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Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

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Journal of Industrial and Engineering Chemistry


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

Oil-in-water Pickering emulsions stabilized with functionalized


multi-walled carbon nanotube/silica nanohybrids in the presence
of high concentrations of cations in water
Amir Hossein Bornaee a, Mehrdad Manteghian a,*, Alimorad Rashidi b, Mahshad Alaei b,
Mahshid Ershadi c
a

Department of Chemical Engineering, Tarbiat Modares University, Jalal Ale Ahmad Highway, P.O. Box 14115-111, Tehran, Iran
Catalysis and Nanotechnology Research Division, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-1998, Tehran, Iran
c
Department of Chemistry, University of Zanjan, P.O. Box 45195-313, Zanjan, Iran
b

A R T I C L E I N F O

Article history:
Received 4 June 2013
Accepted 19 August 2013
Available online 30 August 2013
Keywords:
Pickering emulsion
Nanohybrid
Enhanced oil recovery
Silica
Carbon nanotube

A B S T R A C T

Functionalized multi-walled carbon nanotube (MWCNT)/silica nanohybrid was synthesized and


proposed as a stabilizer for oil-in-water Pickering emulsion. Carbon nanotube-to-silica weight ratio
was a decisive factor inuencing the performance of the synthesized nanohybrid. The results showed an
appropriate value of such a ratio for a solgel synthesized nanohybrid structure was 2833%. The
emulsion formation time was dictated by the adopted mixing strategy such that without any mixing or
ultrasonication it took 12 days for stabilization to be established. Conversely, the use of ultrasonication
accompanied by mechanical mixing reduced this time to less than 4 h. Another key factor pertained to
the type of the cation contained in water. Bivalent cations, such as magnesium and calcium, changed the
hydrophiliclipophilic balance more intensely than the sodium univalent cation. The nanohybrid holds a
great promise to be adopted in enhanced oil recovery (EOR) processes as it does not require any
emulsier and mechanical treatment.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
Gradual reductions in oil extraction from old reservoirs on the
one hand and the increasing demand for oil on the other hand have
encouraged scientists to apply emerging novel technologies for
enhanced oil recovery (EOR) [14]. In this respect, nanotechnology,
as a leading edge and promising technology, has recently attracted
the attention of many scientists. Various strategies have so far been
proposed for implementation of this technology in EOR processes,
among which are the use of polymeric nanocomposites [5,6],
synthesis and application of emulsions and micro-emulsions in
EOR process [79], the use of nanocatalysts in water and oil
interface within oil reservoirs [1012], employing nano-surfactants [13,14], and the injection of metallic nanomaterials into the
oil reservoirs [15]. The diversity in these listed efforts to integrate
nanotechnology in EOR processes can be attributed to the
following factors: (A) intense diversity in the type of oil and its

* Corresponding author. Tel.: +98 21 82883221; fax: +98 21 77832441.


E-mail addresses: ahbornaee@gmail.com (A.H. Bornaee),
manteghi@modares.ac.ir (M. Manteghian).

reservoirs, (B) diversity in EOR mechanisms and methods, (C) the


area in nanotechnology application is still in its infancy and the
effectiveness of each proposed method has to be proved in
practical terms. Difcult conditions such as high temperature (over
80 8C) and pressure of the reservoir, porosity of the media, variety
of reservoir rocks, the presence of electric charges within the rocks,
availability of different ions at high concentrations in the
formation water, and diversity in the type of crude oil are among
the decisive parameters that affect the choice of an EOR method
[3]. Synthesis of nanomaterials as the stabilizing agents for
Pickering emulsions of oil-in-water (O/W) or water-in-oil (W/O)
has been recently addressed [16]. Due to the unique properties of
carbon nanotubes (CNTs) and silica nanoparticles, their nanohybrid structures may be used as the stabilizer for O/W emulsions,
specically. CNTs are inherently hydrophobic, however, their
structures can be modied by functionalization with carboxylic
functional groups through partial oxidation mechanism.
The use of silica as the stabilizer of Pickering emulsions is a
common practice in research [16]. The reasons for the use of CNTs
and silica nanohybrids are as follows: (A) Hydrophilic and
hydrophobic characteristics can be imparted to these two
compounds of different structures and properties. (B) CNTs

