Journal of Molecular Liquids 275 (2019) 265–280

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Journal of Molecular Liquids

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

Wettability alteration in carbonate and sandstone rocks due to low

salinity surfactant flooding
Ali Aminian, Bahman ZareNezhad ⁎
Faculty of Chemical, Petroleum and Gas Engineering, Semnan University, PO Box 35195-363, Semnan, Iran

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

Article history: Commonly, desorption of crude oil from rock surfaces accomplished by the exposure to the decreasing salt con-
Received 23 June 2018 centrations of NaCl, Na2SO4, MgCl2 and CaCl2 solutions. However, adsorption and desorption of crude oil are the
Received in revised form 27 August 2018 functions of several attributing factors at undoubtedly low salinity brine solutions. For silica surfaces, both rock
Accepted 16 November 2018
and oil possess negative charges during low salinity injection that leads to the electrical double layer expansion
Available online 19 November 2018
and electrostatic repulsion between them. For carbonate rocks, rock dissolution and negatively charged surface at
Keywords:
higher pH could be regarded as the driving forces for oil desorption. Thus, adsorption/desorption studies of dif-
Enhanced oil recovery ferent oils over silica and carbonate rocks while considering salinity, ion composition and aging of the rocks
Low salinity surfactant would be sufficient to alter the wettability of the rocks. In the present paper, the effect of saline water containing
pH surfactant has been discussed on the performance of enhanced oil recovery (EOR). Wettability alteration trig-
Smart water gered by the change in interfacial tension (IFT) between crude oil and low salinity surfactant (LSS) is known to
Carbonate be the main factor regarding EOR processes. However, wettability depends on several factors, namely, multiple
Sandstone ion exchange (MIE), interfacial elasticity modulus, cation bridging, acid/base numbers of oil, rock composition
and structure, ratio of divalent/monovalent (M2+/M+) cations in the formation brine, aging time, the status of
zeta potential, surfactant structure and concentration, pH of the medium, T & P of reservoir, permeability and
pressure drop change. Therefore, we thoroughly examine the microscopic mechanisms of LSS flooding via study-
ing individual aforementioned factors that influence the contact angle change in sandstone and carbonate rocks.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Waterflooding process cannot provide complete oil recovery from
porous media in reservoirs; therefore, alternative processes such as sur-
factant or polymer flooding, known as tertiary recoveries, are of consid-
erable importance [1].
Re-injection of produced water from wells is useful for secondary in-
jection that does not produce formation damage similar to what we are
being observed in nanoparticles or surfactant flooding; however, the
amount of produced water is limited and as a result, modified formation
brines are coming to play role.
It is assumed that wettability alteration due to interfacial tension
change is responsible for the enhanced oil recovery, while there are sev-
eral interaction forces behind it. Moreover, the high cost associated with
the surfactant flooding and possibility of damages to the well due to sur-
factant adsorption enforced researchers to put some criterions for the
concentration of surfactants and theirs structure in a brine solution
⁎ Corresponding author.
E-mail addresses: ali_aminian@ymail.com (A. Aminian), bzarenezhad@semnan.ac.ir
(B. ZareNezhad).
[2]. On the other hand, the conditions under which oil recovery can be
attained by LSS flooding have been under question. Identifying the rela-
tionships between wettability and IFT is crucial to quantify the best pro-
cedure for oil recovery. This quantification is complicated due to the
strong interactions within crude oil/brine/rock systems. Interfacial me-
niscus development can also influence the relative permeability of
water in a porous rock that originates from the wettability alteration
of a rock toward water-wetness. Even though, initial wettability and
saturation history of a rock can also affect the wettability [2]. Therefore,
researchers are trying to monitor the wettability of a rock via contact
angle measurements and use IFT to determine the interactions among
fluid phases (brine/surfactant/oil). Another approach is to calculate
total disjoining pressure for a crude oil/brine/rock system that can tell
us the extent of wettability alteration upon injection of low salinity
brine solutions.
Oil recovery depends on the several factors, hence, brine composi-
tion & concentration and initial wetting condition of reservoir rock are
among the most important ones [3]. Frequently, reservoir rocks are ini-
tially oil-wetted, while attempts directed toward turning the oil-wet
rock into a water-wet rock. Wetting alteration by destabilizing the oil
layers adhered to reservoir rock through LSS flooding is a promising

