Chemical Engineering Journal 284 (2016) 343–350

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Hydrophobic coating of expanded perlite particles by plasma

polymerization
Mehmet Gürsoy a, Mustafa Karaman a,b,⇑
a
Department of Chemical Engineering, Selcuk University, Konya 42075, Turkey
b
Advanced Technology Research & Application Center, Selcuk University, Konya 42075, Turkey

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Surfaces of expanded perlites were

modified by a rotating-bed PECVD
method.

The rotating-bed reactor was used for
agitation of particles during the
depositions.

Surface of expanded perlite was
successfully transformed into super-
hydrophobic.

The water content percentage of
expanded perlite was reduced from
70% to below 5%.

PECVD avoids many problems
associated with existing liquid-based
coating techniques.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, an RF plasma discharge was employed to deposit thin poly(hexafluorobutyl acrylate)
Received 26 May 2015 (PHFBA) polymeric films on expanded perlite. A rotating plasma reactor was used to provide effective agi-
Received in revised form 1 September 2015 tation and mixing of the particles during the depositions. Surface of expanded perlite, a hydrophilic por-
Accepted 3 September 2015
ous material, was successfully transformed into super-hydrophobic due to the highly fluorinated chain of
Available online 8 September 2015
PHFBA. Deposition rates up to 42 nm/min were observed. The influences of plasma discharge conditions
on wettability and water holding capacity of expanded perlite powders were investigated. Chemical and
Keywords:
morphological properties of uncoated and coated expanded perlites were determined by SEM (EDS), FTIR,
Expanded perlite
PECVD
and contact angle measurements analyses. It is observed that the pulsed plasma approach helps to min-
Plasma polymerization imize undesirable monomer fragmentation while providing better film structure. It also should be
Hydrophobic emphasized that PECVD experiments did not change the morphology of the expanded perlite powders.
Coating The water holding capacity of expanded perlite was decreased from 70% down to around 4% upon coating
on pulsing mode.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction suitable conditions, it grows up to 20 times its original volume

Perlite is a volcanic glass mineral found extensively in volcanic
rock. When perlite ore is treated and heated (over 870 °C) under
⇑ Corresponding author at: Department of Chemical Engineering, Selcuk Univer-
sity Kampus, Konya 42030, Turkey. Tel.: +90 332 223 2108; fax: +90 332 241 0635.
E-mail address: karamanm@selcuk.edu.tr (M. Karaman).
and becomes porous [1]. After this physical transformation, its
color turns from gray to white. Its unique characteristics of being
lightweight, sterile, insulating and fireproof make perlite an excel-
lent choice for many applications including construction, filtration,
horticulture, and insulation [2,3]. Perlite is naturally incom-
bustible, and thus it can be used in the production of fire resistant
construction materials. The presence of expanded perlite in

http://dx.doi.org/10.1016/j.cej.2015.09.007
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
344 M. Gürsoy, M. Karaman / Chemical Engineering Journal 284 (2016) 343–350

