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8/10/2019 A review in electrospinning
1/8
Formation of fibers by electrospinning
Gregory C. Rutledge , Sergey V. Fridrikh
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
Received 20 December 2006; accepted 14 April 2007
Available online 22 August 2007
Abstract
Electrostatic fiber formation, also known as electrospinning, has emerged in recent years as the popular choice for producing continuousthreads, fiber arrays and nonwoven fabrics with fiber diameters below 1 m for a wide range of materials, from biopolymers to ceramics. It
benefits from ease of implementation and generality of use. Here, we review some of the basic aspects of the electrospinning process, as it is
widely practiced in academic laboratories. For purposes of organization, the process is decomposed into five operational components: fluid
charging, formation of the cone-jet, thinning of the steady jet, onset and growth of jet instabilities that give rise to diameter reduction into the
submicron regime, and collection of the fibers into useful forms. Dependence of the jetting phenomenon on operating variables is discussed.
Continuum level models of the jet thinning and jet instability are also summarized and put in some context.
2007 Elsevier B.V. All rights reserved.
Keywords: Electrospinning; Nanofiber; Electrohydrodynamics
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1384
2. Brief description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
3. Fluid charging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
4. Cone-jet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
5. Slender thinning jet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386
6. Jet instability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1388
7. Fiber collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
1. Introduction
Electrospinning is a term used to describe a class of fiber
forming processes by which electrostatic forces are employed to
control the production of fibers. It is closely related to the more
established technology of electrospraying, which generally refers
to processes in which electrostatic forces are used to control the
formation of droplets. Spinningin this context is a textile term
that derives from the early use of spinning wheels to form yarns
from natural fiber staples like cotton and is commonly used to
identify fiber-forming processes for synthetic fibers as well. In
both electrospinning and electrospraying, the role of the
electrostatic forces is to supplement or replace the conventional
mechanical forces (e.g. hydrostatic, pneumatic) used to form the
jet and to reduce the size of the fibers or droplets, hence the term
electrohydrodynamic jetting. Electrospraying was described in
the technical literature by Zeleny as early as 1914 [1], while
electrospinning first appears in the patent literature in 1902 [2].
Electrospraying has enjoyed a rich history in the intervening
Available online at www.sciencedirect.com
Advanced Drug Delivery Reviews 59 (2007) 1384 1391www.elsevier.com/locate/addr
Corresponding author. Tel.: +1 617 253 0171.
E-mail address:[email protected](G.C. Rutledge).
0169-409X/$ - see front matter 2007 Elsevier B.V. All rights reserved.doi:10.1016/j.addr.2007.04.020
mailto:[email protected]://dx.doi.org/10.1016/j.addr.2007.04.020http://dx.doi.org/10.1016/j.addr.2007.04.020mailto:[email protected]8/10/2019 A review in electrospinning
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century, with commercial applications in ink jet printing, mass
spectrometry, and fuel injection, to name a few. Electrospinning
on the other hand has developed more slowly. Notable early
studies are those by Baumgarten [3], and by Larrondo and St.
John Manley [4] but apparently neither received subsequent
follow-up. In the 1990's Reneker and co-workers [5,6], drew
attention to electrospinning as a means to produce small diameter,continuous filaments. In contrast to conventional synthetic fiber
forming processes such as those used for high speed spinning of
nylon or polyester, where continuous fibers ranging from 10 to
500 m are produced, electrospinning readily leads to the
formation of seemingly continuous fibers with diameters ranging
from0.01 to 10m. The literature on electrohydrodynamic jetting
and atomization for electrosprays is extensive, and relevant to
electrospinning as well [79]. This brief review is intended to
provide an overview of the electrospinning process, a subjective
assessment of the primary operational variables as they are
understood at the current time, and some of the mathematical
modeling that has been instrumental in developing our under-standing of the process. Due to its brevity and the rapid growth of
the field in the past few years, it is necessarily incomplete, as our
understanding of the technology continues to improve with the
benefit of on-going research.
