Petrophysics

Wettability

Dr.Falan Srisuriyachai
Outline
• Definition and type of wettability
• Point of zero charge and surface chemistry
• Alteration of natural wettability
• Wettability alteration of reservoir rocks
• Wettability measurement
• Restoration of wettability
• Artificial wettability
• The effect of wettability on fluid displacement process
Definition and type of wettability
Definition of Wettability
• Wettability is defined as the tendency of a fluid to
spread or adhere onto the solid surface in the
presence of other immiscible fluids.

• Wettability is considered an important factor that

controls the location, flow, and the distribution of fluid
in the reservoirs.

• Wettability affects most of the petrophyscal properties

including capillary pressure, relative permeability, and
electrical properties.
Type of Wettability
• Water-wet is a surface that prefers to adhere by water when there is a
presence of oil phase.

• Water wet is generally considered as a favorable condition for oil

production.

• Oil-wet is a surface that tends to attach with oil in the presence of water
phase.

• Therefore, additional energies are generally added to improve this attached

oil. The condition is unfavorable for oil production.

• Neutral-wet (so called intermediate-wet) is a surface having either water-

wet or oil-wet characters or a surface without wettability preference. Several
studies concluded that neutral-wet is the most favorable condition for oil
production.
Mixed-wet

when more than one pore size is present, mixed-condition can emerge

• Mixed-wet was termed by Salatiel (1973) as a rock contains oil-wet surfaces

which form the continuously paths through lager pores, while smaller pores
remain water-wet.

• Mixed-wet condition can be naturally generated during oil migration to an

original water-wet reservoir.

• Mixed-wet can be restored at the reservoir conditions in laboratory.

Fractional-wet
• Rock is composed of many minerals with
different surface chemistry and adsorption
properties, leading to the variation of wettability.

• Fractional wettability can be called

heterogeneous, spotted or dalmatian wettability.

• Fractional-wet sample can be created by mixing

grains with different surface properties
(treatment with Drifilm) at certain ratio and then
finally being packed.

• Property of fractional-wet is proportionally

influenced by portion of water and oil-wet
surface.
Point of zero charge and
surface chemistry
Point of zero charge
• The point of zero charge (p.z.c.) is the point of pH value at which
the surface charge density charges from positive to negative or vice
versa.

• Silica (SiO2) representing sandstone surface has the p.z.c. of 2.5.

• Calcite (CaCO3) representing carbonate surface has the p.z.c of 9.0.

• Therefore, the sandstone formation saturated with brine (pH

around 6-7) is negatively charged, where as the carbonate is
positively charged.
 Point of zero charge (cont.)
• Therefore, at the reservoir condition where pH value
varies from 6-8, sandstone (silica) and carbonate (calcite)
formations have different surface charge properties that
consecutively results in different wettability.
Sandstone OH-
H+ OH -
P.Z.C = 2.5 OH-
H+ H+
+ -

pH = 0 + -
pH = 14
H+ Carbonate
H + OH-
Reservoir P.Z.C = 9.0 OH-
H+ OH-
condition P.Z.C
around 6-8
 Sandstone surface chemistry

Tetrahedral structure Lacttice structure

of silicon dioxide of sandstone
• Sandstone is composed mainly of Silicon dioxide. However the molecules do not stay
separately but are attached with other molecules forming the net structural lattice.

• Bulk structure has the continuity of molecule orientation but, the surface structure of
sandstone is different. The discontinuity of structure results in un-balance charge.

• The oxygen atoms that are not bounded with other silicon atoms results in abundant of
negative charges. In the presence of water, this charges results in the weak acidity of
surface.
 Carbonate surface chemistry
• Carbonate surface has its molecular structure
Bulk structure different from bulk structure as same as
of calcite sandstone.

• At the surface, the continuity of net structure

terminates, resulting in rearranging of molecular
structure.

• Oxygen atoms are left un-bonded and quickly

bind with protonated hydrogen atom in water
resulting in forming of calcium hydroxide
(Ca(OH)2) which is a weak base.

