Escolar Documentos
Profissional Documentos
Cultura Documentos
T.A. Baede
DCT 2009.052
Masters thesis
Coach(es):
Supervisor:
Table of contents
Summary......................................................................................................................................................... 1
Introduction ..................................................................................................................................................... 3
Chapter 1: Electrostatics ................................................................................................................................. 8
1.1: Electric field without dielectric ............................................................................................................. 8
1.2: Refinements ...................................................................................................................................... 10
Chapter 2: Process parameters, materials and cabin ................................................................................... 13
2.1: Process parameters .......................................................................................................................... 13
2.2: Materials............................................................................................................................................ 14
2.3: Electrospinning cabin ........................................................................................................................ 14
Chapter 3: Pre-design experiments .............................................................................................................. 16
3.1: Introduction ....................................................................................................................................... 16
3.2: Experiments and results.................................................................................................................... 16
3.2.1: Fiber deposition: experiments.................................................................................................... 16
3.2.2: Fiber deposition: results ............................................................................................................ 17
3.2.3: Writing: experiments.................................................................................................................. 19
3.2.4: Writing: results........................................................................................................................... 20
3.2.5: Influence of collector thickness: experiments ............................................................................ 22
3.2.6: Influence of collector thickness: results ..................................................................................... 22
3.2.7: Influence of collector-electrode airgap: experiments ................................................................. 24
3.2.8: Influence of collector-electrode airgap: results .......................................................................... 24
3.3: Design implications ........................................................................................................................... 25
Chapter 4: Design of a new electrospinning setup........................................................................................ 26
4.1: Introduction ....................................................................................................................................... 26
4.2: Design requirements ......................................................................................................................... 26
4.3: Configurations ................................................................................................................................... 27
4.4: The cylinder spinner .......................................................................................................................... 29
4.5: Material selection .............................................................................................................................. 30
4.6: Rotation axis ..................................................................................................................................... 30
4.7: Translation axis ................................................................................................................................. 30
4.8: Realisation ........................................................................................................................................ 30
4.9: End stops, homing strategy, endpoint detection................................................................................ 34
4.9: Control design ................................................................................................................................... 35
4.9.1: System identification.................................................................................................................. 35
4.9.2: Inter-axis disturbances .............................................................................................................. 36
4.9.3: GUI and real-time control .......................................................................................................... 36
4.9.4: Feedback control ....................................................................................................................... 37
4.10: Spacing error................................................................................................................................... 40
Chapter 5: Post-design experiments............................................................................................................. 42
5.1: Stationary deposition experiments on glass cylinder......................................................................... 42
5.1.1: Experiments............................................................................................................................... 42
5.1.2: Results ...................................................................................................................................... 42
5.2: Testing with motion ........................................................................................................................... 42
5.3: Troubleshooting ................................................................................................................................ 43
5.4: Stationary deposition experiments on PET ....................................................................................... 46
5.4.1: Experiments............................................................................................................................... 46
5.4.2: Results ...................................................................................................................................... 46
Conclusion and recommendations................................................................................................................ 48
References.................................................................................................................................................... 49
Summary
Electrospinning is a powerful and versatile technique for the fabrication of very thin fibers from
polymer solutions. In contrast to mechanical drawing processes, spinning with an electric field
provides the ability to produce fibers with much thinner diameters, typically in the micro- and
nanometer range.
In a conventional electrospinning process, a polymer solution is fed to a metallic nozzle so that a
drop appears at the tip of this nozzle. A high voltage is then applied to the nozzle, while at some
distance below it a grounded plate electrode is placed. The potential difference between both
points generates an electric field. The drop becomes charged and a thin jet is ejected from the
nozzle. Due to electrostatic forces, the jet is pulled towards the electrode. By placing a thin sheet
of collecting material between nozzle and electrode, the fiber is deposited on this so-called
collector.
Due to instabilities in the process, the material is deposited randomly, forming a so-called
nonwoven mesh with a chaotic structure. For future electrospinning applications in the fields of
filtration, tissue engineering and nano-electronics, it is necessary to make the fiber deposition
controllable. A technique developed at Eindhoven University of Technology consisting of a
moving collector and a thin, positionable grounded needle electrode makes this possible and was
implemented in an electrospinning setup. However to improve fiber deposition control, more
knowledge of the electrospinning process is required. The goal of this research study is to acquire
this knowledge through experiments.
In a first experiment, the deposition mechanisms for the grounded plate and needle electrodes
were studied. It was learned that although the deposition mechanisms are different, the
deposition looks similar. Secondly, PEO and PCL fibers were written on a moving collector
consisting of a mylar sheet in a straight line. Interestingly, it was discovered that both fibers had a
rectangular cross section. In a third experiment, it was investigated whether the collector
thickness influences the amount of deposition. It was discovered that the collector thickness does
indeed play a role and that reducing this thickness leads to more pronounced deposition. This
experimental result corresponds with electrostatic analysis, which suggests that although a
dielectric collector does not change the overall shape of the electric field, it does locally reduce
the field strength. This leads to a decrease in electrostatic pulling force and thus the amount of
deposition. In a fourth experiment, the goal was to find out whether a small airgap between
electrode and collector prevents, hinders or otherwise alters the deposition. No apparent visible
difference was detected in deposition between both types of samples. The airgap did not prevent
or hinder deposition.
Although great strides have been made in the control of the fiber deposition point, there is still a
difference between desired and realized deposition points. To further improve fiber deposition
control, it is imperative to find out which process parameters influence the fiber deposition error.
The current electrospinning setup lacks the required position accuracy to successfully investigate
this. Therefore, a new setup must be designed.
