Subscriber access provided by La Trobe University Library

Article
MOLECULAR DYNAMICS METHODOLOGY FOR THE EVALUATION OF
THE CHEMICAL ALTERATION OF WETTABILITY WITH ORGANOSILANES
Ivan Moncayo-Riascos, Jennifer De León, and Bibian Alonso Hoyos
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.5b02074 • Publication Date (Web): 14 Jan 2016
Downloaded from http://pubs.acs.org on January 18, 2016

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street
N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 30 Energy & Fuels

1
2
3
4
5
6
7
8
MOLECULAR DYNAMICS METHODOLOGY
9
10
11
12 FOR THE EVALUATION OF THE CHEMICAL
13
14
15
16 ALTERATION OF WETTABILITY WITH
17
18
19
20
21
ORGANOSILANES
22
23
24
25
Ivan Moncayo-Riascos1*, Jennifer de León1, Bibian A. Hoyos1
26
27
28
29 (1) Universidad Nacional de Colombia-Sede Medellín, Facultad de Minas, Departamento de
30
31 Procesos y Energía. (idmoncay@unal.edu.co)
32
33
34
35 KEYWORDS: Wettability alteration, organosilane, contact angle, molecular dynamics.
36
37
38 ABSTRACT: In this work, a methodology to evaluate and represent the wettability alteration
39
40 phenomenon caused by the action of organosilane surfactants using molecular dynamics
41
42
43 simulations is presented. This methodology is based on four major steps: i) the tuning of the
44
45 energetic parameter of the surface potential to achieve an adequate description of the initial
46
47
wettability state; ii) the representation of the adsorption/reaction of the surfactant on the surface;
48
49
50 iii) the evaluation of the coverage degree of the surface and the alteration of the wettability
51
52 promoted by the surfactant; and iv) the prediction of the alteration of the wettability of the
53
54
55
surface in contact with a hydrocarbon phase. To evaluate this methodology, a case study is
56
57 presented, in which the variation of the contact angle of water drops on a glass surface by the
58
59
60
ACS Paragon Plus Environment
1
 Energy & Fuels Page 2 of 30

1
2
3
action of the surfactant C8F17CH2CH2Si-[O-CH2CH3]3 is determined. The methodology results in
4
5
6 an adequate reproduction of the contact angle of water drops on untreated surfaces (24.7°) and
7
8 enables the calculation of the adsorption energy of individual molecules on the surface (44.93
9
10
11
kJ/mol). Additionally, it was found that with a surfactant surface concentration of 0.76 µmol/m2,
12
13 the water contact angle on the surfactant-covered surface is properly reproduced (94°). This
14
15 methodology is sufficiently robust to extend the results obtained for the water system to the
16
17
18 evaluation of the contact angle of a system where n-heptane is the fluid phase (60.7°). All these
19
20 results are in excellent agreement with experimental findings. These procedures have shown that
21
22 the presence of surfactant molecules reduces the affinity of the fluid phase (water or n-heptane)
23
24
25 with the surface, increasing the compactness and the height of the resulting drop.
26
27
28 Introduction. Formation damage due to condensates is one of the most dramatic factors
29
30
31
contributing to the production loss of a gas reservoir. The obstruction of the pore channels
32
33 available for gaseous hydrocarbon extraction greatly increases the capillary forces, sometimes
34
35 causing changes in the natural rock wettability and originating a stronger restriction on the
36
37
38 mobility of production fluids. In some cases, this phenomenon can also lead to an increase in the
39
40 irreducible water saturation, which reduces gas permeability1,2.
41
42
43 There is a substantial amount of literature reports, both based on field and laboratory work, that
44
45
46 quantify the formation damage associated with condensate banks. Productivity losses vary
47
48 between 20 and 80% for field data3–8. These cases suggest that viscous forces alone are not able
49
50
to improve gas production due to the magnitude of capillary forces generated by the formation of
51
52
53 condensate banks.
54
55
56
57
58
59
60
ACS Paragon Plus Environment
2
Page 3 of 30 Energy & Fuels

1
2
3
Laboratory tests performed in adequate cores show reductions in the relative permeability of up
4
5
6 to 95% and a reduction in the capillary number for rocks of both high and low permeability. The
7
8 extent of the blockage due to the condensate depends indirectly on a combination of factors,
9
10
11
including the fluid properties, formation characteristics, flow rate and pressure. The difficulty in
12
13 quantifying all these factors arises from the fact that accurate laboratory tests involving
14
15 condensates are extremely difficult to design and perform9.
16
17
18
19 Among the many methods proposed to restore gas production rates after the formation of
20
21 condensate banks, the chemical alteration of the wettability of the formation around the wellbore
22
23 appears to be a promising alternative. In general, polymers or surfactant agents can be added to
24
25
26 fulfill this mission6,7. Numerous studies have focused on surfactants such as polyacrylates and
27
28 fluorinated polymers with high molecular weight, reaching the conclusion that fluorinated
29
30
31
compounds are ideal for wettability alteration projects because of their low interfacial tension,
32
33 high thermal stability and amphiphilic molecular structure10–15.
34
35
36 The majority of works available in the literature oriented to the study of the alteration of natural
37
38
39 wettability are of an experimental nature9,16,17. These studies allow establishing the feasibility of
40
41 altering the wettability of the porous media but do not offer any insights on the alteration
42
43 mechanism. In this sense, recent work has focused on theoretical studies using Monte Carlo18–21
44
45
46 and molecular dynamics (MD)22–34 simulations. These types of studies allow evaluating, from a
47
48 molecular point of view, relevant aspects of the phenomena, such as the adsorption
49
50
configurations at the equilibrium state and the quantification of the different energetic
51
52
53 contributions (Van der Waals interactions, electrostatic forces, dipoles, etc.)35. This knowledge is
54
55 crucial when identifying the most important features in the performance of a wettability
56
57
58
59
60
ACS Paragon Plus Environment
3
 Energy & Fuels Page 4 of 30

1
2
3
alteration treatment in a porous media and also enables different scenarios for reservoir condition
4
5
6 testing, which is often a very expensive and difficult task35.
7
8
9 A great number of the wettability alteration studies using molecular simulation techniques aim at
10
11
12 evaluating the contact angle between a drop of fluid and the surface of interest. Those studies
13
14 conducted on a silica surface28,30,32,34,36,37 are particularly relevant to the oil industry, as these
15
16 surfaces can properly represent the sandstone formations28,31,36,38 that commonly occur in
17
18
19 condensate gas reservoirs39,40. However, the reported results for contact angles measured
20
21 experimentally and calculated using molecular simulation techniques are significantly different.
22
23 Experimentally determined contact angle values for water drops on quartz surfaces are between 0
24
25
26 and 90°41. This dispersion of the results seems to be associated with the cleaning protocols of the
27
28 surface. When rigorous cleaning procedures are enforced, the contact angle varies between 0 and
29
30
31
30°41. Theoretical studies using molecular simulation techniques place this value above 60° on
32
33 the same surface28,34,36. This discrepancy between theoretical and experimental results can be
34
35 explained by multiple reasons. Among them, the difference in the scale of the measurement is a
36
37
38 strong one, as the line and contact radius are used to explain the difference in results42–44. The
39
40 difference can also be attributed to the difficulty of properly representing, in a molecular
41
42 simulation, all the morphological features of a real surface (rugosity, surface substituents,
43
44
45 crystalline defects, fractures, etc.). To solve this last difficulty, it has been proposed to tune the
46
47 energetic parameter of the potential that describes the molecular interaction between the surface
48
49
and the fluid that forms the drop36. This implies finding an effective energetic parameter that
50
51
52 includes all the features of the surface that are not explicitly included in the simulation to
53
54 reproduce the contact angle values found experimentally.
55
56
57
58
59
60
ACS Paragon Plus Environment
4
Page 5 of 30 Energy & Fuels

