OTC 20718

Wettability Studies Using Low-Salinity Water in Sandstone Reservoirs

M.B. Alotaibi, R.M. Azmy, and H.A. Nasr-El-Din, Texas A&M University, all SPE members

Copyright 2010, Offshore Technology Conference

This paper was prepared for presentation at the 2010 Offshore Technology Conference held in Houston, Texas, USA, 36 May 2010.
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Abstract
It has been reported that the ionic strength of injection water can have a major impact on the recovery of hydrocarbons during
waterfloods, with increased recovery resulting from the use of low salinity brines. Understanding how the water and oil
chemistry affects the final recovery from a physicochemical point of view is necessary in order to optimize low salinity water
flooding process. It is clear from the literature over the last two decades that wettability is considered a key factor in achieving
the low salinity effect. Optimum ionic strength and conditions for low salinity flood with respect to wettability is still
uncertain.
In this study, we studied oil/water/rock interactions at different salinity level and elevated temperature conditions.
Wettability is determined by a HTHP contact angle method and zeta potential technique. Outcrop rocks and stock-tank crude
oil sample are utilized in all experiments. Synthetic formation brines, aquifer, and seawater are evaluated under high pressure
conditions. We determined zeta potential of sandstone rocks and selected clays minerlas as a function of ionic strength.
Wettability of oil-brine-sandstone systems depends on the brines salinity, temperature, rock nature and minerlogy. Aquifer
water decreased the Berea sandstone wettability toward strong water wet condition. But, different sandstone rock showed
opposite result completely. In Scioto sandstone, aquifer water enhanced the wettability to neutral state. The optimim salinity
for this rock was seawater. We observed direct relationship between the zeta potential and ionic strength. High salt ions in the
seawater showed excellent stability for sandstone particles and others clay minerals. The zeta potential moved too close to zero
point of charge after using only the seawater.
Introduction
Wettability is considered a key factor that affects fluids distribution in a porous medium. Reservoir wettability depends
strongly on oil composition, surface chemistry of the rock, and presence or absence of the other aqueous phase. In addition, the
composition of the aqueous phase, temperature, pressure, and contact time can be considered important parameters. Any
wettability adjustment will affect capillary pressure, relative permeability, and waterflooding behavior. Recently, the ionic
strength of the injected water proved to significantly improve oil recovery in many sandstone fields (Morrow et al., 1998;
Zhang et al., 2007; Alotaibi and Nasr-El-Din, 2009a; Agbalaka et al., 2009). However, the reaction mechanism is still not well
understood. Therefore, wettability alteration is believed to be a main factor behind this mechansim. For that reason, we
decided to study the effect of low salinity water on the contact angle, and ultimately on oil recovery. In all contact angle
experiments, reservoir temperature and pressure conditions were simulated.
Sandstone rock has negative surface charges; therefore, monovalent and divalent cations will interact with rock surface and
fluids in the reservois. Hence, this complex interaction will disturb the charges stability. We measure zeta potential to examine
the effect of ionic strength on the surface charge of various clays. Sandstone rocks and several clays minerals (illite, kaolinite,
chlorite, and montmorillonite) were tested at ambient temperature (77F).
Literature Review
Contact angle. Researchers are using contact angle methods to evaluate the wetting characteristics of solid surfaces. This
method is usually applied by using a small piece of rock and two immiscible fluids. To avoid any hystereies issue, the rock
surface should be smoothed and well polished.
Wang and Gupta (1995) studied the influence of temperature and pressure on wettability of reservoir rocks. They
concluded that contact angle was not sensitive to pressure. In contrast, temperature showed significant effect on the wettability
of crude oil/brine/quartz system. As the temperature increased from ambient to 130F, the contact angle increased by 10.
Increasing the temperature higher than 130F slightly decreased the contact angle. Fluids interface chemistry at high

