Contact Angles for Equilibrated
Microemulsion Systems
Ronald L. Reed, SPE, Exxon Production Research Co.
Robert N. Healy, SPE, Exxon Production Research Co.
Abstract
Advanced and receded contact angles have been
measured on various high- and low-energy substrates as
functions of microemulsion-excess phase interfacial ten-
sions (1FT's). Many experimental difficulties peculiar to
these low-tension systems caused large measurement er-
rors. But with this constraint and with one exception,
contact angles were hysteresis-free and independent of
the substrate.
For lower-phase microemulsions and high-energy
substrates, it is proposed that the surfactant polar group
adsorbs on the solid and then a surfactant bilayer forms.
This bilayer provides the effective substrate that relates
to contact angle and 1FT's through Young's equation.
An optimal salinity for contact angles is defined and
related to previously introduced optimal salinities, in
particular to that associated with best oil recovery.
Results suggest the optimum attainable contact angles
for microemulsion-based oil recovery may not be 0°.
Introduction
1FT and contact angle do not occur explicitly in the
macroscopic equations governing multiphase flow
through porous media; rather their impact is manifested
implicitly through the relative permeability and capillary
pressure functions. This dependence has been estab-
lished experimentally, but there is not yet a satisfactory
theoretical treatment. It is partly for this reason that it is
difficult to ascribe with confidence the individual and
collective effects of these two parameters and partly
because contact angles measured on idealized substrates
may not accurately imitate those obtained in situ.
So far, attention has focused primarily on the roles
played by independently specified 1FT's and contact
angles in the displacement of isolated residual oil
ganglia. 1-4 One conclusion of these studies is that the
most favorable wettability condition for tertiary oil
recovery is 100% water-wet (i.e., (1=0°) when
measured through the aqueous displacing phase. 1,2,4
However, as we have pointed out, 5 oil mobilization is
not the central question. Rather, from the onset of oil
bank formation, the essential problem is to "maintain
continuity of the flowing oil filaments to as Iowa satura-
tion as possible before they rupture and are irretrievably
lost. " Since the mechanism of this rupture-trapping
process is different from that of oil mobilization, it is
quite possible (in fact likely) that the effects of contact
angle and 1FT also are different. The only specific pro-
posal germane to this line of inquiry has been made by
Morrow. 6
0197-7520/84/0006-8262$00.25
Copyright 1984 Society of Petroleum Engineers of AIME
342
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In view of these considerations, the possibility must be
entertained that (I = 0 ° is not optimal for tertiary oil
recovery.
Measurement of contact angles for high-tension
systems such as liquid/vapor or nonpolar liquid/water is
exacting for a variety of reasons. For example, surface
preparation is critical and requires meticulous attention
to asperity, heterogeneity, chemical composition, and
contamination. Fluids must be scrupulously purified or
be at least of reproducible composition.
Avoiding these pitfalls was a prime consideration in
this study. So first, a surface preparation technique was
developed that guaranteed a clean smooth substrate. Sec-
ond, it seemed obvious a priori that the presence of sur-
factant in high concentrations would completely
dominate the usual laboratory contaminants. However,
new difficulties attended contact angle measurements at
the low 1FT's common to multi phase microemulsion
systems, and these may have clouded results.
The most that can be claimed is that a start has been
made toward acquiring techniques needed to measure
contact angles potentially pertinent to flow of
microemulsions through porous media. Some trends
have been developed, correlations made, a model pro-
posed, and a few conclusions and conjectures outlined,
but much more and much better work will be required
before significant advances in understanding are made.
Terminology
It is conventional to measure contact angles through the
more dense phase. Thus, for a drop of oil against air, the
contact angle is measured through the oil. For a drop of
the same oil against water, the contact angle would be
measured through the water.
A similar convention holds in regard to moving inter-
faces; they are called advancing or receding depending
on motion of the more dense fluid with respect to
substrate it has contacted. In the experiments reported
here a drop is placed on a substrate previously
equilibrated with cell fluid and allowed to spread. When
the drop fluid is more dense than the cell fluid, contact
angles obtained during spreading are advancing angles.
Otherwise they are receding. Eventually, motion ceases
and the contact angle adopts a constant value. This is the
recorded value and, as suggested by Huh and Scriven, 7
it is correspondingly labeled advanced or receded.
Fig. 1 illustrates the various configurations of cell and
drop fluids. For example, a lower-phase microemulsion
can be the drop fluid and the excess oil phase can be the
cell fluid. In this event the contact angle is advanced and
since the oil contacted the substrate first, it is written
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
ogm' If the cell fluid is microemulsion and the drop is ex-
cess oil, then one has OirlO' as illustrated. For a middle-
phase microemulsion, six angles can be measured, but
