Colloids and Surfaces A: Physicochem. Eng.

Aspects 520 (2017) 622639

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Experimental and theoretical study of wettability alteration during

low salinity water ooding-an state of the art review
Hongna Ding, Sheik Rahman
School of Petroleum Engineering, University of New South Wales, UNSW, Sydney, NSW, 2052 Australia

g r a p h i c a l a b s t r a c t

Initially oil-wet carbonate reservoirs as the carbonate rock is positively charged and crude oil is negatively charged at reservoir conditions (pH 7-8,
T 100 C), therefore, the oil adheres strongly onto the carbonate rock that makes it oil-wet (left). Low saline with potential determining ions (pdi) injected
into carbonate reservoirs will increase the negative surface charge/potential due to chemisorption, therefore, enhance the repulsive part of disjoining
pressure and changes the wettability to water-wet. At equilibrium, a stable thin lm will be formed by double layer expansion mechanism (right).

h i g h l i g h t s

Wettability alteration is considered as the main reason for low salinity effect in sandstone and carbonate reservoirs.
The microscopic phenomenon, double layer expansion (DLE), is contributed to the wettability alteration caused by low saline.
Intermolecular interactions in an oil/brine/rock system are quantied collectively by DLVO and non-DLVO theory.
Interactions between crude oil and raw rock sample immersed in low saline are determined by surface force apparatus, especially by AFM.
Chemically force microscopy and force volume technique are able to reveal the intrinsic nature of wettability alteration.

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

Article history: Low salinity waterooding (LSW) has been proved to be a promising technique in improving oil recovery
Received 10 October 2016 for both sandstone and carbonate reservoirs. Sandstone and carbonate are two completely differ-
Received in revised form 24 January 2017 ent minerals but the mechanism of LSW can both be contributed to wettability alteration. Though
Accepted 3 February 2017
many reasons regarding wettability alteration have been proposed, central to the entire subject is the
Available online 6 February 2017

Corresponding author.
E-mail addresses: sheik.rahman@unsw.edu.au, sghasemi@umz.ac.ir (S. Rahman).

http://dx.doi.org/10.1016/j.colsurfa.2017.02.006
0927-7757/Crown Copyright 2017 Published by Elsevier B.V. All rights reserved.
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639 623

Keywords: double layer expansion (DLE), which can be quantitatively explained by disjoining pressure. Disjoining
Low salinity water ooding pressure is the sum of van der Waals force, electrical double layer force and structural force, which is
Wettability alteration not a new concept, however, it attracted a lot of attention with the growing popularity of LSW. The
Double layer expansion three inter molecular forces are explained by DLVO (Derjaguin-Landau-Verwey-Overbeek) theory and
Disjoining pressure
in an oil/brine/rock system these forces can be accurately measured by atomic force microscopy (AFM).
Atomic force microscopy
The extracted information from force vs distance curves and topographical images are used equally to
evaluate the theoretical model. In petroleum industry, the two theories are linked together to explain the
wettability alteration induced by DLE as a result of an alteration from high salinity water to low salinity
water in sandstone and carbonate reservoirs.
Crown Copyright 2017 Published by Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
2. Theoretical background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
2.1. DLVO forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
2.1.1. Van der Waals Force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
2.1.2. Electrical double layer force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
2.1.3. Modied poisson-Boltzmann . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
2.2. Non-DLVO forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
2.2.1. Structural force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
2.2.2. Hydration force. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .628
2.2.3. Hydrophobic force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
2.2.4. Steric force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
2.2.5. Depletion force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
2.2.6. Born repulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
3. Direct force measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
3.1. Interactions of pH-dependent sandstones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
3.1.1. VDW force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
3.1.2. EDL force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
3.1.3. Hydration force. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .631
3.1.4. Structural force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
3.1.5. Hydrophobic force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
3.2. Interactions of deformable oil surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
3.2.1. Rigid tip-oil droplet and drop-drop interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
3.2.2. Chemical force microscopy (CFM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
3.3. Interactions of chemical active carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636

1. Introduction salinities (30,00050,000 ppm) [139]. LSW actually is an ambigu-

ous concept and the salinity of the injected water is not restricted to
The wettability of an oil reservoir can be categorized into three some specic values. As suggested by some researchers, chemistry-
types: oil-wet, mix-wet and water-wet. It is believed that most optimized water or smart water seems make more sense as it
sandstone reservoirs are mix-wet after some extent of oil migra- emphasizes not only the salinity but also the adjusted composition
tion [1]. About 80% carbonate reservoirs, on the other hand, around of the injected water. Low salinity water with less multivalent ions
the world are oil-wet amongst which 15% is strongly oil-wet [43]. is more protable for sandstone reservoirs, while seawater with
It is estimated that the average oil recovery factor worldwide is more potential determining ions (Ca2+ , Mg2+ and SO4 2 ) is more
only 2040% and more than half is still left underground [149]. Low benecial for carbonate reservoirs.
salinity waterooding (LSW) is, therefore, applied as a low cost sec- The mechanism behind LSW ooding for improving oil recovery
ondary or tertiary enhanced oil recovery (EOR) method to extract is proven to alter wettability of reservoir rocks [17,190]. A number
extra oil from sandstone or carbonate reservoirs. Compared to other of explanations for change of wettability of an oil reservoir from
EOR methods (e.g. chemical ooding, thermal ooding, CO2 ood- oil-wet to mix-wet (carbonates) or from water-wet to mix-wet
ing etc.), LSW is more economically applicable and environmentally (sandstones) are given by numerous authors: pH effect [144], multi-
friendly. component ion exchange (MIE) [134], double layer expansion (DLE)
Despite its success in laboratory core displacement tests and [138], salt in and salt out effect [185] and the chemical mechanisms
some limited scaled eld trials in both sandstone and carbonate proposed by Austad et al. [12]. These mechanisms are primarily pro-
reservoirs, there are two major differences between these two posed based on the low salinity effect observed on sandstones and
kinds of reservoirs. One distinct difference is the salinity of the clays are necessary to observe the low salinity effect. It is not the
injected water. It is concluded that the optimal salinity for LSW case for carbonates but these mechanisms can be extended to car-
in sandstone reservoirs is less than 4,000 ppm [135], but the salin- bonates provided, calcite dissolution takes place in order to trigger
ity reported is sometimes as high as 5,000 to 7,000 ppm. Seawater all the above processes [216] and DLE is the leading mechanism
with a salinity of more than 10, 000-20, 000 ppm is commonly used responsible for wettability alteration both for sandstones Ligthelm
for LSW in carbonate reservoirs, but many reported even higher et al. [138] and carbonates [3].
624 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
Fig. 1. A conceptual model of a thin water lm formed between oil/brine and
brine/solid interface.
DLE is closely correlated with the electrochemical interactions
among mineral surfaces, oil and injected brine. These interactions,
namely van der Waals force (vdW), electrical double layer force
(edl) and structural force, were introduced by Hirasaki [103]. This
electrochemical interaction model is further illustrated by study-
ing the wetting lm stability and contact angle variation as direct
indicators of wettability alteration during LSW ooding [119,212].
It is suggested that the wettability of mineral surfaces is highly
dependent on the micro-topography and physical and chemical
properties of minerals, crude oil quality (acidic and basic groups),
brine composition (ionic strength, pH), and ambient conditions
(e.g. temperature, pressure and dissolved CO2 ) [199]. These factors
were vastly investigated by laboratory core imbibition/ooding
experiments, contact angle and interfacial tension analysis, other-
wise by zeta potential measurements [5,152,153,212,139], directly
intermolecular forces measurements, and wetting lm thickness
measurements [135,148].
In this paper, we will review the theoretical and experimen-
tal studies corresponding to wettability alteration during LSW
ooding process. Accordingly the paper is organized in the fol-
lowing orders: rstly, it introduces the theoretical background of
wettability alteration induced by DLE. An electrochemical model
based on augmented Young-Laplace equation is established and
is further used to explain how disjoining pressure controls the
stability of wetting lm and therefore the rock wettability. Then
a detailed description of disjoining pressure is given in order to
fulll the framework of the electrochemical model; secondly, it
overviews the measurement of direct intermolecular forces as an
evaluation of the electrochemical model. We focus on the force
curves and topography images that are obtained from surface force
apparatus because the experimental methods like core imbibi-
tion/ooding, contact angle/interfacial tension analysis and zeta
potential measurements are so well developed and broadly used
in petroleum engineering. This part is further divided into three
categoriessandstone, clay and carbonate; at last, it draws a brief
conclusion based on the historical theoretical and experimental
studies. Moreover it discusses our further research interests regard-
ing to wettability alteration of LSW ooding in carbonate reservoirs.
2. Theoretical background
The residual water on mineral surfaces appears in two kinds of
congurations: as pendular rings at grain-to-grain contact points
and as a roughly 10 nm thick lm which cover the mineral surface
[197,148] (Fig. 1). In the oil/brine/rock system, the equilibrium of
the interactions between oil, brine and rock can be expressed by
the augmented Young-Laplace equation,
Pc = (h) + 2ow cos /r
where, Pc is capillary pressure (Pa) between wetting (water) and
non-wetting phase (oil), (h) is disjoining pressure (Pa),  ow is
interfacial tension (N/m),  is contact angle ( ), r is mean radius of
pores [119]. In most cases, the capillary pressure is larger than the
disjoining pressure in microscope pores, but if the rock surface is
at the capillary pressure equals to disjoining pressure.
Disjoining pressure ((h)) is regarded as the force tends to
separate two phases (oil and water), results from molecular and
interionic interactions between the rock, oil and brine phases [103].
Therefore, three different components of disjoining pressure are
generally considered: electrical, molecular and structural forces
[61]. These contributions are broken into three forces in unit surface
area:
(h) = VDW (h) + EDL (h) + STR (h) (2)
where, (h) is disjoining pressure (Pa) as a function of wetting lm
thickness h (nm), VDW is the London van der Waals forces (Pa),
EDL is the electrostatic forces in the electrical double layer (Pa) and
STR is the structural force (Pa). The rst two forces are introduced
as DLVO theory [63,64,207], the last one is usually introduced as a
part of non-DLVO theory.
For oil to be detached from carbonate minerals, low salinity
water should overcome the capillary pressure to get into the throats
and disjoining pressure acts to increase the water lm thickness.
A schematic representation of DLE which corresponds to disjoin-
ing pressure of oil/brine/rock system is shown in Fig. 2. The lm
thickness of wetting phase (water in this case) is a nal result of
the competition of repulsive and attractive forces. The repulsion
between the charges/ions in brine/oil and brine/rock interfaces pre-
vents the oil from reaching the rock surface and wetting it. In oil
wetting reservoirs, however, it is desired to change the state of
wettability from oil-wet to water-wet and to further increase the
thickness of the newly formed water lm as much as possible. This
helps to increase the mobility of the oil and eventually increase the
amount of recoverable oil.
On the basis of augmented Young-Laplace equation (Eq. (1)), a
quantitative relationship of wettability and disjoining pressure can
be established [16]. Contact angle is therefore expressed as,
 Pc
1
cos  = 1 + I Where I= hd (3)
ow 0
a. the water lm is unconditionally stable (Fig. 3a) if I > 0 ( = 0 );
b. the water lm is meta-stable (Fig. 3b) if  ow < I <0, (0 < < 90 ,
water-wet); or if 2 ow < I <- ow (90 < < 180 , oil-wet);
c. the water lm is unstable (Fig. 3c) if I <-2 ow .
A stable water lm on silica/clay surface is proved to be with
a thickness of 10 nm from the small angle neutron scattering
performed by Lee et al. [135]. It is suggested that the water lm
thickness of silica/clay-like particles is thinner at lower salt con-
centrations (e.g., 0.001 M) compared with higher concentrations
(e.g., 0.1 M). Experimental data presented also supported divalent
ions have a smaller water layer thickness than monovalent ions.
The thickness is mineral different: the water lm thickness for clay
like particles is 12 nm larger than those for silica like particles. Fur-
thermore, the variations of lm thickness with salinity for clay like
particles are more signicant than silica like particles, especially in
the divalent ion cases. Similarly, it is again shown by imaging ellip-
sometry technique that the lm thickness at mica surface in 1 M
NaCl solution is about 10 nm but it decreases from 8 nm to <1 nm
(1) with increase in CaCl2 concentration [148].
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639 625

