T. P.
8069
Observations Relating to the Wettability of Porous Rock
EARL AMOTT
MEMBER AIME
ABSTRACT
A test is described in which the wettability of porous
rock is measured as a function of the displacement prop-
erties of the rock-water-oil system. Four displacement
operations are carried out: (1) spontaneous displace-
ment of water by oil, (2) forced displacement of water
by oil in the same system using a centrifuging pro-
cedure, (3) spontaneous displacement of oil by water,
and (4) forced displacement of oil by water. Ratios of
the spontaneous displacement volumes to the total dis-
placement volumes are used as wettability indices.
Cores having clean mineral surfaces (strongly prefer-
entially water-wet) show displacement-by-water ratios
approaching 1.00 and displacement-by-oil ratios of zerO.
Cores which are strongly preferentially oil-wet give the
reverse results. Neutral wettability cores show zero
values for both ratios. Fresh cwes from different oil
reservoirs have shown wettabilities in this test covering
almost the complete range of the test. However, most
of the fresh California cores tested were slightly prefer-
entially water-wet.
The changes in core wettabilities, as indicated by this
test, resulting from various core handling procedures
were observed. In some cases the wettabilities of fresh
cores were changed by drying or by extracting with
toluene or dioxane; in other cases they were not
changed. Contact of cores with filtrates from water-base
drilling muds caused little change in wettability while
contact with filtrates from oil-base muds decreased
the preference of the cores for water.
Using this test to evaluate wettability, a study was
made of the correlation of wettability with waterflood
nil recovery for outcrop Ohio sandstone and for Alun-
dum. Results indicate that no single correlation between
these factors applies to different porous rock systems.
It is thought that differences in pore geometry result in
differences in this correlation.
INTRODUCTION
Most investigators who have reported on the wetta-
bility of porous rock have described such rock as prefer-
entially water-wet or preferentially oil-wet. In some
cases a third classification, neutral wettability, has been
used. The efficiency of water floods in each of these
wettability groups has been described in numerous
publications. Several methods for characterizing porous
Original manuscript received in Society of Petroleum Engineers
office Sept. 12, 1958. Revised manuscript received March 9" 195~,
Paper presented at Fall Meeting of Los Angeles BasIn SectIOn in
Los Angeles, Calif., Oct. 16-17, 1958.
lReferences given at end of paper. SPE 1167-G
COPYRIGHT, 1960, BY THE
A::\fERICAN IXSTlTUTE OF .l'rhNING, METALLURGICAL,
& PETROLEUM ENGINEERS
(INCORPORATED)
156
UNION OIL CO. OF CALIFORNIA
BREA, CALIF.
rock wettability more precisely have been reported,'-"
but it appears that because of one weakness or another,
none of these has been generally accepted. Early in our
studies in this field, it was found that the displacement
efficiency of oil by water in a particular porous rock
having a strong preference for water was quite different
from that in a similar rock having only a moderate
preference for water. Thus, there appeared to be a
need for a practical, reasonably precise wettability
test, one which could classify porous rocks into 10 to
20 different groups rather than the two or three broad
groups listed above.
The test developed to meet this need is described in
this paper. Also, changes in wettability, as indicated by
this test, resulting from various core handling pro-
cedures are discussed. Finally, data showing the corre-
lation of wettability with waterflood oil recovery for
two different types of cores are presented and discussed.
Some confusion has resulted from the failure of
certain writers to define clearly some of the wettability
terms they have used. Accordingly, the following com-
ments concerning definitions are offered. The wetta-
bility of a solid surface is the relative preference of
that surface to be covered by one of the fluids under
consideration. It is felt that this is the generally accepted
definition. The fluids being considered must be specified
(or understood) before the term wettability has any
significance. In the work reported here these fluids are
water (3 per cent brine) and oil (kerosene). The term
preferential wettability is sometimes used, but we think
that the word preferential is redundant here and should
not be used.
In line with the definitions of Jennings" a prefer-
entially oil-wet solid surface is regarded as a surface
which will show an oil advancing contact angle less
than 90 (measured through the oil) in the water-oil-
solid system. Oil will spontaneously displace water, if
both are at the same pressure, from such a surface.
A preferentially water-wet surface is analogous. This is
consistent with the wettability definition above. As
Jennings has said, frequently the term oil-wet is used
to mean the same thing as preferentially oil-wet. How-
ever, oil-wet also has been used occasionally referring
to an oil-covered surface when the availability of water
was limited. To avoid confusion from this source,
we do not use the terms oil-wet and water-wet.
DESCRIPTION OF WETTABILITY TEST
The following points were considered desirable in
a wettability test for our purpose.
1. The test should be a displacement test resembling
PETHOLEl!:II TRA'iSACTIONS, ,U:IIE
in some degree the displacement which is to be studied.
Thus, surfaces of very small pores and of cul-de-sacs
within the rock would exert little influence in both the
wettability test and in oil production from the rock by
the water flooding under investigation .
