PROPERTIES AND ADHESION BEHAVIOR OF ELECTROSPUNNED

POLYCAPROLACTONE (PCL)/ HALLOYSITE NANOTUBE (HNT) MODIFIED WITH

ADDED (3-AMINOPROPYL) TRIETHOXYSILANE (APTES)
Jianne Enriquez, Pamela Gahol, and Rochelle Jane Bejer
MSE Students of CHE-CHM Department, Mapua University, Manila Philippines

Abstract Nanofibers have emerged as exciting one-dimensional nanomaterials for a broad spectrum of research and commercial
applications owing to their unique physicochemical properties and characteristics. Compared to protein nanofibers, PCL nanofibers
exhibited lesser adhesion behavior, slipping on the substrate when manipulated physically. HNT is known for being successfully
applied to the modification of PCL which is a nanofiller that leads to simultaneous reinforcement, compatibilization, and improvement
of other material parameters with potentials to being beneficial. HNT affects the production of nanofibers at which it leads to the
varied orientations and dispersions resulting to agglomeration where organosilanes (such as APTES) are injected in the substance. The
research characterized the properties and adhesion behaviors of nanofibers generated through electrospinning of PCL/HNT from
analysis on contact angles, particle size, zetta potential, and fiber diameter and its pore areas using SEM images.

Keywords — Nanofiber, PCL, HNT, APTES, Electrospinning, Contact Angles, Particle Size, Zetta Potential, SEM Images

improve the advances of PCL to nanotechnology and to other

I. INTRODUCTION1 fields of science, substances (such as HNT) can be added.

A s a class of nanomaterials with cross-sectional

diameters ranging from tens to hundreds of nanometers,
nanofibers possess extremely high specific surface area
and surface area-to-volume ratio. They can form networks of
highly porous mesh with remarkable interconnectivity
between their pores, making them an attractive choice for a
host of advanced applications. In fact, the significant impact
of nanofiber technology can be traced from the wide range
of fundamental materials that can be used for the synthesis
of nanofibers. The relatively high production rate and
simplicity of the setup makes electrospinning highly
attractive to both academia and industry. Compared to
protein nanofibers, PCL nanofibers exhibited lesser adhesion
behavior, slipping on the substrate when manipulated
physically (2015, Baker, S., etc.).
PCL is a biodegradable polyester that is easy to
manufacture, manipulate and blend, resulting to a great deal
of attention in use of a long term degradable implants and
into a wide range of three-dimensional platforms (ie, porous
scaffold, micro- and nanocarriers, and implantable devices).
PCL is one of the earliest, commercially available, synthetic
polymers characterized by a large set of biodegradation and
mechanical properties that can be finely controlled by
regulating the local environmental driving forces (ie,
microorganisms, enzymes, hydrolysis). Despite its
semicrystalline character and relatively high content of
crystalline phase, mostly over 50%, its poorly organized
crystalline structure in combination with low glass transition
temperature (Tg) are the main reasons of relatively poor
mechanical performance (2015, Kelner, I., etc). To further
Halloysite (HNT) is a naturally occurring aluminosilicate
nanosized tubular clay mineral that has many potentially
important uses in different industrial fields. Both
hydrophobic and hydrophilic agents can be entrapped after
an appropriate pre-treatment of the halloysite surface. There
would certainly be an effect on the properties of PCL and the
behavior of the water droplet when in contact to the surface
when HNT is added. The research has determined the
varying results and its interpretation of the different
concentrations of HNT added to the pure PCL material.
Consequently, for its hollow cavity, HNT is mainly used as
nanocontainer for the controlled release of several chemicals.
Specifically, chemical modification of HNT surfaces
generates a nanoarchitecture with targeted affinity through
outer surface functionalization and drug transport ability
from functionalization of the nanotube lumen. HNT is
known for being successfully applied to the modification of
PCL which is a nanofiller that leads to simultaneous
reinforcement, compatibilization, and improvement of other
material parameters with potentials to being beneficial.
However, HNT affects the production of nanofibers at which
it leads to the varied orientations and dispersions resulting to
agglomeration where organosilanes (such as APTES) are
injected in the substance. The (3-Aminopropyl)
Triethoxysilane (APTES) is an organosilanes/ silane
percursors that are used as surface modification of the HNTs.
With the introduction to the fabrication of nanofibrous
membrane, electrospinning is an electrostatic fiber
fabrication technique that has evinced more interest and

