REE160876 DOI: 10.
2118/160876-PA Date: 19-July-14 Stage: Page: 365
A Procedure for Measuring Contact
Angles When Surfactants Reduce
the Interfacial Tension and Cause
Oil Droplets to Spread
O.O. Adejare, SPE, R.A. Nasralla, SPE, and H.A. Nasr-El-Din, SPE, Texas A&M University
Summary
Viscoelastic surfactants (VESs) are used as diverting agents in
carbonate matrix acidizing. However, these surfactants can
adversely affect the wettability around the wellbore.
Receding contact angles were measured with the conventional
method to study the effect of spent-acid solutions with an ampho-
teric amine-oxide VES and the mutual solvent ethylene glycol
monobutyl ether (EGMBE) on the wettability of Austin cream
chalk rocks. The conventional method involves the injection of
oil droplets into the surfactant solution. However, contact angles
could not be measured when oil droplets were injected into spent-
acid solutions with VES and EGMBE, because low oil/acid inter-
facial tensions (IFTs) cause them to spread on the rock surface.
A new procedure was used for these contact-angle measure-
ments. Rocks were centrifuged in spent-acid solutions with VES
and EGMBE, so that the surfactant changed the interfacial proper-
ties of the rock. Then, contact angles were measured in spent acid
with hydrochloric acid (HCl) only, to prevent VES and EGMBE
from reducing the oil/acid IFT. The effect of the surfactants in the
spent acid on the acid/rock and acid/oil IFT, which is the wettabil-
ity, is shown by the difference in contact angles before and after
centrifuging.
With the new procedure, a spent-acid solution with HCl, 1
vol% of VES, and 10 vol% of EGMBE made an oil-wet rock
water-wet and a water-wet rock strongly water-wet at 25 C. This
suggests that an EGMBE post-flush enhances the relative perme-
ability to oil, under the parameters investigated.
Contact angles are a function of the oil/rock, acid/rock, and
oil/acid IFTs. However, the wettability of the rock is a function of
the oil/rock and acid/rock IFT only. The new procedure measures
contact angles in such a way that the surface-active agents change
the oil/rock and acid/rock IFT only so that spreading, an artifact
caused by oil/acid IFT reduction, may not occur.
Introduction
The new procedure was necessitated by the need to study the
effect of spent-acid solutions with an amphoteric amine-oxide
VES, used in carbonate matrix acidizing, on wettability. A US
patent and the rheological properties for the VES were described
by Caweizel (2007) and Li et al. (2010, 2011), respectively. Field
applications were described by Nasr-El-Din et al. (2006a, 2006b,
2006c).
Matrix acidizing is used to improve production from oil and
gas wells and to improve injection into injection wells. An acid or
solvent is injected into the reservoir below the fracturing pressure
to create channels that bypass the damage in carbonates. Carbon-
ate reservoirs are stimulated primarily with HCl. Diversion is
needed because of permeability contrasts and lithological differ-
ences in the reservoir (Taylor et al. 2004). Without diverting
Copyright V
C 2014 Society of Petroleum Engineers
This paper (SPE 160876) was accepted for presentation at the 2012 SPE Saudi Arabia
Section Technical Symposium and Exhibition, AlKhobar, Saudi Arabia, 811 April 2012, and
revised for publication. Original manuscript received for review 22 March 2013. Paper peer
approved 5 March 2014.
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agents, only a small fraction of the producing interval will be
