Journal of Petroleum Science and Engineering 52 (2006) 172 – 186

www.elsevier.com/locate/petrol

Pore-scale modelling of NMR relaxation for the

characterization of wettability
S.H. Al-Mahrooqi a , C.A. Grattoni b,⁎, A.H. Muggeridge b ,
R.W. Zimmerman b , X.D. Jing b,1
a
Petroleum Development Oman (PDO), P.O. Box 81, PC.113, Muscat, Oman
b
Department of Earth Science and Engineering, Imperial College, Prince Consort Road, London SW7 2AZ, UK
Received 19 June 2004; accepted 7 March 2006

Abstract

Several research groups are currently investigating the determination of wettability using NMR relaxation times. Although
correlations with traditional wettability indices have been presented with some success, further effort is needed to relate the
wettability at pore-scale to a core-scale measurement of NMR response. For example, a qualitative method using the arithmetic
mean of relaxation times at various saturations has been presented [Guan, H., Brougham, D., Sorbie, K.S., Packer, K.J., 2002.
Wettability effects in a sandstone reservoir and outcrop cores from NMR relaxation time distributions. J. Petroleum Sci. and Eng.
34, 35–54] and a wettability index that quantifies the amount of surface area that is wetted either by oil or by water, by using the T2
peak at four different saturations has been proposed [Fleury, M., Deflandre, F., 2003. Quantitative evaluation of porous media
wettability using NMR relaxometry. Mag. Reson. Imaging 21, 385–387]. Our group at the Imperial College have previously shown
experimentally that the T2 distribution provides valuable information about wettability and overall fluid distribution within the
pore-space, which is lost if only a single value from the T2 distribution is considered [Al-Mahrooqi, S.H., Grattoni, C.A., Moss, A.
K., Jing, X.D., 2003. An investigation of the effect of wettability on NMR characteristics of sandstone rock and fluid systems. J.
Petroleum Sci. and Eng. 39, 389–398].
In this paper we use a simple pore-scale model to understand the effect of wetting and its relationship with NMR relaxation
times. The model uses triangular capillary pores with a given pore size distribution. The oil/water distribution within the pores is
obtained as a function of capillary pressure and wettability. At a given capillary pressure, the volumes and surface areas of water
and oil are calculated for each individual pore. This allows us to calculate the theoretical T2 distribution for that pore size
distribution as a function of wettability and saturation.
We have used the model to study the T2 distribution for a range of wettabilities and saturations. Results from the model
confirmed previous observations from experiments regarding the effect of wettability on NMR T2 distributions. Based on these
qualitative results, an improved index for characterising wettability from the T2 distribution has been proposed. We tested the
proposed index using NMR T2 data from synthetic and real sandstone core plugs with different wettabilities, ranging from strongly

⁎ Corresponding author. Present address: Rock Deformation Research Limited (RDR), Earth Sciences, University of Leeds, Leeds LS2 9JT, UK.
Tel.: +44 20 7594 7371; fax: +44 20 7594 7444.
E-mail addresses: sultan.mahruqy@pdo.co.om (S.H. Al-Mahrooqi), c.grattoni@imperial.ac.uk (C.A. Grattoni), a.muggeridge@imperial.ac.uk
(A.H. Muggeridge), r.w.zimmerman@imperial.ac.uk (R.W. Zimmerman), x.d.jing@imperial.ac.uk (X.D. Jing).
1
Currently with Shell International Exploration and Production B.V., Rijswijk, The Netherlands.

