Boundary Tension

and Wettability
Immiscible Phases
Earlier discussions have considered only a
single fluid in the pores
porosity
permeability
Saturation: fraction of pore space
occupied by a particular fluid (immiscible
phases)
S
w
+S
o
+S
g
=1
When more than a single phase is present,
the fluids interact with the rock, and with
each other
DEFINITION OF INTERFACIAL
TENSION
Interfacial (boundary) tension is the energy
per unit area (force per unit distance) at the
surface between phases
Commonly expressed as mN/m (also,
dynes/cm)
BOUNDARY (INTERFACIAL) TENSION
Modified from PETE
311 Notes
Imbalanced molecular forces at phase boundaries
Boundary contracts to minimize size
Cohesive vs. adhesion forces
LIQUID
(dense phase)
Molecular
Interface
(imbalance
of forces)
GAS
SOLID
LIQUID
GAS

SOLID
Cohesive force
Adhesion force
DEFINITION OF WETTABILITY
Wettability is the tendency of one fluid
to spread on or adhere to a solid
surface in the presence of other
immiscible fluids.
Wettability refers to interaction between
fluid and solid phases.
Reservoir rocks (sandstone, limestone,
dolomite, etc.) are the solid surfaces
Oil, water, and/or gas are the fluids
WHY STUDY WETTABILITY?
Understand physical and chemical interactions between
Individual fluids and reservoir rocks
Different fluids with in a reservoir
Individual fluids and reservoir rocks when multiple
fluids are present

Petroleum reservoirs commonly have 2 3 fluids
(multiphase systems)

When 2 or more fluids are present, there are at least 3
sets of forces acting on the fluids and affecting HC recovery
DEFINITION OF
ADHESION TENSION
Adhesion tension is expressed as the
difference between two solid-fluid
interfacial tensions.

wo wo sw so T
A cos
A positive adhesion tension indicates that the denser phase (water)
preferentially wets the solid surface (and vice versa).
An adhesion tension of zero indicates that both phases have equal
affinity for the solid surface
CONTACT ANGLE
The contact angle, , measured through
the more dense phase, defines which
fluid wets the solid surface.
A
T
= adhesion tension, milli-Newtons/m or dynes/cm)
= contact angle between the oil/water/solid interface measured through the more dense phase, degrees

so
= interfacial energy between the solid and oil, milli-Newtons/m or dynes/cm

sw
= interfacial energy between the solid and water, milli-Newtons/m or dynes/cm

wo
= interfacial energy (interfacial tension) between the water and oil, milli-Newtons/m or dynes/cm

Solid
Water
Oil

so

sw

wo


Wetting phase fluid preferentially wets the
solid rock surface.
Attractive forces between rock and fluid draw
the wetting phase into small pores.
Wetting phase fluid often has low mobile.
Attractive forces limit reduction in wetting
phase saturation to an irreducible value
(irreducible wetting phase saturation).
Many hydrocarbon reservoirs are either totally
or partially water-wet.
WETTING PHASE FLUID
Nonwetting phase does not preferentially
wet the solid rock surface
Repulsive forces between rock and fluid
cause nonwetting phase to occupy largest
pores
Nonwetting phase fluid is often the most
mobile fluid, especially at large
nonwetting phase saturations
Natural gas is never the wetting phase in
hydrocarbon reservoirs
NONWETTING PHASE FLUID
WATER-WET RESERVOIR ROCK
Reservoir rock is water - wet if water preferentially
wets the rock surfaces
The rock is water- wet under the following
conditions:

so
>
sw

A
T
> 0 (i.e., the adhesion tension is positive)

0 < < 90

If is close to 0, the rock is considered
to be strongly water-wet

WATER-WET ROCK
Interfacial tension between the rock surface
and water is less than between the rock
surface and oil.

0 < < 90
Solid
Water
Oil

so

sw

wo


OIL-WET RESERVOIR ROCK
Reservoir rock is oil-wet if oil preferentially
wets the rock surfaces.
The rock is oil-wet under the following
conditions:

so
<
sw

A
T
< 0 (i.e., the adhesion tension is negative)
90 < < 180
If is close to 180, the rock is considered to
be strongly oil-wet

OIL-WET ROCK
90 < < 180
The interfacial tension between the rock
surface and oil is less than between the rock
surface and water.

Solid
Water
Oil

wo


From Amyx Bass and Whiting, 1960; modified from Benner and Bartel, 1941
INTERFACIAL CONTACT ANGLES,
VARIOUS ORGANIC LIQUID IN
CONTACT WITH SILICA AND CALCITE
SILICA SURFACE
CALCITE SURFACE
WATER
WATER
GENERALLY,

Silicate minerals have acidic surfaces
Repel acidic fluids such as major polar
organic compounds present in some crude oils
Attract basic compounds
Neutral to oil-wet surfaces
Carbonate minerals have basic surfaces
Attract acidic compounds of crude oils
Neutral to oil-wet surfaces
Tiab and Donaldson, 1996
Caution: these are very general statements and relations
that are debated and disputed by petrophysicists.