Fig. 2. (a) Mix-wet state after high salinity (sea water or formation water) ooding, (b) Low salinity brine increases the repulsive disjoining pressure and changes the
wettability to water-wet, (c) At equilibrium, a stable thin lm will formed by DLE (the electrical potential at oil/brine interface and brine/rock interface is expressed as 1
and 2 , respectively), indicating a fully water-wet state [Reconstructed from Myint and Firoozabadi [15]].

Fig. 3. Disjoining pressure prole and its correspondence to wetting lm stability: (a) unconditionally stable, (b) meta-stable, (c) unstable [Reconstructed from Basu and
Sharma [15]].

Fig. 4. Schematic diagram of (a) permanent dipole and permanent dipole interactions, (b) permanent dipole and induced dipole interactions, (c) temporary dipole and
temporary dipole interactions [from youtube: https://www.youtube.com/watch?v=cERb1d6J4-M].

2.1. DLVO forces
2.1.1. Van der Waals Force
Van der Waals (vdW) force between any two atoms or molecules
has been divided into Keesom force, Debye force and London dis-
persion force; also known as orientation force, induction force
and dispersion force, respectively [112]. Keesom force arises only
in the case of polar molecules (static dipoles, quadrupoles, etc.)
which have permanent multiple moments. Debye force arises
from induced polarity by a polar molecule in a nearby neutral
molecule and results in an attractive induction force between them.
Non-polar molecules have nite uctuating dipoles and higher
multipole moments at very short intervals, these instantaneous
moments induce polarity in neighboring atoms or molecules to give
rise to an attractive force called London dispersion force [112] (see
Fig. 4).
626 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
Hamaker [94] rst gave the exact calculation of vdW force
between spherical particles by integrating the point-by-point inter-
actions. Then the vdW force for two macro-bodies with other
geometries can be calculated based on the pairwise additivity
assumption. One should note that this assumption is met with-
out intervening or interlayer (such as in vacuum) between two
macro-bodies and it may break down otherwise [115]. With the
popularity of the quantum electrodynamics, Lifshitz [137] pro-
posed the famous Lifshitzs theory for calculating the vdW force
lw (7)
between two bodies separated by vacuum. In his theory, vdW is
directly linked to the dielectric constants and optical properties
lw is London wavelength (nm) and it is assumed to be
(such as reective index and absorption frequency) of the interlayer
and macro-body materials. A generalized vdW force for multi-
ple interlayers has been proposed by Parsegian and Ninham [168]
which facilitates the usage of vdW force in colloidal and biochemi-
cal science. An exact calculation of the Hamaker constant based on
Lifshitzs theory is given by Hough and White [109]. However, some
approximation equations only render slight differences; no more
than 5% compared with the exact result [115]. For a comprehen-
sive understanding of the history, developments and applications
in various areas of vdW force one can reference to Frenchs work
[80].
In the oil/brine/rock system, vdW force is always present as part
of disjoining pressure. The vdW force for two at planes can be
calculated by,
A
VDW (h) = (4)
6h3
where, A is Hamaker constant [94] for the oil/brine/rock system
(J). An approximated non-retarded Hamaker constant based on Lif-
shitzs theory is given by Overbeek and Sparnaay [166],
3
   layer become more diffuse due to less binding strength. The com-
1 3 2 3
Anon = A=0 + A>0 = kB T
4 1 + 3 2 + 3
(n21 n23 )(n22 n23 ) (5)
3pe
+   Helmholtz plane (OHP) or slipping plane. The potential on slipping
8 2 (n2 + n2 ) (n2 + n2 )1/2 (n2 + n2 )1/2 + (n2 + n2 )1/2
1/2
1 3 2 3 1 3 2 3
where, A=0 is the zero-frequency energy and includes the Kee-
som and Debye dipolar contribution, A > 0 is the dispersion energy
and includes the London energy contribution. kB is the Boltzmanns
constant (1.38 1023 J K1 ), T is absolute temperature (K), P is the
Planks constant (6.63 1034 J s),  e is electronic adsorption or ion-
ization frequency in the UV range (3.0 1015 s1 ). 1 , 2 and 3 are
the dielectric constant of oil, rock and brine, respectively and n1 , n2
and n3 are the refractive index of oil, rock and brine, respectively.
The zero-frequency energy, A = 0 only dominates in small dis-
tances (below 2 nm), while at long distance, the dispersion energy
would take over the zero-frequency energy part and control the
vdW force. A = 0 is related to the temperature and therefore kB T,
dielectric constant and refractive index of the oil/brine varies as
temperature changes, indicating that the vdW force is affected by
the thermal conditions of the reservoir. However, the temperature
sensitivity of Hamaker constant is negligible as it only produces
3.5% difference results when temperature fries from 20 C to
200 C for ceramic systems [80]. Its fact that A=0 undergoes ionic
screening at high ionic strength conditions because of its low fre-
quencies (Mahanty and Ninham [140]. The screening effect at a
limit where h  1 could be given by [23],
Ascreen = A=0 (1 + 2 h) exp (2 h) + A>0 (6)
where, is the inverse of the Debye length (nm). Eq. (6) suggests
that A=0 decays exponentially in electrolytes and with a decay
length equals to Debye length.
Butkus and Grasso [31] had experimentally proven the ionic
screening A = 0, but it is not the only contributor to decreasing the
total vdW energy. Previous measurements of vdW force between
glass surfaces have conrmed the existence of retardation. vdW
force between mica surfaces in air also has shown retardation effect
above 50 nm [112]. Even at smaller distances (h 510 nm) retar-
dation effect should be considered [116,181] because of a strong
absorption of electromagnetic waves in water.
Retarded Hamaker constant becomes h2 -dependent for two
planes and is given by [88] as:,
 