0920-4105/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2006.03.008
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186
water-wet to strongly oil-wet. Comparison between the proposed index and wettability for the synthetic samples and Amott–
Harvey index for core plugs show good correlation.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Wettability; NMR; T2 relaxation; Pore-scale modelling; Wettability index
1. Introduction
There is a great deal of interest within the oil
industry in applying NMR measurements to improve
reservoir characterisation, thereby helping to reduce
uncertainty in the prediction of oil recovery. Both the
spin lattice (T1 ) and spin–spin (T 2) relaxation
distributions are sensitive to the fluid properties and
the fluid interaction with the pore structure of the
surrounding rock. For example, the NMR signal due
to the spin–spin relaxation of fluid contained in a pore
consists of three components: (i) the bulk or free
relaxation of the fluid in the interior of the pore, (ii) a
surface relaxation due to the fluid interacting with the
surface of the pore, and (iii) relaxation as a result of
molecular diffusion. Thus, the overall spin–spin
relaxation time is given by
1 1 1 1
¼ þ þ ;
T2 T2S T2B T2D
where 1/T2S is the surface relaxation time, 1/T2B is the
bulk relaxation time, and 1/T2D is the relaxation due to
molecular diffusion. In the fast diffusion limit, the
relaxation rate of a fluid is directly proportional to the
surface (S) to volume (V) ratio of the pore (Brownstein
and Tarr, 1979). In this case the surface relaxation time
can be expressed as:
1 S
¼q ;
T2S V
where ρ is the surface relaxivity of the pore walls
[LT− 1]. The T2 response of a fluid filled porous
medium is directly sensitive to the nature of the fluid
(oil, gas or water), their properties (viscosity), the pore
size distribution and the interaction of the fluid with
the rock surface.
The sensitivity of the T2 signal (or T1) to the fluid-
rock surface interaction indicates that should be possible
to use the NMR response to measure wettability.
Eventually it may even be possible to use it to measure
wettability directly down-hole, as it is already used to
measure other reservoir properties, such as permeability
(Kenyon et al., 1988; Coates et al., 1998). This is
173
particularly appealing, as existing methods of measuring
wettability such as the Amott (Amott, 1959) and USMB
(Donaldson et al., 1969) tests are time-consuming and
confined to the laboratory.
Different approaches and attempts have been
described in the literature to measure wettability
quantitatively using NMR relaxation time. For exam-
ple, Howard (1998) chose chalk samples for his
wettability study. First, he used the Amott index to
characterise the wettability of the chalk samples, and
then he attempted to correlate the relative shifts of
water relaxation component as function of water
saturation and wettability. His NMR based wettability
index is defined as
Tn ¼ CSwb ; ð3Þ
where Tn is the normalized relaxation time of the water-
filled component compared to a fully saturated state
ð1Þ (i.e, Tn = T2,Sw/T2,Sw=1 where T2,Sw and T2,Sw=1 are the
T2 of the water peak at partially and fully saturated
states, respectively), C is an empirical constant, and the
exponent b is correlated with wettability. However, his
technique relied upon a separation between the oil and
water signals, due to his choice of light oil and chalk
samples with a narrow pore-size distribution. Guan et
al. (2002) presented two empirical methods using the
arithmetic mean of relaxation times at various satura-
tions to obtain information on the wettability state of
sandstone rock. These are based on the difference and
ð2Þ ratio of the mean relaxation time at connate water and
residual oil saturation.
Method 1: DT2 ¼ ðT2;Swi −T2;Sor Þ ð4aÞ
Method 2: T2 ¼ ðT2;Swi =T2;Sor Þ ð4bÞ
Both methods show a relatively good correlation
with the Amott–Harvey index for sandstones, but have
a different range of values and cannot be directly
compared with the traditional wettability indices. More
recently, Fleury and Deflandre (2003) proposed a more
physically based NMR, wettability index. They
defined a wettability index based on the amount of
surface area that is wetted either by oil or by water,
174 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186
and evaluated this index by using the T2 values at four
different saturations:



