrospinning technologies with a good
collection of references are reviewed.
Currently, the results of the electrospinning process are still
greatly unpredictable and exhibit a time varying diameter distribu-
tion which limits its usefulness in industrial applications. It is
therefore critical, especially for high-tech applications, to narrow the
diameter distribution of the electrospun fibers and to increase the
robustness and reliability of the process. This study is devoted to
analyzing the three main equations appearing throughout the liter-
ature [14] in this field. In the vicinity of the nozzle we employ the
expression proposed by Rutledge et al. [4] which links the fiber
diameter with the kinematic viscosity of the polymer solution,
nozzle-collector distance, solution density, liquid flow, electric cur-
rent and intensity of the electrostatic field. At larger distances from
the nozzle, the fiber diameter can be expressed as a function of so-
lution density, liquid flow, intensity of the applied electrostatic field
and distance from the nozzle [5]. Close to the collector the fiber
diameter can be expressed with respect to the superficial tension of
the polymer solution, dielectric permittivity, liquid flow and in-
tensity of the electric current [6]. Under specific constrains, the su-
perposition of the plots obtained. These equations connect the
diameter of the electrospun fibers with the process parameters and
the characteristics of the materials used for electrospinning. In the
following we present the characteristics of the fiber diameter as
function of the parameters contained in each of the three equations.
The results obtained with the three equations are compared with our
own original experimental results and other experimental results
documented in the literature. Consequently, useful information is
obtained that can be directly used in the practical electrospinning
applications. A methodology is suggested for the pre-determination
of the fiber diameter depending on the target application.
2. Prediction of the fiber diameter
2.1. The scaling law of the diameter of the jet near the nozzle
The scaling law of the diameter of the jet near the nozzle [4]
shows the role of viscosity in controlling the stable jet:

1
6mrQ 2 2 1
h ¼ $z ½m
pIEN
where : h is the jet radius [m]; z is the distance from the nozzle to
the collector [m]; m is the kinematic viscosity [m2/s]; r is the density
[kg/m3]; Q is the flow rate [m3/s]; EN is the external electric field [V/
m]; I is the electric current [A].
The whipping and stretching of the jet is greatly determined by
its behavior near the nozzle [1]. Modeling of the jet profile near the
nozzle in the stable regime has established the role of viscosity in
controlling the stable jet. It was found that in viscous fluids such
a glycerol the shape of a rather long segment of the jet is controlled
by the balance of viscous friction and electric field pulling on the
surface charges.
2.2. The scaling law of the diameter of the jet far from the nozzle
The scaling law of the diameter of the jet far from the nozzle [5],
is determined by the operating conditions as follows:

14
rQ 3
$z4
1
h ¼ ½m (2)
2p2 IEN
where: z is the distance from the nozzle to the collector [m], r is th
density [kg/m3], Q is the flow rate [m3/s], EN is the external electric
field [V/m] and I is the electric current [A].
2.3. The scaling law of the shape of the jet, for the diameter, at the
collector
The scaling law of the shape of the jet, for the diameter, at the
collector [6] predicts that the terminal diameter of the whipping jet
is controlled by the flow rate, electric current and the surface
tension of the fluid:

2 1
Q 2 3
h ¼ g3 ½m (3)
I pð2 ln c  3Þ
where: g is the surface tension of the fluid [N/m], 3 is the dielectric
permittivity [F/m], c ¼ R=h is the dimensionless whipping insta-
bility, with R being the radius of the instability jet and h the fiber
diameter, and Q/I is the inverse of the net volume density of the
charge induced in the fluid at the top electrode [m3/C]. Eq. (3) pre-
dicts that the terminal diameter of the whipping jet is controlled by
the flow rate, electric current and the surface tension of the fluid.
3. Theoretical characteristics of the fiber diameter from Eqs.
(1)e(3)
3.1. Fiber diameter versus flow rate for different currents (Eq. (2))
The initial parameters are: solution density r ¼ 1300 kg/m3,
electric field E ¼ 400 kV/m, distance from the nozzle z ¼ 0.1 m and
applied voltage U ¼ 40 kV.
Fig. 1 and Table 1 show the variation of the diameter (h) with the
increase of flow rate for different currents.
In Eq. (2), like for the other ones, we consider current I as an
independent parameter [4]. In reality, current I depends on the
applied voltage and on the conductivity of the solution. The total
current is the sum of the contributions made by two different
currents: conduction current and convection current. In Fig. 1, if the
voltage is maintained constant, to vary the current we have to
change the conductivity of the solution. Based on Fig. 1 and Table 1
we can notice that increasing the current we decrease the diameter
of the fiber. The same dependency can also be observed from Fig. 5
when the conductivity of the solution increases.
(1)
Fig. 1. Fiber diameter versus flow rate for different currents (Eq. (2)).
 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198 191

Table 1 Table 2
Fiber diameter [mm] for flow rate 0.1 ml/min, for different currents (Eq. (2)). Fiber diameter [mm] for flow rate 0.1 ml/min, for different electrical fields (Eq. (2)).

