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Nettability Literature Survey

Part 1: Rock/OiVBrine Interactions

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

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.

This paper is the first of a series of literature surveys demonstmted by allowing water to imbibe into the core.
covering the effectsof nettability on core analysis. 1-3 The water will displace the oil from the rock ,surface, ~-
Changes in nettability have been shown to affect capil- dicating that the,rock suiface prefers? to be in contact
Iq pressure, relative permeability, waterflood behavior, with water rather than oil. Simjkwly, a cow samra!ed with
dispersion of tracers, simulated terdaiy recovery, imedn- water is oil-wet if oil will imbibe into the core and dis-
cible water saturation (IWS), residual 01 saturation place water from the rock surfuce. Depending on the spe-
(ROS), and electilcal properties. 4-26 For core analysis citic interactions of rock, oil, and Mne, the wwab@
to predict the behavior of a reservoir accurately, the net- of a system can range from itrongly water-wet to str022g-
tability of a core must be the same as tbe nettability of Iy oil-wet. When the rock his no strong preference for
the undisturbed reservoir rock. A seriousproblem occurs either oif or water, the system is said to be of neufml (or
because many aspects of core handling can drastically af- intermediate) wettabfi~. Besides strong and neutkd net-
fect nettability. tability, a third ~pe is fracdonsl nettability, where differ-
ent areas of the core have different wibing preferences. 27
Water-Wet, Oil-Wet, and Neutrafly Wet. Wettabfity The wettabfity of the rocklfluid system is impoitant
is defined as the tendency of one fluid to spread on or because it is a major factor controlling the location, flow,
adhere to a solid surface in the presence of other irmnis- snd distribution of fluids in a reservoir. .Jn general, one
cible fluids. 7 In a rock/oif/brine system, it is a meas- of the flizids in a porous medium of uniform wettabilky
ure of the preference that tie rock has for either the oil that contis at least two immiscible fluids will be the wet-
or water. When the rock is water-wet, there is a tenden- ting fluid. When the system is iu equilibrium, the wet-
cy for water to occupy the smsll pores and to contact the ting fluid will completely OCCUPY the smsllest pores and
majority of the rock surface. Siarly, in an oil-wet sys- be in contact with a majoriv of the rock s~face (ass~-
tem, the rock is preferentially in contact with the oil; the ing, of course, that the saturation of the weting fluid is
location of the two fluids is reversed from the water-wet sufficiently high). The nonwetting fluid will occupy tie
case, and oil will occupy the small pores and con~ct tie centers of the larger pores and form globules that extend
majority of the rock surface. It is importunt to note, how- over several pores.
ever, that the teim wettabWy is used for the wetting In the remainder of this survey; the terms wetdizg snd
preference of the rockand does not necessarily refer to nonwetting fluid wilf be used in addkion to water-ivet and
the fluid that is in contact with tie rock at any given time. oil-wet. This will help us to draw conclusions about a SYS-
For example, consider a clean sandstone core that is tern with the oppositi wetibility. The behavior of oif in
saturated with a refined ofl. Even though the rock sur- a water-wet system is very similar to tle behavior of water
face is coated with oil, the sandstone core is still preferen- in an oil-wet one: For exmuple, it is generally assumed
tially water-wet. Thk wetting preference can be that for a system with a strong wetting prefererice, the
coP&h!1986society.+Pe!role.mEngineers tietting-phase relative permeab~ky is only a function of
lmral of Petmlc.mTechnology,October19S6 1125

Angle Silicate Carbonate Total
(degrees) Resewoirs Reservoirs Reservoirs
Water-wet o to 75 13 2. 15
Intermediate wet 75 to 105
Oil-wet 105to 180 1: A 3;
Total 30 25 55

its own saturation-i. e., it shows no, hysteresis. 7,12,28 fected the wettsbflity behavior in the contsct-migle tests.
Owens and Arch&28 measured the gas/oil drainage per- As ,iiscussed later, this probably causes amoverestima-
mea.bflily, where the oif was the strongly wetting fluid, ticm of the oil-wetness. Therefore, the large percentage
and compared it with the water/ofi imbibition relative por- of reservoirs found tobe ol-wet is less significant than
meahii@, where the water was tie strongly wetting fluid. the general indications that not all reservoirs are water-
The water-imbibkioi reIative permeability (strongly wet and that the r&ervoir wettabilky varies widely.
water-wet system) was a continuation of the oil-drainage Contact-sngJe measurements made by Clilingm snd
relative permeability (strongly oif-wet system), demon- Yen35 suggest that most carbonate reservoirs ramge fiorn
strating the amdogy between systems of opposite wetta- neutrally to oif-wet. They measured the we~bdity of 161
bilities. limestone, dolomitic liiestone, calcitic dolomite, arid
Historically, afl petroleum reservoirs were believed to dolomite cores. The cores tested included (1) 90 cores
be strongly water-wet. This was based on tyo mjor fac~. from Asrnari limestones and dolomites from tie Mid$e
Fust, almost allclean sedentary rocks are strongly EasG (2) 15 dolotite cores from west Texas; (3)3 cores
water-wet. Second, sandstone reservoirs were deposited of Madison liiestone from Wyoming; (4) 4 cirbonate
in aqueous erivironments into which oil later migrated. cores from Mexican oil fields; (5)4carbonate cores from
It was assumed that the comate water woufd prevent the the Rengiuoil field in the Peoples Republic of China;
oil from touching the rock surfaces. In 1934, Nuttingzg (6) 16 csrbonate cores from Albe~ (7) 19 chalk cores
realized that some producing reservoirs were, in fact, ac- from tie North.,SeT (8) 5 samples from India+ amd (9)
@ally strongly oil-wet. He found that the quaitz surfaces 5 samples from Soviet oil fields in the Urals-Volga region.
of the Tensleep sandstone in Wyoming had adsorbed Table2 shows the distribution of wettsbfities with 80%
heavy hydrocmbons in layers about 0.7pm tldck (about of the reservoirs either oil-wet or strongly oil-wet. Some.
1,000 molecules) so fdy that they could not be removed of the strongly oil-wet reservoirs were oil-wet bew+se
by gasoline or vzrious solvents.When $e hydrocarbon of a bitumen coating. Note that the range of contact an-
film was removed by ,fuing the core, the film could be gles considered to be neutrslly wet is smaller thari the
restored by soaking the cores in crude oil overnight. range given in Table 1. This demonstrates the variation
Examples of other reservoirs that are genertiy recog- , from paper to paper of the cutoff angles between ?Je
nized as sirongly oil-wet are the Bradford sands.of the different wetting statea.
Bmdford pool,, Pennsylvania, 30-32 and the Ordovicisrr As discussed iu more detiril later, reservoir rock can
ssmds of the Okkiborns City field. 33 More recentfy, change from its &iginal, strongly water-wet condition by
Treiber et aL % used the water advancing contact angle adsorption of polar compounds and/or the de ositjon of
to eiamine the wettabdity of 55 oil reservoirs. fn this orgsnic matter originally in the crude oil. 7,3P 6-42 Some
procedure, deoxygenated synthetic fofmation brine and crude oils make a rock oil-wet by depositing a thick or-
dead anaerobic crudes were tested on quartz and calcite ganic film on the mineral surfaces. Ofher crude oils con-
c~stafs at rescrvom temperamre. COnta~. angles (mea.+. ti pOlar compounds that cm be adsorbed to make the
ured through the water) fromOto750 [0 to 1.3 rad] were rock more oif+vet. Some of these compounds are srrffi-
dipmed water:we~ from .75 to 105 [1.3 t6 1.83 rad], ciently water soluble to pass throu~ the aqueous phase
intermediate wet; and from 105 to 180 [1.83 to 3:14 red], to the rock.
oil-wet. As summarized in Table 1, 37 of the reservoirs
tested were classified as oil-wet, 3 were of intemnetilate Fractiormf Wettabilfty. The retilzation that rock wetta-
wegabtity, and 15 were water-w.et. Most of the oil-wet bflity can be akercd by adsorbable crude oil components
reservoirs were mildly oil-wet, with a contact angfe be- lexito tie idea that heterogeneous forma of wettabiity exist
tieen 120 and 140 [2:1 and 2.4 rad]. Of the carbonate in reservoir rock. Generally, the intend surface of re.ser-
resemoirs included, 8 % were water-wet, 8 % were inter- voir rock is composed of many minerals with different
mediate, and S4% were oil-wet. Most of the carbonate surface chemistry and adsorption properties, which may
. . reservoim were from the west Texas area, however, so lead to variations in nettability. Fractional nettability
there is a geographical bias in the data. slso called heterogeneous, spotted, or fhlmation
Treiber et al. cautioned that these tindlngs could not wettabifky-was proposed by Brown and Fatt27. aud
be considered representative of a trufy random samplhzg others. 43* fn fkactioml wegsbdity, crude oif compo-
of petroleum reservoirs. The sainples were bkmed because nents are strongly adsorbed in certain areas of the rock,
(1) all were operations for the sarnb company, (2) most so a portion of the rock is strongly oil-wet, whie the rest
were being considered for some type of flooding, and (3) @strongly water-wet. Note tit this is cqncepty+fly differ-
some of the reservoirs had demonstrated unusual be- ent from intermediate wettsbtity, which assumes that all
havior. A fourth consideration is how much the use of portioim of the rock surfsce have a slight but equal prefer-
degassed fluids rather than the real formation fluids af- ence to being wetted by water or oil.
1126 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
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 Several researchers 57,5s analyzed wetkbiliw-afterirw
compounds that contain oxygen, nit@gen, and/or suffer. compounds extracted from cor~. Jennings58 r~moved ~
The oxygen compounds, which are usually acidic, include portion of the nettability-altering cornpotirids by extract-
the phenols and a bwge number of different carboxylic tig a non-water-wet core with tolnene,, followed by a cfdo-
acids. 67$5,86Seifert mid Howellsw showed that the car- rofordmethanol mixiure. An imblbitioiz test showed tbst
boxylic acids are titerfaciilfy active at alkaline PH. The some of the wettabil@-idtering compounds had been re-
sulfor compounds include the sulfides and tilophenes, moved during the s~ond extraction because the core was
with smaller amounts of other compormda, such as mer- more water-wet. The material remo+ed dtiring the sec-
~ap~s ~d polysulfides. 87,88The nitrogen compo~da ond extraction contained porphytis ~d bigh-moledor-
are generaUy either basic or neutral and include csrba- weight pamffinic and aromatic cbmpoiihds.
xoles, tides, pyridenes, quinoliies, and porphy- Denekaa et al, 41 used a d~tiflntion pro;exs to separate
~~. 40.s7-90me pVhYtis camf&m imerfadly active cmde oifs into fractions of different molecular weight.
metal/porphyrin complexes with a number of dii%erentm> A clean, dry core wax saturated with the crude oil frac-
tds, including nickel, vanadium, iron, coppr, tic, titani- tion to be tested, then aged for 24 hotii:. An imbibition
um, calcium, aud mirgnesinm. 9*-95 test based on the relative rate of imbibkion waa nsed to
Because the .9zrfactarrts in cnrde oil are composed of determine the wettxbility Alteration..1.1 The originxl
a lsrge number of very complex chemicals that represent crqde oil and the heaviest residue left a,fterdistillation had
onfy a small fraction of the,crude, identi@g which com- the greatest effect on the nettability; they were the only
pounds are im ortam in aftering the wettabtity has not fluids that nzadetbe rock oil-wet.fhia fiplies that a con-
beeipossible 6 h addkion, attempts to correlate bulk siderable portion of the surfact+ds, in the crude oiI had
crude propert;ei with the abflity of the crude to ~ter wet- a large molecular weight. Many of the lower-molecular-,
tabiliw have been unauccessf+ McGhee et al. 62 satn- weight fractions, however, also debreaaed the water-
rated Berek cores with brink, od flooded them to IWS with nettability, demonstrating that the surfactants in crude
different cnides, then incubated them at 140F [60C] have a broad range of molecufa.r weights. Cuiecg6 ob-
for 1,0+30hours to allow the wet@bfity to reach equilib- tained similar results. Note that Denekas et al. and Cuiec
rium. .The U.S. BWearr of Mines (USBIvf)wettsbllily in- botlr used@ cores and that idso~tiob of the w&ttnbility-
dex wasthen meaaured and compared with bulk propwties .ikering cOnzpoundswoufd probably have been iltered if
of the crude. They found no correlation between the the cores contained brine during tie aging process..
USBM index and interfaci.d tension (IFT), organic acid A number of roaearchera have examined the i@rfacinUy
content, percerit nitrogen, or percent suIfnr of the cnrde. active materiak that are cOncentrat&dat the Oil/water in-
oCuiec96 measured the Arnott nettability index of terface. Generalfy, these materi~s can iilso be adsorb@
restored-stnte cor6s and found no correlation between ivet- on tie rock surface to sfter wettsblli~. 3.7,8~g9-*mBar-
tabilky and amonnta of acids, basea, aromatics, resins, tell and Nlederhauser 103managed @ sepirate these, ma-
nitrogen, or srdfur. In all cases, when the restored-state terials from ~e crude oil dqd f6und that they, formed a
cores were water-wet, the crndes bad low sapha.ftenesnd hxfd, black. noncrys@fline substxnce tit was sapI@tic
anffur contents., However, other low-asphaftenexnd low- in nature.
mdtirr c@des rendered cores neutrally or oil-wet. . .
Experiments that determined the general mtnre of the Adsorption Through Water F~s. Experiments hove
surfactxnts xnd the crude oil fractions in which they are shown tfiat nataml surfactants. ii cimde.are often suffl-
concentrated without attempting ~ determine exactly cienify soluble in water to a&sorb onto the rock surface ,-
which compounds cause wet@bifity alteration have been &r passing tbrougb a thin ld~er. of water. 42,60>69-71
more success~. Jolwnsen and Danningw,9s found that Meaauremerits comparing aaphd~ene a+orption in cores
asphzdtenea were responsible for changing some cmde- with and without water show tlwt m many. caaes a water
oiWwater/glass systems from water-wet to oil-wet. The film wiUreduce but not completely ir@it =pk+lterfend-
system ,was oil-wet when the cmde was used but wat&r- sowtion. 6M9,70 Be&use the wa~ei .qzd asphaltenes wM
wet when the deasphalted crude was used; The addkion coadsorb, however, the wat4.r film may alter tie detailed
of a very small amount (0.25%) of the whole crude to adsorption mechanism. 70,1w Lyutin @d Burdynm found
Ozedeasphalted crnderestored the oif-wettingness of the that the asphalt&e adsorption f$orn A&h ,crude in an yn-
system. Donafdsbn aud Crocker55 and Donafdson56 consolidated sandpack wai about 80% of the dry y~ue
measured wepabilky alte@ion caused by the polar coin- at a water saturation of 107. PV, decreasing to 40 % when
poaada extracted from aeveml different mincmf oifa. First, the water sapration was incrth+ed to 30% PV. Berezin
the nettability of a series of uizcontanzinated Berea plugs et al. 69 exmzzizzedthe adsorption of .&phalten&s&d ;ex-
was mcasnredwith brine agd a refied mineral oiL The ins from crude onto cleaned sandstone cores. With Tui-
average USBM wettabilky iizdex was 0.81, or strongly mazy crude, a water,satnration of about 17% reduced the
water-wit. After cleanirig, the USBM nettability index adaozption by about a factor. of three. With two other
of the plugs was measured with brine and a 5 % mixture crndes, a water saturation of about 20% completely. in-
of the extracted polar organic componnda in the retined hibited the adsorption. Such complete inhibition by tie,
mineral oil., The phtgs were significantly leas water-wet, water fifm woidd be expected in reservoirs that remain
with USBM wettabtity indices ranging from 0.45 (water- water-wet, with no significant ,adsorption:from the cmde.
wet) to -0.W (xretitmlfy.wet), demonstrating that polar Reisberg ad Doscherbs aged clean glaas slides in
compmmda in cnide can alter the wettabtity. Note that c~de ofi.floating above brine and observed the forma-
there was appsfentfy no aging time with the polar cOm- tion of oif-wet fti. The formation i.nd s~bility of the
ponnds in the plugs, so equilibrium wettxbifities may be oif-wet fti on the slide was observed by lowering .!-be
more strongly oil-wet. slide into the brine and observing whether the brine dis-
112s 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 of the anil after the.asphalt tre@zent waa greatly increaaed
char ed when the pH is increased above about 2 to by pretreating the soif with a solution of ferric or @mi-
3.7, ! 3,105 whfle calcite does not become negatively IJU222sulfate.
char ed untif the pH is greater than about 8 to Morrow et al. xl aged glass sfidca in Moutray crude,
9.5. &,05.111As discussed in the previous section, sili- waahed the slides to remove the bufk crude, and then used
ca is negatively charged near neutral pH and tends to ad- isooctafre and distilled water. to meaaure tie water-
sorb organic acids, whiIe cafcite is positively charged and advancing angle. They fonnd that the wettabifity strong-
tends to adaorb organic bsaes. Calcite will adsorb cation- ly depended on the sfnount of trace ions iJJthe system.
ic smf@mJts rather than anionic surfactants., however, When the glaas slide was extremely clean, no residual fb
if the pH of the solution iJJ which it is immersed is in- was depnsited by the crnde, and the system was water-
creased above 9.111 wet. Next, they treated the glass with femic (Fe3 ) or
The pH also affects the iotiation of the snrface-active orler transition metal ions before exposing it to drecnide.
organic acids and basea in the crude.. fn afkahe water- They obtained contact angles up to 120 to 140 [2.1to
flooiling, a relatively inexpensive caustic chemical 2.4 rad], with the angle dependent on the choice of ion
typically sodium hydroxide or sndium ofiosificate-is and its c&rcentration. Theferric ion was pxrticulady ef-
added to the injection ,water. 112The hydroxide ion mscts fective in altering the wettabilky.
with organic acids in acidic crude oils to produce surfac- There appexr to be two related reasons for ~e effects
tanta that after the wettabiti~ ador adsorb at the oilhine of these mnftiv#ent ions on the wettabili~. Fiiat, they ~,
interface to lower f.FT. Seifert and How.ells85 exsmined can reduce the snlubility of the surfactants in the crude
the interfaciafly active materials in a California cnrde oil. andbrine, helping to promote oil-wetting. 6,113Second,
They found that the crude contained. a large mount Of they behave as activators for the smfactants in the
carbnxylic acids that form soaps it ilkaline PH. crnde. Acdvator .la a term used in the floption indus-
The possibfity of EOR during amalkaline flocaldepcnda try for ions or cnmpounds thst, while not snrfact@ them-
on the pH and salinity of the brine, the a.sidi of the crude, selves, enhance surfactant adsorption on the mizreraf
and the origiwd wettabtity of the system. 2,113,114Cooke smface snd increase the flnatabifity. Generally, the acti-
et al. 6 discussed the effects of salkhy nn wettxb~ky in vators act like a bridge between the mineraI surface and
alkaline flonds where the soaps are formed by the inter- tie adsorbing surfactant, helping tn bmd the snrfactant
action of the alkaline water with the acidic crude oil. In to the NIffsce. go AS shown previously, clean @J~ haa
relatively fresh water, the snaps that are formed are soht- a negatively charged surface nnd tends to adsorb @osi-
ble in water; promoting water-wetness. If the system is tively charged) orgnnic bases from solution. The (nega-
initially oif-wet, EOR may occur b a wettabdity rever- tively chsrged) acida in solution will not adsorb on the
~~ from ~fi..wet to ~a~r-wet. 17.2.?, 114J 15 On the ~ther surface because they will be repelled by the like charge
hand, in high-salinity systems, EOR may occur as, a re- on the quartz surface. For example, clean quartz is not
sult nf awater-wet-to-oil-wet wettnbifky reveraaf. Aa the floated by fatty acids, ideating that tie quartz remains
saliniw is increased; the soaps become almost in.duble, water-wet. At the proper pH conditions, however, the
adsorb on the rock surfaces, and. promote oil- wettabfity can be changed and the quartz can be floated
~en~g, 6.113If the system is initially water-wet, COok by the additidn of smafl nmounts of marry multivalent
et al. ststf that EOR in a highly sshme ~ystem may oc,cur metalfic cations, including Ca2, Ba 2, Cu2, Al3 i
by a water-wet-to-oil-wet tiettability reversaf mech- ad Fe +3. WT%Q.107These ions adsorb on tie qun3t2
~sm.6 ,113,114 surface, providing positively char.r@ sites for the adso% ,-.
In silkdoillbrine systems, multivalent metsl cations tion of&e fstty ;~ds. -. -
in @ebrine can reduce the solubilky of the crude sur- For exam 1. Ga.din and Chang7s imdGaudm and
factants andlor promote adsorption at the mineraf sur- Fuerstemm% staled the adsorption of laurnte ions on
faces, causin the system to become more oil- auartz. When sodium Iaurate, CHa (CH2.) toCOONa, is
wet. 6,W,77,79,8 ? .116,117Multivalent metal ions that have ~ded to the water, it dissociates @~ a ne~ati;ely charged
altered the wettabifity of such systems include Ca 2, laumte ion and a positively charged Na ion. Because
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- the dissociation of H + ions from the Si-OH groups on
tab~hy. They meakured the contact angles on quartz of ihe silica surface, the negatively charged laurate ion is
dead Werobic cmdes in deoiygenated synthetic fofma- repelled ffom tie negatively charged quartz surface.
tion brine and found that as little as 10 ppm of Cu2 or Hence no adsorption occurs. However, adsorption occurs
Ni2 coufd change the wettab~ky fcom watdr-wet to oiI- when, for example, divafent Ca2 or Ba2 ions are
wet. Brown and Neusta.dterm placed cmde oil droplets added aa the activator. These positive djwdent ions can
in a contact-angle apparatus tilled with dktifled water. adsorb on the surface, allowing the negatively chmged
They found that Oreaddition of.less than 1 ppm of Ca2 surfaciant (in this caae, the laurate ions) to adaorb in as-
or Mg2 would alter the nettability, making the system sociation wia them. Researchers with other experimen-
more oil-wet. The addition of trace amounta of Fe2 also tal systems also state that divalent ions can bind to a
changed the wettabiIity with some of the crudes tested. negatively chargedsurfactant to fogn a positive, cationk
The.$emultivalent ions have SISObeen ahown to incresae surfactant/metal ~mplex, w.bich is then attracted to and
the od wetness of soils stab~ied with cut-back adsorbs on the negatively charged quartz snrf?ce, 116,117
xaphalt..11S,119 (Cutback ~~~t is ml MPildt ==ted iti
an inexpensive solvent, such as gasoline, to reduce the CIays. Several researchers have studied tie adsorption
viscosi~.) HaiIcnck 11s - Seved strongly water-wet of aiphaftcnis Wd resipa onto clays, and found that.ad- ;
soils with cut-back asphalt. He fokd that the oil wetness sorption can make the clays more oil-wet. 70,76.1~, 120-133
1130 Journalof Pmol&m Technology,October1986
Clementz %120,121 eximined adsorption under mhy- may be a:rcauft of dif3i3si0nof organic cmnpounda released
droua conditions of the heafl endsthe nonvolndle, high- during diagenesis from the small, organic, detrital pard-
molecuiar-weight fraction-of cmde oil, which are cles of cod scattered throughout the zone. Unforhmate-
primarily asphal~nes snd resins. He found that rhe com- ly, this is unclear at present. Thin sections from both
pounds adsorbed rapidly onto montmorillonhe, forming water-wet and neutrally wet (tier clcaqing) zones show
a stable clay/organic compound and chsnging the netta- that both contain approqtely equal amounts and dis-.
bility from water-wet to oil-wet. Clementz also looked @bution of woody coal; algae coal, and pyrite. Conse-
at adsorption under anhydrous coiiditions of the heavy quently, it is unknown what causes the postcleaning
ends onto Berwcorca that contain significant amounts of neutral tiettability of this neutrally wet zone.
kaolinite. The adsorption of tie heavy ends made the core Boneauand Cfampitt 131and Trantham and Cknnpitt 132
neutrally wet as determined by an imblbhion test. The ad- stite that the oil wetness of the North Burbank unit is
sorption also,reduced the expansion of swelling clays, clay caused by a coating of chamosite clay (Fe3Al zSi2O IO
surface area, cation exchange capacity, and water sensi- . 3HzO) on the pore surfaces rather than the more com-
tivity. The materials that adsorbed onto both the mont- mon, strongly adsorbed organic coating. The chamosite
morillonite and kaolinite were difficult to remove, clay, which is iron rich, covers about 70% of the rock
although most of them could be exmacted with a chloro- surfaces It seems plausible that tbe chamosite cfay renders
formlacetone mixture. the core oil-wet because, as discussed earlier, iron ions
Clementzused dry cores and clays. As discussed C& are strong activators, promoting o~-weufng. Cl~pitt*
er, the presence of a water fdm will gen@ly reduce the states that unpubliahti contact-angle measurements made
adsorption of wettabfity-altering materials, typically by with all of the ~emls inthe No&Burbank core ahowed
a factor of two to four, although in some cases, it will that chamosite M naturally oil-wet.
completely inhibk adsorption. >@ Collins and Melmse70
measured the adsorption onto kaolinite of asphaltenes dk- Artificial Variation of Wettabifity
solved in tolucne. The dry clay adsorbed a maximum of Aadescribed previously, a native-state core contains a
about 30 mg asphaltene/g clay. The addkion of 6.6% cmmplex mixture of different compounds that can adsorb
water t? the clay reduced the adsorption to 13 mg/g. In and deaorb, possibly altering the wettabdity during an ex-
addition to reducing the adsorption, the water l@ may periment. Msny re8esrchers have tried to simpfify their
alter the d:tied mechanism of asphaltene adsor@on be- experiments by artificially control~mg the wettabfii~ to
cause the asphaltenes and water will coadaorb. 7 For ex- some constant, uniform value. The three methods most
ample, in contrast to his work with anhydrous cores, commonly used are (1) treabnent of a clean, dry core with
ClemenE found that the adsorption of asphaltene onto various chemicals, generally orgWOcMOrOsfl~es fOr.
Berea cores in the presence of water dld not reduce the sandstone cores and naphtienic adds fOrwbOnat~ core~
water sensitivity of the kaoliidte. lW (2) using sintered cores witi, pure fluids; and (3) adding
surfacthnts to the fluids. A sintered tdlon core with pure
Non-Water-Wet Mineral.% When all of the surface con- fluids is the preferred method to obtain a uniformly wet-
taminants are carefully removed, most minerals, includ- ted core because tic wetrabili~ of these coma is constant
ing quartz, carbonates, and sulfates, are wrongly snd reproducible. The fiettabilhy of cores treatid with
water-wet. go,1o7,lx From flotation studies, however, a
brganochlorosilan:s, naphthenic acids, or stirfactanta is
few minerals have been found that are naturally but weakly much more variable because it afso depends on such vari-
water-wet or even oil-wet. These minerals include sul- ablesas the chemical uked, the concentration, tie treat-
fnr; graphite, talc, coal, snd msny sulfides. Pyrophyllhe ment time, the rock surface, and the brine PH. These
and other talc-like silicates (sificates with a sheet-liie treatments have advantages, however, when he~rOgen~-
&rncture) are ~obably also neutrally wet to Oil- ous wettabtity or wettsbil~ alter~tion is studied.
~et, 30,107,134-12~ese finer~~ ~ ~OW~ tO be SO~e-
what hydrophobic because air can be used to float them Organochlorosffanes and Other Core Tr&dmMa. One.
on water ir3froth flotation, implying a large waterlairhnin- method of making a sandatone core uniformly non-watcr-
eral contact angle. Because they are non-water-wet with wet is to treat it with a solution conpining an OrganO-
air, it is probable that they are also oil-wet. ~~oro~~e ~ompond, 133-139vm~tiom of ~~ tf~~t-
On the bsais of core-cleaning attempts in a limited num- ment have also been used to create fractionally wetted
ber of reservoirs, it appears that cores containing conl are ~mdpacf&&+$50.1@h!2~d mixed-wet cores. 143me ~r-
sometimes na.tur@ly neutrally wet because they can be ganosilane compounds contain silicon molecules with at-
cleaned only to a neutfsll wet condition rsther than a tached chlorines and non-water-wet organic groups, with.
~Uon lY wa~r.wet one. 1za,129 Cuiec96 and Cuicc et the general formufa RnSiC14-n where R is usually
al. 138 cleaned unpreserved cores with different solvents methyl or phenyl and n =0, 1, 2, or 3.133 These sub-
and then measured wettabdity. In four cases where cores stances ,react with the hydroxyl (OH) groups on silicon
contained large ixnounts of unexmactable organic carbon, dioxide surfsces, exposing the organic groups and ren-
they were able to clean the cores only ti neutmf nettabil- dering the surface non-water-wet. For example, dimerhyl-
ity. Wendel et al. 12s cleaned core from the Hutton reser- dichlorosilane, (CH3)2SiC12 (Drifilm@ or Teddol@ ),
v6ii contaminated with an invefi-oil-emulsion drilling chemisorbs on the outside of the sificate lattice of glass,
mud. Core from most zones in thk reservoir could be eliminating HC1 and exposing CH groups, which reduce
cleaned to a water-wet state. However, in one zone that the wata-wetness of the surface 1h Other compounds il3-
contained si=tilcant amounts of coal, the core was neu- clude heximethyldkilazane 138 and trimethyMdo!Osi-
trally wet after cleaning. About 50% of the rock surface kme. 145The wettabfily of the core is altered by flowing
in tie neutrally wet zone was covered by a thin layer of .P.rsmtic.nnm.nimtimwithR.L.Clmnpiu,Ptiltip Petroleum,BaII[esvilleOK,
organic matter less than 300 ~ [30 mn] thick. ThIS fayer Dac.1S83.