2. Brief description
In its simplest incarnation, the process of electrospinning is
relatively easy to implement. In the laboratory, a glass pipette is
filled with a solution comprising the spin dopeand mounted at
an angle sufficient to prevent discharge of the fluid from the
pipette under its own weight. A wire electrode inserted into the
fluid reservoir in the pipette and charged to a relatively highvoltage, typically around 10 kV, provides the necessary charging
potential. Under such conditions, the fluid itself charges to a high
potential (positive or negative, depending on polarity of the
voltage generator). The typical spin dope has sufficient
conductivity for the induced charge to relax to a free surface or
interface on a time scale short compared to the experimental time
scale, but it otherwise acts as a dielectric. The term leaky
dielectric is descriptive of such fluids [10]. The repulsion
between charges at the free surface then works against surface
tension and fluid elasticity to deform the droplet into a conicalshape, called a Taylor cone after the pioneering work of G.I.
Taylor[11]. Beyond a critical charge density, this cone is unstable
and a jet of fluid is emitted from the tip of the cone. This charged
jet then seeks a path to ground. As it does so, the fluid filament is
accelerated and stretched and may experience any of a number of
instabilities, the relative importance of which depends on
numerous variables, including the properties of the fluid, the
electric field environment and the dynamical behavior of the
jetting phenomenon. A suitable collector electrode is used to
direct this path to ground. Thus, the electrospinning process may
be broken down into several operational components: (i) charging
of the fluid, (ii) formation of the cone-jet, (iii) thinning of the jet inthe presence of an electric field, (iv) instability of the jet, and (v)
collection of the jet (or its solidified fibers) on an appropriate
target. A simple schematic of the process is shown inFig. 1.
3. Fluid charging
In electrospinning, generation of charge within the fluid
usually occurs by virtue of contact with and flow across an
electrode held at high (positive or negative) potential, referred to
as induction charging[12]. Depending on the nature of the fluid
and the polarity of the applied potential, free electrons, ions or
ion pairs may be generated as charge carriers in the fluid; the
generation of charge carriers can be very sensitive to solutionimpurities. The formation of ions or ion pairs by induction
results in the formation of an electrical double layer. In the
absence of flow, the double layer thickness is determined by the
ion mobility in the fluid; in the presence of flow, ions may be
convected away from the electrode and the double layer
continually replenished. Charging of the fluid in electrospinning
is typically field-limited, with the break-down field strength in
dry air being on the order of 30 kV/cm between flat plates.
Inductive charging is generally suitable for fluids with
conductivities of the order of 102 S/m. For nonconductive
fluids such as hydrocarbons and polymer melts, charge may be
injected directly into the fluid, as is done in electrostaticthrusters, by the use of two electrodes, one having a needle-like
geometry. An early example of this was reported by Kim and
Turnbull for electrospraying [13]. For electrospinning, Kelly
has reported the production of fibers using a charge injection
device originally developed for fuel atomization[14]. Relative-
ly high throughputs were achieved in the latter case, but the
resulting jet deviates from the conventional cone-jet/thinning jet
mode described in detail below.
4. Cone-jet
Cloupeau and Prunet-Froche [15] have described several
functioning modes of operation for electrohydrodynamic jets
Fig. 1. Schematic of the electrospinning process. (a) high voltage power supply;
(b) charging device; (c) high potential electrode (e.g. flat plate); (d) collector
electrode (e.g. flat plate); (e) current measurement device; (f) fluid reservoir; (g)flow rate control; (h) cone; (i) thinning jet; (j) instability region.
1385G.C. Rutledge, S.V. Fridrikh / Advanced Drug Delivery Reviews 59 (2007) 13841391
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leading ultimately to the formation of charged droplets or aerosol.
For the case of electrospinning, the cone-jet regime is of particular
note since it represents the initial stage of formation of the fiber.
Available information on charge injection devices suggests that
these often form what Cloupeau and Prunet-Foche callramified
jets. At sufficiently high voltages, multiple jetting from the
spinneret may also be observed in the conventional electrospin-ning process [8,16], but is not discussed further here. Tracer
particles have been used to reveal an axisymmetric circulation
flow within the cone, suggesting that the stable jet forms by
shearingfluid off the surface of the cone[9]. Ganan-Calvo[17]
has developed an asymptotic solution for the cone-jet configu-
ration that provides expressions for the electric current, cone-jet
shape, and charge distribution within the jet. Yan et al.[18]have
modeled the steady jet equations of the cone-jet numerically as a
2-dimensional free surface flow.
