Colloids and Surfaces A: Physicochem. Eng.

Aspects 402 (2012) 13–23

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Colloids and Surfaces A: Physicochemical and

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

Removal of crude oil from kaolinite by water flushing at varying salinity and pH
Andrew Fogden ∗
Department of Applied Mathematics, Research School of Physics and Engineering, Australian National University, Canberra ACT 0200, Australia

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

Article history: The ability of crude oil to adhere to kaolinite in an aqueous environment by adsorbing or depositing its
Received 25 October 2011 polar components (asphaltenes and resins), and the ability of subsequent water flushing to remove this
Received in revised form 4 March 2012 bound oil, were compared for two oils and varying salinity and pH of the flushing solution. A scanning
Accepted 6 March 2012
electron microscopy technique was used to image the locations of oil residues on and between kaolinite
Available online 15 March 2012
platelets, while fluorescence spectroscopy yielded the corresponding amount of asphaltenics. Consid-
eration of the mechanisms of electrostatic interfacial attraction and surface precipitation giving rise to
Keywords:
the adsorption/deposition of asphaltenics on kaolinite were used to interpret the extent of their removal
Kaolinite
Crude oil
by flushing. The oil exhibiting greater surface precipitation was fairly unresponsive to flushing, with
Asphaltene displacement of the bulk oil leaving residues substantially lining the kaolinite platelets and filling the
Wettability pores between them. The oil which adsorbed by electrostatic attraction was more amenable to removal
Oil recovery of residues, to partially reinstate the water-wetness of the pristine kaolinite, by flushing with salt solu-
Environmental remediation tions which weakened this attraction. In particular, higher salinity of the flush minimized the attractions
between oppositely charged sites on the heterogeneous interfaces, and pH shift to higher or lower levels
rendered the interfacial charges more similar and mutually repulsive.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction Crude oils and asphaltic petroleum products contain a

Wettability plays a key role in two-phase flow through porous
media, in applications such as formation of crude oil reservoirs and
oil recovery by water flooding [1,2], or contamination of subsur-
face environments by dense non-aqueous phase liquid (DNAPL)
and its remediation by aqueous flushing [3]. Mineral surfaces of
pores originally saturated with water (brine) are generally intrinsi-
cally hydrophilic. Partial displacement of water by the immiscible
oleic phase during reservoir formation, by upwardly accumulating
crude oil, or soil contamination, by downwardly migrating DNAPL,
is a drainage process driven by the capillary pressure arising from
the density difference. Displacement mechanisms at the pore scale
have been investigated in idealized porous media, such as glass
bead or sand grain packs [4–6], etched glass micromodels [4,7] and
epoxy replicas of rock fractures [8]. These surrogate rocks and soils
are amenable to video microscopy of multiphase flow, which has
guided development of theoretical and computational models of
meniscus configurations in pore networks [9]. During drainage, it
has been well established that the non-wetting oleic phase enters
the interiors of sufficiently large pores, with the wetting aqueous
phase thinning to a film lining their surfaces and filling smaller
pores.
∗ Tel.: +61 261254823; fax: +61 261250732.
E-mail address: andrew.fogden@anu.edu.au
high molecular weight, polar fraction called asphaltenes. These
comprise polycondensed aromatic sheets substituted with hetero-
atoms in acid and base groups, and naturally associate with lower
molecular weight analogs termed resins [10]. At locations where
the oil has drained the aqueous phase to a thin film, this film can
rupture over time if the interfacial interactions are insufficiently
repulsive. This allows the asphaltenics to adsorb or surface precip-
itate onto the mineral to locally alter its surface chemistry toward
oil-wetting [1,2]. The tendency for local wettability alteration has
been studied for single mineral surfaces in isolation, idealized as
smooth flat substrates of quartz, mica or glass, by contact angle
measurement of oil in aqueous phase or atomic force microscope
imaging of the absorbed/deposited asphaltenics [3,11–16]. The
mixed-wet state of locally adhering or non-contacting oil in pores
is thought to pertain to the majority of reservoirs. This state has
been directly evidenced in glass bead packs drained with crude oil
and aged [17].
The wettability and its pore-scale distribution impact the mech-
anisms and efficiency of subsequent oil removal by flooding or
flushing. The above-mentioned idealized media have been used to
visualize and quantify the oil displacement and residuals, mainly in
the extreme cases of uniformly water-wetting or oil-wetting pores
[4,5,7]. For the former, slow flow readily removes some of the oil
in larger pores, but isolates the remainder as snapped-off blobs or
bypassed clusters. In the oil-wet case, oil lining larger pores and
filling smaller ones will tend to be retained.

