Advances in Colloid and Interface Science 220 (2015) 54–77

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Advances in Colloid and Interface Science

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

Historical perspective

Wettability alteration: A comprehensive review of materials/methods

and testing the selected ones on heavy-oil containing oil-wet systems
Mohammedalmojtaba Mohammed ⁎, Tayfun Babadagli
University of Alberta, Canada

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

Available online 5 March 2015 Changing the wetting state of materials is a growing field of research in many areas of engineering and science. In
the oil industry, the term wettability alteration usually refers to the process of making the reservoir rock more
Keywords: water-wet. This is of particular importance in naturally hydrophobic carbonates, fractured formations, and
Wettability alteration heavy-oil systems. This shift in wettability enhances oil recovery in oil-wet and weakly water-wet reservoirs
Heavy-oil and eventually increases the ultimate oil recovery.
Solvent injection
For wettability alteration, two methods have been traditionally used: Thermal and chemical. Although many
attempts have been made on reviewing the advancement of research in certain aspects of wettability, a compre-
hensive review of these techniques, especially in terms of the classification of the chemicals used, has been
ignored. In this paper, we begin with this review and provide the past experience of wettability alteration in
sandstone and carbonate reservoirs. More than 100 papers were reviewed extensively with an in-depth analysis
of different methods suggested in literature. The areas of controversy and contradicted observations are
discussed. The limitations and the applicability of each method were analyzed. Concerns on up-scaling laboratory
findings to field scale are also addressed. The most promising potential methods are identified and their critical
conditions highlighted.
At the end, a selection of reviewed methods is validated experimentally for one of the most challenging cases:
Extra heavy-oil and bitumen recovery from fractured-strongly-oil-wet carbonates. Berea sandstone (aged to be
oil-wet) and Indiana limestone samples were saturated with heavy oil (3600 cp). Next, the process was initiated
by soaking the cores into solvent (heptane or diluent oil) and the oil recovery was estimated using refractive
index measurements. Note that solvent was selected to dilute the oil and recover a considerable amount of oil
as any chemical or thermal methods yielded inefficiently low recoveries. After the solvent phase, the samples
were exposed to wettability alteration through selected chemicals at different temperature conditions through
spontaneous imbibition tests to recover more oil and retrieve the solvent diffuse into the sample back. The
most promising wettability alteration agents for each type of rock were marked and optimal application condi-
tions (temperatures, injection sequence) were identified. Selected wettability alteration chemicals were finally
tested on the bitumen (5–9° API-1,600,000 cp) containing Grosmont carbonate sample from Alberta, Canada.
It is hoped that this review fills in the gap in the area of wettability alteration processes by summarizing, critically
analyzing, and testing the methods suggested in the literature.
© 2015 Elsevier B.V. All rights reserved.

Contents

1. Why wettability alteration? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

2. The mechanisms of wettability alteration by enhanced oil recovery (EOR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
3. Interaction of crude oil/brine/rock in petroleum reservoir . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.1. Carbonates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
3.2. Sandstone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4. Wettability alteration measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.1. Contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2. Spontaneous imbibition (SI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

⁎ Corresponding author at: Department of Civil and Environmental Engineering, School of Mining and Petroleum Engineering, 3-112 Markin CNRL-NREF, Edmonton, AB T6G 2W2,
Canada.
E-mail address: [email protected] (T. Babadagli).

http://dx.doi.org/10.1016/j.cis.2015.02.006
0001-8686/© 2015 Elsevier B.V. All rights reserved.
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 55

4.3. Surface imaging tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

4.4. Zeta potential measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
5. Capillary and gravitational forces as an indicator of the state of wettability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
6. Chemically induced wettability alteration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
6.1. Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
6.2. Alkaline-anionic surfactant mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6.3. High pH solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
62
6.4. Low salinity water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
62
6.5. Smart water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.6. Nanofluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.6.1. Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.6.2. Stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6.6.3. Wettability alteration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
7. Wettability alteration at high temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
8. Potential wettability modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
8.1. Microbial method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
8.2. Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
9. Opportunities and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
9.1. Surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
9.2. High pH solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
9.3. Nanofluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
9.4. Thermal methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
9.5. Smart water and low salinity water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
10. Wettability alteration in heavy-oil containing oil-wet fractured reservoirs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
10.1. Sandstone case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
10.2. Limestone case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
10.3. Bitumen containing carbonate samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
11. Conclusions and remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

1. Why wettability alteration? agreement that wettability alteration of strongly oil-wet reservoir is fa-
vorable, no conclusive statements can be made about the extent of the
Wettability of surfaces is preferred to be hydrophilic or hydrophobic alteration that would lead to the optimum oil recovery.
depending on the type of the application. Self-cleaning surfaces, for In the following discussion, we analyze the balance of capillary and
example, are designed to be hydrophobic. This can be achieved using gravitational forces during the wettability alteration. Consider a porous
different techniques such as increasing the roughness of these surfaces medium wettability that is altering from strongly oil-wet state to
[92]. Another methodology to modify surface wettability is coating neutral-wet state and then to strongly water-wet state. This shift in
these surfaces with low surface energy materials that can be used to wettability may enhance oil recovery by different mechanisms:
render them super-hydrophobic [33]. In petroleum reservoirs, the
term wettability alteration usually refers to the process of restoring 1. While the wettability of reservoir is shifting from strongly oil-wet to
the original reservoir wettability, which is presumed to be water-wet. neutral wet state, capillary forces that retain oil in porous medium
The target of this restoration treatment is the unrecoverable oil by are reduced and then eliminated. The gravitational forces may start
conventional waterflooding. An early study showed that altering the playing a role on recovery at this stage. In this range, water contact
wettability toward more water-wet increases enhanced oil recovery angle decreases but does not drop below 90°. While wettability alter-
[111]. In gas condensate reservoirs, wettability alteration induces a ation may not have a direct impact on oil recovery at this stage, it
shift in relative gas permeability, which can increase gas well deliver- reduces negative capillary forces, which, in turn, enhance the oil
ability [57]. recovery by gravity forces.
The great role of reservoir wettability on primary oil recovery 2. Alteration of wettability from neutral-wet state toward strongly
methods such as water drive was recognized by early research [24]. water-wet state induces capillary imbibition. Both gravity and capil-
Secondary recovery by waterflooding is directly related to wettability lary forces are expected to contribute in oil recovery in this range.
of oil reservoir as well. Wagner and Leach [111], for example, stated Water contact angle needs to be brought below 90°.
that oil recovery during water flooding for an oil-wet reservoir can be
less by 15% compared with water-wet reservoir. Most of reservoirs, on 2. The mechanisms of wettability alteration by enhanced oil
the other hand, exhibit some degree of oil-wetness and it is rare to recovery (EOR)
find a strongly water-wet reservoir. If reservoir has similar affinity to
oil and water, the wettability is defined as neutral, and when some As previously explained, a reservoir responds differently to water
parts of the reservoir exhibit a different wettability than other parts, flooding based on its wettability. The recovery rate becomes lower as
the term mixed-wet is used [83]. the rock behaves more oil-wet. Many of the succeeding enhanced oil
Jadhunandan and Morrow [48] tested the effect of wettability on recovery (EOR) applications target improving oil recovery by altering
oil recovery during water injection and concluded that ultimate oil the wettability to more water-wet. Several chemical and thermal EOR
recovery reaches its maximum near the neutral-wet state and not at a process were reported to alter the wettability of a reservoir toward
strongly water-wet state. Salathiel [83] showed that reservoirs with water-wetness. The degree of water-wetness that can achieve by EOR
mixed wettability can display a higher oil recovery during water immensely depends on how it affects crude oil/brine/rock properties.
flooding than water-wet reservoir. He referred to a field scale experience On the other hand, the mechanisms of crude oil interaction with rock
where a mixed-wet reservoir had an exceptionally high oil recovery and brine for each petroleum reservoir are different depending on
compared to water-wet reservoirs. Although there is a general crude oil and brine composition, rock mineralogy, and other reservoir
56 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

properties. Changing the wetting state of the reservoir requires the rock surfaces and oil. If this water layer is preserved through the history
understanding of the mechanisms that have altered the reservoir rock of a reservoir, water-wetness of that reservoir will be maintained. The
surfaces to be oil-wet. wettability of the reservoir changes when water layer is destabilized
EOR process may change the crude oil/brine/rock properties by two as a result of oil/water/rock interaction. As a result of this interaction,
mechanisms: Coating and cleaning [34]. Coating refers to the process the reservoir may become oil-wet [25]. Wettability alteration of a
of covering the oil-wet layer by water-wet materials. For example, reservoir, therefore, refers to the reversal process by which the reservoir
zirconium nanoparticles are hydrophilic and when they adsorb on the wettability is restored back to be water-wet. Accordingly, understand-
rock surface and form nanotexture coating the oil-wet surfaces [53], ing the mechanisms by which a reservoir has acquired oil-wet state is
wettability changes to more water-wet. Cleaning mechanism is normal- the first step in any wettability alteration scheme.
ly associated with surfactant induced wettability alteration. Cationic Destabilization of the layer of water that covers the rock surface
surfactants, for instance, desorb the oil-wet layer and thus render the occurs when attraction forces between rock/brine and brine/oil inter-
surface to a more water-wet state [94]. faces exceed the repulsion forces, water layer will then collapse and
Another example for the cleaning mechanism is oil-wet fines oil contacts the rock surface [25]. Heavier end of the crude oil contains
detachment when high temperature is applied [89]. When more than components that can be adsorbed on the rock surfaces and revert its
one EOR process is applied, both cleaning and coating mechanisms wettability from water-wet to oil-wet [24,111]. The type of crude oil
may take place. Giraldo et al. [34] observed that both mechanisms be- components that adsorbs on the rock surface depends on the rock min-
came effective when a dispersion of alumina nanoparticles in anionic eralogy. It is believed that basic components in crude oil are adsorbed on
surfactants was used to alter the wettability of oil-wet sandstone. silica surface, which is negatively charged on pH ranges under reservoir
Selection of the EOR process that alters the wettability of reservoir is conditions. Acid components in crude oil such as naphthenic acid [10,
often related to mechanism that suit a specific rock type. For example, 67] or carboxylic acids [94], on other hand, are adsorbed on carbonate
cationic surfactants are normally associated with wettability alteration surface, which is positively charge [10,25] under reservoir conditions.
in carbonates while anionic surfactants were more frequently used for Depending on crude oil/brine/rock interaction, a reservoir may have a
sandstones. Despite the need for wettability alteration in all types of homogenous wettability, which can be oil-wet, neutral-wet or wet–wet.
reservoirs, wettability alteration is of greater importance in naturally The wettability can also be any value in the range of wettability between
fractured carbonate reservoirs (NFCRs). This has been reiterated in a strongly oil-wet to strongly water-wet [10]. Wettability of a reservoir
large number of publications in this field over more than several may not be necessarily homogenous. Salathiel [83] found that reservoir
decades [12,36,39,44,56,74,79,83,94,111]. In the present paper, 35% of may exhibit mixed-wet state where different parts of the reservoir
the studies reviewed focused on the wettability alteration in NFCRs. have different sates of wettability. The percentage of the oil-wet
This can be explained by two main reasons. Firstly, most of the NFCRs reservoir in the world is controversial, however, it is generally agreed
are either oil-wet or have a neutral wettability. Thus, primary and that most of sandstone reservoirs are water-wet while carbonate reser-
secondary processes usually fail to mobilize oil that locked tightly by voirs are believed to be mostly oil-wet [28]. Most of oil-wet sandstone
capillarity. Secondly, the NFCRs are composed of matrix and fracture reservoirs were found to have considerable clay content.
system where most of the oil is contained in the low permeability ma-
trix. This implies that imbibition process is the most reliable mechanism 3.1. Carbonates
to reach oil that retained in the matrix as viscous forces usually are
inefficient to sweep matrix oil in such heterogeneous systems. An early study by Denekas et al. [30] examined the effect of
In this study, wettability alteration in both sandstones and carbonates surfactant in crude oil on the wettability of limestone. They found that
was reviewed. Section 3 provides an insight into different mechanism of limestone is sensitive to basic nitrogenous surfactants in crude oil.
crude oil/rock/brine interaction. Understanding how a reservoir Austad and Standnes [13] related the oil-wetting state of carbonates
becomes oil-wet is the first step in restoring the wettability of that to another parameter: acid number (AN). Acid number measures the
reservoir. Section 4 gives a summary of different wettability alteration content of carboxylic acid groups in crude oil (crude oils with higher
techniques and the advantages and drawbacks of each tool. The knowl- acidic number are more likely to render the carbonate surface oil-
edge of how principal forces interact during wettability alteration project wet). They found no direct effect of asphaltene content of crude oil on
is crucial for the success of project design and implementation. There- the wettability of carbonate. A study presented by Zhang and Austad
fore, the interplay among these forces, i.e., gravity, capillary, and viscous [127] reached a similar conclusion on the effect of AN on wettability of
forces, is discussed in Section 5. Section 6 covers chemical wettability carbonate. Carbonate rock samples were aged in crude oils that had
alteration methods including surfactants, low and high pH solutions, AN range of (0.17–2.07 mg KOH/g). Samples exhibited different wetting
low salinity water and smart water, and nanofluids. Wettability states based on AN. Crude oils with higher AN are more able to change
alteration by thermal methods is discussed in Section 7. In Section 8, the wettability of samples to be oil-wet. Xie et al. [120] showed the
challenges and opportunities of wettability alteration are summarized. same effect of AN on volcanic reservoir plugs.
Section 9 provides an overview of new chemicals that may represent
potential opportunities as wettability modifiers including ionic liquids 3.2. Sandstone
and microbial enhanced oil recovery. In Section 10, we report wettability
alteration test results in which the selected chemicals from this literature Acid number may not be as an important factor in sandstones as in
review were used on heavy oil containing sandstone and carbonate carbonates. This is attributed mainly to the negative charges of sand-
samples. Finally, conclusions and recommendations are presented in stone, which favors basics over acids [10]. Buckley et al. [25] saturated
Section 11. sandstone with eight types of oils with different acid/base number
values. No correlation between the wettability index and acid number
3. Interaction of crude oil/brine/rock in petroleum reservoir was found. Denekas et al. [30] conducted an experimental study on
the wettability modification by crude oil in sandstone. A distillation
It is generally agreed that petroleum reservoirs were occupied by process of crude oil was performed and fractions with different molec-
water before oil migration at later stages. When oil invaded the porous ular weight (MW) were collected and used to saturate sandstone core
medium, it did not displace water completely due to the water-wetness samples. The wettability of the core samples was then measured by
of the most of minerals that form reservoir rock such as silica and car- spontaneous imbibition test. Fractions with low MW were not able to
bonate [1,32]. Consequently, a thin layer of water has remained change the wettability of sandstone. As MW of fractions increases, sand-
covering the rock surface. The water layer acts as a barrier between stone becomes more oil-wet. The maximum degree of oil-wetness is
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 57