2. On the other hand , results of the test should re-
flect rock wettability in a reaso nably direct way. To ac-
complish this, the test should be independent of easily
described properties such as rock permeability and
fluid viscosities.
3. To avoid changes in rock wettability during test-
ing, drastic core handling procedures should be avoided.
It was thought, for example, that extracting or drying
cores should be avoided.
4. Results of the test should be capable of being ex-
pressed in a simple way, preferably on a numerical scale
covering the entire wettability range.
5. The test should be convenient to run.
A modified imbibition test was devised to meet these
requirements. It involves measuring (1) volume of
water spontaneously displaced by kerosene from the test
core containing water and residual kerosene, (2) total
volume of water displaced by kerosene after applying
a high displacement pressure, (3) volume of kerosene
spontaneously displaced by water from the test core
containing kerosene and resid ual water, and (4) total
volume of kerosene displaced by water after applying
FIG. I - DISPLAC EMEN T CE LLS.
a high displacement pressure.
No part of the test is radically different from conven-
tional core handling procedures used in imbibition tests ery. No problems were encountered when cores 1 in. in
and in capillary pressure tests . However, the particular diameter by 3-in. long were used. Unconsolidated sand
combination more nearly meets the requirements listed has been tested successfully by encasing it in a Lucite
than do other tests which have been described . shell perforated at each end.
The core testing procedure is as follows. Typical test results are listed in Table 1 for three
1. Flush core with water and with kerosene to re- cores: (1) fired Ohio sandstone (Berea formation), (2)
move most of the crude oil and formation water. a sand pack in which sa nd grains are covered (and
2. Evacuate under kerosene to remove gas. bonded) with an epoxy resin , and (3) silicone-treated
3. Centrifuge under water to obtain core at residual Ohio sandstone.
oil saturation. Preferentially water-wet cores are characterized by
4. Blot core and immerse in kerosene. Record volume a positive displacement-by-water ratio and a value of
of water spontaneously released after 20 hours. zero for the displacement-by-oil ratio. The magnitude of
5. Centrifuge under kerosene and record total volume the preference for water parallels the value of the dis-
of water displaced. placement-by-water ratio; a strong preference is indi-
6. Blot core and immerse in water. Record volume cated by a value approaching one, a weak preference
of oil spontaneously released after 20 hours. by a value approaching zero. Cores which are neutral
7. Centrifuge under water and record total volume of in wettability show zero for both displacement ratios.
oil displaced. Preferentially oil-wet cores show a positive displace-
Test results are expressed by two numbers, the ratio ment-by-oil ratio and a displacement-by-water ratio of
of spontaneous to total oil volumes displaced by water zero. The magnitude of the preference for oil, in this
(displacement-by-water ratio) and the ratio of spon- case, parallels the value of the displacement-by-oil ratio.
taneous to total water volumes displaced by oil (dis- As before, a strong preference is indicated by a value
placement-by-oil ratio) . approaching one, a weak preference by a value ap-
The core holders used during the water displacement proaching zero.
steps are funnel-shaped Lucite tubes calibrated so that Test repeatability for a given core is good. One Ohio
the volume of water released can be read easily. Calibra- sandstone core was tested eight times. The mean dis-
ted glass tubes of a similar shape are used in an inverted placement-by-water ratio was 0.74; average deviation
position for the oil displacement steps. These are shown from the mean was 0.02; m aximum deviation from the
in Fig. 1. These tubes are of such a size that they will mean, 0.05; standard deviation, 0.03. Also, agreement
fit into the standard metal shields (tubes) used in a between adjacent small plugs cut from the same piece
laboratory centrifuge. of rock is reasonably good. Twelve test plugs cut from
a piece of fresh oil reservoir core (San Joaquin Valley,
In our work a centrifugal force of about 1,800 times
gravity has been used to force displacement of oil and
water. This is the maximum convenient force obtainable TABLE I-TYPICAL TEST RESULTS
in our equipment. A centrifuging time of one hour is Di splacement of Wafer by Oil Di splacement of Oil by Water
Ratio Spon- Ratio
arbitrarily used. Spon-
taneous Total _spo nt . taneous Total ! pont .
