Fuel 196 (2017) 431–441

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

The effect of gas-wetting nano-particle on the fluid flowing behavior in

porous media
Jiafeng Jin a,b, Yanling Wang a,⇑, Tuan A.H. Nguyen b, Anh V. Nguyen b, Mingzhen Wei c, Baojun Bai c,⇑
a
Petroleum Engineering College, China University of Petroleum (East China), Qingdao, Shandong 266580 PR China
b
School of Chemical Engineering, The University of Queensland, QLD 4072, Australia
c
Department of Geological Science and Engineering, Missouri University of Science and Technology, 1400 N Bishop Avenue, Rolla, MO, USA

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

Nano-silica particle is functionally
modified by fluorosurfactant.

The wettability is dominated by the
morphology of adsorption layer on
core.

Wettability alteration can facilitate
enhanced oil recovery.

The mobility of fluids trapped in
porous media can be improved.
The influence of gas-wetting alteration on the flow and distribution of fluids in porous media was studied
with visualization flooding on a transparent glass micromodel whose original wettability is liquid-
wetting. The glass model was first saturated with brine before gas-flooding to simulate the liquid-
blocking effect near the wellbore region, as can be seen from Fig. 1a. As a result, severe liquid-blocking
regions within the core did not allow gas passing through the outlet end of the micromodel (Fig. 1b).
Fig. 1c shows how the liquid trapped in the outlet end of the micromodel is mostly removed after a cer-
tain amount of FG40-NP solution was injected. The red arrows in Fig. 1b show flow paths formed by the
displaced. The liquid saturation in visualized flooding was calculated using MATLAB, which shows a sharp
decline in liquid saturation after gas-wetting alteration, as shown in Fig. 1(g)–(i). If the initial liquid sat-
uration in the micromodel is considered as 100%, the liquid saturation after gas-flooding is 33.23%. A
liquid-blocking region can be observed in the top right corner of Fig. 1(h). Fig. 1(i) shows the liquid in
the liquid-blocking region scattering as discontinuous phase after gas-wetting alteration, the liquid sat-
uration declines to 20.77% in this stage. Hence, the flow path for fluids in porous media can be seen
clearly. The amount of trapping liquid in micromodel decreased sharply after gas-wetting alteration.
Therefore, the novel gas-wetting alteration agent can be applied to solve the liquid-blocking effect near
wellbore region on the gas-condensate reservoir.

Fig. 1. Visualization flooding: (a) before gas-flooding, (b) gas-flooding until liquid-blocking, and
(c) gas-flooding after gas-wetting alteration. Figs. 1(d), 1(e), and 1(f) are magnified areas of Figs.
1(a), 1(b), and 1(c). As shown in Figs. 1(g), 1(h), and 1 (i), the liquid saturations in Figs. 1 (a), (b),
and (c) are 100%, 33.23%, and 20.77%, respectively. The liquid saturation significantly decreased
from 100% to approximately 20.77% after treatment; hence, a clear flow path in model can be
observed. The black region represents liquid in porous media, the white region corresponds to the
flow path and rock.

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

Article history: The effect of gas-wetting on the liquid-blocking effect near a wellbore region is significant. Here, we func-
Received 7 November 2016 tionally modified nano-silica particles with a size of approximately 40 nm each by using a fluorosurfac-
Received in revised form 22 January 2017 tant and obtained a super gas-wetting nano-silica particles, which could improve the contact angles of

⇑ Corresponding authors.
E-mail addresses: wangyl@upc.edu.cn (Y. Wang), baib@mst.edu (B. Bai).

http://dx.doi.org/10.1016/j.fuel.2017.01.083
0016-2361/Published by Elsevier Ltd.
432 J. Jin et al. / Fuel 196 (2017) 431–441

Accepted 26 January 2017 brine and hexadecane from 23° and 0° to 152° and 140°, respectively, and decrease the surface free
Available online 12 February 2017 energy of rock surface from 72 to 1.6 mN/m. The decrease in the gas displacement was approximately
30%. FT-IR, SEM and EDS were employed to determine the morphological change in the rock surface
Keywords: before and after gas-wetting alteration. Results indicate that when the fluorosurfactant molecules are
Nano-silica joined to the nano-silica surface, and CAF bond is recognized. The grape-like particles forming a multi-
Functional modification adsorption on the rock surface, which play an important role in super gas-wetting by decreasing surface
Super gas-wetting
free energy and increasing roughness on the rock surface. The data of EDS was consistent with the results
Grape-like particle
of FT-IR and SEM. To further understand the influence of gas-wetting alteration on the flow and distribu-
tion of fluids in porous media, visualization flooding was conducted. The results show that the initial liq-
uid saturation in the micromodel decreased sharply from 33.23% to 20.77% after the gas-wetting
treatment, and the contact angle of isolated brine droplet on the treated pore-wall was approximately
125°, which also verifies that pore wettability can be altered to gas-wetting. The analytical data of the
oil displacement experiment demonstrates that the substantial decrease in oil saturation may contributes
to enhancing oil recovery. Furthermore, the mobility of oil trapped in micro channels can also be
enhanced significantly after gas-wetting alteration due to the presence of methane.
Published by Elsevier Ltd.

