Nettability Literature Survey

Part 1: Rock/OiVBrine Interactions

and the Effects of Core Handling
on Wettabiiity
William G. Anderson, SPE, Conoco Inc.
s

Summary. Nettability is a major factor controlling the location, flow, +d .@stributiOn Of fl~d? @ a
reservoir. The wettabdity of a core will affect almost all types of core analyses, including capillary pressure,
refative permeability, waterflood behavior, electrical properties, and simulated tertiary recovery. The most
accurate resuks are obtained when natiye- or restored-state cOr~ Me ~ with native cmde Oil~d brine at
reservoir temperattrre and pressure. Such conditions provide cores that have the same wettab~ky as the
reservoir. ~. .
The wettabih@ of, ori&lly water-yet reservoir rock can be altered by the adsorption of polar com~ounds
and/or the deposition of organic materiaf that was originally in tie crude oil. The degree of alteration is deter-
mined by the interaction of the oil constituents, the mineral su~ace,. and tie brine chefi$~. The PrO:~ures
for obtaining native-irate, clesned, and rsstored-state cores are diSCUSSe4ss we~ aS the eff@s Of cOnng,
preservation, and experimental conditions on nettability. Also reviewed are methods for artificially controlling
the wetmbflity during laboratory experiments.

htrodirotion
This paper is the first of a series of literature surveys
covering the effectsof nettability on core analysis. 1-3
Changes in nettability have been shown to affect capil-
Iq pressure, relative permeability, waterflood behavior,
dispersion of tracers, simulated terdaiy recovery, imedn-
cible water saturation (IWS), residual 01 saturation
(ROS), and electilcal properties. 4-26 For core analysis
to predict the behavior of a reservoir accurately, the net-
tability of a core must be the same as tbe nettability of
the undisturbed reservoir rock. A seriousproblem occurs
because many aspects of core handling can drastically af-
fect nettability.
Water-Wet, Oil-Wet, and Neutrafly Wet. Wettabfity
is defined as the tendency of one fluid to spread on or
adhere to a solid surface in the presence of other irmnis-
cible fluids. 7 In a rock/oif/brine system, it is a meas-
ure of the preference that tie rock has for either the oil
or water. When the rock is water-wet, there is a tenden-
cy for water to occupy the smsll pores and to contact the
majority of the rock surface. Siarly, in an oil-wet sys-
tem, the rock is preferentially in contact with the oil; the
location of the two fluids is reversed from the water-wet
case, and oil will occupy the small pores and con~ct tie
majority of the rock surface. It is importunt to note, how-
ever, that the teim wettabWy is used for the wetting
preference of the rockand does not necessarily refer to
the fluid that is in contact with tie rock at any given time.
For example, consider a clean sandstone core that is
saturated with a refined ofl. Even though the rock sur-
face is coated with oil, the sandstone core is still preferen-
tially water-wet. Thk wetting preference can be
coP&h!1986society.+Pe!role.mEngineers
lmral of Petmlc.mTechnology,October19S6
demonstmted by allowing water to imbibe into the core.
The water will displace the oil from the rock ,surface, ~-
dicating that the,rock suiface prefers? to be in contact
with water rather than oil. Simjkwly, a cow samra!ed with
water is oil-wet if oil will imbibe into the core and dis-
place water from the rock surfuce. Depending on the spe-
citic interactions of rock, oil, and Mne, the wwab@
of a system can range from itrongly water-wet to str022g-
Iy oil-wet. When the rock his no strong preference for
either oif or water, the system is said to be of neufml (or
intermediate) wettabfi~. Besides strong and neutkd net-
tability, a third ~pe is fracdonsl nettability, where differ-
ent areas of the core have different wibing preferences. 27
The wettabfity of the rocklfluid system is impoitant
because it is a major factor controlling the location, flow,
snd distribution of fluids in a reservoir. .Jn general, one
of the flizids in a porous medium of uniform wettabilky
that contis at least two immiscible fluids will be the wet-
ting fluid. When the system is iu equilibrium, the wet-
ting fluid will completely OCCUPY the smsllest pores and
be in contact with a majoriv of the rock s~face (ass~-
ing, of course, that the saturation of the weting fluid is
sufficiently high). The nonwetting fluid will occupy tie
centers of the larger pores and form globules that extend
over several pores.
In the remainder of this survey; the terms wetdizg snd
nonwetting fluid wilf be used in addkion to water-ivet and
oil-wet. This will help us to draw conclusions about a SYS-
tern with the oppositi wetibility. The behavior of oif in
a water-wet system is very similar to tle behavior of water
in an oil-wet one: For exmuple, it is generally assumed
that for a system with a strong wetting prefererice, the
tietting-phase relative permeab~ky is only a function of
1125
 ABLE 1DISTRIBUTION OF RESERVOIR WETTABILITIES BASED ON CONTACT ANGLE34
Contact
Angle Silicate
(degrees) Resewoirs
Water-wet o to 75
Intermediate wet 75 to 105
Oil-wet 105to 180
Total
its own saturation-i. e., it shows no, hysteresis. 7,12,28
Owens and Arch&28 measured the gas/oil drainage per-
mea.bflily, where the oif was the strongly wetting fluid,
and compared it with the water/ofi imbibition relative por-
meahii@, where the water was tie strongly wetting fluid.
The water-imbibkioi reIative permeability (strongly
water-wet system) was a continuation of the oil-drainage
relative permeability (strongly oif-wet system), demon-
strating the amdogy between systems of opposite wetta-
bilities.
Historically, afl petroleum reservoirs were believed to
be strongly water-wet. This was based on tyo mjor fac~.
Fust, almost allclean sedentary rocks are strongly
water-wet. Second, sandstone reservoirs were deposited
in aqueous erivironments into which oil later migrated.
It was assumed that the comate water woufd prevent the
oil from touching the rock surfaces. In 1934, Nuttingzg
realized that some producing reservoirs were, in fact, ac-
@ally strongly oil-wet. He found that the quaitz surfaces
of the Tensleep sandstone in Wyoming had adsorbed
heavy hydrocmbons in layers about 0.7pm tldck (about
1,000 molecules) so fdy that they could not be removed
by gasoline or vzrious solvents.When $e hydrocarbon
film was removed by ,fuing the core, the film could be
restored by soaking the cores in crude oil overnight.
Examples of other reservoirs that are genertiy recog- ,
nized as sirongly oil-wet are the Bradford sands.of the
Bmdford pool,, Pennsylvania, 30-32 and the Ordovicisrr
ssmds of the Okkiborns City field. 33 More recentfy,
Treiber et aL % used the water advancing contact angle
to eiamine the wettabdity of 55 oil reservoirs. fn this
procedure, deoxygenated synthetic fofmation brine and
dead anaerobic crudes were tested on quartz and calcite
c~stafs at rescrvom temperamre. COnta~. angles (mea.+.
ured through the water) fromOto750 [0 to 1.3 rad] were
dipmed water:we~ from .75 to 105 [1.3 t6 1.83 rad],
intermediate wet; and from 105 to 180 [1.83 to 3:14 red],
oil-wet. As summarized in Table 1, 37 of the reservoirs
tested were classified as oil-wet, 3 were of intemnetilate
wegabtity, and 15 were water-w.et. Most of the oil-wet
reservoirs were mildly oil-wet, with a contact angfe be-
tieen 120 and 140 [2:1 and 2.4 rad]. Of the carbonate
resemoirs included, 8 % were water-wet, 8 % were inter-
mediate, and S4% were oil-wet. Most of the carbonate
. . reservoim were from the west Texas area, however, so
there is a geographical bias in the data.
Treiber et al. cautioned that these tindlngs could not
be considered representative of a trufy random samplhzg
of petroleum reservoirs. The sainples were bkmed because
(1) all were operations for the sarnb company, (2) most
were being considered for some type of flooding, and (3)
some of the reservoirs had demonstrated unusual be-
havior. A fourth consideration is how much the use of
degassed fluids rather than the real formation fluids af-
1126
Carbonate Total
Reservoirs Reservoirs
13 2. 15
1: A 3;
30 25 55
fected the wettsbflity behavior in the contsct-migle tests.
As ,iiscussed later, this probably causes amoverestima-
ticm of the oil-wetness. Therefore, the large percentage
of reservoirs found tobe ol-wet is less significant than
the general indications that not all reservoirs are water-
wet and that the r&ervoir wettabilky varies widely.
Contact-sngJe measurements made by Clilingm snd
Yen35 suggest that most carbonate reservoirs ramge fiorn
neutrally to oif-wet. They measured the we~bdity of 161
limestone, dolomitic liiestone, calcitic dolomite, arid
dolomite cores. The cores tested included (1) 90 cores
from Asrnari limestones and dolomites from tie Mid$e
EasG (2) 15 dolotite cores from west Texas; (3)3 cores
of Madison liiestone from Wyoming; (4) 4 cirbonate
cores from Mexican oil fields; (5)4carbonate cores from
the Rengiuoil field in the Peoples Republic of China;
(6) 16 csrbonate cores from Albe~ (7) 19 chalk cores
from tie North.,SeT (8) 5 samples from India+ amd (9)
5 samples from Soviet oil fields in the Urals-Volga region.
Table2 shows the distribution of wettsbfities with 80%
of the reservoirs either oil-wet or strongly oil-wet. Some.
of the strongly oil-wet reservoirs were oil-wet bew+se
of a bitumen coating. Note that the range of contact an-
gles considered to be neutrslly wet is smaller thari the
range given in Table 1. This demonstrates the variation
from paper to paper of the cutoff angles between ?Je
different wetting statea.
As discussed iu more detiril later, reservoir rock can
change from its &iginal, strongly water-wet condition by
adsorption of polar compounds and/or the de ositjon of
orgsnic matter originally in the crude oil. 7,3P 6-42 Some
crude oils make a rock oil-wet by depositing a thick or-
ganic film on the mineral surfaces. Ofher crude oils con-
ti pOlar compounds that cm be adsorbed to make the
rock more oif+vet. Some of these compounds are srrffi-
ciently water soluble to pass throu~ the aqueous phase
to the rock.
Fractiormf Wettabilfty. The retilzation that rock wetta-
bflity can be akercd by adsorbable crude oil components
lexito tie idea that heterogeneous forma of wettabiity exist
in reservoir rock. Generally, the intend surface of re.ser-
voir rock is composed of many minerals with different
surface chemistry and adsorption properties, which may
lead to variations in nettability. Fractional nettability
slso called heterogeneous, spotted, or fhlmation
wettabifky-was proposed by Brown and Fatt27. aud
others. 43* fn fkactioml wegsbdity, crude oif compo-
nents are strongly adsorbed in certain areas of the rock,
so a portion of the rock is strongly oil-wet, whie the rest
@strongly water-wet. Note tit this is cqncepty+fly differ-
ent from intermediate wettsbtity, which assumes that all
portioim of the rock surfsce have a slight but equal prefer-
ence to being wetted by water or oil.
lomnalof PetmlaunTechmlo8y,@to&r 1986
hfi@ Wettibifity. Salatfrie147 introduced the term
ririxed wettabilby for a special type of fractional netta-
bility iri which the oil-wet surfaces form continuous paths
I TABLE 2DiStribUtiOn OF dARBONATE
RESERVOIR WETTABILITIES35 I
through tie larger porca. 48-50The smafler pores remain contact
water-wet and contsin no oil. The fact that sll of the oil Angle Percent of
(degreas) Reservoirs
.
in a miixed-wettabflity core is located in the lager oif-
Water-wet O to 80 a
tvet pores causes a.smdlbut finite oil permeabtlty to ?x- Intermediate wet .80 to 100
ist down to very low oil sahrrdtiom. T@ in mm pertits oil-wet 100to 160 :
the drainage of oil during a waterflood to continue until Strongly oil-wet 160 to 180 15
verj low oil saturations are reached. Note that the main
distirrction betywen mixed md fractional wettsbtity is that
@.elatter, implies neither specitic locations for the oil-wet be used. only for such measurements as, porosity and air
surfaces nor continuous oil-wet paths. permeability where the wettab~lty will not affect the
SalatMet visualizes the generation of mixed nettability results.
ih,,tie following manner, When od yufially invaded an The third type of core is the restored-state core, in which
ciiiginilly water-wet reservoir, it displaced waler from the the mtive nettability is restored by a three-step process.
larger pores, while the smaller pores remained water-fi!kd The core. is cleaned and then satrmtcd with brine, fol-
becairse 6f capillary forces. A mixed-tiettabihty condl-: lowed by crude oil. F,@ally, @e core is aged at reservoir
tion occuried if the oif deposited a layer of oil-wet or- temperature for about 1,000 hours. The methods used to
ganic, material ody on those rock surfaces tliat were in obtain the.three different types of cnres will be discussed
direct contsct with the oil but not on Me brine-covered in more detail later.
surfaces. Oil-wet deposits would not be formed in the
small water-ffled. pores, snowing them to remain water-
Factors Affecting the Original
wet. The question that Salatliel did not address was how
the oil first came into direct contact with the rock. As the Reservoir Wenabiiity
oil moyes into the larger pores, a tfdn layer of interstitial The &igiaal strong wa~r-wetness of most, rcservoi ~n-
water remains on @pore walls, preventing the oil from erals csn be altered by the adsorption of polar compounds.
contacting the rock. Under certain conditions, however, and/or the deposition of qr tic matter that was origi-
@e waterfdrn separating the crude and the mineml sur- $
nally in the crude oil. 7,20,3,32,36+155-63 fhe surface-
face cm mpture. Hall et al. 51 sad Melrose52 recently active agents io the oil aze generally believed to be p+w
developed a theoretical model for the stability of these com ounds that contsin oxygen, nitrogen, andlor SU1-..
thiri water films that shows fiat the water ftis become ,@r. ! 6,37,40,41,SS,56,W68 These compounds con@in both
thiier and thinner as more oil enters the rock. The water a polar and i hydrocmbon end. The polar end adsorbs
fim is $tabflized by electrostatic forces arising from the on the rock surface, exposing the hydrocsrbqz end and
eIectficaf double layers at the oillwater and wateif rock making the s+face more oil-wet. Experiments haveshown
interfaces. 5154As tie water fifmthickness is further re- fhat some.of these aaturaf surfacfants are sut%cientfysolu-
duced, a critical tlickness is reached where the water films ble iizwater to adsorb onto tic rock surface aftcrpassing
in the larger pores become unstable. The films rupture through a thin layer of water. 42,60S69-71
and are dkplaced, aflowing oil to contact ~e rock. In addition to the oif composition, the degree to.which
the wettabllity is aftcred by fhese surfactants is also deter-
minqi by the pressure, tcmpermmc, mineml surface, and
Native-State, Cleaned, and ReStored-State Coraa.
brine chemistry, including ionic composition and PH. The
Cores in three different stitei .of ,presepatioh are used
in core anafysis: native .Xaie,cleaned, and restored state. effects of pressure and temperature will be discussed Mcr
The best results for mrrftiphase-type flow mialyses are ob- @the section on experimental conditions. The importance
of the mineral surface is shown by the contact-angle @eas-
klincd with mtive-ststi cmes, where alterations to the wet-
tabfity of the un@rrbed reservoir rock are minimized. . orementa +cbssed esrlier, ,3s in which a large majority
Ii thk set of paper~ the term native-state is used for of tie carbonate reservoirs tested were. oil-wet, while
Many.of the sandstone reservoirs were water-wet: Seveml
niry core that was obtained and stored by methods that
preserve the Nettability of the reservoir. No distinction researchers have found that some polar compounds af-
fect the wettabilky of sandstone and carbmaitc surfaces
is made between cores taken with oil- or water-baked in ~lfferent ~ays, 37,+42,6672-76 The. chemistiy of the
fluids, as long as the native wektabflity is maintained. Be
aware, however, that some papers dktin=gish on tie ba- brine can also alter the. wettabtity. Mrdtivafent cations
sis of drilliig fluid (e.g., see Treiber et al. 34), In these sometimes enhance the adsorption of surfactants on the
finer~ ~rface. %77-s3 fhe brine pH is also impOrt8nt
papers, native-state refers only to cores taken with a
suit8bIe ofl-fjjhte.t~e rhill:mg,mud, which nrtintains the in determination of the nettability and other interfacisf
original connate water saturation. :Fresh:state refers properties of the cmdelbrinelrock system. 6Z26,~In afka-
Iine floodmE, for example, allmhne chemicals can react
to a core with unaltered wettabtity that was taken with
with some c-fides to pr~duce surfactqts that sfter wett?-
a water-base d@ling mud that cbntsins no compounds that b~lty, 6,26
can alter core tiettabdity. Here, the term native-state is !.
used for both cases.
The second type of core is the cleaned core, where an Surface-Active Compormda in Crude Oil. ~ie the
attempt is made to remove all the fluids and adsorbed or-. surface-acfive components of crude tie found in a wide
ganic msterid by flowing solvents through the cores. ~ge ofWrolem fractions, 41 they are more prevalent
Cleared cores are ususlly strongly water-wet and should m gze heavier fractions of cmde, such as re$ina and
\
Journalof PetroleumTechnology,October19S6 1:127

aaphaftenes. These surfactants are believed to be polar
compounds that contain oxygen, nit@gen, and/or suffer.
The oxygen compounds, which are usually acidic, include
the phenols and a bwge number of different carboxylic
acids. 67$5,86Seifert mid Howellsw showed that the car-
boxylic acids are titerfaciilfy active at alkaline PH. The
sulfor compounds include the sulfides and tilophenes,
with smaller amounts of other compormda, such as mer-
~ap~s ~d polysulfides. 87,88The nitrogen compo~da
are generaUy either basic or neutral and include csrba-
xoles, tides, pyridenes, quinoliies, and porphy-
~~. 40.s7-90me pVhYtis camf&m imerfadly active
metal/porphyrin complexes with a number of dii%erentm>
tds, including nickel, vanadium, iron, coppr, tic, titani-
um, calcium, aud mirgnesinm. 9*-95
Because the .9zrfactarrts in cnrde oil are composed of
a lsrge number of very complex chemicals that represent
onfy a small fraction of the,crude, identi@g which com-
pounds are im ortam in aftering the wettabtity has not
beeipossible 6 h addkion, attempts to correlate bulk
crude propert;ei with the abflity of the crude to ~ter wet-
tabiliw have been unauccessf+ McGhee et al. 62 satn-
rated Berek cores with brink, od flooded them to IWS with
different cnides, then incubated them at 140F [60C]
for 1,0+30hours to allow the wet@bfity to reach equilib-
rium. .The U.S. BWearr of Mines (USBIvf)wettsbllily in-
dex wasthen meaaured and compared with bulk propwties
of the crude. They found no correlation between the
USBM index and interfaci.d tension (IFT), organic acid
content, percerit nitrogen, or percent suIfnr of the cnrde.
oCuiec96 measured the Arnott nettability index of
restored-stnte cor6s and found no correlation between ivet-
tabilky and amonnta of acids, basea, aromatics, resins,
nitrogen, or srdfur. In all cases, when the restored-state
cores were water-wet, the crndes bad low sapha.ftenesnd
anffur contents., However, other low-asphaftenexnd low-
mdtirr c@des rendered cores neutrally or oil-wet.
Experiments that determined the general mtnre of the
surfactxnts xnd the crude oil fractions in which they are
concentrated without attempting ~ determine exactly
which compounds cause wet@bifity alteration have been
more success~. Jolwnsen and Danningw,9s found that
asphzdtenea were responsible for changing some cmde-
oiWwater/glass systems from water-wet to oil-wet. The
system ,was oil-wet when the cmde was used but wat&r-
wet when the deasphalted crude was used; The addkion
of a very small amount (0.25%) of the whole crude to
Ozedeasphalted crnderestored the oif-wettingness of the
system. Donafdsbn aud Crocker55 and Donafdson56
measured wepabilky alte@ion caused by the polar coin-
poaada extracted from aeveml different mincmf oifa. First,
the nettability of a series of uizcontanzinated Berea plugs
was mcasnredwith brine agd a refied mineral oiL The
average USBM wettabilky iizdex was 0.81, or strongly
water-wit. After cleanirig, the USBM nettability index
of the plugs was measured with brine and a 5 % mixture
of the extracted polar organic componnda in the retined
mineral oil., The phtgs were significantly leas water-wet,
with USBM wettabtity indices ranging from 0.45 (water-
wet) to -0.W (xretitmlfy.wet), demonstrating that polar
compmmda in cnide can alter the wettabtity. Note that
there was appsfentfy no aging time with the polar cOm-
ponnds in the plugs, so equilibrium wettxbifities may be
more strongly oil-wet.
/.,
112s
,,
Several researchers 57,5s analyzed wetkbiliw-afterirw
compounds extracted from cor~. Jennings58 r~moved ~
portion of the nettability-altering cornpotirids by extract-
tig a non-water-wet core with tolnene,, followed by a cfdo-
rofordmethanol mixiure. An imblbitioiz test showed tbst
some of the wettabil@-idtering compounds had been re-
moved during the s~ond extraction because the core was
more water-wet. The material remo+ed dtiring the sec-
ond extraction contained porphytis ~d bigh-moledor-
weight pamffinic and aromatic cbmpoiihds.
Denekaa et al, 41 used a d~tiflntion pro;exs to separate
cmde oifs into fractions of different molecular weight.
A clean, dry core wax saturated with the crude oil frac-
tion to be tested, then aged for 24 hotii:. An imbibition
test based on the relative rate of imbibkion waa nsed to
determine the wettxbility Alteration..1.1 The originxl
crqde oil and the heaviest residue left a,fterdistillation had
the greatest effect on the nettability; they were the only
fluids that nzadetbe rock oil-wet.fhia fiplies that a con-
siderable portion of the surfact+ds, in the crude oiI had
a large molecular weight. Many of the lower-molecular-,
weight fractions, however, also debreaaed the water-
nettability, demonstrating that the surfactants in crude
have a broad range of molecufa.r weights. Cuiecg6 ob-
tained similar results. Note that Denekas et al. and Cuiec
botlr used@ cores and that idso~tiob of the w&ttnbility-
.ikering cOnzpoundswoufd probably have been iltered if
the cores contained brine during tie aging process..
A number of roaearchera have examined the i@rfacinUy
active materiak that are cOncentrat&dat the Oil/water in-
terface. Generalfy, these materi~s can iilso be adsorb@
on tie rock surface to sfter wettsblli~. 3.7,8~g9-*mBar-
tell and Nlederhauser 103managed @ sepirate these, ma-
terials from ~e crude oil dqd f6und that they, formed a
hxfd, black. noncrys@fline substxnce tit was sapI@tic
in nature.
. .
Adsorption Through Water F~s. Experiments hove
shown tfiat nataml surfactants. ii cimde.are often suffl-
cienify soluble in water to a&sorb onto the rock surface ,-
&r passing tbrougb a thin ld~er. of water. 42,60>69-71
Meaauremerits comparing aaphd~ene a+orption in cores
with and without water show tlwt m many. caaes a water
film wiUreduce but not completely ir@it =pk+lterfend-
sowtion. 6M9,70 Be&use the wa~ei .qzd asphaltenes wM
coadsorb, however, the wat4.r film may alter tie detailed
adsorption mechanism. 70,1w Lyutin @d Burdynm found
that the asphalt&e adsorption f$orn A&h ,crude in an yn-
consolidated sandpack wai about 80% of the dry y~ue
at a water saturation of 107. PV, decreasing to 40 % when
the water sapration was incrth+ed to 30% PV. Berezin
et al. 69 exmzzizzedthe adsorption of .&phalten&s&d ;ex-
ins from crude onto cleaned sandstone cores. With Tui-
mazy crude, a water,satnration of about 17% reduced the
adaozption by about a factor. of three. With two other
crndes, a water saturation of about 20% completely. in-
hibited the adsorption. Such complete inhibition by tie,
water fifm woidd be expected in reservoirs that remain
water-wet, with no significant ,adsorption:from the cmde.
Reisberg ad Doscherbs aged clean glaas slides in
c~de ofi.floating above brine and observed the forma-
tion of oif-wet fti. The formation i.nd s~bility of the
oif-wet fti on the slide was observed by lowering .!-be
slide into the brine and observing whether the brine dis-
Joumalof PetroleumTechnology,October1986
placed alf of the cmde ofl from the slide. They first aged oxygen compounds gave higher airgles on dolumite.tbsn
a clean glass slide in crude mrdfound that a film, d6posited quartz, up to 145 [2.5 rad] for. octanoic acid
over several days, made the slide moderately oil-wet. [CH3(CH2)6COOHJ and up to 165 [2.9 rad] foc law-
They modified the experiment by immersing the slide in ic acid [CH3 (CH2),0 COOH]. Note, however, that tbe
water before aging it in crude. Surprisingly, the oil-wet uxygen-containing acidic compounds appesr to react
fti formed much more rapidly. when a NaCl solution gradualfy with the dolomite, so the contacf angles ae un-
was used instead of water, the slide also became oil-wet, stable and the sy$em gadu?dly becomes more water-wet.
but it was necessary to age the slide for a longer period Cram if.ail noted that none of the relatively simple com-
of time. pounds they tested could create a stcble, oil-wet yuface.
There fure, they cuncluded that the compounds respomi-.
Sandston& mrd Carbonate Surfaces. The types of min- blefor wettabihty alteration in crude were higher-weight
eral surfaces irr a reservoti are also im ortarrt in deter- polar compounds and other po+ons of the asphaltenes
mi@rg wettabfity. Both Treiber et cd. E and ClriHngai and resins.
ad Yen35 found that carbonate reservoirs are wpi@y. In the inure complex crudeibrinelrock systems, the nrin-
more oil-wet than sandstone ones. Two other sets of ex- er# surface will not necessarily have a preference for
periments show that the mineral surface interacts with the compounds of the opposite acidhy. The simple systems
cmde oil imposition to detefine wettabWy. The first dkcussed here tested each surfactcrd individpaUy and re-
set e~nes the adsorption onto silica and cmbonatesur- moved the effects of brine chemismy. @ tke section on
faces of relatively simple polar crrmpoundy the second brine chemistry, it will be shown thnt multivalent cations
set exnmines the adsorption of crirde. cnn promote the adsorption of surfactants with the same
Simple Pokr Compounds. Whsin the effects of brine acidigi as the surfcqe. fir addition, the adsorption of auy
chemistry are removed, silica tends to adsorb simple or- single surfactant in the crude might be enhanced or
gtic bases, wh~e the carbonates tend to adsorb simple depressed by the adsorpion of other compounds.
~rgaic tilds. 37,Q83 This occurs because silica normallY Adsor@on From Crude. A nnmber of researchers
has a negatively charged, weakly acidic surface in water found differences in the adsorption of crude oil cum-
nenr neutral pH, while the carbonates have positively punerits onto dry sandstone and carbonate sur-
charged, weakly bssie surfaces. 37,@,83,105 faces. 41,72-74,l@,110Denekss et al. 41 sepmated out the
These surfaces will preferentially adsorb compounds acidic and basic orgaric compounds from crude arrd test-
of the opposite polarity (acidity) by m acidbase reaction. ed them in initially clean, dry cores by tie method de-
Wettabili~ of silica will be more strongly affected by the scribed earlier. They found that the wettabfity of
organic bases, whfie the carbonates will be more strong- snndstone was altered by both the acidic and basic com-
ly affected by the organic acids. This was found to be the pounds, while the Iiiestone was more sensitive to the ba-
CW+in experiments on the adsorption and nettability al- sic nitrogenous orgmric compounds.
te~tion of refntively simple polar ,compormds oir sand- Several experimenters have compared the adsorption
stone and carbonates. The compounds were dksolved in of asphnbenes from crude onto initially clean, dry sazrd-
a nonpolm oil, and the contact angkeof the oillwatcrhnin- packs composed of either quartz or disaggregared core
eral system was measured on mr initially km, strongly material that contained both quartz and carbonate. 72,110
water-wet aystal surface. &xreraHy, adsorption mrd wet- They found that adsorption was greater in disaggregate
tabifity nkemtion occurred with basic compounds on the core material. Tumasyan and Babclyan 110.measured the
acidic silici surfaces and acidic compounds on the basic adsorption, of asphaltenes from Kyarovdag cmde onto
ccrbomte surfaces. Acidic compounds had very little ef- quartz and cleaned, disaggregate Kynrovdag core m~-
fect. on sifica, and basic com ounds had litde effect on terial @atconticd 10.4 % carbonate. The adsorption wnc
fieCabonat=. fo~l~Note,
37A42,66.7S.7J. however, that about 8x 104 mg/cm2 for qumtz nnd about 18x 104
most of the ,adsorbed compounds chmrged the wettabfiV mglcmz for the core material, mr iacrease of more than
only from strongly to mildly water-wet, rather than to a factor of two: Abdurashitoi ef al. 72 meaarzzedthe ad-
oil-wet. sorption of asphnftenesonto sida-sized fractions of pure
The acidic compounds that adsorbed and nftered the quartz samds and sends containing both quartz and car-
wettab~l~ of the carbonates in preference to silica in- bonate. They found that the adsorption on the qunrtz sands
cluded naphtherric acid 37.109mrd a number of carbox$; was as much as an order of magnimde lower Own the ad-
ic acids (RCOOH), including capryfic (octanoic , sorption on the sands containing both minerals. These re-
psfmitic (.hexadecarroic), 42 stearic (@adecanoic), 102,10s srrks are very qualitative, however, because the speCXc
and oleic (cis-9-octadecnnoic) acids. 42 Basic compounds surface arei of the quartz packs was lower dum the area
that adsorbed on the acidic silica surfaces included iso- of the mixed mineral smrdpacks, which afso reduces the
qrdno~ne37and octadccykmzine [CH3(CH~17NH~. 1ffi,108 ~onnt of adsorption.
@mz40 and Morrow ei al. 66 exded dze adsorption
and wettabilhy alteration on quartz imddolomite of a num- Brine Chemistry. The salhrity nrzdpH of brine ae very
ber of relatively low-molecukw-weight compounds found imw-t in determining wettabiilg because they strongly
in crude oils. Basic nitrogen compounds gave advancing affect the surface charge on the rock surface and fluid in-
contact angles up to 66 [1.15 rad] (water-wet), with terfaces, which in turn can affect the adsorption of .srrr-
higher angles for qrrnrtz than dolumite. Sulfur compounds factants. o,m Positively charged, cationic srrrfactanta
tested provided arzgfes of 40 [0.7 rad] or less with wifl be attracted to negatively chnrged surfaces, while
rto systematic dlffercrrces between the two surfaces, The negatively charged, anionic surfactcnts will be attracted
contact angles either were stable or decreased with time to positively charged sin-faces. The surface charge of Q.
(i.e., the system became more water-wet). The acidic ica and ccfcite in water is positive at low pH, but nega-