contact angles between excess phases were not routinely
determined.
Background Information
Levine and Zisman 8 found that contact angles of
methylene iodide on platinum, stainless steel, or
borosilicate glass are all the same when the substrates are
coated with a monolayer of n-octadecylamine, indepen-
dent of the method of film preparation. Further, Zisman
et al. 9 showed that advancing and receding contact
angles of water on long chain paraffinic films retracted
from aqueous solution were identical, whereas they were
different if the film was retracted from a- nonaqueous
solution in a nonpolar liquid. The reason is that, in the
first case, water had already permeated the film during
preparation, so that further contacting it with a water
drop made no difference. In the second case, the film in-
itially contained no »,ater, so contacting it with a water
drop in the advancing mode altered the film by water
permeation' 'between the long, adlineated, hydrocarbon
chains of a close-packed monolayer of a fatty acid,
alcohol or primary amine. "
Fox and Zisman 9 studied equilibrium contact angles
of n-alkanes on low-energy surfaces and found cosO is a
linear function of alkane surface tension, and the in-
tercept of this line at 8=0° (cosO = 1) was defined to be
the critical surface tension for wetting, 'Y c' Even when
nonhomologous liquids were used, the character of this
relation was preserved, so that 'Y c was considered a
characteristic of the surface. It was concluded that "wet-
tability of low-energy organic surfaces or of high-energy
surfaces coated by organic films is determined essential-
ly by the exposed surface atoms, and is otherwise in-
dependent of the underlying atoms and molecules."
When 'Y c was measured for a variety of well-defined
low-energy surfaces, it was found to vary from 6 to 45
dyne/cm [6 to 45 mN/m]. Of special interest is the
critical tension for -CH3 of 24 dyne/cm [24 mN/m]
since this is the value appropriate to a monolayer of sur-
factant having polar groups adsorbed on the solid.
Experiment
The apparatus used to measure contact angles is nearly
the same as that previously employed for estimation of
1FT using the sessile-drop method. 10 Contact angle, 0,
was measured directly from an enlarged photograph us-
ing a protractor. Substrates were Teflon@, fractured
Pyrex™, polished quartz, Pyrex, and titanium.
Measurement of contact angles to a precision of ± 1 to
2° is commonly claimed (e.g., see Ref. 11). However,
to our knowledge, contact angle measurements have not
previously been reported for ultralow-tension systems
containing surfactants and, in particular, for equilibrated
microemulsions in a multiphase regime. For these
systems a variety of new problems is encountered that
adversely affect measurement precision.
When 1FT is very low, even extremely small sessile
drops are flat, and no method was found to circumvent
this. When ·a drop is flat, its profile is obscure near the
three-phase contact. Hence, as 1FT decreases, so does
precision of the contact angle. Also, when 1FT is ex-
JUNE 1984
o a
/IT:2\e om
I
ADVANCED RECEDED
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Fig. 1-Microemulsion-excess phase drop configurations.
tremely low, perhaps 0 (10- 3 dyne/cm [10- 3 mN/mD,
it may not be possible to form a drop; instead, fluid can
stream out of the needle and disappear.
Multiphase microemulsion systems are temperature
sensitive and this causes two problems. First, in
response to small temperature fluctuations, a second
phase can nucleate from the cell fluid and deposit on the
cell windows, which obscures vision. Second, the same
can happen inside the syringe needle, making deposition
of a symmetrical drop difficult. Even though uniform
temperature is maintained throughout, a second phase
can nucleate simply because conditions required to main-
tain equilibrium have been altered. Thus, if a middle-
phase microemulsion is removed from its excess phases
and placed in a new container, a small amount of one of
the excess phases has been observed to nucleate. This
may result from a small temperature change, from ad-
sorption on container walls, or simply because an
isolated middle phase is not an equilibrium system.
Finally, the broad range of wettabilities encountered
makes countercurrent imbibition of cell fluid into the
needle and flow of drop fluid along the exterior of the
needle common and exasperating events.
Some of these problems have been solved recently, but
many of them attended accumulation of data included
here. It is for these reasons that contact angles reported
have a precision ranging from ±5 to ± 12°. Most
measurements were within ± 10° .
Substrate Preparation. It has been demonstrated both
experimentally and theoretically that one reason for con-
tact angle hysteresis is surface roughness. 12-14 Also, vir-
tually every publication concerning experimental estima-
tion of contact angles dwells on cleaning and handling
techniques used to avoid contamination of fluids and
surfaces.
Quartz, Pyrex and titanium surfaces were carefully
polished. Teflon surfaces were neither polished nor heat-
treated but appeared smooth and shiny. Substrates were
cleaned with solvents, strong acids, in boiling 30%
hydrogen peroxide, and distilled water, and stored under
distilled water. Contact angle measurements showed no
significant effects of different cleaning procedures.
Concern that polished surfaces might not be sufficient-
ly smooth and that cleaning procedures might be inade-
quate or affect results in some way led to the following
technique. A Pyrex rod is notched, cleaned, and inserted
343
 'n'

