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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 11925–11932
www.elsevier.com/locate/ceramint

Zeolite decorated highly porous acicular calcium silicate ceramics

Cekdar Vakifahmetoglun
Department of Mechanical Engineering, Istanbul Kemerburgaz University, 34217 Istanbul, Turkey
Received 27 February 2014; received in revised form 3 April 2014; accepted 4 April 2014
Available online 13 April 2014

Abstract

Macrocellular calcium silicate (wollastonite) ceramic foams possessing
86 vol% total porosity were produced from commercial calcium
silicate hydrate (xonotlite) nano-size acicular crystals and poly-methyl-methacrylate microbeads (PMMA) (used as sacrificial pore formers). Open
cell wollastonite foams had a bi-modal pore size distribution with major modes located
100 nm due to interparticle porosity and
100 mm due
to the sacrificial pore former. These macrocellular ceramics were then used as a scaffold for MFI type zeolite (silicalite-1) synthesis. Monolayer
coffin shaped zeolite crystals (
3 mm size, measured from the c-axis and
300 nm thickness) were observed with almost full coverage on the
inner macro-cell walls. The specific surface area of the components increased from 9.6 m2/g to 108.2 m2/g via zeolite functionalization, leading to
components possessing multiscale porosity.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Zeolite; Wollastonite; Xonotlite; Foams; Hierarchical porosity

1. Introduction o2 nm, are difficult to be assembled in hierarchically porous

High surface area porous ceramics find numerous applications
in various fields, such as filtration (of liquids or gases), catalysis,
gas storage, sensing, etc. due to their unique properties compared
to those of their dense counterparts [1,2]. These ceramics can be
produced through several manufacturing methods covering wide
range of chemistries. The selected method affects the properties
of the formed component. For example, parts with different
microstructural characteristics such as porosity (size, shape,
distribution, interconnectivity, etc.) can be produced [1]. Among
high surface area porous ceramics, the ones including macro-
porosity together with micro/meso or both (i.e. with bi/tri-modal
hierarchical porosity), can be considered as a particular class. For
such materials the macroporous framework offers chemical and
mechanical stability, as well as low pressure drop and high mass
transfer rate due to macropore interconnection, while the
micro/mesoporous system provides the functionality of a given
application. As documented in a recent and comprehensive
review, zeolites, crystalline microporous materials with pore size
n
Tel.: þ90 212 6040100; fax: þ 90 212 4459255.
E-mail address: cekdar.vakifahmetoglu@kemerburgaz.edu.tr
architecture including macroporosity [3].
Currently, an alternative way in which zeolites are anchored
onto the cell walls of ceramic foams, forming the so called
structured zeolite composites or micro-reactors, attracts growing
attention in several industrial processes such as heterogeneous
catalysis and separation [3,4]. In such composite design, unlike
the common usage of zeolites, they are not employed in powder/
pellet form (like in fixed-bed reactors). Therefore the key problem
typical for such type of approach, namely the excessive pressure
drop over the reactor, is minimized. Besides, utilization of
ceramic foams as scaffold brings other advantages such as low
thermal expansion and high thermal, mechanical and chemical
stability. Recently, porous biomorphic ceramics [5,6], glass [7,8],
Al2O3 [9], SiC [10], and polymer derived (PDC) SiOC ceramics
[4,11] have been investigated for hydrothermal synthesis (in situ
or direct coating) of zeolite layer on the macropore support
surface. To that end, a SiC foam/zeolite composite was shown to
perform better as catalyst in the methanol-to-olefins (MTOs)
reaction than that of a fixed-bed of zeolite pellet [10].
Silicates are widely demanded in industries such as automotive,
textile, cement, etc. due to their high strength, chemical inertness,
thermal stability, low thermal expansion and low conductivity.