Q [ml/min] I [nA] Q [ml/min] E [kV/m]

45 55 65 75 85 95 100 50 100 150 200 250 300 400

0.1 3.61 3.43 3.29 3.17 3.08 2.99 2.95 0.1 4.97 4.18 3.78 3.51 3.32 3.17 2.95

3.2. Fiber diameter versus flow rate for different voltages (Eq. (2))
The initial parameters are: density r ¼ 1300 kg/m , z ¼ 10 cm, 3
I ¼ 100 nA. Fig. 2 and Table 2 show the variation of the diameter (h)
with the increase of flow rate for different voltages.
In Fig. 2 we consider a setup where the current is constant and
the applied voltage is variable. In this case, due to the fact that the
current depends upon the applied voltage, to keep the current
constant we have to modify the conductivity of the solution. The
resistivity of the solution must increase with the increase of the
applied voltage. This increase in the resistivity of the solution will
lead to the increase of the fiber diameter. The reduction of the
diameter noticed in Fig. 2 is determined by the increase of the
electric field as result of the increase in the applied voltage. In order
to emphasize this we will modify Eq. (2):

14
rQ 3
$z4
1
h ¼ ½m
2p2 IEN
where: I ¼ U=R (we consider only conduction current), R ¼ rs l=S is
the electrical resistance of the jet, l ¼ z is the length of the jet [m],
S ¼ ph2 =4 is the section of the jet [m2] and rs is the resistivity of
the solution [U m]. Making the replacements following equation is
obtained:

1
2rs rQ 3 Z 6
h ¼ ½m
p3 U 2
In this case the dependence of the fiber diameter on the applied
voltage and the distance needleecollector is obvious.
The increase in the viscosity determines an ‘almost linear’
increase of the fiber diameter, fact that can be noticed in Table 3.
Moreover, the viscosity is an important factor controlling the
morphology of the fiber, fact that will be further be analyzed in the
experimental section of this paper.
3.4. Fiber diameter versus Q/I (Eq. (3))
The initial parameters: g surface tension of the fluid ¼ 7.62E02 N/
m, 3 dielectric permittivity ¼ 8.85E12 F/m, K e the dimensionless of
the whipping instability ¼ 1.00Eþ05 (R ¼ 1 cm; h ¼ 100 nm).
Fig. 4 and Table 4 show the variation of the diameter (h) with the
increase of inverse volume charge density (Q/I).
The increase in the current density, determined by the increase
in the current, produces a decrease of the fiber diameter. This
dependence can be noticed both in Tables 1 and 4.
3.5. Fiber diameter versus conductivity of solutions (Eq. (2))
The initial parameters are: density r ¼ 1300 kg/m3, Q ¼ 0.1 ml/
min ¼ 1.67  109 m3/s, z ¼ 0.20 m, U ¼ 30 kV. In order to
emphasize the conductivity of the solution we rewrite Eq. (2) as:

14
rQ 3
$Z 4
1
h ¼ ½m
p
2 2 IEN
(4)
where: I ¼ U/R, E ¼ U/Z, R is the electrical resistance of the jet [U], U
is the applied voltage [V]. Replacing these in Eq. (2) we obtain:
0 11
4

3.3. Fiber diameter versus flow rate for different viscosities (Eq. (1)) B rQ 3
C 1
h ¼ B
@
C $Z 4
2A
½m (5)
U
2p2
The initial parameters: density, r ¼ 1300 kg/m3, electric field RZ
E ¼ 400 kV/m, z ¼ 10 cm, U ¼ 40 kV. Fig. 3 and Table 3 show the
variation of the diameter (h) with the increase of flow rate for where : RZ [U m] is the resistivity of the solution and 1/RZ [S/m] is
different viscosities. the conductivity of the solution. Fig. 5 shows the variation of the

Fig. 2. Fiber diameter versus flow rate for different voltages (Eq. (2)). Fig. 3. Fiber diameter versus flow rate for different viscosities (Eq. (1)).
192 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198

Table 3 Table 4
Fiber diameter [mm] for flow rate 0.1 ml/min, for different viscosities (Eq. (1)). Fiber diameter versus Q/I [m3/C] (Eq. (3)).

