Colloids and Surfaces A: Physicochem. Eng.

Aspects 384 (2011) 98–108

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Colloids and Surfaces A: Physicochemical and

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

Characterization of wettability alteration of calcite, quartz and kaolinite:

Surface energy analysis
V. Alipour Tabrizy a , R. Denoyel b , A.A. Hamouda a,∗
a
Department of Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway
b
CNRS/Université de Provence, Madirel, Centre de Saint-Jérôme 13397, Marseille Cedex 20, France

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

Article history: The paper addresses wettability alteration of calcite, quartz and kaolinite powders, with stearic acid
Received 29 December 2010 (SA), N,N-dimethyldodecylamine (NN-DMDA) and asphaltene as oil soluble additives. It is a challenge
Received in revised form 5 March 2011 to convert silicate based mineral surfaces from strongly water-wet to more oil-wet. Thermogravimetric
Accepted 8 March 2011
analysis (TGA) of the modified powders is used to quantify the monolayer adsorption and is suggest-
Available online 16 March 2011
ing the possible molecular orientation on the mineral surfaces. Characterization of the mineral surface
hydrophilicity/hydrophobicity due to modification is determined by the enthalpy of the water vapor
Keywords:
adsorption isotherm. From the quantity and the affinity to water vapor adsorption, a new wettability
Wettability
Calcite
index is suggested. The enthalpy of water adsorption relative to liquefaction enthalpy shows that stearic
Quartz acid and asphaltene deeply modify the calcite toward more oil-wet for treated humidified surfaces. It
Kaolinite is interesting to observe that although the presence of a water film on quartz and kaolinite surfaces,
Asphaltene enhance the adsorption of N,N-dimethyldodecylamine (NN-DMDA), does not eliminate but reduces the
Polar components asphaltene adsorption.
TGA © 2011 Elsevier B.V. All rights reserved.
Water adsorption isotherm
Water adsorption enthalpy
Surface energy

1. Introduction which was further supported by the observation that de-asphalted

crude oils cannot adsorb on minerals surface [10,11].
It is well documented that the presence of asphaltene and natu- Hamouda and colleagues in series of work dealing with cal-
ral polar components (acids and bases) soluble in the crude oil and cite, water and oil revealed that the adsorption of long chain fatty
their interaction at solid surface are important factors in altering acids on the calcite surface depends on several factors such as
solid surface wettability to more oil-wet and enhanced retention of chemical structure of fatty acid, pH, brine composition and temper-
crude oil in reservoir rock pores [1–5]. The analysis of crude oil from ature [5,12–16]. They have also shown a synergistic effect between
Norwegian continental shelf showed that carboxylic acids with car- asphaltene and fatty acids for alteration of chalk to more oil-wet [5].
bon number ranging from 16 to 20 are the most abundant acids in Recent publications for wettability characterization using surface
the crude oil, thus they can play a critical role in oil recovery by energy data shows that combination of thermogravimetric anal-
water flooding [6]. The systematic study on the stability of aqueous ysis (TGA), microcalorimetry and vapor adsorption isotherms are
films between oil and silica showed that in the presence of amine, suitable alternative techniques comparing to contact angle, relative
below a defined pH, the aqueous film becomes unstable and oil permeability and capillary pressure measurements [12,13,17–20].
phase can spread at the silica/water interface [7]. The heavy ends Thermo gravimetric analysis provides a quantification of the
in the crude oil (asphaltene and resins) also contain surface active adsorbed material as well as a measure of the adsorption enthalpy.
components which adsorb on reservoir rock and clay minerals [8]. This method has advantages comparing to other techniques (such
Adsorption of asphaltene on clays can change the wettability and as spectroscopy) since it can be applied to all organic adsorbates
reduces swelling, effective surface area and cation exchange capac- and it does not require aromaticity or a certain functional group for
ity [9]. Liu and Buckley (1994) also reported that the wettability detection [21,22].
alteration has often been ascribed to the adsorption of asphaltene, Microcalorimetry can be used also to characterize a surface in
terms of hydrophilicity/hydrophobicity by measurement of inter-
action energy between adsorbed water vapor and solid surface
∗ Corresponding author. Tel.: +47 957 026 04; fax: +47 518 317 50. [17,23,24]. The obtained values can be compared to the water
E-mail address: aly.hamouda@uis.no (A.A. Hamouda). latent heat of liquefaction and from this comparison, the wettability

0927-7757/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2011.03.021
 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108 99

