Wettability and Its Effect

on Oil Recovery
SP~, New Mexico Petroleum Recovery
Research Center, New MexIco Inst. of Mining & Technology

Norman R. Morrow,

Introduction
Reservoir wettability is determined by complex interface boundary conditions acting
within the pore space of sedimentary rocks.
These conditions have a dominant effect on
interface movement and associated oil displacement. Wettability is a significant issue
in multiphase flow problems ranging from
oil migration from source rocks to such enhanced recovery processes as alkaline flooding or alternate injection of CO2 and water.
In this paper, wettability will be discussed
mainly in the context of recovery of light
Oow-viscosity) oils by waterflooding.
Waterflooding has been widely applied for
more than half a century; secondary recovery by waterflooding presently accounts for
more than one-half of current U.S. oil production. Many research papers have addressed the effect of wettability on
waterflood recovery during this period. For
much of the past 50 years, however, a large
body of reservoir engineering practice has
been based on the assumption that most
reservoirs are very strongly water-wet
(VSWW); i.e., the reservoir-rock surface always maintains a strong affmity for water
in the presence of oil.
The rationale for assuming VSWW conditions was that water originally occupied
the reservoir trap; as oil accumulated, water
was retained by capillary forces in the fmer
pore spaces and as films on pore surfaces
overlain by oil. Wettability behavior other
than VSWW was observed for reservoir
core samples, but was often ascribed to artifacts related to core recovery and testing
procedures. The majority of reservoir engineering measurements have been made on
cleaned core with refined oil or air as the
nonwetting phase to give results for, or
equivalent to, VSWW conditions. Examples
of such measurements are laboratory waterfloods, determination of electrical resistivity
vs. water saturation relationships, and capillary pressure measurements for determination of reservoir connate water saturation.
Mounting evidence on the effects of crude
oil on wetting behavior l has now led to
Copyright 1990 Society of Petroleum Engineers

1476

wide acceptance of the conclusion that most

reservoirs are at wettability conditions other
than VSWW. This conclusion has led to a
resurgence of interest in satisfactory procedures for measuring reservoir wettability
and determining its effect on oil recovery,
especially with respect to waterflooding. Determination of reservoir wettability and its
effect on oil recovery by methods that involve core samples will be referred to as advanced core analysis for wettability
(ACAW).
Reservoir wettability is not a simply defined property. Classification of reservoirs
as water-wet or oil-wet is a gross oversimplification. Various procedures for measuring wettability have been proposed. Two
methods of quantifying wettability based on
rocklbrine/oil displacement behavior, the
modified Amott test 2 and the USBM test, 3
are in common use. Each method depends
on water saturation measurements and related capillary pressures or flow conditions
to define a wettability scale. The tests show
that reservoir wettability can cover a broad
spectrum of wetting conditions that range
from VSWW to very strongly oil-wet. Within this range, complex mixed-wettability
conditions given by combinations of
preferentially water-wet and oil-wet surfaces
have been identified. In this paper, the
'adopted scales of reservoir wettability and
their relationships to interface boundary conditions are considered together with the dramatic effects that wettability can have on oil
recovery.

Contact Angles, Spreading,

and Adhesion
Contact Angle and Spreading. Contact angle is the most universal measure of the wettability of surfaces. Fig. 1 shows idealized
examples of contact angles at smooth solid
surfaces for oil and water of matched density. Early studies of wetting phenomena
showed that the wetting properties of a solid
are dominated by the outermost layer of
molecules. (Films that result from spreading
and other thin adsorbed fIlms are not indicated in Fig. 1.) Large change in the wettability of a surface, such as quartz, can be
achieved by adsorption of a monolayer of
polar molecules so that the outermost part

of the surface is composed of hydrocarbon

chains. Extreme change in wettability (see
Fig. 1), such as from a or b to e or f, or
vice versa, is called wettability reversal. Adsorption of polar compounds from crude oil
plays a critical role in determining the wetting properties of reservoir-rock surfaces.
Many early studies of wetting behavior,
even for comparatively simple systems,
were plagued by problems of reproducibility. Aside from surface contamination,
other forms of heterogeneity in chemical
composition, surface roughness, and static
and dynamic interface properties contribute
to the complexity of observed wetting phenomena. Large differences in contact angles,
depending on whether an interface was advanced or receded, called into question the
validity of attempting to describe wettability
by a single-valued equilibrium contact angle.
Successful systematic studies of closely
reproducible equilibrium-contact-angle
measurements have been summarized by
Zisman. 4 By use of smooth (often polymeric), solid surfaces and pure liquids,
contact-angle hysteresis was limited to within 1 or 2. In contrast, contact-angle hysteresis is observed almost invariably for
crude-oillbrine systems. Fig. 2 shows examples of contact angles that exhibit small
and large hysteresis. Receding angles are
generally low ( < 30) and seldom exceed
60 , whereas a wide range of advancing angles is observed. The shaded regions in Fig.
2 show the range of possible contact-angle
values for a fixed position of the three-phase
line of contact.
Contact-angle measurements on reservoircrude-oillbrine systems provide one approach to measuring reservoir wettability.
For the most extensive set of data yet reported,5 contact angles for crude oil and simulated reservoir brine were measured at
reservoir temperature and ambient pressure.
Choice of mineral substrate, usually quartz
or calcite, was based on what was judged
from petrographic examination to be the
predominant mineral at pore surfaces.
(There are obvious limitations to representing the rock surface by a single mineral.)
To determine contact angles, two parallel
mineral plates are submerged in brine and
December 1990 JPT

sPEDistinguished

Author

then a drop of oil is introduced between the

plates. When the plates are moved relative
to each other, advancing and receding conditions can be observed. Water-advancing
contact angles, (J A' are reported as defining
wettability because these are considered
relevant to waterflooding. 5 Figs. 3a and
3b show the distribution of advancing contact angles observed for quartz and calcite,
respectively.

