JCIS Open 4 (2021) 100026

Contents lists available at ScienceDirect

JCIS Open
journal homepage: www.journals.elsevier.com/jcis-open

Novel adsorption mechanisms identified for polymer retention in

carbonate rocks
Eseosa M. Ekanem a, *, Maja Rücker a, d, Sherifat Yesufu-Rufai a, Catherine Spurin b, Nicholas Ooi a,
Apostolos Georgiadis c, a, Steffen Berg c, b, a, Paul F. Luckham a
a
Department of Chemical Engineering, Imperial College London, London, SW7 2AZ, United Kingdom
b
Department of Earth Science and Engineering, Imperial College London, London, SW7 2AZ, United Kingdom
c
Shell Global Solutions International B.V, Amsterdam, Grasweg 31, 1031, HW, Amsterdam, the Netherlands
d
Department of Mechanical Engineering, Eindhoven University of Technology, 5600, MB, Eindhoven, the Netherlands

A R T I C L E I N F O A B S T R A C T

Keywords: Hypothesis: High molecular weight polymers are widely used in oilfield applications, such as in chemical enhanced
Viscoelastic polymer oil recovery (cEOR) technique for hydrocarbon recovery. However, during flow in a porous rock, polymer
Porous media retention is usually a major challenge, as it may result in the decrease of polymer concentration or lead to
Polymer retention
plugging of pores with significant permeability reduction and injectivity loss. Hence, an understanding of the
Estaillades carbonate rock
retention mechanisms will have a profound effect in optimizing the process of polymer flooding, in particular, for
Atomic force microscopy
Calcite carbonate rocks, which hold more than half of the world's oil reserves. Therefore, in this study, the retention of
hydrolysed polyacrylamide (HPAM) polymer, a commonly used chemical for EOR, is investigated during flow in
Estaillades carbonate rock.
Experiments: A novel approach of investigating HPAM retention in Estaillades carbonate rock was carried out using
Atomic force microscopy (AFM). Since Estaillades carbonate rock is ~98% calcite, HPAM retention was first
characterised on a cleaved flat calcite mineral surface after immersing in HPAM solution. Afterwards, HPAM was
flooded in Estaillades carbonate to observe the effect of flow dynamics on the retention mechanisms.
Findings: We find that the dominant mechanism for retention of HPAM on calcite after fluid immersion is polymer
adsorption, which we believe is driven by the electrostatic interaction between the calcite surface and the so-
lution. The thickness of the adsorbed layer on calcite is beyond 3 nm suggesting it is not adsorbed only flat on the
surface. Different types of adsorbed layers were formed representing trains, and the more extended loops or tails
with the largest polymer layer thickness about 35 nm, representing the longer loops or tails. Layers of this
thickness will begin to impair the permeability of the rock. However, in Estaillades, thicker adsorbed layers are
observed in different regions of the rock surface ranging between 50 and 350 nm. We suggest that this is due to
either mechanical entrapment and/or polymer entanglement during flow in Estaillades carbonate rock, which will
cause the major permeability impairment in porous rocks.

1. Introduction weight polyelectrolyte polymers of hydrolysed polyacrylamide (HPAM),

High molecular weight polymers are of great importance in a variety
of industrial applications, such as waste water treatment and in oil field
applications, where polymer retention in a porous rock is of significant
importance, in the context of chemical enhanced oil recovery [1,2].
Polymer solutions are used in enhanced oil recovery processes, because
the remaining oil saturation is reduced, making the displacement of oil
more effective and improving the sweep efficiency [3–7]. High molecular
in the million Dalton range are preferred, because low concentrations of
such polymers will cause a significant increase in polymer solution vis-
cosity, such that, the mobility of the polymer solution is lowered relative
to the oil, thereby improving sweep efficiency. Since HPAM is a poly-
electrolyte, at the molecular level, their structure changes due to the
nature of the ionic strength, such that they may behave as a random walk
of chains at high electrolyte concentrations and/or low charge density,
whilst at low electrolyte concentrations the molecule is much more

* Corresponding author.
E-mail address: e.ekanem16@imperial.ac.uk (E.M. Ekanem).