alteration of solid surfaces and the heterogeneity/homogeneity of Table 1

Polar components.
surface modification can be assessed [25].
From the shape of adsorption isotherms one can determine the Components Supplier and purity Structural formula
wetting state of a solid [19,26]. For a high energy solid surface, Stearic acid (SA) Aldrich ≥ 99% CH3 (CH2 )16 COOH
the amount of adsorbed vapor is infinite at saturation pressure, N,N-Dimethyldodecylamine Fulka ≥ 99% CH3 (CH2 )11 N(CH3 )2
and the area under the adsorption isotherm is large. Such behavior (NN-DMDA)
is defined as complete wetting behavior when vapor at satura-
tion pressure forms a macroscopically thick film and spreads on
the solids [19]. For a low energy surface, the area under satura- oil. Their structural formula, suppliers and purities are shown in
tion isotherm is finite and the amount of vapor adsorption is low. Table 1. Asphaltene precipitated from crude oil in excess of normal
This case is defined as partial wetting when a thin film (with the heptane (1:40) is used to represent the polar and heavy fraction of
thickness of one or few monolayers) is formed at saturation [19]. crude oil. After 48 h of equilibrium between crude oil and normal
The combination of these techniques is presented in this work heptane, the solution was filtered through a 0.22 mm filter (Milli-
to draw possible reliable conclusions on the adsorption of asphal- pore) to separate the asphaltene and then asphaltene was dried for
tene, natural surfactant (fatty acid and amine) and co-presence of 24 h under vacuum at room temperature.
these organic components over carbonate, silicate and clay min-
erals. The purpose of the work is to investigate the consequence 3. Methods
of surface modification with organic compounds on hydrophilic-
ity/hydrophobicity of minerals surface in the presence or the 3.1. Surface modification
absence of humidity. Characterization of the wettability of modified
minerals has been performed using a dimensionless index. Two types of modification were carried out. One is dry modifi-
cation where both solid and liquid were dried and the other is the
2. Materials wet modification. In the first case the powder was dried at 150 ◦ C
for at least 48 h under vacuum condition and the liquids (normal
2.1. Solids decane or toluene) were dried over molecular sieves (0.4 nm) for
one night before modification. In the second case the dried solids
Three types of powdered solid were used in this work; quartz, were first placed in a desiccator in the presence of a saturated
calcite and kaolinite which represent sandstone rock, carbonate solution of K2 SO4 for a period of 10 days at 25 ◦ C. The saturated
rock and clay minerals, respectively. Quartz and kaolinite were sup- solution of a salt provides constant relative humidity and vapor
plied by Sigma–Aldrich and their chemical compositions are SiO2 pressure [27]. For K2 SO4 solution, the relative humidity reaches
and Al2 O7 Si2 ·2H2 O, respectively. Calcite was provided by Norwe- near 97% at 25 ◦ C which provides a sufficient amount of water on
gian Talc AS. the solid surface to investigate its effect on subsequent adsorption
of organic adsorbates [12]. For both types of modification, 0.01 M
2.2. Liquids and additives solution of stearic acid (SA) and N,N-dimethyldodecylamine (NN-
DMDA) in normal decane were prepared. To investigate the role of
Normal decane (n-C10 ) and toluene (C7 H8 ) are used in this asphaltene and co-presence of asphaltene and natural surfactants
study as base solvents for added polar components. Both liq- on wettability alteration of minerals, 0.35 wt% of asphaltene was
uids were supplied by Chiron AS in HPLC grade (purity >99%). dissolved in toluene and added to 0.01 M solution of stearic acid
The water was purified through Milli-Q Millipore and was used and N,N-dimethyldodecylamine (NN-DMDA).
in adsorption isotherm experiments. Stearic acid (SA) and N,N- Two grams of powder were weighted in stopper glass tubes
dimethyldodecylamine (NN-DMDA) were used as oil soluble and 20 ml of solution were added. The samples were stirred with a
additives to mimic natural fatty acid and amine in the crude slowly rotating agitator (50 rpm) for 24 h. This period of time was

Fig. 1. Schematic representation of the microcalorimetric set up.

100 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108

found to be sufficient to reach equilibrium as reported in the lit- interfacial tension  SV ( ) of the same surface in contact with
erature [8,12,28]. The suspension was centrifuged for 30 min at adsorbing vapor V of a liquid L [19]:
4500 rpm/min. Then the solid phase was separated from the liq-
SV ( ) =  S −  SV ( ) (1)
uid, redispersed in toluene for washing, and centrifuged again for
10 min at 4500 rpm. Finally, the solid was dried under vacuum con- From the Gibbs surface energy and application of first and second
dition at 25 ◦ C. law of thermodynamic at constant temperature, the differential of
the interfacial tension is deduced [29]:
3.2. Gas and vapor adsorption isotherms 
d = − i di (2)
The specific surface areas of the unmodified solid powders
where  i is the excess adsorbed amount of component i per unit
were determined by nitrogen and krypton adsorption at 77 K using
area and i is the chemical potential of component i. In the case
manometric apparatus, ASAP 2010 and AUTOSORB-1, respectively.
of vapor adsorption on insoluble non-volatile solids, the surface
Vapor adsorption isotherm experiments also were determined by
pressure can now be obtained directly by integration of Eq. (2).
gravimetry at 25 ◦ C with a TGA Q 5000 apparatus both for unmodi-
At constant temperature, the surface pressure can be rewritten as
fied and modified samples to measure the surface areas and obtain
follows:
further information in terms of surface energy. The temperature for
 
treatment of unmodified and modified samples before water vapor
adsorption was adjusted to 60 ◦ C. The accuracy of TGA Q 5000 appa- SV ( ) =  ()d (3)
 =0
ratus is 10−5 mg. The average experimental error is about 11% with
5% standard deviation is added to the experimental part. If the vapor behaves ideally, then d = RT dln p and therefore:
 

