~% L

A Laboratory Evaluation of the Nettability of Fifty

Oil-Producing Reservoirs
.

I
L. E. TREIBER
DUANEL. ARCHER AMOCO PRODUCTION CO.
W. W. OWENS TULSA, OKLA.
MEMBERS AIME

by air and ~ertain metallic ions can seriously alter

the wetting properties of many reservoir crude oils.
A knowledge Of the preferential wetting
characteristics of a reservoir can frequently be of
INTRODUCTION
assistance to the field or reservoir engineer,
particularly in such areas as (1) assessing the The reiative preference of reservoir rock pore
applicability of restored state data; (2) interpreting surfaces to be wet by water or oil has long been of
electric Iogs; (-3) selecting well workover fluids; concern, and perhaps some bewilderment, to the oil
(4) applying laboratory capillary pressure data; and industry. Several early investigators J2 of the
(5) applying special fluid injection processes. relative wetting tendencies of solids by water and
Because of this broad usefulness, nettability various hydrocarbons found that some solid surfaces
information was gathered on more than 50 oil- exhibited a definite affinity to be wet preferentially
producing reservoirs from many areas of the world. by hydrocarbons. Other early researchl3-610
One-half of the reservoirs studied, however, were demonstrated that many crude oils contain natural
located in West Texas and Wyoming. surface-active agents that are readily adsorbed at
Tbe reservoirs studied ranged in depth from 1,700 solid-liquid interfaces to render the solid surface
to 13,000 /t, in temperature from 80 to 240F; tbe oil-wet. Numerous subsequent studies of flow in
reservoir oils ranged from 14 to 50 API gravity. porous media7-9,1 l! 12 have demonstrated the
Contact angle measurements in a glass- teflon cell significant effect of rock wetting preference on oil
using uncontaminated samples of the reservoir displacement by water. Some of the more recent
crudes provided a quantitative indication of the studies 10~13 would appear to provide rat her
ability of the various crudes to wet reservoir mck conclusive evidence that reservoir rock wetting
minerals in the presence of water. The minerals preference may cover a broad spectrum. However,
used were selected fmm petrographic studies of there is still a strong tendency by some in the
cores /?OTZ tb~ R?S~TVOEi S ..4 u!
2-.4A.--*
ubet vat. .EA.
U, -e.
W.w,.y ! ~~f ~p.&u~q7 rQ accept the implications of research
the reservoirs studied, flow data on native-state or conducted by Leverett 14 and others that all
fresh cores were available to provide a qualitative reservoirs are preferentially water-wet.
comparison of the reservoir wetting preference. If reservoir rock wetting preference were not an
~be ~eS,,7tC
-.,- c.h+nimo~ AI tho
.-. ,..- .- .,.. .. -- rnmfnrt
------- mw~~
..b cg(l important factor in many aspects of oil production,
tests indicated that for approximately 27 percent of further elucidation on the subject would be of little
the reservoirs studied, water wets the mck mineral practical importance. Its real significance, however>
surfaces more strongly than oil; for about 66 percent can perhaps best be demonstrated by a few examples.
of t be reservoirs, oil wets the mck mineral surfaces 1, The quantitative interpretation of water
more strongly than water; and in the remaining 7 saturation from electric log response by Archies
percent of the reservoirs, the mineraI surfaces were method 15 requires a numerical value of the
not wet strongly by either water or oil. Excellent saturation exponent, n, which is directly related to
agreement was found between these results and the nettability. 16
qualitative indication of rock nettability obtained 2. In well completions or workovers, it is
from native-state or fresh core relative permeability desirable that the kill fluid or wellbore fluid itself
tests. The tests further showed that contamination not have a prolonged adverse effect on the welI
productivity. If a formation is oil-wet, microscopic
trapping of water (as a nonwetting phase), which
Original manuscript received in Society of Petroleum Engineers
office July 26, 1971. Revised manuscript received May 19, 1972. may have invaded the formation during its use as a
Paper (SPE 3.326) was presented at SPE 46th Annual Fall
Meeting, held in New Orleans, Oct. 3-6, 1972. @ Copyright 1972
well controI fluid, could result in serious, prolonged
American Institute of Mining, Metallurgical, and Petroleum reduction in formation oil flow rates 20 after putting
Engineers, Inc.
lR=feren~es given at end of paper.
the well on production.
This paper will be published in Transactions volume 253, 3. The valid application of laboratory displace-
which will cover 1972. ment tests on cores to predict reservoir performance