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temperature played a major role in determining the contact angle. Wettability results of quartz surface suggested strongly
water-wet condition.
Buckley et al. reported the water film stability at different temperatures, brine salinity and pH condition (Liu and Buckley,
2000; Buckley and Liu, 1998; Buckley et al., 1996). The authors used different mica minerals as a rock surface, crude oil, and
sodium and calcium brines as aqueous phases. Mica surfaces showed intermediate-wet condition in the absence of water film.
Two different crude oils were used as well as three different brines: 1.0M, 0.01M, and 0.001M. Acid/base interactions
significantly affected water film stability. Calcium chloride-Moutary oil results suggested oil-wet surface at 176F while
intermediate at 77F. The other crude oil/CaCl2 test resulted in water-wet condition at both temperatures. Xie et al. (2002)
showed variable interactions between different oils/brine/mica surfaces.
Yang et al. (1999) studied the mechanisms for contact angle hysteresis using crude oil/NaCl/mica surface. Contact angle
and AFM results suggested the presence of brine was critical to alter wettability towards oil-wet. This brine film enhanced the
electrical interactions between brine-oil and brine-mica interfaces. Without the brine layer, asphaltenes adsorbed loosely on the
mica surface through van der Waals interactions. Presence of brine film increased the contact angle from 41 (water-wet) to
144 (oil-wet). Anderson (1986) classified the wettability, in terms of contact angle, as water-wet (075), intermediate
(75115), and oil-wet (115180). Weakly water-wet and oil-wet conditions can be also represented by (5575) and
(115135), respectively.
Zeta Potential (). Zeta potential measurements facilitate understanding and controlling colloidal suspensions. The double
layer on a colloid is formed in order to neutralize the charged colloid and, in turn, causes an electrokinetic potential between
the surface of the colloid and any point in the mass of the suspending liquid. This voltage difference is on the order of
millivolts and is referred to as the surface potential. The magnitude of the surface potential is related to the surface charge and
the thickness of the double layer. By measuring potential, we can understand the stability of solutions as if the charge on
colloid is high enough, the colloids will remain discrete, disperse and in suspension. Reducing or eliminating the charge has
the opposite effect. The colloids will steadily agglomerate and settle out of suspension or form an interconnected matrix.
Hussain et al. (1996) studied potential measurements to determine the properties of kaolinite, illite, and chlorite in terms
of their surface charges and point of zero charge (pzc) values. They found the three clays in distilled water were negatively
charged over pH range from 2.5 to 11. Kaolinite was the most negative clay, and it has no pzc. Chlorite and illite have pzc at
pH 3 and pH 2.5, respectively.
Clays consist of plate-like particles, and usually have negatively charged faces and positively charged edges when get in
contact with water. The physical properties of clay-water systems are very sensitive to the nature of the electric double layer
around the particles and the tendency of the particles to aggregate. Some examples of physical properties are sedimentation,
filtration, swelling, viscosity, yield stress and structural strength (Weiner et al. 1993).
Yukselen and Kaya (2003) reported potential of kaolinite using electrophoretic mobility in the salt and heavy metals ions
as a function of pH and concentration. They concluded that with increasing pH, potential became more negative. Zeta
potential of kaolinite had higher values in the presence of Li+ and Na+, compared to ions free water. Zeta potential of kaolinite
decreased with divalent cations such as Ca2+ and Mg2+.
Zeta potential used to explain the observed macroscopic behavior through complex, and theoretical analyses. Stephan and
Chase (2001) used zeta potential difference as a measurable indicator for deep bed filtration behavior. In their experiments,
they used clay particles migrating through sandstone media. The authors studied pH and salinity effect on potential behavior
of Berea sandstone and three types of clays (illite, kaolinite, and halloysite). The results showed that under water shock
condition, high pH and low salt concentration, potential of clay was not changing. Berea sandstone experiments suggested
sharp decrease in potential. Under high pH and salt concentration, potential values decreased. In contrast, potential
increased for clays and decreased for sandstone surfaces at low pH and salt concentration.
Experimental Studies
Porous media. In this paper, we used Scioto, and Berea sandstone outcrop rocks for contact angles experiments. Scioto
samples source obtained from Ohio outcrop rock in the USA. The rocks permeability varied from 0.01 to 0.1 md. Rock
mineralogy is given in Table 1. The porosity and permeability were measured using coreflood apparatus and high salinity
formation brine, Table 2 (Alotaibi et al. 2010). The porosity and permeability ranges were 1820 vol% and 144 to 198 md,
respectively.
Fluids. Table 2 shows the composition of formation brine, seawater and aquifer water with wide ranges of salinity levels. We
selected high, medium and low salinity brines to simulate Middle East field case. Field operators collected crude oil samples
from a single well and then sent for testing. We measured oil density at high temperature (194F) to use that for interfacial
tension analysis. Oil density was 0.87 g/cm3. Capillary viscometer was used to determine oil viscosity at ambient temperature.
The average viscosity measurement equals to 7.21 cP. To avoid any solids plugging problems, we filtered the oil samples
through 1 m filter paper, and then re-filtered through sandstone core plug.
Drop Shape Analysis System (DSA). The Pendant drop method is well known to determine interfacial property from the drop
shape that generated inside a view chamber (Andreas et al. 1938). Experiments results were subject to fairly high errors due to