https://doi.org/10.1016/j.molliq.2018.11.080
0167-7322/© 2018 Elsevier B.V. All rights reserved.
266 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
EOR technology due to enhanced capillary number. Once capillary num-
ber increased, the higher permeability and lower pressure drop at the
pore entrance will result [4,5].
Usually, LSS provides driving factors for: (a) the interfacial tension
reduction, (b) the change in three-phase contact angle among solid
rock-oil-water, and (c) instability in interface at the oil-water leading
to oil-drop detachment due to the action of buoyancy force [6]. The suc-
cess of a LSS flooding heavily depends on the ionic strength and ion
compositions. On the other hand, aging and dissolution of a carbonate
rock exposed to low salinity brines may contribute to the process of
change in wettability and oil detachment [7,8].
Performance of a successful LSS is strongly depends on the preflush
of the reservoir with injecting the low or high salinity water (LSW or
HSW). On the other hand, a LSS process possesses lower capillary num-
ber because of its higher IFT than that of optimal salinity surfactant in-
jection primarily because of the stronger interaction exist between
rock and fluid in the case of a LSS. However, surfactant retention in
LSS process is lower than that of optimal salinity surfactant case, al-
though its IFT is higher than the IFT of the optimal salinity surfactant
[9–11]. The main advantage of LSS is the prominent wettability alter-
ation of rocks in the presence of oil at which wettability increases to-
ward water phase as the rock surface exposed to LSS. Also, there are a
number of cases which show an increase in the ratio of divalent to
monovalent cations could greatly augment the reduction in the IFT of
LSS without increasing the concentration of surfactant [12–14].
For example, the vast amount of recent experiments show that low
concentration of monovalent sodium cation can reduce the contact
angle of brine droplet on the muscovite surface in n-decane + stearic
acid solution, while decreasing the sodium concentration as calcium
concentration rises yield higher contact angle [15,16]. The acidic com-
ponents of oil can heavily influence both pH-state of the medium and
the hydration state of ions that leads to a repulsive force. Specifically,
deporotonated acid components at higher pH bridged to the divalent
cations on the muscovite surface that makes the surface turned into
more oil-wet. Since the hydration energy of sodium ion is much lower
than that of Ca2+, the monovalent cation Na+ at lower pH will provide
conditions for the water bridging that leads to the oil release from the
surface as the bond between Ca2+ and oil breaks [17].
In order to accurately examine the role of LSS in oil displacement in
reservoir conditions, it is necessary to separate different forces among
different phases. One of the most important interactions is fluid-fluid in-
teractions that can be quantitatively verified by IFT measurements. This
kind of IFT refers to the interfacial tension between oil drop and sur-
rounding fluid comprising surfactant dissolved into a brine solution
[18]. Surfactant concentration is often chosen to be low in the range of
0.1 to 0.5 wt% of brine solution. The other crucial interaction is between
rock and fluid that literally refers to surfactant adsorption at the solid in-
terface. The surfactant concentration at the effluent stream versus time
can be a representative of the amount adsorbed on the solid rock sur-
face. The rock-fluid interactions is also characterized through wettabil-
ity alteration measurement, which can be represented by contact
angle [19,20].
The experiments are showing that after LSS flooding of a
preflushed LSW rock, water relative permeability is improved com-
pared to that of LSW alone did [21]. This is because of the reduction
in IFT, which in turn increases the mobilization of oil, water satura-
tion and finally increases the water relative permeability. In order
to examine the role of salts in the wettability alteration of a rock sur-
face, researchers carried out experiments on the state of being
water-wet upon injection of brines with different ratios of divalent
to monovalent ions. The results showed that LSS dissolved only in so-
dium chloride has better performance under initially water-wet con-
ditions, while the opposite is true with calcium under initially less
water-wet conditions. A salinity shift after LSS to HSW can reduce
IFT roughly an order of magnitude and this will intensify both in-
situ oil and surfactant solution.
Another aspect of LSS flooding is the reduction in the differential pres-
sure just at the start of the injection, which is especially important for low
permeability reservoirs. The experiments showed that LSW could in-
crease the differential pressure at the beginning of injection due to the oc-
currence of emulsification, which is much lower in the presence of
surfactants. Moreover, a decrease in the IFT to ultra-low values (i.e.
~10−2 to 10−4 mN/m) greatly increased the oil displacement efficiency
[22]. They claimed that emulsification could deteriorate displacement ef-
ficiency, because IFT reduction accomplished by varying the salinity at
constant concentration of the ethoxylated fatty alcohol carboxylate
(AEC) surfactant. They gradually increased NaCl and CaCl2 concentration
at constant surfactant concentration of 0.2 wt% to reach an IFT about
1.44 × 10−4 mN/m and then flew the solutions over the initially water-
wet quartz particles. It might be linked to the accumulation of salts at
the interface between solid and brine that prevents the hydrogen bonding
between nonionic components of oil and the solid surface; therefore, ions
electrostatically screen off from the interface and oil displacement in-
creases [22,23]. In both Refs. [22,23], oil components were nonionic that
could not electrostatically adsorb onto the surface, and as a result high
concentration of salts deterred them from attaching onto the rock (Fig. 1).
Therefore, the following guidelines are presented when the LSS
flooding is considered for oil displacement applications:
– The loss of surfactant due to adsorption on the solid rock surface in-
creases once its concentration increased in the solution.
– The surfactant adsorption can be lowered by preflushing rock with a
LSW solution.
– Further mobilization of oil after LSS flooding can be obtained by
injecting HSW solutions other than surfactant.
– IFT of a surfactant strongly depends on the pH. IFT between surfac-
tant solutions and oil droplets can be further lowered by increasing
pH. However, since IFT change due to change over the entire pH is
very small it is worthwhile to focus on the LSS and its salinity to ad-
just the IFT rather than adjusting PH.
– Low salinity effect may be worked for brine compositions of up to
5000 ppm.
– Surfactant concentration should be kept as low as possible in order
to increase the phase transition toward intermediate oil-water
solubilization.
Referring to the fourth item of the above guideline, the presence of
divalent Ca2+ cation in the surfactant solution can greatly adjust the
amount of surfactant adsorbed on the solid rock surface. The phenome-
non called as cation bridging with the aid of divalent cations dictate the
rate and the quantity of surfactant adsorption with no contributions
from Na+ monovalent cation [24]. Thus, decreasing the concentration
of Ca2+ in the brine can readily reduce adsorption of surfactant onto
the rock and it could trigger fines migration with oils attached to
them. At LSS solutions with low ratio of Ca2+/Na+, pH could be raised
via H+/Na+ exchange and as a result repulsion contribution to the
DLVO formulation exceeded the attraction one; leading to the expan-
sion of electrical double layer and fines migration [25].
Compared to LSS, tertiary flooding with HSW cannot overcome the
energy barrier of the overlapped hydration shells of polar/acidic compo-
nents of oil and the cations adsorbed on the mineral surface of reser-
voirs. However, in the low salinity flooding divalents are exchanged
with the monovalents due to high exchange rate capacity of the me-
dium that makes the surface more water-wet as the electrical double
layer thickness increases [26]. Due to the complex nature of crude oil-
LSS-rock system, there is no clear comprehensive challenging view
over the influence of above-mentioned factors on the mechanisms of
wettability alteration using LSS flooding. Thus, we summarize the indi-
vidual deciding factors that determine the wettability alteration of car-
bonate and sandstone rocks in the presence of surfactant in low salinity
brine solutions.
 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280 267

Fig. 1. MD simulations for nonionic α-D-glucopyranose monomers between calcite slabs terminated with (1014) plane with different concentration of brines. The atom colors correspond
to O: red, C: cyan, H: white, Na: blue, Cl: yellow, Ca: green and Mg: pink. The water molecules not showed [23].

2. Factors affecting contact angle
Fig. 2 depicts a schematic of the contact angle of an oil droplet over a
rock surface in aqueous brine solution. As shown, increasing the contact
angle leads to more oil-wet conditions.
A contact angle decrease about a few degrees can also trigger a con-
siderable increase in oil recovery with low salinity surfactant flooding in
the absence of divalent ions [28]. For the LSS flooding systems, three
main mechanisms have been suggested, in which water molecules pen-
etrate to attach to the solid surface by destroying the organized layer of
oil molecules in initially oil-wet rocks:
1- Hydrophobic interactions of the chains of surfactant with the oil de-
stroy the upper layer molecules and creates a way for the water to
penetrate,
2- DLVO and non-DLVO forces between water and solid surface will
pave the way for disturbing the remaining layers of oil, and
3- Once water reached on the top of the solid, hydrogen bonding breaks
the contact lines of oil-solid surface and creates water channel to
augment the detachment process of oil from solid surface known
as water bridging. Upon arrival on the silica solid surface, water mol-
ecules breakdown the bond between Si atoms and oxygen atoms to
establish hydroxylated silica surface under the force of hydration.