(a)
= 0
(water spreading)

(b)

e=

(c)

25

WATER

Adhesion Behavior of Crude-Oil/Brine/

Solid Systems. Because of problems in
making definitive contact-angle measurements, a simpler approach to characterization of the wetting behavior of crude oils has
recently been adopted. 6-8 Smooth mineral
surfaces are first pre-equilibrated for about
7 days with brine. A drop of oil is contacted
with a surface overlain by brine for a standardized time of 2 minutes. The oil drop
maintains a low water-receding angle during
enlargement. Upon withdrawal, one of two
extremes of behavior are usually observed.
Either the drop detaches from the surface
(nonadhesion) or the interface boundary remains pinned at the three-phase line of contact (adhesion) (see Fig. 4).
For adhesion, the contact angle generally
increases during withdrawal of oil until the
liquid bridge ruptures because of capillary
instability; after rupture, a drop of oil still
remains on the solid surface. In some instances, an excess of surfactant, caused by
a decrease in interface surface area after rupture, causes the oillbrine interface to become
rigid. The interface eventually returns to its
normal appearance with a few minutes (see
Fig. 4). The area over which the oil drop
remains attached to the solid is usually very
strongly wetted by oil. Thus, adhesion corresponds to large hysteresis of contact angle
(Figs. 2 and 4). The angle at which the
liquid-bridge rupture occurs is not necessarily the maximum advancing contact angle.
In testing the adhesion properties of 22
crude oils as a function of brine composition
and pH, remarkable similarities in results
were obtained for 20 oils, with pH being the
dominant factor. 8 Two examples of pH vs.
salinity mapping shown in Fig. 5 indicate
the general form of these plots. The two oils
that did not conform gave adhesion at both
JPT December 1990

e = 100

(e)

e = 600

OIL.

mJfIfl;)~l7nm!flm
(d)

SERIES

OIL

J11IJ1II1IIIIJJJlllllj'llllljjjj)lIj)llfllI

(f)
e = 180
(oil spreading)

e = 160

Fig. i-Idealized examples of contact angles and spreading.

(a) Small Hysteresis

(b)

Large Hysteresis

Fig. 2-Possible ranges of stable contact angle, 8, for small and large hysteresis of
contact angle, with location of oil Indicated for 8A'

low and high pH. In comparable tests on refined oil, adhesion was not observed at any
of the tested pH levels.
The transition pH for nearly all the crude
oils tested fell within the narrow pH band
of about 6.5 2. For a given oil, only slight
changes in pH at close-to-neutral conditions
can cause a drastic change in adhesion behavior. This may explain the problems often
experienced in obtaining reproducible crudeoillbrine/mineral wetting behavior. A crude
oil recovered and tested for adhesion behavior under anaerobic conditions gave results similar to those obtained after
deliberate exposure to oxygen. Thus, the
general form of the adhesion behavior is not
an artifact of oxidation. 8

"Contact angle is the

most universal
measure of the
wettability of
surfaces."

1477

16

Non-adhesion

Adhesion
14

f!

f!

12

0
II>

10

'5

a:
'5

Q)
Q)

z"

"

0-20
0-20

20-..0

Water Advancing Contact Angle

eo.eo

80-100

1~120

120-140

1<40-180

1eo-18O

Water Advancing Contact Angle

(a) Quartz

(b) Calcite

Fig. 3-Distribution of contact angles for crude-oil/brine systems on (a) quartz (29 measurements), and (b) calcite (30 measurements) (after Treiber et al. 5 ).

The similarity in effect of brine properties or wetting behavior observed for all but
two crude oils provides a case for the use
of crude oil rather than a refined oil as a
reasonably definitive and certainly, for
reservoir engineering purposes, a more relevant model for the oleic phase. Note that the
advancing contact angle values for crude
oil/brine on quartz (see Fig. 3a) fall into two
classes that seem to be consistent with observed adhesion tests conducted on glass or
silica surfaces. In spite of the chemical complexity of crude oils, a distinct possibility
exists that crude oils will give consistent results with respect to other phenomena that
depend on wetting properties.

Stability of Thin Films. The outcome of

adhesion tests depends on the stability of the
water film between the solid and the oil
drop. Stabilization of the thin film by electrostatic repulsion requires that the charge
at the brine/solid interface and the net charge
of the brine/oil interface have the same sign.
Film thickness, generally much less than 100
nm, is determined by a balance between van
der Waals attractive forces and repUlsion by
electrostatic and hydration forces. 9 The
much-less-understood hydration forces come
into play in the stabilization of very thin
water films at high ionic strength. The highcontact-angle values shown in Fig. 3b are

consistent with adhesion occurring more

readily on calcite than quartz because, under
comparable conditions, calcite has a more
positive surface charge. It follows that the
types and distribution of minerals such as
carbonate cements or clay minerals at the
surface of pore walls, even if they make up
only a minor part of the total mineral constituents ofthe rock, also play an important
role in how crude oil alters wetting properties. With respect to the effect of pH in the
reservoir, rock minerals will tend to buffer
reservoir pH at some fixed characteristic
value that is close to neutraL Because pH
cutoff values are also close to neutral, adhe-

NONADHESION

..
LOW ADVANCING ANGLE
BEFORE DETACHMENT ad'

LOW RECEDING ANGLE 30)

ADHESION

AFTER DETACHMENT

j
=.----,

..
TEMPORARY
ADHESION

HIGH ADVANCING ANGLE (>9<1')

TYPICAL DROP SHAPE

IF RIGID FILM
FORMS UPON RUPTURE

AFTER RUPTURE OF OIL BRIDGE

DROP SHAPE JUST

BEFORE DETACHMENT

Fig. 4-lIIustrations of interface configurations for adhesion and nonadhesion of crude oil.
1478

December 1990 JPT

14

14

Crude, 50 C
........... , ., ...... Moutray
, ....... , ........... ':' .................... : .................... .
~.

12

~
~. Noriad.hesion
.................... :......................,.........~..... Adtlpsloo............ .

10

10

----- ~H cutoff

NS-3,50C
,.................................................................
.
~
~. Nonkdhesion
....................!..................... i .... x .... Adhi,sion .......... .
i
~
----- pH cutoff
....................

12

+~-::::r:::;;::F

a.

1;::::;:1;::::::::[::

a.

....................~ .................... .;. .....................; .................... .

~x

1.~

............ :.....................
.'
.

:::::.::.::::::J::::::::::::::::::::r:::::::::::::::::r::::::::::::::::::
.
.

:.