0927-7757/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2012.03.005
14 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23
Many reservoir sandstones and soils contain a sizable fraction
of clays, of which one of the most common minerals is kaolinite.
The presence of kaolinite reduces pore sizes and increases surface
area, also increasing structural heterogeneity due to the variable
aggregates of its individual platelets and their variable distribu-
tion as pore-filling, pore-spanning and/or grain-lining. Extensions
of bead or sand pack studies to include kaolinite are scarce
[6]. Most pore-scale investigations have instead used the natural
kaolinite-containing rock or soil, in which the distributions of oleic
and aqueous phases after drainage or after flooding or flushing
have been imaged by cryogenic or environmental scanning elec-
tron microscopy (cryo-SEM or ESEM) or confocal laser scanning
microscopy [18–21]. These studies have shown that the pore-scale
textural and chemical influences of kaolinite are often at odds. The
capillarity of its tight pores tends to lock in the original aqueous
phase and limit drainage by oil. On the other hand, kaolinite has a
high chemical affinity for most crude oils and related DNAPL, thus
during prolonged aging it can alter wettability to become a sink for
oil, limiting its removal by flooding or flushing.
Over the past decade, experiments mimicking crude oil recovery
from clay-rich sandstone reservoirs by draining brine-filled rock
cores with crude oil and aging, followed by flooding with a second
brine, have often demonstrated improved recovery using flooding
brines of reduced salinity [22–26]. The boost is thought to be due to
removal of oil associated with kaolinite, as suggested by pore-scale
cryo-ESEM imaging [25]. However, the intermolecular interactions
giving rise to this oil liberation remain unclear. One proposed mech-
anism is desorption of divalent cations from kaolinite in response
to their lowered bulk concentration, causing detachment of asphal-
tenics bonded by these cation bridges [24]. Another hypothesis is
that adsorption of protons on kaolinite causes an upward shift in
pH, increasing the negative charge on both oil and mineral inter-
faces to favor their mutual repulsion [23,26].
Improved design and predictability of recovery or remediation
strategies in kaolinite-rich rocks or soils requires that macro-scale
flow experiments and pore-scale imaging are complemented by
analyses at length scales approaching the molecular level. A body
of the literature deals with asphaltene adsorption and desorp-
tion from solution (usually toluene) onto kaolinite particles [27].
However, for relevance to flooding or flushing, kaolinite should be
exposed to aqueous and oleic phases in a manner closely imitat-
ing the real processes. Recent work has prepared model substrates
comprising a thin, smooth coat of kaolinite on glass [28,29]. Con-
tact angles of crude oil drops in brine were measured to probe the
development of oil–kaolinite adhesion during the early stages of
drainage [28]. Later stages were studied by aging the model sub-
strate in oil to analyze the adsorbed/deposited asphaltenics by field
emission SEM (FESEM) and fluorescence spectroscopy [29]. The
current study extends this work by performing slow flushing of the
aged state with brines of varying salinity and pH to investigate the
amount and distribution of oil residues remaining on and between
individual kaolinite platelets. This provides insight into the intrin-
sic contribution of oil–brine–kaolinite interactions to the efficacy
of oil removal.
2. Materials and methods
2.1. Materials
Two asphaltic crude oils commonly studied in the literature
were used, namely WP (Alaska) [30,31] and Minnelusa (Gibbs Field,
Wyoming) [13,17,28,29,32,33], referred to here as Oil A and B,
respectively. At room temperature, Oil A has density 0.9125 g cm−3 ,
viscosity 111 mPa s, n-C6 asphaltene content 6.3 wt%, and acid
and base numbers 1.46 and 2.49 mg KOH/g [30]. Oil B has
density 0.9062 g cm−3 , viscosity 77.2 mPa s, n-C7 asphaltene con-
tent 9.0 wt%, and acid and base numbers 0.17 and 2.29 mg KOH/g
[13]. Both were filtered at 5 psi through three Whatman no. 4 filter
papers before use. The kaolinite used (KGa-1b; Washington County,
Georgia; Clay Minerals Society) comprises 96% kaolinite and trace
dickite, 3% anatase and 1% crandallite plus mica and/or illite, and has
cation exchange capacity 3.0 mequiv./100 g and BET surface area
11.7 m2 /g [34–36]. Salt solutions were made by dissolving NaCl and
CaCl2 ·2H2 O (both AnalaR) in deionized water (Millipore Milli-Q) at
the fixed salt ratio of 90 wt% NaCl and 10 wt% CaCl2 , to the two
total concentrations of 50 g/l (i.e. 770 mM NaCl + 45 mM CaCl2 ) and
1 g/l (15 mM NaCl + 0.90 mM CaCl2 ). Each was vacuum degassed and
prepared at three pH values, namely unadjusted (pH 5.9 ± 0.2) or
adjusted to 4.0 ± 0.1 with HCl or 9.0 ± 0.2 with NaOH.
2.2. Substrate preparation and treatment
A kaolinite substrate comprising a relatively smooth and uni-
form, porous coat of chemically unmodified platelets on a clean
microscope glass slide (Knittel Gläser) was prepared by casting a
7 wt% aqueous suspension of stable, fine kaolinite using a published
method [28,29]. These thin coats, of ∼0.5 ␮m thickness, remained
robust, without platelet movement or loss, throughout all ensuing
treatment steps. The sequence of steps was based on procedures