Fig. 2. Contact angle of an oil droplet over solid substrate in brine. The final contact angle is
an average between the right and left contact angles [27].
Churaev et al. [29] have shown that for a secure hydrophilic quartz
surface, it is required to use high concentration of CTAB solutions
(N10−3 M), which in turn led to creation of hydrophilic silica and oil sur-
faces. Thus, wetting of silica surface and preventing the oil droplets from
attaching to quartz need strong electrostatic and hydrophilic repulsion
that may occur upon high CTAB solutions. However, at low CTAB con-
centrations (b10−5 M), both surfaces became hydrophobic and strong
hydrophobic attraction persisted the attachment of oil droplets to silica
surface due to hydrophobic attraction.
268 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Khanamiri et al. [30] revealed that tertiary low salinity surfactant so-
lution with only sodium cations could act better than LSS with sodium
and calcium cations. The surfactant was a blend of alkyl benzene sulfo-
nates with CMC of 0.059 wt%. As shown in Fig. 3, contact angle of oil/LSS/
Berea sandstone increased in the presence of LSS aqueous solution con-
taining only sodium chloride that lead to a wettability shift from
strongly water-wet to intermediate water-wet. However, for LSS-
NaCa, the presence of calcium cations enforce the surfactant molecules
to align more compactly to each other, and as a result interfacial elastic-
ity increases and contact angle has smaller value. It is theoretically
proved that monovalent cations like Na+ and K+ contribute positively
to the DLVO formulation through MIE and DLE mechanisms, which
could increase the overall value of the disjoining pressure [31]. Also, it
is worth mentioning that different surfactant should be tested against
salinity to obtain a stable LSS solution.
Nourani et al. [32] showed that upon exposing silica and alumina sil-
ica surfaces to HSW, LSW and LSS aqueous solutions, contact angle al-
tered from partially water-wet to completely water-wet conditions as
the injected brine diluted in divalent concentrations and as surfactant
added into the medium [33–35]. LSW and LSS solutions added to the
core samples of silica and alumina silica surfaces as secondary and ter-
tiary flooding modes, respectively, after the core initially flooded with
HSW solution. For both silica and alumina silica surfaces, LSS flooding
over silica resulted in much more lower contact angles compared to
those of alumina silica surfaces. The differences between contact angles
between two mineral surfaces originated from the crystal structures, in
which silanol (Si-OH) groups of silica surfaces showed higher hydrophi-
licity with respect to the less hydrophilic natures of the Brønsted acidic
silanol and Lewis acidic aluminol (Al-OH) groups of alumina silica sur-
faces. The latter caused extra interactions with Lewis basic functional
groups in the asphaltenes of the oil [36]. In addition, higher density of
Fig. 3. Contact angle (θ) of three-phase contact line of oil/LSS interface with rock surface
for both LSS-Na and LSS-NaCa. Surfactant: blend of alkyl benzene sulfonates, rock: Berea
sandstone, cations: sodium and calcium [30].
OH groups at alumina silica surfaces compared to the silica allowed
more polar interactions between oil components and alumina silica
surface.
Moreover, contact angle at three-phase contact line is depend on the
temperature, composition of the brine (pH) and oil, and aging of the
core sample flooded by the low salinity brine solutions. An oil with
large value of acid number will raise contact angles as more oil compo-
nents adsorbed on the mineral surfaces. Increasing the temperature and
aging time would increase the contact angle at three-phase contact line
[37].
2.1. Multiple ion exchange (MIE)
Clays are layers of several tetrahedral and octahedral sheets that the
number of tetrahedral and octahedral sheets comprising a layer deter-
mines the type of a clay, namely, 1:1, 2:1, and 2:1 with a hydroxide in-
terlayer clay minerals [38]. Depending on the structure of multi-layered
clay minerals, compensating cations can be exchanged with other cat-
ions present in the brine solutions providing cation-specific sites on
the mineral surfaces. Theses compensating cations that regulate the
charge equality of tetrahedral and octahedral sheets can be exchanged
with cations presented in the brine solution, which control oil desorp-
tion or adsorption. For example, an initial structure of muscovite clay
mineral with different cations is shown in Fig. 4. If Na-muscovite ex-
changed with Ca2+ in the brine, then cation bridging can adsorb
deprotonated oil components onto the clay mineral and makes the sur-
face more oil-wet.
Furthermore, potential of mean force (PMF) and adsorption Gibbs
energy can be used to investigate the occurrence of cation exchange be-
tween muscovite surface and porotonated and deporotonated decanoic
acid molecules [16]. The results showed that at very low pH (pH b 2),
uncharged acidic oil molecules have not any interaction with the Mus-
covite surface regardless of cation exchange condition of the surface.
The repulsion between the Muscovite surface and oil molecules ex-
plained through the magnitude of adsorption Gibbs energy and the sta-
tus of overlapped layers of hydration between –COOH group of oil
molecules and cations adsorbed on the surface of Muscovite. In contrast,
at higher pH where oil molecules are deporotonated, the PMF and ad-
sorption Gibbs energy curves revealed Muscovite surface strongly inter-
act with deporotonated oil molecules through cation exchange in the
order of Ca2+ N K+ N Mg2+ N Na+ (Fig. 5). In conclusion, the effect of cat-
ion type on oil-wetness of muscovite surface is larger at high pH. On the
other hand, low salinity surfactant could destabilize the cation bridging
and alters the wettability of rock surface to partially water-wet. Ca2+
and K+ interacted with oil molecules via cations bridging while Mg2+
and Na+ on the Muscovite did not directly interacted with oil molecules
as the higher hydration energy of later cations proved it. The study also
demonstrated that between Ca2+ and Mg2+ divalent cations only Ca2+
can alter the wettability of the Muscovite surface toward more oil-wet.
This behavior toward more oil-wet via cation bridging in the order of
Ca2+ N K+ N Mg2+ N Na+ were observed for illite, smectite and Berea
sandstone. For K+ and Ca2+, cation bridging occurs directly between
cation and deporotonated oil as this is the case in the bulk aqueous so-
lution, while for Mg2+ and Na+ water film bridges cations and
deporotonated oil molecules, which differs from that exist in the bulk
aqueous solution [16].
For carbonate rocks, MIE occurs if SO42− ions presented in the low sa-
linity surfactant solution; so, low salinity surfactant containing SO42− or
diluted seawater can be useful to change the wettability of carbonate
reservoirs toward more water-wet [39,40]. Ca2+cations on the calcite
surface can be exchanged with SO42− ions in the diluted surfactant solu-
tion and as result, the hydrophobic interactions between polar compo-
nents of oil and negatively charged calcite surface will repel each
other [41]. This may also happen when Mg2+ cations substitute Ca2+
on the calcite surface and make the breakdown of bond between Ca2+
and the polar components of oil. As the concentration of SO42− on the
 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Fig. 4. Muscovite structure with different compensating cations. a) Na+, b) K+, c) Mg2+ and d) Ca2+ cations [16].
calcite surface increased, it released complexes of Ca2+-polar compo-
nents of oil and hindered adsorption of further oil components due to
the creation of electrostatic repulsion between them [42]. In addition
to SO42−, BO32−and PO43−are also useful to improve oil recovery from car-
bonate rocks [43]. Even though, cores containing anhydrite produce
SO42− ions upon rock dissolution via LSS injection. Thus, LSS can be
used instead of diluted seawater in such cases.
Haagh et al. [44] proposed that for the sandstone rock, the two pos-
sible mechanisms for wettability alteration are: double layer expansion
and multicomponent ion exchange (MIE). It was declared that DLE has
minor effect on the wettability alteration, while MIE has a pronounced
effect on water-wetness of sandstone surface by cation bridging and
complexion mechanism. Therefore, they proposed that overlap of the
hydration layers of ions/surfaces and MIE play much more important
roles than double layer expansion. Since DLVO formulation fails in thin
film, short-range forces like overlapped layers of hydration (non-
DLVO forces) is the key for the success of LSS flooding.
The main advantage of LSS flooding with decreasing concentration
of divalents is the occurrence of MIE in which divalents cannot bridge
surfactant to the rock surface. Another reason pertains to the
screened-off ions from the rock surface that help the compact arrange-
ment of surfactants at the oil/brine interface, in turn, disturbance in oil
layers because of lower IFT resulted.
2.2. Rock dissolution
PHREEQC software is being used in order to determine the potential
effect of mineral dissolution upon low salinity water/surfactant injec-
tion. The modeling results showed that Ca dissolution for the calcite
rock can be ignored in the presence of low salinity water, hence, core
plugs containing anhydrites (CaSO4) could trigger SO42− ions into the
aqueous solution. Since Ca2+ dissolution in formation brine solution is
limited, therefore, mineral dissolution has not anything to do with low
salinity water/surfactant injection [36,45].
In another calculation, formation water and 100-times diluted for-
mation water injected onto the limestone core containing anhydrites
in secondary and tertiary modes, respectively [46]. The simulations re-
vealed that in the case of core plugs with anhydrites oil recovery in-
creased for formation brine and injection of diluted formation brine
(after 6 PV). However, in another simulation where anhydrites removed
(simulation B), no oil recovery observed proving that even diluted brine
269
could not improve oil recovery (injection after 6 PV, Fig. 6). Thus, low sa-
linity water should contains some SO42− ions when rock is depleted
from anhydrites [46]. A diluted seawater with or without surfactant is
recommended in this case.
On the other hand, in sandstone rocks, dissolution of silicate min-
erals is too slow that can be neglected. However, as salinity of formation
brine decreases the accumulation of negative charges increased on the
silica surface and upon electrostatic repulsion between negatively
charged fines and silica surface, they migrate from the surface and oils
attached to them will be released. In some situations, throat plugging
of the core may occur because of fines migration leading to the increase
in pressure drop. Also, production of oil-free kaolinite fines in the water
or fines adhered to the oil as a Pickering emulsion observed [47,48].
2.3. Cation bridging
By referring to Fig. 7, only divalent cations can adhere to the polar
components of oil when they exchanged with the compensating cations
on the clay minerals. As a result, they bridged between clay surfaces and
polar components of oil and surface becomes oil-wet. For carbonate res-
ervoirs, specifically at lower pH and higher acid numbers of oil, the min-
eral surface becomes abundant in positive charges and therefore Ca2+
cation can readily adsorb negatively charged components of oil.
In a study, Allen et al. [49] investigated monovalent cesium cation
bridging between mica and AOT anionic surfactant. It was under-
stood that anionic surfactants can adsorb to mica through Ca2+cat-
tion bridging, but this was not the case for monovalent ions Na+ .
Therefore, Na+ of AOT surfactant cannot bridge mica to the surfac-
tant. The studies show that metal cations have the affinity toward
mica in the order K+, Rb+ , Cs+ N Na + N Li+ [7,8]. On the other
hand, for smectites/montmorillonite clay surfaces the binding
strength is K+ N Na+ N Ca2+ N Cs+ N Ba2+. Lower hydration energy
of Cs+ monovalent ion than that of Na+ makes the cation bridging
between negative AOT and the negative mica surface (Fig. 7).
Generally, at low PH, cation bridging effect is ignored because of the
overall repulsive force that originates from the overlapping of the hy-
dration layers of mineral surface and acidic groups of oil. Whereas at
high pH, ionized state of acidic groups tend to adhere to the counter
ions on the mineral surface. The adsorption Gibbs energy in this case
is negative showing the tendency of oil molecules to adsorb on the min-
eral surface.
270 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280