Sw T1w − T1bw −Cq So T1o − T1bo
NMR
IF&D ¼

; ð5Þ
Sw T1w − T1bw þ Cq So T1o − T1bo
where Tw and To are the relaxation times of the peaks
in the T2 distribution for water and oil saturated rock,
respectively, Tbw and Tbo are the bulk relaxation times
of water and oil, respectively, So and Sw are the oil and
water saturation, and Cρ is the water–oil surface
relaxivity ratio (i.e, Cρ = ρw/ρo). Their results for the
wettability index agreed with the standard USBM test
in the range − 0.3 to 1.0.
Although empirical correlations with the traditional
wettability indices have been used with some success, it
is still not possible to make quantitative predictions of
wettability from a single NMR measurement, as the link
between pore scale physics and core-scale properties is
not fully understood. The difficulty of achieving this
relationship is due to the fact that the NMR signal is
influenced by many factors, such as pore size distribu-
tion, fluid viscosity, surface relaxivity, saturation,
wettability, etc.
In this paper, a pore-scale model is used to improve
our understanding of the relationship between surface
wetting and T2 relaxation, e.g., how the fluid/solid
interactions alter the NMR response. The model is used
to investigate how pore scale pore size distribution, fluid
saturation, and surface relaxivities interact with surface
wetting effects in controlling the overall T2 response
from a given sample. The predicted NMR response is
then used to interpret the observed changes in the
experimental data with wettability and saturation. The
different NMR-based wettability indices described in
the literature are compared using the model. Finally, The
Amott index for sandstone samples and the improved
NMR-based wettability index show a good agreement.
2. The model
The model is based on idealising the pore space as a
bundle of capillary tubes. Each tube has a cross-section
described by an equilateral triangle whose size can be
drawn from a given pore-size distribution. The oil/water
distribution within each tube can then be obtained from
the capillary pressure and the saturation history. At a
given capillary pressure, the volumes and surface areas
of water and oil are calculated for each individual pore.
This allows the calculation of the theoretical T2
distribution for the given pore size distribution,
wettability state and saturation. The model is based on
the following assumptions:
1. The NMR relaxation is dominated by surface
relaxation when a pore is fully saturated with water.
2. Internal field gradients are negligible.
3. For partially saturated pores, the wetting phase
relaxation rate is dominated by surface relaxation,
whereas for the non-wetting phase it is dominated by
bulk relaxation.
4. The magnetisation within individual pore decays
independently of the magnetisation of the other
pores; diffusion effects are neglected.
5. The pores are initially water-wet, although wettabil-
ity alteration may occur at the end of primary
drainage.
2.1. Modelling process
The model simulates first primary drainage and then
imbibition. The calculation is based on the following
steps:
1. Assign a number of pores (capillary tubes) and their
sizes based on a user-specified pore size distribution.
2. At each capillary pressure during drainage and
imbibition obtain the volume of each phase, its
distribution within each pore, surface in contact with
water and oil, and the fluid saturations.
3. Calculate the surface to volume ratio for each fluid in
contact with the pore wall within each pore.
4. Generate the theoretical T2 distribution for this
capillary pressure.
5. Increase the capillary pressure and return to step 2.
2.2. Water-wet system
2.2.1. Drainage
All the pores (capillary tubes) are initially fully
saturated with water, and strongly water-wet (Fig. 1A).
Oil will invade a given pore once the threshold pressure
for that pore is exceeded. At this point the oil will
immediately fill the centre of the pore in the form of a
cylinder with radius Rt (Fig. 1B). The threshold
capillary pressure for a pore whose cross-section is
described by an equilateral triangle of side a is given
by
" rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi#
row ptan30-
Pc ¼ 1þ coshr ; ð6Þ
Rt 3
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186 175

Fig. 1. Schematic representation of the triangular pore model. A—Fully water-saturated pore; B—pore at the threshold capillary pressure; C—pore at
high capillary pressure.

