5

Liquid Crystal-Functionalized Nano- &

Microfibers Produced by Electrospinning I

5.1 Introduction: Why Electrospinning with LCs?

5.2 What is Electrospinning?
5.3 Low Molar Mass LCs inside Electrospun
Fibers
5.4 Application Potential of LC-Containing
Electrospun Fibers

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

5.1 Introduction: why electrospinning

with LCs?
Although electrospinning () is actually a rather
old invention, it is currently attracting rapidly increasing
attention
throughout
the
international
research
community.

 Among the reasons is the potential of the technique for

producing extremely thin polymer fibers, which can easily
be functionalized () by inorganic as well as organic
non-polymeric additives.
By including LCs inside the fibers, or by spinning the fibers from
LC polymer (LCP), a number of interesting phenomena
arise, inspiring new directions of academic research and
holding potential for innovative () applications.
The extreme stretching during the spinning process aligns a
main-chain LCP very well as the fiber, and
electrospinning a lyotropic cellulose ( )based chiral nematic phase results in helical fibers.

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 If a low molar mass LC is enclosed inside the polymer fiber,

the strong encapsulation () in a cylindrical space
with diameter in the nano-to micrometer range can have
dramatic effects, e.g., expanding the LC phase sequence,
inducing unusual structures of the director field or restricting
normally continuously varying parameters to quantized values.
Compared to other approaches of studying LC confinement
effects, electrospinning has the attractive property that
the mesogenic material is incorporated at the time of
producing the fiber no time-consuming filling procedure is
required.

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 On the other hand, the various types of unique

properties of different LC phases strong response
function to applied fields or temperature changes, birefringence,
photonic band gap, spontaneous polarization, etc. can all be
transferred to the polymer fiber, giving it a responsiveness
( ) and functionality ( ) that regular polymer
fibers do not exhibit.
This is wherein the main potential for applications lies,
relevant in particular for the field of wearable electronics
and smart textiles ().

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 LC electrospinning ( ) is a very young

research field and it is presently studied by only a handful
of groups around the world.
Considering the numerous opportunities for curiositybased as well as applied research and the simplicity and
low investment costs of the experimental equipment a
strong development of the LC electrospinning in the near future can
be expected.
It is the hope of the author that this will inspire new players
to enter the field, taking it into new directions and
initiating further original thrusts in the field. It is still
largely unexplored and thus offers many attractive
opportunities for innovative research.

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

5.2 What is Electrospinning?

Electrospinning provides a convenient means of
producing exceptionally thin fibers from a variety of polymers.
In contrast to standard spinning ( ) techniques, the
driving force in electrospinning not being mechanical but
electrostatic.
The physics and chemistry involved in the process are
fascinating from a fundamental research point of view,
and the produced fibers have considerable potential for new
devices and composite materials as they can exhibit
properties that are quite unique.
The first patents related to electrospinning are now more
than a century old (a crucial patent by Anton Formhals
appearing some 30 years later).

 Recently there has been a strong revival () of the

interest in the technique, largely because it offers a number
of attractive features which fit very well with todays focus on nano-,
micro- and biotechnologies and advanced materials research.
X The technique allows easy fabrication of exceptionally thin
continuous fibers with diameters down to some 3 nm in extreme
cases, difficult if not impossible to achieve with other
spinning techniques.
Y By using different variations of the basic electrospinning
set-up, a range of different fibers with varying functionalities can
be produced, including composite fibers with different materials
in the core and in the sheath, and they can be collected aligned or
unaligned, the latter resulting in non-woven textiles (
).

Z The equipment needed is of very small-scale and

compared to the equipment for standard spinning
techniques inexpensive, such that an electrospinning set-up
can easily be incorporated in a standard research lab.
[ The understanding of the electrospinning process has
dramatically improved during the last 10-20 years.
h largely due to seminal () works, e.g., from the groups

of Darrel Reneker (University of Akron), Alexander Yarin

(University of Illinois at Chicago), Joachim Wenndorf and
Andreas Greiner (Universitat Marburg), Gregory Rutledge
(MIT), Seeram Ramakrishna (National University of
Singapore) and Younan Xia (Georgia Institute of
Technology).

