Dispersibility of Hydrophilic and Hydrophobic Nano-silica Particles in Polyethylene Terephthalate Films: Evaluation of Morphology

and Thermal Properties

Dispersibility of Hydrophilic and Hydrophobic Nano-silica Particles

in Polyethylene Terephthalate Films: Evaluation of Morphology and
Thermal Properties
Mazeyar Parvinzadeh Gashti1*, Siamak Moradian2, Abosaeed Rashidi3, and
Mohamad-Esmail Yazdanshenas4
1
Department of Textile, College of Engineering, Yadegar-e-Imam Khomeini (RAH) Branch, Tehran, Iran
2
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, Tehran, Iran
3
Department of Textile, Islamic Azad University, Science and Research Branch, Tehran, Iran
4
Department of Textile, Islamic Azad University, Yazd Branch, Yazd, Iran
Received: 20 August 2012, Accepted: 24 July 2014

SUMMARY
The development of polyethylene terephthalate (PET) nanocomposites with different nano-fillers has been an especially
intense area of research due to an enhancement in thermal and physical properties of nanocomposites compared to
pure PET. In this regard, the surface properties of nano-particles and their interactions with PET chains have a critical
role on different properties of prepared nanocomposites. The aim of this paper is to study the influence of the type of
nano-silica particles with different surface properties on the dispersibility, the interfacial adhesion, surface morphology,
nucleation and thermal properties of the resultant PET/silica nanocomposites. For this purpose, PET composites
containing hydrophilic or hydrophobic nano-silica were prepared by melt compounding. Different properties of
nanocomposites were investigated using polarized optical microscopy (POM), scanning electron microscopy (SEM),
differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), dynamical mechanical thermal analysis
(DMTA) and contact angle measurements (CAM). POM images indicated that nano-silica tended to increase the
number of spherulites in the PET composite structure depending on the type of particles. The thermal studies of the
nanocomposites showed a slight decrease in the melting temperature compared to the pure PET.

Keywords: Polymer-matrix composites; Thermal properties; Nano-silica

1. INTRODUCTION well as improvement in the dyeability the hydrophilic surface of fumed

In recent years poly(ethylene
terephthalate) (PET)-nanometric
filler composites have attracted
significant attention due to their diverse
applications in various areas such as
transportation vehicles, construction
materials, electronics, sporting goods,
packaging, household goods and textiles
industries. Application of nanoparticles
in polymer processing aimed at
enhancing a wide range of properties
including mechanical properties
(modulus, stiffness and strength),
barrier, flame retardancy, solvent and
heat resistance, biodegradability and
chemical and thermal stability, as
Email: mparvinzadeh@gmail.com. Tel: +98 912313715, Fax: +98 2122593135
©
Smithers Information Ltd., 2015
of the modified PET1-6. On this point,
nanocomposites containing different
nanoparticles of cellulose, clay, calcium
carbonate, carbon and different types of
metal oxides have been developed4-6.
The geometrical shape of the particles
plays an important role in determining
the properties of the composites. Fumed
silica as important filler is characterized
by its spherical shape, extremely small
particle size and large surface area. There
are three chemical groups i.e., isolated
hydroxy, hydrogen-bonded hydroxy,
and siloxane groups on the surface
of fumed silica. The surface of silica
is hydrophilic, although the siloxane
groups are hydrophobic. However,
silica can be rendered hydrophobic
through the reaction of the surface
hydroxyl groups with hydrophobic
reagents such as polydimethylsiloxane,
dimethyldichlorosilane and
hexamethyldisilane7.
Polymeric nanocomposites are more
difficult to process compared to the
corresponding pure polymers due to
the fact that the inorganic nanoparticles
have strong tendencies to agglomerate.
To overcome such difficulties, the
sol-gel method, in-situ polymerization
and melt processing can be employed.
Among all these procedures, melt
processing is considered to be the
most cost effective, simple, feasible
and environmentally benign process
for the mass production of polymeric
nanocomposites8-11.