http://dx.doi.org/10.1016/j.ceramint.2014.04.028
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 Author's personal copy
11926 C. Vakifahmetoglu / Ceramics International 40 (2014) 11925–11932
Xonotlite, a wollastonite-type hydrated calcium silicate (CSH),
with chemical formula of 6CaO  6SiO2  H2O can be synthesized
in high purity and desired morphology using different starting
materials [12–17]. CSHs can be used to obtain well known
calcium silicate (CS) wollastonite (CaO  SiO2) via thermal treat-
ment [18], and in this way for example 1D nanostructures of
wollastonite were obtained [12,19,20]. While data on the synthesis
and characterization of particulate forms can be found in the
literature, production of porous components (such as monoliths)
made from CS and CSH have been rarely investigated [21–23],
and to the best of the author's knowledge no studies have yet
explored the formation of structured CSH–CS/zeolite composites.
In this study, ceramic foams made of acicular CS crystals were
obtained by thermal treatment of CSH nano-sized acicular crystals
and sacrificial pore formers (PMMA microbeads), and the forma-
tion of structured CS/zeolite composites was investigated.
2. Experimental procedure
2.1. Materials
Calcium silicate monoliths were produced from commer-
cially available xonotlite (Ca6Si6O17(OH)2) based CSH pow-
der (Promaxon D, Promat International NV, Tisselt, Belgium).
For the preparation of porous monoliths, xonotlite:H2O (DI)
with a ratio of 7:55 were put in a flask, mixed with a magnetic
stirrer for 10 min at 350 rpm and ultrasonicated for 10 min.
After homogenization, 20, 50 or 80 wt% (relative to CSH
weight) poly(methyl methacrylate) (PMMA with d50
100
mm) beads and 25 wt% (relative to CSH weight) of poly(vinyl
alcohol) (PVA) solution (CAS 7732-18-5, Fisher Scientific) as
binder were added. Upon 30 min of additional untrasonication,
the suspension was shell-frozen by vigorously rotating the
glass container in liquid nitrogen for 5 min. When frozen, the
flask was removed and freeze–dried (10  2 mbar,  82 1C,
Piatkowski-Forschungsgeräte, Germany) for 24 h. The freeze
dried powder was mixed with a mortar and pestle and then
pressed into cylindrical tablets having 30 mm diameter. Addi-
tional green bodies (the term “green body” will hereafter be
used to define samples pressed to tablet form but not-yet heat
treated) without PMMA beads were also prepared in the same
way. All the green bodies were heated in air in the range of
400–1000 1C in 100 1C steps (2 1C/min heating rate, 1 h
dwelling) by a bench-top muffle furnace (L5/11, Nabertherm,
Germany) and furnace cooled.
2.2. Cell surface functionalization
Heat treated bodies were infiltrated with a solution prepared
from tetraethyl orthosilicate (TEOS, Si(OC2H5)4, 98%, CAS
78-10-4, Sigma-Aldrich), tetrapropylammonium hydroxide
(TPAOH, C12H29NO, 1M, CAS 4499-86-9, Sigma-Aldrich)
used as structure-directing agent (SDA), and DI water. All
chemicals were used as is to prepare the reaction solution
(SOL) in a molar ratio SiO2/H2O/TPAOH of 0.1/10/0.1. Heat
treated (1000 1C) pellets or pieces from them were placed into
a Teflon (PTFE) (200 ml capacity) reactor liner and the volume
was partially (
70 vol%) filled with solution. The liner was
then placed in stainless steel autoclave assembly (250 ml, high
pressure reactor, Berghof, Germany). Sealed autoclaves were
placed in a heating block (DAH-904, Berghof, Germany)
heated to 150 1C and kept at this temperature for either 72 or
120 h to conduct hydrothermal treatments. Upon reaction
completion, the compacts were taken out, washed several
times with DI water in air then dried at 90 1C overnight, prior
to further investigations. Selected samples were additionally
heat treated at 600 1C/1 h for template removal after hydro-
thermal synthesis.
2.3. Materials characterization
FEI (Oregon, USA) Quanta 400 (Field-Emission Gun Environ-
mental Scanning Electron Microscope, FEG-ESEM) and Versa 3D
DualBeam (Focused Ion Beam combined with a Scanning Electron
Microscope, FIB/SEM) were used to examine the fracture surfaces
of the samples which were coated with
20 nm of Au–Pd alloy
prior to investigations. The porosity of the samples was measured
by a mercury intrusion porosimetry (MIP, Porosimeter 2000, CE
Instruments, Milano, Italy). Nitrogen adsorption/desorption at 77 K
was measured using a Quantachrome Autosorb-iQ system (Quan-
tachrome, FL, USA). The samples were first degassed at 250 1C
for 15 h. The specific surface area (SSA) was calculated from N2
adsorption data at relative pressures below 0.20, by the multipoint
Brunauer–Emmett–Teller (BET) method. Pore size distributions
(PSDs) were determined using the non-local density functional
theory (NLDFT) method provided by Quantachrome's data reduc-
tion software for N2 isotherms collected. X-ray diffraction (XRD)
data for bare CS samples (not hydrothermally treated) were
collected from 2θ between 201 and 601 using scan step size of
0.051, counting time of 3 s/step (Bruker D8-Advance, Karlsruhe,
Germany), while for the hydrothermally treated (surface functio-
nalized) samples, Philips X'Pert MRD four circle X-ray diffract-
ometer, equipped with a sample Cradle was used by varying 2θ
between 61 and 1001 with a scan step size of 0.01251, counting
time of 400 s/step. An incident beam programmable divergence slit
in combination with a position sensitive detector (X'Celerator) on
the diffracted beam side was used. Both diffractometers were
operated at 40 kV and 30 mA, using Cu Kα (λ=0.15413 nm) as
incident radiation. Rietveld refinement was carried out on the
diffraction data obtained to quantify the phases present in the
hydrothermally treated samples using Diffracplus TOPAS (Bruker
AXS). All the XRD data are given as background subtracted and
normalized but for the Rietveld analysis data was used as is.
Infrared absorption spectra were recorded by Fourier transform
infrared spectroscopy (FTIR) (Jasco 620 Spectrometer, Essex,
UK), in the range 4500–400 cm  1 from an average of 50 scans
on each sample, with a resolution of 2 cm  1. Samples were
ground and mixed with potassium bromide (KBr) in 1:100 ratio by
weight, and then pressed into a pellet form for FTIR test. Thermal
analysis (DTA/TGA, STA 409; Netzsch, Gerätebau GmbH, Selb,
Germany) measurements were carried out with a 2 1C/min heating
rate up to 1000 1C in air.
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C. Vakifahmetoglu / Ceramics International 40 (2014) 11925–11932 11927