.:

:.

o
10-3

10-2

10"1

10-1

10-2

10-3

101

1.,0

101

100

Molar Concentration of Na +

Molar Concentration of Na +

(b)

(a)

Fig. 5-Adheslon maps (pH vs. NaCI brine concentration) for two crude oils (after Buc.kley and MorrowS).

sion tests may not provide a definite prediction of the wetting condition that crude oil
will establish witl1in a rock.
Just as the outcome of the adhesion test
depends on the stability of thin water films,
maintenance of water-wetness in a reservoir
depends on the stability of thin water films
at pore walls. If the water films are unstable, crude oil has access to solid surface in
the region of contact and adsorption of polar
compounds can drastically, and often permanently, alter the wetting properties of the
solid. The adhesion test studies show adsorption to be specific to the area contacted
by oil. This type of adsorption gives rise to .

what is known as mixed wettability because

the surface wetting properties of the contacted area are distinctly different from the
neighboring surface. Differences in adhesion and adsorption behavior at different
mineral surfaces, together with the effects
of rnicroporosity and surface roughness, will
obviously contribute to the complexity of
mixed-wettability systems.

Asphaltenes. Wettability alteration has often

been ascribed to the adsorption of highmolecular-weight colloidal particles known
as asphaltenes suspended in crude oil. 10
Asphaltenes are operationally defined as the

precipitate resulting from adding a large

volume of low-molecular-weight hydrocarbon to the crude oil (typically 40 volumes
of pentane). Their role in wettability alteration was further confirmed by the observation that deasphalted crude oil no longer
exhibited adhesion in the low-pH range. 8
Stabilization of water films by electrical
double-layer repulsion in the Athabasca tar
sands explains the strong water-wetness
often observed for this sand. 11 When a
sample of freshly mined Athabasca tar sand
is kneaded under water, an abundance of
clean sand grains fall from the sample. Thus,
even though the tar sands have very high

100

80
Primary
DRAINAGE
/(FOrced)

ii:"

~(+ve)

Secondary
DRAINAGE
(Forced)

>a:
w
>

IMBIBITION
(spontaneous)

60

0
0
w

a:

...J

6. Sws
w= - AS
WI

40
CURVE

IAH

IMBIBITION

I
0

~(-ve)

= 4S

wt

2
3

IAH=lwl o

Nw (USBM) =

1.0
0.9
0.7
0.5
0.3

(F=edi

It.Sos

DRAINAGE
log

20

Secondary /

0.1
0.1
0.3
0.5

(Spontaneous)

A1
A2

8
S,,'"

100

WATER INJECTED Vp

Fig. 6-Relatlonshlp of wettablllty measurement by Amott and

USBM tests to Pc curves for a mlxed-wettability system.
JPT December 1990

Fig. 7-011 recovery vs. brine injected for COBR systems with
Amott-Harvey wettability Index ranging from 1.0 to - 0.5 (after
Jadhunandan and Morrow 15 ).
1479

16
Kyt8 at al. (1961)23

14

Donaldson at at (1969)'
SalalhulIl (1973)24

en

Wang (1986)21

G
z

2.0

Rathme!1 at al. (1973)n

Q)
()

COBR Systems (s8e Fig.7)

u::
U-

r-:=-- :

(.\~ .................

1.5

::;;
W

Cl.
(Jl

is
w

>

1.0

~w

~:~c:::=~. -~
. . -.. -.~
. -.. ~'().51
~
\
\,

vsww /REFERENCE

\~<ssnEXAS

a:

lauoONCR\J~D:"E--------~o;;-;-,

I-

~ 0.5

.....

0
W

_---

."

(;
W

..:,.

..,.....-.- .-'

()
()

'0
....
Q)

-------------

:::J

_._._._. _._._. _._._.-. -':-:J. ._.-' _

6
4

10% SILICON

-.~

O~~~~~~I~~~I~~~~~~~

0.5

1.0

1.5

2.0

2.5

3.0

WATER INJECTED Vp

Fig. B-Effect of wettability on laboratory waterfloods relative

to recovery at strongly waterwet conditions.

asphaltene contents (about 15%), the sand

remains strongly water-wet over geologic
time.
Perfect Wetting and the Effect of Capillary Pressure on Thin Films and Contact
Angles. Under the early working assumption that reservoir rocks were VSWW, the
rock surface was often discussed and illustrated as if a drained rock surface were still
overlain by a thick fIlm of water. Even when
water spreads, however, retained water
fIlms at drained solid surfaces that are in
equilibrium with the neighboring bulk water
will be extremely thin relative to typical pore
dimensions.
Perfect wetting, or spreading, is the most
extreme wettability condition that can be expressed by contact angle-0 for water or
180 for oil (see Fig. I). As a general rule,
liquids such as water or hydrocarbons will
spread against air on the surface of a mineral such as quartz or calcite. Systems exhibiting water spreading and oil spreading
will be called perfectly water-wet, PWW,
and perfectly oil-wet, POW, respectively.
PWW systems are a special subset of
VSWW systems because the latter can include systems of low, but fmite, contact angle. Even though a PWW condition may be
difficult to achieve for crude-oil/brine systems, it provides a useful reference state.
Contact angles cannot be measured directly for porous media, and it may not always
be possible to distinguish PWW (0 contact
angle) and VSWW (low, finite contact angle) systems by their displacement behavior.
In mathematical treatments of capillarity ,
a common practice is to neglect the thick1480

........ 10
:::J

.0

_---------LCONVENT10NAL CORE

12

Q)

10
20
30 40
Residual Oil, percent

50

Fig. 9-ROS measured by the single-well tracer test for 112

reservoirs.

ness of drained fIlms, even though their

presence is of crucial importance to wetting
behavior. If an adsorbed fIlm is at equilibrium with the bulk liquid at its prevailing
capillary pressure, the fIlm's thickness will
depend on the combined effect of the capillary pressure of the bulk liquid and the curvature of the solid overlain by the film. A
disjoining pressure, IT, which for a zerocurvature solid surface is equal to the
prevailing capillary pressure, is identified
with the fIlm. 9
If the adsorbed fIlm thickness changes
with capillary pressure"then, in principle,
the contact angles can also change. Then,
scaling of displacement pressure will not be
. exactly linear with respect to pore size.
While the theory of equilibrium relationships
between capillary liquid, thin fIlms, and
vapor have been the subject of numerous
scientific pUblications, as yet no consistent
body of experimental evidence shows that
such effects produce measurable changes in
the wetting properties of porous media.
Thus, it can be assumed for most practical
purposes that the boundary conditions that
determine wettability are independent of the
prevailing capillary pressure.