https://doi.org/10.1016/j.jciso.2021.100026
Received 6 August 2021; Received in revised form 23 September 2021; Accepted 30 September 2021
2666-934X/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
E.M. Ekanem et al.
expanded due to strong repulsion of same charges and ultimately adopts
a rigid rod like conformation [8–10].
Furthermore, at the macro-scale these polymers show both shear-
thinning and “shear thickening” rheology in porous media [6,7]. How-
ever, in bulk flow, they have a favourable shear thinning behaviour,
which at high flow rates near the well bore and during injection will
cause the viscosity to be low, meaning that the injection pressure remains
low i.e., below the fracture pressure of the rock. Furthermore, there are
technical challenges associated with the use of high molecular weight
polymers like HPAM, for e.g., adsorption (or more generally retention),
which reduces the permeability of the rock and the polymer concentra-
tion available for an effective sweep, because the polymer solution vis-
cosity is reduced. Previous studies on polymer retention [11,12], were
carried out mostly in sandstone rocks and successfully implemented both
in the laboratory and commercially [5,13,14].
For carbonate rocks, the laboratory studies conducted have shown
some success especially with oil-wet reservoir cores and in the use of
modified polymer solutions [15–19]. In a pilot test carried out by Levitt
et al. [20] in carbonate reservoirs, lower oil recovery, due to reduced oil
bank formation caused by reservoir heterogeneity, is perhaps, the reason
no commercial full field level polymer flood, in a carbonate rock, has
been successful at the time of writing. Therefore, an understanding of the
root cause of polymer retention is required, in carbonate rocks, for an
efficient flooding process, since more than half of the world's oil reserves
are in carbonate rocks [21].
In general, the propagation of polymer solution in porous media is
controlled by retention and inaccessible pore volume (IPV). The mech-
anism of polymer retention conceptually can comprise of polymer
Fig. 1. Schematic representation of the different mechanisms of polymer retention in porous media. (b) Schematic description of the mechanism of polymer retention
on surfaces represented by trains, loops and tails.
2
JCIS Open 4 (2021) 100026
adsorption, mechanical entrapment and hydrodynamic retention [22]
[see Fig. 1a]. In polymer adsorption, high molecular weight polymers
attach to different polar points on the rock surface adopting the trains,
loops and tails configuration [23,24] as shown in Fig. 1b. This process of
adsorption is essentially irreversible, because certain parts of the polymer
chain may detach, whilst other parts reattach onto the rock surface, it
being very unlikely that all attached points of the polymer chain will
detach from the rock surface at the same time [25]. Also, adsorption can
be induced by surface charge, where unlike charges between the fluid
and the rock mineral surface drives adsorption because of electrostatic
interaction. For instance, sandstones are predominantly quartz, which
are negatively charged. Therefore, retention with HPAM is minimised
due to similar charges except in the event of clay swelling, due to
screening of the surface charge by positively charged counter-ions pre-
sent in the electrolyte occurring more nearest to the pore walls compared
to the bulk [26–28]. Carbonate rocks are positively charged [29,30]
therefore, retention increases due to difference in charge between the
rock and polymer solution. However, there have been instances where
carbonates and calcite minerals were found to be negatively charged
depending on the pH and salinity conditions [27,31].
In the process of mechanical entrapment, large sized polymer mole-
cules become trapped in the porous media, while hydrodynamic reten-
tion is when the polymer solution is hydrodynamically trapped in the
pore space due to changes in flow rate. Some other phenomena which
relate to entrapment of polymer solutions are filtration; where the
polymer solution becomes filtered at the porous media entrance, trapping
in dead-end pores and polymer chain bridging; where polymer chains
form bridges and become trapped within the pore space above a critical
E.M. Ekanem et al.
shear rate, especially in low permeability rocks [32]. Consequently, some
retention mechanisms are reversible such as hydrodynamic retention due
to changes in flow rate while others may not be, like adsorption [33,34].
There have been significant advancement in the description of poly-
mer adsorption e.g., in the recent work of Ferreira & Moreno [5], in
sandstone rocks, polymer adsorption was modelled by both type I and
type IV adsorption isotherms depending on the overlapping concentra-
tion of the polymer and the modes of adsorption and re-adsorption. The
fundamental question; however, is how the adsorption of a molecule
monolayer lying on a flat substrate, assuming a thickness of a few
nanometres, can possibly cause significant permeability reduction in
pores of a few micrometers and larger. Perhaps the assumptions of
molecules lying flat on the surface of minerals and monolayer adsorption,
in general, are not applicable for the situation in the porous media
application.
Numerous studies have investigated experimentally the cause of
polymer adsorption on flat surfaces, using the surface forces apparatus,
atomic force microscopy and ellipsometry [1,35–38]. Investigations of
polymer solution flowing in capillaries by Grattoni et al. [39] showed
that dynamic polymer retention (i.e. during flow) is significantly greater
than static retention and termed the mechanism of retention in capillaries
as adsorption entanglement, which implies that in the context of polymer
flooding the porous media is more than an assembly of flat surfaces, but is
rather an assembly of capillaries. Zitha et al. [40] suggests that polymer
retention is primarily due to adsorption and bridging, by elongated
polymer chains during flow. Polyacrylamide retention on silicate sur-
faces by Bessaies et al. [27], and some simulation work by Dang et al.
[41] point to the nature of the polymer and the mineral surface as major
contributors towards retention. This further implies the importance of
the solution quality and surface heterogeneity, which in this case will
notably impact the retention of polymer solution in porous media.
Significant impact on adsorption can also arise from the fact that
mineral surfaces of carbonate rocks are often rough. Hence, in-
vestigations on rough surfaces by Chauveteau [32] using glass bead
packs, showed that the mechanism of polymer retention was a conse-
quence of flow-induced adsorption, where hydrodynamic forces normal
to the pore walls become large, such that, it induces adsorption of
polymer chains into region of previously adsorbed polymer layers. Most
of these investigations focus on clastic rocks, such as sandstones. For this
class of rock, the application in the field shows that in many cases, the
adsorption/retention related problems can be controlled [42,43]. How-
ever, for carbonate applications, this is not the case as adsorption/re-
tention is significantly larger, which in many field trials have led to the
loss of injectivity [20,21] suggesting a much more significant and po-
tential conceptual difference of the retention mechanism.
Therefore, the focus of this work is a detailed study on the mechanism
of polymer retention on smooth and rough surfaces. This work studies the
root cause of polymer retention in Estaillades carbonate rock, using the
latest state-of-the-art atomic force microscopy (AFM). The AFM, which is
traditionally a topographical imaging tool capable of measuring surface
features, ranging from the micrometer to atomic scale, has been extended
for force-distance mapping, which provides local mechanical properties
of the surface and in our case gives insight into the nature of an adsorbed
polymer layer. This technique is used to probe, the mechanism of poly-
mer retention, the impact of surface charge and electrostatic interactions,
and roughness on the mode of polymer retention on carbonate mineral
surfaces. By comparing the adsorbed layer thickness of the polymer on
flat calcite surfaces to Estaillades after polymer flooding, so that the
mechanisms of adsorption and mechanical entrapment can be
categorized.
The paper is structured as follows. First, we present the material and
methods section which focusses on the experimental set up and the
characterisation of polymer retention on calcite. Afterwards, the results
obtained for retention during polymer flooding in Estaillades carbonate is
presented and discussed. Finally, we draw conclusions on the retention of
polymer solutions in low permeability heterogeneous rocks.
3
JCIS Open 4 (2021) 100026
2. Material and methods
In this section, characterisation of polymer retention on calcite min-
eral surface is discussed following the experimental set-up carried out for
the investigation of polymer retention in a heterogeneous porous media.
2.1. Polymer preparation
Hydrolysed polyacrylamide was obtained from SNF Floerger with a
molecular weight range of 11–13 MDa (FP3330) and 18–20 MDa
(FP3630) as shown in Table 1. Two solutions were prepared in the
presence of brine purchased from Sigma Aldrich, the first (HPAM-Na) in
the presence of 0.5% NaCl was prepared for characterising polymer
retention on a bare calcite surface and (HPAM-Ca) in the presence of
0.5% CaCl2 was used to investigate polymer retention in Estaillades
carbonate rock. We use CaCl2 brine to achieve a target zero-shear rate
viscosity between 0.01 and 0.05 Pas. During the preparation of polymer
solution, ITW (15% Isopropanol, 7.5% thiourea and 77.5% water) a
protective package to minimise polymer degradation was added at 20%,
such that the final concentration of isopropanol is 20% of the polymer
concentration. Afterwards, polymer powder was introduced, and mixed
using a stirrer rod for 10 minutes following a magnetic stirrer for 48
hours to ensure individual polymer molecules had enough time to
dissolve [44].
2.2. Atomic force microscopy
Atomic force microscopy (AFM) is a topographical imaging technique
capable of measuring surface features ranging from the micrometer to
atomic scale. The images were obtained mechanically using a sharp tip,
which raster-scans the surface of the sample. The tip is mounted on a
cantilever and moved along the scanning grid, using piezoelectric
transducers. The position of the tip is thereby monitored with a laser. In
this study, we scanned the samples in quantitative imaging (QI)-mode
with a PPP-NCHAuD probe obtained from NANOSENSORS™ (tip radius:
< 10 nm, tip height: 10–15 μm, nominal force constant: 42 N/m), using a
Nanowizard 4 AFM from JPK instruments (now Bruker). In the QI-mode,
the tip is moved vertically towards and from the sample at each indi-
vidual pixel, and then advances to the next pixel. This allows the full
force profile at that point to be obtained, whilst approaching and
retracting from the surface, and therewith to obtain additional infor-
mation about the surface properties, such as the stiffness of the sample
[45]. The stiffness (Young modulus – YM) of the probed surface, was
estimated by fitting the Hertz model to the force profiles obtained at each
point, the tip shape was considered parabolic, with a radius of 10 nm
[46–51]. The Poisson ration was assumed to be 0.5. In addition to the
automated fit, which considers the full force profile provided by JPKSPM
data processing software (JPK instruments), we conducted a manual fit
by adjusting the fitting range for selected force-distance curves to probe
the initial stiffness of the polymer layer.
The image processing, including the application of line levelling and a
median filter, was conducted with the standard JPKSPM data processing
software. The 3D visualization was obtained using MATLAB (R2018b).
Table 1
Description of polymer solutions.
Solution Polymer Salt Salt Ionic Polymer η0
Conc. Conc. strength Mwt. (Pas)
(ppm) (wt.%) (mM) (MDa)
HPAM- 2000 0.5 NaCl 86 18–20 0.6
Na
HPAM- 5000 0.5 CaCl2 90 11–13 0.02
Ca
E.M. Ekanem et al. JCIS Open 4 (2021) 100026