3.3. Thermo gravimetric analysis (TGA) SV ( ) = RT  ()d ln p (4)

 =0

High resolution Thermo Gravimetric Analyzer (TGA Q500 from In this equation, SV ( ) is the surface pressure (mN/m), R is the
TA instrument) was applied for the measurement and characteri- ideal gas constant (J/K/mol), T is the temperature (K),  is the sur-
zation of adsorbates on modified and unmodified solid powders as face excess of vapor on the solid surface (mol/m2 ) and P is the vapor
a rapid procedure which can scan a wide variety of potential adsor- pressure (Pa). As it can be seen from this equation, the surface pres-
bates. The sample was placed in an alumina pan, equilibrated at sure at certain amount of adsorbed vapor follows directly from the
30 ◦ C and was heated at 6 ◦ C/min for high resolution under dried area under the adsorption isotherm plotted as  versus ln p. The
air flow (40 ml/min) up to 600 ◦ C. The accuracy of TGA Q 5000 area under the adsorption isotherm thus determines the surface
apparatus is 10−5 mg. pressure [19].
In a closed system, the adsorbed film near the saturation pres-
3.4. Enthalpies of adsorption sure can therefore be in equilibrium with a droplet of bulk liquid.
The liquid droplet in equilibrium with the vapor phase and solid
Interaction of water vapor on the modified sample with differ- surface can be characterized by the contact angle ˛ [19]. By applying
ent organic adsorbates can be compared with unmodified sample the Young–Dupre equation in the presence of three phases (solid,
in terms of adsorption enthalpy. The experimental results are inter- liquid and vapor), surface pressure can be linked to the contact
preted by coupling of heat effects measured by microcalorimetry angle as follows:
and the amount of water adsorbed on the sample from adsorption
 LV cos ˛ =  SV −  SL (5)
isotherms. The schematic of microcalorimetric set up is shown in
Fig. 1. To perform the experiment, the sample was introduced inside In this equation,  is interfacial tension (mN/m) and S, L and V
the calorimetric cell and was dried under nitrogen flow (25 ml/min) denote for solid, liquid and vapor, respectively. By substitution of
until thermal equilibrium was observed. In order to control vapor Eq. (1) in Eq. (4):
pressure inside calorimetric cell, mass flow meter (MFC provided by
 LV cos ˛ =  S − SV ( ) −  SL (6)
Bronkhorst) has been used to inject water continuously. Distilled
water for this mass flow meter was supported from small reser- For a system, where contact angle (˛) between liquid phase and
voir near the calorimeter and Helium gas bottle supplies the back vapor phase is close to zero, the surface pressure can be expressed
pressure of this reservoir. Nitrogen was provided by another bot- as follows:
tle and performed as a carrier gas. Digital acquisition system was
used to record calorimetric signal, water relative humidity inside SV ( ) =  S − ( LV +  SL ) (7)
the calorimetric cell and flow properties. If we assume that the liquid (in the presence of vapor phase at equi-
librium) can completely wet the surface, the interfacial pressure of
4. Theory liquid on the solid can be expressed as follows:

SL = SV ( ) +  LV (8)

Characterization of a solid in terms of surface energy can be used
to determine the wetting state of the solid. This characterization can This means that the liquid surface pressure values (SL ) for different
be done by physisorption of vapor on the solid particles [12]. If the liquids can be obtained using the vapor surface pressures which is
adsorption of vapor increases from vacuum to the vapor pressure calculated from the adsorption isotherms.
of a liquid, the interfacial tension of the solid decreases depending From Eqs. (1)–(8), one can find out the behavior of individual
on the nature of the adsorbing molecules, adsorbed amount and the liquid in contact with the solid surface. In the oil reservoirs, where
surface charge. This adsorption on a solid also affects the interfacial two liquids, oil and water, are present, one can use the above theory
Gibbs energy [19]. to calculate the surface pressure of water and hydrocarbon phases.
For vapor adsorption on a solid the surface pressure SV ( ) The higher is the value of surface pressure the more hydrophilic
is defined as the difference between the interfacial tension of is the surface. In addition, hydrophilicity of surface can be distin-
the clean (i.e. in vacuum) solid surface S, denoted as  S , and the guished based on the amount of work used for different stages of
 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108 101

wetting process [19]. The work of spreading, Ws , performed if a 2

clean solid is brought into contact with water (in equilibrium with
its vapor) which spreads on the surface, is given by [19]: Unmodified quartz
1.5 Unmodified kaolinite
Ws = SVw ( ) (9)

Adsorbed mass (mg/m )

2
Unmodified calcite
If the solid is immersed in the water, the work of immersional
wetting, Wi , can be expressed as [19]: 1

Wi = SVw ( ) +  VW (10)

