Nettability Literature Survey

Part 1: Rock/OiVBrine Interactions

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

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

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

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

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

1132 Journal of Pekole.m Technology, October 1986

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

Jownd of PetJolam Technology, October 1986 1133

Native.State Core
Coring. In a nativi-stite (fresh) core, every precaution
is taken to minimtie changes from the undkturbed reser-
voir nettability condhion, starting when the core ig frost
flushed by the dr~g mud. In pyticukw, a mid with s~-
factants or a pH that differs greatly from the reservoir
fluids must be avoided. Ofl-based-emulsion muds ?nd
other muds containing surfactaits, caustics, mud thinners,
organic coriosion, in&itors, and lign@fonates must be
avoided. 175,177Note that, @hIle they probably exist, no
commercially available oil-based muds have been m rted
P
thatcan preserve the reservoir nettability. 175>17178
The different coring fluids for obtaining native-stati
cye have been recomriended. (1) synthetic formation
brine, (2).unoxidized lease crude oil, or (3) a water-breed
mud with a miniznuin of addhives. Bobek et al. 175rec-
ommend coring with brine and noadditives. If ,.hk is not
possible, a water-based mud containing only bentonite,
cnrboxymeibyl cellulose, rock salt,, and barite should be
used. This is recommended b~ause they found that this
would not alter the wembfiity of strongly water-wet cores.
Note, however, that the carboxymethyl celkdose,may ~ter
the wettabfit of oil-wet cores, rendering them more
water-wet, 152.~75 Bbrlich and Wygsl 179 recommend a
synthetic formation brine coritaining CaC12 powder for
fluid loss control and no o~er additives. Mungait 180rec-
otiends coriug with lease crude oil. Note f.hatthere are
tio possible problems with the use of crude oil: (1) it
is flammable, and (2) surfactams can be formed by oxi-
dation. of the cmde, which could alter tie wetta-
bili@. ,103
rhfortummly, very MtIe work has been published about
the effects of individual drilling mud components cmwet-
tabiihy, particularly for oif-wet cores. Burkhardt .r al. 176
exaniined the effects of mud filtrate flushing on restored-
,stitecores snd found no significant effects. Unfortunate-
ly, the cores were in contact with the crude oil for only
12 to 16.hours, so it is doubtfol that the wettabtity was
restored before testing.
Bobek ei al. 175 tested several dit%r<nt drillkm mud
componerits used in water-baaemuds on both wat~r-wet
and oil-wet pings The drilling mud :omp6nen@ to be test-
ed were dksolved in or leachdwith distied water then
the resulting solntion was filtcreii. Concentrations of the
compamds were chosen to duplicate those encountered
in the field: Water-wet limestone and s~dstone plugs were
saturated .wltb the test solution and wetibflity alteration
monitored by the irgblbkion method., As,dkcussed earli-
er,.theyfonnd flat rock salt, carboxymethyl celhdose,.
bentonite, and bake had ho effect on tie wetmbfli~ Of
these initially water-wet plugs. Starch, lime, tetmsoditirn
phosphate, and calcium lignosujfomte altered the wetta-
btity of the sandstone and/or limestone plugs.
Drilhg components that, did not.affect the water-wet
plugs were tested on oil-wet sandstone plugs. The dry,
initially water-wet plugs were made oil-wet before test-
ing by saturation with Elk Basin crude and aging for one
day. Notethit becanse of the short duration of the aging,
the wettabiity may not have been in equilibri~. The aged
cores were flushed witi a drilling mud component fkraW,
then the wettabfity was measured. by the imbibition
method. .Sa.kdid not affect the wettabfity, whfle carb-
oxymethyl cellulose made. the plugs more water-wet
(bariti was not tested). Bobck et al. found that the PH
,.
1134
of the filtrates was an iinpotit factor in we~bdity al-
teration. The origti bentonite filtrate changed me wet-
tzbtity from oil-wet to water-wet. When the pH was
lowered into the neutml or acidic rsnge, however, no wet-
tabtitjI reversaIoccurr+.
Sharma snd Wunderlich 158meaaurcd the wettabi!.iwaf-
teration caused by different drilliig mu@components in
water-wet and oif-wet Berea plugs. The oil-wet Berea
plugs were prepared by treatmentwiti an asphaltic crude
and pcntane, as discussed previously. Dry plugs were
saturated with brine, injected with 10 to 12 PVs of the
drilling fluid component, aged for 15 hours; tien flushed
with 5 to 6 PVs of brine. Wettabilky was measurd af-
ter contamination by a combined USBM/Aniotl method
developed by Shagna and Wunderlich 158and compared
with the we~bility of control samples. The driiing comp-
onents tested included bentonite,, carboxymethyl cellu-
lose, Dextrid@ (an organic polymer), D~spac@ (a
polyanionii ceflukiwe polymer), hydroxyetbylcelhdose,
pregelatinized starch, and xanthm gum. These compo-
nents are generally considered relatively bltid, with onfy
small effects on the wettiibilky. None of the components
affected the nettability of ~e water-wet plugs. However,
N of the components, with the exception.of the bentonite
fdtrate, made the oil-wet plugs significantly less oil-wet.