Measurement of WettabUlty of
OIl/Brine/Rock Systems
Capillary Pressure Behavior of CrudeOil/Brine/Rock Systems. Understanding
the relationships between wettability, capillary pressure, and the distribution of oil and
water in pore spaces is a necessary step in
the difficult problem of quantifying wettability and its relation to oil recovery. Basic

relationships between capillary pressure,

surface curvature, and interfacial tension
(1FT) and the use of contact angle in describing boundary conditions in cylindrical pores
are well known. For crude-oil/brine/rock
(COBR) systems, relationships between wettability and capillary displacement pressures
are complicated by the complex pore structure and mineralogy of reservoir rocks and
the effects of adsorbed organic components
from the crude oil.
Fig. 6 shows an augmented sketch 12 of
relationships between primary drainage, imbibition, and secondary drainage; a full data
set for all the curves shown is not available
for COBR systems. (The curves in Fig. 6
are not representative of all types of COBR
behavior. For example, imbibition capillary
pressures sometimes fall close to zero, but
then the rock continues to imbibe water very
slowly.) The curves shown are useful in
comparing the three commonly used
methods of measuring wettability for COBR
systems: the Amott test,2 the USBM test,3
and imbibition rate measurements. 13 In discussing capillary pressure curves and wettability, uncertainty can arise in what is
meant by the terms drainage and imbibition.
For the nomenclature used in Fig. 6,
drainage is defined as a decrease in water
saturation and imbibition as an increase. The
forced drainage mechanism is characterized
by larger pores tending to empty before
smaller pores. The spontaneous imbibition
mechanism is characterized by smaller pores
filling before larger pores. For systems in
which capillary pressure changes sign, as
when spontaneous imbibition is followed by
forced displacement, a further increase in
December 1990 JPT

water saturation occurs by a drainage mechanism. Similarly, a system can exhibit spontaneous imbibition of oil, which by
definition is a spontaneous drainage process
(see Fig. 6).

Amott Test. In the Amott test,2 water is

first displaced by oil by centrifuging or by
use of a high flowing pressure gradient.
Pressure levels and time taken to reach initial water saturation, Swi, are somewhat arbitrary. The aim should be to begin at the
same water saturation as in the reservoir.
The core at Swi is then immersed in water
to allow spontaneous imbibition. Spontaneous imbibition of water ceases at some
change in water saturation, ~ws, when the
oil/water surface curvature falls to zero.
Further oil can usually be recovered by
forced displacement to give an overall increase in water saturation, ~wt' by flowing water at a high pressure gradient or
centrifuging. Fig. 6 shows the relationships
of saturation changes to capillary-pressurevs.-saturation curves. The wettability index
to water, Iw, is given by
Iw=~wsf~wt .

................ (1)

An analogous index (see Fig. 6) can then

be measured for oil such that
Io=~osf~wl .

................. (2)

The difference, Iw-Io ' is often used to

characterize wettability by a single number,
I AH , known as the Amott-Harvey index.
Several points should be noted. Cessation
of spontaneous imbibition of either water or
oil occurs when the relevant interfacial curvatures fall to zero. (The generally minor
effect of buoyancy is neglected.) In practice,
this exact condition can be difficult to identify if imbibition rates become very low. An
operational definition for the endpoints for
spontaneous imbibition is then needed, such
as allowing a period of 1 week or so. The
use of CAT scanning 14 to check on the
uniformity of distributions obtained by spontaneous imbibition could provide especially valuable information on the character of
spontaneous imbibition behavior in mixedwettability systems.
. The endpoints achieved for forced displacement sometimes change with each displacement cycle and may be somewhat
arbitrary in any case. Waterflooding of
mixed-wettability systems is often characterized by continued production of oil down
to low residual oil saturations (ROS's). If
forced displacement is performed at excessive capillary number, the residual oil obtained will be lower than that given by
normal laboratory waterflooding procedure.
When the Amott tests are used, even
though the wettability may be expressed as
a single value, IAH =(/w-Io)' it is better to
report all/w and 10 values (one of which is
often zero) and associated saturations as part
of the wettability result. Each time saturation data are converted to wettability indices
and the difference between the indices is
used to obtain a wettability number, valuable information is lost. In quoting indices,
JPT December 1990

saturation values from which they were derived should also be provided together with
operational details of how Swi' ~ws.
~wt. ~os, and ~ot were determined. A
weakness of the Amott test is its failure to
distinguish between important degrees of
strong water-wetness, all of which will give
an Iw of, or very close to, unity.
USBM Method. In the USBM method, 3
drainage and imbibition capillary pressures
are measured, usually by centrifuging. As
with the Amott test, the method was developed from observation of COBR displacement behavior. The wettability number is
defined (see Fig. 6) by
Nw=log(AI/A2)' ............... (3)
where A 1 =area under the secondary waterdrainage curve (drainage from residual oil)
and A2 =area under the imbibition curve
falling below the zero-Pc axis. The chief
advantages of this method are the speed and
simplicity of the procedure and its adaptation to relative permeability measurements.
Points to note, with respect to this interpretation, are that corrections must be applied
to the average saturations measured by centrifuging, the claimed thermodynamic basis
for the method that equates work of displacement to change in surface free energy does
not recognize the effects of irreversibility
in capillary pressure relationships, and systems that imbibe to give positive A 2, for example VSWW systems, are not recognized
in the proposed interpretation.

Imbibition Rates. The driving force for

spontaneous imbibition rates is proportional to the imbibition capillary pressure. Measurements of spontaneous imbibition rate 13
provide an especially useful supplement to
Amott indjces or USBM wettability numbers. Whereas the Amott test depends mainlyon the saturation at which imbibition
capillary pressure falls to zero, spontaneous
imbibition rate depends on the magnitude of
the imbibition capillary pressure. Measurements of imbibition rates are of special value
as a sensitive measure of wetting in the range
where the Amott index is at or close to unity. Quantitative interpretation obviously will
be aided by having reference results obtained
at or very close to perfect wetting conditions. Improved interpretation of spontaneous imbibition behavior for COBR systems
is likely to provide an important advance in
wettability characterization. Measurements
of imbibition rates also provide information
on dynamic IFf and wetting phenomena that
may be important in the reservoir but are
not reflected by Amott or USBM wettability
tests. Advances in interpretation of spontaneous imbibition results will depend on improved methods of scaling and comparison
of results from one system to another.