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analogous photographing images and an empirical evaluation method. Electronic data processing is developed lately to
digitalize drop images and solve the theoretical equation of a drop profile. Drop Shape Analysis System (DSA) is a technique
to determine liquid-fluid interfacial tensions and contact angles from the shape of axisymmetric menisci, for example, from
sessile as well as pendent drops (Li and Neumann 1992), Fig. 1.
Interfacial Tension. A pendant oil drop is formed at the tip of a stainless steel capillary needle. Then, digital image of the drop
is acquired by an image acquisition system. By applying digital computer image analysis and processing techniques, the
accurate interfacial profile of the pendant drop can be obtained (Hjelmeland and Larrondo 1986). Finally, the DSA analysis
software solves capillarity Laplace equation to find the best fit of the numerical interfacial profile to the physical drop.
The maximum operating pressure and temperature are 10,000 psi and 392F. To apply high pressure, we used compressed
nitrogen cylinder. Temperature was increased gradually using a digital temperature controller. Three drops were usually
evaluated at each temperature. Vibration and temperature variations are the most usual sources of experimental errors when
dealing with small drops. Ideally, the pendent drop apparatus should be mounted on a vibration-free base. More details on IFT
were given by Alotaibi and Nasr-El-Din (2009b).
Contact Angle. The application of Drop Shape Analysis to sessile and captive drop contact angles requires the solid surface
to be smooth and homogenous. Otherwise, the drop will not be axisymmetric. The software determined the angles between the
baseline and the tangent at the drop boundary.
Rock Substrates
We applied certain procedure to prepare Scioto, and Berea sandstones substrates for contact angle measurements.
Cut the substrate from small core plug with certain dimensions: 0.62 in. x 0.72 in. x 0.25 in.
Polish one slide of the rock substrate using a sand paper (600-mesh and then 300-mesh) to minimize the contact angle
hysteresis due to surface roughness.
Load all substrates into an empty glass flask, and then apply vacuum pressure for at least 2 hrs.
Introduce formation brine (174 kppm) and keep the substrates soaking under vacuum for at least 3 hrs. To remove the
contaminants and surface charges induced by polishing, the substrates were left in the brine for at least 24 hrs.
Place the rock substrates in the crude oil and centrifuged them at 3,000 rpm for 30 min.
Wait for 30 min. before centrifuging the rock substrates again at the same speed and time period.
The centrifuge step was to displace the water droplets on the rock surface to keep only the irreducible water (Swi)
Age your samples at 194F for different time periods
To simulate the in-situ state of the mineral surface under reservoir conditions, we applied the previous procedure.
Soak the substrates in toluene for 2 seconds to remove the bulk oil from the rock surface.
Load the substrates in the sample holder before inserting it in the instrument chamber.
A very important step before any experiment is a thorough cleaning of the apparatus, because even trace amounts of
contamination can alter the results. The system was tested for leakage with deionized water before each experiment. We
placed the rock substrate inside the chamber. Then, we introduced brine solution into the cell until completely cover the rock
substrate. To pressurize the system to 2000 psi, we applied N2 slowly into the chamber until reach the target pressure.
Temperature was controlled manually to the set point (122, 194, and 266F). For at least 20 h, the rock substrate left in brine
solution for equilibration. Captive drop of crude oil was injected through capillary tube to the rock substrate. To an extent, the
quality of the measurements depends very much on rock substrates heterogeneity. In this paper, we studied only advanced
contact angle at static conditions.
Zeta Potential (). ZetaPALS technique (Phase Analysis Light Scattering) was applied to measure zeta potential for brinesclays-rocks systems. The instruments electrodes coated by palladium and HeNe laser as a light source. It determined the
electrophoretic mobility of charged, colloidal suspensions. Polystyrene cuvette was used to hold 1 to 1.5 ml of the solution
sample. The mobility range for this instrument was 10-11 to 10-7 m2/V.s. The temperature was controlled from 42.8 to 212F.
Clay minerals and sandstone rocks were separated using a nest of standard sieves, where the lowest mesh size was 45 m. We
agitated the samples for 10 min on a sieve shaker. The particle size that used in this study was less than 45 m. All brines
solutions were prepared in 1 wt% of 4 clays (montmorillonite, kaolinite, illite, and chlorite) as well as two sandstone rocks
(Berea and Scioto). We sieved all particles. Then, we mixed them gently for 2 weeks using magnetic stirrer. Samples of
supernatant were transferred to a standard four-sided, 1 cm polystyrene cuvette. The mixture solution was shaked many times.
Particles were then extracted and transferred to the supernatant solution. We inserted a parallel plate electrode in the cuvette.
The instrument measured Electrophoretic mobility and calculated the potential. We selected an average of 5 runs using at
least 30 cycles of measurement for each run.
Results and Discussion