achieved with the heavier components that remained after distillation. than 90° to describe water-wet state. The neutral state is determined
This study concluded that surface active materials that change the by a contact angle that is about 90°. Two types of dynamic contact
wettability of sandstone possess a high MW and that when sandstone angle are usually measured: advance contact angle and receding contact
is saturated with higher concentrations of these materials, a more oil- angle. Advanced contact angle is more frequently utilized to assess the
wet state will be acquired. Buckley and Liu [26] suggested four mecha- wettability alteration. Morrow [67] provided relationships between in-
nisms of wettability alteration by crude oil including polar interaction, trinsic contact angle and advanced/receding contact angles under dif-
surface precipitation, acid/base interaction, and ion binding. Crude oils ferent roughness conditions.
with high base number and low acid number can alter the wetting of Reduction in water contact angle on a rock surface implies that wet-
silicate surfaces by acid/base interactions. Crude oils with higher AN tability of that surface has changed to more water-wet and less oil-wet.
and low base number (BN) can alter wetting by ion-binding interactions. Solid surfaces usually made oil-wet by aging in crude oil or coating them
Crude oil that contains asphaltenes alters the wettability by surface with chemicals such as CTAB [126] or SURFASIL™ [5]. To assess the
precipitation. A correlation between AN/BN, API degree, and wettability degree of wettability alteration after these processes practically, static
index showed that API degree is the governing factor in wettability or dynamic contact angle measurements can be applied. Contact angle
alteration by crude oil for sandstones. measurements can also be performed at high temperatures. Rao [79]
Another possible mechanism of wettability alteration by crude oil in was able to measure receding contact angle on quartz surface at a
sandstone is the effect of clay content. Schembre et al. [89] observed temperature range from 25 to 200 °C.
that sandstone becomes more oil-wet when the clay content increases. Although contact angle allows fast and economical mean of wetta-
They referred to a previous study by Tang and Morrow [105] which bility alteration assessment, it has many limitations. It is, for example,
found that clay is a dominant factor in changing the wettability of highly sensitive for contaminations. Accurate measurement of wettabil-
Berea sandstone toward water-wetness. Vledder et al. [108] explained ity alteration by contact angle at surfaces that exhibit high contact angle
that at high concentration of multi-divalent ions in high salinity reser- hysteresis represents another challenge. There is no agreement in liter-
voir brine minimizes the negative electrical charge on clay surface ature on whether it is more representative to measure contact angle on
resulting in a reduction in repulsive force. Surface active material in mineral plates or porous rock plates. Mica and silica (typically glass) are
crude oil will then adsorb on clay surface rendering it oil-wet. used to represent sandstones while marble and calcite are used in place
A conclusion that can be drawn from this discussion is that AN is the of carbonate. While using porous rocks may be more realistic, issues
most important factor of changing wettability of carbonates by crude such as surface heterogeneity may interfere with the accuracy of the
oil; water-wetness increases as the AN decreases. In sandstones, API, measurement. On the other hand, measuring contact angle on pure
asphaltene content, and clay content are the most dominant factors mineral may be misleading as the mineralogy of the rock will not be
that control the wettability alteration by crude oil. Integration of API, accurately represented. Thus, another challenge emerges: finding a
AN, clay content, and asphaltene content measurement would provide representative surface that can capture the properties of the surface of
valuable information to evaluate the mechanism or composite of mech- the reservoir rock properly [67]. Many studies showed that composition
anisms by which the original wettability of sandstone and limestone is and mineralogy can have a great effect on wettability. Sharma and
changed to be oil-wet. Mohanty [91] stated that contact angle cannot conclusively affirm the
ability of surfactant to change the wettability. They experimentally
4. Wettability alteration measurements demonstrated that some of the surfactants that are able to change the
wettability on calcite plates failed to imbibe spontaneously into reser-
Reliable wettability alteration measurement tools are essentially voir core sample. A common practice in contact angle measurement
needed to evaluate and monitor the efficiency of wettability alteration that is used to reduce the limitation of this technique is repeating a
treatment. It can be observed that most of the above reviewed studies measurement several times until the minimum acceptable margin of
focused on spontaneous imbibition tests to evaluate the wettability of error is achieved.
core samples. Other options exist to measure wettability before and Mohammed and Babadagli [65] found that ionic liquid 1-butyl-3-
after wettability treatment. Anderson [10] provided a review of different methylimidazolium tetrafluoroborate BMIM BF4 is able to imbibe spon-
types of wettability measurement tools. Each of these tools measures the taneously into oil-wet limestone but they did not test it on sandstones.
manifestation of wettability alteration from different perspectives. There Contact angle measurement serves as a faster (and economical) tool to
is no agreement, however, on standard wettability alteration test [79]. explore if this ionic liquid affects the wettability of sandstone. Fig. 1
The following is a summary of common wettability measurement tests. shows droplets of oil on oil-wet glass surface that immersed in BMIM
BF4 solutions at different concentrations. As seen, the contact angle is
4.1. Contact angle reduced as concentration increased from 0.25 wt.% to 0.5 wt.% and
then to 1.0 wt.% indicating wettability alteration of silica surface from
Contact angle can be defined as the point at which oil and water oil-wet to water-wet. Imbibition tests on sandstone can be used to
interface meet at rock surface. It can be used to analyze the alteration confirm this observation.
of surface wettability as it measures the shift in rock surface affinity of
one fluid to another in a continuous manner. In other words, the contact 4.2. Spontaneous imbibition (SI)
angle can be measured both in static and dynamic states [68]. Many
studies on wettability alteration processes were carried out using SI test measures the ability of the wetting phase to displace the non-
contact angle measurement; however, there is no universal protocol wetting phase under static conditions. The relationship between
on how this test should be performed. Techniques of contact angle can capillary pressure and wetting phase saturation is highly dependent
be as simple as taking readings of contact angle using photos by digital on the wettability of the rock surfaces. Water easily displaces oil in
camera or as complicated as taking high resolution images using envi- water-wet system as it has positive capillary pressure. In oil-wet
ronmental scanning electron microscope (ESEM) [115]. Yuan and Lee systems, capillary pressure is negative and water does not imbibe into
[125] provided a comprehensive review on the recent advancements porous medium as oil is firmly attached to the rock surface by capillarity.
on contact angle measurement techniques. The SI test demonstrates the contribution of capillary and gravity
The question of how to define wettability by contact angle values forces during wettability alteration and can be conducted in the lab by
and terminology used to describe the level of wettability are still contro- placing a core sample that saturated with crude oil in a graduated cell
versial. However, it is generally accepted to use water contact value filled with water. Imbibition curve can then be established by plotting
greater than 90° to indicate oil-wet state and water contact angle less oil production versus time. Imbibition curve is used to interpret the
58 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

Fig. 1. Contact angle images of oil droplets on oil-wet glass surface that immersed in A: 0.25 wt.% ionic liquid solution, B: 0.5 wt.% ionic liquid solution, and C: 1.0 wt.% ionic liquid solution.

wetting properties of core samples. As will be explained later, other distinguish the duration and the degree of the wettability alteration,
visual information can be obtained from imbibition tests such as the which may lead to capturing the underlying mechanics behind the
contribution of each face of the core in the oil recovery, as a delineation process.
of wettability. The production of oil from lateral surfaces of the core As wettability altered to be water-wet, capillary forces dominate the
indicated that counter-current capillary imbibition took place. The SI oil displacement. It is also apparent that there is a cross over region in
test may also be used to study the effect of boundary condition on the the imbibing mode from gravity dominated displacement to capillary
imbibition process. Due to all of this valuable information that can be dominated flow. This behavior is, in a way, contrary to what we see in
generated by the SI test; it is considered one of the most reliable the spontaneous imbibition of low-IFT solutions in water-wet systems
measurements of wettability alteration. where flow is crossed over from capillary dominated flow at the start
This type of “dynamic” wettability measurements, i.e., SI tests, is to gravity controlled regime at late times.
more advantageous over “static” wettability measurement tests like con- Høgnesen et al. [45] used a special imbibition cell to monitor the oil
tact angle experiments in the evaluation of wettability alteration process. that is produced from the top surface by gravity forces and that which
To clarify the usefulness of the “dynamic wettability” measurements, we produced from the lateral surfaces by capillary forces. A chalk core
present a case in Fig. 2, which shows the spontaneous imbibition curves was immersed in C12TAB at 1.0 wt.% concentration. They observed
for two limestone core samples exposed to two different aqueous phases that most of the oil is produced from the top surface at early stages of
[65]. One core was soaked into distilled water while the other one was imbibition. The main difference between the imbibition of low-IFT
immersed into cationic surfactant C12TAB solution at 1.0 wt.%. A quick solutions in water-wet systems and the imbibition of C12TAB in oil-wet
look to this curve indicates the oil-wet nature of the core samples as no carbonate is the dynamic alteration of wettability by C12TAB. The ability
water imbibes into porous medium spontaneously. The gravity forces of C12TAB to change the wettability of oil-wet toward water-wetness
barely displace 2% PV as it is resisted by negative capillary forces. A carbonate was explained by Standnes and Austad [95].
similar trend for the C12TAB case is observed for the same period
of time (first 10 days) indicating slow recovery (mainly due to high 4.3. Surface imaging tests
viscosity of oil) driven by gravity forces with minimal contribution
from capillary imbibition. After 10 days, however, a sudden change in Surface imaging techniques such as scanning electron microscope
the recovery is observed. This can be attributed to wettability alteration (SEM), atomic force microscopy (AFM), and nuclear magnetic resonance
phase by surfactant that enhances capillary imbibition intake. In other (NMR) give insight into changes in rock surface characteristics as a result
words, the rate of spontaneous imbibition increases with time showing of wettability modification treatment. Schembre et al. [89] used SEM im-
the alteration of core wettability. ages to understand the mechanisms by which sandstone surfaces become
Three different trends are obvious in the recovery curve of C12TAB. water-wet at high temperature. In a study of wettability alteration
The third trend shows more accelerated recovery, which can be attrib- by nanofluids, Karimi et al. [53] used SEM images to investigate the
uted to accelerated gravity due to reduced interfacial tension. Hence, adsorption of zirconium nanoparticles on carbonate surfaces.
one may note that there are two effects of using surfactant solutions
instead of water: (1) IFT reduction and (2) wettability alteration. 4.4. Zeta potential measurement
When the capillary pressure is negative, the reduction of IFT would be
favorable as it minimizes the resisting forces that act against oil recovery Zeta potential measurements were applied by many experimental
by gravity forces. The dynamic nature of the SI tests allows us to studies to measure the change in electrostatic forces. A shift in Zeta
potential on carbonate surface from positive values to negative values
was used to explain the mechanism of wettability alteration by alkaline
anionic surfactant in carbonate reservoir [44].
0.5
Wettability alteration is a complex process that involves a change in
0.45
many surface properties. A review of different methods for wettability
Oil Recovery (fraction)

0.4 alteration measurements shows that each wettability alteration test

0.35 Distilled
water
can give valuable information to evaluate the wettability alteration
0.3 process. However, comparative study of results obtained by different re-
0.25 search studies may not be an easy task as each test measures different
0.2 Cationic surface properties and performs a different methodology, and therefore
0.15 surfactant they may not be easily accessible methods and are also expensive (SEM,
C12TAB AFM, NMR, Zeta potential).
0.1
0.05
5. Capillary and gravitational forces as an indicator of the state
0
1 10 100 of wettability
Time (days)
Fluid displacement in porous medium is controlled by three types of
Fig. 2. Spontaneous imbibition behavior for limestone cores. forces: capillary forces, gravity forces, and viscous forces. In oil reservoir,
Reproduced after Mohammed and Babadagli [65]. the extent and the rate of oil recovery are determined by the interplay of
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 59

these forces. Two useful numbers that describe the relationship interfacial tension weakens capillarity and oil is expected to be
between these forces are the Inverse Bond Number (BN−1) and Capillary produced by gravitational forces. Many research studied the capillary
Number (CN) as described below: imbibition process, which is driven primarily by wettability at different
BN−1 values. At a high BN−1, fluid dynamic is controlled by the large
Gravity forces capillary forces [4,88]. When the BN−1 is low, both capillary and gravity
Inverse Bond Number ¼
Capillary forces forces contribute to oil recovery. In a study by Schechter et al. [88], dif-
F capillary ¼ 2σ ow Cosθc =r ð1Þ ferent IFT values were tested. When the IFT was high (38 dyn/cm),
counter current imbibition was observed at early times and oil was
F capillary : Capillary forces
produced from lateral faces of the core sample. At an intermediate IFT
σ ow : Oil−water interfacial tension (around 1.07 dyn/cm), oil production was observed from all faces of
the core indicating that both capillary and gravity forces took place. A
Viscous forces minor increase in oil recovery was observed in comparison with high
Capillary Number ¼
Capillary forces IFT. When the IFT was as low as 0.1 dyn/cm, oil recovery was slow but
ð2Þ
F gravity ¼ Δρgh eventually reached a higher recovery than the other two cases. Similar
F gravity : gravity forces: observations were made by Babadagli et al. [21] for kerosene–surfactant
solution systems.
The dominator in both relationships is capillary force, which is a The flow of fluids at low IFT is controlled by gravity forces compared
function of interfacial tension (IFT) between oil and water, radius of to oil recovery by imbibition for high ranges of IFT. Schechter et al. [87]
pores (r), and surface wettability, which is represented by contact and later Babadagli [16] showed that this can be scaled by the gravity
angle (θ). For homogenous water-wet reservoirs, capillary number scaling group. Both studies showed that higher oil recovery is acquired
plays an important factor in recovery evaluation and viscous forces at low IFT. The reduction of residual oil entrapment at low IFT enhanced
control the dynamic of fluid displacement. Increasing capillary number the oil recovery at low IFT when no initial water is present in the system.
by reducing capillary forces is favorable as it reduces the residual oil, An explanation to this reduction of residual oil at low IFT was discussed
which is normally performed by reducing IFT. For heterogeneous oil- by Al-Lawati and Saleh [4]. They showed that relative permeability of oil
wet reservoir and naturally fractured carbonate reservoirs (NFCRs) in and water becomes low in the counter current type of flow that is typ-
particular, the viscous forces cannot be applied efficiently as high pore ically encountered during capillary imbibition, and each fluid resists the
volume matrix possesses low permeability and much lower volume flow of the other fluid. During the gravity dominated imbibition, fluid
fracture system controls the flow by viscous displacement. Fluid flow is in co-current fashion and relative permeability of both fluids is
dynamic in this type of reservoir is controlled by the inverse BN. high. Note that flow is governed by the density difference and the per-
Imbibition into wetted cylindrical tubes could be scaled depending meability of the core. Although final recovery is higher for low IFT, the
on the cosine of the contact angle [70]. According to Eq. (1), the sign rate of imbibition is higher for intermediate IFT [70,87]. When the IFT
of the capillary forces may be reversed from negative to positive value value is intermediate, recovery by gravity force is in co-current manner
depending on the wettability of reservoir. In a water-wet cylindrical (thus relative permeability is high) and the capillary forces also contrib-
core sample, contact angle would be less than 90° and capillary forces ute to the imbibition process [16]. Al-Lawati and Saleh (1996) referred
initiate and maintain imbibition of water and the displacement of oil to an earlier study by Saleh and Graves [85] in which they suggest
in counter current fashion. In an oil-wet core, the contact angle is greater that there is critical IFT after which considerable amount of trapped oil
than zero, and no capillary imbibition takes place. can be freed. At that critical IFT, oil bubbles elongate and then broke
Two parameters that can be changed to enhance the capillary forces down into smaller bubbles. The small bubbles then flow through the
are oil/water interfacial tension (σ)ow and surface wettability (Cos θc). pore throats easily. In a study by Morrow and Mason [70] on the effect
While reduction in water contact angle is favorable for capillary imbibi- of IFT on oil recovery by imbibition, the researchers found that reducing
tion, interfacial tension should be maintained as high as possible. These IFT may increase or decrease imbibition depending on the contribution
two parameters, however, are not independent of each other. This fact of gravity forces. Babadagli [18] documented a similar observation re-
complicates the process of wettability alteration as many of wettability garding the rate effect lowering IFT. Morrow and Mason [70] observed
modifiers change the wettability to water-wet state but they reduce that higher ultimate oil recovery is achieved by the lowest IFT. Babadagli
the interfacial tension at the same time. The Young equation gives the et al. [21] stated that low IFT surfactant solutions can be used to contact
contact angle as a function of IFT tensions between oil and rock, oil the part of the matrix that can be inaccessible by the brine.
and water, and water and rock: The above discussion shows that reducing IFT gives rise to gravity
forces. The magnitude of gravity forces is a function of the density differ-
Cos θc ¼ ðσ os −σ ws Þ=σ ow ð3Þ ence between oil and water. In heavy oil, extra heavy oil, and bitumen
reservoirs this value is quite low. Høgnesen et al. [45] stated that the
σos oil–solid interfacial tension gravity forces will dominate the flow of fluids during wettability alter-
σws water–solid interfacial tension ation by cationic surfactant. In a study of the wettability alteration by
σow oil–water interfacial tension thermal treatment in carbonate reservoirs, Al-Hadhrami and Blunt [6]
θc contact angle of oil and water in solid surface. showed that the gravity forces may only be efficient in recovering oil
at the bottom part of reservoir. The hydrostatic head in the upper part
Consider a water-wet cylindrical core sample that was saturated may not produce quite enough gravitational force to displace the oil
with oil placed in an imbibition cell filled with water. Reducing oil– spontaneously. Therefore, it was concluded that the capillary forces
water interfacial tension (σow) would: should be essentially activated to increase oil recovery.
The main mechanism of wettability alteration by cationic surfactant
is to change wettability to the extent that it induces capillary spontane-
a) directly reduce capillary forces according to Eq. (1); and ous imbibition [94]. Alkaline anionic surfactants, on the other hand,
b) reduce contact angle according to Eq. (3), which increases capillary adopted a different mechanism. While negative capillary forces are not
forces according to Eq. (1). totally eliminated, they will be reduced significantly and hence gravity
forces will be active and oil will be recovered by gravity-induced imbibi-
Reducing θc may also be achieved by decreasing (σ os–σ ws) value; i.e. tion [44]. The determination of whether wettability alteration by cationic
reducing the affinity of rock to oil in favor of water. Reducing oil–water surfactant or alkaline anionic surfactant is more efficient for carbonate
60 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