Design requirements for such a new electrospinning setup have been set. Two designs that meet
these requirements were generated, one with a planar and another with a cylindrical configuration.
A cylindrical configuration was determined to be superior and was further developed. It consists
of a rotating, thin-walled glass, cylindrical collector that can also translate along its center axis.
This cylinder spinner was built and equipped with a homing mechanism to enable reproducible
results. Furthermore, a motion control scheme was implemented.
Introduction
Electrospinning is a powerful and versatile technique for the fabrication of very thin fibers from
polymer solutions or melts. The resulting fibers are continuous and have a uniform diameter. This
diameter can vary from tens of micrometers down to a few nanometers, depending on the
process parameters. Furthermore, fibers with both solid and hollow interiors can be achieved. It is
also possible to give the fibers special properties by adding metallic, ceramic or even biological
compounds such as proteins or DNA to the source polymer material.
In literature, the technique is often compared to the traditional fiber spinning process where a
polymer melt or solution is extruded through a die with a small hole. In electrospinning, however,
instead of using mechanical forces to form the fibers, electrostatic forces are employed. The
advantage of this contactless drawing is that fibers with significantly smaller diameters can be
produced.
As mentioned before, both polymer solutions and melts can be used as a source material, but in
this report we will focus on electrospinning using polymer solutions.
In a typical procedure (see Fig. 1), a syringe with polymer solution is placed in an infusion pump
to generate a constant flow of fluid through the needle. This needle is connected to a metallic
capillary, the so-called nozzle, with a transport tube. The polymer solution is pumped through the
tube and a small liquid drop appears at the tip of the nozzle. A high voltage is then applied to the
nozzle, usually between 5 and 50 kV, while at some distance below the nozzle a grounded
electrode is placed. The potential difference generates an electric field between nozzle and
electrode.
Charged nozzle
Taylor cone
Jet
High voltage
supply
Syringe
Collecting material
Infusion pump
Grounded electrode
The jet does not follow a straight path to the electrode, however. Instead, shortly after exiting the
nozzle, a chaotic oscillation occurs, caused by charge repulsion between material elements of the
jet and an aerodynamically driven bending instability. The oscillation is known as the whipping
phenomenon in literature [2]. Because of this phenomenon, the material is randomly deposited,
creating a so-called nonwoven mesh (see Fig. 2). It is also possible to place a thin sheet of
collecting material (also called collector) on the electrode so that the electrospun material is
deposited on this sheet instead of directly on the electrode.
Liquid bath-as-collector
X
X
V
V
V
X
V
Electrode-gap spinning
V
V
X,Y,Z-positioned collector
Cylinderspinner
Bobbin collector
Near-field electrospinning
Both:
Electrostatic:
V
X
Alignment
Mechanical:
Method
Controllable spacing
Bhattarai
Teo
Teo
Sun
Kameoka
Mitchell
Sundaray
Theron/Zussman
Katta
Gibson
Yarin
Dersch
Li/Xia
Huang
Kim
Deitzel
Jaeger
Smit
Bhattarai
Subramanian
Huang
Author
[31]
[30]
[30]
[29]
[28]
[27]
[26]
[25]
[24]
[23]
[22]
[21]
[20]
[15]
[19]
[18]
[17]
[16]
[13]
[12]
[15]
Ref.
Alignment is defined as whether there is control over how parallel all fibers are positioned to each
other.
Controllable spacing is defined as whether or not it is possible to deposit two fibers next to each
other with a controllable spacing between them.
From the results in Table 1, it follows that achieving alignment of nanofibers along a single axis is
currently well-understood. The controllable spacing, however, is a different issue. Only two
groups, [27] and [29], report that they can carefully control the distance between two fibers.
At Eindhoven University of Technology, a new technique has been devised and patented to
carefully control the position of the fiber deposition point. Instead of using a grounded plate as
electrode, a grounded needle is used which can be actuated in the plane (see Fig. 3). This
technique can potentially improve the alignment and degree of spacing control significantly.
The feasibility of the technique was demonstrated by Solberg [32]. He also implemented the
technique in an experimental setup and showed that it is possible to align and deposit a single,
continuous fiber on the collecting material by moving the collector with respect to the electrode.
Fig. 4 shows a glass sample with neatly aligned electrospun fibers deposited on it using this
setup.
The experimental setup by Solberg has provided much insight into the electrospinning process.
Due to its components, however, the attainable position accuracy of the electrode and collecting
material is limited and this prevents the precise fiber deposition that is required for advanced
oriented fiber meshes necessary for many future applications. Therefore, a new electrospinning
setup is required.
Acquire more knowledge of the fiber deposition process for future improvements of
orientation control.
Design, build and test a new electrospinning setup with higher position accuracy than the
current one which is capable of depositing straight fibers with an adjustable spacing in a
reproducible manner.
Chapter 1: Electrostatics
In order to control the location of material deposition and improve deposition accuracy, good
knowledge of the underlying electrospinning process is required. Key to this control is the electric
field. First, the overall shape of the field is discussed based on electrostatics. Thereafter, a
number of effects that also influence the shape will be described to refine the situation description.
1.1: Electric field without dielectric
From an electrical standpoint, the electrospinning setup is composed of two elements: the
charged nozzle at the top and the grounded needle electrode at the bottom. This situation can be
modeled as an electric dipole. It consists of two point sources of charge, one at the tip of each
element, with a certain separation distance h. A positive charge is applied to the nozzle; hence
negative charge accumulates on the electrode to maintain equilibrium. The potential difference V
between both elements is kept constant.
Figure 5: (a) Electric field for two point sources. Blue lines represent the field lines with
the arrows indicating the direction of the electrostatic force. Red contour lines represent
the equipotential lines. (b) The same plot, but incorporating a dielectric collector.