Aretardation = A=0 + A>0 / 1 + 5.32h/
where,
100 nm. The power law n of vdW force increases with separation
which indicating the vdW force decreases much lower at long dis-
tance.
The ionic screening effect usually signicantly reduces the
strength of electrostatic force compared with vdW force and also
there is a limit for ionic strength from where vdW force stops
decreasing. However, vdW force becomes less attractive due to the
combination of retardation effect and ionic screening. It is often the
case that in real reservoir condition where high salinity formation
water or sea water exists. As a result, the electrical double layer
force becomes the dominant component of disjoining pressure
which inuences the stable water lm thickness on oil/brine/rock
system.
2.1.2. Electrical double layer force
The electrical double layer (edl) force is derived from the
Coulombic interactions between charged ions or a charged ion
and a polar particle. Counterions from the solution balance the
excess surface charge of the solid particle forming an immobile
layer referred to as the Stern layer. The counterions in the following
bination of Stern layer and diffuse layer is the so-called electrical
double layer. The plane from where the counterions concentra-
tion begins to obey Poisson-Boltzmann equation is called outer
plane is referred to as the zeta potential (). Formation of edl can
be derived from preferential adsorption of potential-determining
ions and interior crystal imperfections [59]. Adsorption can occur
through chemical bonds or physical adsorption (e.g., hydrogen
bonds and vdW forces). The preferentially adsorbed ions will form
the inner layer and the counter ions will be accumulated on top to
form a second layer. Upon changing the salinity, the surface poten-
tial will remain constant whilst the surface charges change. The
second type of double layer forms due to imperfections in lattice
layers, especially for clay crystals. Upon injecting low salinity water,
though the surface charge cannot be changed, the surface potential
will become smaller. This type of edl is regarded as being of more
importance in low salinity waterooding.
The edl force can be either repulsive or attractive depending on
chemical structures, suspending medium properties and surface
charges. The sign of surface charge is determined by isoelectric
point (iep), which is dened as the pH at which no net electri-
cal charge exists on the particle surface. Sandstone is negatively
charged above pH 23 [76,118]. Crude oil is positively charged at
pH < 4 [29,30]. Carbonate rock (iep 911) is positively charged in
reservoir condition [211,5,118].
The mathematical procedures to gain insight into the electro-
static forces are derived from PoissonBoltzmann (PB) distribution
[115] which is used to describe the electrical potential in the direc-
tion normal to a surface where electrolytes are present,
d2 enb ze
= e kB T (8)
dx2 z0 r
where, 0 is the dielectric constant of vacuum, r is the relative
dielectric constant of the aqueous medium, kB is the Boltzmanns
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639 627

constant (1.38 1023 J K1 ), T is absolute temperature (K), e is < 2) and moderately ranges of ionic strength. However, they rep-
the electron charge (1.60 1019 Coulomb), z is ion valence. A resent two extremes with the correct answer lying in between
simple algorithm has been developed by Chan et al. [41] to solve [87]. A linear superposition approximation (LSA) or weak overlap
this non-linear differential equation for identical, parallel planes in approximation between the constant charge and constant potential
symmetrical/unsymmetrical valent electrolytes at various bound- assumptions is given as follows,
ary conditions,    
The surface potential for an isolated surface at a certain distance 1 2
EDL (h) = 64nb kB T tanh tanh exp ( h) (18)
is given by Gouy-Chapman equation, 4 4

2kB T

1 +  exp ( x)

4kB T where,  i is zeta potential of each surface (V). The prerequisite for
(x) = ln exp ( x) (9)
ez 1  exp ( x) ez this equation is the lm thickness is relatively large than the char-
acteristic length ( h > 1) far from where the surface potentials for
The parameter is given by,
each interface become additive. The LSA is favored for tting the
 
e 0 surface force measurement data [115].
 = tanh (10)
4kB T
2.1.3. Modied poisson-Boltzmann
where 0 is surface potential (V). In general the surface potential is
In the classical DLVO theory, ions are regarded as point charges,
experimentally immeasurable, so the zeta potential  is often used
the mean electrostatic potential is proportional to the potential
as an estimate [206].
of mean force (PMF) and the medium is assumed as a dielectric
 z

continuum up to the OHP characterized by its dielectric constant
0 = 1+ e z (11)
[136]. Comparisons between the theoretical predictions and exper-
where z is the distance between the surface of the charged particle imental results reveal some inconsistencies which led to attempts
and the slipping plane (z 0.5 nm), is the Stokes radius of the to modify the PB equation and they are summed up as Modied
particles. PoissonBoltzmann (MPB) equations. The modications have been
It is important to note that the zeta potential is a highly sen- investigated to include the following effects:
sitive property that varies with pH, temperature and the molar i. Excluded-volume effect [136,165,22] due to the nite size of
concentration of the solution. Extensive laboratory measurements ions. In Stern-Gouy-Chapman (SGC) model [52], non-specically
are needed to measure the zeta potential for both the oil/brine and adsorbed counterions carry full solvation shells bound to the sur-
brine/solid interfaces. face that form the OHP and specically adsorbed counterions
The inverse of the Debye length is given by, with residual solvation shells chemically bound with charged sur-

face, and their centers form the inner Helmholtz plane (IHP), which
e2 nb makes the plane a few angstroms further from the physical solid-
= (12) liquid interface (vdW plane). The OHP at the mica-water interface
r 0 kB T
is 2.5 nm farther out from each surface [116]. A shift of 0.9 nm
where, nb is the charge density and given by, has been assumed by Pashley and Israelachvili [174] to describe
the high apparent surface potentials on mica surfaces. Shubin and
nb = 2INA (13)
Kkicheff [191] considered 0.75 nm which equals to two hydrated
where NA is conversion coefcient (6.022 1023 m3 ), I is ionic molecules is a more reasonable value, but Kkicheff et al. [124] have
strength given by, chosen 0.54 nm (one hydrated Ca2+ diameter) instead for mica sur-
1 n
faces which leads to a lowering of 10% apparent surface potential.
I= ci zi2 (14) ii. Self-atmosphere-image effect. The mean potential of a given
2 i=1
ion is lowered by the ionic atmosphere of a local opposite ion,
where ci is ionic concentration in the bulk solution (mol L1 ), zi which gives rise to self-atmosphere potential. Image effect is
is ion valence. more signicant at higher salinity [161]. Levine [136] had modeled
Modeling electrostatic double layer force requires proper the self-atmosphere as an asymmetrical sphere in bulk solu-
boundary conditions for the Poisson-Boltzmann equation either tion and discontinuities in the dielectric constant at the interface.
using a constant potential or constant charge assumption. The con- Simulation results suggested that dielectric constant varies little
stant potential condition assumes that there is always attraction therefore dielectric continuum assumption was acceptable with-
between plates with unequal potentials even if they have the same out render seriously error. However, the potential at the middle
charge sign. The contribution inside the electrical double layer plane decreases signicantly and produces a change of 50% in the
under constant potential is given by [87], possibly the upper limit, electrostatic force.
 2 2
 iii. Variations of dielectric constant in the diffuse layer. A dielec-
2 r1 r2 cosh ( h) r1
r2
EDL (h) = nb kB T (15) tric sandwich the IHP and OHP which separate the target domain
2
(sinh ( h)) into three layers is common practice. Another one is introducing a
Conversely, the constant charge condition assumes a repulsion variable dielectric constant regarding electric led or ionic concen-
force between unequal plates and is given [87], possibly the lower tration into the PB equation [85,194,92,93].
limit, by, iv. Static or dynamic surface roughness. DLVO theory assumes
 2 2
 perfectly smooth and geometrically regular surfaces, however for
2 r1 r2 cosh ( h) + r1
+ r2 natural particles or surfaces, discrepancies frequently shown when
EDL (h) = nb kB T (16)
(sinh ( h))
2 comparing the interactions predicted by theory and measured by
force apparatus. These discrepancies are largely attributed to het-
where, ri is reduced potential and is given by, erogeneity either in the form of static surface roughness which
is simply modeled as hemispherical asperities [19,209], or non-
ri = zei /kB T (17)
uniform charge density [67,68]. Dynamic surface roughness is
The above analytical compression approximation (CA) model another contributor to the failure of DLVO theory. A great exam-
is suitable for low to intermediate electrostatic potential (ze /kB T ple is that the negative charges possessed by silica are located at
628 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
the ends of silica hairs and they are dynamically mobile and their
values vary with pH or ionic strength [208].
v. Charge regulation is ascribed to the cause of intermolecular
interactions intermediate between constant charge and constant
potential [158]. Thence edl force is modied to include charge
regulation model in order to describe the association/dissociation
of surface charges. Mass action (site binding) model [169], which
assumes competitive binding of hydrogen ions and metal ions with
dissociated, negative surface sites, is commonly used to character-
ize the regulated surface. It is capable of describing the variations in
mica/glass surface potential with an enlarged, hydrated counterion
size without the existence of a Stern layer [169]. The mass action
model gives a good agreement with experimental data [39,84],
however, Ducker et al. [71] has discussed that the surface potentials
could not be perfectly predicted by the mass action model and the
potentials obtained by tting the experimental data are not con-
rmed by zeta potential measurements. Also, some differences in
force behavior happen by using different charge regulation model.
For example, hydration forces were not observed at low electrolyte
concentrations (0.0001 M to 0.001 M) at small distances ( < 1.0 nm)
by Basu and Sharma [15], but Pashley [170] have reported compara-
ble hydration forces with mass action model. The charge regulation
model used by Basu and Sharma [15] is Yatess model [213] which
takes into account the interfacial ion pairs formed with neutral
surface site by potential determining ions (pdi) and coions. But
H+ is not considered as pdi and no amphoterism. Charge regula-
tion is more important for asymmetric surfaces [81]. Two surfaces
each carrying either positive charges or negative charges main-
tain constant charge, for which the total intermolecular force is
always repulsive. If the two surfaces maintain constant potential,
the repulsion turns into attraction on approach to each other as a
result of charge reversal at the surface with the lower potential. The
more extreme the ratio between the two surface charge densities
at innite separation, the larger the separation and at this innite
separation the interaction reversal occurs [81].
vi. Ion-ion correlation effect due to the connement of ions
when two particles approach one another [132]. Ion-ion correla-
tion force is usually attractive, short-range ( < 4 nm) [132] and is
characterized with exponentially decaying with separations. It is
far more larger than vdW force [66]. Within the scope of prim-
itive model [128,129,127,130,131], the ionion correlation force
becomes stronger as the ionic strength increases. It is assumed that
ionion correlation at low to medium concentrations is a result
of correlations between counterions but coions at concentrated
concentrations [124]. More specically, at concentrated ( > 0.24 M)
Ca(NO3 )2 solutions a triple layer forms on mica surface: a Stern
layer consists of excess counterions near each surface, a middle
layer compacted with coions, and the bulk solution with discrete
coions. Increasing the ionic strength, the coions are expelled by
counterions to escape from the gap and results in a strong ionion
correlation attraction. At even higher concentrations the interac-
tions turn into oscillatory thus causing each successive layer to be
expelled from the gap [124].
vii. Repulsive hydration energy. Intermolecular force measure-
ments have proven that there exist repulsive hydration forces,
which brings about an additional energy need to be considered
into traditional DLVO theory [92,93,89,90,47]. It was argued that
hydration force and edl force cannot be considered separately
[159,157] as hydration force is intrinsically another kind of force
arises from Coulombic forces. Gur et al. [92,93] have incorporated
the hydration free energy term for individual ion into the Boltz-
mann distribution of ions in the double layer. Basu and Sharma
[15] extended Gur et al.s model into two overlapping double lay-
ers. The ions in the double layer are subjected to both electrostatic
potential and their own hydrated potential. It was turned out
that the hydration free energy will lower the surface ion concen-
tration, break the linear connection between surface charge and
surface electrical eld, bend the differential capacity curves of the
double layer and separate the adsorptions of ion species of monova-
lent electrolyte. Another attempt was by incorporating a negative
adsorption energy of counterions and an increased size of hard-
sphere ion (including hydration shell 2.7 ) with the anisotropic
HNC model to quantitatively evaluate the hydration energy [124].
viii. Ion penetration. Another issue regarding edl force is
the penetration of ions into the surface, especially for bilayers.
The structural charges smear perpendicular into the membrane
plane and cause an average transverse displacement of the struc-
tural charges, which reduces the electrostatic potentials near the
membrane-solution interface. In this area (a zone of relatively small
electric eld strength), the edl force will be canceled out by vdW
or hydrophobic interactions [37]. The reduction in edl force will
increase at much higher salinity. Penetration effect has been exten-
sively considered by Ohshima and coworkers. Ohshima and Kondo
[162,163] assumed that the penetrated charges are distributed uni-
formly within the membrane but the potential remain constant
(equal to Donnan potential) independent of membrane separations.
The edl force at Donnan potential lies between constant charge and
constant potential; similar phenomenon exists at linear approx-
imation model. Ohshima and Kondo [163] further compared the
ion-penetrable model to LSA model and it turned out that penetra-
tion effect gives a comparable repulsive edl force to that LSA model
at low surface potentials.
2.2. Non-DLVO forces
At very small distance, DLVO theory often fails to describe some
experimental phenomena exist in colloid or polymer stability mea-
sured by surface force microscopy. That is where non-DLVO theory
comes into play (see Israelachvili [115] and the references therein).
The forces which belong to the category of non-DLVO theory gener-
ally consist of structural force, hydration force, hydrophobic force,
steric interaction, depletion interaction and born repulsion.
2.2.1. Structural force
Structural force arises for two reasons: (i) a thin lm formed
between smooth surfaces due to molecular structuring and (ii)
macromolecules like polymers exist in liquid lm owing to volume
restriction and exclusion [60]. The rst gives rise to solvation force
related to polar solvents, and if the solvent is water it is referred to as
hydration force [217]. Surfactants, on the other hand, can generate
hydrophobic force by bonding on a surface. However, the aflia-
tion is not rigorous in aqueous solutions and Horn and Smith [107]
distinguished the structural force, hydration force and hydropho-
bic force by their features. Hydration force is usually monotonic
repulsion and decays exponentially at small distances. Structural
force is characterized as oscillated and with a periodicity equals to
the diameter of one hydrated molecule. It arises from the packing
limitation of nite sized liquid molecules which is predominantly
an entropic effect. Hydrophobic force is discovered on hydrophobic
surfaces which are modied by adsorption of surfactants. This dis-
tinction is adopted in the present paper. The second case normally
brings about steric force and depletion force, separately.
2.2.2. Hydration force
Hydration force appears ascribed to different mechanisms [86].
More widely recognized mechanisms include physical adsorption
of hydrated cations which induced by ion exchange progress with
hydrogen ions [169] and formation/breakage of hydrogen bonding
network [42], which links to secondary hydration force and primary
hydration force, separately. Primary hydration force is related to the
enthalpic energy of adsorbed water layers, thus its decay length is
associated with the thickness of water layers (0.20.4 nm). Sec-
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639 629