If a solid and water interface are brought into contact, we are deal- 0.5

ing with a situation of adhesional wetting. The work of adhesional

wetting, Wa , or the work of adhesion is given by [19]:
0
Wa = SVw ( ) + 2 VW (11) 0 10 20 30 40 50 60 70 80 90 100
o
P/P (%)
High values of spreading, immersional and adhesional work for
water phase indicates the surface has a large affinity for adsorbed Fig. 2. Comparison of water vapor adsorption isotherms on unmodified minerals.
water.
The specific surface area of solid powders should be calculated 5. Results and discussion
based on gas or vapor isothermal adsorption from the BET mono-
layer capacity (nm ) by applying the following equation [23]: 5.1. Unmodified surfaces
˛(BET) = nm NA  (12)
The water vapor adsorption isotherms at 25 ◦ C for unmodi-
where NA is the Avogadro constant (6.02214 × 1023 molecule/mol) fied quartz, calcite and kaolinite powders are shown in Fig. 2. The
and  (Å2 /molecule) is the average area occupied by each molecule isotherm for quartz surface appears to be type II according to IUPAC
in the completed monolayer (i.e. the molecular cross-sectional classification, where the isotherm curve is concave to the P/Po axis,
area). Emmett and Brunauer [29] proposed that the molecular then almost linear and finally convex to the P/Po axis. The sharp
cross-sectional area can be calculated from the density of the liquid point between the concave and linear part of the curve indicates a
adsorptive in the bulk liquid state as follows: formation of monolayer at low relative vapor pressure. This is the
 M 2/3 main characteristic of hydrophilic and high energy surfaces [23].
=f (13) The isotherm for kaolinite shows lower affinity to adsorb water
NA
and appears between type II and type III in IUPAC classification.
where f is a packing factor, which for hexagonal close-packing Nevertheless the measured adsorption isotherm in this plot is cal-
becomes 1.091,  (g/m3 ) is the absolute density of the liquid adsorp- culated based on surface area (mg/m2 ) while the comparison based
tive at the operational temperature and M (g/mol) is the molar on weight (mg/g) is misleading as the surface area of kaolinite is 15
mass of the adsorptive. The adsorbed monolayer (nm ) is estimated times higher than quartz. In contrast to quartz and kaolinite, the
from the linear plot of BET equation [23]. The linear region of BET calcite surface shows type III and the interaction of water and sur-
equation can be expressed as follows: face is weak. However, the interaction of calcite and water may be
P/P o 1 C −1
P underestimated when it is compared to quartz and kaolinite sur-
= + (14) faces in Fig. 2. From the work done at a molecular level using atomic
n(1 − P/P o ) nm C nm C Po
force microscopy (AFM) by Karoussi et al. [31], it was shown that
where P/Po , is the partial pressure of adsorbing vapor, n is the at the crystalline calcite surfaces, dissolution and re-crystallization
amount of adsorbed vapor (mol/g) on the solid powder, C is constant processes in thin water film that adsorbed from the humidity in
and nm is the monolayer capacity. Thus, the plot of P/Po /n(1 − P/Po ) air occur even after short exposure to air during the experiments.
versus P/Po should be a straight line with an intersection (i) and In addition, the powder samples are treated at 60 ◦ C before vapor
slope (s). The monolayer capacity is representing as follows [23]: adsorption isotherm experiments. This may explain the apparent
1 low hydrophilicity of the calcite powder in adsorption isotherm
nm = (15)
(s + i) experiment comparing to atomic force microscopy. To examine the
magnitude of water vapor adsorption on the solid surface in details,
In the original work of Brunauer et al. [30], it was found that the
the number of water layers is compared when the relative vapor
type II and III isotherms on various adsorbents give the linear plots
pressure (P/Po ) is equal to 0.15 [12]. At this relative vapor pressure,
over the approximate range of P/Po between 0.05 and 0.35 [23].
the number of adsorbed water layers is estimated to be 1.13, 0.52
In this paper, comparison of surface areas measured by water
and 0.19 for quartz, kaolinite and calcite, respectively. This may
vapor adsorption for unmodified and modified solid surfaces has
be interpreted that quartz surface is the most hydrophilic of the
been done as a criterion for wettability characterization. The fol-
surfaces studied here.
lowing wettability index (WI) is defined based on the measured
In order to determine the specific surface areas of unmodified
monolayer capacity.
powders by nitrogen and krypton adsorption isotherms, the molec-
H2 O (BET)
˛m ular cross sectional areas are estimated as 16.2 Å2 and 20.5 Å2 for
WI = (16)
˛uH2 O (BET)
where ˛H 2O H2 O (BET) are measured surface areas Table 2
m (BET) and ˛u
BET Surface area (m2 /g) calculated from nitrogen, krypton and water adsorption
covered by monolayer of water over modified and unmodified isotherms.
samples, respectively. In this equation, WI = 1 is representing the
strongly hydrophilic surface and WI = 0 is representing the strongly N2 Kr H2 O

hydrophobic surface. This wettability index can be interpreted as Quartz 0.62 0.67 0.65
the fraction of the solid surface which remains hydrophilic after Kaolinite 8.56 9.47 9.95
Calcite 0.76 0.64 0.23
modification.
102 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108

300 100.2

250
Surface pressure (mN/m)

100
200

Weight (%)
150 99.8
Unmodified quartz
Unmodified calcite
100
Unmodified kaolinite Dreid calcite modified by SA
99.6 Dried calcite modified by Asph.
50 Unmodified calcite
Dried calcite modified by SA and Asph.
0
0 20 40 60 80 100 120 140 160 180 200 99.4
0 100 200 300 400 500 600
Adsorbed amount (µmole/m2 ) o
Temprature ( C)
Fig. 3. Surface pressure calculated from adsorption isotherms for unmodified min-
erals. 100.2

nitrogen and krypton using Eq. (13), respectively. The surface area
100
of powder can be calculated also from water vapor adsorption

Weight loss (%)

isotherm. The molecular cross sectional area of water is considered
as 10.51 Å2 using the above equation. Table 2 summarizes the esti-
99.8
mated surface areas using BET equation. As it can be seen from the
table, the variations of surface areas are less significant for quartz Unmodified calcite