DECEMBER, 1972 6/?5% 531

depends to a great extent on the degree to which very probably wets the mineral in the reservoir also.
the test core represents the reservoir, or a portion The contact angle test may be thought of as an
thereof. If the nettability of the test core is not the adsorption test to determine if components are
same as that of the reservoir, due to contamination adsorbed from the crude oil onto a rock surface in
by mud filtrate, air, or laboratory testing procedures, the presence of water to cause the surface to
then the performance prediction will be inaccurate .17 become oil-wet.
4. The saturation and vertical distribution of The contact angle test is simple in concept; a
connate water in reservoirs is often evaluated by drop of oil is placed on a mineral surface in the
means of laboratory capillary pressure tests on presence of formation water, and the angie through
cores.i~ ~ the reservoir is strongiy oii-wet, the -1-- waLe&. ~,,aa=
b Ic -- ..L--a .= ;- ,,,e==
- _=,,.aA (r;.6. ~,.
U.&u ,. 1) .1{. r~e
. . - nil
. . . ddr~p
laboratory displacement test does not simulate the beads up, the surface is water-wet and the angle is
process by which the reservoir connate water low. If the oil drop spreads over the surface, the
saturation was established; thus such laboratory surface is oil-wet and the angle is high.
data are not applicable to the predictions of In the l$)th century, Young 21 developed the
reservoir saturations. One additional difficulty in following relationship between contact angle and
applying laboratory capillary pressure data to the wetting:
reservoir is that of converting the laboratory data u - Uws
obtained using an air-brine or mercury-air system to Cose= 0s ,
thereservoir oil-water system. Values for interracial *o w
tension and contact angle in the reservoir control
where d is the contact angle through the water
the results obtained and must be assumed to make
phase and u is the interracial tension; the subscripts
the conversion. The values for these parameters
refer to the oil-solid (o s), water-solid (w.s) and oil-
are usually not known with any degree of certainty.
water (OW) interfaces. In more recent years,
5. Tertiary oil recovery possibilities in a
Johnson22 has given a general thermodynamic
particular reservoir may be related not only to the
derivation of the equation, and the theoretical
oil saturation remaining in the reservoir and its
aspects have been much discussed. (See Melrose23
areal and vertical distribution, but also to the
for a recent review.) The contact angle as a tool
microscopic continuity of that oil. Thus, for such
had not seen great use until more recently, when a
recovery mechanisms, which include nettability
great bulk of reproducible data have been
adjustment flooding, 12)19 the original wetting
published. 24
properties of the reservoir may play an important
Theoretically, as shown by Youngs equation,
role in the choice of improved recovery processes
the contact angle should have only one value for a
to be applied.
given nettability condition, but in practice there
From these few examples, it is apparent that
are two values, depending upon whether the water
knowiedge of reservoir wettabiiiry can be a
significant asset in making decisions concerning
many different aspects of oil production. It is the
purpose of this paper to describe the use of contact
angle measurements using reservoir crude oil,
water, and a solid mineral surface like that
predominating in the reservoir to aid in defining CONTACT ANGLE
OIL
reservoir nettability. The results of such measure-
ments for more than 50 oil-producing reservoirs are \
presented. In addition, the qualitative confirmation \ WATER /
of many of these findings through the interpretation
of relative permeability measurements on native-
state and fresh cores is presented and discussed. WATFR
. . . . . . .. -WIT
..-,

METHODS FOR DEFINING NETTABILITY

CONTACT ANGLE TESTS

~
Background
Thecontact angle test is used as a procedure for MINERAL
determining whether or not one or more components --
of an uncontaminated crude oil sample will cause OIL J
e

w
the oil to wet a reservoir rock mineral in the f---d CONTACT ANGLE
presence of formation water at formation temperature.
If the crude oil does not wet the mineral under
conditions similar to those that exist in the
reservoir, it very probably does not wet the mineral
OIL+EI
in the reservoir. Conversely, if the crude oil does
wet the mineral under reservoir like conditions, it FIG. 1 CONTACT ANGLES MEASURED THROUGH
THE AQUEOUS PHASIL

S32 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

is advancing over a previously oil-covered surface are not suited for contact angle measurements. In
or vice versa. For crude oil-water-mineral systems the contact angle tests the quartz silica surface is
the water-advancing angle correlates weii with -:?:-,. ...*-
useri to sltnuiate die a~~~c--by~ .S&face of ~~~
other nettability indicators while the water-receding clays. These simplifications have appeared to be
angle does not. Apparently, in these systems justified by the good. qualitative agreement between
equilibrium conditions are reached quicker where contact angle derived wettabilities and wettabilities
water advances and desorption probably occurs derived from the interpretation of core flow tests?25
rather than where oil advances over a previously All the crystals used in this study are polished,
water-covered surface and adsorption from the oil flat, single crystals. One average quartz crystal
has to take place. As is now general practice, only was examined with a scanning electron microscope
the advancing angles are reported in this paper. and no surface typography was observed up to a
The practical basis for the use of the laboratory- magnification of 10,000 times. The quartz crystals
measured contact angle as a criterion to infer and the cell are cleaned with chromic acid. Calcite,
reservoir wettabiiity is its success in distitigiiisiiirig Sid--
CL LLt?,
~fi~ ~eien~te -.,ervcral=
---.
are cleaned
--- ----.. -
bv,
between ~e~ervoir~ ~f various wettabilities. Wagnet scrubbing them with precipitated chalk.
and Leach 12 showed how the contact angle concept
Experimental Procedure
could be used, and this paper demonstrates the
practical application of the concept. The chief In this test even trace amounts of any material
advantage of the contact angle method of determining that are not present in the reservoir must not be in
nettability is its relatively low cost as compared the contact angIe system. Therefore, the system is
with the expense of obtaining cores in their native rinsed with a chlorinated solvent, acetone, distilled
nettability condition needed for most other types of water, hydrochloric acid and distiIled water. Then
wearability tesrs. Another advantage is the ease of hot chromic acid is allowed to sit in the system for
testing various chemical agents that may affect 3 to 4 hours. The chromic acid is removed b~
wertabiiity. repeated rinsing wirh conductivity water (< 0.05
megamho/cm). The final rinses are made with
Apparatus conductivity y water deoxygenated by passing
The contact angle tests were conducted in a laboratory grade nitrogen through the system.
glass and teflon cell with uncontaminated crude oil Deoxygenated synthetic formation water is then
and synthetic formation water on flat, polished placed in rhe cell. For these tests synthetic
crystals of a reservoir rock mineral at formation formation water was constituted with conductivity
temperature. The basic cell design and operation water and reagent grade salts on the basis of an
are similar to that described by Leach et al. 19 ordinary water analysis of the formation water. The
However, substantial improvements have been made synthetic water is preferred because its use
so that the test fluids come in contact with only preciudes the iiittiXiitiCtiM Of ftxeign t13iXt3i ions
glass and teflon during a test. A sketch of the (from the well tubular goods) into the contact angle
apparatus is shown in Fig. 2. The holding vessels, system.
contact angle cell and lines are constructed of The system is then raised to reservoir temperature
Pyrex glass. The valves are teflon stopcocks. The and the crude oil introduced into the system under
crystal holders are machined from electrical grade anaerobic conditions. Since the glass-teflon system
teflon. The sliding seal between the teflon crystal described will only withstand about 5 psig internal
holders and the glass celi is achieved with O
ring-type rings machined on the crystal holders
sliding in precision-bore l-in. glass tubing. The
teflon rings are preloaded with a mechanical packer
arrangement inside the crystal holders. The crystals
are held in a simple wedge device. Both crystals
A .
--
OIL RESERVOIR
I

