OTC-26068-MS

Wettability Alteration of Heavy-Oil/Bitumen Containing Carbonates Using

Solvents, high pH Solutions and Nano/Ionic Liquids
Nahai Cao,M. Almojtaba Mohammed, and Tayfun Babadagli, University of Alberta

Copyright 2015, Offshore Technology Conference

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Abstract
Capillary imbibition tests are commonly applied to measure wettability alteration potential of chemicals.
However, these tests are exhaustive, time-consuming, expensive, and the underlying physics of the
alteration process from a surface chemistry point of view is often limited and/or unexplained. Contact
angle measurement is a quicker and more feasible screening tool to assess the emerging wettability
modifiers. They also provide visual data on the mechanics of the wettability alteration process. This paper
focuses on contact angle measurements as a mean to evaluate the wettability alteration on mineral plates
and porous rock samples. Imidazolium ionic liquids were tested at different concentrations. To study the
effect of pH on the wettability, sodium chloride and sodium borate were used at different concentrations.
The composition of divalent ions was varied due to their possible use with low/high salinity water as
wettability alteration agent. Unmodified and surface modified silica, zirconium, and alumina nanoparticles
were also tested.
Contact angle measurements were performed initially on mica, marble, and calcite plates. Experiments
were repeated on polished surfaces of Berea sandstone, Indiana limestone, and -cleaned- Grosmont
carbonate cores. Oils (pure and solvent mixed crude oils) with different viscosities and densities were used
to test the effect of oil type on the process. The images were obtained by an SLR camera at different
temperatures ranging from 25 to 80°C. By testing with different concentrations, the optimum chemicals
were found for different mineral plates/porous rock systems. Then, the results were cross-checked with the
imbibition tests performed on the same samples to validate the contact angle measurement observations.
Thermal stability tests were also performed in case of their use during or after a thermal method. For
the thermal stability tests, contact angle experiments were conducted in a high pressure and high
temperature (up to 200°C) cell. It was shown that certain ionic liquids and nanofluids are stable at high
temperatures and can be efficiently used at low concentrations.
Keywords: Heavy-oil/bitumen · wettability alteration · solvents · ionic/nano liquids · high pH solutions · contact angle
measurements

Introduction
Unfavorable wettability is one of the problems associated with extracting heavy-oil/bitumen oil from
fractured carbonates, which typically hinders capillary imbibition transfer and decelerates gravity drainage
2 OTC-26068-MS

rate. It is essential, therefore, to use methods to alter wettability during enhanced oil recovery applications.
Using chemicals in addition to water is one of the ways to achieve this. Earlier studies tested surfactants,
high pH solutions, low/high salinity water, and nanofluids as wettability alteration agents on different
types of rock systems containing light oil. Studies on the wettability alteration for heavy-oil systems are
very limited.
For light oil systems, surfactants have been used to alter the wettability of oil-wet rocks but this is a
rather slow process (Standnes and Austad 2000; Babadagli et al. 2005; Stoll et al. 2008). Obviously, the
problem becomes more challenging as the oil becomes heavier. Babadagli (2002) tested the imbibition of
surfactant solutions into weakly water-wet limestone cores saturated with heavy oil and observed an
increase in ultimate oil recovery but the recovery rate was negatively affected by surfactant addition.
Beyond these issues, the stability of these chemicals at reservoir conditions limits their use.
These negative effects entailed the search of different chemicals for wettability alteration during
heavy-oil recovery (Mohammed 2014; Mohammed and Babadagli 2015). One option is nanofluid
dispersion of nanoparticles in base fluids (Yu and Xie 2012). A number of studies showed that these
relatively new agents are able to alter the wettability of oil-wet carbonates (Karimi et al. 2012) and
sandstones (Ju and Fan 2009; Giraldo et al. 2013). Specifically, alumina, silica, and zirconium nanofluids
were found to be effective in changing the characteristics of sandstones and carbonates. However, studies
on the effect of temperature on wettability alteration are rare.
Through a micro scale study, Maghzi et al. (2012) showed that dispersed silica nanoparticles in water
solution were able to decrease the contact angle from 100° to 0°. The suggested mechanism was the
adsorption of silica nanoparticles at the interface of silica-oil and eventually the reduction of interfacial
tension and thereby contact angles (Ju et al. 2012). Also, Zhang et al. (2014) showed that hydrophilic silica
nanoparticles can imbibe into Berea sandstone core. Their results revealed that nanofluid made of silica
displaced nearly 55% of oil in place; displacement with de-ionized water was only 5%.
Nanofluids were also used in carbonate experiments. Karimi et al. (2012) conducted contact angle
measurement and imbibition tests using zirconium nanofluids on oil-wet carbonates. Zirconium nanofluid
decreased water contact angle significantly; i.e., reversed the wettability of carbonate. The spontaneous
imbibition tests yielded 60% OOIP recovery; OOIP with distalled water was less than 5%.
Ionic liquids are defined as salts with low melting temperature (Wasserscheid and Keim 2000).
Although they were tested to separate bitumen from oil sand (Painter et al. 2009; Williams et al. 2010;
Painter et al. 2010), their potential use for wettability alteration is limited. Mohammed and Babadagli
(2014) found that ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate BMIM BF4 is able to
imbibe spontaneously into oil-wet limestone.
Contact angle is a direct manifestation of the wettability of surfaces. It can provide a fast and efficient
tool to evaluate the wettability alteration by new chemical solutions. In this work, we used contact angle
measurement technique to confirm the results from previous imbibition tests (Mohammed and Babadagli
2014) and provide more data on the wettability alteration capabilities of nanofluids and ionic liquids under
high pressure and high temperature. Contact angle measurements were performed on two groups of solid
surfaces. The first group includes sandstone experiments (mica plate and Berea sandstone), the second
contains experiments conducted on carbonates (marble plate, calcite plate, Indiana limestone, and
Grosmont cores). These mineral or rock surfaces (which may be water-wet in nature, like sandstones),
were aged in heavy oil for about one month to render them oil-wet. It is believed that surface active
materials from crude oil adsorbs on sandstone and carbonate surfaces over time and thus changes their
wetting characteristics. Aging surfaces were used to perform six groups of experiments to test the
influence of different parameters, including chemical type, chemical concentration, solvent concentration,
temperature, and pressure.
OTC-26068-MS 3