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- MICRO-SYRINGE

FRACTURED /
~0
SURFACE

Fig. 2-Sessile-drop cell and fracturing device.

into the clean cell. The cell is then filled with fluid and
equilibrated at temperature . As shown in Fig. 2, a rod-
breaker is provided to grasp the Pyrex rod and twist it off
at the notch. The needle-syringe is then used to place a
drop of a phase immiscible with the cell fluid on the new
surface. In this way a perfectly clean, smooth Pyrex sur-
face is provided that has been exposed only to the pre-
equilibrated fluids whose tension and contact angle are to
be estimated.
Fig. 3 shows two electron microscope scans ofa frac-
tured Pyrex surface. The upper micrograph at 1,OOOX
magnification (note 20-micron [20-JLm] bar) shows con-
taminants not removed , so . as to provide objects on
which to focus. The debIis-free shaded rectangle is
enlarged in the lower micrograph at 20,oooX (note
I-micron [1-JLm] bar) . No surface irregularities are c1ear-
lyvisible at this magnification so it can be concluded that
surface asperity is less than' about 250 A [25 nm]. How
smooth a surface must be to avoid effects of roughness
on the contact angle is not resolved. In one study 1,000
A [100 nm] was cited as a critical dimension,15 but
other work on high-energy surfaces suggests lower
values are needed. 16
It has been pointed out that this process of cleavage
within a fluid may cause a surface chemical reaction and
result in a surface different from Pyrex prepared in some
other way. However, any rigorous cleaning/polishing
procedure may be subject to similar criticism. In any
event, the method provides a smooth surface that has
been affected only by the test fluids, and in this sense it
is desirable.
Figs. 4 and 5 show sessile drops on fractured Pyrex,
quartz crystal, Teflon and titanium, giving an idea of
surface smoothness and the definition obtained of drop
profile. Profiles were seldom better than these and often
not as well defined . . crystal.
Results
Effect of Time and Substrate. Many lower-phase
microemulsions in equilibri~m with excess oil were
344
Fig. 3-Scanning electron microscope studies of fractured
Pyrex .
prepared from 63/37 monoethanol amine salt of C 12
o-xylene sulfonate/t-amyl alcohol mixed with various
amounts of I % NaCl brine and 90/10 IsoparTM M/heavy
aromatic naphtha oil (see Ref. 17 for descriptions of
these chemicals). A ternary diagram for this system ap-
pears in Fig. 6 and many overall compositions for the
two-phase system are shown along with the 1FT between
phases and a receded contact angle . It can be seen that
1FT's are low and contact angles high (preferentially oil-
wet) on the oil-rich side of the diagram, whereas 1FT's
llre higher and contact angles lower (preferentially
rnicroemulsion-wet) on the brine-rich side.
For each composition studied, contact angles were
measured on several different substrates. Figs. 7 and 8
show the time dependence exhibited by receded contact
angles of about 90° (neutral) and about 30°
(microemulsion-wet) . In neither case can a trend be iden-
tified that would distinguish one type of surface from
another. In Fig. 8, angles on Teflon are lower than on
most of the other substrates , but so are those on quartz
. Figs. 9 and 10 illustrate the time and substrate
dependence for advanced contact angles, and again,
nothing distinguishes the various surfaces. In both cases
fractured Pyrex required about 11 minutes to reach a
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
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Fig. 4-Sessile drops on fractured Pyrex and on quartz Fig. 5-Sessile drops on Teflon and on titanium.
crystal.