stimulated, making the treatment ineffective.
VES is a chemical diverting agent used in carbonate matrix
acidizing. VES-based acid systems divert acid by a buildup of vis-
cosity as the acid spends. Hydrocarbons or mutual solvents break
down the structure of the VES gel into spherical micelles and
reduce the viscosity of the acid (Nasr-El-Din et al. 2008). Mutual-
solvent flushes are also used to make rocks water-wet.
Chemical treatments designed to enhance well performance
can often create instead another form of damage (Nasr-El-Din
2005). Wettability changes caused by stimulation can induce for-
mation damage. The wettability and relative permeability of a for-
mation at any saturation depend on the coatings of surface-active
agents in the reservoir fluids or stimulation fluids (Economides
and Nolte 2000).
Laboratory and field studies suggest that significant amounts
of VES are retained in the reservoir (Nasr-El-Din et al. 2006a;
Crews and Huang 2007; Huang and Crews 2008; Yu et al. 2011).
Retained VES can affect wettability and reservoir performance by
affecting the displacement of spent acid or the production of
hydrocarbons (Jennings 1975; Hinkel et al. 2003).
Contact angles are a quantitative measurement of reservoir
wettability (Anderson 1986). They are used to compare the effect
of the different fluid chemistries on wettability. One can calculate
contact angles from the mass of fluids imbibed into air-saturated
sand columns (Hinkel et al. 2003). With imbibition-rate calcula-
tions, a spent-acid solution with VES only was found to be water-
wetting, and a spent-acid solution with VES and EGMBE was
strongly water-wetting (Lungwitz et al. 2007). The spent-acid sol-
utions represented the mixing that occurs after an acid treatment.
These imbibition experiments allowed a quick study of the effect
of different surfactants and additives on wettability. The contact
angles calculated represent wettability as stimulation fluids
advance over oil- or gas-saturated rocks. However, the wettability
(as stimulation fluids displace oil) is represented by receding con-
tact angles.
One can calculate advancing and receding contact angles from
adhesion/tension measurements with Wilhelmy plates. This tech-
nique does not simulate the reservoir conditions of temperature
and pressure (Muhammad and Rao 2003), and was found to be
insensitive at low IFTs (Vijapurapu and Rao 2004). One can mea-
sure advancing and receding contact angles from the images of oil
droplets on rock surfaces. One can conduct these contact-angle
measurements at reservoir temperature and pressure. Temperature
and pressure can significantly affect wettability (Xu et al. 2008).
The conventional procedure for contact-angle measurements
involves measuring contact angles with the rock in the solution
whose effect on wettability is to be studied. Ayirala et al. (2006)
studied the effect of surfactant adsorption on dolomite crystals
with the dual-drop/dual-crystal technique (Rao and Girard 1996)
to measure advancing and receding contact angles as surfactants
were injected into the optical cell. Similar experiments were per-
formed by Xu et al. (2008). In these experiments, some of the sur-
factants reduced the oil/brine IFT. The low IFTs caused oil
droplets to escape from the lower rock surface and to spread
quickly beneath the upper rock surface. Variations in temperature
365
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Fluids. ACS-grade chemicals were used to prepare the formation