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Interfacial Tension. DSA instrument measured the interfacial tension of oil droplet in brine solution at different temperatures,
and pressure of 2000 psi. We inserted a small capillary tubing (size= 1/32 in.) inside the chamber before filled with seawater.
Then, compressed N2 was applied to pressurize the fluids at 2000 psi. To heat the system, we used temperature controller to
increase the set point to 122F. After that, oil droplet was injected at slow flow rate using a 500D syringe pump. Any
contaminations in the crude oil sample, for instance surfactant, scale and corrosion inhibitors can decrease IFT value
significantly with time. For that reason, we watched the IFT measurements with time for 30 min. Interfacial tension results in
Fig. 2 showed a slight decrease in IFT from 32.2 to 29.2 mN/m. These results suggested that the crude oil used in the present
study was not significantly contaminated with corrosion inhibitors and/or scale inhibitors. Some of these chemical may affect
interfacial tension between the crude oil and brines (Hirasaki and Zhang 2003).
Contact Angle. We examined three brines with different salinity ranges simulating a Middle East field at the same reservoir
temperature condition. Seawater injection into the reservoir can do some cooling effect to injection wells with time. For that
reason, three different temperatures were examined. Formation brine has a high ionic strength value more than 174 kppm and
that represented the highest salinity brine in this study. The other two brines are seawater and aquifer water. The total
dissolved solids in seawater are 54,680 ppm, where 5,436 ppm for aquifer water. Two sandstone outcrop rocks were dried
before testing them. In all tests, we used filtered crude oil with no dissolved gases (dead oil).
Berea Sandstone. We kept the rock substrates in a closed glass jar for 5 days, and aged in the oven at 194F. We shaked the
glass jar from time to time to ensure that fresh oil covered the rock substrates. Fig. 3 shows the contact angle of crude oilformation brine-Berea sandstone system at 122F and 2,000 psi. As expected, wettability of the solid surface was water-wet,
especially most of sandstone rocks are water-wet. Formation brine film covered the rock surface, which believed to
significantly affect the contact angle. The right (RA) and left angles (LA) reached equilibrium after 10 min. of contact time.
Both angles were too close, where RA and LA increased slightly and remained stable at 45 and 48.
We increased the system temperature from 122 to 194F, while maintain the pressure at 2,000 psi. Contact angles increased
gradually with temperature for both right and left sides, Fig. 4. Within 10 minutes, the new set temperature was reached.
Contact angles stabilized at 50 and 51.5 for RA and LA, respectively. Fig. 5 represents contact angles at 194F for 22 h.
The equipments software recorded the contact angles every 10 min. The recording time can be adjusted by the user. All
images were saved, and randomly checked to ensure similar results are obtained. The surface wettability remained unchanged
after increasing the temperature, but the angles increased up to 55. Increasing the cations can reduce the solubility of crude oil
surfactants and/or activate the adsorption of anionic surfactants onto the sandstone rock. Anderson (1986) reported multivalent ions