Journalof PetroleumTechnology,October1986 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 of the filtrates was an iinpotit factor in we~bdity al-
Coring. In a nativi-stite (fresh) core, every precaution teration. The origti bentonite filtrate changed me wet-
is taken to minimtie changes from the undkturbed reser- tzbtity from oil-wet to water-wet. When the pH was
voir nettability condhion, starting when the core ig frost lowered into the neutml or acidic rsnge, however, no wet-
flushed by the dr~g mud. In pyticukw, a mid with s~- tabtitjI reversaIoccurr+.
factants or a pH that differs greatly from the reservoir Sharma snd Wunderlich 158meaaurcd the wettabi!.iwaf-
fluids must be avoided. Ofl-based-emulsion muds ?nd teration caused by different drilliig mu@components in
other muds containing surfactaits, caustics, mud thinners, water-wet and oif-wet Berea plugs. The oil-wet Berea
organic coriosion, in&itors, and lign@fonates must be plugs were prepared by treatmentwiti an asphaltic crude
avoided. 175,177Note that, @hIle they probably exist, no and pcntane, as discussed previously. Dry plugs were
commercially available oil-based muds have been m rted saturated with brine, injected with 10 to 12 PVs of the
thatcan preserve the reservoir nettability. 175>17178 drilling fluid component, aged for 15 hours; tien flushed
The different coring fluids for obtaining native-stati with 5 to 6 PVs of brine. Wettabilky was measurd af-
cye have been recomriended. (1) synthetic formation ter contamination by a combined USBM/Aniotl method
brine, (2).unoxidized lease crude oil, or (3) a water-breed developed by Shagna and Wunderlich 158and compared
mud with a miniznuin of addhives. Bobek et al. 175rec- with the we~bility of control samples. The driiing comp-
ommend coring with brine and noadditives. If ,.hk is not onents tested included bentonite,, carboxymethyl cellu-
possible, a water-based mud containing only bentonite, lose, Dextrid@ (an organic polymer), D~spac@ (a
cnrboxymeibyl cellulose, rock salt,, and barite should be polyanionii ceflukiwe polymer), hydroxyetbylcelhdose,
used. This is recommended b~ause they found that this pregelatinized starch, and xanthm gum. These compo-
would not alter the wembfiity of strongly water-wet cores. nents are generally considered relatively bltid, with onfy
Note, however, that the carboxymethyl celkdose,may ~ter small effects on the wettiibilky. None of the components
the wettabfit of oil-wet cores, rendering them more affected the nettability of ~e water-wet plugs. However,
water-wet, 152.~75 Bbrlich and Wygsl 179 recommend a N of the components, with the exception.of the bentonite
synthetic formation brine coritaining CaC12 powder for fdtrate, made the oil-wet plugs significantly less oil-wet.
fluid loss control and no o~er additives. Mungait 180rec- This indicat&stie need for further rese~ch on acceptable
otiends coriug with lease crude oil. Note f.hatthere are drillings muds for obtaining native-state core.
tio possible problems with the use of crude oil: (1) it Several researchers have attempted unsuccessfully to
is flammable, and (2) surfactams can be formed by oxi- fmd suitable commercially available oil-based muds for
dation. of the cmde, which could alter tie wetta- ~btig ~tive.sate core, 175, 177, 178,~ of tie ~fi.ba~~
bili@. ,103 drilling mud iiltrates tesied made water-wet cores more
rhfortummly, very MtIe work has been published about oil-wet. Unfortunately,. none of the reports identify tlze
the effects of individual drilling mud components cmwet- specific drilling mud components used. ,
tabiihy, particularly for oif-wet cores. Burkhardt .r al. 176
exaniined the effects of mud filtrate flushing on restored- Cm-e Packaging and Preierv&ion. Once the core is
,stitecores snd found no significant effects. Unfortunate- brought to the surface, it must be protected from wetW
ly, the cores were in contact with the crude oil for only btity alteration caused by the loss of light ends or depo-
12 to 16.hours, so it is doubtfol that the wettabtity was sition snd oxkldion of heavy ends., On exposure to air, .
restored before testing. subticei k crizdecan rapidly okidize to form wkw prod-
Bobek ei al. 175 tested several dit%r<nt drillkm mud ucts that are surfactants, altering ihe wettabili-
componerits used in water-baaemuds on both wat~r-wet ,W,34,73,103,115,175,181,182 M ad&tiOn, a tick ofl-w@
and oil-wet pings The drilling mud :omp6nen@ to be test- residue from the crude will be deposited on &e rock sur-
ed were dksolved in or leachdwith distied water then face if the core is allowed to dry out. To prevent wetE-
the resulting solntion was filtcreii. Concentrations of the bility alteration, Bobek et al. 175 recommended two
compamds were chosen to duplicate those encountered sltemitive packaging procedure: that are now gene@y
in the field: Water-wet limestone and s~dstone plugs were used for native-state cores. The fwst ia to wrap the cores
saturated .wltb the test solution and wetibflity alteration at the weUii@in polyethylene or polyvinylidene film and
monitored by the irgblbkion method., As,dkcussed earli- then in aluminum foil. The wrapped cores we then sealed
er,.theyfonnd flat rock salt, carboxymethyl celhdose,. with a thick layer of paraffin or a special plastic sealer
bentonite, and bake had ho effect on tie wetmbfli~ Of designed to exclnde oxygen aid prevent evaporation. The
these initially water-wet plugs. Starch, lime, tetmsoditirn second, preferred method is to immerse the cores at tip
phosphate, and calcium lignosujfomte altered the wetta- wellsite in deoxygenated formation or synthetic brine in
btity of the sandstone and/or limestone plugs. a glass-lined steel or plastic tube, which is then seafid
Drilhg components that, did not.affect the water-wet to prevent leakage and the entrance of oxygen. ImbibG
plugs were tested on oil-wet sandstone plugs. The dry, tion wettabihw tests showed that the nettability of core
initially water-wet plugs were made oil-wet before test- packaged by either of these WO methods was unchanged
ing by saturation with Elk Basin crude and aging for one from the wettabfily mesaimed at the wellsite. Instid of
day. Notethit becanse of the short duration of the aging, deoxygenated brine, Mungari180 recommended tit the
the wettabiity may not have been in equilibri~. The aged cores be cut and stored in degassed l&ae crude oil. Mor-
cores were flushed witi a drilling mud component fkraW, gan and Gordan 183and McGhee et al. 62 recommended
then the wettabfity was measured. by the imbibition that the cores be stored in their wetting fluid, either for-
method. .Sa.kdid not affect the wettabfity, whfle carb- ntstion brine or crude oil. Thewettabiky would be,deter-
oxymethyl cellulose made. the plugs more water-wet mined by an imblbhion test at the wellsite. Finally, not?
(bariti was not tested). Bobck et al. found that the PH that cores taken in a robber sleeve, fiberglass, or PVC
1134 Journalof Petroleum Tedmo108y, Octpber 1986