Journd of Petml..m T-hnology, October 1986 1129

 tive at high PH. For sifica, the surface becomes negatively
char ed when the pH is increased above about 2 to
3.7, ! 3,105 whfle calcite does not become negatively
char ed untif the pH is greater than about 8 to
9.5. &,05.111As discussed in the previous section, sili-
ca is negatively charged near neutral pH and tends to ad-
sorb organic acids, whiIe cafcite is positively charged and
tends to adaorb organic bsaes. Calcite will adsorb cation-
ic smf@mJts rather than anionic surfactants., however,
if the pH of the solution iJJ which it is immersed is in-
creased above 9.111
The pH also affects the iotiation of the snrface-active
organic acids and basea in the crude.. fn afkahe water-
flooiling, a relatively inexpensive caustic chemical
typically sodium hydroxide or sndium ofiosificate-is
added to the injection ,water. 112The hydroxide ion mscts
with organic acids in acidic crude oils to produce surfac-
tanta that after the wettabiti~ ador adsorb at the oilhine
interface to lower f.FT. Seifert and How.ells85 exsmined
the interfaciafly active materials in a California cnrde oil.
They found that the crude contained. a large mount Of
carbnxylic acids that form soaps it ilkaline PH.
The possibfity of EOR during amalkaline flocaldepcnda
on the pH and salinity of the brine, the a.sidi of the crude,
?
and the origiwd wettabtity of the system. 2,113,114Cooke
et al. 6 discussed the effects of salkhy nn wettxb~ky in
alkaline flonds where the soaps are formed by the inter-
action of the alkaline water with the acidic crude oil. In
relatively fresh water, the snaps that are formed are soht-
ble in water; promoting water-wetness. If the system is
initially oif-wet, EOR may occur b a wettabdity rever-
~~ from ~fi..wet to ~a~r-wet. 17.2.?, 114J 15 On the ~ther
hand, in high-salinity systems, EOR may occur as, a re-
sult nf awater-wet-to-oil-wet wettnbifky reveraaf. Aa the
saliniw is increased; the soaps become almost in.duble,
adsorb on the rock surfaces, and. promote oil-
~en~g, 6.113If the system is initially water-wet, COok
et al. ststf that EOR in a highly sshme ~ystem may oc,cur
by a water-wet-to-oil-wet tiettability reversaf mech-
~sm.6 ,113,114
In silkdoillbrine systems, multivalent metsl cations
in @ebrine can reduce the solubilky of the crude sur-
factants andlor promote adsorption at the mineraf sur-
faces, causin the system to become more oil-
wet. 6,W,77,79,8 ? .116,117Multivalent metal ions that have
altered the wettabifity of such systems include Ca 2,
Mg2, Cu2, Ni2, and Fe3. Treiber et al. 34 exam- quartz develops a negative surface charge as a result of
ificd the effects of trace metalions in the brine on the wet-
tab~hy. They meakured the contact angles on quartz of
dead Werobic cmdes in deoiygenated synthetic fofma-
tion brine and found that as little as 10 ppm of Cu2 or
Ni2 coufd change the wettab~ky fcom watdr-wet to oiI-
wet. Brown and Neusta.dterm placed cmde oil droplets
in a contact-angle apparatus tilled with dktifled water.
They found that Oreaddition of.less than 1 ppm of Ca2
or Mg2 would alter the nettability, making the system
more oil-wet. The addition of trace amounta of Fe2 also
changed the wettabiIity with some of the crudes tested.
The.$emultivalent ions have SISObeen ahown to incresae
the od wetness of soils stab~ied with cut-back
xaphalt..11S,119 (Cutback ~~~t is ml MPildt ==ted iti
an inexpensive solvent, such as gasoline, to reduce the
viscosi~.) HaiIcnck 11s - Seved strongly water-wet
soils with cut-back asphalt. He fokd that the oil wetness
,.
1130
of the anil after the.asphalt tre@zent waa greatly increaaed
by pretreating the soif with a solution of ferric or @mi-
IJU222sulfate.
Morrow et al. xl aged glass sfidca in Moutray crude,
waahed the slides to remove the bufk crude, and then used
isooctafre and distilled water. to meaaure tie water-
advancing angle. They fonnd that the wettabifity strong-
ly depended on the sfnount of trace ions iJJthe system.
When the glaas slide was extremely clean, no residual fb
was depnsited by the crnde, and the system was water-
wet. Next, they treated the glass with femic (Fe3 ) or
orler transition metal ions before exposing it to drecnide.
They obtained contact angles up to 120 to 140 [2.1to
2.4 rad], with the angle dependent on the choice of ion
and its c&rcentration. Theferric ion was pxrticulady ef-
fective in altering the wettabilky.
There appexr to be two related reasons for ~e effects
of these mnftiv#ent ions on the wettabili~. Fiiat, they ~,
can reduce the snlubility of the surfactants in the crude
andbrine, helping to promote oil-wetting. 6,113Second,
they behave as activators for the smfactants in the
crnde. Acdvator .la a term used in the floption indus-
try for ions or cnmpounds thst, while not snrfact@ them-
selves, enhance surfactant adsorption on the mizreraf
smface snd increase the flnatabifity. Generally, the acti-
vators act like a bridge between the mineraI surface and
tie adsorbing surfactant, helping tn bmd the snrfactant
to the NIffsce. go AS shown previously, clean @J~ haa
a negatively charged surface nnd tends to adsorb @osi-
tively charged) orgnnic bases from solution. The (nega-
tively chsrged) acida in solution will not adsorb on the
surface because they will be repelled by the like charge
on the quartz surface. For example, clean quartz is not
floated by fatty acids, ideating that tie quartz remains
water-wet. At the proper pH conditions, however, the
wettabfity can be changed and the quartz can be floated
by the additidn of smafl nmounts of marry multivalent
metalfic cations, including Ca2, Ba 2, Cu2, Al3 i
ad Fe +3. WT%Q.107These ions adsorb on tie qun3t2
surface, providing positively char.r@ sites for the adso% ,-.
tion of&e fstty ;~ds. -. -
For exam 1. Ga.din and Chang7s imdGaudm and
Fuerstemm% staled the adsorption of laurnte ions on
auartz. When sodium Iaurate, CHa (CH2.) toCOONa, is
~ded to the water, it dissociates @~ a ne~ati;ely charged
laumte ion and a positively charged Na ion. Because
the dissociation of H + ions from the Si-OH groups on
ihe silica surface, the negatively charged laurate ion is
repelled ffom tie negatively charged quartz surface.
Hence no adsorption occurs. However, adsorption occurs
when, for example, divafent Ca2 or Ba2 ions are
added aa the activator. These positive djwdent ions can
adsorb on the surface, allowing the negatively chmged
surfaciant (in this caae, the laurate ions) to adaorb in as-
sociation wia them. Researchers with other experimen-
tal systems also state that divalent ions can bind to a
negatively chargedsurfactant to fogn a positive, cationk
surfactant/metal ~mplex, w.bich is then attracted to and
adsorbs on the negatively charged quartz snrf?ce, 116,117
CIays. Several researchers have studied tie adsorption
of aiphaftcnis Wd resipa onto clays, and found that.ad- ;
sorption can make the clays more oil-wet. 70,76.1~, 120-133
Journalof Pmol&m Technology,October1986
Clementz %120,121 eximined adsorption under mhy-
droua conditions of the heafl endsthe nonvolndle, high-
molecuiar-weight fraction-of cmde oil, which are
primarily asphal~nes snd resins. He found that rhe com-
pounds adsorbed rapidly onto montmorillonhe, forming
a stable clay/organic compound and chsnging the netta-
bility from water-wet to oil-wet. Clementz also looked
at adsorption under anhydrous coiiditions of the heavy
ends onto Berwcorca that contain significant amounts of
kaolinite. The adsorption of tie heavy ends made the core
neutrally wet as determined by an imblbhion test. The ad-
sorption also,reduced the expansion of swelling clays, clay
surface area, cation exchange capacity, and water sensi-
tivity. The materials that adsorbed onto both the mont-
morillonite and kaolinite were difficult to remove,
although most of them could be exmacted with a chloro-
formlacetone mixture.
Clementzused dry cores and clays. As discussed C&
er, the presence of a water fdm will gen@ly reduce the
adsorption of wettabfity-altering materials, typically by
a factor of two to four, although in some cases, it will
completely inhibk adsorption. >@ Collins and Melmse70
measured the adsorption onto kaolinite of asphaltenes dk-
solved in tolucne. The dry clay adsorbed a maximum of
about 30 mg asphaltene/g clay. The addkion of 6.6%
water t? the clay reduced the adsorption to 13 mg/g. In
addition to reducing the adsorption, the water l@ may
alter the d:tied mechanism of asphaltene adsor@on be-
cause the asphaltenes and water will coadaorb. 7 For ex-
ample, in contrast to his work with anhydrous cores,
ClemenE found that the adsorption of asphaltene onto
Berea cores in the presence of water dld not reduce the
water sensitivity of the kaoliidte. lW
Non-Water-Wet Mineral.% When all of the surface con-
taminants are carefully removed, most minerals, includ-
ing quartz, carbonates, and sulfates, are wrongly
water-wet. go,1o7,lx From flotation studies, however, a
few minerals have been found that are naturally but weakly
water-wet or even oil-wet. These minerals include sul-
fnr; graphite, talc, coal, snd msny sulfides. Pyrophyllhe
and other talc-like silicates (sificates with a sheet-liie
&rncture) are ~obably also neutrally wet to Oil-
~et, 30,107,134-12~ese finer~~ ~ ~OW~ tO be SO~e-
what hydrophobic because air can be used to float them
on water ir3froth flotation, implying a large waterlairhnin-
eral contact angle. Because they are non-water-wet with
air, it is probable that they are also oil-wet.
On the bsais of core-cleaning attempts in a limited num-
ber of reservoirs, it appears that cores containing conl are
sometimes na.tur@ly neutrally wet because they can be
cleaned only to a neutfsll wet condition rsther than a
~Uon lY wa~r.wet one. 1za,129 Cuiec96 and Cuicc et
al. 138 cleaned unpreserved cores with different solvents
and then measured wettabdity. In four cases where cores
contained large ixnounts of unexmactable organic carbon,
they were able to clean the cores only ti neutmf nettabil-
ity. Wendel et al. 12s cleaned core from the Hutton reser-
v6ii contaminated with an invefi-oil-emulsion drilling
mud. Core from most zones in thk reservoir could be
cleaned to a water-wet state. However, in one zone that
contained si=tilcant amounts of coal, the core was neu-
trally wet after cleaning. About 50% of the rock surface
in tie neutrally wet zone was covered by a thin layer of
organic matter less than 300 ~ [30 mn] thick. ThIS fayer
Journalof PetroleumTechnology,October1986
--
may be a:rcauft of dif3i3si0nof organic cmnpounda released
during diagenesis from the small, organic, detrital pard-
cles of cod scattered throughout the zone. Unforhmate-
ly, this is unclear at present. Thin sections from both
water-wet and neutrally wet (tier clcaqing) zones show
that both contain approqtely equal amounts and dis-.
@bution of woody coal; algae coal, and pyrite. Conse-
quently, it is unknown what causes the postcleaning
neutral tiettability of this neutrally wet zone.
Boneauand Cfampitt 131and Trantham and Cknnpitt 132
stite that the oil wetness of the North Burbank unit is
caused by a coating of chamosite clay (Fe3Al zSi2O IO
. 3HzO) on the pore surfaces rather than the more com-
mon, strongly adsorbed organic coating. The chamosite
clay, which is iron rich, covers about 70% of the rock
surfaces It seems plausible that tbe chamosite cfay renders
the core oil-wet because, as discussed earlier, iron ions
are strong activators, promoting o~-weufng. Cl~pitt*
states that unpubliahti contact-angle measurements made
with all of the ~emls inthe No&Burbank core ahowed
that chamosite M naturally oil-wet.
Artificial Variation of Wettabifity
Aadescribed previously, a native-state core contains a
cmmplex mixture of different compounds that can adsorb
and deaorb, possibly altering the wettabdity during an ex-
periment. Msny re8esrchers have tried to simpfify their
experiments by artificially control~mg the wettabfii~ to
some constant, uniform value. The three methods most
commonly used are (1) treabnent of a clean, dry core with
various chemicals, generally orgWOcMOrOsfl~es fOr.
sandstone cores and naphtienic adds fOrwbOnat~ core~
(2) using sintered cores witi, pure fluids; and (3) adding
surfacthnts to the fluids. A sintered tdlon core with pure
fluids is the preferred method to obtain a uniformly wet-
ted core because tic wetrabili~ of these coma is constant
snd reproducible. The fiettabilhy of cores treatid with
brganochlorosilan:s, naphthenic acids, or stirfactanta is
much more variable because it afso depends on such vari-
ablesas the chemical uked, the concentration, tie treat-
ment time, the rock surface, and the brine PH. These
treatments have advantages, however, when he~rOgen~-
ous wettabtity or wettsbil~ alter~tion is studied.
Organochlorosffanes and Other Core Tr&dmMa. One.
method of making a sandatone core uniformly non-watcr-
wet is to treat it with a solution conpining an OrganO-
~~oro~~e ~ompond, 133-139vm~tiom of ~~ tf~~t-
ment have also been used to create fractionally wetted
~mdpacf&&+$50.1@h!2~d mixed-wet cores. 143me ~r-
ganosilane compounds contain silicon molecules with at-
tached chlorines and non-water-wet organic groups, with.
the general formufa RnSiC14-n where R is usually
methyl or phenyl and n =0, 1, 2, or 3.133 These sub-
stances ,react with the hydroxyl (OH) groups on silicon
dioxide surfsces, exposing the organic groups and ren-
dering the surface non-water-wet. For example, dimerhyl-
dichlorosilane, (CH3)2SiC12 (Drifilm@ or Teddol@ ),
chemisorbs on the outside of the sificate lattice of glass,
eliminating HC1 and exposing CH groups, which reduce
the wata-wetness of the surface 1h Other compounds il3-
clude heximethyldkilazane 138 and trimethyMdo!Osi-
kme. 145The wettabfily of the core is altered by flowing
.P.rsmtic.nnm.nimtimwithR.L.Clmnpiu,Ptiltip Petroleum,BaII[esvilleOK,
Dac.1S83.
1131
 a solution of the organosilane through it, snowing a suffi- ~onmt, Newcombe et d. 136 stated that contact an~es
cient time for the reaction to occur, and then flushing the sa large aa 154 [2.7 rad] could be obtained for aK1casur-
unreacfed compound from the core. Some control of the faces mated with different conqamations of methylsilOx-
change in we,ttabifi~ can be achieved by variation in the ane polymer, but these contact angles tended to decrease
concentration of organosilsne in the solution. For a com- towsrd 90 [1.6 rid] as they aged. Memwat $?ral. l@
plete description of the method, see Ref. 134. tmatcd silica surfaces with various concentrations of four
In addition tu unifoqnly treating cores, organocldorosi- different organochlorosilanes and obtnincd contact angles
kmca are used to prepare fractionally wetted sand- ffom 75 to 160 [1.3 to 2.8 rad] with water and xylene
Packs, 43,46.50,140-142 Sand gtins txeated with 6rgm30- on the treated surfaces. Depcndmg on the specific treat-
chlorosilmies sre mixed witkuntrcated; water-wet sands. ment, they found that the contact angle could gradually
The fraction of oil-wet surface is aasumed to be the sb.me increase or decrcaae aa the system aged. Because&e wet-
as the fraction of orgnndcblorosilane-treated sand. One tabtity of cores treated with organosikmes can range from
problem, however, is that some of the organocblorosi- mildly water-wet to strongly oil-wet depending on the Spe:
lane is known to be transferred to the water-wet sand cific treatment, the Amott or USBM method shoufd be
grains, likely changing their wettabtity.43 Auother used to determine the wettabllity of the treated core.
method of obtaining fractioml nettability is to form tie Quilon@ treatments are mother method that has been
porous medium from water-wet (gkMs)beads and oil-wet used to alter the wettabiIity of sandstofie cores. Tiffii hnd
(tcflon) beads. 146 Yellig 149treated Berea cores with Quiion-C@ to render
Moh~~ ad s~tcr 143have reqedfy publiahcd a tech- them uniformly oil-wet. Workers at tie Petroleum Recov-
nique to generate mixed-nettability cores so that the large ery Inst. have used Quilon-S@, i related com-
pores have continuous water-ivet surfacca, leaving the ~md, 15~153 me won compounds consist of a chrome
smalf pores ofi-wet. Note that in these cores, the netta- complex containing a hydrophobic fatty acid group in an
bility is reversed from Salatbiels47 mixed-wettability isopropyl alcohol solution. When @iiori is injected into
cores. Cleaned cores are first treated witi orgagosikmes tie core, the molecules bmd to the surface, expose the
to render them uniformly oil-wet. The treated cores are fatty acid group, and render the rock surface oil-wet. 1X
saturated with oil, flooded with heptadecane to dkplace Note that wettabtity of the treated core probably v~ies,
the oil, and then flooded with brine to ROS. Because the depending on concentration, tfcatment time, etc., so it
core is oil-wet, the large pores are fdlcd with brine, but should be meaaured with the USBM or Amott metbnds.
the small ones are fdled with oil. Brine and heptadecane In many crises, the treated core is probably OIIIYneutral-
IMY then be injected simu&aneously to alter the fraction ly to mildly oil-wet.
of pores ffled with oil or water. After the desired satura- These trcatmerita have been used on sandatone core with
tion is reached, the core is fust placed in a cold water the chemical binding to the s~Ica surfaces. Orgsno-.
bath (50F [1OC])to freeze the heptsdecane, then an 11.5 chlorosikme treatments, which adsorb on silica surfaces
pH sodium hydroxide solution is injected to diapfimc the by reacting with the hydro+yl grou$a, are generally not
brine. Mohanty and Sslter state that the alkaline solution effective on carbonate surfacea. 1 5,1% A number of
removes the orgnnosilane coating from the lnrger, brine- ~Wche~~ 109.155-157bWe used m hthenic acids to
tilled pores, leaving them strongly water-wet, while the render carbomtc cores more ofl-wet. ?7 The naphtle~c
frozen heptadecane prevents auy change in nettability in acids react with the calcium carbonate to form cslcium
tie small oiLffled, oil-wet pores. Folly, t+e alksdine so- naphthenates, which are ofi-tiening. 109 Note that
lutiori is displaced with brine, arid all of the fluids are re- naphthenic acida will not nlter the wettabtity of saudatone.
moved, leaving a mixed-wet@ ility core. After this s~faces. w
treatment, the cores imbibed both oil and water, indicat- Sharma and Wuuderlich15s altered the nettability of
ing that areas of the. core were both water- and oil-wet. Berea pIugs by saturating them with au asphaltic crude:
Unfortunately, Moh&y and Salter did not test the cores Drv Dlum were vacuum-saturated with isrhaltic cmde oil,
: by oil flooding them to determine whether they had a very th&fl~shed with pentane, which ten& to precipita~
low water.saturation after tie injection of manyPVs of asphakenca onto the pore walls. 67 The pentane wasre-
oil. This would have verified the formation of continu- moved in a vacuum, kwiug behind a layer of asphaltenes.
ous water-wet paths through the large pores, which would Tim plugs probably had mixed wettnb~ky after Ecatmenc
be analogous to oil-wet paths in Sala~eli cores. boti,oil snd water would imbibe spontaneously. 3 An ad-
One problem with orgamochlorosilane treatments is that vsutage of thk method is that it uses com@mda found
the nettability of the tmatcd core varirs depending on such natnrslly in the resetioir and ,pight be a more realktic
variables as the orgtiocidorosil~e used, the concentra- ticatrnent than the other trcahnenta discussed above. Note,
tion, the treatment iiine, the time elapsed since the sur- however, that it is necessary to verify tiat the crude is
face was treated, and the pH of the brine. 147 No compatible with the pentie because some cmdes will plug
dependable treatment has been reported for acgeving a the core when pentane is injeded.
given: core wettahilhy. Note that many organosilane-
treated cores ze only neutrally to mildly oil-wet, instead Artificial Coma. Several rcaearchera have used artificial
of strongly ofl-wet. Coley et al. 134used General Elec- cores and pure fluida to control wettab~hy. The uniform
tric Co. s~lcone fluid No. 99 in concentrations ranging composition of tie core and the absence of surfactimts
from 0.002sto 2.0% and were nhle to vmythe contact combine to give a constant; uniform, and reproducible
angle, in. glass capillaries only from 95 to 115 [1.7 to nettability. The most popular material for the artificial
2 fad]. RathnieO et al. 137found that cores treated with core baa been polytetiafluoroethylene (teflon). Stegemeier
dmethyldichlorosikme would still slowly imbibe water, fid Jess&n159used porous packa of tcflon particles. More
indicating that the cores were at most neutrslly wet. In recent experiments hsve used consolidated teflon