1
2
3
Organosilane surfactants are considered excellent candidates as treatments for the alteration of
4
5
6 the natural wettability of silica surfaces. These structures have the advantage of being able to
7
8 form bonds with the silica atoms available at the surface, which has a strong impact when
9
10
11
considering the durability of the proposed treatment9,16.
12
13
14 In this work, a methodology based on molecular dynamics simulations for evaluating the
15
16 alteration of wettability caused by the implementation of organosilane structures on organic or
17
18
19 inorganic surfaces (such as minerals, fillers, metals and cellulose) is presented, where the
20
21 interaction between the surface and surfactant can be described by bond formation or hydrogen
22
23 bonding. This methodology is based on four major actions: first, the energetic parameter of the
24
25
26 interaction potential of the surface must be tuned to achieve a proper description of the initial
27
28 wettability state. This is done by evaluating the contact angle of a drop of water on the surface in
29
30
31
the absence of surfactant molecules. Second is the representation of the adsorption/reaction of
32
33 the surfactant molecules on the surface. Third, the coverage degree is evaluated, as is the
34
35 wettability alteration caused by the surfactant action, as evidenced by contact angle
36
37
38 measurements of the water drop on the surfactant-covered surface. Finally, the alteration of the
39
40 wettability of the surface is predicted, using n-heptane as the fluid phase.
41
42
43 The methodology here described can be applied, in general, to study the alteration of wettability
44
45
46 due to a large number of species that integrate members of the organosilane structure family,
47
48 applied on surfaces on which they can adsorb or form bonds. As an illustration of this
49
50
methodology, the study of the alteration of the wettability of glass surfaces by implementing the
51
52
53 partially fluorinated organosilane agent 1H,1H,2H,2H-perfluorodecyltriethoxysilane,
54
55 C8F17CH2CH2Si-[O-CH2CH3]3 (in short, perfluorodecyl),16 is here presented.
56
57
58
59
60
ACS Paragon Plus Environment
5
 Energy & Fuels Page 6 of 30

1
2
3
Model. The model used for the representation of the glass surface (eq. 1) is the well-known 10-
4
5
6 4-3 potential45,46. This potential is only dependent on the perpendicular distance, z, between the
7
8 atoms of the liquid molecules and the surface.
9
10

‫ۍ‬ ‫ې‬
11

‫ێ‬ 2 ߪ ଵ଴ ߪ ସ √2 ‫ۑ‬
12
ܷ(௥೔ೕ) = 2ߨ߳ ‫ ێ‬ቀ ቁ − ቀ ቁ − ଷ‫ۑ‬
5 ‫ݖ‬ ‫ݖ‬
13
‫ێ‬ ‫ ݖ‬0.61 ‫ۑ‬
(1)
3൬ + ൰
14
15
‫ۏ‬ ߪ √2 ‫ے‬
16
17
18
19 Where σ and ϵ are the LJ length and energy parameters for the interaction of the solid with the
20
21 liquid.
22
23
24
25 The 10-4-3 potential results from a 3D representation of the solid interacting with the fluid
26
27 through a LJ potential. The expression is obtained by integration of energy contributions of the
28
29 atoms at the plane of the surface, considered infinitely extended, on an infinitely thick slab of
30
31
32 solid. The atoms at the plane of the solid in direct contact with the fluid contributes the terms
33
34 proportional to z−10 and z−4 and the term proportional to z−3 is from the bulk solid. This potential
35
36
precalculates the energy of interaction that infinite layers of solid exerted on the fluid.
37
38
39
40 Because the potential 10-4-3 does not consider the corrugation potential (has no dependence on
41
42 horizontal position) and does not consider fractures and surface defects, is required to tune the
43
44
45 energetic parameter to reproduce the initial wettability state.
46
47
48 The SPC-E47 potential was used to represent the water molecules (eq. 2). This potential has three
49
50 interaction points and considers the water molecule to be a rigid structure, with a Lennard-Jones
51
52
53 term to evaluate repulsion interactions, a Van der Waals term for the oxygen atoms, and a
54
55 coulombic term for the electrostatic interactions due to the localized charges in the two hydrogen
56
57
atoms and the oxygen atom. The SPC-E potential is widely used in these types of studies28,34,36.
58
59
60
ACS Paragon Plus Environment
6
Page 7 of 30 Energy & Fuels

1
2
ଷ ଷ
ߪ௢௢ ଵଶ ߪ௢௢ ଺ 1 ‫ݍ‬௜ ‫ݍ‬௝
3
ܷ(௥೚೚ ,௤೔ೕ) = 4ߝ௢௢ ቆ൬ ൰ − ൬ ൰ ቇ + ෍෍
4
‫ݎ‬௢௢ ‫ݎ‬௢௢ 4ߨߝ௢ ‫ݎ‬௜௝
5 (2)
6 ௜ୀଵ ௝ୀଵ
7
8
9 To represent the n-heptane molecule, which was used to represent the liquid hydrocarbon phase,
10
11
12 the TraPPE-UA48 potential was used, as it is widely used to model linear and branched alkanes,
13
14 alcohols, and aldehydes (eq. 3). This potential considers hydrogen atoms implicitly, and thus, the
15
16 n-heptane molecular structure is represented using CH3 and CH2 groups. According to this
17
18
19 model, n-heptane has no partial charge distribution, so the intermolecular interactions are only of
20
21 a Van der Waals nature. For the intramolecular interactions, the bonds, angles and dihedral
22
23
contributions are considered.
24
25
ଵଶ ଺
ߪ௜௝ ߪ௜௝ ݇ఏ
26

ܷ(௥೔ೕ,ఏ,௟) = ෍ ෍ 4ߝ௜௝ ൭ቆ ቇ −ቆ ቇ ൱+ ෍ ‫ݑ‬ௗ௜௛ (߶) + ෍ (ߠ − ߠ௘௤ )ଶ

27
‫ݎ‬௜௝ ‫ݎ‬௜௝ 2
28
29 ௗ௜௛௘ௗ௥௔௟௦ ௔௡௚௟௘௦
30 (3)
31
݇௟
+ ෍ (݈ − ݈௘௤ )ଶ
2
32
௕௢௡ௗ௦
33
34
35
36
37 To represent the perfluorodecyl surfactant, the CVFF (Consistent Valence Force Field) potential
38
39 was used, as it has shown good results for fluorocarbonated structures49. This potential is a
40
41
function of the Van der Waals and coulombic intermolecular interactions, as well as of the
42
43
44 bonds, angles and dihedral intramolecular interactions (eq. 4). The equivalent charges method
45
46 (Qeq)50 was used to assign partial charges to each atom in the surfactant structure (figure S1 of
47
48
49
the supporting information). The partial charges for the atoms change at the end of the simulation
50
51 of the adsorption/reaction of the surfactant on the surface, as will be explained later on.
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
7
 Energy & Fuels Page 8 of 30