This indicat&stie need for further rese~ch on acceptable
drillings muds for obtaining native-state core.
Several researchers have attempted unsuccessfully to
fmd suitable commercially available oil-based muds for
~btig ~tive.sate core, 175, 177, 178,~ of tie ~fi.ba~~
drilling mud iiltrates tesied made water-wet cores more
oil-wet. Unfortunately,. none of the reports identify tlze
specific drilling mud components used. ,
Cm-e Packaging and Preierv&ion. Once the core is
brought to the surface, it must be protected from wetW
btity alteration caused by the loss of light ends or depo-
sition snd oxkldion of heavy ends., On exposure to air, .
subticei k crizdecan rapidly okidize to form wkw prod-
ucts that are surfactants, altering ihe wettabili-
,W,34,73,103,115,175,181,182 M ad&tiOn, a tick ofl-w@
residue from the crude will be deposited on &e rock sur-
face if the core is allowed to dry out. To prevent wetE-
bility alteration, Bobek et al. 175 recommended two
sltemitive packaging procedure: that are now gene@y
used for native-state cores. The fwst ia to wrap the cores
at the weUii@in polyethylene or polyvinylidene film and
then in aluminum foil. The wrapped cores we then sealed
with a thick layer of paraffin or a special plastic sealer
designed to exclnde oxygen aid prevent evaporation. The
second, preferred method is to immerse the cores at tip
wellsite in deoxygenated formation or synthetic brine in
a glass-lined steel or plastic tube, which is then seafid
to prevent leakage and the entrance of oxygen. ImbibG
tion wettabihw tests showed that the nettability of core
packaged by either of these WO methods was unchanged
from the wettabfily mesaimed at the wellsite. Instid of
deoxygenated brine, Mungari180 recommended tit the
cores be cut and stored in degassed l&ae crude oil. Mor-
gan and Gordan 183and McGhee et al. 62 recommended
that the cores be stored in their wetting fluid, either for-
ntstion brine or crude oil. Thewettabiky would be,deter-
mined by an imblbhion test at the wellsite. Finally, not?
that cores taken in a robber sleeve, fiberglass, or PVC
Journalof Petroleum Tedmo108y, Octpber 1986
 TABLE 3EFFECTS OF EXPOSURE TO AIR AND PARTIAL DRYING ON
NATIVE-STATE CORE
Number
of Cores
Tested iescriplion
2 Native state
3 Exposed to air at
70 to 100nF for 1 day
2 Exposed to air at
75F for 60 days
4 Exposed to air at
225F for 7 days
Cay$btdnedbyuse ofthe Amattwellafl~v,,s, natNeNatecorefrom0,! Zone8., SterlingConly,
L
liner can be DESeNed if the ends are cappedand sealed.
A number-of experiments have dem&strated that ex-
posure to air and drying cao alter the nettability of core.
As discussed earlier, Treiber et al. w measured the. net-
tability of 50 reservoirs usfig deoxygemted synthetic for-
mation brine and anaerobic crude. In some cases, the
contact angle showed that the reservoir was water-wet.
For some of those cnrdes, exposure to oxygen changed
the wettabili~ to ofi-wet. Bartell mrd Niederhauser103
stodied interracially active materials in crude, which con-
centrate and form solid fflms at the oil/water interface.
These materiils can also be adsorbed on the rock surface,
rendering it oil-wet. Crodes and brines were obteined and
stored without exposure to oxygen. Most of these crudes
showed very little interfaciel activity. On exposure to air,
the cmdes developed moderate-to-strong fdrn-fomning
tendencies, while the oil/water IFT was lowered by as
much as 50 %, indicating that surfactants were formed by
oxidatiori of the crude...
Richadson et al. 1s2 stored core from a mixed-
wettability reservoir47 using four different methods. Ox-
idation snd drying of the core tiere prevented with the
first two methods: (1) core wrapped in foil and scaled in
paraffh and (2) core stored in evacuated (deoxygenated)
formation water. The other methods were (3) core stored
in aerated formation water and (4) core stored in cloth
core bags. The cores were oilflooded with kerosene to
IWS and then waterflooded. The average ROS for the
samples protected from oxidation and drying (Methods
1 and2) was about 13%; forthesamples submergedin
aerated water, about 24%; and for the samples storedin
core bags, about 25%.