3. Results and discussion

3.1. The effect of reaction temperature on CSH conversion

A typical TGA plot of the as-received CSH powder is

presented in Fig. 1. The data closely resembles the ones
published in the literature for xonotlike and other CSHs which
undergo a slight weight loss ( o 5%) below 200 1C associated
to the loss of physisorbed water [24]. The technical data sheet
of as received xonotlite powder (Promaxon-D) states that in
between 620 and 750 1C a slight dehydration occurs due to
loss of crystalline water. The data, given in Fig. 1, indeed show
the presence of such effect around 730 1C which might be
associated with the probable intermediate structure occurring at
735 1C prior to complete topotactical conversion of xonotlite
(CSH) to wollastonite (CS) as observed also in other studies
[14,25]. At 800 1C, total weight loss of 8.5% was observed,
and this remained almost constant with an additional 0.4%
weight loss up to 1000 1C. On the other hand, TGA data shows
that PMMA micro-beads decompose completely around
400 1C.
Wollastonite could be obtained by calcination of CSHs like
xonotlite or tobermorite above 800 1C [14,19,20,24]. XRD
patterns of the samples heat treated at different temperatures
are given in Fig. 2(a). While below 700 1C all the observed
peaks can be resolved for xonotlite (CS, ICDD ♯ 23-0125), at
700 1C wollastonite (CSH, CaSiO3, ICDD ♯ 84-0655) related
peaks appear, particularly the one due to (320) plane of
wollastonite at 2θ of
301. Above 800 1C all peaks were
indexed as monoclinic parawollastonite, in agreement with a
previous study [18]. Similar observations were obtained from
FTIR data given in Fig. 2(b). While below 700 1C, typical Fig. 2. Data taken from the samples heat treated at different temperatures
CSH band at
970 cm  1 due to the Si–O stretching mode of (400–1000 1C) together with greensample; all normalized (a) XRD and
non-binding oxygen is seen [26], at this temperature additional (b) FTIR.
bands, such as the ones due to Si–O–Si around 1000–
1055 cm  1, and those due to Si–O–Ca (CS) at
890 and
i.e. phase pure wollastonite can evidently be obtained by the