1
2
௖௛௔௥௚௘௦ ଵଶ ଺
‫ݍ‬௜ ‫ݍ‬௝ ߪ௜௝ ߪ௜௝
3

ܷ൫௥೔ೕ,௤೔ೕ,ఏ,௟൯ = ෍ + ෍ ෍ 4ߝ௜௝ ൭ቆ ቇ ቆ ቇ ൱+ ෍ ‫ݑ‬ௗ௜௛ (߶1)

4
5
4ߨߝ଴ ‫ݎ‬௜௝ ‫ݎ‬௜௝ ‫ݎ‬௜௝
6 ௜௝ ௗ௜௛௘ௗ௥௔௟௦
7 (4)
݇ఏ ݇௟
+ ෍ (ߠ − ߠ௘௤ )ଶ + ෍ (l − lୣ୯ )ଶ
8

2 2
9
௔௡௚௟௘௦ ௕௢௡ௗ௦
10
11
12
13
14 All parameters of the intermolecular and intramolecular potentials for the perfluorodecyl, water
15
16 and n-heptane are reported in tables S1 to S3 of the supporting information.
17
18
19
20
Methodology. As was previously mentioned, the methodology here proposed is based on four
21
22 steps. First, the energetic parameter ϵs, used to evaluate the interaction between the surface and
23
24 the liquid phase, must be tuned. To achieve this, the contact angle made by a drop of water on
25
26
27 the surface was evaluated, using values varying from 0.01 to 1.5 kcal/mol for that parameter. A
28
29 simulation box was then constructed with dimensions of 240x240x140 Å, and 5 832 water
30
31 molecules were placed inside, occupying an initial cubic volume of 55.8 Å on each side in
32
33
34 vacuum (Figure S2 of the supporting information). In this study, the air atmosphere was
35
36 neglected, as it has been previously established that there is no significant difference for the
37
38
calculation of the contact angle of water drops on silica surfaces in vacuum and in an air
39
40
41 atmosphere, even for pressures up to 150 bar36. Periodic boundary conditions were used in the x
42
43 and y directions. The wall potential 10-4-3 was placed at the bottom edge of the z direction, and
44
45
46
at the upper edge, a reflective wall was placed to maintain a constant number of molecules. A
47
48 total of 10 ns of simulation time was calculated, using a timestep of 1.0 fs in a canonical
49
50 ensemble (NVT) at 298 K.
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
8
Page 9 of 30 Energy & Fuels

1
2
3
To evaluate the contact angle of the drops, a procedure previously reported by Fan51 was used.
4
5
6 This procedure was developed for non-symmetrical drops and quantifies the contact angle from
7
8 the geometry of the drop (equations 5 to 7):
9
10
ℎ
11
ܿ‫ = ߠݏ݋‬1 −
ܴ
12 (5)
13
14
15
16 ܵ = ߨ‫ ݎ‬ଶ (6)
17
18
ℎ ܵ
19
ܴ= +
2 2ߨℎ
20 (7)
21
22
23
24 Where θ is the contact angle between the drop and the surface, and h and r are the drop height
25
26
27
and radius, respectively.
28
29
30 To obtain more accurate results, the drop geometry was measured at three different simulation
31
32 times during the last two nanoseconds (8, 9 and 10 ns). At each time point, four planes were
33
34
35 taken to determine the height and diameter of the drop (Figure 1).The average values were then
36
37 calculated for the geometric dimensions of the drop and the contact angle with the surface.
38
39
40
Using an interpolation of the results for the contact angle at different values of ϵs, the
41
42
43 experimental value of the water drop contact angle is used to determine the appropriate value of
44
45 the adjusted energetic parameter ϵs*. Finally, to verify the effect of the size of the system on the
46
47
48
value of the contact angle of water drops, additional simulations using 19 683 and 125 000 water
49
50 molecules were conducted, using the adjusted parameter ϵs*.
51
52
53 Once the energetic parameter is properly tuned, the second step is to simulate the
54
55
56 adsorption/reaction of the surfactant molecule on the surface. To achieve this, an initial NPT
57
58
59
60
ACS Paragon Plus Environment
9
 Energy & Fuels Page 10 of 30

1
2
3
simulation was conducted to relax the surfactant structure (at 298 K and 1 atm). A single
4
5
6 perfluorodecyl molecule was placed in a simulation box for 1 ns with a timestep of 0.01 fs, with
7
8 periodic boundary conditions. Next, an equilibration simulation of the surfactant on the surface
9
10
11
was conducted: 225 replicas of the relaxed structure of the perfluorodecyl were placed in a
12
13 simulation box of dimensions 168x168x112 Å, with the wall potential placed at the bottom edge
14
15 of the box, as in the previous step, using the adjusted energy parameter ϵs*. The number of
16
17
18 surfactant molecules is consistent with the number of molecules forming a complete monolayer
19
20 (1 ML) of molecules on the surface, according to the area occupied by a single molecule. The
21
22 perfluorodecyl molecules were initially located 4 Å above the surface, and a NVT simulation
23
24
25 was conducted for 2 ns, using a timestep of 1 fs.
26
27
28 From the previous configuration and to simulate the reaction of the perfluorodecyl surfactant on
29
30
31
the surface, a value of 140 kcal/mol was assigned to the energetic interaction parameter between
32
33 the surface and the oxygen atoms (similar to the energy of a Si-O bond). Finally, the CH2-CH3
34
35 chains still attached to the oxygen atoms were removed, and the partial charges of the remaining
36
37
38 atoms in the adsorbed molecule were recalculated. From this point on, the oxygen atoms were
39
40 considered fixed, while the rest of the atoms in the perfluorodecyl molecule were considered
41
42 mobile. In this manner, the restriction of movement generated by the formation of the Si-O bond
43
44
45 was included in the simulations. Figure 2 shows a schematic of the process of the coverage of the
46
47 external layer of a silica surface by the perfluorodecyl surfactant. Figure 2 (a) illustrates the
48
49
strong interaction between the oxygen atoms in the perfluorodecyl structure and the silica atoms
50
51
52 on the outer layer of the surface. The reaction proceeds by the loss of the organic substituents
53
54 attached to the oxygen atoms and the formation of the Si-O bond. Figure 2 (b) shows a schematic
55
56
57
58
59
60
ACS Paragon Plus Environment
10
Page 11 of 30 Energy & Fuels

