Applied Surface Science 273 (2013) 205–214

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Applied Surface Science

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

Synthesis of fluorinated nano-silica and its application in wettability alteration

near-wellbore region in gas condensate reservoirs
∗
M.A. Mousavi, Sh. Hassanajili , M.R. Rahimpour
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71348-51154, Iran

article info abstract

Article history: Fluorinated silica nanoparticles were prepared to alter rock wettability near-wellbore region in gas con-densate reservoirs.
Received 23 September 2012 Hence fluorinated silica nanoparticles with average diameter of about 80 nm were prepared and used to alter limestone core
Received in revised form 31 January 2013 wettability from highly liquid-wet to intermediate gas-wet state. Water and n-decane contact angles for rock were measured
Accepted 2 February 2013 ◦ ◦
before and after treatment. The contact angle measured 147 for water and 61 for n-decane on the core surface. The rock
Available online 16 February 2013
surface could not sup-port the formation of any water or n-decane droplets before treatment. The functionalized fluorinated
silica nanoparticles have been confirmed by the C F bond along with Si O Si bond as analyzed by FT-IR. The elemental
Keywords:
composition of treated limestone core surface was determined using energy dispersive X-ray spectroscopy analyses. The final
Surface modification
Fluorinated nano-silica
evaluation of the fluorinated nanosilica treatment in terms of its effectiveness was measured by core flood experimental tests.
Hydrophobicity
Oleophobicity
© 2013 Elsevier B.V. All rights reserved.

1. Introduction gas-wetting gives lower liquid saturation. Altering of rock wett-ability is

In some gas reservoirs, known as retrograde gas condensate reservoirs,
when the bottom hole pressure in a drilled well falls below the dew point, a
liquid phase rich in heavier hydrocarbons is dropped out of gas. This liquid
phase is commonly known as “con-densate”. The condensate is trapped by the
capillary forces or it is retained in the rock as a result of low liquid mobility.
This con-densate blockage around the well bore chocking can reduce the
productivity of well by a factor of two or more.
The Arun field in Indonesia, one of the world’s retrograde gas condensate
reservoir for example, showed that about 1.1% liquid drop out in the reservoir
brings down the well productivity by about 50% as pressure falls below dew
point pressure [1]. Wettabil-ity plays an important role in condensate
accumulation around the well bore. The liquid low mobility because of heavy
liquid-wetting of rocks around well bore is a major factor in liquid
accumulation so it is regarded to be a key strategy for recovering of depleted
pro-ductivity in gas condensate reservoir by altering the wettability of the
rock from liquid-wetting to intermediate gas-wetting. Through wettability
alteration, the liquid phase mobility for a gas–liquid sys-tem increases
significantly showing capacity to improve gas well deliverability in a gas
condensate reservoir.
Jadhunandan and Morrow [2] and Owolabi and
[3] have shown that altering the wettability to intermediate
∗
Corresponding author. Tel.: +98 7116133797; fax: +98 7116474619.
E-mail addresses: ajili@shirazu.ac.ir, dr.hasanajili@gmail.com (Sh. Hassanajili).
achieved by adsorption of a surface tension reducing agent that causes
repellency of the water and oil. Li and Firoozabadi [4] were the first who
proposed the enhancement of gas well deliver-ability by wettability alteration
of the near-wellbore region from strong liquid-wetting to preferential gas-
wetting state. They used chemicals with fluoro functional group to alter
wettability and showed that permanent gas-wetting state can be established in
Berea sandstone and Kansas chalk through chemical treatment.
Tang and Firoozabadi [5], Mohanty and co-workers [6], Fahes and
Firoozabadi [7], Kumar et al. [8] and Bang et al. [9] experimen-tally
investigated the possible improvements in gas and condensate relative
permeability by using flouro surfactants to alter the wett-ability of sandstone
and limestone cores.
Dynamic fluidity in porous media can be changed by mod-ifying the
wettability of porous walls. Generally there are two factors affecting the
wettability of solid surface: surface energy and surface roughness. Roughness
on two or more length scales has been suggested to be responsible for
superhydrophobicity observed on some plant leaves like the lotus leaf [10].
Therefore, superhydrophobic surfaces can be produced by creating rough
structures by compounds with low surface free energy [11]. Vari-ous synthetic
methodologies for obtaining such hydrophobic and oleophobic surfaces have
been presented by electrochemical reac-tion and deposition [12], plasma
Watson etching [13], phase separation [14,15], sol–gel [16,17], solution-immersion
[18], etc. Some of these methods suffer from certain limitations such as
complicated pro-cess control, sever synthetic conditions and long preparation
time, and hence it was necessary to find simple and effective techniques

