LABORATORY REPORT IN MEASUREMENTS IN

MATERIALS SCIENCE AN D ENGINEERING

Properties and adhesion behavior of electrospinned polycaprolactone (PCL)/

halloysite nanotube (HNT) modified with added (3-aminopropyl)
triethoxysilane (APTES)
Nicole Jaine Bridgette S. De Leon, Kiara Pauline Devanadera, Alyssa Nicole Duena

REPORT INFO ABSTRACT

Nanofibers are fibers that has a diameter in the nanometer scale.

Nanofibers can be produce from different polymers and hence have
Keywords:
different physical properties and application. used for its properties that
Polymer opens new windows for the innovation in our technology. Electrospinning
Zeta Potential is a simple and versatile fiber synthesis technique in which a high-voltage
PCL electric field is applied to a stream of polymer melt or polymer solution,
Halloysite Nanotubes (HNT) resulting in the formation of continuous micro/nanofibers. Halloysite
APTES nanotubes (HNT) is found to improve the structural and mechanical
properties when embedded into various polymer matrices. Since, HNT
Microfluidics
are incompatible with polymers we treated it with (3-Aminopropyl)
Porosity
Triethoxysilane (APTES). This paper focuses on combining the
Polycaprolactone (PCL) with halloysite nanotube (HNT) that has been
treated with APTES to achieve a hydrophobic material.

1. Introduction electronic fabrication and other high-tech ceramic-

Microfluidics is the study of systems that
processes small quantities of fluids by using small
channels having with dimensions in the
microscales. The typical dimensions are tens to
hundreds of micrometers. Some applications of
microfluidics in diverse fields that ranges from
biology and chemistry to information technology
and optics. The modified fibers will make the
material more efficient in terms of encapsulating the
unnecessary specie so that the material will only
release the components needed.
Halloysite nanotubes (HNT) do not
clump together, making them ideal for use in
composite applications. Halloysite nanotubes (HNT)
are ultra-tiny hollow tubes with diameters typically
smaller than 100 nanometers (100 billionths of a
meter), with lengths typically ranging from about 500
nanometers to over 1.2 microns (millionths of a
meter). Unlike carbon nanotubes, naturally occurring
halloysite nanotubes are inexpensive, readily
available in quantity, environmentally benign, and
safe and easy to process but this material is not very
much compatible with polymers and so we treated it
with (3-Aminopropyl) triethoxysilane (APTES).
When the contact angle θ is >90° it means
that the surface is hydrophobic. Now the
polycaprolactone (PCL) a polyester, which will be
used as a fiber to make a membrane, treating it with impart good resistance to water, oil, solvent and
(3-Aminopropyl) triethoxysilane (APTES) is to be chlorine to the polyurethane produced.
mixed compatibly with Halloysite Nanotube (HNT)
Filler, this will make the fiber’s diameter much smaller  HALLOYSITE NANOTUBES (HNT)
and make the membrane hydrophobic. APTES is
Halloysite is an aluminosilicate clay material.
commonly used in salinization basically means
Its main constituents are aluminum, silicon, and
covering or coating the PCL and HNT to form bond
hydrogen.
forces with each other and make them as one solution
while modifying the surface properties. The B. MATERIAL CHARACTERIZATION
Concentration of HNT (0%, 1%, 3% and 5%) will be
set as a parameter to determine the change of 1. Contact Angle Measurement
wettability property of the PCL/HNT nanofiber
membrane. The varying concentration of HNT is to be The procedure for the measurement of the
observed if it will affect the contact angle of the contact angle done by using a syringe with a needle
PCT/HNT Nanofibrous Membrane since APTES is a tip, a plate and an illumination lamp and CCD
hydrophobic substance and by adding that we are camera. The syringe was cleaned first with ethanol
achieving a hydrophobic material. before conducting the test. Then the illumination
lamp was turned on. The syringe was filled with
Zeta potential also known as the
deionized water and the liquid was dropped to the
electrokinetic potential, is measured in millivolts
surface.
(mV). It is measured by the magnitude of the
electrostatic or charge repulsion or attraction between
particles and it is one of the fundamental parameters
known to affect stability. The measurement of Zeta 2. Measuring Particle Size and Zeta
potential gives a detailed insight into the causes Potential
formulation of dispersions, emulsions and
Before conducting the experiment, the syringe
suspensions. It can also be defined as the potential
that was used for transferring the liquid was washed
difference across phase boundaries between solids and
with ethanol. After that, pure HNT was added into
liquids. It is a measure of the electrical charge of
the flow cell, making sure that there were no
particles that are suspended in the liquid. Now in
bubbles inside.
determining the zeta potential, we are actually
considering the mobility of the particle which is
converted into zeta potential.