1
2
3
of the final configuration of the perfluorodecyl molecule on the surface, as well as the
4
5
6 recalculated partial charge distribution.
7
8
9 With 225 molecules of perfluorodecyl on the simulated surface, a coverage degree of 0.94
10
11
12 µmol/m2 is achieved. This value is within the experimental values of the coverage degree for
13
14 different functional groups (phenyl, trimethyl and octadecyl) on silica surfaces (0.56-1.83
15
16 µmol/m2)52. Because the obtained coverage degree does not consider side interactions or steric
17
18
19 repulsions that may occur in the real system, the value of the coverage degree might be
20
21 overestimated. To verify this, the same procedure was performed using only 112 perfluorodecyl
22
23 molecules, which represents 50% of the monolayer (0.5 ML).
24
25
26
27 To evaluate the coverage degree of the surface and the alteration of the wettability caused by the
28
29 surfactant (third step in the methodology), 5 832 water molecules were added to the adsorbed
30
31
32
surfactant system, and the contact angle of the water drop was calculated from the geometry of
33
34 the drop following the same procedure as used in the first step. Using an interpolation between
35
36 the values obtained with 1 ML, 0.5 ML, and the initial simulation in the absence of surfactant,
37
38
39 the real coverage degree was evaluated to reproduce the experimental results for the contact
40
41 angle.
42
43
44 Taking advantage of the predictive power of molecular dynamics techniques, the ability of the
45
46
47 perfluorodecyl surfactant to generate lipophobic surfaces was evaluated. Using the obtained
48
49 adjusted parameter ϵs* and the calculated coverage degree, the contact angle was evaluated for n-
50
51
52
heptane drops on the surface (fourth step). In this case, 5 832 n-heptane molecules were placed in
53
54 a simulation box of dimensions 480x313x172 Å.
55
56
57
58
59
60
ACS Paragon Plus Environment
11
 Energy & Fuels Page 12 of 30

1
2
3
In all simulations, the SHAKE53 algorithm was used to maintain the structural features of the
4
5
6 water, perfluorodecyl and n-heptane molecules. To evaluate the long-range electrostatic
7
8 interactions, the pppm (particle-particle-particle-mesh)54 method was used. The Lorentz-
9
10
11
Berthelot mixing rules were used to obtain the molecular interaction parameters for atoms of
12
13 different natures. A Nose-Hoover thermostat and barostat were used to control the temperature
14
15 and pressure, respectively. Simulations were conducted using a parallelized code of the
16
17
18 LAMMPS55 package. The images used to determine the drop geometry were generated using
19
20 VMD56 visualization software.
21
22
23 Results and discussion. The results obtained from molecular simulation studies using the
24
25
26 proposed methodology are presented in this section. Contact angle values for water drops in the
27
28 absence and presence of perfluorodecyl surfactant are compared with the experimental
29
30
31
measurements made for these systems, using ionized water and meticulously washed and dried
32
33 glass surfaces16.
34
35
36 For the tuning of the energetic parameter of the surface ϵs, the drop geometry was evaluated
37
38
39 (height and radius) and the contact angle for the system was calculated using values from 0.01 to
40
41 1.5 kcal/mol for ϵs with 5 832 water molecules.
42
43
44 Figure 3 shows the results of the contact angle of the water drop over the entire range of ϵs. As
45
46
47 expected, the water molecules are more drawn to the surface as the energetic parameter ϵs
48
49 increases. On the one hand, taking ϵs = 0.01 kcal/mol, a contact angle of 168° is obtained,
50
51
52
indicating that the water molecules do not wet the surface. On the other hand, taking ϵs = 1.5
53
54 kcal/mol results in a water monolayer (complete wetting of the surface) and a contact angle of
55
56 2.3°. Taking an intermediate value of the energetic parameter, ϵs = 0.75 kcal/mol, a contact angle
57
58
59
60
ACS Paragon Plus Environment
12
Page 13 of 30 Energy & Fuels

1
2
3
of 67° is obtained, which is near to a neutral wettability state. These results were adjusted to a
4
5
6 third-degree polynomial function (dotted line). Using the experimental value of the water contact
7
8 angle on the glass surface of 23.8°16 and interpolating with the polynomial-adjusted function, it
9
10
11
is found that a value of ϵs* = 1.02 kcal/mol is adequate to describe the initial wettability state.
12
13 The relatively high value of ϵs* resulting from this tuning is the product of the hydrophilic
14
15 character of the surface, and is the required to represent the affinity of the water molecules to the
16
17
18 untreated surface.
19
20
21 Figure 4 shows the geometrical configuration of the water drop after 10 ns of simulation time,
22
23 using the adjusted interaction parameter of the glass surface ϵs*. The geometric dimensions of the
24
25
26 water drop were h = 20.2 Å ± 1.6 and r = 92.2 Å ± 2.3. This gives a contact angle of 24.7° ± 1.7,
27
28 which shows that this tuning procedure presented here effectively allows finding the energetic
29
30
31
parameter that properly describes the initial wettability state. This procedure can be easily
32
33 applied to the wettability study of other surfaces.
34
35
36 With the energetic parameter ϵs* suitably tuned, the adsorption of a single water molecule on the
37
38
39 surface was also evaluated, and the adsorption energy was determined to be 44.93 kJ/mol. This
40
41 result is in excellent agreement with the adsorption energy of a single water molecule on an
42
43 amorphous silica surface (45 kJ/mol)36 and is in reasonable agreement with the results published
44
45
46 by Du et al.57, which vary between 48 kJ/mol and 98 kJ/mol for a water molecule on H-
47
48 terminated and pure silica clusters.
49
50
51
52
To verify the effect of the size of the system on the contact angle results, additional simulations

were conducted using 19 683 and 125 000 water molecules and the adjusted parameter ߳௦∗ found
53
54
55
56 in the previous step. The procedure was similar to that used in the case of 5 832 molecules,
57
58
59
60
ACS Paragon Plus Environment
13
 Energy & Fuels Page 14 of 30

1
2
3
except that the box dimensions were recalculated to properly host the larger water drops. The
4
5
6 contact angle for the system with 19 683 water molecules was found to be 22.6° ± 1.8, while for
7
8 the system with 125 000 water molecules, it was found to be 21.3° ± 1.6 (Figure S3 of the
9
10
11
supporting information). These results allow establishing that the contact angle variations are
12
13 within the statistical uncertainty for the three system sizes evaluated and that simulation results
14
15 using 5 832 water molecules are an acceptable compromise between the computational cost of
16
17
18 the simulation and the accuracy of the results. This finding is consistent with the results obtained
19
20 in similar molecular simulation works on water drop formation on flat graphite surfaces58–60 and
21
22 PTFE (for which a contact angle variation of less than 5° for simulations using from 8 000 up to
23
24
25 20 000 water molecules61 was reported). Additionally, the contact angle calculated for water
26
27 drops on amorphous or crystalline polymeric surfaces has insignificant variations for drops with
28
29
a radius greater than 33 Å62 (all radii measured in this study were larger than 38 Å).
30
31
32
33 It is expected that representing the surface as a structureless solid (Eq. 1), have a rather small
34
35 effect on the results obtained: the fluid density profiles63 and the amount of fluid adsorbed at the
36
37
38 surface64 are practically not affected when a wall potential is used. On the other hand, the results
39
40 of adsorption energy of water on the surface and the small variation of contact angles calculated
41
42 for different sizes of the system, provide evidence that, once the potential energy parameter is
43
44
45 tuned, the 10-4-3 potential is a good representation of interaction energy and space irregularities
46
47 that may arise on the surface.
48
49
50
Figure 5 shows the results for the reaction simulation of the surfactant on the silica surface using
51
52
53 225 and 112 perfluorodecyl molecules. Figure 5 (a) shows that the coverage with 225
54
55 perfluorodecyl molecules (which is consistent with a monolayer with a surface density of 0.94
56
57
58
µmol/m2) exhibits very little free glass surface available for direct interaction with the water
59
60
ACS Paragon Plus Environment
14
Page 15 of 30 Energy & Fuels