concrete or mortar improves the heat insulation in buildings due to
its very high porosity [4–6]. Due to its extremely low density,
expanded perlite can also be used in lightweight aggregate con-
crete [7,8]. In addition, expanded perlite is chemically inert, which
makes it environmentally friendly and safe. Owing to its high
water absorption capacity, it is used in horticultural applications
as a soil conditioner [9].
These are just a few examples where expanded perlite particles
find themselves useful among a wide range of applications in
diverse areas. It is apparent that the surface properties of the par-
ticles play a crucial role in determining the overall function and
performance of the final product. For example, high water content
of expanded perlite is not desired for the applications requiring
heat and sound insulations, because it is well known that the
material moisture content increases the heat and sound transfer
coefficients [10,11]. Moreover, such a high moisture content in
the final structure can cause physical damages [12,13]. These
necessitate good strategies for modification or functionalization
of perlite particle surfaces with an optimal method.
The main objective of this study is to make expanded perlite
surfaces hydrophobic through an all-dry encapsulation process,
namely rotating plasma enhanced chemical vapor deposition
(rotating-bed PECVD) method. In this way, this modified expanded
perlite could be more efficient insulating material and that may
create many more usage areas. The wetting behavior of a material
can be modified by changing the chemistry and/or roughness of its
surface [14]. Usually a thin layer of a low-surface energy polymer
such as a fluoropolymer, is coated on a surface to obtain sufficient
hydrophobicity [15,16]. Usually liquid-based techniques are uti-
lized to coat or encapsulate particles and such methods rely on
applying a polymer coating solution onto the particle surface with
the subsequent removal of solvent. Another solution based
method, atom transfer radical polymerization (ATRP) was also suc-
cessfully applied to coat polymer onto the surfaces of multiwalled
carbon nanotubes [17], microspheres [18] and nanoparticles
[19,20]. However, it is very difficult to coat particles uniformly
without agglomeration with liquid-based methods, especially for
particle sizes below 100 lm [21]. Plasma enhanced chemical vapor
deposition (PECVD), on the other hand, is a dry process that is able
to provide uniform solid coatings around particles under a gaseous
environment. Previously, fluorocarbon coatings have been depos-
was employed externally to activate the deposition reactions. The
resultant surface-modified perlite particles were found to be highly
water-repellent. The effects of various deposition conditions on the
structure, morphology, and the wetting behavior of the final mate-
rials are discussed.
2. Materials and methods
2.1. Materials
The expanded perlite was received from Tesar Püskürtme
Granit (Konya, Turkey). The chemical composition and the physical
properties of expanded perlite are given in Tables 1 and 2, respec-
tively. The test liquid n-heptane and the monomer 2,2,3,4,4,4-
hexafluorobutyl acrylate (HFBA) (95%) were purchased from
Sigma–Aldrich. They were used as-received without any further
modification and purification. The chemical structure of HFBA is
shown in Fig. 1.
2.2. PECVD polymerization
The experiments were carried out in a rotating-bed PECVD sys-
tem (Fig. 2) designed by Plazmatek, Turkey.
In this system, a cylindrical Pyrex tube (6 cm inner diameter,
30 cm length) was used as the vacuum reactor, which was induc-
tively coupled by a copper antenna connected to a 13.56 MHz radio
frequency (RF) plasma generator. The copper antenna was exter-
nally wound around the reaction chamber. An LC matching circuit
was placed between the coil and the generator for impedance
matching. The 360° rotation of the reactor chamber under vacuum
conditions was achieved by vacuum compatible ferrofluidic rotary
feed throughs placed at both ends of the Pyrex reactor. Rotation of
the expanded perlite particles provided agitation and continuous
exposure of the particle surfaces to the plasma gases.
HFBA monomer was vaporized in a glass jar at room tempera-
ture. The flow rate of monomer (1.2 sccm) was controlled by a
needle valve. A capacitance pressure gauge is used to measure
Table 1
The main chemical composition of expanded perlite.

ited on micron-sized silica particles by means of atmospheric pres- The main components Weight percentage
sure PECVD [22]. Carbon nanotubes have been encapsulated by Silicon dioxide 71.0–75.0
polymethyl methacrylate using fluidized-bed PECVD [23]. Passiva- Aluminum oxide 12.5–18
tion coatings around aluminum nanoparticles were achieved by Sodium oxide 2.9–4.0
PECVD using organic precursors [24]. Besides, PECVD was also uti- Potassium oxide 4.0–5.0
Calcium oxide 0.5–2.0
lized for encapsulation of drug particles by the formation of thin Iron(III) oxide 0.1–1.5
layer of functional polymers [25,26]. PECVD is advantageous over
other traditional wet coating techniques of particles such as sol–
gel and spin coating. The versatility of CVD and the inherent
plasma polymerization enables solvent-free, conformal, environ- Table 2
mentally friendly and safe depositions at low temperatures The typical physical properties of expanded perlite.