Number Average . Average

of Cores Dlsplacement- Oisplacement-
Tested iescriplion by-Water Ratio by-oi Ratio
2 Native state 0,97 0,00
3 Exposed to air at
70 to 100nF for 1 day 0.63 0.00
2 Exposed to air at
75F for 60 days 0.42 0.00
4 Exposed to air at
225F for 7 days 0.18 0.00

Cay$btdnedbyuse ofthe Amattwellafl~v,,s, natNeNatecorefrom0,! Zone8., SterlingConly,


liner can be DESeNed if the ends are cappedand sealed. approaches one as the water-wetness increases. Siniiiar:
A number-of experiments have dem&strated that ex- ly~ the displacement-by-oil ratio is zero for neutrally and
posure to air and drying cao alter the nettability of core. water-wetcores aod approaches one as the oil-wetness
As discussed earlier, Treiber et al. w measured the. net- increases. The cores became more oil-wet as they were
tability of 50 reservoirs usfig deoxygemted synthetic for- either exposed to the air for longer periods of time, o!
mation brine and anaerobic crude. In some cases, the at higher temperatures. Similar tests on an initially weakly
contact angle showed that the reservoir was water-wet. water-wet core showed elmost no change. On the other
For some of those cnrdes, exposure to oxygen changed hand, Mungan 115used the imbibition method to meas-
the wettabili~ to ofi-wet. Bartell mrd Niederhauser103 ure the wettabilhy of native-state cores. In contrast to tie
stodied interracially active materials in crude, which con- experiments discussed above, cores preserved in deaer-
centrate and form solid fflms at the oil/water interface. ated water were oil-wet, but becsore water-wet when ex-
These materiils can also be adsorbed on the rock surface, posed to ti for 1 week. Chfingar and Yen35 have also
rendering it oil-wet. Crodes and brines were obteined and reported that some cores became more water-wet on ex-
stored without exposure to oxygen. Most of these crudes posure to sir, indicating that it is bnpossible to predict
showed very little interfaciel activity. On exposure to air, how the wetfsbtity will be altered by tie oxidation of tie
the cmdes developed moderate-to-strong fdrn-fomning cmde.
tendencies, while the oil/water IFT was lowered by as Mungao 180recnmmendsflushing native-state core with
much as 50 %, indicating that surfactants were formed by five erode oil before sny flow studies are startsd. After
oxidatiori of the crude... native-state cores .havc been prepared, they are usually
Richadson et al. 1s2 stored core from a mixed- nm at reservoir conditions with crude oil and brine.
wettability reservoir47 using four different methods. Ox- Probably the greatest, uncontrollable problem with
idation snd drying of the core tiere prevented with the nstive-state core is the alteration of nettability as the core
first two methods: (1) core wrapped in foil and scaled in is brought m the surface., When the pressure is lowered
paraffh and (2) core stored in evacuated (deoxygenated) to atmospheric, light ends are lost from the erode, chang-
formation water. The other methods were (3) core stored ing its properties. In addition, heavy components cm come
in aerated formation water and (4) core stored in cloth out of solution and deposit on the rock, making it more
core bags. The cores were oilflooded with kerosene to oil-wet. 137 The decrease in temperature wilf also
IWS and then waterflooded. The average ROS for the decrease the solubili~ of some wettebfli~-altering com-
samples protected from oxidation and drying (Methods pounds. Pressure coring prevents tie loss of light .erids.
1 and2) was about 13%; forthesamples submergedin However, the cores are frozen before removal, so
aerated water, about 24%; and for the samples storedin wetta.bflity-altering compounds W deposit. Unfortunate-
core bags, about 25%. ly, there is no experimental work avsilableon wettabfli-
Bobciket al. 175used the imbibition method to compare ty alteration as the core is brought to the surface. ..
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 Cleaned Core
cores stored by either of the two recommended methods The second type of core used in core aoalyais is the
was the same as the nettability measured at the wellsite, cleaned core. Cr&ig7 recommends that cleaned core be
while most of the weathered cores became more oil-wet. used for multiphase flow measurements only when the
Am0tt177 used bismethtidt ocomparith ewettabihy reservoir is known to be strongly water-wet because errors
of native-state cores with similar cores that were exposed iq the core am.lysis will be introduced otiimvise. There
tooxygen ayd~owed to partially dry, asshownin Ta- are two main reasons to clean wre. The first is to remove
ble 3. The native-stste cores were strongly water-wet, with all liquids fromthe core so that. porosity, permeability,
a dkplacement-by -water ratio of 0.97. In the Amott test, and fluid saturations can be measured. Core cleaning for
the displacement-by-water ratio is the ratio of the oil these roudoe core measurements will not be considered
volume displaced by spontaneous imbibition to the total in this paper. The second reason for cleaning is to obtain
oil volume displaced by .botb imbibition and forced dis- a strongly water-wet core, generally as a first step in
placement. Itiszero forneuqally mdofl-wetcO~~s aod restoring the wettabfity of a contaminated core.
J&mal of Petroleum .Tecbnology, October 1986 1135
In obtaining a cleaned core, an attempt is made to re- tenes 130JW and some of the weakly polar compcmmi.s,lW
move all of the fluids and adsorbed material, leaving a wbiletbe more,spongly polar methanol (ethanol) qcmoves
clean rock surface. Gant aid Anderson 129 discuss the the strongly adsorbed polar compounds that are often
meibcdsused,tu clean core. One common method is reflux responsible for altering wettabilky. In addition to
extraction (l)ean-Stark or Soxhfet) with a solvent such as toluenelmethanol and tolueneletbonol, successful clean-
toluene, sometimes followed by extraction with cfdoro- ing has ako been reported with cbforoforndace-
form or methanol. Alternatively, a flow-through system tone 1wZ120. 1= and cfdorofordmetfranol, 1s4 as well as
where the solvents are injected under pressure is some- a number of different series of solvents. ,65
times used. 57,&,65lf the cleaning procedure is success- CuieCand his coworkers made the most extensive study
ful, the core is left strongly water-wet. Cuiec$5 mid of core cleaning for nettability restoration. In a recent
others 57,1w discussed the chemicalreactions involved in paper, Cuiec et az. 130statkd that their core cleaning al-
the cleanin process. ways begins with a toluene flush to remove hydrocarbons
Cui&ca,& compared me efficiency of different solvents and asphaltenes. A number of solvents are then.tested to
in flow-through core cleaning. Initially water-wet outcrop determine the most effective, including (1) a series of non-
sandstone and limestone cores were saturated with differ- polar solvents, e.g., cyclohexane or heptane; (2) acidic
ent cntdes (sometimes the cores also contained brine), then solvents, e.g., cblorofonn, ethanol, or metbanoh (3) ba-
aged. The aged cores ivere ncyrmfly neutr~- to oil-wet, sic solventi, e.g., dioxane or pyridine; ond (4) mixtures
as determined. by the Amott wettabflity test. The cores of solvents, e.g., methanollacetoneltoluene. When none
were then cletied with dlffererit solvents, and the Amott of these procedures are effective, other tests are performed
test was used to determine cleauing efficiency. Cuiec by combining the above procedural, using otler solvents,
found that he could clean both sandstone and liiestone ad incremfig the Circdatiog time.
cores by flowing the f?ll@ig seven solvents through the Tohtene is generally not a very effective solvent, but
core: pdarte, hexane, heptane, cyclobexane, beuzene, it canalter the nettability of some core. Jennings 186
pyridine, and ethanol. Chloroform, tohtene, and methanol cleaned sever,d cores by toluene extraction and found that
used singly were not very effective. Cuiec also looked the wettabilities and relative penn.eabilities were not
at several dtiercnt acidic and basic solvents used individu- changed. He stoted that this indicated that toluene-
ally and found that the acidic solvents tended to be more extmcted core retoined the reservoir wettabi!ity and coufd
effective in cleaning sandstone, whiie the basic solvents be used for relative p+mneabtity rneosurements, However,
were better in cleaning Iimcstone. This difference was at- this generally is not the case. Aftbough it is less et%cient
tributed to the acidic nature of the sandstone surface and than other solvents, we have found that toluene extrac-
the basic mture of the limestone surface. For examplei tion can alter the wettabili@ and relative penneabtitics
because sandstone (silica) has a weakly acidic surface, of native-state core. fn some cases, neutmlly wet or tidly
it tends to adsorb bases from tie crude oif. When a oil-wet mtive-state core becomes strongly water-wet ti-
stronger acid flows through the sys@m, it will gradually ter extraction witi toluene. The relative permeability
react with and strip off the adsorbed bases, Ieaviug a clean cume~ ~~o ~E,fi. AMOU177 ako found that toluene ex-
silica surface. traction can clean some cores, while it had Wt3e effect
G@ and Anderson 129 surveyed most of the core- for other ones, such as the strongly oil-wet Bradford cores.
cleouing experiments in the literature. They found that Therefore, because tolueneextraction will alter the wet-
the best choice of solvents depends heavily on the cmde tabilky and relative permeability of many. native-state
~d the mineral surfaces becavse they help determine the cores, m%uremcnts shouId be tie on mtive-state cores
amount and @pe of nettability-altering compounds ad- before toluene extinction.
sorbed. Solvents that give good results with some cores One problem with a cleaned core is that it is sometimes
and cmdes often faif in other cases. For example, Grist difficult, if not impossible, to remove all of the adsorbed
et al. 1s4 and Holbrook and Beruard45 both found that material. If this occurs, the wetta.bfity of tie cleaned core
they could clean core to a strongly water-wet state using wifl be left in some indefinite staie, causing variations in
a cliloroformfmerhanol mixture, while Jennings5s repOrt- core analyses. Grist et al. lW cleaned cores by three cu-
ed. fiat thk was unsuccessful. For cleaning for routine rently used methods and then examined how ROS and end-
core analysis, API 1s5 reports that cbfom form is excel- point effective permeabilities vtied after a waterflood.
lent for many midcontinent .ctudes,wh~e toluene is us6- ROS was very similar for W methods. However, the end-
ful for asphaltic cntd:s.. point effectiye water permeability varied by more than
hi many cases, it appears that any single solvencis rela- a factor of three betwtin different cleaning methods. Their
tively ineffective in core cleaning and that much better explanation for this behavior was that some methods were
results can be obtained wiih a mixtttfe or series of able to extract more of the adsorbd. components, leav-
solvents. 129 The followhg solvents have, been rCpOfi- ing.the rock more water-wet. In the more water-wet cores,
ed for specflc binbinations of crude and core to give the rwidti oil had a greater tendency to form trapped
pcor resufts when used alone: chloroform, ,65 ben- droplets, blocking pore throats and lowering water per-
zene, 5S,1M,120~=bon di~~fide, lU,120 ~~mol, @ ~d meabtity. The least effective of the three cleaniug me~ods
toluene.5@.@.65 .1~.120,1T.l~,1s6 was overnight reflux extinction with toluene. More ef-
Many of the researchers cited above have found that fective was reflux extraction with toluene followed by 2
toluene used alone is one of the least effective solvents. days of extraction with a mixture of cbloroforin oud
However, when combined with other solvents, such as methanol. Finally, tie most efficient method was reflux
methanol (CHs OH) 184 or ethanol (CH3 CH zOH), 61 extraction with tcduene followed by 3 weeks of extrac-
toluene is often ve~ effective. The toluene is effective tion with chloroform and methanol. In the last stage of
in removing the hydrocarbons, including asphal- cleaning, methanol was used alone.

1136 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 Fig. 1Wettabitity changes for a restored-state core and
the equivalent, containing 1% ammonium hydroxide. A the effects of flushing restored-state cores with refined
three-step method (three successive Dean-Stark OIIS. Berea core and Big Muddy crude.
extractions-toluene, foffowed by glacial acetic acid, fol-
lowed by ethanol) was the second best choice for Berea, error process because the best choice of solvents depends
while 2-methoxyetiyl ether was the second best choice heavily on the crude oil, the mineraf surfaces, and any
for dolomite, demonstrating that the choice of solvents &idling mud contaminant. Further discussion can be
can depend O? the mineral surfaces in the core. foundin Ref. 129.
In the second step, sequentially flowing reservoir fftids
Restored-State Core btto the core, the core is saturated with deoxygenated syn-
If one conld be positivethat the original reservoir wetta- thetic or formation brine and then flooded with crnde oil
bilhy hadizotbeen inadvertently modified, a native-state to simnla.tsthe intlow of oil into the resemoir. When cmde
core would give resnks closest to those of the reservoir. oil for wettahifity restoration is obtained, precautions
However, riative-st@ecores present scveraf problems. The should be taken to minimize alterations to the crude. The
necessary procedures to preserve the wettabtiq are hnple must be taken before tiy Sm&ct.mrts or Ofier
troublesome and time-consuming. Even when sll of the chemicals ae added to treat the crude. It should be taken
precautions iwe tsken, there is still a possibility that the as Iong as possibIe after any wefl treatments to aIIow time
nettability has been chtiged through oxidation or through for these chemicafs to be flushed from the well. Finally,
deposition as tie temperature and pressure dropped when the cmde should be sealed in air:tight containers as soon
the core was brought to the surface. In addition, tic ques- as possible to minimize oxidation and the 10SS of light.
tion arisesabout tie procedure to follow to obtah the most ends.
reliable information from cores in which the nettability The fired step in wettsbfity restoration is to age tie core
WaS aftered at the reservoir temperature for a stilcient time to es-
When onfy core with alt&ed wei@bfity is available, tablish adso~tion e&libzium. The aging time required
the best possible mukiphase measurements ore obtained to re-eatabfish reservoir nettability varies, depending on
by resto& the resefioir wettabfi~ with a three-step the crude, brine, and reservoir rock. Generally, we feel
~roces~. 47,F0,64,65.,96,115,128,130,1S0,18SThe f~st ste~ is to &at core shoufd be aged for 1,000 hours (40 days) at the
~leaa the core to rernoVeall compounds from th~ rock reservoir temperature. 128This a&ng period was chrken
surface. After the core is cleaned, the second step is to for two reasons several experiments have shown that up
flow reservoir fluids into the core sequentially. F~y, to 1,000 hours is required to reach wetting equilibri-
the core is aged at the reservoir temperamre for a suKL- um ~$s. 115,189-lgl and 1,000 hours is roughly the length
cient dine b establish adsorption equilibrium. Seversl ex- of ~me required for the contact ~gle measnred on a flat
perimenters have compared measurements made on core surface to approach its equilibrium value. 7>26,34.191 III
in the native, cleaned, and rsatored states. In each experi- some cases, the restoration time can be significantly less
ment, measurements in the restored state were slmost than l,OW hours. MunganlsO was able to restore the wet-
identical to the,previous mtive-sta.te ones,demons@atin tabilky after aging for 6 days, while the nettability of the
that this procedure will restore nettability. 50,115Js0;18~ rocfuoilhine system used by Schmid50 and Riibl et
~,, The first and most @fficult step in nettability restora- ~. lss was restord after only 3 days. Salathie147was able
tion is to clean the contaminated core by use of the to restore a mixed-wettabilhy qate to samples after 3 days.
methods described to remove all compounds adsorbed on Cuiec et al. 130describes two reservoirs in which the wet-
the surfaces and to make the core as water-wet as possi- tabtity was restored after only a few hours, with no fur, <
ble. All compounds must be removed from the core be- ther cbamges in tie wettabiIity for aging times as long as
cause we have no knowledge of which compounds were 1,000 ho;rs.
adsorbed on the undisturbed reservoir rock and which There are two basic options to determine the aging time
were deposited afterward. The USBM or Amott netta- to restore wettabllitv. We feel that it is ,most convenient
bility measurements are used to verify that the core is to age afl cores for l:W hours, which is roughly the mm-
strongly water-wet., Unforttzmtely, detemining which sol- imum time that the experiments discussed previously re-
vent wiII successfoffy clean the core is still a trial-and- quired to achieve wetting equilibrium. While cores may