reservoir depends on many factors. Understanding which mechanism is [45] showed that the interplay between gravity and capillary forces
more suitable for a reservoir wettability alteration depends on many fac- depends greatly on the IFT value.
tors such as crude oil properties including density and viscosity, reservoir Consequently, surfactant flooding should be evaluated based on
characteristic such as permeability, current status of wettability, size of the reservoir characteristic, the appropriate parameters to be used
the matrix and contact area between the fracture and matrix, vertical including the type of surfactant, concentration, and expected range
continuity of the reservoir, and the effect of boundary condition. of IFT. Reservoir temperature, for example, may limit the range of appli-
The contribution of the capillary and gravity forces on incremental oil cable surfactant. Thermal stability tests should be performed as well as
recovery is very much related to the effect of boundary conditions as well the aging tests to examine the precipitation rate of surfactant. Spinler
(Babadagli, 1999). Density difference evaluation is also important [45]. and Baldwin [93] aged surfactants for up to 16 months during the
For the heavy oil and bitumen cases where the density of water and oil screening test to select the most useful surfactants. Generally, stability
is almost identical, gravity contribution should not be overestimated. of surfactant solution should be tested at the application condition [44].
Density should be reduced first to activate the gravitational forces. Floating tests can also be considered as a screening test [119]. This test is
Otherwise, any attempt for wettability alteration solely rely on activating used to determine the ability of surfactant to change the wettability of
the capillary force, which is impractical at the field scale. Evaluation of rock surfaces by using oil-wet calcite powder with different surfactants.
the interplay of capillary forces and gravity forces under the effect of If the wettability of calcite is changed from oil-wet to water wet, it will
temperature should also be considered if the wettability is to be altered float.
by thermal means. Babadagli [15] observed that capillary imbibition The most frequently used surfactant screening test is contact angle
can be enhanced at elevated temperature as a result of viscosity measurement. Contact angle study provides fast and efficient tool to
reduction. screen the ranges of surfactants for their ability to change the surface
In summary, to produce oil from oil-wet reservoirs, the following wettability. After the screening test and narrowing down the number
systematic steps can be followed: of suggested surfactants, original reservoir plug or outcrop saturated
with oil is placed in an imbibition cell filled with surfactant solution
1. Establish the mechanisms that shifted the wettability to oil-wet. and oil recovery is monitored over time. A plot of oil recovery versus
2. Determine the reservoir and fluid characteristics (current status of time during imbibition test indicates two valuable pieces of information,
wettability, size of the reservoir, vertical continuity, fluid densities namely the rate of the recovery and the ultimate oil recovery. Capillary
and viscosities, etc.). imbibition effect can be noticed in early time and the effect of gravity
3. Study the interplay between different forces under reservoir condi- forces is observed in later times [27].
tions (capillary, gravity, and viscous force). In addition to the imbibition curves, other information that can
4. Determine which properties to be changed (viscosity, density, wetta- be obtained from the imbibition tests is the visual evidence of the
bility, etc.). contribution of these phases. An advanced visualization technique
5. Screen wettability alteration methods based on the reservoir rock type such as computerized tomography (CT) scans can be used to view the
(sandstone, limestone, etc.) and the mechanism that had changed the distribution of fluids during the imbibition test [27]. The production
reservoir wettability. from top surface usually results from co-current buoyancy forces and
6. Optimize the parameters of wettability alteration. oil recovered from the lateral faces indicates counter-current capillary
imbibition [45]. One of the limitations of the imbibition test is that oil
6. Chemically induced wettability alteration recovery is not necessarily recorded at the correct time of production.
Oil droplets that displaced out of porous medium may need additional
6.1. Surfactants time to detach from the core surface.
The application of anionic, cationic, and non-ionic in wettability
The main function of surfactant solutions is to reduce the interfacial alteration for sandstone and limestone was documented in literature
tension between oil and water from moderate to ultra-low values. at concentrations lower or higher than critical micelle concentration
When mixed with oil and water, they form a microemulsion of different (CMC). Researchers found that C12TAB at concentrations equal [35] or
types depending on the solubility of each phase on the other phase; higher than CMC [94] can alter the wettability of carbonates better
i.e., Windsor phase behavior, which was defined by Winsor [118] than anionic surfactants. Note, on the other hand, that Wu et al. [119]
describing different types of microemulsions that result when salinity concluded that no obvious correlation is found between oil recovery
is varied in an oil/water/surfactant system. These two characteristics and CMC. Standnes and Austad [95] proposed ionic-pair interaction as
are the major factors that play a role in enhanced oil recovery. the mechanism of wettability alteration by cationic surfactant type
In addition to those, surfactants contain a hydrophobic tail and a CnTAB (n is the carbon atom number). The degree of wettability
hydrophilic head that can be positive (cationic surfactant) or negative alteration was based on two factors: CMC value and the hydrophobicity
(anionic surfactant). Nonionic surfactant has no charge. Depending on of cationic surfactant. The higher the CMC value of CnTAB, the higher its
their spreading on the surface that is controlled by these charges and ability to change the wettability. However, this is also conditioned
the charges of the rock surface, they may alter wettability. Surfactant by the degree of hydrophobicity, which is determined by the n value.
flooding in oil-wet reservoirs is expected to serve both purposes: Wettability alteration was associated with both conditions. For
wettability alteration and IFT reduction. Two mechanisms of wettability example, while C10TAB has a higher CMC, C12TAB was found to have
alteration normally cited are removal of the oil-wet layer to expose the a better ability to modify the wettability than C10TAB as it is more
underlying originally water-wet surfaces or setting up a water-wet hydrophobic.
layer on the top of the oil-wet layer [94]. IFT reduction weakens the Another condition that is needed to activate capillary imbibition is
adhesive forces that retain oil by capillarity while wettability alteration the existence of relatively high IFT between water and surfactant.
activates capillary imbibition of water. Morrow and Mason [70] stated Temperature improves the wettability as it increases the rate of diffu-
that the ratio of gravity forces to capillary force is of great importance sion of surfactant monomers and micelles. Anionic surfactants generally
and that lowering IFT may have a positive or negative effect on imbibi- do not have the ability to alter the wettability of calcite surfaces, even
tion. While lowering IFT reduces the capillary imbibition, imbibition can when a very low IFT is achieved. Oil recovery is typically low for this
occur as a result of gravity forces. Furthermore, wettability alteration kind of system and is mainly due to bouncy forces. Salehi et al. [86] tested
may still be able to overcome the passive effect of IFT reduction [93]. the same principle on sandstones. They found that anionic surfactant
As long as IFT is not reduced below certain critical values, capillary im- STEOL C330 can change the wettability of sandstones better than cationic
bibition can be initiated and maintained. A study by Høgnesen et al. surfactants. They concluded that ionic-interaction between anionic head
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 61

group and positively charged basic materials that were adsorbed onto 6.2. Alkaline-anionic surfactant mixtures
the sandstone surface is the mechanism of wettability alteration. Also,
they also found that wettability alteration is improved by increasing As explained, anionic surfactants are not as efficient as cationic
the negative charge of anionic surfactants. Even with lower IFT, a surfac- surfactants in altering the wettability of carbonates. For example, anionic
tant with two negative charges on the head group (surfactin) causes a propoxylated ethoxylated surfactants (POEO) do not alter the wettability
very fast improvement in oil recovery, which is attributed to higher per- of carbonate surfactant and the acquired IFT is such low that no imbibi-
formance of surfactin in terms of wettability alteration in comparison tion occurred [94].
with STEOL CS 330. Ethoxylated surfactants (EO-sulfonates), on the other hand, induce
Nonionic surfactants were observed to be unable to change the higher IFT and are able to decrease the contact angle to values below
wettability of carbonate surfaces by Standnes and Austad [94,96]. 90°. Although they may induce wettability alteration by setting up a
Nevertheless, Vijapurapu and Rao [107] tested the ability of nonionic sur- water-wet layer on the top of the oil-wet rock surfaces, spontaneous
factant to change the wettability using contact angle with the Yates crude imbibition by this type of anionic surfactants was observed to be weak
oil. IFT was significantly modified (reduced from 29 to 0.19 dyn/cm) and inefficient [94]. This is mainly because their mechanism in altering
and contact angle measurements showed that nonionic surfactants the wettability is easily reversible. Other anionic surfactants that do not
are able to reduce the advancing contact angle from 156° to 39°. Golabi have EO group were found to cause no change in the wettability of
et al. [36] demonstrated that nonionic surfactant Triton X-100 has carbonates [94]. Addition of alkaline at optimal salinity was observed
higher ability to change the wettability of carbonate than cationic and to improve the ability of anionic surfactant rendering carbonate surfaces
anionic surfactants. They also noticed that increasing temperature and more water-wet [2,39,44,90,126]. Unlike cationic surfactants, the
increasing concentration improve the process of wettability alteration. concentration used in alkaline-anionic systems was reported to be far
An earlier study by Xie et al. [121] documented that nonionic surfac- below the CMC. The presence of alkaline in the system reduces the ad-
tants are more efficient in wettability alteration than other types of sorption of anionic surfactant. In two different studies by Tabatabal
surfactants. Most of the recovered oil occurred as a result of capillary et al. [101] and Seethepalli et al. [90], Na2CO3 was observed to minimize
forces and the production by gravity forces is insignificant. The better the adsorption of anionic surfactant on carbonate surfaces. Another
performance is attributed to the higher IFT that can be acquired with advantage of using alkaline with anionic surfactant is the generation
nonionic surfactant. of in situ surfactants by alkaline. These surfactants are believed to
Wettability alteration by surfactants seems to be a slow process, yet dissolve naphthenic acids that had adsorbed in the carbonate surfaces
is effective in reaching considerably high oil recovery. However, up and established the oil-wetness state [39,44].
scaling the results of many wettability alteration studies shows that Na2CO3 is the most frequently used chemical in alkaline anionic
spontaneous imbibition process, which takes months in the lab, might surfactant systems as the CO−2 3 group reduces the positive charges on
require several hundred years at the field scale [97]. Hence, the limitation carbonates and thus, the adhesion of negatively organic acids to the
of surfactant diffusion may threaten the feasibility of wettability rock surfaces is weakened [44]. Different alkaline anionic surfactant
alteration. One factor that can accelerate the process is temperature; systems were investigated. For example, ethoxylated and propoxylated
however this implies additional cost to the process. To reduce the anionic surfactants such CS-330 and TDA-4PO at low concentrations
cost of surfactants, researchers tested many commercial surfactants. (~0.05%), when mixed with Na2CO3 were able to change the wettability
Standnes and Austad [96] found that commercial-cheap surfactants can of carbonate surface surfaces [44]. The ethoxylated anionic surfactants
alter the wettability of carbonate samples as efficient as C12TAB as that were tested by Gupta and Mohanty [39] showed potential ability
they have the same effective material. to alter the wettability of oil-wet carbonate surfaces. They were
One of the major challenges of surfactant flooding application in oil observed to improve this process when the ethoxylated group (EO) in-
reservoirs is their adsorption on the rock surfaces. The effect of the creases [39,94]. Other researchers stated that CS-330 is too hydrophilic
type of the rock surfaces (carbonate/sandstone) on the adsorption of and therefore it was mixed with another anionic surfactant [126]. The
cationic and anionic surfactants is still a controversial issue. A study by mixture of anionic surfactant at optimal alkaline salinity reduces
Tabatabal et al. [101] on the adsorption of cationic and anionic surfac- water contact angle with time from 180° to 80–140°.
tants on sandstone and carbonate rocks reported that the adsorption In certain cases, alkaline anionic surfactants provided a better
of cationic surfactants on carbonates is less than the anionic surfactants performance than cationic surfactants as revealed by Seethepalli et al.
of similar hydrophilic chain length. This can even be further decreased [90]. They showed that alkaline (Na2CO3) anionic surfactant (Alfoterra)
by the addition of multi-divalent ions. Addition of alkaline was observed system solution is able to induce higher reduction in water receding
to reduce the adsorption of anionic surfactants on carbonate surfaces contact angle than cationic surfactant DTAB. Note that concentrations
significantly as stated by Seethepalli et al. [90]. They showed that at that are usually applied in alkaline anionic surfactant systems are
higher pH values, carbonate surfaces' charge reverted from positive to below or slightly above CMC concentration [90,126]. Although IFT re-
negative, leading to an increasing repulsive force between carbonate duction decreases the ability of alkaline anionic surfactant to imbibe
surface and anionic surfactant. On the other hand, Spinler and Baldwin by capillary forces, the buoyancy forces tend to compensate this effect
[93] suggested that anionic surfactants may have low adsorption on as explained by Hirasaki et al. [44] and Morrow and Mason [70]. Using
chalk surfaces. Generally, there is an agreement that adsorption a narrow gab that was created from oil-wet microglasses and saturated
increases as surfactant concentration increases, reaching a maximum with crude oil, Zhang et al. [126] illustrated that alkaline anionic surfac-
at the CMC value [90,93]. tant solution can displace the oil by water by spontaneous imbibition.
As seen, wettability alteration by surfactants is mostly tested for One of the important factors on designing a successful alkaline
light oil and the application of surfactants on heavy oil is rare. Babadagli anionic surfactant system is optimum salinity. Selecting an alkaline
[17] tested the imbibition of surfactant into limestone cores saturated concentration that provides the best solubility of crude oil reduces the
with heavy oil. A positive effect in ultimate oil recovery was observed total cost and maximizes the efficiency of wettability alteration by
but the recovery rate was negatively affected. This was expected as alkaline anionic surfactant mixtures. The optimal salinity may be deter-
surfactant reduces the IFT and capillary forces consequently. Howev- mined using the phase behavior test [44,90], or by IFT measurements.
er, the increase in recovery was minor and the application of surfac- Once the optimal salinity is determined, other electrolytes such as
tant for such conditions deemed economically unfeasible. Addition NaCl can be used to enhance the electrical strength of the system [44].
of alkaline may improve the efficiency of surfactant flooding in Other factors such as tolerance of alkaline to the water hardness should
heavy oil reservoir by emulsification of heavy oil in formation brine also be carefully considered. NaBO2 for example has higher tolerance
[58]. of water hardness than Na2CO3. The selected published studies on
 62
Table 1
A selection of published studies on wettability alteration by surfactants and alkaline surfactant mixtures.