1. Introduction
The pressure of gas-condensate reservoir declines isothermally
during the primary production. When the reservoir pressure
decreases to the dew point, gas will condensate into liquid near
the wellbore region, leading to an increase in liquid saturation
and decrease in flow efficiency of fluids. Consequently, gas-
deliverability will be killed instead of having gas evolution. This
so-called liquid-blocking effect is one of the most serious threats
to a low-permeability reservoir [1–3]. Wettability alteration has
been well known as one of the most efficient approaches to miti-
gate the liquid-blocking effect and improve liquid distribution in
porous media [4,5]. Li and Firoozabadi [6,7] reported that gas-
well productivity could be enhanced significantly if the rock wetta-
bility near the liquid-blocking region is altered from liquid-wetting
to gas-wetting in a gas-condensate reservoir; Estimates of gas
deliverability are conducted by measuring the flow rate, inflow
performance curve or gas-backpressure curve. Gas-wetting alter-
ation can effectively improve gas deliverability by improving the
flow rate of liquid in porous media. Wu and Firoozabadi [8]
demonstrated that rock wettability can be permanently altered
to intermediate gas-wetting by fluorosurfactants at a temperature
of 90 °C. Wang et al. [9] found that flow efficiency of fluids in the
liquid-blocking region can be improved by approximately 25%
compared to that of fluids before gas-wetting alteration at an ele-
vated temperature of 120 °C. The improved flow efficiency was
reported to become even more pronounced with rising tempera-
tures. Elsharafi and Bai investigated the effect of particle size on
the permeability and wettability of reservoir was that small-
sized particle could decrease oil production by blocking porous
media in high-permeability reservoir [10–12].
Mousavi et al. [13] recently observed that fluorinated silica
nanoparticles with an average diameter of 80 nm can alter the rock
wettability from preferential liquid-wetting to intermediate gas-
wetting, and the amount of liquid trapped in pore media can also
be efficiently reduced by this gas-wetting alteration. Jin et al.
[14] suggested that super gas-wetting rock can be achieved by
using nano-silica particles which were functionally modified by
fluorochemicals. As a results of the fluorochemicals intervention,
the contact angles of brine and hexadecane on the modified rock
surface can be increased from 23° and 0° to 150° and 140°,
respectively.
Wettability alteration can also play a vital role in enhanced oil
recovery (EOR). Anderson [15] found that more oil could be recov-
ered from the preferential water-wet reservoir than from an oil-
wet reservoir in the primary production. Newcombe and McGhee
[16] indicated that oil recovery from the cores of intermediate
wettability might be greater than that from more strongly water-
wet cores. Investigations in recent years have shown that oil dis-
placement efficiency in porous media improved by approximately
32% after enhanced oil recovery (EOR) [4,5,17,18]. This also pre-
sents a new challenge of finding ways to extract the remaining
two-thirds of oil in place. Thus, it will be very interesting to see
if oil recovery will show a greater increase if the wettability of por-
ous media is altered from liquid-wetting to gas-wetting. However,
conventional EOR methods, such as surfactant flooding and poly-
mer flooding, still have the limitations of high doses, low efficiency,
and heavy pollution. Therefore, a more efficient approach to
enhanced oil recovery is needed.
Jiang et al. [19] investigated the effect of gas-wetting alteration
on the flow behavior and distribution of fluids in micromodels with
different wettability levels. They found the displacement front
could be transformed from concave to convex when liquid wetta-
bility was replaced by gas-wetting. Seyyedi et al. [20] observed
that discontinuous water phase in an oil-wet micromodel tends
to appear as an isolated droplet on the core wall after a long water
injection duration. Hou et al. [21] found oil-wet sandstone could be
altered to water-wet by the adsorption of surfactants on the core
surface, and the neutral-wet micromodel performed the highest
oil recovery by waterflooding. However, few research has covered
visualization flooding by gas-wetting nano-silica solutions, and the
mechanism of flow behavior in the presence of gas-wetting nano-
silica particles in porous media is not yet fully understood.
In this article, the research attempts to bridge the information
gaps that prevents utilization of the modification mechanism
between fluorochemicals and nano-silica particles. Another great
challenge is to delineate the flow behavior of fluids in the trapping
region after gas-wetting alteration in porous media. To address this
challenge, we are presenting experimental evidence showing the
effect of the presence of gas-wetting nano-silica particles at
increasing concentrations on rock wettability and imbibition. We
also perform a visualization flooding with a liquid-blocking effect,
which explains the decreasing amount of liquid trapped in porous
media by gas-wetting nano-silica particles.
2. Materials and experimental methods
2.1. Surface modification of silica nanoparticle with fluorosurfactant
Silica nanoparticles with the mean diameter of approximately
40 nm were prepared in our laboratory by the advanced Stöber
method [22]. Fluorosurfactants exhibit extraordinary properties
such as good gas-wettability and thermostability, thus being
 J. Jin et al. / Fuel 196 (2017) 431–441 433