Fig. 6. Simulations for oil recovery in cores with anhydrite dissolution (simulation A) and
without anhydrite dissolution (simulation B). FW: formation water, rock: limestone with
or without anhydrite, CATIONS: NaCl solution with equal amounts of Ca2+ and Mg2+ [ 46].

at the interface. Upon adsorption of second layer, zeta potential starting

to decrease since columbic repulsion overcomes the hydrophobic
attraction force. Furthermore, in the absence of surfactant, divalent cat-
ions are more likely to decrease the value of zeta potential as more pos-
itive charges accumulate at the interface. When surfactant and Ca2+
cations are both present, zeta potential increases suggesting that Ca2+
is responsible for the adsorption of surfactant via cation bridging,
while monovalent cations have a little contribution to the bridging ef-
fect. Increasing the concentration of Ca2+ beyond the formation of sur-
factant monolayer would not have any significant effect on the previous
recorded zeta potential and the formation of second layer is less likely to
occur. Generally, Ca2+ facilitates the adsorption of surfactant to the
rock; however, low salinity injection and layering phenomena along
with ions confinement inhibit the surfactant adsorption that enhances
the repulsive hydration forces between rock/brine surfaces.
Divalent cations stabilize solid by lowering the zeta potential, and as
a result the repulsive force lowered and higher amounts of charge
added to the surface. Therefore, after secondary flooding with high sa-
linity water and through multiple ion exchange, zeta potential de-
creases resulting in a new equilibrium that established between oil-

Fig. 5. Cation bridging for Ca2+ and K+ and water bridging for Mg2+ and Na+ on the
muscovite surface [16].

