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Article

Mechanistic Study of Wettability Alteration of Quartz Surface

Induced by Nonionic Surfactants and Interaction between
Crude Oil and Quartz in Presence of Sodium Chloride Salt
Achinta Bera, Kissmathulla S, KEKA OJHA, T. Kumar, and Mandal Ajay
Energy Fuels, Just Accepted Manuscript Publication Date (Web): 25 Apr 2012
Downloaded from http://pubs.acs.org on April 25, 2012

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Energy & Fuels

Mechanistic Study of Wettability Alteration of Quartz Surface Induced by

Nonionic Surfactants and Interaction between Crude Oil and Quartz in
Presence of Sodium Chloride Salt
Achinta Bera, Kissmathulla S, Keka Ojha, T. Kumar and Ajay Mandal*
Department of Petroleum Engineering, Indian School of Mines, Dhanbad-826004, India

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ABSTRACT
Experimental investigations have been conducted in order to elucidate the mechanism
responsible for wettability alteration of quartz surface in presence of nonionic surfactants. The
wettability alteration has been verified by measuring the contact angle on quartz-crude oildistilled water system by systematic variation of surfactants, temperature and water salinity. In
all cases, contact angle decreases with elapse of time. As ethylene oxide number of nonionic
surfactant increases the initial equilibrium contact angle decreases. Results also show that as
temperature increases contact angle decreases due to reduction of oil viscosity. With increasing
water salinity contact angle decreases up to a certain salinity and then increases. This salinity
may be termed as optimal salinity for the system. Scanning electron microscopy analysis shows
the roughness of quartz surface. Infrared spectroscopy analysis of quartz sample indicates the
presence of Si-O group. Fourier transform infrared (FTIR) spectroscopy and acid number
analysis of crude oil suggest the acidic nature of the oil. Critical micelle concentrations of the
surfactants were also measured by surface tension method. The lowest surface tension value
achieved by Tergitol 15-S-12 is 28 mNm-1.

Keywords: Wettability alteration, Contact angle, Nonionic surfactant, Quartz, Water salinity

1. INTRODUCTION
Wettability of solid surfaces can be modified by introducing surface active agents or surfactants
and ionic substances into the solid-liquid systems and also by regulating the thermodynamic
parameters such as temperature1-3. According to Craig4, wettability is defined as the tendency of
one fluid to spread on or adhere to a solid surface in presence of other immiscible fluids.
Wettability of a solid surface relates directly to the solid-fluids and fluid-fluid interactions. The
interaction between two immiscible phases implies the interfacial energy. Attraction between the
substrates causes lower interfacial energy, and repulsion forces result in higher energy surface.
The interfacial forces in a three-phase system relate to one another in a famous equation known
as Youngs law5-7,
(1)

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where is contact angle and values indicate the interfacial tensions between solid-water (
solid-oil (