chosen to modify the nanoparticle. FG40 is a fluorosurfactant 2.3. Surface free energy calculation
offered by Harbin Xuejia Silicofluoride Chemical Reagent Co., Ltd.
The surface modification process involves dehydration condensa- Free energy of a rock surface, which defined as the sum of con-
tion between the OH group of the FG40 molecule and the OH group tributions from different intermolecular forces on the rock surface,
of the nano-silica at 80 °C. Then, the nonpolar end of the CAF bond is one of the vital parameters to evaluate the rock’s wettability
of the molecule exposes to the fluid phase after the reaction. Due to [26]. In this study, the Owens two-liquid method was used to
the abundance of OH group on Nano-silica surface, a substantial investigate the wettability alteration of rock before and after treat-
number of molecules can react with a single nanoparticle when ment [27]. The thermodynamic equilibrium on rock surface can be
they encounter. Thus Silica nanoparticles can be achieved. Gas- prescribed by the Young’s equation,
wetting nano-silica solution also is with characteristics of the
excellent dispersion to avoid aggregation, which can facilitate the cos hclv ¼ csv  csl  pe ð1Þ
adsorption of FG40-NP on rock surface. These gas-wetting and
nanoparticles (FG40-NP) can absorb and form a multilayer on rock
surface by electrostatic attraction and van der Waals forces [23]. As clv ¼ cdl þ chl ð2Þ
a result, the structure of rock surface is altered from a smooth sur-
face to a botryoidal structure, as shown in Fig. 1. csv ¼ cds þ chs ð3Þ
The Fourier transform infrared spectrograph (FTIR) of fluorosur-
where clv and csv denote the surface free energy of a liquid droplet
factant was recorded by a Nexus FTIR spectrometer. The morphol-
and its rock against their saturated vapor, respectively; csl is the
ogy of cores before and after surface modification was evaluated by
the Nova Nano Scanning Electron Microscope SEM (FEI Ltd., USA). interfacial free energy between the liquid droplet and rock. h is
All the samples were coated with platinum for 5 min before the the contact angle of the liquid droplet on the rock surface; pe is
analysis. The surface element analysis of rock before and after the equilibrium pressure of the adsorbed vapor of liquid on the rock
treatment is determined by an Energy Dispersive Spectrometer surface, and is equal to 0 in our case. Generally, the equilibrium
(EDS (EDAX Ltd., USA). pressure of the adsorbed vapor depends on temperature and speci-
fic area of solid surface, the temperature and pressure in this study
are low enough to prevent vapor adsorption; where cdl and chl corre-
2.2. Contact angle measurement spond to the dispersion force and hydrogen bonding, respectively,
the values of which can be obtained from the published data [28],
The sessile droplet method is used to evaluate static contact then the surface free energy of liquids can be described as the fol-
angles of different fluids on the rock surface. A rock surface is rec- lowing equations:
ognized as preferential liquid-wetting when the contact angle qffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffi
h < 90°; while it is preferential gas-wetting when 90° < h < 140°; csl ¼ csv þ clv  2 cds cdl  2 chs chl ð4Þ
otherwise the solid surface will be considered as super gas-
wetting when h > 140° [24]. To imitate the real conditions of the and
reservoir, the contact angle measurement is conducted in a qffiffiffiffiffi qffiffiffiffiffi2 qffiffiffiffiffi qffiffiffiffiffi2
methane-liquid-rock system rather than the traditional air- csl ¼ cds  cdl þ chs  chl ð5Þ
liquid-rock system. The liquids used in the study are brine and
hexadecane. Hexadecane is in analytical reagent grade and is sup- Using Eqs. (1)–(3), the Eqs. (4) and (5) can be expressed as follow:
plied by Sinopharm Chemical Reagent Co., Ltd. Rock and brine were 0qffiffiffiffiffi1 0qffiffiffiffiffi1
qffiffiffiffiffi cdl qffiffiffiffiffi chl
provided by the Shengli Oilfield. Rock used in this study are sand-
1 þ cos h ¼ 2 cds @ A þ 2 ch @ A ð6Þ
stone, which were cut into wafers with a size of 5  25 mm, then clv s
clv
sandpapers were used to polish the rock surface to obtain a smooth
and horizontal surface. Placing the polished rock onto the contact The liquids used in this study were brine and hexadecane. The con-
angle meter, and moving the contact angle meter into a tact angles of the brine and hexadecane were h1 and h2 , respectively.
40  25  40 cm sealed glass container which was filled of Thus,
methane, it’s very important to make sure there is no flame sur- 0qffiffiffiffiffiffi1 0qffiffiffiffiffiffi1
rounding the container; Contact angle measurements of the qffiffiffiffiffi cdl1 qffiffiffiffiffi chl1
1 þ cos h1 ¼ 2 cds @ A þ 2 ch @ A ð7Þ
methane-liquid-rock system were conducted on the JY-82 contact cl1 v
s
cl1 v
angle meter [14,15,25].

Fig. 1. Sketch of surface modification of a silica nanoparticle and its gas-wetting alteration application. The fluorosurfactant is chemically bonded onto the surface of silica
nanoparticle by dehydration condensation reaction and formed a compact layer which is able to alter the wettability of the original silica nanoparticle.
434 J. Jin et al. / Fuel 196 (2017) 431–441

Fig. 2. Sketch of the apparatus for the spontaneous imbibition test: (a) imbibition in core before treatment (concave interface) where the capillary force for water flow has a
displacing force; (b) imbibition in the core after treatment (convex interface) where the capillary force for water flow has a resistance force.

Fig. 3. Schematic of visualization apparatus. The resolution of HD camera is 1280  720, the size of 2D micromodel is 5  5 cm. The velocity of micropump is 1 mL/min. The
temperature is 25 °C, can be regulated from 25 to 50 °C by isothermal control. The gas used in this study is composed of CH4 and CO2.

and The scale is used to record the imbibition data automatically of

0qffiffiffiffiffiffi1 0qffiffiffiffiffiffi1 the rock is connected to a computer. The spontaneous imbibition
qffiffiffiffiffi cdl2 qffiffiffiffiffi chl2 test was conducted in a methane-liquid-rock system. This
1 þ cos h2 ¼ 2 cds @ A þ 2 ch @ A ð8Þ
cl2 v s
cl2 v improved apparatus helps suppressing evaporation, thus having
smaller errors compared to the traditional one.
cds and chs can be calculated using Eqs. (7) and (8), then the surface
free energy of rock surface cs can be determined by Eq. (9), i.e., 2.5. Visualization of gas-wetting nano-silica in micromodel
cs ¼ cds þ chs ð9Þ
Fig. 3 depicts a visualization apparatus used to investigate flow
behavior and interaction between gas-wetting nanoparticle and
2.4. Spontaneous imbibition fluids in flooded porous media. A HD camera was mounted on
top of the rock model and connected to a computer to monitor
Imbibition has long been recognized as one of the most impor- the flow behavior of fluids in porous media. The size of micromodel
tant factors, which plays a vital role in EOR from water-wet, is 50  50 mm, the average diameter of pore throat in which is
fractured-matrix reservoirs subjected to water-flooding [29]. The approximately 2 mm. The experimental procedures were as fol-
principle of an imbibition test is based on the idea that one fluid lows: (1) The micromodel was saturated with synthetic brine for
can be spontaneously imbibed into the porous media saturated 8 h; followed by (2) a drainage process using gas or crude oil until
with another fluid, as shown in Fig. 2. The rock hangs vertically the residual saturation of liquid was reached [30]; and finally (3) a
and is in contact with the air-liquid interface in the container. gas-wetting nanoparticle suspension FG40-NP was injected into
 J. Jin et al. / Fuel 196 (2017) 431–441 435