 The two key components of an electrospinning set-up are

X high-voltage DC power supply Y a syringe () pump (or
two or three of them) or microfluidics control unit.
Other needs
* containers and tubing () for the fluids to be spun (when a
syringe pump is used a syringe can basically fill both purposes),

* a metal capillary () that acts as the spinneret () (the

nozzle () through which the fluid to be spun is ejected),
* a target electrode or combination of electrodes on which the fibers
can be collected (while this is often referred to as the collector, fiber
collection is in fact often done on an object inserted between the
spinneret and the target electrode),
* a construction for conveniently varying the distance between
spinneret and target electrode.

* one generally closes off () a volume of air in which the spinning

takes place using, e.g., a plexiglass (), in order to
have some control over the atmosphere in which the fibers are
spun, the relative humidity being of particular importance.

5.2.1 Polymers and Solvents Convenient for

Electrospinning
The fluid to be spun needs to be non-Newtonian. The
typical choice is a polymer solution (although polymer melts
() can be spun successfully).
The solvent evaporates during the spinning process, leaving
the polymer or polymer blend to form the solid fiber. Also
non-polymeric fluids or particles can be incorporated
within the polymer fiber by using variations of the basic
technique.

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 While many different polymers have been electrospun

(Tab. 7.1) using a variety of solvents, water- or ethanolsoluble polymers such as poly(ethylene glycol/oxide) (PEG/PEO
/), poly(vinyl pyrrolidone) (PVP
), poly(vinyl alcohol) (PVA), and various cellulose
( ) derivatives are convenient to work with from a
practical and environmental point of view.
Fibers of poly(styrene) (PS ), poly(acrylonitrile)
(PAN), polylactide (PLA), and polyamides
(PA ) are also commonly produced by
electrospinning, but they require organic solvents that
may be less pleasant to work with.

5.2.2 The First Zone: Formation of the Taylor

Cone
In contrast to ordinary spinning processes, the pressure
on the spinning fluid is weak and the flow consequently
becomes very slow in electrospinning.
If no electric field is applied there will be a drop of the
spinning fluid leaving the spinneret perhaps every 110 s.
Thus, the flow is not a driving force in the spinning
process; it is only required to constantly replenish ()
the spinning solution at the spinneret.
The driving force is instead an electric field applied to the fluid,
typically by attaching the metal capillary to the hot pole of the
DC power supply, whereas the ground is connected to the
collector.
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

 The voltage applied to the capillary is very high in the

range of 10-20kV, hence the power supply must be a
rather special one (in fact, most groups doing
electrospinning use the same brand ( ) of power
supply: Gamma High Voltage Research).
The current should however be very low (if not there is a
short-circuit () and something is severely wrong),
hence the power supply will deliver only some hundred A,
rendering the set-up quite safe to work with.
The distance between the spinneret and the collector is
typically around 10 cm, so the applied field is on the
order of kV/cm or 0.1 V/m. It is thus comparable to the
electric fields typically applied for switching LCs, which
may however also be even an order of magnitude or two
higher.

 Basis of electrospinning and fabrication of the fibers

(a) The spinning fluid is slowly pumped through a capillary (the

spinneret) until it protrudes () slightly from the capillary orifice.

FIGURE 7.2 The different steps in the formation of the Taylor cone and jet ejection, the first stage of electrospinning.
(a) Spinning fluid is slowly pumped through a capillary (the spinneret) until it protrudes slightly from the capillary orifice.
(b) Electric voltage applied to the spinneret separates the ions in the fluid, those with the same charge as the voltage
being repelled towards the boundary of the protruding drop.

(b) The electric field leads to a separation of charges in the spinning

fluid, e.g., the positive charges accumulating at the surface of the
drop protruding from a positively charged spinneret (or negative
charges for a negative spinneret voltage).