(≈3%) and kaolinite (≈13%) compared to calcite (≈69%). In case of Dreid calcite modified by SA
calcite, the calculated specific surface areas vary from 0.76 m2 /g 99.6 Dried calcite modified by Asph.
for N2 to 0.64 m2 /g for Kr and 0.23 m2 /g for H2 O. The difference in Dried calcite modified by SA and Asph.
the specific surface areas using N2 and Kr for calcite is near to 15%,
which may be considered to be within the calculated difference of 99.4
0 100 200 300 400 500 600
about 13% that is obtained in the case of kaolinite (including the
o
water vapor adsorption isotherm). The observation of the differ- Temprature ( C)
ence in the obtained surface areas for calcite by water and nitrogen
Fig. 4. Thermogravimetric analysis for modified and unmodified calcite mineral for
adsorption isotherms has also been reported by Hansen et al. [20]
dry treatment.
and Hamouda et al. [12].
The surface pressure values are calculated by integrating the
areas under the adsorption isotherm curves for the unmodified steps for weight loss can be recognized due to temperature increase
minerals as shown in Fig. 3. Surface pressure of quartz is esti- from 30 ◦ C up to 600 ◦ C. The minor step belongs to the physisorbed
mated to be 265 mN/m, which is approximately twice as high as molecules on the surface of minerals which occurs between about
that for kaolinite (140 mN/m) and three times higher than calcite 30 ◦ C and 195 ◦ C. This may be related to the evaporation of the used
(75 mN/m). solvents such as n-decane and toluene and/or to the excess of mod-
The estimated immersional and adhesional work of wetting ifying organic compounds which were not removed completely by
(Wi , Wa ) for quartz are 337 mN/m and 409 mN/m, respectively, toluene during the washing step of the surface modification.
and those for kaolinite are 212 mN/m and 284 mN/m, respectively. The major weight loss, which is used in calculation of the surface
The high surface pressure and works of wetting for kaolinite and coverage, occurs above 195 ◦ C. High-temperature weight loss may
quartz may be related to strong hydrogen bond between water and indicate the presence of strong ionic or chemical bond (chemisorp-
OH groups at the surface of the silica. These results are compa- tion). For the calcite mineral modified by stearic acid (SA), the
rable to the literature. In case of some hydrophobic surfaces like weight loss occurred between about 195 ◦ C and 300 ◦ C while as for
graphite and carbon the range of 20–150 mN/m for surface pres- the modified calcite surface by asphaltene, the weight loss occurred
sure is reported by Kelebek et al. [32]. For calcite, Rezaei Gomari at higher temperature, between about 300 ◦ C and 450 ◦ C. The final
et al. (2006) also reported the value of 62 mN/m as surface pres- weight loss is recorded at about 580 ◦ C, which corresponds to the
sure, which is close to the value obtained in this work [12]. For decomposition of calcite mineral. The observation of the weight
hydrophilic solids such as mica (Rezaei Gomari et al., 2006), silica loss regions is in a good agreement with the literature [3,12]. It is
(Schlangen et al., 1993), and talc (Douillard et al., 2002) the high also shown in Figs. 5 and 6, the thermal desorption behavior of the
values of surface pressure of 193, 160, and 137 mN/m were also dried quartz and dried kaolinite modified by NN-DMDA, asphaltene
reported in the literature, respectively [12,19,33]. and co-presence of NN-DMDA and asphaltene. Thermal desorption
of NN-DMDA occurs between about 195 and 250 ◦ C, which is low
5.2. Modified surfaces compared to the interval of desorption for stearic acid. Thomas et al.
(1993) also observed that thermal desorption of amines occur at
Three methods (thermo gravimetric analysis, vapor adsorption lower temperature comparing to carboxylic acids [22]. At temper-
isotherm and microcalorimetry) were combined to determine the ature of about 500 ◦ C, constitutional OH in the kaolinite may be
amount of grafted organic adsorbates over the mineral surface and lost. In the case of quartz, thermal decomposition does not seem to
to quantify the modification (described in Section 3.1) in terms of occur in the studied range of temperature.
surface energy. The TGA results for unmodified and modified calcite The adsorptions of asphaltene, stearic acid and NN-DMDA over
samples by stearic acid (SA), asphaltene (Asph.) and co-presence the minerals may be classified as chemisorbed with a reducing
of these organic components are illustrated in Fig. 4. Three main strength from asphaltene (Asph.) to stearic acid (SA) and amine
 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108 103

100.1

100
Weight (%)

99.9

99.8 Unmodified quartz

Dried quartz modified by NN-DMDA

99.7 Dried quartz modified by Asph.

Dried quartz modified by NN-DMDA and Asph.

99.6
0 100 200 300 400 500 600
o
Temprature ( C)

100.1 Fig. 7. Estimated amount of adsorbed stearic acid on calcite calculated from TGA
results in the temperature range of 195–300 ◦ C.

100
to 9.78 ␮mol/m2 in case of quartz and kaolinite, respectively. In
Weight loss (%)

contrast to calcite, humidified kaolinite and quartz have negative

99.9 surface charge. Ionized NN-DMDA has a positive surface charge that
occurred due to protonation of amine, which is the functional group
of NN-DMDA, hence enhancing the adsorption of NN-DMDA on the
99.8 Unmodified quartz
negative sites of quartz and kaolinite.
Dried quartz modified by NN-DMDA In contrast to the above-mentioned influence of the humidity
99.7 Dried quartz modified by Asph. on enhancing the adsorption of stearic acid and NN-DMDA over
calcite and silicate minerals (quartz and kaolinite), respectively, its
Dried quartz modified by NN-DMDA and Asph.
effect on asphaltene adsorption is negative. The adsorbed amount
99.6 of asphaltene on the mineral surface, expressed as (mg/g) and
0 100 200 300 400 500 600
(mg/m2 ) are shown in Figs. 9 and 10 for the dried and wet mod-
o
Temprature ( C) ifications, respectively. The results based on mineral weights for
kaolinite shows a higher range of value comparing to the others.
Fig. 5. Thermogravimetric analysis for modified and unmodified quartz mineral for This seems reasonable, as 15-fold of increase in specific surface
dry treatment.
area is observed for kaolinite. Generally clays, which have large sur-
face area, enhance the adsorbed amount of asphaltene and play an
(NN-DMDA). Fig. 7 shows the amounts of adsorbed stearic acid important role in hydrophobization. From this figure, it can be seen
on the calcite estimated from thermal desorption for the two that the presence of humidity enhances the adsorption of asphal-
types of modification (dried and humidified systems). As can be tene on calcite surface from 3.30 mg/m2 to 5.22 mg/m2 for dried
seen, the adsorbed stearic acid increased from 5.97 ␮mol/m2 to and wet systems, respectively. However, reductions of the adsorbed
10.02 ␮mol/m2 in the humidified system. This is due to the disso- asphaltene from 3.10 mg/m2 to 2.40 mg/m2 and from 3.23 mg/m2
ciation of the SA and subsequent reaction with calcium ions at the to 2.71 mg/m2 are reported, respectively, for quartz and kaolinite.
calcite surface [12,19,34–36]. Similarly, it can be seen from Fig. 8
adsorption of NN-DMDA increased from 5.40 to 8.89 and from 6.15

100

99

98
Weight (%)

97

96 Unmodified kaolinite

Dried kaolinite modified with NN-DMDA

95
Dried kaolinite modified by Asph.
94
Dried kaolinite modified by NN-DMDA and Asph.

93
0 100 200 300 400 500 600
o
Temprature ( C)

Fig. 6. Thermogravimetric analysis for modified and unmodified kaolinite mineral Fig. 8. Estimated amount of adsorbed N,N-dimethyldodecylamine on quartz and
for dry treatment. kaolinite calculated from TGA results in the temperature range of 195–250 ◦ C.
104 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108

Table 3
Calculated surface area coverage  (Å2 /molecule) per molecule of organic adsorbate
for dried and wet system.