2.3. Polymer retention characterisation with calcite
2.3.1. Calcite crystal
Optical quality colourless, rhombohedral crystals of Iceland Spar
calcite were purchased from Manchester Minerals, United Kingdom. The
sample used for AFM experiment was obtained from the parent crystal by
cleaving twice with a clean, sharp bladed tool to ensure that an original
surface was exposed. The cleaved sample of ~ 7 mm length and a
thickness of ~ 2 mm, was relatively smooth, and thus suited to nanoscale
investigations of the solid-liquid interface. Cleavage was performed in air
just prior to the measurements, and immediately placed within a
stainless-steel fluid cell, with the inlet and outlet sealed with silicone
tubing. The polymer solution was slowly injected through the silicone
tubing using a syringe, until the calcite crystal was fully immersed. An
additional reference sample was prepared using the same methodology,
for a cleaved calcite immersed in 0.5% NaCl solution, without the
polymer solution. For imaging the calcite sample with AFM, we chose a
scan area of 10 μm
10 μm with 256
256 sampling points using a set
point of 30 nN and a z-length of 0.2 μm.
2.3.2. Polymer characterisation on calcite
AFM topography image of HPAM-Na adsorbed onto the calcite sur-
face is shown in Fig. 2. The imaged area 10 μm by 10 μm is composed of
three readily visible regions: a thin polymer layer (between 3 and 10 nm
thick) looking like freckles that is pervasive over the whole sample, with
patches of medium thickness (25 nm), and areas that are much consid-
erably thicker (35 nm) than the surrounding surface [52–55].
The force-distance curves are measured between the probe and the
polymer layer on the calcite surface. As the probe is extended towards the
surface of the polymer, no interaction occurs, until the probe touches the
surface of the polymer layer at a certain distance, represented by the
point of elevation in the approach curve. The interactions measured at
these observed regions of low, medium, and high adsorbed polymer layer
thickness are displayed, together with a control measurement of bare
calcite surface in brine, illustrated in Fig. 2(c-f). Contrary to the mea-
surements of the bare calcite surface in brine, that reveal no detectable
interaction on approach Fig. 2c (AFM images of bare calcite can be seen
in the work by Ricci et al. [56]), force curves obtained in the polymer
solution, show consistent repulsive interactions, with the repulsive force
increasing in magnitude with decreasing tip-sample separation and
becoming longer ranged as adsorbed layer thickness is increased.
For regions with lowest adsorbed polymer layer thickness, a repulsive
force is evident beginning from a tip-sample separation of 10 nm, before
contact was made with the calcite surface. Force measurements con-
ducted on regions of median height, a repulsive force at about 25 nm
from the calcite surface, exponentially increasing before contact was
made with the calcite surface. This is indicative of the adsorbed tail
polymer structure being compressed. Likewise, at the highest adsorbed
structure of long dangling polymer tails, the repulsive force rises even
more steeply at 35 nm, where the tip pushes through to the calcite sur-
face. In the supplementary information, we further confirm a polymer
layer thickness of up to 40 nm in Fig. S1, by studying the force-distance
curves at a different location, which represent the high polymer region.
Hysteresis is also present in all three adsorbed layer structures
measured, as the retract curves do not follow the approach curves, as has
been observed before for the interaction between polymer layers [36,39,
57,58]. This symbolises that, the polymer solution may have been pushed
onto the rock surface and so does not relax quickly from the compression,
as the tip disengages the calcite surface.
The interaction between polar groups on the polymer chain and polar
sites of the calcite surface, would support the adsorption of flat-lying
continuous chains of small loops and train structures, with thickness ~

Fig. 2. HPAM-Na retention on calcite with 10 μm
10 μm x - y axis. (a) height image indicating regions of high, medium, and low polymer retention (b) Young
Modulus. The red regions are polymer layers having lower Young modulus compared to the yellow region (calcite surface) with higher Young modulus values. Force
curves obtained from the AFM with Young Modulus fit for (c) calcite in brine (0.5% NaCl). Force-distance curves representing HPAM-Na retention on calcite for (d)
low polymer region, representative of a monolayer adsorption of trains (e) medium polymer region, representing polymer tails, attached to previously adsorbed
monolayer and (f) high polymer region, representing extended polymer tails and/or microgels, attached to previously adsorbed polymer layer. (For interpretation of
the references to colour in this figure legend, the reader is referred to the Web version of this article.)