FIGURE 7.2 The different steps in the formation of the Taylor cone and jet ejection, the first stage of electrospinning.
(a) Spinning fluid is slowly pumped through a capillary (the spinneret) until it protrudes slightly from the capillary orifice.
(b) Electric voltage applied to the spinneret separates the ions in the fluid, those with the same charge as the voltage
being repelled towards the boundary of the protruding drop.

(c) With the application of the electric field a conflict between surface
tension and electrostatic forces arises: while the former promotes a
spherical droplet shape in order to minimize the surface of the liquid,
the latter promotes a movement of the positive ions closer to the
collector. The result is a deformation of the droplet into a cone
shape, referred to as the Taylor cone.

Taylor
cone
FIGURE 7.2 The different steps in the formation of the Taylor cone and jet ejection, the first stage of electrospinning.
(b) Electric voltage applied to the spinneret separates the ions in the fluid, those with the same charge as the voltage
being repelled towards the boundary of the protruding drop.
(c) These charges are attracted so strongly towards the collector that the drop deforms into a cone.

(d) Once the electric field is sufficiently high, the electrostatic repulsion
between the ions at the cone tip, and the attraction of the ions
towards the collector, are so strong that they overcome the surface
tension, leading to a liquid jet shooting out from the Taylor cone.
* The region with the capillary orifice (,) and the Taylor cone can
be called the first zone of electrospinning.

first zone

electrostatic repulsion
between the ions at
the cone tip

FIGURE 7.2 The different steps in the formation of the Taylor cone and jet ejection, the first stage of electrospinning.
(d) Self repulsion between the accumulated charges and their attraction towards the collector overwins the surface
tension of the fluid, leading to the ejection of a thin jet of highly charged fluid from the cone tip towards the collector.

 Some delay between field application and jet formation

may occur, the magnitude depending on the rheological
( ) properties of the spinning solution. In typical
cases, it is less than a second but with a highly viscoelastic
spinning fluid such as a polymer melt the jet ejection can
be delayed by as much as 90 s.
The size of the capillary orifice (,) has little impact on
the jet diameter when it leaves the Taylor cone, as long
as it is not so small that it leads to viscous flow restriction.

5.2.3 The Second Zone: Jet Formation or

Electrospray
If the spinning solution would be water or another
ordinary Newtonian liquid, the jet would soon break up
into droplets as a result of the Rayleigh instability
(capillary instability) that minimizes the surface energy of
the liquid.
When this happens we have electrospray ( ), a
technique that has become very important at the sample
preparation stage of mass spectrometry, in particular in
the study of large biomolecules such as proteins (John B.
Fenn was awarded the 2002 Nobel prize for chemistry for the introduction of
electrospray ionization into the field of mass spectrometry).

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 The division into droplets leads to rapid evaporation of

liquid and a consequent strong increase in charge density
within each droplet, quickly becoming so high that the
initially formed droplets break up into much smaller ones,
a process referred to as atomization.
Electrospray ( ) is something we wish to avoid in
electrospinning and we do this by using non-Newtonian liquids
as spinning solutions, which are most often solutions or
melts of polymers with very high molecular weight.
The viscoelastic ( ) properties of the polymer
solution/melt counteract (...,,) the
separation into drops due to the Rayleigh instability and
stabilize the jet, which thus stays intact ( ) and
moves towards the collector.

 Nevertheless, the Rayleigh instability may be partially effective,

producing a chain of regularly spaced drops (beads) along the fiber.
This morphology is normally not desired and one must
then modify the spinning parameters to regain continuous, smooth
fibers.
To some extent beading can be counteracted by
increasing the feed rate of the spinning solution but more
effective is to modify the composition of the solution.
If one cannot switch () to a polymer with higher
molecular weight one can either raise the polymer
concentration, although this will also give thicker fibers,
or increase the conductivity of the solution, e.g., by salt
addition (). Since thin fibers are typically desired the
latter option is often to prefer.

FIGURE 7.3 The character of the produced fibers can be tuned between beads on a string and
smooth fibers with constant thickness by varying the composition of the spinning solution. The
polymer concentration can be changed (thereby also influencing the fiber thickness) and/or the
solution conductivity may be raised (e.g., by salt addition).