Gerold and Henry [50] investigated surfactant adsorption on a solid

rock surface in the presence of metal cations through zeta potential
measurements. For a pair of surfactant-rock system with the same
charge, adsorption being started as the hydrophobic interaction over-
comes the columbic repulsion. Once an adsorbed monolayer formed, Fig. 7. Cation bridging between AOT anionic surfactant and negatively charged mica
zeta potential increases because of the accumulation of negative charges surface. Cation: Cs+ [49].
 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
brine and brine-rock interfaces. Depending on the initial wetness of the
rock and upon low salinity surfactant injection the following events
may occur: the strongest cation exchanges with the weakest cation,
acid/base components of the oil bond with the solid surface or break
down may happen, surfactant molecules bridge with new cations, inter-
facial oil-brine decreases, interfacial elastic modulus changes and over-
all result would be the alteration in wettability of the solid surface.
Underwood et al. [51] proposed a twofold description for the low-
salinity flooding over Montmorillonite clay surfaces. Under initially
oil-wet clay surface, cation bridging is present between oil-wet clay
and organic compounds, while for the initially water-wet conditions
cation exchange occurs through replacement of divalents by monova-
lents. The first reason for this phenomenon is described by the level of
PH and the extent of protonation/charge of organic oil molecules. The
level of CO2 concentration dissolved in the formation water, generation
of hydroxyl ions from a clay‑calcium sites, the existence of multicompo-
nent ion exchange mechanisms through which oil bond to the clay sur-
face and acid number of crude oil would affect the overall pH level of the
fluid adjacent to the rock surface. The second reason is the ratio of diva-
lent to the monovalent cations present in the low salinity injection. The
lower ratios enhance the thickness of electrical double layer in which
replacement of divalents by monovalents occurs. Also, lower hydration
of Na+ along with higher bonding strength compared to those of Ca2+
and Mg2+ divalents boost water-wetness of the clay surfaces in which
cation bridging between divalents and oil molecules breaks and the sur-
face wettability alters from oil-wet to water-wet. Fig. 8 shows the state
of cation bridging between clay and organic compounds and cation
bridging among identical molecules via MD simulations [51].
Binding energies was used in order to predict the interactions be-
tween oil organic species and clay minerals [52]. For a crude oil mixture
comprising hexane, cyclohexane, toluene and decahydro-2-naphthoic
acid (DHNA), the DFT calculation results indicated that clay minerals
had higher affinity toward deprotonated anionic DHNA− resin and Ca2
+
presented in the brine solution. Also, binding energies showed that
adsorption of the oil organic molecules on the mineral surface enhanced
with Ca2+ and Na+, while the binding energy for the later was smaller
than the Ca2+ cation. For instance, toluene binding energy onto the ka-
olinite clay surface enhanced 363 kcal/mol with the aid of Ca2+.
Negatively-charged montmorillonite with exchangeable Ca2+cations
slightly intensified adsorption of oil organic molecules compared to
the uncharged kaolinite surface. This can be explained via cation
Fig. 8. a) Cation bridging between like-charged clay and oil organic molecules by a cation. b) Cation bridging among identical molecules by cations [51].
271
bridging effect between Ca2+ and carboxylate group of DHNA− on kao-
linite and montmorillonite surfaces (Fig. 9).
However, hydrophobic pyrophyllite surface had the strongest ad-
sorption of oil molecules than neutral kaolinite and hydrophilic
montmorillonite surfaces, primarily because of the hydrophobic in-
teractions (in the absence of hydrogen bonding or cations) that did
exist between oil molecules and basal hydrophobic surface [52].
Neutral oil molecules and protonated DHNA through hydrophobic
interactions strongly adsorbed onto the basal pyrophyllite surface, and
therefore higher ionic strength resulted in lesser adsorption of DHNA
on the pyrophyllite. This is because of the electrostatic repulsion be-
tween adsorbed counter ions and hydrophobic DHNA. On the other
hand, deprotonated DHNA− adsorption on the hydrophilic surfaces of
kaolinite and montmorillonite was not significant, because hydrophobic
DHNA− had not noticeable affinity toward hydrophilic surface [52].
2.4. pH
At moderate pH, the cation bridging between cations of brine solu-
tion and acid components of oil make the oil attachment to the solid
surface because ionized acid groups attract to the counter ions, and con-
sequently surface charge at the interfaces decrease. In order to maintain
the water-wetness of a surface in this condition, it is preferred to use LSS
containing monovalent cations because these ions have lower affinity to
interact with deporotonated acid components in the oil and have lower
hydration state with respect to divalent ones either.
Sandstone and carbonate minerals dissolution may increase the
medium's pH. This effect can be viewed from ion exchange between
Na+ and H+, as follows:
NNa þ Hþ ⟷NH þ Naþ
where N denotes adsorbed ion. The uptake of H+ in this ion exchange
reaction will raise pH. Specifically for sandstone rocks at low level of
Ca2+in low salinity aqueous surfactant solution, the above ion exchange
reaction increases pH and as pH soars the magnitude of total disjoining
pressure will augment and the height of the barrier energy occurs at
lower distances between rock/brine interfaces that leads to higher elec-
trostatic repulsion.
The point at which silica surfaces are isoelectric (neutral charge) is
pH ~ 2. Thus, at pH N 2, silica surfaces demonstrate negative charge
272 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Fig. 9. Optimized structures of cation bridging effect through DFT calculations, (a) Ca2+-DHNA− on kaolinite, and (b) Ca2+-DHNA− on montmorillonite [52].
and the charge density increases with pH. Therefore, by using LSS de-
pleted in Ca2+, and as result of Na+/H+ ion exchange pH will increase
that makes negatively-charged silica surfaces repel negatively-charged
polar components of oil. The experiments showed that by using a low
salinity solution free from divalent cations, it is possible to have very
low contact angle, while a small increase in contact angle increases ad-
sorption of acid components of oil onto the silica surfaces.
The negative adsorption Gibbs energy reveals the affinity of oil to-
ward silica surfaces at higher pH. Specifically, divalent cations such as
Ca2+ makes the surface more oil-wet at high pH, whereas at very low
pH (pH b 2), a low salinity aqueous solution will result a silica surface
with no affinity toward oil regardless of its nature of cation exchange.
(See Fig. 10.)
For calcite surfaces, the surface charge is positive due to the high
concentration of Ca2+ in the crystal structure. Also, at high pH (i.e. pH
N 8), the increase in concentration of CO32−, HCO3− and OH− is in line
with pH that leads to a less positive surface. Also, dissolution of carbon-
ate rocks increases the pH and shifting to low salinity intensifies this
trend toward higher pH in such a way that more and more divalent-
oil complexes released from the calcite surface upon replacement by
SO42− ions. Therefore, switching to low salinity seawater/surfactant-
containing SO42− can screen off counter ions and the electrical double
layer expansion will increase the height of energy barrier against oppo-
sitely charged oil components. However, very diluted seawater (i.e., 50-
times diluted seawater) losses its efficiency for increasing the negative
Fig. 10. Adsorption Gibbs energy for the adsorption of protonated C9H19COOH and
deprotonated C9H19COO− oil molecule. The inset figure represents contact angle versus
pH of the medium, while increasing the concentration of electrolytes will result in
higher contact angles [16,53].
charges on the calcite surface, because concentration of SO42− ions de-
creases as seawater diluted largely.
As shown in Fig. 11, for calcite surface, increasing pH above 8 will re-
sult in the decrease of zeta potential as more CO32−, HCO3−, and OH−
dissolution occurs. However, for instance at pH 8, lowering the salinity
of the solution makes Ca2+ and Mg2+ cations screened off from the sur-
face, which led to the expansion of double layer and the accumulation of
negative charges on the surface. Hence, at ultra-low salinity, polar com-
ponents of oil enter into the aqueous phase from the interface and
higher IFT at oil-brine and lower negative charges at rock-oil interfaces
happen. At conditions where oil acid number is high, the positively
charged of calcite surface can strongly adsorb negatively charged acid
components, while adsorption decreases as the acid number lowered.
By switching to low salinity, zeta potential of calcite surface decreases
and deprotonated acid components repelled from the calcite surface
due to the electrostatic repulsion between calcite and acid components
[54].
Since pH range prevailed in most seawaters is between 5.7 and 6.77,
the effect of pH increase on IFT is strongest at low pH values (pH b 5),
and therefore increasing pH due to low salinity slightly increases the
IFT values at the oil/brine interface created by the surfactant [55]. So,
it is worthwhile to adjust the salinity of the solution to affect the IFT
rather than focusing on the pH, because ions decrease the electrostatic
repulsion among surfactants and arrange them more compactly at the
interface.
2.5. Zeta potential
Through zeta potential measurements it is possible to determine the
magnitude of surface potential at rock-brine and brine-oil interfaces,
which denotes the amount of charge accumulated at the interfaces.
For instance, when brine is deionized water, zeta potential at calcite-
deionized water interface is always positive as a sign of the presence
of positive charges on the calcite surface over wide ranges of pH
(Fig. 12). Increasing pH results in decrease in zeta potential for calcite
minerals [54].
In Fig. 12, the dissolution of ions of the calcite lattice in deionized
water makes an increase in pH and more negative charges accumulate
at the surface. The equilibrium reactions during dissolution of calcite
particles are as follow:
CaCO3 þ Hþ ↔Ca2þ þ HCO3− @pHb3:5 ð1Þ
CaCO3 þ 2Hþ ↔Ca2þ þ H2 CO3 ð2Þ
CaCO3 þ H2 CO3 ↔Ca2þ þ 2HCO3− @3:5bpHb7 ð3Þ
 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Fig. 11. Switching from high salinity to low salinity effects on the averaged zeta potential of calcite rock/brine at pH 8. FW: formation water, SW: seawater, 10d: 10 times diluted [54].
CaCO3 þ H2 O↔Ca2þ þ HCO3− þ OH− @pH N7
If zeta potential of brine/rock and oil/brine has the same polarity,
then they repel each other, and as a result the rock surface would be
more water-wet. Therefore, contact angle decreases as sum of brine/
rock and oil/brine zeta potentials increases:
As shown in Fig. 13, interface at oil/brine is usually charged posi-
tively at low pH, however, the quantity of positive charges decrease as
pH increased and at sufficiently high pH, the interface becomes nega-
tive. Thus, as the pH increases, the same polarity between brine/rock
and oil/brine interfaces makes the rock surface more water-wet.
In sandstone rocks this situation is much more better since surface
zeta potential is always negative at low and high (i.e., 54,680 mg/L)
ionic strengths. Brines with high ionic strength, such as seawater,
strongly shrink the extent of electrical double layer as the concentration
of divalent cations increases, and consequently zeta potential moves to-
ward positive charge.
As can be seen from Fig. 14, for both quartz and calcite minerals, high
salinity brines will result in near-zero and even positive zeta potentials,
while divalent cations speed up the rate of increasing zeta potential be-
cause the charge density at the interface much more influences in this
case. Also, temperature has not any significant thing to do with the
zeta potential. A similar trend to what we saw in Fig. 14 can be ex-
plained for the oil/brine interfaces in such a way that increasing the sa-
linity of the brine solution raises the accumulation of cations at the
interface, and therefore the interface becomes less negative and even
positive at higher concentrations. The large negative value of zeta po-
tential at low salinity brine is due to the adsorption of hydroxyl ions
and oil's asphaltene and resins, however, at high salinity brine, adsorp-
tion of Na+ and Mg2+ reduce the large values of negative charge at the
interface (Fig. 15) [58].
Fig. 12. pH-dependent zeta potential at calcite-deionized water interface [54].
273
ð4Þ When surfactant adsorbed onto the rock surface, indeed, it can mod-
ify the rate of changing in the zeta potential at both the oil/brine and the
rock/brine interfaces. For instance, cationic surfactant adsorption at the
rock surface increases the zeta-potential toward more positive values
and an ionic surfactant has the opposite impact. While the concentra-
tion of ions is high, the accumulation of these ions near the solid wall
and competition for the adsorption decreased the adsorption of surfac-
tants and therefore, the rate of increasing in zeta potential slowed [59].
For the silica surface, the presence of Ca2+ is essential to bridge between
surfactant and the rock surface, while Na+ has not anything to do in this
regard.
2.6. Disjoining pressure: DLVO and non-DLVO forces
Total disjoining pressure can be summed up over three main terms
including, long-range electrostatic repulsion, short-range Van der
Waals attraction and structural forces [60–62]. Van der Waals forces
contribute negatively to the disjoining pressure because they represent
the attraction between two surfaces, while electrostatic forces
strengthen total disjoining pressure as Debye length increases with
the expansion of electrical double layer due to low saline water [63].
Structural forces are hydrophobic and solvation forces, which cannot
be explained through Van der Waals or electrostatic forces [64,65]. Hy-
drophobic surfaces are generating hydrophobic attraction forces and
adsorption of a surfactant can change the hydrophobicity/hydrophilicity
of a surface, hence, it is possible to calculate the magnitude of
Fig. 13. Effect of the sum of brine/rock and oil/brine zeta potentials on the contact angle
over carbonate rocks. Red-line from [36], green-line from [56], blue, black, yellow, and
orange-lines from [57].
274 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280