developed and tested in a recent publication [33]. The first step
entailed exposure of the kaolinite-coated glass in salt solution to
crude oil, to allow its original water-wet state to be altered by
adsorption/deposition of asphaltenics. This defined the initial state,
pertaining to an established oil reservoir or contaminated zone
prior to recovery or remediation. The initial state was created by
immersing a rectangular piece (7 mm × 26 mm) of the substrate in
the initial salt solution (50 g/l at pH 6) in a 3 ml vial, with Oil A or B
then added on top, and equilibrated for 6 h at 22 ◦ C. The salt solu-
tion was then withdrawn by pipette from the vial bottom, and the
aqueous film enveloping the oil-immersed substrate was further
drained by centrifuging the vial at 1000 × g for 10 min. The sealed
vial was then aged for 30 ± 2 days at 60 ◦ C. In the second step, the
bulk oil was removed by flushing with a second salt solution, as in
recovery or remediation. With the vial partly immersed in a 60 ◦ C
water bath, slow flushing was performed using a syringe pump to
inject one of the six salt solutions into the vial bottom at 2.5 cm3 /h
for 1 h, after which the oil level had risen above the substrate. The
vial was then centrifuged twice at 1000 × g for 10 min to strip any
larger oil drops adhering to the substrate. The oil in the upper phase
was decanted and any slick at the air interface was removed using
lint-free tissue. In the third step, the substrate was taken from its
vial and immersed in organic solvents to facilitate analysis of the
micro/nano-scale oil residues on the substrate. The solvents used
depended on the analysis method, described below.
2.3. Analysis of adhering oil residues
For each flushing salt solution, a replicate pair of substrate pieces
was thus treated; one for imaging of adhering oil residues by FESEM
and the other to determine the amount of asphaltenic residues by
fluorescence spectroscopy. For the former, the substrate after the
second step was immersed in methanol (99.8%; Sigma–Aldrich) for
10 min to remove salt and water, and dried ambiently. FESEM (Zeiss
UltraPlus Analytical) was performed under high vacuum in sec-
ondary electron mode at 1 kV, prior to which the substrate was
lightly sputter coated with platinum. For spectroscopy, the treated
substrate was instead immersed in decalin (decahydronaphtha-
lene, 98%; Sigma–Aldrich) to dissolve bulk oil, first for 20 min and
then for 2 h in fresh decalin, which remained colorless. This was fol-
lowed by the above-mentioned methanol immersion, and vacuum
 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23
drying for 3 h at 22 ◦ C. After cleaning of its uncoated backside, the
piece was soaked in 3.1 g of the azeotropic blend of 87.3 wt% chloro-
form (99%; Sigma–Aldrich) and 12.7 wt% methanol, in a sealed flask
at 50 ◦ C for 24 h, to extract the asphaltenics. Their total dissolved
amount was determined using a FluoroMax-3 spectrofluorometer
(Horiba Jobin Yvon), utilizing the natural fluorescence of these pol-
yaromatic asphaltenics [29]. The solution was analyzed in a quartz
cuvette (10 mm × 10 mm × 40 mm; Starna Cells) to record emis-
sion spectra over 380–560 nm from 340 nm excitation. In separate
experiments, the asphaltene fraction of the two crude oils was iso-
lated by heptane precipitation, from which asphaltene solutions
were prepared in this same solvent blend. Their fluorescence was
analyzed similarly to calibrate intensities of sample extracts to con-
centration.
Other related control experiments were performed to exam-
ine the initial state, in the absence of salt solution flushing, by
omitting this second step. In these cases, the substrate after the
first step of oil drainage of the initial salt solution (50 or 1 g/l
at pH 6) and aging was directly immersed in decalin, and then
methanol, and vacuum dried, as per the above-mentioned pro-
cedures. The adsorbed/deposited asphaltenics were analyzed by
FESEM as above.
3. Results and discussion
3.1. Morphology of oil residues on kaolinite
For each treated kaolinite substrate, 20 FESEM images at 100k×
magnification were acquired at a fixed pattern of locations over the
piece. Fig. 1 shows representative micrographs of the initial wet-
tability state, resulting from displacement of the bulk salt solution
by the crude oil and adsorption/deposition of its asphaltenes and
resins on exposed platelets during the 1 month of aging. The subse-
quent decalin rinse removes all bulk oil to leave only this adhering
asphaltenic footprint on kaolinite. For both oils and both concen-
trations of the pH 6 salt solution, the thin films of water sheathing
the platelets rupture to allow a significant alteration of their wetta-
bility. The adsorbate/deposit takes the form of primary-aggregated
asphaltenic nanoparticles which often build irregular, secondary-
aggregated chains. All visible platelets, at the coat surface or one or
more layers down, bear this same texture. Moreover, in the occa-
sional locations at which the underlying glass can be seen through
inter-kaolinite pores, it too bears this nanoparticulate deposit. As
the capillary pressure applied during the centrifugal drainage is far
below that required to force oil into such tight pores, the oil infiltra-
tion occurs spontaneously during aging, driven by the concomitant
alteration of wettability to progressively favor expulsion of water.
From Fig. 1 it is apparent that Oil B produces thicker deposits,
which more completely cover platelet faces and extend to lining