• The hydroxide part can be liberated as water

molecule (in abundant of H+),leaving the surface
Surface structure model unbalanced with positive charge of calcium.
Alteration of natural wettability
Wettability alteration mechanism
• Originally, all reservoir rocks are believed to be water-wet
since they are deposited in aqueous environment and hence,
water prevent the direct contact between the rock surface
and oil.

• During the oil migration into the reservoir rock, the

naturally water-wet condition is altered from the induced
component came with migrated oil.

• Four mechanisms alter the original wettability to an oil-wet

condition: polar interaction, surface precipitation, acid-base
interaction and ion-binding.
Polar interaction
• Polar interaction is a direct interaction between the charges from rock
surface and the opposite charge of polar compounds in crude oil.

• The interaction occurs when crude oil is in direct contact with rock
surface.

Acid molecule • Polar compounds in crude oil generally contain a non-polar part which
is normally a long chain of hydrocarbon.

• This long-chain of hydrocarbon exposes outward from rock surface,

causing a monolayer of non-polar compounds and results in an oil-wet
condition.

• In general, sandstone (acidic surface) forms the polar interaction with

basic compounds (nitrogen heteroatoms) and carbonate (basic surface)
Base molecule forms the polar interaction with acid compounds (oxygen heteroatoms)
Surface precipitation
Good solvent • Surface precipitation depends primarily from the
solvent property of crude oil itself to asphaltene
compounds.

• The wettability alteration occurs when crude oil is

a poor solvent for its asphaltenes.
surface

• Consequently, asphaltenes cannot be dissolved

Poor solvent and they precipitate onto the rock surface.

• Asphaltene compounds alter wettability by

exposing their non-polar part to stick with oil
phase.

surface • Asphaltene precipitation normally occurs when

the temperature declines (reduction of solubility).
Acid-base interaction
• Acid-base interaction occurs when there is a
presence of water layer covering the rock surface.

• Basic compounds providing positive charges,

interact with negatively- charged surface
(sandstone).

• Acid compounds providing negative charges,

interact with positively-charged surface
(carbonate).
Acid-base interaction in
sandstone and carbonate • The interaction is getting stronger as the water
formations film covering rock surface is thinner.

• Eventually the water film is ruptured and the

direct interaction is completed.
Ion binding • Ion binding plays a major roll only when the
rock surface is negatively charged (sandstone).

• The ions in this mechanism primarily refer to

the most-found divalent ions in brine phase
which are calcium and magnesium ions (Ca2+
and Mg2+ ).

• Divalent ions acts as the linking bridge

between the negative charges of rock surface
and the negative charges of ionized acid.
Ion-binding in sandstone
surface • By this mechanism, both acidic and basic
compounds can be absorbed onto the
sandstone surface depending on the presence
of divalent ions.
Wettability alteration
of reservoir rock
Wettability of sandstone rock
• Sandstone surface is initially water-wet but this condition can turn
into neutral-wet or oil-wet during the oil migration period.

• Since sandstone is initially negatively charged, polar interaction,

surface precipitation, interaction with base compounds and ion
binding are the mechanisms that reverse sandstone surface to an
oil-wet direction.

• In nature, sandstone can be mostly found as water-wet (or

intermediate-wet).

• Therefore, sandstone in general is favorable for oil production

since oil has less attraction with rock surface.
Wettability of carbonate rock
• Carbonate surface which is positively charged surface is also water-wet at
its origin.

• But the surface can be alter by several interactions with compounds

mostly found in oil, causing a strongly oil-wet which is unfavorable
condition for oil production.

• Acid compounds are the most significant material that changes the
original wettability of carbonate rock.

• Together with its structural complexities, carbonate rock is extremely

unfavorable for oil production.

• The amount of residual oil is currently considered as potential source for

oil production by the aid of EOR.
Wettability measurement
Contact angle oil
σow

water
• Contact angle is a direct σos θc σws
wettability measurement of a
rock surface
pure solid surface.