930 cm  1 start to appear. Above 800 1C, the typical FTIR
heat treatment at 1000 1C, as reported also in the literature
spectra of wollastonite was obtained [27]. Together with TGA,
[18–20].
these data demonstrate that the transformation of xonotlite
(CSH) to wollastonite (CS) was almost completed at 800 1C,
3.2. Formation of macrocellular CS components

Porous CS monoliths were prepared by using PMMA

Fig. 1. Thermal analysis conducted on as received xonotlite (CSH) powder
and PMMA beads.
microbeads of
100 mm (d50) diameter, as sacrificial pore
forming agents. SEM images taken from the fracture surfaces
of the sample made by using 20 wt% PMMA are given in
Fig. 3(a) for the green body, and in Fig. 3(b) for the same
sample after 1000 1C heat treatment. During the heat treatment
process that transformed CSH into CS, the PMMA beads were
eliminated and left behind similarly sized spherical cells with
cell walls made of acicular CS crystals.
Increasing the PMMA amount from 20 wt% to 50 wt% and
then to 80 wt% resulted in a much improved interconnection
between the cells, due to an increased number of contact points
among the beads after pelletizing (see Fig. 4(a–c)). However,
this also led to thinner struts and the presence of flaws,
thereby limiting the structural integrity of the component
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11928 C. Vakifahmetoglu / Ceramics International 40 (2014) 11925–11932
Fig. 3. SEM images take from the fracture surface of the sample made by using 20 wt% PMMA; (a) green body, and (b) after 1000 1C heat treatment.
(see Fig. 4(c and d)). Due to that, only samples made from
50 wt% PMMA microbeads were selected for further experi-
ments. By using such samples, cellular CS ceramics having
cells with r 100 mm diameter (see Fig. 4(b and c)) and inter-
particle spaces Z 100 nm (see Fig. 4(d, inset)), i.e. bi-modal
macroporosity, were obtained. The matrix phase consisted of
acicular CS crystals typically having Z 100 nm thickness and
Z 1 mm length.
Taking the true density of wollastonite as 2.91 g/cm3, from
volumetric measurements it was calculated that samples made
from 50 wt% PMMA microbeads had a relative density of
0.166 7 0.004 which was parallel to the MIP data, showing
85.5 vol% total porosity. As observed also in morphological
observations, MIP shows that the sample had, generally
speaking, bi-modal porosity having pores ranging from 10 to
1000 nm (interparticle porosity) and pores 4 10 mm (due to
PMMA burn out), see Fig. 5. The volumetric shrinkage was
computed from an average of 10 measurements, and was found
to be 12.77 2.5%.
3.3. Surface functionalization of porous components
After the formation of macro-cellular CS monoliths, zeolite
formation was followed via hydrothermal reactions (in-situ) as
simplified in schematic representation given in Fig. 6.
Microstructural examinations conducted on the fracture
surfaces of the hydrothermally reacted samples are reported
in Fig. 7(a–f). Compared with the micrographs of the untreated
(not hydrothermally reacted) samples having merely acicular
shaped wollastonite crystals (see Fig. 4(b and d)), the micro-
graphs of the hydrothermally treated samples reveal the
presence of new, coffin-shaped (a common silicalite-1 mor-
phology) crystals, indicating the formation of silicalite type of
zeolite on the cell walls and corroborating the XRD data (see
later). The synthesized hexagonal flat plate/coffin-shaped
crystals with
3 mm size (measured from the c-axis) were
observed to be almost homogeneously covering the cell walls
as a monolayer (with a thickness
300 nm), while the rest of
the substrate remained comprised of acicular wollastonite. The
obtained morphology indicates that the starting synthesis
solution for the formation of the zeolites was able to penetrate
homogeneously in the cellular component.
XRD patterns of the hydrothermally treated samples
together with un-treated sample are given in Fig. 8. All the
peaks obtained from the substrate (bare CS foam: only heat
treated at 1000 1C but not yet hydrothermally reacted) used for
the zeolitization process are assigned to wollastonite (CaSiO3,
ICDD ♯ 84-0655). For hydrothermally reacted samples, the
new peaks appeared at
7.91 and 8.91 (2θ) and triplet in
between 231 and 251 (2θ) which are typical reflections of the
MFI structure of silicalite-1, i.e. aluminum-free ZSM-5 (SiO2,
ICDD ♯ 089-1421) material [6,28,29]. Rietveld analysis was
used to obtain quantitative information regarding the phases
present after the hydrothermal reaction for 120 h. The obtained
fit (Fig. 8) had goodness-of fit (GoF) value of 1.78, expected R
factor (Rexp) value of 4.26, weighted profile R-factor (Rwp)
value of 7.57, and unweighted profile (Rp) value of 5.92. The
