Journal of Molecular Liquids 250 (2018) 396–403

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Journal of Molecular Liquids

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

Drivers of low salinity effect in sandstone reservoirs

Ehsan Pooryousefy, Quan Xie ⁎, Yongqiang Chen, Ahmad Sari, Ali Saeedi
Department of Petroleum Engineering, Curtin University, 26 Dick Perry Avenue, 6151 Kensington, Western Australia, Australia

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

Article history: Wettability of oil/brine/rock system is a fundamental petro-physical parameter, governing the subsurface multi-
Received 22 October 2017 phase flow behaviour, thus affecting hydrocarbon recovery. However, understanding the controlling factor(s)
Received in revised form 25 November 2017 which drives the process is incomplete. Therefore, a detailed examination and characterization of reservoir sur-
Accepted 28 November 2017
face forces as well as pore-surface chemistry are of vital importance. We combined contact angle, zeta potential
Available online 8 December 2017
and surface complexation modelling to demonstrate that DLVO theory and surface complexation modelling pre-
Keywords:
dict the same wettability trends. Moreover, we introduced Z* parameter (Z∗ = |Zoil/brine + Zbrine/rock |) to manage
Low salinity water flooding low salinity water flooding, thus mitigate the uncertainty of low salinity effect.
Wettability © 2017 Elsevier B.V. All rights reserved.
Contact angle
Zeta potential
Surface complexation modelling

1. Introduction
Wettability of oil/brine/rock system governs subsurface multiphase
flow behaviour and saturation distribution of the fluids, thus affecting
oil recovery from hydrocarbon reservoirs [1,2]. Water-flooding tech-
nique has been widely used to maintain reservoir pressure, thereby im-
proving oil recovery [3]. Recent studies [4–6] proposed a novel means to
enhance oil recovery by manipulating the composition of injected water
chemistries, in a process called LoSal flooding by BP [7,8], Smart Water
flooding by its originators, Austad and co-workers at the University of
Stavanger, Saudi Aramco [9], and Designer Water flooding by Shell [10,
11].
Several mechanisms was proposed to decipher what factors control
the low salinity effect: fines mobilization [12], limited release of mixed-
wet particles [12], increased pH and reduced IFT similar to the alkaline
flooding [13], multi-component ion exchange (MIE) [8,14–16], expan-
sion of the electrical double layer [17], salt-in effect [18], salting-out ef-
fect [19] and osmotic pressure [20].
However, the main mechanism behind low salinity water flooding is
thought to be wettability alteration [21,22]. Yet, knowing what specific
factors govern the reservoir wettability in the presence of crude oil and
formation brine has long been a goal of reservoir engineers. To under-
stand the factors controlling the interplay between fluid-fluid and
fluid-rock interfaces, atomic force microscopy (AFM) [23,24] and quartz
crystal microbalance with dissipation (QCM-D) [25] were used to inves-
tigate the effect of water chemistry on adhesion force at nano-scale. In
addition, surface complexation modelling (SCM) was also applied to un-
derstand the wettability of reservoir rocks to relate the surface
⁎ Corresponding author.
E-mail address: quan.xie@curtin.edu.au (Q. Xie).
chemistry to measured zeta potential [26,27]. However, the factors con-
trolling the wettability in oil/brine/rock system is yet to be clearly ex-
plained, thus limiting the implementation of low salinity water
flooding in oil fields. For instance, while most reports suggest that the
presence of divalent cations, clays, and acidic compounds from crude
oils, are of vital importance to yield wettability transition towards
more water-wet [8,16], Hassenkam et al. [28] found the opposite, argu-
ing that a reduction in adhesion force of the oil/brine/rock system can be
achieved even from a pure quartz surface with a model oil composed
only of CH3. To date, uncertainties about the nature of the physics con-
trolling the interaction of the oil/brine/rock system remain, with some
reports suggest using salinity level to interpolate between the relative
permeability curves [29,30], whereas others suggest using individual
ion, e.g., Ca2+, Mg2 + and SO2− 4 in the solution [31,32]. The nature of
the wettability in oil/brine/rock system remains something of a mys-
tery, with many questions about its chemical nature at a molecular
level.
To better model and manage the low salinity water flooding, we
hypothesised that zeta potential at the interfaces of oil/brine and
brine/rock govern the wettability transition because zeta potential is a
reflection of geo-chemical reactions and physisorption in oil/brine/
rock system. To test this hypothesis, we measured the contact angle of
oil droplets on the surface of muscovite sheets in the presence of CaCl2
with various salinity levels (2000, 10,000, 30,000 and 50,000 mg/l), at
temperatures (50 and 100 °C). We also measured the zeta potential of
oil/brines and brines/muscovite. Moreover, we did a geochemical
study to decipher the factors governing the wetting characteristics of
the oil/brine/muscovite system. Furthermore, to correctly predict the
performance of the low salinity water flooding, we proposed a new pa-
rameter (Z*), which is the absolute sum of the zeta potential of oil/brine,
and brine/rock, to correlate with contact angle, thus system wettability.