the micromodel, which was able to transform the wettability of particles exhibit their characteristic peak at 1050 cm1 corre-
porous media from liquid-wetting to gas-wetting after a certain sponding to ASiAOASi bond. However, the peak located at 1160
time. is replaced by an additional new bond at 1140 cm1 due to the
dehydration condensation between the FG40 and nano-silica parti-
3. Results and discussion cles; hence, the presence of the new ASiAOAC bond confirms that
nano-silica particles were functionally modified by FG40 molecules
3.1. FTIR spectrum due to the dehydration condensation.
The efficiency of dehydration condensation between the nano-
Fourier Transform Infrared Spectroscopy (FT-IR) analysis was silica particle and FG40 molecules depends on the distribution of
used to explore chemical component of the fluorosurfactant FG40 OH groups on the surface of nano-silica particle [31], which is
and the functional groups presented at the pore surface of the linked closely to the processes of silica preparation and treatment.
modified nanoparticle FG40-NP solution. The FT-IR were recorded The coverage of hydroxyl group on the surface of nano-silica parti-
in wavenumber ranging from the 4000 to 500 cm1 and is shown cle decreased with the rising temperature. The initial coverage of
in Fig. 4. It is clear that both of FG40 molecules and FG40-NP the hydroxyl group was 100%, as can be seen from Table 1 [32].
showed their characteristic peak of the AOH group at 3420 and
3450 cm1. The peaks at 2930 cm1 and 1740 cm1 prove the pres-
ence of the methyl and carbonyl group on the FG40 and FG40-NP, 3.2. Morphology of the rock surface
respectively. The stretching peak at 1100 cm1 is indicative of the
ACF group. The peaks near 1210 and 1450 cm1 correspond to the A gas-wetting rock can be obtained by injecting either the fluo-
characteristics of symmetric and asymmetric ACF2 group, and the rosurfactant FG40 or the silica–fluoropolymer hybrid nanoparticles
stretching peak at 960 cm1 presents the ACF3 group. Nano-silica FG40-NP into the rock. These gas-wetting components adsorb on
the pore wall and modify both surface chemistry and physical
topology. Fig. 5 shows the microscopic structure of the rock before
and after treatment with FG40 or FG40-NP. A smooth surface can
be clearly observed in Fig. 5(a), which provided good adsorption
sites for fluorosurfactant molecules and nano-silica particles.
Fig. 5(b) presents the microscopic structures of the rock surface
after 0.3% FG40 solution treatment at a temperature of 80 °C. This
was followed by an amorphous adsorption layer formed by FG40
molecule, which made the roughness of the rock surface increase.
Fig. 5(c) depicts a botryoidal adsorption structure, which is fully
coated on the rock surface, and consists of modified nano-silica
particles. It is well known that there are the attractive or repulsive
forces between molecules or atomic groups, named van der Waals’
forces [33]. In the first stage, the modified nano-silica nanoparti-
cles with a grape-like structure will adsorb on the rock surface
due to van der Waals’ forces, and an electrostatic force of attraction
can also accelerate the adsorption process between rock surface
and modified nano-silica particles since both of them are charged;
Fig. 4. FTIR spectra of FG40 and FG40 modified-nano-silica.
The other modified nano-silica particles will aggregate randomly
on the first adsorption layer after the first stage as they are drawn
by the van der Waals’ force, forming a multi-adsorption on the rock
Table 1 surface, as shown in Fig. 5(c). The hybrid silica nanoparticles have
Average concentration of OH groups on the surface of nano-silica at different diameter in the range of 30–45 nm, which is slightly increased
temperatures.
compared to that of the untreated nano-silica.
Temperature of Number of OH Coverage of the surface of In addition, energy-dispersive spectroscopy was employed to
treatment/°C group/nm2 nano-silica with OH group/% investigate the elemental content of rock surface before and after
180 4.9 100.0 gas-wetting alteration, as exhibited in Table 2. Sample 1, Sample
300 3.6 70.0 2, and Sample 3 represent the untreated, FG40 treated, and
500 1.8 40.0 FG40-modified-nano-silica treated rocks, respectively. EDS results
700 1.1 20.0
1000 0.2 5.0
show that a fluorine element was detected after FG40 and FG40-
NP treatment, the weight percentage of F on sample 3 was much

Fig. 5. SEM of gas-wetting core surfaces: (a) untreated core, (b) FG40-treated core, and (c) FG40-modified-nano-silica treated core.
436 J. Jin et al. / Fuel 196 (2017) 431–441

Table 2
The EDS of the core surface before and after gas-wetting alteration.