that have altered the wettability of oil-brine-silica systems from water to oil-wet condition. The ions included Ca+2, Mg+2, Cu+2, Ni+2,
and Fe+2.
Interfacial energies of solid/fluids and fluid/fluid interface are affected by different ionic strength solutions. Hence,
wettability and contact angle will be altered. We measured contact angle of crude oil-seawater-sandstone system at 122, 194,
270F and 2,000 psi. The contact angle at 122F decreased slightly to 38 and 37 over time duration of 30 min, Fig. 6. This
result suggests more water-wet surface as reducing the salinity from formation brine to seawater. At 194F, Fig. 7 displayed a
stability of contact angles at 51 and 49.5 after 19 h. The rock surface changed towards intermediate state as a result of heating
the fluids to a higher temperature. Furthermore, we increased the temperature to 271F to confirm that behavior. The results in
Fig. 8 showed an increase in the contact angle from to 54.8 and 55.8. After we adjusted the temperature to 271F, fluids/rock
system inside the chamber took 10 min. to reach to the set point. During two hours, contact angles results at 271F showed no
change with time, where LA and RA were 57 and 56.5.
We noticed the wetting characteristics of oil/aquifer water/rock system changed dramatically towards strong water-wet
case. For that reason, the oil droplet was unstable and remained on the rock surface for only 20 s. We recorded images
immediately to measure contact angles. The results showed to be 30 at 122F. Increasing the test temperature to 194F had no
significant effect on the angles, too. Right and left angles decreased slightly to 26.1 and 28.4, Table 3. The result suggests
that the oil/aquifer water/Berea sandstone system is water-wet at temperatures of 122 and 194F. It indicated that the water
film on the rock was stable and thus prevented any direct contact between the heavy ends in crude oil and the rock surface. For
that reason, the aquifer water resulted in a strong water-wetting surface.
Scioto Sandstone. In Scioto sandstone tests, we followed the same preparation and procedure for the rock substrates, except
one sample was aged for a day. The aging time for other Scioto samples remained unchanged at 5 days. Wettability of crude
oil/formation brine/Scioto rock behaved as an intermediate condition, Fig. 9. It indicates that conact angles depend on the
nature of the rock. Increasing the temperature to 194F showed no change on the surface wettability over time duration of 17 h.
Brine composition influenced the adsorption of insoluble components from crude oil on the rock surface (Xu et al. 2006).
Addition of more divalent cations in the formation brine resulted in more positive charges on rock surface. Hence, these
charges acted as attractive sites for the negative ends of polar components in crude oil (Xu et al. 2006). Xu et al. reported that
monovalent ions (Na+) can covered the rock surface and prevented the contact between the rock and crude oil. Therefore, it
may keep the interface neutrally charged, so that the thin wetting water film would not be disturbed by acids/bases in the crude
oil. The multivalent and monovalent cations acted oppositely on the adsorption and electrostatic of the thin wetting film. This
is the main reason behind having different wetting characteristics. Xu et al. (2006) reported that silica (quartz and Berea)