Polymers & Polymer Composites, Vol. 23, No. 5, 2015 285

 Mazeyar Parvinzadeh Gashti, Siamak Moradian, Abosaeed Rashidi, and Mohamad-Esmail Yazdanshenas
Considerable efforts have been
demonstrated to improve various
physical, mechanical and barrier
properties of PET through mixing it
with nanoclays to produce layered
clay-incorporated PET composites12-31.
However, in comparison with
polyamides and polyolefins, there
have been relatively few studies related
to PET/silica nanocomposites 31-42.
Experimental evidence indicated that
nano-silica has a little effect on the
degree of crystallinity and that it does
not act as a nucleating agent in PET
nanocomposite, while it postpones the
appearance of crystallites and improves
the spinnability of PET polymer33,36,37.
Modulus, tenacity, thermal stability and
amorphous orientation of PET/silica
nanocomposites are higher than those
of the pure PET, while heat shrinkage
and chain mobility, as important
parameters to improve the dimensional
stability of the fibres, are lower34,35,38,40.
It was revealed that hydrophobic fumed
silica effectively reinforces PET matrix
while hydrophilic fumed silica showed
a marked improvement in the dynamic
rheological properties, such as shear
thinning behaviour and viscosity41.
According to above-mentioned studies,
none of previous research is focused
on the effects of the type of nano-
silica on crystallization, surface and
thermal properties of the resultant
Table 1. Specifications of various nano-silica particles
Characteristic properties
BET surface area (m2/g)
Primary particle size (nm)
Ignition loss (%)
pH in 4% aqueous solution
Tapped density (g/cm ) 3
Moisture (%)
Purity (% of nano-silica)
C-content (%)
Al2O3 -content (%)
Fe2O3 -content (%)
TiO2 -content (%)
HCI -content (%)
Sieve residue-content (%)
286
PET/silica nanocomposites. PET
containers reinforced with silica are
highly recommended for thermal
insulation of food products. These
nanocomposites are also used for
production of packages in order to
avoid their stress cracking42. In this
regard, surface properties of nano-
silica particles, their compatibility with
PET polymer and mixing conditions are
very important parameters influencing
the degree of dispersion of particles
within the polymer matrix39. Our group
has previously shown that silica affects
the reflectance properties of PET matrix
by shifting the curves to the shorter
wavelengths in the UV-Vis region.
Optical characteristics of the resultant
nanocomposites depend on the type of
nano-silica which could be attributed to
the quantum size effect of particles42.
The aim of this research is thus to
study the influences of hydrophilic or
hydrophobic nano-silica particles on
the morphology and thermal properties
PET nanocomposites produced by melt
processing method.
2. EXPERIMENTAL
2.1 Materials
Pure PET granules were provided by
Tondgooyan Petrochemical Co. (Iran).
Various fumed nano-silica particles (i.e.
Aerosil 200 Aerosil TT 600
Hydrophilic (1) Hydrophilic (2)
200±25 200±50
12 40
≤1 ≤ 2.5
 3.7-4.7 3.6-4.5
approx. 50 approx. 60
≤ 1.5 ≤ 2.5
≥ 99.8 ≥ 99.8
- -
<0.05 <0.05
<0.003 <0.003
<0.03 <0.03
<0.025 <0.025
<0.05 <0.05
Polymers & Polymer Composites, Vol. 23, No. 5, 2015
hydrophilic Aerosil 200, hydrophilic
Aerosil TT 600, and hydrophobicAerosil
R 972) were supplied by Degussa GmbH
(Germany). The hydrophilic nature
of nano-silica powders is attributed
to the presence of hydroxyl or silanol
groups on their surface. Aerosil R 972
is a fumed silica after-treated with
DDS (dimethyldichlorosilane). All of
the particles were spherical and free
of pores. The specifications of the
various nano-silica powders are listed
in Table 1.
2.2 Nanocomposite Preparation
PET granules and the three different
nano-silica particles were dried in an
oven for 24 h at 110 °C, prior to the melt
processing. Each nanocomposite was
prepared by mixing it in a C.W. Brabender
PL2000 Plasticorder (Germany). The
mixing temperature was kept at 255 °C
in order to ensure the proper viscosity for
the mixing. The rotation speed was set
at 60 rpm for 20 min. The total weight
of the material per batch was 40 g. The
content of each nano-silica particle
in the matrix was 1, 3 or 5 percent by
weight (wt.%) in different samples.
The specimens to be tested were further
processed by the means of a laboratory
compression moulding press at a pressure
of 40,000 psi. The temperatures of both
upper and lower plates of the press
were kept at 260 °C. The samples were
Aerosil R 972
Hydrophobic
110±20
16
≤2
3.6-5.5
approx. 50
< 0.5
≥ 99.8
0.7 – 1.3
<0.05
<0.003
<0.03
<0.025
<0.05
Dispersibility of Hydrophilic and Hydrophobic Nano-silica Particles in Polyethylene Terephthalate Films: Evaluation of Morphology
then quickly cooled down to room
temperature using cold water.
2.3 Study of Morphology
The morphology of the nanocomposite
films was observed with a Projectina
4014 microscope from Projectina AG
(Switzerland) under polarization and
crossed polarization. The magnification
was at 10× using a CCD camera. For this
purpose, the nanocomposite films were