their edges. A previous study [29] of the initial wettability state cre-
ated by Oil B on kaolinite showed that this substantial and pervasive
deposition was manifested for most of the salt solutions tested. For
Oil A, the coexistence of deposit with uncovered nano-domains, due
to undrained trapped water, on platelets is far more pronounced.
In comparison, the influence of salinity in Fig. 1 is less apparent,
although the 1 g/l solution leads to somewhat greater deposition
from Oil B than its high salinity counterpart, which is also in line
with the trend from the previous study of this oil [29]. Some stud-
ies [21] have inferred that asphaltic DNAPL only penetrates pores
larger than ∼50 nm in clay-rich soil aggregates. As most pores in
the kaolinite coats are slightly wider than this, it is not possible to
determine whether such a lower bound applies here.
The remainder of this sub-section addresses FESEM images of
the oil residues remaining on and in the kaolinite coats after salt
solution flushing of their aged, initial state. This initial state is
15
established in the high salinity solution at pH 6, with subsequent
flushing performed using the high or low salinity solution at pH
4, 6 or 9. Figs. 2 and 3 show representative micrographs of these
six flushed states for Oil A and B, respectively. It must be empha-
sized that these FESEM images cannot be directly compared to
those in the corresponding initial state (Fig. 1a and c). For the latter,
decalin rinsing to dissolve the surrounding oil is necessary for imag-
ing of the substrate, while the displacement of this surrounding
oil during salt solution flushing and ensuing centrifugation allows
imaging without the artificial step of decalin post-rinsing. In both
states, methanol post-rinsing is required prior to drying to avoid
salt crystallization. While the initial-state samples bear only the
adsorbed/deposited asphaltenics, the flushed-state counterparts in
Figs. 2 and 3 bear all adhering oil components, aside from the more
volatile fraction evaporated during drying and in the vacuum of the
FESEM chamber.
The oil residues in Figs. 2 and 3 appear fluidic, as was also the
case in a recent study [33] of smooth glass substrates exposed to
Oil B and flushed with various NaCl solutions using an analogous
procedure. There, the remaining oil typically took the form of a
sparse scattering of nano-droplets, implying that the oil interfacial
film at the substrate in the initial state becomes increasingly per-
forated by the advancing water during flushing, partly by swelling
of the undrained trapped water. The oil film retracts and detaches
with the bulk oil, decomposing to a foam-like network of connected
struts, which decompose further to nano-droplets via Rayleigh
instability. Similar mechanisms apparently occur during flushing
of the kaolinite coats, although the oil retraction and detachment is
less fully developed than for glass. As oil substantially occupies the
inter-platelet pores within the coat in the initial state, the amount
of surface oil and its anchoring are clearly greater than for a smooth
impervious substrate. The platelet edges and gaps between them
also provide sites where oil retraction can terminate or become
snagged, leading to its disconnection from the bulk oil. Accord-
ingly, the oil residues on and in the kaolinite coats generally take
the form of more irregularly shaped nano-droplets, together with
larger blobs and pools.
By the same token, Figs. 2 and 3 demonstrate that the asphalten-
ics adsorbed/deposited on kaolinite in the initial state can locally
detach with the oil during flushing. Further, this response can be
quite rapid, as the average rate of advance of the bulk water front
over the substrate during injection is 10 ␮m/s, amounting to traver-
sal of the length of the images of Figs. 2 and 3 in ∼0.3 s. The lesser
residues after flushing of Oil A in Fig. 2 compared to B in Fig. 3 tally
with its deposits in the initial state of Fig. 1a being thinner and of
lower coverage than those of Fig. 1c. Thus for Oil A, somewhat less
oil is initially present in coat pores, its bonding area with kaolin-
ite is smaller, and the more connected nano-domains of undrained
water give greater access pathways during flushing. Note that the
solidified deposits after decalin rinsing in Fig. 1 are not indicative
of their fluidic, responsive nature in the oil. In particular, analyses
[11,13,29] in which such rinsing of the initial state is performed
for subsequent measurement of contact angles of a probe oil (e.g.
decane) in salt solutions on the footprint-bearing substrate will
under-represent the in situ changes in wettability during flushing.
For Oil A, its residues strongly depend on the salinity and pH
of the flushing solution. The 50 g/l flush at pH 4 in Fig. 2 exhibits
isolated nano-droplets on platelet faces, and also tendril-shaped
analogs lining edges, while the inter-kaolinite pores are mainly
vacated. For the 50 g/l flush at pH 9, residues are somewhat more
prevalent, as nano-droplets on faces and larger blobs stranded in
pores. The high salinity flush at intermediate pH 6 shows oil films
sheathing many platelets and substantially filling pores, smoth-
ering much of the angular features of the kaolinite coat. The
corresponding images in Fig. 2 for the 1 g/l flush show similar
trends in pH, although in each case with systematically greater
16 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23