https://doi.org/10.1016/j.molliq.2017.11.170
0167-7322/© 2017 Elsevier B.V. All rights reserved.
 E. Pooryousefy et al. / Journal of Molecular Liquids 250 (2018) 396–403
2. Methods
2.1. Materials
2.1.1. Substrates
To examine the effect of water chemistry on the contact angle of oil
droplet on the surface of minerals, we used muscovite sheet (supplied
by Wards Scientific) as substrates. This is due to muscovite being the
main constituent of different formed minerals in sedimentary rocks
[33]. In addition, muscovite represents the common clay minerals in
sandstone reservoirs and has a similar chemical structure to Illite [34].
Furthermore, muscovite has a cation exchange capacity 3–4 times
greater than kaolinite [35], which is believed to be important to exhibit
low salinity EOR effect at reservoirs [6,36].
To avoid the effect of surface roughness on the contact angle, we
used the atomic force microscopy (AFM) (WITec, ALPHA 300 RA for
combined Raman-AFM imaging) to examine the surface roughness of
the muscovite substrate after cleaving prior to contact angle measure-
ments. AFM test shows that the surface roughness of the muscovite
was in a range of 0–2.5 nm (Fig. 1), implying that the effect of roughness
on contact angle test is negligible because the surface roughness is
much less than the thickness of the water film at the surface [14].
Note: to obtain a clean surface, the muscovite substrates was simply
cleaved after each experiment.
2.1.2. Ionic aqueous solutions
To test our hypothesis, we used CaCl2 with various concentrations
to examine the contact angle of oil/brine/rock system. This is because
Ca2 + is a major divalent cation component in formation brines, and
Ca 2 + ions can act as bridges to bond the polarized ends from the
crude oil to the surface of pore wall [35,37]. Furthermore, Ca2 + has
been identified as one of the main PDI (potential determining ions)
which has been previously confirmed to be the main contributors
to low salinity effect compared to monovalent cations such as Na+
[38,39]. Meanwhile, previous studies has also confirmed that Mg2 +
has a similar behaviour to Ca2 + [40,41]. However, the affinity of
Ca2 + towards clay surfaces is stronger than that of Mg2 +. We there-
fore used CaCl2 at different salinity level (2000, 10,000, 30,000 and
50,000 mg/l) to test zeta potential and contact angle in oil/brine/
muscovite system.
Given that pH strongly affects oil and mineral surface chemistry,
which consequently changes the zeta potential and the physisorption
[42,43], we manually adjusted the pH of the ionic aqueous solutions to
7 using HCl and NaOH standard solutions before aqueous solutions
were degassed in the desiccator for a period of 24 h.
Fig. 1. AFM topographic image of the cleaved muscovite substrate used for contact angle measurements.
397
2.1.3. Crude oil
Texas crude oil with acid number 1.58 mg KOH/g and base number
1.02 mg KOH/g was used in this work to measure the contact angle on
the muscovite substrate in the presence of the various salinity level.
The density of the experimental oil was 0.89 mg/ml.
2.2. Experimental procedure
Contact angle measurements were conducted using high pressure/
high temperature IFT 700 cell (Fig. 2). This apparatus is equipped with
a high resolution camera and a built-in contact angle measurement soft-
ware enabling the constant monitoring of contact angle alteration. The
treated substrates were placed into the IFT 700 cell and vacuumed for
1 h until the pressure stabilised at 0.1 bar. The degassed solution was de-
ployed into the cell with pressure and temperature adjusted to 200 bar
at 50 °C. Subsequently, the oil droplet was released on the substrate
from a capillary needle with diameter of 0.06 mm. In order to obtain a
reliable contact angle measurement, the contact angle was monitored
for a period of 72 h. The standard deviation for contact angle measure-
ments was ±2°.
2.2.1. Zeta potential measurements
Surface charges would be generated at the interfaces of fluid-fluid
and fluid-rock due to the ionization of the chemical group in the pres-
ence of aqueous ionic solutions [43]. The strength of electrostatic
charges at interfaces can be determined by zeta potential, which may
control the oil/brine/rock system wettability. We thus measured the
zeta potential of interface of oil/brine and brine/muscovite at various sa-
linity level using Zetasizer Nano ZS manufactured by Malvern.
Due to the fact that measured zeta potentials are much more stable
at 25 °C than high temperatures, we performed all zeta potential mea-
surements at 25 °C to examine the surface potential dependencies of
oil and rock surface reactivity. Note: at higher temperatures, zeta poten-
tials tend to decrease uniformly with an increase in temperature [44].
The experimental procedures to test zeta potential follow the proce-
dures proposed by Xie et al. [45]. The standard deviation for zeta poten-
tial measurements was ±1 mV.
3. Results and discussion
3.1. Effect of salinity and temperature on contact angle
Water contact angle of oil droplets on muscovite surface decreased
with increasing salinity, implying that the system wettability was
shifted from slightly oil-wet to slightly water-wet with increasing salin-
ity. (Note: all final contact angle results were reported after the
398 E. Pooryousefy et al. / Journal of Molecular Liquids 250 (2018) 396–403