Bobciket al. 175used the imbibition method to compare
the nettability of native-state cores at the wellsite, cores
allowed to weather, and cores stored by the two recom-
mended metiods discnssed above. The nettability of the
cores stored by either of the two recommended methods
was the same as the nettability measured at the wellsite,
while most of the weathered cores became more oil-wet.
Am0tt177 used bismethtidt ocomparith ewettabihy
of native-state cores with similar cores that were exposed
tooxygen ayd~owed to partially dry, asshownin Ta-
ble 3. The native-stste cores were strongly water-wet, with
a dkplacement-by -water ratio of 0.97. In the Amott test,
the displacement-by-water ratio is the ratio of the oil
volume displaced by spontaneous imbibition to the total
oil volume displaced by .botb imbibition and forced dis-
placement. Itiszero forneuqally mdofl-wetcO~~s aod
J&mal of Petroleum .Tecbnology, October 1986
1
Average . Average
Dlsplacement- Oisplacement-
by-Water Ratio by-oi Ratio
0,97 0,00
0.63 0.00
0.42 0.00
0.18 0.00
approaches one as the water-wetness increases. Siniiiar:
ly~ the displacement-by-oil ratio is zero for neutrally and
water-wetcores aod approaches one as the oil-wetness
increases. The cores became more oil-wet as they were
either exposed to the air for longer periods of time, o!
at higher temperatures. Similar tests on an initially weakly
water-wet core showed elmost no change. On the other
hand, Mungan 115used the imbibition method to meas-
ure the wettabilhy of native-state cores. In contrast to tie
experiments discussed above, cores preserved in deaer-
ated water were oil-wet, but becsore water-wet when ex-
posed to ti for 1 week. Chfingar and Yen35 have also
reported that some cores became more water-wet on ex-
posure to sir, indicating that it is bnpossible to predict
how the wetfsbtity will be altered by tie oxidation of tie
cmde.
Mungao 180recnmmendsflushing native-state core with
five erode oil before sny flow studies are startsd. After
native-state cores .havc been prepared, they are usually
nm at reservoir conditions with crude oil and brine.
Probably the greatest, uncontrollable problem with
nstive-state core is the alteration of nettability as the core
is brought m the surface., When the pressure is lowered
to atmospheric, light ends are lost from the erode, chang-
ing its properties. In addition, heavy components cm come
out of solution and deposit on the rock, making it more
oil-wet. 137 The decrease in temperature wilf also
decrease the solubili~ of some wettebfli~-altering com-
pounds. Pressure coring prevents tie loss of light .erids.
However, the cores are frozen before removal, so
wetta.bflity-altering compounds W deposit. Unfortunate-
ly, there is no experimental work avsilableon wettabfli-
ty alteration as the core is brought to the surface. ..
.
Cleaned Core
The second type of core used in core aoalyais is the
cleaned core. Cr&ig7 recommends that cleaned core be
used for multiphase flow measurements only when the
reservoir is known to be strongly water-wet because errors
iq the core am.lysis will be introduced otiimvise. There
are two main reasons to clean wre. The first is to remove
all liquids fromthe core so that. porosity, permeability,
and fluid saturations can be measured. Core cleaning for
these roudoe core measurements will not be considered
in this paper. The second reason for cleaning is to obtain
a strongly water-wet core, generally as a first step in
restoring the wettabfity of a contaminated core.
1135
 In obtaining a cleaned core, an attempt is made to re-
move all of the fluids and adsorbed material, leaving a
clean rock surface. Gant aid Anderson 129 discuss the
meibcdsused,tu clean core. One common method is reflux
extraction (l)ean-Stark or Soxhfet) with a solvent such as
toluene, sometimes followed by extraction with cfdoro-
form or methanol. Alternatively, a flow-through system
where the solvents are injected under pressure is some-
times used. 57,&,65lf the cleaning procedure is success-
ful, the core is left strongly water-wet. Cuiec$5 mid
others 57,1w discussed the chemicalreactions involved in
the cleanin process.
Cui&ca,& compared me efficiency of different solvents
in flow-through core cleaning. Initially water-wet outcrop
sandstone and limestone cores were saturated with differ-
ent cntdes (sometimes the cores also contained brine), then
aged. The aged cores ivere ncyrmfly neutr~- to oil-wet,
as determined. by the Amott wettabflity test. The cores
were then cletied with dlffererit solvents, and the Amott
test was used to determine cleauing efficiency. Cuiec
found that he could clean both sandstone and liiestone
cores by flowing the f?ll@ig seven solvents through the
core: pdarte, hexane, heptane, cyclobexane, beuzene,
pyridine, and ethanol. Chloroform, tohtene, and methanol
used singly were not very effective. Cuiec also looked
at several dtiercnt acidic and basic solvents used individu-
ally and found that the acidic solvents tended to be more
effective in cleaning sandstone, whiie the basic solvents
were better in cleaning Iimcstone. This difference was at-
tributed to the acidic nature of the sandstone surface and
the basic mture of the limestone surface. For examplei
because sandstone (silica) has a weakly acidic surface,
it tends to adsorb bases from tie crude oif. When a
stronger acid flows through the sys@m, it will gradually
react with and strip off the adsorbed bases, Ieaviug a clean
silica surface.