Effects of WettabllHy on
011 Recovery-Laboratory
Waterfloods
The effects of wettability on oil recovery
have been investigated through laboratory
displacement tests. Wettability of COBR

systems is usually characterized by the

Amott test or the USBM method. Results
for VSWW conditions are commonly used
as a reference state. Reported changes in
recovery as systems become less water-wet
range from being much lower to being much
higher than those given by VSWW conditions. Important goals of wettability research
are to provide rational and consistent explanations of these apparent inconsistencies and
to identify optimum conditions for oil
recovery.
In reviewing wettability effects, oil recovery will be described by displacement efficiency , ED, defined as
ED=[(Soi-.tT)1 Soi]100%, ....... (4)

where Soi is the initial oil saturation and SOT

is the ROS of the core sample. When the
ROS continues to decrease with Vp
throughput, SOT and ED are functions of Vp:
.. ED(~)={[Soi-.tT(Jj,)]1 Soi} 100%.

..................... (5)

Plots of ED(~) vs. Vp of water injected

provide a convenient way of comparing results of laboratory waterflood tests.
Several early examples of laboratory
waterfloods show oil recovery decreasing
with decreasing water-wetness. This is consistent with the intuitive notion that strong
wetting preference of the rock for water and
associated strong capillary imbibition forces
give the most efficient oil displacement:
However, an increasing number of examples of improved recovery with shift from
strongly water-wet conditions are being
reported for weakly water-wet or intermediate wetting condition, particularly for COBR
systems. (These results generally involve
displacement of crude oils or refined oils
from cores in which organic films have been
deposited from crude oil.) Fig. 7 shows
averaged results 15 for an extensive COBR
data set. In preparation of these samples, it
was found that an increase in aging temperature, a decrease in water saturation, and to
a lesser extent, aging time, aU tended to
make the cores less water-wet. Recovery is
seen to pass through a maximum when I AH
is close to zero.
If E Dsw is the displacement efficiency at
strongly water-wet conditions and Eoo is
the wettability at some other global wetting
then the effects of wettability
condition,
on recovery curves can be conveniently
compared by plotting the relative displacement efficiency,

e,

Eoo(~)=(EooIEDsw)100%, .... (6)

against the number of Vp injected, as

shown in Fig. 8. The selected results 3 15-19
show that a shift toward less water-wet conditions can range from being highly adverse
to being highly beneficial to oil recovery.
The validity of the EDsw data is obviously
an important aspect of this interpretation.

Reservoir Residual 011

The greatest practical significance of wettability is its effect on oil recoveries achieved
in the reservoir by waterfloOding. The need
1481

for accurate ROS measurements was stimulated by the prospect of tertiary recovery.
Many methods of measuring residual oil
have been proposed. The single-well tracer
test, which measures ROS for a radius of
about 10 m around the wellbore, has been
widely applied to reservoirs viewed as likely
candidates for tertiary recovery. 20 Results
for 114 reservoirs are plotted as a histogram
in Fig. 9. ROS's remaining after waterflooding range from as low as 4 % to more
than 40%. The results show that low values
of residual oil that can be achieved in the
laboratory are also commonly observed in
watered-out reservoirs. Obvious goals in
wettability research are to explain why high
waterflood recoveries are observed in some
oil reservoirs and how they might be obtained in others.

Pore-Level Displacement
Mechanisms
The results presented in Fig. 7 show that
departure from VSWW conditions can give
distinctly reduced oil entrapment. Flowexperiments in 2D pore networks (micromodels) permit observation of pore-level
displacement mechanisms that affect displacement efficiency. Under VSWW conditions in systems of high aspect ratio (high
ratio of pore body to throat size) believed
to be typical of reservoir rocks, residual oil
is trapped as disconnected blobs in pore bodies. Numerous theoretical and experimental
investigations 2l have been reported on
mechanisms of entrapment (snap-off) and
mobilization of oil blobs at VSWW.
Simulated waterfloods of crude oil from
micromodels have also been made at various wettability conditions achieved by
changes in brine pH and salinity. While a
great variety of distributions have been observed, no crude-oillbrine system showed
the extensive trapping of oil in pore bodies
that is characteristic of VSWW systems. *
Overall, the most important observation with
respect to crude oil displacement was that
the process by which oil becomes disconnected (snap-off) tended to be inhibited.
Furthermore, the oil phase often maintained
continuity through capillary structures with
oil/water surface boundaries that were
pinned at the solid surface. Local (porelevel) changes in saturation and capillary
pressure were accommodated by changes in
contact angle within the range permitted by
hysteresis. Low advancing angles and high
receding angles were seen to coexist, even
for capillary structures within a single pore.
The most important difference between refined oil and crude oil displacements in
micromodels was that displacement of crude
oil from at least some of the pore bodies always made a significant contribution to
overall recovery.
Experimental studies by Li and
Wardlaw 22 showed that snap-off in simple
pore models of rectangular cross sections
can be inhibited if the water-advancing con"These results were provided by Charles T. Carlisle, Chemical Tracers Inc., Houston, and Harry A. Deans, U. of
Wyoming, Laramie.

1482

tact angle exceeds about 60. Further important advances in theoretical and experimental accounts of snap-off mechanisms
will continue to be made through study of
capillary pressure and instability behavior
in pores that have comers and are of nonuniform cross section.
During the past lO years, there has been
a notable revival in analysis of pore networks for modeling displacement processes
in porous media. The relevance of results
given by such models depends on the validity of the rules adopted in the analysis. The
choice of rules to account for wettability effects in network models is a problem that
has only just begun to be explored.