):

CONTACT ANGLE
are movable and the horizontal crystal holder is GLASS ENCASED CELL
held in a mechanism that allows the crystal to be
moved horizontally in increments to provide for the +*
advancing contact angle.
)IL
A large crystal of the mineral type lining the pore

h?
space of the reservoir rock is used in the contact WATER -J
angle test. In generaI, sandstones are predominantly . : RESERVOIR
w
quartz and carbonates are predominantly calcite, 2
.
so these two minerals are chiefly used. Dolomite 3
[MgCa(C03)2], another common reservoir mineral,
~~ ~nccm=en in ~he !argej single crystals needed
for this test, so calcite (CaC03) is used ro
simulate dolomite in the contact angle tests. In
sandstones, clays are common minerals lining the L
pore space of many reservoir rocks; however,
FIG. 2 SCHEMATIC DIAGRAM OF CONTACT ANGLE
clays are by definition finely divided particles and APPARATUS.
DECEMBER, 1972 533
pressure, the maximum reservoir temperature that crude oil as the drilling fluid. The fresh core
can be practically duplicated is 212T. For the samples were obtained using water-base drilling
same reason the bubble-point pressure of the crude fluids that were specifically formulated to be free
oil samples used is reduced to a low value by of surface-active agents that would alter core
passing laboratory-grade nitrogen through the crude nettability. Both the native-state and fresh core
oil sample before using it. No problem with samples were preserved at the well site to prevent
precipitation of components from the oil has been evaporation of the fluids from the cores and to
observed during this procedure. The crude oil and prevent contamination of the cores. None of the
water are equilibrated and a drop of oil is placed core samples were clean ed before the relative
between the two crystals in the water-filled cell. permeability tests, other than f Iushing the cores
After a period of time the top crystal is moved in with a refined oil to remove the crude oil and any
relation to the bottom crystal to give a water gas saturation present. In the case of the fresh
advancing contact angle. This procedure is cores, the flushing with a refined oil also reduced
continued until the value of the contact angle the water saturation to a pseudoconnate water
remains constant. The contact angles are measured saturation. The various relative permeability tests
with a goniometer on Polaroid photomicrographs were conducted using procedures that have been
taken of the system. described earlier. 13$2627
The time required to attain a constant value of
contact angle varies widely from several days to NETTABILITY EVALUATION CRITERION
several months for different contact angle systems.
CONTACT ANGLE TEST
The long times sometimes required for equilibrium
are a disadvantage of the contact angle test, For discussion in this paper the range of contact
although not much attention to the test is required angles has been rather arbitrarilyy divided into three
during this period. These long times have also been regions. From O to 75 is termed water-wet, 75 to
found necessary to obtain wetting equilibrium in 1050 intermediate nettability, and 105 to 180
cleaned cores with crude oil. oil-wet. The intermediate range has been included
to recognize that the flow behavior in this
Data Form nettability range is not easily distinguishable as
The contact angle test is conducted by moving a either water-wet or oil-wet. The water-wet region
crystal so that the oil drop is shifted to allow water ranges from the very strongly water-wet to a
to advance or move over a very small portion of the moderately water-wet condition. Likewise the oil-wet
crystal surface previously covered by the oil drop. region includes wettabilities that are moderately
If material is adsorbed from the oil to cause it to oil-wet to strongly oil-wet. Unfortunately, an oil-wet
partially wet the crystal, the contact angle will reservoir is frequently thought of as one which is
increase as the age of the oil-solid interface strongly oil-wet, such as some Tensleep reservoirs;
increases. Immediately after the drop is moved, a those reservoirs of moderate oil nettability have
tensional force exists on the drop and a nonequilib- been mostly ignored. Although the range of wetta-
rium contact angle is observed. As a result the bilities has been divided for lack of clear-cut
angle decreases for a day or two until a constant divisions into just three regions, it should be
value of contact angle is achieved for that age of the strongly emphasized that these are arbitrary
oil-solid interface. Fig. 3 illustrates the process. divisions and that the nettability of different
The a points represent the contact angle at a point reservoirs can vary within the broad spectrum from
in time when the water is initially advanced. The x strongly water-wet to strongly oil-wet.
points represent the equilibrium contact angle for In many cases the reservoir may be more oil-wet
that age drop when the water has stopped advancing. is indicated by the contact angle test since
Other data points are obtained to define the
approach tO equilibrium and tO insute that equilibrium
has been achieved for that age drop. It is the x
points that are plotted in the later figures presenting
contact angle data.