 Directly after leaving the Taylor cone the acceleration of

the fluid in the electric field is so strong that the jet
acquires translation velocities of about 5 m/s.
This should be contrasted with the typical drift speeds of
the ions in the solution on the order of 0.1 m/s and the
very slow flow rate of the fluid(s) involved. This means
that translational flow as well as charge translation within
the jet can essentially be neglected from the point where
the jet leaves the Taylor cone.
In a first approximation, we can consider the
electrospinning process as pure elongational flow (
) and the relevant viscosities of the involved fluids are
thus the elongational rather than the shear viscosities (The
elongational/shear viscosity of a fluid expresses its resistance to
elongational/shearing flows).

5.2.4 The Third Zone: Bending Instabilities and Fiber

Stretching
On the way from the spinneret to the collector the jet is
longitudinally stretched due to the repulsion between the likecharged ions that the jet carries with it.
It also repeatedly experiences a second instability which is
of great importance for the electrospinning process and
the resulting fibers.
h This is a bending instability, also fundamentally

resulting from the electrostatic repulsion between like-charged

elements along the jet, but now in conjunction with a
lateral fluctuation ().

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 Considering only three charges

distributed along a certain
length
of
the
jet,
the
electrostatic self repulsion will
lead to no net force on the
central element as long as the
jet is absolutely straight.
The forces from the upper and
lower charges (Fu and Fd,
respectively, with u for up and
d for down) are equal and
oppositely directed; thus they
compensate each other such
that the net electrostatic force
Fr=0 (Fig. 7.4a).

FIGURE 7.4
A simplified model for explaining
the bending instability at the core
of the exceptional stretching of the
jet during electrospinning.

 But with a highly-possibly occurred slight lateral fluctuation of

the fiber (Fig. 7.4b), the forces are no longer balanced,
yielding a nonzero lateral Fr. This amplifies the fluctuation
and thus eventually giving rise to the bending instability,
occurring when Fr is strong enough to overcome the elastic and
viscous forces which promote the linear
jet path (which is the shortest).
h The process is analogous to the

Euler buckling process in mechanics

(and thus also to the Frederiks transition, at the
core of most electrooptic applications of LCs),
where a pillar () compressed
along its axis eventually breaks
with a lateral movement as a lateral
fluctuation is amplified by the
axially applied force.

FIGURE 7.4
A simplified model for explaining
the bending instability at the core
of the exceptional stretching of the
jet during electrospinning.

h The bending instability gives rise to a

spiral-shaped continued
path of the jet with a conical envelope (Fig. 7.5), first with a
long pitch and relatively large (and increasing) spiral
diameter. Eventually a second bending instability will
typically appear, resulting in a smaller diameter spiral
modulation of the jet, and this can
go on to a third and fourth or
even fifth hierarchical instability.

FIGURE 7.5
A simple cartoon of the envelope of the
jet
during
electrospinning,
characterized by multiple superposed
spiral modulations due to subsequent
electrostatically induced bending
instabilities.

h The reason for the

multiple bending instabilities is the

continuously increasing charge density during the flight of the
jet; although one might at first think that the substantial
stretching would reduce the local charge density (
) in the jet one must remember that the rapid
evaporation of the solvent reduces
the total jet volume, generally
leading to a net increase in charge
density.

FIGURE 7.5
A simple cartoon of the envelope of the
jet
during
electrospinning,
characterized by multiple superposed
spiral modulations due to subsequent
electrostatically induced bending
instabilities.

h As a result of the

multiple bending instabilities the jet follows a

very complex path from the spinneret to the collector,
with a path length that is orders of magnitude greater
than the actual spinneret-collector distance, and the
continuous stretching along this path renders () the
jet very much thinner at the end of the
spinneret
at the begging
process than at the beginning. This is (thicker)
what allows such exceptionally thin
fibers
to
be
produced
by
at the end
(thinner)
electrospinning.

collector
FIGURE 7.5
A simple cartoon of the envelope of the
jet
during
electrospinning,
characterized by multiple superposed
spiral modulations due to subsequent
electrostatically induced bending
instabilities.