where σow is the oil/water interfacial tension (N/m), and water coating the surface of the sides of the pores, which
θr is the receding contact angle (θr = 0, as our system in keeps them water-wet. The volume of this water-film is
this study is initially strongly water-wet) and Rt (m) is assumed to be negligible. Thus, the volume of water is
the inscribed radius given by mainly contained in the corners of the triangle, Vw_corner,
a that can be calculated as the total volume of the pore, V▵
Rt ¼ pffiffiffi ; ð7Þ minus the oil volume, Vo = πRt2l:
2 3
Eq. (6) is derived from the relationship given by Oren a2 lsin60-
Vwcorner ¼ VD −Vo ¼ −kR2t l: ð12aÞ
et al. (1998) for threshold capillary pressure in a pore 2
with an arbitrary cross-sectional shape. As the capillary
Substituting a from Eq. (7) then yields
pressure is increased further, the oil will displace more
and more of the water, leaving water in the corners of pffiffiffi
Vwcorner ¼ R2t lð3 3−kÞ: ð12bÞ
the pore and coating the pore walls in a thin film (as
the pores are water-wet). This is illustrated in Fig. 1C.
For pores whose threshold capillary pressure is less
At any given capillary pressure, pores with an
than the current capillary pressure, the volume of water
inscribed radius greater than Rt will have been invaded
pinned in the corners is the same as that in pores whose
by oil, whereas pores smaller than Rt will be filled with
threshold pressure is equal to the current capillary
water.
pressure. The volume of oil in these pores can thus be
For pores fully saturated with the wetting phase
calculated from
(water), the surface to volume ratio is defined as
  a2 lsin60-
SD 6 Vo ¼ −Vwcorner : ð13Þ
¼ ; ð8Þ 2
VD w asin60-
where S▵ is the surface area of an equilateral triangular It can be seen that for a given capillary pressure, the
prism length l, given by system comprises two groups of pores, invaded and
un-invaded. The un-invaded group is formed of small
SD ¼ 3al; ð9Þ pores whose threshold capillary pressure has not yet
been reached, and so remain filled with water. The
and V▵ is the volume of the prism, given by invaded group contains oil in the centre and water in
the corners, as described above. Thus, the T2 signal due
a2 lsin60-
VD ¼ : ð10Þ to the water is controlled purely by surface relaxation
2 while that due to the oil is controlled by bulk relaxation
By substituting Eq. (8) into Eq. (2), the relaxation (as oil is never in contact with the pore walls). As a
rate of a water saturated pore can be expressed as result there are three components to the synthetic T2
  response:
1 SD 6qw
¼ qw ¼ : ð11Þ
T2Sw VD w asin60- 1. The signal from the small water filled pores:

However, if a pore has just been invaded by the non-  

1 SD
wetting fluid (oil), then the invaded pore contains oil in ¼ qw : ð14Þ
the centre, water in the corners and a very thin film of T2Sw VD w
176 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186

Fig. 2. Schematic representation of the triangular pore. A—after wettability alteration; B—after spontaneous imbibition; C—after forced
imbibition.

2. The signal from the water contained in the corners of surfaces become oil-wet (Fig. 2A). Water remains in the
the larger pores and the surface of the pore walls: corners which stay water-wet, as do all the un-invaded
  pores that are still full of water. Using the notation of
1 SD Fig. 2A, the surface to volume ratio for both water and
¼ qw ; ð15Þ
T2wcorner Vwcorner oil in a pore of size a (Fig. 2A) is now calculated as
 aged
3. The signal from the oil contained in the centre of the S 6x
¼ ; ð18Þ
larger pores: V wcorner Vwcorner

1 1
¼ : ð16Þ  aged
T2o T2Bo S 3ða−2xÞ
¼ ; ð19Þ
V o Vo

2.2.2. Imbibition where Vw_corner and Vo are given by Eqs. (12a), (12b),
At the end of primary drainage process, water- (13), and x is the length that remains water-wet.
flooding (imbibition) is modelled by increasing the Obviously in this case the synthetic T2 response of
wetting phase pressure and keeping the pressure of the the system has 2 components which is controlled by
non-wetting phase fixed. During this process the water surface relaxation for both oil and water:
spontaneously fills the invaded pores. For an equilateral  aged
triangular pore invaded with oil, with an inscribed radius 1 S
¼ qw ; ð20Þ
Rt and advancing a contact angle θa, the capillary T2Sw V wcorner
pressure at which spontaneous imbibition occurs is
given by (Hui and Blunt, 2000)
 aged
1 S
row ½cosha −sinha tan30- ¼ qo : ð21Þ
Pc ¼ : ð17Þ T2So V o
Rt
If the system is completely water-wet (θa = 0), then at
2.3.2. Imbibition
the end of spontaneous imbibition all the pores will once
After wettability has been changed, waterflooding is
again be fully water saturated. It should be noted that the
performed (imbibition). First, spontaneous imbibition is
model can take contact angle hysteresis into account, so
modelled by decreasing the oil/water capillary pressure.
there is a difference between drainage and imbibition
The oil/water/solid contact line is pinned and cannot
capillary pressure (Ma et al., 1996).
move, so water bulges from the corner towards the
centre of the pore (spontaneous imbibition). At this
2.3. Mixed-wet system stage (Fig. 2B), the oil/solid and water/solid contact
surface area remains unchanged, whereas both the oil
2.3.1. Wettability alteration and water volume change. The surface to volume ratio
Wettability alteration only takes place in oil-invaded for both water and oil at this stage are given by
pores. This effect is modelled by assuming that the thin  si
S 6x
water films separating the oil from the pore-surface ¼ ; ð22Þ
collapse at the end of primary drainage, and these V wcorner Vwsicorner
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186 177