Most of the consolidated cores tested in this labora- Core Description (m!) (mil total (mil (ml) total

tory were about % in. in diameter and I-in. long. It Fired Ohio Sandstone 0 .00 1:24 0.00 0.79 0.85 0.93 '
Epo xy-bonded sand
was desirable to test larger cores, however, in an at- pa ck 0.00 1.16 0.00 0.00 0.96 0.00
Silicone-treated
tempt to correlate wettability and waterflood oil recov- Ohio sandstone 0.43 0 .51 0 .84 0.00 0.56 0.00

VOL. 216, 1959 157

Calif.) showed a mean displacement-by-water ratio of TABLE 2-IMBIBITION DATA AND WETTABILITY TEST DATA FIRED
OUTCROP SANDSTONE CORES
0.17. Average deviation from the mean was 0.04; maxi- Wettability test dota
mum deviation from the mean, 0.14; and standard Air Displace Displace-
Volume of water imbibed a (PV)
deviation, 0.06. Core perm. ment-by- ment-by-
No. (md) 5 min 2 hr 24 hr ~ater ratio oil ratio
1 2,490 0.50- Q.5O 0.54 0.98 0.00
SIGNIFICANCE OF WETIABILITY TEST DATA 2 2,520 0.53 0.55 0.60 0.97 0.00
3 507 0.48 0.50 0.51 0.96 0.00
4 496 0.50 0.51 0.51 0.93 0.00
Using the procedure just described, wettability tests 5 130 0.34 0.39 0.39 0.82 0.00
6 130 0.34 0.38 0.38 0.78 0.00
were run on unconsolidated sand packs which were 7 26 0.15 0.30 0.30 1.00 0.00
mixtures of different compositions of two sands. One 8 27 0.16 0.30 0.30 1.00 0.00
aCores were initially saturated with kerosene.
sand was a clean sand as strongly preferentially water-
wet as could be prepared. The other was a second por-
tion of the same sand strongly silicone-treated to make In Table 2 imbibition data and results of our wet-
it as strongly preferentially oil-wet as possible. Wetta- tability test are listed for eight out-crop sandstone cores
bility test results for these sands (presented in Fig. 2) covering a wide permeability range. These cores were
led to the following conclusions. cleaned prior to testing by firing at 500C. It was ex-
1. The sands which represent extremes in wettabil- pected then that all surfaces in these rocks would bc
ity give results in our test which approach the extremes strongly preferentially water-wet. Thus, differences in
on the test scale. imbibition behavior would be due mainly to differences
2. Mixtures containing more than about 25 per cent in rock properties other than wettability. The data show
of each sand give wettability test results which are al- that the cores had varying imbibition rates, depending
most a linear function of composition. on permeability, but all were strongly preferentially
3. Limited amounts (less than about 25 per cent) of water-wet according to our test.
either sand added to the other sand result in little or While rock wettability (as reflected by average con-
no change in wettability test results. This probably fol- tact angle) is important in determining results in the
lows from the inability of isolated sand grains of either proposed test, we believe that pore geometry also plays
type to affect displacement in this test. a part. In sandstone cores and in sandstone-type lime-
It is felt that these observations indicate that results stone cores this has not appeared to be a serious weak-
of this test are a measure of average surface wettability ness of the test. However, it is expected that the test
weighted by the distribution of these different surfaces would not measure wettabiIity in a precise way in a core
within the rock. consisting of a parallel bundle of tubes. In vugular lime-
How well does this rather empirical test meet the five stone with large, irregular vugs, results varied markedly
requirements listed earlier? for different plugs cut from the same core. This was
1. It is a displacement-type test and, therefore, re- thought to be due to variations in pore geometry.
sembles in some degree the displacement of oil by water 3. It is believed that none of the operations in the
in water flooding. proposed wettability test is objectionable from the view-
2. We think that it indicates in a reasonably direct point of changing the rock wettability during testing,
way the wettability of the porous rock surfaces. Cer- Almost all the rock surfaces are in contact either with
tainly wettability is one of the factors which control im- water or with kerosene throughout the test. (There is
bibition rates and equilibrium imbibition volumes in a limited contact with the core holders and with air and
porous rocks. However, other factors such as permeabil- paper during blotting.) Surface-active contaminants are
ity affect these properties. It was thought that permeabil- removed from the kerosene by filtration through silica
ity and possibly certain other core characteristics should gel prior to its use. Thus, it is felt that a minimum
affect in the same way the imbibed volume and the total chance exists for adsorbed organic materials already on
displaced volume measured in the proposed test. Thus, the rock surfaces to be removed or for new films to be
by using the ratio of these volumes as a wettability in- deposited. In a later part of this paper wettability
dex, the effects of some core properties, other than wet- changes resulting from more drastic core handling pro-
tability, should be eliminated. cedures are discussed. Among these are core drying and
extracting.
~IOO~
4. As already stated, results of the proposed test are
two numbers, a displacementooby-water ratio and a dis-
~
f-
<t
I placement-by-oil ratio. For most natural cores one of
these is zero, as data presented later will show. Thus,
~ 75
/
the test results may be listed numerically or shown
,
f-
/ graphically in the same way as permeability or porosity
W /
Z
o
data. In a few artificial cores both displacement ratios
o are positive, i.e., spontaneous displacement occurs in
.J
V> 50 both directions. Here the situation is not so simple; when
plotting data of this type we have used the difference in
displacement ratios to represent the average wettability.
This peculiar behavior has not been observed in fresh
:g 25
I natural cores.
0..