TABLE 1COMPOSITION OF FORMATION BRINE AND brine (Table 1). Spent acid was prepared from ACS-grade dihy-
PROPERTIES OF CRUDE OIL USED TO SATURATE ROCK drous calcium chloride (CaCl2), HCl, and calcium carbonate
SAMPLES (CaCO3). All solutions were prepared with deionized water with a
resistivity of 17.8 mXcm at 25 C. Sour crude oil from a west
Brine Composition Texas field was used. Its viscosity, density, total acid number, and
total base number are given in Table 1.
Salt (TDS* 230,000 ppm) Concentration (mg/L)
Spent-acid solutions were prepared with the reaction products
NaCl 127 523.3 of 20 wt% of HCl and CaCO3, as described by Chang et al.
CaCl22H2O 109 162.66 (2001) and Nasr-El-Din et al. (2008). The following procedure
MgCl26H2O 35 657.7
was used:
1. CaCl2 was added to deionized water and stirred with a mag-
BaCl2 15.16
netic stirrer.
Na2SO4 159.69 2. HCl was added until the pH was between 4 and 5 because
NaHCO3 483.26 the pH at the surface of the rock (when acid reacts with carbonate)
SrCl26H2O 3149.41 was approximately 4.5 (Nasr-El-Din et al. 2009).
Oil Properties From Step 2, spent-acid solutions with HCl and VES only were
Density at 70 C (g/cm3) 0.8015 prepared as follows:
Viscosity at 50 C (cp) 7.1615 3. The desired vol% of VES was added.
Total acid number (mg KOH/g) 0.18 4. It was stirred for 30 to 45 minutes with a magnetic stirrer
Total base number (mg HCl/g) <0.01 until a thick gel was formed.
5. The gel was transferred to a blender and blended for a few
*TDS total dissolved solids.
seconds. This step removed most of the air bubbles.
6. The solution was centrifuged at 3,000 to 6,000 rev/min to
(Rao 1999) and brine concentration (Vijapurapu and Rao 2004) remove the remaining air bubbles.
also resulted in low IFTs that caused oil droplets to spread in From Step 6, spent-acid solutions with HCl, VES, and EGMBE
receding-contact-angle experiments. One cannot determine wett- were prepared as follows:
ability from contact-angle measurements when low IFTs cause 7. A desired vol% of EGMBE was added and stirred with a
spreading and droplet instability. magnetic stirrer until the solution was uniform.
Similarly, spent-acid solutions with VES and EGMBE cause
low oil/acid IFTs. The objective of this study was develop a proce- Contact-Angle Apparatus. A high-pressure/high-temperature (HP/
dure for contact-angle experiments for surfactant solutions that HT) drop-shape-analysis (DSA) instrument (Kruss DSA-100) was
cause oil droplets to spread. The new procedure will allow wettabil- used to measure the static contact angle (Fig. 1).
ity evaluations that were not possible with the conventional method. The major component is the see-through windowed optical
cell (Fig. 1). The maximal operating pressure and temperature of
the cell were 10,000 psi and 200 C, respectively. Heat was
Experimental Studies applied through a heating jacket wrapped around the optical cell.
Porous Media. Austin cream chalk from the Edwards limestone Pressure was applied from a nitrogen cylinder (Fig. 1). A lamp
outcrop was used. Rock samples were prepared to simulate reser- illuminated the sample chamber and rock. The spent acid was
voir conditions (Tiab and Donaldson 1996) using an oven for injected through the top port of the optical cell (not shown). Oil
aging with a centrifuge to simulate brine and oil drainage and stored in an accumulator was injected through the capillary needle
imbibition. and then passed through the bottom port of the chamber. The
Samples were cut to dimensions of approximately 1  0.8  camera captured the image of the oil droplet beneath the rock sur-
0.25 in. and air vacuumed in formation brine for 30 minutes at 25 face. A desktop computer was used to store the images from the
psi. The brine-saturated samples were water-wet at room tempera- camera for subsequent analysis to determine the contact angle.
ture. They were centrifuged at 3,000 rev/min for 30 minutes to For the conventional procedure, rock samples were placed on
approach irreducible brine saturation. They were then centrifuged the sample holder, which was placed in the optical cell, and the
in crude oil at 3,000 rev/min for 30 minutes. The oil-saturated rocks optical cell was filled with the fluid whose effect on wettability
were aged in oil at 200 F for 60 hours. Aged rocks were oil-wet at was to be studied (Tiab and Donaldson 1996). An oil droplet was
room temperature. then injected.