), and water-oil (

),

) interfaces. Figure 1 illustrates the situation how the oil drop

will reside on solid surface in presence of another immiscible liquid such as water. The Youngs
equation is valid at equilibrium condition for ideal state of a perfectly smooth, chemically
homogeneous, rigid, insoluble, and nonreactive surface.
Understanding the mechanism of spreading of a liquid over a solid substrate is crucial in several
engineering applications. Some of these applications are enhanced oil recovery (EOR),
lubrication emulsion, and film coating as in pulp and paper, photographic emulsions, and plastic.
In oil recovery process wettability alteration of reservoir rocks by surfactants is very much
important as it controls the multiphase flow problems regarding the oil migration from source
rocks to primary production, capillary pressure, imbibitions, drainage, dispersion, irreducible
water saturation, residual oil saturation and EOR. The factors which can play major role on the
reservoir rock wettability are the presence of surface active agent in the crude oil, type of mineral
surfaces in the reservoir, presence of salts in formation fluids, temperature, pH value of brine and
cementing clay. Sodium chloride (NaCl) salt causes an increased tendency to form monolayer,
which decreases liquid-liquid interfacial tension and an increased tendency to accumulate the
surface active agents produced from crude oil; these two trends acting together to alter
wettability of solid surfaces. An interesting property that enables the surfactants to alter
wettability of solid surfaces is amphiphilicity. The amphiphilicity of surfactants makes them to
form a multitude of different structures in solution and to adsorb at interfaces8. Such an
adsorption makes the surface of solids more nonpolar. The formation of the adsorbed film on
polar or ionic solid surface causes changes in the surface free energy of the solid, solid-liquid
interfacial free energy, surface tension of water and decreases the spreading coefficient. Due to
presence of polyethylene oxide chain in nonionic surfactants in which a hydrophobic part is
attached are widely used in technological applications9-12. The hydrophilic-lipophilic
balance (HLB) of the nonionic surfactant also plays an important role on wettability alteration of
solid surface. However, there are many studies available dealing with wettability of solids and
the acid-base intermolecular interactions in the presence of the surfactants but till now proper
explanation is not satisfactory3, 13-21.
Reservoir rocks as a whole may not show the same wettability. It depends upon the reservoir
rock properties, oil chemistry and water salinity of the system. The rocks may be oil-wet, water3
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wet or intermediate-wet. This wetting behavior depends upon interaction between rock and crude
oil. In case of silica surface, the surface charge of silica in water is positive at low pH but
negative at high ph value. The silica surface remains negatively charges at neutral pH and hence
the affinity to adsorb organic acids which are naturally occurring in the oil. A number of
investigators have been working on wettability alteration by adsorption from crude oil22-30.
Different experimental methods such as contact angle measurement, Li and Horne method,
Amott wettability index (AWI), USBM (U.S. Bureau of Mines) wettability index for quantitative
results and imbibitions rate, flotation, microscopic examination, capillary pressure curves,
reservoir logs, permeability, saturation relationship, nuclear resonance, and dye adsorption for
qualitative results have been used to measure the surface wettability of a system31-34. For most of
the cases, the contact angle method (sessile drop method) is commonly used to measure the
wetting properties of the solid surface with respect to a liquid in presence of another immiscible
liquid. Water salinity also affects the contact angle on quartz-crude oil-distilled water system.
The effect of water salinity on contact angle using different concentration of NaCl have been
studied by several researchers35,36 and they reported that contact angle can be noticeably
influenced by variation of NaCl concentration. Temperature has an important effect on the
contact angle of solid/crude oil/water system due to change in viscosity and density of oil and
this effect introduces an additional force on the oil drop.
In the present paper, wettability alteration of quartz surface has been determined by sessile drop
method to study the effect of different nonionic surfactants, water salinity, and temperature.
Effect of ethylene oxide number (EON) on contact angle between solid-liquid systems has also
been examined. Scanning electron microscopy (SEM) images were taken for surface morphology
study. Infrared spectroscopy analysis of quartz has been performed to know the presence of Si-O
group. Critical micelle concentrations of the employed nonionic surfactants were also measured
by surface tension method. Physicochemical properties of crude oil have been studied by
viscosity, asphaltene content, acid number, API gravity measurements and FTIR of crude oil has
been done to summarize the information about the chemical groups that are present.

2. EXPERIMENTAL SECTION
2.1. Materials used

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Four nonionic surfactants such as Tergitol 15-S-5, Tergitol 15-S-7, Tergitol 15-S-9 and Tergitol
15-S-12 were procured from Sigma-Aldrich, Germany. The details physicochemical properties
of the surfactants have been given in Table 1 and all the surfactants are 99.9 % pure in nature.
Sodium Chloride (NaCl) with 99% purity was used for preparation of different concentration of
brines and it was supplied by Qualigens Fine Chemical, India. Quartz was used as solid surfaces
for contact angle measurement. The crude oil sample collected from Ahmadabad oil field, India
was used in the experiment. Reverse osmosis water from Millipore water system (Millipore SA,
67120 Molshein, France) was used for preparation of solutions.

2.2. Apparatus and Methodology

2.2.1. Characterization of Crude oil and Quartz
The crude oil sample used for this work was characterized by measurement of its density,
viscosity, API gravity, total acid number. Density of the crude oil was determined by pycnometer
and from the density data API gravity was calculated. Viscosity of the crude oil at different
temperature was measured by Rheometer (Physica MC1). The asphaltenes content was
determined by n-pentane precipitation. The physicochemical properties of the crude oil are listed
in Table 1. FTIR analysis of the crude oil was also done to determine the functional groups that
are present.
Microscopic images of quartz sample were taken in a sophisticated SEM (Hitachi S-3400N
Scanning Electron Microscope) for morphological studies of quartz surface. Infrared spectra of
the quartz and crude oil samples were recorded between 400 and 4000 cm-1 using KBr pellet
techniques on a Buck Scientific infrared (IR) spectrophotometer, M500. The spectra were
interpreted using the Ganz and Kalkreuth method.