1132 Journal of Pekole.m Technology, October 1986

 ,.
cores, 160-68 which are prepared by compressing teflon wet when, water conta.inhg a mild acid is injected. The
powder and sintering it at elevated temperatures to most cofnrnonly used amines have been hexylamine and
produce a consolidated core. Mungan 167 completely n-@ylamine. Mungan 174measured the water-advancing
describes the process. Lefebvr.e du Prey lm has 81s0us<d cOnmct a@ on a siliii, syficc u8ing water, n-
Sinter.Sd5tifle88 8tee] and altina cores. ~, hexylamine, and a refined bid. Tbe contact angle with no
Teflon is preferred for two reaaons: it is chemically inert aminca present was about 60 [1 rad], or water-wet. As
and has a low surface energy. 16g Most minerals found the concentration of tines tias increaaed, tie contact an-
in reservoir rock have ahigh sutface energy, soabn08t gle gradually changed to about 120 [2.1. rad], or mildly
all liquid8 will spread,,op and wet them against $r. The oil-wet. In addition to iltering the wettab~ky, the amines
w&abiMy of such high-energy solids must bec$mtroUed partition between the oil and water and lower IFT.
with either adsorbed fti on the solid 8urface or 8urfac-
tants in the fluids. Both of these inethod8 raise the prob- Alteration of the OrighraI Wettabflity
lem of changes in the wettab~ty during the experiment
as a result of adsorptionldesorption phenomena. On the As mentioned previously, alterations in nettability can
other hand, the surface energy of teflOn iS low enouti. affect the iesuks of moat core analyses. IdcaOy, tieie @-
that a wide range of contact angles can be obtained with yse8 shordd be mu with core wettabfity that is identical
various combinations of pure fluids that do not contain to the nettability of the undisturbed reservoir rock. Un-
surfactants. The u8e of pwe flbids with teflon also avoids fortunately, many factors can significantly alter *i. wet-
difflcukies with contact-angle hysteresis associated with tabilky of thecore. The8e factors can be divided into two
adsorption/desorption equilibrium and the problems as- general categories (1) tho8e that influenc&core wettsbik
sociated with contact angle and IFT aging phenomena. ity before testing, such as drilliig fluit is,packaging,
Thisis dlscus8ed in more detail in Ref. 1. fiany experi- preservation, and cleanin% and.(2) those that influence
ments in tetlon cores use air or Nz anfl various fluida to wettabiitv dtig testing, such m test fluids, temperahue,
va~ the contact angle. Contact angles from Oto 1080 [0 and pres&re. - -
to 1.9 rad] can be obtained by the proper ChOiCeof liq- The wettabili~of a.core can be altered during the drill-
ui~gas pati8. 161For ~x~ple, an air/water/teflOn sYs- ing process by the flushhg aitionsof driig fluids, par-
tern hasa contact angle through the water of 108 [1.9 ticularly if the fluid contsim 8urfactimts 128> 175or ha8 a
pH~~.1i~.1?6 different 1% that of the reservoir fluids.
rad]. Lefebvre du Prey 160 used mixtures of water,
glycerol, glycol, and alcohols to represent the water pbaae The w@@biiv may also be changed by the pressure and
and mixtures of pure hydrowbons for the oil phaae. Con- temperature drop that occurs as the core is brought to the
tact angles through the oil phase of from O to 168 [Oto. surface. This action expels fluids, particularly the light
2.9 rad] were reported for hk teflm, steel, and alumina ends, and changes the spatial dkribution of the fluids.
cores. In addition, asphaltenes and other heavy ends may deposit
on the rock suifaces, making them more oil-wet. The tech-
niques used in ba@.ling, packaging, and preserving the
Surface-Active Agents. The use of clean cores and pure core & slso alter the .wettability through a 10SSof light
tkdd8 with various C0nCenmati013S of a SiJigle Surfactant ends, deposition of heavy ends, and ofidation. The labo-
isthe third way that re8e81Cher8have controlled the net- ratory procedures for cleaning and preparing the core cm
tability of cores: Owens ,and Archerzs used biwium change the wettabfity by altering the amount and type of
dlnonyl 8ulfonate in the oil and reported stable contsct material adsorbed on tie rock surface.
angles up to 180 [3.1 rad] on a quartz crystal. Morrow Factors that can alter wettabfity diuing testing include
et al. 66 were uriable to reproduce this work, finding a the test temperature and pressure. Generally, cores nm
strong time dependence for the contact angle. They tried at atmospheric coiidition8 are more oil-wet than those mn
to control the wetfabtity with octanoic acid, obtaining@- at ,reservoir conditiom becau8e of.the reduction iriSOIU-.
gles from Oto 155 [0 to 2.7rad] on dolomite. They found bility of wettabfity-akering compotindi. An additional
that the wettabflity could be maintained for less than a factor iMuencing -he wettabfl~ is the choice Of test
day, however, after which tlesystem became increa.$ingly fluids; certain migerd oils camalter the wettqbility. Core
water-wet as tie octanoic acid 81OWIY reacted with the analyses ze sometimes run with air/brine or airlmercu-
dolomite. v,in place of ofl and brine. ,These analyses ~nplicitly as-
A number of res&hers 17,26.17&174haVe I18Sd8mkJeS, sume that wetfabfity effects are unimportant.
R-NH2, to study EOR caused by Wettab~hy dtemtion iII Currently, three different *of cores ae used in core
laboratory &#.wflmds. Wwtability reversal from Ofi-wet analysis: (1) the mtive-state ,core, where every effort is
to water-wet and. from water-wet tooil-wet are two of made to maintiin the nettability Of the in-situ roch (2)
the proposed mechanism for enhanced recove~ during the cleaned core, where the intent is to remove all of the
alkaline waterflooding. 114 In Oiese laborato~ 8tudies, adsorbed compounds from the rock and to leave the core
clean core, a refined oil, and ibrine containing mines strongly water-we! and (3) the restored-state mm, where
were used. The wettabili~ was rever8ed by changing the the core is first cleaned apd ~en returned toits original
pH from alkaline. to acidic. When the PH was alkalime, wettabti~. These definitions are used in the majority of
the amine group physically adsorbed on tie rock surface, the more recent literature. However, in some papers, par-
exposing t& hydrocwhn cl@ to make the sUrfaCe0~- ticuk@y older ones, the term restored-state is used for
wet. 173The wettabilhy was altered when the PH became what are actually cleaned cores (e.g., see Craig7 ). The
acidic because tie mines formed water-soluble salts that work with native- and restored-state core is at either mm
rapidly desorbed from the rock surfaces, leaving thern- bient or reservoir temperature and pressure, i.idfe cleaned
water-wet, Hence a core that is oil-wet becomes water- cores are usually tested at ambient temperature.