63/31 MEACI20XS/TU
steady value and in Fig. 10, Teflon required 40 minutes
to do so. However, once steady values are achieved,
there is no effect of substrate. The appearance of I
relatively long time effects such as these could not be 81~M'
correlated with type of substrate or character of the con- 1
tact angle. OIL
Similar contact-angle-time graphs were prepared for
all systems studied and no distinction between substrates
was evident within the experimental error associated
MICRO-
[MULSION
B
with these measurements .
• y. e~o; mdyne /cm. O
Critical Surface Tension. As illustrated in Fig. 11, 3.1,156
spreading for the lower-phase microemulsion system can
happen in two ways. In the upper diagram a drop of
microemulsion is shown spreading with a vel)' large ad-
vancing contact angle over a substrate pre-equilibrated Fig. 6-Compositions, 1FT's, and contact angles.
with excess oil. In the lower diagram, a drop of excess
oil is shown spreading with a vel)' large receding contact
angle over a substrate pre-equilibrated with microemul-
sion . If the 1FT is sufficiently low, these drops will con- parently spreading drop on the substrate , it was assigned
tinue spreading until the confines of the substrate provid- 8= 1800.
ed are exceeded. Since substrates were small in lateral Using Zisman's approach, the cosines of receded con-
extent (3 mmx6 mm [0.12 in.xO.23 in.]), it could not tact angles on Pyrex fractured under microemulsion are
be determined with certainty that spreading was ob- graphed as a function of 1FT in Fig. 12. When angles
tained, but if repeateq attempts failed to retain an ap- less than 45° are excluded, remaining data appear
JUNE 1984 345
 120 160
° '<J
100 o g~ '<J
140 c-
'<J 60 6 0 0
0
6 0 '<J
00
0° 6 120 r- 0
80
r
0~o 8 0m 100 0
RECEDED 60 0 FRAC.PYREX
ADVANCED
CONTACT 0 PYREX ROD
CONTACT
0 tj>0 OQJ CO 00 0
ANGLE .• 6 TITANIUM 80 - 0
ANGLE:
40 '<J QUARTZ ROD
<0 0 FRAC.PYREX
° QUARTZ CRYSTAl 60
0 TEflON 0 PYREX ROD
20
0 QUARTZ CRYSTAL
40 -
0
0 TEFLON