1
This characterization paper is to be submitted on the date of March 13,
2018 on the class of MSE21L (Measurements in Material Science and
Engineering) by Sir Millare.
attention in recent years due to its versatility and potential for base anion resin volume and in the regeneration reagent
applications in diverse fields. The nanoscale fibers are requirements (1991, Degremont).
generated by the application of strong electric field on
polymer solution or melt. A polymer solution, PCL, was
introduced into the electric field. The polymer filaments
were formed, from the solution, between two electrodes
bearing electrical charges of opposite polarity. One of the
electrodes was placed into the solution and the other onto a
collector. Once ejected out of a metal spinnerette with a small
hole, the charged solution jets evaporated to become fibers
which were collected on the collector. The potential
difference depended on the properties of the spinning
solution, such as polymer molecular weight and viscosity.
When the distance between the spinnerette and the collecting
device was short, spun fibers tended to stick to the collecting
device as well as to each other, due to incomplete solvent
evaporation. When a solid polymer is dissolved in a solvent, Figure 1. Strong acid cation + strong base anion resin
the solution viscosity is proportional to the polymer systems for deionization of water.
concentration. Thus, the higher the polymer concentration
the larger the resulting nanofiber diameters will be. 2) Polycaprolactone (PCL)

3) Pure Halloysite Nanotube (HNT)

The research focused on the effects of HNT as a nanofiller
for PCL polymers through contact angle measurements as
observed to its interaction to water droplet, and the surface
modification and characterization of APTES on
electrospunned PCL/HNT nanofibers through particle size
analysis and the method of phase analysis light scattering
(PALS) for the zetta potential. The results from nanofiber
diameter measurements and spatial areas of pores were also
interpreted in this paper through an application from the
SEM images retrieved.
II. METHODOLOGY
A. Material Preparation
1) Purification of Water (De-ionized) for contact
angle measurement and zetta potential.
Deionization entails removal of electrically charged
(ionized) dissolved substances by binding them to
positively or negatively charged sites on a resin as the
water passes through a column packed with this resin.
This process is called ion exchange, specifically using
the: strong acid cation + strong base anion resin systems.
These systems consist of two vessels - one containing a
cation-exchange resin in the hydrogen (H+) form and the
other containing an anion resin in the hydroxyl (OH-)
form (Figure 1). Water flows through the cation column,
whereupon all the cations are exchanged for hydrogen
ions. The decationised water then flows through the
anion column. This time, all the negatively charged ions
are exchanged for hydroxide ions which then combine
with the hydrogen ions to form water (H2O). Reduction
of the flux of ions passed to the anion exchanger is done
by installing a CO2 removal unit between the ion
exchange vessels. This reduces the CO2 content to a few
mg/l and brings about a reduction of the following strong
4) (3-Aminopropyl) Triethoxysilane (APTES)
B. Materials Synthesis
1) APTES – HNT Preparation (Reflux Method)
Silanation was the conventional process utilized for the
functionalization of the external silica surface of HNTs.
HNTs were immersed into a toluene consisting of
minimum volume of APTES then ultrasonified for 30
minutes for HNT dispersion. The suspension was then
refluxed for 20 hours at 120oC with constant stirring. The
solid residue in the solution was filtered using vacuum
pumps and washed with toluene six times remove excess
silanes. Subsequently, the organosilane persursors were
decomposed by treating the sample at 120oC in dry oven
overnight to form functionalized HNTs.
2) Electrospinning Process
The laboratory setup for electrospinning consists of a
spinneret connected to a high-voltage direct current
power supply, a syringe pump, and a grounded collector.
A polymer solution (PCL) was loaded into the syringe
and this liquid is extruded from the needle tip at a
constant rate by a syringe pump. Alternatively, the
droplet at the tip of the spinneret can be replenished by
feeding from a header tank providing a constant feed
pressure. This constant pressure type feed works better
for lower viscosity feedstocks.