Methodology

Static contact angle measurement was used to explore the abilities of different chemicals to alter the
wettability on different surfaces (Figure 1). In these experiments, the contact angle is defined as the angle
through the denser phase (water), which is between the surface and water. The contact angle photos were
captured by a digital SLR camera. For higher pressure and higher temperature experiments, an IFT device
was used to perform experiments (Figure 2).

Figure 1—Static contact angle measurement.

Figure 2—IFT device for high pressure and high temperature experiments.

The above mentioned tests were performed at ambient conditions. Chemicals yielding strong wettability
alteration were further tested at higher temperature and pressure conditions. Temperature was raised up
to steam injection conditions, however, to keep the water in liquid phase, pressure was increased
accordingly. In conjunction with those experiments, thermal stability tests were also conducted on
selected chemicals by visually inspecting the clarity and precipitation of chemical solutions under high
temperature and high pressure.
Experimental Design and Setup
Chemicals
Including the base case (tap water), 13 chemicals were tested (Table 1). For the high salinity solution and
high pH solution cases, the concentration was 2.5 % wt. For the nanofluid and ionic liquid cases, the
4 OTC-26068-MS

concentration was 1 % wt. These values were selected based on previous imbibition tests (Mohammed and
Babadagli 2014).

Table 1—List of tested chemicals and concentrations used in this research.

Chemical type Chemical name Concentration

1. Base Case Tap Water –

2. Low salinity solution Distilled water (H2O) –
3. High salinity solution Sodium chloride (NaCl) 2.5% wt
4. High pH solution 1 Sodium hydroxide (NaOH) 2.5% wt
5. High pH solution 2 Sodium metaborate (NaBO2) 2.5% wt
6. Nanofluid 1 Silicon Oxide (SiO2) 1% wt
7. Nanofluid 2 Aluminum oxide (Al2O3) 1% wt
8. Nanofluid 3 Zirconium oxide (ZrO2) 1% wt
9. Ionic liquid 1 1-Ethyl-2,3-dimethylimidazolium tetrafluoroborate 1% wt
10. Ionic liquid 2 1-Ethyl-3-methylimidazolium tetrafluoroborate 1% wt
11. Ionic liquid 3 1-Butyl-3-methylimidazolium tetrafluoroborate 1% wt
12. Ionic liquid 4 1-Butyl-2,3-dimethyl-imidazolium tetrafluoroborate 1% wt
13. Cationic surfactant C12TAB 1% wt

Solid Surface
Two types of surfaces were used to represent sandstones and carbonates:
● Group 1—Sandstone: 1. Mica plate, 2. Berea sandstone;
● Group 2—Carbonates: 1. Marble plate, 2. Calcite plate, 3. Indiana limestone, 4. Grosmont
carbonates.
Studying multiple carbonate types is important to investigate the effect of rock mineral composition.
Mica plate was used as the base case for sandstone experiments while marble plate was used as the base
case for carbonates. All mineral or rock samples were carefully polished and then aged in heavy oil for
one month until they were oil-wet. Then, the solid samples were rinsed by toluene carefully, without
damaging the oil-wet surface.
Oil Sample
The oil sample used in this research was heavy oil obtained from western Alberta. The viscosity and
density of oil were 15,172 cp and 0.97 g/cc, respectively.