Valve Hand pump

(brine)
High definition camera

Light source

HT-HP IFT cell

Valve Hand pump
(crude oil)

Fig. 2. Schematic diagram of the high pressure-high temperature IFT cell for contact angle measurements.

equilibrium was reached, and the standard deviation for contact angle
measurements was ±4°.). For example, at temperature 100 °C, the con-
tact angle was 118° in the presence of 2000 mg/l CaCl2. However, the
contact angle decreased from 118° to 102° when salinity increased to
10,000 mg/l. Further increasing the ionic concentration to 30,000 mg/l
decreased the contact angle to 89°, and the smallest contact angle was
recorded when the salinity increased to 50,000 mg/l. Together, the re-
sults show that low concentration of Ca2+ triggered an oil-wet system.
Yet, the high concentration of Ca2+ led to a slightly water-wet system.
The similar results were reported by Mohsenzadeh et al. [46] who
found that successive dilution of formation brine (FB) increased the
contact angle from 63° in formation brine (203,000 ppm), to 130° in
20 times diluted formation brine, altering wettability from water-wet
to oil-wet. This may explain why the low salinity water flooding is not
always observed using the conventional dilution approach.
Contact angle also decreased slightly with decreasing temperature,
but temperature played a minor role in the wetting characteristics of
the muscovite surface compared with salinity of Ca2+ (Fig. 3). For in-
stance, the contact angle decreased by 2-5° as the temperature dropped
to 50 °C from 100 °C. However, the salinity variation rendered 35° de-
crease with increasing Ca2+. The similar trend were also reported by
Xie et al. [42] Who found that the contact angles increased with temper-
ature for all brines (formation brine, softened brine and 100 times dilut-
ed formation brine), but the effect of temperature on the contact angle
was not as pronounced as that of water chemistry. They observed that
the contact angle varied from 39° to 42° with increasing temperature
from 60 to 140 °C in the presence of softened brine.
muscovite due to the opposite polarity of the zeta potential of oil/
brine and brine/muscovite. This triggers oil-wet characteristics because
the Van-der-Waal force is always attractive. Yet, the 50,000 mg/l CaCl2
yielded a positive zeta potential for both oil/brine (14.73 mV) and
brine/muscovite (6.92 mV), thus triggering positive double layer expan-
sion forces [47,48]. The positive double expansion forces in return com-
pensate the Van-der-Waal attractive force, thus likely shifting the
disjoining pressure from negative to positive [49]. Note: a negative
disjoining pressure means attractive forces, indicating an oil-wet sys-
tem. Rather, a positive disjoining pressure means repulsive forces, indi-
cating a water-wet system [50].
While multicomponent ion exchange (MIE) [51] has long been con-
sidered as one of the main mechanisms of low salinity water flooding,
our wettability alteration results on Texas crude, did not support this
theory. Lager et al. [16] discussed four main mechanisms of adsorption
of organic matter to the surface of rock (former proposed by Sposito
[52]) and hypothesised that removing divalent cations, such as Ca2+
and Mg2+ from the solution, would break the bonds between the oil
and the rock surface, which eventually dissociate the crude oil from
the rock surface, leading to a more water-wet surface. They also