Figure 2. Schematic diagram for electrospinning apparatus.
3) Ultrasonic Nano-fibrillation
The chemically purified residues were soaked in
deionized water and then subjected to ultrasonic
fibrillation using an ultrasonic generator equipped with a
1.5 cm cylindrical probe. The process was performed at
a frequency of 25 kHz with an output power of 750W for
30 min. The ultrasonic fibrillation was conducted in an
ice bath, and the ice was maintained throughout the entire
process.
C. Characterization
1) Contact Angle Measurement
The sessile drop contact angle was measured by a
contact angle goniometer. The apparatus uses an optical
subsystem that captures the profile of a pure liquid on top
of the substrate. In this experiment, several trials were
performed, and each having its own respective samples.
The first substrate had pure PCL and was placed onto the
stage. 1µL of deionized water was dropped onto the
substrate and its contact angle was measured. The
succeeding samples had HNT added. The concentration
of HNT gradually increased per sample reaching up to
5%.
2) Particle Size Analyzer and Zetta Potential
The zeta potential was measured by injecting a solution
into a flow cell. The flow cell is then inserted inside the
particle size analyzer. The particle size analyzer
measures the radius of the particles, but it also measures
how fast particles move. Through this the zeta potential
is measured. The Flow cell is cleaned three times by
injecting deionized water type 1. Shortly after, Pure HNT
was injected into the flow cell. To make sure that the
solution is properly injected into the flow cell, the process
is repeated twice or thrice.
3) Nanofiber Diameter and Spatial Areas
Measurement through SEM Images
The nanofibers were seen under an SEM (Scanning
Electron Microscope) at various magnifications. The
fibers size and porosity are measured through the
application ImageJ a public domain Java image
processing program inspired by NIH Image for the
Macintosh.
a) Image Acquisition. Nanofiber webs were
prepared using PCL solution modified with
1,3, and 5 percentage HNT via electrospinning
process as shown in Figure 1. The nanofiber
web images for the image process were
obtained using SEM.
b) Image Analysis Processing. The conduction
of the analysis of the SEM image were done
through the measurements of the fibers’
diameters and the area of the pores using the
application of Image J. There were 50
measurements done for each trial for the
diameter and spatial areas of the pores of the
nanofibrous membrane.
III. INTERPRETATION OF RESULTS
A. Contact Angle Measurement
The contact angle is the angle that is formed during the
intersection of the liquid-solid interface and the liquid-
vapor interface. In our experiment, the sphere image of the
samples geometrically creates a tangent line from the
contact point along the liquid-solid interface in the droplet
outline. Figure below shows the difference between a small
contact angle and a large contact angle.
Figure 3. Pure PCL, PCL+1HNT, and PCL+3HNT shows
that a small contact angle is observed when the liquid
spreads on the surface
Figure 4. PCL+5HNT show that a large contact angle is
observed when the liquid beads on the surface.
A contact angle less than 90° indicates that wetting of the
surface is constructive, and the fluid will spread over a
large area on the surface; Pure PCL, PCL+1HNT, and
PCL+3HNT are the three solutions that have values less
than 90°. While contact angles that is greater than 90°
generally means that wetting of the surface is
unconstructive so the fluid will decrease its contact with
the surface and form a dense liquid droplet. PCL+5HNT is
the only solution that is greater than 90°.
As shown in the graph below (figure 5); pure PCL,
PCL+1HNT, PCL+3HNT, and PCL+5HNT has a mean of
63.91°, 72.92°, 80.11°, and 99.99°, respectively. This
shows that the addition of HNT and higher concentration
of HNT also leads to the increase of the contact angle. The
addition of HNT increased the solution viscosity and the
diameter decreased (based on the photos) with the
increasing of HNT concentration. Generally, if the water
contact angle is smaller than 90°, the solid surface is
considered hydrophilic and if the water contact angle is
larger than 90°, the solid surface is considered
hydrophobic. In this experiment, pure PCL is hydrophilic,
but the addition of 5HNT concentration can make it
hydrophobic.
Figure 5. Contact Angle Mean Average of the Four
Solutions
B. Zeta Potential Model
Particle Size Analysis are procedures or laboratory that
determines the size range and mean size of the particles in
a liquid or powder sample. While Zeta potential in some
textbooks, it is defined a parameter characterizing
electrochemical equilibrium on interfaces. In this
experiment, the Zeta Potential model used is the
Smoluchowski.
Table 1. Particle Size and Zetta Potential Results
For first sample pure HNT, shown on table 1, the zeta
potential is lower with the radius smaller for first trial in
comparison with the second, third, and fourth trial. For the
addition of GMA with HNT, the fourth trial has the lowest
zeta potential having a value of -14.9. For the addition of
APTES with HNT, trial one is the lowest in zeta potential
followed by trials three, four, one and five. The addition of
GMA concentration to HNT affects the pure HNT by
infinitesimally increasing the zeta potential, while the
addition of APTES concentration to HNT affects the pure
HNT by decreasing the zeta potential.
Based on the graph, we can’t say that zeta potential is
dependent on the size of the particle because it is just more