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adsorbed and transferred electrons very rapidly.

Seawater altered the Scioto rock surface towards water-wet condition at low and high temperature conditions. At 122F,
Fig. 10 showed some kind of stability at 68 and 76 for RA and LA during 75 min. Increasing the temperature further to 194F
displayed a slight decrease up to 7 in both angles. Therefore, surface wettability became more water-wet, especially after 15 h
of contact time as shown in Fig. 11. Aquifer water changed the rock wettability from water to intermediate wet at 122, 194 and
270F, Figs. 12 and 13. This is unexpected especially the aquifer water in Berea sandstone provided strong water-wet surface.
Using similar brines and crude oil, but different rock mineralogy can alter the surface wettability.
We examined the aging time effect on the wettability of oil-seawater-Scioto system. Aging the rock for one day displayed
more water-wet surface in comparison to 5 days at 122F. Surface wettability at 194F reached to intermediate state after 16 h
Contact angles at the beginning suggested weak water surface but that changed with time at HTHP condition. In conclusion,
aging Scioto rock at 194F and 2,000 psi for a day showed similar contact angles results to the 5 days aging test. We think
aging the sample at static condition changed the surface wettability within a certain time. Table 3 shows the contact angles
results for both Berea and Scioto sandstone experiments using three different brines and the same crude oil. Images of crude
oil-brines-sandstone systems at different salinity and elevated temperature conditions are described in Figs. 14 and 15.
Zeta Potential (). We tested aquifer, and seawater to determine the interactions between the clay minerals as well as
sandstones in high and low saline solutions. Deionized water was used in this set of experiments as reference for comparison.
Zeta potential results showed negative charges for all samples except chlorite in seawater, Fig. 16. We observed from this
figure that zeta potential is strongly dependent on the ionic strength and clays minerals. In addition, zeta potential of sandstone
poweders bahaved differently in DI water and other two brines. We believed different percentage of clays in sandstone
particles affected zeta potential results.
Zeta potential was negative even at high ionic strength such as seawater (54,680 ppm) except chlorite mineral. Fig. 16
shows the highest potential for Scioto sandstone in DI water (-28.4 mV). Kia et al. (1987) reported potential of Berea
sandstone in NaCl solutions at different pH. Zeta potential values varied from 0 to -10 mV at highest concentration of NaCl
solution. In our study, Berea sandstone particles produced negative potential results, which varied between -8.0 to -14.2 mV.
Scioto sandstone showed lower zeta potential in seawater than Berea sandstone. However, the opposite was noticed at the
aquifer and DI water systems. We noticed a direct releationship between ionic strength and potential for individual tests.
For seawater cases, the high salt concentration led to significant shrinkage of the electrical double layer. Hence, they are no
longer overlap and that increased potential values. Seawater as depicted in Fig. 16 decreased the zeta potential charges
toward zero charge. Adsorption of divalent cations on the particles belived to significantly reduce potenitl compared to
monovalent cations (Kia et al. 1987). We concluded that seawater produced stability to the clays and sandstone samples as
moving closer to the zero point of charge. Aquifer and DI water resulted in close potential values for illite and
montmorillonite. Aquifer water reduced the potential of chlorite particles by 50% compared to DI water. A similar behavior
(25%) in potential reported for kaolinite after using aquifer water. Table 4 described the mobility and potential results for
kaolinite in DI water. This is a good example of instrument reproducibility for 5 runs. The results were too close. Zeta
potential affected by pH, therefore, Table 5 showed all solution pH at 77F.
Conclusions
1. Injection water had a significant effect on rock wettability. This effect was found to be a function of rock mineralogy,
brine salinity and temperature.
2. Aging time impacted contact angle. This effect should be considered when measuring the contact angle of oil, brine
and rock system.
3. Surface charges of clays and sandstone particles are highly affected by the ionic strength of injection water.
Based on these results and conclusions, it is very important to assess the impact of injecting given water into a sandstone
reservoir. Our results indicated that injection of low salinity water may not change rock wettability into water-wet. Rock
mineralogy was also found to play key role which determine the effect of low salinity on contact angle. It is recommended to
use reservoir cores when examining the impact of a given injection water on the wettability of the rock.
Nomenclature
AFM
Atomic Force Microscope
cP
Centipoise
DSA
Drop Shape Analysis
IFT
Interfacial tension, mN/m
LA
Left angle,
pzc
Point of zero charge
RA
Right angle,
TDS
Total dissolved solids, ppm