3.2. Effect of salinity on zeta potential

To gain a deeper understanding of the results from the contact angel

tests, we examined the effect of salinity on zeta potential of fluid-fluid
and fluid-rock. Our results show that zeta potential of oil/brine in-
creased from − 2.82 to 14.73 mV as salinity increasing from 2000 to
50,000 mg/l, suggesting a significant adsorption of the Ca2+ at the oil/
brine interface due to the presence of huge amount of Ca2+ in high sa-
linity level. Zeta potential of brine/muscovite increased from 4.96 to
6.92 mV with increasing salinity, showing that effect of Ca2 + on the
zeta potential of brine/muscovite was not as pronounced as the inter-
face of oil/brine. Together, 2000 mg/l CaCl2 generated an attractive dou- Fig. 3. Contact angle vs. salinity level (CaCl2) at temperature of 50 and 100 °C at constant
ble layer force (collapse of thin water film) in the system of oil/brine/ pH 7.
 E. Pooryousefy et al. / Journal of Molecular Liquids 250 (2018) 396–403
observed a higher oil recovery by removing the Ca2+ and Mg2+ from
the solution compared to the injection of a high concentration of NaCl
solution [16]. In contrast to MIE theory, we observed a shift from oil-
wet to slightly water-wet with increasing concentrations of Ca2+. This
discrepancy is very likely attributed to the surface chemistry of crude
oil and minerals. For example, low concentration of the polarized ends
(COO−, –NH+, and –COOCa+) from crude oil (e.g., low acid number
and base number) may not trigger the shift of the zeta potential of oil/
brine from negative to positive with increasing salinity, particularly in-
crease in concentrations of divalent cations, e.g., Ca2+, Mg2+. This is due
to a lack of –COOCa+ at the interface of oil/brine. Moreover, the mineral
surface chemistry is an essential factor to cause this discrepancy. For ex-
ample, as pointed out by Brady et al. [53], MIE may work for the min-
erals with surface charges governed by edge charges, like kaolinite,
rather than minerals controlled by basal plane charges, e.g., muscovite,
illite, chlorite, smectite. This also explains why Seccombe et al. [15] ob-
served a shift of wettability from slightly water-wet to strongly water-
wet in Endicott Field with high content of kaolinite with decreasing sa-
linity. They also reported that improvement in incremental oil recovery
with decreasing salinity is proportional to the kaolinite content in the
reservoir. Similar to Sccombe et al.'s report [15], Xie et al. [42] also ob-
served a wettability (rock is rich in kaolinite) shift from slightly
water-wet to strongly water-wet in high temperature (140 °C) with de-
creasing salinity. Therefore, we believe that decreasing salinity and re-
moving divalent cations (Ca2+ and Mg2+) would trigger low salinity
EOR-effect in kaolinite-bearing sandstone reservoirs. This is because
the surface charge of kaolinite-bearing sandstone is governed by edge
charges which controls the surface complexation of oil/brine/rock sys-
tem [43]. However, in this context, for muscovite or a mineral with
the same structure-bearing as sandstone, decreasing salinity level
would yield oil-wet wetting characteristic of the system of oil/brine/
rock, thus hindering low salinity EOR-effect. This may explain the ques-
tion: why did the conventional dilution approach do not trigger incre-
mental oil recovery in high temperature for the reservoir with a
certain amount of illite and crude oil with low acid number (0.25 mg
KHO/g) [54]. Similar experimental results were also observed by
Brady et al. [55] who reported that the oil adsorption in the middle
Bakken with clay mainly composed of illite, decreased with increasing
salinity level (NaCl) at a given pH, suggesting that decreasing salinity
shifts the wettability of oil/brine/rock system from water-wet to oil-
wet surface, in line with this work. While the wettability of oil/brine/
rock system strongly relates to the surface chemistry of oil/brine and
brine/rock, zeta potential of the fluid-fluid, and fluid-rock is believed
to be the parameter that correlates surface chemistry to physical ad-
sorption and gives a reasonable prediction of low salinity water
flooding. Note: in this work, pH was kept constant which might be the
reason of why we observed the trend: increasing salinity triggers a
more water-wet system.
3.3. Surface complexation modelling
In this context, a surface complexation model developed by Brady et
al. [27,55] was applied to identify the individual charged species that
give rise to oil and rock zeta potentials, and then used to calculate the
degree of electrostatic bridges between the oil and rock. DLVO theory
and surface complexation modelling both recognize an electric double
layer and the existence of charged surface species whose concentrations