 si
S 3ða−2xÞ 2.4. T2 distribution
¼ ; ð23Þ
V o Vosi
The signal amplitude as a function of T2 is calculated,
where si
Vw_corner is the volume of water after spontaneous for any saturation state, by adding the contributions from
imbibition (Pc = 0) and is given by all the pores with the same T2 value. For fully water-
pffiffiffi saturated pores, T2 is given by Eq. (11), and the signal
Vwsicorner ¼ R2t l3 3; ð24Þ amplitude associated with that T2 is the volume of the
pore divided by the total pore volume of the system. For
and Vosi is the oil volume and is equal to the total pore partially saturated pores, each pore will contain varying
volume minus the water volume, Vosi = V▵ − Vw_corner
si
. As amounts of water and oil, each with its own surface to
a result, the relaxation rate of both water and oil will volume ratio and hence a distinct value of T2. The
change during this process. amplitude associated with each value of T2 is the volume
After spontaneous imbibition, the water is forcibly fraction of water or oil relaxing at that value of T2. The
injected into the centre of the pore. The capillary sum of amplitude at each T2, S(T2), is calculated as
pressure for this displacement is negative, and the radius
of curvature of the water in the centre of the pore is SðT2 Þ ¼ fw ðT2 Þ þ fo ðT2 Þ; ð29Þ
given by Eq. (6). After forced imbibition, there is water
where fw and fo are the volume fraction of water and oil,
in the centre of the pore and water in the corners. A layer
respectively, at each value of T2.
of oil is sandwiched between them, as shown in Fig. 2C.
The water in the corners will then have a surface to
volume ratio given by Eq. (22). However, the water in 3. Experimental details
the centre is surrounded by oil, so we assume that its
relaxation rate is dominated by bulk relaxation. The The experimental work was carried out on three
volume of this water, Vw_center is calculated similarly to different sets of samples: synthetic, outcrop and
that of oil during drainage, Vw_center = πRt2l and the oil reservoir. The synthetic samples were used because
volume, Vofi is given by they have very similar porosity, permeability, pore size
distribution, etc., and because it is possible to control
Vofi ¼ VD −Vtw ; ð25Þ
their wettability. These two factors made it easier to
where Vtw is the total water volume, given by Vtw = isolate the T2 signal due to wettability changes from the
si influence of other sample properties. The outcrop and
Vw_center + Vw_corner . Thus, the three components of the
oil and water relaxation are described by: the reservoir samples were chosen because they were
typical sandstone rocks, allowing us to compare the
1. The signal from the water in the corner of the pores: relative influences of saturation, permeability, complex
 si mineralogy and wettability of real rock on the T2 signal.
1 S Both the dry helium porosity, ϕ, and Klinkenberg
¼ qw ; ð26Þ
T2Sw V wcorner permeability, k, of the all samples were determined prior
to the start of the experiments. The samples were then
2. The signal from the oil layer: fully saturated with brine. For reservoir samples, this
 fi was simulated formation brine, degassed and filtered to
1 S 0.45 μm, introduced under vacuum. For the outcrop and
¼ qw ; ð27Þ
T2So V o the synthetic samples simple brine (5% NaCl and 1%
KCl), degassed and filtered to 0.45 μm, was used. The
3. The signal from the water contained in the centre of complete saturation of the samples was verified using
the forcibly imbibed pores: the dry weight, the saturated weight, helium grain
volume and brine density. All samples attained complete
1 1
¼ : ð28Þ brine saturation. Table 1 gives the properties of the
T2B T2Bw fluids used in this study.