ondary hydration force comes from the hydrated energy of cations
adsorbed at the interface. The decay length of weaker secondary
hydration is usually equaled to the Debye length [167].
Many mathematical models have been developed for character-
izing the hydration forces [86]. An empirical exponential hydration
force is proposed by Molina-Bolivar and Ortega-Vinuesa [147] for
hydrophilic systems ( a < 15 , Derjaguin and Churaev [62],
2.2.5. Depletion force
Depletion force occurs as a result of volume exclusion effect;
when two large particles approach each other, the smaller
molecules will be excluded from the gap between them. It leads
to a reduction of osmotic pressure between the particles and gives
rise to an attractive depletion interaction force [86].

STR (h) = C1 eh/1 + C2 eh/2 (19) 2.2.6. Born repulsion

Born repulsion is a very short-range molecular interaction that
where, CH is force coefcient, hs is decay length (0.61.1 nm) and originated from the overlap of electron clouds. Many studies have
an estimate hs = 1.0 nm was attained for mica in monovalent taken born repulsion into disjoining pressure to explicate the strong
and divalent electrolytes from 104 to 102 M [114,169,170] and repulsive at short range [125,126,187,123,119]. The born repulsion,
hs = 0.85 nm for glass laments in KCl solutions [181].  a refers to BR is given by [126],
advancing contact angle.
 