::t I
5. Experience has shown that the proposed test is

O~ ~~ ~~ ~~ ~
o
u
o convenient to use. Equipment required is either already
Z
<t ___ ____ ______ ____ on hand in most laboratories or is easily obtained. Se-
V>
1.00 0.50 0.00 0.50 1.00 lection of a centrifuging procedure for forced displace-
~'SPLt.crMENT - BY- WATER RATIO DISPlACEMENT- BY- Oil RATIO
WETTABILITY ments was based upon its convenience and rapidity. This
FIG. 2-WETTABILITY TEST DATA FOR UNCONSOLI choice has worked out quite well since the complete test
DATED SAND MIXTURE. can be run in about two hours of operator's time and

158 PETROLEITM TRANSACTIONS, AIMF.

 TABLE 3-WETTABllITY TEST RESULTS-FRESH CORES moderately prererentially oil-wet after saturating with
Displace- Displace-
ment-by- ment-by- brine, then flushing with crude oil and drying at 225F.
Core description water ratio oil ratio Wettability changes caused by solvent extraction are
Fired Ohio sandstone, Core 1 0.88 0.00
Fired Ohio sandstone, Core 2 0.93 0.00 listed in Table 5. Apparently toluene extraction either
Silicone-treated Ohio sandstone, Core 1 0.00 0.84 mayor may not remove the adsorbed organic film
Silicone-treated Ohio sandstone, Core 2 0.00 0.65
Well 1, Oil Zone A, San Joaquin Valley, from the core surface. None was removed from Brad-
Calif., Core 1 0.12 0.00
Well 1, Oil Zone A, San Joaquin Valley, ford Third Zone fresh core surfaces; almost all was re-
Calif 0, Core 2 0.12 0.00 moved from the surfaces of Ohio sandstone cores flushed
Well 2, Oil Zone A, San Joaquin Valley,
Calif., Core 1 0.17 0.00 with crude oil and dried. Our data indicate that dioxane
Well 2, Oil Zone At San Joaquin Valley,
Calif., Core 2 0.14 0.00 is more effective in removing adsorbed organic material
Well 3, Oil Zone A, San Joaquin Valley, than is toluene.
Calif., Core 1 0.11 0.00
Well 3, Oil Zone A, San Joaquin Valley, Fired Ohio sandstone cores (strongly preferentially
Calif., Core 2 0.12 0.00
Well 4, gray sand b~low Oil Zone A, San water-wet) were saturated with brine and then flushed
Joaquin Valley, Calif., Core 1 0.90 0.00 with crude oil. When the contact time with crude oil
Well 4, gray sand below Oil Zone At San
Joaquin Valley, Calif., Core 2 1.00 0.00 was short (15 minutes), little or no decrease in pref-
Oil Zone B, Sterling County, Tex., Core 1 0.94 0.00
Oil ZO'1e 8, Sterling County, Tex., Core 2 1.00 0.00 erence for water was found; when the contact time was
Bradford 3rd Zone, Bradford field, Pa., Core 1 0.00 0.79 longer (two hours), a considerable decrease in pref-
Bradford 3rd Zone, Bradford field, Po., Core 2 0.00 0.77
Bradford 3rd Zone, Bradford field, Po., Core 3 0.00 0.82 erence for water occurred. Data showing this are listed
Bradford 3rd Zone, Bradford field, Po., Core 4 0.00 0.80
Oil Zone C, Ochiltree County, Texas, Core 1 0.42 0.00 in Table 6. Similar data are included showing the wet-
Oil Zone C, Ochiltree County, Texas, Core 2 0.36 0.00 tability changes resulting from flushing dry, fired Ohio
Oil Zone 0, Chaves County, N. M., Core 1 0.10 0.00
Oil Zone E, Alberta, Canada, Core 1 0.35 0.00 sandstone cores with crude oil or with asphalt solution.
Oil Zone E, Alberta, Canada, Core 2 0.26 0.00
Oil Zone E, Alberta, Canada, Core 3 0.24 0.00 Also, the wettability changes resulting from refluxing
Oil Zone E, Alberta, Canada, Core 4 0.25 0.00 dry cores in crude oil are shown.
Using the proposed wettability test, an attempt was
made to find out if mounting cores in Lucite changes
two days of elapsed time. No unusual operating skills
their wettabilities. Fired Ohio sandstone was selected
are required.
as a porous rock having a surface very susceptible to
contamination (i.e. wettability change). Two such
WETTABILITY TEST DATA FOR FRESH cores were mounted in Lucite, and then the Lucite was
CONSOLIDATED CORES AND peeled off leaving cores of slightly smaller dimensions
TREATED CORES than the original cores. Test results for the original
cores and processed cores were identical. Two more
In Table 3 results of the proposed wettability test fired Ohio sandstone cores were mounted in Lucite,
are listed for a number of "fresh" cores. Water-base and only the Lucite from the ends was removed. Tests
drilling muds were used in coring the formation from of these partially Lucite-encased cores likewise gave
which these samples came, and the cores were canned results identical with results for the untreated cores. It
in brine or in preservative oil soon after they were re- was concluded from these tests that mounting in Lucite
moved from the core barrel. They were removed from does not change the wettability of clean porous rock.