Surfactant type Materials Synthetic brine Tests Est. final oil recovery General comments Reference
ranges

C12TAB Outcrop chalk Sea water Imbibition 50–90% – Light oil Høgnesen et al. [45]
0.6–3.5 wt.% – Observed the oil production from different surfaces of the cores.
– Compared the contribution of gravity and capillary forces
– Surfactants of the type tetra alkyl Outcrop chalk 3 Brines with different content of dissolved – Contact angle 10-75 % – Light oil Standnes and
ammonium solid (Na+, K+, Mg+2, Ca+2, Cl−, SO−24 , – IFT (4 days–1 month) aging Austad [94]
– Anionic surfactant HCO−13 ) – Imbibition – Imbibition with Cationic N anionic
0.1 wt.% – Tests run under different temperatures (40–70 °C)
Surfactant Concentrations N CMC
C(10-12)-amine – Outcrop chalk 2 Brines with different content of dissolved – IFT 50-75 % – 60% Crude and 40% Heptane Standnes and

M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77
1.0 wt.% – Dolomite solid (Na+, K+, Mg+2, Ca+2, C, SO24, HCO− 3 ) – Contact angle – C12-amine insoluble and is not a wettability modifier Austad [95]
reservoir cores – Imbibition – C-10 amine can change the wettability at low temp but not at high
temperature
C12TAB, 1.0 wt.% Outcrop Chalk Brines with Imbibition 20–60% – 60% Crude and 40% Heptane Strand et al. [98]
NaCl, NaHCO3, KCl, MgCl2·6H2O, CaCl2·2H2O – Temperatures ranges (90–130C)
and Na2SO4. KSCN – Ion pair interaction as a wettability alteration mechanism
C12TAB, C14TAB, Outcrop Chalk Synthetic formation brine (NaCl, Na2SO4, – IFT 50–70% – 60% Crude and 40% Heptane Austad and Milter
C16TAB alkyl propoxy ethoxy sulfate NaHCO3, KCl, MgCl2, CaCl2) Imbibition test – C12TAB changes wettability of chalk [12]
(mixture of anionic and nonionic)
1.0 wt.%
CTAB and Ethoxylated sulfonates Short and long Synthetic brine – Imbibition test 50–70% – Crossover in the imbibition mechanism from capillary-dominated Austad and
1.0 wt.% outcrop Chalk flow at 70 °C to more Standnes [13]
– Gravity-dominated flow at 40 °C in long cores
C12TAB Outcrop Chalk Brines (Na+, K+, Mg+2, Ca+2, Cl−, SO−2
4 , – Imbibition test 50–85% – Aging 4 weeks at 90 °C Austad et al. [14]
1.0 wt.% HCO−3 ) – Temperatures ranges (40–130 °C)
– Temperature is a crucial factor for sulfate to be effective as well as
(Ca+2/SO−24 ) concentration ratio
Anionic surfactant Berea Brine 1.5% NaCl imbibition Sor reduced to 0% – Light oil: Heptane Alveskog et al. [8]
(n-dodecyl-o-xylene-sulfonate) Sandstone – As surfactant concentration increases the residual oil decreases and
(0.001–0.1 wt.%) the wettability is changed to neutral then oil wet
Anionic surfactant Chalk core plugs Synthetic brine Phase study 60–70% – Light oil: Heptane Austad, and Milter
(Alkyl-propoxy-ethoxy-sulfate) and – Cationic surfactant is able to change the wettability of oil wet chalk, [12]
Cationic surfactant (CTAB) The wettability mechanism provided in this paper (reverse micelle
1.0 wt.% formation) is revised by the author in his more recent published
papers
Surfactants of the type R-N(CH3) Dolomite and Chalk Low and high salinity brines IFT 70–90% – 60% Crude and 40% Heptane Austad and
Arquad Dodigen core samples Contact angle – Arquad and Dodigen surfactant are able to change the wettability of Standnes [13]
1 wt.% Imbibition carbonate
– Recovery is more from dolomite cores compared to chalk
– As temperature 01 decreases, recovery is more influenced by gravity
– Anionic surfactant (Ethoxylated Limestone Formation brine (NaCl, MgCl2) Contact angle 70–80% – Aging (1–2 months) Sharma and
sulfonate) CTAB, DTAB, Aaqud Imbibition test – Mixture of cationic and non-ionic is stable at high Temperature and Mohanty [91]
– Non-ionic, exthoxylated high salinity and can be effective in wettability alteration of carbonate
Concentration b 0.2 wt.% — Cationic and
non-ionic
Anionic surfactant and Sodium Dolomite Formation brine Contact angle 40–50% The wettability of calcite can be changed by anionic surfactant and Hirasaki and Zhang
carbonate mixture (NaCl, KCl, CaCl2, MgCl2, Na2SO4) Imbibition test Na2CO3 or NaHCO3 [44]
0.05–0.1 wt.% Displacement in
narrow gap
Non-ionic ethoxy alcohol surfactant Dolomite Synthetic brine Contact angle – Non-Ionic surfactants can decrease the contact angle from 156° to 39° Vijapurapu and Rao
b3500 ppm Actual reservoir brine (CaCl2, MgCl2, Na2SO4) [107]
– Cationic surfactant (C12TAB) and an Sandstone cores Synthetic brine – IFT 10–30% – Light oil (5 cp) Salehi et al. [86]
anionic Synthetic cores (10 g/L NaCl), – Imbibition test – Aging at 90 °C for 1 month
surfactant (STEOL CS-330) Deionized water – Anionic surfactant changes wettability of wet sandstone by ion-pair
bio surfactant exchange
– Surfactin – Electrostatic interaction Increases when the negative head group
1 mmole/l increases
– Dimeric surfactants might be effective for sandstone
Anionic and non-ionic surfactants Calcite plates Na2CO3 and NaCl – IFT 60–75% – Light oil (24 cp) Gupta and Mohanty
0.1 wt.% Limestone core – Phase behavior – Temperatures ranges (25–90 °C) [38]
– Contact angle Temperature increase the effect of anionic and non-ionic surfactant
– Imbibition test – Gravity driven process
Anionic surfactants (sulfate and Calcite plates Synthetic brine (Na2CO3, NaCl, Na2SO4, CaCl2, – IFT 30–50% – Light oil (24 cp) Gupta and Mohanty
sulfonate) Limestone core and MgCl2) – Contact angle – Imbibition testes run at high Temperature (90 °C) [39]
0.1–.5 wt.% – Imbibition test – Optimum surfactant concentration is directly linked with brine
salinity
– Anionic surfactants desorbs the naphthenic acid from carbonate
surface when mixed with NaCO3 (calcite charge is switched from
positive to negative charged at high pH)
Anionic surfactant: Ethoxylated (EO) Calcite plates Sodium chloride is used along with 1% – IFT 60–90% (narrow gap) – Problems with IFT measurements for alkaline anionic surfactant Zhang et al. [126]
and propoxylated (PO) sulfates Marble plates sodium carbonate – Phase behavior systems
0.05 wt.% – Contact angle – Adsorption of anionic surfactant decreases with addition of sodium
– Imbibition test – carbonate
in narrow gap – Adsorption of anionic surfactant decreases when flow rate decreases
– Alkaline anionic surfactant is able to alter the wettability of

M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77
carbonate
– Anionic ethoxylated (EO) and Calcite, limestone, Synthetic brine (Na2CO3) – IFT 35–55% – Light oil (20 cp) Seethepalli et al.
propoxylated (PO) sulfates and cationic marble, and – Phase behavior – Anionic surfactant in presence of Sodium carbonate is able to change [90]
(CTAB) dolomite – Contact angle the calcite wettability of carbonate from oil-wet to water-wet similar
0.05 wt.% plates – Imbibition test or even better than cationic surfactant
– Adsorption of anionic surfactant decreases when sodium
Carbonate is added to the system
Cationic surfactant (CAC) and non-ionic Dolomite cores Synthetic brine (Na2CO3) – IFT 5–15% – Light oil (25 cp) Xie et al. [123]
surfactant ethoxylated alcohol – Imbibition test – Aging (10 days) at (55–60 °C)
75–2600 ppm – Surfactant concentration slightly above CMC
– Non-ionic performance is better than cationic for wettability
alteration of carbonate and faster recovery is achieved (the effect of
high IFT)
– Nonionic ethoxyl alcohol 3500 ppm Yate reservoir core Yates field synthetic brine CT scan 40% increase in oil – Light oil (13 cp) Chen et al. [27]
– Anionic ethoxyl sulfate 3500 ppm (limestone and imbibition recovery compare to – Aging with oil: 6 weeks
dolomite) brine – Surfactant concentration above CMC
– Both non-ionic and anionic change the wettability to moderately oil
wet state but not water wet.
– Oil is produced because of the capillary at early time and gravity
effect is dominated at late time
Anionic surfactant: Ammonium salt of Outcrop chalk North sea water IFT Up to 24% – Light oil Spinler and Baldwin
ethoxylated and sulfated Alcohols Reservoir chalk imbibition – When the concentration of surfactant is below CMC, adsorption [93]
(C8–C10 alkyl ethers) plugs Flooding decreases
300–3000 ppm – Surfactant stability can be measured through cloud points and onset
of precipitation
Anionic surfactant Berea Brine 1.5% NaCl imbibition Sor down to 0% – Light oil Alveskog et al. [8]
n-dodecyl-o-xylene-sulfonate Sandstone – As surfactant concentration increases the residual oil decreases and
(0.001–0.1 wt.%) the wettability is changed to neutral state.
Commercial surfactants Berea Deionized water IFT 50–70% – Light oil ALawati and Saleh
Sandstone – imbibition can occur in three different regimes: [4]
• Capillary-dominated
• Gravity-dominated
• Intermediate regime where both forces affect Imbibition
– Reduction of IFT may increase or decrease imbibition rate,
depending on the relative contribution of capillary and gravity forces
C12TAC heavy Water – Molecular 35–44% – Heavy oil and light oil Pons-Jiménez et al.
0.01 to 0.5 wt.% oil-impregnated modeling – C12TAC might change the wettability of cores contain light oil not [78]
calcite cores – Imbibition tests heavy oil
– C12TAC was not able to detach asphaltene and resin for carbonate
surface
Two anionic and two non-ionic Siliceous and Water Contact angle – Anionic and non-ionic surfactants have the ability to change the Alvarez et al. [7]
(0.2, 1 and 2 gal per thousand gpt) carbonate shale Imbibition tests wettability of carbonate shale reservoirs
cores – Anionic surfactant showed better oil recovery from shale than
non-ionic