Advanced Core Analysis

for WeUablllty
The decision to investigate the wettability
of a reservoir and the level of effort expended in ACAW work to match reservoir conditions should be based on the level of
significance these results will have on
making reservoir decisions. Determination
of reservoir wettability and measurement of
valid relative permeability curves are both
very difficult problems. The time and expense of making reservoir-condition tests result in few being performed on anyone
reservoir. Although there is no guaranteed
prescription for measurement of reservoir
wettability, its effect on reservoir performance may be of sufficient importance that
the effort to obtain the best possible data is
worthwhile. The basic problem in ACAW
is knowing whether the nature and distribution of surface properties and fluid phases
as they occur in the reservoir are maintained
or restored.
Within the general topic of ACAW many
areas can be identified: (1) recovery of
cores; (2) core handling at the wellsite and
core storage; (3) core cleaning; (4) restoration of reservoir wettability, including the
correct connate water saturation; (5) measurement of wettability; (6) measurement of
waterflood displacement behavior and associated relative permeabilities; and (7) ef. fect of wettability on electrical resistivity.
Each of these topics has an extensive literature; useful bibliographies have been provided by Anderson. 23 -28 ACAW procedures
are usually influenced by the character of
the particular reservoir under study and experience gained in working with that reservoir. API core analysis procedures for
wettability determination are now recognized to be largely outdated. Attention currently is being turned to the greater
standardization of ACAW within the industry.
Recovery of Reservoir Cores. Alteration
of the wettability of core samples from their
reservoir state during cutting, surfacing, and
subsequent handling can occur for a number of reasons. These include (1) drillingfluid contamination, (2) temperature and
pressure reduction effects on crude oil composition such as asphaltene precipitation or

wax deposition, (3) oxidation, (4) drying,

and (5) flashing of connate water with pressure reduction.
When coring with water-based drilling
fluids, emphasis has been placed on the use
of s<xalled bland muds. Because particulates from the mud are retained mainly at
the surface of the cut core, studies of wettability alteration caused by flushing are
made with the mud filtrates. Early work
concentrated mainly on identifying mud
compositions that caused no alteration in the
wettability of strongly water-wet cores.
More recently, attention has been given to
changes in mixed- and oil-wet cores.
Cores cut with reservoir crude, diesel, or
other oil-based drilling muds of low water
content as the drilling fluid have the distinct
advantage (because of the importance of the
amount and distribution of connate water to
wetting behavior) that the connate water is
left relatively undisturbed. Drilling conditions and other safety considerations may
often preclude this approach. Increased use
of oil-based (emulsion) muds has resulted
in special attention being given to cleaning
oil-based cores and restoring them to reservoir wettability conditions. Wunderlich 29
has given a detailed review of the various
options and comparisons in recovering cores
with unaltered wettability.
Core Handling and Storage. There may
commonly be long time delays between core
recovery and core testing during which cores
must be stored. Cores are commonly preserved in mud filtrate or brine. They are
generally protected from oxygen, evaporation, light,. and extreme temperature
changes. Unconsolidated cores are usually
subjected to freezing as part of the recovery process. In ACAW work, preserved
cores are generally called fresh cores, even
though testing may continue for several
years after the cores were taken.
Core CIeaoing. The usual objective of core
cleaning by flow of organic solvents or extraction is to remove all organic compounds
without altering the basic pore structure of
the rock. 23 ,30 A wide range of combinations and/or sequences of solvents have been
proposed. The type of crude oil and core lithology are used for guidance in selection
of solvents, but procedures are far from
standardized. 1
Methods commonly used in judging that
the cleaned cores give a completely waterwet condition may be inadequate with
respect to the requirement that all adsorbed
organic material be removed. For example,
achievement of an Amott index of unity for
refined oil, after cleaning, does not necessarily mean that all the adsorbed organic material has been removed or that a VSWW
system has been achieved. More reliable
checks on removal of adsorbed hydrocarbons would be provided by measurement of
spontaneous imbibition rates for displacement of refined oil.
In early core analysis work, the objective
of core cleaning was to restore the core to
a VSWW condition that would represent the
December 1990 JPT

wettability believed to pertain in the reservoir. Subsequent displacement tests, such as

relative permeability measurement, were
performed with brine and a refined oil. With
growing recognition that VSWW conditions
are not common, core cleaning in ACAW
work is now a fIrst step in restoring the core
sample to reservoir wetting conditions.
Restoration of Reservoir Wettability. In
restoration procedures, the objective is to
re-establish reservoir wettability conditions
by contacting the core with reservoir crude
oil. More widespread acceptance of the importance of reservoir wettability has resulted
in special attention being given to adopting
ACAW restoration procedures to old core
samples that have been allowed to age and
weather with little attention to the storage
enviromnent.
An important step in wettability restoration is to establish an Swi that corresponds
to the reservoir. This requires knowledge
of the reservoir water saturation and a
method of establishing this initial saturation
in the core. Determination of reservoir connate water, aside from problems of wettabiIity, is much more difficult than sometimes
assumed. 31 If a satisfactory determination
of Swi has been made, displacement procedures are designed to achieve this value in
the laboratory core sample. This may involve flooding at high pressure, sometimes
with a high-viscosity refIned oil, centrifuging, or removal of water by desaturation by
means of a porous plate or partial drying.
The core is flushed with crude oil and then
aged at reservoir temperature for about 1 to
4 weeks. The objective of the aging process is to re-establish adsorption equilibrium
between the rock surface and the crude oil
that had been established in the reservoir
over geologic time.
Various degrees of sophistication can be
used.in the restoration procedure to achieve
systems that are more closely representative
of reservoir conditions. IdentifIcation of the
key parameters that affect wettability in
COBR systems will obviously lead to much
greater confIdence in design of ACAW
procedures.
Comparison of Fresh Core and RestoredState Results. A major concern in ACAW
work is that there is no sure way to check
the validity of results. Comparison of results
for fresh cores to restored-state results for
the same cores provides the closest approach. 1 The best possible indication that
the results are valid is that the two data sets
agree. If they do not, the various possible
causes of disagreement are reviewed in
deciding which data set is likely to be more
reliable.
Measurement of Relative Permeabilities.
Having obtained a reservoir core sample
andlor fluids, with careful attention being
paid to maintenance or restoration of
reservoir conditions, laboratory tests are
conducted to obtain relative permeability
JPT December 1990