G@ and Anderson 129 surveyed most of the core-
cleouing experiments in the literature. They found that
the best choice of solvents depends heavily on the cmde
~d the mineral surfaces becavse they help determine the
amount and @pe of nettability-altering compounds ad-
sorbed. Solvents that give good results with some cores
and cmdes often faif in other cases. For example, Grist
et al. 1s4 and Holbrook and Beruard45 both found that
they could clean core to a strongly water-wet state using
a cliloroformfmerhanol mixture, while Jennings5s repOrt-
ed. fiat thk was unsuccessful. For cleaning for routine
core analysis, API 1s5 reports that cbfom form is excel-
lent for many midcontinent .ctudes,wh~e toluene is us6-
ful for asphaltic cntd:s..
hi many cases, it appears that any single solvencis rela-
tively ineffective in core cleaning and that much better
results can be obtained wiih a mixtttfe or series of
solvents. 129 The followhg solvents have, been rCpOfi-
ed for specflc binbinations of crude and core to give
pcor resufts when used alone: chloroform, ,65 ben-
zene, 5S,1M,120~=bon di~~fide, lU,120 ~~mol, @ ~d
toluene.5@.@.65 .1~.120,1T.l~,1s6
Many of the researchers cited above have found that
toluene used alone is one of the least effective solvents.
However, when combined with other solvents, such as
methanol (CHs OH) 184 or ethanol (CH3 CH zOH), 61
toluene is often ve~ effective. The toluene is effective
in removing the hydrocarbons, including asphal-
1136
tenes 130JW and some of the weakly polar compcmmi.s,lW
wbiletbe more,spongly polar methanol (ethanol) qcmoves
the strongly adsorbed polar compounds that are often
responsible for altering wettabilky. In addition to
toluenelmethanol and tolueneletbonol, successful clean-
ing has ako been reported with cbforoforndace-
tone 1wZ120. 1= and cfdorofordmetfranol, 1s4 as well as
a number of different series of solvents. ,65
CuieCand his coworkers made the most extensive study
of core cleaning for nettability restoration. In a recent
paper, Cuiec et az. 130statkd that their core cleaning al-
ways begins with a toluene flush to remove hydrocarbons
and asphaltenes. A number of solvents are then.tested to
determine the most effective, including (1) a series of non-
polar solvents, e.g., cyclohexane or heptane; (2) acidic
solvents, e.g., cblorofonn, ethanol, or metbanoh (3) ba-
sic solventi, e.g., dioxane or pyridine; ond (4) mixtures
of solvents, e.g., methanollacetoneltoluene. When none
of these procedures are effective, other tests are performed
by combining the above procedural, using otler solvents,
ad incremfig the Circdatiog time.
Tohtene is generally not a very effective solvent, but
it canalter the nettability of some core. Jennings 186
cleaned sever,d cores by toluene extraction and found that
the wettabilities and relative penn.eabilities were not
changed. He stoted that this indicated that toluene-
extmcted core retoined the reservoir wettabi!ity and coufd
be used for relative p+mneabtity rneosurements, However,
this generally is not the case. Aftbough it is less et%cient
than other solvents, we have found that toluene extrac-
tion can alter the wettabili@ and relative penneabtitics
of native-state core. fn some cases, neutmlly wet or tidly
oil-wet mtive-state core becomes strongly water-wet ti-
ter extraction witi toluene. The relative permeability
cume~ ~~o ~E,fi. AMOU177 ako found that toluene ex-
traction can clean some cores, while it had Wt3e effect
for other ones, such as the strongly oil-wet Bradford cores.
Therefore, because tolueneextraction will alter the wet-
tabilky and relative permeability of many. native-state
cores, m%uremcnts shouId be tie on mtive-state cores
before toluene extinction.
One problem with a cleaned core is that it is sometimes
difficult, if not impossible, to remove all of the adsorbed
material. If this occurs, the wetta.bfity of tie cleaned core
wifl be left in some indefinite staie, causing variations in
core analyses. Grist et al. lW cleaned cores by three cu-
rently used methods and then examined how ROS and end-
point effective permeabilities vtied after a waterflood.