63
64 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

wettability alteration by surfactants and alkaline surfactants mixtures imbibition and increases oil recovery. Nasralla et al. [73] also observed
are summarized in Table 1. an improvement of oil recovery with low salinity water (LSW) injection.
It is believed that wettability alteration is one of the effective mecha-
6.3. High pH solutions nisms in this process [69]. There has been a growing interest in LSW
as an EOR agent in the recent years. Morrow and Buckley [69] provided
Early studies showed that alkaline flooding in sandstones can the recent bibliography in that area. They noted that mixed wet fine
increase oil recovery [32,56]. Many mechanisms were suggested includ- particles (e.g., kaolinites), which are believed to be the cause of reversal
ing wettability alteration and the formation of in situ-surfactants as a wettability, can be removed during LSW injection. Vledder et al. [108]
result of alkaline reaction with acids in crude oil. Ehrlich and Wygal reported similar observation. Although pH was increased during the
[32] showed that alkaline flooding using NaOH solution improves oil process of low salinity water injection due to ion change, they suggested
recovery for crude oils with acid numbers more than 0.1–0.2 mg KOH that this was not the reason for increased oil recovery because IFT was
per gram of oil. Relative permeability measurements indicated that wet- high during the process.
tability of Berea cores is changed to be more water-wet after flooding Berg et al. [23] used open flow model geometry where drops of oil
with 1.25 N NaOH solution. In only one crude oil among those tested, that attached to clay particle were displaced by LSW (TDS 2 g/l of
it was found that emulsification is responsible for improved oil recov- NaCl) and high salinity water (TDS 25.95 g/l). The amount of oil that
ery. In that sample, the acid number was considerably high (1.39 mg detached from the clay was significantly higher when LSW is used and
KOH per gram of oil). Calcite surfaces normally have positive charges this was attributed to its ability to minimize the adhesion forces
at pH less than 9, which encourages the attachment of negative acidic between clays and oil droplets. Wickramathilaka et al. [116] performed
components from crude oil to the carbonate rock surfaces and renders imbibition tests on limestone and sandstone cores using brine with
them oil-wet. Reduction of pH will decrease the positive charges on different salinities. No effect of high salinity water on the recovery was
the calcite surface and consequently increase repulsive forces between observed for limestone while LSW was effective in increasing the oil
the calcite surface and adsorbed organic components. Changing pH recovery from Berea sandstone and original reservoir sand. They also
value was suggested as a mean to change the wettability of carbonate noticed a decrease in pH for reservoir sandstone cores. LSW was also
reservoirs. An experimental study by Zhang et al. [128] investigated tested at field scale. Vledder et al. [108] reported that 5–15% incremen-
the effect of different high pH solutions on carbonate reservoirs. tal oil recovery was achieved in oil-wet sandstone reservoir by LSW. The
Contact angle measurements were performed on silica and carbon- clay content of this reservoir was in the range of 0.5–4% and was mostly
ate plates using Na2CO3 and NaBO2 solutions. While NaBO2 does not composed of kaolinites. LSW was injected from a river with the salinity
reduce the contact angle significantly, Na2CO3 changes the wettability about 500 mg/l.
of both silica and carbonate from oil-wet to water-wet. On the other Recent spontaneous imbibition tests for low, moderate, and high
hand, natural imbibition tests using porous flat plates and short carbon- salinity water showed that both recovery rate and ultimate oil recovery
ate cores indicated that NaBO2 causes stronger imbibition than Na2CO3 were higher for LSW [69,80]. According to these authors, salting-in
in spite of the fact that both solutions have the same pH (~11.5). The mechanism may be the main reason of wettability alteration in sand-
same study reported that the performance of high pH solutions is better stones by LSW if clay is responsible for oil-wetting state. Salting-in
than surfactants and that no improvement in the recovery was observed refers to the process of reducing the salinity of water to increase the
when NaOH was used. solubility of organic compounds [80].
The oil recovery mechanism by NaBO2 is attributed to its high pH In addition to the mineralogy of sandstone, composition of oil [73]
value and the tolerance of NaBO2 to high cation concentrations. In could play a role in wettability alteration by LSW. Alotaibi et al. [9]
their experimental study of alkali injection after water flooding in lime- reported that LSW was efficient in changing the wettability Berea
stone, Najafabadi et al. [72] showed that the wettability of limestone is sandstone but not the Scioto sandstone. These two types of rocks have
changed from oil-wet to water-wet. Capillary forces are reverted from different rock composition. Advanced oil contact angle measurements
negative sign to positive sign and oil is recovered by capillary forces indicated that the wettability of the Scioto sandstone was not altered
and viscous forces. Spontaneous imbibition tests on siliceous shale indi- by LSW. On the other hand the same authors reported that LSW modi-
cated that high pH solutions have the highest efficiency in wettability fied the wettability of Berea sandstone making it strongly water-wet.
alteration followed by low pH solution, whereas neutral pH solutions Surface charges were significantly affected by LSW injection. LSW
are not able to induce any wettability alteration [102]. Zeta potential resulted in a significant decrease in the Zeta potential of clay particles.
measurement on siliceous shale [103] also supports this result as it Note that these experiments were performed in porous rock. Nasralla
showed that aqueous film is not stable at neutral pH causing non- et al. [73] suggested using mica for contact angle measurement for sand-
water-wet state. High pH solution is able to stabilize the water film stones as it does not have the interference in the data (hysteresis) due to
and modifies the wettability into more-water wet. surface roughness.
A field trial in the Harrisburg Muddy reservoir was conducted to test Nasralla et al. [73] evaluated the injection of different salinities from
the possibility of using alkaline flooding to increase oil recovery by wet- 0 mg/l up to 17,400 mg/l in oil-wet sandstone using mica plates. The
tability alteration. Injection of 2% NaOH was carried out in multiple decrease in water contact angle measurements on mica shows that
wells followed by water injection. A gradually increased oil recovery low salinity water can alter the wettability of mica surfaces. They stated
was observed in many wells indicating that reservoir wettability was that double layer expansion is the main mechanism of wettability
changed from oil-wet to water-wet [56]. They pointed out that alteration. They also showed that the composition of oil is an important
conducting wettability alteration at early stages of water flooding in factor. Zeta potential study indicated that repulsive forces between oil
oil-wet reservoirs can reduce the residual oil to extent similar to that and sandstone surface increase as the negative charges on the rock/
of water-wet reservoir. A selection of published studies on wettability brine brine/oil increase resulting in an alteration of wettability toward
alteration by high pH solutions is provided in Table 2. water-wet state. Core flooding experiments on Berea sandstone
confirmed this observation. Flooding with de-ionized water (DI) resulted
6.4. Low salinity water in the highest oil recovery while the solution that had the highest salinity
yielded the lowest oil recovery [73].
The injection of low salinity water (LSW) to increase oil recovery Double layer expansion was also suggested as the main mechanism
provides low cost EOR method. In their study about the effect of low sa- for wettability alteration earlier by Vledder et al. [108]. Using oil-wet
linity oil recovery by water flooding, Tang and Morrow [104] showed sandstone samples, they concluded that the high concentration of
that lowering the salinity of water results in enhanced spontaneous multi-divalent ions in high salinity reservoir brine reduces the negative
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 65

Table 2
A summary of selected published studies on wettability alteration by high pH solutions.

Alkaline pH range Rock type Brine Experiments tests Results Reference

NaOH–HCl (0.1–0.4 M) – Berea – Fresh water – Contact angle – As NaOH increased contact angle reduced from Leach et al. [56]
sandstone – 5500 ppm KCL – Field test (135°–170°) to (40°–70°)
– Formation brine – Injection of NaOH alters the wettability of oil-wet
Harriburge Muddy oil
– wet formation to be more water-wet
NaOH 1.25 N – Berea Water Core flooding – Light oil (API N 30) Ehrlich and
sandstone – The wettability Berea sandstone was altered to be Wygal [32]
more water-wet after acoustic flooding
– Higher clay content or acoustic consumption
reduces the improved oil recovery by NaOH
NaOH–Na2CO3–NaBO2 11–11.5 Texas cream Water Surfactants – Dynamic contact angle – Light oil 36.2 API Zhang et al. [128]
(1–4.8 wt.%) limestone – CT-aided visualization of – NaBO2 showed higher potential to alter the
in-situ imbibition wettability of carbonate than other alkalis
– NaBO2 has high tolerance to high divalent ion
concentration in the brine

electrical charge on clays' surface and consequently weakens the repul- surface. Based on this fact it is expected that high salinity water that
sive forces. Thus, surface active materials in crude oil come into direct contains multi-divalent ions, such as sea water [99,130] may change
contact with clay making it oil-wet. Decreasing the amount of divalent the chemical equilibrium of crude oil–brine and rock system in carbon-
ions by injecting low salinity water reverses this effect by expanding ate reservoirs into more favorable water-wetting.
the double layer and thus increases in repulsive force between crude A study by Strand et al. [98] explained that when high salinity sea
oil and clay surfaces. water is injected into carbonate reservoirs, the concentration of two
determining ions increases calcium and sulfate. The result will be an
6.5. Smart water increase in the adsorption of sulfate in rock surface.
Co-adsorption of calcium ion will also increase calcium ion concen-
Smart water refers to the process of customizing water composition tration in the system. Consequently, positive sites on carbonate surface
to serve specific applications. RezaeiDoust et al. [80] used this term to will be minimized, repulsive forces between crude oil and carbonate
describe the injection of sea water into chalk reservoirs. In wettability surface will increase and carboxylic acid will be removed from carbon-
alteration, this term has been used to indicate the injection of water ate surface by sulfate ion, which leads eventually to more water-wet
with different brine properties to modify the wetting properties of state.
petroleum reservoirs toward more water-wet. Quite a number of Recovery by spontaneous imbibition was 40% higher when sea
studies [111,123,130] showed that the modification of water composi- water is used compared with brine solution [80,98,130]. Note that
tion, pH or salinity might lead to improved oil recovery by wettability high temperature was reported to be significantly important in this
alteration. Wagner and Leach [111] concluded that the addition of process [37,100,130]. The importance of sulfate ion was tested by Strand
simple chemicals such as acids, basics, or salts may alter the wettability. et al. [99,100] who found that oil recovery by multi-divalent ion
As explained in the previous (LSW) section, the modification of injected solutions is reduced 15% when sulfate ion was not included in the com-
water composition and salinity can have a positive impact on oil recovery position. Note that sulfate ion concentration in the formation of brine in
in sandstones. Many studies observed similar results in carbonate carbonate reservoirs is low. This is due to the fact that sulfates precipi-
reservoirs at different water composition [37,80,98,122,123,130]. While tate during the chemical reaction with calcium ions (from carbonate
wettability alteration to more water-wet was observed generally in rock surfaces). Contact angle measurement and NMR study conducted
sandstones, these studies showed that high salinity water is successfully by Yousef et al. [122] suggested that contact angle is more affected by
used to improve the water-wetness in carbonates. RezaeiDoust et al. [80] the composition of injected water than IFT. Yousef et al. [123] revealed
discussed the difference in wettability alteration mechanisms by smart that smart water flooding in a field scale trial is able to reduce the resid-
water in sandstone and limestone. They explained the difference in ual oil saturation about 7 units in comparison with conventional sea
wettability alteration mechanisms between sandstone and carbonates water injection. A summary of selected published studies on wettability
based on the strength of adhesion force of adsorbed material in clays alteration by low and high salinity water is given in Table 3.
and carbonates. This force, they mentioned, is relatively strong in carbon-
ates and salting-in effect that occurs during the injection of low salinity 6.6. Nanofluids
water is not efficient in modifying the surface properties. In sandstones,
the adhesion force is relatively weak and low salinity water can lead to Nanofluid is designed by dispersion of nanoparticles in base fluids
desorption of organic material from sandstone surfaces that rendered it [124] and nanoparticles with size less than 100 nanometer (nm) have
oil-wet. been applied in different aspects of oil industry. For example, when
The composition of injected water for wettability alteration is usual- mixed with heavy oil, metal nanoparticles reduce viscosity [40].
ly customized by changing the composition of multi-divalent ions such Nanofluids can be customized according to the specific application
as calcium, magnesium, and sulfate ions. A study by Gupta and Mohanty and are characterized by the size and concentrations of nanoparticles
[37] showed that magnesium ions and sulfate ions are not efficiently and the wettability of these particles. Nanoparticles could be either
able to change the wettability of carbonate surface. Calcium ions, on hydrophilic or hydrophobic based on the functionalized group. Nanofluid
the other hand, can change the wetting state of carbonate surface into is also characterized by the properties of the suspending fluid such as
more water-wet state and the efficiency is increased when both sulfate chemical composition and pH value. The suspending fluid can be water
and magnesium ions are added to the solution. A study by Zhang et al. [43,75], brine [64], or surfactant solution [34,53].
[130] also showed that magnesium ion can substitute calcium ion. A
more recent study by Sakuma et al. [82] using molecular modeling sug- 6.6.1. Preparation
gests that this substitution in addition to the replacement process of Different methods that are used to prepare nanofluids have been
CO−23 by SO−2
4 reduces the adsorption of organic material on carbonate well documented in literature. One- or two-step methods are the
 66
Table 3
A selection of published studies on wettability alteration by low and high salinity water.

Wettability modifier Materials Brines Tests Range of Results Reference

recoveries

– SCAL, NMR – Light oil 0.3 cp

M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77
Low salinity water Oil-mixed wet sandstone River water, Salinity 500 mg/l, bivalent 5–15% Vledder et al.
reservoir cations b b 100 mg/l Log – Discussed reasons why sandstone might exhibit oil wet behavior [108]
– Core flooding
Low salinity water Outcrop sandstone Brine composition – Imbibition test 50–75% – Light oil (17 cp) Austad et al.
(Na+, Ca+2, Cl−) – Aged at 60° for two weeks [131]
Low salinity water Berea sandstone core plug Brine with salinity b 5000 ppm – Imbibition test 20–40% – Provided bibliography of literature in wettability alteration by LSW Morrow and
– Identified the conditions necessary for LSW Buckley [69]
Low salinity water Berea sandstone core plug Brine salinities vary with different TDS – Imbibition test 10–75% – Light oil (300 cp) Tang and Morrow
concentration – Core flooding – Swi established for all cores [104]
– Wettability toward water wetness is increased as temperature
increases
Low salinity water Reservoir sandstone core – Synthetic reservoir brine – Imbibition 50–75% – Light oil (70 cp) Tang and Morrow
– Synthetic sea water brine Composition – Core flooding – Swi and presence of clay particles are essential factors for low [105]
(Na+, K+, Mg+2, Ca+2, l−, SO4−2, HCO−) salinity
T = 55 °C
Low salinity water Mica minerals Brines with different compositions of (Na+, – Contact angle 8–22% – Light oil (20–30 cp) Nasralla et al.
Berea sandstone K+, Mg+2, CaSr, Cl−, SO42, HCO3−) – Core flooding improvement in – Change in electric charges at CBR interfaces causes the wettability [73]
recovery alteration
Low salinity water sandstone core plug Brine composition (NaCl, KCl, CaCl2, MgCl2) Flow cell Up to 80% – Effect of clay and clay swelling Berg et al. [23]
– Mechanism of wettability alteration
– Low salinity can cause formation damage
Low salinity water Mica plates Brines with different pH and salinities Contact angle – – Double Layer Expansion was found to be the mechanism of oil Nasralla and
Zeta potential recovery by low salinity water Nasr-El-Din [74]
– Reducing pH suppresses the ability of low salinity water to change
the wettability from water-wet to oil-wet
Divalent ions Indiana limestone cores Cationic and Non-ionic surfactants Imbibition tests Up to 60% – 0.01 M of SO−24 Dakik and Gupta
(Mg+2, Ca+2, and SO−2
4 ) or Ca+2 lead to oil high recovery in carbonate [29]
– Mixture of non-ionic and cationic
surfactants in high salinity brine improves the oil recovery
Sea water Outcrop chalk Two modified reservoir brines Synthetic – Imbibition 20-65 % – 60% crude and 40% heptane Zhang et al. [126]
– Seawater – Core flooding – Temperatures range
– Brine with potential determining ions (70–100–130 °C)
(Ca2+, Mg2+, and SO−24 ) – The presence of Ca2+, Mg2+, and SO−2 4 can change the wettability
but needs high temperature
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 67

most frequently cited. In the two-step method, a dry powder of nano-

particles is created first and then nanoparticles are dispersed in a
suspending fluid using ultrasonic vibration or strong shear mixing. Yu
and Xie [124] provided a review on a number of nanofluid preparation
methods.