5. Slender thinning jet
As it emits from the cone, the fluid jet forms a slender,
continuous liquid filament. The fluid is charged and accelerates
in the presence of the electric field created by the high potential
of the spinneret and by the charged fluid itself. Fig. 2. shows
images of several representative jets for different flow rates ( Q)
and applied electric fields (E). Numerous attempts have been
made to decipher trends in electrospun jet operation as functions
of fluid and operating parameters under experimental control.
Within certain limits, for a given fluid there exist ranges of
driving voltage (V) and flow rate over which the electrospinning
can be maintained stably for long periods. The electrospinning
process constitutes an electrical circuit, so one can measure as
well the current (I) flowing through this circuit. Numerousinvestigators have reported currentI increasing with voltage V
in a nonlinear fashion[16,1923]. Theron et al. and Demir et al.
fit their data to power laws, IVx, with values ofx =2.17 and
2.7, respectively, while Deitzel et al. and Shin et al. attributed
the nonlinear behavior to the onset of fluid instabilities which
they observed to occur at a critical voltage. Shin et al. [22]and
Demir et al. [16] also showed that for sufficiently large flow
rates, currentIis roughly proportional to flow rate Q, indicative
of a volumetric charge density,I/Q, independent of flow rate. At
low flow rates,I/Qtends to increase asIbecomes less sensitive
to Q [24]. Theron et al., on the other hand, reported IQx,
1.04bb0.26, for a range of fluids, which they attributed to
ion mobility-limited charging of the fluid in their equipment
configuration[23].
Mathematical description of the thinning liquid jet can be
formulated within the context of conventional electrohydrody-
namics[17]. One such exposition is that presented by Hohman
et al.[25]for Newtonian fluids, which makes use of the slender
body approximation to write perturbative expansions in the
aspect ratio of the jet for the relevant jet characteristics, such as
diameter (h), velocity (v), surface charge density () and local
electric field strength (E), in terms of radial (r) and axial (z)
coordinates. These are substituted into the equations for
conservation of mass (for an incompressible fluid), conserva-tion of charge, differential momentum balance and the
electrostatic field arising from a line of charge whose potential
is expressed by Coulomb's law. The resulting equations are then
truncated after the leading order terms, leading to a relatively
simple 1D model for the slender thinning jet. The relevant fluid
properties, all of which can be characterized independently of
the electrohydrodynamic model, are viscosity (), density (),
surface tension (), conductivity (K) and dielectric constant ().
Operational parameters for the electrospinning process, within
this model, are flow rate (Q), electric current (I), and applied
field (E
), the last of which arises as a consequence of the
applied voltage (V) and inter-electrode distance (D), E
= V/D.
The model was shown to describe well the jet shape for lowconductivity fluids. For high conductivity fluids, convergence
of the equations to a solution was found to be laborious, a
problem associated with specifying the (unknown) initial
surface charge density on the fluid jet exiting the spinneret.
Alternatively, Hartman [26] proposed a different boundary
Fig. 2. Cone-jets of 2% solutions of polyethylene oxide (MW=920 k g/mol) in water. D =45 cm in all cases. (a)Q = 0.02 ml/min,E=0.282 kV/cm; (b)Q =0.10 ml/min,E=0.344 kV/cm; (c) Q = 0.50 ml/min,E= 0.533 kV/cm; (d) Q = 1.00 ml/min, E=0.716 kV/cm. Images courtesy of Dr. Jian Yu.
1386 G.C. Rutledge, S.V. Fridrikh / Advanced Drug Delivery Reviews 59 (2007) 13841391
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condition with specified initial slope (dh/dz)0 at the nozzle.
Feng [27] subsequently reformulated the slender body model
for Newtonian jets using an approximation for the electric field
equation that, fortuitously, circumvents the convergence
problems of Hohman et al. The resulting steady state equations
can then be written as follows[27]:
h2v 1 1
Eh2 Pehvr 1 2
vv0 1
Fr
3
Re
1
h2 gh2v0 0
1
We
h0
h2
X rr0 bEE0 2Er
h
3
E El
ln v rh
0
b
2 Eh
2 00 4
where the relevant dimensionless groups (indicative of the
relative strengths of different terms) are:
electric Peclet number charge convection=conduction:
Pe2
P
e v0
Kh05
Froude number: inertia=gravity Fr v20gh0
6
Reynolds numberinertia=viscosity: Re
qv0h0
g 7
Weber number:inertia=surface tension Weqv20h0
g8
Aspect ratio: v D
h09
Electrostatic force parameter electrostatic=inertia
XP
eE20qv20
10
Charge induction beP
e1 11
and the corresponding characteristic values employed are h0forlength,v0 Q= ph
20
for velocity, E0 I= ph
20K
for electric
field and 0=E0for charge density.is the dielectric constant
of the outer fluid (typically, air in conventional electrospinning).