2.2.2. Measurement of Surface Tension

Measurement of surface tension is very much useful supplementary test method for
determination of critical micelle concentration (CMC). It is particularly useful when only very
small quantities of an experimental surfactant are available. In the present study surface tension
of the different concentrated surfactant solutions were measured by a programmable tensiometer
(Kruss GmbH, Germany, model: K20 EasyDyne) under atmospheric pressure by the Du Noy
ring method. During the measurement, the experimental temperature was maintained at 298 K.
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The platinum ring was thoroughly cleaned with acetone and flame-dried before each
measurement. In all cases the standard deviation did not exceed 0.1 mN/m.

2.2.3. Measurement of Contact Angle

The schematic diagram of experimental set up of contact angle method used to measure the
wettability of solid surfaces is shown in Figure 2. The contact angle was measured by placing
crude oil droplet (constant volume of 20 l) in direct contact with the flat horizontal solid surface
of quartz which is hanging from the clamp of the stand attached with a glass rod and the solid
surface and the droplet of oil were completely submerged under the water. After submerging the
attached system, photographs were taken few minutes later on reaching the equilibrium. The
angle between the solid surface and oil-water interface was measured on all enlarge photograph
of the drop. Photographs were taken by a high resolution and magnification digital camera (Sony
DSC-HX100V). The quartz was cleaned in boiling concentrated nitric acid and then washed with
distilled water and store in that distilled water. The dynamic contact angle was measured in
different time intervals for all the solutions. To test the temperature effect on the contact angle
water bath was used and the system was placed in the water bath and measurements were carried
out at different temperatures.

3. RESULTS AND DISCUSSION

3.1. Characterization of Crude Oil
The chemical groups present in the crude oil were determined by FTIR spectra. FTIR spectra of
the crude oil used in the present study were recorded between 400 and 4000 cm-1. In the FTIR
spectrum, certain groups of chemical bonding give rise to bands at or near the same frequency,
regardless of the structure of the rest of the molecule. The absorption bands of aliphatic C-H
bonds, with additional bands originating from groups containing aromatics, oxygen, sulfur, and
nitrogen, usually dominate the spectra of crude oils37,38. A typical FTIR spectrum of the crude
oil is shown in Figure 3. The prominent functional groups present in the oil are given in Table 3.
The major functional groups identified on the FTIR spectra of the oil include C-H stretching of
the saturate (2923 and 2852 cm-1), C-H deformation of the saturate (1460 cm-1), and C-H
symmetric deformation of the saturate (1376 cm-1). The peak at 722 cm-1 indicates the presence
of long-chain alkyl groups, (CH2) n, with n > 4, in saturates. The region between 1800 and 1640
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cm-1 corresponds to carbonyl groups such a carboxylic acids. The absorption at 1643 cm-1 is due
to vibration of the carboxylic acid group present in the crude oil. The absorption at the wave
number range of 3700-3100 cm-1 is due to the presence of a small amount of phenolic functional
groups39. There are weak bands at 1590-1470 cm-1 because of the presence of C=C ring
stretching. The presence of acidic groups in crude oil has been identified by FTIR analysis of
crude oil. This is also supported by the total acid number (0.040 mg of KOH/g) of the crude oil.

3.2. Surface Morphology and Quantitative Analysis of Quartz Sample

SEM images in Figures 4 (a) and (b) show the morphology of clean quartz plate before aging
with surfactant at 500X and 1500X magnifications respectively. It can be observed from the
figure that clean substrate has a surface containing quartz particles with sharp edges. The
roughness of the quartz surface influences the contact angle. The effect of roughness on contact
angle was investigated by Wenzel40 and stated that in a simple equation as:
(2)
where

is contact angle on the rough surface and r is the roughness factor. The roughness is a