PC

Optical cell
Light source
Digital camera
Compressed N2

Oil

Accumulator

Syringe pump

Fig. 1The HP/HT tensiometer was used to measure contact angles and IFTs between oil and spent acid with HCl only. This sche-
matic is from Alotaibi et al. (2011).

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TABLE 2NOT POSSIBLE TO MEASURE CONTACT ANGLES FOR EXPERIMENTS WITH

SPENT ACID WITH VES AND EGMBE WITH THE CONVENTIONAL PROCEDURE

Temperature EGMBE Contact Angle

( C) VES (vol%) (vol%) (degrees) Wettability

25 1,2,3,4,6 0 Oil droplet spread Indeterminate

60 3 0 Oil droplet spread Indeterminate
80 1 0 Oil droplet spread Indeterminate
110 1 0 Oil droplet spread Indeterminate
25 1 1,5 Oil droplet spread (Fig. 3) Indeterminate
110 1 5,10 Oil droplet spread Indeterminate
25, 50, 80, 110 No VES No EGMBE 50 to 160 (Fig. 2) Water-wet to oil-wet

The following procedure was used:
1. The rock sample was fixed onto the sample holder; the sam-
ple holder was placed in the optical cell of the HP/HT pendant-
drop tensiometer.
2. The spent-acid solution was injected into the optical cell.
3. Compressed nitrogen was applied to the desired pressure.
4. The temperature controller was set to the desired temperature.
5. The lamp was turned on to illuminate the sample.
6. The valve leading to the accumulator was opened to inject
an oil droplet into the optical cell by means of the capillary needle
below the rock. The droplet rises by buoyancy and spreads or
forms a captive droplet on the lower surface of the rock.
7. Images were captured with the camera. Spreading oil drop-
lets were captured by setting the camera to take pictures at inter-
vals of 0.04 seconds.
8. For nonspreading droplets, DSA (Ro and Neumann 1997)
software was used to analyze the pendant-drop image and to cal-
culate the contact angle.
9. At the end of the experiment, the sample chamber was
cleaned with xylene to remove the crude oil, cleaned with acetone
to remove xylene, and then cleaned with deionized water.
The wettability criteria for contact angles vary (Anderson
1986), with 0 to 75 defined as water-wet and 105 to 180 defined
as oil-wet. In this work, contact angles between 0 and 70 were
considered water-wet. Angles between 110 and 180 were consid-
ered oil-wet.
IFT Measurements. A University of Texas Model 500 spinning-
drop tensiometer was used to measure IFTs between oil and
spent-acid solutions with VES and EGMBE.
IFTs were calculated from measurements of the width of oil
droplets viewed through the microscope of the spinning-drop ten-
siometer. IFTs were calculated from the width of oil droplets in
the spinning-drop tensiometer, as described by Gardner and Hayes
(2007). The widths were measured at rotational speeds of 6 to 20
milliseconds/rev.
IFTs were measured between oil and spent-acid solutions with
HCl only with the HP/HT pendant-drop tensiometer (Fig. 1). DSA
software was used to analyze the drop images and to calculate
IFTs. IFT calculations require density measurements. An Anton
Paar digital density meter was used to measure the spent acid and
oil densities at the temperatures at which IFTs were measured.
Results and Discussion
Conventional Contact-Angle Experiments. The conventional
procedure was applied to study the effect of the following spent-
acid solutions on the wettability with receding-contact-angle
measurements: (1) spent acid with HCl only and (2) spent acid
with HCl, VES, and EGMBE.
Aged rock samples were placed in the optical cell of the HP/
HT tensiometer. The cell was then filled with the spent-acid solu-
tion, and oil droplets were injected. The objective of these experi-
ments was to compare the effects of the surfactants in the spent
acid on wettability. The contact angles measured were static/
receding contact angles. Table 2 summarizes the results.
The conventional procedure was effective for spent-acid solu-
tions with HCl only. In contrast, oil droplets spread in spent-acid
solutions with VES and EGMBE because of low oil/acid IFTs.
The spreading shows the effect of spent acid with VES and
EGMBE on the oil/acid interface and does not represent the wett-
ability of the rock.
Effect of Spent-Acid Solutions with HCl Only on Wettability.
The wettability changed from oil-wet to water-wet as the tempera-
ture increased for rocks in spent-acid solutions with HCl only
(Fig. 2 and Table 2, bottom row). Contact angles decreased from
154 to 54 as temperature was increased from 25 to 110 C.
The contact angle was 154 at 25 C, and decreased to 127 at
50 C, 108 at 80 C, and 54 at 110 C, respectively. This trend
shows that the conventional procedure was effective for studying
the effect of spent-acid solutions with HCl only on wettability.
The tendency for carbonates to become more water-wet as the
temperature increases was reported by Rao (1999), Wang and
Gupta (1995), and Hjelmeland and Larrondo (1986). A decrease
in the surface activity of surfactants in oil as the temperature
increased may cause the wettability to change to water-wet (Hjel-
meland and Larrondo 1986). Our oil/acid IFT measurements are
consistent with this.

25C 50C 80C 110C

Rock
Oil droplet
Spent acid with
HCl only
Spent acid with
HCl only
= 154 = 127 = 106 = 52

Increasing water-wetness

Fig. 2The conventional procedure for contact-angle measurements was effective for spent-acid solutions with HCl only. The
wettability of Austin cream chalk changed from oil-wet (154 ) to water-wet (52 ) as temperature increased.