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.08.022

A.H. Bornaee et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

structure and metal oxides have favorable catalytic properties, and


their nanohybrids would inevitably inherit the catalytic properties
[12].
Generally, the multi-walled carbon nanotube (MWCNT)/silica
nanohybrids can be synthesized through the following two
methods: the implementation of silica structures in MWCNT
formation reaction [17], and incorporating MWCNT in the reaction
to form silica structure. The most important parameters that affect
the synthesis of nanohybrid through inclusion of MWCNT into
silica structure formation reactions are as follows: nanohybrid
synthesis method, type of silica structure that is formed in the
nanohybrid production process, and the ratio of silica to MWCNT.
Silica has different structures, namely MCM41, SBA15, spherical
nanoparticles and aerogel. The structure and synthesis method
have considerable effects on the properties of silica including
hydrophilicity or hydrophobicity. Several important techniques to
synthesize silica structures are solgel, hydrothermal, and coprecipitation [1823].
The type of silica structure is dependent on its formation
method; so when a nanohybrid is formed by inclusion of MWCNT
in the reaction to form silica structure, the selected method affects
the type of nanohybrid structure. In addition, low thermal
resistance of functionalized carbon nanotubes at high temperatures (above 100 8C) is a limitation for choosing the nanohybrid
formation method.
In this research, functionalized MWCNT/silica nanohybrid was
synthesized through a modied solgel method in which oil-inwater Pickering emulsions were used as stabilizers at high
concentrations of Na+, Ca2+, and Mg2+ cations. Taking into
consideration the fact that the formation water in real systems
may contain other ions at lower concentrations than the above
ions, the behavior of the nanohybrid that stabilizes Pickering
emulsion was studied in the water samples taken from two oil
reservoirs from the southwest of Iran. Emulsion stabilization rate
was also studied at various conditions. To this end, the rates of
spontaneous emulsication were evaluated rst without using a
mixer, then by using a mixer, and nally by using an ultrasonic
homogenizer. Finally, a set of analyses including SEM, TEM, XRD
were conducted to give insights to characterization and morphology of the nanohybrid structure. In addition, FTIR spectroscopy and
zeta potential measurements were carried out in order to study the
interactions between cations and the nanohybrid.
2. Experimental

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sodium silicate was transformed by dripping into mixture with the


rate of 10 drops per minute until a viscous and cloudy gel was
formed. The nal product was dried at 80 8C for 24 h.
Weight ratio of MWCNT to silica played a key role in the
properties of the product. The weight ratio of MWCNT was
adjusted to achieve the hydrophilicity and hydrophobicity
structural balance. A ratio of 2833% (weight of MWCNT to the
overall weight of the nanohybrid structure) was determined in
experiments as an appropriate ratio to create the desirable HLB.
2.3. Two-phase systems
Three types of two-phase systems were prepared and analyzed
in this research: de-ionized water/oil system, salts-containing
water/oil, and formation water/oil. The behavior of the nanohybrid
was studied individually and all together in the presence of the
three ions Na+, Ca2+, Mg2+ in salts-containing water/oil system. The
ratio of ions in the sample was determined according to the ratio of
ions in formation water samples of reservoir located in the
southwest of Iran. Table 1 lists the samples concentration while
Table 2 summarizes the ion content of the water samples taken
from the two oil elds in the southwest of Iran.
In addition to the ions mentioned in Table 2, there were other
ions in water, including sulfate, sulte, ferrite, lithium, and nitrate.
Relatively, the amounts of these ions were negligible. Due to the
simultaneous presence of calcium and magnesium ions in the
formation water samples, these ions were considered in one group
while sodium ion was considered in another group. The ratios of
calcium, magnesium, and sodium were determined according to
the ratios of the samples denoted by f and g in Table 2. The amount
of nanohybrid in all samples was constant and it was equal to
0.1 wt%. Water oil volume ratio was equal to 10 in all the samples
(water/oil = 10).
2.4. Method of nanohybrid distribution in water and oil two-phase
system
Nanohybrids distribution was compared through three following methods: without using a stirrer, by using a mechanical stirrer,
and by using an ultrasonic bath and stirrer. When a mechanical
stirrer (400 rpm) was used, the mixture was mixed for 24 h at room
temperature. In the third method, the mixture was put in the bath
for 15 min and then they were stirred for 30 min with a mechanical
stirrer. Stable emulsion formation time was different in each of the
methods.