• Quartz and calcite are used

θc
θc

to represent sandstone and water-wet oil-wet

carbonate rock respectively. Wettability of oil-water-solid system

• In general contact angles crystal crystal

water
advancing
refers to water advancing water oil water oil contact angle

water receding
(θadv) which are measured by contact angle

crystal crystal
pulling the periphery of a
drop over a surface. Contact angle measurement by sessile method
Determination of adhesion tension

• The adhesion tension, which is a function of the interfacial tension,

determines which fluid will preferentially wet the solid.

• The expression of adhesion tension is defined as

AT = σos - σws = σow cosϴc

where AT is adhesion tension, σos is the interfacial tension between solid and
oil phase, σws is the interfacial tension between solid and water phase, σow is
the interfacial tension between oil and water phase, and ϴc is contact angle.
Amott method
• Amott method is principally based on the fact that fluid imbibes
spontaneously into rock, displacing the non-wetting phase.

• Amott method is performed by two main process: spontaneous

imbibition and forced displacement.

• The Amott-Harvey wettability index (I) obtained from the test is

used to classify the type of rock wettability.

• The index ranges from -1.0 to 1.0 where;

• -1.0< I < -0.3 indicates an oil-wet condition;
• -0.3< I < 0.3 indicates a neutral-wet condition;
• 0.3< I < 1.0 indicates a water-wet condition.
Measurement of Amott index
1) Saturate cleaned and dry core with formation oil.
2) Centrifuge core with formation brine until it reaches the Residual
Oil Saturation (ROS).
3) Immerse core in formation oil and measure the volume of brine
displaced after 20 hours.
4) Centrifuge core with formation oil until it reaches the Irreducible
water saturation (IWS) and measure the total volume of water
displaced (including water from the previous step)
5) Immerse core in formation brine and measure the volume of oil
displaced after 20 hours.
6) Centrifuge with formation brine until it reaches the ROS and
measure the total volume of oil displaced (including oil from the
previous step)
 Measurement of Amott index (cont.)
The Amott index is a summation of displacement-by-oil ratio and
displacement-by-water ratio which can be calculated from:

δo = Vwsp/ Vwt and δw = Vosp/ Vot

And I = δw - δo

where I = Amott-Harvey wettability index, δo = displacement-by-oil ratio, δw =

displacement-by-water ratio, Vwsp = volume of water displaced from imbibition of oil,
Vwt = total volume of water displaced from forced displacement by oil, Vosp = volume of
oil displaced from imbibition of water, Vot = total volume of oil displaced from forced
displacement by water
Amott method (example)
• A core plug with 2.54 cm. diameter and 5.42 cm. long is used in wettability
determination by Amott method.

• The water saturation is detected during the imbibitions and centrifuges.

• Determine the Amott-Harvey wettability index and the wettability condition of

this rock sample.
USMB method
• The USMB method had been developed by Donaldson to determine the average
wettability of core.

• A major advantage over Amott method is its sensitivity near the neutral wettability.

• The measurement is performed over the capillary curves.

• In general, the rock sample is initially saturated with aqueous phase.

• The displacement process by oil phase results in reduction of water saturation and
the capillary pressure (Pc) is detected.

• Once the water saturation cannot be further reduced, water is re-injected in the
sample and again, the Pc is detected.

• The experiment terminates when no oil can be further displaced.

 a) 10

USMB method
8

capillary pressure, psi

(cont.)
4
II
2

Water-wet
A1
0
A2
I
-2

• The area under the driving curves represents -4

work that is required to displace another -6

b) 10

immiscible fluid.
-8
8

-10
6
0 20 40 60 80 100

average water saturation, %

capillary pressure, psi

4

• The USMB index (W) is expressed as 2 II

A1
0

W = log(A1/A2) Oil-wet -2
A2A2

-4
I
c) 10
-6

where A1=area under oil-drive curve and 8

-8

A2=area under brine-drive curve.

6
-10
0 20 40 60 80 100
capillary pressure, psi
4
II average water saturation, %
2 A1

• When W is higher than zero core is water-wet 0

and when W is less than zero core is oil-wet. -2 A2

-4
I

Neutral-wet
-6

• The value of W near zero indicates the neutral- -8

wet condition. -10

0 20 40 60 80 100

average water saturation, %

Restoration of wettability
State of core
State of cores can be categorized in 3 types, according to the their ambient
conditions:

• Native state core: core is preserved from the disturbances. However, this
state is extremely difficult to maintain and most of the time several reservoir
properties (also wettability) are easily altered.