Jownd of PetJolam Technology, October 1986 1133

Native.State Core
Coring. In a nativi-stite (fresh) core, every precaution
is taken to minimtie changes from the undkturbed reser-
voir nettability condhion, starting when the core ig frost
flushed by the dr~g mud. In pyticukw, a mid with s~-
factants or a pH that differs greatly from the reservoir
fluids must be avoided. Ofl-based-emulsion muds ?nd
other muds containing surfactaits, caustics, mud thinners,
organic coriosion, in&itors, and lign@fonates must be
avoided. 175,177Note that, @hIle they probably exist, no
commercially available oil-based muds have been m rted
P
thatcan preserve the reservoir nettability. 175>17178
The different coring fluids for obtaining native-stati
cye have been recomriended. (1) synthetic formation
brine, (2).unoxidized lease crude oil, or (3) a water-breed
mud with a miniznuin of addhives. Bobek et al. 175rec-
ommend coring with brine and noadditives. If ,.hk is not
possible, a water-based mud containing only bentonite,
cnrboxymeibyl cellulose, rock salt,, and barite should be
used. This is recommended b~ause they found that this
would not alter the wembfiity of strongly water-wet cores.
Note, however, that the carboxymethyl celkdose,may ~ter
the wettabfit of oil-wet cores, rendering them more
water-wet, 152.~75 Bbrlich and Wygsl 179 recommend a
synthetic formation brine coritaining CaC12 powder for
fluid loss control and no o~er additives. Mungait 180rec-
otiends coriug with lease crude oil. Note f.hatthere are
tio possible problems with the use of crude oil: (1) it
is flammable, and (2) surfactams can be formed by oxi-
dation. of the cmde, which could alter tie wetta-
bili@. ,103
rhfortummly, very MtIe work has been published about
the effects of individual drilling mud components cmwet-
tabiihy, particularly for oif-wet cores. Burkhardt .r al. 176
exaniined the effects of mud filtrate flushing on restored-
,stitecores snd found no significant effects. Unfortunate-
ly, the cores were in contact with the crude oil for only
12 to 16.hours, so it is doubtfol that the wettabtity was
restored before testing.
Bobek ei al. 175 tested several dit%r<nt drillkm mud
componerits used in water-baaemuds on both wat~r-wet
and oil-wet pings The drilling mud :omp6nen@ to be test-
ed were dksolved in or leachdwith distied water then
the resulting solntion was filtcreii. Concentrations of the
compamds were chosen to duplicate those encountered
in the field: Water-wet limestone and s~dstone plugs were
saturated .wltb the test solution and wetibflity alteration
monitored by the irgblbkion method., As,dkcussed earli-
er,.theyfonnd flat rock salt, carboxymethyl celhdose,.
bentonite, and bake had ho effect on tie wetmbfli~ Of
these initially water-wet plugs. Starch, lime, tetmsoditirn
phosphate, and calcium lignosujfomte altered the wetta-
btity of the sandstone and/or limestone plugs.
Drilhg components that, did not.affect the water-wet
plugs were tested on oil-wet sandstone plugs. The dry,
initially water-wet plugs were made oil-wet before test-
ing by saturation with Elk Basin crude and aging for one
day. Notethit becanse of the short duration of the aging,
the wettabiity may not have been in equilibri~. The aged
cores were flushed witi a drilling mud component fkraW,
then the wettabfity was measured. by the imbibition
method. .Sa.kdid not affect the wettabfity, whfle carb-
oxymethyl cellulose made. the plugs more water-wet
(bariti was not tested). Bobck et al. found that the PH
,.
1134
of the filtrates was an iinpotit factor in we~bdity al-
teration. The origti bentonite filtrate changed me wet-
tzbtity from oil-wet to water-wet. When the pH was
lowered into the neutml or acidic rsnge, however, no wet-
tabtitjI reversaIoccurr+.
Sharma snd Wunderlich 158meaaurcd the wettabi!.iwaf-
teration caused by different drilliig mu@components in
water-wet and oif-wet Berea plugs. The oil-wet Berea
plugs were prepared by treatmentwiti an asphaltic crude
and pcntane, as discussed previously. Dry plugs were
saturated with brine, injected with 10 to 12 PVs of the
drilling fluid component, aged for 15 hours; tien flushed
with 5 to 6 PVs of brine. Wettabilky was measurd af-
ter contamination by a combined USBM/Aniotl method
developed by Shagna and Wunderlich 158and compared
with the we~bility of control samples. The driiing comp-
onents tested included bentonite,, carboxymethyl cellu-
lose, Dextrid@ (an organic polymer), D~spac@ (a
polyanionii ceflukiwe polymer), hydroxyetbylcelhdose,
pregelatinized starch, and xanthm gum. These compo-
nents are generally considered relatively bltid, with onfy
small effects on the wettiibilky. None of the components
affected the nettability of ~e water-wet plugs. However,
N of the components, with the exception.of the bentonite
fdtrate, made the oil-wet plugs significantly less oil-wet.
This indicat&stie need for further rese~ch on acceptable
drillings muds for obtaining native-state core.
Several researchers have attempted unsuccessfully to
fmd suitable commercially available oil-based muds for
~btig ~tive.sate core, 175, 177, 178,~ of tie ~fi.ba~~
drilling mud iiltrates tesied made water-wet cores more
oil-wet. Unfortunately,. none of the reports identify tlze
specific drilling mud components used. ,
Cm-e Packaging and Preierv&ion. Once the core is
brought to the surface, it must be protected from wetW
btity alteration caused by the loss of light ends or depo-
sition snd oxkldion of heavy ends., On exposure to air, .
subticei k crizdecan rapidly okidize to form wkw prod-
ucts that are surfactants, altering ihe wettabili-
,W,34,73,103,115,175,181,182 M ad&tiOn, a tick ofl-w@
residue from the crude will be deposited on &e rock sur-
face if the core is allowed to dry out. To prevent wetE-
bility alteration, Bobek et al. 175 recommended two
sltemitive packaging procedure: that are now gene@y
used for native-state cores. The fwst ia to wrap the cores
at the weUii@in polyethylene or polyvinylidene film and
then in aluminum foil. The wrapped cores we then sealed
with a thick layer of paraffin or a special plastic sealer
designed to exclnde oxygen aid prevent evaporation. The
second, preferred method is to immerse the cores at tip
wellsite in deoxygenated formation or synthetic brine in
a glass-lined steel or plastic tube, which is then seafid
to prevent leakage and the entrance of oxygen. ImbibG
tion wettabihw tests showed that the nettability of core
packaged by either of these WO methods was unchanged
from the wettabfily mesaimed at the wellsite. Instid of
deoxygenated brine, Mungari180 recommended tit the
cores be cut and stored in degassed l&ae crude oil. Mor-
gan and Gordan 183and McGhee et al. 62 recommended
that the cores be stored in their wetting fluid, either for-
ntstion brine or crude oil. Thewettabiky would be,deter-
mined by an imblbhion test at the wellsite. Finally, not?
that cores taken in a robber sleeve, fiberglass, or PVC
Journalof Petroleum Tedmo108y, Octpber 1986
 TABLE 3EFFECTS OF EXPOSURE TO AIR AND PARTIAL DRYING ON
NATIVE-STATE CORE
Number
of Cores
Tested iescriplion
2 Native state
3 Exposed to air at
70 to 100nF for 1 day
2 Exposed to air at
75F for 60 days
4 Exposed to air at
225F for 7 days
Cay$btdnedbyuse ofthe Amattwellafl~v,,s, natNeNatecorefrom0,! Zone8., SterlingConly,
L
liner can be DESeNed if the ends are cappedand sealed.
A number-of experiments have dem&strated that ex-
posure to air and drying cao alter the nettability of core.
As discussed earlier, Treiber et al. w measured the. net-
tability of 50 reservoirs usfig deoxygemted synthetic for-
mation brine and anaerobic crude. In some cases, the
contact angle showed that the reservoir was water-wet.
For some of those cnrdes, exposure to oxygen changed
the wettabili~ to ofi-wet. Bartell mrd Niederhauser103
stodied interracially active materials in crude, which con-
centrate and form solid fflms at the oil/water interface.
These materiils can also be adsorbed on the rock surface,
rendering it oil-wet. Crodes and brines were obteined and
stored without exposure to oxygen. Most of these crudes
showed very little interfaciel activity. On exposure to air,
the cmdes developed moderate-to-strong fdrn-fomning
tendencies, while the oil/water IFT was lowered by as
much as 50 %, indicating that surfactants were formed by
oxidatiori of the crude...
Richadson et al. 1s2 stored core from a mixed-
wettability reservoir47 using four different methods. Ox-
idation snd drying of the core tiere prevented with the
first two methods: (1) core wrapped in foil and scaled in
paraffh and (2) core stored in evacuated (deoxygenated)
formation water. The other methods were (3) core stored
in aerated formation water and (4) core stored in cloth
core bags. The cores were oilflooded with kerosene to
IWS and then waterflooded. The average ROS for the
samples protected from oxidation and drying (Methods
1 and2) was about 13%; forthesamples submergedin
aerated water, about 24%; and for the samples storedin
core bags, about 25%.
Bobciket al. 175used the imbibition method to compare
the nettability of native-state cores at the wellsite, cores
allowed to weather, and cores stored by the two recom-
mended metiods discnssed above. The nettability of the
cores stored by either of the two recommended methods
was the same as the nettability measured at the wellsite,
while most of the weathered cores became more oil-wet.
Am0tt177 used bismethtidt ocomparith ewettabihy
of native-state cores with similar cores that were exposed
tooxygen ayd~owed to partially dry, asshownin Ta-
ble 3. The native-stste cores were strongly water-wet, with
a dkplacement-by -water ratio of 0.97. In the Amott test,
the displacement-by-water ratio is the ratio of the oil
volume displaced by spontaneous imbibition to the total
oil volume displaced by .botb imbibition and forced dis-
placement. Itiszero forneuqally mdofl-wetcO~~s aod
J&mal of Petroleum .Tecbnology, October 1986
1
Average . Average
Dlsplacement- Oisplacement-
by-Water Ratio by-oi Ratio
0,97 0,00
0.63 0.00
0.42 0.00
0.18 0.00
approaches one as the water-wetness increases. Siniiiar:
ly~ the displacement-by-oil ratio is zero for neutrally and
water-wetcores aod approaches one as the oil-wetness
increases. The cores became more oil-wet as they were
either exposed to the air for longer periods of time, o!
at higher temperatures. Similar tests on an initially weakly
water-wet core showed elmost no change. On the other
hand, Mungan 115used the imbibition method to meas-
ure the wettabilhy of native-state cores. In contrast to tie
experiments discussed above, cores preserved in deaer-
ated water were oil-wet, but becsore water-wet when ex-
posed to ti for 1 week. Chfingar and Yen35 have also
reported that some cores became more water-wet on ex-
posure to sir, indicating that it is bnpossible to predict
how the wetfsbtity will be altered by tie oxidation of tie
cmde.
Mungao 180recnmmendsflushing native-state core with
five erode oil before sny flow studies are startsd. After
native-state cores .havc been prepared, they are usually
nm at reservoir conditions with crude oil and brine.
Probably the greatest, uncontrollable problem with
nstive-state core is the alteration of nettability as the core
is brought m the surface., When the pressure is lowered
to atmospheric, light ends are lost from the erode, chang-
ing its properties. In addition, heavy components cm come
out of solution and deposit on the rock, making it more
oil-wet. 137 The decrease in temperature wilf also
decrease the solubili~ of some wettebfli~-altering com-
pounds. Pressure coring prevents tie loss of light .erids.
However, the cores are frozen before removal, so
wetta.bflity-altering compounds W deposit. Unfortunate-
ly, there is no experimental work avsilableon wettabfli-
ty alteration as the core is brought to the surface. ..
.
Cleaned Core
The second type of core used in core aoalyais is the
cleaned core. Cr&ig7 recommends that cleaned core be
used for multiphase flow measurements only when the
reservoir is known to be strongly water-wet because errors
iq the core am.lysis will be introduced otiimvise. There
are two main reasons to clean wre. The first is to remove
all liquids fromthe core so that. porosity, permeability,
and fluid saturations can be measured. Core cleaning for
these roudoe core measurements will not be considered
in this paper. The second reason for cleaning is to obtain
a strongly water-wet core, generally as a first step in
restoring the wettabfity of a contaminated core.
1135
 In obtaining a cleaned core, an attempt is made to re-
move all of the fluids and adsorbed material, leaving a
clean rock surface. Gant aid Anderson 129 discuss the
meibcdsused,tu clean core. One common method is reflux
extraction (l)ean-Stark or Soxhfet) with a solvent such as
toluene, sometimes followed by extraction with cfdoro-
form or methanol. Alternatively, a flow-through system
where the solvents are injected under pressure is some-
times used. 57,&,65lf the cleaning procedure is success-
ful, the core is left strongly water-wet. Cuiec$5 mid
others 57,1w discussed the chemicalreactions involved in
the cleanin process.
Cui&ca,& compared me efficiency of different solvents
in flow-through core cleaning. Initially water-wet outcrop
sandstone and limestone cores were saturated with differ-
ent cntdes (sometimes the cores also contained brine), then
aged. The aged cores ivere ncyrmfly neutr~- to oil-wet,
as determined. by the Amott wettabflity test. The cores
were then cletied with dlffererit solvents, and the Amott
test was used to determine cleauing efficiency. Cuiec
found that he could clean both sandstone and liiestone
cores by flowing the f?ll@ig seven solvents through the
core: pdarte, hexane, heptane, cyclobexane, beuzene,
pyridine, and ethanol. Chloroform, tohtene, and methanol
used singly were not very effective. Cuiec also looked
at several dtiercnt acidic and basic solvents used individu-
ally and found that the acidic solvents tended to be more
effective in cleaning sandstone, whiie the basic solvents
were better in cleaning Iimcstone. This difference was at-
tributed to the acidic nature of the sandstone surface and
the basic mture of the limestone surface. For examplei
because sandstone (silica) has a weakly acidic surface,
it tends to adsorb bases from tie crude oif. When a
stronger acid flows through the sys@m, it will gradually
react with and strip off the adsorbed bases, Ieaviug a clean
silica surface.
G@ and Anderson 129 surveyed most of the core-
cleouing experiments in the literature. They found that
the best choice of solvents depends heavily on the cmde
~d the mineral surfaces becavse they help determine the
amount and @pe of nettability-altering compounds ad-
sorbed. Solvents that give good results with some cores
and cmdes often faif in other cases. For example, Grist
et al. 1s4 and Holbrook and Beruard45 both found that
they could clean core to a strongly water-wet state using
a cliloroformfmerhanol mixture, while Jennings5s repOrt-
ed. fiat thk was unsuccessful. For cleaning for routine
core analysis, API 1s5 reports that cbfom form is excel-
lent for many midcontinent .ctudes,wh~e toluene is us6-
ful for asphaltic cntd:s..
hi many cases, it appears that any single solvencis rela-
tively ineffective in core cleaning and that much better
results can be obtained wiih a mixtttfe or series of
solvents. 129 The followhg solvents have, been rCpOfi-
ed for specflc binbinations of crude and core to give
pcor resufts when used alone: chloroform, ,65 ben-
zene, 5S,1M,120~=bon di~~fide, lU,120 ~~mol, @ ~d
toluene.5@.@.65 .1~.120,1T.l~,1s6
Many of the researchers cited above have found that
toluene used alone is one of the least effective solvents.
However, when combined with other solvents, such as
methanol (CHs OH) 184 or ethanol (CH3 CH zOH), 61
toluene is often ve~ effective. The toluene is effective
in removing the hydrocarbons, including asphal-
1136
tenes 130JW and some of the weakly polar compcmmi.s,lW
wbiletbe more,spongly polar methanol (ethanol) qcmoves
the strongly adsorbed polar compounds that are often
responsible for altering wettabilky. In addition to
toluenelmethanol and tolueneletbonol, successful clean-
ing has ako been reported with cbforoforndace-
tone 1wZ120. 1= and cfdorofordmetfranol, 1s4 as well as
a number of different series of solvents. ,65
CuieCand his coworkers made the most extensive study
of core cleaning for nettability restoration. In a recent
paper, Cuiec et az. 130statkd that their core cleaning al-
ways begins with a toluene flush to remove hydrocarbons
and asphaltenes. A number of solvents are then.tested to
determine the most effective, including (1) a series of non-
polar solvents, e.g., cyclohexane or heptane; (2) acidic
solvents, e.g., cblorofonn, ethanol, or metbanoh (3) ba-
sic solventi, e.g., dioxane or pyridine; ond (4) mixtures
of solvents, e.g., methanollacetoneltoluene. When none
of these procedures are effective, other tests are performed
by combining the above procedural, using otler solvents,
ad incremfig the Circdatiog time.
Tohtene is generally not a very effective solvent, but
it canalter the nettability of some core. Jennings 186
cleaned sever,d cores by toluene extraction and found that
the wettabilities and relative penn.eabilities were not
changed. He stoted that this indicated that toluene-
extmcted core retoined the reservoir wettabi!ity and coufd
be used for relative p+mneabtity rneosurements, However,
this generally is not the case. Aftbough it is less et%cient
than other solvents, we have found that toluene extrac-
tion can alter the wettabili@ and relative penneabtitics
of native-state core. fn some cases, neutmlly wet or tidly
oil-wet mtive-state core becomes strongly water-wet ti-
ter extraction witi toluene. The relative permeability
cume~ ~~o ~E,fi. AMOU177 ako found that toluene ex-
traction can clean some cores, while it had Wt3e effect
for other ones, such as the strongly oil-wet Bradford cores.
Therefore, because tolueneextraction will alter the wet-
tabilky and relative permeability of many. native-state
cores, m%uremcnts shouId be tie on mtive-state cores
before toluene extinction.
One problem with a cleaned core is that it is sometimes
difficult, if not impossible, to remove all of the adsorbed
material. If this occurs, the wetta.bfity of tie cleaned core
wifl be left in some indefinite staie, causing variations in
core analyses. Grist et al. lW cleaned cores by three cu-
rently used methods and then examined how ROS and end-
point effective permeabilities vtied after a waterflood.
ROS was very similar for W methods. However, the end-
point effectiye water permeability varied by more than
a factor of three betwtin different cleaning methods. Their
explanation for this behavior was that some methods were
able to extract more of the adsorbd. components, leav-
ing.the rock more water-wet. In the more water-wet cores,
the rwidti oil had a greater tendency to form trapped
droplets, blocking pore throats and lowering water per-
meabtity. The least effective of the three cleaniug me~ods
was overnight reflux extinction with toluene. More ef-
fective was reflux extraction with toluene followed by 2
days of extraction with a mixture of cbloroforin oud
methanol. Finally, tie most efficient method was reflux
extraction with tcduene followed by 3 weeks of extrac-
tion with chloroform and methanol. In the last stage of
cleaning, methanol was used alone.
Journalof PetroleumTechnology,October1986
 Another draivback of cleaned cores is that it is occas-
sionafly possible for cIeaning to change an originally
water-wet rock to an ofi-wet one. The extraction process
may quickfy boil off the connate water, allowing the re-
maining oif to contact the rock surface and form oil-wet
deposits that are afmost impossible to remove. 187
The cleaning experiments discussed examine the best
methods to remove. cmde oil constituents from the pore
walk. In many cases, core is also contaminated with drill-
ing mud surfactits, which mustalso be removed before
the wettabifity of acore can be restored. 12ar129The best
choice of solvents depends on the crude, the mineraf s~r-
faces, and the drilfiig mud surfactsnts. Gant and
Anderson 129cleaned Berea sandstone and Guelph (Bak-
er) dolomite plugs contaminated with an invert-oil-
emufsion rfrifling mud. filtrate. The best solvent fOr bOfh
rock types was a 50/50 mixture of toluene/methanol, oi
the equivalent, containing 1% ammonium hydroxide. A
three-step method (three successive Dean-Stark
extractions-toluene, foffowed by glacial acetic acid, fol-
lowed by ethanol) was the second best choice for Berea,
while 2-methoxyetiyl ether was the second best choice
for dolomite, demonstrating that the choice of solvents
can depend O? the mineral surfaces in the core.
Restored-State Core
,
If one conld be positivethat the original reservoir wetta-
bilhy hadizotbeen inadvertently modified, a native-state
core would give resnks closest to those of the reservoir.
However, riative-st@ecores present scveraf problems. The
necessary procedures to preserve the wettabtiq are
troublesome and time-consuming. Even when sll of the
precautions iwe tsken, there is still a possibility that the
nettability has been chtiged through oxidation or through
deposition as tie temperature and pressure dropped when
the core was brought to the surface. In addition, tic ques-
tion arisesabout tie procedure to follow to obtah the most
reliable information from cores in which the nettability
WaS aftered
When onfy core with alt&ed wei@bfity is available,
the best possible mukiphase measurements ore obtained
by resto& the resefioir wettabfi~ with a three-step
~roces~. 47,F0,64,65.,96,115,128,130,1S0,18SThe f~st ste~ is to
~leaa the core to rernoVeall compounds from th~ rock
surface. After the core is cleaned, the second step is to
flow reservoir fluids into the core sequentially. F~y,
the core is aged at the reservoir temperamre for a suKL-
cient dine b establish adsorption equilibrium. Seversl ex-
perimenters have compared measurements made on core
in the native, cleaned, and rsatored states. In each experi-
ment, measurements in the restored state were slmost
identical to the,previous mtive-sta.te ones,demons@atin
that this procedure will restore nettability. 50,115Js0;18~
~,, The first and most @fficult step in nettability restora-
tion is to clean the contaminated core by use of the
methods described to remove all compounds adsorbed on
the surfaces and to make the core as water-wet as possi-
ble. All compounds must be removed from the core be-
cause we have no knowledge of which compounds were
adsorbed on the undisturbed reservoir rock and which
were deposited afterward. The USBM or Amott netta-
bility measurements are used to verify that the core is
strongly water-wet., Unforttzmtely, detemining which sol-
vent wiII successfoffy clean the core is still a trial-and-
Iourmt of Petroleum Technology, October 1986
Fig. 1Wettabitity changes for a restored-state core and
the effects of flushing restored-state cores with refined
OIIS. Berea core and Big Muddy crude.
error process because the best choice of solvents depends
heavily on the crude oil, the mineraf surfaces, and any
&idling mud contaminant. Further discussion can be
foundin Ref. 129.
In the second step, sequentially flowing reservoir fftids
btto the core, the core is saturated with deoxygenated syn-
thetic or formation brine and then flooded with crnde oil
to simnla.tsthe intlow of oil into the resemoir. When cmde
oil for wettahifity restoration is obtained, precautions
should be taken to minimize alterations to the crude. The
hnple must be taken before tiy Sm&ct.mrts or Ofier
chemicals ae added to treat the crude. It should be taken
as Iong as possibIe after any wefl treatments to aIIow time
for these chemicafs to be flushed from the well. Finally,
the cmde should be sealed in air:tight containers as soon
as possible to minimize oxidation and the 10SS of light.
ends.
The fired step in wettsbfity restoration is to age tie core
at the reservoir temperature for a stilcient time to es-
tablish adso~tion e&libzium. The aging time required
to re-eatabfish reservoir nettability varies, depending on
the crude, brine, and reservoir rock. Generally, we feel
&at core shoufd be aged for 1,000 hours (40 days) at the
reservoir temperature. 128This a&ng period was chrken
for two reasons several experiments have shown that up
to 1,000 hours is required to reach wetting equilibri-
um ~$s. 115,189-lgl and 1,000 hours is roughly the length
of ~me required for the contact ~gle measnred on a flat
surface to approach its equilibrium value. 7>26,34.191 III
some cases, the restoration time can be significantly less
than l,OW hours. MunganlsO was able to restore the wet-
tabilky after aging for 6 days, while the nettability of the
rocfuoilhine system used by Schmid50 and Riibl et
~. lss was restord after only 3 days. Salathie147was able
to restore a mixed-wettabilhy qate to samples after 3 days.
Cuiec et al. 130describes two reservoirs in which the wet-
tabtity was restored after only a few hours, with no fur, <
ther cbamges in tie wettabiIity for aging times as long as
1,000 ho;rs.
There are two basic options to determine the aging time
to restore wettabllitv. We feel that it is ,most convenient
to age afl cores for l:W hours, which is roughly the mm-
imum time that the experiments discussed previously re-
quired to achieve wetting equilibrium. While cores may
1137
 be aged for a period longer than the minimum necessary,
thk is not a serious drawback because the aging cores re-
quire minimal attention. Another possibtity is to deter-
mine the minizhtzmaging time by measuring the wetrabfity
of the core with the USBM or Amen methods at frequent
intervals during the aging period. The aging is stopped
when the wettabflity reaches its cquilibtium value.
Although this minimizes aging time, it is much less con-
venient because it is labor intensive nnd requires frequent
disturbances to the plug.
The core is aged at either the reservoir pressure with
live cmdeso, 180,188,191or ambient pressure with dead
cmde. 115.128.190 When live crude oils a~d the reservoir
pressure are used, the solubflities of the wettabilhy-
altering compounds should have their reservoir values.
It is possible that the nettability will differ when dead
cmdes .at nmblent pressure are used. At the present time,
however; it is not known whether the difference is im-
portazm
Fig. 1 shows the chsnges in the USBM wettabfity in-
dex as a core was restored. * A series of Berea plugs was
saturated with brine and driven to IWS by centrifugation
in crude oil. Each core was aged in dead crude for a differ-
ent period, of time, after which the USBM wettabtity was
measured. As can be seen, the wettabilky changed from
water-wet (W =0.8) to moderately oil-wet ( W= O.3)
over a 40-day period. The plugs flushed with Soltrol@
and Blnndol@ will be dkcussed later.
Lorcnzetal. 190and Cuiec65 found tbatitissometknes
possible to speed up the approach to wetting equilibrium
by saturating.thecore with oil alone. The approach to
equilibrium is fastix because the polar compounds no
longer have to dlffase across a water layer to adsorb on
the rock. This procedure should be avoided, however, be-
cause it can give iriaccuratc results. For example, con-
sider the restoration of a core that originally had
Salatbiels47 mixed wettab~ity, where &e large pores are
oil-wet nndthesma!.l ones are water-wet. During tbeag-
ing process, thesmall pores must contain comate.water
to prevent the deposition of au oil-wet fiim, leaving them
water-wet. Onthe other hand, ifaclcan core is saturated
only with oil, tbe entire core, includlu gtbesmallpores,
will become uniforndy oil-wet, whlchis the wrong wet-
tability. Anaddhionalp roblemw ithsaturadngt iec ore
solely with oil istbat the effects of brine chemistry are
ignored. As discussed previously, the wettabtity of the
core depends on the ionic composition and pH of the brine.
Finally, Clementz10?.120,121$howedtbat flowing cntde
oiltbrougha dry core camcause tbeformition of very
stable oil-wet, claylorganic complexes. Thepresenceof
an initial water film on the clay surfaces haa been shown
to reduce but not completely inhibit the adsorption of the
nettability-akering materkds. @@.70 The effects of brine
OtI wearability make it necesssry to saturate the core with
brine, then oil, during the nettability restoration process.
Experimental Conditions
Once a mtive or restored-state core is obtained, core anal-
yses can be performed. These tests can be mn with either
crude or refined oil at ambient or reservok temperature
and pressure. Because wettabfity effects are being ig-
Personalc.mmlcati.nwl,hD..J.Wendel,Pe!r.aleum
TestingSeMceS,Smta
Fe SPringS,CA,No.19S0.
1138
nored, cleaned cores are generally mn with refined oif
(or even mercury or air) at room temperature and pres-
sure. From the viewpoint of titaining the nettability,
the best laboratory tests should be mn with native or re-
stored cores at reservoir conditions with live cntde oil and
brine because this is the best simulation of reservoir con-
ditions possible. Cor~ are generally more water-wet .at
rese~oir conditions tbzn they are at rooin temperature
ad pressure, 62,180,192-195 The effects of the following
experimental conditions on nettability will be dkcussed:
(1) rcaervoir vs. room temperature, (2) live vs. &ad cmde
at reservoir pressure, and (3) refined vs. crude oils.
Changing the temperature has two different effects, both
of wtich tend to make the core mom water-wet at higher
temperamres. First, an increase in temperature tends to
increase the solubtity of wettabtity-altering cOm-
pounds. 196 some of ~eSe compounds will even desorb
from the surface as the temperature increases. Second,
the IFT and the contact angle measured through -bewater
will decreaae as the temperate increases. This effect has
been noted in experiments with cleaned cores, minernl
oil, and brine, where it was found that cores at higher
temperatures were more water-wet even though there
were no compounds that could adsorb and desorb. 19-2?
For example, McCaffery201 measured the water-
advancing contact angle on qWrtz of n-tetradecane and
brine. The amglewas about 40 [0.7 rad] at 77F [25C],
but decreased to about 15. [0.3 rad] as the temperature
was raised to 300F [150 C].
when live crude oils at the reservoir pressure and tem-
perature are used, the solubilities of.dzewettabfity-afteting
compounds have their reservoir values. The use of dead
crude at ambient or reservoir prcasure may change the
nettability kmzse the properties of the crude are altered.
Light ends are lost from the crude, while the heavy ends
are, less soluble, which may make the core more oil-wet.
However, the effects of pressure are not known at pres-
ent. The two reported experiments found that ressure
is much less important than temperature. 18~,1~ Hje~.
meland and Lamondo 192 found little difference in con-
tact angles measured using stock-tank vs. live cmde at
the reservoir temperature (190F 88C]) and pressure
(3,800 psi [26.2 MPa]). Mtmgan 10 i measured a water-
advancing contact angle ,of $7 [1.5 rad] using live reser-
voir crude and synthetic formation brine at resemok tem-
perikurc (138F [59C]) and pressure (1,200, psi [g.3
MPa]). The water-advwcing contact angle was almost
identical, 85 [1.48 rad], using degassed crude and brine
at ambient pressure and reservoir temperamre.
Because refined oifs are much easier to work with tlum
cmde, it is a common laboratory practice to flush native-
or restored-state cores with refined oil before testing.
However, there is a possibilky that this idters the netta-
bility. Craig7 poshdated that it would be possible, once
the original wettabtity was restored, to use refined nzin-
eml oil in place of crude oil in laboratory tests without
adversely affecting the wetk+bility. Test times are shor!
compared with the time it takes to achieve adsorption equi-
librium and obtain native wettsbtity (about 1,000 hours).
Craig hypothesized that the desorption of wettability-
Mbzencing materials would require a correspondingly
long period of time. If this is correct, @e orig@l wetta-
btity wotdd be unchanged if laboratory tests using refined
oil and brine were conducted quickly enough.
Journal of PetroleumTechnology,October1986
 The onfy experinient to teat this hypothesis that we are
aware of was conducted by Wendel. * He aged ,Blg Mud-
dy crude in Berea sandstone at IWS to develop his
restorer-state cores. The cores. were flushed with one of
two refinkdoik, Soltrol 170 or Bkmdol, to detexmine how
they affected the wettabfily. The results&e show in Fig.
1. Bkmdol did not si@ficantly affect the we~btity, while
Soltml 170 changed tbe core from oil-wetto neutrally wet.
The wettabdity: alteration could be caused by either
surface-atilve impurities in the Soltrol 175or desorption
of previously depositwj oti-wetdng crude compounds from
the pore walls into tie Soltrol. It i; not known which ex-
planation is correct. Wendel did not attempt to fflter the
refined oils tfmugh a cbromatogmphic coltmm tn remove
surface-active compounds. These contamiim ts are known
to have a large effect on corit.w-migle measurements,
which are extremely seyitive to small amounts of con-
taminants. Wettabifity measurements in core should be
less sensitive, however, because the ratio of smface area
to volume is much higher.
Conc133sioris
1. The nettability of a rsaeryoir ample affects ita capil-
lmy pressure, relative pe,rmwbtity, waterflood behavior,
dispersion, mid electrical properties. fn addhion, simu-
lated teftiary recovery can be 51ter,cd.The tcfi,~ recov-
e~ PrOcesses affected by we~biE~ include hot-water,
surfactant, miscible, aid caustm floodlng.
2. Cleaned, strongly water-wet cores should be used
onfy in such c6re analyses as porosity. and air permeabil-
ity, where the wettabilky is unhpportmrt. h addition, they
may be used in other tests when the reservoir is known
to be strongly water-wet.
3. The nettability of originally water-wet mineral sgr-
faces can be altered by the adsorption of pokw compounds
aui/or the deposition of orgariic rnattertlmtwas origi-
MUY in the crude oil. Fmrfactants in the crude oil are
generally believed to ,be polar compounds that contain
oxygen, nitrogen, ,mdlor sulfur. These compounds ~
most prevalent in the heavier fractions of crude oil, such
as the resins and asphaltenes.
4. Nettability alteration is determined by the interac-
tion of the oil constituents, the mineral surface, and the
brine chemistfy, including ionic composition and pH. In
siIicafoiVbrine systems, trace amounts of mukivalent me-
M. cations can alter *e nettability. The catiom can reduce
the solubti~ of crude oil surfactants and/or activate the
adsorption of aniotiic surfactants onto the silks. Mfdtiva-
lent ions :$tathave altered tie wettabfity of sihcafoil/brine
systems tnclude Ca2, .Mg2, Cu2, Ni2, and Fe3.
5. Work on mineral flotation indicatca that coal,
graphite, sulfur, talc, the talc-liie silicates, and many sul- Acknowledgments
tidca are probably naturally,neutrally wet to oil-wet. Most
other minerals-includhg quartz, carbonates, and
sulfatesare strongly water-wet in their natural s@.te.
6. Contact-angle measurements suggest ti.at most car-
bonate reservoirs range frpm neutralIy to oil-wet as a re- References
sult of the adsorption of surfactimts from the crude oil.
7. Very little work has been reported about the changes
in wetibility caused by drioiig mud addhives. Three
different Cciring.flrtidshave been recommended to obtain
native-state core: (1) synthetic formation brine, (2) un-
-PemmalmmmunlcatimwilhD,J.Wend.at,PetroleumTestingS6wkeS,Santa
Fe SP,ingS,GA,N.. 19S0,
oxidized lease crude oil, or (3) a water-based mud with
a minimum of iddkives. B&use of surfactits in the SYS-
tern, no conimercitiy available oil-based or oil-ernukion
muds are khown that preserve the native wt?ttability.
8. The wetr?bility of a native-state core. cambe altered
by loss of light ,ends and/or the deposition aid oxidation
of heayy ends. TWOalternative pac@ging procedures cam
be used to miniinize these effects. The first is to immerse
the corei in deoxygenatdd formation or synthetic brine
and place !hem in a glass-lined steel or plastic tube, which
is then seaIed against leakage aud the entrance of oxy-
gen. An alteinaiive procedure is to wrap the cores at the
welksite in polyethylene or pglyvinylidene fdm and tien.
in ihunirimn foil. The wrapped pore is tlyn coated with
i+thick layer of paraffin or a plastic sealer.
9. Because of the increased solublky of the wettability-
altering compounds at the higher temperature spd pres-
sure, the cmde-odtbrinetcore system is usually more
water-wet at reservoir condition than at ambient con&-
tions. In addition, the contact angle measured tluough the
water will generslly decrease as the tempetatufe is in-
creased, and the system will become more water-wet,
even if no surfactauts are present.
10. Extraction with toluene cti alter the wettabil.ity of
some iiative-state cores, causing someinitially neutrally
wet or qikfly oil-wet cores to become strongly water-wet.
Measurements on native-state iorei should be made be-
fore toluene extraction.
11. During the attempted restoration of a cleaned core
to ita orig$al wetrabtity, the core should be saturated with
brine, @lflooded, md then aged at the reservoir corrdi-
tiom for 1,COOhours. This will embie a inixed-wettabtity
condhkin to be restored, if thk was the original wettabd-
ity. In addition, it will allow the brine chemistry to influ-
ence tie r~tored nettability. An alternative procedure,
which completely saruratea the core with cmde oil, should,
be avoided.,
12. The three commonly used methods for artificially
conrrolEng wettabfity during laboratory experiments are
(1) treatment of the core with chemicals, generally or-
ghocblorosilane solutions for sandstone. cores and
naphtbenic acids for carbonate cores; (2) using sintered
teflon cores with pure fluids; and (3) adding surfacmnts
to the fluids. To obtain a uniformly wetted core, a sin-
teredteflon core with pure fluids is preferred because its
nettability is more constant and re reducible than the wet-
tabilby of cores treated WI# organochlorosilanes,
naphthenic acids, or smfactants. However, these treat-
ments have advantages when heterogeneous wettabllity
or nettability alteration isstudied.
I w grateful to Jeff Meyers for hk many helpful sugges-
tions and comments. I also thank the management of
Conoco h.c. for permission to publish this paper,
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....,
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?x9-31q.
167. Mmrgan,N.:`7n
terfaciaJEffecLsinkmniscibleL@id-Li quidDis-
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hfE, 237.
168. Mngam N, and Moor6, E,J.: Certai Wetlabilily Effectson
ElecfriwJ Resisfivityin Porous Media, J. Cdn. Per. Tech. (Jm.-
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169, Zisman, W.A.: RelationoftheEq.ilibri.mC onIactAngleto
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170. Michaels, A.S. and Timmins, R.S.: ,Chromatogsa@dcTinns-
Prl of Reverse Wetting Agents and 1S Effect on Oil Displace-
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171. Michads, A. S., StanceII, A., and Porter, M. C.: Effect of Chro-
matographic Transpoti in Hexylandne on Displacement of OiJby
Wateri Pom.s Media,, >SPEJ (Sept. 1964) 231-3% Trans.,
.4M13, 231.
172. Michaels, A.S, and Pmter, M.C.: L`Water-OilDqbicemenmfmm
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179. EJufich, R., and WygaJ, R.J.: kkxektio.. ofCmde0llmd
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Water SZurationand Relafive Permeability of Unconsolidated
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on Dmimge CapiJkuy Pressnre in Rocks Using a Modified Cen-
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1143
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tit AngI~ at High Temw#ure and Fmsyre, J. C&. Pet Tech. Dec. %,19%. PW.raCCePted f.r P"bU.atlon J"ly23,'19ffi. Rmn&mm"9CtiPt Te-
(J.ly-Sept. 1972) 11, NO. 3,26-32. . ,. ceived Feb.3, 1986.

1144 Jomtiof Pewoleum Te&olo~, October 1986

Nettability Literature Survey
Part 2: Nettability Measurement
William G. Anderson, SPE, Conoco Inc.

5?E 13933

Summary. Many methuds have been used to measure wettabtity. This paper describes the three quantitative
methods in use to&y: contact angle, Amott method, and the U.S. Bureau of Mines (USBM) method. The
advantages and fimitationa of alf the qualitative methods-inrblbition, microscope examination, flotation, glaas
slide, relative permeability curves, capilkmy pressure curves, capiffarinretric method, displacement capillary
pressure, penneabiLhy/saturation relationships, and reservoir logsare covered. Nuclear magnetic resomnce
(NMR) and dye adsorption, two methods for measuring fractional wettabflily, are also discussed. Fdy, a
metbud is proposed to determine whether a core haa mixed wettabilhy.

Introduction
Thispaper is the second in a series of fitcrature surveys
covering the effects of nettability on core analysis. 1-3
Changes in the wettabtity of cores have been shown to
affect electrical propertica, capillary pressure, waterflood
behavior, relative penncabtity, dispersion, and simulated
EOR. For core analysis to predict tbe behavior of the
reservoir, the nettability of the core must be the sime
aa the nettability of the undisturbed reservoir reck.
When a drop of water is placed on a surface immersed
in oil, a cuntsct angle is formed that rsngis from Oto 180
[0 to 3.14 rad]. A typical oil/water/soIid system is shown
in Fig. 1, where the surface energies in the system are
reIated by Youngs equation, 4
am Cos 19=uo$-u . . . . . . . . . . . . . . . .. . . (1)
rad], the greater the wetting preference for one fluid over
another. If 8 is exactly 90 [1.6 rad], neither fluid
preferentially wets the solid. As shown in Table 1, when
O is behveen O and 60 to 75 [0 and I twl.3 rad], the
system is defined as water-wet. When 6 is between 180
and 105 to 120 [3.1 and 1.8 tu 2.1 rad], the system is
defined m oil-wet. In the middle range of cnntsct angles,
a systcm is neutrally or intermediately wet. The contact
angfe that is chosen as the cutoff varies fmrn paper to
paper.
The term am n., is sometimes called the adhesion
tension, LTA 5:
~A=v m Ows=aowcose. . . . . . . . . . . . . . . . ...(2)

where The adh+ion tension is positive when the system is water-

aow = interracial energy [interracial tension (IFT)]
between the oil and water,
LTO,= interfaced energy between the oil and
did,
o~, = interracial energy between the water and
solid, and
9 = contact angle, the angle of the
waterloillsolid contact line.
By convention, the contact angle, O, is me~ured
tbrougb the water. Tbe interracial energy uOWis equal to
o, the IFT.
As sbowmin Fig. 1, when the contact angle is less than
90 [1.6 rad], the surface is preferentially water-wet, and
when it is greater than 90 [1.6 rad], the surface is
preferentially oil-wet. For almoat all pure flrdda and clean
rock or F&shed crystal surfaces, IJo, and UWhave values
such that O=0 [0 rad]. When compounds such as crude-
oil components are adaorbed on rock surfaces, these in-
tcrfacisl energica arc changed unequalfy. fMs changes
Oand hence the wettabtity. The farther Ok from 90 [1.6
CQwrmltsm %e~.! Pemleum
Em.e.=
wet, negative when the system is oil-wet, and near zero
when thesystem is neutmfly wet.
Mathods of Wettabitity Measurement
MaJJy different methods have been proposed for meas-
uring the wettabtity of a system. 616 They include quan-
titative methods-contact angles, imbibition and forced
displacement (Amott), and USBM wettabfity method
and qualitative mcthoda-imbibition rates, micmscope ex-
amination, flotation, glaas slide method, relative p&rnre-
abdity curves, penneabilitykdumtion relationships,
capillary pressure curves, capiflmimetric method, dis-
placement capif.larypressure, reservoir logs, nuclear nrsg-
netic resonance, and dye adsorption.
Although no single accepted method exists, tbrcc quan-
titative methods generally are used: (1) contact-angle
measurcnrent, (2) the Amntt 6 method (imbibition and
forced displacement), and (3) the USBM method. g.17.18
The contact angle mcasurea the wettsbilhy of a spccitic
su$ace, while the Amott and USBM methods measure
the average wettsbility of a core. A comparison of the
wettsbllhy criteria for the three metbuds is shown in Ta-
ble 1. we remaining tests in the fist are qualitative, each
with somewhat different criteria to determine the degree
of water or oil wetness. Unfortunately, tbk leads to am-

1246 JourmJo! PetroleumTechnology,November1986

bigrritieswhen expainrenta in the literature are compared.
Many of the wettsbfity measurements arc alao imprecise,
partimdzrly near neutral nettability. One, method may
show that a core is mildly oil-wet, while soother shows
that the core is mildly water-wet. In tlrk paper, the differ-
crrt methnds of wettabfity mcaaurement are described, be-
ginning with the quantitative methods. The more
qualitative methods are then described, followed by the
metfroda for measuring the nettability of fm@onal and
mixed-wettabfity cores.