Type of modification  (Å2 /molecule)

Calcite Quartz Kaolinite

Dried system
Stearic acid 27.81
N,N-Dimethyldodecylamine 30.75 27.01
Asphaltene 48.10 53.63 51.36

Wet system
Stearic acid 16.58
N,N-Dimethyldodecylamine 18.68 16.97
Asphaltene 30.36 68.26 61.25

the mineral surface, respectively. A mixture of perpendicular and

parallel orientation of adsorbate toward the mineral surface would
Fig. 9. Estimated amount of adsorbed asphaltene (mg/g) on quartz and kaolinite
calculated from TGA results in the temperature range of 300–435 ◦ C. give an intermediate value. Accordingly, it may be concluded that
stearic acid is oriented perpendicular to the calcite surface, both
for dried and wet modification regimes. NN-DMDA has similar ori-
entation on both quartz and kaolinite for the two modification
systems. Nevertheless it seems that the packing of stearic acid and
N,N-dimethyldodecylamine over mineral surfaces is tighter in wet
system compared to that of the dry surface. In previous study by
Rezaei Gomari et al. (2006), similar values of cross sectional molec-
ular area have been reported for the modified calcite by stearic acid
in the presence and the absence of humidity [12].
In contrast to the studied fatty acid and amine, asphaltene seems
to orient in a parallel mode for all minerals in dried and wet sys-
tems. This is reasonable, as asphaltene has a large molecule and
its significant spatial position will not allow it to adsorb in paral-
lel orientation toward the mineral surface. Several studies suggest
that asphaltene are sheet-like in structure and hence can be con-
sidered roughly as a disk-like molecule [38–40]. It is shown that
during the asphaltene adsorption on surface minerals, the shape
Fig. 10. Estimated amount of adsorbed asphaltene (mg/m2 ) on quartz and kaolinite and size of asphaltene is not altered [41]. This is rather comparable
calculated from TGA results in the temperature range of 300–435 ◦ C. to parallel orientation of asphaltene over the mineral surface which
is proposed here. The thickness of asphaltene molecule have been
This may be explained based on that asphaltene molecules are neu- reported to vary from 0.34 nm to 2.3 nm by Dicike et al. [38], Parkash
tral or have an insignificant positive charge at very low pH values. et al. [40], Speight [39] and Sheu [42]. Measurements by Parkash
At higher pH, asphaltene particles carry a net negative charge in et al. (1979) for density of asphaltene molecule suggest a value of
the aqueous solution as they have many electronegative sites, for 1.28 g/cm3 . Assuming, a molecular weight of 1000 g/mol, a thick-
example –OH, C O, N-, which are capable of attracting proton ness of 1.1 nm and diameter of 2.2 nm is obtained [38]. In this work
[8]. In another words, a negative surface charge on asphaltene arises also, the value of 1000 g/mol is used for molecular weight of asphal-
upon dissociation of carbonyl groups. tene to estimate the cross-sectional area of asphaltene over the
mineral. The molecular weight of asphaltene calculated by solubil-
5.3. Surface coverage ity, interfacial tension and chemical ionization mass spectroscopy
also showed that asphaltene molecular weights are between 600
In this section the apparent molecular coverage of mineral sur- and 1000 g/mol [42].
face area and possible molecular orientation of the adsorbates The interpretation of the adsorbed asphaltene molecular ori-
toward mineral surfaces are addressed. To obtain the surface area entations on the mineral surfaces is affected by the used molecular
coverage per molecule of adsorbate (i.e. the cross sectional area weight. For example, based on the above equation, reducing molec-
of adsorbate) from the TGA results, the following equation is used ular weight increases  (␮mol/m2 ), hence lower apparent molar
[12,13,37]: surface coverage (). This leads to a possible formation of mixed
orientation on the surface (perpendicular/parallel).
SA
= (17)
 × NA
5.4. Wettability index
In this equation,  (Å2 /molecule) is the surface area coverage per
molecule of adsorbate, SA (m2 /g) is the specific surface area of min- To explore the effect of different organic adsorbates on the
eral,  (␮mol/m2 ) is the adsorbed amount of organic compounds wettability of solid surfaces and characterization of modified sam-
over the mineral surface and NA (molecule/mol) is the Avogadro ples, water vapor adsorption isotherms are measured. Figs. 11–13
number. Table 3 shows the calculated cross-sectional surface area show the surface pressure calculated from the area under water
per molecule of adsorbate based on the above equation for dried vapor adsorption isotherms using Eq. (4) for modified quartz, cal-
and wet systems. Wright and Pratt [37] suggested that the occu- cite and kaolinite. For unmodified quartz and modified quartz
pied areas by organic functional group are between 22 and 26 Å2 by NN-DMDA, the adsorption is type II while modified quartz
and above 51.5 Å2 for perpendicular and parallel orientations with by asphaltene and modified quartz by co-presence of amine and
 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108 105

300 the amount of vapor adsorbed on the surface and the degree of
hydrophilicity may be classified by the following order: unmodi-
250 fied quartz > dried quartz modified with NN-DMDA > dried quartz
modified with asphaltene > dried quartz modified by co-presence
Surface pressure (mN/m)