[27,28]. However, plasma-based techniques suffer from drawbacks The physical properties of expanded perlite
of loss of monomer functionality, excessive crosslinking, and other Color White
uncontrolled side reactions [29]. Recently it has been shown that Density 2.2–2.4 g/cm3
Heat conductivity 0.04–0.06 W/mK
pulsing the electric discharge can give rise to high levels of struc-
Melting point 1300 °C
tural retention [30]. Therefore, in this work, we have chosen to Specific heat 837 J/kgK
use pulsed plasma to deposit thin poly(hexafluorobutyl acrylate) Rough density 30–190 kg/m3
(PHFBA) film around expanded perlite particles. A comparison is
made between the surface chemistry of continuous wave plasma
and pulsed plasma PHFBA films. Besides, the use of an electrode-
less rotating-bed PECVD system allowed sufficient mixing of parti-
cles during the depositions, hence the entire surface of the each
expanded perlites is exposed to the reactant gases [31]. As-
received hydrophilic expanded perlite particles were loaded into
a rotary cylindrical reactor vessel for which an RF plasma source Fig. 1. The chemical structure of HFBA.
 M. Gürsoy, M. Karaman / Chemical Engineering Journal 284 (2016) 343–350 345

the pressure inside the reactor. The rotation speed of the reactor Table 3
was adjusted at 30 rpm with a stepper motor. During all plasma The deposition rates of PHFBA at different plasma powers.

polymerization experiments, pressure in the vacuum chamber Plasma Deposition rate (continuous Deposition rate (pulsed-
was kept constant at 100 mTorr. The effects of plasma power and powers (W) wave) (nm/min) plasma) (nm/min)
plasma operation mode (either continuous or pulsed) on the final 10 41 42
properties of PHFBA surfaces were investigated. In all experiments 20 40 39
a silicon wafer (100, p-type) was also placed in the reactor for 30 27 28
40 22 23
thickness measurement and characterization purposes.

2.3. Materials characterization

Thickness measurements were carried out using an AEP 500LS

profilometer.
Fourier transform infrared spectroscopy (FTIR), X-ray photo-
electron spectroscopy (XPS) and Scanning Electron Microscopy
(SEM) coupled with Energy Dispersive X-ray Spectroscopy (EDS)
were employed to analyze the chemical and the morphological
properties of the surfaces of expanded perlite before and after
coatings. FTIR spectra were obtained in a Bruker Vertex 70 FTIR
spectrometer between 400 and 4000 cm1 wavenumbers at a
resolution of 4 cm1 using an attenuated total reflectance (ATR)
accessory. XPS analysis of the polymer surfaces was performed
using a Specs spectrometer equipped with monocromatized Al
source. SEM experiments were performed using a Zeiss LS-10
scanning electron microscope with EDS detector.

2.4. Water contact angle measurements and water content

experiments

Water contact angle measurements were performed at five

points on each PHFBA coated Si wafer samples using a contact
angle goniometer (Kruss Easy Drop) equipped with an automatic
dispenser. Moreover, Washburn capillary rise method (thin-layer
wicking) was utilized to determine the water contact angles of
coated and uncoated expanded perlite surfaces. The glass capillar-
ies used in these experiments were 8 cm in height.
In order to investigate the effect of fluoropolymer coatings onto
water holding capacity of expanded perlite, the same quantities of
uncoated and coated expanded perlite powders that were pro-
duced at different experimental conditions were placed in separate
cells. Then, they were exposed to water. After water treatment,
expanded perlite powders were filtered, and the remaining water
was collected in graduated cylinders. The contents of the water
percentage in coated and uncoated expanded perlite were deter-
mined according to Eq. (1)
Fig. 3. Infrared spectra of (a) 20 W continuous wave plasma PHFBA, (b) 20 W
pulsed-plasma of PHFBA, and (c) HFBA monomer.
In Eq. (1) W A is the volume of water initially added in the cell, and
W C is the volume of collected water, after treatment. Capillary rise
and water content measurements were repeated at least three
times using different samples in order to calculate the standard
deviations.
3. Results and discussion
3.1. PECVD of PHFBA and film characterization

Except from expanded perlites, Si wafers were also placed into

WA  WC
Water content ð%Þ ¼  100 ð1Þ the reactor to determine the polymer deposition rates in all PECVD
WA
experiments. The film thickness measurements on Si wafers were

Fig. 2. The schematic diagram of experimental system.