WATER-WET OIL-WET
Ayers, 2001
FREE WATER
GRAIN
SOLID (ROCK)
WATER
OIL

SOLID (ROCK)
WATER
OIL

GRAIN
BOUND WATER
F
R
E
E

W
A
T
E
R

OIL
OIL
RIM
< 90
> 90
WATER


Oil
Air
WATER
OIL-WET WATER-WET
WATER


WATER WATER
Air
Oil
From Levorsen, 1967
Brown, G.E., 2001, Science, v. 294, p. 67-69
From Tiab and Donaldson, 1996
n = 161 ls., dol.
CONTACT ANGLE: Triber et al.
-Water-wet = 0 75 degrees
-Intermediate-wet = 75 105 degrees
-Oil-wet = 105 180 degrees
n = 30 silicate and 25 carbonates
CONTACT ANGLE:
-Water-wet = 0 80 degrees
-Intermediate-wet = 80 100 degrees
-Oil-wet = 100 180 degrees
WETTABILITY IS AFFECTED BY:
Composition of pore-lining minerals

Composition of the fluids

Saturation history (hysteresis effects)
WETTABILITY CLASSIFICATION
Strongly oil- or water-wetting

Neutral wettability no preferential wettability
to either water or oil in the pores

Fractional wettability reservoir that has local
areas that are strongly oil-wet, whereas most
of the reservoir is strongly water-wet
- Occurs where reservoir rock have variable
mineral composition and surface chemistry

Mixed wettability smaller pores area water-wet
are filled with water, whereas larger pores are
oil-wet and filled with oil
- Residual oil saturation is low
- Occurs where oil with polar organic compounds
invades a water-wet rock saturated with brine
IMBIBITION
Imbibition is a fluid flow process in which
the saturation of the wetting phase
increases and the nonwetting phase
saturation decreases. (e.g., waterflood of an
oil reservoir that is water-wet).
Mobility of wetting phase increases as
wetting phase saturation increases
mobility is the fraction of total flow capacity for a particular
phase

WATER-WET RESERVOIR,
IMBIBITION
Water will occupy the smallest pores

Water will wet the circumference of most larger pores

In pores having high oil saturation, oil rests on a water film

Imbibition - If a water-wet rock saturated with oil is
placed in water, it will imbibe water into the smallest
pores, displacing oil
OIL-WET RESERVOIR,
IMBIBITION
Oil will occupy the smallest pores

Oil will wet the circumference of most larger pores

In pores having high water saturation, water rests on a
water film

Imbibition - If an oil-wet rock saturated with water is
placed in oil, it will imbibe oil into the smallest
pores, displacing water

e.g., Oil-wet reservoir accumulation of oil in trap

DRAINAGE
Fluid flow process in which the
saturation of the nonwetting phase
increases
Mobility of nonwetting fluid phase
increases as nonwetting phase
saturation increases
e.g., waterflood of an oil reservoir that is oil-wet
Gas injection in an oil- or water-wet reservoir
Pressure maintenance or gas cycling by gas injection
in a retrograde condensate reservoir
Water-wet reservoir accumulation of oil or gas in trap

IMPLICATIONS OF WETTABILITY
Primary oil recovery is affected by the
wettability of the system.
A water-wet system will exhibit
greater primary oil recovery.
WATER-WET OIL-WET
Ayers, 2001
FREE WATER
GRAIN
SOLID (ROCK)
WATER
OIL

SOLID (ROCK)
WATER
OIL

GRAIN
BOUND WATER
F
R
E
E

W
A
T
E
R

OIL
OIL
RIM
< 90
> 90
WATER


Oil
Air
WATER
IMPLICATIONS OF WETTABILITY
Oil recovery under waterflooding is
affected by the wettability of the
system.
A water-wet system will exhibit
greater oil recovery under
waterflooding.
From Levorsen, 1967
Effect on waterflood of an oil reservoir?
Water-Wet System
Oil-Wet System
IMPLICATIONS OF WETTABILITY
Wettability affects the shape of the
relative permeability curves.
Oil moves easier in water-wet rocks
than oil-wet rocks.
IMPLICATIONS OF WETTABILITY
1 2 3 4 5 6 7 8 9 10 11 12
0
20
40
60
80
1
2
3
4
5
Core
no
Percent
silane Wettability
0.00
0.020
0.200
2.00
1.00
0.649
0.176
- 0.222
- 1.250
- 1.333
Curves end at WOR=100
1
2
3
4
5
Water injected, pore volumes
R
e
c
o
v
e
r
y

e
f
f
i
c
i
e
n
c
y
,

p
e
r
c
e
n
t
,

S
o
i

Modified from Tiab and Donaldson, 1996
IMPLICATIONS OF WETTABILITY
Water injection, pore volumes
0
20
40
60
80
1 2 3 4 5 6 7 8 9 10
Squirrel oil - 0.10 N NaCl - Torpedo core ( 33 O W 663,
K 0945, S
wi
21.20%)
Squirrel oil - 0.10 N NaCl Torpedo Sandstone core,
after remaining in oil for 84 days ( 33.0 W 663, K
0.925, S
wi
23.28%)
R
e
c
o
v
e
r
y

e
f
f
i
c
i
e
n
c
y
,

p
e
r
c
e
n
t

S
p
i

Modified from NExT, 1999
WETTABILITY AFFECTS:
Capillary Pressure

Irreducible water saturation

Residual oil and water saturations

Relative permeability

Electrical properties
LABORATORY MEASUREMENT OF
WETTABILITY
Most common measurement techniques
Contact angle measurement method
Amott method
United States Bureau of Mines
(USBM) Method

References
1. Amyx, J.W., Bass, D.M., and Whiting, R.L.: Petroleum Reservoir Engineering, McGrow-Hill Book
Company New York, 1960.
2. Tiab, D. and Donaldson, E.C.: Petrophysics, Gulf Publishing Company, Houston, TX. 1996.
3. Core Laboratories, Inc. A course in the fundamentals of Core analysis, 1982.
4. Donaldson, E.C., Thomas, R.D., and Lorenz, P.B.: Wettability Determination and Its Effect
on Recovery Efficiency, SPEJ (March 1969) 13-20.