of NN-DMDA and asphaltene. The same behavior is seen from

200
the figure for calcite and kaolinite, where the co-presence of
asphaltene and natural surfactant (stearic acid for calcite and
150 NN-DMDA for kaolinite) shows synergistic effect on wettabil-
ity alteration toward oil wet comparing to the presence of one
100
Dried quartz polar component. Chukwudeme and Hamouda [5] reported the
Dried quartz modified by NN-DMDA same observation using contact angle measurement for wetta-
Dried quartz modified by Asph. bility alteration of calcite mineral modified by co-presence of
50
asphaltene and stearic acid. The comparison of surface pressure
Dried quartz modified by NN-DMDA and Asph.
curves show that near saturation pressure where formation of sev-
0 eral layers of water occurs on the surface, the surface pressure
0 20 40 60 80 100 120 140 160
approaches to a plateau. Therefore, the magnitude of this value
Adsorbed amount (µmole/m )
2
at the plateau can be used to investigate the hydrophilicity or
hydrophobicity of the surfaces. In the case of unmodified quartz,
Fig. 11. Comparison of water vapor surface pressure curves on modified quartz the calculated surface pressure is equal to 265 mN/m, this value
minerals.
corresponds to the formation of 9 layers of pre-adsorbed water on
the surface. For modified quartz by NN-DMDA, asphaltene (Asph.)
80 and co-presence of these organic components, the calculated sur-
face pressure at saturation pressure are 155 mN/m and 41 mN/m,
70
respectively, which corresponds to 7.4 and 3.3 and 2.7 water
layers.
Surface pressure (mN/m)

60
The application of this calculation shows that asphaltene and
50 NN-DMDA have higher affinity to change the wettability of kaoli-
nite toward oil-wet as the surface pressure of modified kaolinite
40 Dried calcite
by NN-DMDA is estimated to be 92 mN/m and the surface pres-
30 Dried calcite modified by SA sure of modified kaolinite by asphaltene is near to 47 mN/m. It
is interesting to see that modification of calcite with stearic acid
20 Dried calcite modified by Asph.
and asphaltene is shown to be more hydrophobic compared to the
10
Dried calcite modified by SA and Asph. treated quartz and kaolinite with NN-DMDA and asphaltene where
the surface pressure of modified calcite by SA and modified calcite
0 by asphaltene are varying from 32 mN/m to 8.7 mN/m, which cor-
0 20 40 60 80 100 120 140 respond to 1.56 and 0.66 water layers, respectively. These results
2
Adsorbed amount (µmole/m ) are comparable to number of water layers which have been calcu-
lated by Rezaei Gomari et al. (2006) for modified calcite by different
Fig. 12. Comparison of water vapor surface pressure curves on modified calcite
long chain fatty acids [12].
minerals.
A suggested method to estimate the wettability index (WI) is
using Eq. (16). WI is defined here as the ratio of the adsorbed mono-
asphaltene appear to be type III according to IUPAC classification layer of water of a modified surface to that of unmodified surface.
where the amount of water adsorbed is very low near the satura- This also gives indication of the remained unmodified areas after
tion pressure. The surface modification in terms of hydrophilicity
and hydrophobicity is compared from the relative position of
the surface pressure curves. As it can be seen from the figure,

150

120
Surface pressure (mN/m)

90

60
Dried kaolinite
Dried kaolinite modified by N,N-DMDA

30 Dried kaolinite modified by Asph.

Dried kaolinite modified by NN-DMDA and Asph.

0
0 20 40 60 80 100 120 140
2
Adsorbed amount (µmole/m )

Fig. 13. Comparison of water vapor surface pressure curves on modified kaolinite Fig. 14. Comparison of wettability index for modified quartz minerals for the dried
minerals. and wet systems.
106 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108

5.5. Water vapor adsorption enthalpy

The measurement of the adsorption energy of water molecules

with unmodified and modified minerals as function of surface
coverage was carried out by microcalorimetry. Microcalorime-
try technique gives direct relationship between the adsorption
enthalpy as a function of coverage [43]. In this work, the cross
plot of adsorption enthalpy (H), at a constant vapor pressure
(P/Po = 0.4), as a function of surface coverage is used to classify
the modified samples. Classification is based on that proposed in
the literature [44]. In their definition, they set the latent heat of
liquefaction for water (44 kJ/mol) as a reference for hydrophilic-
ity/hydrophobicity characteristic of surfaces. Accordingly if the
adsorption enthalpy lies above this value the surface is hydrophilic
while if it lies below, then the surface is hydrophobic. The results
of the adsorption enthalpy versus surface coverage of dried min-
erals modified by different components are presented in Fig. 17.
From this cross plots, it can be seen that asphaltene molecule has
Fig. 15. Comparison of wettability index for modified kaolinite minerals for the
dried and wet systems.
more affinity to change the hydrophilicity of minerals compar-
ing to other types of modifying components. NN-DMDA changes
quartz and kaolinite surface properties to less hydrophilic where
the treatment and the effect of the dryness of the surface on the as shown in Fig. 17. The enthalpy of adsorption for quartz is
adsorption efficiency of modifying substances. Figs. 14–16 com- reduced from 103.48 kJ/mol for unmodified sample to 89.44 kJ/mol
pare wettability index for different modified minerals in dry and after the modification with amine. Kaolinite also showed a same
humidified system. The wettability index of modified quartz is trend when treated with NN-DMDA, as the adsorption enthalpy
reduced from 0.6 for dried condition to 0.44 for treated humidi- is reduced from 77.54 to 64.45 kJ/mol after the modification. Sim-
fied surface with NN-DMDA. However, the index increased from ilar behavior is observed in which the enthalpy of the modified
0.5 to 0.63 for treated dry and humidified quartz surface with calcite with stearic acid (SA) is reduced from 68.46 (untreated
asphaltene, respectively. In other words, humidification of quartz surface) and to 52.45 kJ/mol (for the treated surface), indicating
surface enhances the adsorption of NN-DMDA, while it has a reverse the wettability alteration of calcite from hydrophilic surface to
effect in case of asphaltene, where less hydrophobic surface as partially hydrophobic surface. In summary, isothermal adsorption
also shown from the obtained results by TGA results. Similarly, enthalpy of the water vapor on the surfaces is lower in case of
the treated kaolinite surface with NN-DMDA, shown in Fig. 15, the modification with asphaltene, than that for NN-DMDA and
WI changes from 0.71 for the dry to 0.6 for the humidified sur- SA, hence higher hydrophobicity of the used dry mineral surface,
face. In contrast to amine, asphaltene makes the kaolinite surface in this work, when treated with asphaltene. In general, samples
less hydrophobic in the presence of humidity as the wettability in the right corner of the cross plot (considerable water adsorp-
index increases from 0.38 for dried system to 0.53 for wet sys- tion enthalpy and surface coverage) have stronger hydrophilicity
tem. However, it is interesting to see that the presence of humidity behavior comparing to the samples in the left corner. Fig. 18
will enhance adsorption of both organic compounds (asphaltene compares the adsorption enthalpies versus surface coverage of
and stearic acid) over calcite mineral as the wettability index is minerals for dried and wet modification. Based on this graph, it
reducing for modified calcite by SA from 0.5 to 0.32 for dried and can be inferred that the change in water adsorption due to mod-
wet system, respectively. The index also is changing during modi- ification of quartz and kaolinite by N,N-dimethyldodecylamine
fication by asphaltene from 0.28 in dried condition to 0.20 in wet are similar in the presence of humidity. There is an enhance-
condition. ment for adsorption of NN-DMDA on the quartz, kaolinite and
SA on calcite surfaces in wet modification system compared to
modification of dry surfaces. From Fig. 18 it can be deduced also
that the enthalpy of isothermal water adsorption increased for
quartz and kaolinite modified by asphaltene (Asph.) in case of wet
modification compared to that of modification for the dried sur-
face. This means that the presence of humidity will inhibit the
adsorption of asphaltene on the quartz and kaolinite. However,
the trend for calcite is reverse meaning that wet modification of
calcite by asphaltene makes it more oil-wet comparing to dry
modification.
It is possible to conclude the negatively charged asphaltene
particles adsorb on the positively charged calcite ions, which is
in contrast to the asphaltene behavior for kaolinite and quartz,
whose surfaces are negatively charged. Collions and Melrose
[41] have shown that asphaltene adsorption is reduced by 60%
when the water saturation in unconsolidated sand increases to
30%. The studies reported by Bantignies et al. [46], Pernyeszi
et al. [45] and Collions and Melrose (1983) also have revealed
the presence of thin film of water over the kaolinite will
reduce but does not eliminate the adsorption of asphaltene
Fig. 16. Comparison of wettability index for modified calcite minerals for the dried
[44].
and wet systems.
 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108 107

