The 23rd Formation Evaluation Symposium of Japan, October 11-12, 2017

WETTABILITY ALTERATION OF SANDSTONE WITH

ZINC OXIDE NANO-PARTICLES
Sreu Tola1, Kyuro Sasaki1 and Yuichi Sugai1
1.
Resources Production and Safety Engineering Laboratory, Kyushu University, 744 Motooka, Nishi-ku, 819-0395
Fukuoka-city, Fukuoka, Japan

This paper was selected for presentation by a JFES program committee for enhanced oil recovery by IFT reduction of residual
following review of an abstract submitted by the author(s). crude oil in sandstone reservoirs.

ABSTRACT MATERIALS
In this research, we have investigated wettability Nanoparticles: Nanoparticles of Zinc Oxide (ZnO) is a
alteration of sandstone and crude oil surfaces contacting power (average diameter =25nm) was produced by
nanofluids formulated by ZnO nanoparticles. The ZnO Navarrean Nanoproducts Technology Company. It was
nanofluid was mixed by dispersing into water solution used to formulate ZnO nanofluid formulated ZnO
of Sodium Dodecyl Sulfate that is an anionic surfactant. nanopowder (average diameter =25nm) dispersing into
ZnO concentration (w/w) in the fluid ranges from 500 distilled water with SDS. The physical and chemical
ppm to 5000 ppm. Oil film spread on glass plate and properties of ZnO nanofluids are descripted in Table 1.
surface of Berea sandstone saturated by light crude oil
were used to measure fluid wettability evaluated by the Crude Oil: Light crude oil sample from a Japanese oil
contact angle of fluid droplets with the sessile drop field was used to conduct measurements of contact
methods. It has been confirmed that the ZnO nanofluid angle with sandstone and surface tension. The density,
has a potential to shift wettability to more water wet viscosity and API gravity of the crude oil are listed in
condition on the surfaces of oil film and sandstone Table 2.
saturated by oil.
Surfactant: Anionic surfactant Sodium Dodecyl Sulfate
INTRODUCTION (SDS) was purchased from Junsei Chemical Co., Ltd. It
was used to add to disperse the ZnO nanoparticles in
The uses of nanoparticles are raised an interest in the water.
petroleum industry recently. This is so because
nanoparticles have a proven potential to decrease the Sandstone Core: Berea sandstone cores were used to
interfacial tension (IFT) and change the wettability state age in crude oil. Its porosity is 15%, permeability is
of formation rock from strongly oil-wet or oil-wet to around 50md, and pore diameter is ranged 100 µm to
water-wet or to strongly water-wet. Wettability is 200 µm.
defined as the relative adhesion of two fluids to a solid
surface. In petroleum reservoirs, wettability is one of Table 1. Physical and chemical properties of ZnO
important factors that effect on production increment in nanofluids:
oil recovery, because it is a major target of the
enhanced oil recovery process. Al-Anssari et al. (2016) Chemical formula ZnO
have studied about wettability alteration of oil-wet Molecular weight, 81.38 g/mole
carbonate by silica nanofluid and their result show that Color White
rock surface wettability shifts from oil-wet to water-wet. Average particles size 20-30 nm (Average: 25nm)
Sepehrinia and Mohammadi (2016) conducted a Specific surface area 35-50 m2/g
research on aluminum oxide and zirconium oxide on Density 5.6 g/cm3
oil-wet dolomite surface with different dispersing pH 7
medium such as cationic, anionic or nonionic surfactant. Solubility 1.6 mg/L (water, 29 oC)
Their result showed that cationic surfactant is more
effective in altering wettability of oil-wet dolomite rock Table 2. Physical properties of crude oil:
to more water-wet condition.
Properties Value
In this study, the nanofluid formulated by ZnO Density at 25 °C 0.8905 g/ml
nanoparticles with anionic surfactant Sodium Dodecyl Viscosity at 25 °C 8.46 cP
Sulfate (SDS) (ZnO nanofluid) was investigated to use o
API gravity 27.4

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 The 23rd Formation Evaluation Symposium of Japan, October 11-12, 2017