measurements. 30 32 These measurements

are used in reservoir simulation to obtain
production forecasts. Design of surface facilities is often tied to these forecasts.
The most commonly used and convenient
method of measuring relative permeability
is by the unsteady-state method. This
method was originally developed and applied with strongly wetted systems and high
displacement rates. It is now widely recognized that such an approach cannot be expected to simulate conditions of intermediate
or mixed wettability. However, if tests are
run at reservoir rates, the results may be influenced by capillary end effects (mainly
holdup of oil at the outflow face). Coreflood
simulation can be used to correct for end effects. There is growing evidence that end
effects for waterfloods at reservoir rates in
mixed-wettability systems can be quite
small. In-situ measurements of saturation by
X -ray adsorption or CAT scanning to check
for end effects and general uniformity of
fluid distributions provide for improved confIdence in procedures and results.
Reservoir Wettability and Electrical
Resistivity. Electric logging is the most
widely used method of identifying
hydrocarbon-bearing intervals in a wellbore.
Standard methods of relating oil saturation
to electrical resistivity are based on measurements of brine in cleaned cores, usually
with air as the nonwetting phase. These
measurements will generally correspond to
VSWW conditions. Most investigations of
the effect of wettability on resistivity showed
increases in resistivity with decreases in
water-wetness that were often too large to
be reasonable. However, most of these results were for systems in which wettability
change was induced by artifIcial means, such
as silane treatment of cores. Relatively little
information is available on saturation exponents for COBR systems. Swanson 33 and
Longeron et at. 34 showed that Archie saturation exponents were only moderately
higher for COBR systems than for a clean
core and refIned oil. Further systematic
study of electrical resistivity of COBR systems is needed, with special attention being
given to wettability variation and obtaining
data at low water saturations.

Remarks
A practical solution commonly suggested for
ACAW is to measure relative permeability
and other parameters that enter reservoir
simulation at conditions that duplicate the
reservoir. However, the understanding of
wettability gained by this approach and the
overall value of data specifIc to a piece of
core are very limited. Even more serious is
the inability to check the validity of the data.
With greater attention being paid to mixedwettability systems and the use of CAT scanning to obtain direct measurements of fluid
distribution, uncertainties in relative permeability measurement are being identifIed. Interpretation of relative permeability curves
in terms of interface behavior and fluid dis-

tributions is still fairly primitive. Rules of

thumb commonly used in the interpretation
of the effect of wettability on relative permeability behavior should be treated with
caution. Mechanistic accounts of the effect
of wettability on capillary pressure, fluid
distribution, and oil retention provide a more
direct approach to understanding interactions
between wettability and pore geometry and
a logical starting point for developing a
fuller understanding of relative permeability
relationships.

Conclusions
1. Reservoir wettability can cover a wide
spectrum of conditions. Systems of intermediate or mixed wettability are quite common, whereas VSWW systems may be a
rarity.
2. Contact-angle behavior of crude-oill
brine systems falls into two main classes distinguished by either small or large hysteresis.
3. Adhesion behavior of crude oils is
strongly dependent on pH.
4. Methods in most general use for measuring the wettability of COBR systems (the
Amott test, the USBM test, and imbibition
rate measurements) are strongly dependent
on capillary pressure. In all three tests, .
decrease in interface curvature to zero is a
key condition.
5. Laboratory waterfloods on COBR systems show that oil recovery is optimum at
neutral wettability.
6. Agreement in results for fresh core
with those for restored core provides the best
indication that reservoir wettability has been
duplicated in the laboratory.
7. ROS values obtained in the laboratory
for mixed-wettability systems and those
determined by in-situ measurements show
that it is possible for waterfloods to achieve
very high displacement effIciencies.

Nomenclature
A 1 = area under secondary drainage
curve
A2 = area under imbibition curve
falling below zero-Pc axis
ED = displacement effIciency
E Dsw = displacement effIciency at
strongly water-wet conditions
E De = displacement efficiency at
some global wetting
condition e
IAH = Amott-Harvey wettability
index
10 = wettability index (for oil)
Iw = wettability index (for water)
N w = wettability number by USBM
centrifuge test
Pc = capillary pressure
Soi = initial oil saturation of core
sample
Sor = ROS of core sample
Sw = water saturation
Swi = initial water saturation
~ = pore volume
A = difference
1483

-- ......

Author

.... heads the

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....... CIIien*b'l
Group at the New
IIuIco PeIr6Ieum
Recovery All .. ICh
Center end .. ell-

)unct prot or of

peIraIeum . . . . .
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Tech. He .. euthor or coauthor of more
. . . ., ....... lIIIIInIyon CIIpII.tty ...
IuId
poroue medIL He hoIcIe
88 ...... In chemIcIII . . . _rIng

.......,In

.... PhD _ _ 1n ...........,;..

from the U. of LeecIL He recetnd the
1110 New . . . . TeICh DIItInguIehed
A dI AWM'd; eerved on
c:ommItIMe for the 1178, 11", end
1tI7 AnnuIII _ Unge; end ...".. on
the EdItorI8I . . . . . CommIttee.

'**'...

(J =

contact angle

= global wetting condition

IT = disjoining pressure

Subscripts
A = advancing
i = initial
0= oil
r = residual
R = receding
s = spontaneous
t = total (with saturation change AS')
w = water

References
1. Cuiec, L.E.: "Evaluation of Reservoir Wettability and Its Effect on Oil Recovery," Interfacial Phenomena in Oil Recovery, N.R.
Morrow (ed.), Marcell Dekker, New York
City (1990) 319-75.
2. Amott, E.: "Observations Relating to the
Wettability of Porous Rock," Trans., AIME
(1959) 216, 156--62.
3. Donaldson, E.C., Thomas, R.D., and
Lorenz, P.B.: "Wettability Determination
and Its Effect on Recovery Efficiency," SPFJ
(March 1969) 13-20.
4. Zisman, W .A.: "Relation of the Equilibrium
Contact Angle to Liquid and Solid Constitution," Contact Angle, Wettability and Adhesion, Advances in Chemistry Series 43,
American Chemical Soc., Washington, DC
(1964) 1-51.
5. Treiber, L.E., Archer, D.L., and Owens,
W.W.: "Laboratory Evaluation of the Wettability of Fifty Oil Producing Reservoirs, "
SPFJ (Dec. 1972) 531-40.
6. Morrow, N.R., Lim, H.T., and Ward, I.S.:
"Effect of Crude-Oil-Induced Wettability
Changes on Oil Recovery," SPEFE (Feb.
1986) 89-103.