RELATIVE PERMEABILITY TESTS

Gas-oil relative permeability tests, 26 water-oil ~
relative permeability tests, 27 and gas-water relative az
tests in the presence of residual oil +
:;:::::i3 were performed on native-state and
fresh core samples obtained from producing oil -1
I
wells in a number of the fields for which contact
angle data were obtained. The native-state core
samples are those that were obtained using an
AGE OF THE OIL-MINERAL INTERFACE
oil-filtrate-type drilling fluid, thus maintaining the
native connate water saturation. The majority of
3 THE CONTACT ANGLE ADVANCING AND
these core samples were obtained using reservoir AGING PROCESS.

534 SOCIETY OF PETROLEUM ENGINEERS InrrRNA1.

the adsorption time available is much less in the relative permeability to a wetting phase tends to
contact angle cell than in the reservoir. For this be a function only of its own saturation. Thus,
reason, and because of the differences between the for strongly water-wet core samples, agreement
laboratory system and the reservoir, it isprobable should be evident if the relative permeability to oil
that the contact angle measured in the laboratory (the effective wetting phase with respect to gas) in
test cell is not the same as the contact angIe that a gas-oil relative permeability test is compared with
exists within the pore spaces of the reservoir rock. the relative permeability to water (the wetting phase)
However, the laboratory measured contact angle in a water-oil relative permeability test at comparable
does provide an indication of the presence of wetting - phase saturations. When significant
adsorbable surfactants in the crude oil which differences in these curves are noted (at comparable
influence the wetting condition that exists in the saturations) the test sample obviously cannot be
reservoir. strongly water-we t. Another indication of rock
wetting preference can be obtained by comparing
RELATIVE PERMEABILITY TESTS
the water-oil relative permeability test results with
The criteria for qualitatively defining rock the gas-water relative permeability test results
wetting preference from the results of laboratory obtained in the presence of a residual oil
relative permeability tests have been developed saturation. 13 For strongly water-wet core samples,
over a 20-year period from the observation of data the relative permeability to water curves in both
obtained on more than 1,000 core samples. tests should be the same, even though the direction
Experience has indicated that only when a core has of saturation change is different, because the
a strong wetting preference, either for oil or water, wetting-phase permeability is a function only of its
is it possible to define qualitatively its nettability own saturation. In a similar manner, core samples
on the basis of its flow behavior during an oil-water performing in a strongly oil-wet manner should show
relative permeability test. This is because the agreement at comparable gas saturations between
shapes of the reiati~e permeability LLU --------
VC=
,... A .$a:.
~IIU . . ~.. the ~~i,%t?~bili~~ CO gi3S C&V~S chahd h -a

position relative to the saturation scale are gas-displacing water test at residual oil saturation
functions, not only of the core nettability, but also and in a two-phase gas-displacing oil test.
its initial or connate water saturations and its The above criterion for defining core sampie
pore-size distribution characteristics. Results of a nettability on the basis of its gas-oil, oil-water
recent study17 of the effects of nettability on
relative permeability, which are reproduced in Fig.
COMA(7I AN(IE
4, clearly show the significant difference in
lP
oil-water flow behavior between a strongly oil-wet ---- 470
and strongly water-wet system. But for the spectrum . . . . . . . ..~o
of nettability between these extremes, it would be - 1380
difficult, if not impossible, to judge the degree of 100 1800
oil or water nettability of the system if at least
one of the curves for an extreme wetting condition
were not available for comparison. Some generalities,
however, are obvious. As examples, consolidated
water wet porous media will normally show 15
percent or less relative permeability to water* at
floodout; values as low as 1 to 2 percent krw have 5
been measured on some strongly water-wet cores. glo -

Conversely, oil-wet porous media will normally E

show 50 percent or higher relative permeability to >

=
water* at floodout. h-t addition, the magnitude of
the connate water saturation existing in a native-
i
state core can sometimes provide an indication of g
wetting preference. Formations considered to be
5
strongly oil-wet (Tensleep, Bradford, Wilcox) have
~ 1.0 -
been found to contain much lower connate water %
saturations than formations having other
,a+roh:l:+:a=
Wc.l.a . . . ..va . t
Repraimd From Reference 17
Although the use of oil-water relative permeability
data alone has been found insufficient to clearly t
define sample nettability, the comparison of such
data with other flow data obtained on the same core t
has proved to be a useful qualitative indicator of
)
nettability. As noted in the literature, 13~28 the WATER SATURATION, PERCENT PORE SPACE

* The effective permeability to oil measured at the initial

FIG, 4 IMBIBITION RELATIVE PERMEABILITIES
water saturation is used as the. base permeability for the calcu- FOR SPECTRUM OF WETTING CONDITIONS, TORPEDO
tion of relative permeability. SANDSTONE.