ROS was very similar for W methods. However, the end-
point effectiye water permeability varied by more than
a factor of three betwtin different cleaning methods. Their
explanation for this behavior was that some methods were
able to extract more of the adsorbd. components, leav-
ing.the rock more water-wet. In the more water-wet cores,
the rwidti oil had a greater tendency to form trapped
droplets, blocking pore throats and lowering water per-
meabtity. The least effective of the three cleaniug me~ods
was overnight reflux extinction with toluene. More ef-
fective was reflux extraction with toluene followed by 2
days of extraction with a mixture of cbloroforin oud
methanol. Finally, tie most efficient method was reflux
extraction with tcduene followed by 3 weeks of extrac-
tion with chloroform and methanol. In the last stage of
cleaning, methanol was used alone.
Journalof PetroleumTechnology,October1986
 Another draivback of cleaned cores is that it is occas-
sionafly possible for cIeaning to change an originally
water-wet rock to an ofi-wet one. The extraction process
may quickfy boil off the connate water, allowing the re-
maining oif to contact the rock surface and form oil-wet
deposits that are afmost impossible to remove. 187
The cleaning experiments discussed examine the best
methods to remove. cmde oil constituents from the pore
walk. In many cases, core is also contaminated with drill-
ing mud surfactits, which mustalso be removed before
the wettabifity of acore can be restored. 12ar129The best
choice of solvents depends on the crude, the mineraf s~r-
faces, and the drilfiig mud surfactsnts. Gant and
Anderson 129cleaned Berea sandstone and Guelph (Bak-
er) dolomite plugs contaminated with an invert-oil-
emufsion rfrifling mud. filtrate. The best solvent fOr bOfh
rock types was a 50/50 mixture of toluene/methanol, oi
the equivalent, containing 1% ammonium hydroxide. A
three-step method (three successive Dean-Stark
extractions-toluene, foffowed by glacial acetic acid, fol-
lowed by ethanol) was the second best choice for Berea,
while 2-methoxyetiyl ether was the second best choice
for dolomite, demonstrating that the choice of solvents
can depend O? the mineral surfaces in the core.
Restored-State Core
,
If one conld be positivethat the original reservoir wetta-
bilhy hadizotbeen inadvertently modified, a native-state
core would give resnks closest to those of the reservoir.
However, riative-st@ecores present scveraf problems. The
necessary procedures to preserve the wettabtiq are
troublesome and time-consuming. Even when sll of the
precautions iwe tsken, there is still a possibility that the
nettability has been chtiged through oxidation or through
deposition as tie temperature and pressure dropped when
the core was brought to the surface. In addition, tic ques-
tion arisesabout tie procedure to follow to obtah the most
reliable information from cores in which the nettability
WaS aftered
When onfy core with alt&ed wei@bfity is available,
the best possible mukiphase measurements ore obtained
by resto& the resefioir wettabfi~ with a three-step
~roces~. 47,F0,64,65.,96,115,128,130,1S0,18SThe f~st ste~ is to
~leaa the core to rernoVeall compounds from th~ rock
surface. After the core is cleaned, the second step is to
flow reservoir fluids into the core sequentially. F~y,
the core is aged at the reservoir temperamre for a suKL-
cient dine b establish adsorption equilibrium. Seversl ex-
perimenters have compared measurements made on core
in the native, cleaned, and rsatored states. In each experi-
ment, measurements in the restored state were slmost
identical to the,previous mtive-sta.te ones,demons@atin
that this procedure will restore nettability. 50,115Js0;18~
~,, The first and most @fficult step in nettability restora-
tion is to clean the contaminated core by use of the
methods described to remove all compounds adsorbed on
the surfaces and to make the core as water-wet as possi-
ble. All compounds must be removed from the core be-
cause we have no knowledge of which compounds were
adsorbed on the undisturbed reservoir rock and which
were deposited afterward. The USBM or Amott netta-
bility measurements are used to verify that the core is
strongly water-wet., Unforttzmtely, detemining which sol-
vent wiII successfoffy clean the core is still a trial-and-
Iourmt of Petroleum Technology, October 1986
Fig. 1Wettabitity changes for a restored-state core and
the effects of flushing restored-state cores with refined
OIIS. Berea core and Big Muddy crude.
error process because the best choice of solvents depends
heavily on the crude oil, the mineraf surfaces, and any
&idling mud contaminant. Further discussion can be
foundin Ref. 129.
In the second step, sequentially flowing reservoir fftids
btto the core, the core is saturated with deoxygenated syn-
thetic or formation brine and then flooded with crnde oil
to simnla.tsthe intlow of oil into the resemoir. When cmde
oil for wettahifity restoration is obtained, precautions
should be taken to minimize alterations to the crude. The
hnple must be taken before tiy Sm&ct.mrts or Ofier
chemicals ae added to treat the crude. It should be taken
as Iong as possibIe after any wefl treatments to aIIow time
for these chemicafs to be flushed from the well. Finally,
the cmde should be sealed in air:tight containers as soon
as possible to minimize oxidation and the 10SS of light.
ends.