replaced between the slide and the cover
glass for observation of the spherulites.
Surface morphology analyses of
the nanocomposites were carried
out employing a scanning electron
microscope, (SEM, XL30 Philips,
Netherlands). The samples were first
coated with a thin layer of Au using a
208HR High Resolution Sputter Coater.
The microscope has a pumping system
and a coating thickness controller of
MTM-20 using a sputtering power of
30 W. The process was operated in an
argon gas medium and under a pressure
of ca. 0.1 mbar. The deposition rate was
0.1 nm/s and separate rotary, planetary
and tilting staged movements with four
holders ensured coating with excellent
uniformity. The thickness of the coatings
was 10 nm with a target-to-substrate
distance of 50 mm. The SEM working
distance was 9 mm for all samples. The
presence of silica on each nanocomposite
surface was determined by an energy
dispersive X-ray microanalysis (EDX)
attached to the SEM.
2.4 Evaluation of Thermal
Properties
Calorimetric analyses (DSC) of the
pure matrix and the nanocomposites
were performed using a Perkin Elmer
Pyris 6 model (USA) integrated with
an IBM personal computer. The
samples were heated from 30 °C up
to 300 °C at a rate of 20 °C/min in
a nitrogen atmosphere. In order to
gain an insight into the effects of the
loaded silica particles on the degree of
crystallinity (Xc) of the PET matrix, the
normalized Xc values of the samples
were calculated using Equation (1):
Polymers & Polymer Composites, Vol. 23, No. 5, 2015
and Thermal Properties
Xc= (ΔHm/ΔH0m) ×100 (1)
where ΔH0m is the melting enthalpy of
100% crystalline PET (ΔH0m= 105.97 J/
g20-24) and ΔH m is the normalized
melting enthalpy of the sample during
the first heating.
The thermogravimetric analysis (TGA)
was performed on a Perkin Elmer
thermoanalyzer (Pyris Diamond SII,
USA). In each case a 5 mg sample was
examined under a nitrogen atmosphere
at a heating rate of 5 °C/min from room
temperature up to 600 °C.
The tensile storage modulus and
tensile loss factors of the films were
measured by a dynamic mechanical
thermal analyzer (DMTA) (DMA-
TRITON Tritec 2000 DMA model)
from Netzsch Co. (Germany). The
scans were made in a single cantilever
mode at a constant heating rate of 5 °C/
min and at a frequency of 1 Hz, from
25 °C to 300 °C.
2.5 Evaluation of Surface Free
Energies
The surface free energies of the
nanocomposites were estimated by
the Owens–Wendt method7, utilizing
the theory of adhesion work between
solid and liquid phases from which
polar (γP) and non-polar or dispersive
(γD) surface free energies can be
derived. Water, diiodo-methane and
benzyl alcohol were used as the probe
liquids at 23±2 °C and 65% relative
humidity. The average contact angle
from six different locations on each
nanocomposite was determined and
the experimental uncertainty was
within ±2°.
3. RESULTS AND
DISCUSSION
3.1 Microscopic
Characterization
Figure 1 shows the polarized
optical micrographs of the pure PET
and PET/silica nanocomposites.
Distinct large spherulites formed
in the pure PET, while only small-
sized ones and relatively uniform
dispersions appeared in PET/1%-silica
nanocomposites. This was probably
due to the hydrophilic and hydrophobic
nano-silica particles dispersion in PET
matrix acting as a nucleating agent in the
crystallization process. Our previous
study demonstrated a strong interaction
between the terminal carboxylic groups
of the PET chains with the surface
groups of hydrophilic nano-silica
particles. These interactions restrict
the motions of the PET molecular
segment and prohibit the growth of
large spherulites in the PET structure41.
This result is in good agreement with
those by other researchers for PET/
hydrophilic silica nanocomposites34-37.
However, the crystalline morphologies
of the PET/silica nanocomposites
were quite different depending on the
type of silica. The polarized optical
micrographs of the hydrophobic
nanocomposites indicated that the
hydrophobicity of the surface of
the silica particles led to a different
morphology of the spherulites. As
the hydrophilic nano-silica content
was increased to 3% and 5%, the
PET nanocomposites tended to form
agglomerated particles and dense
clusters due to the strong interactions
between the nanoparticles themselves.
As mentioned in our previous study,
FTIR spectra showed more interfacial
interactions between PET and the
hydrophilic nano-silica particles
compared with the hydrophobic ones42.
It seemed that these interactions were
not strong enough to enable a good
dispersion of the hydrophilic nano-
silica particles within the PET matrix.
PET chains were more compatible
with the hydrophobic nano-silica
particles compared to the hydrophilic
ones41. Agglomeration of particles
within the matrix could be attributed
to the generation of hydrogen bonds
between the surface hydroxyl groups
of the hydrophilic nano-silica. It was
interestingly shown that some growth
patterns of the spherulites were made in
287
 Mazeyar Parvinzadeh Gashti, Siamak Moradian, Abosaeed Rashidi, and Mohamad-Esmail Yazdanshenas