DECEMBER, 1972 535

 L RESULTS AND DISCUSSION

CONTACT ANGLE TEST

(37) Typical Data
Characteristically, pure hydrocarbons such as
Phillips pure grade decane when tested in a
contact angle cell against quartz in the presence of
conductivity water at room tems3erature
...- .-.. - ~.
Rive data
-
such as those shown as Curve A in Fig. 5. The
AGEOF THEOIL-MINERALIN7ERFACE
IHOURSI
contact angle, as near as could be determined,
.-. ,, :..,.J
.S,ua., .-.,. ,...
cu 6=. v CLa. ~ble ~,m,:ire 1 ozns.,.... I-.. ,.+9. -~
FIG. 5 TYPICAL CONTACT ANGLE NETTABILITY ., 7UW-MUULAcIL&LllUL
SITUATIONS. the test. Refined hydrocarbons in the kerosene or
C IO. 12 range generally have contact angles in the
20 to 40 range in an oil-water-quartz system. A
and gas-water relative permeability behavior is 760-hour test of Brainerd Deosol is shown as Curve
strongly dependent upon the homogeneity of the B in Fig. 4. Typical crude oil-synthetic formation
sample. The presence of fractures or stratification water data are shown in Table 1 and by Curves C,
in laboratory test samples can lead to erroneous D and E of Fig. 4. Curve C is an example of a
conclusions as to their nettability since the sample water-wets ystem and represents data on the Tertiary
nonuniformities may overbalance the effects of Kenai sand (2) oil-quartz-synthetic formation water
nettability on the measured flow behavior. It is for contact angle systems. The number, 2 in this
this reason that samples to be used in such tests case, refers to the position of the Tertiary reservoir
should be screened carefully to insure the maximum in Table 1. Several of the crude oil systems have
degree of homogeneity possible.
smaller contact angles than the kerosene systems,

TABLE 1 SUMMARY OF RESERVOIR AND NETTABILITY INFORMATION

Oil-Uimral ~t 3
1
Contact Angl.s, Interf.ce Age, T-p. > Cont*ct Sal.
S@ss FOLmation P.trolo~ Uineralsz ~rcu WI. x -Es??h
1 Almb.a COnglooerate OxscL. Q 0 900 155 36 w w
2 Alaska TertiaryK.mi Sand Ss Q,C,Fe 15, 145,20 900,15C4,900 136 39 w w
3 Argentina 1 nd L Sands Ss 20 lMO 165 -- w 1
4 Argentina flSand Ss : 10 810 165 w w
5 Cmada Beaverhill c.alu LS c 140 450 225 38 Ou w
6 Colorado lhber Ss Q,c 140, 145 960,-&2 160 34 OH Ix
7 Iran Burgan Sand Ss Q 140 1060 152 16 Ou 0ss
9 Louisiana Patin Sand Ss Q 50 1490 170 37 W w
9 Nebraska IhddyD Ss 0 10 330 200 36 w --
10 Nw tf8XiC0 Afw Seef OT c 37 1070 109 43 w
11New tkRXiCO Gallup Ss Q 120 600 158 -- Ow .-
12 N- tkXiCO Grqbur8 OT c 130 600 102 34 Ow --
13 New *XiCO San An6ru D? c 120 lDOD 100 27 Ow --
14 N. Dakota Heath Ss C.Q 130. lW 310,1200 1s9 36 Ofs --
15 N. Dakota Nadison LS c 156 430 150 39 ok
16 N. Dakots Nsdi..m LS 130 190 165 37 Ow
17 N. Daknta Srnl-h Ss : 140 440 24o 46 Ofs --
18 Oklahc,a Oeewe,Eason Ss 0 100 1900 112 32 1
19 Okhhou Cme#e , Tusmy Ss Q 125 112 Ow
20 ok2ahcl- Htmphrq Ss Q iDO :$% 116 1
21 Oklaha=a Wilcox Ss Q 160 730 160 36 Ow
22 Texam(Gulf) Glen SOse or c 160 430 140 -- Ow
23 T_ (Gulf) UpperFric. Ss 0 40 1600 162 30 w w
Z4 fuu (u., t) canyonSeef w? c 140 330 151 42 Ou 1
25 hxastlht) Clurfmk OT c 125 750 109 20 Osl w
26 Texa, (VU t) Clearfork DT c 140 950 110 40 w --
27 TuufJlest) Clurferk c 127 440 107 26 Ob Ow
28 Texas(West) Devc.nian Chert CST Q 12s lWO 120 Ow Ou
29 7exu (W8t) Ellatk.rger or c I&s 450 204 % Ou --
. --- ... -.
30 mxas(sst) 5600 ft. UT c 1*U am lU> -- Ow --
31 Texaa(Si-t) Grayburn DT c 130 5s0 94 36 Ou --
32 T-(!Jest) Grayburg m c 120 5W 90 Ow Ow
33 Texas (West) Grayburs DT c 3CQ lm ; m Ols
34 TexaB (We-c) C.rayburg m C,s 125,45 650, 1270 100 34 Cos Ou
35 Texu OSast) salt m c 130 470 100 38 Ou
36 T*H (West) Lawr Bolt m c 0 5W 120 w IUS
37 Texas(Ucct
) San Andrea m c 88 2400 115 30 1 Ow
38 Texas(SSe-t) San Andre- DT c 130 106 33 Ou Ou
39 Taxu @Ht) SandyDolomite m, Ss c .Q 125,145 2WD, 1550 90 -- Ow --
..- .= --
40 fexu(uWt) Spraberry Ss o 55 1020 lQa 39
41 rexu(west) Spraberry Ss 6 50 1100 115 34 w --
42 Taxas(Wcst) Upper Holt DT c 125 300 120 -- Ow --
43 UAS bream Ss Q,S,C 160,140,135 1900.13W,740 174 30 Osl Ow
44 Utah Weber 0 130 300 139 32 Ow
45 Ss7cdw Dakota Ss Q o 810 124 33 w --
46 Uy-mitv Madison LS c 140 330 100 33 Ow
47 Isyoairls Slinnelusa Ss Q 130 630 134 27 w
48 uymins ninnelusa 135 66 170 10 071
69 Uymiw Muddy Ss o 870 120 w
Nusgec Ss 0 1200 so 14 w w
30 Wy.mins, 0ss
51 19ymins Phc.sphc.ria m 115 S20 88 24 Ou
m 130 400 130 25 0ss --
52 WYmtms Ph.xphoria
Tmuleep Ss 125 890 135 25 Ou
53 S&mini .-
54 Uymins Tms18eP Ss 120 480 100 34 w
Ss 70 2255 96 24 w --
55 ~ ~1-P
1. ss - Sdmt-, WNGL. - conul-r~t=. Ls - 1~-tom. Oc - dOl~it*. CRT chert
2. Q - Quartz, C - Galcite, S - Selenite, Fe - Sidarice.
3. w - w.t.r-wet, 1 . intermadtite nettability, OIS - oil-wet.