The fired step in wettsbfity restoration is to age tie core
at the reservoir temperature for a stilcient time to es-
tablish adso~tion e&libzium. The aging time required
to re-eatabfish reservoir nettability varies, depending on
the crude, brine, and reservoir rock. Generally, we feel
&at core shoufd be aged for 1,000 hours (40 days) at the
reservoir temperature. 128This a&ng period was chrken
for two reasons several experiments have shown that up
to 1,000 hours is required to reach wetting equilibri-
um ~$s. 115,189-lgl and 1,000 hours is roughly the length
of ~me required for the contact ~gle measnred on a flat
surface to approach its equilibrium value. 7>26,34.191 III
some cases, the restoration time can be significantly less
than l,OW hours. MunganlsO was able to restore the wet-
tabilky after aging for 6 days, while the nettability of the
rocfuoilhine system used by Schmid50 and Riibl et
~. lss was restord after only 3 days. Salathie147was able
to restore a mixed-wettabilhy qate to samples after 3 days.
Cuiec et al. 130describes two reservoirs in which the wet-
tabtity was restored after only a few hours, with no fur, <
ther cbamges in tie wettabiIity for aging times as long as
1,000 ho;rs.
There are two basic options to determine the aging time
to restore wettabllitv. We feel that it is ,most convenient
to age afl cores for l:W hours, which is roughly the mm-
imum time that the experiments discussed previously re-
quired to achieve wetting equilibrium. While cores may
1137
 be aged for a period longer than the minimum necessary,
thk is not a serious drawback because the aging cores re-
quire minimal attention. Another possibtity is to deter-
mine the minizhtzmaging time by measuring the wetrabfity
of the core with the USBM or Amen methods at frequent
intervals during the aging period. The aging is stopped
when the wettabflity reaches its cquilibtium value.
Although this minimizes aging time, it is much less con-
venient because it is labor intensive nnd requires frequent
disturbances to the plug.
The core is aged at either the reservoir pressure with
live cmdeso, 180,188,191or ambient pressure with dead
cmde. 115.128.190 When live crude oils a~d the reservoir
pressure are used, the solubflities of the wettabilhy-
altering compounds should have their reservoir values.
It is possible that the nettability will differ when dead
cmdes .at nmblent pressure are used. At the present time,
however; it is not known whether the difference is im-
portazm
Fig. 1 shows the chsnges in the USBM wettabfity in-
dex as a core was restored. * A series of Berea plugs was
saturated with brine and driven to IWS by centrifugation
in crude oil. Each core was aged in dead crude for a differ-
ent period, of time, after which the USBM wettabtity was
measured. As can be seen, the wettabilky changed from
water-wet (W =0.8) to moderately oil-wet ( W= O.3)
over a 40-day period. The plugs flushed with Soltrol@
and Blnndol@ will be dkcussed later.
Lorcnzetal. 190and Cuiec65 found tbatitissometknes
possible to speed up the approach to wetting equilibrium
by saturating.thecore with oil alone. The approach to
equilibrium is fastix because the polar compounds no
longer have to dlffase across a water layer to adsorb on
the rock. This procedure should be avoided, however, be-
cause it can give iriaccuratc results. For example, con-
sider the restoration of a core that originally had
Salatbiels47 mixed wettab~ity, where &e large pores are
oil-wet nndthesma!.l ones are water-wet. During tbeag-
ing process, thesmall pores must contain comate.water
to prevent the deposition of au oil-wet fiim, leaving them
water-wet. Onthe other hand, ifaclcan core is saturated
only with oil, tbe entire core, includlu gtbesmallpores,
will become uniforndy oil-wet, whlchis the wrong wet-
tability. Anaddhionalp roblemw ithsaturadngt iec ore
solely with oil istbat the effects of brine chemistry are
ignored. As discussed previously, the wettabtity of the
core depends on the ionic composition and pH of the brine.
Finally, Clementz10?.120,121$howedtbat flowing cntde
oiltbrougha dry core camcause tbeformition of very
stable oil-wet, claylorganic complexes. Thepresenceof
an initial water film on the clay surfaces haa been shown
to reduce but not completely inhibit the adsorption of the
nettability-akering materkds. @@.70 The effects of brine
OtI wearability make it necesssry to saturate the core with
brine, then oil, during the nettability restoration process.
Experimental Conditions
Once a mtive or restored-state core is obtained, core anal-
yses can be performed. These tests can be mn with either
crude or refined oil at ambient or reservok temperature
and pressure. Because wettabfity effects are being ig-
Personalc.mmlcati.nwl,hD..J.Wendel,Pe!r.aleum
TestingSeMceS,Smta
Fe SPringS,CA,No.19S0.