Fig. 1. FESEM images of asphaltenics bonded to kaolinite coats after drainage of the initial salt solution of 50 or 1 g/l at pH 6 by Oil A or B and aging, without flushing prior
to decalin–methanol post-rinsing. Images are 3.0 ␮m × 2.0 ␮m; the scale bar in the bottom left image is 500 nm and applies to all.

Fig. 2. FESEM images of Oil A residues on/in kaolinite coats after flushing with high (left column) or low (right column) salinity solution at the three pH values. Samples were
methanol post-rinsed. Images are 3.0 ␮m × 2.0 ␮m; the scale bar in the bottom left image is 500 nm and applies to all.
 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23
Fig. 3. FESEM images of Oil B residues on/in kaolinite coats after flushing with high (left column) or low (right column) salinity solution at the three pH values. Samples were
methanol post-rinsed. Images are 3.0 ␮m × 2.0 ␮m; the scale bar in the bottom left image is 500 nm and applies to all.
residues than for 50 g/l flushing. For Oil B in Fig. 3, its residues
are much greater, in the form of more stranded oil lining platelet
edges, sheathing faces and filling pores. Its thicker and more com-
pletely covering layer of adsorbed/deposited asphaltenics in the
initial state (Fig. 1c) presumably limits the dynamics and extent
of retraction and detachment during flushing. Even for the 50 g/l
flush at pH 4 which best removes Oil B, the residue is high by the
standards of Oil A. Its low salinity counterpart at pH 4 appears to
be least capable of removing Oil B from kaolinite.
In a recent study [33], the Oil B residues on glass after flushing
could be quantified by segmentation and analysis of FESEM images,
yielding measures of area coverage of the substrate and lateral
size of nano-droplets. For kaolinite-coated glass, the FESEM surface
images do not reveal all residues, and those that are visible are dif-
ficult to segment from the locally varying brightness of the stacked
platelets. However, one measure was able to be obtained, as shown
in Fig. 4. The edge-finding tool of the ImageJ software was applied to
each FESEM image to identify and count the white edge pixels, i.e.
of grayscale value (GSV) 255. This was compared to the correspond-
ing average edge pixel count for micrographs of untreated kaolinite
coats to determine the percentage of platelet edge pixels obscured
by residues. This measure was termed the SEM image edge loss, and
its average and standard deviation over the 20 FESEM images for
each sample were calculated, and are plotted in Fig. 5. The trends
agree with the above-mentioned hierarchy of remaining oil from
inspection of Figs. 2 and 3. Edge loss for Oil A peaks at flush pH 6,
and decreases with salinity, in line with the observed extent of its
residues. Edge loss for Oil B is substantially greater, and approaches
100%, i.e. with residues almost totally obscuring platelets.
17
3.2. Amount of asphaltenics on kaolinite
The residues, such as in Figs. 2 and 3, after displacement of
oil from a kaolinite-bearing rock or soil pore are indicative of the
adhesion which resisted this removal. Further, for bulk oil which
subsequently enters the pore during the course of continued flush-
ing, the residues will influence its ability to adhere to kaolinite and
resist displacement. Even in the idealized case of these relatively
smooth, coated, planar substrates, occasional larger oil droplets or
puddles (of micron to millimeter size) remain after flushing and
centrifugation. Wetting and adhesion of newly arriving oil is thus
dictated by the contribution of nano-scale residuals to the surface
chemistry and larger-scale residuals to bulk coalescence. Contact
angle measurements of a macroscopic pendant drop of oil con-
tacted with the treated substrate in the salt solution would thus
be problematic to perform reliably and to interpret.
Accordingly, the sister samples of those analyzed above by
FESEM were instead characterized here by their total amount of
asphaltenics in the residues. As mentioned in Section 2.3, this
necessitated decalin post-rinsing of the flushed substrates to dis-
solve the other oil components. Recent work [33] showed that such
rinsing of flushed states retains the substrate-bound asphalten-
ics, but causes asphaltenics at the oil–water interface of droplet
residues to also be deposited on the substrate. Thus the amounts
determined by their chloroform/methanol extraction and solution-
phase fluorescence spectroscopy are best regarded as including
both bonded and non-bonded asphaltenes. FESEM images in Fig. 6
of kaolinite substrates after extraction, for the Oil A and B sam-
ples with most residue after flushing, verify that the extraction of
18 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23