depend upon the chemical composition of the water, oil and minerals
[42]. In the surface complexation model, the muscovite surface area
was assumed to be 100 m2/g with site density of 10 μmol/m2. The chem-
ical reactions on the surface of muscovite and crude oil can be described
by the following reactions (Table 1). For comparison with the zeta po-
tential results obtained at 25 °C, we used the Log K at 25 °C (Table 1)
for all of the chemical reactions as temperature has a minor effect [42]
and water chemistry dominated the surface complexation species at
399
Table 1
Surface complexation model input parameters [27].
Reaction Log K25oC
−NH+ = −N + H+ −6.0
−COOH = –COO− + H+ −5.0
−COOH + Ca2+ = −COOCa+ + H+ −3.8
NNa + Ca2+ ≥ Ca + 2Na+ 0.21
NNa + H+ ≥ H + Na+ 4.6
the oil/brine/rock interfaces (Note: the surface species were calculated
by PHREEQC version 3.30 (Parkhurst and Appelo 2013)).
Where the “N” denotes negatively charged site on muscovite surface
while the “−” denotes negative charged site on oil surface. When the oil
adheres to the rock surface, ion exchange occurs, which can be
expressed as the chemical reaction: NNa + − NH− ≥ − NH + Na+,
and NNa + −COOCa+ ≥ −COOCa + Na+.
3.4. Effect of salinity on number of oil/brine surface species
Salinity strongly affected the number of oil/brine surface species,
named site density, particularly at the pH values lower than 7.5 (Fig.
5). For example, the concentration of the –COO− and –NH+ at the inter-
face decreased with increasing salinity at a given pH level, although the
magnitude of the decrease of –NH+ was greater than –COO−. Yet, the
site density of –COOCa+ increased with increasing salinity. Together,
these imply that the oil surface charge is likely to be dominated by –
COOCa+ with the increasing Ca2+, particularly for crude oil with high
acid number. This is because that more carboxyl groups (–COO−) will
diffuse from the interior to the surface at pH N 5, but these –COO−
would not be stable in the presence of Ca2 + and will be easily trans-
formed to –COOCa+ [43].
pH played a great role in the site density of oil/brine at a given salin-
ity. For example, the site density of both –NH+ and –COO− decreased
with increasing pH, particularly at pH b 7.5. Moreover, the site density
of –NH+ declined much faster than that of –COO– because the depro-
tonation of –NH+ is more active than that of –COO− at low pH level.
Yet, the surface site density of all of the surface chemical groups
remained constant at pH N 8. Also, at this range of pH level, the effect
of salinity on the surface site density was negligible (Fig. 5).
Surface complexation modelling show that the site density of the
surface chemical groups strongly correlated with the zeta potential of
oil/brine in the presence of the various salinity level. For instance, at
pH = 7, the site density of the –COOCa+ increased from 14.76 to
19.55 mmol/m2 as the salinity level increased from 2000 to
50,000 mg/l. Yet, the site density of the –COO− and –NH+ decreased
from 20.90 and 4.98 to 18.39 and 0.66 mmol/m2 as the salinity level in-
creased from 2000 to 50,000 mg/l, respectively. Together, the increase
of the –COOCa+ at the interface of oil/brine caused a shift in the zeta po-
tential from negative to positive as the salinity increased from 2000 to
50,000 mg/l. This was supported by the zeta potential results, showing
that the zeta potential of oil/brine increased from −2.82 to 14.73 mV
as the salinity increased from 2000 to 50,000 mg/l (Fig. 4). Note: the in-
crease of the Na+ in the aqueous solution would decrease the site den-
sity of –COOCa+ at a given pH [43] largely because of decreasing the
activity coefficient of dissolved Ca2 +. Brady et al. [43] reported that
the surface concentration of –COOCa+ decreased with increasing NaCl.
Yet, the surface concentration of –COO− increased with increasing the
concentration of the NaCl. This imply that negative zeta potential likely
be observed in the presence of high salinity level but with low concen-
tration of the Ca2+.
The variation of the site density of the surface chemical groups in the
presence of aqueous ionic solutions likely alters the interfacial tension of
the oil/brine. For example, Tang and Morrow [12] reported that the IFT
decreased from 20 to 16 mN/m from high to low salinity brine. This is
attributed to the increase of pH, which governs the oil/water surface
400 E. Pooryousefy et al. / Journal of Molecular Liquids 250 (2018) 396–403
Fig. 4. Zeta potential of oil/brine and brine/muscovite in the presence of different
concentration of CaCl2.
charge [56,57]. However, due to the limited reduction of interfacial ten-
sion, the decrease in capillary number with low salinity water is negligi-
ble to cause chemical water EOR effect [12,58].