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Greek Symbols

Zeta potential, mV
Acknowledgments
The authors would like to thank Petroleum Engineering Department in Texas A&M University for their support. M. Alotaibi
would like to acknowlege Saudi Aramco Company for Ph.D degree sponsorship. We thank Philip Jaeger from Eurotechnica
GmbH Company for useful discussion and ConocoPhillips Company for providing crude oil.
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Table 1: Mineralogy of Berea and Scioto sandstones

Mineral

Berea Sandstone*

Scioto Sandstone

Quartz

71

70

Plagioclase
Feldspar

5
2

Pyrite

traces

Mica+illite
Kaolinite

15

18
traces

Chlorite

14

Concentration, wt%

*Kia et al. (1987)

Table 2: Geochemical analysis of formation, aquifer, and seawater

Ions

Formation water

Seawater

Na+
Ca2+

54,400
10,600

Concentration, mg/l
16,877
664

Mg2+
Sr

Aquifer water
1,504
392

1,610

2,279

66

2+

107,000

31,107

2,577

176

193

192

Cl

HCO3
2

370

3,560

700

TDS, mg/l

174,156

54,680

5,436

SO4

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Table 3: Contact angles for Berea and Scioto sandstone rocks as a function of salinity and temperature
Rock & Oil
information

Brine Type

Aging Period

Temperature

Days

Left

Right

122

47.3 4.87

45.2 6.00

194

54.0 2.06

53.3 8.91

122

38.0 0.90

36.6 0.65

194

51.0 0.71

49.5 0.78

270

57.0 1.19

56.1 1.33

122

30.1

194

27.9 1.81

26.1

122

106.9 0.86

97.0 1.32

194

101.0 5.65

105.7 3.80

122

76.2 1.31

68.8 1.09

194

69.2 2.41

61.5 5.12

122

56.0 2.68

56.0 2.67

194

65.3 6.72

62.4 7.22

122

114.3 0.91

105.8 1.01

194

107.8 1.38

99.4 1.97

270

105.4 1.80

96.5 1.58

Berea sandstone/crude oil

Formation Brine
(174kppm)
Seawater
(54kppm)

5 days

Aquifer Water
(5436ppm)

Scioto sandstone/crude oil

Formation Brine
(174kppm)
5 days
Seawater
(54kppm)
1 day

Aquifer Water
(5436ppm)

5 days

Contact angles,

Table 4: Zeta potential and mobility results for Kaolinite in DI water at 77F

Table 5: pH of aqueous solution at 77F

Clays & Sandstone Rock
Montmorillonite
Kaolinite

De-ionized water
8.04

Aquifer water
7.64

Seawater
7.86

8.93

7.12

7.41

Chlorite

8.41

7.66

7.67

Illite
Berea sandstone

8.71
7.29

8.24
7.3

8.03
7.47

Scioto sandstone

7.29

7.45

7.84

Wettability mode

Water wet

Intermediate wet

Water wet

Intermediate wet

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N2 for Pressure

PC

Light source
Digital camera

Oil
Accumulator

Syringe pump

Fig. 1: Axisymmetric Drop Shape Analysis Instrument

35
33

IFT, mN/m

Seawater

31
Crude oil

29
27
Capillary tube, 1/32

25

Time, min.

Fig. 2: Interfacial tension (IFT) of crude oil droplet in seawater at temperatures and pressure of 122F and 2000 psi

10

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60

Contact Angle,

55
50
45
40

Left angle
Right angle

35
30
0

10

15

20

25

30

35

40

45

Contact time, min.