difference between advancing and receding angle. From the Wenzel wetting equation, as the
surface roughness increased, the solid
liquid contact area increased, leading to a large contact
angle. The roughness of the surfaces, as obvious from SEM image in Figure 4, is related to the
surface morphology of the surface. Therefore, after treatment with surfactant the surface
properties have been changed due to formation of surfactant layer over the quartz surface leading
to reduced contact angle.
The infrared spectra of clean quartz and surfactant treated quartz are shown in Figures 5 and 6.
The spectra of the quartz before and after surfactant treatment used in the present study were
recorded between 400 and 4000 cm-1. The band assignments are listed in Table 4. The difference
between the two spectra is the additional peak at 3450 cm-1 of O-H stretching of treated quartz
sample. This is due to adsorption of ethoxylated secondary nonionic surfactant on quartz surface.
Band intensities were determined by the baseline method and the characteristic absorption values
were calculated. No internal reference band was found in the infrared spectra of quartz because
all band intensities were changed by the action of grinding. The quartz band at 1095 cm-1 occurs
as a shoulder because it partly overlaps the strongest absorption band of quartz at 1085 cm-1. The
Si-O asymmetric stretching and bending vibrations have been found at 1095 cm-1 and 465 cm-1.
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On the other hand the Si-O symmetric stretching and bending vibrations have been found at 785
cm-1 and 695 cm-1. Examination of a number of quartz infrared spectra showed that the
resolution of this shoulder appears to be very sensitive to the crystallinity of the quartz sample.

3.3. Reduction of Surface Tension by the surfactants

It is well known that the surfactants reduce the surface tension of water by getting adsorbed on
the liquidgas interface. The critical micelle concentration (CMC), one of the main parameters
for surfactants, is the concentration at which surfactant solutions begin to form micelles in large
amount41. Surface tensions of the above three surfactants (Tergitol 15-S-5, Tergitol 15-S-7,
Tergitol 15-S-9, and Tergitol 15-S-12) solutions at different concentrations were measured and
plotted as a function of concentration in Figure 7. The concentration at the inflexion point of the
curve is critical micelle concentration. The lowest surface tension value achieved by Tergitol 15S-12 is 28 mNm-1 which is significantly lower than the surface tension value of water. For
ethoxylated nonionic surfactant CMC increases with increase in EON of the surfactant42. In the
present study same result has been also found in case of the employed nonionic surfactants that
with increasing EON, the CMC value of the surfactant increases. The CMCs values for the
surfactants with EON 5, 7, 9, and 12 are 0.002, 0.0031, .0042 and 0.0051 wt% respectively.

3.4. Factors Influencing the Contact Angle (c)

The effect of surfactants and their ethylene oxide number, water salinity, temperature on
wettability of quartz surface has been determined by measuring the contact angles. The contact
angles are largely influenced by the above factors. The effects of the above factors are discussed
below.

3.4.1. Effect of Surfactants and their EON

Wettability of solid surface is largely affected by application of surfactants. The interfacial
crude oil-aqueous solution-solid substrate interactions are characterized by the formation of a
contact angle on solid surface. Understanding contact angle behavior, in general, is one of the
challenging problems in surface science due to its role in all processes involved in three-phase
interfacial phenomena. Two fundamental problems can be associated with contact angle
behavior. The first is related to solid substrate structure and its surface roughness, whereas the
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second is associated with the mutual interactions of immiscible liquids in contact with the solid
substrate. The investigation has been made on the fundamental problems related to crude oilaqueous solution interfacial interactions in the close vicinity to the contact line with solid
substrate. Figure 8 shows the contact angle behavior versus time of rest on the quartz substrate
for crude oil droplets in the presence of nonionic surfactants (Tergitol 15-S-5, Tergitol 15-S-7,
Tergitol 15-S-9, and Tergitol 15-S-5). Contact angle decrease initially sharply for all surfactant
but for water the effect is not so prominent. In case of water, contact angle decreases due to
interaction of Si-O group with water molecules that makes the quartz surface oil-wet. In presence
of surfactants, the solid surface has been become more oil-wet by lowering the contact angle.
After an hour the lowering of the contact angle shows the time independent behavior up to 3
hours. In Figure 9 the surface activity of the surfactants has been plotted as contact angle versus
ethylene oxide number. The values were recorded after 2 hours equilibrium in each surfactants
solution at their critical micelle concentration value. The figure shows that with increase in
ethylene oxide number of the surfactants, contact angle decreases. As ethylene oxide number
increases the surface activity of the surfactant increases and also the wetting property of the solid
surface is modified to more oil-wet. An example of the attained photographs of the variation of
contact angles over different time intervals is shown in Figure 10 for Tergitol 15-S-7.
On the other hand, HLB value of the surfactant also increases with increasing EON. As HLB
value is related to wetting ability of surfactant, with increase in HLB value surfactant makes the
solid surface more oil-wet. In presence of surfactants wettability alteration of quartz follows a
different mechanistic path. Quartz wettability is connected with adsorption of surfactants at
waterair and quartzwater interfaces. Surfactant adsorption at waterair interface causes a
decrease of the water surface tension, however, the quartzwater interface tension can increase
or decrease under the influence of the surfactant depending on the orientation of its molecules in
the adsorbed layer. The mono- and bilayer adsorption model are responsible behind the
mechanism of the wettability alteration of solid quartz surface. The mechanism of monolayer
adsorption suggests that at a low concentration of surface active agents they are adsorbed on the
quartz surface, and their hydrophobic parts are arranged parallelly to quartzwater interface.
When the concentration of surfactant in the bulk phase increases the density of surface layer
increases, too, and the hydrophobic part of the adsorbed surfactant becomes oriented into the