Fig. 4. FESEM images of oil residues on/in kaolinite coats after flushing with (a) 50 g/l salt solution at pH 4 for Oil A, (b) 50 g/l at pH 6 for Oil A, and (c) 1 g/l at pH 4 for Oil
B. Samples were methanol post-rinsed. Images are 3.0 ␮m × 2.0 ␮m; the scale bar in (a) is 500 nm and applies to all. Images at right highlight the edges (bright) within the
micrographs at left, from which the edge loss metric is calculated.

asphaltenics is very close to complete, as also seen in a previous Fig. 7 plots the difference in fluorescence emission intensity
study [29]. The slight residue persisting after extraction corre- between solution and background solvent for the calibration solu-
sponds to the occasional lighter dots in Fig. 6a and faint trails in tions of pure asphaltenes of the crude oils and the extracts from the
Fig. 6b. treated kaolinite samples. The calibration solutions for Oil A and B
display a broad peak (dotted line) at 499 and 492 nm in Fig. 7a and
b, respectively. In both cases the peak intensity is very well fitted
100 to the power law in asphaltene concentration shown in Fig. 7c and
d, with exponent close to unity. The highest concentration point is
90
SEM image edge loss, %

not included in the fit, as its slight downturn marks the onset of re-
80
absorption of emitted fluorescence. For the spectra of the extracted
70 residues from the six flushed substrates, the average peak position
60 is shifted substantially for Oil A (to 476 nm in Fig. 7e) and slightly
50 for Oil B (to 494 nm in Fig. 7f). Moreover, in both graphs the max-
40 ima for the pH 6 and 9 flushings lie systematically to the left of
30
these dotted line averages, while those for pH 4 lie to the right.
These shifts relative to Fig. 7a and b are due to the added pres-
20 Oil A, 50 g/l Oil B, 50 g/l ence of resins in the extracts, together with a possible preference
10 Oil A, 1 g/l Oil B, 1 g/l for the flush pH to remove polar components bearing acid or base
0 groups. However, without calibration spectra for these subclasses
3 4 5 6 7 8 9 10 in isolation, no further interpretation of the shifts can be made.
Flush pH From the intensities at 499 and 492 nm in Fig. 7e and f for Oil
A and B, respectively, the equivalent concentrations of extracted
Fig. 5. Percentage of kaolinite platelet edges obscured by oil residues in FESEM
images for the two oils flushed with salt solutions of varying concentration and pH,
asphaltenics were back-calculated from Fig. 7c and d, and from the
and post-rinsed with methanol. known mass of solvent used, the solute mass was determined. The
 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23
Fig. 6. FESEM images of kaolinite coats after flushing with 1 g/l salt solution at (a) pH 6 for Oil A and (b) pH 4 for Oil B, with decalin–methanol post-rinsing, followed by
chloroform/methanol extraction of asphaltenic residues. Images are 3.0 ␮m × 2.0 ␮m; the scale bar in (a) is 500 nm and applies to both.
masses are presented in Fig. 8a, normalized by the total planar area
of the underlying glass piece (as distinct from the kaolinite particle
surface area). The overall trends between the samples are not influ-
enced by whether the wavelengths corresponding to the peaks of
the calibration or extract solutions are used. The plots are very sim-
ilar to their analogs for the edge loss measure from FESEM image
analysis in Fig. 5, as shown by the correlation in Fig. 8b. The agree-
ment suggests that the FESEM images such as in Figs. 2 and 3 are
indeed reasonably representative of the entire sample. Compared
at the same flushing conditions, the residue amount for Oil B in
Fig. 8a is on average 2.4 times greater than for Oil A. The decrease
in flush salinity at fixed pH increases residue amount for Oil A on
average by a factor of 1.4, while for increase in flush pH from 4 to
6 at fixed salinity, the corresponding averaged factor is 1.9.
A previous study [29] of the initial state of wettability alteration
of kaolinite substrates by Oil B showed that the relative amount
of adsorbed/deposited asphaltenics could be estimated by a simple
non-destructive technique in which the sample pieces were digi-
tally scanned with a document scanner (Konica Minolta C252) for
image analysis. The reduction in average GSV over each piece due
to the brownish tinge of the deposits (compared to an untreated
coated substrate) correlated well with their absolute amount from
extraction and fluorescence spectroscopy. The scanned images of
the flushed samples for Oil B are displayed in Fig. 9, and Fig. 10
shows that the average GSV loss due to the asphaltenic residues is
reasonably correlated to their amount in Fig. 8a. This lends further
support to the trends described above. For Oil A, the residues were
too slight to be clearly distinguished by scanning.
3.3. Interpretation of mechanisms
The differences in initial-state deposits and flushed-state
residues for the varying oils and salt solutions are dictated by the
interactions of the asphaltenes and resins with the other compo-
nents of the oil, with the aqueous phase at its interface, and in turn
with the kaolinite aqueous interface. The salinity and pH effects
derive from the electrostatic interactions of the two interfaces. The
zeta potentials of these interfaces in isolation were measured in
all salt solutions with a Zetasizer Nano-ZS (Malvern Instruments),
using the Smoluchowski equation, and are plotted in Fig. 11.
Kaolinite and the oil’s polar molecules are amphoteric, so zeta
potential transitions from more positive at pH 4, due to base group
protonation, to more negative at pH 9, due to acid group deproto-
nation. The magnitude of the potential naturally increases for the
lower salinity in Fig. 11b, due to the increased Debye screening
length. This increase in the range of interactions also more clearly
reveals the positive surface potential at pH 4 by reducing the con-
centration of counterbalancing anions in the diffuse double layer
at the shear plane where zeta potential is measured. The dissolved
19
calcium ions are also potential determining; their binding to kaoli-
nite basal planes is evidenced by the shift in its isoelectric point
(IEP) from pH ∼2 in the absence of calcium [28] to pH ∼5 in the
1 g/l solution of Fig. 11b. Calcium also binds to acid groups at the
oil interface, apparent from the corresponding increase in IEP of
Oil B from pH ∼4 [28] to ∼5. In spite of its substantially higher acid
number, Oil A has similar, but slightly higher, zeta potential to Oil
B in Fig. 11, and thus presumably also binds calcium to boost its
positive charge.
In addition to these considerations of the charges on the oil
and kaolinite interfaces and their electrostatic interactions, the
likelihood and extent of asphaltene deposition on the substrate
will increase if they are less stably dispersed in the oil [15,16].
The oil’s robustness against asphaltene flocculation can be quan-
tified by the decrease in its refractive index, RI, required to reach
the onset of flocculation, PRI , by the addition of precipitant (n-
heptane) [16]. From the CO-Wet database [15], the value of RI − PRI
is 1.5184 − 1.4469 = 0.0715 for Oil A, with 57% heptane in the onset
mixture, while that for Oil B is 1.5144 − 1.4831 = 0.0313, with 26%
heptane at onset. This difference for Oil B is very low relative to the
average of ∼0.06 over all crude oils in the database [15], hence it is
prone to asphaltene precipitation.
During establishment of the initial state in Fig. 1a and c at pH 6,
it appears that the kaolinite and oil interfaces (for Oil A and B) are
sufficiently close to their IEP’s for a substantial fraction of positive
and negative charges to coexist on each, leading to local attraction
of oppositely charged interfacial patches to instigate wettability
alteration. As the zeta potentials of the two oils are quite similar, the
heavier deposition for Oil B is presumably the result of asphaltene
precipitation accompanying the adsorption.
The lesser and more variable amount of residues of Oil A after
flushing in Fig. 8a thus probably reflects both the lesser oil amount
on and in the kaolinite coat in the initial state and the greater
reversibility of electrostatically driven adsorption. For the 50 g/l
flush, the residue is maximized at flush pH 6, matching the pH of
the initial state. For flush pH 4, the zeta potentials of both inter-
faces in Fig. 11a become weaker and more positive, while at pH 9
both potentials become stronger and more negative. In either case,
the electrostatic interactions between kaolinite and oil become less
attractive, favoring removal of oil to give the observed lowering of
the residue. Alternatively, the flush may proceed too rapidly for
re-equilibration of the interfacial interactions to the new pH of 4
or 9, in which case disturbance of the acid–base adhesive inter-
actions from their pre-equilibrated initial state at pH 6 would be
responsible for the greater oil removal.
For the 1 g/l flush in Fig. 8a, the Oil A residue is also maxi-
mized at flush pH 6, and the amounts are consistently higher than
for the high salinity counterparts. This latter trend may appear
somewhat incongruous, as reduced salinity increases the strength
20 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23