In Fig. 5a, the shape of the electric field is shown. The red dashed contour lines represent the
equipotential lines. As the name suggests, all points on such a line are at the same electric
potential. The nozzle is at the maximum potential, while the electrode is at zero potential due to
grounding. Hence, the potential decreases while moving downwards from one equipotential line
to the next. The blue solid lines represent the electric field lines and are always perpendicular to
the equipotential lines. By convention, the direction of the lines is from positive to negative charge.
The closer the field lines are to each other, the stronger the field in that region. The field is thus
strongest near nozzle and electrode.
The relationship between potential difference and electric field strength is given by:
r r
V = E dl
b
(1.1)
Here V is the potential difference between the nozzle at location a and the electrode at location b
E=
V
h
(1.2)
with h in [m].
From this equation it can be concluded that the electric field strength is highest on the vertical
field line since the field line is shortest. In order to investigate what this means for the
electrospinning process, assume that a positive test charge is inserted in the field. The force that
this test charge will experience can be calculated from:
r
r
F = QE
(1.3)
with the force F in [N], the test charge Q in [C] and the strength of the electric field E in [V/m].
The electrostatic force acts in the direction of the electric field and therefore the pulling force on
the vertical field line will be highest. All field lines converge towards the electrode and thus the
point of the needle there will exert the largest pulling force.
Although in reality the electric field is clearly not uniform over the distance, the order of the field
strength can be estimated with Eq. 1.2. When we enter a characteristic V = 12 kV and
5
h = 0.1 m, we arrive at a field strength of E = 1.210 V/m. This is one order of magnitude below
6
the dielectric strength of air, Ebreakdown = 3.0 10 V/m, which is the field strength at which air
becomes electrically conductive [33]. The breakdown phenomenon puts a limit on how far the
field strength can be increased to accomplish focusing.
In the above text, we started from point charges. However, in reality both electrical elements have
finite dimensions and their shape influences how the electric field looks like. In Fig. 6, the electric
field around real needle or nozzle configurations is shown. The equipotential lines wrap around
the contour of the nozzles.
1.2: Refinements
Field with dielectric:
In the electrospinning setup, we use a dielectric, which we have called collector to capture the
spun polymer fibers. When a dielectric is inserted in an external electric field, the shape of the
overall electric field is not influenced, see Fig. 5b. Only within the dielectric itself, the electric field
will change. This effect is called polarization. The externally applied electric field will induce some
separation of charge in the dielectric molecules. Negative charge will orient itself towards the
upper boundary of the dielectric; positive charge orients itself towards the lower boundary of the
dielectric. Therefore, the net effect is as if there is a negative charge on the upper surface and a
positive charge on the lower surface of the dielectric. A close-up of the dielectric, demonstrating
the polarization effect, can be seen in the following figure:
The field in the dielectric E d is a vector sum of the externally applied field E ext and the field
r
Eind due to the induced charge on the surfaces of the dielectric:
r
r
r
E d = E ext + Eind
(1.4)
r
r
Eind = f ( 0 , P)
The exact definition depends on the geometry of the dielectric. In this equation,
r
2
2
2
constant of vacuum [C /Nm ] and P is the polarization density vector in [C/m ].
(1.5)
0 is the dielectric
The level of polarization that occurs can be calculated from the following relation:
r
r
P = 0 e Ed
(1.6)
where e is the electric susceptibility of the dielectric [-]. Note that the polarization depends on the
total electric field inside the dielectric.
Since in the electrospinning setup the induced field and external field are in opposite directions,
the field in the dielectric Ed is weaker than the external field Eext.
10
In the discussion above, we assumed that the dielectric is one layer of a single material. When
the collector consists of two or more layers of different materials, then
r
Eind in those layers will
differ from each other. However, as for one layer, the shape of the electric field outside of the
dielectric will not be influenced.
The same holds for a collector that is not positioned exactly halfway between nozzle and
electrode, but closer to one of the two. Although the field within the collector is no longer uniform,
the electric field outside the dielectric will keep its shape.
Introduction of the polymer:
During the electrospinning process, a drop of polymer solution is elongated and guided towards
the grounded electrode by a combination of gravity and electrostatic force. Since the polymer
solution is charged, in essence it can be seen as an extension of the nozzle. When the material
moves towards the dielectric, this is equivalent to the dielectric moving towards the nozzle.
The distance between the upper needle and dielectric decreases and thus the electric field
strength and consequently the electrostatic force increases. This leads to a distortion of the
electric field (see Fig. 8a). However, since the accumulated charge is hard to measure, the
amount of field distortion is currently unknown.
Nozzle with polymer
Nozzle with polymer
Dielectric
Dielectric
(a)
(b)
Figure 8: (a) Distortion of the electric field due to presence of polymer. (b) Contact
situation.
While the material travels downwards in the form of a jet, the solvent evaporates. Consequently,
the conductive properties of the jet change, as the material changes from a solution to a solidified
polymer.
Contact situation:
When the polymer fiber comes into contact with the dielectric, a new situation occurs. A current
will start flowing through the conductive polymer fiber.
I = Qv + E
(1.7)
where Q is the charge [C], v is the polymer flow velocity [m/s], the conductivity [m/] and E the
electric field strength [V/m].
The first term represents transport of charge due to movement of the polymer. The second term
is conduction following Ohms Law. Whether this latter term plays a role depends on the
conductive properties of the polymer when it comes into contact with the dielectric.
11
Since the collector is fabricated from an electric isolator, the charge deposited by the polymer
cannot flow away (see Fig. 8b). Therefore, the collector will become locally charged because of
the presence of charged fiber segments. These deposited segments will repel newly spun
material that arrives at the collector. On a flat collector, this leads to a radially expanding drop of
solidified polymer as this distributes charge in the most optimal way [32]. The repulsion effect is
expected to be localized; however experiments are necessary to confirm this hypothesis.