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solution, making thus a larger number of active sites available for adsorption. In such way the
quartzwater interface tension increases and make the quartz surface oil-wet.
In the bilayer mechanism the initial stage of adsorption of surface active cations at quartzwater
interface is similar to that of monolayer. However, it is assumed that after neutralization of the
surface charges the adsorption of the surface active cations proceeds further on the hydrophobic
parts of the previously adsorbed ions. So a second adsorbed layer is formed, where the charged
hydrophilic parts of ions are oriented towards the solution. It causes a decrease of the quartz
solution interface tension and simultaneous increase the oil-wet property of the quartz surface.

3.4.2. Effect of Water Salinity

The effect of salinity on contact angle for constant volume (20 l) of oil droplet has been
measured on quartz surface. The variation of the contact angle with time has been measured with
different salinity systems and the results are depicted in Figure 11. With elapse of time, the
interaction between crude oil and salt present in solution increases and hence, the transfer of
surface active agents from crude oil to solution also increases which can decrease the contact
angle. After certain time the behaviour of contact angle decrease is independent of time due to
completion of transfer of surface active agent into the solution phase. In addition with this there
are several types of interactions are available in crude oil-quartz-liquid systems such as polar
interactions that predominate in the absence of a water film between oil and solid, surface
precipitation which depends on mainly crude oil solvent properties with respect to the
asphaltenes, acid/base interactions that control surface charge at oil/water and solid/water
interfaces, and ion bonding or specific interactions between charged sites and higher valence
ions. These two types of interaction are shown in Figure 12. In Figure 13, contact angle versus
salinity curve has been depicted. It is clear from the figure that with increase in salinity contact
angle decreases up to certain salinity and then increases. This salinity can be assigned as optimal
salinity for the system. This reduction in contact angle can be attributed to the effect of salt on
the interfacial tension between crude oilaqueous phases. The presence of salts in the aqueous
phase has strong ability to increase the accumulation of the surface-active species; these are
available in crude oil, at the crude oilaqueous phase interface, and thereby reduce the interfacial
tension and contact angle43. As the salinity concentration more than 6 wt% then the repulsive
electrostatic double-layer forces and repulsive hydration forces increase to avoid the spreading of
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crude oil. This influence causes a significant increase in contact angle over the range of NaCl
concentration of 6 wt% to 8 wt%. When NaCl concentration increases to exceed 8 wt%, it
prevents the surface-active material from dissolving into the aqueous phase. Therefore, the
activity of the nonionic surfactant as well as produced surfactant from the crude oil has been
reduced and it could not further reduce the contact angle. Instead, the surface-active material will
adsorb onto the solid surface, which will enhance the oil-wetting behaviour on the solid surface.