It should be noted that there is no diffusion terms, as 3.1. Preparation of synthetic samples
the model assumes no communication between the
water in the corner and in the pore body; ie., the oil layer Five synthetic samples were made from quartz sand
is assumed to be stable at the end of forced imbibition. with a density of 2.64 g/cc, and grain sizes ranging form
178 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186
Table 1
Properties of the fluids used
Fluids Density@ Viscosity@ T2B
20 °C (gm/cm3) 20 °C (mPa s) (ms)
5% NaCl + 1% KCl 1.03 1.08 2210
Formation brine 1.23 1.98 1570
Multipar H 0.76 1.13 980
Crude oil 0.83 4.22 1380
0 to 125 μm. Their wettability ranged from strongly
water-wet (clean sand) to strongly oil-wet (the sand was
treated as described below). The samples were approx-
imately 3.6 cm in diameter and approximately 5 cm in
length. Two samples were built with only one type of
sand (cleaned or treated), so one was strongly water-wet
and the other was strongly oil-wet. The other samples
were built using a mixture of water-wet (clean sand) and
oil-wet sand (treated sand) in different proportions.
These synthetic samples allowed a systematic investi-
gation of the effect of fractional wettability on NMR
measurements. The synthetic samples were prepared
using the following sequence:
1. Some sand was converted to oil-wet by mixing it
with Repelcote and Heptane both from VWR Int. The
treated sand was then dried in an oven at 70 °C for
24 h. The wettability of the treated sand was tested by
first placing a drop of water in contact with a small
amount of sand, repeating the process with a drop of
oil and observing which fluid preferentially wetted
the sand. This test confirmed that the clean sand was
strongly water-wet, while the treated sand had
become strongly oil-wet.
2. The required quantities of water-wet and oil-wet
sand were weighed and poured into a container.
Subsequently the container was placed on a roller to
ensure the treated and clean sand were completely
mixed.
3. The homogeneous mixture was then poured into a
pre-formed heat-shrink sleeve in which the sample
was packed. Sintered glass discs were placed at both
ends of the sample to hold the sand in place.
The sample was then put into an oven at 100 °C for
2 h. Next, the sample was loaded in a Hassler Cell core
holder at an effective confining pressure of 2.07 MPa for
1 h. This ensured a proper grain compaction and hence
good packing. Table 2 gives a description of the
synthetic samples in terms of water-wet sand concen-
tration and their petrophysical properties.
The fully brine saturated sample was loaded into a
Hassler cell and a confining pressure of 2.07 MPa was
then applied. Multipar H oil was injected into the sample
by using a slow rate piston pump. The flow rates used
were 0.1 cm3/min for 3 h, 0.5 cm3/min for 1 h and
1.0 cm3/min for 0.5 h until the initial irreducible water
saturation Swi was reached. Similar procedure was used
to drive the samples to residual oil saturation, Sor.
3.2. Preparation of outcrop and reservoir core plugs
The outcrop core plug samples were cleaned using
Soxhlet extraction with methanol, and then dried in a
vacuum oven and fully saturated with brine. The
reservoir samples were cleaned using the method
described earlier (Al-Mahrooqi et al., 2003). The
samples were selected on the basis of porosity and
permeability. Table 3 lists all the outcrop and reservoir
samples and their petrophysical properties.
The fully brine saturated outcrop and reservoir
samples were loaded into a multi-sample test cell.
Confining pressure was then applied in increments from
0.69 MPa to a maximum of 15.86 MPa. The samples
were then flooded with Multipar H oil to initial water
saturation, Swi by using dedicated slow rate syringe
pumps. The wettability of samples D-4, X-4 and 40 was
altered to a mixed-wet state by aging them in crude oil.
After the lowest brine saturation was attained during
continuous injection, the Multipar test oil was replaced
with dead crude oil. The samples were loaded into a
pressure vessel and a pore pressure of 1.38 MPa applied.
The samples were aged in an oven at 85 °C for 40 d. At
the end of this period the samples were cooled to room
temperature, the pressure reduced to atmospheric and
the crude oil in the pore space flushed out with the
Multipar test oil.
3.3. Wettability determination
The Amott method (Amott, 1959) was used to obtain
the Amott–Harvey index (AHI). The index is calculated
by measuring the volume of water displaced during first
spontaneous (Vos) and then forced imbibition, and then
repeating the two cycles with oil instead of water
Table 2
Petrophysical properties of the synthetic cores
Sample Water-wet Oil-wet Porosity Klinkenberg
ID sand (%) sand (%) (%) permeability (mD)
S100 100 0 35.8 442
S75 75 25 30.9 376
S50 50 50 31.1 342
S25 25 75 31.9 366
S00 0 100 30.5 366
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186 179