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0 10 15 20 25 30 I I I I I I
20
DROP AGE. MIN. 0 5 10 15 20 25 30
DROP AGE. MIN.
Fig. 7-Effect of substrate and drop age on receded contact
angles.
Fig. 9-Effect of substrate and drop age on advanced con-
tact angles.
60,---------------------,
°o FRAC. PYREX
PYREX ROD 140,----------------------------------,
e~o 40 r- "il QUARTZ ROD
RECEDED o QUARTZ CRYSTAl 120 I-
o FRAC. PYREX
COIlTACT
AIIGLE: 20 f-=..$
o ° ~Q)Q(!J ~g {;> <J:j;J°o o TEFlOII
100 I-
'<J QUARTZ ROD

el 00 0
o TEFLON
°0L---~---,~0--~,5~--2~0--~25 "om 801- 0 o
ADVANCED
DROP AGE. 11111. CONTACT o
ANGLE.o 60 I- 0 0 o
Fig. 8-Effect of substrate and drop age on receded contact
40
angles. o oct
20 I-

OL-~ __- i_ _- L_ __ L_ _~_ _~_ _L_l__l~

o 10 15 20 25 30 35 40
reasonably linear. In view of the uncertainty about DROP AGE. MIN.
spreading discussed earlier, it cannot be guaranteed this
graph is linear and intercepts cosO = -I (spreading) at 4 Fig_ 10-Effect of substrate and drop age on advanced con-
mdyne/cm [4 x 10 -3 mN/m] as drawn; it is conceivable tact angles.
that it has a toe at very low tensions and passes through
°
cosO = - I, 'Y = or some other, intermediate value of 'Y.
For this reason we say only that 'Y c $ 4 mdyne/cm these angles are hysteresis-free, again, with reservations
[4XIO- 3 mN/m]. concerning Teflon.
When 0 < 45 0 , data level off and 0 assumes small If for 0 > 45 the graph in Fig. 13 is indeed linear, as it
0

values largely independent of 'Y. All graphs of cosO vs.'y
represented in Figs. 12 to 15 had this character indepen-
dent of substrate and whether angles were advanced or
receded.
The same kind of graph appears in Fig. 13 with reced-
ed angles measured on all five high-energy substrates
represented. The straight line drawn is the same as in the
previous figure for fractured Pyrex alone and the fit is
good.
Fig. 14 shows receded angles measured on Teflon.
The dashed line is the one drawn for high-energy
substrates, but here scatter is worse and data are better fit
with a line through the origin. Hence, it may be that
receded contact angles on Teflon are different from those
on high-energy substrates, but results are not conclusive.
Finally, advanced contact angles on Teflon, fractured
Pyrex, and quartz crystal are all graphed in Fig. 15, and
the original straight line fits the data well, except for one
point.
In summary, advanced and receded contact angles are
pairwise the same and independent of substrate within
± 10 0 , with the possible exception of Teflon. Hence
346
appears, then the intercept at cosO= -I can be inter-
preted as a critical surface tension for spreading, 'Y c' and
'Y c $4 mdyne/cm [4 x 10 -3 mN/m]. Such a remarkably
low value could not relate to the underlying substrate but
rather must represent the net effect of one or more lay~rs
of surfactant that provide an "effective substrate" of
very low energy.
In any event, the interpretation is analogous to that in
Zisman's work; if 'Y rna exceeds 'Y c' then a drop of lower-
phase microemulsion will not spread over an excess-oil
equilibrated substrate, nor will a drop of excess oil
spread over a microemulsion equilibrated substrate. If
'Y c =0, then all such drops will be nonspreading, and the
microemulsion might be considered autophobic 18 in the
sense that the surfactant-filled liquid/liquid interface will
not spread over the surfactant-filled solid/liquid
interface.
Contact Angle and Salinity. Because all data
presented thus far refer to constant salinity but great
variety in oil, brine, and surfactant proportions, the con-
centration of surfactant and alcohol will be fixed
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 1.0 0
o FRACTURED PYREX

~ ~
0 30
0.8 o PYREX ROD
45 t:,. TITANIUM
m 0.6
60 '1 QUARTZ ROD
0.4 o QUARTZ CRYSTAL
0.2 75
ADVANCING r
cose rno CONTACT
0 90 ANGLE,o
-0.2 105
-0.4
RECEDING 120
-0.6
135
-0.8
~ ~ 150
0 180
-1.0