Iourmt of Petroleum Technology, October 1986 1137

be aged for a period longer than the minimum necessary, nored, cleaned cores are generally mn with refined oif
thk is not a serious drawback because the aging cores re- (or even mercury or air) at room temperature and pres-
quire minimal attention. Another possibtity is to deter- sure. From the viewpoint of titaining the nettability,
mine the minizhtzmaging time by measuring the wetrabfity the best laboratory tests should be mn with native or re-
of the core with the USBM or Amen methods at frequent stored cores at reservoir conditions with live cntde oil and
intervals during the aging period. The aging is stopped brine because this is the best simulation of reservoir con-
when the wettabflity reaches its cquilibtium value. ditions possible. Cor~ are generally more water-wet .at
Although this minimizes aging time, it is much less con- rese~oir conditions tbzn they are at rooin temperature
venient because it is labor intensive nnd requires frequent ad pressure, 62,180,192-195 The effects of the following
disturbances to the plug. experimental conditions on nettability will be dkcussed:
The core is aged at either the reservoir pressure with (1) rcaervoir vs. room temperature, (2) live vs. &ad cmde
live cmdeso, 180,188,191or ambient pressure with dead at reservoir pressure, and (3) refined vs. crude oils.
cmde. 115.128.190 When live crude oils a~d the reservoir Changing the temperature has two different effects, both
pressure are used, the solubflities of the wettabilhy- of wtich tend to make the core mom water-wet at higher
altering compounds should have their reservoir values. temperamres. First, an increase in temperature tends to
It is possible that the nettability will differ when dead increase the solubtity of wettabtity-altering cOm-
cmdes .at nmblent pressure are used. At the present time, pounds. 196 some of ~eSe compounds will even desorb
however; it is not known whether the difference is im- from the surface as the temperature increases. Second,
portazm the IFT and the contact angle measured through -bewater
Fig. 1 shows the chsnges in the USBM wettabfity in- will decreaae as the temperate increases. This effect has
dex as a core was restored. * A series of Berea plugs was been noted in experiments with cleaned cores, minernl
saturated with brine and driven to IWS by centrifugation oil, and brine, where it was found that cores at higher
in crude oil. Each core was aged in dead crude for a differ- temperatures were more water-wet even though there
ent period, of time, after which the USBM wettabtity was were no compounds that could adsorb and desorb. 19-2?
measured. As can be seen, the wettabilky changed from For example, McCaffery201 measured the water-
water-wet (W =0.8) to moderately oil-wet ( W= O.3) advancing contact angle on qWrtz of n-tetradecane and
over a 40-day period. The plugs flushed with Soltrol@ brine. The amglewas about 40 [0.7 rad] at 77F [25C],
and Blnndol@ will be dkcussed later. but decreased to about 15. [0.3 rad] as the temperature
Lorcnzetal. 190and Cuiec65 found tbatitissometknes was raised to 300F [150 C].
possible to speed up the approach to wetting equilibrium when live crude oils at the reservoir pressure and tem-
by saturating.thecore with oil alone. The approach to perature are used, the solubilities of.dzewettabfity-afteting
equilibrium is fastix because the polar compounds no compounds have their reservoir values. The use of dead
longer have to dlffase across a water layer to adsorb on crude at ambient or reservoir prcasure may change the
the rock. This procedure should be avoided, however, be- nettability kmzse the properties of the crude are altered.
cause it can give iriaccuratc results. For example, con- Light ends are lost from the crude, while the heavy ends
sider the restoration of a core that originally had are, less soluble, which may make the core more oil-wet.
Salatbiels47 mixed wettab~ity, where &e large pores are However, the effects of pressure are not known at pres-
oil-wet nndthesma!.l ones are water-wet. During tbeag- ent. The two reported experiments found that ressure
ing process, thesmall pores must contain comate.water is much less important than temperature. 18~,1~ Hje~.

to prevent the deposition of au oil-wet fiim, leaving them meland and Lamondo 192 found little difference in con-
water-wet. Onthe other hand, ifaclcan core is saturated tact angles measured using stock-tank vs. live cmde at
only with oil, tbe entire core, includlu gtbesmallpores, the reservoir temperature (190F 88C]) and pressure
will become uniforndy oil-wet, whlchis the wrong wet- (3,800 psi [26.2 MPa]). Mtmgan 10 i measured a water-
tability. Anaddhionalp roblemw ithsaturadngt iec ore advancing contact angle ,of $7 [1.5 rad] using live reser-
solely with oil istbat the effects of brine chemistry are voir crude and synthetic formation brine at resemok tem-
ignored. As discussed previously, the wettabtity of the perikurc (138F [59C]) and pressure (1,200, psi [g.3
core depends on the ionic composition and pH of the brine. MPa]). The water-advwcing contact angle was almost
Finally, Clementz10?.120,121$howedtbat flowing cntde identical, 85 [1.48 rad], using degassed crude and brine
oiltbrougha dry core camcause tbeformition of very at ambient pressure and reservoir temperamre.
stable oil-wet, claylorganic complexes. Thepresenceof Because refined oifs are much easier to work with tlum
an initial water film on the clay surfaces haa been shown cmde, it is a common laboratory practice to flush native-
to reduce but not completely inhibit the adsorption of the or restored-state cores with refined oil before testing.
nettability-akering materkds. @@.70 The effects of brine However, there is a possibilky that this idters the netta-
OtI wearability make it necesssry to saturate the core with bility. Craig7 poshdated that it would be possible, once
brine, then oil, during the nettability restoration process. the original wettabtity was restored, to use refined nzin-
eml oil in place of crude oil in laboratory tests without
Experimental Conditions adversely affecting the wetk+bility. Test times are shor!
compared with the time it takes to achieve adsorption equi-
Once a mtive or restored-state core is obtained, core anal-
librium and obtain native wettsbtity (about 1,000 hours).
yses can be performed. These tests can be mn with either
Craig hypothesized that the desorption of wettability-
crude or refined oil at ambient or reservok temperature
Mbzencing materials would require a correspondingly
and pressure. Because wettabfity effects are being ig-
long period of time. If this is correct, @e orig@l wetta-
TestingSeMceS,Smta btity wotdd be unchanged if laboratory tests using refined
Fe SPringS,CA,No.19S0. oil and brine were conducted quickly enough.

1138 Journal of PetroleumTechnology,October1986

The onfy experinient to teat this hypothesis that we are oxidized lease crude oil, or (3) a water-based mud with
aware of was conducted by Wendel. * He aged ,Blg Mud- a minimum of iddkives. B&use of surfactits in the SYS-
dy crude in Berea sandstone at IWS to develop his tern, no conimercitiy available oil-based or oil-ernukion
restorer-state cores. The cores. were flushed with one of muds are khown that preserve the native wt?ttability.
two refinkdoik, Soltrol 170 or Bkmdol, to detexmine how 8. The wetr?bility of a native-state core. cambe altered
they affected the wettabfily. The results&e show in Fig. by loss of light ,ends and/or the deposition aid oxidation
1. Bkmdol did not si@ficantly affect the we~btity, while of heayy ends. TWOalternative pac@ging procedures cam
Soltml 170 changed tbe core from oil-wetto neutrally wet. be used to miniinize these effects. The first is to immerse
The wettabdity: alteration could be caused by either the corei in deoxygenatdd formation or synthetic brine
surface-atilve impurities in the Soltrol 175or desorption and place !hem in a glass-lined steel or plastic tube, which
of previously depositwj oti-wetdng crude compounds from is then seaIed against leakage aud the entrance of oxy-
the pore walls into tie Soltrol. It i; not known which ex- gen. An alteinaiive procedure is to wrap the cores at the
planation is correct. Wendel did not attempt to fflter the welksite in polyethylene or pglyvinylidene fdm and tien.
refined oils tfmugh a cbromatogmphic coltmm tn remove in ihunirimn foil. The wrapped pore is tlyn coated with
surface-active compounds. These contamiim ts are known i+thick layer of paraffin or a plastic sealer.
to have a large effect on corit.w-migle measurements, 9. Because of the increased solublky of the wettability-
which are extremely seyitive to small amounts of con- altering compounds at the higher temperature spd pres-
taminants. Wettabifity measurements in core should be sure, the cmde-odtbrinetcore system is usually more
less sensitive, however, because the ratio of smface area water-wet at reservoir condition than at ambient con&-
to volume is much higher. tions. In addition, the contact angle measured tluough the
water will generslly decrease as the tempetatufe is in-
Conc133sioris creased, and the system will become more water-wet,
1. The nettability of a rsaeryoir ample affects ita capil- even if no surfactauts are present.
lmy pressure, relative pe,rmwbtity, waterflood behavior, 10. Extraction with toluene cti alter the wettabil.ity of
dispersion, mid electrical properties. fn addhion, simu- some iiative-state cores, causing someinitially neutrally
lated teftiary recovery can be 51ter,cd.The tcfi,~ recov- wet or qikfly oil-wet cores to become strongly water-wet.
e~ PrOcesses affected by we~biE~ include hot-water, Measurements on native-state iorei should be made be-
surfactant, miscible, aid caustm floodlng. fore toluene extraction.
2. Cleaned, strongly water-wet cores should be used 11. During the attempted restoration of a cleaned core
onfy in such c6re analyses as porosity. and air permeabil- to ita orig$al wetrabtity, the core should be saturated with
ity, where the wettabilky is unhpportmrt. h addition, they brine, @lflooded, md then aged at the reservoir corrdi-
may be used in other tests when the reservoir is known tiom for 1,COOhours. This will embie a inixed-wettabtity
to be strongly water-wet. condhkin to be restored, if thk was the original wettabd-
3. The nettability of originally water-wet mineral sgr- ity. In addition, it will allow the brine chemistry to influ-
faces can be altered by the adsorption of pokw compounds ence tie r~tored nettability. An alternative procedure,
aui/or the deposition of orgariic rnattertlmtwas origi- which completely saruratea the core with cmde oil, should,
MUY in the crude oil. Fmrfactants in the crude oil are be avoided.,
generally believed to ,be polar compounds that contain 12. The three commonly used methods for artificially
oxygen, nitrogen, ,mdlor sulfur. These compounds ~ conrrolEng wettabfity during laboratory experiments are
most prevalent in the heavier fractions of crude oil, such (1) treatment of the core with chemicals, generally or-
as the resins and asphaltenes. ghocblorosilane solutions for sandstone. cores and
4. Nettability alteration is determined by the interac- naphtbenic acids for carbonate cores; (2) using sintered
tion of the oil constituents, the mineral surface, and the teflon cores with pure fluids; and (3) adding surfacmnts
brine chemistfy, including ionic composition and pH. In to the fluids. To obtain a uniformly wetted core, a sin-
siIicafoiVbrine systems, trace amounts of mukivalent me- teredteflon core with pure fluids is preferred because its
M. cations can alter *e nettability. The catiom can reduce nettability is more constant and re reducible than the wet-
the solubti~ of crude oil surfactants and/or activate the tabilby of cores treated WI# organochlorosilanes,
adsorption of aniotiic surfactants onto the silks. Mfdtiva- naphthenic acids, or smfactants. However, these treat-
lent ions :$tathave altered tie wettabfity of sihcafoil/brine ments have advantages when heterogeneous wettabllity
systems tnclude Ca2, .Mg2, Cu2, Ni2, and Fe3. or nettability alteration isstudied.
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 I w grateful to Jeff Meyers for hk many helpful sugges-
other minerals-includhg quartz, carbonates, and tions and comments. I also thank the management of
sulfatesare strongly water-wet in their natural s@.te. Conoco h.c. for permission to publish this paper,
6. Contact-angle measurements suggest ti.at most car-
bonate reservoirs range frpm neutralIy to oil-wet as a re- References
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1140 Journal of Pecrolewn Technology, October 19S6

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Journalof Petroleum Technology, October 19S6 1141

100. Hasiba, H,H.andJessen,F.W.:cFiJmForming CompoundsFrom don/Gas$s!ems; Applicadonsm Fforadm Research,P. Somasum
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1142 lo.maf of Petroleum Technology, Ocfob&r1986

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(@t. -Dec. 1974) 13, N0.4 ,, q-C*
...., 18S. Rthl, W., Scbndd, C., and Wissrnm, W.:``Displaccment TesS
163. Mwmw,k!.R.andM. ninth N,: .%Nettability and CapiJJariV in With Porous Rink, Samples Under Reservoir Conditions, Proc.,
Porous Media,,, Petroleum Remvery Research Inst., Caf@ry> Sfi World pet. Cong., Frad=km (1963), Sec. 2, PaFr 11, PD6,
F@rLRR-7( Jan. 1971). 467-S1.
164. Morrow, N. R.: TbeEffectso fSurfaceR oughnessonC ontact 1S9. EhrJich, R., Hasiba, H.H., and Raimondi, P.:``Alkafine Water-
Angle Wifh Special Reference mPelmlenm Recovery,J. cd.. tlooding for Wetfabiliw Alteration-Evaluating. PotenfiaJ Field
Pet. Te-ck. (Oct.-Dee. 1975) 14, NO. 4,42-53. .APPJicatiOn, JPT@= 1974) 1335-43.
165. Momow, N. R.: ~pmPressureC omlatiosf orutifotiY 190. Lorenz, P.B., Domddson,E. C., and Thom2.s,R.D.:`<ti5=of Cen-
Weti Porous Meda.J. Cdn. Pet. Tech. [Oct.-Dee. 1976) mifugaJMeasurements of Wettabtity to Predict Oif Recovery,
15(4),49-69. U.S. Burem of M@, BartJesvilfe Enera Technology cater.
166. Morrow, J.J.R., and McCaffery, F. G.:`` Displacement Smdiesin repmt7873 (1974).
uniformly wetted Porou,Media,3, Wem.g,Spreadi.S, andAd6e- 191. Emery, L.W., M.ngan, N., mdNichoIm", R.W.:``Causti. Sl.s
sion, G.F. Padday (cd.), Academic Press, New York Cky (197S) Injection in the Singleton Field,,, JPTfDec. 1970) 1569.76.
?x9-31q. 192. Hjelmeland, 0.S. and Larmndo, L. E.: ExperimenfaJJnvti-
167. Mmrgan,N.:`7n
terfaciaJEffecLsinkmniscibleL@id-Li quidDis- gation of the Effects of Temperature, Pressure, and Cmde OiJ
placemem in Porous Media,! SPEJ(Sept. 1966)24753; Tran.s., Conm.mition o InterfaciaJ Prmerdes. SPERE (JuIY 1986)
hfE, 237.
168. Mngam N, and Moor6, E,J.: Certai Wetlabilily Effectson 193. Colpitm, G.P. and FJmter, D. E.: LaboratoryDkplacementof
ElecfriwJ Resisfivityin Porous Media, J. Cdn. Per. Tech. (Jm.- Oil by Water Under Simulated.Rescmoir Condifions,J. Gfn.
March 1968) 7, N;. 1,20:25.. PeL Tech. (1964) 3, NO. 2,66-70.
169, Zisman, W.A.: RelationoftheEq.ilibri.mC onIactAngleto 194. EbOg-Economides, C. A.and Economides, M. J.: c$Presmueand
Liquid and Solid ComtiNtio., Con&cz Angl., Wermbilitymwi Temperamre Dependent Properties of the Rock-Fluid Systems in
Adhesion, Advmces in Chemistry Series 43, American Chemi- Petroleum and Geotierrmd Formations, paper SPE S919present-
caJSoc., Washington, DC (1964) 1-51. edatfhe 1982 SPEC#lfonda Re.@aJMeed ng,Bakersfield,
170. Michaels, A.S. and Timmins, R.S.: ,Chromatogsa@dcTinns- Mmh 2S-26.
Prl of Reverse Wetting Agents and 1S Effect on Oil Displace- 195. Kyte, J.R., Naumann, V.O., mdMatlax, C.C.; ..Eff0=tofReser-
nmncinPoromMedia,,, Tram., AfME(1960)219, 150-57. vou Envktimnent on Water-C6iDkrdacemetm. IFT (June 1961)
171. Michads, A. S., StanceII, A., and Porter, M. C.: Effect of Chro- 379-8Z Trans., AJME, 222.
matographic Transpoti in Hexylandne on Displacement of OiJby 196. Jobnson, R.E. and Deti, R.H.: Wetti+biMyan dConmct&-
Wateri Pom.s Media,, >SPEJ (Sept. 1964) 231-3% Trans., gles,,, .9+.. and CoUoidScience, E. Madjevic (d.), WiJeyh-
.4M13, 231. terscieme, New York C@ (1969)2, 85-153.
172. Michaels, A.S, and Pmter, M.C.: L`Water-OilDqbicemenmfmm 197. Poston, S.W. eral.:``The Effect of Ternperafure on Imedicibk
Porow Media UdJizing Transient Adhesion Tension Akemdom,,, Water SZurationand Relafive Permeability of Unconsolidated
AJChEJ. (MY 1965) 11, NO. 4,617-24. .%@,> SPEJ(Jme 1970) 17180; Tram., AJME, 249.
173. Morris, E.E. and Wieland, D:R.: AMicrmcopicS Ndyof the 198. S-ca, B.H. and Guemero, E.T.: TheEffecto fTemperaNre
Effect of Variable Wetfabiliw Condidons on immiscible Fluid Dis- on Dmimge CapiJkuy Pressnre in Rocks Using a Modified Cen-
placement,,, paper SPE 7ti presented at the 1963 SPE AnnuaJ trifuge,>papm SPE 10153presentedat tie 1981SPE AmwaJTech-
Meeting, New Orleans, Oct. .5-9. nical Cofermce and Exh,%ition, San Antonio, Od. 5-7.