Table 3
Petrophysical properties and Amott–Harvey Index (AHI) of the outcrop and reservoir samples, δw: water ratio (Eq. (30)), δo: oil ratio (Eq. (31))
Sample ID Core plug state Klinkenberg Helium NMR δw δo AHI = δw − δo
permeability (mD) porosity (%) porosity (%)
X-3† Clean 17 18.1 18.4 0.89 0.00 0.89
X-4† Aged 17 18.3 18.4 0.04 0.23 − 0.19
S-4† Clean 38 17.3 17.7 0.87 0.00 0.87
40‡ Aged 516 23.2 23.2 0.03 1.00 − 0.97
94‡ Clean 564 21.3 21.1 0.54 0.32 0.22
D-4† Aged 2220 21.6 22.5 0.02 0.27 − 0.25
†
Outcrop sample.
‡
Reservoir sample.

entering the sample. The wettability index to water, δw is was obtained with the DXP program from Resonance
then calculated as Instruments. The NMR T2 was determined at different
saturations for all the samples:
Vos
dw ¼ ð30Þ
Vot 1. At 100% brine saturation;
where Vos is volume of oil displaced by spontaneous 2. At initial water saturation, Swi, after the samples were
imbibition of water and Vot is the total displaced oil flooded or desaturated with Multipar oil;
volume. Similarly, the wettability index to oil, δo, is 3. After each Amott test cycle, i.e., after spontaneous
given by and forced drainage/imbibition.

Vws Before performing the T2 measurements, each

do ¼ ; ð31Þ
Vwt
where Vws is the volume of water displaced by
spontaneous drainage of oil and Vwt is the total displaced
water volume. The Amott–Harvey wettability index is
then calculated by combining the two ratios into single
wettability index, AHI = δw − δo. The Amott–Harvey
index varies from + 1 for strongly water-wet to − 1 for
strongly oil-wet.
sample was first rolled gently across a piece of damp
tissue paper to remove the excess fluid on its surface.
They were then wrapped with cling-film and then Saran
film to prevent further fluid loss by evaporation. Finally
they were placed in an oven at 35 °C for approximately
one hour to achieve temperature equilibrium, before
measuring the T2 relaxation.
4. Results and discussions

3.4. NMR measurements 4.1. Modelling

The NMR relaxation measurements were performed
on a Resonance Instruments MARAN2 bench top
spectrometer at ambient pressure and 34 °C, operating
at 2 MHz. The CPMG sequence was used to generate
the magnetisation decays with an inter-echo time of
200 μs, 8000 echoes, 100 scans and signal to noise ratio
of around 100. The inter-echo time was selected to
minimise diffusion effects due to internal field gradients
(Zhang et al., 2001). The T2 relaxation time distribution
The effects of saturation and wettability on T2
relaxation time were studied using Case l and Case2.
The input parameters for each model are summarised in
Table 4. The values used for oil and water bulk
relaxivity are typical for laboratory fluids, while the
surface relaxivities depend on the presence of paramag-
netic sites and the amount of adsorbed oil components
on the surfaces (Bryar and Knight, 2003). The capillary
pressure curves for the water-wet and mixed-wet for

Table 4
Input parameters used in the pore scale model to study the effect of saturation and wettability
Pore size Pore size Pcmax ρo ρw T2Bw T2Bo θr θa θa
distribution (μm) (psi) (μm/s) (μm/s) (s) (s) Water-wet Mixed-wet
Case-1 Triangular 1–10 25 1 1.5 2 1 0° 20° 180°
Case-2 S-4 PSD 0.001–20 5 20 25 2 1 0° 20° 180°
180 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186