Quantitative Nettability Measurements

Contact Angle. The contact angle is the best wettabiity
rncasurement method when pure fluids and artificial cores
are used because there is no possibility of surfactants or
other compnrmda aitcring the wettabthy. The method is
also used to determine whether a crude oil can alter wet-
tabilhv and to examine the effects of temperature. ures-
sure, and brine chemistrv on wettsbility~ Howe&, as
discussed in more detaif _latcr, some dlff%ultiea arein-
volved in applying contact-angle meaaurementa to reserv-
oir cores. Marty methods of contact-angle measurement
have been used. They include the tilting plate method,
sessile drops or btibbles, vertical rod method, tensiomet-
ric method, cylinder method, and capillary rise method.
Descriptions of these methods can be found irr Admn-
Son>4 Jobnaon and Dettre, 19 Good, 20 Neumann and
0ood,21 and Popiel. 22 MO~t of these methods are nOt
generally used in the petroleum industry, however, be-
cause they are better suited for pure fluids with no ad-
sorption or desorption of surfactants. Because of the
surface-active agenta in crude, a significant length of tine
is needed for a contact angle to reach equ~lbrium.
The methods that aregenerally used in the petroleum
industry are the sessile drop method 21.23-25and a modif-
ied form of the sessile dro method described by Iezch
ef al. 26 and Treiber et al. ! 7 In both methods, the nrin-
eral crystal m be tested is moumcd in a test cell compixed
entirely .of inert materisls to prevent contamination. The
sessife drop method uses a single flat, polished mineraf
cryataf (see Fig. 1). The modified sessife drop method
uses two flat, polisbcd mineral crystals that are mounted
parzllel to each other on adjustable posts, as shnvnr irr Fig.
2a. Becauae sandstnnea are ohcn composed primarily of
quartz and limestones of calcite, quartz or calcite crys-
tals are used to simulate the pore snrfaces of the reser-
voir rock. Obviously, the nettability of clays in the
reservoir cannot be examined tit-h this method.
The first step in mcastuing contact angle is to cl+ the
app~ams thoroughly, because even tmce arnounta of cOn-
tammants can alter the contact angle. Then the cell cOn-
F1.a. 1Wettabilitv of the oil/water/rnck svstem. 16
tainin~ the mineral crystals is tilled with brine.
DenW-gemted synthetic ~ormztion brine is used to pre-
vent the introduction of foreign metal ions, which irrcon-
centrations of only a few parts per million can alter the
~e~bfi~.127 For the mOdifid aessile chop method, an
oil drop is placed between the two crystals so fhat it con-
tacts a large area of each crystal. After the oil/crystal in-
terface hzs aged for a few days, the two crystals are
displaced pamflel to each other. As shown in Fig. 2b, this
shifts the oil drop and allows brine to move over a por-
tion of the surface previously covered with oil. The corr-
tact angles measured in this fashion are called
water-advancing contact inglea. A nonequilibriunr an-
gle is obacrvcd inrmediately.after the drop is moved. Thk
angle decreases for a day or two until a constant value
is obtained for that age of the oiUsolid irrterfacc. The
oilhnineral surface is then aged further, the water is ad-
vanced again, and a new value is obtained.
The procedures sre similzr in the sessife drop methnd.
A drop of crude oil is formed at the end of a fine capil-
lary tube and brought into contact with the flat mineral
surface (see Fig. 1). The droplet is allowed to age on the
surface. The water-advancing and water-receding contact
angles are measurd by usirrg the capillary tube to expand
zrrd contract the volume of the cmde-oil drop. 23,24
When the crude oil containa naturaf surface-active sub-
stances; the water-advancing contact angle increases aa
the OiUcrystafinterface ages, approaching a iimhing value
as adsorption equilibrium is reached. To achieve this liit-
ing vahre may require hmrdrcds or even tbOm~ds Of
hours of interface-aging time. Fig. 327 gives examples
of tbe change in the water-advancing contact angle as the
oilholid interfke ages. This demon~es that early mcaa-

TABLE 1APPROXIMATE RELATIONBHIP BETWEEN WSTTABILITY, CONTACT ANGLE,

AND THE USSM AND AMOTT WETTABIUTY INDZXES

Water-Wet Neutrally Wet Oil-Wet

Contact angle
Minimum 00 60 to 75 105 to 1200
Maximum 60 to 75 105 to 1200 160
USBM nettability index W naar 1 W near O W near -1
Amott nettability index
Displacement.by-water ratio Positive Zem Zero
Displacement-by-nil ratio Zero Zero Positive
Amoti-Harvey nettability index 0.3s/s1.0 -0.3 </<0.3 -1.0</s -0.3

Joumal of Peuoleum Technology, .November 1986 1247

 ~ 1
:E
i CRKiTAL
I
WATER OIL
/
CRYSTAL
/
l. ____.. __J
[a)
Hysteresis resulting from surface heterogeneity can be
1- .1
I compounds. This problem is generally avoided by mcas-
I @g tie angle on a singfe crystal and by rigorously &an-
I fluid motion necesssry for the contact angle to reach ita
I factant from the soIid/Iiquid interface into the brdk liquid
1~
L__.___; (b)
I Fig. 2Contar$angle measurement. 7 I
urements can show that the system is water-wet even
though it is actnally oil-wet at equilibrium. Because it con-
tains no surfactmrts, the contsct angle for pure &cane
(Curve A) did not change from zero as the interface was
aged.
Orie problem in contact-angle measurements is hyste-
resis, because it is genirally found experimentally that
a liquid drop on a surface cm have msny different stable
contact angles. The contact angles reported in the litera-
ture sre either the water-advancing or water-~~g FOn-
tact angle because these two angles are the most
reproducible. Tbe water-advancing angle cmr also be
thought of as the oil-receding one. The advmrcing angle,
Oad,, is measured by pulling the periphery of a drop over
a surface, while the reding contact angle, @~; is meaa-
ured by pushing it back. The dMference, O,~, - @,e., is
the contact-angle hysteresis snd can be greater thsn 60
[1 rsd]. 19
Johnson and Dettre 19 and Adanrson4 state that there
appear to be three causes of contam-zngle hysteresis: (1)
smface roughness, (2) surface heterogeneity, and(3) sur-
face immobility on a macromolecular scale. To see how
surface ruughness can cause hysteresis, consider a
horizontal but rough plate. Because tie rough surface con-
tains pesks and vslfeys, a liquid drop WY generslly be
attached to a surface that is not horizontal. The macm-
scupically observed contact sngle will not be the same as
the true contact angle on a microscopic scale. The rough-
ness of the surface will 2U0w a large number of metaata-
ble states of the drop to exist with different contact angles.
The surface roughness wilJ generally diminish the appar-
ent cuntsct nn e for water-wet mck and increase it for
oil-wet reck. 19 ,22
1248
*~ l-&#.
..
Fig. 3-Approach to equilibrium contact angla.m I
caused by either heterogeneity in the rock surface com-
position or differential adsorption of wettabifity-akcring
mg the entire appsmms before measurement. Finslly,
surface immobiihy can cause hysteresis by preventing the
equilibrium value. For example, slow adsorption of a arw-
can cause hysteresis. Some cmde oils w even form a
solid film at the oil/water interface. 2s-30Tlwse Iihna sre
particularly likely to form if the crude has been exposed
to oxygen, but have even been found in some anaerobic
cmdes.
Even though it is possible, with great care, to get exact
and reproducible contact-mrgle measurements, the ques-
tion of how representative these results are of the wetta-
btity of reservoir core arises. The contsct angle cannot
mke into account rhe roughness, heterogeneity, and com-
plex geometg of reservoir reck. First, consider the prob-
lems caused by muglrness. Morrow31 bsa pointd out that
roughness and pore geumetry will intluence the
oiJ/water/solid contact line and can change the apparent
contsct srrgle. On a smooth surface, the contact angle is
tixcd. On the sharp edges found in reservoir rock, how-
ever, this condition is relaxed, and there is a wide range
of pussible contsct angles. 31.32Morrow postulates that
most of the oillwatcrfrock contact limes will be located
at the sharp edges because, at these edges, the cuntact an-.
gle can change without movirr~ the position of the con-
tact line.
A second problem with applying contact-angle meas-
urements to reservoir rocks is that the contact angle can-
not take into account the heterogeneity of the reck surface.
Contact angles sre measured on a single mineral crystal,
while a core contains many different constituents. As dis-
cussed preciously, surfactmrts in the cmde can affect the
wettzbility of the sands and clays differently, causing
localized heterogencmrs wettabifity.
A Wlrd limitation is that no information can bs gaind
about the presence or absence of permanently attached
organic coatings on reservoir rocks. 33 These films can
be detected ordy by making other nettability measure-
ments. This is particrdsrly importrurt when workirrg with
~e~mr~-mte ~ores. 3435 Before the original we~bfity
can be restored, all the adsorbed materials must be re-
moved, wbicli will generally leave the cure in astfongly
water-wet stste. The only way to determine whether the
cleaning prccess b+ been successfid is to measure the wct-
Jo.mal of Petrol..m Technology,November1986
 tabiilty of the cleaned core. If it is not strongly ivater-
wet, addhional cleaning is necessay.
AIuott Method. The Amott method 6.8.36combines im.
hibition and forced displacement to mcaaure the average
wetmbili~ of a core. Both reservoir core and fluids can
be used in the test. The Amott method is baaed on the
fact that the wetting fluid will generally imbibe spontane-
ously into the cure, dkplacing the nonwetting one. The
tatio of apontaneouaimbibition to fumed imMbition is used
tu kduCe the influence of other factors, such m Elative
permeability, viscosity, and the initial saturation of the
rock.
Core is prepared by centrifuging under brine until the,
residwd oil saturation (ROS) is rcabhed. The Amott wet-
tabilhy measurement then consists of the following four
atcps: (1) immerse the core in oil, and meamre the volume
of water displaced by the spontaneous (free) imbibition
of oil after 20 hours; (2) centrifuge the core in oil until
the irreducible water saturation (lWS) is reached, and
measure the total amount of water displaced, including
the volume displaced by spontaneous imbibition; (3) im-
merre the core in brine, atrd measure the volume of 01
spontaneously displaced by imbibition of water after 20
hours; and (4) centrifuge the core in oil until ROS is
reached, atrd meaaure the total amount of oil displaced.
Note that the core may be driven to IWS and ROS by flow
rather than with a centrifuge. This is especially necessary
for unconsolidated material that cannot be centrifuged.
The tmt restdta are expressed by (1) the displacement-
by-oil ratio the ratio of the water volume displaced by
spnntatmms oil imbibition alone, VW,P to the total dis-
placed by oil imbMion and centrifugal (forced) displace-
ment, Vm,
~o=+, .............................(3a)
w,
and (2) the displacement-by-water ratio the ratio of
the oif volume displaced by spontaneous water imbibi-
tion, V..p, to the total oif volume dkplaced by itnbibi-
tion and ccntritkgal (forced) displacement, Vol:
L=+. .. . . . . . . . . . . . . . . . . . . . . ..(3b)
0,
..
As shown in Table 1, preferentially water-wet cores
have a pusitive displacement-by-water ratio and a zero
value for the displacement-by-d ratio. The displacement-
by-water ratio approaches 1 aa the water wetness in-
creases. Simifarly, oif-wet cores have a positive
displacement-by-nil ratio and a zero displacement-by-
water ratio. Both ratios are zero for neutrally wet cores.
Amott chose an arbitraty time period of 20 hours for
the spmmmeous oil and water imbibition steps in his
metbcd. If possible, we recommend instead that the cores
be allowed to imbibe until either imbibition is complete
or a time liit of 1 to 2 weeks is reached. imbibition can
@e from several hour.. to more tlIan 2 months to com-
plete. M If the imbibition is stop~d after a short period
of time, then the measured spontaneous itnblbition volume
will be lower than the equilibrium value for low-
Jaud of PetroleumTechnolo~,i%enber 1986
permeability samples, causing an underestimation of 60
or ~~. 8.36The mcaaurcd displacement ratios wilf under-
estimate tie water- or oil-wemess of the ruck. Of course,
it is necessafy to choose some upper time limit to finish
Ore measurement in a reasonable length of time. If the
core is still itnbibmg when the time limit is reached, how-
ever, then the measured spontaneous imbibition volume
will underestimate the rcaemoir wettabfity, and the AIZIOtt
ratios should be interpreted with caution. 8.36
A number of researchers37.3s used a modification of
the Amott nettability test called the AntomHarvey relat-
ive displacement index. This procedure haa an addi-
tional step in the core preparation before the testis run:
the cure is centrifuged first under brine and then under
crude to reduce the plug to fWS. The displacement-by-
water and dkplacenzent-by-oil ratios are then calculated
by the Atnott method. The Amott-Hawey relative dis-
placement index is the displacement-by-water ratio mi-
nus the displacement-by-oil ratio:
I=8W80=++. - . . . . . . . . . . . . . . . ...(4)
01 w
This combmes the two ratios into a single wettabflity
index that varies from + 1 for complete water wetness
to 1 for cnmplete oif wetness. Cuiec 39 states that the
system is water-wet when +0.3s I< 1, intermediate wet
when 0.3<1<0.3, and oif-wet when 1 S2S 0.3.
The Amott test measures the total volume of spnntane-
oua and forced oif and water imbibition. Morrow et al. a
developed a modified form of rhe Amott test, which nfao
measures the imbibition rates during the sfmntammus im-
bibition measurement. In tbk test, the core is suspended
in oil or water from an electronic bafance by a small
monofilament line. Weight change is monitored ac a tilnc-
tion of time as the spontaneous imbibition occurs. The
nettability of the core is then determined from both the
Antott weteabifity index and the spontaneous imbibition
rates. This test may offer snme advantage over the atan-
dad Amott tmt because it is based on additional .@ata.
The main problem with the Amott wetmbfity test and
ita modifications is that they are insensitive near neutral
wetmbfity. The teat measures the ease with which the wet-
ting fluid can spontaneously displace the nonwetting one.
However, neither fluid will apnntanemrsly imbibe and dis-
pkice the other when the contact angle varies tlom roughly
60 to 120 [1 to 2.1 rad]. 3.4145 In addition, the limiting
contact angfe above which spontammus intbibltion wilf not
occur depcnda on the initial saturation of the core.
McCaffery41 and Morrow and McCaffery4s examined
the spontaneous imbibition of pure fluids with a known
contact angle into a synthetic teflon core that initially cOn-
tained air. IiI the experiments, n-dodecane @=42 [0.7
rad]) wotid always spontaneously imbibe into the core,
while ct-bromomphtbalene (0=73 [1.3 rad]) would never
spontartermsly imbibe. Dioctyl erfrer (0=49 [0.9 rad])
would not imbibe into a dry core but would imbibe into
a core with an initial diomyl ether saturation of 30 %. Tbe
Amott method would classi@ the teflon core with n-
dodecane aa mildly water-wet, while c+bromomphtfmlene
would be neutmlly wet. The core with dioctyl ether
(6=49 [0.9 rad]) would be classified as water-wet if it
already conmincd some fluid or as neutrally wet if the
core waa initialfy dry.
1249
~

*
10
~ OIL WET LOG A,,A2=-O.5+ ~

.
I 00 0 I 00
iVERAGE WATER SATURATION, PERCENT AVERAGE WATER SATURATION , PERCENT
\
*

Ii NEUTRAL LOQA,/A~= 0.02

k/ERAGE WATER SAT URATION, \ PERCENT

!
lg. 4-USBM wettcbility measurement 9: (Ibrine drive. U-oil drive) (a) untreated core, (b) cora treated with organochlo-
osilanes, (c) core pretreated with oil for 324 hours at 140R brine contains 1,000 ppm sodium tripolyphosphdte.

USBM Wettabiity Index. The third quantitative test that
is used to measure tie nettability is the USBM test de-
veloped by Donaldson et al. 9,17,18The USBM test olso
measures the average nettability of the core. The test is
relatively rapid, requiring a few &ys to test four to eight
plugs. A major advsntage it has over the Amott wettabfl-
ity test is its sensitivity near neutral nettability. A minor
disadvantage is that the USBM wettabili~ index can only
be measured on plug-size samples because the samples
must be.spun in a centrifuge. The USBM test compares
the work necessary for one fluid to displace the other.
Because of the favorable free-energy change, the work
required for the wetting fluid to displace the nonwetdng
fluid from the core is less than the work required for the
oppsite displacement. It has been shown that the required
work is pro rtionsl to the area under the capillary pres-
aue ~umeY,46 ~ ~ti~~ ~~~~a, wh~~ a ..~~ is ~at~~.
1250
wet. the area under the bfinedrive cntdlkwv messure
cu~e (when the water displaces the oifj is srn~ler than
the area under the capillary pressure curve for the reverse
displacement. In fact, if the water-wetting is stiong
enough, most of the water wifl spnntmeously inddhe into
the core, and the area under the brine-drive curve will
be very small.
Before the testis mn, plugs are prepared by centrifi-
gation under oil at high speed to drive them to lWS. This
point is denoted by the satefiaka (*) in ,Flgs. 4a though
4c, which represent wettabfli~ test results in cores with
three tifferent sufface treatments. During the USBM
measurement, a modified version of the procedure de-
scribd by Hassler and Bnmner47 and Slobod et al. 4s is
used to calcnlate the centrifigaf capillary pressures. (The
USBM method uses the avefage saturations in the core. 17
J.o mntrsat, the centrifugal capillary pressure cufve is
Journalof PetroleumTechnology,November1986
based ontbe saturation at the face of the core, which is
czfculated from the ayerage saturation by the method
found in Ref. 47.) In the first step of the measurement,
cores are placed in brine and centrifuged at imcrementzl-
ly increasing speeds until a capilla~ pressure of 10 psi
[70 kpa] is reached. This step is known as the brine
drive becauae brine displaces oil from the core. At each
incremental capiflary pressure, the average saturation of
the plug iz calculated from the volume of expelled oif.
Curve I (Figs. 4a through 4c) is a pIot of capiIlary przs-
aure vs. the average saturation for the brine drive.
In the second step, the core is placed in oif znd cen-
trifuged. During this oil-drive step, oil dkplacea brine
from the core. As in the first step, the capillzry pressures
znd averzge saturation are measured until a capillary
pressure of 10 psi [70 kpa] is reached. In each czae, the
curves sre Iinezrly extrapolated or truncated if the last
pressure ia not exactly 10 psi [70 Wa]. The results of the
oil drive are plotted as Curve II in Figs. 4a through 4c.
The USBM method uses the ratio of zreas under the.
two capillary prezzure curves to czlctdate a we~btily in-
dex according to l?.q. 5..
w=10g(,4, /A*), . . . . . . . . . . . . . . . . . . . . . . . . ...(5)
where,4 ~ snd A2 we the areas under the oil- and brine-
drive curves, respectively. As shown in Table 1,. when
W is greater thzn zero, the core is water-wet, znd when
W is less that zero, the core is oil-wet. A wettzbilty in-
dex nezr zero mezns that the cure is neutrzlly wet. The
lzrger the absolute vzlue of W, the greater the wetting
preference.
Exzmplcz of water-wet, oil-wet, znd neutrzlly wet cores
sre shown in Figs. 4a though 4C for an initizlly water-
wet outcrop Torpedo sandstunc core. Fig. 4a shows the
USBM wettahility index of the untreated water-wet core.
The srea underthe oil-drive curve is much lsrger thsn
rhe zrez under fhe water-drive curve, yiehiing a wettz-
bility index of 0.79. In Fig. 4b, tbe core was treated with
zn organosibne compound, which rendered it oil-wet. Ike
zrea under the oil-drive curve is now much smzller thsn
the mea under the water-drive curve because oif is the
wetting fluid, yielding a wettabWy index of 0.51. In
Fig. 4c, the core was aged with crude, znd the brine wzz
treated with sodium tripoIyphosphate. The core is now
neutrzlly wet, znd both of the areas zre equal, mzking
the USBM wettabfity index zero.
A major advantzge of the USBM wettzbility test over
the Amott testis its sensitivity nenr neutrzl wettzbflity.
On the other band, the USBM test cannot determine
whether a system has fractions or mixed wettzb~ity,
while the Amutt test is sometimes senzitive. In some
fractional- or fixed-wet systemz, both water znd oil will
fiblbe frmly. 49-51me AMUti method will have pOSitiVe
displacement-by-wster znd displacement-by-d rstios, in-
dicating that the system is nonuniformly wetted.
Cumbined Amutt/USBM Methud. Sharma and
Wunder1ich51 bzve recentfy developed a modification of
the USBM method that ZIIOWS, the czdculation uf buth the
Amott ind USBM wettzbdity indices. The procedure,
shown in Fig. 5, haa tive steps: (1) initizl oil drive, (2)
spontaneous (free) imbibition of brine, (3) brine drive,
(4) spontanecma (free) imbibition of oil, znif (5) oil drive.
Journal of PetroleumTechnology,
November19s36
The zreas under the brine- znd oil-&lve curves zre used
to calcufate the USBM index, while the Amott index uses
the volumes of free and totzl water znd oil displacements.
During the initizl oil-drive step (Curve 1), the plugs are
driven to IWS. Next, the cores we immersed in water,
and the vulume of water that imbibes freely is measured
(Curve 2). During the brine-dive step (Curve 3), the aver-
age saturation of the plug is determined from the zmount
of expelled uil at each incremental capilla~ pressure.
These data zre used to cslculate the area under the brine-
drive curve, A2, for the USBM method. At the end of
the brine-drive step, the plug is left at ROS. The Amott
displacement-by-water ratiu, 5 ~, is the ratig of the oil
vulume displaced by free brine imbibition to the totzl
volume displaced by free imbibition znd centrifugzJ dk-
placement (Eq. 3a).
In the fourth step (Curve 4), the plug is immersed in
oil, znd the volume uf oil thzt imbibes spontaneously is
measured. The finzl step is the oil drive (curve 5), where
the czpillmy pressures znd average saturations are used
to czhxdate A, for the USBM method. Eq. 5 is then used
to calculate the USBM wettzbili~ index. At the end of
the oil drive, the plug is left at IWS. The Amott dkplace-
ment-by-oil ratio, 60, is the ratio of the free oil imbibi-
tion to the totzl volume displaced by free imbibkion and
centiitlzgal displacement (Eq. 3b).
There zre two advzntzges of the combined USBM/
Amott method over the stzndard USBM method51: tbe
resolution of the USBM method is improved by account-
ing for the saturation chznges that occur at zero capillary
pressure, znd the Amott index is ZISOcalculated. As dis-
cussed eadier, the AMOttmethod will sometimes indicate
that a system is nonuniformly wetted.
Qualitative Wettabiti,tyMeaaurementi
Imbibition Method. The most cummonly used qunMz-
tive nettability measurement is the imbibition meth-
od, 52.57because it gives a quick but rough idea of the
wettsb~hy without requiring zny complicated equipment.
The originzl imbibition appzrztus tested the wettabfity
at mom temperature and pressure. 52
More recently, Kyre er al. 57 described a modification
of the apparatus that zllows wettzbility to be measured
at reservoir conditions. In zn imbibition test, a core at
IWS is first submerged in brine undementb a graduated
cyliider, znd the rzte and zmount of oil dkplzced by brine
imbbitiun zre measured. The core ii strongly watier-wet
if l.zrgevolumes of brine are rzpidly imbibed, while low-
er rates znd smzller volumes imply a more wezkfy water-
wet core. If no water is imbibed, the core is either oil-
wet or neutrzlly wet. Non-water-wet cores zre then driven
to ROS znd submerged in oiI. The imbibition apparaNs
is inverted, with the grzduated cylinder below the core
to measure the rate and volume of water dkplaced by uil
imtdbltiom If the core imbibes oil, it is oil-wet. The
strength of uil-wetness is Miczted by the rste and volume
uf oif imbibition. If neither oil nor water is imbibed, the
cure.is neuuslly wet. Finzlly, some cores will imbibe both
water ~d ofi. 49-s] These cores hzve either fiaCtiOnidor
mixed wettab~ky. One problem with the imbibition
method is that, in addition to wettahiity, imbMion ratez
zlso depend on relative permeabfity, viscosity, IFT, pure
structure, znd the initial saturation of the core. 3,10 Fre-
quently, this dependence on other vzriables ia reduced by
1251
 1.0

0.8 -

0.6 -
zL

:
2 0.4-
$2
K
5 0.2-
5
# WATER
:

WATER SATURATION , % PV
(0)