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206 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214
Fig. 1. The state of liquid droplet through the pores: (A) containing liquid film and (B) after the adsorption of SiO 2 nanoparticles.
for rapid screening of large amounts of chemicals in altering wett-ability for
delivering solvents to these chemicals at appropriate concentrations. There
have been some reports on preparation of fluorinated silica nanoparticles in
alcohol solutions, for example Wang et al. [19] and Brassard et al. [20]
prepared fluorinated silica nanoparticles to generate surface
superhydrophobicity for rou-tine applications such as production of coating
that can impart waterproof and anti-soiling properties to clothes, footwear, car
windshields and urban monuments or anti-corrosion. Because dis-crete
particle size of silica nanoparticles can diffuse deep into the layers of rock
with low permeability, it seems that such particles can effectively remove the
liquid film of pore surfaces and reduce the flow resistance significantly by
preparing low drag surface for microchannels in rock. Fig. 1 shows the state
of liquid droplet through the pores before and after adsorption of fluorinated
silica nanoparticles on the pore surface.
The literature on nanoparticles used in reservoir application to change
wettability of reservoir rock by their adsorption on porous walls is hardly
reported, though Binshan et al. [21] have used one kind of polysilicon, with
sizes ranging from 10 to 500 nm, in oil field to enhance water injection by
changing the wettability of porous media. Also Onyekonwu and Ogolo [22]
studied wettabil-ity and permeability changes caused by adsorption of
nanometre structured polysilicon on the surface of porous media. Their stud-
ies showed that some kind of polysilicons dispersing in ethanol are very good
agents for enhancing oil recovery and in this respect ethanol is very good for
dispersing polysilicon in reservoirs, in order to change rock wettability. Both
studies showed that wettability of reservoir rock is altered by adsorption of
polysilicon nanoparticles on the rock surface.
It seems that in gas condensate reservoirs, the nanostructure of fluorinated
nanoparticles on the pore surface allows for increased stability of gas pockets
formation and reducing the contact area of a liquid droplet with the rock
surface.
Recently, our group has reported the change of wettability of limestone
rock in such a manner that showed remarkable charac-teristics of
hydrophobic/oleophobic properties by using a sol–gel process [17]. By sol–
gel process a fluorinated polymeric network was formed, as a smooth coated
film, on the rock surface that behaved as water and oil repellent by
mechanism of lowering the surface energy.
Here we report a simple method to create a superhydrophic sur-face using
fluorinated silica nanoparticles by combination of two phenomena: surface
roughening and adjustment of surface free energy.
In this study, we tried to find a new and effective method to remove liquid
banking near-wellbore region in gas condensate reservoir by modifying the
reservoir rock wettability with fluo-rinated nanoparticles. Four series of
fluorinated nano-silica were prepared by changing the ratio of reactants and
tried to find the best samples. The fluorinated silica nanoparticles were
synthesized by co-hydrolysis of tetraethylorthosilicate (TEOS) and a
fluorinated alkylsilane (FAS) in ethanol/NH 4 OH solution by changing the
ratio of FAS/TEOS. Fluorine is the most electronegative element which
interacts with carbon atom to form strong carbon–fluorine bond resulting in a
fluorinated chemical with low reactivity which also exhibits high degree of
water and oil repellency [23]. In this method a flouroalkylsilane was used as
an additional functional group which possessed water and oil repellency.
Flouroalkylsilanes are classes of synthetically produced organic chemicals
containing per-fluoroalkyl residues (all hydrogen atoms replaced by fluorine).