Sample Weight percentage (%)

O Si Na Al K Ca C F Pt
1 29.81 35.78 5.39 9.86 0.24 0.14 – – 18.78
2 34.41 17.71 0.85 7.93 3.17 10.34 14.48 2.58 8.53
3 35.66 19.10 0.87 7.81 2.96 0.73 8.43 6.42 18.02

higher than that of on Sample 2, revealing that more fluorosurfac-
tant molecules can be joined to nano-silica due to a large number
of hydroxyl groups on the nano-silica surface.
3.3. Wetting alteration results
3.3.1. Contact angle measurement
Adsorption of either FG40 or FG40-NP on the rock surface is
chemically and physically modify the rock’s surface, thus alters
the rock wettability. Contact angle of the probe liquid droplets
on the rock surfaces after treatment with different concentration
of FG40, and FG40-NP solutions as exhibited in Fig. 6. It can be seen
that the initial wettability of rock is liquid-wetting because the
contact angles of the brine and hexadecane on the untreated rock
surface are 23° and 0°, respectively. Liquid droplet might spread
easily on the rock surface due to the smooth surface, then the con-
tact angles of the liquid droplets on the untreated surface are sig-
nificantly less than that of the liquid droplets on the treated
surface. A significant increase in the contact angles of brine and
hexadecane can be observed as the concentration of gas-wetting
agents continues to increase, the contact angles of the brine
reached up to 138° and 129° by 0.3% FG40 solution treated, respec-
tively. Super gas-wetting is based on two requirements: (i) A low
surface energy which generally can be achieved by an adsorption
layer of fluorochemicals, and (ii) a rough surface, which can be
obtained by the arrangement of nano-silica particles at the rock
surface [24]. Thus, FG40-NP exhibits a better performance in gas-
wetting alteration, the contact angles of brine and hexadecane on
rock surface by which treated, increased to 152° and 140°, respec-
tively. The contact angles of the probe liquid droplets remained
almost unchanged when the concentration of the treatment solu-
tions increased up to 1 wt.%. Based on the above findings, we con-
clude that it might be possible to achieve super gas-wetting by
functionally modifying nano-silica with fluorosurfactant.
As shown in Fig. 6(c), the diameter of a liquid droplet which
attaches to the rock surface is inversely proportional to the gas-
wetting of the rock surface; The stronger gas-wetting, the smaller
diameter. Thus, it can be reasonably be concluded that the wetta-
bility of treated surface is super gas-wetting if d1  d2, where d1
and d2 are the contact line of the liquid droplet on the rock surface
before and after treatment, respectively. Generally, the rock wetta-
bility is liquid-wetting (water-wet, oil wet, or mixed wet), the vis-
cous resistance of liquid droplet is proportional to the contact area
between liquid and rock surface, the more contact area, the more
viscous resistance. Gas-wetting can effectively reduce the contact
area of liquid droplet (water or oil droplet) on rock surface, and
the moving force required for the liquid droplet is less than that
for liquid droplet on liquid-wet surface [24,34]. Thus, the mobility
of the liquid in porous media might be effectively enhanced, as will
be discussed in the following sections.

3.3.2. The surface free energy of gas-wetting rock and fluorosurfactant

Fig. 6. The contact angles of liquid droplets on gas-wetting cores: (a) FG40, (b)
FG40-NP, and (c) schematic of the liquid droplet on core surface before and after
treatment.
The adsorption of fluorosurfactant molecules on rock surface
can change the surface free energy of the solid surface, which is
calculated by the Owens two-liquid method. As shown in Fig. 7,
the surface free energy of the rock sharply decreases after being
treated with a concentration of 0.1% for each fluorosurfactant from
70.2 mN/m to approximately 47.5 for FG40 and 2.0 mN/m for
FG40-NP, respectively. Fig. 7 reveals that FG40-NP has a pro-
nounced effect on the surface free energy of rock surface compared
to that of FG40 at an equivalent concentration, especially at a low
concentration. The surface free energy gradually remained stable
as the concentrations range from 0.3 to 0.7%. The main factor con-
tributing to the decrease in surface free energy is fluorine-
containing adsorption layer on the rock surface. The surface free
energy of untreated rock surface is approximately 70 mN/m, which
can decrease to about 2 mN/m after gas-wetting alteration. Since
the CAF bond can stretch out when the polar-end of FG-40 adsorbs
 J. Jin et al. / Fuel 196 (2017) 431–441
Fig. 7. The surface free energy of the gas-wetting cores.
onto the rock surface, which possesses the characteristics of low
surface free energy and repelling liquid phase (water or oil. For
FG40-NP, the surface of nano-silica particle is coated with CAF
bond after modification, which exhibits a better performance in
reducing surface free energy.
3.3.3. Imbibition
The spontaneous imbibition is closely related to the rock wetta-
bility, and gas displacement significantly decreases as the wettabil-
ity is altered from preferential liquid-wetting to super gas-wetting.
Fig. 8 plots the spontaneous imbibition of brine and hexadecane
into rock before and after gas-wetting alteration treatments, the
gas displacement is represented by the saturation of gas in place.
There is a significant decrease in liquid imbibition rate after treat-
ment with gas-wetting agents, and gas displacement by hexade-
cane is obviously higher than that by brine. For untreated cores,
the residual gas saturation to brine is 38.2%, and to hexadecane
is approximately 45.6%. However, the residual gas displacement
by brine and hexadecane sharply decreased to 2.5% and 17.6% after
FG40 treatment, respectively. For FG40-NP treatment, the residual
gas displacement to brine and hexadecane are approximately 2.0%
and 17.1%. A substantial decrease in the amount of liquid imbibi-
tion into the air-saturated rock after treatment can be observed
in Fig. 8(a), which is consistent with the results of contact angle
measurement and surface free energy calculation. Our possible
explanation to this question is that the oleophobicity for FG40-
NP and FG40 might be equivalent in imbibition because of the con-
stant pore volume of rock sample. However, FG40-NP could
achieve the equivalent performance in a shorter time compared
with FG40-hexadecane. Fig. 8(b) demonstrates that the imbibition
rate for liquids into the rock significantly decreased from 11 lL/h
to approximately 4  102 lL/h in less 1 h after FG40-NP treat-
ment, which could be attributed to the adsorption of the modified
nano-silica that had suitable characteristics for super gas-wetting
in porous media.
3.4. Liquid blocking effect
The influence of gas-wetting alteration on the flow and distribu-
tion of fluids in porous media was studied with visualization flood-
ing on a transparent glass micromodel whose original wettability
is liquid-wetting. The glass model was first saturated with brine
before gas-flooding to simulate the liquid-blocking effect near
the wellbore region, as can be seen from Fig. 9a. As a result, severe
liquid-blocking regions within the rock did not allow gas passing
through the outlet end of the micromodel (Fig. 9b). Fig. 9c shows
how the liquid trapped in the outlet end of the micromodel is
437
Fig. 8. Imbibition by liquid into the core before and after treatment: (a) Gas
recovery, and (b) imbibition rate.
mostly removed after a certain amount of FG40-NP solution was
injected. The red1 arrows in Fig. 9b show flow paths formed by
the displaced.
The liquid saturation in visualized flooding was calculated using
MATLAB, the principle mechanism for calculating the liquid satura-
tion is to calculate the saturated pixels in an image, the proportion
of which in image represents the saturation. There is a sharp
decline in liquid saturation after gas-wetting alteration, as shown
in Fig. 9(g)–(i). If the initial liquid saturation in the micromodel
is considered as 100%, the liquid saturation after gas-flooding is
33.23%. A liquid-blocking region can be observed in the top right
corner of Fig. 9(h). Fig. 9(i) shows the liquid in the liquid-
blocking region scattering as discontinuous phase after gas-
wetting alteration, the liquid saturation declines to 20.77% in this
stage. Hence, the flow path for fluids in porous media can be seen
clearly. The amount of trapping liquid in micromodel decreased
sharply after gas-wetting alteration. Therefore, the novel gas-
wetting alteration agent can be applied to solve the liquid-
blocking effect near wellbore region on the gas-condensate
reservoir.
3.5. The effect of gas-wetting on oil saturation
The effect of gas-wetting on the flow behavior of oil phase in
porous media is shown in Fig. 10. The micromodel is saturated
with oil (hexadecane and crude oil) at a temperature of 70 °C for
1
For interpretation of color in Fig. 9, the reader is referred to the web version of
this article.
438 J. Jin et al. / Fuel 196 (2017) 431–441