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¢ m Q 0 10 20
INTERFACIAL TENSION, rndyne/crn
30 40

Fig. 13-Receded contact angles on various substrates,

0>45°.
Fig. 11-Spreading drops for lower-phase microemulsion
systems.
1.0 0
30
1.0
0.8
0 45
0 CO CO
0 30 0.6
0.8 00

0.6 c
P
0
45
0.4
cb , 60
60 ,0
0.4 0.2 '0
75
75
r
0.2 c
0 CONTACT COS e~o 0 ~ 90
CONTACT
ANGLE,o
COS e mo 0 90 ANGLE,o
-0.2
o
,
,0

-0.2 105
105 01
-0.4
-0.4 120
120
-0.6
-0.6
-0.8
- 135
-0.8
,
r9 145
150 150
-1.0 l<t I i ~ I I
180 -1.0 180
0 10 20 30 40 50 0 10 20 30 40
INTERFACIAL TENSION. mdyne/cm INTERFACIAL TENSION. mdyne/cm
Fig. 12-Receded contact angles on fractured Pyrex. Fig. 14-Receded contact angles on Teflon, 0>45°.

henceforth at 3%, the oil content at 48.5%, and the re- 1.0 0
mainder will be composed of X% NaCI in water, where 30 o FRACTURED PYREX
0.8
X=1.0, 1.25, 1.4, 1.5, 1.75,2.0,2.5, and 3.0. As sa- 45 0 TEFLON
0.6 0 QUARTZ CRYSTAL
linity varies from 1 to 3 % the multi phase system makes 60
transitions from lower- to middle- to upper-phase. 17 0.4
Receded angles were measured on fractured Pyrex, +0.2 75
quartz crystal, and Teflon. Hence the more dense fluid 90 CONTACT
COS e~rn 0 ANGLE,o
filled the cell and the less dense fluid composed the drop
(or sessile bubble in this case). -0.2 '0 105
In Fig. 16, all receded contact angle data are graphed -0.4
120
as a function of salinity. 0:"0 is independent of substrate -0.6
within ± 10° and increases with salinity. For the high- 135
-0.8 150
energy substrates, O:;'m is independent of substrate (ex-
cept for the single quartz datum at 1.75% NaCI) and -1.0 180
0 10 20 30 40
decreases with increasing salinity. The Teflon data also INTERFACIAL TENSION, rndyne/cm
fall in with this trend at 1.4 and 1.5 % NaCl; however, at
higher salinities, contact angles on Teflon are very large Fig. 15-Advanced contact angles on various substrates,
and increase with salinity. It may be that this atypical 0>45°.
behavior of Teflon is related to very low surfactant con-
centrations in the aqueous phase at the higher salinities,
JUNE 1984 347
 180 but why this would affect angles on Teflon so much dif-
IZl ferently from those on quartz and Pyrex is unknown.
160
IZl
IZlIZl o FRAC. PYREX The solid line segments in Fig. 16 are drawn through
140 o QUARTZ CRYSTAL the fractured Pyrex data, and it will be noted that O!no in-
120
o TEflON
tersects O{;,m at 1.7% NaCl in the middle-phase region.
0'
RECEDED
100
This will be defined as the optimal salinity for contact
CONTACT
ANGLE. angle in analogy to the three previously defined optimal
DEGREES 80 salinities lO ,17: Cni (miscibility), C-y (1FT) and C",
60 (phase behavior or solubilization parameter). All of these
are illustrated in Fig. 17, and it can be seen that .their
40
values are nearly the same, varying from 1.4 to 1.7%
20 NaCl.
The value of receded contact angle at optimal salinity,
0
0 1.0 1.5 2.0 2.5 3.0 3.5 or (C 0), is approximately 68 0 • Recall that when the