They have excellent thermal stability. Fourier transform infrared spec-
trophotometer (FT-IR), energy dispersive X-ray spectroscopy (EDX) and
scanning electron microscope (SEM) images were used to char-acterize the
nanoparticles.
The prepared nanoparticles in ethanol solution can be easily used in gas
condensate reservoirs to change the liquid wettability of pore surfaces to gas
wettability state by adsorption of fluorinated silica nanoparticles. We believe
that this fluorinated nano-silica can improve the productivity of the reservoirs
and mitigate condensate and water blocking in gas wells.
2. Experimental
2.1. Chemicals
Tetraethoxysilane (TEOS, 98%) and ethanol were
purchased from Merck. Ammonium hydroxide (25% in water)
was obtained from Arman Sina. Nonafluorohydroxyltriethoxy
silane (FAS-9, 95%) was purchased from ABCR. We also used
n-heptane, n-decane
 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214
Table 1
Chemical composition of the reservoir rock [17].
Formula wt%
SiO2 1.15
Al2 O3 0.45
Fe2 O3 0.14
CaO 29.10
MgO 20.91
IL 47.74
(Merck, Germany) and methane to prepare a synthetic gas mixture.
Methane was purchased from Abughaddare Gas Co., Shiraz, Iran.
2.2. Rock
Limestone rock samples from Sarkhun reservoir, with chemical
composition given in Table 1, were used in laboratory experiments. In this
study we used cylindrical cores that were approximately 1.5 in. in diameter
with different lengths of 6–8 in. Physical prop-erties of the rock were
measured. The absolute permeability varied from 1.5 to 2 mD which was
determined by core flood test method [17]. Mercury intrusion measurements
were carried out by a Pas-cal 404 (Thermo Finnigan) to characterize the
porous media. The porosity was around 28.4% with mean pore size of 4.3 m.
Cumu-lative mercury intrusion in the porous media is given in Fig. 2. It is
important that before starting the experiments, the cores were placed in an
◦ 2.4. Measurements
ultrasonic bath for 30 min and dried in an oven at 116 C for 12 h.
2.3. Preparation of fluorinated nano-silica solution
The Stöber process [24] which is adopted for preparation of silica
nanoparticles consists of a water-soluble amine as catalyst and
tetraethoxysilane (TEOS) as the silica source. Nanoparticles with varying
sizes were prepared and further functionalized with
Fig. 2. Cumulative mercury intrusion in the porous media.
207
Table 2
Chemicals for preparation of fluorinated silica nanoparticles with different sizes.
Test number FAS-9/TEOS (molar ratio) with Diameter
constant molar ratio of (nm)
NH4 OH/TEOS = 6:1
1 0.05 500 ± 9
2 0.1 119 ± 12
3 0.2 77 ± 21
4 0.4 –
fluoroalkylsilane in ethanolic solution to obtain fluorinated sil-ica
nanoparticles. The synthetic procedure was as follows: TEOS (5 ml) together
with FAS-9 in different ratios were dissolved in 12.5 ml ethanol. The solution
was mixed with ammonium hydrox-ide/ethanol solution (6.5 ml of 25% NH 4
OH in 12.5 ml ethanol, molar ratio of 6:1), and stirred at room temperature for
12 h. The solu-tion was then ultrasonicated for 30 min. Nanoparticles of
different sizes were produced by changing the ratio of the reactants. The
experimental details are presented in Table 2.
The outcrop limestone core plug, shown in Fig. 3, which was pre-pared
beforehand was immersed in nanoparticles solution for 24 h. Upon drying at
◦
room temperature, the treated core was further dried at 80 C for 5 h before
subjected to different tests.
Fourier transform infrared spectrophotometer (FT-IR) was used to confirm
the formation of chemical bonds between fluoroalkyl-silanes and TEOS in
functionalized silica nanoparticles which were used as surfactants and the
recorded data were compared with those of silica nanoparticles. FT-IR spectra
of the powder samples prepared with silica nanoparticles and fluorinated silica
nanopar-ticle were recorded with a Perkin-Elmer RX1 spectrometer.
The elemental composition of core surface after treatment was
investigated by electron dispersive X-ray analysis (EDX). To study
208 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214