4
E.M. Ekanem et al.
10 nm, constituting the thinnest adsorbed layer of polymer solution on
the calcite surface. We believe polymer retention was predominant on
the entire calcite surface, because of the affinity between the charged
COO groups on the polymer chain and cations present on the calcite
surface [56,59–61] as well as the hydrogen bonds between HPAM and
the calcite surface as discussed by Wang et al. [55]. Areas of median
thickness ranging between 10 and 25 nm, correspond to polymer chain
tails, closely situated with areas where the adsorbed layer was thickest,
ranging from 25 to 40 nm, denoting longer polymer chain tails and/or
entangled chains, that are perpendicular to the calcite surface.
The force curves were fitted with the Hertz model to obtain the Young
Modulus values, in other to have a more understanding of the stiffness.
The automatic fits were obtained from the JPK software and the manual
fits were carried out to ensure proper fitting by the software. The
continuously low Young Modulus values obtained at all locations of the
polymer treated sample is shown in Fig. 2b and Table 2, ranging in the
order of 107–109 Pa for the automated fit and continuously in the range
of 107 Pa when fitted manually, compared to the non-treated sample with
a continuous Young modulus in the range of 1010 Pa. This indicates a
continuous surface coverage of calcite by HPAM and agrees with the AFM
topography image, showing extensive microgel-like structures on the
sites where highest amount of polymer layer thickness was observed.
2.4. Core-flood investigation
2.4.1. Estaillades
Estaillades is a Cretaceous bioclastic limestone from the Estaillades
quarry in south east France. The rock has a typical porosity φ ¼ 30% and
permeability of ~ 100 mD [62]. It consists predominantly of calcite
(97.9%) with minor quartz (2.1%) components [63]. Due to its bioclastic
composition, the rock has a complex pore-structure illustrated by the
micro-CT image, shown in Fig. 3a and b, containing heterogeneities
across different length scales.
Estaillades has a dual-porosity system as shown by the mercury
intrusion porosimetry (MIP) results shown in Fig. 3c. It is a rock
commonly used for flow dynamics investigations during core flooding
experiments [64,65].
2.4.2. Core-flood experiment
Two sets of core flooding experiments were carried out on Estaillades
with core characteristics listed in Table 3 and set up detailed in Fig. 4.
The first core flood experiment was a drilled core sample with a large size
of length 10 cm and diameter 3.8 cm, investigating polymer rheology and
the implications of permeability impairment. Due to the small sized
samples required by the AFM, the second core flood experiment had core
of length 2 cm and diameter 0.5 cm for sub-pore scale assessment of
polymer retention with AFM.
2.4.2.1. Core-flood investigations to assess rheology. The core holder for
the first flooding experiment [see Fig. 4a], which investigates rheology
and permeability impairment, was fabricated with stainless steel. The
Estaillades core was introduced into the core holder, sealing with a dual-
epoxy adhesive araldite 2014, purchased from RS Components, Ltd UK,
such that the core becomes coated with araldite resin. The pressure
transducers used were purchased from Keller UK Ltd, with ratings of 100,
30, and 10 bar with an accuracy of 0.05% full scale. The set up was built
Table 2
Young Modulus with automatic and manual Hertz model fit of HPAM-Na
retention on calcite, at no polymer (only 0.5% NaCl) low, medium, and high
polymer.
Hertz Model fit No Low Medium High
Polymer Polymer Polymer Polymer
Automatic 43 GPa 1.94 GPa 77 MPa 56 MPa
Manual 35 GPa 40 MPa 27 MPa 25 MPa
5
JCIS Open 4 (2021) 100026
to allow for five pressure measurement. Three measurements within the
core, and two measurements upstream and downstream of the core. The
epoxy glue was drilled through three openings on the core holder, in
other to allow PT2, PT3 and PT4 direct pressure measurements on the
core. Pump A was used for fluid injection, while Pump B acted as a
pressure regulator.
As evident from the characterisation of polymer solution on calcite,
where microgel-like structures were observed (Fig. 2a). The formulation
of the polymer solution injected into Estaillades core was refined, such
that, the solution viscosity was reduced to 0.02 Pas by using a lower
molecular weight and introducing a divalent salt of CaCl2. This was done
because of the low permeability and heterogeneity of Estaillades and to
achieve a target flooding viscosity that is between 10 and 50 times the
viscosity of water [66,67]. The divalent cation was also introduced to
allow for a more practical scenario of the salts present in an actual
reservoir.
A filtration step was also introduced, such that the polymer solution
was filtered using a 2 μm filter paper under a pressure of 5 bar in a
filtration cell, to remove any microgels, and the filtration ratio was
estimated to be about 1.01. The equation for filtration ratio was obtained
from Thomas [68] and defined as the time for 100th ml minus the time
for the 80th ml divided by the time for the 80th ml minus the time for the
60th ml and expressed in Eq. (1) as follows;
t100ml  t80ml
FR ¼ (1)
t80ml  t60ml
Before injecting the polymer solution into the core [see Fig. 4a], CO2
was injected for about 10 min to remove dirt and debris. We use CO2
instead of inert gas because the pressure required for dissolving CO2
during subsequent brine saturation to remove any gas phase is simply
much less than for e.g., nitrogen or other inert gases. Afterwards, brine
was injected into the core to flush out CO2 [65,69]. The pressure drop
was recorded during brine injection, and the permeability of the core was
estimated based on the Darcy equation in Eq. (2) [4,70].
μuL
k¼ (2)
ΔP
where k is the permeability, μ is the brine viscosity, L is the length of the
core, u is the fluid velocity and ΔP is the pressure drop across the core.
The residual resistance factor (RRF) is also estimated in Eq. (3) [68].
kPrepolymer
RRF ¼ (3)
kPostpolymer
where kPrepolymer is the permeability of the core before polymer injection
and kPostpolymer is the permeability of the core after polymer is injected.
Afterwards, polymer solution (HPAM-Ca) was injected at different
flowrates ranging from 1 ml/min to 40 ml/min. The stabilised pressure
drops between PT2 and PT4 were recorded. The core was flushed after-
wards with brine to remove the polymer solution and the permeability
determined.
2.4.2.2. Core-flood investigations to assess retention with AFM. Prior to the
AFM measurements, the second Estaillades carbonate sample was placed
in a Viton sleeve and mounted into the flow cell, and a differential
pressure transducer was connected across the sample as shown in Fig. 4b.
A confining pressure of 2 MPa was applied to the sample within the flow
cell. The sample was flushed with brine to remove air, keeping the back
pressure at 4 MPa (with the confining pressure always kept at an addi-
tional 2 MPa over the pore pressure). Once the air was removed, the
sample was returned to ambient pressure (and a confining pressure of
2 MPa).
The polymer was then injected to displace the brine. This was un-
dertaken at a constant flow rate of 0.05 ml/min, until the pressure drop
across the sample had plateaued (at which point the system was assumed
E.M. Ekanem et al. JCIS Open 4 (2021) 100026

Fig. 3. μCT greyscale images of an Estaillades carbonate (a) 2D-slice and (b) 75% cut 3D-volume, consisting of different recrystallized fossils, the rock shows a
complex pore-structure and a dual porosity as shown in the MIP-curve in (c). (adapted from Ref. [64]).

to be at equilibrium). Afterwards, the sample was retrieved from the flow

Table 3
cell, whilst constantly keeping it within the brine solution of 0.5% CaCl2.
Core characteristics.
The Estaillades sample after polymer flooding was scanned by the
Estaillades Core flood 1 (Rheology and Core flood 2 (retention AFM, along the radial surface of the pores adjacent to the cut edge of the
permeability investigation) investigation with AFM)
Estaillades core [see Fig. 4c] [45,71,72] on a 10 μm
10 μm area, with
Length 10 cm 2 cm 128
128 sampling points, using a set point of 180 nN and z-length of
Diameter 3.8 cm 0.5 cm
2 μm to accommodate for the sample roughness. A dry reference was
Porosity 32% 30.4%
Permeability 128 mD 175 mD
obtained from a twin sample. The sample was scanned using the same
Pore volume 36.19 34.23 settings as in the polymer flood experiment except a lower set point of
140 nN.

Fig. 4. Core flooding experimental setup for flooding polymer solution (HPAM-Ca), in order to (a) investigate rheology and changes to core permeability. The
Estaillades core has a length of 10 cm and diameter of 3.8 cm (b) investigate mechanism of polymer retention with AFM. Core length is 2 cm and a diameter of 0.5 cm
(c) Estaillades core sample showing the radial surface that was imaged with AFM [34].