Subscript 0 is used to indicate values taken at the nozzle.
Gravitational and aerodynamic contributions were analyzed by
Reneker et al. and determined to be inconsequential for the
steady electrospun jet[28].
In general, the results of Hohman et al. and of Feng indicate
that the shape of the jet is strongly dependent upon the evolution
of surface charge density and local electric field. Concurrent
with the initial rapid reduction in jet diameter, the latter two
quantities rise quickly to maximum values as charges relax to
the jet surface and surface advection current becomes more
important relative to bulk conduction current. The characteristic
length over which the initial dramatic thinning of the jet takes
place can be identified with the axial distance where advectionand conduction currents are equal. Analysis of these equations
(Fridrikh, unpublished) leads to the following relation for this
nozzle regime length L:
L5 K4Q7q3 ln v 2
8p2El
I5P
e 2 12
Beyond this characteristic length, the jet thins more slowly.
Sufficiently far from the nozzle (circa 30h0), the jet approaches
the asymptotic regime where all terms except electrostatic and
inertial must eventually die out. In this asymptotic regime, the
following scaling relations for jet diameter, charge density and
local electric field[29,30]have been derived:
h Q3q
2p2El
I
14
z14 13
r I3q
32p2El
Q
14
z14 14
EEl
IQq
2El
12 lnv
4pP
e
z
32 15
The scaling expression for jet diameter was first derived by
Kiricheneko et al.[29]and more generally for pseudoplastic and
Fig. 3. Schematic illustration of perturbations associated with several of the
lowest order instabilities, distinguished by their azimuthal wave number, s. Top
views illustrate cross-sections of the jet at maximum amplitudes of (oscillatory)
perturbation, with bold and dashed contours representing different positions
along the jet length. Bottom views illustrate changes in shape and centerline
down the length of the jet.+/ are used to indicate regions of positive or negative
deviation from the unperturbed jet shape. Perturbations are exaggerated beyond
the linear instability regime. (a) unperturbed cylindrical fluid element; (b)
varicose (s =0) instability; (c) whipping (s =1) instability (also called bending
or kink instability in the literature); (d) splitting (s =2) instability. Growth of
the varicose instability leads to equal sized droplets; growth of the splitting
instability leads to two equal sized sub-jets. Higher order (sN2) instabilities are
also conceivable.
1387G.C. Rutledge, S.V. Fridrikh / Advanced Drug Delivery Reviews 59 (2007) 13841391
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dilatant fluids by Spivak and Dzenis [31]. It was confirmed
experimentally by Shin et al.[22].
In between the nozzle regime and asymptotic regime,
viscosity may play a role in determining the rate of thinning
of the jet. A balance between electrostatic and viscous terms
(Fridrikh, unpublished) suggests the following scaling in this
regime:
h 6gQ2
pEl
I
12
z1 16
Feng [27] and more recently Carroll and Joo [32] have
furthermore extended the slender jet model to include
viscoelastic effects. Here too, the primary role of extensional
thickening is to alter the shape of the jet in the intermediate
regime of the thinning jet, resulting in sharply thinning cone-jets
such as that shown in Fig. 2a. Recent experimental studies of
model Boger fluids by Yu et al. confirm the rapid initial thinning
of the cone-jet, for viscoelastic fluids, and suggest theemergence of a new regime where the scaling of diameter
with distance along the jet increases from the inverse 1/4 power,
typical of Newtonian fluids, towards the inverse 1/2 power for
fluids with strong extensional thickening[33].
Although illuminating, these analytical solutions for the steady
jet behavior are limited by the breakdown of the slender jet
approximation in the nozzle regime, where the cone-jet occurs.
Numerical methods such as that employed by Yan et al. [18]for
the cone-jet can be matched to the slender thinning jet solutions.
6. Jet instability
In principle, the cone-jet operation is sufficient to draw outcontinuous fibers to very small diameter by electrospinning.