The dielectric will not stay charged forever, however, as charge will diffuse into the surrounding
atmosphere. Therefore, deposited segments will gradually lose their charge.
12
Molecular weight
Molecular weight distribution
Architecture, such as linear, branched, etc.
Viscosity
Electrical conductivity
Surface tension
Operational parameters:
The electric field strength is determined by the applied voltage V and the layout of the setup.
The deposition time period t plays a role in the characteristics of the produced mesh. A number
of operational parameters are shown in Fig. 9.
13
2.2: Materials
As mentioned in the first Chapter, the research described in this report focuses on using polymer
solutions for electrospinning. A solution is made by dissolving polymer powder in a suitable
solvent. Huang [3] lists over forty different polymers that have been electrospun in solution form
using a wide range of solvents. In this research project, two polymer solutions were used
extensively. These are listed in Table 2.
Table 2: Used polymer solutions
Polymer
Molecular weight
PEO (Polyethylene oxide)
400,000
PCL (Polycaprolactone)
200,000
Solvent
Distilled water / ethanol
(2:3)
Chloroform
Concentration
8 wt%
18 wt%
Polyethylene oxide solution is by far the most used material in electrospinning studies as it is
relatively simple to prepare and use. Therefore, a lot is known about this material, its behaviour
and properties. For these reasons, PEO was selected as main component of this research.
Polycaprolactone is a biodegradable polymer used extensively in tissue engineering research,
which is one of the proposed fields of application for oriented fiber meshes. A drawback of this
material is that it is commonly dissolved in chloroform, which evaporates during electrospinning
and leads to harmful gas formation. As a result, the use of PCL solution was limited in this project.
2.3: Electrospinning cabin
All experiments have been performed in a dedicated cabin (see Fig. 10). This cabin is outfitted
with a high voltage supply that can be controlled from an operating panel. It also protects the user
from a number of risks.
14
One risk is the high voltage (up to 25 kV). When a user accidently comes into contact with an
electrified element of the setup, the voltage enables a current to flow through the body which is
harmful and could potentially lead to death. Therefore, the cabin, which is equipped with a door
that provides access to the electrodes and other parts of the setup placed inside, is outfitted with
a safety mechanism that shuts down the voltage when the door is opened.
In the previous Paragraph it was mentioned that harmful gases may be produced during
electrospinning. Therefore, the cabin is connected to a forced ventilation system that captures
and leads any emitted gases away from the setup.
15
16
Figure 11: Fiber deposition setup. (a) With grounded plate electrode. (b) With grounded
needle electrode.
In the second test, the plate electrode is exchanged for a grounded, conical-shaped needle
electrode with an outer diameter of 0.9 mm (see Fig. 11b). All other elements of the setup and
procedure are kept the same.
For these tests, the spinning parameters are chosen such that a stable polymer jet is established
and deposition is clearly visible. Note that the main focus of the present tests is not to compare
deposition for different parameters, but rather to assess the deposition mechanisms that occur.
In the following table, the spinning parameters for both tests are summarized for reference, where
V is the applied voltage in kV, f is the polymer solution feed rate in [l/min], t is the time period in
which deposition occurs in [s] and d is the vertical distance between nozzle tip and collecting
material in [cm].
Table 3: Spinning parameters for fiber deposition experiments
Experiment
Electrode type
Collecting material
V [kV] f [l/min]
t [s]
d [cm]
1
2
3
4
120
120
60
120
13
13
12
12
plate
plate
needle
needle
mylar
glass
mylar
glass
17
17
17
17
18
18
18
8
These tests are different from those described by Solberg [32] as a higher V and different values
for f have been used. Furthermore, in this research both mylar and glass are studied, while [32]
solely studied mylar.
3.2.2: Fiber deposition: results
The first results that will be discussed are those of the fiber deposition experiments.
In experiments 1 and 2, where a plate electrode is used, it is observed that the polymer jet is
ejected straight down from the Taylor cone. Several centimeters above the collecting material, the
jet starts to diverge from its vertical path and an oscillating haze is observed. The first segment of
the incoming polymer has no preference for a specific point of the plate electrode and is thus
deposited randomly on the collecting material. Upon deposition, the segment retains a residual
charge that exerts a repulsive force on subsequent segments and sweeps them to another
location. As a result, the collecting material is covered with randomly deposited fibers that
17
ultimately form a nonwoven fabric. Images of these results are shown in Figs. 12.1 and 12.2,
respectively. Note that special care was taken to visualize the delicate fiber deposition using
optimal camera angles and with optimal lighting conditions and these might differ from sample to
sample. The mylar sheets and glass samples shown in the images of this Chapter are
occasionally kept up with black foam tubing or a combination of thin white and red strips and pins
to facilitate photography. These aids are not important and should be ignored. The bright, little
drops in the center of the photographs in this Chapter are caused by the initial polymer drop when
the voltage is applied or the last drop after the voltage has been removed. They are not part of
the main deposition process we want to study and should therefore be ignored.
18
point which ultimately buckles. The already deposited fiber segments charge pushes the new
fiber away to another location. As more fiber is collected, the repellant forces will direct new
material further out of the center of the deposition spot. The spot remains circular, however, since
the needle electrode is still attracting charged fiber segments. From these experiments, it can be
concluded that a needle electrode focuses fiber deposition. After a limited time, material is no
longer deposited directly above the electrode because of repulsive forces. A solution to this
problem is to move already deposited fiber segments away from the deposition point and put
untouched collecting material in the path, so that incoming fiber segments stay attracted to the tip
of the needle electrode and focusing is maintained.