346 M. Gürsoy, M. Karaman / Chemical Engineering Journal 284 (2016) 343–350
Fig. 4. C1s XPS spectra of PHFBA deposited onto silicone substrate: (a) 20 W continuous wave plasma polymer, (b) 20 W pulsed plasma polymer.
obtained ex-situ from profilometry measurements. The deposition
rates of PHFBA at different conditions are given in Table 3. The fas-
ter deposition rates of PHFBA were obtained at the low plasma
powers (10, 20 W) as compared to those deposited at higher
plasma powers (30, 40 W) for both continuous and pulsed modes.
On the other hand, in terms of plasma operation modes, the results
are very close at the same plasma powers. Usually, for plasma
polymerizations, increasing the plasma power results in higher
deposition rates at sufficiently low energy inputs. However, as
the power is increased further, ablation caused by energetic glow
discharge may compete with deposition, hence decreasing the
overall deposition rates. In our case, it can be assumed that abla-
tion or plasma etching is an important rate determining factor at
plasma powers of 30 and 40 W. The reported rate data here is
based on film thicknesses on reference silicon wafer because the
thickness of the PHFBA coating is difficult to determine directly
on the expanded perlite surfaces. It should also be kept in mind
that, coating thicknesses measured on reference silicon wafers
are probably higher than the thicknesses on the perlite particles
due to the high surface area of the expanded perlite particles.
Fig. 3 shows a comparison of FTIR spectrum of PHFBA deposited
at different plasma modes (a, b) to that of HFBA monomer (c). The
intensities of the peaks were normalized at 1758 cm1 (C@O
stretching). The spectrum of the HFBA monomer can be identified
with the following major peak assignments: C@O stretching
(1758 cm1), C@C peak (1641 cm1), CAH bending (1500–
1350 cm1), asymmetric ACF2A peak (1297 cm1), symmetric
ACF2A peak 1207 cm1), and ACFHACF3 peak (1114 cm1) [32–
34]. The spectra of PECVD synthesized polymers do not involve
peak related with C@C bond (1641 cm1) that exists only in the
monomer spectrum, which proves that the polymerization pro-
ceeded through unsaturated C@C double bonds. Spectral broaden-
ing was observed for the plasma polymer film deposited under
continuous wave conditions (Fig. 3b) as a consequence of the
extensive fragmentation and cross-linking reactions due to the
high and continuous energy inputs supplied to reactor. At contin-
uous wave plasma conditions, more energy is delivered per chem-
ical species inside the reactor. For example, the appearance of a
new absorption peak at 1845 cm1 in the spectrum of the films
deposited at high plasma powers is most probably due to co-
 M. Gürsoy, M. Karaman / Chemical Engineering Journal 284 (2016) 343–350 347

Fig. 5. The SEM images of uncoated (a, c), and PHFBA coated (b, d) expanded perlite.

Table 4 showed a decrease in fluorine atomic concentration (25.9 at.%)