Journal of Petroleum Technology, October 1986 1143

199. Sanyal, S,K., Kamey, H.J. Jr., and Mars6en, S.S.: TheEffect S1 Metric Conversion Factors
of Tempaauue on CapiUW Pressure Pm.verdesof Recks, Proc.,
SPWL.4AnnualLogging Symposium, Lafayene, LA, MaY6-9, degrees X 1.745329 E.O2 = rad
= .0c
1973, N1-N16. F (F32)/l.8
200. Simokiot~A3.~,Rarney,H.J.Jr.,an dMarsde%S. S.: <Effect
of Temperature Level Upon Capihy Pressure Curves, SPJ?J
(March 1971) 13-22,
ZOI. Mc&ffeV, F,G.:<<M~umentofln feCf&ialTemiOm and COn- m
Ori@.d !m..mdpt (SPE1 3932) recai.ed in the Sociely of Pelrolwn Enginem oMce
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.

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

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

wet, negative when the system is oil-wet, and near zero
when thesystem is neutmfly wet.
aow = interracial energy [interracial tension (IFT)]
between the oil and water,
Mathods of Wettabitity Measurement
LTO,= interfaced energy between the oil and
did, MaJJy different methods have been proposed for meas-
uring the wettabtity of a system. 616 They include quan-
o~, = interracial energy between the water and
titative methods-contact angles, imbibition and forced
solid, and
displacement (Amott), and USBM wettabfity method
9 = contact angle, the angle of the and qualitative mcthoda-imbibition rates, micmscope ex-
waterloillsolid contact line. amination, flotation, glaas slide method, relative p&rnre-
abdity curves, penneabilitykdumtion relationships,
By convention, the contact angle, O, is me~ured capillary pressure curves, capiflmimetric method, dis-
tbrougb the water. Tbe interracial energy uOWis equal to placement capif.larypressure, reservoir logs, nuclear nrsg-
o, the IFT. netic resonance, and dye adsorption.
As sbowmin Fig. 1, when the contact angle is less than Although no single accepted method exists, tbrcc quan-
90 [1.6 rad], the surface is preferentially water-wet, and titative methods generally are used: (1) contact-angle
when it is greater than 90 [1.6 rad], the surface is measurcnrent, (2) the Amntt 6 method (imbibition and
preferentially oil-wet. For almoat all pure flrdda and clean forced displacement), and (3) the USBM method. g.17.18
rock or F&shed crystal surfaces, IJo, and UWhave values The contact angle mcasurea the wettsbilhy of a spccitic
such that O=0 [0 rad]. When compounds such as crude- su$ace, while the Amott and USBM methods measure
oil components are adaorbed on rock surfaces, these in- the average wettsbility of a core. A comparison of the
tcrfacisl energica arc changed unequalfy. fMs changes wettsbllhy criteria for the three metbuds is shown in Ta-
Oand hence the wettabtity. The farther Ok from 90 [1.6 ble 1. we remaining tests in the fist are qualitative, each
with somewhat different criteria to determine the degree
CQwrmltsm %e~.! Pemleum
Em.e.= 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
F1.a. 1Wettabilitv of the oil/water/rnck svstem. 16
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 tainin~ the mineral crystals is tilled with brine.
discussed in more detaif _latcr, some dlff%ultiea arein- DenW-gemted synthetic ~ormztion brine is used to pre-
volved in applying contact-angle meaaurementa to reserv- vent the introduction of foreign metal ions, which irrcon-
oir cores. Marty methods of contact-angle measurement centrations of only a few parts per million can alter the
have been used. They include the tilting plate method, ~e~bfi~.127 For the mOdifid aessile chop method, an
sessile drops or btibbles, vertical rod method, tensiomet- oil drop is placed between the two crystals so fhat it con-
ric method, cylinder method, and capillary rise method. tacts a large area of each crystal. After the oil/crystal in-
Descriptions of these methods can be found irr Admn- terface hzs aged for a few days, the two crystals are
Son>4 Jobnaon and Dettre, 19 Good, 20 Neumann and displaced pamflel to each other. As shown in Fig. 2b, this
0ood,21 and Popiel. 22 MO~t of these methods are nOt shifts the oil drop and allows brine to move over a por-
generally used in the petroleum industry, however, be- tion of the surface previously covered with oil. The corr-
cause they are better suited for pure fluids with no ad- tact angles measured in this fashion are called
sorption or desorption of surfactants. Because of the water-advancing contact inglea. A nonequilibriunr an-
surface-active agenta in crude, a significant length of tine gle is obacrvcd inrmediately.after the drop is moved. Thk
is needed for a contact angle to reach equ~lbrium. angle decreases for a day or two until a constant value
The methods that aregenerally used in the petroleum is obtained for that age of the oiUsolid irrterfacc. The
industry are the sessile drop method 21.23-25and a modif- oilhnineral surface is then aged further, the water is ad-
ied form of the sessile dro method described by Iezch vanced again, and a new value is obtained.
ef al. 26 and Treiber et al. ! 7 In both methods, the nrin- The procedures sre similzr in the sessife drop methnd.
eral crystal m be tested is moumcd in a test cell compixed A drop of crude oil is formed at the end of a fine capil-
entirely .of inert materisls to prevent contamination. The lary tube and brought into contact with the flat mineral
sessife drop method uses a single flat, polished mineraf surface (see Fig. 1). The droplet is allowed to age on the
cryataf (see Fig. 1). The modified sessife drop method surface. The water-advancing and water-receding contact
uses two flat, polisbcd mineral crystals that are mounted angles are measurd by usirrg the capillary tube to expand
parzllel to each other on adjustable posts, as shnvnr irr Fig. zrrd contract the volume of the cmde-oil drop. 23,24
2a. Becauae sandstnnea are ohcn composed primarily of When the crude oil containa naturaf surface-active sub-
quartz and limestones of calcite, quartz or calcite crys- stances; the water-advancing contact angle increases aa
tals are used to simulate the pore snrfaces of the reser- the OiUcrystafinterface ages, approaching a iimhing value
voir rock. Obviously, the nettability of clays in the as adsorption equilibrium is reached. To achieve this liit-
reservoir cannot be examined tit-h this method. ing vahre may require hmrdrcds or even tbOm~ds Of
The first step in mcastuing contact angle is to cl+ the hours of interface-aging time. Fig. 327 gives examples
app~ams thoroughly, because even tmce arnounta of cOn- of tbe change in the water-advancing contact angle as the
tammants can alter the contact angle. Then the cell cOn- oilholid interfke ages. This demon~es that early mcaa-



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



*~ l-&#.

l. ____.. __J
Fig. 3-Approach to equilibrium contact angla.m I
Hysteresis resulting from surface heterogeneity can be
1- .1 caused by either heterogeneity in the rock surface com-
position or differential adsorption of wettabifity-akcring
I compounds. This problem is generally avoided by mcas-
I @g tie angle on a singfe crystal and by rigorously &an-
mg the entire appsmms before measurement. Finslly,
surface immobiihy can cause hysteresis by preventing the
I fluid motion necesssry for the contact angle to reach ita
equilibrium value. For example, slow adsorption of a arw-
I factant from the soIid/Iiquid interface into the brdk liquid
can cause hysteresis. Some cmde oils w even form a
L__.___; (b)
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
I Fig. 2Contar$angle measurement. 7 I Even though it is possible, with great care, to get exact
and reproducible contact-mrgle measurements, the ques-
urements can show that the system is water-wet even tion of how representative these results are of the wetta-
though it is actnally oil-wet at equilibrium. Because it con- btity of reservoir core arises. The contsct angle cannot
tains no surfactmrts, the contsct angle for pure &cane mke into account rhe roughness, heterogeneity, and com-
(Curve A) did not change from zero as the interface was plex geometg of reservoir reck. First, consider the prob-
aged. lems caused by muglrness. Morrow31 bsa pointd out that
Orie problem in contact-angle measurements is hyste- roughness and pore geumetry will intluence the
resis, because it is genirally found experimentally that oiJ/water/solid contact line and can change the apparent
a liquid drop on a surface cm have msny different stable contsct srrgle. On a smooth surface, the contact angle is
contact angles. The contact angles reported in the litera- tixcd. On the sharp edges found in reservoir rock, how-
ture sre either the water-advancing or water-~~g FOn- ever, this condition is relaxed, and there is a wide range
tact angle because these two angles are the most of pussible contsct angles. 31.32Morrow postulates that
reproducible. Tbe water-advancing angle cmr also be most of the oillwatcrfrock contact limes will be located
thought of as the oil-receding one. The advmrcing angle, at the sharp edges because, at these edges, the cuntact an-.
Oad,, is measured by pulling the periphery of a drop over gle can change without movirr~ the position of the con-
a surface, while the reding contact angle, @~; is meaa- tact line.
ured by pushing it back. The dMference, O,~, - @,e., is A second problem with applying contact-angle meas-
the contact-angle hysteresis snd can be greater thsn 60 urements to reservoir rocks is that the contact angle can-
[1 rsd]. 19 not take into account the heterogeneity of the reck surface.
Johnson and Dettre 19 and Adanrson4 state that there Contact angles sre measured on a single mineral crystal,
appear to be three causes of contam-zngle hysteresis: (1) while a core contains many different constituents. As dis-
smface roughness, (2) surface heterogeneity, and(3) sur- cussed preciously, surfactmrts in the cmde can affect the
face immobility on a macromolecular scale. To see how wettzbility of the sands and clays differently, causing
surface ruughness can cause hysteresis, consider a localized heterogencmrs wettabifity.
horizontal but rough plate. Because tie rough surface con- A Wlrd limitation is that no information can bs gaind
tains pesks and vslfeys, a liquid drop WY generslly be about the presence or absence of permanently attached
attached to a surface that is not horizontal. The macm- organic coatings on reservoir rocks. 33 These films can
scupically observed contact sngle will not be the same as be detected ordy by making other nettability measure-
the true contact angle on a microscopic scale. The rough- ments. This is particrdsrly importrurt when workirrg with
ness of the surface will 2U0w a large number of metaata- ~e~mr~-mte ~ores. 3435 Before the original we~bfity
ble states of the drop to exist with different contact angles. can be restored, all the adsorbed materials must be re-
The surface roughness wilJ generally diminish the appar- moved, wbicli will generally leave the cure in astfongly
ent cuntsct nn e for water-wet mck and increase it for water-wet stste. The only way to determine whether the
oil-wet reck. 19 ,22 cleaning prccess b+ been successfid is to measure the wct-

1248 Jo.mal of Petrol..m Technology,November1986

tabiilty of the cleaned core. If it is not strongly ivater- permeability samples, causing an underestimation of 60
wet, addhional cleaning is necessay. or ~~. 8.36The mcaaurcd displacement ratios wilf under-
estimate tie water- or oil-wemess of the ruck. Of course,
AIuott Method. The Amott method 6.8.36combines im. it is necessafy to choose some upper time limit to finish
hibition and forced displacement to mcaaure the average Ore measurement in a reasonable length of time. If the
wetmbili~ of a core. Both reservoir core and fluids can core is still itnbibmg when the time limit is reached, how-
be used in the test. The Amott method is baaed on the ever, then the measured spontaneous imbibition volume
fact that the wetting fluid will generally imbibe spontane- will underestimate the rcaemoir wettabfity, and the AIZIOtt
ously into the cure, dkplacing the nonwetting one. The ratios should be interpreted with caution. 8.36
tatio of apontaneouaimbibition to fumed imMbition is used A number of researchers37.3s used a modification of
tu kduCe the influence of other factors, such m Elative the Amott nettability test called the AntomHarvey relat-
permeability, viscosity, and the initial saturation of the ive displacement index. This procedure haa an addi-
rock. tional step in the core preparation before the testis run:
Core is prepared by centrifuging under brine until the, the cure is centrifuged first under brine and then under
residwd oil saturation (ROS) is rcabhed. The Amott wet- crude to reduce the plug to fWS. The displacement-by-
tabilhy measurement then consists of the following four water and dkplacenzent-by-oil ratios are then calculated
atcps: (1) immerse the core in oil, and meamre the volume by the Atnott method. The Amott-Hawey relative dis-
of water displaced by the spontaneous (free) imbibition placement index is the displacement-by-water ratio mi-
of oil after 20 hours; (2) centrifuge the core in oil until nus the displacement-by-oil ratio:
the irreducible water saturation (lWS) is reached, and
measure the total amount of water displaced, including
the volume displaced by spontaneous imbibition; (3) im- I=8W80=++. - . . . . . . . . . . . . . . . ...(4)
merre the core in brine, atrd measure the volume of 01 01 w
spontaneously displaced by imbibition of water after 20 This combmes the two ratios into a single wettabflity
hours; and (4) centrifuge the core in oil until ROS is index that varies from + 1 for complete water wetness
reached, atrd meaaure the total amount of oil displaced.
to 1 for cnmplete oif wetness. Cuiec 39 states that the
Note that the core may be driven to IWS and ROS by flow system is water-wet when +0.3s I< 1, intermediate wet
rather than with a centrifuge. This is especially necessary when 0.3<1<0.3, and oif-wet when 1 S2S 0.3.
for unconsolidated material that cannot be centrifuged. The Amott test measures the total volume of spnntane-
The tmt restdta are expressed by (1) the displacement-
oua and forced oif and water imbibition. Morrow et al. a
by-oil ratio the ratio of the water volume displaced by developed a modified form of rhe Amott test, which nfao
spnntatmms oil imbibition alone, VW,P to the total dis- measures the imbibition rates during the sfmntammus im-
placed by oil imbMion and centrifugal (forced) displace- bibition measurement. In tbk test, the core is suspended
ment, Vm, in oil or water from an electronic bafance by a small
monofilament line. Weight change is monitored ac a tilnc-
~o=+, .............................(3a) 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-
and (2) the displacement-by-water ratio the ratio of dad Amott tmt because it is based on additional .@ata.
the oif volume displaced by spontaneous water imbibi- The main problem with the Amott wetmbfity test and
tion, V..p, to the total oif volume dkplaced by itnbibi- ita modifications is that they are insensitive near neutral
tion and ccntritkgal (forced) displacement, Vol: 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-
L=+. .. . . . . . . . . . . . . . . . . . . . . ..(3b) pkice the other when the contact angle varies tlom roughly
0, 60 to 120 [1 to 2.1 rad]. 3.4145 In addition, the limiting
contact angfe above which spontammus intbibltion wilf not
As shown in Table 1, preferentially water-wet cores occur depcnda on the initial saturation of the core.
have a pusitive displacement-by-water ratio and a zero McCaffery41 and Morrow and McCaffery4s examined
value for the displacement-by-d ratio. The displacement- the spontaneous imbibition of pure fluids with a known
by-water ratio approaches 1 aa the water wetness in- contact angle into a synthetic teflon core that initially cOn-
creases. Simifarly, oif-wet cores have a positive tained air. IiI the experiments, n-dodecane @=42 [0.7
displacement-by-nil ratio and a zero displacement-by- rad]) wotid always spontaneously imbibe into the core,
water ratio. Both ratios are zero for neutrally wet cores. while ct-bromomphtbalene (0=73 [1.3 rad]) would never
Amott chose an arbitraty time period of 20 hours for spontartermsly imbibe. Dioctyl erfrer (0=49 [0.9 rad])
the spmmmeous oil and water imbibition steps in his would not imbibe into a dry core but would imbibe into
metbcd. If possible, we recommend instead that the cores a core with an initial diomyl ether saturation of 30 %. Tbe
be allowed to imbibe until either imbibition is complete Amott method would classi@ the teflon core with n-
or a time liit of 1 to 2 weeks is reached. imbibition can dodecane aa mildly water-wet, while c+bromomphtfmlene
@e from several hour.. to more tlIan 2 months to com- would be neutmlly wet. The core with dioctyl ether
plete. M If the imbibition is stop~d after a short period (6=49 [0.9 rad]) would be classified as water-wet if it
of time, then the measured spontaneous itnblbition volume already conmincd some fluid or as neutrally wet if the
will be lower than the equilibrium value for low- core waa initialfy dry.