3.5. Effect of salinity on the electrostatic bridges
Similar to the oil surface, the salinity level strongly affected the elec-
trostatic bridges for oil-muscovite. For example, the electrostatic brid-
ges of N−NH decreased with increasing salinity at a given pH. Fig. 6
shows that at pH = 7, the electrostatic bridges of N−NH decreased
from 2.68 to 0.66 μmol/m2 as the salinity increased from 2000 to
50,000 mg/l. This is because the exchangeable Na+ embedded into the
muscovite was exchanged by Ca2+ with increasing the concentration
of Ca2+. In return, the chemical equilibrium of NNa + −NH− ≥ − NH
+ Na+ shifted to left, thus decreasing N− NH. This implies that the
rock surface likely becomes more water-wet as increasing salinity for
the system with basal charged minerals (e.g., illite, smectite and chlo-
rite), particularly for the crude oil with high base number.
Fig. 6 also shows that the number of electrostatic bridges (N−
COOCa) increased with increasing salinity. For example, N−COOCa in-
creased to 9.27 from 7.26 μmol/m2 with increasing salinity from 2000
to 50,000 mg/, because the site density of –COOCa+ increased with in-
creasing salinity (Fig. 5), enabling the chemical equilibrium (NNa +
−COOCa+ ≥ −COOCa + Na+) to shift towards right-hand side. This im-
plies that the oil/brine/rock system likely becomes more oil-wet with
increasing salinity. This might explain why the low salinity EOR effect
was observed using oil with high acid number [42].
Fig. 5. Site density of the surface chemical group vs pH at the interface of the oil/brine in the presence of various salinity level.
Given that the surface chemistry of the experimental oil consists of –
COO-, −COOCa+ and –NH+, the electrostatic bridge of −COOCa+ and –
NH+ were summed up to show the total electrostatic bridges at the sur-
face of muscovite in the presence of different salinity level of CaCl2. Re-
sults show that at pH = 7, the electrostatic bridges decreased with
increasing salinity, implying the wettability of the system is shifting to-
wards water-wet, consistent with the contact angle test (Fig. 3). Fig. 7
also shows that the total electrostatic bridges was strongly affected by
pH apart from the salinity. For example, at pH b 6, the total electrostatic
bridges increased with increasing salinity, suggesting that with the
presence of mineral surface like muscovite, the wettability of rock sur-
face may shift towards more water-wet with decreasing salinity. How-
ever, at pH N 7, decreasing salinity may generate oil-wet surface. This
may explain that why the low salinity EOR-effect is not always observed
using conventional dilution approach.
3.6. Implications
Understanding the governing factor(s) and mechanism(s) of the low
salinity water flooding in sandstone reservoirs is of fundamental impor-
tance to constrain the intrinsic uncertainties in implementation of low
salinity water flooding technique. This study provides insights into the
interaction of interfaces of fluid-fluid and fluid-rock, and provided evi-
dence relating the zeta potential of interface of oil/brine and brine/
rock to wettability. We also demonstrate that the surface complexation
modelling essentially contributes to a deeper understating of the factors
controlling low salinity effect in sandstone reservoirs at the interfacial
scale (nano-scale).
Moreover, given that charged surfaces, e.g. negative surface in posi-
tively charged solution, the brine chemistry, e.g., salinity and ions
strength, dominate the Debye-length and zeta potential [59], decreasing
the salinity and ionic strength causes the zeta potential of fluid-fluid and
fluid-rock to become strongly negative [60], thus resulting in a larger
double layer expansion force, which compensates the Van-der-Waal at-
tractive force, thereby shifting the reservoir wettability towards more
water-wet [49]. We therefore particularly focused on the electrical dou-
ble layer force, assuming that the geometry of oil and rock surfaces is
simplified as flat-charged surfaces with different potentials separated
by a thin film of electrolyte [61]. Considering that the same polarity of
the zeta potential of oil/brine and brine/rock triggers repulsive electrical
double layer force, and the opposite polarity of the zeta potential of oil/
brine and brine/rock generates the attractive electrical double layer
force [1], we proposed a new parameter, Z*, which is the absolute
value of zeta potential of oil/brine and brine/rock (Eq. 1). Note: Z* can
be applied with both opposite, and same polarity of zeta potential at
the interface of fluid-fluid and fluid-rock. A plot of Z* versus contact
angle for various references [42,45] was then constructed (Table 2 and
 E. Pooryousefy et al. / Journal of Molecular Liquids 250 (2018) 396–403 401