Fig. 9. Visualization flooding: (a) before gas-flooding, (b) gas-flooding until liquid-blocking, and (c) gas-flooding after gas-wetting alteration. Fig. 9(d), (e), and (f) are
magnified areas of Fig. 9(a), (b), and (c). As shown in Fig. 9(g), (h), and (i), the liquid saturations in Fig. 9(a), (b), and (c) are 100%, 33.23%, and 20.77%, respectively. The liquid
saturation significantly decreased from 100% to approximately 20.77% after treatment; hence, a clear flow path in model can be observed. The black region represents liquid
in porous media, the white region corresponds to the flow path and rock.

Fig. 10. Visualized flooding: (a) saturating crude oil, (b) gas-flooding, (c) gas-wetting alteration and (d) end gas-flooding. The oil saturations in above figures are 100%, 55.02%,
42.76%, and 29.12%, respectively.
 J. Jin et al. / Fuel 196 (2017) 431–441 439

24 h, as exhibited in Fig. 10(a). Fig. 10(b) shows that gas phase
mixes up with oil phase due to the miscibility effect [35], the vis-
cosity of the oil phase significantly decreases. A flow path for gas
formed after the mobility of fluids in porous media increased, as
can be seen from Fig. 10(c). Several paths leading to the outlet were
formed, and partial miscibility can also be observed in Fig. 10(d).
The oil saturation before and after treatment was measured to
investigate the effect of gas-wetting on oil recovery. The initial
oil saturation in the micromodel is 100%, which decreases to
42.76% after the first gas-flooding. However, the distribution of
oil in the micromodel is uneven enough after first gas-flooding
because of partial bubble breakage. The oil saturation decreases
to 29.12% after injecting gas-wetting nano-silica solution. In this
stage, more bubbles are generated due to the miscibility effect,
meanwhile, the wettability alteration on the pore wall facilitates
the mobility of oil tremendously.
Fig. 11 depicts the interaction between the gas and oil phases in
porous media after gas-wetting alteration. The bubbles aggregated
in the pore throat extrude against each other when the displacing
force is greater than the bubble pressure, resulting in a decrease in
film thickness. A flow path is formed after penetration, as shown in
Fig. 11(b). Meanwhile, bubbles are more inclined to adsorb on the
pore wall due to gas-wetting, which enables oil to be extruded and
carried out through the interaction between the bubbles. It is
worth noting that there is miscibility effect, which dominates the
flow and distribution of fluid (oil phase) in porous media by reduc-
ing the viscosity and improve the mobility of oil phase. The phe-
nomenon might attribute to the high oil saturation in this region.
The thick film of oil on pore wall weakens wettability alteration.
However, wettability alteration still facilitates the mobility of oil
phase on rock surface when oil film flows.
gas-wetting or even super-gas-wetting when a sufficient amount
of FG40/FG40-NP were used. These modifications have been then
proved to significantly mitigate the fluid blocking effect as well
as facilitate the mobility of oil from the rock sample. In this section,
we will focus on the behavior of: (i) a single droplet trying to
detach from the pore wall and (ii) a fluid membrane at the pore
throat, to further understand the effect of gas-wetting treatment
on the flow behavior of fluid.
3.6.1. Detachment of a fluid droplet from gas-wetting pore wall
Fig. 12 exhibits a series of photograph of gas-wetting alteration
in the micromodel channels after the FG40-NP solution treatment.
Fig. 12(a) shows that the contact angle of brine on the treated pore-
wall is approximately 125°, which is much higher than that of
brine on the untreated pore-wall. As gas-flooding continues, the
liquid droplet tends to move forward by deformation. Meanwhile,
the advancing and receding angle of liquid are at approximately
136° and 78°, respectively, as shown in Fig. 12(b). The contact
angle hysteresis is normally described by the difference between
the advancing angle and receding angle [36], CAH ¼ ha  hr . It is
considered that the contact angle hysteresis arises if the wettabil-
ity of the solid is altered due to its previous contact with the treat-
ing liquid. Fig. 12(c) demonstrates that the liquid droplet has rolled
away under the displacing force. The above-captured figures reveal
that the wettability of the pore wall becomes gas-wetting, which is
verified by the results of the contact angle measurement and sur-
face free energy. It is worth noting that a rock surface in reservoir is
not always horizontal, so the advancing angle ha might be more
than 180° which accelerates the detachment of a liquid droplet
from the rock surface.