All photographs show similar circular deposition although the deposition mechanisms of a plate
electrode and a needle electrode, as described earlier, are clearly different.
3.2.3: Writing: experiments
In the previous section, focusing on a stationary collecting material was investigated. To obtain a
single straight fiber and create oriented fiber meshes, however, it is necessary to create a velocity
difference between nozzle and electrode on one hand and the collector on the other hand. In this
simple test, the grounded needle electrode setup introduced earlier is reused. PEO and PCL will
be selected as polymer solutions. The same experimental procedure is followed with the
exception that a long strip of mylar sheet is used which protrudes from the electrospinning cabin
through a slit on one end. During electrospinning, the strip is manually pulled further out of the
cabin with a velocity of several cm/s. In this way, the mylar translates over the needle electrode
while it keeps in direct contact with it (see Fig. 13). Deposited fiber is thus transported away from
the deposition point above the electrode and we expect that focusing is maintained.
d [cm]
PEO
PCL
13
7
20
22
18
30
19
Figure 14: Writing test result for PEO. Height of image = 10 cm.
Figure 15: Writing test result for PCL. Length of image = 12 cm.
20
From these experiments, it is learned that it is possible to write polymer tracks on mylar sheets.
These results correspond with those of Solberg [32]. By increasing the collection velocity, it
should therefore be possible to write a single, straight fiber on a collector.
21
rectangular shape. The PEO fibers had a height of 380 nm and a width of 8 m, thus a h:w ratio
of 1: 21. The PCL fibers had a height of 14 m and a width of 27 m, which is a h:w ratio of
approximately 1:2. Results are shown in Figs. 16 and 17 for PEO and PCL, respectively.
3.2.5: Influence of collector thickness: experiments
One research question that has not been properly addressed in electrospinning research at
Eindhoven University of Technology is whether the collector thickness influences the amount of
deposition. To investigate this question, the grounded plate electrode setup will be used and
strips of glass and polycarbonate with varying thickness are used as collector material and placed
directly on the electrode, while all other spinning parameters are kept constant. The amount of
deposition on the samples will then be compared qualitatively. The plate electrode is chosen over
the needle electrode as the former gives a more pronounced deposition effect in the same time
frame.
Different collector thicknesses lead to different nozzle-collector distances when the vertical
distance between these two points is not adjusted. It is assumed for these experiments that this
difference of a few millimeters is negligible when considering a vertical distance of 5-15 cm and
will not lead to different electrospinning behaviour.
Four experiments will be performed, as two polymer solutions (PEO and PCL) and two collector
materials (glass and polycarbonate) will be investigated. For each experiment, either two or three
collector thicknesses are compared. In the following table, the spinning parameters are
summarized. Here t1, t2 and t3 are the thickness of the collectors that are compared in [mm].
Table 5: Spinning parameters for collector thickness experiments
V [kV]
f [l/min]
d [cm]
t1 [mm]
t2 [mm]
t3 [mm]
Experiment
17
Experiment
17
Experiment
12
Experiment
12
t [s]
120
120
60
3.0
60
22
23
Fig. 21 shows the results of the last experiment where polycarbonate is used as collector in three
thicknesses. The deposition is marked with black circles. Again we observe that the thinnest
sample is covered with the most polymer fibers and this amount of deposition diminishes nicely
with increasing collector thickness.
From these experiments, it can be concluded that the collector thickness does indeed play a role
and reducing this thickness leads to a more pronounced deposition. This can be understood by
taking into account that the collector partially shields off the electrode and thus locally reduces the
field strength. It acts as a sort of resistor in the field. This reduces the electrostatic pulling force
and therefore the amount of deposition. The shape of the overall field is not changed, however.
a [mm]
1
2
3
4
1
1
1
2
12
13.5
13.5
13.5
24
Both pictures show a similar circular deposition with some fibers that are deposited radially
outward from the deposition point on these 6 x 6 cm mylar sheets. One possible explanation of
the deposition of this radial arrangement is that the fibers are created when the area immediately
above the needle electrode is covered with deposition. The electrode is essentially shielded off
and thus the polymer jet follows the electrostatic field lines which now curve from nozzle towards
electrode over the edge of the mylar sheet. The fibers dry before reaching their ultimate target.
25
nozzle
desired deposition point
collector
actual deposition point
electrode
26
or, where this is not possible, these conducting elements should be shielded off.
4. Compatible with existing infrastructure
Electrospinning experiments are always conducted in a dedicated cabin which protects
the user from exposure to high voltages and is outfitted with a dedicated ventilation
system. The new electrospinner should fit within this existing cabin. The maximum
dimensions of the new design are therefore: length < 0.48 m, width < 0.66 m, height <
0.56 m.
5. Spinnable area at least 0.12 x 0.12 m
A spinnable area of at least 0.12 x 0.12 m is desired, based on application considerations.
The fibers are to be positioned as parallel lines with an adjustable spacing s in[m].
4.3: Configurations
With the before-mentioned requirements as constraints, a number of designs were generated.
In order to fulfill the first and second requirements simultaneously, there are two practical options:
The nozzle and electrode need to be mechanically coupled, for instance by a U-shaped frame.
When we select the first option, the frame will have to move. To study the deposition behaviour,
this option would require a moving camera which is not practical. Therefore, the second option is
selected.
Now that the moving and stationary parts are known, a collector configuration can be selected.
Essentially, there are two configurations that fit the requirements mentioned above: planar and
cylindrical (see Figs. 24a and 24b, respectively).
x&
x&
y&
27
A truly two-dimensional mesh with spacing s can only be woven with a planar configuration (see
Fig. 25). Note that the fiber will only be straight if it is deposited at the required collecting speed.