Q[ml/min] m [cP] I/Q (C/l) Q/I (l/C) h (mm)

13 32 74 160 289 527 1250 1835 1.23 0.81 0.24

1.77 0.56 0.19
0.1 0.15 0.23 0.36 0.52 0.71 0.95 1.47 1.78
3.03 0.33 0.13
6.57 0.15 0.08
8.67 0.12 0.07
28.80 0.03 0.03
diameter (h) with the increase of conductivity of solutions (Eq. (2)).
In a similar way we can rewrite Eq. (1) as:
0 11 4.3. Fluids
2

B6mrQ 2 C
h ¼ B
@
C $Z 1 ½m (6) A wide range of fluids can be spun using the electrospinning
U2 A
p technique. In the current paper, we focused on studying the fol-
RZ lowing solutions: the PEI polymer (polyetherimide) with various
solvent concentrations, dimethylacetamide/tetrahydrofuran (DMA/
Fig. 6 shows the variation of the diameter (h) with the increase of
THF), chloroform (Clf), dichloromethane (DCM), dimethyl sulfoxide
conductivity of solutions (Eq. (1)) for the initial parameters: density
(DMSO), tetrachloroethane (TCE), dimethylacetamide/tetrahy-
r ¼ 1300 kg/m3, Q ¼ 8 ml/min ¼ 1.33  107 m3/s, z ¼ 0.10 m,
drofuran/dimethyl sulfoxide (DMA/THF/DMSO), tetrahydrofuran/
U ¼ 20  103 V, m ¼ 13  103 Pa s.
dimethyl sulfoxide (THF/DMSO), chloroform/dimethyl sulfoxide
Regarding the diameter of the fiber we can notice in Fig. 6 that
(Clf/DMSO), ethylacetamide/ethylacetamide (EA/DMSO), N-
(Eq. (1)), for the region close to the injection system (needle), the
methyl-2-pyrrolidone (NMP). The solutions used in each experi-
value of the fiber diameter varies from 1 to 8 nm, for the range of
ment are given in the figure captions.
used conductivities. Similarly, in Fig. 5 (Eq. (2)), for the region far
from the injection system (needle), for the same range of solution
conductivities, the diameter of the fiber varies from 10 to 40 nm. The 4.4. Experimental characterization methods
increase of the diameter with distance is well captured in Eq. (4).
Quantitative analysis of the electrospinning process can be
4. Experimental results structured into three categories.

4.1. Design of the experiments
The set of experiments has been designed with the purpose of
determining the limitations of the theoretical models for the
determination of the fiber diameter, as a function of the process
parameters and the materials used for electrospinning.
4.2. Equipment design
The electrospinner design used for experiments is illustrated
in Fig. 7. Flow rate is controlled using a syringe pump. Applied
voltage is regulated up to 30 kV using a dc power supply. Typical
operating regimes are flow rates between 0.05 and 2 ml/min,
voltages between 5 and 30 kV, and spinnerette-to-collector dis-
tance of 5e20 cm. Fig. 7 illustrated the general aspect of the
equipment.
(1) Solution properties. The relevant fluid properties are density,
viscosity, surface tension, permittivity, conductivity and vis-
coelasticity. Of these, viscosity and conductivity appear to play
the greatest role in the electrospinning of dilute solutions.
(2) Operating parameters. The relevant operating parameters are
flow rate, electric field strength [11], and electric current flow
between the spinnerette and collector. The volumetric flow
rate is closely controlled through the use of the syringe pump.
Field strength may be varied by changing either the applied
voltage or the distance between injector and collector. Both
variables have been used. Thinning of the jet depends princi-
pally on the field strength; however, the development of in-
stabilities in the jet requires sufficient distance of travel for
the instabilities to grow in amplitude. The total electric current
contains contributions from both convection and conduction
currents, both we have discussed.
(3) Fiber characterization. Fiber diameter distributions are measured
using scanning electron microscopy (SEM, Model PHENOM).