6
E.M. Ekanem et al.
3. Results
In this section, we present the results obtained from the measure-
ments of polymer rheology and retention in Estaillades carbonate.
3.1. Rheology of HPAM
Results presented in Fig. 5 were obtained using the larger core sam-
ple, where HPAM-Ca was injected at different velocities. In Fig. 5a, the
apparent viscosity is estimated using the well-known Darcy equation in
Eq. (2) and the result of the apparent viscosity as a function of Darcy
Fig. 5. (a) Rheology of HPAM-Ca showing the apparent viscosity versus Darcy
velocity (b) Changes in Estaillades pressure drop after HPAM-Ca was injected.
Solid line is injected brine pressure drop before polymer injection and dotted
line is the injected brine pressure drop after polymer injection. The latter has a
higher pressure drop indicating a reduced permeability of Estaillades carbonate
core (c) The viscosity versus shear rate of the effluent polymer solution after
injection in Estaillades core showing a reduction in polymer viscosity.
7
JCIS Open 4 (2021) 100026
velocity are presented. As the shear rate increases, the in-situ rheology
changes from shear thinning to shear thickening at a critical Darcy ve-
locity of 3 ft/day corresponding to 0.01 mm/s. As the shear rate con-
tinues to increase, a second critical Darcy velocity of 10 ft/day
(0.035 mm/s) is reached. This introduced a sudden reduction in polymer
apparent viscosity, which we believe is related to either polymer reten-
tion, where some polymer solution is retained within the rock or polymer
degradation, where some polymer chains are broken into smaller chains
leading to a reduction in solution viscosity. The simulation work by
Pierleoni et al. [73] showed that shearing of polyelectrolyte polymers can
lead to the destruction of polymer chain blob thereby reducing chain
length [8,73].
The permeability of the rock before and after polymer injection were
compared to assess structural alteration of the rock by polymer flooding.
The changes in permeability were determined at conditions when brine
was injected before and after polymer injection. The results shown in
Fig. 5b for pressure drop as a function of the Darcy velocity show a large
difference in pressure drop. The residual resistance factor (RRF) was
determined to be 2.8 suggesting that retention is still within the low
range based on K.Sorbie [4]. However, we estimated a permeability
reduction of ~ 55%.
The effluent polymer solution after polymer injection in the core were
characterised in a rheometer and compared with same polymer solution
prior to injection in the core sample. The results in Fig. 5c showed a
decrease in the zero-shear rate viscosity from 20 mPas to 4 mPas. These
results of increased pressure drop and changes to the fluid viscosity
suggests polymer retention, which changed the geometric structure of
the rock and possibly degradation of the polymer chains. These results
also show that, with low permeability rock cores, retention, and degra-
dation of HPAM polymers is very probable and the mechanism of
retention will be discussed in the subsequent sections.
3.2. Imaging HPAM retention on mineral surfaces in 3D porous rock
(Estaillades)
Estaillades carbonate core was first imaged in air with AFM and the
results are presented in Fig. 6. The height map in Fig. 6a shows the degree
of rock roughness, with regions of hills and valleys. The yellow regions
are representative of the rock peaks and the dark regions representative
of the valleys. As the AFM tip is not able to pass through the narrow
pores, it is likely that some of the valleys represent the inlets to the nano-
pores, reflected by the MIP curves in Fig. 3c. This assumption is sup-
ported by the similar diameter of about 600–700 nm in the valleys to the
lower peak pore-diameter of the MIP results. Furthermore, the structural
attributes of the rock need to be considered in interpreting the force-
distance curves obtained, because the structures may redirect the tip
on approach to the surface which causes slide artefacts or even prevent
the contact of the tip with the underlying surface entirely.
The Young Modulus (YM) of the displayed structure is represented in
Fig. 6b. The yellow regions, which are stiffer, represent higher YM
values, where the peaks of the rock are situated, while dark regions
represent the edges of the rock. However, the lower YM values, which
represent the dark regions are a consequence of the sliding of the tip
along the sharp edges before the very tip touches the rock surface.
In the presence of HPAM-Ca, after imaging with the AFM, the polymer
solution adhered to the surface of the rock sitting at the peaks and edges
of the rock, as can be seen in Fig. 7a of the height map. In the Young
Modulus map of Fig. 7b, the region marked “”in Fig. 7a representing the
rock mineral surface in the height map, has a higher YM value compared
to the region marked “x”, in Fig. 7a where we believe adsorbed HPAM is
present. The HPAM retained on the rock surface after polymer injection,
is represented by the red areas in the YM map, which are the softer areas,
compared to the YM values of the rock surface, which are much stiffer.
The images in Fig. 7a suggest that the mechanism of retention is related
to both adsorption and mechanical entrapment. However, this will be
discussed in more detail in the discussion section.
E.M. Ekanem et al. JCIS Open 4 (2021) 100026

Fig. 6. Images of Estaillades in air with AFM, axis are 10 μm
10 μm. (a) Height map, nano-pores are indicated with sizes around 600 nm to 700 nm (b) Young
modulus (YM) (c) 3D height map of a.

Fig. 7. HPAM-Ca retention in Estaillades. Image axis are 10 μm
10 μm (a) Height map showing regions of polymer retention and rock mineral surface (b) Young
modulus (YM) with regions of adsorbed polymer and rock surface representing red and yellow colours respectively. (c) Force-distance curves for Estaillades carbonate
for the region marked “x” in a for adsorbed polymer layer and the region marked “” in a for the Estaillades mineral surface. Force-distance curves are also fitted with
the Hertz model using both automatic and manual fit. (d) 3-dimensional height maps of a. Red regions represent polymer solution and yellow region represents rock
surface. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

The 3-dimensional height map in Figs. 6c and 7d is a clear depiction
of the roughness of Estaillades rock surface. In Fig. 7d, the roughness of
the rock is high with a high peak to valley ratio, but we observe less-stiff
regions, due to HPAM retention on the rock represented in red, along the
peak and edges of the rock confirming the observations in Fig. 7a and b.
The force-distance curves in Fig. 7c were obtained from Fig. 7a, in the
region marked “x” and “”, which were fitted with the Hertz model to
obtain the Young Modulus values. Similar to the characterisation on the
calcite mineral, the automatic fits were obtained from the JPK software
and the manual fits were carried out to ensure proper fitting by the
software. The YM values were significantly higher for Estaillades mineral
surface than the adsorbed polymer layer in both automatic and manual
fits, suggesting that the region marked “x”, due to a lesser stiffness, is
definitely an adsorbed polymer layer than the region marked “”, which
is clearly the mineral surface. Also, close ranged YM values of ~ 25 MPa
and 20 MPa were estimated in the highest adsorbed polymer layer on
calcite surface and in the region marked “x” of the Estaillades surface as
shown in Tables 2 and 4 respectively. To further confirm our results of