Figure 3—Experimental setup for room temperature and atmospheric pressure experiments.
OTC-26068-MS 5

Six groups of experiments were performed to study the effects of different parameters:
● Group 1—Effect of different chemicals: Tests done on various types of rock of surfaces.
● Group 2—Effect of different concentrations: Only chemicals with better performance from the
base case were selected and applied on Indiana limestone and Grosmont carbonates since they
represent the most challenging (strongly oil-wet) rock type.
● Group 3—Effect of solvent: Determines the solvent effects on the wettability alteration. Heavy oil
was mixed with a solvent at variable concentrations (from 0% to 50%) to mimic chemical injection
conditions after solvent injection. Only selected chemicals and rock types were tested in this part.
● Group 4—Effect of temperature: Measurements were taken under atmospheric pressure. The
temperature range was from room temperature to 80°C. Only selected chemicals and rock types
were tested in this part.
● Group 5—Effect of high pressure (up to 500 psi) and high temperature (up to 200°C): Experi-
ments performed using an IFT setup. While no pressure was applied in Group 4 experiments,
pressure was increased in Group 5 while increasing the temperature according to the values given
in Table 2 to keep water in the liquid form. The applied pressure was then decreased to measure
the contact angle under steam conditions (steam-oil system).

Table 2—Pressure value at different temperatures.

Pressure (psi) Temperature (°C)

14.7 25
30 60
50 90
200 120
350 150
400 180
500 200

● Group 6 —Effect of thermal stability: The best performing chemicals were tested in case they are
applied at steam conditions. The purpose of these experiments was to test if the interested
chemicals were stable at high pressure and high temperature. More emphasis was given to ionic
liquids and nanofluids since they are relatively newer chemicals to be applied in heavy-oil
recovery at thermal conditions.
Results and Analysis
Contact angle, as it is generally agreed, less than 90° indicates water-wetness state of surface while values
larger than 90° reflect oil-wetness. During this study, different types of aged sandstone samples showed
water contact angle ranging from 55° to 70°. This indicates that sandstone is weakly water-wet for the
heavy-oil/water system used. On the other hand, most of the carbonate samples tested exhibited water
contact angle more than 100°, which is a clear sign of oil-wetness.
The negatively charged heavy ends in crude oil are strongly attracted to carbonate surface which is
known to be positively charged under typical pH (⬃7). Sandstone is negatively charged under this pH
range and therefore maintains a water-wet state unless it is contaminated with clay and other fines that are
mixed-wet. In this case, sandstone wettability becomes less water-wet.
Effects of Chemical Type and Surface
Figure 4 shows the change of contact angles on a mica plate by different chemical solutions. It is clear
that NaBO2, ionic liquids 1, 3, and 4, have a better performance than other chemicals as they reduce the
6 OTC-26068-MS

contact angles and hence make the surfaces more water-wet. Since mica plates were used as the base case
for sandstone, we selected three chemicals (NaBO2, ionic liquid 3 and 4) and tested them on Berea
sandstone. The results displayed in Figure 5 show that NaBO2 can significantly reduce the contact angle
from 65° to nearly 30°.

Figure 4 —Results on mica plates.

Figure 5—Results on Berea sandstone.

Being able to reduce the contact angle on both mica and Berea sandstone is evidence that high pH
solution can alter the wettability of sandstone to a more water-wet state. Buckley et al. (1989) discussed
the effect of brine pH on contact angle and reported that advanced contact angle was reduced on glass and
mica when the pH was increased from 4 to 8. A deposition of complex structure particles was captured
by atomic-force microscopy AFM when low pH solution was used. These particles were removed at high
pH values. Note that they increased the concentration of NaCl in the solution while increasing the pH. In
our experiment, we also observed a positive response when NaCl was used. Similarly, Hamouda and
Valderhaug (2014) reported the release of clay fines from sandstone as pH increases. The liberation of
OTC-26068-MS 7