EDS experiment for uncoated expanded perlite. compared to the theoretical structure (40 at.% fluorine), whereas
Element at.% [uncoated] at.% [coated]
the polymer deposited under pulsed plasma conditions closely
resembled the theoretical PHFBA structure with 35.7 at.% fluorine
Oxygen 67.61 52.98
Silicon 16.95 17.89
content.
Aluminium 4.54 4.58 Fig. 4a and b show the high resolution C1s spectra for continu-
Sodium 3.1 2.65 ous and pulsed wave PHFBA films, respectively, together with the
Potassium 1.53 2.11 spectrum deconvolutions.
Fluorine 0 18.44
Both spectra can be described using seven bonding environ-
Others 6.27 1.35
ments including the following peak components: AC⁄F3
(293.4 eV), AC⁄F2A (290.9 eV), AC⁄@O (289.2 eV), ACH2ACF2AC⁄
HFA (287.5 eV), AOAC⁄H2A (286.2 eV), AC⁄HACOA (285.5 eV),
deposition of acyl fluoride-like moieties. Pulsing the electric and ACAC⁄H2ACA (285 eV) [36,37]. The C(1s) spectrum of the
discharge during the depositions may improve the structural pulsed plasma polymer (b) has intense perfluoroalkyl (290.9 and
retention due to low levels of precursor fragmentation during the 293.4 eV) moieties, whereas the continuous wave plasma polymer
on-period in association with conventional polymerization exhibited a more intense hydrocarbon component at 285.0 eV in
reaction pathways predominating during the pulsed plasma duty conjunction with a lower concentration of fluorinated species.
cycle off-period [35]. Indeed, in terms of retention of functional Therefore, both XPS and FTIR analyses confirm that PECVD carried
groups, pulsed-plasma PHFBA gives better results than those of out under pulsed plasma discharge produces PHFBA thin films that
continuous wave deposition of PHFBA. At 20 W, pulsed plasma retain higher fraction of functional perfluoroalkyl groups.
conditions, FTIR bands are narrow, and the peak assignments are Fig. 5 shows the SEM images of expanded perlite surfaces before
similar to the assignments for the monomeric precursor. This and after PHFBA coatings. The conformal nature of the rotating-bed
may be attributed to the low plasma powers applied during the PECVD process results in little overall change in the morphological
depositions. The high retention of the monomer structure during structure of the perlite particles, the only notable difference being
pulsed plasma deposition was also confirmed by XPS analysis. the change in particles surface chemistry. During SEM, EDS analy-
The elemental analysis of the continuous wave plasma polymer sis was also made to reveal the change of surface chemical
348 M. Gürsoy, M. Karaman / Chemical Engineering Journal 284 (2016) 343–350

composition after coating. As determined by EDS (Table 4), the pre-

dominant elements in the pristine expanded perlite samples were
oxygen, silicon, aluminum, sodium, and potassium in various com-
pounds. After coating, the results verify the presence of fluorine
coating with almost 18.5% fluorine at the surface. Therefore it
can be concluded that although rotating plasma deposition chan-
ged surface chemistry, expanded perlite powders have still high
porosity, which is one of the most important features as a con-
struction material.