Figure 1: Optical micrographs of various produced nanocomposites (5000 the form of line-like network structures
microns): (a) Pure PET, (b) PET/1% hydrophilic nanosilica (1), (c) PET/3% in the PET composites containing 3%
hydrophilic nanosilica (1), (d) PET/5% hydrophilic nanosilica (1), (e) PET/1% hydrophilic and hydrophobic nano-
hydrophilic nanosilica (2), (f) PET/3% hydrophilic nanosilica (2), (g) PET/5% silica particles34-37.
hydrophilic nanosilica (2), (h) PET/1% hydrophobic nanosilica, (i) PET/3%
hydrophobic nanosilica, (j) PET/5% hydrophobic nanosilica
Figures 2a to g indicate the SEM
of the surfaces of pure PET together
with those of various PET/silica
nanocomposites. Pure PET showed a
relatively smooth and uniform surface.
Various nano-silica particle-particle
and nano-silica particle-PET chain
interactions were formed by addition
of the nano-silica particles to the PET
matrix. This enabled formation of
aggregates and agglomerates on the
surface of the PET composites which
in turn resulted in an increased surface
roughness. Such agglomerations were
less evident for PET/hydrophobic
silica nanocomposite causing smoother
surfaces compared with hydrophilic
nanocomposites.

Figure 3 shows the presence of

chemical elements on the surface
of pure PET and various PET/silica
nanocomposites as investigated by
EDX analysis. The electron beam
for EDX analysis was focused on
the composite surfaces at a low
magnification. In these patterns, Au
peaks clearly showed that gold was
successfully coated on the surfaces of all
PET/silica nanocomposites, and there
was no Si and Al elements present on
the pure PET. EDX analysis of the PET/
hydrophobic silica nanocomposites
illustrated more efficient interactions
and higher compatibility between
the PET chains and the hydrophobic
nano-silica leading to a lower presence
of Si and Al at the surface of these
nanocomposites. Nevertheless, the
hydrophilic nano-silica particles
containing the hydroxyl groups have
a strong tendency to agglomerate,
possibly due to an incompatibility with
the matrix leading to their migration
to the surface of such composites,
which is in good agreement with the
SEM images. This finding is further
supported by other authors39-43.