clay, which is regarded as an oil-wetting material in sandstone, is a possible reason for the improvement
in water-wetness of sandstone at high pH.
Ionic liquid is believed to reduce the adhesive forces between sands and bitumen (Painter et al. 2010).
By doing so, the water contact angle is reduced and the surface becomes more water-wet.
In summary, ionic strength and pH played an important role in the wettability of sandstone.
We used marble plates as the base case for carbonates (Figure 6). NaBO2and ionic liquid 4 were the
best chemicals to change the surface from oil-wet to water-wet and therefore, were selected them for
further tests on calcite plates, Indiana limestone, and Grosmont samples (Figure 7). It is obvious that
Grosmont carbonates are more oil-wet than the other two carbonate surfaces. Injecting high pH solution
is known to decrease the positive charge of carbonate. Hence, the surface of carbonate becomes less
attractive to negatively charged components on the crude oil and eventually these components are
removed rendering the surface more water-wet. The mechanism of wettability alteration by ionic liquids,
on the other hand, is not fully understood. Mohammed and Babadagli (2015) suggested that ionic liquid
may reduce the adhesive forces between carbonate surface and oil components deposited on the rock.

Figure 6 —Results on marble.

Figure 7—Results on calcite, Indiana limestone and Grosmont carbonate.

8 OTC-26068-MS

Compared with imbibition tests reported by Mohammed and Babadagli (2014), the ionic liquid 4 and
NaBO2 successfully increased the oil recovery by changing the wettability (Figure 8). For ionic liquid 4,
the contact angle reduced from about 103° to 51° and the oil recovery increased from about 2% to 37%
OOIP. Similarly, the NaBO2 increased the oil recovery to 34% OOIP.

Figure 8 —Results compared with the imbibition tests.

Oil recovery by spontaneous imbibition of NaBO2 and ionic liquid 4 indicates that either negative
capillary pressure, which retains the oil in porous medium, is weakened or is converted to become
positive. The reduction of contact angle to less than 90° is directly related to the balance of thermody-
namic equilibrium between water (w), oil (o) and solid (s). The agreement in results between contact
angles and imbibition tests for high pH solutions and ionic liquids was analyzed to understand the
mechanism of wettability alteration in both chemicals.
There are two conditions that need to be satisfied in order for a chemical solution to spontaneously
imbibe in a previously oil-wet system:
1. Contact angle needs to be reduced to less than 90°;
2. IFT needs to be high enough to support capillary pressure.
Considering the representation of contact angle in Figure 1, we can define cos␪ by Young’s equation
as follows:
(1)

(2)

The Young–Laplace equation gives the following:

(3)

In Eq. 2, (␴SW - ␴SO) reflects the affinity of solid surfaces to oil or water. Oil-wet surfaces have more
affinity toward being oil and therefore will display a higher water-contact angle. The wettability alteration
of a surface implies that ␪ is higher than 90°. At this range of contact angles, cos␪ is negative and ␴SW
OTC-26068-MS 9

⬍ ␴SO. To reduce the contact angle below 90°, the surface must have higher affinity water than oil; i.e.
␴SW ⬍ ␴SO.
As discussed, high pH solution reduces the positive charge on carbonate and thus becomes less
attractive to heavy end components in oil. The mechanism of wettability alteration ionic liquid is thought
to be the reduction of adhesive forces between crude oil and carbonate surfaces. By affecting the
electrostatic forces between rock-oil-water interfaces, these chemical can maximize the value of ␴SW until
it exceeds the value of ␴SO.
According to Eq. 2, there is another factor that must be considered for the first condition: the value of
oil-water interfacial tension needs to be brought down to reduce the contact angle. Once the first condition
is satisfied, the surface becomes water-wet; however, no capillary imbibition occurres unless the second
condition is maintained. According to Eq. 3, capillary forces require relatively high oil-water interfacial
tension, which partially contradicts the first condition. Obviously, this means that interfacial tension has
to be reduced but no less than what is required to support capillary pressure, enough to draw the oil out
of the porous medium.
Therefore, it is believed that the ability of the chemical solution to reduce the contact angle and
spontaneously imbibe into previously oil-wet system indicates an optimum interplay between these two
conditions, as demonstrated by NaBO2 solution and ionic liquid 4.

Effects of Concentration
As shown in Figures 9a and b, higher concentration leads to smaller contact angle for both NaBO2 and
ionic liquid 4 and, consequently, higher ability of wettability alteration. On Grosmont carbonates, the
change in the contact angle is less critical compared to Indiana limestone, especially at higher concen-
trations.