1138
nored, cleaned cores are generally mn with refined oif
(or even mercury or air) at room temperature and pres-
sure. From the viewpoint of titaining the nettability,
the best laboratory tests should be mn with native or re-
stored cores at reservoir conditions with live cntde oil and
brine because this is the best simulation of reservoir con-
ditions possible. Cor~ are generally more water-wet .at
rese~oir conditions tbzn they are at rooin temperature
ad pressure, 62,180,192-195 The effects of the following
experimental conditions on nettability will be dkcussed:
(1) rcaervoir vs. room temperature, (2) live vs. &ad cmde
at reservoir pressure, and (3) refined vs. crude oils.
Changing the temperature has two different effects, both
of wtich tend to make the core mom water-wet at higher
temperamres. First, an increase in temperature tends to
increase the solubtity of wettabtity-altering cOm-
pounds. 196 some of ~eSe compounds will even desorb
from the surface as the temperature increases. Second,
the IFT and the contact angle measured through -bewater
will decreaae as the temperate increases. This effect has
been noted in experiments with cleaned cores, minernl
oil, and brine, where it was found that cores at higher
temperatures were more water-wet even though there
were no compounds that could adsorb and desorb. 19-2?
For example, McCaffery201 measured the water-
advancing contact angle on qWrtz of n-tetradecane and
brine. The amglewas about 40 [0.7 rad] at 77F [25C],
but decreased to about 15. [0.3 rad] as the temperature
was raised to 300F [150 C].
when live crude oils at the reservoir pressure and tem-
perature are used, the solubilities of.dzewettabfity-afteting
compounds have their reservoir values. The use of dead
crude at ambient or reservoir prcasure may change the
nettability kmzse the properties of the crude are altered.
Light ends are lost from the crude, while the heavy ends
are, less soluble, which may make the core more oil-wet.
However, the effects of pressure are not known at pres-
ent. The two reported experiments found that ressure
is much less important than temperature. 18~,1~ Hje~.
meland and Lamondo 192 found little difference in con-
tact angles measured using stock-tank vs. live cmde at
the reservoir temperature (190F 88C]) and pressure
(3,800 psi [26.2 MPa]). Mtmgan 10 i measured a water-
advancing contact angle ,of $7 [1.5 rad] using live reser-
voir crude and synthetic formation brine at resemok tem-
perikurc (138F [59C]) and pressure (1,200, psi [g.3
MPa]). The water-advwcing contact angle was almost
identical, 85 [1.48 rad], using degassed crude and brine
at ambient pressure and reservoir temperamre.
Because refined oifs are much easier to work with tlum
cmde, it is a common laboratory practice to flush native-
or restored-state cores with refined oil before testing.
However, there is a possibilky that this idters the netta-
bility. Craig7 poshdated that it would be possible, once
the original wettabtity was restored, to use refined nzin-
eml oil in place of crude oil in laboratory tests without
adversely affecting the wetk+bility. Test times are shor!
compared with the time it takes to achieve adsorption equi-
librium and obtain native wettsbtity (about 1,000 hours).
Craig hypothesized that the desorption of wettability-
Mbzencing materials would require a correspondingly
long period of time. If this is correct, @e orig@l wetta-
btity wotdd be unchanged if laboratory tests using refined
oil and brine were conducted quickly enough.
Journal of PetroleumTechnology,October1986
 The onfy experinient to teat this hypothesis that we are
aware of was conducted by Wendel. * He aged ,Blg Mud-
dy crude in Berea sandstone at IWS to develop his
restorer-state cores. The cores. were flushed with one of
two refinkdoik, Soltrol 170 or Bkmdol, to detexmine how
they affected the wettabfily. The results&e show in Fig.
1. Bkmdol did not si@ficantly affect the we~btity, while
Soltml 170 changed tbe core from oil-wetto neutrally wet.
The wettabdity: alteration could be caused by either
surface-atilve impurities in the Soltrol 175or desorption
of previously depositwj oti-wetdng crude compounds from
the pore walls into tie Soltrol. It i; not known which ex-
planation is correct. Wendel did not attempt to fflter the
refined oils tfmugh a cbromatogmphic coltmm tn remove
surface-active compounds. These contamiim ts are known
to have a large effect on corit.w-migle measurements,
which are extremely seyitive to small amounts of con-
taminants. Wettabifity measurements in core should be
less sensitive, however, because the ratio of smface area
to volume is much higher.
Conc133sioris
1. The nettability of a rsaeryoir ample affects ita capil-
lmy pressure, relative pe,rmwbtity, waterflood behavior,
dispersion, mid electrical properties. fn addhion, simu-
lated teftiary recovery can be 51ter,cd.The tcfi,~ recov-
e~ PrOcesses affected by we~biE~ include hot-water,
surfactant, miscible, aid caustm floodlng.