Fig. 14. Experimental values of zeta potential at rock/brine interfaces at different temperatures and salinity [58].

hydrophobic force of a surface, while surfactant changes the wettability ψ0 illustrates the potential of the isolated surfaces; h is the film thick-
of the surface: [66] ness and κ is: [69]

Πhydrophobic ¼ −C1 e−h=λ1 ð5Þ
1=2

κ−1 ¼ εε0 kT=2ρ∞ e2 ð9Þ
 
3 2
Πvdw ¼ ð−Hð15:96h=λ þ 2ÞÞ= 12πh ð1 þ 5:32h=λÞ
where ρ∞ is the charge density in the bulk, e stands for the electron
3
 −H=12πh ðfor thin filmsÞ ð6Þ charge 1.602 × 10−19C, ε0 symbolizes the vacuum permittivity
8.854 × 10−12 C2 /J·m, ε is the dielectric constant of the solution,
where H is Hamaker constant usually taken as 1 × 10−20 J and h denotes and T is 298 K [70,71].
film tickness [67]. For calcite surface with its (1014) cleavage plane exposed to low sa-
   linity brine solution comprising Ca2+, Na+ and Cl−, the atomic force mi-
2 croscopy revealed that a tightly-arranged layer of water molecules
Πelectst ¼ nkT 2ψr1 ψr2 coshðκhÞ þ ψr1 2 þ ψr2 2 = sinh ðκhÞ ð7Þ
formed adjacent to the calcite surface in which hydrated ions should
consume energy in order to overcome the energy barrier to leave the
where n is the number of ions (cations or anions) per unit volume, k
hydration shell and close themselves to the calcite surface [72]. The
represents Boltzmann constant, 1.381 × 10−23 J/K, ψr1 and ψr2 are the
MD simulations showed that Na+ is the closest one on the top of the
potentials at oil/water and water/solid interfaces, respectively: [68]
water film; Cl− and Ca2+ are arranged next to the sodium ions far
from the water film. Na+ cations have 6 water molecules in their hydra-
ψh ¼ ψ0  e−κh ð8Þ tion shell, while this number is 8 for Ca2+; therefore Ca2+ cations should