EXPERIMENTAL PROCEDURES (DropMaster DMs-401) was used to measure the

Nanofluid preparation: ZnO nanofluids were prepared
by mixing ZnO nanoparticles into SDS solution. ZnO
nanoparticles 40 μm to 50 μm in diameter were
weighted and diluted in SDS solution and stirred for
12h. Then the mixture was sonicated in ultrasonic bath
for 2h to disperse ZnO particles. Adding SDS in
distilled water helps to disperse ZnO nanoparticles and
stabilize solution for longer period than without SDS.
The optimum SDS concentration was decided as 2500
ppm based on Critical Micelle Concentration (CMC) of
SDS dissolve in distilled water by changing from 1000
ppm to 5000 ppm by measuring its surface tension (see
Figure 2). The surface tension and contact angle of ZnO
nanofluid formed with SDS solution (2500 ppm) were
measure as shown in Table 3.
surface tension and IFT of ZnO nanofluid by pendant
drop method in atmospheric condition (see Figure 1).
ZnO concentration in the nanofluids was varied from 0
to 400 ppm without adding SDS are prepared for IFT
measurement with crude oil. However, since the ZnO
nanofluids from 500 ppm to 5000 ppm are very strong
effects to reduce IFT at the interface between oil and
the nanofluids, and measurement using crude oil could
not determine with the apparatus.
Japanese Crude oil

Table 3. Properties of ZnO nanofluids:

ZnO, SDS, Density, Viscosity, pH

ZnO ppm ppm g/ml cP at 25 oC
nanofluid (w/w) (w/w) at 25 oC at 25 oC

#1 500 2500 1.0954 0.96 7.8

#2 1000 2500 1.0958 1.29 7.9 Figure 1. An instrument to measure surface tension by
#3 2000 2500 1.0966 1.21 8.1 pendant drop method. (Saito et al. 2016)
#4 3000 2500 1.0974 1.41 8.1
#5 4000 2500 1.0982 1.11 8.0 55
#6 5000 2500 1.0990 1.11 8.2
50
Preparation of sandstone plates: Berea sandstone core
was cut into thin plates around 3mm in thickness using 45
mN/m

cutting machine and polished to get flat and smooth

surface then those plates were cleaned in ultrasonic bath 40
for 1h to remove all contaminants and placed in oven
for 24h at 80oC.
35
Contact Angle Measurement: The sessile drop method
is often used to make direct measurements of the 30
contact angle to determine preferential wetting of a 1000 2000 3000 4000 5000
given solid by oil and water (Tiab and Donaldson, SDS concentration, ppm
2012). In this study, the sessile drop method was used
to measure contact angle of ZnO nanofluid droplets on Figure 2. Surface tension of SDS to define CMC
sandstone surface saturated oil and oil film on glass
plate. The first series of measurements was done using RESULTS
the sandstone plate saturated by the oil for 24h in room
temperature. Then place a drop of ZnO nanofluids on
IFT of Japanese crude oil: The IFT values of Japanese
the oil saturated plate then measure contact angles. As
crude oil were measured in air and water as shown in
the second series of the measurements, the contact
Figure 3 (a) and (b). IFT of crude oil in air and in water
angle of each droplet was measured on oil film spread
were 17.5 and 26.4 mN/m, respectively. Figure 4 shows
over a glass plate. All experiments are conducted in
the result of IFT of oil and ZnO nanofluids from 0 ppm
atmospheric condition.
to 400 ppm without adding SDS. The increment of ZnO
nanofluids concentration (0 ppm to 400 ppm) can
Surface Tension and interfacial tension Measurement: reduce a little bit of IFT value from 26.4 mN/m to 24.4
Japanese crude oil and ZnO nanofluids were used to mN/m. Moreover, the ZnO nanofluids (500 ppm to
measure surface tension and IFT. Surface tension was 5000 ppm) are likely to reduce more IFT since there is a
also measured together with IFT. The instrument

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 The 23rd Formation Evaluation Symposium of Japan, October 11-12, 2017

present of SDS which is a surfactant that can reduce on the sandstone plate saturated by oil. The case of the
IFT to ultra-low IFT with crude oil. 0 ppm, the contact angle was measured as 29.3°. The
contact angles of ZnO nanofluid droplet was decreased
to around 25° which indicates strong water-wet. Figure
6 shows comparisons of the contact angles ZnO
nanofluids from 0 ppm to 5000 ppm. The contact angles
of ZnO nanofluids at concentration of 1000 ppm has
ability to shift contact angle to 25° which is a better
concentration than other concentration.