1
2
3
molecules. On the other hand, the coverage using only 112 perfluorodecyl molecules (consistent
4
5
6 with a surface density of 0.42 µmol/m2) exhibits a larger available surface area, which allows
7
8 more direct adsorption of water molecules on the surface. Perfluorodecyl adsorbed molecules
9
10
11
exhibit mostly a configuration parallel to the plane of the surface, although a small proportion of
12
13 perpendicularly adsorbed molecules can also be appreciated. The obtained coating is
14
15 characterized by having the silane group in contact with the surface (representing the formation
16
17
18 of the Si-O bond), and displaying a portion of the fluorinated chains to water molecules. The
19
20 representation of the surface using the 10-4-3 potential results in a coating configuration which is
21
22 very close to that obtainable using an atomistic representation: because perfluorodecyl is a
23
24
25 nonionic surfactant, the net effect of surface-perfluorodecyl electrostatic interactions is near zero.
26
27 Therefore, the predominant interaction is of Van der Waals type, which is well represented by
28
29
the wall potential used.
30
31
32
33 The geometric dimensions of the drop of 5 832 water molecules on 225 perfluorodecyl
34
35 molecules adsorbed on the surface (1 ML) were h = 51.2 Å ± 4.3 and r = 38.2 Å ± 2.3. With
36
37
38 these dimensions, the contact angle was found to be 106.5° ± 7.2. This result gives a total
39
40 deviation of 14.6% with respect to the experimental value of 93°16. The contact angle obtained
41
42 using a coverage of 0.5 ML (0.47 µmol/m2) was 74.2° ± 1.9, which represents an
43
44
45 underestimation of 20.1% compared to the experimental value.
46
47
48 To find the coverage degree of the surface that accurately reproduces the measured value of the
49
50
contact angle for this system, the results using 1 ML, 0.5 ML, and the simulation in the absence
51
52
53 of surfactant were interpolated, as shown in Figure 6. It was found that 182 perfluorodecyl
54
55 molecules, consistent with a coverage of 0.81 ML or 0.76 µmol/m2, are adequate to reproduce
56
57
58
the experimental value of the contact angle.
59
60
ACS Paragon Plus Environment
15
 Energy & Fuels Page 16 of 30

1
2
3
Figure 7 illustrates the configuration of the water drop after 10 ns of simulation time, using a
4
5
6 coverage degree of 0.81 ML (0.76 µmol/m2). The geometric measurements of the water drop
7
8 were h = 43.9 Å ± 1.5 and r = 40.9 Å ± 0.8 (these measurement were taken after the system
9
10
11
reached the equilibrium, as seen in the supporting information), which give a total contact angle
12
13 of 94° ± 1.96. This value is in excellent agreement with the experimental findings (93°)16. For
14
15 the simulations with the surfactant, the water molecules are at greater distance from the surface,
16
17
18 which causes the simplification of considering a non-atomistic wall potential have even minor
19
20 effect on their spatial configuration.
21
22
23 To evaluate the effect of the surfactant on the spatial distribution of the water molecules, the
24
25
26 radial distribution function (RDF) and the density profile in the z direction (the direction
27
28 perpendicular to the surface plane) were calculated. The RDF results for the water molecules in
29
30
31
the absence and presence of the perfluorodecyl surfactant layer are reported in Figure 8. For both
32
33 cases, the peak associated with the nearest neighbors is at roughly the same distance (≅ 2.7 Å).
34
35 However, in the case of the system with perfluorodecyl, a higher density of neighbors around
36
37
38 each water molecule is registered, which indicates that the presence of the surfactant molecules
39
40 generates a more compact distribution of the molecules in the water drop.
41
42
43 Figure 9 shows the density profile of water molecules in the direction perpendicular to the
44
45
46 surface (z direction). As seen from the figure, the system in the absence of perfluorodecyl
47
48 exhibits two well-defined adsorption layers of water molecules in the region near the surface and
49
50
51
less definite layers at a greater distance. This is evidence of the high affinity of the water
52
53 molecules to the surface. In the case of the system with perfluorodecyl, the two adsorption layers
54
55 are also observable, but they are less definite than in the case without surfactant. This behavior is
56
57
58 due to a reduction of the affinity of the water molecules to the treated surface. Additionally, it is
59
60
ACS Paragon Plus Environment
16
Page 17 of 30 Energy & Fuels

1
2
3
noticeable that the water molecules are at greater distances than in the previous case, which is
4
5
6 explained by an increase in the height of the water drop in the presence of the perfluorodecyl
7
8 surfactant.
9
10
11
12 The results of the contact angle, density profile and RDF for the water systems are consistent and
13
14 show that the presence of the surfactant reduces the affinity of the water molecules to the treated
15
16 surface. This reduced affinity and the wettability alteration produced can be explained by the
17
18
19 difference in the energy of interaction of water molecules with each surface: the interaction
20
21 energy of water with the untreated surface is high (characterized by ϵs* = 1.02 kcal/mol),
22
23 compared with the interaction between the water molecules themselves (0.16 kcal/mol), which
24
25
26 explains why the water molecules are preferentially locate on the solid surface rather than in the
27
28 droplet bulk, and the small contact angles. On the other hand, with the treated surface, water
29
30
31
interacts mainly with fluorine, carbon and hydrogen atoms of perfluorodecyl, with which the
32
33 interaction energy is much lower (between 0.04 and 0.07 kcal/mol). This reduced interaction
34
35 energy with the treated surface generates a more favorable energy configuration for the water
36
37
38 molecules to be located within the drop, thus causing a higher density of neighbors around each
39
40 molecule (increase in the compactness and a greater height of the water drop).
41
42
43 Seizing the predictive power of molecular simulation techniques, the results obtained for the
44
45
46 energetic parameter of the surface ϵs* and the surface concentration of the covering, previously
47
48 tuned with experimental information for water drops on glass surfaces, were then used to
49
50
evaluate the contact angle for n-heptane drops on the same surface treated with perfluorodecyl
51
52
53 (fourth step). The aim of these simulations was to verify if the results obtained here are
54
55 sufficiently strong to study wettability alteration with other fluid phases.
56
57
58
59
60
ACS Paragon Plus Environment
17
 Energy & Fuels Page 18 of 30