2.1. Materials
2.5. Analysis methods
MWCNT was supplied by Nanotechnology Research Center of
Research Institute of Petroleum Industry (RIPI) [24]. Functionalized nanotubes were prepared through reuxing by a 12 molar
nitric acid solution (70 mL acid/g MWCNT). Sodium silicate (SiO2/
Na2O = 2.1) was used as the precursor to form the silica structure.
CaCl22H2O, MgCl26H2O, and NaCl (Merck) were the ionic salts
used in this study. The oily phase used in this research was
kerosene supplied by Tehran Oil Renery. Formation water
samples and their analyses were taken from Water and Environment Research Centre of Research Institute of Petroleum Industry
(RIPI).
2.2. Production of nanostructured nanohybrid
Functionalized MWCNTs were added to silica formation
reaction in order to produce these types of nanohybrids by sol
gel method. The functionalized MWCNT was kept in 50 mL of 2.5%
hydrochloric acid at 80 8C with a stirring rate of 300 rpm until the
functionalized MWCNT was fully distributed. Afterwards, the

Images of nanohybrid structures were obtained by a Hitachi


SEM (F4160) and a Philips TEM (EM208). The structure was
analyzed prior and subsequent to the formation of emulsion by
XRD using a Philips XPrert MPD with a copper anodic tube. FT-IR
(Perkin Elmer FrontierTM) analysis was also carried out in order to
study the probable effects of ions dissolved in water on the
functional groups of nanohybrid structure. Accelerated surface
area and prosimetry system (ASAP) (Micromeritics ASAP 2010)

Table 1
Concentration of ions in water in various synthesized samples.
Sample

Ca2+ (mg/L)

Mg2+ (mg/L)

Na+ (mg/L)

a
b
c
d
e

0
0
3000
6000
6000

0
0
750
1500
1500

0
40 000
0
0
10 000

A.H. Bornaee et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

1722

Table 2
Concentration of cations in formation water taken from southwestern oil elds in Iran.
Sample

Ca2+ (mg/L)

Mg2+ (mg/L)

Na+ (mg/L)

K+ (mg/L)

Sr2+ (mg/L)

Oil (mg/L)

f
g

9400
11 650

2420
3061

29 900
31 100

270
4

1715
15

113
42

was used in order to determine the porosity of the nanohybrid


structure and the average diameter of the pores. Zeta potential
(Malvern Zetasizer Nano ZS) of the obtained nanohybrid was
calculated in various conditions to study the probable changes in
the surface charges of the nanohybrid which affects its behavior in
high concentrations of ions. A Nikon LV100D optic microscope was
used to take images from the droplets.
3. Results and discussion

similar in size, it seems that the type of ionic charge is the most
important parameter in changing the structural behavior. Studies
also reveal that the ions bring about irreversible changes in the
nanohybrid. The effect of ion interactions on the nanohybrid
behavior was also studied in multi-ionic systems. It appeared that
sodium ions did not disturb the magnesium and calcium ions. The
images, taken by the optic microscope, show that the drop size in
all systems is approximately equal.
Nanohybrid behavior was studied in formation water (f and g
samples). Stable emulsion was formed as an intervening phase.

3.1. Stable emulsication


The nanohybrid exhibited very different behavior in de-ionized
water and salt-containing water media. In de-ionized water, the
nanohybrid was totally hydrophilic and it exhibited very high
stability. This behavior of the nanohybrid can be explained by the
hydrophilicity of the functionalized MWCNT. Contrary to deionized water, the nanohybrid tended to form sediments in saltcontaining water to the extent that the proper distribution of the
particles was not possible even by ultrasonication. However, the
nanohybrid behavior changed and particles migrated to the
interface to spontaneously form Pickering emulsion after a while
(emulsion formation time taken for the distribution of nanohybrid
depends on distribution methods, to be discussed in Section 3.1.1).
Fig. 1 displays the nanohybrid condition before and after the effect
of the dissolved ions.
In salt-containing water/oil system, the type of cations in water
affected the formation of stable emulsion. Samples shown in Tables
1 and 2 display the effect of various cations and ions interaction on
the formation of Pickering emulsion. Fig. 2 demonstrates the twophase system of the sample series. Images of oil in water drops
taken by the optic microscope are shown in Fig. 3 for each of the
samples. Sample b consists of only ion. By comparing Figs 2 and 3,
it is found that although Na+ ion changes the charges on the
nanohybrid and forcing the particles to migrate to the interface, it
does not lead to the creation of water and oil emulsion. Sample b is
a representative for series of experiments in which the effect of
various concentrations of Na+ ion has been studied on the
nanohybrid behavior. No emulsion formation was observed in
Na+ single ion system in the concentration range of 500
40 000 mg/L.
The experiments show that magnesium and calcium ions are
individually able to change the nanohybrid and force ions to
migrate to the interface of the two phases and to create a stable
emulsion. Because magnesium and sodium ions are approximately