• Clean core: core is cleaned by solvent extraction. The cleaned core returns to
the virgin state which is water-wet.

• Restored state core: cleaned core is restored to the reservoir condition by

saturating reservoir fluid at the reservoir temperature and reservoir pressure.

• The restoring of core is very important for the condition of petrophysical

experiments.
Wettability restoration procedure
• Core is cleaned by Soxhlet extractor with toluene until the
impurities and residual fluids are totally removed. Frequently, core
is extracted with ethanol to remove toluene.

• Core is left to dry and re-saturated with reservoir brine under

vacuum saturation.

• Saturated core is flooded with reservoir oil. This could be

achieved by core flooding or centrifuge.

• Core is left to age with reservoir brine and oil. After aging, the
original wettability of rock at reservoir condition can be attained.
Artificial wettability
Artificial wettability
• In many wettability studies, it is difficult to preserve the original
wetting condition as in reservoir condition.

• Oil-wet samples are generally obtained by the artificial method

since it is more difficult to achieve compared to water-wet
condition.

• Direct adsorption of carboxylic acid in carbonate rock can be

easily accomplished by saturating core sample with oil containing
carboxylic acid.

• For sandstone, oil-wet condition can be performed direct

adsorption of organic base or the use of organochlosilane
compounds.
 Organochlorosilane
• The sample preparation with
organochlorosilane is simple.
Dichloromethylsilane
• Organochlorosilane is dissolved in
tetradydrofuran and flowed through
core sample.

Hexamethyldisilane
• After than sample is aged with
sufficient period to complete the
reaction with organochlorosilane.

Triehtylchlorosilane
• Finally, sample is flushed by un-
reacted compounds to remove solvent.
Organochlorosilane (cont.)

The wettability alteration by organochlorosilane on sandstone

surface: before and after.
• The reversal of wettability by organochlorosilane in sandstone is cause by the reaction of
organosilane molecule with hydroxide group attaching with silicon atoms at surface.

• Chlorine ion from organochlorosilane bides with hydrogen ion to form hydrochloric acid (HCl).

• Silicon atoms of rock are bided with silicon atoms of organosilane via oxygen atoms.

• Consequently, the hydrophobic parts of organosilane expose outward from the surface,
resulting in an oil-wet condition.
The effect of wettability on
fluid displacement process
Water-wet system
• During a horizontal flooding at the moderate oil/water viscous ratio,
water moves through rock with a uniform flood front.

• Water imbibes oil from small, medium pores into large pores. So only oil
that moves in front of the flood front.

• After the water flood front passes, no further oil or only a little amount
can be produced.

• The non-producible oil is left as small spherical globules in the large pores
or lager patches of oil extending over many pores surrounding by water.

• The ultimate oil recovery is independent from a number of injected

water.
Oil-wet system
• Oil occupies small pores and covers rock skin as layers, whereas water
occupies the center of the large pores.

• During the water flooding, water forms continuous channels of fingers

through the center of large pores where water is located and push oil in front
of it.

• Most oil is left in the small pores.

• As a number of injected water increases, water invades small and medium

pores, pushing oil into lager pores and hence, oil recovery is slightly
increased.

• More water in required to be injected in a strongly oil-wet rock in order to

obtain give amount compared to a strongly water-wet case.
Non-uniformly wetted system
• Mixed-wet rock represent the best case for water flooding:
oil-wet rock in larger pore while small pores are water-wet.

• In the mixed-wet rock the ROS reaches very low value and
the water flood is very efficient.

• In the fractional-wet rock, the ROS increases with the

number of oil-wet grains.

• The water flood behavior is in between the 100 percent of

water-wet and 100 percent of oil-wet sand packs.
Comparison: water flooding in water and
oil-wet rock

Oil Oil Oil Oil Oil Oil

Water Water Water Water Water Water

water-wet oil-wet