Fig. 6. Electrostatic bridges vs pH of surface species in the system of oil/brine/muscovite.

Fig. 8). sandstone used by Nasralla et al. were rich in clays (illite = 2.7 wt%,
  and kaolinite = 3.7 wt%), we assumed that the contact angle of oil on
Z
¼ Zetaoil=brine þ Zetabrine=rock  ð1Þ
We demonstrate that the wettability of the oil/brine/rock system
can be correlated with the zeta potential of fluid-fluid and fluid-rock.
For example, we show that the contact angle decreased linearly with in-
creasing the Z* for various oil/brine/rock system [42,45], implying that
wettability of the system shifts towards more water-wet due to the
same polarity of the zeta potential of fluid-fluid and fluid-rock. More-
over, we found that the slope of the function of zeta potential versus
Z* is almost the same, implying that the wettability of oil/brine/system
follows the same trend with change of Z* regardless of the water chem-
istries, composition of crude oil and mineral surface chemistry. This
demonstrates that Z* should be used as a strong indicator to reflect
the wettability shift of the oil/brine/rock system. Meanwhile, we also
observed that the intercept at the Y axis varies with various system of
oil/brine/rock. We believe that this is attributed to the nature of the
given oil/brine/rock system, which is again also related to the surface
complexation and physisorption although a more quantitative analysis
remains to be made.
To the best of our knowledge, while zeta potential of oil/brine and
brine/minerals have been widely measured to understand the wettabil-
ity alteration induced by low salinity water, we did not find any litera-
ture reporting the zeta potential of oil/brine and brine/rock, and
contact angle using the same brine and rock. Nasralla and Nasr-El-Din
[17] measured zeta potential of oil/brines, brines/sandstone, but the
contact angle was measured at the surface of mica. Given that the
Fig. 7. Calculated electrostatic bridges between the surface chemical groups from oil and
the surface of the muscovite.
the mica substrate approximately represent the contact angle of oil on
the sandstone substrates in the presence of the same brines.
Together, although zeta potential was proposed to interpret the low
salinity effect [17,45,60,62–64], we believe this is the first work to ex-
plicitly relate zeta potential of oil/brine and brine/rock to contact
angle using Z*, thus providing a framework to design injected water
chemistry. Note: oil composition, to be more specific, the acid number
and base number, affects number and type (− NH+, − COO−, and –
COOCa+) of the surface species, thereby the zeta potential of oil/brine
[27,65].
In general, to constrain the intrinsic uncertainty of low salinity water
flooding in field, we therefore proposed Z* (Eq. 1), relating the zeta po-
tential of the oil/brine/rock system to the wetting characteristic of the
reservoir rock. We argue that the new parameter, Z*, may be used to in-
terpolate between the bounding curves (relative permeability curves
from formation water and low salinity water), correctly simulating the
low salinity water flooding performance rather than using the salinity
level and individual ion (e.g., Ca2+, SO2− 4 etc.). This is because the Z*
of the oil/brine/rock system is the physical reflection of the salinity
level, ion type, pH, oil and mineral surface chemistry [17,26,60]. Note
that to gain a complete understanding of oil/brine/rock system, we be-
lieve that both electrostatic (double layer expansion) and non-electro-
static physisorption (van der waals forces) together with competitive
ion chemisorption (ion exchange and surface complexation) govern
the interaction of oil/brine/rock system, thus wettability. To understand
the relative contribution of double layer expansion and surface com-
plexation, we believe that the mechanisms outlined above need to be
incorporated into total surface energy [66] which needs to be investigat-
ed in future.
Fig. 8. Contact angle vs Z parameter with various oil/brine/rock system.
402 E. Pooryousefy et al. / Journal of Molecular Liquids 250 (2018) 396–403

Table 2
Oil/brine/rock system data from previous work [17,42,45] and this work.