h The elongation of the jet due to the

multiple bending
instabilities will normally continue until it hits the collector
(or an object inserted in the spinning path) or until the
polymer solidifies due to solvent evaporation or, in case
of melt spinning, to cooling.

h During the elongation stage the jet

experiences stretching ratios in the

range of 105 and stretching rates
up to 105/s, values which are
unmatched by other methods like
fiber extrusion () followed
by mechanical stretching.

at the begging
(thicker)

spinneret

at the end
(thinner)

collector
FIGURE 7.5
A simple cartoon of the envelope of the
jet
during
electrospinning,
characterized by multiple superposed
spiral modulations due to subsequent
electrostatically induced bending
instabilities.

5.2.5 The Fourth and Final Zone: Fiber Collection

Just before the jet reaches the collector its translational
speed is very high ~ order of 40 m/s. When it hits the
collector the motion is abruptly stopped. Because of the
bending instabilities during the jet flight, the motion is
largely lateral in the plane of the collector, and the fiber
can therefore be deposited as a relatively straight fiber.
Depending on the vertical position of the collector, the
impact () of the jet may however be more or less
head on, and in that case the buckling instability (,
,) arising upon impact will lead to a
characteristic small-diameter spiral ( ) pattern of the
deposited fibers.

By Prof. Chia-Rong Lee

Liquid crystal Photonics lab.

 Normally one tries to optimize a set-up such that the jet

solidifies just before or just after it hits the collector.

* If it is too wet the fiber morphology is not stable and deposited fibers
will merge as a result of flow after deposition.
* If it is entirely dry then the decharging of the fiber via the contact with
the grounded collector takes longer time. Since the fiber is still
highly charged when it lands on the
collector it repels the jet that
approaches from above, which therefore
moves laterally towards a different
collection spot.
* As long as the charge on the deposited
fiber is quickly neutralized this is fine; it
results in a criss-cross ()
FIGURE 7.6 SEM images of coaxially
electrospun fibers with a NLC core and a
deposition of fibers producing a
composite sheath of PVP and TiO . The
characteristic open network mat (,,
fibers were collected as a random nonwoven () mat (a) and aligned
) structure (Fig. 7.6a).
2

between the arms of a tweezer (b).

 In many cases an aligned collection of fibers is desired for

device applications, especially in the fabrication of electric
and photonic devices like field effect transistors, sensors
and diodes, and a number of approaches have been
developed to achieve this.
* The most obvious solution is to collect the fibers on a quickly rotating
drum (), leading to fibers aligned perpendicular to the rotation
axis.
Drum

Collected
fibers

P. Katta et al., Continuous electrospinning of

aligned polymer nanofibers onto a wire drum
collector. Nano Lett. 2004, 4, 22152218.

* Quite well aligned fibers can be achieved in a much easier way,

simply by splitting up () the collector electrode in two parallel
grounded plates or wires.

* The electric field profile has a horizontal component that promotes

stretching of the fibers across the gap between the electrodes.
Together with the repulsion between fibers that are suspended
between the electrodes, thus only slowly discharged, this leads to
an alignment of the fibers across the gap that can be quite good.

(a) Schematic illustration of the setup for collecting nanofibers as a uniaxially aligned array. The collector contains an insulating void,
such as the air gap between two strips of silicon wafers. (b) Electrostatic force analysis of a charged nanofiber spanning across two
silicon strips. The orientation of the nanofiber is mainly controlled by the stretching force originating from the attractive electrostatic
forces. (c)-(f) SEM images of uniaxially aligned nanofibers made of (c) carbon, (d) anatase TiO2, (e) NiFe2O4, (f) TiO2/PVP

* An interesting variation of this alignment technique was introduced

recently by Yan et al. Rather than splitting up the target electrode in
two, they placed two parallel blocks of a high permittivity dielectric
material on top of the single grounded target electrode, again
resulting in a lateral component of the electric field that stretches
the fibers across the gap between the dielectric blocks. They
demonstrated the concept with PVA fibers spun from aqueous
solution onto water containers, blocks of wood, or ferrite (),
the latter yielding the best results.
r=4