8
E.M. Ekanem et al.
the different regions of polymer retention, and regions of Estaillades
mineral surface, force-distance profiles at different locations of Fig. 7a,
were carried out, and the results are shown in Fig. S2 – S4 of the sup-
plementary information.
4. Discussion
Calcite is positively charged at neutral pH [30], thus attractive elec-
trostatic interactions between Ca2þ on the calcite surface and negatively
charged COO groups in HPAM, will drive the adsorption of the polymer
onto the mineral surface by electrostatic interaction. The formation of
surface-polymer hydrogen bonds also makes a substantial contribution to
the adsorbed layer structures. Indicated in Fig. 2, three different ranges of
polymer layer thickness (low, medium and high), are spread over the
entire surface of the calcite mineral. Regions of low polymer layer
thickness between 3 and 10 nm have a continuous widespread adsorption
on calcite, in the form of small loops and trains. This is due to the high
percent hydrolysis; hence, increased amount of polyacrylic acid group on
the HPAM backbone; together with the high salinity of the brine. This
reduces the hydrodynamic size, and increases the density of the polymer
chain loops and trains close to the calcite surface, allowing for more
surface coverage [5]. The medium polymer adsorption layer of 25 nm
represent tails, while the high polymer adsorption layers of 35 nm are
representative of either longer length tails, entangled HPAM molecules or
weakly cross-linked HPAM microgels [74–77].
In the Estaillades carbonate rock, the degree of HPAM retention
increased due to rock roughness, which induced more retention by me-
chanical entrapment. In Fig. 7a, retention of HPAM occurred at different
regions, with the region marked “x” having an apparent thickness of ~
80 nm, as shown by the force-distance curves in Fig. 7c, albeit the dif-
ficulty in knowing the true height of polymer retention on rough mineral
surfaces. Consequently, there are other regions, where the apparent
thickness of the adsorbed polymer layer in Fig. 7a is larger, having
thickness of up to ~ 350 nm [78], we show the force-distance curves in
Fig. S2 and Fig. S3 of the supplementary information. In these larger
regions, we presume the effect of adsorption entanglement, as discussed
in the work of Grattoni et al. [25], for polymer adsorption during flow in
a capillary.
Furthermore, in places the polymer layer thickness was observed to
be larger in Estaillades, ranging between ~ 50 nm and ~ 350 nm in
Fig. 7a, compared to the thickness observed on calcite, ranging between
~ 3 nm and ~ 35 nm. Mechanical entrapment is likely to be the reason
for increased retention because during flow, more polymer chains may
get attached onto previously adsorbed polymer layer, increasing the
thickness of the polymer layer. This is captured in Fig. 7a in the region
marked “x”, which we believe represents one of the highest points on the
rock surface closest to the Viton sleeve used during core flood injection,
such that, some of the polymer chains would appear to become entangled
by hooking onto the loops of previously adsorbed polymer chain layer, as
the polymer solution flows through the rock. We also note that in some
areas, polymer seems to be present in the valleys between calcite grains,
see the regions indicated in Fig. 7a (labelled as microgel bridging), where
in the YM image of Fig. 7b, softer regions are detected which are likely to
be polymer solutions. Again, this may be due to the entanglement of
polymers in solution adsorbed directly on the mineral surface and
causing bridging. Therefore, these results suggest a situation where the
underlying adsorption induces more retention by mechanical entrapment
and has the capability of creating even larger sized adsorbed polymer
layers or aggregates that may form microgels in-situ of the porous media.
Consequently, this study shows that the thickness of an adsorbed polymer
layer on a flat mineral surface, which is between 3 and 40 nm, in com-
bination with more polymer retention caused by mechanical entrapment
is much of a challenge for low permeability carbonate rocks, because an
adsorbed polymer layer thickness of ~ 350 nm can fill the 0.69 μm pores
(if filled on both sides of the pore) in Estaillades [Fig. 3c] and definitely
lead to an impairment in the permeability.
9
JCIS Open 4 (2021) 100026
Table 4
Young Modulus with automatic and manual Hertz model fit for Estaillades
mineral surface and adsorbed polymer layer (HPAM-Ca) on Estaillades.
Hertz model fit Estaillades mineral Adsorbed polymer
Automatic 731 MPa 150 MPa
Manual 1300 MPa 20 MPa
5. Conclusion
Estaillades carbonate is known to possess a wide distribution of pore-
throat sizes, with nano and micro pores, and in this work, the dynamic
retention of HPAM has been studied to understand the mechanism of
polymer retention in the complex rock structure of Estaillades carbonate.
The retention of HPAM, which was first characterised on a flat calcite
surface, was found to be by adsorption, suggesting electrostatic in-
teractions between negatively charged polymer chains and the positively
charged calcite surface. The adsorption was arranged as trains, loops and
tails with the tails representing entangled polymer chains, as an extra
layer on the previously adsorbed layer on the flat calcite surface [74–77].
After flooding HPAM in Estaillades, a significant increase in the rock
pressure-drop was a strong indication that the rock structure had been
altered with the rock permeability decreasing by ~ 55%. The AFM study
revealed some structural changes in the rock, where larger sized polymer
aggregates of different layer thickness ranging between 50 and 350 nm
were formed in-situ of the porous media due to mechanical entrapment
as a result of the rock roughness [39].
Results show that the mechanism of polymer retention (adsorption by
electrostatic interaction) on a flat calcite surface also takes place in the
rock (because Estaillades contain 98% calcite mineral) with an additional
effect of mechanical entrapment, which leads to the formation of thicker
polymer layers within the rock pore space, which within narrow con-
straints of the rock, may have the potential to lead to pore blockage, or
partial blockage, and hence, lead to the permeability impairment
observed.
Therefore, this study provides a basis for the effective flooding of
polymer solutions in low permeability porous media structures like car-
bonate reservoirs, where the actual cause of the permeability impairment
is shown, to ensure that the consequence of polymer retention in reser-
voirs can be minimised.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
The author thanks Shell Global Solutions International, B.V.,
Amsterdam, The Netherlands for funding the project and grateful to the
Shell Digital Rocks team for the technical discussions and support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jciso.2021.100026.
References
[1] A.R. Al-Hashmi, P.F. Luckham, J.Y.Y. Heng, R.S. Al-Maamari, A. Zaitoun, H.H. Al-
Sharji, T.K. Al-Wehaibi, Adsorption of high-molecular-weight EOR polymers on