0 100
1(
AvERAGEWATERSATURATION,
PERCENTW

Fig. 5Combhmd Amott/USBM method.51

comparison of the measured imbibition rate with a refer-

ence rate measured when the core is strongly water-wet.
To do this, the core is cleaned by heating at 750F
[400C] for 24 hours to oxidize alf of the organic materi-
al, leaving the core strongly water-wet. The core is then
remturated m ita origiual oiJ aatnration with a refined white
oil having the same viscosity aa the crude oiJ, and fhe
reference imbibition rate is measured. Denekaa et al. 53
~~~ nettability changes in terms of the relative rate
of Imbibitiorx
R=<, . . . . . . . . ... . . ... . . . . . . . . . . . . . . . ...(6)
m.
where
If = relative rate of imbibition,
A = initial imbibition rste of the cnre just after
it is submerged (cm3 /s), and
ritr = iuitial imbibition rate of the cleaned,
strongly water-wet core (cm3 Is).
If,the core is water-wet, m is the initial water imbMiOn
rate. If the core is oil-wet, ri is the initial oil imbibkion
rate, and the relative imbibition rate, R, is reported as
a negative number. Note, however, that whife the use of
a reference rate reduces tie effect of other variables, tie
irnbMion method still suffers from the same problem as
the Arnott method-insensitivity near neutraf wettabifily.
Bobek et al. 52 alau suggested an imbibition.teat for un-
consolidated cores. In tbia test, a thin layer of sand is
spread on a microscope slide, after which the oif satura-
tion is increased by addition of a refined minemf oil.
Dropleta of water am then placed on the surface of the
sand, srrd the movement of the fluid k observed by rnicm-
WATER SATURATION , O/. PV
(b)
Fig. 6Typh2al water/oil relative pemreabilily curvaa bc!
on the effective permeability to oil, at the resetvoir cl
nate water saturation; (a) strongly water-wet rock,
strongly oil-wet rock.
scope. Jf the ample is water-wet, the water wilf move
readiiy into the as.nd, displacing oil from the surface of
the sand mains. In addition. the oil will form sr3hericaI
droplets, ~dicadng that it is he nonwetdng phaaeuA sind-
Iar procedure is used to test for oil wettabiMy. This test
is similar to the microscope examination method.
Microscope Exmrdrratiotr. Microscope examination is
sometimes used in laboratory flow viaualiiation studies.
The wettabtity is determined from w description of the
flow on a single pure level in an ideafized porous medi-
UITl during Watedooding. 58.59TM.Sdescription includes
the structure of the residual Oi and the changes in the lo-
cution of tbe oil and water that occur during watertlood-
ing. ff the system is stfongly water-wet, the water
surrounds the groins as a thin fifrxr.The large pools of
residual oil rest on a water fti, while the smafIer drops

1252 Journalof PetroleumTechnology,November1986

of residual oil form spherical drups in the center of the
pores. If the system is intermediately wet, ,both oil and
water will be found in contact with the rock surfaces, ,~d
both can be found in the smslf pores. Finally, if the sys-
tem is oil-wet, the roles of the oil and water are reversed.
The ofl forms a fti around the grain surfaces and is found
in the small pores, whfle the water rests on an oil tilm
or forms small spheres.
The method of quzlitstively dete ruining the wettabfi-
ty by microscope examination is pmticukly important
in the study of wettabil@ reversaJs, 58>m&one of the
propoacd mechanisms for EOR that occurs dining alka-
fine waterfloodmg. m In ~e~e ex~tienta, a chefi~
that changes the nettability is injected into the porous
medium during a waterflood, causiug a zone of wettabd-
ity reversal to propagate through the core. A microscope
is used to follow wettabtity changes and to determine
whether EOR will occur by thk mechaniam.
Flotation Methods. Flotation methods are fast but work
only for strongly wetted systems. In the sinrpleat method,
water, oil, arrd sand are placed in a glass bottle. The bot-
tle ia shaken, and tie experimenter observes the fate of
tie smd gains. 65-6s This method is recommended by
API for determining the effects of surfactarrts on netta-
bility. C If the system is strongly water-wet, clean sand
grains will settle to the bottom of the bottle. Sand grains
placed in the oil wilI aggregate aud form small clumps
of grains surrounded by a thii layer of water. If the sys-
tem is oil-wet, some of the grains can be suspended at
the oil/water interface. Oil-wet sand grains in the water
will clump together, forming small oil globuka coated
with sand. This flotation system is qualhative and worka
only for strongly wetfed systems.
SeVeFJ experimenters 69.70 have used more elaborate
flotation tests developed in the minin industry that were
based on liquid/liquid extraction. 22,7? In these tests, par-
ticles are initially suspended in water. A second fluid,
either oil or sir, is bubbled from below. The parricles that
are water-wet remain in the water, while the hydropho-
bic, oil-wet particles adhere tu the oil (air) and rise to the
surface. The fraction of articles in each phaae can then
be measured. elenrmtz% used the flotation method to
meaaure the wettsbihty of small clay particka, which cmr-
not be conveniently me$suked in any other way. Untreat-
ed, strongly water-wet particlea would not float. After
expusrue to cmde, the clay particles floated, demonatrat-
irrg that their nettability had been altered:
Flotation tests based on liquid/liquid extraction appear
tn divide particles intu two categoria$ stron 1 water-wet
and mildly water-wet tu strongly oil-wet. ~2~~BesidG
, ~~
wettabilky, flotation of a particle also depends on parti-
cle size, particle density, and IFT. A small particle with
low density and high IFT might float if the contact angle
was ~eater than about300 [0.5rad]. On the other hsnd,
the minimum contact angle for flotation of a large, dense
particle could bc 90 [1.6 rad]. 72,73
Glass SIide Method. Another esrly qualitative nettabil-
ity meaaurcment tcduzique is the @as slide methnd, 30,m
which assumes thst a glass surfsce is representative of
the reservoir rock. A clean, dry, glaas microscope slide
is suapmrded in a layer of cmdc oif floating on water in
a transparent contsiuer ~d aged. The glaas slide is then
Journal of PetroleumTechnology, November 1986
lowered iuto the water. If tie slide is water-wet, the water
quickly displacea the oif on the slide. On the other hand,
if the slide is oil-wet, a stable oil-wet tilm is formed, and
the oil is very slowly d~placed. Reisberg and Doscher30
aged slides in crude oil snd found that it took up to 30
days for the 6MI wettabtiiy to be reached. Cwke st al. 5s
used a simple variation of the glass slide method as a
quick, qrmlitative test tu screen different acidic-oil/alka-
lii~water comblnationa for uae in zdkaliie waterflood-
ing experiments They placed oil and water without
-g fi a glass vkd and waited to see whether a stable
od-wet tihn formed on the vial. This was determined by
tilting the vial srrd seeing how the water and oil behaved
on the previously oil-covered surface.
Relative Permeabfity Methods. A number of quaMa-
tive methuda are baaed on the effects of wettabfity on rela-
tive penneabtity. However, they are all suitable ordy for
discriminating between strongly water-wet and strongly
oil-wet cores. A smaller change in nettability- e.g.,be-
tween strongly and muderstely water-wetmay not k nn-
timd by these methcda. One method developd by Ehrlich
~d WYg~74 is based on the rules of thumb given by
Craig7 to differentiate be~een stmmgly water-wet aud
~mon~y ~fi-wet ~or=. C~g, ~ 16,52,75 fieS ~ f ~mb me
. .
aa fouows.
1. Connate water saturations are usually greater than
20 to 25% PV in a water-wet rock, but less than 10%
PV in an oil-wet rock.
2. Water aaturztion at which oil and water relative pcr-
meabtities are equal is generally greater than 50% for
water-wet cores and less than 50% for oil-wet ones.
3. The relative permeabfity to water at floodout is
generally less than 30% in water-wet rocks, but frnm 50
to 100% in oil-wet ones.
These relative permeabtities are based on the oil per-
meabtity at the comate water saturation. Examples of
relative perrneabfity curves in strongly water-wet snd oil-
wct corer taken from Craig7 are given in Fig. 6. Note
that Raza et al. 16 state that there are exceptions tn the
gezieral rule that the connate water saturation is higher
for a warcr-wet rock than for an oil-wet one.
Treiber et al 27 pro~sed a secrmd quali@ve technique
for strongly wetted rocks The method comp=es the
oil/water, gas/oil, and gas/water relative permeabilkie.s
and takes advantage of the fact that relative permeability
:E.;E?JF2:EP;:,:EZZ$2:E;
water-wet, the relative perrneab~ky tu oil (the preferen-
tially wetting phaae with respect to the gas) in the gas/oil
relative pcrmeabtity test shordd be a continuation of the
relative permeabdity to the water (the wetting phzae) in
the water/Oil relative pcmzeabil~ test. 76 If significant
differences are observed, the sample is not strongly
water-wet.
An example of the comparison of the relative perr22ea-
btity curves in a strongly water-wet core taken from
Owens and Archer76 is shown in Fig. 7. The gas/oil
drainsge relative perrneabfity, where the oil ia the stron-
glywetting fluid, is shown as the dotted Iiues. The water/oil
relative pcrrneabfity, where tbe water is the strmrgly wet-
dug fluid, ia shown aa the solid lines. Note that the water
relative penneabi3ity, where the wetting fluid saturation
is iricreasing, is a continuation of the oil relative pe2n2ea-
1253
 o
CO

OIL
%

h
\
a% .: *3
AA
AAA

& A
WAT&T ROCK
(NUGGET SAND]
T
AA

A
\GA2 0

\ A
A
\ 0 ~3
\ m
A :
wATER
\ C.L

\ 0
A
00
I 0 OIL-WET ROCK
o 0 [SWINGER ~D1
./ .0

Ok
0.1 1 1 1 1 ~
0 20 40 60 60
WE771NGFtlXi5 SATURATION,PERCENTFORE ?PACE CONNATE WATER SNUR.T,ON % W

i9. 7cOMpariSOfl of gasioil drainage and water/oil im. ~9. 8Relatiom~~ betwean connate water saturation at
ibition relative permeabltity relationships. Torpedo !urpermeabltity.
andstone. 76

bditv. where the wetting fluid saturation is decreasing.
Thi~ demonstrates that iite core is water-wet.
Ba~c~ et al. 78 developd a third wettSb~@ memu~-
ment technique that is based on unsteady-state relstive per-
meability. Their method uses the capillary end effect that
occurs when a core initially at IWS is waterflooded at a
constant, slow injection rate. The end effect is the accumtJ-
Iation of wetting phase near the outlet end of the core
caused by the discontinuity between the porous medium
~d the otfet pipe. 79 An ihcreased pressure drOP cm
occur because of tbia wetting fluid accumulation. Batycky
et al.s relative-permeab fitytwettabihty tests are run at
very slow flow rates, so end effects are very important
in determination of the pressure drop across the core. In
contrast, standard unsteady-state relative pertneabilty
measurements use high flow rates to minimize the end
effect.
Batycky et a-f.determined the wettabfky by waterflcod-
ing the core at very low rstesuntil the ROS WS.V reached.
The flow was stopped to alfow the fluid to redistribute,
then restarted in the reverse direction. The core k water-
wet if there is no change in the pressure drop after the
flow reversal snd oil-wet if the pressure drop is reduced
immediately after the reversal. In a water-wet core at
ROS, the wetting fluid saturation will bc high through-
out the cure, with no addkional water accumulation at ibe
outlet end. 7s,s0 There will be no redismibution of fluids
when the flow is stopprG consequently, the pressure drup
will not change. On the other hand, if the core is oil-wet,
capillaty fortes will cause oil (the wetting phase) to .ac-
cumtdate near the outfet. The pressure drop caused by
this oil accumulation is detected by stopping the flow,
thereby allowing capillary forces to redistribute the oil
evenly throughout the core. When flow is started in the
reverse direction, the pressure drop will initially be low-
er, gradually rising to its original value as the end effect
is re-established on the opposite end of the core.
Permeahiity/Saturation Relationships. Two qwdiative
methods based on sir permeability and fluid saturations
have been proposed. Both methods are statistical, require
a relatively tige number of sqnples, and give only a very
rough idea of the wettabfli~. The advantage of the
methods is that only routine core anafysis measurements
are required. However, the reliability of these methods
is unknown. The methods are afso limited to core sam-
ples without significant fractures or vugs, in which the
pore structure determines the air permeability.
~ et al. 16 proposed an empirical methud to deter-
mine reservoir nettability based on connate water satu-
ration and air penneabihy. To obtain the connate water
sau.tration,core is obtained with an oil-based drilliig fluid,
then the freshly cut cores are analyzed for their water con-
tent. The cores are extracted and dried, and the air per-
meabi@ is messured. A qualitative measure of the
wettabtity ii obtained by plotting the comate water satu-
ration vs. the sir permeability. Fig. 8 shows exanrples
of tlte plot for strongly oil-wet and smonglyw6ter-wet con-
ditions. 16For the oil-wet case, the average connate water
saturation is generally relatively low. The curve is near-
ly vertical and extends over only a smsll saturation inter-
val. Conversely, for the water-wet reservoir, the curwe

12s4 Jourmtof PetroleumTechnology,November1986

 has a gentle slope and extends over a large saturation in-
terval.
Frehse81 proposed a second statistical method .b,ascd
on the assumption that low-permeability core samples wiJl
have a higher wetting-phase saturation than the high-
perrnmbilhy ones. For a uniformly wetted rock, the small
pores are fdled with the wetting fluid, while the large
pores contain both the wetting and nonwetting fluids. In
comparison to higher-permeability samples, a low-
permeability sampIe will generally have spore structure
containing a larger number of small pores that are filled
with the wetting fluid. To determine the nettability,
Frehseclassifica the routine core mralysis samples into
different permcab~ky ranges. The saturation distributions
for the bighfit and lowest permeability ranges are then
v
compared. For example, consider a core taken with a
water-based mud, where the reaiduaJ oil saturations are
known. The rcacrvoir is assumed to be oil-wet if the 10W-
permeability samples haye a higher average ROS and
water-wet if the high-permeability sarnpIes have a higher
oil saturation. Currently, this method appears to be theo-
retical only. We are not aware of auy.tests comparing the
results of tbk method with more standard nettability
measurements, such as tbe Amott nr USBM indices.
We feel that wettabflty evaluations based on air per-
meabili~ and fluid saturations should not be used at pres- Fig. 9CapilIarlmetric method.
ent. Rara et d.s method is empirical, and it is not kuown
whether it is generally vrdid. Frebaes method hw not been
tested. UntiI tbesemethods are evaluated hy comparison tive to the oil cohunn, changing the hydrostatic head. As
with standard wettabdity measurement, they should be the hydrostatic head is changed, the oil/water interfaces
considered mrreliable. will rise or fall in the tube until the capillary forces bal-
Grigorevs2. proposed a theoretical method for deter- ance the gravitational forces:
mining an appwent contact angle based on the IWS and
ROS. The method is probably not generally valid. It is
20 cos e
based on a large number of unprovenasaurnptions about P,= =$(poho-p~hv+), . . . .. . . (7)
the bebavior of the waterloillrock system. In addhion, r
there do not appew to be my testa comparing thk method
with other wettabdit y measurements. where
r = radius of the capillary tube,
CapilJ~3 Pressure Curves. As far back as 1951, P. = oil demi~,
Calhoun suggested that tire entire capillary pressure
p ~ = water density,
curve should be used to measure the nettability of the
ho = height of the oil column above the
core. Gatenby and MaradenM were the first to examine
the use of tbeareas under the capillary pressure curves oil/water interface, and
for thk purpose. The capillary pressure curves used were h~ = height of the water column above the
the complete drainage and imbibition curves for both pesi- o-illwater interface.
tive and negative capillary pressures measured by the
porous plate method. The two areai that they examined Eq. 7 can be rearranged to calculate the product of aand
were the total area surrounded by the drainage and imbL cos 0, which Johansen and Dunning called the dkplace-
bhion capillary pressure curves and the area under the ment energy (adhesion tension):.
oil-drive c!rrye. They found that neither of these areas cor-
related well with the nettability of the cnre. However, w
Donaldaon et at. 9 later showed that the areas that should ED=acos @= T(poho-pWhJ. . . . . . . . . . ...(8)
be measured were the areas under both the oil-drive and
brine-drive curves. Tbii is the basis of the quantitative
USBM method dkcussed earlier. The dkplacement energy is positive if water wets the
glass and negative if oil weta it. If one of the liquids com-
Capillarimetric Method. Johansen and Dunnirigg547 de- pletely wets the glaas, then the contact angle is zero, cos
veloped a qimhtative wettabdity measurement that meas- 8 ia unity, and the displacement energy is equal to the IFT.
ured the adhesion tension, a cos .9, in a glass capillary Johansen and Dunning usually changed the height of the
Nbe. In this capilkwimetric method, the top of the tube water column so that the interface moved over an area
is connected to a column filled with oil, wh]le the bottum previously cnvered by oil; hence the contact angle in Eq.
is connected to a column filled with water (see Fig. 9). 8 k water advancing. The capillarimetric methcd assumes
The top of the water colunru cm be raised or lowered rela- that glass is representative of the reservoir rock and there:

Joumalof PetroleumTcchnoloa, Novgmber1986 1255

fore is generslly only qualitative. Because this method
measures the product .s cm 0, the problems dkcussed in
the section on contnct angles SISOhinder this meifmd.
Displacement Capiffary Pressure. One of the earliest
wettabWy measurements was the displacement capillsry
pressure method, which uses the threshoId capillary pres-
sure to calculate am apparent contact augle. 8894This
method is now used infrequently, however, because pore
geometry effects can cause the calcqated contsct angle
to differ greatly from the contact angle measured on a flat
plate. 3 The displacement (or threshold) capilla~ pres-
sure is the capillaty pressure at which nonwetting fluid
will first enter a core initially 100% satorated with the
preferentially wetting fluid. h apparent contact sngle is
cdcnlatcd from the threshold capillary prssaure by mcdel-
ing the mck as a straight, cylindrical capillary tube4, 10:
20 Cos 8=
P~=, . . . . . . . . . . . . . . . . . . . . . . . ...(9)
Tmx
where PT is the displacement capillary pressure, a is the
IFT, O= is tbe apparent contsct nngle, and r- is the
radius of the pure through which the nonwetting fluid be-
gins to enter the core. Because the capillsry pressure need-
ed to inject nonwetting fluid is reduced as the pore radius
is increased, rmax is m mfersge of the radii of the lar-
gest pores in the core. Note. @it one limitation of this
method is that it examines the wettabfity of only the lsr-
gest pores. Because Eq. 9 has two unknowns, 0. ~d
rm=, the oofy way to solve for the apparent contact an-
gle is to mske additional assumptions. It is usually
assumed that some fluid exists that wfil completely wet
the core, so cos 8=1, and rmax csn be calculated. This
allows the contact angle, to be computed for other fluid
pairs.
Slobod and Blum~3 proposed two aenriqnantirativewet-
tsbility measurements baaed on the displacement capjl-
fary pressure, the wettabfity number, and the apparent
contact angle. The wettabfity number is calculated by car-
ving out two dkplacement experiments-first, water by
oil, and second, oil by sir. Eq. 9 for the oillwatcrlrock
system becomes
2U0-W Cos &o.w
P(o-w)r= . . . . . . . . ... . ... (lOa)
TIM.
and for the nirJoil/rock system,
2U=.-0 Cos %.-O
P(.-O)T= . . . . . . . . . .. . . . . ..(lOb)
rmax
In hth equations, the radius of the pore is assumed to
be the ssme. The wettrrbiMy number, N, is determined
by solving Eq. 10 for the ratio of the cos O terms:
cm O.-.
D.-OP(O-W)T
N== . . . . . . . . . . . . ..(11)
Cos 6.-0 uo-w%m
12.56
Slobod snd Blum stated that if it were assumed that the
oif is.completely wetting in the oillairlrock system, then
cos .9..0 is unity. An apparent contnct angle for the
oil/water system can then be computed from Eq. 11:
C.-OP[O-W)T
... . . . . . . . . . . . . . ., (12)
cOs(oo_w)= =
Oo-wp(a-o)T
Slobod snd Bhuu resEzed that their nasumptions were
onfy approximately true and that the contact angle that
could be calculated from the displacement pressure was,
at best, only semiquantitative. In general, the apparent
contact angle measured from the displacement pressnfe
is not cqusl to the contact angle messured on a smooth
surface because of pore geometry effects. Morrow snd
MS c0workers4345 compared apparent contact ~~es
computed in sintercd teflon cores using pure fluid with
the true contact sngles measured on a smcotl teflon plate.
There wss no chnnge in the apparent contact sngle when
the tme contact angle was varied from Oto 22 [0 to 0.4
rsd]. In addition, when@ was greater than 22 [0.4 radl,
the apparent contact sngle wna always less thsn the true
contact angle. Fiiy, in some cases, the apparent cOn-
tact angle calculated from the dkplacement pressure csn
show the wrong fluid to be the wetting phase. Positive
displacement pressures for both fluids, particularly when
the mre is initially 100% saturated with the other fluid,
have been frequently reported in the litera-
ture. 41.U.B,W,W.95-W When a positive displacement pre3-
aure is required for both fluids, the fluid with the lower
displacement pressure is the preferentially wetting flqd
because less energy is required to force. it into the
core, S3.98 &der~0n3 provides further discussion.
Reservoir Logs. Grshamw proposed a method to meas-
ure the.nettability of in-situ reservoir mck with logs that
wsa baaed on rhe fact that the electrical resistivity of an
oil-wet rock is hi her than that of a water-wet rock at the
ssrne saturation. f In Grahams method, the formation is.
injectd with brine, and resistivity logs are run. The for-
mation is then injected with the same brine containing a
reverse wetting agent, which will change a water-wet for-
nrstion to sn oil-wet one; if the formation is already oil-
wet, the reverse wetting agent will not alter the wettdil-
ity. After logs sre rerun, the nettability of the formation
cm be determined by comparing the two resistivity meas-
urements. If the formation was originally water-wet, the
change to oil-wet will increase the resistivity. If the fOr-
mation was oil-wet, no change in rcsistivity will be ob-
served.
Holmes and Tlppie lm proposed a second method that
compsres lugs with core data. The saturation in a forma-
tion is first measured with logs and the data converted
into a capillsry pressure curve. Next, the capillaW pres-
sure is messured in a clean water-wet core where it is
sssumed that the contact angle is zero, snd the two cspif-
lnry pressure curves nre compared. If they agree, the
reservoir is strongly water-wet. If they do not agree,
Hofmes snd Tlppie model the porous medium as a series
of strsight cylindrical capillaries and determine the ap-
parent contact angle with equations similsr to those dis-
cusacd in the previous section on displacement capiffary
pressure. Because of the number of approximations, this
Journalof PetroleumTechnolom..November1986
 aPPafent cOntactangle wfi provide only a rough estimate
of tfre actual reservoir wettabdity.
hleaaurement of Fractional and
Mixed Nettability
Infractional wetted cores, a p@ion of the rock is strongly
water-wet, whtie the rest is strongly oif-wet. The term
mixed wettabifhy was introduced by SalatMeI lol to
refer to a special type of fractional wettablli~ in which
the oil-wet surfaces form continuous paths through the
farger pores. Additional information can be found in
Ref. 1.
Nuclear Magnetic Relaxation. Brown and Fatr 102and
uthers 103,lW proposed a nuclear magnetic resonance
f,NMR) method for determining the fraction of the core
that is oil-wet vs. water-wet irr a core with fractional net- my way to use this to measure the wettabfity.
tability. The method rrses the nuclear magnetic thermal
relaxation time for water protons (hydrogen) in poruus
media. To measure the relaxation time, the sample is first
expused to a smmrgmagnetic field, which makes the nuclei
of the hydrogen atoms line up with the field. The core
is then exposed to a much weaker field. The nuclear mag-
netic relaxation time, which is the time it takes for the
hydrogen nuclei to adjust (relax) to the new field, is meaa- tohrene or hexane to displace all of the brine and oil. Af-
ured. There are two relaxation times: relaxation of the
component parallel m the field is called thermal relaxa-
tion, and relaxation of the component pe errdicrdar to
the field is cabl transverse relaxation. T 05 The ther-
maf relaxation time is the time used to measure fractiOn-
SI wettabifity.
For thermal relaxation to occur after the magnetic field tbe adsorbed surface material. The nuclear magnetic ther-
is changed, Oreprutuns rnuat dissipate some of their energy
to random thermal motion of the molecufes. The protons
are only lurwely coupled to their environment, so they re-
quire a time on the order of seconds to adjust to the new
magnetic field, which is a verj long time for atomic
proceasca.
The use of nuclear magnetic relaxation times to meas-
ure wettabflity ia based on the observation that the sur-
faces of the porous media can significantly reduce the
measured relaxation time. 102.105When a proton is near
a surface, it cmr bccume temporarily bound to the sur-
fiace,relaxing much faster than in tie bulk fluid. The wet-
tabili of the surface can influence the relaxation
dine. ? ~-1135 oil-wet surfaces cause ~ SmWer ~~ction
in relaxation time than water-wet surfaces.
Brown and Fatt 102 exmnincd 100% water-saturated
sand packs in which a fraction of the aand grains were
water-wet and the remainder bad been treated with an or-
garmchforosilarre tu render them oil-wet. They found a
finear rclatiun between the rafaxation rate and the frac-
tion of oil-wet surface area. f,The relaxation rate is the
inverse of the relaxation time.) The greater the fraction
of oil-wet grairra, the longer the relaxation time, and the
slower the relaxation rate. Krmrar et al. lM measured
relimtion times with 100% water-saturated bead packa
composed of water-wet glass beads and non-water-wet
polymetlryhnethacrylate beads. The relaxation time in-
creased heady as the fmctiun of non-water-wet beads
increased.
Brown and Fattlm and Knmar et al. lM applied their
methud only to sandpack and beadpacka. Deveraaux los
Journalof petroleum Technology,November1986
found that aaphaftene adsorption in sandstone cores coufd
afso increase the relaxation time. In one set of experi-
ments, clean smrdstone plugs were saturated with cm&
oil, then aged for several days. The bulk of the uil was
removed by flushing with cyclohexane, leaving bebind
a Iilm of asphaltenes on the ruck surfaces. The plugs were
saturated with water, and the relaxation time rneasurcd.
The adaorbed film increased the relaxation trme when