the preservative liquid in the laboratory, core plugs In similar tests it was found that wettability of this
were cut under brine, and their wettabilities tested as rock was not changed by coating with a phenolic resin
described. For comparison, results are listed for fired
Ohio sandstone and strongly silicone-treated Ohio sand-
stone. TABLE 4-WETTABILITY TEST RESULTS-DRIED CORES
Displace- Displace-
Natural fresh cores cover the same very broad wet- ment-by- ment-by-
tability range as do outcrop sandstone cores treated Core description water ratio oil ratio
Oil Zone B, Sterling County, Tex., fresh Core 1 0.94 0.00
drastically in the laboratory to make them extremes in Oil Zone B, Sterling County, Tex., fresh Core 2 1.00 0.00
wettability. They cover the range from strongly prefer- Oil Zone B, Sterling County, Tex., fresh core exposed
to air at 70-1000f for 1 day, Core 3 0.65 0.00
entially water-wet (displacement-by-water ratio of 1.00) Oil Zone B, Sterling County, Tex., fresh core exposed
to air at 70-100F for 1 day, Core 4 0.65 0.00
to strongly preferentially oil-wet (displacement-by-oil Oil Zone B, Sterling County, Tex., fresh core exposed
ratio of 0.82). Most of the cores from California fields to air at 70_100F for 1 day, Core 5
Oil Zone B, Sterling County, Tex., fresh core exposed
0.58 0.00
were found to be slightly preferentially water-wet, hav- to air at 75F for 60 days, Core 6 0.43 0.00
Oil Zone B, Sterling County, Tex., fresh core exposed
ing displacement-by-water ratios between 0.05 and 0.25. to air at 75F for 60 days, Core 7 0.41 0.00
In no case (excepting the vugular limestone cores pre- Oil Zone B, Sterling County, Tex., fresh core exposed
to air at 225F for 7 days, Core 8 0.18 0.00
viously discussed) was a large difference found for dif- Oil Zone B, Sterling County, Tex., fresh core exposed
to air at 225F for 7 days, Core 9 0.13 0.00
ferent cores from a given zone. The gray sand below Oil Zone B, Sterling County, Tex., fresh core exposed
the oil zone in one California field was tested and, as to air at 225F for 7 days, Core 10 0.22 0.00
Oil Zone B, Sterling County, Tex., fresh core exposed
might be expected, was found to be strongly preferen- to air at 225f for 7 days, Core 11 0.19 0.00
tially water-wet (displacement-by-water ratio, 0.90), Oil Zone A, San Joaquin Valley, Calif., fresh Core 1 0.12 0.00
Oil Zone A, San Joaquin Valley, Calif., fresh Core 2 0.12 0.00
while the overlying oil sand was only slightly preferen- Oil Zone A, San Joaquin Valley, Calif., fresh core
exposed to air at 70-100 F for 7 days, Core 3 0.10 0.00
tially water-wet (displacement-by-water ratio, 0.12). Oil Zone A, San Joaquin Valley, Calif., fresh core
exposed to air at 70-100 f for 7 days, Core 4 0.12 0.00
In Table 4 data are listed showing the effects on Oil Zone A, San Joaquin Valley, Calif., fresh core
wettabiIity, as indicated in the proposed test, of partial exposed to air at 225f for 7 days, Core 5 0.09 0.00
Oil Zone A, San Joaquin Valley, Calif., fresh core
or complete drying of cores. Fresh cores (containing exposed to air at 225F for 7 days, Core 6 0.09 0.00
Fired Ohio sandstone, Core 1 0.88 0.00
crude oil) which were strongly preferentially water-wet Fired Ohio sandstone, Core 2 0.93 0.00
became less so after exposure to air at atmospheric tem- fired Ohio sandstone, core saturated with brine
0.53
then flushed with crude oil, Core 3 0.00
perature. They became much less so after exposure to fired Ohio sandstone, core saturated with brine
then fiushed with crude oil, Core 4 0.57 0.00
air at 225F. Similar cores which were only slightly Fired Ohio sandstone (Core 3 above) dried at 225F
preferentially water-wet underwent almost no change for 10 days, Core 5 0.00 0.29
Fired Ohio sandstone (Core 4 above) dried at 225f
when dried in either way. Ohio sandstone cores became for 10 days, Core 6 0.00 0.41

VOL. 216, 1959 15<;

 TABLE 5-WETTAB[lITY CHANGES RESULT[NG FROM SOLVENT EXTRACT[ON