6.6.2. Stability
Stability of nanoparticles dispersion is one of greatest challenges of
nanofluids application in oil industry. To achieve homogenous stable
Fig. 3. Wage film of nanoparticles displacing crude oil from a solid surface.
nanofluid, different techniques are applied including addition of non- Reproduced after McElfresh et al. [64] and Wasan and Nikolov [112].
ionic surfactants [53], anionic surfactants [34], surface modification
[124], and using ultrasonic vibration [113].
Williams et al. [113] used ultrasonic vibration (+12 h) to prepare with 10% NPD. Core flooding in sandstones and limestone showed an
nanofluids using zirconium and alumina nanopowder. The prepared improvement in oil recovery after silica NPD injection.
nanofluids were observed to be unstable and most of the particles The application of nanofluids in wettability alteration is relatively
were agglomerated. To increase the stability of the nanofluids, an “ener- new. A number of studies showed that nanoparticle dispersions can
gy barrier” was generated using two mechanisms: (1) By maximizing alter the wettability of oil-wet carbonates [53,54] and sandstones [34,
either electrostatic or steric repulsive force over attraction forces 51]. When hydrophilic nanoparticles adsorb on the rock surface, a thin
and (2) by modifying pH by adding HCl acid, which enhances the nanotexture is formed, coating the rock surface. As a result, wettability
electrostatic repulsive force and lead to more stable nanofluid when of the surface becomes more water-wet [34,53,61]. Alumina, silica,
accompanied with ultrasonic vibration. Williams et al. [113] and Safari and zirconium nanofluids were found to have significant effect
and Jamialahmadi [84] used surfactants to enhance the steric repulsive in changing the characteristic of sandstone and carbonate. Ju and Fan
forces. The efficiency of surfactant in the stabilizing nanofluids is [51] tested the effect of LHPN on wettability of oil-wet sandstone rock
controlled by the dielectric constant; high and low dielectric constants slices. They found that LHPN could alter the wettability of sandstone
are more efficient than moderate constants. Wamkam et al. [109] toward water-wetness. Maghzi et al. [61] used micromodel to study
provided a relationship between the Zeta potential and pH with the the effect of silica nanoparticles on the wettability alteration. After
average particle size (nm). To obtain the lowest particle size the pH of aging glasses in crude oil for 40 days, contact angle measurements
the solution has to be at the maximum or the minimum pH value. The were performed and indicated that surfaces of glasses became oil-wet.
lowest values of average particle size can be found at the highest and A dispersed silica nanoparticle in water solution is able to decrease the
the lowest pH value and the Zeta potential. Hamedi Shokrlu and contact angle from above 100° down to 0°. The ultimate oil recovery
Babadagli [41] used Xanthan gum polymer to stabilize nickel nanoparti- by silica nanofluid increased substantially and the suggested mecha-
cles. They conducted a micromodel visualization experiment using nickel nisms were the adsorption of silica nanoparticles on the oil-wet
nonparties with and without this type of polymer. When no polymer was surfaces. The adsorption of silica nanoparticles reduced silica-oil surface
added to the solution used to inject nanoparticles, they were not stable tension and thus decreased contact angles [61].
and trapped in the model. Surfactants were also tested as a suspending Karimi et al. [53] studied the spontaneous imbibition of zirconium
agent but they were not able to stabilize the nickel nanoparticles. nanofluids into oil-wet carbonate plugs. Zirconium nanofluids were
composed of zirconium nanoparticles that dispersed in the mixture of
6.6.3. Wettability alteration nonionic surfactants at 5 wt.%. The concentration of zirconium nanopar-
Silica nanoparticles in water solution are able to decrease the contact ticles was 0.05 g/cm3 and the pH value ranged from 2 to 3. The contact
angle of water in aged glasses form above 100° down to 0° [61]. This angle of n-heptane/water for oil-wet carbonate rocks showed that zir-
is achieved by the adsorption of nanoparticles on the silica surfaces. conium nanofluid can reduce the water contact angle significantly,
A study by Onyekonwu and Ologo [75] examined the effect of which implies that zirconium can reverse the wettability of carbonate
lyophobic–hydrophilic polysilicon nanoparticle (LHPN of 20–60 nm) surface. Spontaneous imbibition tests were also carried out using oil-
on oil recovery from water-wet sandstones. Water was used as a wet carbonate core samples. It was demonstrated that up to 60% OOIP
suspending fluid. Interestingly, a negative effect of using LHPN on can be recovered during spontaneous imbibition of zirconium
water-wet sandstone was reported. LHPN increases the water- nanofluids in comparison to less than 5% OOIP by distilled water.
wetness of the originally water-wet core. However, this effect decreases Spontaneous imbibition tests were performed at 70 °C but the effect
the oil recovery, which indicates that LHNP is not suitable for water-wet of the temperature on the process was not analyzed. Apparently, the
reservoirs. These core flooding experiments also indicated that perme- surfactant also contributed to the recovery but spontaneous imbibition
ability is affected negatively by this type of nanofluid. The visualization of surfactants without nanoparticles was not performed to quantify this
of the color change of the injected nanofluid from cloudy to colorless effect. Finally, Karimi et al. [53] developed a theoretical model to explain
demonstrated that most of nonparties had been adsorbed on the rock the change in wettability by nanofluids. They concluded that nanofluid
surface and damaged the rock permeability [75]. On the contrary, can form smooth surfaces with neutral wettability.
the LHPN did have a positive impact on oil-wet reservoir carbonate as Safari and Jamialahmadi [84] conducted contact angle measure-
it is able to alter the wettability to be more water-wet, more oil was ments using above mentioned LHPN nanofluid with 14 nm size (0.01–
recovered consequently. 0.5 wt.%) and pH ranged from 3.7 to 4.7. Results indicate that carbonate
Nanofluids increase the oil recovery by reducing the IFT and changing rock surfaces altered to be more water wet by nanofluid. Alumina
the wettability. McElfresh et al. [64] stated that nanoparticles arrange nanofluids were tested by Giraldo et al. [34]. They revealed that alumina
themselves in wedge form (Fig. 3) referring to an earlier study by nanofluids can enhance the ability of surfactant to change the wettabil-
Wasan and Nikolov [112] that explained the mechanism of removing ity of oil-wet sandstone as it adsorbs on rock surface and cover oil-wet
oil from soil by nanofluid. The wedge-like structure enhances the ability surfaces.
of nanoparticles to displace the oil phase from the rock surface. Displacement tests for secondary and tertiary recovery were also
McElfresh et al. [64] used stabilized nanoparticle dispersion (NPD) of performed by many studies. For example, Hendraningrat et al. [43]
silica nanoparticles (4–20 nm) in imbibition tests using sandstone cores. tested lyophobic and hydrophilic polysilicon LHP nanofluid for oil-wet
The result indicated that both NPD 10% solution and brine solution yield and intermediate water-wet sandstones. The core flooding tests
the same ultimate oil recovery. However, a faster recovery was observed indicate that wettability was altered by LHP silica nanofluid. After
68 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

water flooding, the cores were flooded with nanofluids. Incremental oil

McElfresh et al. [64]

Vafaei et al. [106]

Maghzi et al. [61]
Giraldo et al. [34]
recovery was higher for intermediate water-wet core. Note that the

Karimi et al. [53]

same core achieved the lowest recovery during previous water flooding.
They also found that increasing the flow rate decreases the recovery.

Reference
Another observation was made by Hendraningrat et al. [43] that
decreasing the size of the particles enhances the recovery and the
displacement efficiency. The highest oil recovery was achieved at

– Contact angle increased when concentration is increased until reaching a maximum and then started
– Contact angle and imbibition tests indicated the ability of ZrO2 to alter the wettability of carbonate

– At concentrations lower than 500 ppm, alumina nanoparticles enhances the ability of surfactant to
7 nm size indicating that the optimization of nanofluid should consider
decreasing the size of nanoparticles to a minimum. No adverse effects
on permeability were observed.
Silica nonparties can be used for wettability alteration and for im-
proving the water infectivity. Ju et al. [52] used water-wetting control

– Core flooding – Silica nanofluid altered the wettability of oil-wet glass from oil-wet to water-wet
agent that is designed by nanometer scaled powder formed mainly

– Contact angle – Adsorption of silica nanoparticles increased when concentration was increased

– Core flooding – Core flooding with silica nanofluid after brine showed improve in oil recovery
from silica nanoparticles. This agent was able to decrease the water con-
tact angle indicating wettability alteration. Zhang et al. [129] showed
that hydrophilic silica nanoparticles (19 nm) can imbibe into Berea

– SEM showed the adsorption of silica nanoparticles at the interface

sandstone core displacing about 55% of oil in place. De-ionized water

– SEM showed the adsorption of ZrO2 nanoparticles on the surface

– Smaller nanoparticles size led to larger change in contact angle

recovered less than 5% after two weeks of imbibition tests on the
same type of core sample. Their visualization experiment using capillary

– Faster imbibition of silica nanofluid compared with brine

tube yielded similar results. They stated that silica nanofluid is unstable
when pH of suspending fluid is varied. They suggested modifying

– Contact angle – Addition of nanoparticles increased contact angle

injected fluid (and nanoparticle type and concentration) to suit high
salinity and high temperature applications. Ahmadi and Shadizadeh

– Reduce water contact angle from 142° to 0°.

[63] also tested hydrophilic silica nanoparticles (12 nm) as a mobility

– Contact angle – Mixture of kerosene and 425cSt at 25 °C

control agent. Core flooding experiments were conducted using carbon-
ate cores. They indicated that silica nanoparticles increase the viscosity

alter the wettability of sandstone

of the injecting fluid and thus reduce its mobility. A selection of
published studies on wettability alteration with nanofluids is presented
in Table 4.

7. Wettability alteration at high temperature

is slow process

decreasing
Thermal operations improve oil recovery by different mechanisms
Results

such as viscosity and IFT reduction, thermal expansion and wettability

alteration. Distinguishing the contribution of each mechanism has
been a controversial issue in the literature. Different opinions in litera-
Contact angle

ture regarding the influence of high temperature on the wettability of

– Imbibition

– Imbibition
Imbibition

sandstone and carbonate were documented by Rao [79]. Using contact

angle measurements, he showed that sandstone may acquire oil-wet – SEM
Tests

SEM

or water-wet state at high temperature while carbonate becomes

more water-wet when the temperature is increased.
Distilled water

Silica surfaces generally alter to be oil-wet in high temperature.

surfactants

surfactants

De-ionizer

However, the opposite effect was also observed. High temperature

Nonionic

Anionic

Water

water

may induce calcium carbonate precipitation from reservoir brine on

Brine

the silica surface. When covered by calcium carbonate silica surface

becomes water-wet Rao [79]. He concluded that many factors control
– Silicon wafer substrates
– Oil-wet sandstone core
– Oil-wet carbonate core
Selection of published studies on wettability alteration by low nanofluids.

how high temperate influences the wettability of sandstone including

– Oil-wet sand pack

– Indiana limestone

brine composition and pH.

– Berea sandstone

2.5–10.4 – Glass substrates

Schembre et al. [89] found that sandstone becomes more water-wet

– Micromodel

at high temperatures. This was attributed to fine detachment from rock

Materials

surface at elevated temperature [89]. They also mentioned that water

– Glass

film on pore surfaces becomes more stable at high temperature. Tang

and Morrow [105] referred to crude oil brine rock (COBR) as the possible
mechanism of wettability alteration and not only rock/brine interaction.
35 ± 4
(nm)

4–20

The range of the temperature that was tested was up to 230 °C.
Size

24

14

Babadagli [15] carried out capillary imbibition tests on Berea sand-

stones at different temperatures. The results indicated that increasing
range

2–3

9.3
pH

temperature from 27.5 °C to 80 °C enhances the imbibition rate

–

and final recovery. The decrease in oil viscosity and IFT at elevated
Nanoparticle type and

(5.75 to 12.68) grams

temperature contributes to improved oil recovery. He indicated that

Silica (0.1–5.0) wt.%

Modified silica 10%

(100–10,000 ppm)

per gram of water

higher imbibition rate at higher temperature is mainly due to viscosity

Bismuth telluride
Zirconium oxide

Alumina oxide

reduction and the effect of wettability alteration and IFT reduction on

concentration

(0.05 g/cm3)

the improved recovery was minimally low.

Gupta and Mohanty [38] conducted imbibition tests using several an-
Table 4

ionic and nonionic surfactants under different temperatures up to 90 °C.

They found that high temperature increases the ability of surfactants to
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 69

imbibe spontaneously into limestone samples. Improvement of sponta- A study on the effect of Enterobacter cloacae strain bacteria on the
neous imbibition is attributed to the gravity forces that are enhanced by wettability was reported by Karimi et al. [54]. Both contact angle and
viscosity reduction. Al-Hadhrami and Blunt [6] conducted an analytical AFM were used to investigate the ability of E. cloacae to change the wet-
study based on an earlier experimental research. The data used shows tability of oil-wet silica surfaces. This bacterium was observed to change
that spontaneous imbibition of water at elevated temperatures (around the wettability of aged microscope glass slides toward more water-wet.
240 °C), enhanced leading to about 27 to 35% OOIP incremental oil Bacteria were believed to adsorb on the silica surface removing the
recovery. As no imbibition occurred at the reservoir temperature, the organic layer that renders the surface oil-wet. Water contact angle
authors attributed this improvement to wettability alteration at elevated was reduced from 115° to 8.7° after 2 days of bacterial solution exposure
temperatures. Based on this data, a 1 D model for imbibition and heat when mineral salt solution was used. The wettability consequently
transport in the rock matrix was developed. The model predicted changed from oil-wet to water-wet [54].
that approximately 30% OOIP could be achieved in a single matrix after The above discussion indicates that bacteria may have different
700 days of steam or hot water flooding in comparison with only 2% effects on wettability depending on their composition. In fact, a similar
production under natural aquifer drive. observation was reported by Afrapoli et al. [3]. They tested the sponta-
Hamouda and Gomari [42] conducted a wettability alteration study neous imbibition of two growth variants of alkane oxidizing bacterium,
on carbonate reservoirs using contact angle, IFT, and Zeta potential Rhodococcus sp. 094. Surfactant producing bacterial solution was
measurements to account for the effect of temperature. They found observed to reduce the water-wetting of silica, while non-surfactant-
that changes in contact angle at high temperatures follow the same producing bacteria were able to alter the wettability to be more
trend as the changes of IFT. The contact angle reduced from 160° to water-wet. Further investigations on the mechanism of wettability
68° at high temperatures, indicating that the wettability of carbonate alteration by microbial methods are needed to clarify these controversial
is reversed from oil-wet to water-wet when temperature is increased. effects.
As temperature increases, the positive charge on the calcite surface is
reduced, which in turn increases the repulsive forces between the
calcite surface and the adsorbed organic components. They concluded 8.2. Ionic liquids
that there is a critical temperature for maximum possible wettability
alteration that can be attained. If the temperature increases above this Ionic liquids are new type of chemicals that have been recently stud-
value, no further wettability alteration can be achieved [42]. A summary ied extensively for different fields of applications. These applications
of selected published studies on wettability alteration nanofluid is given include thermo-electrochemical cells [11], CO2 capture [50], catalyzed
in Table 5. reaction [31], and even as a green solvent [81]. Ionic liquids are defined
as salts that have low melting temperature [114], and, therefore, can be
found in liquid state at ambient conditions. They are environmentally
8. Potential wettability modifiers friendly and considered green solvents [81]. Their low vapor pressure
and strong dissolving characteristics make them safer and more
8.1. Microbial method efficient compared with other organic solvents.
There are a few publications on the application of ionic liquids in oil
Although its effects on the reduction of IFT are well known, microbial refining process. Lo et al. [60] and José-Alberto and Jorge [50] reported
enhanced oil recovery was suggested as a new method for wettability that ionic liquids can be used to extract and oxidize sulfur compounds
alteration. A study by Kowalewski et al. [55] documented the results in light oil. Hu and Guo [47] found that ionic liquids can be efficiently
of microbial enhanced oil recovery in sandstones. They reported that employed to reduce asphaltene precipitation. José-Alberto and Jorge
bacteria may reduce the residual oil saturation by two mechanisms: [50] provided a detailed list of the possible applications of ionic liquids
(1) IFT reduction and (2) wettability alteration. When bacteria are during CO2 injection to reduce asphaltene deposition in the reservoir.
allowed to grow on sandstone surfaces, the IFT is reduced significantly. Joonaki et al. [49] investigated the effect of several ionic liquids in
They also suggested that more IFT reduction can be achieved when heavy oil using spontaneous imbibition and core flooding tests. They
bacterial growth increases. Sandstone cores used during the study concluded that ionic liquid that have hexafluorophosphate anion
were strongly wet–wet and the Amott indices showed no change in [PF6] – and tetrafluoroborate anion [BF4] – will produce hydrogen
the wetting state. The authors, however, stated that dynamic of imbibi- fluoride (HF) gas when they are mixed with heavy oil. They tested a
tion by microbial may indicate an alteration of wettability toward less new ionic liquid on heavy oil sample. Free imbibition tests showed
water-wet state. The behaviors of microbial enhanced oil recovery that recovery factor improved from 41% to 74% when the new ionic
in some core samples were not identical and the authors attributed liquid was mixed with heavy oil. The new prepared ionic liquid was
this difference to bacterial growth rate. They conclude that wettability reported to upgrade heavy oil by reducing asphaltene content, viscosity,
alteration by microbial methods is controlled by the initial state of the and average molecular weight of heavy oil.
wettability. If the initial wetting state is water-wet, it may become less Recently, several studies investigated the use of ionic liquids in oil
water-wet and if it is oil-wet it shifts to be more water-wet. sand extraction. Painter et al. [77], Williams et al. [117], and Painter

Table 5
Selection of published studies on wettability alteration at high temperature.