3.1.1. Effect of mixing conditions on emulsication time


The mode of mixing the nanohybrid with water affects the rate
of emulsication signicantly. Three types of mixing were studied
in this research: (1) without using a mechanical stirrer or
ultrasonic homogenizer, (2) using a mechanical stirrer, and (3)
using an ultrasonic homogenizer and a mechanical stirrer. In the
rst experiment, the nanohybrid was put into salt-containing
water without employing any type of stirrer. The nanohybrid
remained as sediment in water for a very long time, but after about
12 days, the nanohybrid behavior changed from amphiphobic to
amphiphilic. The behavior change occurred much faster when a
stirrer was used. The change in nanohybrid behavior could be
observed by 12 h when a mechanical stirrer (400 rpm) was used.
Ultrasonic bath had a greater effect than the mechanical stirrer.
The results were repeated by using a homogenizer for 15 min (with
a power of 300 W at room temperature) and then using a
mechanical stirrer for 3.5 h. The difference in the termination rate
of the nanohybrid agglomeration condition in these three methods
may be an explanation for the contact taking place between the
nanohybrid surface and ions dissolved in water, and speeds up
their interaction. This study is important because it shows that the
nanohybrid has the potential to change its behavior even in the
absence of mixing although it requires more time. This can be
effective in the application of these materials in EOR processes
where mechanical mixing is not available. Mixing method is
effective in two ways, including the rate of water nanohybrid
distribution and interactions between the nanohybrid structure
and ions dissolved in water.
3.2. Effect of various salts in water on nanohybrid behavior
The concentration of cations with one or two charges in
formation water is higher than that of the other ions. Therefore, the
interaction between the nanohybrid and these ions becomes

Fig. 1. Left: Sedimentation of nanohybrid in the beginning of immersion. Right: Spontaneous emulsication of O/W that tends to be placed in the interface by stirring.

A.H. Bornaee et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

1723

Fig. 2. Two-phase systems of sample series according to Tables 1 and 2.

important. The change in nanohybrid behavior due to the


interaction with water dissolved ions can be studied at microscopic
and macroscopic scales. In macroscopic scale, a change from
amphiphobicity to amphiphilicity can be observed while in
microscopic scale, the changes occur in the structure, surface
charges, and functional groups of the nanohybrid.
The change in the stability of the material in water from very
stable to unstable condition was studied by analyzing the changes
in zeta potential of the structure. In order to study zeta potential,
two samples were prepared through ultrasonic and stirring
methods. One of the samples was put in de-ionized water while
the other was immersed in salt-containing water with sample e
concentration shown in Table 1. The sample immersed in saltcontaining water was removed after 3 h and it was rinsed with deionized water a few times. Then, the sample was distributed by
ultrasonication and then it was subjected to zeta test.

Fig. 4 depicts the zeta potential variations. According to subset


a in Fig. 4, the zeta potential of the structure, once not being
under the inuence of the cations, corresponds to 49 mV which
indicates a perfect stabilization and reects the hydrophilicity of
the structure. Subset b pertains to the case where the structure is
affected by cationic interactions causing a zeta potential equal to
21 mV which implies a reduction in hydrophilicity for the
nanohybrid structure.
As it may be seen in Fig. 4, there is a great change in zeta
potential in both samples, which implies to the structure charge
being affected by dissolved cations to the extent that it is
transformed from a stable structure to a very unstable one. This
may clearly demonstrate the effect of dissolved ions on the charges
of the particles in water.
The structure was also studied by using XRD analysis before and
after being immersed in salt-containing water. Both samples were

Fig. 3. Optic microscopic images from water and oil interface and the emulsion stabilized by functionalized MWCNT-silica nanohybrid with a concentration of 0.1%. No
emulsion has been formed in Sample b, which contained only sodium ions.

