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)
Sw+So+Sg=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
Imbalanced molecular forces at phase boundaries
GAS Boundary contracts to minimize size
Cohesive vs. adhesion forces

LIQUID
GAS
SOLID
Cohesive force
Adhesion force

Molecular
Interface
(imbalance
of forces)

LIQUID
(dense phase)

Modified from PETE

311 Notes
 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.

AT so sw wo cos wo
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
wo Oil

Water

so sw

The contact angle, , measured through

Solid the more dense phase, defines which
AT = adhesion tension, milli-Newtons/m or dynes/cm)
fluid wets the solid surface.

= 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
 WETTING PHASE FLUID
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.
 NONWETTING 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
 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

AT > 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
wo Oil

Water

so sw

Solid
0 < < 90
Interfacial tension between the rock surface
and water is less than between the rock
surface and oil.
 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
AT < 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

Water
wo Oil

Solid

90 < < 180

The interfacial tension between the rock
surface and oil is less than between the rock
surface and water.
 INTERFACIAL CONTACT ANGLES,
VARIOUS ORGANIC LIQUID IN
CONTACT WITH SILICA AND CALCITE
WATER

SILICA SURFACE
ORGANIC
LIQUIDS

WATER

CALCITE SURFACE

From Amyx Bass and Whiting, 1960; modified from Benner and Bartel, 1941
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
Air
OIL Oil OIL

WATER WATER
< 90
WATER WATER > 90
SOLID (ROCK) SOLID (ROCK)
FREE WATER

OIL
GRAIN GRAIN

OIL
RIM
BOUND WATER FREE WATER
Ayers, 2001
WATER-WET OIL-WET

Air Oil

WATER WATER
From Levorsen, 1967
Brown, G.E., 2001, Science, v. 294, p. 67-69
 n = 30 silicate and 25 carbonates n = 161 ls., dol.

From Tiab and Donaldson, 1996 CONTACT ANGLE: Triber et al. CONTACT ANGLE:
-Water-wet = 0 75 degrees -Water-wet = 0 80 degrees
-Intermediate-wet = 75 105 degrees -Intermediate-wet = 80 100 degrees
-Oil-wet = 105 180 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
Air
OIL Oil OIL

WATER WATER
< 90
WATER WATER > 90
SOLID (ROCK) SOLID (ROCK)
FREE WATER

OIL
GRAIN GRAIN

OIL
RIM
BOUND WATER FREE WATER
Ayers, 2001
 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.
 Water-Wet System

Oil-Wet System

Effect on waterflood of an oil reservoir?

From Levorsen, 1967

 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
Core Percent
Recovery efficiency, percent, Soi

no silane Wettability
1 0.00 0.649
80 2 0.020 0.176
1 3 0.200 - 0.222
2 4 2.00 - 1.250
3 5 1.00 - 1.333
60
Curves end at WOR=100
4
40 5

20

0
1 2 3 4 5 6 7 8 9 10 11 12
Water injected, pore volumes

Modified from Tiab and Donaldson, 1996

IMPLICATIONS OF WETTABILITY
Squirrel oil - 0.10 N NaCl - Torpedo core ( 33 O W 663,
K 0945, Swi 21.20%)
Recovery efficiency, percent Spi

Squirrel oil - 0.10 N NaCl Torpedo Sandstone core,

after remaining in oil for 84 days ( 33.0 W 663, K
0.925, Swi 23.28%)

80

60

40

20

0 1 2 3 4 5 6 7 8 9 10
Water injection, pore volumes
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.