3.6.2. The flow behavior of liquid membrane in a gas-wetting pore

3.6. Effect of gas-wetting treatment on the fluid flow behaviors throat
The sectional shape of the liquid membranes located in the pore
Rock treatment with either FG40 or FG40-NP has significantly throat varies with the movement of fluids in the porous media,
modified the rock wall from preference water-wetting to which can tremendously affect the flow behavior and distribution

Fig. 11. Magnified images from oil-methane region: (a) the bubbles in critical state of rupture, (b) partial new path after penetration of nano-silica particles generated by
gas-wetting, and (c) extrusion of oil based on interaction between bubbles as they are absorbed on the pore wall due to gas-wetting.

Fig. 12. The flow behavior of the liquid droplet on gas-wetting pore wall. The contact angle of the liquid droplet on the core wall is 125°, as shown in Fig. 12(a). Fig. 12
(b) and (c) show the interaction between the liquid droplet and displacing force in the flow path. The advancing angle and receding angle of the liquid droplet are
approximately 136° and 78° in Fig. 12(b). Fig. 12(c) illustrates how the droplet is displaced out.
440 J. Jin et al. / Fuel 196 (2017) 431–441
Fig. 13. The flow behavior of liquid membrane in pore throat: (a) moving towards pore throat, (b) concave membrane, (c) convex membrane, and (d) improving mobility. The
shape pf droplet located in pore throat transforms from concave to convex when the liquid in porous media starts to pass through the concave liquid membrane.
of fluids in the liquid-blocking area. Fig. 13 shows that after gas-
wetting alteration, the variation in liquid membrane thickness
facilitates the transformation of the liquid membrane from a stable
condition to an unstable condition, allowing the liquid membrane
moving out from pore throat. The Young–Laplace equation was
used to determine the critical thickness of the membrane. The
influence of gravity or other forces is neglected, the pressure differ-
ence between liquid phase and gas phase can be expressed as [37]:
2c cos h
DP ¼ ð10Þ
R
where c is the surface tension of the liquid-gas interface, R1 and R2
are the radius of rock and concave liquid membrane, respectively. If
the liquid droplet is under the critical detachment condition, the
value of concave membrane R2 reaches to the radius of the convex
membrane, leading to the following equations:
1
R2 ¼ H2 ð11Þ
2 We gratefully acknowledge Fundamental Research Funds for
With the increasing volume of liquid, R2 exceeds to the radius of the
convex membrane, applying Eq. (10) yields the following equations:
2c cos h1 2c cos h1
DP 1 ¼  ð12Þ
R2 R1
2c cos h2 2c cos h2
DP 2 ¼  ð13Þ
R2 R1
where h1 is the average contact angles of corresponding sides of the
concave membrane and h2 is the average contact angles of corre-
sponding sides of the convex membrane. The liquid droplet trapped
in pore throat will be displaced out when the pressure difference is
positive, i.e.
DP ¼ DP 2  DP 1 > 0 ð14Þ
4. Conclusions
Super gas-wetting nano-silica particle have been prepared by
functional modification, which can be quantitatively evaluated by
contact angle measurement, imbibition, and Owens-Two-Liquid
method. The morphological structure of gas-wetting nano-silica
particles was characterized by FT-IR and SEM. The results demon-
strate that fluorosurfactant molecules are successfully modified
onto the nano-silica surface due to dehydration. The modified
nano-silica with a grape-like structure can alter the wettability of
the rock from liquid-wetting to super gas-wetting. The results of
visualization flooding reveal that the saturation of trapping liquid
in micromodel sharply decreased from 100 to 20.77% after gas-
wetting alteration. The contact angle of brine on the treated
pore-wall was approximately 125°, which is consistent with this
research’s finding. The mobility of the oil phase in the micromodel
can improved significantly after FG40-NP injection. The Oil satura-
tion will also decrease to a large extent.
Acknowledgments
the National Key Basic Research Program of China (No.
2015CB250904), Chang Jiang Scholars Program of China (No.
T2014152), Central Universities of China (No. 15CX06034A), China
Scholarship Council (No. 201506450043), and Dr. Bogdan Donose
for fruitful discussions. The financial sponsorships are greatly
appreciated. The funders had no conflict of interest or any role in
the study design, data collection and analysis, decision to publish,
or preparation of the manuscript.
References
[1] Bobek J, Mattax C, Denekas M. Reservoir rock wettability—its significance and
evaluation. Trans AIME 1958;213:155–60.
[2] Fan H, Lyu J, Zhao J, Zhao S, Fan H, Geng J, et al. Evaluation method and
treatment effectiveness analysis of anti-water blocking agent. J Nat Gas Sci Eng
2016.
[3] Bang VSS, Pope GA, Sharma MM, Baran Jr JR. Development of a successful
chemical treatment for gas wells with liquid blocking. Society of Petroleum
Engineers; 2009.
[4] Leslie Zhang D, Liu S, Puerto M, Miller CA, Hirasaki GJ. Wettability alteration
and spontaneous imbibition in oil-wet carbonate formations. J Petrol Sci Eng