Temperature Material Brine Range of Tests Results Reference

recovery

45 to 230 °C Diatomite Na+, K+, ~32% – Contact angle – Light oil (34API) Schembre et al. [89]
(sandstone) plugs Ca2+, Mg2+, – Imbibition test – Contact angle reduced from 18.3° at 45 °C to 0° at 230 °C
Cl−, HCO−3 – Reduction of oil to water viscosity ratio at high temperature
results in less resistance to water imbibition and also change the
wettability to be more water-wet
25 to 130 °C Calcite crystals Distilled ~11% – Contact angle – Model oil and Heptane Hamouda and
Chalk plugs (carbonate) water – Zeta potential – Contact angle decreased from 160° at 25 °C to 68° at 130 °C Gomari [42]
Imbibition test – Zeta potential reduced from 2.95 mV at 20 °C to 0.45 mV at 50 °C
70 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

et al. [76] studied the ability of different ionic liquids to separate bitu- surfactant in carbonates does not usually exceed the CMC concentra-
men from oil sand. They reported that about 95% of oil can be recovered tions. For example, Standnes and Austad [94] found that there is no
using ionic liquid extraction. After oil extraction, ionic liquid can be significant difference in oil recovery by spontaneous imbibition when
separated and recycled several times. They also showed that some the concentration of cationic surfactant was increased from 1.0 wt.% to
of ionic liquids were inefficient because they agglomerated after 5 wt.%. They concluded that wettability alteration by cationic surfac-
interaction with oil sand. Ionic liquids that worked efficiently were tants is optimized at a concentration around or slightly higher than
1-butyl-2, 3-dimethylimidazolium tetrafluoroborate, BMMIM BF 4 CMC. The application of alkaline anionic surfactant requires only dilute
and 1-ethyl-3-methylimidazolium tetrafluoroborate EMIM BF 4 amount of anionic surfactant. Hirasaki et al. [44] used about 0.05 wt.%
([76]; Li et al., 2011). of anionic surfactant CS-330 to successfully alter the wettability of
In attempt to explore the potential of using ionic liquid in enhanced carbonate. The search for cheaper surfactant for wettability alteration
oil recovery, Benzagouta et al. [22] screened different ionic liquids is ongoing. For example, Standnes and Austad [94] found that a low
established from Ammoeng™ group by measuring their IFT with cost ammonium surfactant, which is commercially available surfactant,
crude oil. They found that ionic liquid Ammoeng 2 was able to reduce contains the similar effective materials cationic surfactant C12TAB.
IFT with crude oil better than surfactant Triton X-100. Upon mixing Surfactant adsorption on the rock surfaces is one of the major rea-
Ammoeng and Triton X-100, they showed that the IFT values were a sons that cause surfactant loss. Many studies have investigated reducing
function of different factors such as total concentration and the surfac- the surfactant adsorption to minimize the overall cost of surfactant
tant to ionic liquid mass ratio. Temperature was also found to be critical consumption. Surfactant adsorption usually increases as surfactant
on IFT reduction by ionic liquids. A more recent screening study by Bin- concentration increases and reaches a maximum at critical micelle
Dahbag et al. [132] also listed Ammoeng 2 to be optimum option. The concentration (CMC). Obviously, reducing the surfactant concentration
study screened ammonium and phosphonium ionic liquids based on effectively minimizes the adsorption as well as the cost of surfactant.
their solubility in water, thermal stability and IFT trend with tempera- Another way to reduce the adsorption is to use alkaline with surfactants.
ture. Ionic liquid Ammoeng 2 was observed to be stable at temperatures Na2CO3 can reduce the adsorption of anionic surfactant at low concen-
as high as 80 °C. trations. Wettability alteration by surfactant is limited by the ability of
Mohammed and Babadagli [66] used ionic liquid for wettability surfactant diffusion and adsorption onto the rock surface. Stoll et al.
alteration by dissolving different ionic liquid in water. An ionic liquid [97] showed that a diffusion of surfactant represents a serious challenge
solution was able to recover diluted oil (heavy oil mixed with solvent) when wettability alteration by surfactant is upscaled. Surfactant
from oil-wet carbonate surface after the cores were exposed to pre- diffusion can be enhanced by viscous forces [110] or by increasing the
solvent phase. temperature [94].
Enhanced oil recovery by ionic liquid can be explained based on its Many types of surfactants were suggested in literature. Surfactant
effect on IFT and the adhesion force. Malham et al. [62] and Liu et al. screening study should be performed to select the optimum surfactant
[59] measured the IFT of ionic liquid–water mixtures at different liquid system. Stability of surfactant at high temperature is one of the limita-
concentrations. Only a dilute amount of ionic liquid (~0.03% mass frac- tions of using surfactant in wettability alteration for high temperature
tion) was required to decrease IFT of the mixture from 73 millinewtons and high pressure reservoirs. Dual surfactant was used successfully to
per meter (mN m−1) to its minimum value at 40 mN m−1. It is observed increase thermal stability of surfactant. Sharma and Mohanty [91], for
that the adhesion energy between bitumen and Alberta oil sand was re- example, combined cationic surfactant and nonionic surfactant to create
duced to 0.4 millijoules per millimeter (mJ/m2) compared to 4 mJ/m2 in thermally stable surfactant solution at temperatures higher than 100 °C.
KCl solution [46]. All these evidences indicate that ionic liquid offers a Each of the combined surfactants was not stable at 100 °C.
great potential as a wettability alteration agent as it affects both rock
and fluid properties and because it can be customized to serve specific
9.2. High pH solutions
application.
As explained in Section 6, high pH solutions can be used effectively in
9. Opportunities and challenges
wettability alteration in sandstone and limestone. Alkali consumption on
rock surface could hinder efficiency of wettability alteration process.
To induce wettability alteration, i.e., make the system more water-
Alkalis were found to be consumed on anhydrite more than other min-
wet, a chemical or thermal treatment must be applied. Several chemical
erals. Interactions of alkali with rock minerals can lead to permeability
and thermal methods were suggested in literature and each of these
reduction due to secondary precipitation of minerals. Another limitation
methods has certain limitations and challenges that should be carefully
that could negate the alkali effect is pH buffering. Fortunately, there are
considered. Depending on conditions of the candidate reservoir and the
several alkalis that have relatively low consumption on the rock surface.
availability of wettability alteration agents, some of the chemical and
NaBO2 is less consumed by anhydrite than Na2CO3. One of the other is-
thermal methods may be more attractive than others. For example,
sues that could arise during alkali flooding is the increased sulfate con-
using low salinity water would be more appealing if a fresh water
centration when Na2CO3 are used as alkalis [134].
source is available nearby. The use of some chemicals may be regulated
by environmental legislations. Thermally induced wettability alteration
in deep reservoirs is a challenge as steam loses its quality as it travels 9.3. Nanofluids
deeper into the reservoir and very high temperatures are needed for
this process. The opportunities and challenges of each of the previously Many studies tested the efficiency of combining two or more wettabil-
introduced wettability modifier are presented in this section. ity modifiers. When two wettability modifiers are combined, one of them
will be the primary wettability alteration agent. A secondary wettability
9.1. Surfactant modifier may be used to enhance the efficiency of wettability adjustment
process. For example, nanofluids are usually combined with different
There is a wide range of surfactant that can be selected for wettabil- types of surfactants. In a study by Giraldo et al. [34], anionic surfactants
ity alteration. Surfactants can also be mixed to create a new surfactant were used as a primary wettability modifiers and alumina was observed
blend with different properties. Similar to other EOR processes, using to increase the adsorption of surfactant in oil-wet sandstone and thus
surfactants for wettability alteration has always faced the limitation of enhances its ability to alter the wettability of sandstone. In other
surfactant cost, which is a function on the surfactant concentration. cases, nanofluids are used as a primary wettability alteration agent.
The concentration that is required for wettability alteration by Karimi et al. (2012) used zirconium nanofluid to change the wettability
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 71

of oil-wet carbonate cores. A combination of non-anionic surfactants 10. Wettability alteration in heavy-oil containing oil-wet
was used to stabilize the suspension of zirconium nanofluid. fractured reservoirs
Other methods were also used to stabilize the colloidal dispersion
of nanoparticles such as modification of particle surfaces or the pH Few attempts have been made to investigate the wettability alter-
of the solution. Consequently, the need for surfactant is eliminated. ation in the heavy-oil containing oil-wet fractured reservoirs. In such
For instance, Maghzi et al. [61] employed silica nanoparticles to modify complicated systems not only the rock characteristics should be altered
the wettability of oil-wet microglass only by using water as a (wettability), the crude oil properties must also be changed. Therefore,
suspending fluid. The wettability of silica nanoparticles was modified solvent-based processes can be indispensable for recovering heavy-oil
to be lipophobic–hydrophilic. Acquiring stable nanofluids without from oil-wet fractured reservoirs. When solvent is injected, it diffuses
surfactants is desired to decrease the overall cost of the process. into the matrix system and reduces both density and viscosity of
Note that although many experimental studies show that nanofluids heavy-oil which will then be produced containing fraction of the
can reduce IFT and contact angle, this might not be reflected as improved injected solvent. At the end of the process, a considerable amount of
oil recovery if the nanofluids are not properly designed. Also, similar to diluted oil (original heavy oil mixed with injected solvent) remains in
surfactants, nanofluids are more efficient in light oil than in heavy oil the oil-wet matrix system. Provided that the wettability of the matrix
[135]. is altered from oil-wet to water-wet, diluted oil can be drained by
The limitations of using nanofluid as wettability modifiers are directly water imbibition improving both oil-recovery and solvent retrieval.
related to their tendency to be unstable in the long-term leading to nano- Mohammed and Babadagli [65] tested this hypothesis using recovery
particle agglomeration and precipitation on the rock surfaces. Different process that is composed of two phases: (1) Solvent phase and (2) wetta-
methods for nanofluid stability are given in Section 6. Generally, stability bility alteration phase. Two types of rock were used to represent different
of nanoparticles colloidal suspension can be enhanced by increasing state of wettability. Limestone cores were used as strongly oil-wet sys-
repulsive forces between the nanoparticles over the attraction forces. tems while aged Berea sandstone cores were considered weakly water-
The direct impact of the particles precipitation process is to lose the wet systems. A heavy crude oil of 3600 cp viscosity was used to saturate
unique properties of the nano-suspension and the inability to distribute both types of rocks under vacuum at 65 °C. After one week of saturation,
the particles homogenously in different parts of the reservoir. limestone cores became strongly oil-wet while Berea sandstone cores
The stability of nanofluids is a function of the type, size and concen- were water-wet as indicated by contact angle measurements. Sandstone
tration of the nanoparticles in the suspension. It has been demonstrated cores were aged under the same saturation conditions for 6 weeks before
that if concentration is increased beyond certain limit, particles may acquiring a weakly water-state. Solvent phase was applied using two
agglomerate and form clusters and this consequently leads to porosity/ types of solvent: heptane and diluent oil.
permeability impairment. Therefore, selection of the optimum nanopar- Mohammed and Babadagli [65] compared oil recovery during
ticles' type, size, and concentration in addition to proper stabilization wettability alteration phase for two cases. For the first case, sandstone
method is immensely vital factor for the application of nanofluid in and limestone core samples saturated with heavy oil were placed di-
wettability alteration. rectly into imbibition cells filled with wettability alteration chemicals
(anionic surfactant for sandstone and cationic surfactant for limestone).
9.4. Thermal methods Only 8% of oil was recovered from the sandstone core. The recovery for
limestone was as low as 2%. In the second set of experiments sandstone
Using hot water/steam as a wettability modifier in sandstone and and limestone core samples that were saturated with the same heavy
carbonate reservoir was tested by many studies. Rock mineralogy oil crude oil (3600 cp) were immersed in heptane for 10 days and then
composition appears to have a direct impact on whether sandstone put directly in imbibition cell that was filled with the same wettability
becomes more oil-wet or water-wet. In carbonate reservoir, however, alteration chemical that was used in the first set of experiments. Diluted
temperature seems to adjust the wettability only toward more water- oil recovery increased dramatically from about 8% to 57% for sandstone
wetness. For example, Motealleh et al. [133] observed that hot water while it reached 40% for limestone up from 2% (Fig. 4). These results
(225 °C) resulted in spontaneous imbibition of water into tubes filled show the importance of the solvent phase for the subsequent wettabil-
with oil-wet carbonate samples. Note that applying such high tempera- ity alteration phase.
tures in the field may be faced with many practical, economic, and This was also confirmed by using another solvent, which has a
environmental concerns. For heavy oil, however, this option may be higher mixing capability. Mohammed and Babadagli [65] reported
more attractive than chemical methods. There is no published field that diluent oil recovery for sandstone was increased from 57% to 63%
scale proof of wettability alteration at elevated temperatures. when the diluent oil was used in solvent phase instead of heptane. It
Chemically induced wettability alteration can be enhanced at high is obvious that a higher efficiency of water imbibition during wettability
temperatures. Standnes and Austad [94] showed that the imbibition alteration is directly related to the extent of dilution that can be
rate of surfactant solution into oil-wet carbonate core at 70 °C is twice achieved by solvent. This indicates that both solvent type and soaking
that of at 40 °C. period should be optimized to increase the efficiency of the process.
Another important factor is the type of wettability alteration agent.
9.5. Smart water and low salinity water Based on the discussion provided in previous section, there are list of
chemicals that have higher ability to alter the wettability in sandstone
The chemical composition, salinity, and pH of the injected water play than limestone and vice versa. Screening of wide range of chemicals
a significant role in changing the surface properties of the rock and there- by Mohammed and Babadagli [65] revealed a group of chemicals that
by, the wettability of an oil-wet porous medium. Wettability alteration of could potentially alter the wettability of sandstone and limestone
oil-wet sandstone by low salinity water has been extensively studied by toward water-wetness. Short listed chemicals are provided in Table 6.
many researchers. In addition to satisfying some conditions to be applied
successfully [69], another important factor to be considered is the avail- 10.1. Sandstone case
ability of fresh water sources nearby. High salinity water that contains
multi-divalent ions, on the other hand, is able to change the wettability Fig. 5 shows the wettability alteration indicated by final diluted oil
of oil-wet carbonate reservoir as explained in Section 6. One major limi- recovery for selected experiments from Mohammed and Babadagli
tation of using high salinity water that it is inefficient in low temperature [65]. It can be seen that distilled water was able to produce about 52%.
and high temperature medium is needed to speed the reaction of multi- It was discussed in Section 6 that lowering the salinity of injected
divalent ions. water increases the repulsive forces between rock sandstone surface
72 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