Jaud of PetroleumTechnolo~,i%enber 1986 1249


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

I 00 0 I 00



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

Journal of PetroleumTechnology,
November19s36 1251

0.8 -

0.6 -

2 0.4-
5 0.2-


0 100

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)
Fig. 6Typh2al water/oil relative pemreabilily curvaa bc!
on the effective permeability to oil, at the resetvoir cl
where nate water saturation; (a) strongly water-wet rock,
If = relative rate of imbibition, strongly oil-wet rock.
A = initial imbibition rste of the cnre just after
it is submerged (cm3 /s), and scope. Jf the ample is water-wet, the water wilf move
ritr = iuitial imbibition rate of the cleaned, readiiy into the as.nd, displacing oil from the surface of
strongly water-wet core (cm3 Is). the sand mains. In addition. the oil will form sr3hericaI
droplets, ~dicadng that it is he nonwetdng phaaeuA sind-
If,the core is water-wet, m is the initial water imbMiOn Iar procedure is used to test for oil wettabiMy. This test
rate. If the core is oil-wet, ri is the initial oil imbibkion is similar to the microscope examination method.
rate, and the relative imbibition rate, R, is reported as
a negative number. Note, however, that whife the use of Microscope Exmrdrratiotr. Microscope examination is
a reference rate reduces tie effect of other variables, tie sometimes used in laboratory flow viaualiiation studies.
irnbMion method still suffers from the same problem as The wettabtity is determined from w description of the
the Arnott method-insensitivity near neutraf wettabifily. flow on a single pure level in an ideafized porous medi-
Bobek et al. 52 alau suggested an imbibition.teat for un- UITl during Watedooding. 58.59TM.Sdescription includes
consolidated cores. In tbia test, a thin layer of sand is the structure of the residual Oi and the changes in the lo-
spread on a microscope slide, after which the oif satura- cution of tbe oil and water that occur during watertlood-
tion is increased by addition of a refined minemf oil. ing. ff the system is stfongly water-wet, the water
Dropleta of water am then placed on the surface of the surrounds the groins as a thin fifrxr.The large pools of
sand, srrd the movement of the fluid k observed by rnicm- 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 lowered iuto the water. If tie slide is water-wet, the water
pores. If the system is intermediately wet, ,both oil and quickly displacea the oif on the slide. On the other hand,
water will be found in contact with the rock surfaces, ,~d if the slide is oil-wet, a stable oil-wet tilm is formed, and
both can be found in the smslf pores. Finally, if the sys- the oil is very slowly d~placed. Reisberg and Doscher30
tem is oil-wet, the roles of the oil and water are reversed. aged slides in crude oil snd found that it took up to 30
The ofl forms a fti around the grain surfaces and is found days for the 6MI wettabtiiy to be reached. Cwke st al. 5s
in the small pores, whfle the water rests on an oil tilm used a simple variation of the glass slide method as a
or forms small spheres. quick, qrmlitative test tu screen different acidic-oil/alka-
The method of quzlitstively dete ruining the wettabfi- lii~water comblnationa for uae in zdkaliie waterflood-
ty by microscope examination is pmticukly important ing experiments They placed oil and water without
in the study of wettabil@ reversaJs, 58>m&one of the -g fi a glass vkd and waited to see whether a stable
propoacd mechanisms for EOR that occurs dining alka- od-wet tihn formed on the vial. This was determined by
fine waterfloodmg. m In ~e~e ex~tienta, a chefi~ tilting the vial srrd seeing how the water and oil behaved
that changes the nettability is injected into the porous on the previously oil-covered surface.
medium during a waterflood, causiug a zone of wettabd-
ity reversal to propagate through the core. A microscope Relative Permeabfity Methods. A number of quaMa-
is used to follow wettabtity changes and to determine tive methuda are baaed on the effects of wettabfity on rela-
whether EOR will occur by thk mechaniam. tive penneabtity. However, they are all suitable ordy for
discriminating between strongly water-wet and strongly
Flotation Methods. Flotation methods are fast but work oil-wet cores. A smaller change in nettability- e.g.,be-
only for strongly wetted systems. In the sinrpleat method, tween strongly and muderstely water-wetmay not k nn-
water, oil, arrd sand are placed in a glass bottle. The bot- timd by these methcda. One method developd by Ehrlich
tle ia shaken, and tie experimenter observes the fate of ~d WYg~74 is based on the rules of thumb given by
tie smd gains. 65-6s This method is recommended by Craig7 to differentiate be~een stmmgly water-wet aud
API for determining the effects of surfactarrts on netta- ~mon~y ~fi-wet ~or=. C~g, ~ 16,52,75 fieS ~ f ~mb me
. .
bility. C If the system is strongly water-wet, clean sand aa fouows.
grains will settle to the bottom of the bottle. Sand grains 1. Connate water saturations are usually greater than
placed in the oil wilI aggregate aud form small clumps 20 to 25% PV in a water-wet rock, but less than 10%
of grains surrounded by a thii layer of water. If the sys- PV in an oil-wet rock.
tem is oil-wet, some of the grains can be suspended at 2. Water aaturztion at which oil and water relative pcr-
the oil/water interface. Oil-wet sand grains in the water meabtities are equal is generally greater than 50% for
will clump together, forming small oil globuka coated water-wet cores and less than 50% for oil-wet ones.
with sand. This flotation system is qualhative and worka 3. The relative permeabfity to water at floodout is
only for strongly wetfed systems. generally less than 30% in water-wet rocks, but frnm 50
SeVeFJ experimenters 69.70 have used more elaborate to 100% in oil-wet ones.
flotation tests developed in the minin industry that were These relative permeabtities are based on the oil per-
based on liquid/liquid extraction. 22,7? In these tests, par- meabtity at the comate water saturation. Examples of
ticles are initially suspended in water. A second fluid, relative perrneabfity curves in strongly water-wet snd oil-
either oil or sir, is bubbled from below. The parricles that wct corer taken from Craig7 are given in Fig. 6. Note
are water-wet remain in the water, while the hydropho- that Raza et al. 16 state that there are exceptions tn the
bic, oil-wet particles adhere tu the oil (air) and rise to the gezieral rule that the connate water saturation is higher
surface. The fraction of articles in each phaae can then for a warcr-wet rock than for an oil-wet one.
be measured. elenrmtz% used the flotation method to Treiber et al 27 pro~sed a secrmd quali@ve technique
meaaure the wettsbihty of small clay particka, which cmr- for strongly wetted rocks The method comp=es the
not be conveniently me$suked in any other way. Untreat- oil/water, gas/oil, and gas/water relative permeabilkie.s
ed, strongly water-wet particlea would not float. After and takes advantage of the fact that relative permeability
expusrue to cmde, the clay particles floated, demonatrat-
irrg that their nettability had been altered: :E.;E?JF2:EP;:,:EZZ$2:E;
Flotation tests based on liquid/liquid extraction appear water-wet, the relative perrneab~ky tu oil (the preferen-
tn divide particles intu two categoria$ stron 1 water-wet tially wetting phaae with respect to the gas) in the gas/oil
and mildly water-wet tu strongly oil-wet. ~2~~BesidG
, ~~ relative pcrmeabtity test shordd be a continuation of the
wettabilky, flotation of a particle also depends on parti- relative permeabdity to the water (the wetting phzae) in
cle size, particle density, and IFT. A small particle with the water/Oil relative pcmzeabil~ test. 76 If significant
low density and high IFT might float if the contact angle differences are observed, the sample is not strongly
was ~eater than about300 [0.5rad]. On the other hsnd, water-wet.
the minimum contact angle for flotation of a large, dense An example of the comparison of the relative perr22ea-
particle could bc 90 [1.6 rad]. 72,73 btity curves in a strongly water-wet core taken from
Owens and Archer76 is shown in Fig. 7. The gas/oil
Glass SIide Method. Another esrly qualitative nettabil- drainsge relative perrneabfity, where the oil ia the stron-
ity meaaurcment tcduzique is the @as slide methnd, 30,m glywetting fluid, is shown as the dotted Iiues. The water/oil
which assumes thst a glass surfsce is representative of relative pcrrneabfity, where tbe water is the strmrgly wet-
the reservoir rock. A clean, dry, glaas microscope slide dug fluid, ia shown aa the solid lines. Note that the water
is suapmrded in a layer of cmdc oif floating on water in relative penneabi3ity, where the wetting fluid saturation
a transparent contsiuer ~d aged. The glaas slide is then is iricreasing, is a continuation of the oil relative pe2n2ea-

Journal of PetroleumTechnology, November 1986 1253



a% .: *3

& A

\GA2 0

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

\ 0
o 0 [SWINGER ~D1
./ .0

0.1 1 1 1 1 ~
0 20 40 60 60

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

12s4 Jourmtof PetroleumTechnology,November1986

has a gentle slope and extends over a large saturation in-
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
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 Slobod snd Blum stated that if it were assumed that the
measures the product .s cm 0, the problems dkcussed in oif is.completely wetting in the oillairlrock system, then
the section on contnct angles SISOhinder this meifmd. cos .9..0 is unity. An apparent contnct angle for the
oil/water system can then be computed from Eq. 11:
Displacement Capiffary Pressure. One of the earliest
wettabWy measurements was the displacement capillsry
... . . . . . . . . . . . . . ., (12)
pressure method, which uses the threshoId capillary pres- cOs(oo_w)= =
sure to calculate am apparent contact augle. 8894This Oo-wp(a-o)T
method is now used infrequently, however, because pore
geometry effects can cause the calcqated contsct angle Slobod snd Bhuu resEzed that their nasumptions were
to differ greatly from the contact angle measured on a flat onfy approximately true and that the contact angle that
plate. 3 The displacement (or threshold) capilla~ pres- could be calculated from the displacement pressure was,
sure is the capillaty pressure at which nonwetting fluid at best, only semiquantitative. In general, the apparent
will first enter a core initially 100% satorated with the contact angle measured from the displacement pressnfe
preferentially wetting fluid. h apparent contact sngle is is not cqusl to the contact angle messured on a smooth
cdcnlatcd from the threshold capillary prssaure by mcdel- surface because of pore geometry effects. Morrow snd
ing the mck as a straight, cylindrical capillary tube4, 10: MS c0workers4345 compared apparent contact ~~es
computed in sintercd teflon cores using pure fluid with
20 Cos 8= the true contact sngles measured on a smcotl teflon plate.
P~=, . . . . . . . . . . . . . . . . . . . . . . . ...(9) There wss no chnnge in the apparent contact sngle when
Tmx 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
where PT is the displacement capillary pressure, a is the
contact angle. Fiiy, in some cases, the apparent cOn-
IFT, O= is tbe apparent contsct nngle, and r- is the
tact angle calculated from the dkplacement pressure csn
radius of the pure through which the nonwetting fluid be-
show the wrong fluid to be the wetting phase. Positive
gins to enter the core. Because the capillsry pressure need-
displacement pressures for both fluids, particularly when
ed to inject nonwetting fluid is reduced as the pore radius
the mre is initially 100% saturated with the other fluid,
is increased, rmax is m mfersge of the radii of the lar-
have been frequently reported in the litera-
gest pores in the core. Note. @it one limitation of this ture. 41.U.B,W,W.95-W When a positive displacement pre3-
method is that it examines the wettabfity of only the lsr-
aure is required for both fluids, the fluid with the lower
gest pores. Because Eq. 9 has two unknowns, 0. ~d
displacement pressure is the preferentially wetting flqd
rm=, the oofy way to solve for the apparent contact an-
gle is to mske additional assumptions. It is usually because less energy is required to force. it into the
core, S3.98 &der~0n3 provides further discussion.
assumed that some fluid exists that wfil completely wet
the core, so cos 8=1, and rmax csn be calculated. This
Reservoir Logs. Grshamw proposed a method to meas-
allows the contact angle, to be computed for other fluid
ure the.nettability of in-situ reservoir mck with logs that
wsa baaed on rhe fact that the electrical resistivity of an
Slobod and Blum~3 proposed two aenriqnantirativewet-
oil-wet rock is hi her than that of a water-wet rock at the
tsbility measurements baaed on the displacement capjl-
fary pressure, the wettabfity number, and the apparent ssrne saturation. f In Grahams method, the formation is.
injectd with brine, and resistivity logs are run. The for-
contact angle. The wettabfity number is calculated by car-
mation is then injected with the same brine containing a
ving out two dkplacement experiments-first, water by
reverse wetting agent, which will change a water-wet for-
oil, and second, oil by sir. Eq. 9 for the oillwatcrlrock
nrstion to sn oil-wet one; if the formation is already oil-
system becomes
wet, the reverse wetting agent will not alter the wettdil-
ity. After logs sre rerun, the nettability of the formation
2U0-W Cos &o.w cm be determined by comparing the two resistivity meas-
P(o-w)r= . . . . . . . . ... . ... (lOa) urements. If the formation was originally water-wet, the
TIM. change to oil-wet will increase the resistivity. If the fOr-
mation was oil-wet, no change in rcsistivity will be ob-
and for the nirJoil/rock system, served.
Holmes and Tlppie lm proposed a second method that
compsres lugs with core data. The saturation in a forma-
2U=.-0 Cos %.-O tion is first measured with logs and the data converted
P(.-O)T= . . . . . . . . . .. . . . . ..(lOb)
rmax 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-
In hth equations, the radius of the pore is assumed to lnry pressure curves nre compared. If they agree, the
be the ssme. The wettrrbiMy number, N, is determined reservoir is strongly water-wet. If they do not agree,
by solving Eq. 10 for the ratio of the cos O terms: Hofmes snd Tlppie model the porous medium as a series
of strsight cylindrical capillaries and determine the ap-
cm O.-. parent contact angle with equations similsr to those dis-
N== . . . . . . . . . . . . ..(11) cusacd in the previous section on displacement capiffary
Cos 6.-0 uo-w%m pressure. Because of the number of approximations, this