2006;52:213–26.
 J. Jin et al. / Fuel 196 (2017) 431–441
[5] Salehi M, Johnson SJ, Liang J-T. Mechanistic study of wettability alteration
using surfactants with applications in naturally fractured reservoirs. Langmuir
2008;24:14099–107.
[6] Li K, Firoozabadi A. Experimental study of wettability alteration to preferential
gas-wetting in porous media and its effects. SPE Reservoir Eval Eng
2000;3:139–49.
[7] Li K, Firoozabadi A. Phenomenological modeling of critical condensate
saturation and relative permeabilities in gas/condensate systems. SPE J
2000;5:138–47.
[8] Wu S, Firoozabadi A. Permanent alteration of porous media wettability from
liquid-wetting to intermediate gas-wetting. Transp Porous Media
2010;85:189–213.
[9] Wang Y, Jin J, Ma L, Li L, Zhao X. Influence of wettability alteration to
preferential gas-wetting on displacement efficiency at elevated temperatures. J
Dispersion Sci Technol 2015;36:1274–81.
[10] Bai B, Wei M, Liu Y. Field and lab experience with a successful preformed
particle gel conformance control technology. In: SPE Production and
Operations Symposium. Society of Petroleum Engineers; 2013.
[11] Elsharafi MO, Bai B. Effect of weak preformed particle gel on unswept oil
zones/areas during conformance control treatments. Ind Eng Chem Res
2012;51:11547–54.
[12] Elsharafi MO, Bai B. Effect of back pressure on the gel pack permeability in
mature reservoir. Fuel 2016;183:449–56.
[13] Mousavi MA, Hassanajili S, Rahimpour MR. Synthesis of fluorinated nano-silica
and its application in wettability alteration near-wellbore region in gas
condensate reservoirs. Appl Surf Sci 2013;273:205–14.
[14] Jin J, Wang Y, Wang K, Ren J, Bai B, Dai C. The effect of fluorosurfactant-
modified nano-silica on the gas-wetting alteration of sandstone in a CH4-
liquid-core system. Fuel 2016;178:163–71.
[15] Anderson W. Wettability literature survey – Part 2: Wettability measurement.
J Petrol Technol 1986;38. 1,246–241,262.
[16] Newcombe J, Mcghee J. Wettability versus displacement in water flooding in
unconsolidated sand columns. Trans AIME 1955;204:227–31.
[17] Dag TA, Standnes C. Wettability alteration in chalk 2, mechanism for
wettability alteration from oil-wet to water-wet using surfactants. J Petrol
Sci Eng 2000;28:123–43.
[18] Seethepalli A. Wettability alteration during surfactant flooding of carbonate
reservoirs. SPE 2004;89423.
[19] Jiang G, Li Y, Zhang M. Evaluation of gas wettability and its effects on fluid
distribution and fluid flow in porous media. Petrol Sci 2013;10:515–27.
441
[20] Seyyedi M, Sohrabi M, Farzaneh A. Investigation of rock wettability alteration
by carbonated water through contact angle measurements. Energy Fuels
2015;29:5544–53.
[21] Hou B, Wang Y, Cao X, Zhang J, Song X, Ding M, et al. Surfactant-induced
wettability alteration of oil-wet sandstone surface: mechanisms and its effect
on oil recovery. J Surfactants Deterg 2016;19:315–24.
[22] Liu J, Qiao SZ, Liu H, Chen J, Orpe A, Zhao D, et al. Extension of the Stöber
Method to the preparation of monodisperse resorcinol–formaldehyde resin
polymer and carbon spheres. Angew Chem Int Ed 2011;50:5947–51.
[23] Lalatonne Y, Richardi J, Pileni M. Van der Waals versus dipolar forces
controlling mesoscopic organizations of magnetic nanocrystals. Nat Mater
2004;3:121–5.
[24] Butt H-J, Semprebon C, Papadopoulos P, Vollmer D, Brinkmann M, Ciccotti M.
Design principles for superamphiphobic surfaces. Soft Matter 2013;9:418–28.
[25] Huang N, Yang P, Leng YX, Chen JY, Sun H, Wang J, et al. Hemocompatibility of
titanium oxide films. Biomaterials 2003;24:2177–87.
[26] Good RJ. Surface free energy of solids and liquids: thermodynamics, molecular
forces, and structure. J Colloid Interface Sci 1977;59:398–419.
[27] Owens DK, Wendt R. Estimation of the surface free energy of polymers. J Appl
Polym Sci 1969;13:1741–7.
[28] Fowkes FM. Attractive forces at interfaces. Ind Eng Chem 1964;56:40–52.
[29] Mohammed M, Babadagli T. Wettability alteration: a comprehensive review of
materials/methods and testing the selected ones on heavy-oil containing oil-
wet systems. Adv Colloid Interface Sci 2015;220:54–77.
[30] Demond AH, Roberts PV. Effect of interfacial forces on two-phase capillary
pressure-saturation relationships. Water Resour Res 1991;27:423–37.
[31] Mueller R, Kammler HK, Wegner K, Pratsinis SE. OH surface density of SiO2 and
TiO2 by thermogravimetric analysis. Langmuir 2003;19:160–5.
[32] Zhuravlev LT. Concentration of hydroxyl groups on the surface of amorphous
silicas. Langmuir 1987;3:316–8.
[33] Margenau H. Van der Waals forces. Rev Mod Phys 1939;11:1.
[34] Morrow NR, Mason G. Recovery of oil by spontaneous imbibition. Curr Opin
Colloid Interface Sci 2001;6:321–37.
[35] Price LC, Wenger LM, Ging T, Blount CW. Solubility of crude oil in methane as a
function of pressure and temperature. Org Geochem 1983;4:201–21.
[36] Parmesan C, Yohe G. A globally coherent fingerprint of climate change impacts
across natural systems. Nature 2003;421:37–42.
[37] Shuttleworth R. The surface tension of solids. In: Proceedings of the physical
society. Section A, 63 (1950) 444.