Final Diluted Oil Recovery

60% 57%

50%
40% Sandstone

Oil Recovery
40% Limestone
30%

20%
8%
10%
2%
0%
With solvent phase Without solvent phase

Fig. 4. Diluted oil recovery during wettability alteration phase for cases with and without solvent phase.

and the adsorbed organic components. A recent study by Morsy and surfactant C12TAB, on the other hand, imbibed spontaneously into
Sheng [71] performed on shale core samples showed that distilled limestone displacing about 40% of the diluted oil. As stated in
water improved oil recovery in shale core samples almost double 2% Section 6, Standnes and Austad [94] observed that cationic surfactant
KCl brine. They attributed the efficiency of distilled water to the clay type CnTAB can alter the wettability of chalk which saturated with
swelling effect. light oil (crude oil: heptane 60:40 by volume). A similar conclusion
Oil recovery by ethoxylated sulfate anionic surfactant STEOL™ can be made on heavy oil if a solvent phase is applied. While anionic sur-
CS-330 (3 ethylated groups) was increased to 59%. Salehi et al. [86] factants cannot alter the wettability of limestone by ion pair interaction,
showed that anionic surfactants can desorb the cationic organic compo- they can still improve oil recovery by reducing IFT [94]. About 30% of di-
nents from sandstone surface and thus adjust the wettability to be more luted oil was recovered using ethoxylated sulfate anionic surfactant
oil-wet. Propoxylated sulfate anionic surfactant Alfoterra™ 145-8S STEOL™ CS-330.
(8 propoxylated group) was not efficient as CS-330 with a final recovery Zirconium nanoparticles dispersed in water were tested as wettability
of 30%. Ionic liquid BMMIM BF4 was able to increase diluted oil recovery modifier in light oil systems by Karimi et al. [53]. Mixture of non-ionic
to more than 63% better than all other chemicals that were tested. As surfactants was used as suspending fluid. Mohammed and Babadagli
explained in Section 6, ionic liquid can affect both rock characteristics [65] used water as a suspending fluid. As shown in Fig. 6, zirconium
and fluid properties. Mohammed and Babadagli [65] attributed the effi- nanofluid was able to recover an amount of diluted oil that is similar to
ciency of ionic liquid to its ability to reduce the IFT and adhesive forces. anionic surfactant. Ionic liquid BMMIM BF4 resulted in the best diluted
Alumina nanofluid was reported by Giraldo et al. [34] to have the ability oil recovery as was the case in sandstone, which indicates that it can ad-
to enhance the wettability alteration induced by surfactant solution. just the wettability of both silica and carbonate to be more water-wet. No
About 25% diluted oil recovery was obtained when alumina nanofluid conclusive explanation of the mechanisms of wettability alteration by
was used in aged sandstone core. No surfactant was added to the ionic liquids was provided by Mohammed and Babadagli [65]. However,
system. this study shows that both reduction of IFT and adhesive force might con-
High pH solution with NaBO2 resulted in a relatively slow but even- tribute to the improved oil recovery.
tually resulted in the second highest oil recovery. The 60% of diluted oil Similar high pH brine that was used to alter the wettability of sand-
that was recovered by NaBO2 shows that increasing the pH of injected stone was tested on limestone by Mohammed and Babadagli [65]. They
water may reduce the attraction forces between silica and organic referred to a study by Zhang et al. [128], which pointed out the efficiency
materials that caused the oil-witness of rock surface. of NaBO2 to alter the wettability of carbonate better than other alkalis.
Fig. 6 indicates that NaBO2 was able to alter wettability in the limestone
10.2. Limestone case cores as strongly as the cationic surfactant C12TAB. It was explained in
Section 6 that reducing pH of oil-wet system is believed to decrease pos-
Overall, it appears that diluted oil recoveries in limestone were less itive charges of carbonate rock surfaces and hence increase the repulsion
than those with the sandstone samples which can be attributed to the force between the surface and organic adsorbed matter. Wettability will
strong oil-wetness characteristics of the limestone (Fig. 6). Cationic be then altered to be more water-wet.

Table 6
Chemical used for wettability alteration tested by Mohammed and Babadagli [65].

Core# Chemical solution Core# Chemical solution

S1 Anionic surfactant CS-330 L1 Cationic surfactant C12TAB

(1 mmole/l) (1 wt.%)
S2 Anionic surfactant Alfoterra-8S (Alf-8S) L2 Anionic surfactant CS330
(1 mmole/l) (1 mmole/l)
S3 Distilled water L3 Distilled water
S4 NaBO2 L4 NaBO2
(2.5 wt.%) (2.5 wt.%)
S5 Ionic liquid BMMIM BF4 L5 Ionic liquid BMMIM BF4
(1 wt.%) (1 wt.%)
S6 Alumina nanoparticles L6 Zirconium nanoparticles
(1 wt.%) (1 wt.%)
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 73

Final Diluted Oil Recovery

70% 63%
58% 60%
60% 54%
50%

Oil Recovery
40%
30%
30% 25%

20%

10%

0%
Distilled Anionic Anionic Ionic liquid Al2O3 NaBO2
Water surfacatant surfactant BMMM BF4 nanofluid
CS330 Alf-8S

Fig. 5. Diluted oil recovery during wettability alteration phase for sandstone cores.
Reproduced after Mohammed and Babadagli [65].

Note that one has to be critical in the analysis of such data in terms of drive support. The trends seen in the first 10 days did not change
wettability alteration since the ultimate recoveries by spontaneous between days 10 and 100 even though the recoveries were accelerated.
imbibition (SI) tests may not be totally due to wettability alteration. During this period, additional recovery can be expected due to gravity
Reduction in the IFT when surfactants are used and gravity accelerated drainage accelerated by IFT reduction. But, one may argue that this
by this may result in additional recovery. Although it is rather difficult will be relatively small compared to the contribution by capillary imbi-
to fully distinguish the effect of different causes on the SI recovery, the bition that was improved by wettability alteration. For example, surfac-
“dynamic” data obtained would be helpful to clarify the wettability tant solutions are expected to yield accelerated recovery in late times
alteration effects as done in Section 4.1. To achieve this, a modified due to IFT reduction for light oil cases [18–20,88]. But, this is not seen
version of the SI data generated by Mohammed and Babadagli [65] in the case of all surfactants (S1 yielded good recovery but S2 did not,
corresponding to the ultimate oil recovery values in Figs. 5 and 6 is as seen in Fig. 7). The nanometal solution (S6), distilled water (S3),
displayed in Figs. 7 and 8. and ionic liquid (S5) are not expected to change IFT and accelerate the
It should be noted before further analysis that only dilute amount of gravity but they yielded as high ultimate recovery as case S1. Based on
chemicals was used in water and the oil used is highly viscous. There- this analysis and considering the heavy nature of oil, one may conclude
fore, there was no significant change in density before and after using that the gravity forces are not strong enough to dominate the process
chemical solutions. Also, the core samples are only about 9 cm in length even if they are accelerated by reduced IFT. Hence, the ultimate recover-
which does not provide significant hydrostatic head for gravity forces. ies are predominantly controlled by the wettability alteration and not
Thus, oil recovery by gravity is a slow process and one may need wetta- by the change in IFT or the effect of gravity forces. In fact, Mohammed
bility alteration to obtain enhanced spontaneous imbibition process to and Babadagli [65] reported through their visual analysis that the
reach the recovery values given in Figs. 5 and 6. droplets of oil accumulated at the different faces of core samples as an
The SI curves given in Fig. 7 for sandstones show two distinct indication of capillary imbibition enhancement due to wettability
behaviors for all six cases. Although it is an aged sample, it shows alteration.
weak water-wet nature and an amount of recovery is observed by cap- Oil-wet carbonate samples showed a bit different behavior than
illary imbibition in the first 10 days. The difference in the recovery rates sandstones (Fig. 8) due to more oil-wet nature. When an oil-wet core
among the six cases is due to wettability alteration with minimal gravity limestone sample immersed in water for more than three months, the

Final Diluted Oil Recovery

60%

50% 48%

40%
40%
Oil Recovery

34%

30% 25% 25%

20%

10%
2%
0%
Distilled Cationic Anionic Ionic liquid ZrO2 nanofluid NaBO2
Water surfactant surfactant BMMIM BF4
C12TAB CS-330

Fig. 6. Diluted oil recovery during wettability alteration phase for limestone cores.
Reproduced after Mohammed and Babadagli [65].
74 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77

0.7
including gravity driven by reduction of IFT are limited due to shortness
of the core samples, heavy nature of oil, and tightness of the rock in case
0.6 of carbonates.
Recovery factor (fraction)

0.5 10.3. Bitumen containing carbonate samples

S1
S3
S5 The challenge of recovery bitumen (5–9° API-1,600,000 cp) from the
0.4
Grosmont carbonates was studied by Mohammed and Babadagli [65]. A
S4
preserved core was immersed in heptane for 3 weeks and then put into
0.3 water for one week. Oil recovery during this period was negligible,
S2 which confirmed the oil-wetness of the Grosmont core. Water was
0.2 then exchanged with alkaline NaBO2 solution (2.5 wt.%). Oil displace-
S6 ment started immediately indicating that wettability of Grosmont was
altered to more water-wet. Changing the pH of the injected water
0.1
using NaBO2 was shown to significantly affect the electrostatic forces
between carbonate surfaces and adsorbed organic matters. It was con-
0 cluded that a combination of solvent phase can efficiently improve oil
1 10 100
recovery in heavy-oil/bitumen containing oil-wet fractured carbonate
Time (days)
reservoirs [65].
Fig. 7. Spontaneous imbibition test results with different chemicals given in Table 6. Rock
type: Sandstone (Berea). 11. Conclusions and remarks
Reproduced after Mohammed and Babadagli [65].
Wettability is one of the most critical characteristics of rock–fluid
systems in oil recovery. Its alteration to more favorable water-wetness
oil production was very low indicating that gravity forces could not
efficiently is a critical problem. A systematic approach for a wettability
exceed the negative capillary forces (L3 case in Fig. 8). Obviously, the
alteration processes was provided in this paper. The following are the
“negative” sign of the capillary forces is assigned by the large values of
highlights from this extensive review.
contact angle of water on oil-wet surfaces. Reduction of this contact
angle is fundamentally important to initiate any type of spontaneous
1. Wettability alteration process in each reservoir is a unique process
imbibition in this type of oil-wet surfaces. As similar to the sandstone
and requires the understanding of the mechanisms that caused a
cases, an increasing trend started after 10–20 days. But this increase
reservoir to be oil-wet.
was not as fast as in the sandstone case but it is primarily due to wetta-
2. Chemical induced wettability alteration is suitable in light oil
bility alteration. At later times (typically after 20–30 days), there was a
reservoirs while thermal methods are more attractive in heavy oil
steep increase in oil recovery as indicated by the imbibition curves,
reservoirs. To apply chemical wettability alteration in heavy oil
which can be attributed to additional support from gravity induced by
reservoirs, oil properties have to be changed thermally or using
IFT. Note, however, that the highest recovery was obtained with ionic
solvents.
liquid (L5) and no IFT reduction is expected as is in the case of cationic
3. Although contact angle measurement gives a fast and economical
surfactant (L1). The anionic surfactant case (L2) did not show high
mean to evaluate the alteration of surface wettability, the results
recovery as the cationic one (L1) even though they both significantly
might be misleading; therefore, it should be integrated with another
reduced the IFT. Hence, one may conclude that the SI recovery is
measurement tool.
predominantly due to wettability alteration and cationic surfactants
4. Spontaneous imbibition test is the most reliable tool for wettability
are expected to alter wettability more strongly compared to the anionic
alteration measurement. The shape of imbibition curve, ultimate
ones in oil-wet carbonates [12,13].
oil recovery and the visualization of the oil production from different
The above analysis indicates that the SI recovery performance data
core faces provide valuable information to analyze the mechanisms
given in Figs. 5 through 8 for different chemicals is primarily due to wet-
of wettability alteration.
tability alteration that leads to enhanced imbibition. The other effects
5. Wettability alteration may increase oil recovery by gravity or capil-
lary imbibition.
0.6 6. Surfactants are the most studied wettability modifier in literature.
Yet, there is no agreement on screening criteria to determine
0.5 which type of surfactant is best for carbonate or sandstone. It is
Recovery factor (fraction)

L5
difficult to describe a general type of surfactant (i.e., anionic, cationic,
0.4
or non-ionic) as a better wettability modifier than the other type. An
efficient wettability modifier for certain type of rock can be found in
L1
any of these surfactant groups.
0.3 L4
7. Ammonium surfactants are the most cited successful wettability
L2
modifier for carbonates, while ethoxylated surfactants are the most
0.2
cited successful wettability alteration agent in sandstones.
L6
8. High pH solutions represent one of the most feasible wettability
0.1
modifiers. They can alter the wettability of sandstone and carbonate.
L3 Alkaline may be injected with surfactant to enhance the wettability
0 alteration at optimum salinity. The type and the concentration of al-
1 10 100
kaline should be carefully selected to minimize the consumption of
Time (days)
alkaline on the rock surfaces.
Fig. 8. Spontaneous imbibition test results with different chemicals given in Table 6. Rock
9. Low salinity water may adjust the wettability of oil-wet sandstone
type: Carbonate (Indiana Limestone). to be more water-wet while high salinity water that contains opti-
Reproduced after Mohammed and Babadagli [65]. mum composition of divalent ions shifts the wettability of oil-wet
 M. Mohammed, T. Babadagli / Advances in Colloid and Interface Science 220 (2015) 54–77 75

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