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 in milli-

Newtons/meter (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   os   ws    ow cos 
• A negative adhesion tension indicates that the denser phase (water)
preferentially wets the solid surface (and vice versa).
• An adhesion tension of “0” indicates that both phases have equal
affinity for the solid surface
 CONTACT ANGLE
Oil
ow

Oil  Water Oil

os ws os

Solid The contact angle, , measured through
the denser liquid phase,
defines which fluid wets the solid
AT = adhesion tension, milli-Newtons/m or dynes/cm) surface.
 = contact angle between the oil/water/solid interface measured through the water, degrees

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

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

 = interfacial energy (interfacial tension) between the oil and water, 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:
 ws > os

• AT < 0 (i.e., the adhesion tension is negative)

• 0 <  < 90

If  is close to 0, the rock is considered

to be “strongly water-wet”
 WATER-WET ROCK

ow Oil

 Water
os ws os
Solid

• 0 <  < 90

• Adhesive tension between water and the
rock surface exceeds that between oil and
the rock surface.
 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:
 os > ws
• AT > 0 (i.e., the adhesion tension is positive)
• 90 <  < 180
If  is close to 180, the rock is considered to
be “strongly oil-wet”
 OIL-WET ROCK

ow
Water
Oil


os ws os Solid

• 90 <  < 180

• The adhesion tension between water and the
rock surface is less than that between oil and the
rock surface.
 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
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 silicone Wettability
1 0.00 0.649
80 2 0.020 0.176
1 3 0.200 - 0.222
2 4 2.00 - 0.250
60
3 5 1.00 - 0.333 ?
Curves cut off at Fwd •100
4
p. 274
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
 NOMENCLATURE

AT = adhesion tension, milli-Newtons/m or dynes/cm)

 = contact angle between the oil/water/solid interface measured through

the water (more dense phase), degrees

os = interfacial tension between the oil and solid, milli-Newtons/m or

dynes/cm

ws = interfacial tension between the water and solid, milli-Newtons/m or

dynes/cm

ow = interfacial tension between the oil and water, milli-Newtons/m or

dynes/cm
 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.

 Introduction to
Capillary Pressure

.
 Applications of Capillary
Pressure Data
• Determine fluid distribution in reservoir (initial conditions)
• Accumulation of HC is drainage process for water wet res.
• Sw= function of height above OWC (oil water contact)
• Determine recoverable oil for water flooding applications
• Imbibition process for water wet reservoirs
• Pore Size Distribution Index, 
• Absolute permeability (flow capacity of entire pore size distribution)
• Relative permeability (distribution of fluid phases within the pore size
distribution)
• Reservoir Flow - Capillary Pressure included as a term of flow potential for
multiphase flow

• Input data for reservoir simulation models

ρw g Z
Φ w  po   Pc,ow ; Z , water wet
D
 DRAINAGE AND IMBIBITION
CAPILLARY PRESSURE CURVES DRAINAGE

• Fluid flow process in which the saturation

of the nonwetting phase increases

• Mobility of nonwetting fluid phase

increases as nonwetting phase saturation
increases
Drainage IMBIBITION

• Fluid flow process in which the saturation

Pc of the wetting phase increases

• Mobility of wetting phase increases as

wetting phase saturation increases
Pd
Four Primary Parameters
Si = irreducible wetting phase saturation
Imbibition
Sm = 1 - residual non-wetting phase saturation
Si Sm
Pd = displacement pressure, the pressure
required to force non-wetting fluid into largest
0 0.5 1.0
pores
Swt
 = pore size distribution index; determines
Modified from NExT, 1999, after … shape
 DRAINAGE PROCESS
• Fluid flow process in which the saturation of the nonwetting phase
increases
• Examples:
• Hydrocarbon (oil or gas) filling the pore space and displacing the
original water of deposition in water-wet rock
• Waterflooding an oil reservoir in which the reservoir is oil wet
• Gas injection in an oil or water wet oil reservoir
• Pressure maintenance or gas cycling by gas injection in a retrograde
condensate reservoir
• Evolution of a secondary gas cap as reservoir pressure decreases
 IMBIBITION PROCESS
IMBIBITION
•Fluid flow process in which the
saturation of the wetting phase increases

•Mobility of wetting phase increases as

wetting phase saturation increases
Examples:
Accumulation of oil in an oil wet reservoir
Waterflooding an oil reservoir in which the reservoir is
water wet
Accumulation of condensate as pressure decreases in
a dew point reservoir
 Pc vs. Sw Function
Reflects Reservoir Quality
Core Pore Petrophysical Gamma Ray Flow
Core Lithofacies
Plugs Types Data Log Units
vs k Capillary
Pressure

High Quality
5

2
Function moves up
and right, and
becomes less “L”
1
shaped as reservoir Low Quality
quality decreases
Effect of Permeability on Shape
20

16
Decreasing
Capillary Pressure

Permeability,
Decreasing 
12

A B
8

0
0 0.2 0.4 0.6 0.8 1.0

Water Saturation
Modified from NExT 1999, after xx)
 Effect of Grain Size Distribution on Shape

Poorly sorted
Capillary pressure, psia

Well-sorted

Decreasing 

Modfied from NExT, 1999; after …) Water saturation, %

 CAPILLARY PRESSURE
- DEFINITION -
• The pressure difference existing across
the interface separating two immiscible
fluids in capillaries (e.g. porous media).
• Calculated as:
Pc = pnwt - pwt Where:

Pc = capillary pressure
• One fluid wets the surfaces of the formation
rock (wetting phase) in preference to the other Pnwt = pressure in nonwetting phase
(non-wetting phase).
• Gas is always the non-wetting phase in both
oil-gas and water-gas systems.
pwt = pressure in wetting phase
• Oil is often the non-wetting phase in water-oil
systems.
 Capillary Tube - Conceptual Model
Air-Water System

 Air
h

Water

• Considering the porous media as a collection of capillary tubes provides useful

insights into how fluids behave in the reservoir pore spaces.
• Water rises in a capillary tube placed in a beaker of water, similar to water (the
wetting phase) filling small pores leaving larger pores to non-wetting phases of
reservoir rock.
 CAPILLARY TUBE MODEL
AIR / WATER SYSTEM
• The height of water in a capillary tube is a function of:

2  aw cos 
– Adhesion tension between the air and water
– Radius of the tube
h 
– Density difference between fluids r g  aw
This relation can be derived from balancing the upward force due to adhesion
tension and downward forces due to the weight of the fluid (see ABW pg 135).
The wetting phase (water) rise will be larger in small capillaries.
h = Height of water rise in capillary tube, cm
aw = Interfacial tension between air and water,
dynes/cm
 = Air/water contact angle, degrees
r = Radius of capillary tube, cm
g = Acceleration due to gravity, 980 cm/sec2
aw = Density difference between water and air, gm/cm3
Contact angle, , is measured through the more dense phase (water in this
case).
Rise of Wetting Phase Varies with
Capillary Radius

1 2 3 4

AIR

WATER

Ayers, 2001
CAPILLARY TUBE MODEL
AIR/WATER SYSTEM
pa1
pw1 Air
h
pa2
pw2

Water

Water rise in capillary tube depends on the density difference of fluids.

Pa2 = pw2 = p2
pa1 = p2 - a g h
pw1 = p2 - w g h
Pc = pa1 - pw1
= w g h - a g h
CAPILLARY PRESSURE – AIR / WATER
SYSTEM
• Combining the two relations results in the following
expression for capillary tubes:

2  aw cos 
Pc 
r
CAPILLARY PRESSURE – OIL / WATER
SYSTEM
• From a similar derivation, the equation for
capillary pressure for an oil/water system is

2  ow cos 
Pc 
r

Pc = Capillary pressure between oil and water

ow = Interfacial tension between oil and water, dyne/cm
 = Oil/water contact angle, degrees
r = Radius of capillary tube, cm
Fluid Distributions in Reservoirs
SAMPLE CASE STUDY
•In deltaic-type deposition sands may be laid down in fan-
like bodies. The current that is responsible for the
deposition is fast in the proximal region and becomes
progressively slower as one progresses distally or laterally.
Hence, in the proximal region the grain size of the resulting
rocks is large (only large grains have time to fall from the
fast current). Distally and laterally the grain size of the
resulting rocks becomes finer as smaller sand particles
have time to fall out of the slower current. Eventually, at the
extreme edges of the fan, the current is so slow that very
fine clay particles are also deposited, becoming
interspersed with the fine sand grains.
RESERVOIR APPLICATIONS
 QUESTIONS
• What is the trend from well A- E of the
following parameters
• initial displacement pressures
• Initial water saturation
• Which producing well will experience
highest water production and why
• The first part shows the fan geometry and position of
the wells (labeled A to E).
• The second part shows the capillary pressure curves for
each of 5 samples taken from each of the wells with the
100% water point labeled S100A to S100E, the initial
displacement pressure labeled DIA to DIE, the 50%
water
• point labeled as S50A to S50E, and the irreducible water
saturation labeled SwiA to SwiE.
• The third part shows the height above the free water
level as a function of facies and water saturation, with
the same saturation labels as in part 2.
 KEY NOTES
• The initial displacement pressure becomes greater as the sample becomes
more shaly (finer grained) as one moves distally.
• The irreducible water saturation becomes greater as the sample becomes more
shaly (finer grained) as one moves distally.
• The capillary pressure curve for the proximal samples are quite flat from 100%
water to about 60% water indicating that only low pressures are required to
replace about the first 40% of water with oil (in the largest pores with the
largest and most accessible pore throats).
• At any given capillary pressure, more water is retained as the sample becomes
more shaly (finer grained) as one moves distally.
• The height above the free water level of 100% water saturation increases as the
sample becomes more shaly (finer grained) as one moves distally.
• The height above the free water level of 50% water saturation increases as the
sample becomes more shaly (finer grained) as one moves distally.
 KEY NOTES
• So, the grain size controls the height of the 100% water
saturation level. Now imagine four layers of sand that have
different grain sizes, porosities and permeabilities, and that have
become folded (Fig.4.20). Each layer has its own capillary
pressure characteristics associated with its grain size, and that
capillary pressure is related to the height of the 100% water level
above the free water level as shown.
• It can be seen that it is possible to drill through layers which are
100% water zones existing between oil or gas zones from the
same reservoir. In this case Well C has two oil water contacts.
• It is the bottom one that is the true OWC. Because multiple
OWCs are confusing, we tend to talk about oil down to (ODT)
and gas down to (GDT) levels when there are multiple
hydrocarbon/water contacts.