However, the fluids typically used in electrospinning do not
always solidify sufficiently en route to the collector to remain
fibrous after impact on the collector. In practice, as the jet thins,
it ultimately succumbs to one or more fluid instabilities which
distort the jet as they grow. A family of such instabilities exists
and can be analyzed for different conditions of the symmetry
(axisymmetric or nonaxisymmetric) of the growing perturba-
tions of the jet, using linear instability analysis [34,35].Fig. 3
illustrates the perturbations associated with several of the lowest
order instabilities. Although splaying of the jet was proposed in
the 1990's as the primary mode of instability [5], and someevidence has been found for splitting in post mortem
micrographs of fibers[36]and for secondary jetting in images
of jets[21,28](a particularly beautiful example appears in the
book by Frankel[37]), such events are relatively rare; the most
common mode of instability in electrospun jets appears to be the
growth of lateral excursions of the jet, the so-called whipping
mode[3,28,38]. This phenomenon is illustrated inFig. 4for jets
of water and polymer solution; it should be noted that this
instability is not a consequence of viscoelasticity of the fluid
and may occur for Newtonian[25,39]as well as non-Newtonian
fluids. The main competing mode of instability, at least for the
relatively dilute solutions often employed to achieve the
smallest fiber diameters in electrospinning, is that of droplet
break-up, the mode that leads to electrospraying. For the steady
thinning jets described above, Hohman et al.[25]performed the
linear instability analysis for both droplet break-up and
whipping modes and produced operating diagrams for
electrospinning that illustrate the combinations of controllable
parameters (flow rate, Q, and applied field, E
= V/D) under
which a particular fluid will electrospin (whipping) rather thanelectrospray (droplet breakup). The full dispersion relation for
the whipping instability of viscous, charged fluids in a finite
electric field was reported by Hohman et al.[25]. In the vicinity
of the onset of whipping, charge repulsion is relatively strong
compared to electrical shear stress, and surface tension effects
are relatively minor, allowing one to neglect the contributions to
the dispersion relation arising from the electric field, surface
tension and finite conductivity. In this approximation, consid-
erable simplification of the dispersion relation is obtained
[40,41]:
xk4 3qQh2
4p3Reh0 k2
2pr2
P
e 32ln v x2q: 17
where is the growth rate and k is the wave number of the
perturbation. Solving for and differentiating this with respect
tok, one obtains the growth rate and wave number for the most
unstable (i.e. fastest growing) mode:
xmax 9p5r4h0Re
8h2q2QP
e 2 2ln v 3 2
1=318
kmax p3rh0Re
h2qQ 1=3
2pqP
e 2ln v 3
1=6
19
These equations reflect the destabilizing effect of charge
repulsion (strongest for short wave length perturbations) and the
stabilizing effect of viscosity (also strongest for short wave
length perturbations), as well as the damping of the instability
growth rate due to inertia.
With respect to droplet breakup, surface stresses due to
charge-charge repulsion and due to interaction of charges on the
fluid with the applied electric field serve to destabilize the
whipping instability relative to droplet breakup, making the
former the more important mode at high field strength and
charge density. As a caveat, however, it should be borne in mind
that multiple instabilities can grow simultaneously, and even awhipping jet can ultimately decay into droplets, as illustrated by
the water jet inFig. 4. Of particular note, Hohman et al. reported
a second, electrically driven droplet breakup instability that
becomes important at high electric fields in fluids of finite
conductivity, in addition to the conventional, surface tension-
driven instability. Hohman et al. interpreted their equations for
both droplet breakup and whipping instabilities in terms of their
underlying physical mechanisms for a number of limiting cases.
From the equation of motion reported by Hohman [25],
Fridrikh et al. [24] also obtained an expression for the lateral
growth of the jet excursions arising from the whipping
instability far from its onset, deep in the nonlinear regime.
This equation contains terms due to acceleration of the charged
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presence can have benefits for selected applications, such as
wettability [49]. At least one strategy to overcome this
phenomenon involves stabilization of the jet against the droplet
breakup by introducing a more viscoelastic outer fluid in a
two-fluid co-axial jet configuration[5052]. The resulting core-
shell fiber morphology may be of interest in its own right;
alternatively, either the shell or core may be removed to yieldsolid or hollow fibers, respectively. On a related note, Gupta and
Wilkes [53] have reported a side-by-side configuration for a
two-fluid spinneret.