1484

7. Buckley, J.S., Takamura, K., and Morrow,

N.R.: "Influence of Electrical Surface
Charges on the Wetting Properties of Crude
Oil," SPERE (Aug. 1989) 332-40.
8. Buckley, J.S. and Morrow, N.R.: "Characterization of Crude Oil Wetting Behavior by
Adhesion Tests, " paper SPE 20263 presented at the 1990 SPEIDOE Symposium on Enhanced Oil Recovery, Tulsa, April 22-25.
9. Hirasaki, G.l.: "Wettability: Fundamentals
and Surface Forces," paper SPE 17367
presented at the 1988 SPEIDOE Symposium
on Enhanced Oil Recovery, Tulsa, April
17-20.
10. Dubey, S.T. and Waxman, M.H.: "Asphaltene Adsorption and Desorption From MineraI Surfaces," paper SPE 18462 presented
at the 1989 SPE International Symposium on
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11. Takamura, K. and Chow, R.S.: "A Mechanism for Initiation .of Bitumen Displacement
from Oil Sand," J. Cdn. Pet. Tech. (Nov.Dec. 1983) 22, 22-30.
12. Sharma, M.M. and Wunderlich, R.W.: "The
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G. T.: "Effect of Crude Oil Components on
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Trans., AIME, 216.
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Computerized Tomography," JPT (Aug.
1987) 885-98.
15. Jadhunandan, P. and Morrow, N.R.: "Crude
Oil Recovery In Laboratory Water Floods,"
paper presented at the 1990 IFP Research
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The Fundamentals of Fluid Transport in
Porous Media, Aries, May 14-18.
16. Kyte, J.R., Naumann, V.O., and Mattax,
C.C.: "Effect of Reservoir Environment on
Water-Oil Displacements," JPT(luly 1961)
579-82; Trans., AIME, 222.
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Film Drainage in Mixed-Wettability Rocks,"
JPT (1973) 1216-24.
18. Rathrnell, 1.1., Braun, P.H., and Perkins,
T.K.: "Reservoir Waterflood Residual Oil
Saturation From Laboratory Tests," JPT
(Feb. 1973) 175-85; Trans., AIME, 255.
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Dispersion, and Flowable Saturation in
Porous Media," paper SPE 15019 presented at the 1986 SPE Permian Basin Oil and
Gas Recovery Conference, Midland, March
13-14.
20. Deans, H.A.: "Single-Well Tracer
Methods," Determination of Residual Oil
Saturation, Interstate Oil Compact Commission, Oklahoma City (lune 1978) 156-76.
21. Mohanty, K.K., Davis, H.T., and Scriven,
L.E.: "Physics of Oil Entrapment in WaterWet Rock," SPERE (Feb. 1987) 113-28.
22. Li, Y. and Wardlaw, N.C.: "The Influence
of Wettability and Critical Pore-Throat Size
Ratio on Snap-off," J. Colloid Interface Sci.
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23. Anderson, W.G.: "Wettability Literature

Survey-Part 1: RocklOillBrine Interactions
and the Effects of Core Handling on Wettability," JPT (Oct. 1986) 1125-44.
24. Anderson, W.G.: "Wettability Literature
Survey-Part 2: Wettability Measurement,"
JPT (Nov. 1986) 1246--62.
25. Anderson, W.G.: "Wettability Literature
Survey-Part 3: Effects ofWettability on the
Electrical Properties of Porous Media," JPT
(Dec. 1986) 1371-78.
26. Anderson, W.G.: "Wettability Literature
Survey-Part 4: Effects of Wettability on
Capillary Pressure," JPT (Oct. 1987)
1283-1300 .
27. Anderson, W.G.: "Wettability Literature
Survey-Part 5: Effects of Wettability on
Relative Permeability," JPT (Nov. 1987)
1453-68.
28. Anderson, W.G.: "Wettability Literature
Survey-Part 6: Effects of Wettability on
Waterflooding," JPT(Dec. 1987) 1605-22.
29. Wunderlich, R.W.: "Obtaining Samples with
Preserved Wettability," Interfacial Phenomena in Oil Recovery, N.R. Morrow (ed.),
Marcell Dekker, New York City (1990)
289-318.
30. Hirasaki, G.l., Rohan, J.A., and Dubey,
S. T.: "Wettability Evaluation During
Restored-State Core Analysis," paper SPE
20506 presented at the 1990 SPE Annual
Technical Conference and Exhibition, New
Orleans, Sept. 23-26.
31. Morrow, N.R. and Melrose, J.C.: "Applications of Capillary Pressure Data to the Determination of Connate Water Saturation,"
Interfacial Phenomena in Oil Recovery, N .R.
Morrow (ed.), Marcell Dekker, New York
City (1990) 257-87.
32. Heaviside, 1.: "Measurement of Relative Permeability," Interfacial Phenomena in Oil
Recovery, N.R. Morrow (ed.), Marcell Dekker, New York City (1990) 377-411.
33. Swanson, B.F.: "RationaIizingthelnfluence
of Crude Wetting on Reservoir Fluid Flow
With Electrical Resistivity Behavior," JPT
(Aug. 1980) 1459-64.
34. Longeron, D.G., Argaud, M.l., and Feraud,
J.P.: "Effects of Overburden Pressure, Nature, and Microscopic Distribution of the
Fluids on Electrical Properties of Rock Samples," paper SPE 15383 presented at the 1986
SPE Annual Technical Conference and Exhibition, New Orleans, Oct. 5-8.

SI Metric Conversion Factors

A x 1.0*
E-Ol = om
ft x 3,(148*

E-Ol = m

'Conversion factor is exact.

This paper is SPE 21621. Distinguished AutMr SerIes articles are general, descriptive presentations that summarize the state of the art in an area of technology by describing
recent developments for readers who are not specialists in
the topics discussed. Written by individuals recognized as
experts in the area, these articles provide key references
to more defin~ive work and present specific details only to
illustrate the technology. Purpose: To inform the general
readership of recent advances in various areas of petroleum
engineering. A softbound anthology, SPE Dislinguished
Author SOOes: Dec. 1981-Dec. 1983, is available from SPE's
Book Order Dept.

JPT

December 1990 JPT