Fig. 15. Experimental values of zeta potential at oil/brine interfaces at different temperatures and salinity [58].
 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Fig. 16. Density profiles (mol/L) of MD simulations for different ions (and water
molecules) perpendicular to the calcite surface exposed to low salinitybrine. The density
of the water atoms at the bottom. Red: oxygen, blue: hydrogen [72].
pay larger energy to leave its hydration shell and consequently it stays
farther from calcite surface and sodium cations (Fig. 16) [73].
This hydration repulsion force exerted between two oppositely
charged interfaces at short ranges can be calculated through a two or
more exponentially-decayed terms as follow: [70,74,75]
Πhydration ¼ C2 e−h=λ2 þ C3 e−h=λ3 ð10Þ
where C2, λ2, C3 and λ3 are the coefficients and decay lengths of short-
range and long-range forces, respectively.
Or,
Πhydration−extended ¼ C4 e−ðh−b4Þ2=ðλ4Þ2 þ C5 e−ðh−b5Þ2=ðλ5Þ2 þ … ð11Þ
where C4, λ4, C5 and λ5 are the coefficients and decay lengths of short-
range and long-range forces, respectively; b4 and b5 are constants; and
h corresponds to the film thickness [70,76].
Through a chemical force microscopy (CFM) with a functional tip
near mica surface that resembles solid/oil interactions, different ions
injected in order to quantify the magnitude of interfacial forces contrib-
uting to the total disjoining pressure. The CFM results demonstrated
that in the brine solution containing Na2SO4 the least adhesion force be-
tween water film and functional tip of CFM apparatus obtained, which is
a sign of a stable water film. Whereas, brine containing CaCl2 revealed
the maximum adhesion due to the interruption of water layers and
break down of H-bonds between film and mica surface, which produced
Fig. 17. Functional tip interaction with mica surfaces in the presence of a) sodium chloride, b) calcium chloride, and c) sodium sulfate brine aqueous solutions (dark blue balls denoting
water molecules) [70].
275
Fig. 18. Prediction of total disjoining pressure in sodium sulfate aqueous solutions of
10 mM over mica surface. Blue squares represent experimental data of CFM
measurements, red circle are predictions with considering hydration forces and green
triangles denote calculations in the absence of hydration forces [70].
an oil-wet rock. Also, brine solution of NaCl showed a little amount of
adhesion, however, water film did not interrupted significantly
(Fig. 17) [77].
Therefore, in the absence of the calculation of hydration forces the
net total disjoining pressure may not accurately predict the nature of in-
teraction among solid/brine/oil interfaces. For instance, total disjoining
pressure for sodium sulfate brine aqueous solutions without considerig
the hydration forces of ions largely deviates from the real experimental
data.
As we can see in Fig. 18, total disjoining pressures are all positive
through the entire water film demonstrating the stability of water film
over the mica surface that enhances the water-wetness of the surface.
When surfactants are present in the aqueous solution, hydration
forces between monovalents and the charged rock surface on one
hand, and hydrated head group interaction with the rock on the other
hand add the total value of disjoining pressure. Monovalents are more
prone to leave their hydration shell and close themselves to the rock
surface, while hydrated cations do stay away hydrated head group
from attaching to the rock surface. Thus, repulsive hydration force
must be took into account because of the ions confinement between
rock and surfactant that produces layering phenomena controlling the
interaction between hydrated surfaces in the aqueous solution.
2.7. Interfacial elasticity moduli
The two predominant mechanisms in water injection system are
well known to be sweep-like and snap-off oil displacements. After
276 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Fig. 19. Oil phase snap-off through pore throat in low and high salinity brines [80].
LSW injection, snap-off of oil decreases and amount of entrapped oil re-
covery improves. However, in the case of HSW, structural forces
weakens against increasing rate of capillary forces, hence, addition of
surfactants could greatly reduce interfacial surface tension and increase
interfacial viscoelasticity (Fig. 19) [78,79].
An increase in interfacial elastic and viscous moduli elucidated as the
salt concentration decreases and with further decrease in salt concen-
tration, there was a decline. It was also shown that adsorption of surfac-
tant at the oil-brine interface strongly affected its viscoelasticity [81].
Surfactants may prevent the interaction between the oil's polar compo-
nents and the ions in the aqueous phase or even could avoid
asphaltenes from forming aggregations as depicted in Fig. 20.
Experimental measurements of oil recovery in microfluidic device
showed that low salinity surfactant solution was superior to the slightly
high salinity water solution, in which a maximum of 15% increase in oil
recovery obtained compared to the high salinity water [81]. The in-
crease in oil recovery suggested to be due to the intensification of elas-
ticity of the brine-oil interface. They reported an increase in interfacial
elastic and viscous moduli at lower to intermediate concentration of
NaCl and MgCl2 brine solutions, because diffuse layer is broader and,
Fig. 20. Effect of surfactant at the brine-oil interface [81].
Fig. 21. Elastic modulus (G′) and viscous modulus (G″) vs NaCl concentration at the oil-
brine interface without and with 100 ppm of DEM surfactant [81].
as a result, oil's polar components accumulate at the interface [81].
However, it was mentioned that surfactant molecules were predomi-
nant at intermediate concentration of brines. At high salinity brine solu-
tions, pressure fluctuations due to snap-off of the oil phase observed
after water breakthrough. On the other hand, adding nonionic surfac-
tants to slightly higher salinity brine could develop interface viscoelas-
ticity, while pressure fluctuations and pressure drop were much lower
than those of high salinity water and, furthermore, addition of nonionic
surfactant canceled the effect of salt concentration by providing a stable
oil/brine interface that is not affected too much with the salt concentra-
tion (Fig. 21) [81].
Khanamiri et al. [30] pointed out that interfacial rheology is the main
cause for the wettability alteration in LSS oil recovery processes. The
higher ratio of Ca2+/Na+ is responsible for the lower performance of
oil recovery in the presence of a surfactant. Generally, Ca2+ changes
the interfacial shear viscosity at the three-phase contact line. Ca2+ cat-
ion tightens surfactant assembly at low salinity solution/oil interface,
which is produced a gel-like film that does not possess the power to
sweep the oil effectively. However, in the absence of Ca2+cation in LSS
 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
Fig. 22. The largest residual oil clusters in a) LSS-NaCa and b) LSS-Na. The images are in the
same scale [30].
Fig. 23. Shifting the primary alkyl chain of the surfactant from the para to the meta position and the aromatic substitution on the head of the surfactant [85].
277
solution and the initially water wet rock surfaces, a large amount of fine
oil clusters with lower interfacial dilational elastic modulus compared
to LSS with Ca2+/Na+ pushed the oil away from the rock instead of wet-
ting the rock or adhering to it. Fig. 22 compares the formation size of the
oil clusters in low salinity surfactant with and without Ca [30].
On the other hand, the initially oil-wet solid surfaces are more prone
to produce higher amount of oil with LSS-Ca2+/Na+. In addition, this is
also true for secondary low salinity water flooding, in which LSW con-
taining Ca2+/Na+ is more efficient than LSW without Ca2+. The forma-
tion of gel-like layer in LSW-Ca2+/Na+ adjacent to the rock surface
pushed the oil away from the rock instead of just wetting the rock sur-
face [30,82,83].
2.8. Surfactant structure
To prevent the formation of undesirable phases or instability of sur-
factant at reservoir conditions, surfactant-brine system usually supple-
mented with alkali and co-solvents. For instance, alkyl benzene
sulfonate anionic surfactants are often combined with alkyl ethoxy car-
boxylate in order to mitigate the precipitation of the surfactant at high
salinity environments by forming hydrogen bonding with water leading
to the change in the polarity of the surfactant [84]. Also, studies show