Fig. 4. Fiber diameter versus Q/I [l/C] (Eq. (3)). Fig. 5. Fiber diameter versus conductivity of solutions (Eq. (2)).
 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198
Fig. 6. Fiber diameter versus conductivity of solutions (Eq. (1)).
4.5. Experimental results
4.5.1. Fiber diameter versus flow rate for different fluids
Within the experiments for the study of the “Fiber diameter
versus flow rate” we used the solution: 4% PEO (polyethylene ox-
ide) with ethanol/water (4/6). This material allowed the production
of fibers at flow rates in the range 1e4 ml/h. The results are given in
Fig. 8 where we can notice an almost linear increase of the fiber
diameter with the increase of the flow rate, for the range of rela-
tively small flow rates used.
Fig. 8 corresponds to Eq. (1) in the region close to the injector. In
this equation the diameter of the nanofiber, h, is proportional to the
flow rate, Q. The values used in the experiment are: r ¼ 1300 kg/m3,
m ¼ 0.032 Pa s, z ¼ 60 mm, U ¼ 12 kV, I ¼ 100 nA (considered
constant in this case. In reality the current increases with the flow
rate and in Eq. (1) the fiber diameter is proportional with the
inverse of the square root of the current). For these values we
obtain the following values for h: for a flow rate Q ¼ 1 ml/h we get
h ¼ 292 nm and for a flow rate Q ¼ 4 ml/h we get
h ¼ 4  292 ¼ 1168 nm. The values obtained correspond relatively
well with the experimental values.
Fig. 9 shows the dependence of the final fiber diameter on flow
rate for three different PCL solutions and for bigger flow rates [5].
In this case while the average fiber diameter increases with the
flow rate, it appears to saturate at high flow rate. Models of the
electrospinning [5] process indicate that the final fiber diameter
should be strongly dependent on the amount of charge present
in on the jet. Coulombic repulsion between charges and torques
arising from the interaction of charge with the electric field are
Fig. 7. Schematic of the electrospinning setup for polymer solutions.
193
among the mechanisms proposed to be responsible for diameter
reduction. In this case the linear regions are not proportional to the
flow rate but are closer to a dependency similar to Q1/2, according to
Eq. (4), or Q3/4 according to Eq. (2).
4.5.2. Fiber diameter versus conductivity for different fluids
Fig. 10 shows the average fiber diameter versus conductivity for
two different solutions: (a) 10% PCL in 3:1 toluene:methanol, (b)
15% PCL in 3:1 toluene:methanol [5].
Theoretical Figs. 5 and 6 reveal that the fiber diameter increases
toward infinity when the conductivity decreases toward zero, i.e.
the resistivity Rz also increases toward infinity. For high conduc-
tivity values the fiber diameter decreases slowly. The same de-
pendency h ¼ f(1/Rz) plotted based on experimental values (Fig. 10)
has a slightly different shape than the theoretical figures. At large
conductivity values the fiber diameter starts to increase again after
exhibiting a minimum, evidencing the fact that more complex
phenomena need to be taken into account when addressing the
conductivity dependence.
4.5.3. Average fiber diameter versus the applied voltage
In Fig. 11(a) it is presented the effect of the applied voltage on
the diameter of the fiber, effect obtained experimentally using the
solution and parameters mentioned in the figure caption. Fig. 11(b)
presents the same effect, as predicted theoretically using Eq. (4).
Regarding the study of the influence of the applied voltage on
the diameter of the nanofibers obtained from a 12% PEI/DMA/THF
(1:1) using the “ELECTROSPIN” equipment, the experiments have
shown the fact that the diameter of the fibers decreases with the
increasing applied voltage in the range 2193.28e973.08 nm. These
results were obtained using the following parameters: Q ¼ 0.1 ml/h,
d ¼ 80 mm, V1 ¼ 15 kV, V2 ¼ 20 kV, V3 ¼ 25 kV, V4 ¼ 30 kV,
V5 ¼ 35 kV, syringe diameter 10 mm, syringe capacity 3 ml, interior
diameter of the needle 0.4 mm.
Regarding the electric field, the experiments have shown that
the strength of the electric field it is not constant along the longi-
tudinal axis of the jet exiting the needle, fact which explains the
nonuniformity of the fiber mats obtained. Increasing the applied
voltage increases the strength of the field but its structure remains
the same.
Theoretical values, mentioned in Fig. 11(b), obtained with Eq.
(4), under the same conditions of flow, distance between the needle
and the collector plate (nm), applied voltage and polymer solutions
are smaller than the experimental values including the decreasing
ratio. The values range from 415 nm (at 15 kV) to 332 nm (at 30 kV)
with a decreasing ratio of 415/332 ¼ 1.25. The experimental values
194 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198

Fig. 8. Average fiber diameter versus flow rate for voltage 12 kV, the distance between
the needle and the collector d ¼ 60 mm, solution 4% PEO [15].