3.2. Wettability and water content measurements

In order to understand the influence of the plasma operation

modes on the wettability of the surfaces, substrates were depos-
ited at the same plasma powers in both pulse and continuous
modes. For this purpose, contact angle measurements were carried
out in two different ways: goniometer contact angle device for
PHFBA deposited Si wafer and Washburn method for expanded
perlites. Fig. 6 demonstrates the contact angle values obtained
from Si wafer as a function of the plasma power.
The contact angle values of pulsed-plasma polymer were found
higher than continuous plasma polymer films at four different
plasma powers. This result is in agreement with the literature,
where the higher water contact angle values for fluoropolymer
films were obtained in pulsed-mode as compared to those depos-
ited in continuous wave mode at the same deposition conditions
[38,39]. The high contact angle can be attributed to high retention
of long perfluoroalkyl chain at low plasma energy inputs. The
mechanisms of polymerization reactions are quite different
between pulsed and continuous modes [15,40]. As a result of con-
tinuously energy feeding, conventional plasma creates energetic
environment that cause fragmentation of monomer molecules
[41]. The idea behind the use of pulsed-plasma, instead of the con-
tinuous wave plasma, is to reduce ion, electron, UV bombardments
in the plasma off time. In this way, pulsed-plasma avoids extensive
fragmentation and premature terminations and offers a high
degree of retention of chemical groups [42–45]. Thus, polymer thin
films can be deposited without damages and defects. In our study,
FTIR analysis of as-deposited polymers also verified the retention
of functional groups in the pulsed-plasma mode. These results
Fig. 7. Distance squared versus time for uncoated and PHFBA coated expanded
perlite using Washburn method.
are consistent with the literature that substantiates the idea that
functional groups are preserved in pulsed-plasma by comparison
with conventional plasma polymerization [35,46].
Direct contact angle measurement methods cannot be used for
very small and porous substances such as powders. For this reason,
the effect of PHFBA coating on wettability was investigated by
using an indirect analysis, namely Washburn method. For this
method, Washburn equation (Eq. (2)) is used [47]
2 Reff cL cos h
h ¼ t ð2Þ
2g
where, h is the liquid height, Reff is the effective pore radius, cL is the
surface tension of liquid, g is the dynamic viscosity of liquid, t is
time, h is the contact angle. In order to calculate h for water, firstly
Reff must be determined. In practice, low energy liquids are used to
find Reff. These fluids are spreading liquids, therefore the contact
angle can be assumed to be zero that means cos h ¼ 1. For this pur-
pose, heptane was used as a wetting fluid in this study. Then,
according to Fig. 7 and using Eq. (2), the contact angle of uncoated
expanded perlite was found 41.9°. Therefore, as expected, uncoated
expanded perlite can be considered to be highly hydrophilic. On the
other hand, when PHFBA coated expanded perlite was used for
Washburn method, water didn’t penetrate through the capillary
tube (during 12 h).
Actually, the surface modified expanded perlite particles were
never wetted by water, until all of the water in the experiment

Fig. 6. Contact angle values at different plasma powers for continuous wave and Fig. 8. The water content value of PHFBA coated expanded perlite produced at
pulse conditions. different PECVD conditions.
 M. Gürsoy, M. Karaman / Chemical Engineering Journal 284 (2016) 343–350
tube shown in cover picture is evaporated. Therefore we can con-
sider coated expanded perlite highly hydrophobic. In order to
investigate the effect of hydrophobic coating on water absorption
capacity of expanded perlites, swelling tests were performed using
a cell method. The water content value of uncoated expanded per-
lite was found as 70%. Fig. 8 demonstrates the water content
results of PHFBA coated expanded perlites. After coating, water
content values decreased dramatically down to almost 4%. Accord-
ing to the figure, water-holding capacity is decreasing with
increasing hydrophobicity. These results correlate well with con-
tact angle experiments. The lowest water content value was
observed for the expanded perlite which has the highest water
contact angle.
4. Conclusions
Based on results of this study, it can be concluded that rotating-
bed PECVD method can be used for conformal coatings around par-
ticles having complex geometries like expanded perlite. PECVD
avoided many problems associated with existing liquid-based par-
ticle coating techniques such as particle agglomeration, toxic sol-
vents, and poor uniformity. Surface of expanded perlite, a
hydrophilic material, was successfully transformed into a highly
hydrophobic using PECVD. The important plasma deposition
parameters, specifically plasma power and operation mode (con-
tinuous vs. pulsed) were found to be effective in providing control
of the surface hydrophobicity. The pulsed plasma approach helps
to minimize undesirable monomer fragmentation while providing
better film structure. It also should be emphasized that PECVD
experiments did not change the morphology of the expanded per-
lite powders. The water holding capacity of expanded perlite was
decreased from 70% down to around 4% upon coating on pulsing
mode. These features can widen the area of use of expanded perlite
especially in building industry and open up new application areas.
The method of this study can be extended to functionalize many
other types of particles having dimensions down to micro and even
nano scale.
Acknowledgements
This project was supported by the Scientific and Technological
_
Research Council of Turkey (TÜBITAK) with a grant number of
213M399. The author M. Gürsoy was supported by TÜBITAK- _ Pulsed plasma deposition of super-hydrophobic nanospheres, Chem. Mater. 14
_
BIDEB. Authors would like to thank also MCM ARGE Ltd. Company
for their help in reactor design and optimization.
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