536 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

evidently indicating that the y contain less behavior.
adsorbable components. The San An&es (37) oil- Of the 55 reservoir crude oil-water-mineral contact
calcite-formation water system, Curve D, is an angle systems teated, 27 percent were indicated to
example of intermediate nettability. Curve E be water-wet; 7 percent intermediate nettability;
represents the oil-wet behavior of the KMeem (43) and 66 percent oil-wet. Thus, of the systems tested,
oil-calcite-water system. This system was also the majority were in the oil-wet range. This is
oil-wet against silica and gypsum surfaces. When perhaps surprising since it has been generally
an oil-wet system is tested, an attempt is usually assumed that few reservoirs are oil-wet. Part of the
made to find an agent that will reverse the reason for this assumption may be because the
nettability of the contact angle system. Agents oil-wet reservoirs that have been widely discussed,
found in this manner have been shown to increase such as the Bradford reservoir and some Tensleep
waterflood oil recovery in core and field tests. 12 reservoirs, are unusual. They apparently have
This is additional supportive data for the contact bituminous coating on the rock and probably have a
angle cell results. contact angle in the range of 160 to 180. This type
of reservoir is obviously oil-wet and is difficult to
Effect of Contamination make water-wet. However, about 80 percent of the
The contact angle system is extremely sensitive reservoira indicated to be oil-wet in this study lie
to contamination. The Lower Holt (36) crude oil gave in a moderately oil-wet region (i. e., from 120 to
water-wet results under anaerobic conditions, but 1409. These moderately oil-wet systems are difficult
gave oil-wet results after being aerated. Some to recognize and the nettability of core samples
contact angle systems have been simiiariy affected from these types of reservoirs can be easiiy
by air while others have not. inadvertently altered. In general, it is difficult to
Trace amounts of metal ions can also affect the determine the nettability of a reservoir, particularly
contact angle test. The Muddy D (9) system was from field observation, since reservoir heterogeneity
water-wet in the glass-teflon cell with just the plays such a commanding role in how a well or
synthetic formation water present, but when 10 ppm field performs.
copper and nickel ions were added to the water the Of the carbonate reservoir crude oil-water systems
system became oil-wet. Similar results were obtained tested, 8 percent were water-wet; 8 percent
with crude oil from the Spraberry (41) formation. It intermediate; and 84 percent oil-wet. Carbonates
is for this reason that we no longer use monel metal constitute 45 percent of the reservoir systems~ but
cells for our contact angle studies. they constitute 58 percent of those found to be
Since the inception of the test, it has been oil-wet. Most of these carbonate reservoirs that
realized that trace amounts of surface-active agents were indicated to be oil-wet are in the West Texas
could influence the results of the contact angle test area and represent a bias in the data toward this
and the findings that air and trace metai ions can geographical area. The contact angie test resuits
also affect it have emphasized the need for indicate that most of these reservoirs are moderately
carefully handled uncontaminated samples. Fortu- oil-wet, and this is supported by the native-state
nately most oil wells, by virtue of producing large relative permeability data. However, contact angle
quantities of fluids, are self-cleaning. If precautions tests on calcium sulfate crystals, a common mineral
are taken to insure that no treating, stimulation or found in West Texas reservoirs, usually indicate a
corrosion inhibiting materials are present in the strongly water-wet condition. Thus the nettability
crude oil stream when sampling, that air does not of these reservoirs could vary microscopically or
enter the sampling device, and that the sampling microscopically, depending on the presence or
device and associated equipment are clean, then absence of anhydrite or gypsum in the flow channels.
good samples can be obtained. Thirty silicate reservoir crude oil-water contact
angle systems were tested; thirteen (or 43 percent
Reservoir Data
are indicated to be in the water-wet range; 7 percent
Listed in Table 1 are the results of contact angle in the intermediate range; and 50 percent in the
measurements using crude oils from 55 reservoirs oil-wet range.
and the qualitative indications of nettability from Five of the reservoir systems tested had contact
relative permeability measurements. Included in the angles of near 0 at the termination of the tests.
table are the type of mineral surfaces used, the Very low contact angles are difficult to determine,
equilibrium contact angle achieved, the age of the but in these five cases the low value was confirmed
oil-mineral interface at the conclusion of the test, at the termination of the test when the complete oil
and other pertinent reservoir data. drop rolled off the crystal. Such low contact
The reservoirs listed should not be considered as angles are perhaps not to be expected since they
a random sampling of petroleum reservoirs in indicate a virtual absence or neutralization of
general. The sampling is significantly biased: adsorbable components in these crude oils. Five
(1) all samples are from Amoco operations areas; reservoirs represent less than ld percent of this
(2) most all of the samples are from reservoirs admittedly biased data and yet most schemes to
considered for some type of flooding operation; and obtain water saturations from capillary pressure
(3) an unknown number of the reservoirs studied curves assume all reservoirs have a near zero
were considered to have demonstrated unusual degree contact angle. The exact effect of the