Core wettability Wettability of extracted core
Displacement- Displacement- Extraction Displacement- Displacement-
Core description by-water ratio ~y-oil ratio solvent by-water ratio by-oil ratio
Bradford 3rd Zone, Bradford fl;ld-:ra., fresh Core 1 0.00 0.79
- Toluene
--- 0.00 0.79
Bradford 3rd Zone, Bradford freid, Po., fresh Core 2 0.00 0.77 Toluene 0.00 0.78
Bradford 3rd Zone, Bradford field, Po., fresh Core 3 0.00 0.82 Dioxane 0.00 0.87
Bradford 3rd Zone, Bradford field, Po., fresh Core 4 0.00 0.80 Dioxane 0.00 0.77
Oil Zone C, Ochiltree County, Tex., fresh Core 1 0.42 0.00 Toluene 0.56 0.00
Oil Zone C, Ochiltree County, Tex., fresh Core 2 0.36 0.00 Toluene 0.67 0.00
Oil Zone D, Alberta, Canada, fresh Core 1 0.35 0.00 Toluene 0.41 0.00
Oil Zone D, Alberta, Canada, fresh Core 2 0.26 0.00 Toluene 0.43 0.00
Oil Zone D, Alberta, Canada, fresh Core 3 0.24 0.00 Dioxane 0.75 0.00
Oil Zone Dr Alberta, Canada, fresh Core 4 0.25 0.00 Dioxane 0.81 0.00
Oil Zone A, San Joaquin Valley, Calif., fresh core exposed to air
at 70-100F lor 7 days, Core 1 0.10 0.00 Toluene 0.03 0.00
Oil Zone A, San Joaquin Valley, Calif., fresh core exposed to air
at 70-100F lor 7 days, Core 2 0.12 0.00 Toluene 0.03 0.00
Oil Zone A, San Joaquin Valley, Calif., fresh core exposed to air
at 70-100F lor 7 days, Core 3 about 0.11 0.00 Dioxane 0.26 0.00
Oil Zone A, San Joaquin Valley, Calif. r fresh core exposed to air
at 70-100F lor 7 days, Core 4 about 0.11 0.00 Dioxane 0.26 0.00
Oil Zone S, Sterling County, Tex., fresh core exposed to air
at 70-100 F lor 7 days, Core 1 0.63 0.00 Toluene 0.94 0.00
Oil Zone B, Sterling County, Tex., fresh core exposed to air
at 70-100F lor 7 days, Core 2 0.65 0.00 Toluene 1.00 0.00
Oil Zone B, Sterling County, Tex., fresh core exposed to air
at 70-100 F lor 7 days, Core 3 0.65 0.00 Dioxane 0.88 0.00
Oil Zone B, Sterling County, Tex., fresh core exposed to air
at 70-100F lor 7 days, Core 4 0.58 0.00 Dioxane 0.95 0.00
Oil Zone B, Sterling County, Tex., fresh core exposed to air
at 225F for 7 days, Core 5 0.19 0.00 Toluene 0.53 0.00
Fired Ohio sandstone flushed with crude oil and dried at 225F, Core 1 0.00 0.29 Toluene 0.85 0.00
Fired Ohio sandstone flushed with crude oil and dried at 225F, Core 2 0.00 0.41 Toluene 0.72 0.00
Fired Ohio sandstone flushed with Clude oil and dried at 225F, Core 3 0.00 0.20 Dioxane 0.87 0.00
Fired Ohio sandstone flushed with crude oil and dried at 225F, Core .4 0.00 0.69 Dioxane 0.88 0.00

TABLE 6-WETTAB[lITY CHANGES RESULTING FROM FLUSH[NG CORES

W[TH CRUDE Oil OR ASPHALT
Wettability
Displace-
ment-by-
Displace-
ment-by-
Core description water ratio oil ratio
Fired Ohio sandstone, Core 1 0.88
Fired Ohio sandstone, Core 2 0.93
fired Ohio sandstone saturated with brine, then flushed
rapidly with crude oil solution Aa, Core 3 0.89
Fired Ohio sandstone saturated with brine, then flushed
rapidly with crude oil solution An., Core .4 0.78
Fired Ohio sandstone saturated with brine, then flushed
slowly with crude oil solution An., Core 5 0.53
Fired Ohio sandstone saturated with brine, then flushed
slowly with crude oil solution An., Core 6 0.57
Fired Ohio sandstone saturated with kerosene, then
flushed with crude oil solution An. I Core 7 0.25
Fired Ohio sandstone saturated with kerosene, then
flushed with crude oil solution All Core 8 0.19
fired Ohio sandstone refluxed in crude oil solution
AU with water trap in system, Core 9 0.18
Fired Ohio sandstone reftuxed in crude oil solution
An. with water trap in system, Core 10 0.18
Fired Ohio sandstone saturated with kerosene, then
flushed with asphalt solution b, Core 1 0.54
Fired Ohio sandstone saturated with kerosene, then
flushed "yith asphalt solution b , Core 2 0.18
n.50 volume-per cent 30 API gravity San Joaquin Valley crude oil with
50 volume-percent kerosene.
b5 weight-per cent steam-blown asphalt with 95 weight-per cent naphtha.
or with Buna rubber and then peeling off the coating.