glass surfaces using AFM and QCM-D, Energy Fuels 27 (2013) 2437.
[2] S. Parsa, E. Santanach-Carreras, L. Xiao, D.A. Weitz, Origin of anomalous polymer-
induced fluid displacement in porous media, Phys. Rev. Fluids 5 (2020) 22001.
[3] J. Sheng, Modern Chemical Enhanced Oil Recovery: Theory and Practice, Gulf
Professional Publishing, 2010.
[4] K.S. Sorbie, Polymer Improved Oil Recovery, 1991.
E.M. Ekanem et al.
[5] V.H.S. Ferreira, R.B.Z.L. Moreno, Polyacrylamide adsorption and readsorption in
sandstone porous media, SPE J. 25 (2020) 497.
[6] E.M. Ekanem, S. Berg, S. De, A. Fadili, T. Bultreys, M. Rücker, J. Southwick,
J. Crawshaw, P.F. Luckham, Signature of elastic turbulence of viscoelastic fluid flow
in a single pore throat, Phys. Rev. E 101 (2020) 42605.
[7] E. Eguagie, S. Berg, J. Crawshaw, S. De, P. Luckham, Flexible coiled polymer
dynamics in a single pore throat with effects of flow resistance and normal stresses,
in: IOR 2019 – 20th European Symposium on Improved Oil Recovery, European
Association of Geoscientists & Engineers, 2019, pp. 1–11, 2019.
[8] P.M. Visakh, B. Oguz, G. Pic
o, Polyelectrolytes: Thermodynamics and Rheology,
first ed., Springer International Publishing, Cham, 2014.
[9] A.V. Dobrynin, R.H. Colby, M. Rubinstein, Scaling theory of polyelectrolyte
solutions, Macromolecules 28 (1995) 1859.
[10] R.H. Colby, M. Rubinstein, Polymer Physics, Oxford University Press, 2003.
[11] G. Fleer, M.A.C. Stuart, J.M.H.M. Scheutjens, T. Cosgrove, B. Vincent, Polymers at
Interfaces, Springer Science & Business Media, 1993.
[12] P.G. De Gennes, Polymers at an interface; a simplified view, Adv. Colloid Interface
Sci. 27 (1987) 189.
[13] D.A.Z. Wever, H. Bartlema, A.B.G.M. ten Berge, R. Al-Mjeni, G. Glasbergen, The
effect of the presence of oil on polymer retention in porous media from clastic
reservoirs in the sultanate of Oman, in: SPE EOR Conference at Oil and Gas West
Asia, Society of Petroleum Engineers, 2018.
[14] E. Unsal, A.B.G.M. ten Berge, D.A.Z. Wever, Low salinity polymer flooding: lower
polymer retention and improved injectivity, J. Petrol. Sci. Eng. 163 (2018) 671.
[15] P. Ghosh, K.K. Mohanty, Study of surfactant-polymer flooding in high-temperature
and high-salinity carbonate rocks, Energy Fuels 33 (2019) 4130.
[16] U. Alfazazi, N.C. Thomas, W. AlAmeri, E.W. Al-Shalabi, A.R. Shaik, An experimental
investigation of polymer performance in harsh carbonate reservoir conditions, in:
SPE Gas & Oil Technology Showcase and Conference, Society of Petroleum
Engineers, 2019.
[17] M.V. Bennetzen, S.F. Gilani, K. Mogensen, M. Ghozali, N. Bounoua, Successful
polymer flooding of low-permeability, oil-wet, carbonate reservoir cores, Soc. Pet.
Eng. - 30th Abu Dhabi Int. Pet. Exhib. Conf. ADIPEC 2014 Challenges Oppor. Next
30 Years 3 (2014) 1801.
[18] L. Rodriguez, B. Giovannetti, G. Dupuis, N. Gaillard, S. Jouenne, G. Bourdarot,
D. Morel, A. Zaitoun, B. Grassl, A new thermally stable synthetic polymer for harsh
conditions of Middle East reservoirs, SEG/AAPG/EAGE/SPE Res. Dev. Pet. Conf.
Exhib. 2018, RDP 2018 (2018) 16.
[19] M. Jabbar, R. Xiao, G.F. Teletzke, T. Willingham, A. Al Obeidli, A. Al Sowaidi,
C. Britton, M. Delshad, Z. Li, Polymer EOR assessment through integrated
laboratory and simulation evaluation for an offshore Middle East carbonate
reservoir, in: Day 3 Wed, November 14, 2018, SPE, 2018.
[20] D. Levitt, A. Klimenko, S. Jouenne, N. Passade-Boupat, P. Cordelier, D. Morel,
M. Bourrel, Designing and Injecting a chemical Formulation for a successful off-
shore chemical EOR Pilot in a high-temperature, high-salinity, low-permeability
carbonate field, SPE Improved Oil Recovery Conference. One Petro (2016), https://
doi.org/10.2118/179679-MS.
[21] D. Tiab, E.C. Donaldson, Petrophysics: Theory and Practice of Measuring Reservoir Rock
and Fluid Transport Properties, Fourth Edi, Gulf professional publishing, 2015.
[22] W.B. Gogarty, Mobility Control with Polymer Solutions, 1967.
[23] G.R. Quezada, R.E. Rozas, P.G. Toledo, Polyacrylamide adsorption on (1 0 1) quartz
surfaces in saltwater for a range of PH values by molecular dynamics simulations,
Miner. Eng. 162 (2021).
[24] A.N. Semenov, J. Bonet-Avalos, A. Johner, J.F. Joanny, Adsorption of polymer
solutions onto a flat surface, Macromolecules 29 (1996) 2179.
[25] D.W. Green, P.G. Willhite, Enhanced Oil Recovery, SPE Textbo, Texas, 1998.
[26] E.C.M. Vermolen, M. Pingo Almada, B.M. Wassing, D.J. Ligthelm, S.K. Masalmeh,
Low-salinity polymer flooding: improving polymer flooding technical feasibility
and economics by using low-salinity make-up brine, in: International Petroleum
Technology Conference, International Petroleum Technology Conference, 2014.
[27] H. Bessaies-Bey, J. Fusier, S. Harrisson, M. Destarac, S. Jouenne, N. Passade-Boupat,
F. Lequeux, J.B. d'Espinose de Lacaillerie, N. Sanson, Impact of polyacrylamide
adsorption on flow through porous siliceous materials: state of the art, discussion
and industrial concern, J. Colloid Interface Sci. 531 (2018) 693.
[28] L. Chiappa, A. Mennella, M. Ortolani, Role of polymer adsorption and of
petrophysical properties in watercut control treatments by polymer injection in gas
wells, in: 9th European Symposium on IOR vol. 4, 1997, pp. 1–11.
[29] H. Mahani, A.L. Keya, S. Berg, W.-B. Bartels, R. Nasralla, W.R. Rossen, Insights into
the mechanism of wettability alteration by low-salinity flooding (LSF) in
carbonates, Energy Fuels 29 (2015) 1352.
[30] A. Al-Khafaji, A. Neville, M. Wilson, D. Wen, Effect of low salinity on the oil
desorption efficiency from calcite and silica surfaces, Energy Fuels 31 (2017)
11892.
[31] D.V. Volodkin, A.I. Petrov, M. Prevot, G.B. Sukhorukov, Matrix polyelectrolyte
microcapsules: new system for macromolecule encapsulation, Langmuir 20 (2004)
3398.
[32] G. Chauveteau, K. Denys, A. Zaitoun, New insight on polymer adsorption under
high flow rates, in: SPE/DOE Improved Oil Recovery Symposium, Society of
Petroleum Engineers, 2002.
[33] C. Huh, E. A. Lange, and W. J. Cannella, Polymer Retention in Porous Media, SPE/
DOE Enhanced Oil Recovery Symposium.
[34] C.A. Browne, A. Shih, S.S. Datta, Pore-scale flow characterization of polymer
solutions in microfluidic porous media, Small 16 (2020) 1903944.
10
JCIS Open 4 (2021) 100026
[35] S. Biggs, Steric and bridging forces between surfaces bearing adsorbed polymer: an
atomic force microscopy study, Langmuir 11 (1995) 156.
[36] J. Klein, P.F. Luckham, Forces between two adsorbed poly (ethylene oxide) layers in
a good aqueous solvent in the range 0-150 nm, Macromolecules 17 (1984) 1041.
[37] J. Klein, P. Luckham, Forces between two adsorbed polyethylene oxide layers
immersed in a good aqueous solvent, Nature 300 (1982) 429.
[38] M. Kawaguchi, A. Takahashi, Molecular weight dependence of the thickness of the
polystyrene layer adsorbed onto a metal surface in good solvent conditions,
Macromolecules 16 (1983) 1465.
[39] C.A. Grattoni, P.F. Luckham, X.D. Jing, L. Norman, R.W. Zimmerman, Polymers as
relative permeability modifiers: adsorption and the dynamic formation of thick
polyacrylamide layers, J. Petrol. Sci. Eng. 45 (2004) 233.
[40] P.L.J. Zitha, G. Chauveteau, L. L