DECEMBER, 1972 537

 contact angle on the level of capillary pressure in substantiate the contact angle test results, which
a rock is not known; but for the capillary tube indicated the reservoir to be strongly water-wet
model normally used in these calculations, capillary (159.
pressure varies as the cosine of the angle and Fig. 7, which presents data for a strongly oiI-wet
would thus have a controlling influence. sample from the Kareem sand (43), Egypt, UAR,
Attempts have been made ~o correlate nettability shows a low connate water saturation of 15.5
with various crude oil and reservoir parameters, percent pore space and a high relative permeability
other than those previously discussed, which are to water at floodout of 65 percent. A comparison of
intrinsically affected by nettability but with little the relative permeability to water curve with the
success. It is often assumed that a correlation relative permeability to oil curve (gas-oil test) does
should exist with API gravity so the API values not show agreement. The oil-wet flow behavior of
of the various crudes tested are included in this sample would appear to substantiate the contact
Table 1, but no correlation was found ro exist. angle test results that indicated this reservoir to
Formation temperature is another variable included be oil-wet (1600).
in Table 1 that undoubtedly affects the results Fig. 8, which presents data for an intermediate
obtained for a single contact angle test, but for nettability sample from the 1 sand (3), Argentina,
which no direct correlation with the nettability of shows a connate water saturation of 40.8 percent
different reservoirs could be found. pore space and a relative permeability to water at
Geographical y, the West Texas - New Mexico floodout of 2$).0 percent. The relative permeability
reservoirs form the largest group of reservoir to water curve (water-oil test) does not show
systems (25) tested. Ninety percent of the carbonates agreement with either the relative permeability to
studied from this area were indicated by the contact oil curve (gas-oil test) or the relative permeability
angle test to be oil-wet, most in the moderately to water curve (gas-water test at residual oil
oil-wet category. This is the largest group of saturation). Although the gas-water relative perme-
carbonates and the most consistent nettability ability test results are not included in this paper,
condition encountered in any area. There were also they were used in all cases where available to aid in
four silicates tested from the area; half were determining the nettability of the core samples.
water-wet and half oil-wet. In Wyoming, 11 reservoir An attempt to compare all of the relative
~~~teml~ lvt?i~ t,~St~ d ~c,~ ~LsG.Jc 4(! ~e:ceflt we:e ..- . ..amh.l:fi,
~dzUG=v..A.y t~~t fe~l~!~~ with t~~ Corltact angle

water-wet with the remainder oil-wet. Two Alaska results would be impractical here; therefore, a
Cook Inlet reservoir systems were indicated to be column has been included in Table 1 to provide the
water-wet. Only two Gulf Coast sand systems were
r-=rerl.
.-----, the
---- lJnner
-==-- -Fr.in
- - .in. . ~~x~s ~~~ chc P~cjn sa~~ p~,~ Tn A In Mnc - . . . .. . . . .,
, ... , r.. -.:
9-0 ~~~ >AIUKAI ION,
in Louisiana, and both systems were indicated to FWOS ITY, PER CENT: 16.8 ~
20 )
be water-wet. The Burgan sand reservoir system in
Iran and the Kareem sand reservoir system in the
United Arab Republic were both indicated to be
oil-wet, and two Argentinean reservoirs were
\
\
indicated to be water-wet. All- this has been %0 \
\
discussed to point out that water-wet and oil-wet \
\
reservoirs are scattered worldwide and that the ~;
\l
wetting condition of a resetvoir should not be
}
assumed even tacitly a priori. fl
[1
I
RELATIVE PERMEABILITY TESTS
---GAS-OIL TEST /
Examples of water-oil and gas-oil relative WATER+IL TEST
/
permeability test results obtained on three cores I
from three different reservoirs that performed in a /
-\ :
strongly water-wet manner, a strongly oil-wet manner
and an intermediate manner are presented in Figs. /
6, 7 and 8, respectively. These examples were /
chosen based upon the criterion discussed
/
previously for obtaining indications of rock
nettability from relative permeability data.
Fig. 6, which presents data for a strongly water-
wet sample from the Tertiary Kenai (2) formation,
Alaska, shows a connate water saturation of 39.0 %

percent pore space and a relative permeability to ,,1,