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 REE160876 DOI: 10.2118/160876-PA Date: 19-July-14
Rock
Oil
Droplet
0 3s
Fig. 3The conventional procedure was not effective for spent-acid solutions with HCl, VES, and EGMBE (in this instance with
HCl, 1 vol% of VES, and 1 vol% of EGMBE) because oil droplets spread on the rock surface.
Effect of Spent-Acid Solutions With VES and EGMBE on
Wettability. Oil droplets spread on the surface of rocks in spent-
acid solutions with VES and EGMBE (Table 2).
Oil droplets spread in spent-acid solutions with HCl, 1 vol% of
VES, and 1 vol% of EGMBE at 25 C (Fig. 3). Oil also spreads in
spent-acid solutions with HCl and 1, 2, 3, 4, and 6 vol% of VES
at 25 C; in spent-acid solutions with HCl and 1 vol% of VES at
110 C; and in spent-acid solutions with HCl, 1 vol% of VES, and
10 vol% of EGMBE at 110 C. Typically, droplets spread com-
pletely within 5 to 10 seconds.
The spreading of oil in spent-acid solutions with VES and
EGMBE could have resulted from either strong oil-wetness or
low oil/acid IFTs. One of the reasons that a person may discount
strong oil-wetness is that the 10:1 ratio of EGMBE to VES is
likely to be water-wetting. An explanation of the results requires a
review of the relationship between contact angles and IFTs.
Explanation of Results. The contact angle is a measure of the
preference of the rock for oil or spent acid. It is a function of the
oil/acid IFT, the oil/rock IFT, and the acid/rock IFT. Youngs
equation expresses the relationship between the contact angle and
the IFTs at equilibrium on a rock surface (Tiab and Donaldson
1996), as shown in Fig. 4.
The oil/rock (cOS ) and the spent-acid/rock (cWS ) IFTs are at the
rock/fluid interface (Fig. 4). The difference between cOS and cWS
determines the wettability of the rock (the preference of the rock
for oil or spent acid). In contrast, the oil/acid IFT (cOW ) is at the
oil/spent-acid interface (Fig. 4) and does not affect the wettability.
Therefore, one should measure contact angles in such a way
that droplet behavior is affected by changes in the rock/fluid inter-
face (the wettability) only. In the conventional procedure, placing
the rock in the surfactant solution will cause the surfactants to
change the rock/fluid IFTs. However, the surfactants can also
change the oil/acid IFT. The change in the oil/acid IFT does not
affect the wettability, and can cause an artifact when oil droplets
spread as a result of low oil/acid IFTs.
In contact-angle measurements in an oil/brine/rock system, the
Rao (1999) plot of contact angles against the IFT (his Fig. 8)
shows that there is a minimal oil/brine IFT, called the critical
spreading tension, below which oil droplets will spread on the
Rock surface
Spent acid- Oil-Rock, Rock-fluid
rock IFT, ws rock IFT, os
interface
Oil
Oil-Spent acid
IFT, ow Spent acid
Fig. 4The contact angle h is a function of the oil/rock, acid/
rock, and oil/acid IFTs. However, the wettability of the rock is a
function of the oil/rock and acid/rock IFT only. The new proce-
dure measures contact angles in such a way that the surface-
active agents change the oil/rock and acid/rock IFT only.
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Spent acid with
HCl, VES and
EGMBE
surface of the rock. Fig. 4 suggests that surfactant solutions that
reduce the oil/acid IFT may introduce an artifact in the experi-
ment by causing oil droplets to spread and by preventing the ob-
servation of changes in the rock/fluid interface, which represents
the wettability.
Spent-Acid Solutions with VES and EGMBE Reduced the Oil/
Acid IFT. Spent-acid solutions with VES and EGMBE reduced
the oil/acid IFT by one to three orders of magnitude at 25 and
80 C when compared with spent-acid solutions with HCl only
(Fig. 5). The oil/acid IFT was reduced from 24.5 mN/m at 25 C
in spent-acid solutions with HCl only to 0.75 mN/m for spent-
acid solutions with 1 vol% of VES and 10 vol% of EGMBE and
to 0.16 mN/m for spent acid with 1 vol% of VES only. At 80 C,
the oil/IFT was reduced from 27 mN/m in spent-acid solutions
with HCl only to 3 mN/m in spent-acid solutions with 1 vol% of
VES and 10 vol% of EGMBE and to 0.04 mN/m in spent acid
with 1 vol% of VES only.
Oil Droplets Spread Because of Low IFTs. Analysis suggests
that oil droplets spread because EGMBE and VES reduce the oil/
acid IFT below the critical spreading tension. Similarly, we can
attribute the spreading observed in experiments by Ayirala et al.
(2006), Xu et al. (2008), Rao (1999) and Rao and Vijapurapu
(2004) to low IFTs between the oil and the surfactant solution.
A procedure for contact-angle measurements that prevents sur-
factants from changing the oil/surfactant solution IFT, while
allowing changes in the rock/fluid interface, can provide new
insights into the effect of surfactants that reduce the oil/surfactant
solution IFT on wettability.
New Procedure
One way to prevent the surfactant from reducing the oil/acid IFT
is to use a surfactant-free fluid for all contact-angle measure-
ments. The fluid should have similar characteristics, such as pH
and brine concentration, to those of the environment in which
wettability is to be studied. In addition, a method was needed to
Oil-acid IFTs at 25C
30
25 24.5 mN/m
IFT (mN/m)
20
15
10
5 0.75 mN/m
0
0 50 100 150 200
0.016 mN/m Time (minutes)
Spent acid with HCl only
Spent acid with HCl, 1 vol% Spent acid with HCl and 1 vol%
VES and 10 vol% EGMBE VES
Fig. 5Spent-acid solutions with VES and EGMBE reduced the
oil/spent-acid IFT by more than a factor of 10 at 25 C (shown
previously) and 80 C. This caused oil droplets to spread.
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Fig. 6Wettability alteration can be achieved by placing rocks in contact with solutions with surface-active agents. Aging rocks in
crude oil caused a wettability change from water-wet (30 to 45 , left) to oil-wet (140 , right) at 25 C.