eger, Unsteady-state flow of flexible polymers in
porous media, J. Colloid Interface Sci. 234 (2001) 269.
[41] T.Q.C. Dang, Z. Chen, T.B.N. Nguyen, W. Bae, Investigation of isotherm polymer
adsorption in porous media, Petrol. Sci. Technol. 32 (2014) 1626.
[42] R.N. Manichand, R.S. Seright, Field vs laboratory polymer retention values for a
polymer flood in the tambaredjo field, in: SPE Improved Oil Recovery Symposium
All Days, Society of Petroleum Engineers, 2014.
[43] D. Broseta, F. Medjahed, J. Lecourtier, M. Robin, Polymer adsorption/retention in
porous media: effects of core wettability and residual oil, SPE Adv. Technol. Ser. 3
(1995) 103.
[44] B.A. Miller-Chou, J.L. Koenig, A review of polymer dissolution, Prog. Polym. Sci. 28
(2003) 1223.
[45] S. Yesufu-Rufai, M. Rücker, S. Berg, S.F. Lowe, F. Marcelis, A. Georgiadis,
P. Luckham, Assessing the wetting state of minerals in complex sandstone rock in-
situ by atomic force microscopy (AFM), Fuel 273 (2020).
[46] J.L. Alonso, W.H. Goldmann, Feeling the forces: atomic force microscopy in cell
biology, Life Sci. 72 (2003) 2553.
[47] H. Hertz, Ueber Die Berührung Fester Elastischer K€ orper, J. Für Die Reine Und
Angew. Math. 156 (1882), 1882.
[48] I.N. Sneddon, The relation between load and penetration in the axisymmetric
boussinesq problem for a punch of arbitrary profile, Int. J. Eng. Sci. 3 (1965) 47.
[49] D.C. Lin, E.K. Dimitriadis, F. Horkay, Robust strategies for automated AFM force
curve analysis–I. Non-adhesive indentation of soft, inhomogeneous materials,
J. Biomech. Eng. 129 (2007) 430.
[50] F. Rico, P. Roca-Cusachs, N. Gavara, R. Farr
e, M. Rotger, D. Navajas, Probing
mechanical properties of living cells by atomic force microscopy with blunted
pyramidal cantilever tips, Phys. Rev. E 72 (2005) 21914.
[51] D. Docheva, D. Padula, C. Popov, W. Mutschler, H. Clausen-Schaumann,
M. Schieker, Researching into the cellular shape, volume and elasticity of
mesenchymal stem cells, osteoblasts and osteosarcoma cells by atomic force
microscopy, J. Cell Mol. Med. 12 (2008) 537.
[52] V. Shubin, P. Linse, Effect of electrolytes on adsorption of cationic polyacrylamide
on silica: ellipsometric study and theoretical modeling, J. Phys. Chem. 99 (1995)
1285.
[53] A.V.P. Gurumoorthy, K.H. Khan, Polymers at Interfaces : biological and non-
biological applications, Recent Res. Sci. Technol. 3 (2011) 80.
[54] P. Linse, Adsorption of weakly charged polyelectrolytes at oppositely charged
surfaces, Macromolecules 29 (1996) 326.
[55] S. Wang, G. Li, Y. Li, J. Guo, S. Zhou, S. Yong, B. Pan, B. Bai, Adsorption of new
hydrophobic polyacrylamide on the calcite surface, J. Appl. Polym. Sci. 134 (2017)
45314.
[56] M. Ricci, P. Spijker, F. Stellacci, J.-F. Molinari, K. Voïtchovsky, Direct visualization
of single ions in the stern layer of calcite, Langmuir 29 (2013) 2207.
[57] G.J.C. Braithwaite, A. Howe, P.F. Luckham, Interactions between poly(ethylene
oxide) layers adsorbed to glass surfaces probed by using a modified atomic force
microscope, Langmuir 12 (1996) 4224.
[58] A.R. Al-Hashmi, P.F. Luckham, Characterization of the adsorption of high molecular
weight non-ionic and cationic polyacrylamide on glass from aqueous solutions
using modified atomic force microscopy, Colloids Surf. A Physicochem. Eng. Asp.
358 (2010) 142.
[59] R.E. Bulo, D. Donadio, A. Laio, F. Molnar, J. Rieger, M. Parrinello, “Site binding” of
Ca 2þ ions to polyacrylates in water: a molecular dynamics study of coiling and
aggregation, Macromolecules 40 (2007) 3437.
[60] Q. Liu, Q. Wang, L. Xiang, Influence of poly acrylic acid on the dispersion of calcite
nano-particles, Appl. Surf. Sci. 254 (2008) 7104.
[61] D.J. Sparks, M.E. Romero-Gonz
alez, E. El-Taboni, C.L. Freeman, S.A. Hall,
G. Kakonyi, L. Swanson, S.A. Banwart, J.H. Harding, Adsorption of poly acrylic acid
onto the surface of calcite: an experimental and simulation study, Phys. Chem.
Chem. Phys. 17 (2015) 27357.
[62] Y. Le Guen, F. Renard, R. Hellmann, E. Brosse, M. Collombet, D. Tisserand,
J.P. Gratier, Enhanced deformation of limestone and sandstone in the presence of
high PCO2 fluids, J. Geophys. Res. Solid Earth 112 (2007) 1.
[63] M. Andrew, H. Menke, M.J. Blunt, B. Bijeljic, The imaging of dynamic multiphase
fluid flow using synchrotron-based X-ray microtomography at reservoir conditions,
Transport Porous Media 110 (2015) 1.
[64] S. Berg, R. Armstrong, A. Georgiadis, H. Ott, A. Schwing, R. Neiteler, N. Brussee,
A. Makurat, M. Rucker, L. Leu, M. Wolf, F. Khan, F. Enzmann, M. Kersten, Onset of
oil mobilization and nonwetting-phase cluster-size distribution, Petrophysics 56
(2015) 15.
[65] C. Spurin, T. Bultreys, B. Bijeljic, M.J. Blunt, S. Krevor, Intermittent fluid
connectivity during two-phase flow in a heterogeneous carbonate rock, Phys. Rev. E
100 (2019) 43103.
E.M. Ekanem et al.
[66] W. Littmann, Polymer Flooding, Elsevier Science Publishers, 1988.
[67] R.S. Seright, How much polymer should Be injected during a polymer flood?, in: All
Days s. 2016-Janua SPE, 2016, pp. 11–13.
[68] A. Thomas, Essentials of Polymer Flooding Techniques, first ed., Wiley-Blackwell,
2019.
[69] T. Kurotori, C. Zahasky, S.A. Hosseinzadeh Hejazi, S.M. Shah, S.M. Benson, R. Pini,
Measuring, imaging and modelling solute transport in a microporous limestone,
Chem. Eng. Sci. 196 (2019) 366.
[70] F.A. Dullien, Porous Media Fluid Transport and Pore Structure, 1992.
[71] S. Yesufu-Rufai, F. Marcelis, A. Georgiadis, S. Berg, M. Rücker, J. van Wunnik,
P. Luckham, Atomic force microscopy (AFM) study of redox conditions in
sandstones: impact on wettability modification and mineral morphology, Colloids
Surf. A Physicochem. Eng. Asp. 597 (2020).
[72] M. Rücker, W.B. Bartels, G. Garfi, M. Shams, T. Bultreys, M. Boone, S. Pieterse,
G.C. Maitland, S. Krevor, V. Cnudde, H. Mahani, S. Berg, A. Georgiadis,
P.F. Luckham, Relationship between wetting and capillary pressure in a crude oil/
brine/rock system: from nano-scale to core-scale, J. Colloid Interface Sci. 562
(2020) 159.
11
JCIS Open 4 (2021) 100026
[73] C. Pierleoni, J.-P. Ryckaert, Deformation and orientation of flexible polymers in
solution under shear flow: a new picture for intermediate reduced shear rates,
Macromolecules 28 (1995) 5097.
[74] R.A.M. Hikmet, K.A. Narh, P.J. Barham, A. Keller, Adsorption-entanglement layers
in flowing high-molecular weight polymer solutions, in: Frontiers in Polymer
Science, Springer, 1985, pp. 32–43.
[75] K.A. Narh, P.J. Barham, R.A.M. Hikmet, A. Keller, Adsorption-entanglement layers
in flowing high molecular weight polymer solutions II. The effect of the nature of
the surface, Colloid Polym. Sci. 264 (1986) 507.
[76] P.J. Barham, R.A.M. Hikmet, K.A. Narh, A. Keller, Adsorption-entanglement layers
in flowing high molecular weight polymer solutions III: solution concentration and
solvent power, Colloid Polym. Sci. 264 (1986) 515.
[77] P.J. Barham, Adsorption-entanglement layers in flowing high molecular weight
polymer solutions IV. The rates of layer formation and decay, Colloid Polym. Sci.
264 (1986) 917.
[78] Y. Cohen, A.B. Metzner, Adsorption effects in the flow of polymer solutions through
capillaries, Macromolecules 15 (1982) 1425.