12.56 Journalof PetroleumTechnolom..November1986

aPPafent cOntactangle wfi provide only a rough estimate found that aaphaftene adsorption in sandstone cores coufd
of tfre actual reservoir wettabdity. afso increase the relaxation time. In one set of experi-
ments, clean smrdstone plugs were saturated with cm&
hleaaurement of Fractional and oil, then aged for several days. The bulk of the uil was
removed by flushing with cyclohexane, leaving bebind
Mixed Nettability
a Iilm of asphaltenes on the ruck surfaces. The plugs were
Infractional wetted cores, a p@ion of the rock is strongly saturated with water, and the relaxation time rneasurcd.
water-wet, whtie the rest is strongly oif-wet. The term The adaorbed film increased the relaxation trme when
mixed wettabifhy was introduced by SalatMeI lol to compared with the time for clean plugs. In another ex-
refer to a special type of fractional wettablli~ in which periment, a plug was saturated with water and crude,
the oil-wet surfaces form continuous paths through the aged, flushed with cyclohexmre, then saturated with water.
farger pores. Additional information can be found in The nuclear magnetic relaxation curve for this sample had
Ref. 1. three components: (1) a fast component for water in the
small pores, (2) an intermediate component for water in
Nuclear Magnetic Relaxation. Brown and Fatr 102and the large pures, mrd (3) a slow compmrent for water in
uthers 103,lW proposed a nuclear magnetic resonance tire large pores that had been fdled with oil and coated
f,NMR) method for determining the fraction of the core with asphaltenes. However; Devercaux dld not suggest
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 Brown and Fatt 102also proposed a nuclear magnetic
relaxation time for water protons (hydrogen) in poruus relaxation method to measure the wettabflity of reacrvuir
media. To measure the relaxation time, the sample is first core, which app=ently has not actually been used. The
expused to a smmrgmagnetic field, which makes the nuclei method compares the nuclear magnetic thermal relaxa-
of the hydrogen atoms line up with the field. The core tion rate of the untreated core with reference measure-
is then exposed to a much weaker field. The nuclear mag- ments on the same core in both strongly water-wet and
netic relaxation time, which is the time it takes for the strongly oil-wet states. The core is. first flushed with
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 ter vacuum drying, the core is saturated with distilled
component parallel m the field is called thermal relaxa- water, and the therrnaf relaxation rate is measured. It is
tion, and relaxation of the component pe errdicrdar to assumed that the preparation procedure above IWSnot al-
the field is cabl transverse relaxation. T 05 The ther- tered the wettahility of the core. Next, the core is made
maf relaxation time is the time used to measure fractiOn- strongly water-wet by flushing with methanol and chlo-
SI wettabifity. roform or by ftig at 950F [51OC] tn remove all of
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 mal relaxation rate of the core in this water-wet iefer-
to random thermal motion of the molecufes. The protons ence stare is mcasrrred. FAy, the core is trcarcd with
are only lurwely coupled to their environment, so they re- an organocbforosikine, which renders it strongly oil-wet,
quire a time on the order of seconds to adjust to the new and the thermal relaxation rate is measured. The refer-
magnetic field, which is a verj long time for atomic ence relaxation rates for the core when it ia strongly water-
proceasca. wet and oil-wet are plotted vs. the percent of oil-wet sur-
The use of nuclear magnetic relaxation times to meas- face, and a straight line is drawn between them. Assum-
ure wettabflity ia based on the observation that the sur- ing a linear relationship between fractional wettabdity and
faces of the porous media can significantly reduce the relaxation rate, the fictional wettabiity of Orenative-state
measured relaxation time. 102.105When a proton is near untreated core is then found by plotting ita relaxation rate
a surface, it cmr bccume temporarily bound to the sur- on this straight line.
fiace,relaxing much faster than in tie bulk fluid. The wet- Unfornrrrately, this proposed procedure suffers from
tabili of the surface can influence the relaxation several problems. First, the functional relationship be-
dine. ? ~-1135 oil-wet surfaces cause ~ SmWer ~~ction tween relaxation rate and fractional nettability is not clear.
in relaxation time than water-wet surfaces. Brown and Fatt found a linear relationship between frac-
Brown and Fatt 102 exmnincd 100% water-saturated tional wettabilhy and reaction rate, whale Kumar et al.
sand packs in which a fraction of the aand grains were found a linear relationship using reaction time (the inverse
water-wet and the remainder bad been treated with an or- of reaction rate). Second, aa discussed in Anderson, 1 the
garmchforosilarre tu render them oil-wet. They found a methnda that Bruwn and Fatt suggest to prepare the origi-
finear rclatiun between the rafaxation rate and the frac- md core will generally after the mtive-state wettabflity.
tion of oil-wet surface area. f,The relaxation rate is the Finally, it is not possible to tell whether the cleaning
inverse of the relaxation time.) The greater the fraction method haa rendered the core totally water-wet or the or-
of oil-wet grairra, the longer the relaxation time, and the ganocblorosilane traamrent has rendered the core totally
slower the relaxation rate. Krmrar et al. lM measured uil-wet. Irr some cases, cure treated with an organo-
relimtion times with 100% water-saturated bead packa cblorosikme is only neutrafly wet. I
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 Dye Adaurption. Holbruok and Bernard lM used the ad-
increased. sorption of metbylene blue from an aqueous solution in-
Brown and Fattlm and Knmar et al. lM applied their jected into a cure to measure fractional nettability. This
methud only to sandpack and beadpacka. Deveraaux los method successfully mcaaured the wettabtity of fraction-
Journalof petroleum Technology,November1986 1257
ally wetted sandpacka containing mixtures of oil-wet and however, that it maybe possible to use supercriticsl dry-
water-wet sands. However, the method will probably not ing to avoid these problems. L13
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 Mixed Wettabfity. At the current time, there is no sin-
assumed to be oil-wet. The technique is based on the ob- gle nettability test that wifl determine whether a core has
servation that a rock surface covered with water will ad- Sslathiels lol mixed wettabiity. It ap- possible, how-
sorb a lsrge nmount of methylene blue, whereas one ever, to make this determination by examining the reardta
covered with oil will not. The dye adsorptionof the test of (1) a glass slide nettability test, (2) a waterflood of
core is measured at ROS, where essentially all of tie wet: the native-state core, and (3) several waterflood of
ting phase is continuous. 107-110 This enables the dye to restored-state coma that were aged with different brine
adsorb on essentially W of.the water-covered, water-wet saturations. As discussed in the introductory paper, 1 in
surfac~. A reference dye adsorption measurement is a mixed-wettabdity core, the oil-wet rock surfaces form
made on an adjacent core plug that is clcancd to render continuous paths throughout the large pores, while the
it totally water-wet. The cleaned reference plug is sao+ smaller pures remain water-wet. Mined wettabilhy can
rated with brine, so the entire rock surface is water- occur in a rock if the crnde forms a thick oil-wet layer
covered. The fractional wettabM~ is then established by on the smface only in those places where it is in dirwt
dividing the dye adsorption of the test core by that of the contact. This can be tested with the glxas slide method,
100% water-wet reference core. When tl@ method wss with half the slide in crude and the other half iu brine.
tested on fractionally wetted sandpacka containing mixt- Quartz or calcite cryatala could also be used to give a sur-
ures of oil-wet and water-wet sands, a Iinear relation- fxce more representative of the reservoir. The core may
ship between the fractional wettab@V and the dye have mixed wettabtity if the haffof the slide aged in cru&
adsorption was found. forms a thick, oil-wet layer, while the half aged in briue
The dye adsorption test actually measures the fraction remains water-wet. If the entire sfide remains water-wet
of the total surface area of the core that is contacted by or becomes oil-wet, the core will probably have a uui-
the injected water. Because of this, both oil und water must form wettsbdity.
be present in the core when the dye adsorption is meaa- The second measurement to iudicate mixed wettabiMy
ured. The dye adsorption method mskes two additional is a waterflood of the native-state core. If the core has
assumption: the water phase is continuous at ROS, so mixed wettabilky, oil will be produced down to a very
the dye contacts all of the water-covered surfaces; and low ROS as many PVs of water sre injected. Uniform-
the thin fk of oiI and water coating the mck surfaces wettabili~ cores wiR generally have a shorter duration
are not affec@d by large changes in saturation. Tracer of production andlor a larger ROS. 6,7,114,115Finally, ,a
experiments have shown that essentially elf of the water series of waterflood in restored-state cures cambe used
is continuous at ROS for both water-wet snd oil-wet to confirm rhe mixed wearability of the core. A series of
~re~, I10 me ~~~uption that the thin fti of@ ad cores is cleaned, saturated in brine, oilflonded with cmde
water are not affected by Iarge changes in saturation seerrra to dfierent brine saturations, then aged to restore its origi-
reasonable because the amount of liquid in the thin films nal wettabtity. Salathiel fonud that the recuve~ fmm his
is very stmdl in comparison with the bulk tluida. Shankar restored-state nrixed-wettabdity cores had a maximum at
and DuMen111 exarrrincd how dye adsorption varied with a pmticuka value of the brine saturation during aging.
water saturation in Berea sandstone cores. They injected When the water aahmmionwas lower than this value, some
oil and brine at currstaut rates and allowed the saturations of the arnidl pores becsme oil-wet, lowering recoveg.
in the core to reach equilibrium. The injection wsa then Conversely, at larger water sahmations, the oil patiways
switched from brine to dyed brine, and the dye adsorp- through the core became discontinuous.
tion was measured. They found that the dye adsorption Two other measurements that will sometimes help in
was ahnoat conatsnt when tie water saturation wsa greater determining whether a core has mixed wettsbifity are im-
thsn 40% PV. The dye adsorption drcreaaed at lower sanr- bibkion meaaurementa aud capillary pressure behavior. 3
rations, where the water stinted to lose continuity. These Spontaneous (free) imbidti,on of both oil snd water h@
measurements show that the wettabihty of a core meas- been reported for some cures with iiactional or mixed wet-
ured by dye adsorption is not dependent on the satura- tabiity. 49-51These corez will have positive diaplacement-
tion, except possibly at water saturations near IWS. by-water aud displacement-by-uil ratios. Another indicakx
Although the fractionally wetted sandpack that were of mixed wettabtity is a comparison of Oil-displacing-
used by Holbrook and Bernard did not contain clays, they brine capillary pressure measured on native-state plugs
retilzed that clays would strongly affect dye adsorption va. meaauremenk on the ssnre plugs after they have been
in reservoir cores. This occurs becanse the surface area clca.ned aud rendered water-wet. In some mixed-wet
aud dye adsorption capacities of clays are much larger plugs, the native-state capillary pressure curve wilf cross
ha those of sad g~ns, 111,112f+olbrook ~d Be~~d over the cleaned curve m the capillary pressure ia in-
stated that their test would measure the fraction of the clay creased. 116118Fticr discussion can be found in Ref. 3.
surface drat was water-wet irr a reservoir core. However, In summary, if the oil forms thick, oil-wet tilms only
they had problems when measuring the dye adsorption on thoac pm-tioui of the glass afide with which it ia iu direct
snd fractional wettabiMy of cores containing a significant contac~ if the core can be flooded down to very low oil
amount of montnrorillouite. Irreversible chsnges in the saturation, yet still produce small smouuta of ofi tid if
clay structnre of the water-wet reference core reaufting the oil recove~ from a rcatored-state core has a nraxi-
from extraction and drying caused them to cuhxdate rela- mum at a sp.%itlc brine saturation during its aging peri-
tive water wettabtitiea that were greater tbau lCO%. Note, od, then the core Iiiely haa mixed wettabil@. ImbMion

1258 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.

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

,4~ = area under the oil-drive centrifigrd RccklOiUSrine Interactions, and the Effects of Core Handling on
Wetmbi[ily,,. JPT (Oct. 1986).
capillary pressure curve, USBM method
2. Anderson, W.O.: ,Wenability Literature Survey-ParI 3: llx Ef-
,42 = area under the brine~tike cenfrifigal fectsof We.uabililyon tie Ekcuical Prqwties of Porous Media,%
capillary pressure curve, USBM method JPT (Dec. 19S6).
3. Anderson,W.G.: WetfabilicyLiterature Survey-Pan 4 The Ef-
ED = displacement energy (adhesion tension)
fects of Wmabilhy OCapillaryFtess.re,x>pap SPE 15271avaJ-
g = acceleration of gravity able at SPE, Richardson, TX..
ho = height of the oil column above the 4. A&mson, A. W.: Physical C6emimy of Swfoct=s.fourlh edticm,
John Wiley and Sons Inc., New York City (1982) 332-6S;
Oil/water inter@ce 5, Amy., J. W., Bass, D., and Whiting, R.L.: PeIroitvun Reservoir
h. = height of the water column above the Ef@eering: physical Propenies, McGraw Hill Beak Co. Inc.,
Oil/water interface New York City (1960).
6. Arnon, E.: CObswvatiomRelating to the WettabiliV of Porous
I = Amots-Harvey relative displacement index
Reck, Trans., AIME (1959) 216, 15&62.
~ = initi~ imbibition ~k of ~ core just after it 7. Craig, F. F.: 2% Res.erwir Engineering Aspects of Wa@ood-
is submerged in a fluid in~, Monograph Series, SPE, Richardson, TX (1971) 3, 12-44.
8. Cuiec, L.E. er aL: Detenninarion of the Wettabilhy of a Sm.
fir, = initial imbibition rate of a core after it is PI. of Reservoir Rwk,S Rev. 1.s. Frcmc. d. P&role (Sept.-Ott.
cleaned and rendered strongly water-wet 197S)33, No. 5,705-28. English fmnslatkm waihable from John
N = wettabfity number, Eq. 11 Cremr Libmrj, translation no. 81-13920-081.
9. Domldmn, E. C., Thomas, R. D:, and Lomnz, P. B., WemabiJi-
P, = capilla~ pressure
ly Determination and Its Effect on RecweIY Efliciency,z, SPEJ
r = capillary tube ra~us (March 1969) 13-20.

Journal of Petroleum Technology, November 1986 1259

10. DuUien, F.A.L.: Porous Media: Fluid Tmnspon and Pow Srruc-
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11. Hjelmekmd,O. and Torsae+er,0.: LWeOabiliW, the Key to Proper presenfed at fhe.1985 SPE Annwd Technical Coif&ence and Ex-
Lat%matov Waterfbdhg Expminurds, Intl. Energy Agency hibition, la.s Vegas, Sept. 22-25. ,
Workshop on Enhanced 011Recovery, BarOesviUeEnergy T.%h- 36. Cuiec, L.E. et aL: Recomcn&tiom for the Dewminatim of
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1981) 1-3A. Fmc. duP&03e fNov. -Dec. 1978) 33, No. 6,907-14. E@sh
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16, J&a, S.H., Treiber, L.E., ad Archer, D. L.: Wettab&ty Of 40. Morrow, N.R., Lim, H.T., and Ward, 1.S.: Effect of Cmde-
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1260 Journal of Pemolcum Technology, November 1986

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Journal of Petroleum TcchnolosY, November 1986 1261

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(1974). rece.w,d March3, 1986.

1262 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

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.

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

Journal of Petroleum Technology, Dec&ber 1986 1371

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

Air/NaCl SOlution OWNaCl Solution

Brine Srine
Saturation Saturation
(o/oPV) n (0/0Py n +
66.2 1.97, 64,1 2.35
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

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

Journal of Petroleum Technology, December1986 1373

I [ I I I I

Core Number Unextracted Extracted

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

: .,
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-
4 ,: 0 Z1erfuss smd Makha25 measvred electrical resiativity
during waterflood of ssdstone tid limestone cores and
artificial packs. Each porous medium was saturated with

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

so the cleaned cores may not have been strongly
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 ,0 <..
.,..,, W.. .,L WC,,.,,, !,,.mc..,
saturation exponent, n, is tie slope of the lines. It is bigher
for the unextmcted core amdappears to be constant. Moore Fig. 3Archie saturation exponent vs. the fraction of sur-
measured the reiistivity of the .unextracted core only for face that is oil:wet.2
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 wet surface was varied from O to 100%. Starting with
Luffel and Randalls26 experiments are particularly im- 100% brine, tbesamration wasgradually reduced when
por@t because they demonstrate that cleaning a core can oif was flowed through the pack, andtheresistivity was
alter the saturation exponent. measured. The Arctic saturation exponent for each pack
Trantham and Clampitt2s measured a saturation expo- was found by plotting resistivi~ vs. the saturation. Tbe
nent of 3.1 on plugs from h-e strongly oikwet North Bur- vaIuesofn shown in Fig. 3 mmgefrom2.5 when all of
bank reservoir. The plugs were cleaned nnd resaturated the beads were water-wet to 25 when all of the beads were
with brine and oil before measurement of the saturation oil-wet. These very high values of n possibly occur be-
exponent. Cleaning thk core apparently dld not affect the cause of the smooth surfaces and homogeneous nature of
wettabllity; the. plugs remained strongly oil-wet even af- the bead pack.
ter cleaning. Trantham and Clnmpitt proposed that the oil- Schmid measured the saturation exponent in fracti&-
wetness. of this reservoir is a result of a coating of ally-wetted sand packs with a portion of the sand grains
chsmosite clay rather than the more common adsorption untreated and water-wet and the remsinder treated to
of surfactants from the cmde. This may explain why the render them o~-wet. The saturation exponent for the IOQ%
saturation exponent is very high even after cleaning. water-wet pack was about 1.8. The resistmty index in-
The differences in the saturation exponent for native- creased ataslowerrateinthk water-wet pack when the
state vs. clcsned core by Mungan and Moore, 6 LuffeIl w&tersaturation wasless tbanabout25% PV. As expect-
and Rxndxll, 26 and Richardson et al. g show that the ex- ed, %&resistivity index at any given water saturation was
ponent should be measured on native-state or restored- bigl@ for the 100% oil-wetpack, with a saturation index
state core, where alterations tothe reservoir wettabilky of@tgbly 2.4. The resistivity indix increased rapidly,
am minimized. Note that it is not known whether the cores whefi the,jjater saturatiori decreased below about 7-O %PV,
used in Refs. 6 nnd 26 had uniform or fractional netta- whit] j:,:iimilar to Munganand Moores6 xnd Sweeney
bility because both types of nettability are possible in and Jennings 920
, tindings.
reservoirs. Schrn;d ako measured the resistivity index of packings
containing 25, 50, or 75% oil-wet sand grains. Unfor-
Fractional and Mixed-Wet Systems. Additional w.ettn- tunately, there does not appeq to be a clenr trend for tiese
b~ity effects can occur when a system has nonuniform packing$. The 75% ofl-wet pack had the same resistivity-
nettability (either fractional or mixed), where portions index/saturation relationship as the 100% oil-we tpack,
of the surface are strongly water-wet, wh~e the remainder except tiere was no rapid increase inresistivity index at
are strongly oil-wet. Sa.latfiel 30 irkrodticed the term lower water saturations. The relationships for the 25 and
mixed nettability for a special type of fractional wetta- 50% oil-wet packs were almost identical and were locat-
bifity in which the oil-wet surfaces form continuous paths ed between the completely oil-wet and comuletelsf
. . water-
through the larger pores. The smaller pores remain water- wet curves.
wet and contain no oil. Note tlat the main distinction be- Mired Wehizbifiiy. Unfortunately, nothing definite can
tween mixed and fractional nettability is that the latter be sxid about the electrical properties of a core with mixed
does not imply either specific locations for the oil-wet and wettab@. Inamixed-nettability core, theoil-wetsur-
water-wet surfaces or continuous oti-wet paths. faces form continuous paths through the Iarger pores,
Fractional Wettabil@. The only researchers who have while the smaller pores remain water-wet and contain no
exmnined the effects of fractional wettab]litj are ~if, 30 A ~ed-wettabifi~ system can be generated in the
Schmid31 and Morgan and Puson.32 Morgan and Pws& following manner. When oil initially invaded an originally
made fractionally wetted bead packs by treating apor- water-wet reservoir, it dkplaced water from the larger
tion of the beads with an organochloroiilane solution to pores, whale the smafler pore: remained water-filled be-
render them miklly oil-wet. Theremainder of the beads ciuse of capillary forces. A mixed-nettability condhion
were untreated andhence water-wet. Witba variation in occurred if the oil deposited a layer of oil-wet organic
the proportion of oil-wet snd water-wet beads, resistivi- material only Orithose rock surfaces that were in direct
ty measurements could tie made as the proportion of oil- contact with the oil, but not on the brine-covered surfaces.