cause surface-active agents in spent acid to change the rock/oil
and rock/acid IFTs by the adsorption of substances or removal of
adsorbed substances.
On the basis of these requirements, the new procedure had the
following steps:
1. The water-wet and oil-wet rocks were centrifuged in differ-
ent spent-acid solutions to simulate the flow of spent acid through
them. This should have caused the surfactants in the spent acid to
adsorb or change the interfacial properties of the rock.
This can be justified because wettability changes occur as a result
of bringing rocks by bringing them in contact with fluids with sur-
face-active agents. Carboxyl groups and polar compounds in oil
cause carbonate rocks to become more oil-wet (Lowe et al. 1973;
Sayyouh et al. 1991; Tiab and Donaldson 1996). Similarly, aging
rocks in crude oil (Graue et al. 1999; Standnes and Austad 2000)
and flowing surfactants and oil- and water-based drilling muds
through these rocks (Cuiec 1989; Mohan et al. 2011) altered their
wettability. In the laboratory, the wettability of Austin cream
chalk rock samples changed from water-wet (approximately 30 to
45 , Fig. 6) to oil-wet (approximately 140 , Fig. 6) after satura-
tion with formation brine and crude oil and then aging for 60
hours in crude oil.
2. The contact angles in spent-acid solutions with HCl only
were measured before and after centrifuging.
This kept oil/acid IFTs large (above the critical spreading ten-
sion) for all contact-angle measurements. It also allowed for a
comparison of the effect of different surface-active agents in the
spent-acid solutions on the rock/fluid interface only, without dis-
tortions caused by changes in the oil/acid IFT. Spent acid with
HCl has the same pH and CaCl2 concentration as spent acid with
VES and EGMBE.
Experimental Studies. The new procedure was applied to study
the effect of wettability of spent-acid solutions with HCl only and
with HCl, VES, and EGMBE. The following steps were followed:
1. Contact angles were measured in spent-acid solutions with
HCl only to determine the initial wettability.
2. The rock samples were centrifuged at 5,000 rev/min for 2
hours in the following:
a. Spent-acid solutions with HCl only.
b. Spent-acid solutions with HCl and 1 vol% of VES and 10
vol% of EGMBE.
The surfactants in the spent acid caused changes in the wettability
of the rock (i.e., changes in the oil/rock and acid/rock IFT).
3. Contact angles were measured in spent-acid solutions with
HCl only to determine the final wettability.
4. The effect of surface-active agents in the spent acid on wett-
ability was determined by comparing contact angles before and
after centrifuging.
Experiments were conducted at 500 psi and 25 C.
Results
Spent-Acid Solutions with 1 Vol% of VES and 10 Vol% of
EGMBE Were Water-Wetting. An oil-wet rock with a contact
angle of 155 became water-wet with a contact angle of 41 after
it was centrifuged in a spent-acid solution with 1 vol% of VES
and 10 vol% of EGMBE (Fig. 7).

Rock surface

Oil droplet Oil-wet before

centrifuging:
Contact angle = 155
Spent acid solution with
HCl only
Centrifuge in spent acid
with HCl, 1 vol% VES,
and 10 vol% EGMBE

Rock surface
Water-wet after
centrifuging:
Oil droplet Contact angle = 41

Spent acid solution with

HCl only

Fig. 7With the new procedure, centrifuging an oil-wet (top, 155 ) rock in a spent-acid solution with HCl, 1 vol% of VES, and 10
vol% of EGMBE resulted in a change of the wettability to water-wet at 41 .