7. Fiber collection
Electrospun fibers are charged in flight, as described above,
and travel downfield until impact with a lower potential
electrode, or collector. A particular strength of the electropin-
ning process is that fiber collection may be guided by
manipulation of the electric field lines. The most straightfor-
ward configuration to analyze is the parallel electrodeconfiguration described by Taylor [7] and subsequently
modified for electrospinning by Shin [36] and illustrated in
Fig. 1 earlier. In this configuration, static parallel plate
electrodes are used at both the nozzle and the collector; this
configuration ensures parallel field lines throughout the process
zone, while the field configuration around the nozzle helps to
suppress corona discharge. A similar observation was made
using a ring electrode near the nozzle[19]. For the simplest case
of a static, planar collection electrode, the conventional
electrospinning process is axially symmetric and provides no
preference of direction for the fibers upon collection, resulting
in a nonwoven membrane of unoriented fibers. The integrity of
the nonwoven fabric depends on the random overlapping offibers, interactions between fibers, and welding that may
occur at contact points between fibers if they are still somewhat
fluid when collected. However, the axial symmetry of the
process is easily overcome by a number of strategies, thus
resulting in different degrees of fiber orientation in the final yarn
or membrane product. One such strategy involves use of a
rotating drum[54]or moving belt collector to produce oriented
fiber membranes. A rotating wheel with beveled edge has been
used successfully to collect fibers into an oriented, multifila-
ment thread[55]. Shaped collectors such as pins [56], parallel
bars[57], or even simple wire meshes can be used to direct fiber
collection preferentially, as the charged fibers tend to formbridges between pins or bars when appropriately spaced. In this
manner, small area arrays of highly oriented fibers have been
obtained. Rotating one of a pair of parallel disks or rings can be
used to produce short sections of twisted yarn[58]. For more
complicated collector shapes, build-up of the polymer mem-
brane on portions of the collector can alter the field lines to
ensure conformal coating of the object. Introduction of
secondary ring electrodes can be used to prolong the steady
jet regime and to focus the fiber deposition, as mentioned earlier
[42]. For the rare case where fiber instabilities are completely
absent, oriented fibers can be collected by writing, for
example on the face of a rotating wheel[59]. Conductive liquid
nonsolvents have also been used as the collector, resulting in a
wet-spinning variant of the electrospinning process and
production of fibers from solutions of nonvolatile liquids[6,60].
8. Conclusion
The main attractions of electrospinning to date have been the
ease of implementation on a lab scale and the very small diameterfibers that are readily obtained. As emphasized by Dzenis [61],
electrospinning is a top-down manufacturing process, which
offers certain advantages to fiber formation in terms of cost and
productivity over more complicated bottom-up approaches.
Fibers diameters between 100 nm and 1 m are most typical,
although fibers with an average diameter as small as 30 nm [62]
and as large as 10 m have been reported. This is two to three
orders of magnitude smaller thanconventional, commercial fibers
(10500 m) and the typical human hair (ca. 100 m).
Furthermore, in contrast to other forms of nanofibers (e.g. carbon
nanotubes), electrospun fibers are essentially continuous. This is
supported by both modeling and observations; fiber ends arerarely observed in micrographs of fibers obtained during steady
state operation. The continuous nature of the fibers is potentially
important for occupational health reasons.
Small diameter implies that a large fraction of the material is
near the surface of the fiber, and molecules embedded within the
fiber encounter shorter diffusion path lengths to the fiber
surface. Commensurate with the reduction in diameter of these
fibers, the resulting nonwoven membranes typically have very
high specific surface area, high porosity and small pore size
(pore size being equated here with some characteristic distance
between fibers) compared to other fibrous materials. These
qualities make electrospun materials attractive as candidates for
tissue engineering scaffolds, drug delivery systems, catalyst andenszyme supports, sensors, and other applications in biology,
medicine and controlled release.
Acknowledgements
The authors are grateful to the National Textile Center
(Project #'s M98-D01 and MD01-D22) and the US Army
Institute for Soldier Nanotechnologies at MIT (ARO contract
DAAD-19-02-D0002) for funding and to our several colla-
borators and team members for enlightening discussions.
References
[1] J. Zeleny, Phys. Rev. 1914, 3, 69; Proc. Camb. Philos. Soc. 1915, 18, 17;
Phys. Rev. 1917, 10, 1.