range from 2193 nm (at 15 kV) to 973 nm (at 30 kV) with

a decreasing ratio of, 2193/973 ¼ 2.25. Difference is determined by Fig. 10. Average fiber diameter versus conductivity: (a) black, 10% PCL in 3:1 tolue-
ne:methanol, (b) red, 15% PCL in 3:1 toluene:methanol [5]. (For interpretation of the
the non-uniformity of the intensity of the electric field, to take into references to colour in this figure legend, the reader is referred to the web version of
consideration, in Eq. (4), only the conduction current and the cli- this article.)
mate conditions in experiments. The decreasing of the fiber
diameter can be seen, also, in Table 1 when the current growths
from 45 nA to 100 nA with a decreasing ratio of 2.95 and Table 2 for fibers for the variants V111 (15 kV) and V121 (20 kV) and stucked
the increasing the intensity of the electric field from 50 kV/m to fibers for V131 (25 kV). For the distance 120 mm no clean fibers
400 kV/m, with a decreasing ratio of 1.68. were obtained. These results were obtained using a polymeric so-
lution PEI/DMA/THF with a PEI concentration of 12%.
4.5.4. The morphology of beaded fibers with increasing voltages
In Fig. 12, the morphology of the fibers for the parameters:
Q ¼ 0.1 ml/h, d ¼ 80 mm (distance between the needle and the
collector), the voltage between 15 and 35 kV is given.
Based on the experiments that were performed for Q ¼ 0.1 ml/h
and the distance needleecollector 80 mm we can draw several
conclusions. Fibers were obtained for the technological variants
V113 (15 kV), V123 (20 kV), V123 (25 kV). For the technological
variants with higher voltages V143 (30 kV) and V153 (35 kV) bea-
ded fibers were obtained. For smaller distances the situation is
favorable at higher voltages. When distance is 45 mm fiber was
obtained for the variants V141 (30 kV) and V151 (35 kV), beaded

Fig. 11. Average fiber diameter versus applied voltage for flow rate Q ¼ 0.1 ml/h and
Fig. 9. Average fiber diameter versus flow rate for different fluids: (a) 15% PCL in 3:1 solution 12% PEI/DMA/THF (1:1). (a) Experimental for distance between needle and
dichloromethane:methanol, (b) 12% PCL in 3:1 dichloromethane:methanol, (c) 20% PCL collector d ¼ 80 mm, V113eV153 different technological variants; (b) theoretical for
in 3:1 chloroform:methanol [5]. d ¼ 45, 80 and 120 mm.
 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198
Fig. 12. The morphology of the fibers for the parameters: Q ¼ 0.1 ml/h; d ¼ 80 mm (distance between the needle and the collector), the voltage between 15 and 35 kV and the
solution 12% PEI/DMA/THF (1:1) [15].
4.5.5. Average fiber diameter versus distance needleecollector
Fig. 13(a) shows the influence of the distance needleecollector
on the diameter of the nanofibers obtained experimentally using
the solution and the parameters mentioned in the figure caption.
Fig. 13(b) presents the same influence this time predicted theo-
retically using Eq. (4).
Theoretical values, mentioned in Fig. 13(b) obtained with Eq. (4),
under the same conditions of flow, distance between the needle
and the collector plate (nm), applied voltage and polymer solutions
are smaller than the experimental values including the increasing
ratio. The values range from 295 nm (at 45 mm distance) to 347 nm
(at 120 mm) with an increasing ratio of 347/295 ¼ 1.18. The
experimental values range from 682 nm (at 45 mm) to 2908 nm (at
120 mm) with an increasing ratio of, 2908/682 ¼ 4.25. Difference is
determined by the non-uniformity of the intensity of the electric
field, to take into consideration, in Eq. (4), only the conduction
current and the climate conditions in experiments.
Electrospinning experiments presented in the literature have
revealed that an increase of the needleecollector distance leads to
larger fiber diameters. Our own experimental results performed
with dimethylacetamide and tetrahydrofuran have also revealed
a direct dependence of the fiber diameter with the needlee
collector distance. At the same time an increase of the distance
above an optimum value, which is determined by the correlation of
constructive and technological parameters, leads to electrospun
fibers with defects (fibers are glued together). From our experi-
ments we also revealed the decrease of the fiber diameter with the
increase of the distance needleecollector. This specific character-
istic is due in our experiments to the differences in evaporation
speeds of the two employed solvents (dimethylacetamide and
195
tetrahydrofuran) and also due to the decrease in electric field
strength at bigger needleecollector distances. We can therefore
conclude that an optimum electric field strength exists below
which the elongation of the polymer jet decreases leading to
increased fiber diameters.
Variation of the needleecollector distance has a direct influence
both on the time of flight and on the strength of the electric field
which is formed between the needle and the collector. In order to
obtain defect free (not glued together) and dry nanofibers the
polymer jet needs to have enough time for the solvent to evaporate,
i.e. large enough time of flight. By decreasing the needleecollector
distance the travel distance of the polymer jet is decreased. At the
same time, the strength of the electric field is increased leading to
an increase of the traveling speed for the polymer jet along his
trajectory to the collector. Consequently, the time needed for the jet
to reach the collector is decreased and can become insufficient for
the evaporation of the solvent. In our particular case, tetrahy-
drofuran is not fully evaporated from the jet.
The morphology of the fibers as function of the distance
needleecollector, for various applied voltages, is similar in variation
to the morphology as a function of the applied voltage for various
distances. In Fig. 13(a) for U ¼ 30 kV clean fibers were obtained for
the variants V141 (45 mm), V142 (70 mm), V143 (80 mm), V144
(100 mm). For V145 (120 mm) beaded fibers were obtained.
4.5.6. Exceptions for average fiber diameter versus applied voltages
Tables 5 and 6 show the values of average fiber diameter for a 5%
PEO solutions at a flow rate of 0.05 ml/min and a 2.5% PEO solutions
at a flow rate of 0.15 ml/min with the increasing applied voltage for
varying distance between the needle and the collector plate [10].
196 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198