3.4.3. Effect of Temperature

Temperature effect on contact angle has been investigated in water solution. Figure 14 depicts
the variation of contact angle with temperature. The figure shows that with increase in
temperature the contact angle gradually decreases. Temperature influences the oil property as
well as bath solution property. The interfacial interaction between crude oil and solution is also
influenced by temperature. The reduction in contact angle may also be attributed to the reduction
in oil viscosity with the increase in temperature. Temperature also affects the density of the
phases differently along with viscosity, which in turn will affect the contact angle. Eq 1 shows
that contact angle is related to oil-water interfacial tension. Again interfacial tension is directly
related to liquid density. As temperature influences the density of liquids, interfacial tension
between oil-water will be also affected by temperature and contact angle also be exaggerated. In
addition with this a thermal gradient acts behind the phenomena. On a thermal gradient, the drop
will move from the warm side to the cool side. It does this because liquid-liquid interfacial
tension is affected by temperature. As temperature increases, interfacial tension decreases, and
vice versa. On each area element at the liquid-liquid interface, there are two forces pulling in
opposite directions trying to reduce the surface area of the drop. Since interfacial tension
decreases with increasing temperature, the tension pulling in the cold direction (cold) is stronger
than the one pulling in the warm direction (warm). This results in a flow around the edge of the
drop, as shown in Figure 15. This flow pushes against the surface under the bottom of the drop
and the reaction force from the surface pushes the drop along the thermal gradient.

4. CONCLUSIONS
Accumulation of surface active agents produced from crude oil plays a vital role on wettability
alteration of solid surface. Adsorption of crude oil components alters the wetting behavior of
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solid surface. The presence of salts in the aqueous phase has strong ability to increase the
accumulation of the surface-active species; these are available in crude oil, at the crude oil
aqueous phase interface, and thereby reduce the interfacial tension and contact angle. In presence
of surfactants the accumulation of the produce surfactant from crude oil shows good activity to
reduce contact angle. Two types of interactions act behind the wettability alteration of soli
surfaces such as acid/base interaction and ion bonding. The major functional groups identified on
the FTIR spectra of the oil include C-H stretching of the saturate (2923 and 2852 cm-1), C-H
deformation of the saturate (1460 cm-1), and C-H symmetric deformation of the saturate (1376
cm-1). The peak at 722 cm-1 indicates the presence of long-chain alkyl groups, (CH2) n, with n >
4, in saturates. The presence of acidic groups in crude oil has been identified by FTIR analysis of
crude oil. This is also supported by the total acid number (0.040 mg of KOH/g) of the crude oil.
It can be observed from SEM study that clean substrate has a surface containing quartz particles
with sharp edges. The difference between the two spectra of quartz before and after surfactant
treatment is due to adsorption of ethoxylated secondary nonionic surfactant on quartz surface.
An empirical relation has been established between ethylene oxide numbers of nonionic
surfactant and wettability of quartz. The increase of HLB value and ethylene oxide number of
nonionic surfactant makes the quartz surface more oil-wet. A new concept about the optimal
salinity has been drawn from contact angle method for determination of wettability. Water
salinity has systematic effects on contact angle at a particular temperature. Temperature has
noticeable effect on contact angle. As temperature of the container liquid increases the contact
angle decreases due to reduction of oil viscosity.

AUTHOR INFORMATION
*Corresponding Author
E-mail: mandal_ajay@hotmail.com. Fax: 91-326-2296632.
Funding
This work was financially supported by the University Grant Commission [F. No.
37203/2009(SR)].

ACKNOWLEDGEMENTS

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The authors gratefully acknowledge the financial assistance provided by University Grant
Commission [F. No. 37-203/2009(SR)], New Delhi to the Department of Petroleum Engineering,
Indian School Of Mines, Dhanbad, India. Thanks are also extended to all individuals associated
with the project.

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Table 1
Physicochemical properties of the surfactants employed in the work
Chemical Name

Linear

Formula

& Trade Name

Molecular Weight

HLB
Value

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Secondary

Alcohol

C12-14H25-29O[CH2CH2O]5H
EON=5
M.W. =415

Tergitol 15-S-5

10.6

Nonionic

Alcohol

C12-14H25-29O[CH2CH2O]7H
EON=7
M.W. =515

Tergitol 15-S-7

12.1

Nonionic

Alcohol

C12-14H25-29O[CH2CH2O]9H
EON=9
M. W.= 584

Tergitol 15-S-9

13.3

Nonionic

Tergitol 15-S-12

14.7

Nonionic

Ethoxylate
Secondary
Ethoxylate
Secondary
Ethoxylate
Secondary
Ethoxylate

Alcohol C12-14H25-29O[CH2CH2O]12H
EON=12
M. W.= 738

Table 2
Physical properties of the crude oil
Asphaltene content (wt%)