GoF value is relatively low ( o 2) suggesting a good fit, which
is also supported by visual observations showing a small
difference between calculated and experimental profiles in the
plot. The amount of the phases present in the sample on 120 h
reaction, unless otherwise amorphous, was calculated as
63.89 wt% wollastonite and 36.11 wt% zeolite.
In the recent review, Lopez-Orozco et al. [3] described that the
formation of zeolite composites by the in-situ method, which
allows an inherent bonding of the zeolites to the substrate, can be
accomplished both by “reactive” (the support itself provides
zeolite framework builders), and by “non-reactive” supports. The
paper due to high silica (so the pool for silicon) content classifies
glass as “reactive”, instead ceramic materials due to their high
chemical stability are classified as “non-reactive” since they do
not continuously provide building blocks of zeolite. In this
context, the wollastonite support utilized in the present study
can be thought as “non-reactive” but we can still speculate. It is
apparent that the inner cell surfaces of macroporous wollastonite
were functionalized with zeolites (silicalite-1) and when the
microstructures at high magnification like the one given in
Fig. 7(f) are analyzed, it can be inferred that the acicular
wollastonite crystals on the cell surfaces, probably underwent a
partial or superficial dissolution, similar to other cases
[6,10,11,30], and allowed bonding of zeolites crystals. This
might also explain why only monolayer zeolite formation was
observed, but further detailed investigations are certainly neces-
sary to clarify the exact zeolite formation mechanism and its
bonding characteristics with the CS substrate.
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C. Vakifahmetoglu / Ceramics International 40 (2014) 11925–11932
Fig. 4. SEM images taken from the fracture surface of 1000 1C heat treated sample made of (a) 20 wt% PMMA, (b) 50 wt% PMMA, (c) 80 wt% PMMA, and (d)
strut detail of the same sample, and the inset on the upper-right corner shows pore wall detail in which acicular CS crystals are assembled with inter-particle spaces
of Z10 nm.
Fig. 5. Pore size (diameter) distribution versus intrusion volume curves
obtained from Hg-porosimetry (MIP) for the 1000 1C heat treated samples.
The N2 adsorption–desorption isotherms for hydrothermally
reacted as-synthesized samples (un-calcined) exhibited mainly
Type II behavior with very narrow hysteresis (type H3) loop
(see Fig. 9(a)). The samples had gradual N2 uptake at moderate
pressure (P/P0) and a predominant N2 adsorption at high P/P0,
associated with the presence of macropores. The SSA of the
samples increased from 9.6 m2/g for bare CS foam (not
hydrothermally reacted, macrocellular) to 16.3 m2/g (72 h),
and 17.5 m2/g (120 h). The small difference in between SSA
values of 72 h and 120 h hydrothermally treated samples
11929
implies that the zeolite formation was mostly completed upon
72 h reaction. It should be noted that the measured surface area
from un-calcined zeolites indicates merely external surface
area since the internal pores of the zeolite structure is blocked
by template molecules which can be removed by additional
processes like calcinations [31]. After heat treatment at 600 1C/
1 h, as expected, samples showed enhanced surface area values
being 105.2 m2/g (72 h) and 108.2 m2/g (120 h) with no major
change in the isotherm shapes compared to that of the
un-calcined samples, apart from a steep initial region at low
P/P0 associated with the micropores. Pore size distributions
(PSDs) data given in Fig. 9(b) indicates that the sample had
predominantly micropores (o 1 nm) and some mesoporosity
with pores below 4 nm, which is probably due the interparticle
spacing [32].
Previous studies documented that the final surface area of the
porous composite component after zeolite formation/deposition
is directly correlated with the amount and the size of the zeolites
formed [6,33–35]. For example, while washcoating of SiC
extrudes after the first coating increased the SSA of the bare
component from 5 to 28 m2/g [10], via in-situ hydrothermal
conversion of the microcellular SiOC substrate, final surface
areas reaching 342 m2/g were able to be obtained [4]. The
amount of zeolite formed in the sample treated for 120 h was
estimated as 36.11 wt% using XRD data. Song et al. [31]
studied the effect of crystal size on the physical properties of
silicalites, and showed that both total and external surface areas
decreased when crystal size increased. While there were no data
for similar sized (
3 mm, measured from the c-axis) crystals,
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11930 C. Vakifahmetoglu / Ceramics International 40 (2014) 11925–11932