Fig. 3. Preparation of superhydrophobic limestone core coated by fluorinated silica nanoparticles.

The contact angles of the liquid–gas system were measured by placing a
droplet of water and n-decane onto the surface of air-saturated core before
and after the treatment. The angles were estimated at room temperature with
DSA 100.
Core flood experiment was carried out at our laboratory to evaluate the
effect of wettability alteration by fluorinated nano-silica. Fig. 4 shows a
diagram of the experimental setup. The design of the setup aimed to effect
condensate blockage condi-tion in the core by the process of dynamic
flashing. The setup is capable of withstanding reservoir condition of
temperature and pressure.
The core holder, back pressure regulators, fluid accumulators and lines are
inside a temperature-controlled oven at fixed tem-perature. The limestone
core of Sarkhun rock was used to conduct synthetic gas mixture floods.
of the test. These have a Teflon floating piston that isolates the test fluid from
the pressurizing fluid.
The cylindrical cores, each with a 1.5 in. diameter and a length of 6–8 in.,
were used in core holder. The core holder consisted of two pressure ports
along the length to measure the pressure drop across the core. The core sleeve
used in the core holder was Viton rubber sleeve. Two back pressure regulators
were used to control the upstream and downstream flowing pressure across
the core.
In this setup, the gas mixture was injected at a constant rate into the core at
◦
80 C and pressure drop across the core was recorded as a function of fluid
injection at a steady state condition before and after treatment.
3. Result and discussion

The synthetic gas condensate mixture described in Table 3 was prepared
for this experiment.
Accumulators were used to maintain fluids (synthetic gas, nanoparticles
solution, etc.) at temperature and pressure condition
The solution of fluorinated silica nanoparticles of varying sizes (Table 2)
was prepared in laboratory. Fig. 5 shows the model of the formation of
functionalized fluorinated silica nanoparticles in ethanol/NH 4 OH solution.
According to our observation, which was also reported by Wang et al. [19],
TEOS during sol–gel process, under alkaline condition, quickly hydrolyzed
into silica particles that turned the ethanol solution milky, while the FAS
formed a thick and clear resin that phase-separated from the solution,
indicating a very slow hydrolysis rate. Thus, co-hydrolysis of these two silane
precursors resulted in quick formation of silica particle cores which were
covered with the slowly-hydrolyzed FAS resin.

The chemical compositions of the prepared nanoparticles were studied by

FT-IR spectroscopy. Fig. 6 shows FT-IR spectra of the powders prepared
from pure silica nanoparticles (A) and fluori-nated silica nanoparticles
designated as samples (B) and (C).
−1
Fig. 6A shows four significant peaks. One peak is at 1039 cm due to the
asymmetric vibration of Si O Si stretching bands in the silica nanoparticles
−1
and another peak appeared at around 794 cm corresponds to Si O Si
−1
symmetric vibrations [13,25–27]. An absorption peak, at 939 cm is due to
−1
presence of Si OH and the fourth peak around 3325 cm is due to free O H
stretching bands [27].

Table 3
Components of synthetic gas mixture.

Component Mole%
Fig. 4. A schematic diagram of core flood test.
Methane 90
n-Heptane 8
n-Decane 2
 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214 209

Fig. 5. Schematic model of the formation of fluorinated silica nanoparticles.