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One can apply it to dynamic contact-angle experiments such as

160 155 the dual-drop/dual-crystal (DDDC) technique. The DDDC technique
involves measuring receding contact angles before merging the
Contact Angle ()

120
Before centrifuging
80 After centrifuging
42
40
40
0 0
oil-wet water-wet water-wet strongly water-wet
Fig. 8The new procedure was effective for studying the effect
on wettability of spent acid with VES and EGMBE. Spent-acid
solutions with 1 vol% of VES and 10 vol% of EGMBE made oil-
wet rocks water-wet (left) and water-wet rocks strongly water-
wet (right).
Centrifuging a water-wet rock in a spent-acid solution with 1
vol% of VES and 10 vol% of EGMBE resulted in the oil droplet
rolling off the surface of the rock. This implies that the oil droplet
did not adhere onto the surface of the rock because the rock sur-
face was strongly water-wet. The contact angle was assumed to
be 0 (Fig. 8).
The change in wettability to water-wet probably occurred
because EGMBE dissolved the crude-oil components that were
adsorbed on the rock surface (Economides and Nolte 2000). The
VES remained in solution, not adsorbing at the rock/fluid inter-
face. Mutual solvents keep surfactants and other stimulation addi-
tives in solution and stop them from adsorbing onto the rock
surface (Hall 1975).
Spent-Acid Solutions with HCl Only Had No Effect on
Wettability. This serves as a control experiment. An oil-wet
Austin cream chalk rock remained oil-wet after it was centrifuged
in a spent-acid solution with HCl only (Figs. 9 and 10). Similarly,
centrifuging a water-wet rock in a spent-acid solution with HCl
only caused no change in wettability (Fig. 10). This is because
there are no surface-active agents in spent acid with HCl only.
Applications. The new procedure was used for receding-contact-
angle measurements with surfactant solutions that cause spread-
ing. These types of measurements were not possible with the con-
ventional method (Adejare et al. 2012).
droplets to measure dynamic contact angles. One can prepare rock
samples by centrifuging them in surfactant solutions. One can mea-
sure advancing and receding contact angles in a surfactant-free fluid,
such as formation brine. Comparing contact angles before and after
centrifuging will show the effect of the surfactant on wettability.
Limitations. Surfactant desorption from the surface of the centri-
fuged rock into the solution may change the IFT between oil/acid
and rock and consequently change the wettability (Adejare et al.
2012). Steps to remove the weakly adhered surfactant (such as
more centrifuging) may prevent a study of the effect of the origi-
nally adsorbed surfactant layer on wettability, by removing some
or all of it. In addition, if IFTs above the critical spreading tension
vary as a result of varying surfactant or brine concentrations
(Vijapurapu and Rao 2004), the effect of the different IFTs on
contact angles and wettability is unknown. Another concern is the
effect on the wettability of exposing the rocks to air when trans-
ferred to and from the tensiometer between centrifuging stages.
In spite of these potential limitations, applying the new proce-
dure can yield many benefits. One can gain new insights on the
effect of surfactants on wettability (Adejare et al. 2012) if contact
angles are measured in a way that ensures that the oil/liquid IFT
does not affect the results.
Conclusions
A new procedure was presented for contact-angle experiments for
surfactants that reduce the IFT between oil and the surfactant so-
lution, such as spent-acid solutions with VES and EGMBE. The
conventional method cannot be used with these surfactants
because low IFTs make oil droplets unstable on the rock surface.
1. The conventional procedure for contact-angle measurements, in
which the tested solutions are injected into the optical cell, is
effective for solutions with no surfactants (Fig. 2).
2. In contrast, the conventional procedure is not effective for sur-
factant solutions, such as with VES and EGMBE, which reduce
the oil/acid IFT below the critical spreading tension (Fig. 5),
because oil droplets spread (Fig. 3 and Table 2).
3. The new procedure involves centrifuging the rock in surfactant
solutions, so that the surface-active agents alter the interfacial
properties of the rock. Contact angles were then measured in a
surfactant-free fluid with a high oil/liquid IFT. The difference
in contact angles before and after centrifuging indicates the
effect of the surfactant on wettability.

Rock surface

Oil droplet Oil-wet before

centrifuging
Contact angle = 155
Spent acid solution with
HCl only
Centrifuge in
spent acid with
HCl only

Rock surface
Oil-wet after
centrifuging
Oil droplet Contact angle = 133

Spent acid solution with

HCl only

Fig. 9Spent acid with only HCl resulted in no change in wettability for an oil-wet rock. This was the control experiment for the
new procedure.