Figure 9a—Concentration effects on contact angle (ionic liquid 4).

10 OTC-26068-MS

Figure 9b—Concentration effects on contact angle (NaBO2).

Effects of Solvent Addition

Dilution of heavy-oil might be needed preceding solvent injection during EOR processes, especially for
bitumen (Al-Bahlani and Babadagli 2009; Pathak et al. 2012). To test the effect of solvent concertation
a series of measurement were performed using variable solvent concentrations. The solvent used in this
experiment is heptane. The results for three different concentrations of solvent are shown in Figure 10.
The base case is 0% solvent, followed by 30% and 50% solvent. Figure 11 is the visual proof of
wettability alteration by addition of solvent. The contact angle decreases from about 80°C to about 40°C
for both NaBO2 and ionic liquid solution.

Figure 10 —Solvent (Heptane) effects on contact angle (Grosmont carbonate).

OTC-26068-MS 11

Figure 11—Change in contact angle at different solvent concentration (Ionic liquid 4, Grosmont carbonates).

Effects of High Temperature (Up to 80°C at Atmospheric Pressure)

Ionic liquid 4 and NaBO2 were chosen to be tested on Grosmont carbonates and Indiana limestone (Figure
12). Measurements were taken at 25, 60 and 80°C. The contact angle was nearly stable over this range
of temperature for the Grosmont samples. Nearly 10° change was observed for the Indiana limestone case
(to more oil-wet) when it is increased to 60°C.

Figure 12—Temperature effects (25°c to 80°c) on contact angle.

Effects of High Temperature and High Pressure (Up to 200°C, 500 psi)
A set of contact angle measurement experiments were performed at elevated temperatures, typically under
steam injection conditions, using the cell shown in Figure 2. First, the effect of increasing temperature was
tested keeping the water in liquid phase by increasing the pressure. Then, keeping the temperature
constant, pressure was released to measure the wettability under the steam conditions.
The resulted contact angles from increasing the temperature up to 200°C are shown in Figures 13a and
13b. Pressure increased automatically with the growth of temperature. For comparison, we set the same
pressure value for different chemicals at the same temperature (Table 2). It is obvious that contact angle
decreases (more water-wet) when the temperature is increased for most selected chemicals. This was
expected as interfacial tensions decreases at high temperature which results in lower contact angles.
12 OTC-26068-MS

Figure 13a—Contact angle under high pressure and high temperature (marble).

Figure 13b—Contact angle under high pressure and high temperature (Grosmont carbonates).

The behavior of chemicals added at this temperature range is critical. As shown in Figure 14, nanofluid
1 precipitated at higher temperature (above 120°C). It is important to consider the precipitation of
nanofluid at reservoir condition to avoid the complication of permeability reduction. Further tests will be
discussed in the next section to clarify the solubility-temperature relationship for the chemicals used.
OTC-26068-MS 13

Figure 14 —Images of marble plate soaked into nanofluid 1 solution at elevated temperatures.

For experiments on Grosmont carbonates (Figure 13b), all chemicals were able to change the
wettability from oil-wet to water-wet under room temperature except the cationic surfactant (C12TAB).
The contact angle increased back to 122° when the temperature rose to 60°C. This can be attributed to the
thermal instability of C12TAB. Standes and Austad (2000) observed that the imbibition rate of surfactant
solution into oil-wet carbonate core increases to double when the temperature is increased from 40°C to
70°C. They concluded that imbibition is enhanced at high temperature due to the increased diffusion rate.
Note that they used light oil, which is composed of 60% heptane, to saturate the core sample. According
to the finding in Figure 13b, imbibition should be reduced at high temperature as C12TAB becomes
unstable and inefficient. The enhancement of imbibition at high temperature may be attributed to other
mechanism such as the contribution of the gravity forces when the viscosity of oil and the interfacial
tension of oil-water are reduced at high temperatures. This result points to the importance of performing
thermal stability tests before conducting spontaneous imbibition tests under high temperatures.
Another observation is that ionic liquids and nanofluids were stable under these conditions. Ionic liquid
4 and nanofluid 3 in particular showed great stability under high pressure and high temperature. The
second part of these experiments was performed to study the pressure effect. The temperature was kept
constant at 200°C and pressure was decreased from 500 psi to 300 psi gradually. As shown in Figures
15 and 16, pressure played a less important role in wettability alteration. The contact angle was nearly
constant for all tested chemicals under this pressure range.