35.8
35 34.1
(a) Oil in air (b) Oil in water
Figure 3. IFT of oil with air and water

Contact angle,𝜃
29.3 29
30 28.5
30 27.4

25 25
25
20
IFT, mN/m

15 20
0 500 1000 2000 3000 4000 5000
10
ZnO nanofluid (+2500 ppm of SDS), ppm
5
Figure 6. Contact angles of droplets on sandstone plate
0 saturated by oil
0 100 200 300 400

ZnO nanofluid (without SDS), ppm Contact angle on oil film spread cover glass plate:
Figure 7 shows the measurement results of contact
Figure 4. IFT of ZnO nanofluid with crude oil angles on oil film in almost constant thickness (around
20 µm) spread over the glass plate. The trend of the
Surface tension of ZnO- nanofluids: Figure 5 shows the contact angle of each droplet is similar to that of the
surface tension of ZnO nanofluid of 500 to 5000 ppm. It contact angles on the sandstone plate saturated by oil.
increases with ZnO concentration in the nanofluid exce- However, the contact angles of the ZnO nanofluid
pt 5000 ppm. The decrease in surface tension of ZnO droplets on the oil film are slightly larger than that of
nanofluid at 5000 ppm was due to the high precipitation the sandstone plate. The reason may be that sandstone
in that concentration. surface consisting different rock properties that are not
the same condition with oil film which has constant
36 thickness. At 500 ppm of ZnO nanofluid in this case, it
has the lowest angle.
35
Surface tension, mN/m

45
34
40 39.3
40 38.1 38.8
33 36.9 37
Contact angle,𝜃

35
32 30.6
30
31
25
30
500 1000 1500 2000 2500 3000 3500 4000 4500 5000 20
ZnO nanofluid (+SDS 2500 ppm), ppm 0 500 1000 2000 3000 4000 5000
Figure 5. Surface tension of ZnO nanofluid ZnO nanofluid (+2500 ppm of SDS), ppm

Contact angle of sandstone plate saturated by oil: Figure 7. Contact angles of droplets on oil film
Figure 6 shows the result of contact angle of nanofluids, spreading over glass plate (thickness of oil film~20 µm)

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 The 23rd Formation Evaluation Symposium of Japan, October 11-12, 2017

Based on both measurements of contact angles, it can

be concluded that the ZnO nanofluids make shift the
wettability to more water wet condition and push the
residual oil out from reservoir rock surface.
CONCLUSION
In this study, the fluids dissolving ZnO nanoparticles in
SDS solution (ZnO nanofluids) were prepared, and its
wettability on sandstone surface saturated by oil or oil
surface on glass plate were measured by the sessile drop
method. The IFT of crude oil with ZnO nanofluid does
not change much at low concentration from 0 ppm to
400 ppm. The ZnO nanofluid by dispersing ZnO
nanoparticles from 500 ppm to 1000 ppm into and SDS
solution of 2500 ppm has a good potential of alter
wettability of sandstone surface to more water wet than
that of other fluids.
ABOUT THE AUTHOR
Sreu Tola is a master student of Kyushu University
majoring in Reservoir Engineering in Department of
Earth Resources Engineering. He graduated his B.Eng.
in Geo-resources Engineering from Institute of Techno-
logy of Cambodia.
Kyuro Sasaki is currently a professor of Department of
Earth Resources Engineering at Kyushu University
(Japan) and responsible for the Resources Production
and Safety Engineering Laboratory.
Yuichi Sugai, he is an assistant professor at Kyushu
University (Japan). He focuses on Microbial Enhance
Oil Recovery for his current researches.

Further studies on wettability alteration for carbonate

rock and different surfactants are needed to extend
nanoparticles for EOR.

ACKNOWLEDGEMENTS

The authors would like to thank to Ministry of

Education, Culture, Sports, Science, and Technology of
Japan (MEXT) for the financial support.

REFERENCES

Al-Anssari, Sarmad et al. 2016. “Wettability Alteration

of Oil-Wet Carbonate by Silica Nanofluid.”
Journal of Colloid and Interface Science 461:
435–42.
http://dx.doi.org/10.1016/j.jcis.2015.09.051.

Saito, Minoru et al. 2016. “Experimental and Numerical

Studies on EOR Using a Biosurfactant.” In Abu
Dhabi International Petroleum Exhibition &
Conference, Society of Petroleum Engineers.
http://www.onepetro.org/doi/10.2118/183496-MS
(August 25, 2017).

Sepehrinia, Kazem, and Aliasghar Mohammadi. 2016.

“Wettability Alteration Properties of Fluorinated
Silica Nanoparticles in Liquid-Loaded Pores: An
Atomistic Simulation.” Applied Surface Science
371: 349–59.

Tiab, Djebbar., and Erle C. Donaldson. 2012.

Petrophysics : Theory and Practice of Measuring
Reservoir Rock and Fluid Transport Properties.
Gulf Professional Pub./Elsevier.
http://www.sciencedirect.com/science/book/9780
123838483.

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