[2] W.J. Morton, US Patent 705,691, 1902.
[3] P.K. Baumgarten, J. Colloid Interface Sci. 36 (1971) 71.
[4] L. Larrondo,R. St. John Manley, J. Polym.Sci.: Polym.Phys. 19 (1981)909;
J. Polym. Sci.: Polym. Phys. 19 (1981) 921; J. Polym. Sci.: Polym. Phys.
19 (1981) 933.
[5] J. Doshi, D.H. Reneker, J. Electrost. 35 (1995) 151.
[6] G. Srinivasan, D.H. Reneker, Polymer Int. 36 (1995) 195.
[7] G.I. Taylor, Proc. R. Soc. Lond. A313 (1969) 453.
[8] I. Hayati, A.I. Bailey, T.F. Tadros, J. Colloid Interface Sci. 117 (1987) 205.
[9] I. Hayati, A.I. Bailey, T.F. Tadros, J. Colloid Interface Sci. 117 (1987) 222.
[10] G.I. Taylor, Proc. R. Soc. Lond., Ser. A 291 (1966) 159.[11] G.I. Taylor, Proc. R. Soc. A280 (1964) 383.
1390 G.C. Rutledge, S.V. Fridrikh / Advanced Drug Delivery Reviews 59 (2007) 13841391
8/10/2019 A review in electrospinning
8/8
[12] A.G. Bailey, Electrostatic Sprayingof Liquids, Wiley and Sons, New York,
1988.
[13] K. Kim, R.J. Turnbull, J. Appl. Phys. 47 (1976) 1964.
[14] Kelly, A.J., U.S. Patent Application 2001/0046599 A1, Nov. 29, 2001.
[15] M. Cloupeau, B. Prunet-Foch, J. Aerosol Sci. 25 (1994) 1021.
[16] M.M. Demir, I. Yilgor, E. Yilgor, B. Erman, Polymer 43 (2002) 3303.
[17] A.M. Ganan-Calvo, Phys. Rev. Lett. 79 (1997) 217.
[18] F. Yan, B. Farouk, F. Ko, J. Aerosol Sci. 34 (2003) 99.[19] R. Jaeger, M.M. Bergshoef, C.M.I. Batlle, H. Schnherr, G.J. Vancso,
Macromol. Symp. 127 (1998) 141.
[20] H. Fong, D.H. Reneker, Electrospinning and the formation of nanofibers,
in: D.R. Salem, M.V. Sussman (Eds.), Structure Formation in Polymeric
Fibers, Hanser, 2000.
[21] J.M. Deitzel, J.D. Kleinmeyer, D. Harris, N.C. Beck Tan, Polymer 42
(2001) 261.
[22] Y.M. Shin, M.M. Hohman, M.P. Brenner, G.C. Rutledge, Polymer 42
(2001) 9955.
[23] S.A. Theron, E. Zussman, A.L. Yarin, Polymer 45 (2004) 2017.
[24] S.V. Fridrikh, J .H. Yu, M.P. Brenner, G.C. Rutledge, Phys. Rev. Lett. 90
(2003) 144502.
[25] M.M. Hohman, Y.M. Shin, G.C. Rutledge, M.P. Brenner, Phys. Fluids 13
(2001) 2201; Phys. Fluids 13 (2001) 2221.
[26] R.P.A. Hartman, D.J. Brunner, D.M.A. Camelot, J.C.M. Marijnissen, B.Scarlett, J. Aerosol Sci. 30 (1999) 823.
[27] J.J. Feng, Phys. Fluids 14 (2002) 3912.
[28] D.H. Reneker, A.L. Yarin, H. Fong, S. Khoombhongse, J. Appl. Phys. 87
(2000) 4531.
[29] V.N. Kirichenko, I.V. Petryanov-Sokolov, N.N. Suprun, A.A. Shutov, Sov.
Phys. Dokl. 31 (1986) 611.
[30] M.M. Hohman, Ph. D. Thesis, University of Chicago, 2000.
[31] A.F. Spivak, Y.A. Dzenis, Appl. Phys. Lett. 73 (1998) 3067.
[32] C.P. Carroll, Y.L. Joo, Phys. Fluids 18 (2006) 053102.