II. METHODOLOGY

A. CHEMICALS USED

 POLYCAPROLACTONE (PCL)

It is one of the earliest, commercially available,

synthetic polymers characterized by a large set of
biodegradation and mechanical properties that can
Figure 1. Adding the liquid to the flow cell
be finely controlled by regulating the local
environmental driving forces. Polycaprolactones
 Table 1. Results for Pure HNT
Sample: HNT + APTES
Trial Zeta Potential Radius Intensity
(mV) (nm) (Cnt/s)
1 -22.19 134.1 573597
2 -23.22 146.9 612793
3 -20.86 135.5 580915
4 -20.26 138.8 578302
5 -21.11 134.4 604521
Table 2. Results for HNT + APTES
Figure 2. Placing the flow cell in the Laser The first part of the experiment is obtaining
Photometer the Zeta Potential of the nanofiber to determine
whether the material could easily go through the
Then, it was placed into the Laser Photometer. After
surface compared to the others.
five trials using pure HNT, APTES was added into
the pure HNT and it was used for the next part As we can see on the obtained results, it can
wherein another five trials were conducted. The be seen that the radius or the particle size of the fiber
results were gathered using DelsaMax software. increased when APTES was added, while the zeta
potential and intensity also increases when APTES
3. Nanofiber Diameter and Porosity
was added. The particle size gets bigger when
Measurements
APTES was added which means that the particles of
A nanofibrous elastic material made with the HNT-APTES are greater than HNT alone. Greater
mixture of Polycaprolactone (PCL) and Halloysite particle size means that means more light are
Nanotube (HNT) was prepared by electrospinning. scattered inside the particle
It is possible to produce continuous fibers from
Meanwhile, for the zeta potential, both
different types of polymer at the nanometer scale by
tests obtained negative results which means that the
electrospinning technique. Four kinds of HNTs with
net charge of the object is negative and it is very
different ratios (0%, 1%, 3%, 5%) were prepared
typical to get a negative value. As you can see on
and examined to determine the effect of HNT to the
the table, the zeta potential increased for HNT-
nanofiber.
APTES, which means that the particle has moderate
stability compared to the pure HNT. However, it
doesn’t mean that the atoms inside the particle are
III. RESULTS AND DISCUSSION
stable enough. Particles with zeta potentials of ±30
Sample: Pure HNT are normally considered stable.
Trial Zeta Potential Radius (nm) Intensity
(mV) For the second part of the experiment, the
(Cnt/s)
1 -18.24 112.7 794334 contact angle of the liquid was determined to test if
2 -17.53 115.5 748087 the surface is hydrophobic or hydrophilic to see if
3 -17.63 114.2 806639 the liquid can easily flow through the surface.
4 -18.20 113.8 809532
5 -18.55 113.2 829760
 Trial Contact Angle

1 122.3˚
2 118.5˚
3 121.8˚
4 136.2˚
Table 3. Contact Angle of Nanofiber Membrane

When an interface exists between a liquid

and a solid, the angle between the surface of the
liquid and the outline of the contact surface is
described as the contact angle. Contact angle is one
of the common way to measure the wettability of a
surface or material. It is the angle between the
surface of the liquid and the outline of the contact
surface.
Figure 4. Schematic Diagram of Contact Angle
Based on the obtained results, the contacts
angles of the four bubbles are higher than 90˚ and
less than 180˚ which means that the liquid used for
the experiment is a non-wetting liquid. The
tendency of the liquid to resist separation is higher
and it has a strong cohesion that its particles stick
together. This type of force is called cohesive force,
it gathers the molecules of a liquid which makes the
form in a large cluster.

The last part of the experiment is the

measurement of the nanofiber’s diameter and
porosity. Porosity is the open spaces between grains
or trapped in grains in a microstructure — the
presence of tiny openings or spaces within a
material. Porous materials can absorb fluids or
moisture, which causes corrosion.

Figure 3. Contact Angle on different materials

The contact angle with one or more liquids

can be used to determine the surface free energy of
a solid. The contact angle is important wherever the
intensity of the phase contact between liquid and
solid substances needs to be checked or assessed:
coating, painting, cleaning, printing, hydrophobic
or hydrophilic coating, bonding, dispersing etc.
Figure 5. Representation of Porosity
 Percent Diameter (nm) Porosity (nm)2
0% 303.75 47095.70
1% 247.71 49810.65
3% 864.69 590944.1
5% 467.741 79846.76
Table 4. Diameter and Porosity

The average diameter and porosity for each

mixture was obtained and there was no trend
observed. Porosity is the quality of being porous, or
full of tiny holes which means that liquids go right
through that things that has porosity. The diameter
of each fiber can also be classified as the grain size.

We can see that at 3% HNT-APTES

mixture, the result for the diameter and porosity
both increased. Because the 3% mixture may have
large fibers yet the spaces between the fibers are
wider compared to the other mixtures.

IV. CONCLUSION