Fig. 6. FT-IR spectra of the powder prepared from pure silica nanoparticles (A) and fluorinated silica nanoparticles with different molar ratios of FAS-9/TEOS: 1:10 (B) and
1:5 (C).

FT-IR spectra of the powder prepared using fluorinated silica −1

nanoparticles is shown in Fig. 6B (FAS-9/TEOS molar ratio of 1:10) and C
(FAS-9/TEOS molar ratio of 1:5). Some additional new peaks are observed as
compared to FT-IR spectra of the powder using only silica nanoparticles
shown in Fig. 6A.
A peak located at 1130 cm is related to Si O C band and shows link
between FAS-9 molecules and silica nanoparticles [28–30]. The presence of
−1 −1
additional new peaks located at 1220 cm and 1170 cm is characteristic of
C F stretching vibration [28–30]. The existence of C F bands in the form of
CF2 or CF3 is also observed

Fig. 7. EDX spectrum of treated limestone surface with fluorinated silica nanoparticles.
210 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214

Table 4
Frequencies of FT-IR absorption bands for prepared nanoparticles.

−1
Group Wavenumber (cm )
(O H) 3325
(C F) 1220–1170
(Si O C) 1130
as (Si O Si) 1039
(Si OH) 939
(CF3 ) 916
s (Si O Si) 794
(CF2 ) 771

−1 −1
at 771 cm and 916 cm [29]. The presence of additional new peaks from
the functional groups confirms that the nanoparti-cles of silica are
functionalized by fluorine from FAS-9 molecules. Decrease in intensity of the
peak related to OH band with increas-ing fluoroalkylsilane shows that the
higher content of OH groups on the surface of silica nanoparticles can be
replaced with fluori-nated groups. Table 4 shows the characteristic
frequencies of IR absorption bands for the nanoparticles.

Fig. 7 shows the EDX spectrum of the treated limestone surface with
fluorinated silica nanoparticles in ethanol solution which were prepared with
FAS-9/TEOS molar ratio of 1:5. In the spectra some elements such as Ca, Al
and Mg which come from the structure of limestone in addition to some
elements such as C, O, Si and F of fluorinated nanosilica are adsorbed on rock
surfaces.
The presence of Si and F elements can be shown by the formation of
covalent bonds between the F coating groups and the silica par-ticles, which
have given rise to fluorinated silica nanoparticles. The presence of the
fluorine atomic percentage of 27.65 on the treated rock surface with a solution
prepared with FAS-9/TEOS molar ratio of 1:5 is an indication of a high
concentration of fluorine on the rock surface which would thus significantly
reduce the surface free energy. Table 5 shows the elemental contents of
treated limestone core surface with solution of fluorinated nanoparticles
prepared with FAS-9/TEOS molar ratio of 1:5.

As shown in Fig. 7 the atomic ratio of elements F and Si on the treated

rock surface can be calculated from molecu-lar stoichiometric data for FAS-9.
The atomic ratio of elements F and Si on the treated rock surface from EDX
spectrum is NF /NSi = 27.65/3.77. As the molecular stoichiometric data of
FAS-9 shows NF /NSi = 20.45/2.27, thus the molar ratio of FAS-9/TEOS the-
oretically should be 3:5, which is higher than FAS-9/TEOS molar ratio of 1:5
used for preparation of treating solution. It shows that fluorine groups from
FAS-9 which have enriched the silica surface are able to coat silica
nanoparticles, thus significantly reducing the surface free energy.

The structure and topography of the rock surface treated by four different
sizes of fluorinated silica nanoparticles were character-ized by SEM which is
shown in Fig. 8. The size of nanoparticles decreases with increase in
FAS-9/TEOS molar ratio due to the reduction of OH group density on the
surface and thus reduc-tion in inter-particle cohesive energy density. Further
increase in FAS-9/TEOS molar ratio from 1:5 to 2:5 produces a quite smooth

Table 5
Atomic composition of coating fluorinated nanosilica measured by EDX.