2. Cleaned, strongly water-wet cores should be used
onfy in such c6re analyses as porosity. and air permeabil-
ity, where the wettabilky is unhpportmrt. h addition, they
may be used in other tests when the reservoir is known
to be strongly water-wet.
3. The nettability of originally water-wet mineral sgr-
faces can be altered by the adsorption of pokw compounds
aui/or the deposition of orgariic rnattertlmtwas origi-
MUY in the crude oil. Fmrfactants in the crude oil are
generally believed to ,be polar compounds that contain
oxygen, nitrogen, ,mdlor sulfur. These compounds ~
most prevalent in the heavier fractions of crude oil, such
as the resins and asphaltenes.
4. Nettability alteration is determined by the interac-
tion of the oil constituents, the mineral surface, and the
brine chemistfy, including ionic composition and pH. In
siIicafoiVbrine systems, trace amounts of mukivalent me-
M. cations can alter *e nettability. The catiom can reduce
the solubti~ of crude oil surfactants and/or activate the
adsorption of aniotiic surfactants onto the silks. Mfdtiva-
lent ions :$tathave altered tie wettabfity of sihcafoil/brine
systems tnclude Ca2, .Mg2, Cu2, Ni2, and Fe3.
5. Work on mineral flotation indicatca that coal,
graphite, sulfur, talc, the talc-liie silicates, and many sul- Acknowledgments
tidca are probably naturally,neutrally wet to oil-wet. Most
other minerals-includhg quartz, carbonates, and
sulfatesare strongly water-wet in their natural s@.te.
6. Contact-angle measurements suggest ti.at most car-
bonate reservoirs range frpm neutralIy to oil-wet as a re- References
sult of the adsorption of surfactimts from the crude oil.
7. Very little work has been reported about the changes
in wetibility caused by drioiig mud addhives. Three
different Cciring.flrtidshave been recommended to obtain
native-state core: (1) synthetic formation brine, (2) un-
-PemmalmmmunlcatimwilhD,J.Wend.at,PetroleumTestingS6wkeS,Santa
Fe SP,ingS,GA,N.. 19S0,
oxidized lease crude oil, or (3) a water-based mud with
a minimum of iddkives. B&use of surfactits in the SYS-
tern, no conimercitiy available oil-based or oil-ernukion
muds are khown that preserve the native wt?ttability.
8. The wetr?bility of a native-state core. cambe altered
by loss of light ,ends and/or the deposition aid oxidation
of heayy ends. TWOalternative pac@ging procedures cam
be used to miniinize these effects. The first is to immerse
the corei in deoxygenatdd formation or synthetic brine
and place !hem in a glass-lined steel or plastic tube, which
is then seaIed against leakage aud the entrance of oxy-
gen. An alteinaiive procedure is to wrap the cores at the
welksite in polyethylene or pglyvinylidene fdm and tien.
in ihunirimn foil. The wrapped pore is tlyn coated with
i+thick layer of paraffin or a plastic sealer.
9. Because of the increased solublky of the wettability-
altering compounds at the higher temperature spd pres-
sure, the cmde-odtbrinetcore system is usually more
water-wet at reservoir condition than at ambient con&-
tions. In addition, the contact angle measured tluough the
water will generslly decrease as the tempetatufe is in-
creased, and the system will become more water-wet,
even if no surfactauts are present.
10. Extraction with toluene cti alter the wettabil.ity of
some iiative-state cores, causing someinitially neutrally
wet or qikfly oil-wet cores to become strongly water-wet.
Measurements on native-state iorei should be made be-
fore toluene extraction.
11. During the attempted restoration of a cleaned core
to ita orig$al wetrabtity, the core should be saturated with
brine, @lflooded, md then aged at the reservoir corrdi-
tiom for 1,COOhours. This will embie a inixed-wettabtity
condhkin to be restored, if thk was the original wettabd-
ity. In addition, it will allow the brine chemistry to influ-
ence tie r~tored nettability. An alternative procedure,
which completely saruratea the core with cmde oil, should,
be avoided.,
12. The three commonly used methods for artificially
conrrolEng wettabfity during laboratory experiments are
(1) treatment of the core with chemicals, generally or-
ghocblorosilane solutions for sandstone. cores and
naphtbenic acids for carbonate cores; (2) using sintered
teflon cores with pure fluids; and (3) adding surfacmnts
to the fluids. To obtain a uniformly wetted core, a sin-
teredteflon core with pure fluids is preferred because its
nettability is more constant and re reducible than the wet-
tabilby of cores treated WI# organochlorosilanes,
naphthenic acids, or smfactants. However, these treat-
ments have advantages when heterogeneous wettabllity
or nettability alteration isstudied.
I w grateful to Jeff Meyers for hk many helpful sugges-
tions and comments. I also thank the management of
Conoco h.c. for permission to publish this paper,
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1144 Jomtiof Pewoleum Te&olo~, October 1986