for whipping region as the fiber diameter can be decreased with the
increased stretching of the electrospun jet. If the distance between
the needle and the collector plate is not large enough, there is not
enough time for the electrospun jet to decrease its diameter even
for higher electric fields, hence increasing the fiber diameter with
increasing electric field. Also, in our experiments, we have observed

Fig. 13. Average fiber diameter versus distance between needle and collector: for flow
rate Q ¼ 0.1 ml/h and solution 12% PEI/DMA/THF (1:1). (a) Experimental for applied
voltage 30 kV, V141eV145 different technological variants [15]; (b) theoretical for
three applied voltages 15, 20 and 30 kV.

By comparing, from Tables 5 and 6, the fiber diameters with the

applied electric field and the distance between the needle and the
collector plate, the authors [10] concluded that the fiber diameter
decreases with increasing the electric field if there is enough space

Table 5
Average fiber diameter with the increasing applied voltage for varying distance
between the needle and the collector plate of 5% PEO solutions at a flow rate of
0.05 ml/min [10].

Voltage [kV] Average fiber diameter for different

distances between the needle and the collector plate [nm]

150 mm 200 mm 250 mm 300 mm

10 532  100 393  50 351  54 320  60
15 e 366  65 407  70 412  50
20 e 330  40 363  75 382  55

Table 6
Average fiber diameter with the increasing applied voltage for varying distance
between the needle and the collector plate of 2.5% PEO solutions at a flow rate of
0.15 ml/min [10].

Voltage [kV] Average fiber diameter for different

distances between the needle and the collector plate [nm]