Joumdof PetroleumTechnology,Deccmber1986 1375

oil-wet deoosits would not be formed in the small water- havior, he stated that the waterflood behavior depended
ffled Pnre;, allowing them to remiin water-wet. on the aging time, a clea indication that the wet~bility
Because the small pores are water-wet, the electrical wsa still changing.
behavior of rnixe&wettab~hy core will probably be differ- The cores were strongly water-wet befoti aging, which
ent from the behavior ii?uniformly oil-wet systems. The is demonstrated by the fact that little or nn oil was pro-
Archie saturation exponent will not reach the very high duced after bre~through during a waterflood. The water-
values that can occur in uniformly wetted systems. In- flood behavior also demonstrated that the wettnbllity was
stead, it seems reasonable to expect that the electrical be- altered after the coreswere aged because oil was produced
havior of mixed-wettability cores wiff be similar to after breakthrough in the aged cores. Unfortunately, be-
water-wet ones because the small pores and clay pat- cause Swanson injected only a few PVs of brine, it is
cles are water-wet and filled with water in both caaes. not possible to determine whether the cores had mixed
As the brine saturation in a mixed-nettability core is re- nettability. On the basis of the waterflood data, the cores
duced, the water in these areas will remain connected and could be either uniformly mifdly water-wet, fractionally
conduct electricity. This will alfow thesaturation expo- wetted, or of mixed wettabllit y. The primary indication
nent to behave as it would in.a water-wet core, remain- of a mixed-nettability state is that very low oil satura-
ing constant even at low brine saturations. tions are reached after the injection of a very large num-
Even though the behavior of mixed-wet and water-wet ber of PVs of brine. Tbis is caused by the conthuous
cores will be sinilar, however, this does not imply that oil-wetted paths through the linger pores. 30 In summary,
measurements on cleaned water-wet core are applicable no conclusions about the electrical properties of mixed-
to reservoir systems. Unless the reservoir is known to be wet cores can be made from Swansons data because the
sfrongly water-wet, the saturation exponent should be wettabdity of the aged cores is unknown.
measured on native- or restored-state core. There are
several reasons why core with the reservoir wettab]lity Experiments irr the Reservoir
is necessary. First, it appears that tie surfactants in some Several researchers have tried to estimate the effects of
cmdelbrinelreservoir rock systems can difise through nettability on resistivi~ in the reservoir. Puson and
a water-film, making the entire rock surface uniformfy Fraser 8 ~d Fraser 38 discussed reservoirs ~Own tO be
oil-wet. 1 Second, if a core has mixed wetta.blity, the pre- intermediate or oil-wet. Resistivity measured by the elec-
cise numerical value of the ArchIe saturation exponent tric logs was compared with neutron logs and data on the
willprobably differ ,fiom that of awater-wet core because saturation from core analysis. An Archi& saturation ex-
ponent of about 3 was then determined to bring the two
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. Gr&aM39 used a reverse wetting agent tO eXfine the,
They measured the resistivity of nat:ve-stnte cores that effects on resistivity as an originally water-wet .iock was
Iater were shown @ have mixed nettability. 30 The changed to oil-wet. Experiments were coriducted both in
resistivity was high in the native-state cores, but gradu- cores snd in situ. For the core experiments, water-wet
ally dropped after repeated cleaning as the cores became Berea pIugs were samratid with brine, oilflonded, rben
more water-wet. The resistivity was measured only at water flooded to a residuaI oil saturation. The resistivity
lWS, however, which was much bigher in the mixerf-wet- of tie water:wet plugs was measured; then the plugs were
tabilily cores tbnn in the cleaned water-wet ones. Richard- injected with brine containing a reverse wetting agent that
son et al. present tie data only after they have been cor- renders sand and clay surfaces oil-wet. The electrical
rected to a 40 % saturation with Arcbies law (Eq. 1). This resistivity of the now-oil-wet cores increased by, 100 to
makes it difficult to compare the resistivi~ measurements 200% because of the redistribution of the fluids in the
before and after cleaning to determine how n was affected. core. Field tests also showed an increase in resistivity af-
Swan~on33 claimed ttvat be saw very little change ~ ter the wettabtity was changed to oil-wet. Graham rec-
the saturation exponent when he compared a water-wet ommended that this treatment be used when logging in
core with the same core after it had been rest6 red to a regions of relatively high conductivi~, where log interpre-
pnssibly mixed-wettabfiity state. His experiments disagree tation is difficult. Od in these regions would be revealed
with the measurements on native-stite, mixed-wettabfity by the imxea.se in re%istivityafter the fo~mation was made
core dkcuased previously. 29 However, several problems oif-wet by the injection of a reverse wetting agent.
with Swamnns work make it impossible to determine the
actual wettabilh y of the restored-state cores. The netta- Formstion Resistivity Factor
bility is indeterminate because the cors were not aged Another equation that Archie5 determined empirically re-
for a long enough period for adsorption equilibrium to lates the resistivity of the 100% brine-saturated core snd
be established and because the waterflood behavior does the resistivi~ of the brine: .
not indicate the nettability.
Swanson first ineasured the waterflood and electrical FR=RO/RW, . . . . . . . . . . . . . . . . . . . . . . . . . . ...(2)
resistivity behavior of clean water-wet Berea sandstone
and Austin limestone cores. The cores were then &lven where
to IWS and aged with crude oil. It is known that many R. = re.sistivity of the brine-saturated, core,
cores must be aged for at least 30 to 40 days before the RW = brine resistivity, and
nettability reaches its tinid state. 1.4,34.37Unfortunately, FR = formation resistivity factor.
Swanson aged the cores only between 12 and 30 days,
so his cores were tested in some ill-defined, nonequilib- Because very little work has been done on we.ttability
rium state. In fact, in his discussion OYthe waterflood be- effects of this pammeter, it k unclearwhether FR, changes
1376 Journal of petroleum Tmh.ology, December 1986
as the nettability of the core is &tired. Sweeney and Acknowledgments
je.~g~ 19,20found hat tie fomtion factor ~as ~hangqd
I armgrateful to Jeff Meyers for his many helpful sugges-
after the nettability was altered. Because their chemical tions and comments. I nlso thank tie management of
treatment with naphthcnic acids was drastic enough that
Conoco Inc. for permission to publish this paper.
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 1.Aoderson, W. G., Wettahility Literamre Survey-Part 1:
RocklOillBcine Interactions and the Effectsof Core Handfimgon
pore$that had previously contributed to current flow. Nettability,,, .fPT (Oct. 1986) 1125-44.
Rust21 compared sandstone cores that were either 2. Anderson, W. G., . Nettability Literature S.meY-ParI 2:
cleaned (water-wet) or cleaned and treated with nR or- Tenability Measurmnenc,,, JPT (No.. 1986) 1246-62.
ganochlorosilane solution (mildly oil-yet). He found no 3. Anderm, W. G.: WwSbiliT Lherature Survey-Pan & The
significant difference in the formation factors. Mungmi Effects of Wmability on Capillary Pressure,,, paper SPE 15271
available.from SPE, Richardson, TX.
and Moore 6 found no effects on the formation factor in 4. Craig, F. F.: T?IeReservoir Engineering Aspecfs of Waterjlooding,
their teflon cores. They realiied, however, that tbk was Monograph Series, SPE, Richardson, TX (1971) 3.
not a conclusive test because of the uniform composition 5. Archie, G.E.: ,The Electrical Resisdvity Log as an Aid in
and wettabiky of the teflon. They went on to state, How- Determining Some Reservoir Characteristics, Trans., AIME
(1942) 146,54-62.
ever, because natural cores contain clays, a chmge in core
6. Mungan, N. and Moore, E.J.:: <Certain Wettahility Effects on
nettability nlways brings about other changes, such as clay Electrical Resistivity in Pomw Media, J. cd.. Pet. Tech. (Jan.-
swelliig and dispersion, ion exchange, effective porosity March 196S) 7, No. 1, 20-25.
change, and surface conductance variations, and these will 7. Marrow, N, R,: .Physics and Thermodynamics of Capillaty Action
affect the measured vslues of R. and FE. Thus preser- in Porous Media,,, Ind, E.g. Chem (June 1970)62, No. 6,32-56.
S, Pir$cih S.1. and Fraser, C.D.: ,LQuandfative Interpretation of
vation of the natursl core nettability is always pmdent. Electric Logs i Oil-Wet Rods Proposed Procedure qd Example
Application s,pa?w SPE 1562-Gpresentedat the 1960SPE AWMJ
Conclusions Mmtimg, Denver, Oct. 2-5.
9. Brown, W. O.: The Mobility of Commtc Water During a Water-
1. The Archie saturation exponeat, n, is almost in- flood,, > Trans., AJME (1957) 210, 190-95.,
dependent of the wettabflity when the brine saturation is 10. Jones, S.C.: Some Surprises in the Tra.sp.mt of Miscible Fluids
sufficiently high that the brine is continuous. in the Presence of a Second Immiscible Phase, SPEf (Feb. 1985)
2. Nettability effects become very important when the 101-12.
brine saturation is lowered. In genersl, essentially all the 11. Raimon~, P., Torcaso, M., ad Hendcrscm, J.: aThe Effectof
Imerstitial Water m the Mixing of Hydrocarbons During a Miscible
brine in a uniformly water-wet core remains continuous Displacernmt Process;<, ,$fitwro[ {ndustrie, Erperimenr Sradon
and electrically conducting as the brine saturation is Circular No. 61, P,cnmylwmia State U., University Park (Oct.
lowered to the irreducible saturation. The Archie satura- 23-25, 1961) 1,-34.
tion exponent has a vnlue of about 2 in water-wet forma- 12. SaJter, S.J. and Mohanty, K. K.: bMuhiphase Plow in Porous
Medix 1. Macroscopic Obsewadons and Modeling, paper SPE
tions sod cleaned water-wet core. 11017Presentedat the 1982 SPE Annual Techiicd Comferw,&md
3. The Archie safurafion exponent can reach <aJues of Exhibition, New Odeam, SeQr. 26-29.
10or more in unifoimly oil-wet core with low brine sahJ- 13. Goddard, R,R,, Gardner, G, H. F., md Wyllie, M. R.J.: Some
rations. This occurs because a portion of the brine is Asped$ of Mukiph&e Distribmioh in Porous Bodies, Proc.,
trapped, wliile addkiomd brine is isolated in dendrhic Europe. Federation of Cbcrnical Egineerig, Third Comgress,
Inst. of Chmnicaf Engineering, London (Jim 1962) 326-32.
fingers where it cannot contribute to the eleCtriCd Con- 14. Raimondt, P. and Torca.m, M.h.: ,Distribwion of the Oil Phase
ductivity. Re.sistivi@ incr@es because tbe brine cross- Ohfab&d U.. Imbihiticmof Waler. SPEJ (March 1964)49-55;
sectionaf conducting area decreases, and the lengrbs of Trans. , tiME, 231.
the conducting paths increase. 15. Shelton, J.L. md Schmider, F.N.: ,The Effects of Water Injection
on Miiscible Flood@ Methods Using Hydrocarbons and Carbon
4. Unless the reservoir ii strongly water-wet, the satu- Dioxide,,, SPEJ (June 197., . .
75) 7.17-16.
ration exponent should be measured on native- or restorex- 16. SmJkup, F. I.: T@dacem.m of Oil by Solvent at High Water
state cores. If a clean core is used to measure the satura- Saturation, SPEI (Dec. 1970) 337-48.
tion exponent and the resewoir is actually oif-wet; the im 17. TKomas, G.H., Countryman, G.R., and Fat, 1.: Miscible Dis-
terstitial water caR be underestimated when logging. placemmt in a Mdtiphase Sysrmn,,, SPEJ (Sept. 1963) 189-96
Tram. , AIME, 228.
5. Although no definite conclusions cm be drawn about 18. Fatt, L: .Influence of Dead End Pores on Relative Permeability
the effects of tiettabdity on the formation factor, FR, it of Porous Media.,, Science (Dec. 1. 1961) 134. 1750-51.
is ~kely that the formation factor is affected by changes 19. Swomcy, S.A. aridJemings,H. Y,: .The Electrical Resistivity of
in nettability. , Preferentially Water-Wet and Preferentially Oil-wetcarbonate
ROCkS,z Producers ,tfonfhly (May 1960) 24, No. 7, 29-32.
20. SWemey,S.A. and Jemi.gs, H. Y.: .Effect of Wetiability on the
Nomenclature Electrical Resistivity of Carbowde Rock from a Petroleum
FR = formation resistivity factor Reservoir,,, J. Phys. Chem. (May 1960) 64, 551-53.
21. Rq C.F.: .,X Laboratory Sfudy of Nettability Effects o Basic
lR = resistivity index Core Parameters, 3spaper SPE 986-G presented at the 1957 SPE
E = ~atm-ati~n exponent Veoezaela, #mnual Meedg, Caracas, Nov. 6-9.
RO = formation resistivity when 100% saturated 22. Keller, G.V.: Effect of Nettability on the Electrical R.sistivity
of Sand,, $ 0/1 & Gas J. (Jan. 5, 1953) 31, No. 4, 62-65.
with water of resistivity R W, Q. m 23. Lkastro, P.H. ?mdKeller, G.V.: .Resisdvity Measuremems as a
R, = formation resistivitj it i water Criteria for Determining Fluid Distribution i the Bradford Sand,
saturation S,O, S7.m Producers Mo/ith[y (May 1953) 17, No. 7, 17-23.
24. Holmes, C; R.: .Progress i Electric Loggin8 Research at the
R ~ = water iesistivity, Q. m ., PennsylvaniaSfateffniversi~ During 1952-53,,, Producers MOMMY
SW = water (brine) saturation .(Jan. 1954) 18; No. 3, 33-38.

Ihmd of F~tdemT&l~O@%December1386 1377

25. Zietiss, H. and MaUha,A.: Re@ding fhe ReiadonshipBefween 33, Sm"~on, B.F.:<` Ra~&nafizi"gtie Inflne.ce of Cmde Weui"gon
tie Fomtkm Resiwivity Index and the Oil Recovery Mechanism Reservoir FlmidFlow With Electrical Resiwivity Behavior, ,SJPT
During WaterRoodiDg Procedures,,. Erd61 und Kohle-Erdgas- (Au~. 1980) 1459-64.
Pemochenie (1967) 20,549-52. E@ish transfaficmavailable from 34, Cui=, L. E.:,< SNdyofPmblems Related titie Resrorationofke
the John Cr.,., Library, translation m. 68-15700. Natuml Shteof C.re Samplcs,,3J. Cdn. Pet. l&h. (Oct.-Dee.
26. Luffel, D.L, md RandJ.U, R.V. : ;Coii Hmdfirig and Measure- 1977) 16. No. 4.68-80.
ment Techniques for Obtinig Reliable Reservoir Chmacreristics,>7 35. Cuiec, L~E., +rigemn, D., a"d Pacsirsz&, J.:``O. the Nec~s$i-
paper SPE 1642-G presented at tbe 1960 SPE Fonyiticm EvahM- ty of Respecting Reservoir Conditions in Labmatmy Displacement
tm Symp.mium, Housbm, Nov. 21-22. Studies,,, paper SPE 7785 presented at the 1979 SPE Middle East
27, Moore, J.: cLaborator$ Determined Electric Logging Pmeters Oil Technical Conference, Bahiain, March 25-29~
of the Bradford Third Sand,27 Producep Monlhly (March 195S) 36. EmeW, L.W., M."San, N,, a"d Nicholso", R.W.:`<&ustic Slug
22, No, 5, 30-39, fn@ctiOni. fhe Singleton Field, JPT(Dec. 1970) 1569-76.
28, Tradmm, J.C, and Clampiti, R.L. aDetmminatioof Oif Samratim 37. Treibsr, L. E., Archer, D.L., and Owms,W.W,:` `Lab6ramVEYd-
After Waterfloodim in a Oil-Wet Reservoir-The Nmfb Burbmk uation of tie Wetfability of F@ Oil Pradwig Reservoirs,, SPEJ
Unit, Tract 97 P+,, JPT (May 1977) 491-500. (Dec. 1972) 5314Cj Tram., AfME,253.
29. Richardson, J. G., Perkins, F. M., and Omba, J.S.: Diffmencss 3S. Fmser, C.D.: AQumtitati,esmdYOfEl?crricL .gsi Doil-wel
i the Behavior of Fresh md Aged East Texas Woodbine Cores, SS and Fracfured Reservoirs,,, MS thesis, U, of Texas, A.sti (J.
TmI.s, , A2ME (1955) 204, S6-91 1C15R).
30. Watiel, R.A.: OflRaveNby Sh#am FUmDtimgein Mtid- 39. Graham, J.W.:&`RevewWetdmg flogging,,, Trans.,.$fME(l958)
Nettability Rocks,,. JPT(Oct, 1973) 1216.24; Tmns., AJME, 255; 213, 30409.
31. Scbmid, C.: ..The Wettabili~yofPctrole.m Rocks and Res.lWof
Experitnepfs to Study the Effects of Variaions in Wetfabiliw, of
,- COre SamP1es,,, Erdal und Kohl<-ErdEas-Perrochemie ( 1$JS4)17,
No, 8, 605-09, English translation availablt from the Job Crerar
Libray, Iramlaticmo. TT-65-12404,
32. Morgan, W,B. and Pin., S.1,.: The Effecf of Fractional m
Wenatifity o"tie Archie Salucation&pone"t,>X Tmm,, SP~,
Orii(nd manuscript (SPE 13S24) received in the Sociely of Pelrdeum Engineers oIW
Fifth Annuaf LoggingSymposium, Midland, TK (May 13-1S, 19@) Dec. 28, 1984. Paper acceped for pubkmio. July 23, ?9G. Revised manuscript re.
Sec. B. mived Jan, 20, 1986.

1378 Jomalof Petroleum TechnoloD, December 1986