A6 8rp + h 6rp h
2.2.3. Hydrophobic force
BR (h) =
7560  7 +
h7
(21)
2rp + h
Although extensive laboratory experiments have shown that
LSW has great potential in improving oil recovery, petroleum engi-
Where, is collision diameter 0.5 nm according to Khilar and
neers are not satised with the incremental recovery from purely
Fogler [125], rp is the radius of sphere particle.
LSW. Surfactant assisted LSW or low salinity surfactant (LSS) has
been performed to further improve the oil recovery [160,188,108].
Adsorption of surfactants modies the rock and oil surface from
3. Direct force measurement
hydrophilic to hydrophobic (or vice versa) and changes the orien-
tation and conguration of water molecules at the interface which
Surface force apparatus (SFA) and atomic force microscope
generates an attractive hydrophobic force [106]. Marcelja and Radic
(AFM) have long been used to measure intermolecular forces
[141] associated the hydrophobic force with a larger density of
[115]. Compared with SFA, which only applicable with molecu-
water molecules next to the surfaces than in the bulk solution and
larly smooth and cylindrical shape surfaces [70], AFM seems to be
expressed it as a double exponential function,
a more powerful tool to quantify atomic forces [84] or to achieve
  true atomic-resolution images of surface topographies [82]. Lots of
6
A 8rp + h 6rp + h materials (mica, clay, silica, glass, sapphire, gold, oil droplets and air
BR (h) =
7560  7 +
h7
(20)
2rp + h bubbles) and geometries (sphere, planar or pyramid) can be han-
dled by AFM technique. Despite the differences in geometry and
where, C1 , C2 are force coefcients determined by boundary con- size of samples, the measured forces by SFA and AFM are all trans-
ditions (Pa),  1 ,  2 are decay lengths (nm),  1 is in the range of formed to surface energy between two planar surfaces through
0.30.5 nm and  2 = 3.0 nm for rutile or mica (Yotsumoto and Yoon,
1993).
Eq. 19 and Eq. 20 are phenomenological model and hence
experimental hydration force or hydrophobic force exhibits indis-
tinguishable behaviors; for example, the hydration force between
silica sheets can be tted by single exponential functions [71],
double exponential function [170], power law function [84], or
mixture of exponential function and power law [15,42]. In gen-
eral, hydrophobic force is determined by the hydrophobicity of
the surface which is indicated by contact angle measurements. For
less hydrophobic surfaces (45 < < 90 ) the hydrophobic force can
be tted by exponential function, while it can be usually tted by
double-exponential function or power law for highly hydrophobic
surfaces ( > 90 ).
2.2.4. Steric force
Polymers have long been used to enhance oil recoveries as a
chemical ooding method. Currently, polymer assisted LSW or low
salinity polymer ooding (LSP) has been addressed to gain more oil
recoveries [138,13]. Adsorption of polymers onto suspended par-
ticles introduces two effects: thermal uctuations/protrusions and
chain bridging as polymer chains overlap [115]. Polymer molecules
are thermally mobile but the movement is constrained by volume.
This restriction effect causes a reduction on the congurational
entropy of polymer chains and gives rise to a repulsive steric force.
Another factor that contributes to steric force is an osmotic inter-
action arises from polymer chains protrude too far to attach and
bind to other particles. This bridging force is usually attractive at
large separations [115].
Derjaguin approximation; in other words, the forces are compara-
ble for these two methods [71,124]. But Derjaguin approximation
fails at small separations when very high load is exerted on the
surface due to elastic deformation in SFA which leads to a progres-
sive attening and enlarging of the tip curvature. The deformation
effect is much less important for AFM [84].
Data that can be generated from force-distance curves by SFA or
AFM can be summarized as follows:
i. Gaining fundamental knowledge of intermolecular forces.
Besides some basic forces, the hydrodynamic interactions between
deformable surfaces (oil droplet and thin lm) can be measured
[53,55,56,57].
ii. Elucidating the nature and characteristics of each force.
Origins of some forces that not included in DLVO theory
are still controversial. Additionally, the factors (ionic strength
[169,171,172], pH [70], et al.) affect intermolecular forces are vastly
investigated by SFA and AFM techniques.
iii. Estimation of surface charge/potential. Surface
charge/potential is acquired by edl force measurements and
theoretical computations with DLVO theory. The potential d at
the boundary of diffuse layer estimated by tting the long-range
edl force curve, therefore, is called effective or apparent surface
potential. SFA or AFM also serves as a quantitative basis for other
methods, such as electrokinetic studies [96], potentiometric and
conductometric titrations, adsorption density measurements,
negative adsorption and colloid stability analyses [191].
iv. Giving indirect clues for mineral chemistry. A monotonic and
short-range repulsion is usually generated between hydrophilic
surfaces, while hydrophobic surfaces create a monotonic but long-
range attraction [107].
630 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
v. Estimating the thickness of surfactant/polymer adsorption
layers. It is also possible to establish the conformation or orien-
tation of molecules in the adsorbed layer [4446,143,36,113].
3.1. Interactions of pH-dependent sandstones
Sandstone is primarily composed of quartz but may incorporate
small amounts of clays. The structural unit of all silicate minerals is
the silicon tetrahedra. Silicates like quartz or K-feldspar consists of
stacked sheets of silicon tetrahedra with oxygen shared between
two tetrahedra. The mutual repulsion between the highly charged
cations (Si4+ ) in those tetrahedra ensures that the framework of the
silicates is fairly open and easily accommodates cations. The most
common substitution is Al3+ or Fe3+ replaces the Si4+ in the tetrahe-
dra, resulting in net negative charges in the crystal lattice. Charge
neutrality is maintained either by inserting appropriate amounts
of Ca2+ , Na+ , Li+ , and K+ or adding H+ which binds to O2 to form
OH (Nesse, 2012). The surface charges of silica partly depend on
the pH of the solution correlates to the following interactions:
At higher pH (7.58), the silica surface becomes increasing
negatively-charged due to the ionization of silanol groups; in the
pH range of 3 7.5, the surface charges are slightly pH-dependent;
however, the surface charges will be positive due to the adsorption
of H+ at pH below 3 [26,27,28]. Reservoir brines are typically at pH
values above the iep (pH = 22.5) of silicates.
Clay minerals contained within sandstones though little, can
exert great impact on the performance of LSW. Typical clay min-
erals include montmorillonite, kaolinite, illite, and chlorite. The
structural unit for clay minerals is octahedral sheet which is made
up of either Al or Mg atoms in octahedral coordination with eight
oxygen atoms, and tetrahedral sheet with each Si atom being coor-
dinated with four oxygen atoms. Octahedral sheet and one or two
tetrahedral sheet then are tied together by sharing common oxygen
atoms and leaving oxygen network or hydroxyls on basal surfaces
[33]. It is proved that three kinds of surface charges present on
clay minerals: (i) Permanent negative charges from isomorphous
substitution of other atoms in crystal lattice. For example, Al3+ in
the octahedral sheet is replaced by Mg2+ and one charge deciency
results. In the presence of other ions in brine solutions, the adsorbed
cations (Mg2+ in the above example) undergo ion exchange process.
The permanent negative charges mostly occur on the surface of
clay minerals. (ii) Variable negative charges which varies with pH.
Two reasons may contribute to the existence of variable negative
charges: rstly, the protons in the hydroxyls, which are attached to
Al atoms on crystal edge, dissociate in alkaline or neutral solutions,
resulting in a negatively charged crystal edge; secondly, adsorp-
tion of OH , SiO3 2 anions, or organic anions makes the edge of the
clay crystals negatively charged. (iii) Positive charges on the crystal
edge when the pH of the solution is lower than 9. This is because
the hydroxyls which bind to Al atoms on the edge of clay crystals
dissolute in more acid conditions. Since the negative charges on the
clay surface overwhelm the positive charges on the edge, the clay
crystals present a negatively charged property in nature [58].
The interactions between brine/oil and brine/sandstone inter-
faces include: (i) electrostatic repulsions between two double
layers formed at the charged brine/oil interface and brine/rock
interface, separately; (ii) hydrogen bonding between polar func-
tional groups in the crude oil and polar groups on clays; (iii) Lewis
acid/base interactions between basic groups (e.g. NH4 + ) in the oil
and negatively charged groups on rock surface; (iv) chemical reac-
tions between acidic groups (e.g. COO) in oil and divalent cations
(usually Ca2+ and Mg2+ ) adsorbed on rock surface which forms
organometallic complexes [24,151]. The last three interactions are
Fig. 5. Retarded van der Waals force in air between crossed mica cylinders with a
character that the power law index (n) changed from 2 (non-retarded) to 3 (retarded)
[112].
qualitatively interpreted by multicomponent ionic exchange (MIE)
mechanism [134,204] and the chemical mechanism proposed by
Austad et al. [12]. Quantitatively measurements of these interac-
tions are extensively available in the literature.
3.1.1. VDW force
Tabor and Winterton [196] rst successful measured the vdW
forces between two mica surfaces in the non-retarded region
(530 nm). The results showed that at separations less than about
10 nm the forces were normal vdW forces whilst at distances
greater than 20 nm they were retarded vdW forces. Israelachvili
and Tabor [112], based on a series of jump and resonance exper-
iments, have observed a gradual transition from non-retarded to
retarded vdW forces and a reduction of Hamaker constant from
12 to 50 nm between curved mica surfaces separated by air (see