288 Polymers & Polymer Composites, Vol. 23, No. 5, 2015

Dispersibility of Hydrophilic and Hydrophobic Nano-silica Particles in Polyethylene Terephthalate Films: Evaluation of Morphology
and Thermal Properties

3.2 Thermal Studies Figure 2. SEM of various produced nanocomposites: a) Pure PET at 2500×, b)
PET/5% hydrophilic nano-silica (1) at 2500×, c) PET/5% hydrophilic nano-
DSC and TGA results of the pure PET silica (1) at 10000×, d) PET/5% hydrophilic nano-silica (2) at 2500×, e) PET/5%
together with those of PET/5%-silica hydrophilic nano-silica (2) at 10000×, f) PET/5% hydrophobic nano-silica at
nanocomposites are given in Table 2. 2500×, g) PET/5% hydrophobic nano-silica at 10000×
The glass transition temperature is
due to the molecular movement of
PET. There was a decrease in Tg for all
PET/silica nanocomposites indicating
that the amorphous molecules became
mobile at a lower temperature than that
in the pure PET. Researchers claimed
that the decrement of Tg for the PET/
silica nanocomposite could be due to
the existence of the low molecular
weight PET chains attached to the silica
particles35-37. DSC results also showed
that Tm ranged from 238 to 241 °C for
the PET/silica nanocomposites which
were slightly lower than that of the pure
PET, 242 °C. There was also a decrease
in the enthalpies and crystallinity
percentages of the PET/silica
nanocomposites. Some researchers
also obtained similar decrease in Tm
for the silica incorporated polymeric
nanocomposites. They confirmed that
the silica particles serve as a nucleating
agent leading to a heterogeneous
nucleation and formation of less
perfect spherulites43-45. Thus, these
spherulites in the presence of silica
particles might not be as large as
those in the pure PET. Other authors
have suggested that the silica particles
cannot increase the crystallinity of
the PET polymer, although they can
accelerate the crystallization of the
PET nanocomposites39,40.

Table 2 and Figure 4 also summarize

the thermal degradation of PET/5%-
silica nanocomposites as a function
of temperature. The weight loss due
to the decomposition of the pure PET
and PET/silica nanocomposites was
nearly the same up to a temperature
of about 315 °C. After this point, the

Table 2. Thermal behavior of pure PET and its various PET/silica nanocomposites
Sample Tg (˚C) Tm (˚C) ΔHm Xc (%) TiD (˚C) T5D (˚C) Wt600ºR (%)
Pure PET 93.8 242 41.6 39 315.4 393.2 13
PET/5% hydrophilic nano-silica (1) 91.2 241 33.5 31 342.7 399.7 18
PET/5% hydrophilic nano-silica (2) 85.6 240 37.9 35 338.1 400.4 16
PET/5% hydrophobic nano-silica 88 238 39.5 37 328.4 394.8 22

Polymers & Polymer Composites, Vol. 23, No. 5, 2015 289

 Mazeyar Parvinzadeh Gashti, Siamak Moradian, Abosaeed Rashidi, and Mohamad-Esmail Yazdanshenas

Figure 3. EDX analysis of various produced nanocomposites: a) Pure PET, b) PET/5% hydrophilic nano-silica (1), c)
PET/5% hydrophilic nano-silica, (2) d) PET/5% hydrophobic nano-silica

Figure 4. TGA thermograms of pure PET and PET/5% silica nanocomposites initial thermal degradation (TiD) was
influenced by the presence of silica in
the PET composite as the TiD of PET/
silica nanocomposites were higher
than pure PET. The type of nano-silica
showed an important role in the initial
thermal degradation temperature. TiD
and the temperature at weight reduction
of 5% (T5D) were observed at 328-
342 °C and 393-400 °C, respectively,
depending on the presence and the
hydrophilicity of the nano-silica
used in the PET matrix. Both PET/
hydrophilic silica nanocomposites
showed a weight reduction at relatively
similar temperatures. The weight of the
residue at 600 °C (Wt600ºR) increased for