370 August 2014 SPE Reservoir Evaluation & Engineering

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 REE160876 DOI: 10.2118/160876-PA Date: 19-July-14
Before
160
centrifuging
155
Contact Angle () After
120 133 centrifuging
80
40
40 40
0
oil-wet oil-wet water-wet water-wet
Fig. 10Spent acid with only HCl did not change the wettability
of oil-wet and water-wet rocks. This was the control experiment
for the new procedure.
The new procedure was effective in studying the effect of
spent acid with VES and EGMBE because the contact angle was
measured in a surfactant-free solution (Fig. 7). The oil/acid IFT is
kept high and constant, so that one can observe the changes in the
oil/rock and acid/rock IFT that represented the wettability.
The new procedure will allow wettability evaluations that
were not possible with the conventional method.
Nomenclature
h oil/spent-acid contact angle, degrees
cow oil/spent-acid IFT, mN/m
cOS oil/rock IFT, mN/m
cWS spent-acid/rock IFT, mN/m
Acknowledgments
The authors would like to thank AkzoNobel Company for sponsor-
ing the project, ConocoPhillips Company for supplying crude oil,
and Baker Hughes for supplying EGMBE. The authors would also
like to thank Kristina Hansen for proofreading the manuscript.
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Oladapo Adejare is a research engineer with Nalco Cham-
pion in Fresno, Texas. He holds a BS degree in mechanical en-
gineering from the University of Lagos and an MS degree in
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petroleum engineering from Texas A&M University. Adejares
current work is on understanding how surfactants affect initial
production and ultimate recovery in unconventional oil and
gas reservoirs. He is an SPE member.
Ramez Nasralla is currently a research reservoir engineer at
Shell Global Solutions International where he works on projects
related to improved oil recovery. He was a research assistant
in the Department of Petroleum Engineering at Texas A&M Uni-
versity while preparing the presented work. Nasralla has more
than 6 years of teaching and research experience at Cairo
University and Texas A&M University. He worked as a geome-
chanics engineer for 3 years with Advantek International on
several projects of produced-water and drill-cuttings reinjec-
tion. Nasralla has authored several publications on topics
related to low-salinity waterflood, well stimulation, well testing,
and reservoir simulation. He holds BSc and MSc degrees from
Cairo University and a PhD degree from Texas A&M University,
all in petroleum engineering. Nasralla is an SPE member and
serves as a technical editor for SPE Journal.
Hisham A. Nasr-El-Din is a professor and holder of the John
Edgar Holt Endowed Chair at Texas A&M University in petro-
leum engineering. Previously, he worked for 15 years as a prin-
cipal professional and team leader of the Stimulation
Research and Technology Team, Saudi Aramco. Before join-
ing Saudi Aramco, Nasr-El-Din worked for 4 years as a staff
research engineer with the Petroleum Recovery Institute in
Calgary. He also worked as a research associate with the Uni-
versity of Saskatchewan, the University of Ottawa, and the Uni-
versity of Alberta, all in Canada. Nasr-El-Dins research interests
include well stimulation, formation damage, enhanced oil re-
covery, conformance control, interfacial properties, adsorp-
tion, rheology, cementing, drilling fluids, two-phase flow, and
nondamaging fluid technologies. He holds several patents
and has published and presented more than 550 technical
papers. Nasr-El-Din has received numerous awards within
Saudi Aramco for significant contributions in stimulation and
treatment-fluid technologies and stimulation design, and for
his work in training and mentoring. He holds BSc and MSc
degrees from Cairo University and a PhD degree from the
University of Saskatchewan, Canada, all in chemical engi-
neering. Nasr-El-Din serves on SPE steering committees on stim-
ulation and oilfield chemistry, is a review chairperson for SPE
Journal, and is a technical editor for SPE Production & Opera-
tions and SPE Drilling & Completion. He was invited to give key-
note presentations at various SPE and National Association of
Corrosion Engineers conferences. Nasr-El-Din received the SPE
Regional Technical Discipline Award for Production and Oper-
ations in 2006, was named a Distinguished SPE Member in
2007, and received SPE awards for Outstanding Associate Edi-
tor (SPE J) and Outstanding Technical Editor (SPE PO) in 2008.
In addition, he received the SPE Production and Operations
Award and Outstanding Associate Editor Award (SPE J) in
2009. Nasr-El-Din received SPE A Peer Apart status in 2011 for
reviewing more than 100 papers. He was named the 2013 re-
cipient of the SPE Distinguished Achievement Award for Petro-
leum Engineering Faculty.
August 2014 SPE Reservoir Evaluation & Engineering