150 mm 200 mm 250 mm 300 mm

10 532  100 393  50 351  54 320  60
15 e 366  65 407  70 412  50
Fig. 14. The morphology of beaded fibers with increasing solution viscosity: (a)
20 e 330  40 363  75 382  55
m ¼ 13 cP, (b) m ¼ 289 cP, (c) m ¼ 1835 cP [12].
 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198
that there are some technological variants where the fiber diameter
increases with increasing electric field.
4.5.7. The morphology of beaded fibers with increasing solution
viscosity
In Fig. 14, the morphology of beaded fibers with increasing solu-
tion viscosity is given: (a) m ¼ 13 cP, (b) m ¼ 289 cP, (c) m ¼ 1835 cP [12].
Fig. 15. Morphology of beaded fibers when the charge density is changing: (a) I/
Q ¼ 1.23 C/l, (b) I/Q ¼ 6.57 C/l, (c) I/Q ¼ 28.8 C/l [12].
197
Observations from Fig. 14. At m ¼ 13 cP (Fig. 14(a)) no fibers are
forming while at m ¼ 289 cP, Fig. 14(b), beads are formed along the
length of the fibers. Uniform fiber diameters and well defined
lengths can be obtained only at values as high as 1835 cP (Fig. 14(c)).
4.5.8. The morphology of beaded fibers with increasing the charge
density
In Fig. 15 is given the morphology of beaded fibers when the
charge density is changing: (a): I/Q ¼ 1.23 C/l, (b): I/Q ¼ 6.57 C/l, (c):
I/Q ¼ 28.8 C/l [12].
It is visible from Fig. 15(a)e(c) that at low values (I/Q ¼ 1.23 or
6.37 C/l) (Fig. 15(a) and (c)) beads can be seen on the electrospun
fibers. Only at values of the charge density higher than 28.60 C/l
(Fig. 15(c)) the fibers have a well define and uniform diameter and
length.
The morphology of fibers versus viscosity (Fig. 14) and charge
density (Fig.15) reveals the restrictions imposed for the choice of the
parameters (the stability zone) such that the production process of
nanofibers is stable. Operating in the “stability zone” allows fab-
rication of nanofibers with predictable and stable characteristics.
5. Analysis and conclusions
Far from the nozzle, the electrospun fiber diameter is well
defined by Eq. (2) which describes the diameter as a function of the
process parameters Q, E and I. The theoretical characteristics of the
fiber diameter given by Eq. (2) and calculated in Table 1 for
Q ¼ 0.1 ml/min, for different values of the current intensity
(h ¼ f(Q)) are plotted in Fig. 1, while Table 2 (Q ¼ 0.1 ml/min) and
Fig. 2 consider different values of the applied voltage. Starting from
Eq. (2), Fig. 5 shows the variation of the diameter (h) with the
increase in solution conductivity (Eq. (2)). Starting from Eq. (1),
Fig. 6 shows the variation of the diameter (h) with the increase of
conductivity of solutions Eq. (1), also, links the fiber diameter with
the kinematic viscosity of the polymer solution.
Our experimental results, given in Fig. 8, associated with Eq. (1),
show the variation of the average fiber diameter versus flow rate for
voltage 12 kV, the distance between the needle and the collector
d ¼ 60 mm and solution 4% PEO. Fig. 8 corresponds to Eq. (1) in the
region close to the injector. In this equation the diameter of the
nanofiber, h, is proportional to the flow rate, Q. The theoretical
values obtained with Eq. (1) correspond relatively well with the
experimental values for the same parameters.
The experimental results associated with Eq. (2) are shown in
Fig. 9 which shows the variation of the diameter (h) with the
increase of flow rate h ¼ f(Q) for different fluids. In this case while
the average fiber diameter increases with the flow rate, it appears
to saturate at high flow rate. Models of the electrospinning [5]
process indicate that the final fiber diameter should be strongly
dependent on the amount of charge present in on the jet. Cou-
lombic repulsion between charges and torques arising from the
interaction of charge with the electric field are among the mecha-
nisms proposed to be responsible for diameter reduction. In this
case the linear regions are not proportional to the flow rate but are
closer to a dependency similar to Q1/2, according to Eq. (4), or Q3/4
according to Eq. (2).
Fig. 9 shows the variation of the diameter (h) with the increase
of conductivity (h ¼ f(1/Rz)) for different fluids. Fig. 5 (h ¼ f(1/Rz)),
Eq. (2), and also Fig. 6 reveal that the fiber diameter increases to-
ward infinity when the conductivity decreases toward zero, i.e. the
resistivity Rz also increases toward infinity. For high conductivity
values the fiber diameter decreases slowly. The same dependency
h ¼ f(1/Rz) plotted based on experimental values (Fig. 10) has
a slightly different shape than the theoretical curve in Fig. 5. At
large conductivity values the fiber diameter starts to increase again
198 B. Cramariuc et al. / Journal of Electrostatics 71 (2013) 189e198
after exhibiting a minimum, evidencing the fact that more complex
phenomena need to be taken into account when addressing the
conductivity dependence. The electric conductivity of the polymer
solution determines the current passing through the electrospun
fibers and so it determines the electric charge density (I/Q C/l).
The dependence of the diameter and the charge density is given
in Fig. 4 and Table 4. We observe that the fiber diameter decreases
with the charge density and that there is no limit to this decrease.
The limit is in fact determined by the aspect of the electrospun fiber
obtained in experiments (see Section 4.5.8). It is visible from