Fig. 5). VdW forces seem to be independent of the cation type and
concentration as the attractive vdW in 102 and 101 M Ca(NO3 )2
were very similar to those measured in 101 and 1 M KNO3
solutions [116]. Also, Israelachvili and Adams [116] observed a
shorter retarded separation (6.5 nm) for mica surfaces immersed
in mono/divalent electrolytes.
Previous force measurements performed on glass surfaces
shown signicant retarded vdW forces in a range of 25 nm to
1200 nm (see Israelachvili and Tabor [112] and the references
therein). Rouweler and Overbeek [186] rst successfully measured
the dispersion forces between a fused glass lens and a at glass at
25350 nm. A d3 -dependent retarded vdW forces at separations
greater than 50 nm were observed and an estimate of a transi-
tion region at 20 nm between retarded and non-retarded forces
characterized with d2 was expected.
VdW force is assumed to be very weak or even not exist for gold
surfaces. This is convinced by trying to reproduce the measured
forces between a gold-coated sphere and a gold surface immersed
in 104 M NaCl [71] that a reasonable t was achieved by eliminat-
ing the vdW force. Similar conclusions also have been reached by
other researchers [20,183,122,74,73]. Giesbers et al. [81] illustrated
that vdW forces between dissimilar surfaces, a silica sphere and a
thin gold lm, are negligible as well.
3.1.2. EDL force
Extensive studies have proven that edl force at low salt concen-
tration (mostly at 104 102 M) could be adequately characterized
by classical DLVO theory; the magnitude, decay length and decrease
in surface potential/charge with increased ionic strength or pH3
[116,181,104]. Discrepancies happen at higher concentrations, for
example at a concentration of 102 101 M the edl forces for K+
solution still decay roughly exponentially with distance but the
mean decay lengths are 25% higher than the theoretical values
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
[116,181]. Above 1 M NH4 Cl concentrations, however, the edl forces
cannot be described by DLVO theory [69]. Toprakcioglu et al. [200]
have reported an even lower concentration ranges ( > 4 102 M)
at which the diffuse potentials dropped to 30 mV that were not
expected by theory for mica surfaces immersed in KNO3 solu-
tions. In particular, the edl forces are much reduced in divalent
solutions than those in KNO3 solutions as the mean decay lengths
are lower by 2045% than the theoretical values even in diluted
(104 103 M) Ca(NO3 )2 and BaCl2 solutions [116].
Possible explanations for the above inconsistencies could be
the limitation of DLVO theory and surface contaminations. For
instance, Shubin and Kkicheff [191] have reported a shorter decay
length 0.25 nm than the expected length 0.36 nm for mica sur-
faces immersed in 7.3 101 M LiNO3 solution. The difference is
attributed to a decrease of effective dielectric constant and thus, a
non-continuum theory should be used. Additionally, the edl plane
may be shifted by approximately one hydrated ion diameter which
indicates that additional hydration force arises at very short dis-
tances. Moreover, as suggested by Pashley [169], a continual ionic
exchange happens between the mineral lattice and the aqueous
solution. Differences between surface preparation and treatment
methods have great inuences on force behaviors. Ducker et al.
[70] noticed that their apparent surface potentials are lower than
those obtained from streaming potential measurements on silica
capillaries but higher than those from tting force curves on large
silica sheets by Horn et al. [105]. Actually, there are great differences
between densities of silanol groups on these surfaces due to differ-
ent surface preparation processes. The edl force for silica surfaces
at a given concentration and separation is increased in the order
of amed <steamed < ammonia-exposed [84]. Even worse is that
the adsorption of other materials may totally change the surface
properties and make the DLVO theory to fail [107,81].Other expla-
nations like pH variations due to the dissolution of atmospheric
CO2 and not strictly following the cleaning procedures, cannot be
ruled out either [107].
The electrostatic nature determines that the edl is rather
sensitive to the ionic strength, which is characterized by ion con-
centrations and valences. Furthermore, the edl also depends largely
on the ionic specicity. This concept is highlighted as specic ion
effect which supposes that ions adsorb specically to the particle
surface and modify its surface charge. It further species the size
and hydration of ions which follows the Hofmeister series [164].
As discussed before, at low concentration range (e.g., <103 M), the
colloids tend to be more stable with decrease in ionic strength
as theoretically predicted. It is the theoretical basis of LSW in
petroleum engineering. However, stability is disturbed because of
ionic screening by further increasing the concentration. Yotsumoto
and Yoon [215] have observed a reduction in stability of silica sus-
pensions at iep with the increase in NaCl concentration up to 2 M.
The repulsive edl and hydration force for silica surfaces can be com-
pletely removed by raising the pH to 10.3 or adding Ca2+ to 1 M
concentration [145]. Same conclusion was reached but half mag-
nitude of values were given by Valle-Delgado et al. Delgado et al.
(2005). EDL repulsion becomes negligible at 1 M NaCl or 0.5 M CaCl2
solution, which highlights the hydration repulsion and vdW attrac-
tion at around 2 nm. This inconsistency may be due to the different
silica materials used by the two authors: the use of a glass sphere
and a silica wafer by Meagher [145] and a nonporous silica sphere
and a very smooth silica plane by Valle-Delgado et al. [205] may
have contributed to different densities of silanol surface groups and
therefore, different numbers of negative sites on silica surface.
At rather high concentrations, the colloids have been observed
to restable. AFM adhesion measurements for silica surfaces at 1:1
(NaCl, KCl and CsCl) and 2:1 (MgCl2 , CaCl2 and SrCl2 ) aqueous solu-
tions suggested that adhesion appears until a specic concentration
is reached, e.g., 0.10.2 M in NaCl, 0.050.1 M for CaCl2 and MgCl2 .
631
It keeps increasing with concentration (e.g., 1 M in NaCl) until
approaching a maximum. The maximal adhesion corresponds to
a full neutralization of surface charges. Then the adhesion starts
to decrease with much higher concentration which implies a re-
emergence of edl repulsion due to the charge reversal caused by
excess adsorption of cations [66], see Fig. 6). An unanticipated
nding was observed in 3:1 electrolytes (LaCl3 , [Co(NH3 )6 ]Cl3 ,
and AlCl3 ). Maximal adhesions, which are twice larger than those
observed in 1:1 and 2:1 electrolytes, are observed at 1 mM con-
centration for all three solutions. This critical concentration is 3
orders of magnitude smaller than those of monovalent and divalent
electrolytes (see Fig. 6). Reasons behind the unexpected behavior
of trivalent ions need to be further explored but may be governed
by ionion correlations. Subsequently, the adhesions vanish above
2 mM owing to overcharging [66]. Charge reversal is also observed
on mica surfaces through zeta potential measurements in the pres-
ence of Ca2+ during LSW. At concentrations beyond 0.05 M due to
a strong adsorption of Ca2+ onto mica surface, the surface charge
turns from negative to positive. Accordingly it will enhance the oil
production by reducing or removing the Ca2+ ions in low salinity
water [148].
3.1.3. Hydration force
Generally, at relatively higher electrolyte concentrations
(102 101 M) and at separations less than 5 nm hydration force
arises [116]. The hydration force between hydrophilic surfaces is
monotonically repulsive and has been measured by AFM at a sepa-
ration of 1.55 nm. In Pashleys serial AFM measurements between
mica surfaces in monovalent ions (Li+ , Na+ , K+ and Cs+ ) [170],
divalent ions (Mg2+ and Ca2+ ) [172], and trivalent ion (Li3+ and
Cr3+ ) [171], all detected additional short-range ( < 2.5 nm) repulsive
forces at higher ionic concentrations. However, the critical con-
centration varies with ion type: in monovalent electrolytes, the
concentrations from which the hydration forces to be observed
are in the order Cs+ <K+ < Li+ Na+ . Divalent ions show a similar
trend with monovalent ions that is in the order Ca2+ < Mg2+ . The
overall trend is given as Cs+ <K+ <Li+ Na+ <Ca2+ <Mg2+ <La3+ and
is interpreted as the higher the hydrated degree, the higher the
concentration required for that cation to displace hydrogen ions
originally adsorbed onto the mica surface [173]. In other words,
hydration forces are originated from the physically adsorbing of
hydrated cations onto mica surface which are subjected to a cation
exchange process with hydrogen ions. The difference between
divalent ions and monovalent ions is that monovalent cations are
more strongly hydrated and therefore do not easily shed their
hydration layers, instead, they keep the residual hydration shells
in order to adhere onto the mica surface [173].This rule is also
reasonable for rutile surfaces [215].
Hydration forces between mica surfaces in K+ and Na+ solu-
tions (above 104 M) have shown to be exponentially repulsive
with decay lengths of 1.0 0.2 nm [169,170]. The decay lengths of
Mg2+ and Ca2+ solutions are much larger (1.8-2.0 nm) which are
enough to remove the hydration minimum as a result of the balance
between repulsive hydration force and attractive vdW force. Hydra-
tion forces in La3+ electrolytes, on the other hand, are extended to
much longer distance (ca. 30 nm) and are quantitatively described
by a double exponential function with decay lengths of 0.5 nm and
3.0 nm, respectively [172]. Inuences of multivalent ions on the
range and decay length of hydration force are assumed to be specic
adsorption and ionic screening. The rst one indicates that divalent
cations (e.g., Ca2+ ) have a favorable adsorption ability compared to
monovalent cations (e.g., Na+ ). Given same concentration divalent
cations as well, have a larger screening effect on reducing the edl
force; Anisotropic Hypernetted Chain Approximation (AHNC) cal-
culation results indicated that the negative charges on each mica
632 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639