Therefore, in the planar case, there is an effective spinning area where the collecting speed is
reached and an area outside where it is not. A major disadvantage of this configuration is that a
collector speed of 8 m/s in the plane is hard to achieve. Especially within the limited confines of
the electrospinning cabin which places rather extreme requirements on the acceleration of the
collector when we want to be able to spin with a constant speed for at least 120 mm. This can be
seen by calculating the available acceleration length:
l acc =
l l eff
(4.1)
here l is the width of the electrospinning cabin in [m], leff is the length over which spinning should
occur with a constant velocity in [m] and lacc is the length available for acceleration in [m].
Entering the corresponding values in Eq. 4.1 yields: lacc = 0.27 m.
leff
s
Figure 25: Schematic of a mesh produced with a linear configuration
The required acceleration follows from:
&x&req =
with
V2
2l acc
(4.2)
&x&req the required acceleration in [m/s2] and V the collecting speed in [m/s]. This gives
&x&req = 119 m/s2. This required acceleration puts very high demands on the actuators.
If we only want parallel fibers, it is possible to use a fast axis to deposit the fiber along the length
of the collector and a short axis to move this axis sideways over a distance that corresponds to
the spacing. However, one fast actuator is still required.
b = 2R
s
Figure 26: Schematic of a mesh produced with a cylindrical configuration (folded out)
Using a cylindrical configuration, the collector is rotated with a surface velocity of 8 m/s.
Translation of the collector is necessary to achieve the spacing and fibers will appear as spirals
28
on the collector. In Fig. 26, a schematic of a mesh produced with the cylindrical configuration is
shown. Note that in this configuration, the cabin dimensions are no longer a constraint when it
comes to the collecting speed. As can be seen in the figure, the width of the mesh b in [m] is
equal to the circumference of the cylinder and thus depends on the radius R in [m]. The required
angular velocity req in [rad/s] to achieve the collecting speed is also dependant on the radius.
Taking all design requirements into account, we select R = 0.02 m. This results in
req = 400 rad/s = 3820 rpm. The required angular acceleration can be set freely as it depends
on how long the spinner is allowed to spin up to the required angular velocity.
Now that the rotation of the cylinder has been investigated, attention can be focused on the
translation. It can be gathered from Fig. 24b that the interfiber spacing s that is realized depends
on the collecting speed V and the selected translation velocity x& . Suppose that x& = 0 and V > 0 ,
then vertical polymer lines will appear. When V = 0 and x& > 0 , horizontal lines will appear.
When V and x& are chosen equal, a 45 line is deposited (see also Fig. 26). Hence, for an arbitrary
angle , we can write:
tan( ) =
V
x&
(4.3)
From this same figure, it can be concluded that the deposition angle can also be expressed in
the spacing:
tan( ) =
2R
s
(4.4)
s=
2Rx&
V
(4.5)
With Eq. 4.5 it is possible to calculate the spacing s for a certain translation velocity of the
cylinder. This equation can also be rewritten to obtain the translation velocity as a function of
spacing:
x& =
Vs
2R
(4.6)
29
Figure 27: Cylinder spinner concept drawing (translation mechanism not shown)
4.5: Material selection
The rotating cylinder will be made from glass with a wall thickness of 2.5 mm. The material is an
electric isolator, readily available, easy to machine and resistant to aggressive solvents which are
occasionally used in electrospinning.
The frame of the cylinder spinner is built from thick polymer sheets. Polyvinylchloride (PVC), with
its good electric isolation properties, was selected for the majority of frame. Polyetheretherketone
(PEEK) was chosen for the electrode arm and polycarbonate (PC) for the nozzle arm because of
the shape retention and moisture resistance properties of these materials.
4.6: Rotation axis
At one of the endpoints of the glass cylinder, a PVC plug is inserted and connected to a Maxon
RE25 (type 118746) electromotor. A WM Berg bellow coupling is used to prevent alignment
problems. The electromotor rotates the cylinder up to 3820 rpm, which corresponds with 8 m/s.
The cylinder is supported by two metal groove contact bearings. A Maxon HEDL5540 encoder
with 500 counts/turn is mounted on the motor to control the angular velocity of the cylinder. This
optical encoder is preferred over a tachometer because we want to be able to control the
deposition position, not just the angular velocity. For data acquisition and interfacing with the
motor and encoder, a TU/e Microgiant is used.
4.7: Translation axis
The translating part in the cylinder spinner design will be mounted on a NSK Monocarrier ball
screw actuator (type MCM05-020-H05K) with a stroke of 200 mm, ball screw lead of 5 mm,
repeatability of 10 m and backlash < 20 m. The ball screw is connected to a Maxon RE30 (type
268219) electromotor with ceramic gear (Maxon, GP32C) via another WM Berg bellow coupling.
A Maxon HEDL5540 encoder with 500 counts/turn is used as sensor. For data acquisition and
interfacing with the motor and encoder, the same TU/e Microgiant as for rotation is used. As
software we employ Matlab Simulink.
4.8: Realisation
The cylinder spinner design was built in Mechanical Engineerings departmental workshop.
Images of the realized design are presented below. In Fig. 28, the stationary part is shown with
the main frame in black PVC. The beige PEEK beam that is mounted to the frame is the electrode
arm. The electrode is made from brass and has a diameter of 0.6 mm and length of 9.5 mm. The
30
matte, glass-like PC beam above it is the nozzle arm. The brass nozzle itself is on the outer edge
on the right. The Teflon polymer transport tube is visible, coming out of the nozzle. The vertical
position of the nozzle arm can be adjusted to change the nozzle-collector and nozzle-electrode
distances. The spindle, carriage, motor and encoder for the spindle axis are also visible in this
photo, but these belong to the translating part which is depicted in Fig. 29.