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A.H. Bornaee et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

Fig. 4. Zeta potential for equal concentrations of the nanohybrid. (A) Nanohybrid in an ion-free environment and (B) nanohybrid after the effect of ions.

dried at 60 8C for 48 h in order to prevent the deformation of silica


structure due to high temperature. Analysis showed that when the
sample was immersed in salt-free water, an orthorhombic
structure, as the metastable form of silica, was formed (see
Fig. 5). However, when it was immersed in water, the analysis
showed an alpha quartz structure. This change was possibly due to
the effect of water ions on the structure, and by the overlap of
various plates formed during the production of nanohybrid, which
was detected in the XRD analysis.

FT-IR analysis was carried out on the structure before and after
being immersed in water in order to study the bonds of the
structure affected by ions dissolved in water. Fig. 6 displays the
results of the analysis. Taking into consideration the nanohybrid
combination, small movements in the peaks seem to be normal.
Sample b was dried at a temperature of 80 8C for 72 h after being
immersed in salt-containing water. However, a great peak
intensity increase is seen for this sample in the range of
3400 cm 1. The reason is the presence of crystal water in the

Fig. 5. XRD analysis and peak list of the structure before and after the effect of ions. (A) Nanohybrid before the effect of ions on its structure: silica structure is seen in form of
amorphous. (B) Nanohybrid after the effect of ions on its structure: nanohybrid has an alpha quartz structure.

A.H. Bornaee et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

1725

BJH Desorption dV/dD Pore Volume

0.0016

Pore Volume, (cm/g-A)

0.0014

0.0012

0.0010

0.0008

0.0006

0.0004

Fig. 6. FT-IR analysis of the nanohybrid: (A) before the effect of ions on nanohybrid
structure and (B) after the effect of ions on nanohybrid structure.
0.0002

structure. BET analysis of the structure showed a surface area of


60 m2/g. By comparison of the results it may be concluded that the
presence of crystal water in the structure is the reason for such
observation. The peak in the range of 1080 cm 1 shows the
presence of SiOSi bonds, but the peak in the range of 1680 cm 1
can be related to the type of the bonds. In this range, sample a
shows its bonds related to C5
5O in its carboxylic groups. The small
size of the peak in comparison with the peak in 3400 cm 1 is a
conrmation for this fact. However, the increase in peak intensity
in sample b can be explained by the partial oxidation which results
in structural defects in the carbon nanotube and creates some
active sites and activating carbons with Sp2 structure. This
condition creates C5
5C bond resonance in the structure. Due to
the interaction between calcium and magnesium ions and the
structure, FT-IR analysis can detect them in the form of alkene
bonds.
Fig. 7 shows the size distribution of the structure pores. Two
types of porosity are distinguishable within this structure: one
with 2 nm order of magnitude and the other one with 20 nm.
SEM and TEM images of the structure are shown in Fig. 8. The
TEM image shows how silica particles are placed on a nanostructure. In this gure, the formation of silica nanoparticles (with
dimensions ranging from 10 to 50 nm) over MWCNT is clearly
evident.

0.0000
1e+02

1e+03

Pore Diameter, (A)

Fig. 7. Average size of pore diameters on the structure is in the two ranges of about
23 nm and 30 nm, which increases the possibility of the presence of water in the
pores.

Based on the results derived from BET analysis, pore size


distribution and TEM analyses, the reduction in specic area and
pore sizes are indicative of: (1) the silica structure is not
mesoporous like SBA-15 or MCM-41, and (2) the decrease in the
specic area of the carbon nanotubes is due to their mode of fusion
with silica.
4. Conclusion
In this research a functionalized multi-walled carbon nanotube/
silica nanohybrid structure was synthesized and shown that it
perfectly enables the stabilization of O/W emulsions. It was found
that the presence of salts in water creates appropriate amphiphilic
properties in nanostructured nanohybrids. The positive effect of
high salinity on the nanohybrid characteristics can improve the
chances of its practical application in EOR processes. It is obvious
that divalent ions such as calcium and magnesium play the key role

Fig. 8. (A) SEM image of nanohybrid structure with clarity of 500 nm. (B) TEM image of nanohybrid structure. Carbon nanotube structure and silica particles can clearly be
distinguished.

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A.H. Bornaee et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 17201726

in changing the behavior of the nanohybrid, although the exact


mechanism of the behavior change is not yet clear when the
structure faces cations. Taking into account the irreversibility of
this process and the results obtained from zeta potential, the
probability of chemical changes is higher than the effects of ion
adsorption.
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