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SALINITY.~ NaCI various microemulsions that obtain at each salinity were
used to recover residual oil, keeping the total quantity of
Fig. 16-Receded contact angles for lower-, middle- and surfactant constant, it turned out that the best recovery
upper·phase microemulsions.
wa!; achieved at optimal salinity. 19 This result is shown
in Fig. 18, along with the contact angle data. Before we
MISCIBILITY PHASE BEHAVIOR
attribute significance to this suggestive correspondence,
it will be necessary to acquire much more data, including
advanced contact angles and data for qualitatively dif-
ferent microemulsion systems. However, two remarks
% seem appropriate. First, as discussed earlier, ganglion
SURF. . V/V s
mobilization is not the essential problem to be solved.
Second, contact angles and 1FT's are dependent and this
provides a constraint on admissible optima. Hence, it
o 123 o 1 3
may be that the best contact angles (there are more than
INTERFACIAL TENSION CONTACT ANGLE one in this multiphase environment) for tertiary oil
recovery using microemulsions are different from 0 0
•

The Effective Substrate

(-) If one supposes, as the data imply, that the substrate that
determines contact angle behavior is a consequence of
surfactant adsorption, then the nature of this adsorbed
layer is of interest.
o 1 2 3 o 1 2 3 Fig. 19 shows the usuai diagrams that remind us of the
SALINITY.% SALINITY.%
form of Young's equation when applied to advanced and
receded configurations, accounting for the order of ex-
Fig. 17-Comparison of four optimal salinities.
posure of the solid surface to oil and microemulsion.
Thus; for example, 1'som is the tension of the solid sur-
face after exposure first to oil and second to microemul-
sion. Then
100
80
60
and
40
20
28
24 so. that a sufficient condition for advanced and receded
contact angles to be the same is 1'som = 1'sm and
20 1'smo = 1'so -i.e., the effective substrate is determined
18 by the last contacting fluid.
12 Fig. 20 illustrates a model of surfactant adsorption for
lower- and middle-phase microemulsions on high-energy
8 surfaces. In the upper drawing the substrate is first
L-~~~-L~~__L-~~ 4 equilibrated with excess oil (which also contains surfac-
o 0.40.8 1.2 1.62.02.42.83.23.4 tant) and, as a result, monolayer adsorption occurs with
SALINITY, % NaCI polar groups oriented toward the substrate.
A drop of microemulsion is placed on the modified
Fig. 18-Comparison of optimal salinities. surface and allowed to advance. Surfactant monomers at
348 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 1mo
CC3?i
1som + - --. 1 so
1smo..-
~~J(.)r
• 1sm
'-11nio
Fig. 19-Advanced and receded contact angles.
the drop interface likely enmesh with those on the
substrate as the drop expands, much like closing two- a
dimensional (2D) "zipper." In this way the effective
substrate for the microemulsion drop is a micellar struc-
ture compose~ of a surfactant bilayer, thus simultaneous-
ly satisfying the affinity of the polar groups for the solid
surface and for the aqueous component of the
microemulsion. '
The equilibrium configuration of the surfactant bilayer
is such that oil is trapped within the lipophilic region ad-
jacent to the solid substrate and not adsorbed on the
substrate.
In the lower drawing the substrate is first equilibrated
with microemulsion, and bilayer adsorption occurs.
Everything is just reve~ed and the 2D zipper opens,
stripping off the exterior layer of surfactant onto the drop
interface.
It now seems reasonable that advanced and receded
angles are the same since molecular configuration of sur-
factant at all interfaces is invariant to expansion or
retraction of either drop shown in Fig. 20.
Bilayer adsorption from an aqueous phase has been
suggested by Gaudin; et al. 20 and others. The zipper-
like action is postulated on transfer of soap films from an
aqueous surface to a solid substrate (Langmuir-Blodgett
techilique 21 ) and was analyzed recently by Stephens 22
and by Honig. 23 A significant difference between the
model proposed here and that appropriate to Langmuir-
Blodgett rilultilayers is t~at now one is confronted with a
dynamic situation involving weak interactions. Thus,
Fig. 20 is very idealized and does not illustrate the more
chaotic behavior envisioned, where surfactant molecules