31
32
33
34
The current spindle position of the spinner is logged by the motion control and this software shuts
the movement down once the endpoint of the slide is reached.
4.9: Control design
4.9.1: System identification
Phase [deg]
Magnitude [dB]
To enable cylinder motion with high position accuracy, controllers will need to be developed.
Frequency response function measurements were done for both axes to get a good view of
system dynamics. The FRF of the translation axis (spindle) is shown in Fig. 35. A constant
velocity of 1.5 rad/s was supplied as reference. This corresponds to a constant movement of the
spindle of 1.2 mm/s (see Paragraph 4.10). A chirp signal with a decreasing frequency from 2000
Hz to 1 Hz was used as noise signal. The chirp signal resulted in better coherence than a
standard Gaussian noise signal over a larger range of frequencies. The response was measured
for 100 s with a sampling frequency of 4000 Hz.
100
0
-100
-200
0
10
200
10
10
10
-200
0
10
1
Coherence [-]
10
10
10
10
10
0.5
0
0
10
10
10
Frequency [Hz]
10
10
H ( j ) = e jTd
(4.7)
where Td is an aggregate of all effects that contribute to delay, such as discretization and
computation time. Fitting this model on the phase loss yields a delay of 0.65 ms.
35
Magnitude [dB]
Phase [deg]
50
0
-50
-100
0
10
200
10
10
10
-200
0
10
1
Coherence [-]
10
10
10
10
10
0.5
0
0
10
10
10
Frequency [Hz]
10
10
36
Phase margin []
Spindle
Cylinder
36.5
95.7
9.9
11.3
49.7
3.7
6.0
3.1
Since the spindle will be operated with real-time control that specifies and changes a seconddegree setpoint on-the-fly, feedforward control will not be implemented. The complete control
scheme is shown in Fig. 38.
To test the system, suitable references need to be supplied. A spacing of 100 m was selected
4
as target. This target can be achieved for x& = 8 10 m/s and V = 1 m/s ( = 50 rad/s). In Fig.
39, reference signals r1 and r2 are shown for the spindle and cylinder axis respectively which are
necessary to achieve this target. The homing procedure takes up the first 50 s of the reference.
37
Then, the spinning procedure starts. For r1, a constant velocity of x& = 8 10 m/s is supplied. For
r2, a smooth third order reference is supplied that accelerates for 100 s until it reaches V = 1 m/s.
7
e1
6
r1
5
y1
8
u1
y1 [rad]
e1
r1
u1
Spindle Ctrl
stop1
u1 [V]
stop1
Spindle Ref
y2 [rad]
start
StartRef3
Ref3
acc
vel
pos
e2
Subsystem1
u2
Cylinder Ctrl
2
r2
stop2
u2 [V]
homing [-]
stop2
SystemIO
3
e2
4
u2
1
y2
r1 [m]
0.05
0
-0.05
-0.1
50
50
100
150
100
150
2500
r2 [rad]
2000
1500
1000
500
0
t [s]
38
-6
10
x 10
e1 [m]
8
6
4
2
50
60
70
80
90
100
110
120
130
140
150
60
70
80
90
100
t [s]
110
120
130
140
150
0.9
e2 [rad]
1.5
0.5
0
50
-40
-50
Power/frequency (dB/Hz)
-60
-70
-80
-90
-100
-110
-120
0.1
0.2
0.3
0.4
0.5
0.6
Frequency (kHz)
0.7
0.8
39
PSD of e2
0
-10
Power/frequency (dB/Hz)
-20
-30
-40
-50
-60
-70
-80
-90
-100
0.1
0.2
0.3
0.4
0.5
0.6
Frequency (kHz)
0.7
0.8
0.9
2
= 5.46 10 4 rad
500 4 23 / 4
(4.8)
0.005m / rev
= 4.35 10 7 m
500 4 23 / 4
(4.9)
The cylinder encoder is directly coupled to the encoder and one count thus corresponds with:
2
= 0.0031rad
500 4
(4.10)
With this information, a measured constant position error e in [rad] can be related to the error
along the associated axis. The error in the spacing can then also be calculated.
40
We define the spacing error s as the difference between the desired spacing s and the realized
spacing s :
s = s s
(4.11)
The desired spacing can be calculated from the desired translation velocity x& and the realized
collecting speed V :
s=
2Rx&
V
(4.12)
The realized spacing can be calculated from the realized translation velocity x& and the realized
collecting speed
s =
2Rx&
V
V :
(4.13)
As the derivatives of the positions of the translation and rotation axes were very noisy, it was not
possible to determine the realized spacing error at the time of writing.
41
42
During further testing it was discovered that the current hardware of the cylinder spinner is not
capable of reaching the required collection speed of 8 m/s. The upper boundary is currently 1 m/s.
This limitation is due to mechanical problems in the rotational axis of the setup. Causes are
expected to be: the out of roundness of the cylinder (measured: 0.3 mm), misalignment between
cylinder axis and rotation motor axis, and significant friction in the bearing.
Figure 43: Representative result of spinning on mylar wrapped around glass cylinder
5.3: Troubleshooting
To locate the cause of the focusing problem, as systematic approach will be undertaken using the
grounded needle electrode setup as reference. Elements of the setup are exchanged with those
of the cylinder spinner and the following combinations are investigated:
1. Grounded needle electrode setup, described in Chapter 3, modified so that the nozzle is
just an injection needle protruding from a charged horizontal copper plate.