It has been reported' that some driIling muds are
capable of changing rock wettability while others are
not. Using the proposed wettability test, we observed
the changes that occurred when two different types of
porous rock were flushed with each of six different driIl-
ing mud filtrates. Fired Ohio sandstone with its clean,
strongly preferentially water-wet surface was used as
~ one test rock; a fresh natural oil reservoir core slightly
0.00
preferentially water-wet was used as the other.
0.00
Test results (Table 7) show that the preference of
0.00 the fired Ohio sandstone for water was reduced little or
0.00 none by contact with the three water-base mud filtrates.
0.00 One of the oil-base mud filtrates changed this rock from
strongly preferentially water-wet to moderately preferen-
0.00
tially water-wet. The second made the rock almost neu-
0.00 tral in wettability (slight preference for water). The
0.09 third caused a marked change; the rock was made mod-
0.08 erately preferentially oil-wet.
0.03
The second type of porous rock tested in this work,
slightly preferentially water-wet fresh oil reservoir core,
0.06
also showed essentially no change in wettability from
contact with water-base mud filtrates. Oil-base mud fil-
trates caused a moderate shift toward increased oil
preference.
The foregoing observations are typical of a large
number that have been made in our laboratory in an
attempt to relate wettability with core handling pro-
cedure. No inconsistencies have been found in the test.

TABLE 7-WETTAB[lITY CHANGES RESULT[NG FROM CONTACT W[TH DR[LLING MUD F[LTRATES
Wettability of Original Core ,Wettability of Flushed Core
Displacement- Displacement- Displacement- Displacement-
Porous rock Drilling mud description by-water ratio by-oil ratio by-water-ratio by-oil ratio

.. .. ..
Fired Ohio sandstone High lime water-base mud
High lime water-base mud
Clay water-base mud
about 0.92
about 0.92
about 0.92
0.00
0.00
0.00
0.77
0.84
0.79
0.00
0.00
0.00
Clay water-base mud about 0.92 0.00 0.80 0.00
Surfactant water-base mud about 0.92 0.00 0.92 0.00
Surfactant water-base mud about 0.92 0.00 0.93 0.00
Water-oil emulsion mud about 0.92 0.00 0.08 0.00
Water-oil emulsion mud about 0.92 0.00 0.09 0.00
Oil-base Mud A about 0.92 0.00 0.45 0.00
Oil-base Mud A about 0.92 0.00 0.46 0.00
Oil-base Mud B about 0.92 0.00 0.05 0.51
Oil-base Mud B about 0.92 0.00 0.00 0.41
California fresh corell High lime water-base mud 0.21 0.00 0.13 0.00
High lime water-base mud 0.18 0.00 0.10 0.00
Clay water-base mud 0.19 0.00 0.10 0.00
Clay water-base mud 0.19 0.00 0.10 0.00
Surfactant water-base mud 0.20 0.00 0.08 0.00
Surfactant water-base mud 0.15 0.00 0.08 0.00
Water-oil emulsion mud 0.16 0.00 0.00 0.13
Water-oil emulsion mud 0.19 0.00 0.00 0.03
Oil-base Mud A 0.03 0.00 0.00 0.10
Oil-base Mud A 0.09 0.00 0.08 0.03
Oil-base Mud B 0.21 0.00 0.00 0.25
Oil-base Mud B 0.24 0.00 0.00 0.06
nOil Zone C, San Joaquin Valley, Calif.

160 PETROLEUM TRANSACTIONS, AIME

Our experience with it shows that it indicates the wetta-
bility of the surfaces in a porous rock fairly precisely
and in a way conveniently expressed. While some of the
cores tested have been uniform in wettability over all
pore surfaces. many have been non-uniform in wettabil-
ity. In cores of the latter type, we believe that the test
indicates an average wettability, weighted by the loca-
tion of the different types of surfaces within the core.
CORRELATION OF WETTABILITY WITH
WATERFLOOD OIL RECOVERY
Several investigators""lO have reported that higher
waterflood oil recoveries were obtained in preferentially
water-wet systems than in corresponding preferentially
oi-wet systems. Others" have shown that recoveries were
high when the rock approached neutral wettability but
relatively low at either extreme on the wettability scale.
Still others" have found little change in recovery as
wettability was changed.
A group of waterflood tests were made in this lab-
oratory with the objective in mind of comparing oil re-
covery with wettability under one arbitrarily selected
standard set of conditions. Rock wettability was the
only factor varied in the tests, and an attempt was made
to vary this factor over as wide a range as possible.
Measurements were made of waterflood oil recovery
and of core wettability using the test discussed above.
The test cores were Ohio stands tone plugs 1 in. in
diameter and 3-in. long, all cut from the same block.
In a preliminary test run of five of these, it was found
that waterflood recoveries and wettabilities were the
same within the errors of the tests. Thus, it was con-
cluded that the test cores used were comparable with
each other. They were cleaned by firing, and some were
flushed with a silicone solution to change their wettabil-
ities. By using solutions of different concentrations,
cores of different wettabilities were obtained. A large
volume of silicone solution was used in the flushing
treatment, and it was flowed through the core first in
one direction and then in the other in an attempt to ob-
tain as uniform wettability as possible throughout the
core.