0.20

Sulfur content (wt%)

0.50

Viscosity at 45C (mPa.s)

51.02

Density at 22C (kg/m3)

855.05

API gravity

33.987

Total acid number (mg KOH/gm)

0.040

Table 3
Functional Group in the IR Spectra of the Crude Oil
Wave length of Absorption (cm-1)

Mode of Vibration

Functional Group

2852-2852

C-H stretching

-CH2 and CH3

of the saturate

2922-2923

C-H stretching

-CH2 and CH3

of the saturate

1460

C-H deformation

1376

C-H symmetric
deformation

-CH2 and CH3

of the saturate
-CH2 of the saturate

722

C-H bending

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1640-1800

C=O stretching

-C=O of
carbonyl/carboxylic groups

3700-3100

O-H stretching

-OH of phenolic groups

1470-1590

C=C ring stretching

-C=C of aromatics

Table 4
Band assignments of Quartz and surfactant treated Quartz
Samples

Wave number (cm-1)

Assignments

Quartz

2930

C-H stretching

1095

Si-O asymmetrical stretching vibration

785

Si-O symmetrical stretching vibration

695

Si-O symmetrical bending vibrations

465

Si-O asymmetrical bending vibration

Quartz with

3450

O-H stretching

Tergitol 15-S-7

2930

C-H stretching

1095

Si-O asymmetrical stretching vibration

785

Si-O symmetrical stretching vibration

695

Si-O symmetrical bending vibrations

465

Si-O asymmetrical bending vibration

Figure 1. Illustration of contact angle in three-phase system on solid surface.

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Figure 2. Schematic diagram of the apparatus used to measure the contact in solid-liquid
systems.

Figure 3. FTIR spectra of the employed crude oil in this experiment.

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(a)

(b)

Figure 4. SEM images of a clean quartz sample. (a) 500X magnification and (b) 1500X
magnification.

Figure 5. Infrared spectra of a Quartz sample before surfactant treatment.

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Figure 6. Infrared spectra of a Quartz sample after surfactant treatment.

70

Tergitol 15-S-5
Tergitol 15-S-7
Tergitol 15-S-9
Tergitol 15-S-12

65

-1

60

Surface Tension, mNm

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CMC
0.0

0.2

CMC CMC CMC

0.4

0.6

Concentration of Surfactant,wt% x 10

0.8
-2

Figure 7. Surface tension of the surfactants with variation of their concentration and CMC
determination.

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Tergitol-15-S-12
Tergitol-15-S-9
Tergitol-15-S-7
Tergitol-15-S-5
Water

95
90

Contact Angle (degree), c

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75
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65
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55
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45
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0

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60

80

100

120

140

160

180

200

Time (min)

Figure 8. Effect of Surfactants on Dynamic Contact Angles on Quartz Surface at 298 K.

60

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Contact Angle (degree), c

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30

20

10

Tergitol 15-S-5

Tergitol 15-S-7

Tergitol 15-S-9

Tergitol 15-S-12

Surfactants

Figure 9. Effect of ethylene oxide number on contact angle on Quartz Surface at 298 K after 2
hrs equilibrium.

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Time 10 Min and contact angle=601. Time 50 min and contact angle= 511
Figure 10. Photographs of sessile oil droplets in Tergitol 15-S-7 surfactant over time on Quartz
surface.

95

0 wt% NaCl
2 wt% NaCl
4 wt% NaCl
6 wt% NaCl
8 wt% NaCl

90
85

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Figure 11. Effect of Salinity on Dynamic contact Angles on Quartz Surface at 298 K.

Figure 12. Mechanism of interaction between crude oil component, salt, and solid surfaces. (a)
acid/base interactions; (b) ion-bonding.

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Contact Angle (degree), c

75

70

65

60

55

50
0

Salinity, wt%

Figure 13. Effect of Salinity on contact Angles on Quartz Surface at 298 K.

90
85
80

Contact Angle, C

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65
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80

90

Temperature,C

Figure 14. Effect of Temperature on contact Angles on Quartz Surface in water.

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Energy & Fuels

Figure 15. Schematic diagram of effect of temperature gradient on contact angle.

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ACS Paragon Plus Environment