surface charge over a large particle that makes zeta
potential remains its same independent of size. The graph
shows that trial two of the Pure HNT has the highest zeta
potential, thus having it the strongest repulsion and more
stable system among all the samples.
C. Nanofiber Diameter and Spatial Areas
Measurement through SEM Images
For the pure HNT, the fibers were clearly intact with each
other. It shows that the number of fibers and number of
pores of the fibers are higher than the other three
concentrations.
For 1% HNT, in comparison with the pure HNT, the
diameter of the fibers is much bigger than the pure HNT.
We can see an infinitesimal change with the number of
fibers in this concentration.
For 3% HNT, the agglomeration of the fibers is more
noticeable than the pure HNT and 1% HNT. We can see a
big difference when it comes with the diameters of the
fibers and the pores are much bigger.
For 5% HNT, the number of fibers in 5000 nm are much
lower than the other concentrations. The dispersion of
HNT are distinct and the number of pore size also increases
compared to 3% HNT.
The agglomeration that we see in the nanofibers is caused
by too much HNT. If there is an ample amount of HNT in
the solution, instead of having a dispersed HNT, there will
be accumulation of HNT that conforms from the polymers
solution leading to larger fiber diameters.
Table 2. Mean Values of the Measured Diameters and
Areas of Pore Spaces Between Nanofibers
 Therefore, increasing the concentration will result to
varying values for the area of the pores and diameter of the
nanofibers. The hypothesis that was made that as the
amount of concentration is increased, the diameter and
pore size of the fiber were not proved, and it varies. There
is no trend with regards with the pore area and diameter of
the nanofibers. It is not possible to relate the structural
property of the membrane with the contact angle but can
only relate that with the amount of APTES.
IV. CONCLUSION
This research displayed results of the substrate containing
5% HNT treated PCL gave the highest contact angle. This
paved to its potential to be used for the study involving
adhesion properties of the generated nanofibrous
membrane. One of the implications of this research in
relation to the study is to find the perfect amount of HNT
to make the PCL hydrophobic. Adding too much HNT can
cause agglomeration on the nanotubes, too few would
mean less air bubbles trapped when a liquid encounters the
nanotube. One can infer that the higher the HNT
concentration and addition of HNT to PCL can increase its
contact angle. Also, pure PCL is considered as hydrophilic
but addition of higher concentration of HNT can make it
hydrophobic. The contact angle goniometer is a source of
error, the quality of the droplet that hit the substrate
depended on how hard the apparatus is tapped, and if
tapped to lightly the water wouldn’t drop. The water would
sometimes split and bounce on the substrate when you tap
the apparatus to hard, making it difficult for the camera of
the apparatus to see the droplet on the substrate therefore
erroneous data might be obtained.
There are several factors that the zeta potential is
dependent: solvent type, viscosity of the dispersion
medium, temperature, and ionic concentration. The
Smoluchowski equation model has all this parameters in
use. For molecules and particles that are small enough, a
high zeta potential will confer stability, the solution or
dispersion will resist aggregation. When the potential is
low, attraction exceeds repulsion and the dispersion will
break and flocculate. According to Singh, the liquid layer
surrounding the particle exists as two parts; an inner
region-where the ions are strongly bound and an outer
region-where they are less firmly associated. The
magnitude of the zeta potential gives an indication of the
potential stability of the colloidal system. The 5% HNT
concentration has the highest zetta potential value implying
greater stability in resisting possible aggregation.
HNT is modified with APTES, which is a hydrophobic
substance. Basically, the more HNT inserted, the substance
will exhibit greater hydrophobic character. With the
solution at 5% HNT, there was an increase of hydrophobic
character and increase in contact angle and it has to do with
the amount of APTES. There is also an increase in
roughness of the surface of the nanofiber but in terms of
area and length of the pore of the nanofibers, the value
varies with the percentage of the HNT solution. Addition
of 1% HNT is the optimum concentration to achieve the
smallest diameter. Image J was used in the measurements
achieved and the source of error as it was difficult to
measure manually.
The added HNT concentration of 5% to PCL solution
exhibited a hydrophobic character of high contact angle,
greater stability in resisting possible aggregation and was
also observed to have a gradual decrease in the nanofibrous
membrane’s diameter and pore area compared to 3% HNT
concentration, proving its high potential to be useful in
relation to the study on adhesive properties and future
applications to real-life situations. This is likely of novel
crosslinking chemistry that has been introduced into the
nanofiber as development to effectivity of its structure as
filter with the diameter abled to be fine-tuned into smaller
pores than meltdown and spunbound layers for
improvement of performance. More potential applications
of there electrospunned nanofibers are on membrane
distillation, geothermal water desalination and capacitive
deionization applications.
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