2. Same as 1, but with the cylinder spinners nozzle arm.
3. Same as 1, but with the cylinder spinners electrode arm.
4. Cylinder spinner setup with mylar sheet as collector.
5. Cylinder spinner setup with glass cylinder (t = 2.5 mm) as collector.
The results of experiments with these combinations will be compared for the same spinning
parameters. Note that all results have been repeated several times and the images of
representative results are presented below.
43
Comparing results of 1 to 2:
In Fig. 44a, the result with combination 1 (grounded needle + nozzle out of plate + mylar) is
shown, while in Fig. 44b combination 2 (grounded needle + nozzle-arm + mylar) is represented.
From the results it is learned that the nozzle arm of the cylinder spinner does not hamper
focusing. On the contrary, deposition seems to be more aggressively focused and resembles
writing.
44
Both figures show a random deposition although this deposition is denser in Fig. 45a. In the right
figure, two big white drops are present. The one in the center of the image was caused by a drop
deposited after the electric field was switched off and should therefore be ignored. It is concluded
that using the cylinder spinners electrode arm gives similar results, although less concentrated.
Comparing results of 2 with 4:
In Fig. 46a, the result with combination 2 (grounded needle + nozzle-arm + mylar) is shown, while
in Fig. 46b combination 4 (electrode-arm + nozzle-arm + mylar) is represented. From this figure it
can be observed that both depositions consist of a writing-like deposition with some thick fibers
produced halfway through the experiment.
45
In Fig. 47a, the result with combination 4 (electrode-arm + nozzle-arm + mylar) is shown, while in
Fig. 47b combination 5 (electrode-arm + nozzle-arm + glass) is represented. When switching
from the thin mylar to the relatively thick glass as collector, the deposition type changes from
focused to random.
From the experiments in this Paragraph it can be concluded that the electrostatic properties of the
nozzle and electrode arms are satisfactory. The glass cylinder is the element that prevents proper
focusing.
5.4: Stationary deposition experiments on PET
Through experiments it was discovered that the glass cylinder with a thickness of 2.5 mm
prevents proper focusing of polymer fibers. While one can produce a glass cylinder with a smaller
wall thickness, one has to take the operating conditions into account. The rotation axis of the
cylinder spinner operates at high angular velocities and therefore a thinner glass tube might be
problematic. Aspects like ease-of-handling, safety and durability could become issues. In
electrospinning experiments we wrap a thin sheet of collecting material around the cylinder on
which the deposition takes place. A thin glass tube breaks easily and special care must be taken
when mounting the collecting material. As mentioned before, high angular velocities are used and
designing a setup that does not vibrate during motion and does not lead to failure of the glass is
nontrivial.
Rather than installing a new cylinder with smaller wall thickness, it was deemed more prudent to
investigate the possibility of using a different cylinder material. Polyethylene terephthalate (PET)
was selected because it cannot break, is easy to process, readily available and essentially the
same material as mylar.
5.4.1: Experiments
Cylindrical PET samples with a diameter of 8.5 cm, length of 9.5 cm and wall thickness of
0.25 mm were obtained from the departmental workshop. For each experiment, a new PET
sample will be mounted in the cylinder spinner setup to replace the glass cylinder. An airgap of 10
mm between PET collector and electrode is established. PEO solution will be electrospun on the
samples using the following spinning parameters:
Table 8: Spinning parameters for PET deposition experiments
V [kV]
f [l/min]
t [s]
D [cm]
a [mm]
17
10
18
60
11
5.4.2: Results
It was discovered that it is relatively easy to electrospin on PET cylinders using the parameters in
the previous section. Even with an airgap of 10 mm, which is significantly larger than the airgaps
used in this research project for mylar and glass, focusing is very good. All three experiments
show similar results. Here, one representative result will be presented (see Fig. 48).
Again, black lines were added to the sample to indicate the location of the needle electrode.
In the first 20 seconds of the experiment, the deposition process resembles the writing-like variety
we are accustomed to from other experiments where the cylinder spinners nozzle arm is used.
This deposition can be recognized as the hazy spot of fibers in the centre of the image. After this
time has lapsed, the deposition becomes less focused. The polymer jet seems to lash from the
centre of the collector outwards. During this movement, the majority of the polymer seems to slide
along the already established or solidified jet while the deposition point traverses radially away
46
from the deposition point. This is not unlike other experiments where the same phenomenon has
been observed. The associated deposition can be seen in the center-left part of the image and
consists of thicker fibers.
47
Although deposition mechanisms for the grounded plate and needle electrodes on mylar
and glass are different, the deposition looks similar.
Mylar writing samples were created with PEO and PCL. Fibers of both polymers have a
rectangular cross section. The PEO fibers had a height of 380 nm and a width of 8 m,
while the PCL fibers had a height of 14 m and a width of 27 m.
It was qualitatively determined for glass and polycarbonate that the influence of collector
thickness does indeed play a role in the amount of deposition that takes place.
No apparent visible difference was detected between deposition on mylar in direct
contact with a needle electrode and with an airgap in between. The airgap did not prevent
or hinder deposition.
The lack of focusing was caused by the relatively high thickness of the glass cylinder.
Changing parameters V, f, d had no effect.
The nozzle arm of the cylinder spinner enables better focusing than a nozzle protruding
from a horizontal charged plate.
A PET cylinder is a good alternative to the glass cylinder currently installed in the setup.
It is suggested to redesign the rotation axis so that the required collecting speed can be
attained.
Another solution is to use a different polymer that requires a lower collecting speed than
PEO.
Better position control might be possible by implementing feedforward control.
The glass cylinder can be replaced with a PET cylinder for better focusing.
The current electronics that are used to operate the cylinder spinner are rather bulky. It
might be practical to rearrange them in a more compact form.
48
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