290 Polymers & Polymer Composites, Vol. 23, No. 5, 2015

Dispersibility of Hydrophilic and Hydrophobic Nano-silica Particles in Polyethylene Terephthalate Films: Evaluation of Morphology
and Thermal Properties

the prepared nanocomposites, ranging PET chains. AFM results also showed particles plays a great role in the
from 18 to 22% as compared to 13% that the hydrophilic nano-silica (2) thermal properties of the prepared
for the pure PET. Similar thermal particles agglomerated and were less nanocomposites. As stated by the
resistance for the cellulose fibres coated dispersed in the PET matrix compared nano-silica manufacturer, hydrophilic
with polycarboxylic acid/hydrophobic to other nano-silica particles used41,47,48. nano-silica (2) shows a particularly
silica nanocomposite was observed in Polarized optical micrographs of the high degree of agglomeration and
our earlier studies46. This enhancement samples showed many spherulites it is more hydrophilic compared
of the thermal properties can be in a limited space within the PET/ with nano-silica (1). Their average
defined to the high heat resistance, heat silica nanocomposites, due to a large primary particle sizes are 40 nm and
insulation effect and the mass transport number of nuclei formed by the strong 16 nm respectively. By comparing
barrier toward PET molecular chains nucleation effect of the nano-silica the results obtained from the thermal
exerted by the nano-silica particles. particles27,33,34,37. measurements in this study with
The maximum amount of char was the FTIR and AFM results in our
observed for the hydrophobic silica It can be suggested that the previous study, it can be concluded
nanocomposite which is related to the hydrophilicity of the nano-silica that the interactions between the PET
surface modification of the nano-silica.
Figure 5. The storage modulus of pure PET and PET/5% silica nanocomposites
The dynamic mechanical thermal
analysis was used to identify the
interfacial interactions in PET/silica
nanocomposites and the results are
presented in Figures 5 and 6. The
storage moduli of the pure PET
and PET/5%-silica nanocomposites
were distinctively different in the
temperatures ranging from -100 to
100 °C in Figure 5. It was gradually
decreased for the pure PET and PET/
hydrophilic silica (1) compared with
PET/hydrophilic silica (2) and PET/
hydrophobic silica nanocomposites,
which can be associated with the
relaxation of the amorphous phases.
Samples were all glossy at the
temperatures above 90 °C due to the
glass-rubber transition (Tg) except Figure 6. The tan delta of pure PET and PET/5% silica nanocomposites
for the PET/ hydrophilic silica (2)
which decreased around 85 °C. An
increase in the cold crystallization
range (around 140 °C) for the pure
PET, PET/hydrophilic nano-silica (1)
and PET/hydrophobic nano-silica is
related to the composite reinforcement
by the crystallites being formed. A
decrease in the modulus values for the
nanocomposites at 140 °C is relevant
to the pre-melting process. However,
there was a different behaviour in the
modulus values for PET/hydrophilic
nano-silica (2) at temperatures above
140 °C. The FTIR and ATR results
obtained in our previous studies
demonstrated that there are some
van der Waals interactions between
the hydrophobic nano-silica and the