During the water floods, cores were held in a Hassler
sleeve. Fluids used in the tests were 3 per cent brine
and kerosene which had been percolated through silica
gel to remove surface-active impurities. In all cases
cores were at restored state when water floods were
..
..J
z
~ ALUNDUM
tl:
0 70
~ run under one standard set of conditions. It is thought
f-..'" 60
=>
Q.
:r:
g 50
~ OIL SATuRATIONS PRIOR TO WATERFLOODING -59!: 5 % OF PV
:I:
f-
>
Q.
OHIO SANDSTONE
V 70
N here, it was felt that a need existed for a more generally
t useful and more precise wettability test than those com-
>- 60
a::
w
E; 50
u
W OIL SATURATIONS PRIOR TO WATERFLOODING - 70
tl:
o..J 1.00 0.50 0.00
DISPlAC[MENT-BY-WATER RAT10 DISPLACEMENT-BY-OIL RATIO
WETTABILITY
FIG. 3-WETTABILITY vs WATERFLOOO OIL
RECOVERY.
VOL. 216, 1959
started. The water injection rate was 0.5 mljmin, which
our tests showed was sufficiently high that the floods
were stabilized as described by Rapoport, et a{"lO.
Waterflood oil recoveries in these tests are shown in
Fig. 3 as a function of rock wettability. Oil recoveries
at 2.4 pore volumes throughput are shown; however,
similar curves were obtained when breakthrough oil re-
coveries or oil saturations at breakthrough or at 2.4
pore volumes of water injected were plotted against
wettability. Recoveries were low in very strongly prefer-
entially water-wet cores. As the preference for water de-
creased to a displacement-by-water ratio of about 0.60,
recovery increased gradually. As the preference for
water decreased further, from a displacement-by-water
ratio of 0.60 to a displacement-by-oil ratio of about
0.05, recovery remained at the high value; then with
further decreasing preference for water, recoveries again
were lower.
These results are in agreement with the general con-
clusions of Moore and Slobod3 , who reported relatively
low recoveries at either wettability extreme. However,
it is obvious from our data that by choosing the posi-
tions on the wettability scale, preferentially water-wet
cores could be selected which would show either higher,
the same, or lower recoveries than selected preferen-
tially oil-wet cores. Thus, it cannot be said that these
data are in disagreement with any of the findings noted
at the beginning of this section. The important point
demonstrated is that the wettability in porous rock
such as Ohio sandstone must be described reasonably
precisely by some such test as the one discussed here.
Othewise apparent wettability correlations may be mis-
leading.
It is generally believed that microscopic non-uniform-
ity in pore shapes and sizes contributes to the by-pass-
ing of oil in a water flood. It would be expected then
that in porous rock, such as Alundum, having more
uniform pores than Ohio sandstone, wettability changes
might have less effect on waterflood oil recovery. To
check this point water floods and wettability tests of a
group of Alundum cores were made, and the data were
compared with data for Ohio sandstone. The results are
shown in Fig. 3. In the strongly preferentially water-
wet range, Alundum did not show the low recoveries
shown by Ohio sandstone. However, in the neutral wet-
tability and the preferentially oil-wet regions, lower re-
coveries were found with increasing preference for oil,
resembling to some extent the behavior in Ohio sand-
stone.
These observations show then that there is no single
correlation of wettability with waterflood oil recovery
for different porous rocks even though the floods are
that differences in pore geometry from rock to rock
cause differences in the relationship between these
factors.
CONCLUSION
Prior to our use of the wettability test described
monly used. This need has been satisfied in our lab-
oratory by the proposed test. Its usefulness is indicated
+ 4" OF PV by the rating of fresh cores and evaluating of several
core handling procedures discussed in this paper. The
0.50 1.00 study reported here of the correlation of wettability
with waterflood oil recovery in two relatively simple
systems further indicates its usefulness.
The possibility of modifying wettability in part or all
161
of a reservoir to increase oil recovery is one of the in-
teresting aspects of this type of study. The flushing
experiments reported here suggest how easily and to
what extent wettability in a porous rock can be changed.
The waterflood studies indicate that certain wettability
changes lead to increased waterflood oil recovery.
ACKNOWLEDGMENT
The author expresses his appreciation to the Union
Oil Co. of California for permission to release this in-
formation and to P. W. McGinnis for assistance with
the experimental work.
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2. Siohod, R. L. and Blum, If. A.: "Method for DNermining
Wettability of Reservoir Rocks", Trans. AnrE (J 952)
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3. Moore, T. F. and Slobod, R. L.: "Displacement of Oil
162
hy Water--Effect of Wettability, Rate and Viscosity on
Recovery", Prod. Monthly (1956) 20, No. 10, 20.
4. Brown, R. J. S. and Fat!, I.: "Measurement of Fractional
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~~~ H*
l'ETROLEUM TIIANSACTIONS, AIME