Fig. 6. Schematic representation of zeolite formation on the cell walls.

Fig. 7. SEM images showing the coffin-shaped zeolite crystals on the cell walls comprised of acicular CS crystals, (a) general view, (b & c) closer view to cell wall,
(d) cell wall detail, (e) detailed view of the silicalite crystals, and (f) detailed view showing crystal contact.

for a rough estimation, the data given for
1 mm sized 4. Conclusions

silicalites, having the total surface area of 343 m2/g after
calcination at 600 1C (duration was not specified) was used. The results of the study demonstrated that in a simple and
This yields in
124 m2/g total surface area fitting reasonably cost effective approach, wollastonite foams with
86 vol%
well with the experimental data obtained. total porosity and interconnected cells can be produced from
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C. Vakifahmetoglu / Ceramics International 40 (2014) 11925–11932
Fig. 8. XRD patterns for the heat treated (1000 1C) cellular CS and hydrothermally
(72 and 120 h) treated samples. The inset above the patterns is the Rietveld
refinement of XRD pattern (obtained in between 51 and 1501 (2θ)) including the
residual fitting error (below the fit, gray line). In the refinement plot red colored
pattern is the experimental data while black and blue colored patterns correspond
zeolite and wollastonite fits, respectively. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)
Fig. 9. (a) N2 sorption isotherms for the produced samples where solid
symbols correspond to adsorption and empty symbols to desorption of N2, and
(b) estimated pore size distributions.
11931
commercial nano-sized acicular xonotlite and PMMA microbeads
used as sacrificial pore former. The produced foams had
100 nm
pores due probably to interparticle spaces and r100 mm pores
due to PMMA burn-out. The formed macroporous CS ceramics
were further used as a substrate for (in-situ) synthesis of MFI type
silicalite-1 zeolite via hydrothermal treatments. A monolayer, coffin
shaped silicalite-1 zeolite crystals with
3 mm (measured from the
c-axis) size and
300 nm thickness, was observed on the cell
walls after hydrothermal reactions. The newly formed zeolite
crystals increased the surface area from 9.6 m2/g to 108.2 m2/g,
making the components posses hierarchical porosity. The process
cast an advantage of deliberate control on the porosity in every
scale by altering the sacrificial pore formers or zeolites.
Acknowledgments
The author would like to thank Johan Decrock (Promat
International NV, Belgium) for providing the xonotlite (Pro-
maxon D) powder, Dr. Giovanni Capurso, Mauro Marangoni
and Mauro Gobbin (UNIPD) for experimental assistance. The
author wants to express his appreciation to Prof. Dr. Volker
Presser (Energy Materials Group) for the use of his laboratory
facilities. Besides thanks to Dr. Jennifer S. Atchison, Dr. Ingrid
Grobelsek, Dr. Daniel Weingarth, Dipl. Ing. Robert Drumm,
Dipl. Ing. Karl-Peter Schmitt from INM – Leibniz Institute
for New Materials (Saarbrücken, Germany) for their support.
This research was supported by TUBITAK (The Scientific and
Technological Research Council of Turkey) under the project
Grant no. CAYDAG-113Y533.
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