1
2
3
For this purpose, 5 832 n-heptane molecules were placed in a simulation box of dimensions
4
5
6 480x313x172 Å. Because the size of the simulation box is larger than in the case of the water
7
8 molecules, 1 260 perfluorodecyl molecules were necessary to achieve the same surface
9
10
11
concentration of 0.76 µmol/m2.
12
13
14 An illustration of the contact angle for n-heptane molecules in the presence of perfluorodecyl is
15
16 shown in Figure 10. The drop dimensions in this case were h = 62 Å ± 1.8 and r = 105.7 Å ±
17
18
19 3.1, which gives a contact angle of 60.7° ± 2.1 (these measurement were taken after the system
20
21 reached the equilibrium, as seen in figure S4 of the supporting information). This result is in
22
23 excellent agreement with the experimental results of 62/59°, obtained with dynamic studies of
24
25
26 the contact angle of n-heptane on quartz surfaces covered with a surfactant with the same
27
28 structure as perfluorodecyl (C8F17CH2CH2Si-[Cl]3)65.
29
30
31
32
Figure 11 shows the density profile of n-heptane in the direction perpendicular to the surface. In
33
34 this case, the behavior of the n-heptane system is very similar to that in the water case, as the
35
36 surface without treatment exhibits an adsorbed layer of hydrocarbon molecules that is displaced
37
38
39 when the treatment with perfluorodecyl is applied. Additionally, after treatment, the presence of
40
41 n-heptane molecules is found at greater distances, which is consistent with the increase in the
42
43 height of the drop.
44
45
46
47 Similar to the case of water, the system with n-heptane exhibits a clear alteration of the spatial
48
49 distribution of n-heptane molecules on the surface due to the presence of the surfactant. This new
50
51
52
distribution is associated with the compactness of the drop and the reduction of the affinity of the
53
54 hydrocarbon molecules to the surface.
55
56
57
58
59
60
ACS Paragon Plus Environment
18
Page 19 of 30 Energy & Fuels

1
2
3
In Figure 12 the deviations between model and experimental contact angle values are
4
5
6 compared. For the case of systems with water on the untreated surface (diamonds), it can be seen
7
8 that for all three sizes of the system (5 832, 19 683 and 125 000 water molecules), the values of
9
10
11
the contact angle obtained are statistically the same. Also the height/radius ratio of the drops
12
13 generated in the three systems has a very small variation (0.22, 0.27 and 0.26, respectively),
14
15 which allows to establish that the structure of the three drops are equivalent. These results show
16
17
18 that it is not necessary to represent all chemical and structural characteristics of the surface to
19
20 obtain an adequate representation of the contact angle of liquid droplets and that by simply
21
22 tuning the energetic parameter of the surface potential it can be found an effective parameter
23
24
25 representing all the details of roughness, electrical charge and atomic structure of the surface,
26
27 making it possible to obtain excellent representations of macroscopic contact angles at a lower
28
29
computational cost.
30
31
32
33 For the two systems in the presence of perfluorodecyl (water and n-heptane), the contact angle
34
35 values are in excellent agreement with experimental measurements. This means that the
36
37
38 representation of the reaction of the perfluorodecyl with the surface (i.e. the formation of the Si-
39
40 O bond) and the model for surfactant-liquid interaction, allow for a correct description of the
41
42 effects of coating on the surface wettability (which was validated with degrees of coverage and
43
44
45 the contact angles measured experimentally). In summary, the alteration of wettability caused by
46
47 the perfluorodecyl is explained by the reduction of the liquid-surface interaction energy: the
48
49
fluorinated part of the surfactant molecule is in contact with the liquid phase (water or n-heptane)
50
51
52 strongly reducing the interaction with the solid. This reduction in the interaction of the liquid
53
54 with the surface is due to the chemical properties of perfluorodecyl, as explained above.
55
56
57
58
59
60
ACS Paragon Plus Environment
19
 Energy & Fuels Page 20 of 30

1
2
3
The accuracy of the contact angle results calculated in the simulations here presented, are
4
5
6 evidence that the methodology proposed in this work is adequate for implementation as a
7
8 prediction tool in wettability alteration studies with different substances than those employed in
9
10
11
this study for tuning the energetic parameter of the surface and the organosilane coverage degree.
12
13
14 Conclusions. In this work, a methodology for the evaluation of the alteration of wettability by
15
16 the action of organosilanes on surfaces was presented, using as an example the implementation
17
18
19 of the surfactant C8F17CH2CH2Si-[O-CH2CH3]3 on glass surfaces. The results show that the
20
21 proposed methodology is adequate, as it permits a proper representation of the real system,
22
23 which consists of a complex surface (with heterogeneities, rugosity, crystalline defects, fractures,
24
25
26 etc.) on which liquid drops are deposited. This methodology is based on the determination of the
27
28 effective interaction parameter of the surface, the representation of the adsorption/reaction of the
29
30
31
surfactant on the surface, and the estimation of the coverage degree of the surface with the
32
33 surfactant molecules.
34
35
36 The tuning procedure for the energetic interaction parameter allows calculating the adsorption
37
38
39 energy of the individual water molecules on the surface (44.93 kJ/mol) and representing the
40
41 initial wettability state by calculating the contact angle for water molecules (24.7°), with high
42
43 agreement with experimental results. Additionally, it was found that the measure of the contact
44
45
46 angle of the water drops does not vary drastically when the number of molecules is increased and
47
48 that with sizes near 6 000 molecules, the desired values of contact angles can be reproduced.
49
50
51
52
The representation of the adsorption/reaction of the surfactant on the surface and the
53
54 determination of the coverage degree are adequate to represent the alteration of wettability and to
55
56 study the redistribution of the liquid molecules caused by the action of the surfactant. In the case
57
58
59
60
ACS Paragon Plus Environment
20
Page 21 of 30 Energy & Fuels

1
2
3
study here presented, it was found that for a surface concentration of the surfactant of 0.76
4
5
6 µmol/m2, the experimental value of the contact angle for the covered surface is closely
7
8 reproduced (94°). These procedures were sufficient to determine that the presence of surfactant
9
10
11
reduces the affinity between the water molecules and the glass surface, leading to compactness
12
13 and an increase in the height of the water drop. This behavior explains the alteration of the
14
15 natural wettability state of the surface. This insight into the phenomena is vital to the process of
16
17
18 proposing alternative treatment options for wettability alteration or improvement of the
19
20 performance of existing ones.
21
22
23 It was possible to verify that this methodology is sufficiently robust to use the results obtained
24
25
26 for the energetic parameter of the surface and the coverage degree, adjusted using experimental
27
28 results for water systems, in the study of the contact angle of n-heptane drops on the surface. It
29
30
31
was found that the surface without the treatment exhibits a layer of adsorbed n-heptane
32
33 molecules, which is later displaced by the action of the surfactant. This leads to an evident
34
35 increase in the height of the drop. The results here obtained by molecular simulations of n-
36
37
38 heptane on the glass surface (60.7°) are in excellent agreement with experimental measurements.
39
40 These results also indicate that organosilane surfactants have the ability to produce both
41
42 hydrophobic and lipophobic surfaces.
43
44
45
46 Finally, from the good approximation of the results here obtained, it can be said that the
47
48 methodology here proposed can be applied as a prediction tool for the oil industry, for instance,
49
50
in the evaluation of contact angles and interfacial tension under reservoir conditions. These
51
52
53 predictions are possible due to the selected features of molecular simulation studies.
54
55
56 FIGURES
57
58
59
60
ACS Paragon Plus Environment
21
 Energy & Fuels Page 22 of 30