compared with the time for clean plugs. In another ex-
periment, a plug was saturated with water and crude,
aged, flushed with cyclohexmre, then saturated with water.
The nuclear magnetic relaxation curve for this sample had
three components: (1) a fast component for water in the
small pores, (2) an intermediate component for water in
the large pures, mrd (3) a slow compmrent for water in
tire large pores that had been fdled with oil and coated
with asphaltenes. However; Devercaux dld not suggest
Brown and Fatt 102also proposed a nuclear magnetic
relaxation method to measure the wettabflity of reacrvuir
core, which app=ently has not actually been used. The
method compares the nuclear magnetic thermal relaxa-
tion rate of the untreated core with reference measure-
ments on the same core in both strongly water-wet and
strongly oil-wet states. The core is. first flushed with
ter vacuum drying, the core is saturated with distilled
water, and the therrnaf relaxation rate is measured. It is
assumed that the preparation procedure above IWSnot al-
tered the wettahility of the core. Next, the core is made
strongly water-wet by flushing with methanol and chlo-
roform or by ftig at 950F [51OC] tn remove all of
mal relaxation rate of the core in this water-wet iefer-
ence stare is mcasrrred. FAy, the core is trcarcd with
an organocbforosikine, which renders it strongly oil-wet,
and the thermal relaxation rate is measured. The refer-
ence relaxation rates for the core when it ia strongly water-
wet and oil-wet are plotted vs. the percent of oil-wet sur-
face, and a straight line is drawn between them. Assum-
ing a linear relationship between fractional wettabdity and
relaxation rate, the fictional wettabiity of Orenative-state
untreated core is then found by plotting ita relaxation rate
on this straight line.
Unfornrrrately, this proposed procedure suffers from
several problems. First, the functional relationship be-
tween relaxation rate and fractional nettability is not clear.
Brown and Fatt found a linear relationship between frac-
tional wettabilhy and reaction rate, whale Kumar et al.
found a linear relationship using reaction time (the inverse
of reaction rate). Second, aa discussed in Anderson, 1 the
methnda that Bruwn and Fatt suggest to prepare the origi-
md core will generally after the mtive-state wettabflity.
Finally, it is not possible to tell whether the cleaning
method haa rendered the core totally water-wet or the or-
ganocblorosilane traamrent has rendered the core totally
uil-wet. Irr some cases, cure treated with an organo-
cblorosikme is only neutrafly wet. I
Dye Adaurption. Holbruok and Bernard lM used the ad-
sorption of metbylene blue from an aqueous solution in-
jected into a cure to measure fractional nettability. This
method successfully mcaaured the wettabtity of fraction-
1257
ally wetted sandpacka containing mixtures of oil-wet and
water-wet sands. However, the method will probably not
work for reservoir cores mntaining krrgearnounKof clay.
Iz3 this merhod, water-covered rock surfaces are
assumed to be water-wet, whfle the oil-covered ones are
assumed to be oil-wet. The technique is based on the ob-
servation that a rock surface covered with water will ad-
sorb a lsrge nmount of methylene blue, whereas one
covered with oil will not. The dye adsorptionof the test
core is measured at ROS, where essentially all of tie wet:
ting phase is continuous. 107-110 This enables the dye to
adsorb on essentially W of.the water-covered, water-wet
surfac~. A reference dye adsorption measurement is
made on an adjacent core plug that is clcancd to render
it totally water-wet. The cleaned reference plug is sao+
rated with brine, so the entire rock surface is water-
covered. The fractional wettabM~ is then established by
dividing the dye adsorption of the test core by that of the
100% water-wet reference core. When tl@ method wss
tested on fractionally wetted sandpacka containing mixt-
ures of oil-wet and water-wet sands, a Iinear relation-
ship between the fractional wettab@V and the dye
adsorption was found.
The dye adsorption test actually measures the fraction
of the total surface area of the core that is contacted by
the injected water. Because of this, both oil und water must
be present in the core when the dye adsorption is meaa-
ured. The dye adsorption method mskes two additional
assumption: the water phase is continuous at ROS, so
the dye contacts all of the water-covered surfaces; and
the thin fk of oiI and water coating the mck surfaces
are not affec@d by large changes in saturation. Tracer
experiments have shown that essentially elf of the water
is continuous at ROS for both water-wet snd oil-wet
~re~, I10 me ~~~uption that the thin fti of@ ad
water are not affected by Iarge changes in saturation seerrra
reasonable because the amount of liquid in the thin films
is very stmdl in comparison with the bulk tluida. Shankar
and DuMen111 exarrrincd how dye adsorption varied with
water saturation in Berea sandstone cores. They injected
oil and brine at currstaut rates and allowed the saturations
in the core to reach equilibrium. The injection wsa then
switched from brine to dyed brine, and the dye adsorp-
tion was measured. They found that the dye adsorption
was ahnoat conatsnt when tie water saturation wsa greater
thsn 40% PV. The dye adsorption drcreaaed at lower sanr-
rations, where the water stinted to lose continuity. These
measurements show that the wettabihty of a core meas-
ured by dye adsorption is not dependent on the satura-
tion, except possibly at water saturations near IWS.
Although the fractionally wetted sandpack that were
used by Holbrook and Bernard did not contain clays, they
retilzed that clays would strongly affect dye adsorption
in reservoir cores. This occurs becanse the surface area
aud dye adsorption capacities of clays are much larger
ha those of sad g~ns, 111,112f+olbrook ~d Be~~d
stated that their test would measure the fraction of the clay
surface drat was water-wet irr a reservoir core. However,
they had problems when measuring the dye adsorption
snd fractional wettabiMy of cores containing a significant
amount of montnrorillouite. Irreversible chsnges in the
clay structnre of the water-wet reference core reaufting
from extraction and drying caused them to cuhxdate rela-
tive water wettabtitiea that were greater tbau lCO%. Note,
1258
however, that it maybe possible to use supercriticsl dry-
ing to avoid these problems. L13
Mixed Wettabfity. At the current time, there is no sin-
gle nettability test that wifl determine whether a core has
Sslathiels lol mixed wettabiity. It ap- possible, how-
ever, to make this determination by examining the reardta
of (1) a glass slide nettability test, (2) a waterflood of
the native-state core, and (3) several waterflood of
restored-state coma that were aged with different brine
saturations. As discussed in the introductory paper, 1 in
a mixed-wettabdity core, the oil-wet rock surfaces form
continuous paths throughout the large pores, while the
smaller pures remain water-wet. Mined wettabilhy can
occur in a rock if the crnde forms a thick oil-wet layer
on the smface only in those places where it is in dirwt
contact. This can be tested with the glxas slide method,
with half the slide in crude and the other half iu brine.
Quartz or calcite cryatala could also be used to give a sur-
fxce more representative of the reservoir. The core may
have mixed wettabtity if the haffof the slide aged in cru&
forms a thick, oil-wet layer, while the half aged in briue
remains water-wet. If the entire sfide remains water-wet
or becomes oil-wet, the core will probably have a uui-
form wettsbdity.
The second measurement to iudicate mixed wettabiMy
is a waterflood of the native-state core. If the core has
mixed wettabilky, oil will be produced down to a very
low ROS as many PVs of water sre injected. Uniform-
wettabili~ cores wiR generally have a shorter duration
of production andlor a larger ROS. 6,7,114,115Finally, ,a
series of waterflood in restored-state cures cambe used
to confirm rhe mixed wearability of the core. A series of
cores is cleaned, saturated in brine, oilflonded with cmde
to dfierent brine saturations, then aged to restore its origi-
nal wettabtity. Salathiel fonud that the recuve~ fmm his
restored-state nrixed-wettabdity cores had a maximum at
a pmticuka value of the brine saturation during aging.
When the water aahmmionwas lower than this value, some
of the arnidl pores becsme oil-wet, lowering recoveg.
Conversely, at larger water sahmations, the oil patiways
through the core became discontinuous.
Two other measurements that will sometimes help in
determining whether a core has mixed wettsbifity are im-
bibkion meaaurementa aud capillary pressure behavior. 3
Spontaneous (free) imbidti,on of both oil snd water h@
been reported for some cures with iiactional or mixed wet-
tabiity. 49-51These corez will have positive diaplacement-
by-water aud displacement-by-uil ratios. Another indicakx
of mixed wettabtity is a comparison of Oil-displacing-
brine capillary pressure measured on native-state plugs
va. meaauremenk on the ssnre plugs after they have been
clca.ned aud rendered water-wet. In some mixed-wet
plugs, the native-state capillary pressure curve wilf cross
over the cleaned curve m the capillary pressure ia in-
creased. 116118Fticr discussion can be found in Ref. 3.
In summary, if the oil forms thick, oil-wet tilms only
on thoac pm-tioui of the glass afide with which it ia iu direct
contac~ if the core can be flooded down to very low oil
saturation, yet still produce small smouuta of ofi tid if
the oil recove~ from a rcatored-state core has a nraxi-
mum at a sp.%itlc brine saturation during its aging peri-
od, then the core Iiiely haa mixed wettabil@. ImbMion
Journalof PetroleumTechnology,November1986
 and capillssy pressure mesanrementa can also help deter- rmm = computed equivalent circular radius of the
mine whether a core-has mixed nettability. largest pores in a core, Eq. 9
R = relative rate of imbibition, Eq. 6
Conclusions VW = volume of oil displaced by sponfsneous
1. Three quantitative wettabdity measurements me in imbibition of water, Amott method
use today contact angle, the Amott method, and the Vo, = toti volume of oil displaced, Amott
USBM me~od. The contact angle measures the wetta- method
bflity of crude and brine on a polished mineral surface. vWSp= volume of water displaced by spontaneous
It is the best method to use when pure fluids and artificial imbibition, of oil, Amen method
cores are used. It is also used to examine the effects on Vw = total volume of water dkplaced, Amen
nettability of experimental conditions, such m pressure, method
temperature, and brine chemistry. The USBM and Amott W = USBM nettability index
methods measure the average wettabil~ of core. They 60 = displacement-by-oil ratio, Amen method
are superior to the contact-angle method when the wetta-
8 ~ = displacement-by-water ratio, Amott method
bflity of native- or restored-state core is measured. They
@= contact angle
also must be used to determine whether a core has been
cleaned completely. The USBM method appsass to be su- p. = oil density
perior to the Amott method, which is insensitive mar neu- P w = water density
tral wettab~lty. A modification of the USBM method, ~.=~
developed by Sharnra and Wunderlich, 57 allows the cal- aA = adhesion tension
culation of both the USBM and Amott nettability indices. 0., = interracial energy between the oil and solid
2. A Iarge.number of qualitative wettabfity measure- LT.. = interfaced energy between the oil and
ment methods are available. The imbibition method is the water
most widely used because it is fast, does not require any
f7w = intefiacid energy between the water and
complicated equipment, mrd gives RJJidea of the average solid
wettabfi~ of the core. Tbe microscope examination
method is otlen used.in flow visualization studies. Final-
ly, wettabilhy measurement methods based on relative Subscripts
permeabdity curves are often used when these data are a = apparent
available. adv = advsncing
3. Two methods have been developed to measure the a-o = sir-oil
fractional wettabtity: the NMR method and the dye ad- 0-w = oil-water
sorption method. Neither method is widely used today. rec = receding
4. There is no mefhod m determine whefher a core has T = fhmahold
mixed wettabfity. However, it appesra that it maybe pGs-
sible to make such determination by examining the re- Acknow[sdgments
sults of a glass slide nettability test, a waterflood of the
native-state core with many PVs of water, several water- I am grateful to Jeff Meyers for his many helpful sugges-
flood of restored-state cores that were aged with differ- tions and comments. I also thank the management of
ent brine saturations, and imbibition and capillary pressure Cormco Inc. for permission to publish this paper.
measurements.

Nomenclature 1. Andersom W. G.: Wertability Literamre Survey-par! 1:

,4~ = area under the oil-drive centrifigrd
capillary pressure curve, USBM method
,42 = area under the brine~tike cenfrifigal
capillary pressure curve, USBM method
ED = displacement energy (adhesion tension)
g = acceleration of gravity
ho = height of the oil column above the
Oil/water inter@ce
h. = height of the water column above the
Oil/water interface
I = Amots-Harvey relative displacement index
~ = initi~ imbibition ~k of ~ core just after it
is submerged in a fluid
fir, = initial imbibition rate of a core after it is
cleaned and rendered strongly water-wet
N = wettabfity number, Eq. 11
P, = capilla~ pressure
r = capillary tube ra~us
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97. Stahl, C.D. and Nielsen, R.F.: .Residual Water and Residua) Oil
By Capillary Pressure Technicpes,,, Producers Jfmubly (Jan.
1950) 14, No. 3, 19-22.
98. Kinney, P.T., Killins, C. R., and Nielsen, R. F.: Worn. Applica-
60., of C@@ Pressure Measurements0 P,wklli. Sands,,,
Bull., TedmicaJ Cofermce o Petroleum Prodmtio, Mineral
Jndu.sfdesExperiment Station, PennsylvaniaState U. (Oct. 24-26,
1951) No. 59, 52-61.
99. Graham, J.W.: Reverse-Wetd.g Logging,,, Trans., AIME
(1958) 233, 304-09.
100. Holmes. M. and TiDDie.D.B.: Comparison Between Loz and
Capillti Bessure Dafato Estimate Rsemoir Wetting, ~aper
SPE 6856 presemed at the 1977 SPE .kmual TechnicaJ Confer-
ence and Exhibifior,> Denver, Oct. 9-12.
10L Salathiel, R. A.: ,.Oil Recovery by Surface Film Drainage in
Mixed-Wetfabilhy RCC!S,9,JPT (Oct. 1973) 1216-2% Trans.,
. ASME, 25S.
102 Brow, R.J.S. and Fan, L: .Measnremems of Fmcdoml Were-
bility of Oilfield Rocks by tie Nuclear Magnetic Relaxation
M@A@SSTram. , A3ME (1956) 207, 262-&.
103, Devereaux, O. F.: .Effect of Cm& Oil o the NMR Relaxation
of Water Rotors in .%ndstonc,,, Nature (Au8. 5, 1967) 215,
614-15.
104. Kumar, J., Fa.tf,L, and Samf, D. N.: Nuclear Magnetic Relu-
xio Time of Water in a Porous Medium wifh HeterogeneousSur-
face Wel!nbdily, J, Appl. Physics (Sept. 1969) 40, No. 10,
4165-71.
105. Brown, R.J.S, and Ganwn, B.W.: Nuclear Magnetism Lo8-
Sing, Trans., ASME (1960) 219, 199-207.
106. JJolbmok, O.C, and Bernard, G, C,: Detmminatio of WeiW
biJity by Dye Adsorption, Trans., AJME (1958) 233, 261-64.
107. Brown, W.O.: The Mobiliy of Connate Water During a Water-
tlccd,,> JPT (July 1957) 190-95; Trans., AIME, 210,
Jones, S.C.: ,,Some Surprises in fhe Tmnsgmrtof Miscible Fluids
in he Freseceof a Second JnmdsciblePhase,,, SPEJ fFeb. 1985)
101-12.
109. P.aimondi, P., Torcaso, M., and Henderson, J.: sThe Effect of
Jnfemtitial Wafm on tie Mixing of Hydrocarbons During a M&
cible Dkplacement prccess, Mineral IA.mies Erpen.men?SIo-
tion CircularNo. 61, PennsylvaniaSfafeU., University park (Oct.
23-25, 1961) 1-34.
1261
110 .%her, SJ. and Mohanly, K.K.: MuMphasz FIOWiu Porous Me-
dia 1. Macroscopic Observations and Mcdeling, paper SPE
11017 presented at fhe 1982 SPE Annual Technica3 Conference
and Exfi%ition, New Orleans, Sept. 26-29.
111 Shankar, P.K. and Dullien, F.A.L., .Eq$erimenti Investigation
of Twc-Liquid RelativePmneabilitj and Dye Adsapiion capaci~
VeraLSSamratiouRelatiomhips in UnUeaIedand Drifdm* Treated
%ndsfone Samples, St@c. PheIwmeIMin Enhanced Oil Recow
e?% DO. Shah (cd.), Plenum Press, New York CIIY (1981)
.<*T
. ..- , ,
112 Hang, P.T. and Brindley, G. W.: M.thylene B1.e Adsorptim
by clay &fineraSs.Detemdnation of Surface b and CMionEx-
chanze
. Csmcities.,
. . Claw
. and I_%V . Minerals [1970) 18.203-12,
113. Heaviside, J,, Langley, G. O., and Pallmt, N.: .~Pekeabtily
Charac&is6cs of Magms R-!voir Rcwk,$3Pw., Euro&an For-
mation Evaluation Symposium, London (iWwcb 1983).
114. Kennedy, H. T., Burja, E.O., and Boykin, R.S.: An Iuvestiga-
tim of tie Effects of Wettabilily on the Recovery of Oil by Water
Flooding,), J. Phys. Chem. (Sept. 195S) 59, 867-69.
115. Lmenz, P.B., DmaSdwn, E.C., and Thomas, R.D.: WJS$of Cen-
trifugal Measurements of Wettabi!iv to Predicf Oil RecovcIY,
Bartlesvilk Energy Technology Center, rep-m 7873, USBM
(1974).
1262
116. Richardson, J. G., Perkins, F. M., and Osota, 1.S.: &Differences
in Behavior of Fresh and Aged East Texas WcmdbineCore, JPT
(June 1955) 86-91; Trans., A2ME, 204.
117. Rf3d, W., Schmid, C., and Wissmam, W.: ccDisplacementTests
with Porom RcwkSamples Under Resermir Conditions,, Proc.,
.W%tiWorld PeuoleIJmCong., Frankfurt (1963) Sec. 2, papr 11,
Pi%
..,..d67-8. I.
118. Scbmid, C.: The WettabiiiV of Petroleum Rocks and tie Results
of Experiments to Study the Effects of Variations in WeuabtiV
of Core Samples, Erdoel und Kohle-Erdgas-Petroch.mfe (1964)
17, No. 8, 605-C9. English translation available from tie John
Crerar Library, Uanslation no. lT-65-12404.
S1 Metric Conversion Factors
degrees X 1.745329 E02 = rad
F (F-32)/l.8 = e~
psi x 6.8947S7 E+OO = kPa
JPT
Ofig(nal !mnuscrlplreceivedin tha Smlmy d Pmro[e.m Engineersoffic. Dec. 2S,
i 9s4. Papet(SPE 13933]accepmdforpubfimtionJuly23, 19s5. Revisedmanuscript
rece.w,d March3, 1986.
Joum+of Petroleum Technology, November 1986
Nettability Literature SurveyPart 3:
The Effects d Nettability on the
Electrical Properties of Porous Media
WMiam G. Andarson, SPE, Conoco Inc

l393f+
Summary. This paper examines the effects of wettabflity on the Archie saturation exponent and the formatiOn
factor, which are determined exper.imentally in cores. These parameters are irhportamt in the investigation of the
hydrocarbon saturation of a formation by use of resistivi~ data. obtained from well logging. The Archie
saturation exponent, n,typically has a value of about 2 in water-wet formations and clearrcd cores, whfle in
native-stnte, non-water-wet cores and formations it is generally larger than 2. In uniformly oil-wet cores with
low brine saturations, n can reach values of 10 or more. The exponent is ~gher inoil-wet cores at low
saturations because a portion of the brine is trapped or isolated in dendritic fingers where it is unable to
contribute to electrical conductivity. If a cleaned water-wet core is used to measure n and the reservoir is
actually oil-wet, interstitial water, will be underestimated during Iogging. No definite conclusions can be drawn
about the effects of nettability on the formation factor. However, the wettabilky of clays in a core is fikeIy to
affect this Lmmn3eter.

Introduction
This paper is the third irr a series on the effects of wetta-
bllity on core analysis. 1-3Changes in the nettability of
the core have been shown to affect electrical properties,
capillary pressure, waterflood behavior, relative permea-
bility, dispersion, tertiary recovery, irreducible water
saturation, and residual oif saturation. For core analysis
to predict thebehavior of a reservoti~ the wettabMy of
the core nmst be the sync as the w.ettabllity of the un-
disturbed reservoir rock.
In the first report, 1 the various kinds of nettability,
such as mixed wettabtity, were discussed. That paper also
detirred native-state, cleaned, nnd restored-state cores nnd
gave the procedures necessary to obtain each type. Note
that a restored-state core has been cleaned and then aged
with native crude oil and brine at reservoir temperature
until the native nettability is restored. This definition is
used in the majority of the more recent literature. Be
aware, however, Ilratin some papers, pwticularly older
ones, the term restored state is used for what are ac-
tually cleaned cores (e..g., see Craig4).
Wettnbtity nnd saturation hktory ire irnpopant factors
in the detcrrrtjnationof the electrical rcsistivity of a porous
medhm because they control the location and distribu-
tion of fluids. The electrical resistivi~ of acore is deter-
mined by the lengths and cross-sectional areas of the
conducting piths through the brine. Large resistivi~ is
caused .by small cross-sectional areas and long conduc-
tion paths. First, consider a 100% brine-saturated core.
The rcsistivity of tie core is much higher than the resistivi-
ty of an cquivgent volume of brine because the noncon-
ductive rock reduces the cross-se:tiorwd area through
which the current can flow. At the same time, the rock
increases the length of the conducting paths.
CQPY@t 1986 So.f.w.f P.tf.!wm %$..-
The resistivitv of the core is increased further by arw
hydrocarbon sat&ation in the core because hydroca;bon_s
are also nonconductive. The incrense will depend on the
saturation, nettability, and saturation history, +e factors
that control the location and distribution of the oil and
water in the reck. Irr a water-wet rock, the brine occupies
the smaIl pores and forms a continuous fflm on the rock
surfaces. In an oil-wet rock, the brine is located in the
centers of the larger pores. Thk difference in brine dis-
tribution caused by the wettabili~ becomes very impor-
tant as the brine saturation is lowered. Generally, almost
nll of the brine in the water-wet rock, remains continuous,
so the resistivity increases because of the decrease in the
cross-sectional area that can conduct flow. In an oil-wet
rock, a pmtion of the brine will lose electrical continuity
as the saturation is lowered, so the electrical rgsistivity
will increase at a faster rate.
Effects of Wettabitity on Resistivity and
the Archie Saturation Exponent
The hydrocarbon saturation of a formatiori is often esti-
mated from resistivity data obtained by well logging. The
empirically determined Arch1e5 saturation equation is
often used
s;=+% ... . . . . . . . . . . . . . . . . . . . . ... ...(1)
o
where
SW = brine saturation in the porous medium,
R, = resistivity of the porous medium at
saturation Sw, and
R. = resistivity of the 100% brine-saturated for-
mation.

Journal of Petroleum Technology, Dec&ber 1986 1371

 The ratio of the two resistivities is called IR, the
resistivhy index. The Archie saturation exponent, n, is
a ditiensionkss erripirical parameter that is determined
experimentally fromcpr~ plugs. The value Of n depends
on the fotiation but ustially has a value of about 2 for
water-wet formations and cleaned water-wet cores.
Oil-Wet vs. Water-Wet Cores. Mungan and Moore6
have puinted out tit the Archie saturation equation rn&es
three implicit assumptions: (1) the saturation/resistivity
relation is unique, so only one resistivity will ever be
measured at a given saturation; (2) n is constant for a
given porous mediw, and (3) all the brtie contributes
to the flow of electric current. It has been shown that tbcse
assumptions are valid only when both the reservoir nud
core tie strongly water-wet because n depends on the dis-
tribtio, of the conductirtg phase .in the porous IIIed@III
and therefore depends on the wettabfily. If the nettability
is sltercd, the change in the spatial distribution of the fluids
alters the lengths and cross-sectional areas of the conduct-
ive pat@, which in turn changes the resistivity. Hence
the Archie equation is nonunique when ibe wettabili~ is
akcred because different resistiviiies iii be measured at
the same satiuition.
The experiments discussed below show that n can be
a great deal higher in oil-wet than in water-wet rocks.
M0rr0w7 provides additional discussion. Because the
saturation exponent depends on the nettability, n must
be measured at reservoir wetting conditions, o: invtild
saturations will be ob@ned from logs. For example, if
n is measured in a cleimed water-wet core and the reser-
voir is actually ox-wet, ihe water saturation in the reser-
voir would be underestimated. Pkson and Fraser 8 cite
an example of a well in an oil-wet reservoir that produced
onfy water. Assuming a water-wet reservoir, logs in this
sape well indicated an interstitial water satiation of only
25%.
TMeeffects of tietiabtity on the Arcbie saturation ex-
ponent become more important as the brine, saturation
decreases because, in an oil-wet system, there is more
@co@ction aid isolation of globules of brine, The iso-
lated brine is surrounded by oil, w~ch acts.as an insiia-
tor snd causes this brine to be unable tu conduct a current
flow. First, consider a water-wet system initially ai a high
brine saturation. The brine is Iocatcd in the smaflpores
and m a thin layer on the rock surfaces, whfie the &i is
located in the. center of the larger pores. All the brine ii
continuous and can conduct current. As the water satura-
tion is lowered to the irreducible water saturation (NW),
essentially all of the brine in a water-wet system remains
continuous and conductive, allowing the saturation expo-
nent to remain about 2. This continuity at all saturations
above fWS has been demonstited experimentally by
atcady:statc mistible flonds. .Thesefloods show that gener-
ally; there. is little or no trapping or isolation of any ,of
the brine by oil. 912 This implies ttiat most of the increase
in the rcsistivity is caused by the decrease in the cross-
sectional area available for conduction, not by increases
in tbe path length or brine t~pping..
In a uniformly oil-wet system, the oil is located in the
smull pores and on the rock surfaces, while .tbe brine is
located in the center of the Itiger pores. At high brine
saturations, the brine is continuous, jtit as it is in a watir-
wet system, even though its location is different. For this
1372
situation, the Arcbie resiativity/saturation relationbehaves
as it does-in the water-wet case, with n around 2. In con-
trast to the water-wet case, however, as the brine satura-.
tion decreases, a portion of the br@e no longer contribute
tothe current flow. In some experiment, the saturation
exponent increases as soon as the brine saturation is de-
creased, while in others the brine saturation must be re-
duced to about 35% before n increases. At very low water
saturations (<35 %), Iarge values of the saturation expO-
nent, n >10 can occur.
Two factors cau cause the resistivity, and hence n, to
ike more rapidiy compared wi@ the water-wet case: the
trapping of a portion of the brine by oil, and the forma-
tion of dendrites or tingera of brine. 13 As stated previ-
ously, these factora decrease the cross-sectiomd area and
increase the length of the conducting paths, thereby in-
creasing electrical resistivi~. Flow vistrilizatiom and
steady-state miscible experiments demonstrate that a sig-
nificant fraction of tie nonwetting phase becomes dkcon-
nected as the nonwetting phase saturation
decreases. 4,12.W~7This isolated brine is surrounded by
nonconducting oil and cannot contribute to the current
flow. As the brine saturation is reduced, the electrical
resistivim will also be increased because some of the brine
will be located in pseudo-dead-end pores, 17,18 As.
known as tingers or dendritic structures. These fingers
consist of brine that is connected to the continuous brine