may enter and exit the various interfaces and transfer be-
tween phases. Perhaps, to emphasize the point, it would
be better to refer to dynamic bilayer adsorption.
The extent to which adsorption on low-energy surfaces
such as Teflon does or does not fit this model is not
clear. If surfactant lipophiles adsorbed on Teflon, the
zipper action would be hindered and large time effects
would be expected. Although this was observed occa-
sionally, it was not the usual situation. Also, it is not ap-
parent why advanced and receded angles should differ in
this Case because symmetry is preserved.
A similar model can be constructed for upper-phase
microemulsions in equilibrium with excess brine (which
also contains surfactant). In this case, however, it is ex-
pected that the surfactant bilayer forms in the excess
brine phase.
Conclusions and Conjectures
A new surface preparation technique was developed that
guarantees a smooth substrate free of contamination.
Contact angles for low-salinity, equilibrated, multi phase
JUNE 1984
Oil
~ MICROEMUlSION
6 ~ 6?6?6?67676
ADVANCING
RECEDING
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e~o '
MICRO EMULSION
Fig. 20-Model for surfactant adsorption.
microemulsion systems were measured as a function of
1FT on this and other substrates ranging from Teflon to
titanium. Large measurement errors were encountered;
but with this constraint, and with respect to the
microemulsion system studied, the following conclu-
sions were reached and conjectures made.
Conclusions. Advanced contact angles are indepen-
dent of substrate and receded contact angles are also in-
dependent of substrate with the possible excepting of
Teflon. There is no hysteresis, again possibly excepting
Teflon. These results imply the effective substrate is not
quartz, titanium, Teflon, etc., rather it is one determined
by the surfactant system.
If spreading occurs, the critical 1FT must be less than 4
mdyne/cm [4 x 10 -3 mN/m].
An optimal salinity for contact angle, Co, has been
defined that is approximately equal to all previously
defined optimal salinities. The value of contact angle at
optimal salinity is approximately 68 0 •
Conjectures. In view of the lack of dependence of
contact angle on substrate, contact angles measured in
the laboratory may be pertinent to those that obtain in
situ.
For () > 45 0, cos() appears to be a linear function of
1FT. If the low value of the intercept at cos()== -1 is in-
terpreted as a critical surface tension, then the corre-
sponding effective substrate behaves like a very low-
energy surface. In the case of lower-phase microemul-
sions, a model for this effective substrate that is consis-
tent with the observations is a surfactant bilayer having
the polar groups of the first layer adsorbed and of the se-
cond extending into the microemulsion. Oil within this
layer is trapped there by constraints of micellar
equilibrium rather than adsorbed on the solid substrate.
Since the best oil recovery occurred at optimal salinity
and () ~ 68 0 there, it may be that for tertiary oil recovery
349
using microemulsions, the optimal contact angles are
different from 0°; a possibility that rests on the func-
tional relation between contact angle, 1FT, and adsorp-
tion, acting as a constraint on feasible optima.
Postscript
In view of the long time lapse between presentation and
publication of this paper (for which the first author
assumes sole responsibility), three papers 24-26 have ap-
peared that augment the work done here.
Nomenclature
C = optimal salinity, %NaCI
'Y interfacial tension, dyne/cm
(J = contact angle, degrees
Subscripts
m microemulsion
0 excess oil
s solid
w excess brine
Superscripts
a advanced
r receded
Acknowledgments
We thank C. W. Carpenter for design of the sessile-drop
apparatus and Patsy Gee and April Grizzle for making
the contact angle and 1FT measurements.
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SI Metric Conversion Factors
dyne x 1.0* E-02 mN
in. x 2.54* E+OO cm
*Conversion factor is exact. SPEJ
Original manuscript received in Society of Petroleum Engineers office Nov. 10, 1982.
Paper accepted for publication March 22, 1983. Revised manuscript received Oct. 3,
1983. Paper (SPE 8262) first presented at the 1979 SPE Annual Technical Con·
ference and Exhibition held in Las Vegas Sept. 23-26.
SOCIETY OF PETROLEUM ENGINEERS JOURNAL