Atom at%
C 33.66 Fig. 8. SEM images of treated rock surface with fluorinated silica nanoparticles using different
O 32.04 molar ratios of FAS-9/TEOS (A) 1:20, (B) 1:10, (C) 1:5 and (D) 2:5.
F 27.65
Mg 1.23
Al 1.28
Si 3.77
Ca 0.37

Total 100
 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214
Fig. 9. The water and n-decane contact angles on the treated rock surface with fluorinated nanosilica of varying FAS-9/TEOS molar ratios (A) 1:20, (B) 1:10, (C) 1:5 and (D) 2:5 (mole/mole).
surface, while many small spherical nanoparticles are absorbed in the
hydrolyzed FAS-9 resin. As no significant nanoparticles can be observed on
the surface, so the air trapping would be lower within such smooth surface.
Fig. 9 shows water and n-decane contact angle data on the treated rock
surfaces. As it is stated before, to maximize the wettability alteration, we have
studied the effect of the ratio of FAS-9/TEOS in sol preparation on the rock
surface oleophobic-ity and hydrophobicity. Within the increase in
FAS-9/TEOS molar ratio from 1:20 to 1:5, the density of the fluorine on the
sil-ica nanoparticles surfaces increases and the effect of low surface energy
molecules increases water and n-decane contact angles. This means that the
nanoparticle coverage is important to render the substrate superhydrophobic.
Further increase in FAS-9/TEOS ratio from 1:5 to 2:5 reduces the contact
angles presumably due to reduced surface roughness for the coating layer
formed by the silica nanoparticles, heavily absorbed in the hydrolysed FAS-9
resin. It is
211
suggested that surface should not be so rough to the extent that to prevent
liquid penetration inside the grooves. We have observed that treated rock
prepared with FAS-9/TEOS molar ratio of 1:5 has higher contact angle. Water
and n-decane contact angles of the fluorinated silica nanoparticles of size 77 ±
◦ ◦
21 nm are found to be 147 and 61 , respectively. It is believed that in FAS-
9/TEOS molar ratio of 1:5, both phenomena of roughness and low surface
energy of molecules result in higher water and n-decane contact angles.
Therefore, this ratio was chosen for further experiments.
In order to examine the penetration of the nanoparticles pre-pared with
FAS-9/TEOS molar ratio of 1:5 into the sandstone core, cross-section of the
treated reservoir rock was analyzed by EDX spectra taken from three different
positions as shown in Fig. 10.
According to elemental contents measured by EDX from the skin to the
centre (Tables 5 and 6), it is obvious that the sur-faces contain a great quantity
of F and C, reflecting the ability of nanoparticles to penetrate into the core and
being adsorbed onto
212 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214

Fig. 10.
the core centre).

the surface. Because, based on reservoir rock analysis (Section 2.2), the size of
pores in the porous media is quite large (4.3 m) and it is able to accommodate
silica nanoparticles almost without any dam-age done to the porous media.
Thus, the whole surface, as shown in Fig. 8C, appears nano-patterned and the
shape of porous core remaining intact, which indicates that entire framework of
the core, is not changed by the fluorinated nanosilica. However, it seems that
the content of nanoparticles near the centre of core is relatively

Table 6

Atom

C
O
F
Mg
Si
Ca

Total
 EDX analysis on the cross-section of the limestone core after treatment in three positions, region 1: d = 3/4 r, region 2: d = 1/2 r and region 3: d = 0 (d: distance from

lower than that of top surface. This can be explained by the increase of mass
transfer resistance with increase of penetration path into the porous media.