(a) electrospun nanofibers

randomly deposited across the
gap as a nonwoven mesh using
epoxy resin as collector
(b) replacing the epoxy collector
with ferrite aligned nanofibers
mesh could be obtained

r=12

 If control of fiber alignment is much more critical than

reduction of fiber diameter an attractive alternative can
be to terminate the flight of the jet prior to (...)
the first bending instability, i.e., the third zone is
eliminated from the process.
Using this so-called near-field or high precision
deposition electrospinning, in which the spinneret
collector distance is often only about a millimeter,
excellent control of the position and alignment of the
fibers can be achieved.

electrode-to-collector distance, h,
is in the range of 500 m to 3
mm to utilize the stable liquid
jets region for controllable
deposition

 Moreover, by using a collector

substrate movable by an xy-translator
very sophisticated patterns can be
spun (In principle also the spinneret could be
moved but this is practically much more
challenging since the spinneret is connected
to the tubes for feeding with spinning solution
& to the hot pole of the power supply.).
This comes at the cost of somewhat thicker fibers and
probably poorer alignment of the polymer chains within
the fiber, since the extreme stretching (induce very thin
fibers) induced by the multiple bending instabilities has
been removed from the process.
Moreover, the fibers may still be deposited with local
spiral morphology due to a buckling instability at impact
on the collector, especially for spinning distances
greater than 1mm.

5.2.6 Coaxial Electrospinning

A version of electrospinning that is
particularly useful for incorporating LMW
LCs is coaxial electrospinning, where one
fluid is spun inside another one.

(A) Schematic illustration of the setup for electrospinning nanofibers having a

core/sheath structure. The spinneret was fabricated from two coaxial
capillaries, through which heavy mineral oil and an ethanol solution containing
PVP and Ti(OiPr)4 were simultaneously ejected to form a continuous, coaxial
jet. (D) SEM image of a uniaxially aligned array of anatase hollow fibers that
were collected across the gap between a pair of electrodes. In the preparation
of all these samples, the feeding rate for heavy mineral oil was 0.1 mL/h and
the concentrations of Ti(OiPr)4 and PVP were 0.3 and 0.03 g/mL, respectively.
The voltage of electrospinning was 12 kV.

 The beauty of coaxial electrospinning is that any fluid with suitable

viscosity that is immiscible () with the polymer solution
(jets produced with miscible fluids do not maintain the coaxial
geometry via the electrospinning process) can be spun into fibers
by pumping this fluid through the inner capillary. The polymer forms
a protective and confining cylindrical wall around the inner fluid.
In other words, coaxial electrospinning produces
fibers with a coresheath structure, and
because the sheath () is a solid polymer the
core can be a LMW liquid (it can of course also
be a polymer), in our case a thermotropic LC.
The inner fluid can give the composite fiber new
functionality, e.g., special optical properties from
a LC core. But even simple alkanes inside the
fibers can functionalize the produced nonwovens ( ) into phase
change materials useful for temperature
stabilization.

 Although we could in principle charge both or either liquid in coaxial

electrospinning by using a metal capillary at the end of the inner
tubing, upon connecting this to the hot pole of the power supply
rather than the outer capillary (which in this case could be made of
glass, for instance), the most common configuration is one where
only the outer fluid is in direct contact with the electrode (the outer
capillary, made of metal) and thus only this fluid gets charged.
The inner fluid then does not experience the electrostatic forces
that drive the electrospinning process, these being active only in the
outer fluid. The jet core is instead stretched only by mechanical
means as a secondary effect from the electrostatic stretching of the
sheath.
This is advantageous when spinning living matter, such as cells,
which may not survive the strong electrical charging, but it may also
be a means of spinning highly conductive solutions, e.g., carbon
nanotube suspensions or conductive polymers. These would shortcircuit () the set-up and thus terminate spinning as soon as the
jet makes contact with the collector.


(Newtonian fluid)

(non-Newtonian fluid)