Fig. 6. (a) Adhesion (full-off force) between a silica bead and a at silica surface as a function of ionic strength in 3:1, 2:1, and 1:1 electrolytes at pH 5.5 (AlCl3 at pH 3.8). (b)
Force vs separation curves in different salt solutions. The ion specic concentration is chosen at which edl was negligible [66].

surface were totally compensated by counterions at intermediate

concentration (0.05-0.24 M) of Ca(NO3 )2 solutions [124].
Unlike molecularly smooth mica, the origin of the additional
short-range repulsion on amorphous silica is still in debate. Ducker
et al. [71] postulated that this additional repulsive force was orig-
inated from a residue water lm or hydrated ions adsorbed on the
glass surface which results in a shift of charge plane. Vigil et al.
[208] proposed another explanation regarding a silica gel-layer
(10 thick of silanol and silicilic acid groups) that shifts the OHP
0.5 nm further out from each surface which effectively enhances
double-layer repulsion at relatively large separations (up to 5 nm),
moreover, the silica hairs along protrude into aqueous solution
which adds a monotonic steric repulsion by overlapping gel-layers
at small separations. They argued that the range of hydration force
decreases with an increase of ionic strength, a decrease of pH or
adding of Ca2+ shrinks the anionic silica gel-layer and hence, gives
rise to a shorter range steric repulsion. It has been assumed that the
overlapping of water layers on silica surface gives rise to the short-
range repulsion. Nevertheless, more studies seem to agree with
the hypothesis that hydration force which arises from the over-
Fig. 7. Schematics of hydration force for mica/silica surface. (a) Ion exchange
lapping of water layers on silica surface that is responsible for the
between the fully hydrated counterions on mica surface. (b) Small counterions
short-range repulsion. with a higher afnity for water penetrate deeper into the hydrated layer than large
Hydration forces between silica surfaces at monovalent solu- counterions on silica surface [51].
tions (104 101 M) are found to be monotonic, exponentially
decaying with a decay length of 0.51.0 nm below 23 nm. The
ter [51]. Because the rst adsorbed layer of hydrated counterions
hydration force is insensitive to ionic strength which is opposed to
is completely neutralized at high concentrations, it is assumed
the secondary hydration force on mica surfaces [181,70,71,84,42].
that the structured water layer is more favorable to accommo-
The more hydrated cations produce the weaker is the hydration
date smaller ions with a higher afnity for water. Larger ions are
forces for silica surfaces, that is Li+ <Na+ <K+ <Cs+ , which is also
more likely to reside outside the hydrated layer (see Fig. 7). Direct
opposite to the general trend for mica surfaces. Moreover, the
verication includes intermolecular force measurements [65,66]
short-range force is always present and is the strongest between
between silica surfaces. The adsorption capacity of monovalent and
silica surfaces in deionized water [42]. Unlike the simple the case
divalent cation onto silica surface is ranked as Mg2+ < Ca2+ < Na+ <
of mica, the hydration force for silica surfaces in fact comes from the
Sr2+ < K+ < Cs+ according to the size of cations as well as solvation
breakdown of hydrogen bonding network built on silanol groups;
energy but not correlating with hydrated radius.
because each cation exchanges a H+ which reduces the extent of
network and in turn diminishes the repulsion. Li+ , for example, is
3.1.4. Structural force
the most hydrated cation and it has the strongest power to break the
Oscillatory structural force arises from closely packed nite
network and therefore the lowest hydration force. Li+ is structure
sized molecules with restricted space between the two surfaces. It
maker in mica, but a structure breaker in silica [42]. A similar
usually extends to about 1.5 nm with a periodicity of 0.25 0.05 nm
conclusion has already been extracted by Peschel et al. [175] on
[117]. Israelachvili and Pashley [117] argued that measurement
studying the interactions between two polished silica plates sepa-
of short-range forces from the deection of a single cantilever is
rated by thin aqueous LiCl, NaCl and KCl layers. They found that the
not enough to disclose the high repulsive forces. In the follow-up
decay lengths increased in the order Li+ <Na+ <K+ which is in agree-
studies, they used a variable stiffness double-spring cantilever and
ment with Chapels [42] work. Conversely, the trend at higher ionic
measured over six orders of forces. Structural forces between mica
strengths for silica is opposite to the ion adsorption sequence at
surfaces in monovalent KCl electrolytes were found to be oscillated
low ionic strength (104 -101 M). An indirect clue showed that the
for several steps with a periodicity 0.24 0.2 nm (almost equals to
highest viscosity, which corresponds to the lowest hydration force,
the diameter of one water molecule) below 1.5 nm. The structural
of silica slurries (1 M and 4 M) was obtained for Li+ ion. The general
force between mica sheets immersed in 1 M NaCl solution reported
order of hydration force hence is in the order of Li+ <Na+ <K+ < Cs+
by McGuiggan and Pashley [143] also showed jagged forces super-
which correlates to the bare size rather than the hydrated diame-
imposed on a strong monotonically repulsive force. The width of
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
these steps was found to be 0.30 0.05 nm, which is slightly larger
than those measured in KCl solutions (0.25 0.03 nm) [173], but the
number of steps is same as observed in KCl solutions. In 0.1 M NaCl
solution, in contrast, an oscillatory force with similar periodicity but
a shorter range was observed. Ducker and Pashley [69] conrmed
the oscillatory nature of structural force by measuring the inter-
actions between two mica crystals in aqueous NH4 Cl solutions. A
short range ( < 1.5 nm) repulsion appeared at concentration above
103 M and oscillated with a periodicity of about 0.4 nm. This peri-
odicity is regarded as an integral of adsorbed hydrated NH4 + and
water molecular packing in thin lm. Overall, it has been observed
that varieties of ions give the similar oscillatory force which sug-
gests that structural force is caused by water molecules layering
in thin lms between molecularly smooth, rigid surfaces. Never-
theless specic ion-water interaction may vary the periodicity of
these oscillations [69]. The oscillatory structural force likewise has
been observed in divalent electrolytes. At concentrated CaCl2 solu-
tion (0.12 M), short-range oscillatory force added to a monotonic
tail appeared for two muscovite mica surfaces due to adsorp-
tion of hydrated Ca2+ ions [131]. Upon detailed examination it
was concluded that the strength of structural repulsion is one to
four orders higher than the hydration force observed at 0.12 M
Ca2+ concentration [172]. Note that in divalent ions like Ca2+ , the
oscillated structural force is also found on the dynamic rough sil-
ica surfaces (ever changing/dynamic). Indeed, Fielden et al. [79]
have observed an oscillatory structural force with the periodic-
ity associated with expulsion of water layers in the direct force
measurements between silica surfaces in 1 and 5 M CaCl2 solutions,
3.1.5. Hydrophobic force
Strong monotonically attraction emerges between two
hydrophobic surfaces and it is referred to hydrophobic force.
Hydrophobic force originates from the expulsion of entropically
unfavorable water molecules from the surface [143] and may
be 10100 times stronger than the vdW attraction [111,107].
Hydrophobic force is commonly of long-range (several tens of
nanometers) and has a decay length of 12 nm [182]. This char-
acteristic force has been observed on hydrophobic mica surfaces
[48,50,49,203], 4hydrophobic glass surfaces [180,182,214] or
dissimilar surfaces [201,202]. Alternative explanation has been
given in terms of ionion correlation by [9] which indicates that
hydrophobic force arises from an enhanced electrostatic response
by large charge/dipole uctuation. Therefore the long-range
attraction decays exponentially with a decay length equals to
half the Debye length at high salt concentration and remains
constant independent of salt concentration in particular at low salt
concentrations.
Hydrophobic force has been measured between hydropho-
bized quartz laments in 102 M KCl solution. Different degrees of
hydrophobicity are achieved by treating the glass surfaces in 10%
DMOCS solution or DMOCS vapor for different times. The advanc-
ing contact angle ( a = 100 ) was independent of time and types of
surface treatment (in vapor or solution). The receding angle var-
ied from 55 to 70 depending on both time and kind of treatment.
The hydrophobic attraction that appears at 15 nm increases with
the growth of contact angle, in other words, the hydrophobicity.
The strength of the attraction is almost 104 times greater than vdW
force and extends to 200300 nm [181].
3.2. Interactions of deformable oil surfaces
It is believed that the oil composition relates to the causes and
consequences of LSW. Crude oil basically contains two kinds of
functional groups: carboxyl group ( COOH) and amide ( NH2 )
derived from carboxylic acids, which are determined by acid num-
ber and basic number (mg KOH/g), separately. COOH is mostly
633
found in heavy fraction of crude oils like resin and asphaltene and
it is suggested that the carboxyl group plays a more important role
on the recovery of LSW compared with base number [195]. Negative
COO binds to the positively charged carbonate surface or adsorbs
on the clay surface on sandstone rock could turn these two surfaces
more oil-wet. Positive NH3 + can also adsorb on the clay/silica sur-
face. The adsorption of acidic and basic groups onto clay surface is
very pH-dependent [11].
3.2.1. Rigid tip-oil droplet and drop-drop interactions
To date, interactions between a rigid probe and a hard sur-
face are well emphasized. Many experiments are also carried
out for a rigid probe approaches using a single air bubble
[198,32,72,78,176,177,18,156,21,83,110,6,75,4]. Models to quan-
tify the probe-bubble interactions are not well developed to
elucidate the deformation characteristics of air bubble. Instead an
air bubble is just treated as a normal hydrophobic surface. In this
paper the probe-bubble interactions in terms of intermolecular
interactions related to oil droplet is of interest. For rigid surfaces,
a complete force curve can be captured in the compliance range of
the cantilever, while a much longer compliance range is required
to achieve constant compliance for oil droplets due to the deforma-
tion. Long range force, such as the edl force is impossible to detect
since a weak deformation of the oil droplet shades the deection of
the cantilever. Weak vdW force may also be masked for the same
reason [55].
A large and growing body of studies has focus on this area
both from experimental and theoretical aspects, e.g., direct force
measurements between a rigid probe and a single oil droplet
[150,193,95,18,7,10,210], and two deformable oil drops immersed
in another immiscible uid [91,34,57,55]. Quantitative description
of forces act on deformable oil droplet relies on a coupling of the
static interactions (edl force, vdW force, and hydrophobic force)
and dynamic drainage. The hydrodynamic force involved here is
referred as the force that exerted on the particles by liquid lm
before a hydrophobized glass colloid approaches an oil drop in
aqueous solution. For soft materials (oil drop) the deformation will
prevent the thinning and rupture of the lm, therefore the drainage
of the thin lm is a function of oil droplet radius and external driving
velocity of the scanner [7,8]. Several models have been proposed to
determine the dynamic interactions between deformable surfaces
[133,38,14,54,154,56,35,83,40].
Drop-drop interactions are measured by mounting one oil
droplet onto a tipless cantilever and the other attaching to a at
base (see Fig. 8a). A thin lm will be formed along the at sur-
face in the surfactant (usually SDS) or protein solutions [91,55].
The presence of thin aqueous lm between oil droplets causes a
change in drainage velocity: the drainage is quickly and evenly for
surfactant system with highly mobile interfacial lm, on the con-
trary, the protein stabilized interfaces are immobile and drainage
is low and unevenly. Drainage is faster at the edges of two oil
droplets than in the center, resulting in a dimple with trapped water
[91]. Force curves at pure anionic surfactant (SDS) shows that the
droplets remain stable due to signicant edl force, but in the mix-
ture of SDS and 1 mM NaCl, the oil droplets tend to approach each
other because of ionic screening by counterions. The oil droplets are
forced to go together in a mixture of SDS and 40 mM NaCl due to
a greater screening effect [91]. For large droplets (above 100 m),
the interfacial deformation and hydrodynamic drainage effect are
obvious due to an equilibrium result with surface forces. However,
there will be no dimple in the interfacial prole for small droplets
with low deformation. At velocities similar to Brownian motion, the
contributions of hydrodynamic and surface forces are strongly cou-
pled and the relative length scales will determine which component
dominates (see Fig. 8b). At higher velocities (about twice Brown-
 634 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
Fig. 8. (a) A schematic of AFM force measurement between two oil droplets (one immobilized on the cantilever and the other immobilized on the substrate). (b) Dynamic
interaction force F versus piezo drive motion
X between two decane droplets in 0.1 mM NaCl solution with SDS at a series of driving velocities (green circles, 2 m/s; blue
triangles, 9.3 m/s; red diamonds, 28 m/s). Open symbols (approach) and lled symbols (retract) refer to the experimental data, and the solid lines are numerical simulation
results based on Stokes-Reynolds-Young-Laplace Model (Dagastine et al., 2006). (For interpretation of the references to colour in this gure legend, the reader is referred to
the web version of this article.).
ian motion), hydrodynamic drainage dominates the total pressure
[55].
3.2.2. Chemical force microscopy (CFM)
Recently, Chemical Force Microscopy (CFM) with different
chemical modied tips has been used to gain insights into LSW
mechanism for sandstones [99,98,142,101,97,120,121] and chalk
[100,192] based on adhesion measurement. The basic idea is to
modify the gold-coated tip with polar/nonpolar or basic/acidic
groups in order to investigate how different oil composition, rock
minerology, and interface physics/chemistry affect LSW. More
specically:
i. CH3 modied tip is used to simulate hydrophobic surface or
nonpolar oil droplet,
ii. CF3 modied tip is used to simulate hydrophobic and polar
surface,
iii. NH2 modied tip is used to simulate basic group NH3 + of oil,
iv. COOH modied tip to simulate acidic group COO of oil,
v. OH modied tip is used to simulate polar groups of oil and also
to detect the effect of hydrogen bonding.
Amongst the above, CH3 and COOH terminated tips are the
most favorable ones to explore the relationship between wetta-
bility and salinity. The extracted force volume maps along with
captured topography images provide us sufcient information
about nanoscale interactions: the adhesion between CH3 tip and
quartz grain is higher (more oil-wet) in articial seawater than
that in dilute seawater (see Fig. 9). Additionally, adhesion is more
signicant in the presence of heterogeneous distributed organic
material as it offers very sticky anchor points for oil molecules
to adhere onto the quartz surface [142] (see Fig. 9). Hilner et al.
[101] has quantied the adhesion between a nonpolar CH3 mod-
ied tip (which served as oil droplet) and sand grains taken from
core plugs in articial formation water and its diluted solutions
as a function of ionic strength (salinity ranges from 28,500 ppm to
1,500 ppm). The results show that the adhesion reduces as salin-
ity decreases below a threshold of 50008000 ppm, indicating a
less oil-wet transition. Clay is necessary in increasing edl expan-
sion either through increasing pore surface charges or providing
higher surface areas and anchor points for the oil compounds. As
a result, clay will enhance wettability alteration from oil-wet or
mix-wet to more water-wet in sandstone reservoirs. COOH ter-
minated tip can be used to elucidate the effect of polar components
in oil on wettability. As shown by Mugele et al. [148] that even small
amount of polar hydrocarbon and stearic acid was able to enhance
the hydrophobicity of mica surface. In fact as proved by AFM imag-
ing, bare mica surface was seen with occasional groups of mono
stearate layer and this layer is much thicker in the vicinity of the
original contact line of the droplet with occasional holes. Meaning
that Ca2+ and S.A., a typical surfactant synergistically transform the
mica surface to a more oil-wet state by promoting the self-assembly
of hydrophobic Ca-stearate monolayers.
3.3. Interactions of chemical active carbonates
Carbonate minerals are divided into calcite, dolomite and lime-
stone, amongst these minerals calcite (CaCO3 ) is the most abundant
carbonate minerals [155]. In this paper calcite is taken as an exam-
ple in order to introduce the crystal structure of carbonate minerals.
The structural element of calcite is the CO3 2 anionic group. The
central Ca2+ coordinates to six oxygens from distinctive CO3 2
group, forming a slightly distort octahedra. Adjacent octahedra are
linked both by CO3 2 groups and sharing corners of octahedra from
layers above and below. Ca2+ layers alternate with CO3 2 layers
along the c axis and CO3 2 groups reverse orientations in successive
layers [184].
Carbonate minerals are chemically active with dissolu-
tion/precipitation, adsorption and substitution happens in an
oil/brine/carbonate system. Calcite can dissolve in brine solutions
to produce Ca2+ , CaH2 O+ , CO3 2 , HCO3 , and H2 CO3 [102]. If pH is
below a certain value (68), the dissolution tends to produce more
Ca2+ and the calcite surface is more positively charged. On the other
hand, if the pH is high enough ( > 8.7), the reactions produce more
CO3 2 and the calcite surface is more negatively charged. In the pH
range of formation water (6.57.5), however, the surface charge of
calcite is positive. Anhydrite dissolution and Ca/Mg substitution are
expressed by the following equations:
CaSO4 (s) Ca2+ +SO4 2
CaCaCO3 (s)+Mg2+ MgCaCO3 (s)+Ca2+
The adsorption of sulfate ions which produced by anhydrite dis-
solution [189] also enhances the negative charges on the carbonate
surface. This leads to co-adsorption of Ca2+ and Mg2+ onto the rock.
The Ca2+ ions then react with carboxylic groups in oil and adhere
to the carbonate surface. The reaction breaks the bonds between
the brine/carbonate and brine/oil interfaces and releases the car-
 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639 635