Fig. 3: Contact angles of crude oil/formation brine/Berea sandstone at T= 122F, and P= 2000 psi

60

Contact Angle,

55
50
45
40
Left angle
Right angle

35
30
130

140

150

160

170

180

190

200

Temperature, F

Fig. 4: Contact angles of crude oil/formation brine/Berea sandstone as a function of temperature 122194F
60

Contact Angle,

55
50
45
40

Left angle
Right angle

35
30
0

10
15
Contact time, h

20

25

Fig. 5: Contact angles of crude oil/formation brine/Berea sandstone at 194F for 22 h

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11

60

Contact Angle,

55
Left angle

50

Right angle
45
40
35
30
0

10

15

20

25

30

35

Contact time, min.

Fig. 6: Contact angles of crude oil/seawater/Berea sandstone at T= 122F, and P= 2000 psi
60

Contact Angle,

55
50
45
40

Left angle
Right angle

35
30
0

10

15

20

Contact time, h

Fig. 7: Contact angles of crude oil/seawater/Berea sandstone at T= 194F, and P= 2000 psi
60

Contact Angle,

55
50
45
40

Left angle

35

Right angle

30
150

170

190

210

230

250

270

290

Contact ime, min.

Fig. 8: Contact angles of crude oil/seawater/Berea sandstone as a function of temperature 190271F

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120
Left angle

Contact Angle,

115

Right angle
110
105
100
95
90
0

10

15

20

25

30

35

40

Contact time, min.

Fig. 9: Contact angles of crude oil/formation brine/Scioto sandstone at T= 122F, and P= 2000 psi (5 days aging)

80

Contact Angle,

75
70
65
60

Left angle

55

Right angle

50
0

10

20

30

40

50

60

70

Contact time, min.

Fig. 10: Contact angles of crude oil/seawater/Scioto sandstone at T= 122F, and P= 2000 psi (5 days aging)
80
Left angle

Contact Angle,

75

Right angle

70
65
60
55
50
0

10

15

20

25

Contact time, min.

Fig. 11: Contact angles of crude oil/seawater/Scioto sandstone at T= 194F, and P= 2000 psi (5 days aging)

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13

120

Contact Angle,

115
110
105
100

Left angle

95

Right angle

90
0

10

20

30

40

50

Contact time, min.

Fig. 12: Contact angles of crude oil/aquifer water/Scioto sandstone at T= 122F, and P= 2000 psi (5 days aging)
120
Left angle

115

Contact Angle,

Right angle
110
105
100
95
90
0

10

15

20

25

Contact time, h

Fig. 13: Contact angles of crude oil/seawater/Scioto sandstone at T= 194F, and P= 2000 psi (5 days aging)

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Formation Brine (174,156 ppm) [aging time: 5 days]

T = 122F, t= 10 s

T = 122F, t= 41 min.

T = 194F, t= 10 s

T = 194F, t= 22 h

Seawater (54,680 ppm) [aging time: 5 days]

T = 122F, t= 10 s

T = 122F, t= 32 min.

T = 194F, t= 10 s

T = 194F, t= 19 h

Fig. 14: Crude oil/brine/Berea sandstone images at different temperatures and time intervals (P = 2,000 psi)

Formation brine (174,156 ppm) [aging time: 5 days]

T = 122F, t= 10 s

T = 122F, t= 17 h

Seawater (54,680 ppm) [aging time: 1 day]

T = 194F, t= 10 s

T = 194F, t= 19 h

Aquifer water (5,436 ppm) [aging time: 5 days]

T = 194F, t= 10 s

T = 194F, t= 20 h

Seawater (54,680 ppm) [aging time: 5 days]

T = 194F, t= 10 s

T = 194F, t= 22 h

Fig. 15: Crude oil/brine/Scioto sandstone images at different temperatures and time intervals (P = 2,000 psi)

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15

35
25
De-ionized water

Aquifer water

Seawater

Zeta potential, mV

15
5
-5
-15
-25
-35
Montmorillonite

Kaolinite

Chlorite

Illite

Bereasandstone

Fig. 16: Variation of zeta potential for different clays and sandstone particles

Scoitosandstone