120 Dried kaolinite

Dried kaolinite modified by NN-DMDA

100
Dried kaolinite modified by Asph.
Adsorption enthalpy 80
Dried quartz
(KJ/mol)
60 Dried quartz modified by NN-DMDA

Dried quartz modified by Asph.

40

Dried calcite
20
Dried calcite modified by SA

0 Dried calcite modified by Asph.

0 5 10 15 20 25 30
Adsorbed mass (µmole/m 2) Latenet heat of liquefacation

Fig. 17. Enthalpies of water adsorption for modified and unmodified minerals for dried modification.

120

Dried kaolinite

100 Dried quartz

Dried calcite
Adsorption enthalpy

80
Wet quartz modified by Asph.
(KJ/mol)

60 Wet quartz modified by NN-DMDA

Wet kaolinite modified by NN-DMDA

40
Wet kaolinite modified by Asph.

20 Wet calcite modified by SA

Wet calcite modified by Asph.

0
0 5 10 15 20 25 30 Latenet heat of Liquefaction
2
Adsorbed mass (µmole/m )
Fig. 18. Enthalpies of water adsorption for modified and unmodified minerals for wet modification.

6. Conclusions It is interesting to see that, although water film enhances

adsorption of asphaltene on calcite surface, it reduces the adsorp-
Wettability modification of silicate surfaces are challenging, in tion of asphaltene on kaolinite and quartz. This may be explained
this work (quartz and kaolinite) are successfully modified by N,N- based on the net negative charge in aqueous solution, hence
dimethyldodecylamine. adsorbed onto the calcite surface. On the other hand, adsorptions
Enthalpy of adsorption for both modified and unmodified min- of N,N-dimethyldodecylamine and stearic acid on silicate (quartz
eral surfaces show that hydrophilic mineral surface are converted and kaolinite) and calcite minerals, respectively, are enhanced in
to partially hydrophobic when treated with stearic acid, N,N- the presence of water film.
dimethyldodecylamine and asphaltene. It also shows that the New wettability index (WI) is proposed in this paper. WI is based
wettability modification depends on the presence of water film. on isothermal adsorption of water vapor on the mineral surfaces.
Thermal gravimetric analysis (TGA) is used to predict WI is defined, in this work, as the ratio of the adsorbed monolayer of
molecular orientation on the modified mineral surfaces. Both the water vapor on the modified surface to that of unmodified sur-
stearic acid (used for modification of calcite surface) and N,N- face. In other words it measures the remained surface area capacity
dimethyldodecylamine (used for modification of silicate surfaces), of the mineral, after modification, to isothermally adsorb water
most likely, are packed perpendicular to the mineral surfaces. vapor. However, thorough investigation and comparison with other
In the case of surface modification with asphaltene (silicates used methods is needed to address its applicability and limitations.
and calcite surfaces), the molecular orientation is less clear
due to the uncertainty of molecular weight hence the estima- Acknowledgments
tion of the occupied molecular area. In this work molecular
weight of 1000 is used. Asphaltene orientation may be parallel This paper has been financially supported by the University of
or a blend of parallel and perpendicular on the mineral sur- Stavanger. The authors thank Professor Philippe Knauth, director of
faces. the MADIREL laboratory in France, for giving permission to perform
108 V. Alipour Tabrizy et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 384 (2011) 98–108

this work at MADIREL. We acknowledge Inger Johanne Olsen from [21] M.M. Thomas, J.A. Clouse, Thermal analysis of compounds adsorbed on
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