System pH Zeta potential Z* (mV) Contact angle (degree)

Brine Crude Oil Substrate Rock/brine Oil/brine

This work 2000 mg/l CaCl2 Texas oil Mica 7.0 4.94 −2.81 2.13 118
50,000 mg/l CaCl2 Mica 7.3 6.92 14.73 21.65 83
Xie et al. work [42] Formation brine Tarim oil Sandstone 6.2 −3.56 −1.89 5.45 53
Softened brine Sandstone 7.7 −6.60 −3.30 9.90 39
100 diluted formation brine Sandstone 6.1 −19.27 −8.68 27.95 28
Xie et al. work [45] Formation brine Changqing oil Sandstone 7.1 −8.70 −7.70 16.40 74
Ion tuning water Sandstone 8.5 −21.70 −18.70 40.40 39
2000 ppm NaCl Sandstone 8.4 −23.70 −21.20 44.90 37
5800 ppm NaCl Sandstone 7.5 −12.00 −10.20 22.20 54
100,000 ppm NaCl Sandstone 7.2 −8.80 −7.70 16.50 75
Nasralla and Nasr-El-Din work [17] Sea water Crude oil ([17], Table 2) Mica 7.6 2.0 −2.0 0.0 75
5000 mg/l CaCl Mica 5.5 4.0 −5.0 1.0 45
5000 mg/l NaCl Mica 5.9 −12.0 −13.0 25.0 30
10% AQ Mica 7.3 −13.0 −22.0 35.0 27
10% AQ Mica 4.8 −8.0 −10.0 18.0 58

Note: the acid number and base number for Tarim oil was 3.98 and 1.3 mg KOH/g [42]. Yet, the acid number and base number for Changqing oil was not available in the literature [45]. The
acid number and base number for Nasralla and Nasr-El-Din experiments was 0.18 mg KOH/g, and 1.65 mg HCl/g [17].

4. Conclusions Competing financial interests

Understanding of the wettability of oil/brine/rock system is of vital
importance to subsurface multiphase flow behaviour. To decipher the
factors controlling the wetting characteristics of reservoirs, we mea-
sured the contact angle of an oil (AN = 1.58 mg KOH/g, BN =
1.02 mg KOH/g) at the surface of muscovite sheet in the presence of
CaCl2 with various salinity levels (2000, 10,000, 30,000 and
50,000 mg/l) at temperatures (50 and 100 °C). We also measured the
zeta potential of oil/brines and brines/muscovite. Moreover, we per-
formed a surface complexation modelling to better understand the fac-
tors governing the wetting characteristics of the oil/brine/muscovite
system.
Our results show that the contact angle of oil droplet on the musco-
vite surface decreased with increasing salinity of CaCl2, implying that in-
creasing salinity level shifted wettability of muscovite from oil-wet to
less water-wet. Zeta potential results supported the contact angle
tests, showing that the polarity of the zeta potential of brine/oil was
shifted from negative to positive with increasing the salinity level
from 2000 to 50,000 mg/l, but the polarity of the zeta potential of
brine/muscovite remained positive. This suggests that 2000 mg/l CaCl2
triggered attractive electrical double layer force, yet the 50,000 mg/l
CaCl2 rendered repulsive electrical double layer force. Surface complex-
ation modelling show that at pH = 7, the electrostatic bridges de-
creased with the increase of the salinity level, implying the wettability
of rock surface shifting towards water-wet, consistent with the contact
angle results. Together, we conclude that DLVO theory is consistent with
the surface complexation modelling because of the same nature of the
physics. Therefore, we proposed a new parameter, Z* (Z∗ = | Zetaoil/
brine + Zetabrine/rock |) to relate the contact angle with zeta potential.
We show that the contact angle of oil on the surface of rock decreases
linearly with increasing Z*. We therefore argue that the manipulation
of Z* (polarity of zeta potential of brine/rock and oil/brine) is of vital im-
portance to shift the reservoir wettability. We suggest that the Z* may
be used as an interpolant to model the low salinity water flooding, rath-
er than using salinity level or individual ion in the solution.
Acknowledgement
This work is supported by Open Fund (PLN201603) of State Key Lab-
oratory of Oil and Gas Reservoir Geology and Exploitation (Southwest
Petroleum University-China). Support from Sandia National Laborato-
ries is also highly appreciated. We would also like to extend our appre-
ciation to Mr. Bob Webb for his help and support towards conducting
the contact angle measurements.
The authors declare no competing financial interests.
Appendix A. Contact angle measurement data were provided below
Salinity, mg/l Contact angle
50 °C 100 °C
2000 114 118
10,000 100 102
30,000 86 89
50,000 78 83
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