Polymers & Polymer Composites, Vol. 23, No. 5, 2015 291

 Mazeyar Parvinzadeh Gashti, Siamak Moradian, Abosaeed Rashidi, and Mohamad-Esmail Yazdanshenas
matrix and the hydrophilic nano-silica
(1) were stronger than those with
hydrophilic nanosilica (2) resulting
to more homogenous matrix.
The dependencies of tan δ on the
temperature for the prepared samples
are shown in Figure 6. The maximum
in tan δ about 90 °C corresponds to
the segmental relaxation related to
the glass-rubber transition in the PET
nanocomposites. The tan δ values
related to the Tg region are higher
for the PET/hydrophilic nano-silica
(1) and PET/hydrophobic silica
nanocomposites. This is attributed to
the elastic nature of the nano-silica
(1) and the surface properties of
the hydrophobic nano-silica which
affects the interactions of the PET-
silica matrix. The nano-silica (1)
particles can decrease the segmental
motions of the PET chains resulting
in an increase of the tan δ value. This
result was in good agreement to those
by other authors for the nano-silica
filled thermoplastic composites38-40.
Another peak appeared at a higher
temperature around 120-140 °C reflects
an increase of the mechanical loss
due to the cold crystallization of PET.
Results showed that the intensity and
temperature of curves varied among
the samples containing different nano-
silica particles36,42.
Table 3. Surface tension of the three probe fluids used in this study
Probe fluid Surface tension
(mN/m)
Diiodo-methane 50.8
Benzyl alcohol 39.0
Water 72.8
Table 4. Variations in the surface free energy of various nanocomposites as calculated by the Owens method
Sample
Pure PET
PET/5% hydrophilic nano-silica (1)
PET/5% hydrophilic nano-silica (2)
PET/5% hydrophobic nano-silica
292
3.3 Contact Angle and Free It is well known that nano-silica
Energy Analysis particles usually have very high surface
free energy because of their surface
Three probe fluids of diiodo-methane,
hydroxyl groups7,42. The adsorption
benzyl alcohol and water were used in
and desorption of water from silica
this study. The surface tension, polar
depends on the concentration and the
(γP) and non-polar or dispersive (γD)
type of the surface functional groups,
surface free energy of these liquids
the specific surface area, the average
are given in Table 3. The variations
particle size and the type of packing of
in the surface free energy of the PET
primary particles in aggregates7,51,56-59.
nanocomposites calculated by the
Obviously, as the chemical end groups
Owens method are summarized in
of PET chains are limited, these
Table 449-55. Hydrophilic nano-silica
particles with high surface free energy
(1) and hydrophobic nano-silica
and bigger sizes do not distribute
particles embedded in PET matrix
uniformly within the PET matrix. In
decreased the average contact angles
contrast, the surface treated nano-silica
for all liquids used while these
particles tend to reside in the polymer
values were increased for the PET/
bulk52. As it was mentioned earlier,
hydrophilic silica (2) nanocomposite.
the hydrophobic nano-silica used
Hydrophilic nano-silica (1) also
in this study was after-treated with
increased the dispersive surface free
dimethyldichlorosilane which results
energy of PET composite (γD) resulting
to an increase in the total and polar
in an increase of the total surface free
surface free energy of the prepared
energy (γT), whereas γD and γT were
nanocomposite41,52-55,60-65.
decreased for the PET/hydrophilic
nano-silica (2) nanocomposite.
There was not a considerable change 4. CONCLUSIONs
in γ D for PET/hydrophobic silica
I n t h i s s t u d y, P E T / s i l i c a
nanocomposite. Nano-Silica (1) has a
nanocomposites were prepared by melt
smaller particle size compared to that
mixing process and the effects of the
of nano-silica (2) and it is more levelly
type of nano-silica on the morphology,
dispersed in the PET matrix. Particles
thermal and surface properties of the
mixed with polymer can change the
composites were elucidated. The SEM,
orientation of chains which may lead
EDX and contact angle observations
to an increased γD of the resulting
demonstrate that the hydrophilic
nanocomposite.
nano-silica tends to migrate to the
surface of the PET composites, while
the hydrophobic nano-silica is more
compatible with the molecular chains
of PET. The results obtained from
γD (mN/m) γP (mN/m)
thermal studies indicate that the nano-
silica particles serve as a nucleating
50.8 0.0
agent leading to the formation of less-
28.7 10.3 perfect spherulites. In conclusion, the
21.8 51.0 hydrophilic nano-silica particles with
Average contact angle (°) γD γP γT
Diiodo Benzyl water (mJ/m2) (mJ/m2) (mJ/m2)
methane alcohol
67.4 56.7 96.7 24.12 1.64 25.76
56.3 41.8 95.4 31.66 0.94 32.61
74.9 60.7 105.4 21.82 0.58 22.40
59.5 51.6 77.6 24.42 7.71 32.13
Polymers & Polymer Composites, Vol. 23, No. 5, 2015
Dispersibility of Hydrophilic and Hydrophobic Nano-silica Particles in Polyethylene Terephthalate Films: Evaluation of Morphology
lower contents of hydroxyl groups
and a smaller particle size, as well
as the surface modified hydrophobic
nano-silica particles are compatible
with PET to produce nanocomposites.
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