Fig. 15(a)e(c) that at low values (I/Q ¼ 1.23 or 6.37 C/l) beads can be
seen on the electrospun fibers. Only at values of the charge density
higher than 28.60 C/l the fibers have a well define and uniform
diameter and length. This value corresponds to a resistivity of
0.462 U m. The dependence of the diameter on the flow rate
(h ¼ f(Q)) at various values of the solution viscosity is given in Fig. 3
and Table 3. The fiber diameter increases with the increase in vis-
cosity without any restriction. Again, the limit is imposed by the
aspect of the electrospun fibers observed in experiments (see
Section 4.5.7, Fig. 14(a)e(c)). At m ¼ 13 cP (Fig. 14(a)) no fibers are
forming while at m ¼ 289 cP beads are formed along the length of
the fibers. Uniform fiber diameters and well defined lengths can be
obtained only at values as high as 1835 cP (see Fig. 14(c)).
Importantly, Eq. (3) introduces an additional limitation. The fiber
diameter expressed by this equation tends to infinity if the denom-
inator ð2 ln c  3Þ tends to zero. In this case, we need to impose
ð2 ln c  3Þ > 0 which results in ln c > 3=2, thus ln c ¼ R=h > 3=2.
The restrictions on the electric field intensity are also determined
experimentally (see Fig. 12, Tables 5 and 6).
In Fig. 11, the average fiber diameter versus applied voltage for
flow rate Q ¼ 0.1 ml/h and solution 12% PEI/DMA/THF (1:1) is given:
(a) experimental for distance between needle and collector
d ¼ 80 mm, V113eV153 different technological variants, (b) theo-
retical for d ¼ 45,80 and 120 mm.
Regarding the study of the influence of the applied voltage on the
diameter of the nanofibers obtained shown the fact that the diam-
eter of the fibers decreases with the increasing applied voltage.
Theoretical values, mentioned in Fig. 11(b), obtained with Eq.
(4), under the same conditions of flow, distance between the
needle and the collector plate (nm), applied voltage and polymer
solutions are smaller than the experimental values including the
decreasing ratio. Difference is determined by the non-uniformity
of the intensity of the electric field, to take into consideration, in
Eq. (4), only the conduction current and the climate conditions in
experiments. The decreasing of the fiber diameter can be seen,
also, in Table 1 when the current growths from 45 nA to 100 nA
with a decreasing ratio of 2.95 and Table 2 for the increasing the
intensity of the electric field from 50 kV/m to 400 kV/m, with
a decreasing ratio of 1.68.
In Fig. 12, the morphology of the fibers for the parameters:
Q ¼ 0.1 ml/h; d ¼ 80 mm (distance between the needle and the
collector), the voltage between 15 and 35 kV and the solution 12%
PEI/DMA/THF (1:1) is given. It was observed, from our experiments
that all areas are highly influenced by the applied electric field,
which results in a considerable variation in the morphology of the
nanofibers.
In Fig. 13, the average fiber diameter versus distance between
needle and collector: for flow rate Q ¼ 0.1 ml/h and solution 12%
PEI/DMA/THF (1:1) is given: (a) experimental for applied voltage
30 kV, V141eV145 different technological variants, (b) theoretical
for three applied voltages 15, 20 and 30 kV.
Theoretical values, mentioned in Fig. 13(b) obtained with Eq. (4),
under the same conditions of flow, distance between the needle and
the collector plate (nm), applied voltage and polymer solutions are
smaller than the experimental values including the increasing ratio.
The difference is determined by the non-uniformity of the intensity
of the electric field, to take into consideration, in Eq. (4), only the
conduction current and the climate conditions in experiments.
In Tables 5 and 6 are given some exceptions for average fiber
diameter versus applied voltages. By comparing, from Tables 5 and
6, the fiber diameters with the applied electric field and the dis-
tance between the needle and the collector plate, the authors in
Ref. [10] concluded that the fiber diameter decreases with
increasing the electric field if there is enough space for whipping
region as the fiber diameter can be decreased with the increased
stretching of the electrospun jet. If the distance between the needle
and the collector plate is not large enough, there is not enough time
for the electrospun jet to decrease its diameter even for higher
electric fields, hence increasing the fiber diameter with increasing
electric field. Also, in our experiments, we have observed that there
are some technological variants where the fiber diameter increases
with increasing electric field.
In conclusion we propose the following methodology to be
employed in electrospinning experiments. The desired fiber
diameter is determined based on the particular application domain
of the electrospun material. For this diameter, Figs. 3, 5 and 6 can be
used to determine the conductivity and viscosity values. These
values are then tested experimentally to determine the aspect of
the fibers. To establish the area of applied voltage we can use in-
formation from Figs. 11e13 and Tables 5 and 6. The area of applied
voltage for a stable operating region of the electrospun jet is a very
narrow region. Once the properties of the polymer solution are
established, also area for applied voltage, the process can be further
controlled by the flow rate and applied voltage.
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