Figure 15—Effects of pressure on contact angle (200°C, Grosmont carbonates)

14 OTC-26068-MS

Figure 16 —Effects of pressure on contact angle (200°C, marble).

To investigate the effect of phase change on contact angle, pressure was decreased slowly from 300 psi
while the temperature was kept at 200°C. When the pressure decreased to the steam pressure some bubbles
appeared. The contact angle was observed to decrease when more steam appeared (Figure 17). As
temperature was further decreased, more steam was generated and visualization became problematic to
capture any image for contact angle measurement. Figures 18 and 19 provide the summary of results for
phase change. It can be seen that this phenomenon is more obvious on Grosmont carbonates.

Figure 17—Example photos for phase change effects.

OTC-26068-MS 15

Figure 18 —Effects of phase change on contact angle (Grosmont carbonate).

Figure 19 —Effects of phase change on contact angle (marble).

Thermal Stability Tests

A group of experiments were conducted to visually test if the selected chemicals were stable under high
temperature (up to 90°C). All seven chemicals were put in a glass jar and heated in oven. The stability
of the chemicals was monitored at 25, 60 and 90°C. As shown in Table 3, most of the chemicals except
zirconium nanofluid (Figure 20) were stable under high temperatures. The solution of zirconium
nanofluid was not stable even when the concentration was decreased from 1.0 to 0.5% wt. In porous
16 OTC-26068-MS

media, excessive precipitation may damage the permeability and thus could affect the oil recovery
negatively.

Table 3—Summary results for thermal stability tests.

Chemical name 25°C 60°C 90°C

Ionic liquid 4 (1% wt) Transparent Transparent Transparent

NaBO2 (2.5% wt) Transparent Transparent Transparent
Nanofluid 1 (1% wt) Transparent Transparent Transparent
Nanofluid 2 (1% wt) White White White
Nanofluid 3 (1% wt) White Light white/Precipitation Light white/Precipitation
Nanofluid 3 (0.5% wt) White Light white/Precipitation Light white/Precipitation
Cationic surfactant (C12TAB, 1% wt) Transparent Transparent Transparent

Figure 20 —Photos of thermal stability tests.

Conclusions
1. Wettability alteration results obtained through imbibition tests was verified by static contact angle
measurements. It was shown that for given chemicals and temperature ranges, quicker contact
angle measurements could be used to gain insight into the degree of wettability alteration for
heavy-oil systems.
2. Ionic liquid 4 and high pH NaBO2 solution could effectively alter the wettability of sandstone and
carbonate. Higher chemical concentration improved the contact angle. The lowest contact angles
were found at 1 % wt concentration of NaBO2 and ionic liquid.
3. Higher temperature rendered the solid surface more water-wet. The effect of temperature was not
OTC-26068-MS 17

significant in the temperature 25°C to 80°C range as they were in the 25°C to 200°C range.
4. Adding solvents resulted in a better wettability alteration. For NaBO2, adding 25% solvents can
make the contact angle decrease by 19° from 80°C to 61°C. 50% solvent addition can further
reduce it by about 20°. Similar values of contact angles were obtained for ionic liquid 4, as well.
5. The contact angle decreased during the phase change (liquid to vapor). This phenomenon was
more obvious on Grosmont carbonates. Before the phase change, the pressure had very limited
effect on the contact angle. However, during the phase change, the contact angle decreased by
approximately 50° for NaBO2 on Grosmont carbonates. Similarly, nanofluid 1 and ionic liquid 4
decreased the contact angle by about 20°.
6. Cationic surfactant (C12TAB) was not stable under high temperature. Increasing the temperature
of C12TAB solution increased the contact angle and consequently the wettability of surfaces was
reverted back to oil-wet. Oppositely, both ionic liquid and nanofluid were stable at high temper-
atures.
7. Nanofluid 3 (zirconium oxide) was not stable (precipitation occurred) at temperature range of
25°C to 90°C. Nanofluid 1 (silicon oxide) precipitated at much higher temperature (120°C). Ionic
liquid 4 and NaBO2 were stable under high pressure and high temperature condition.

Acknowledgments
This research was conducted under the third author’s (TB) NSERC Industrial Research Chair in
Unconventional Oil Recovery (industrial partners are CNRL, SUNCOR, Petrobank, (Touchstone Exp.),
Sherritt Oil, APEX Eng., Husky Energy, Saudi Aramco and PEMEX). We gratefully acknowledge these
supports. We also would like to thank Lixing Lin and Georgeta Istratescu for their technical support
during experiments.

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