that alkyl chain of surfactants have played critical role in the reduction
of interfacial tension of oil-water, which defined as the extent of misci-
bility of the hydrophobic tail of the surfactant in the oil phase. For exam-
ple, aromatic substitution (with shorter alkyl chain) to the head of
surfactant led to the lower CMC, decrease in surface excess concentra-
tion and decline in the interfacial tension compared to that of mono-
alkyl benzene sulfonate at the same surfactant concentration (See
Fig. 23) [85]. Regularly, the head group of an ionic surfactant solvates
into water, while its alkyl chain attracts to the oil. Additional aromatic
substitution caused the higher tendency toward water than oil, and
therefore water tries to maximize the solvation of head group ring. In
the presence of cations, the electrical double layer creates as the cations
attracted toward the ionized water molecules and the length of the EDL
could reach the interface causing more water attracted in the three-
point contact line. Also, the alkyl chain of the para anionic surfactants
completely solvate into the oil phase, while the alkyl chain of the meta
anionic surfactants partially solvates into the oil phase, therefore meta
substitution of the primary alkyl chains increase the efficacy of the sur-
factants [85]. Once the surfactant forms a continuous layer at the inter-
face of oil-water, it can entirely separate the contact line between them
278 A. Aminian, B. ZareNezhad / Journal of Molecular Liquids 275 (2019) 265–280
and by reducing the interfacial tension it could eventually lead to oil de-
tachment and formation of oil-water emulsions.
Surfactant's formulation should withstand high temperature and
pressure prevailed in the reservoirs in order to be soluble in brines
and show proper phase behavior. Thus, cloud point measurements are
performed to quantify the suitable surfactant's formulation. Usually
cloud point of a surfactant should exceed that of reservoir temperature,
proofing the stability of surfactant at high salinity and high temperature
conditions of the reservoir. However, this method cannot be applied for
the ionic surfactant because of its sensitivity toward temperature [86].
Phase behavior tests can be accomplished at interesting tempera-
tures to examine the phase separation of surfactant solution over
time. Nonionic surfactant is useful at high salinity and temperature sit-
uations and can act as a wettability altering agent [87]. Lu et al. [88]
showed that ether sulfate surfactants including Guerbetalkoxy sulfates
have 4 to 6 years stability at 85 °C and ultralow IFT.
It is revealed that linear alkyl benzene sulfonate (ABS) surfactants
are not appropriate at high sanity conditions, whereas ABS surfactants
combined with an alkyl ethoxy carboxylate could endure high salinities
of seawater as the solubility improved. A formulation of ABS/alkyl eth-
oxy carboxylate of 40/60 is useful to create a stable phase with ultralow
IFT [84].
Moreover, sacrificial agents like sodium polyacrylate,
polyethyleneglycol, sodium carbonate, sodium metaborate, glycolic
acid, glyceric acid and disodium EDTA can be utilized to mitigate the ad-
sorption of anionic surfactants on the carbonate, sandstone and clay
minerals. The presence of sacrificial agents reduce the adsorption of pri-
mary surfactant at high salinity environment by screening off the diva-
lent ions from the solid/brine interface that hinder the direct contact
between surfactant/divalents and solid/divalent [89].
Interestingly, Gemini surfactants (a surfactant with more than one
hydrophilic head group) are reported to be promising for low salinity
injection in such a way that it could provide ultralow IFT and very
good interfacial rheology characteristics, which nominate them for
EoR applications [90]. They are comprising greater than one hydrophilic
head group, which can be zwitterionic, anionic, cationic or non-ionic;
and a hydrophobic tail group that linked by a spacer close to the head
groups. The hydrophobic tail may be short or long and the spacer
group contains either polyether, aliphatic or aromatic, benzene or meth-
ylene [91,92]. Shorter length of a spacer leads to the high rheology of the
surfactant that helps improvements in EoR performance. Gemini surfac-
tants often possess a proper value for HLB of around 7 to 13, because
very high values for HLB adversely affects the IFT. Gemini surfactants
Fig. 24. A proper diagram for relative phase volume as a function of salinity for a special
surfactant [96].
can tolerate the hardness of seawater (presence of divalent cations)
by binding Ca2+ to their aggregates that originates from their lower
CMC and special aggregation morphologies (two anionic head groups)
compared to those of conventional anionic surfactants [93].
Saline water containing monovalent and/or divalent cations can suc-
cessfully hinder aggregation of anionic surfactants via binding to the
ionic head groups that leads to the reduction in the electrostatic interac-
tion among them. Through salinity scan tests, it is possible to select a
surfactant that is suitable for a specific type of oil as a function of salinity
[93,94]. For instance, a surfactant that gives higher volumes for micro
emulsions of water in oil at lower salinities is preferred for LSS flooding
(Fig. 24). Also, there are some empirical correlations that relate the sur-
factant formulation to the salinity, temperature, alcohol type and con-
centration and type of the surfactant [95]. However, these correlations
are based on the trial-error fittings and may not respond well to the se-
vere change in the salinity and oil type.
3. Conclusions
LSS flooding can significantly modify the wetting behavior of oils at
the oil/rock/brine interfaces. The adsorption of surfactant at oil/brine in-
terface permits the spreading coefficient to be changed over a wide
range. Use of smart water containing proper types of monovalent and
divalent cations can control the angle of LSS/oil/rock contact line.
Aging time increases the contact angle to an equilibrium value, and con-
tact angle intensifies in the case of low salinity water with increasing
concentration of divalent cations. On the other hand, LSS works better
with a small increase in concentration of divalent, primarily due to the
increase in the interfacial elasticity, because of compact structures of
surfactant at the oil/brine interface in the presence of Ca2+. Oils with
large number of acid or base numbers adhere to the rock surface at
high pH thanks to the presence of divalent cations; hence, low salinity
brine containing higher concentration of monovalents would provide
conditions for water bridging instead of cation bridging that leads to
the oil release from the rock. At the same ionic strength for Berea sand-
stone, brines containing CaCl2 facilitates the oil adsorption much more
than NaCl can do. LSS not only can lower the IFT, but also it can hinder
snap-off of the oil via increasing the interfacial elasticity. The fines mi-
gration due to low salinity injection is a controversial issue; hence, if it
could play role, the oil desorption from the rock assists. Electrical double
layer expansion along with multiple ion exchange should be studied for
desorption studies of low salinity brines, because if EDL expansion alone
cause the detachment of oil, then diluted seawater should work with
sandstone rocks. Silica surface exposed to low salinity brine with
Na2SO4 shows less instability in water thickness than low salinity
brine containing NaCl. pH increase for both sandstone and carbonate
rocks aids oil release from the mineral surface when decreasing salinity
of brine formations used. Anhydrite, a catalyst and essential for the wet-
tability alteration in carbonate rocks, solubility in brine formation de-
creases as temperature increases and its precipitation is along with
the temperature; however, a temperature gradient from the point of in-
jection to the well-head (40 to 130 °C) is useful for the LSS, because it
can maintain the concentration of essential ions at the maximum any-
time. Finally, the changes in pH, salinity, ion composition, type of surfac-
tant, oil composition, and type of rock have profound effect on the
wettability of the rock surface. Therefore, by carefully examining the
surfactant stability in the reservoir condition and selection of appropri-
ate types of salts and a thorough screening test, it can be possible to alter
the wettability of a rock.
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