Core flooding test was used to study the condensate blocking and
◦
wettability alteration in cores at temperature of 80 C. The syn-thetic gas
mixture, given in Table 3, was injected into the core at constant flow rate.
Dynamic flashing method simulated the con-densate accumulation in a
reservoir below the dew point pressure and pressure drop across the core as a
function of fluid injection recorded before and after core treatment. Fig. 11
shows the mea-sured steady state pressure drops across the cores versus fluid

The elemental composition of the limestone cross-section after treatment in three

injection before and after treatment.
positions, region 1: d = 3/4 r, region 2: d = 1/2 r and region 3: d = 0 (d: distance from
the core centre). This experiment clearly demonstrates the occurrence of in situ
condensation and the restricted flow for the gas mixture. As can
Region 1 Region 2 Region 3
be seen from Fig. 11, there is a sharp rise in pressure drop because
at% Atom at% Atom at% of the fact that condensate tends to accumulate and occupy por-
37.31 C 31.28 C 31.40 tions of core pores. This phenomenon restricts gas flow and increase
34.59 O 44.71 O 44.58 pressure drop across the core significantly until reaching a critical
24.57 F 19.39 F 15.00 liquid saturation. At this state both the condensate and gas flow and
1.04 Mg 1.52 Mg 2.35 pressure drop decrease but the condensate continues to form and
2.47 Si 3.11 Si 3.30
- Ca - Ca 3.37
accumulate until a steady state pressure drop is reached. The core
flood procedure was repeated after wettability alteration by using
100 Total 100 Total 100 fluorinated silica nanoparticles. The fluorinated silica nanoparticles
 M.A. Mousavi et al. / Applied Surface Science 273 (2013) 205–214
Fig. 11. Pressure drops across the core versus fluid injection before and after treat-ment.
in ethanol solution were prepared with FAS-9/TEOS molar ratio of 1:5 by
using a magnetic stirrer. After the accumulation of the condensate, 20 pore
volumes of 2 wt% fluorinated nano-silica in ethanol solution was injected into
the core through an accumula-tor and subjected to ageing for 24 h.
Subsequently, the core flood experiment with synthetic gas mixture was
repeated to measure the pressure drop after treatment.
The reduction in pressure drop for pre-treatment flood was compared to
the post-treatment flood. It is clear from Fig. 11 that wettability alteration
would be effective when using fluorinated nano-silica. We observed of about
30% improvement in pressure drop after wettability alteration with
fluorinated silica nanoparti-cles compared to pressure drop before treatment.
4. Conclusion
A unique production challenge associated with gas reservoir is the
condensate blockage problem, which is the build-up of con-densate liquid
around production well as a result of pressure drop below dew point pressure.
Wettability alteration is an appropriate modification for reducing the capillary
pressure which mitigates liquid banking and thus increases gas recovery of
reservoirs.
Our study demonstrates a novel and effective treatment in changing the
wettability of Sarkhun rocks to intermediate gas-wetting using fluorinated
nano-silica. To the inner walls of complicated and non-visible microchannels,
such as rocks porous media, the fluorinated silica nanoparticles adsorption
can be used to form a rough surface with a low free energy. These
hydrophobic/oleophobic surfaces can markedly lead to reduce flow resistance.
Four series of fluorinated nano-silica in ethanol were prepared with changing
the molar ratio of FAS-9/TEOS and used to altering rock wettability. This
affected particle size and morphology of the nanosilica adsorbed on the
surface. Therefore after treatment, different water and n-decane contact angles
◦ ◦
between 124–147 and 50–70 were produced, respectively. We observed that
through increases in FAS-9/TEOS molar ratio from 1:20 to 2:5, the treated
rock with fluorinated nano-silica, prepared with FAS-9/TEOS molar ratio of
1:5, exhibited an interesting structure and high hydropho-bicity/oleophobicity
properties. The best sample based on contact angle and SEM results was
studied by core flood experiment. To this, dispersing fluorinated nano-silica
in ethanol with FAS-9/TEOS molar ratio of 1:5 was used to treat the core.
Our measurement of core flood test showed that treatment of wettability
alteration to gas wetness using fluorinated nano-silica was effective and it was
found that such a wettability alteration reduces the amount
213
of liquid trapping in pore space and decreases the pressure drop across the
core.
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