water at floodout of only 1.15 percent. Also, a Ill
comparison of the permeability to water curve o al 40 60 al 10
shows good agreement with the permeability to oil WATER SATURATION, PER CENT PORESPACE
curve (dashed line) obtained during the gas-oil
FIG. 6 RELATIVE PERMEABILITY TEST RESULTS
relative permeability test. All of these data tend to TERTIARY KENAI FORMATION SAMPLE, ALASKA.

538 sOCIETY OF PETROLEUM ENGINEERS JOURNAL

qualitative
interpretation
results.
-,-
indications

m
of nettability
of the relative

ror tne zz reservoirs for wh~~~!

derived from
permeability

:-1. L=lac..=
.al .;.. =
test

pertnea-
~~

I . TO AIR, MDS. : llU O GAs CjATIJR#JloN,%p.

POROSITY,PER CENT: 18.3 ~

--- %
al
s.
o
I I
I

1)(
!
\\ /
bility interpretations are possible, 27 percent were
water-wet; 9 percent were intermediate nettability; %0 \ /1
/f
\
and 64 percent were oil-wet. These are about the \ \
ro

same percentages that were determined by contact \, /1

angle measurements for the total 55 reservoirs -- GAS- OIL TEST ii
studied. Of the relative permeability interpretations WATER - OIL TEST
/\
available, 18 show good agreement with the contact \
*ml@
-..~.e ~e~1J!t~7 and only four appear to show a / i,
!
disagreement. Three of these fou; are a matter of I \
degree, while only one comparison, the Nugget sand !, Krg
/
\
(50), shows a serious disagreement. Thus, the /
nettability as defined by contact angle measurements
/ \
is qualitatively confirmed by the majority of the Km
It I
relative permeability test results, which tends to I
lend confidence to the use of either procedure for / I
I
defining reservoir nettability. I
/ I
From the foregoing discussions and data 1
presented it is apparent that the nettability of / I
~ II
reservoirs can cover a broad spectrum and can vary, /
almost unpredictably, from one reservoir to the next. /
Furthermore, a knowledge of the wetting character-
t tt
istics of a particular reservoir may be useful in
many production or reservoir engineering
o 20 40 60 80 100
applications. However, if cores are avaiIabIe for
WATER SATURATION, PER CENT PORE SPACE
testing that are representative of the reservoir
(including its nettability), then flow tests on these FIG. 7 RELATIVE PERMEABILITY TEST RESULTS
MIOCENE KAREEM FORMATION SAMPLE, UNITED
cores may provide all the data needed for a given ARAB REPUBLIC.
application, making unnecessary the actual
definition of the reservoir nettability. PERM.To AIR, MIS.: 1840 GAS SATURATION,%P. s.
POROSITY, PER CENT: 23.6 ~
al o
CONCLUSIONS I

//1
1. The results of the contact angle tests and the
flow tests conducted in the laboratory indicate that
the nettability of different reservoirs can cover a
broad spectrum from strongly water-wet to strongly \\
oil-wet. The majority of the reservoir crude oil-
water-minerai systems for which data are presented
were indicated to be moderately oil-wet. \
2. Based on the test methods presented, there
- --GAS-OIL TEST
does not appear to be any correlation between
WATER+IL TEST
nettability and the reservoir temperature or the API I
\
gravity of the reservoir oil. \
If
3. Contact angle and flow test results show \
excellent agreement as to the indication of I
I
nettability in the majority (82 percent) of the () I
reservoirs for which both types of data were I
I
available. This agreement lends confidence to the I
use of either or both of these procedures for I
obtaining a qualitative indication of reservoir I
I
nettability.

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Prod, Prac., API (1941).
WATER SATURATION, PER CENT PORE SPACE
2. Hardy, W. B.: Collected Scientific Papers, Cambridge
FIG. 8 RELATIVE PERMEABILITY TEST RESULTS
U. Press, Cambridge ( 1936).
I SAND FORMATION SAMPLE, ARGENTINA.

DECEMBER, 1972 539

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n{.~t.-~~-+
-. =... -...-... l?ffh-i-mcv
------- ..-, hv
-. Wet@bility Ad@tment~ =.i_.:_-. L:-- >) ~Ftifi~., ~y,~
Reiative i%rineiibiiity KCSUIUUII*II+JS,
Trans., AIME (1959) Vol. 216, 65-72.
(1956) Vol. 207, 275-280.
13. Schneider, F. N. and Owens, W. W.: Sandstone and
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~~rbep~te TWQ- and Tb~e-Phaae Relative Penneabil- .,- A , !,=.. -- : --
Morse, R. a.. =xpcramcntsi L-lV~St@dOi. Gf Fi3CtOtS
it y Characteristics, SOC. Pet. Eng. J. (March, 1970)
Affecting Laboratory Relative Permeability Measure-
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Aid in Determining Some Reservoir Characteristics, ***

540 SOCIETY OF PETROLEUM ENGINEERS JOURNAL