[33] J.H. Yu, S.V. Fridrikh, G.C. Rutledge, Polymer 47 (2006) 4789.
[34] D.A. Saville, Phys. Fluids 13 (1970) 2987; Phys. Fluids 14 (1971) 1095;
J. Fluid Mech. 48 (1971) 815.
[35] V.Y. Shkadov, A.A. Shutov, Fluid Dyn. Res. 28 (2001) 23.
[36] M.M. Bergshoef, G.J. Vancso, Adv. Mater. 11 (1999) 1362.
[37] F. Frankel, Envisioning Science: The Design and Craft of the ScienceImage, MIT Press, Cambridge, MA, 2002, pp. 136137.
[38] Y.M. Shin, M.M. Hohman, M.P. Brenner, G.C. Rutledge, Appl. Phys. Lett.
78 (2001) 1149.
[39] R.H. Magarvey, L.E. Outhouse, J. Fluid Mech. 13 (1962) 151.
[40] A.L. Yarin, S. Khoombongse, D.H. Reneker, J. Appl. Phys. 89 (2001)
3018.
[41] S.V. Fridrikh, J.H. Yu, M.P. Brenner, G.C. Rutledge, in: H Fong, D.H.
Reneker (Eds.), Polymer Nanofibers, American Chemical Society Sympo-
sium Series, vol. 918, American Chemical Society, Washington DC, 2006.[42] J.M. Deitzel, J.S. Kleinmeyer, J.K. Hirvonen, N.C. Beck Tan, Polymer 42
(2001) 8163.
[43] J.S. Stephens, S. Frisk, S. Megelski, F.J. Rabolt, D.B. Chase, Appl.
Spectrosc. 55 (2001) 1287.
[44] R. Jaeger, H. Schnherr, G.J. Vancso, Macromolecules 29 (1996) 7634.
[45] M. Goldin, J. Yerushalmi, R. Pfeffer, R. Shinnar, J. Fluid Mech. 38 (1969)
689.
[46] A.L. Yarin, Free Liquid Jets and Films: Hydrodynamics and Rheology,
Longman, New York, 1993.
[47] J. Eggers, Rev. Mod. Phys. 69 (1997) 865.
[48] H. Fong, I. Chun, D.H. Reneker, Polymer 40 (1999) 4585.
[49] M. Ma, Y. Mao, M. Gupta, K.K. Gleason, G.C. Rutledge, Macromolecules
38 (2005) 9742.
[50] Z. Sun, E. Zussman, A.L. Yarin, J.H. Wendorff, A. Greiner, Adv. Mater. 15
(2003) 1929.[51] D. Li, Y. Xia, Nano Lett 4 (2004) 933.
[52] J.H. Yu, S.V. Fridrikh, G.C. Rutledge, Adv. Mater. 16 (2004) 1562.
[53] P. Gupta, G.L. Wilkes, Polymer 44 (2003) 6353.
[54] B. Ding, H.Y. Kim,S.C. Lee, D.R. Lee, K.J.Choi, FibersPolym.3 (2002)73.
[55] A. Theron, E. Zussman, A.L. Yarin, Nanotechnology 12 (2001) 384.
[56] B. Sundaray, V. Subramanian, T.S. Natarajan, R.Z. Xiang, C.C. Chang, W.S.
Fann, Appl. Phys. Lett. 84 (2004) 12221224.
[57] D. Li, Y. Wang, Y. Xia, Nano Lett. 3 (2003)1167; Adv. Mater. 16 (2004)361.
[58] P.D. Dalton, D. Klee, M. Mller, Polymer 46 (2005) 611.
[59] J. Kameoka, H.G. Craighead, Appl. Phys. Lett., 3 (2003) 371.
[60] M.S. Khil, S.R. Bhattarai, H.Y. Kim, S.Z. Kim, K.H. Lee, J. Biomed.
Mater. Res. B 72 (2005) 117.
[61] Y. Dzenis, Science 304 (2004) 1917.
[62] A.G. MacDiarmid, W.E. Jones, I.D. Norris, J. Gao, A.T. Johnson, N.J.
Pinto, J. Hone, B. Han, F.K. Ko, H. Okuzaki, M. Llaguno, Synth. Met. 119(2001) 27.
1391G.C. Rutledge, S.V. Fridrikh / Advanced Drug Delivery Reviews 59 (2007) 13841391