a 1.E+06 b 1.E+06

Intensity difference, cps

Intensity difference, cps

1.E+05 1.E+05
9.61E-04
8.32E-04
3.28E-04
2.09E-04
2.70E-04
8.31E-05
1.E+04 1.17E-04 1.E+04 2.01E-05
3.77E-05
7.32E-06
1.46E-05
1.88E-06
4.83E-06
1.E+03 1.E+03

1.E+02 1.E+02
380 400 420 440 460 480 500 520 540 560 380 400 420 440 460 480 500 520 540 560
Emission wavelength, nm Emission wavelength, nm
c d
1.E+06 1.E+06
Intensity difference (499 nm), cps

Intensity difference (492 nm), cps

1.E+05 1.E+05

0.898
y = 301401351.609x
2
R = 0.999 0.935
y = 260068680.044x
1.E+04 1.E+04 2
R = 1.000

1.E+03 1.E+03
1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-06 1.E-05 1.E-04 1.E-03 1.E-02

Asphaltene concentration, wt% Asphaltene concentration, wt%

e 1.E+05 f 6.E+04

9.E+04
5.E+04
8.E+04
Intensity difference, cps

Intensity difference, cps

7.E+04 50_4 50_4

4.E+04
50_6 50_6
6.E+04
50_9 50_9
5.E+04 1_4 3.E+04 1_4

4.E+04 1_6 1_6

1_9 2.E+04 1_9
3.E+04

2.E+04
1.E+04
1.E+04

0.E+00 0.E+00
380 400 420 440 460 480 500 520 540 560 380 400 420 440 460 480 500 520 540 560
Emission wavelength, nm Emission wavelength, nm

Fig. 7. Fluorescence emission spectra of the solutions of asphaltenes from (a) Oil A and (b) Oil B, of the wt% concentrations in the legend, yielding the calibration relation
between these concentrations and the peak intensity difference for (c) Oil A and (d) Oil B. Spectra of asphaltenic residues for (e) Oil A and (f) Oil B after flushing the kaolinite
substrates with salt solutions of concentration (g/l) and pH in the legend, followed by decalin–methanol post-rinsing and chloroform/methanol extraction.

of the similarly signed interfacial charges in equilibrium at pH 4
and 9 in Fig. 11b, and also increases the disturbance of the initial
equilibrated state. However, previous studies [28,29] showed that
decreased salinity of sodium–calcium brines typically increased
short-time adhesion and longer-time adsorption of oil on kaolinite,
in agreement with Fig. 8a, by aiding local attraction of oppositely
charged patches on the two interfaces, even if both net zeta poten-
tials were of the same sign. Flushing with the 1 g/l solution also
induces an extra osmotic pressure contribution serving to dilute
the high salinity solution trapped by oil in the confines of the kaoli-
nite coat in its initial state. This film swelling may disconnect oil
in/on the coat from bulk oil ahead of the advancing meniscus of the
flush, to thus hinder its removal.
As the zeta potential behavior of the two oils is comparable,
the dependence of the residue amount for Oil B on flush salin-
ity and pH in Fig. 8a resembles that for Oil A, although with the
 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23 21