in only one location. The brine cannot conduct electricity
because of the oif/water interfaces in the remainder of the
pore throats, so the length of the conducting paths is in-
creased. ,.
Note that the volume of nonconducting dendrites is not
the same as the dendritic fraction measured in steady-stnte
miscible floodhg experiments. The dendritic fraction in
a miscible experiment is ameasurement of the brine that
is continuous but does not flow. 2n a water-wet system,
this includes thetnonflowing brine located in the small
pores, as well as the brine in the fingers On the other
hand, the volume of nonconducting dendrites is a meas-
urement of the brine that is continuous but nonconduct-
ing. These two volnmes me different because the
continuous brine in the smalf pores conducts electrici~,
while the brine in the fingers does not.
I@perimental Measurements.
The experimental systems used to study theeffectsof wet-
tabiity on the saturation exponent can be divided into three
types: (1) uniformly wetted systems; (2) reservoir cores;
which may or may not have nniform nettability; and
(3) fractional and mixed-nettability systems. In the @st
set of experiments with uniforin nettability, the wetw
bility of the entire core is varied from water-wet to oil-
wet. At any given nettability, the wettabfity of the en-
tire sufface is kept as nniform as possible.
In many cases, reservoir core will not have @form
nettability. For example, the dlffefent minerals on the
rock. surface.can have different surface chemis~ and ad-
sorption propefies, possibly causing variations in wetia-
bflity. The second set of experiments discussed is for
reservoir cores. Several of these cores are native-state,
where akcrations to the r+ervoir wettabitty are mini-
mized. Finally, the third set of experiments examines the
wettab]lity effects that occur when a.core has fractions
or mixed wettabflity, where some of the rock surfaces are
,.
Xournalof Petroleum Technology, December 1986
 .Ca
TABLE 1ARCHIE SATURATION EXPONENTS AS A
FUNCTION OF SATURATION FOR A CONDUCTING
NONWETTING PHASES
m,.,.,.,, .... +

Air/NaCl SOlution OWNaCl Solution

Brine Srine
Saturation Saturation
(o/oPV) n (0/0Py n +
66.2 1.97, 64,1 2.35
,m
65.1 1,9s 63.1 2.31
63.2 1,92 60.2 2,46
59.3 2,01 55.3 2.37
51.4 1,93 50.7 2.51
43.6 1.99 44.2 2.46
39.5 2.11 40,5 2.61
23.9 4.06 36.8 2.31
30.1 7,50 34.3 4.00
28.4 8,90 .33.9 7.15
31.0 9 ,0

strongly water-wet but tbe remainder are oil-wet. In these w,,,. w,.
experiments, the effects of wettabllityare studkd by var-
iation of the location and tine proportion of the surfaces :

tiat are water-wet vs. oil-wet.

Uniformly Wetted Systerrrs. Mungan and Moore6 1

studied the effects of wettabfity on resistivity using both
synthetic poiytetrafluoroethylene (teflon) @ natural
cores. They found that n could be as Klgh as 9,when the
conductive liquid was the nonw:tting phase. When it was
the wetting phase, n was around 2 in the same core. The
fluid pairs used in the teflon core were metbnnollair,
airlbrine, and oilibrine. For the methanollair case,
methanol is boQr the wetting and conducting phase and
is analogotis to the brine in a water-wet rock. The satura-
tion exponent was about 1.9, approximately what would
be measured in a water-wet resewoir cor,e with oil and
brine. This demonstrates that the location and resistivity
index of the fluids are similw in the two systems, oiU
brine/reservoir rock and air/m&thsnol/teflon, wheri the
wetting liquid is also the conducting phase.
Next, Mungan and Moore, used airlbrine Or OYbrine
as the two fluids in the teflon core. The brine is then the
conducting, nonwetig phase, bebaving in a fashion sfi-
ku to brine in an oil-wetcore. The saturation exponents
are shown in Table 1. An examination of Mungti and
Moores datXshows what typic611yhappens in io oil-wet
system as the brine saturation is decreased. Above a cer-
tain conducting phase saturation, the exponent n @con-
stant and near 2. Below this saturation, however, the
exponent begins to increase rapidly.
By mimovisunl examination, Mungrin and Moore found
that portions of the brine in the teflon cores started to be-
come disconnected when the brine saturation was lowered
to about 35%. This disctrmrected brine did not conduct
electrical current because it.was completely surrounded
by tire insulating wetting phase (air or oil). Resistivity in-
creased more rapidly as tie brine saturation was lowered
below 35%. Table 1 showsthat the exponent begins to
rise as the brine saturation drops below 40 %, eventually
increasing to about 9. Mungan and Moore concluded that
the Archle saturation equation was not ,vsld at low water
saturations in al oS-wet rock. fliey pointed out, however,
that a vtild saturation-resistivity relationship could be em-
pirically determined if the reservoir wettabfky were pre-
o, 0,2 ..3 ..4 0., m ,,8 !,0
served with a native-state core and reservoir fluids were
used for the measurements.
Sweeney and Jennings 1g,20 measured the effects of
wettabti~ on carbonate cores. The cores were first ex-
tracted with. toluene, which left them in a neutral-
wettabfity state, as determined by the imbibition
method. 1 This method is only qualitative, so the actual
wettsbility of the core was somewhere between mildly
watkr-wet and mildly oil-wet.
The electrical resistitiky of the neutrally wet core was
measured as a functinn of water saturation. The cores were
then fred at S40F [450C] to remove all of the organic
rnateris.l present, rendefing the core strongly water-wet.
Note that thk caused a slight increase in the porosity be-
cause of dksociatitm of a portion of the calcium carbonate
into calcium oxide and carbon dioxide. After the new
resistivity behavior was measured, the cores were treat-
ed witi naphthenic acids to make them oil-wet. The
resistivity bebavinr was measured again,and the results
are shown in Fig. 1. The Archie saturation exponent, n,
is the slope of each line. Ttie saturation exponent Of the
water-wet cores was about 1.6, and for the neutrally yet
cores about 1.9.
There were two different types of behavior for the cores
once they had been rendered oil-wet. In some cores,, the
saturation exponent was high (about 8) even when the
brine saturation was very high, The behavior of.tbe re-
mainder of the cores was similar to the water-wet and neu-
trally wet cores until a brine saturation of about 35% was
reached. At this point, n increased rapidly to a v61ue of
about 12. This is similar to Mun 8n and Moores! find-
ings. Sweeney arid Jennings g,zL?stated that the oil-wet
carbomte cores could also be separated into the same two

Journal of Petroleum Technology, December1986 1373

 ,0
I [ I I I I
I TABLE 2EFFECT OF CLEANING ON THE
ARCHIE SATURATION EXPONENT27

Core Number Unextracted Extracted

m
1 2.37 2.03
2 2.68 2.29
3 2.48 2.07
4 2.71 1.9t
\ 5 2.82 2.44
. 6 2.21 1.91
(0 Aversge 2.55 2.11

.,
g
: .,
state that these high vahres occur becauae a significant part
\
:, 0 of tie nonwetting mercury was either trapped or located
:.
in dendrites where it could not contribute to the conduc-
~
tivity.
;
4 ,: 0 Z1erfuss smd Makha25 measvred electrical resiativity
during waterflood of ssdstone tid limestone cores and
artificial packs. Each porous medium was saturated with

iI
CORE N,.44
. ,,,,.,,,, an aqueous ammonium thiocyanate solution (water),
~ ~ ~ ~TRAc,, D
:J( n. ,,,,
oilflooded, and then waterflooded. The wettsbili~ was
.
controlled by treating the porous medlurn yi~ different
.
concentrations of naphthetic acids. As the system became
more oil-wet, the waterflooding behavior was altered. At
the same time, the resistivity at IWS was increased

Reservoir Core. The experiments dkcussed previously

,0 20 40 m w r,,
WA,,* ,.7,,.,,0., % ,,.
~9. 2Ef~ct of cleaning on the Arcfde saturation
c:xponent.
grotips on the basis of pore-size distribution and petro-
graphic analysis. Unfortunately, they give no detsils.
,Rust21 compared tie saturation exponent for oil and
water in a cleaned sandstone before and after it had been
trded with an orgsnochlorosikme solution to render it
mildfy oil-wet. He found that the saturation exponent for
the clean water-wet sandstone was about 1.7, while for
the oil-wet sandstone it wss about 13.5 even at tigh brine
saturations. Unfortunately, Rust miayhave had problem:
with his experimental apparatus, indkated by saturation
exponent vuluea in the oil-wet sandstone of only 3.5 when
air and water were used.
Keller, 22 Licastro aid Keller, 23 and Holmes24 meas-
ured the resistivity of oil-yet and water-wet reSeIVOir, flooded and then oilflooded to 30% brine saturation, and
cores using air and brine. The restit$ are very Similar to
ttie experiments described previously, even ihough core
saturations were cfianged by evaporation, which possi-
bly caused stilnity variations. In addition, fhe fluid dis-
tribution may have differed from the distribution existing
when oil and brine were used.
Goddard et al. 13 measured the electrical resistivity of
mercury, a nonwetting fluid, as a function of saturation
in seveml sandstone plugs: Mercury was injected into the
dry core and then withdrawn while the resistively was
measured. When the mercury was withdrawn from the
sanrpk, the resistivity ,was at first slightly less than the tained. In contrast, measurements on cleaned plugs gave
injection resistivity at the same saturation. It quicldy be-
cume.much higher than the injection resistivity as the mer-
,cmy saturation was reduced, however, and was essentially
infinite at a residual mercury saturation. Goddard et al.
showed the effects of wettabili~ on the saturation expo-
netit in uniformly wetted cores. Generally, either a teflon
core was used or the entire core was treated with a chem-
ical to make it oil-wet. The experiments ii this section
demonstrate that nettability is SISOa major control pa-
rameter in the determination ofn inreservoir core. While
the Archle saturation exponent will be higher than 2 in
nstive-state oil-wet cores, it will generally not reach the
very high vsfues for uniformly wetted systems. Because
of variations in tiers.i composition, many reservoir cores
will probably have fractional (heterogeneous) wettabfity,
msking a portion of their surface water-wet. This will
decrease the rste at which the wster becomes.discome&?d
at low water saturations and lower the saturation exponent.
In addition to measurements in uniformly wetted teflon
cores, Mungan and Moore6 measured the resistivity of
native-state re;ervoir cores that wete known to be oil-wet
and had an interstitial water saturation of 10%. The
resistivity was too high to be measured; implying that most
of the brine was discomected. The cores were water-
values of n were measured. They varied from 2 to 3.5.
Of course, at this higher brine saturation, the wettabiliv
effects were reduced.
Luffel and Randa1126 gave & example of a resemoir
where saturation exponents must be measured on native-
state core rather than cleuued core. The saturation expo:
pent was first determined induectly on the basis of logs
snd water saturations from core cut with an oil-based mud.
The average saturation exponent wss determined to be
2.6. The saturation exponent was then measured directly
on native-state core,. nnd amaverage value of 2.8 was ob-
g;$ due.f
exarnmedly 18 of cleaning on the Ar-
the effects
cbie saturation exponent of the Bradford Third sand,
which is kuown to be oi3-ivet. Six pairs of adjacent p)ugs

1374 , Journalof Petroleum Technology, December 1986

were cut, and one from each set was extracted with
toluene, mnking it more water-wet. The other core was
unextrscted, and left oil-wet. Note that cores were not
preserved and probably bad wettabilhies that differed from
their native wettnbdity. In sddhion, toluene extraction may
not have removed all of the organic coating on the core
so the cleaned cores may not have been strongly
water-wet.
The changes in the saturation expnnent are shown in
Table 2. Jrt each case, extraction significinily lowered the
Archle satnmtion exponent. Fig. 2 is a plotof the resistivi-
V index vs. the brine saturation for one core pxir. The
saturation exponent, n, is tie slope of the lines. It is bigher
for the unextmcted core amdappears to be constant. Moore
measured the reiistivity of the .unextracted core only for
brine satiations gxeater than 35 %; therefore, it is possible
that the saturation exponent increases rapidly at lower
brine saturations, as obse~ed by Sweeney and
Jer@ngs 19,20and Mung& and Moore. 6 Moores27 xnd
Luffel and Randalls26 experiments are particularly im-
por@t because they demonstrate that cleaning a core can
alter the saturation exponent.
Trantham and Clampitt2s measured a saturation expo-
nent of 3.1 on plugs from h-e strongly oikwet North Bur-
bank reservoir. The plugs were cleaned nnd resaturated
with brine and oil before measurement of the saturation
exponent. Cleaning thk core apparently dld not affect the
wettabllity; the. plugs remained strongly oil-wet even af-
ter cleaning. Trantham and Clnmpitt proposed that the oil-
wetness. of this reservoir is a result of a coating of
chsmosite clay rather than the more common adsorption
of surfactants from the cmde. This may explain why the
saturation exponent is very high even after cleaning.
The differences in the saturation exponent for native-
state vs. clcsned core by Mungan and Moore, 6 LuffeIl
and Rxndxll, 26 and Richardson et al. g show that the ex-
ponent should be measured on native-state or restored-
state core, where alterations tothe reservoir wettabilky
am minimized. Note that it is not known whether the cores
used in Refs. 6 nnd 26 had uniform or fractional netta-
bility because both types of nettability are possible in
reservoirs.
Fractional and Mixed-Wet Systems. Additional w.ettn-
b~ity effects can occur when a system has nonuniform
nettability (either fractional or mixed), where portions
of the surface are strongly water-wet, wh~e the remainder
are strongly oil-wet. Sa.latfiel 30 irkrodticed the term
mixed nettability for a special type of fractional wetta-
bifity in which the oil-wet surfaces form continuous paths
through the larger pores. The smaller pores remain water-
wet and contain no oil. Note tlat the main distinction be-
tween mixed and fractional nettability is that the latter
does not imply either specific locations for the oil-wet and
water-wet surfaces or continuous oti-wet paths.
Fractional Wettabil@. The only researchers who have
exmnined the effects of fractional wettab]litj are
Schmid31 and Morgan and Puson.32 Morgan and Pws&
made fractionally wetted bead packs by treating apor-
tion of the beads with an organochloroiilane solution to
render them miklly oil-wet. Theremainder of the beads
were untreated andhence water-wet. Witba variation in
the proportion of oil-wet snd water-wet beads, resistivi-
ty measurements could tie made as the proportion of oil-
Joumdof PetroleumTechnology,Deccmber1986
.
,,
/)
;
%
../:
; t.
%,.-,.
!:-
~~
,0 <..
.,..,, W.. .,L WC,,.,,, !,,.mc..,
Fig. 3Archie saturation exponent vs. the fraction of sur-
face that is oil:wet.2
wet surface was varied from O to 100%. Starting with
100% brine, tbesamration wasgradually reduced when
oif was flowed through the pack, andtheresistivity was
measured. The Arctic saturation exponent for each pack
was found by plotting resistivi~ vs. the saturation. Tbe
vaIuesofn shown in Fig. 3 mmgefrom2.5 when all of
the beads were water-wet to 25 when all of the beads were
oil-wet. These very high values of n possibly occur be-
cause of the smooth surfaces and homogeneous nature of
the bead pack.
Schmid measured the saturation exponent in fracti&-
ally-wetted sand packs with a portion of the sand grains
untreated and water-wet and the remsinder treated to
render them o~-wet. The saturation exponent for the IOQ%
water-wet pack was about 1.8. The resistmty index in-
creased ataslowerrateinthk water-wet pack when the
w&tersaturation wasless tbanabout25% PV. As expect-
ed, %&resistivity index at any given water saturation was
bigl@ for the 100% oil-wetpack, with a saturation index
of@tgbly 2.4. The resistivity indix increased rapidly,
whefi the,jjater saturatiori decreased below about 7-O %PV,
whit] j:,:iimilar to Munganand Moores6 xnd Sweeney
and Jennings 920
, tindings.
Schrn;d ako measured the resistivity index of packings
containing 25, 50, or 75% oil-wet sand grains. Unfor-
tunately, there does not appeq to be a clenr trend for tiese
packing$. The 75% ofl-wet pack had the same resistivity-
index/saturation relationship as the 100% oil-we tpack,
except tiere was no rapid increase inresistivity index at
lower water saturations. The relationships for the 25 and
50% oil-wet packs were almost identical and were locat-
ed between the completely oil-wet and comuletelsf
. . water-
wet curves.
Mired Wehizbifiiy. Unfortunately, nothing definite can
be sxid about the electrical properties of a core with mixed
wettab@. Inamixed-nettability core, theoil-wetsur-
faces form continuous paths through the Iarger pores,
while the smaller pores remain water-wet and contain no
~if, 30 A ~ed-wettabifi~ system can be generated in the
following manner. When oil initially invaded an originally
water-wet reservoir, it dkplaced water from the larger
pores, whale the smafler pore: remained water-filled be-
ciuse of capillary forces. A mixed-nettability condhion
occurred if the oil deposited a layer of oil-wet organic
material only Orithose rock surfaces that were in direct
contact with the oil, but not on the brine-covered surfaces.
1375
oil-wet deoosits would not be formed in the small water-
ffled Pnre;, allowing them to remiin water-wet.
Because the small pores are water-wet, the electrical
behavior of rnixe&wettab~hy core will probably be differ-
ent from the behavior ii?uniformly oil-wet systems. The
Archie saturation exponent will not reach the very high
values that can occur in uniformly wetted systems. In-
stead, it seems reasonable to expect that the electrical be-
havior of mixed-wettability cores wiff be similar to
water-wet ones because the small pores and clay pat-
cles are water-wet and filled with water in both caaes.
As the brine saturation in a mixed-nettability core is re-
duced, the water in these areas will remain connected and
conduct electricity. This will alfow thesaturation expo-
nent to behave as it would in.a water-wet core, remain-
ing constant even at low brine saturations.
Even though the behavior of mixed-wet and water-wet
cores will be sinilar, however, this does not imply that
measurements on cleaned water-wet core are applicable
to reservoir systems. Unless the reservoir is known to be
sfrongly water-wet, the saturation exponent should be
measured on native- or restored-state core. There are
several reasons why core with the reservoir wettab]lity
is necessary. First, it appears that tie surfactants in some
cmdelbrinelreservoir rock systems can difise through
a water-film, making the entire rock surface uniformfy
oil-wet. 1 Second, if a core has mixed wetta.blity, the pre-
cise numerical value of the ArchIe saturation exponent
willprobably differ ,fiom that of awater-wet core because
0* arge i-wetF.
Richardson et al. 2 prowded an example of the differ- . sets of data into agreement.
ence in resi<tivity for water-wet ~d mixed-wets ystems.
They measured the resistivity of nat:ve-stnte cores that
Iater were shown @ have mixed nettability. 30 The
resistivity was high in the native-state cores, but gradu-
ally dropped after repeated cleaning as the cores became
more water-wet. The resistivity was measured only at
lWS, however, which was much bigher in the mixerf-wet-
tabilily cores tbnn in the cleaned water-wet ones. Richard-
son et al. present tie data only after they have been cor-
rected to a 40 % saturation with Arcbies law (Eq. 1). This
makes it difficult to compare the resistivi~ measurements
before and after cleaning to determine how n was affected.
Swan~on33 claimed ttvat be saw very little change ~
the saturation exponent when he compared a water-wet
core with the same core after it had been rest6 red to a
pnssibly mixed-wettabfiity state. His experiments disagree
with the measurements on native-stite, mixed-wettabfity
core dkcuased previously. 29 However, several problems
with Swamnns work make it impossible to determine the
actual wettabilh y of the restored-state cores. The netta-
bility is indeterminate because the cors were not aged
for a long enough period for adsorption equilibrium to
be established and because the waterflood behavior does
not indicate the nettability.
Swanson first ineasured the waterflood and electrical
resistivity behavior of clean water-wet Berea sandstone
and Austin limestone cores. The cores were then &lven
to IWS and aged with crude oil. It is known that many
cores must be aged for at least 30 to 40 days before the
nettability reaches its tinid state. 1.4,34.37Unfortunately,
Swanson aged the cores only between 12 and 30 days,
so his cores were tested in some ill-defined, nonequilib-
rium state. In fact, in his discussion OYthe waterflood be-
I
1376
havior, he stated that the waterflood behavior depended
on the aging time, a clea indication that the wet~bility
wsa still changing.
The cores were strongly water-wet befoti aging, which
is demonstrated by the fact that little or nn oil was pro-
duced after bre~through during a waterflood. The water-
flood behavior also demonstrated that the wettnbllity was
altered after the coreswere aged because oil was produced
after breakthrough in the aged cores. Unfortunately, be-
cause Swanson injected only a few PVs of brine, it is
not possible to determine whether the cores had mixed
nettability. On the basis of the waterflood data, the cores
could be either uniformly mifdly water-wet, fractionally
wetted, or of mixed wettabllit y. The primary indication
of a mixed-nettability state is that very low oil satura-
tions are reached after the injection of a very large num-
ber of PVs of brine. Tbis is caused by the conthuous
oil-wetted paths through the linger pores. 30 In summary,
no conclusions about the electrical properties of mixed-
wet cores can be made from Swansons data because the
wettabdity of the aged cores is unknown.
Experiments irr the Reservoir
Several researchers have tried to estimate the effects of
nettability on resistivi~ in the reservoir. Puson and
Fraser 8 ~d Fraser 38 discussed reservoirs ~Own tO be
intermediate or oil-wet. Resistivity measured by the elec-
tric logs was compared with neutron logs and data on the
saturation from core analysis. An Archi& saturation ex-
ponent of about 3 was then determined to bring the two
Gr&aM39 used a reverse wetting agent tO eXfine the,
effects on resistivity as an originally water-wet .iock was
changed to oil-wet. Experiments were coriducted both in
cores snd in situ. For the core experiments, water-wet
Berea pIugs were samratid with brine, oilflonded, rben
water flooded to a residuaI oil saturation. The resistivity
of tie water:wet plugs was measured; then the plugs were
injected with brine containing a reverse wetting agent that
renders sand and clay surfaces oil-wet. The electrical
resistivity of the now-oil-wet cores increased by, 100 to
200% because of the redistribution of the fluids in the
core. Field tests also showed an increase in resistivity af-
ter the wettabtity was changed to oil-wet. Graham rec-
ommended that this treatment be used when logging in
regions of relatively high conductivi~, where log interpre-
tation is difficult. Od in these regions would be revealed
by the imxea.se in re%istivityafter the fo~mation was made
oif-wet by the injection of a reverse wetting agent.
Formstion Resistivity Factor
Another equation that Archie5 determined empirically re-
lates the resistivity of the 100% brine-saturated core snd
the resistivi~ of the brine: .
FR=RO/RW, . . . . . . . . . . . . . . . . . . . . . . . . . . ...(2)
where
R. = re.sistivity of the brine-saturated, core,
RW = brine resistivity, and
FR = formation resistivity factor.
Because very little work has been done on we.ttability
effects of this pammeter, it k unclearwhether FR, changes
Journal of petroleum Tmh.ology, December 1986
 as the nettability of the core is &tired. Sweeney and
je.~g~ 19,20found hat tie fomtion factor ~as ~hangqd
after the nettability was altered. Because their chemical
treatment with naphthcnic acids was drastic enough that
other core properties such as the porosity were nlso al-
tered, it is unclear whether nettability effects were dem-
onstrated. They suggested that the naphthenic acidsused
torender the core oil-wet may have partially sealed off
pore$that had previously contributed to current flow.
Rust21 compared sandstone cores that were either
cleaned (water-wet) or cleaned and treated with nR or-
ganochlorosilane solution (mildly oil-yet). He found no
significant difference in the formation factors. Mungmi
and Moore 6 found no effects on the formation factor in
their teflon cores. They realiied, however, that tbk was
not a conclusive test because of the uniform composition
and wettabiky of the teflon. They went on to state, How-
ever, because natural cores contain clays, a chmge in core
nettability nlways brings about other changes, such as clay
swelliig and dispersion, ion exchange, effective porosity
change, and surface conductance variations, and these will
affect the measured vslues of R. and FE. Thus preser-
vation of the natursl core nettability is always pmdent.
Conclusions
1. The Archie saturation exponeat, n, is almost in-
dependent of the wettabflity when the brine saturation is
sufficiently high that the brine is continuous.
2. Nettability effects become very important when the
brine saturation is lowered. In genersl, essentially all the
brine in a uniformly water-wet core remains continuous
and electrically conducting as the brine saturation is
lowered to the irreducible saturation. The Archie satura-
tion exponent has a vnlue of about 2 in water-wet forma-
tions sod cleaned water-wet core.
3. The Archie safurafion exponent can reach <aJues of
10or more in unifoimly oil-wet core with low brine sahJ-
rations. This occurs because a portion of the brine is
trapped, wliile addkiomd brine is isolated in dendrhic
fingers where it cannot contribute to the eleCtriCd Con-
ductivity. Re.sistivi@ incr@es because tbe brine cross-
sectionaf conducting area decreases, and the lengrbs of
the conducting paths increase.
4. Unless the reservoir ii strongly water-wet, the satu-
ration exponent should be measured on native- or restorex-
state cores. If a clean core is used to measure the satura-
tion exponent and the resewoir is actually oif-wet; the im
terstitial water caR be underestimated when logging.
5. Although no definite conclusions cm be drawn about
the effects of tiettabdity on the formation factor, FR, it
is ~kely that the formation factor is affected by changes
in nettability. , Preferentially Water-Wet and Preferentially Oil-wetcarbonate
Nomenclature
FR = formation resistivity factor
lR = resistivity index
E = ~atm-ati~n exponent
RO = formation resistivity when 100% saturated
with water of resistivity R W, Q. m
R, = formation resistivitj it i water
saturation S,O, S7.m
R ~ = water iesistivity, Q. m .,
SW = water (brine) saturation
Ihmd of F~tdemT&l~O@%December1386
.
Acknowledgments
I armgrateful to Jeff Meyers for his many helpful sugges-
tions and comments. I nlso thank tie management of
Conoco Inc. for permission to publish this paper.
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Jomalof Petroleum TechnoloD, December 1986