Fig. 9. Topography and adhesion map created by CH3 modied tip reacts with a quartz grain during articial seawater (ASW) and low ASW ooding. (a) A height map with
a at area enclosed by red line (clean quartz) and several topographically higher features that enclosed by green lines (adsorbed organic material). (be) Adhesion maps after
two cycles of ASW to ASW-low ooding. Note: high adhesion (red spots) is observed on the at area but near the topographically higher parts. Average adhesion corresponds
to different areas as listed in the table [142]. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

tions are activated and make brine/carbonate interface to become

more negatively charged and repelled by the negatively charged
brine/oil interface. Though it is still debated on the reasons for
wettability alteration in carbonate reservoirs, double layer expan-
sion is believed to be the main process responsible for improving
production by LSW ooding [2].

4. Conclusion

This paper gives a review of some theoretical and experimental

Fig. 10. Schematic of wettability alteration induced by seawater in chalk. (a) Ca2+
and SO4 2 involved reactions at lower and high temperatures. (b) Mg2+ and SO4 2
acts in releasing oil at high temperatures [218].
boxylic groups, resulting in improving oil recovery (see Fig. 10).
Another benet of anhydrite dissolution is that it may increase the
connectivity of the pores so that the reservoir becomes more per-
meable to ow. At sufciently high temperatures ( > 100 C), Mg2+ ,
either brings by low salinity brine or dissolves from dolomite, sub-
stitutes Ca2+ from the carbonate surface and thereby displace Ca2+
ions that are bridged to carboxylic groups, thus the Ca/Mg sub-
stitution further improves oil recovery [185,218] (see Fig. 10). To
conclude that Ca2+ , Mg2+ and SO4 2 are the pdi for carbonate reser-
voirs. It should be noted that either Ca2+ or Mg2+ together with
SO4 2 are able to change the wettability of carbonate reservoirs but
SO4 2 alone is not capable to achieve the same outcome [185,146].
It is much favorable to reduce or remove the Na+ ions in injected
brine as the Na+ ions will prevent the pdi from reaching and react-
ing with the oil or carbonate minerals [77]. The chemical response
in carbonate reservoirs during LSW can be simulated with designed
geochemical software like PHREEEQC [59,25], in-house simulator
[178,179,211] which incorporates ow simulation to gain insights
into which chemical process that dominates in LSW.
When low salinity brine is injected into carbonate reservoirs,
the thermodynamic equilibrium among the ions dissolved in the
brine lm, ions adsorbed onto the rock surface and the species
incorporated into the rock matrix is disturbed. All the above reac-
studies on wettability alteration mechanism due to double layer
expansion during low salinity waterooding on both sandstone
and carbonate reservoirs. A few points that addressed in this paper
mainly include:
i. Low salinity waterooding is an efcient way to improve oil
recovery for sandstone and carbonate reservoirs as proved by
eld test and laboratory experiments. However, the content of
low salinity waterooding is different for these two kinds of
reservoirs.
ii. Wettability alteration is regarded as the primary mechanism
of low salinity waterooding in sandstone and carbonate
reservoirs. Wettability alteration is triggered by double layer
expansion mechanism which is correlated to the electrical and
chemical properties of the oil/brine/rock system.
iii. Intermolecular interactions in the oil/brine/rock system can be
qualitatively and quantitatively described by an electrochemical
model. Wettability is directly associated with disjoining pressure
which is responsible for the stability of water lm. Disjoining
pressure is usually composed of van der Waals force, electrical
force and structural force which belong to the domain of DLVO
and non-DLVO theory. Note that it is hard to quantify the dis-
joining pressure in a real oil/brine/rock system because lots of
factors (pH, temperature, oil composition, surface heterogeneity
etc.) may ruin the predicted results. Future trials should be done
to assess the impact of these factors.
iv. Surface force apparatus like atomic force microscopy provides
us a powerful way to handle nanoscale intermolecular forces
among oil/brine/rock system. Along with topography imaging
and tip modied technique, we can qualitatively investigate how
636 H. Ding, S. Rahman / Colloids and Surfaces A: Physicochem. Eng. Aspects 520 (2017) 622639
oil or brine composition and mineral properties affect the per-
formance of low salinity waterooding. Considerably more work
will need to be done with reservoir rock samples and crude oil
in real reservoirs conditions (relatively high temperature and
pressure).
v. The precise mechanism of wettability alteration in carbonates
remains to be elucidated. Although calcite and anhydrite dis-
solution are highly empathized, the nal result is a change of
surface charge/potential which rooted in the territory of double
layer expansion. This paper therefore holds the view that the
wettability alteration caused by double layer expansion is the
nal ending of low salinity waterooding. But the processes (pH
increase, MIE, Austad et al.s chemical mechanism or else may
operate simultaneously) that led to this result are still possible
area of future research.
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