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Figure 1. Measurement of the geometry of the water drop (top: upper view indicating the planes
27
28 for the drop diameter measurement; bottom: front view indicating the measurement of the drop
29
30
31
height).
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
22
Page 23 of 30 Energy & Fuels

1
2
3
Figure 2. Schematic of the reaction of the perfluorodecyl on silica surfaces. (a) Interaction
4
5
6 between oxygen atoms in the surfactant and silica atoms on the surface. (b) Final configuration
7
8 and partial charge distribution of the perfluorodecyl after reacting with the surface, generating
9
10
11
the Si-O bond.
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29 Figure 3. Glass-water contact angle as a function of ϵs. Marks correspond to the simulation
30
31 results, and the dotted line is the polynomial-adjusted function.
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
23
 Energy & Fuels Page 24 of 30

1
2
3
Figure 4. Water drop configuration (5 832 molecules), after 10 ns of simulation time, using ϵs* =
4
5
6 1.02 kcal/mol. Top: upper view with the planes used to measure the radius of the drop. Bottom:
7
8 front view of the water drop and contact angle.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Figure 5. Coverage of the silica surface after the reaction with the perfluorodecyl surfactant.
30
31
32 Top: upper view using 0.94 µmol/m2 (a) and 0.42 µmol/m2 (b) of perfluorodecyl. Bottom: front
33
34 view of the same configurations.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49 Figure 6. Contact angle of the water molecule as a function of the number of molecules of
50
51
52 perfluorodecyl on the surface.
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
24
Page 25 of 30 Energy & Fuels

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 Figure 7. Water drop configuration (5 832 molecules) on 182 perfluorodecyl molecules
26
27
28
adsorbed on the surface (0.76 µmol/m2) after 10 ns of simulation time using ϵs* = 1.02 kcal/mol.
29
30 Top: upper view. Bottom: front view.
31
32
33
34
35
36
37
38
39
40
41
42
43 Figure 8. RDF for the water molecules in the absence and presence of perfluorodecyl surfactant.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
Figure 9. Density profile for water molecules in the absence and presence of perfluorodecyl.
59
60
ACS Paragon Plus Environment
25
 Energy & Fuels Page 26 of 30

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Figure 10. n-Heptane drop configuration (5 832 molecules) on 1 260 perfluorodecyl molecules
27
28
adsorbed on the surface (0.76 µmol/m2) after 10 ns of simulation time with ϵs* =1.02 kcal/mol.
29
30
31 Top: upper view. Bottom: front view.
32
33
34
35
36
37
38
39
40
41
42
43
44 Figure 11. Density profile of n-heptane in the absence and presence of perfluorodecyl.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
26
Page 27 of 30 Energy & Fuels

1
2
3
Figure 12. Model and experimental contact angles for the system with water on the untreated
4
5
6 surface (diamonds), water in the presence of perfluorodecyl (square) and n-heptane in the
7
8 presence of perfluorodecyl (triangle).
9
10
11
12
13 AUTHOR INFORMATION
14
15
16 Corresponding Author
17
18 *Ivan Moncayo-Riascos
19
20
21
22 Universidad Nacional de Colombia, Carrera 80 No 65-223 - Núcleo Robledo, Medellín -
23
24 Colombia.
25
26
e-mail: idmoncay@unal.edu.co
27
28
29
30 Telephone number: (57 4) 4255280
31
32
33
34
35
36 AUTHOR CONTRIBUTIONS
37
38 The manuscript was written through contributions of all authors. All authors have given approval
39
40
41 to the final version of the manuscript.
42
43
44
45
46 ACKNOWLEDGMENT
47
48
49 The authors would like to thank Ecopetrol S.A., Equion Energía Limited and Hocol through their
50
51 Formation Damage program for financial support (Acuerdo de cooperación "AC" 04 derivado
52
53
del convenio marco No. 5211385), and to the Universidad Nacional de Colombia - Sede
54
55
56 Medellín for logistical support.
57
58
59
60
ACS Paragon Plus Environment
27
 Energy & Fuels Page 28 of 30

1
2
3
REFERENCES
4
5
6 (1) Franco, C. A.; Restrepo, A.; Acosta, L. G.; Junca, E. SPE Int. 2006, SPE 98136, 1–11.
7
8 (2) Al-Anazi, H. A.; Solares, J. R. SPE Int. 2005, SPE 93210, 1–11.
9 (3) Afidick, D.; Kaczorowski, N. J.; Bette, S. SPE Int. 1994, SPE 28749, 73–80.
10
11 (4) van de Leemput, L. E. C.; Bertram, D. A.; Bentley, M. R.; Gelling, R. SPE Int. 1995, SPE
12 30757, 252–259.
13
14 (5) Delavarmoghaddam, A.; Mirhaj, S. A.; Zitha, P. L. J. SPE Int. 2009, SPE 122225, 1–12.
15
16 (6) Adibhatla, B.; Mohanty, K. K.; Berger, P.; Lee, C. J. Pet. Sci. Eng. 2006, 52, 227–236.
17
18 (7) Kumar, V.; Pope, G. A.; Sharma, M. M. SPE Int. 2006, SPE 100529, 1–9.
19
20
(8) Nagarajan, N. R.; Honarpour, M. M.; Sampath, K. SPE Int. 2006, SPE 101517, 1–10.
21 (9) Li, K.; Firoozabadi, A. SPE Reserv. Eval. Eng 2000, 3 (2), 139–149.
22
23 (10) Marion, P.; Beinert, G.; Juhué, D. Appl Polym Sci 1997, 64 (12), 2409–2419.
24
25 (11) Marion, P.; Beinert, G.; Juhué, D. Macromolecules 1997, 30 (1), 123–129.
26
27 (12) Zhang, B.; Zhang, Z.; Wan, X.; Hu, C.; Ying, S. Acta Polym. Sin. 2003, 6, 906–909.
28 (13) Huang, J.; Meng, W.; Qing, F. J. Fluor. Chem. 2007, 128 (12), 1469–1477.
29
30 (14) Yu, Z.; Zhang, L.; Lin, Y.; Guo, Y.; Wang, Y. Chem. Res. Appl. 2004, 16 (5), 671–672.
31
32 (15) Lin, Y.; Yu, Z. Nat. Gas Chem. Ind. 2009, 30 (2), 75–77.
33
34 (16) Fuller, M.; Lloyd, T.; Geddes, J. Surface-modifying agents for wettability modification.
35 U.S. Patent 7,921,911, 2011.
36
37 (17) Fahes, M.; Firoozabadi, A. SPE Int. 2005, SPE 96184, 1–14.
38
39
(18) Biscay, F.; Ghoufi, A.; Lachet, V.; Malfreyt, P. J. Chem. Phys. 2009, 131 (12), 124707.
40 (19) Arnold, C.; Ulrich, S.; Stoll, S.; Marie, P.; Holl, Y. J. Colloid Interface Sci. 2011, 353 (1),
41
188–195.
42
43 (20) Howes, A. J.; Radke, C. J. Langmuir 2007, 23 (23), 11580–11586.
44
45 (21) Zehl, T.; Wahab, M.; Schiller, P.; Mo, H. Langmuir 2009, 25 (11), 2090–2100.
46
47 (22) Stephenson, B. C.; Beers, K. J. J. Phys. Chem. B 2006, 110 (39), 19393–19405.
48
49 (23) Yan, H.; Yuan, S.-L.; Xu, G.; Liu, C.-B.; Cheng-Bu, L. Langmuir 2010, 26 (13), 10448–
50 10459.
51
52
(24) Shi, W.-X.; Guo, H. J. Phys. Chem. B 2010, 114 (19), 6365–6376.
53 (25) Rahbar, M.; Ayatollahi, S.; Ghatee, M. H. SPE Int. 2010, SPE 132616, 1–10.
54
55 (26) Domínguez, H. J. Phys. Chem. B 2011, 115 (43), 12422–12428.
56
57 (27) Zhou, M.; Li, K. SPE Int. 2011, SPE 140131, 1–12.
58
59
60
ACS Paragon Plus Environment
28
Page 29 of 30 Energy & Fuels