18
a 30
16

Residue intensity, GSV

2
Residue mass/area, mg/m

25 14
y = 2.9156e0.0552x
12
20 R2 = 0.8146
10

15 8
6
10 4
2
5 Oil A, 50 g/l Oil B, 50 g/l
Oil A, 1 g/l Oil B, 1 g/l 0
0 5 10 15 20 25 30 35
0
2
3 4 5 6 7 8 9 10 Residue mass/area, mg/m
Flush pH
Fig. 10. Correlation between the mass of asphaltenic residue per planar slide area,
from Fig. 8a, and the reduction in average grayscale value of the scanned images in
b 30 Fig. 9 due to the discoloration by these residues, for the six samples treated using
Oil A Oil B.
2
Residue mass/area, mg/m

25 Oil B

20

15 to allow water ingress to prematurely disconnect oil in the coat

10
5 low salinity flooding. Along with the necessary conditions proposed
0 strates that crude oils in which their asphaltenes are relatively
0 10 20 30 40 50 60 70
SEM image edge loss, %
Fig. 8. (a) Total mass of asphaltenic residues per planar area of kaolinite-coated
substrate, for the two oils flushed with salt solutions of varying concentration and
pH, and post-rinsed with decalin–methanol, followed by extraction. (b) Correlation
of the two measures of oil residues in Figs. 5 and 8a.
handicap of limited scope to reverse the non-electrostatic precip-
itation of asphaltenes in the initial state. The recent study [33] of
Oil B residues on glass showed that removal could be extensive,
even in the presence of such precipitation, however the kaolinite
coats can support a complex network of precipitate with far greater
anchoring ability. The only condition for which significant removal
occurs is for the 50 g/l flush at pH 4, which apparently weakens the
oil–kaolinite attraction without inducing such strong repulsion as
from that in the bulk.
The results enable some assessment of the likely mechanisms for
improved oil recovery from kaolinite-rich sandstone reservoirs by
from core-scale experiments [22–26], the current study demon-
80 90 100 stable (at reservoir temperatures and pressures) should gener-
ally be more conducive to wettability change during flooding. For
our model systems, in which the flood exposes kaolinite to a vast
excess of brine, the direct effect of its low salinity at fixed pH is to
favor the retention of oil by kaolinite, relative to the high salinity
flood. In kaolinite-rich sandstone pores, the kaolinite/water ratio
is sufficiently high that cation exchange in response to low salin-
ity flooding can temporally perturb bulk cation concentrations and
pH [22–26]. It appears that increased water-wetness of kaolinite
at the molecular scale cannot occur without the aid of such associ-
ated pore-scale effects. The shift in flood pH imposed in our model
systems to mimic such a spontaneous perturbation can favor water-
wetness. For example, in Fig. 8a, the Oil A residue on kaolinite after
the 1 g/l flood at pH 9 is slightly lower than for the 50 g/l flood at pH
6. More substantial removal of residue, if occurring, must thus be
due to pore-scale perturbation of divalent cation concentrations.

Fig. 9. Scanned images of the kaolinite-coated glass pieces (of average size 7 mm × 26 mm) exposed to Oil B and flushed with the six salt solutions, followed by
decalin–methanol post-rinsing.
22 A. Fogden / Colloids and Surfaces A: Physicochem. Eng. Aspects 402 (2012) 13–23
a 5
Oil A, 50 g/l
Oil B, 50 g/l
Zeta potential, mV
0
Kaolinite, 50 g/l
-5
-10
-15
-20
3 4 5 6 7 8
Brine pH
Fig. 11. Average and standard deviation (error bars) of zeta potential of the crude oils and kaolinite in the salt solutions at their two concentrations of (a) 50 g/l and (b) 1 g/l,
each at three pH values.
4. Conclusions
Smooth, thin and robust coats of kaolinite on glass were used
to analyze the propensity for crude oil to spontaneously displace
an initially surrounding salt solution (as during formation of an oil
reservoir or subsurface DNAPL contamination), and the ability of
salt solutions of varying salinity and pH to subsequently displace
the infiltrated, adhering oil (as during recovery or remediation).
Both of the tested crude oils altered the wettability of kaolinite
by adsorbing/depositing their asphaltenics to penetrate all pores
between platelets. However, the oil with less stable asphaltenes
yielded a much thicker and more completely covering deposit due
to surface precipitation. Accordingly, flushing of this oil with salt
solutions largely failed to remove it from the surface and pores
of the kaolinite coat. The oil with stable asphaltenes was more
responsive to flushing, which yielded lesser residues and partially
reinstated the original water-wetness of the substrate. Its residues
also depended strongly on the salinity and pH of the flushing solu-
tion, displaying more complete removal at conditions conducive
to weakening of the electrostatic local attraction between oil and
kaolinite interfaces, namely at higher salinity and/or by shifting the
initial intermediate pH to higher or lower levels.
Acknowledgments
This study was funded by an ARC Discovery Grant and the mem-
ber companies of the Digital Core Consortium Wettability Satellite.
Warwick Hillier (RSB at ANU) is thanked for access to the FluoroMax
instrument.
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