1
2
3
(28) Iglauer, S.; Mathew, M. S.; Bresme, F. J. Colloid Interface Sci. 2012, 386 (1), 405–414.
4
5 (29) Li, X.; Ross, D. a; Trusler, J. P. M.; Maitland, G. C.; Boek, E. S. J. Phys. Chem. B 2013,
6 117 (18), 5647–5652.
7
8 (30) Zhong, J.; Wang, P.; Zhang, Y.; Yan, Y.; Hu, S.; Zhang, J. Energy 2013, 59, 295–300.
9
10 (31) de Lara, L. S.; Michelon, M. F.; Miranda, C. R. J. Phys. Chem. B 2012, 116 (50), 14667–
11 14676.
12
13 (32) Tummala, N. R.; Shi, L.; Striolo, A. J. Colloid Interface Sci. 2011, 362 (1), 135–143.
14
15 (33) Fan, H.; Resasco, D. E.; Striolo, A. Langmuir 2011, 27 (9), 5264–5274.
16
17
(34) McCaughan, J.; Iglauer, S.; Bresme, F. Energy Procedia 2013, 37, 5387–5402.
18 (35) Ungerer, P.; Lachet, V.; Tavitian, B. Oil Gas Sci. Technol. - Rev. l’IFP 2006, 61 (3), 387–
19
20
403.
21 (36) Zambrano, H. a.; Walther, J. H.; Jaffe, R. L. J. Mol. Liq. 2014, 198, 107–113.
22
23 (37) Ho, T. A.; Argyris, D.; Papavassiliou, D. V.; Striolo, A.; Lee, L. L.; Cole, D. R. Mol.
24 Simul. 2011, 37 (3), 172–195.
25
26 (38) Bagherzadeh, S. A.; Englezos, P.; Alavi, S.; Ripmeester, J. a. J. Phys. Chem. B 2012, 116
27 (10), 3188–3197.
28
29 (39) Alvarado, V.; Manrique, E. Energies 2010, 3 (9), 1529–1575.
30
31 (40) Wang, Y.; Xu, H.; Yu, W.; Bai, B.; Song, X.; Zhang, J. Pet. Sci. 2011, 8 (4), 463–476.
32
33
(41) Iglauer, S.; Salamah, A.; Sarmadivaleh, M.; Liu, K.; Phan, C. Int. J. Greenh. Gas Control
34 2014, 22, 325–328.
35
36
(42) Méndez-Vilas, A.; Jódar-Reyes, A. B.; González-Martín, M. L. Small 2009, 5 (12), 1366–
37 1390.
38
(43) Boinovich, L.; Emelyanenko, A. Adv. Colloid Interface Sci. 2011, 165 (2), 60–69.
39
40 (44) Soeno, T.; Inokuchi, K.; Shiratori, S. Appl. Surf. Sci. 2004, 237 (1-4), 539–543.
41
42 (45) Magda, J. J.; Tirrell, M.; Davis, H. T. J. Chem. Phys. 1985, 83 (4), 1888–1901.
43
44 (46) Magda, J. J.; Tirell, M.; Davis, H. T. J. Chem. Phys. 1986, 84 (5), 2901.
45
46 (47) Berendsen, H.; Grigera, J.; Straatsma, T. J. Phys. Chem. 1987, 91 (24), 6269–6271.
47 (48) Martin, M. G.; Siepmann, J. I. J. Phys. Chem. B 1998, 5647 (97), 2569–2577.
48
49 (49) Senapati, S.; Berkowitz, M. L. J. Phys. Chem. B 2003, 107 (47), 12906–12916.
50
51 (50) Rappé, A. K.; William, A. G. J. Phys. Chem. 1991, 95 (8), 3358–3363.
52
53 (51) Fan, C. F.; Cagin, T. J. Chem. Phys. 1995, 103 (20), 9053–9061.
54
55
(52) Weston, J. S.; Jentoft, R. E.; Grady, B. P.; Resasco, D. E.; Harwell, J. H. Ind. Eng. Chem.
56 Res 2015, 54 (16), 4274–4284.
57
58
(53) Andersen, H. C. J. Comput. Phys. 1983, 52 (1), 24–34.
59
60
ACS Paragon Plus Environment
29
 Energy & Fuels Page 30 of 30

1
2
3
(54) Hockney, R. W. .; Eastwood, J. W. Computer Simulation Using Particles; Hilger, A., Ed.;
4
5 New York, 1989.
6 (55) Plimpton, S. J. Comput. Phys. 1995, 117, 1–19.
7
8 (56) Humphrey, W.; Dalke, A.; Shulten, A. J. Mol. Graph. 1996, 14 (1), 33–38.
9
10 (57) Du, M. H.; Wang, L. L.; Kolchin, A.; Cheng, H. P. Eur. Phys. J. D 2003, 24 (1), 323–326.
11
12 (58) Scocchi, G.; Sergi, D.; D’Angelo, C.; Ortona, A. Phys. Rev. E 2011, 84 (6), 061602.
13
14
(59) Sergi, D.; Scocchi, G.; Ortona, A. Fluid Phase Equilib. 2012, 332, 173–177.
15 (60) Ingebrigtsen, T.; Toxvaerd, S. J. Phys. Chem. C 2007, 111 (24), 8518–8523.
16
17 (61) Chen, S.; Wang, J.; Ma, T.; Chen, D. J. Chem. Phys. 2014, 140 (11), 114704.
18
19 (62) Hirvi, J. T.; Pakkanen, T. A. J. Chem. Phys. 2006, 125 (14), 144712.
20
21 (63) Toxvaerd, S. J. Chem. Phys. 1981, 74 (3), 1998.
22
(64) Striolo, A.; Chialvo, A. a.; Cummings, P. T.; Gubbins, K. E. Langmuir 2003, 19 (11),
23
24 8583–8591.
25
(65) Pellerite, M. J.; Wood, E. J.; Jones, V. W. J. Phys. Chem. B 2002, 106 (18), 4746–4754.
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment
30