Case-1 systems are shown in Fig. 3A. The imbibition
capillary pressure curves were truncated at an oil
saturation larger than zero, to simulate a residual oil
saturation, Sor, as it is not possible to trap oil in a
capillary tube model. The residual oil saturations are
0.17 for the water-wet case and 0.10 for the mixed-wet
case, respectively.
4.1.1. Water-wet system
The predicted T2 distributions at different saturations
during drainage and imbibition are compared with the
signal predicted for 100% water saturation in Fig. 3B, C
and D. Both the overall signals as well as the individual
contributions from the oil and water are shown.
It can be seen that the signal due to the bulk
relaxation of oil increases as the oil saturation increases
(Fig. 3B and C), while the signal from the surface
relaxation of water shifts to lower values of T2 as the
water in the larger pores becomes confined to the
corners and surfaces, increasing its surface area to
volume ratio. This behaviour has already been observed
in real cores by Grattoni et al. (2003). At lower water
saturation during the primary drainage (Fig. 3C), almost
all the pores have been invaded and the signal is
dominated by oil bulk relaxation.
Fig. 3D shows the T2 after imbibition (Sor = 0.17). All
the largest pores are now filled with water again, so the
signal is very similar to that observed initially when the
system was completely filled with water. There is a
small increase in the signal amplitude at T2 = 1000 ms
due to the bulk relaxation of the residual oil in the largest
pores and also at T2 = 500 ms due to the surface

Fig. 3. Modelling results for Case-1, effects of saturation and wettability on T2 relaxation time. A) Capillary pressure (Pc) curves for both drainage
and imbibition. T2 distributions for the water-wet system: B) during primary drainage at Sw = 0.20; C) during primary drainage at Sw = 0.10; D) after
imbibition, Sw = 1–Sor = 0.83. Sw1 indicates fully water saturated; T2w is the NMR signal from water and T2o is the NMR signal from oil.
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186
relaxation of the water in the corners of these pores.
The effect of the contact angle hysteresis on the signal
is minimal compared with the initial response when
the pores are completely filled with water. The signals
due to the oil and water are shown separately to
highlight their individual contributions to the overall
signal.
4.1.2. Mixed-wet system
The mixed-wet system was created at the end of
primary drainage by allowing the water films from the
side of the triangle to collapse and the oil to come into
direct the pore walls. These surfaces are then assigned a
contact angle of 180° (making them oil-wet). The pore-
size distribution used for the mixed-wet system is the
same as for the water-wet case described above.
Fig. 4 compares the predicted T2 distribution
obtained for the mixed-wet case at Swi with that
obtained for the water-wet case at the same Swi and at
the beginning of primary drainage when Sw = 1.0. In this
case, although the system is mainly filled with oil, the
signal more closely resembles that of the water-filled
system, the main difference being that the signal peak
has shifted from around 1000 ms to approximately
800 ms. This is due to the fact that the oil's NMR
response now decays due to surface relaxation rather
than bulk relaxation. There is thus a range of relaxation
times due to the pore-size distribution of the sample. The
shift of the peak is due to the difference between oil and
water relaxivity and the fact that the oil surface area to
volume ratio of in the pores invaded by oil is less than
when they are completely filled with water.
After spontaneous imbibition, there is a very small
change in water volume due to the swelling of the water
trapped in the corners of the larger oil-invaded pores.
Thus, a very small change is observed in the T2
distribution. On the other hand, after forced imbibition,
there is a significant change in the T2 distribution (Fig.
4B). The wide peak at 800 ms is replaced by a narrow
peak at 2000 ms and another peak appears between 40
and 200 ms. Examining the individual contributions of
oil and water, it can be concluded that the maximum at
2000 ms is due to bulk water relaxation, filling the centre
of the larger pores, while the broad secondary peak is due
to the oil films surface relaxation. These films are located
between the water in the centre of the pore and the pore
walls. These oil films relax more quickly as they have an
increased surface to volume ratio, hence the shift in the
distribution to lower values of T2.
Fig. 5 shows another example of the effect of
saturation and wettability on the T2 distribution. The
input parameters for this example are summarised in
181
Table 4 (Case 2). For the water-wet system (Fig. 5A),
there is a small increase in the signal amplitude at
T2 = 1000 ms due to the bulk relaxation of the residual
oil as observed in previous example (Case 1). The
surface relaxation of the water in the corners and coating
the surfaces of large pores for this model is observed at
shorter T2 values (40 to 50 ms), due to the effect of pore
size distribution and surface relaxivities. For the mixed-
wet system (Fig. 5B), the water introduced during
forced imbibition again presents a bulk relaxation of
2000 ms. The NMR signals from oil films located
between the water in the centre of the pore and the pore
walls have shorter T2 values similar to those from the
water in the un-invaded pores and the corners of
imbibed pores (10 to 40 ms). This may be one of the
causes for the oil and water signal overlapping in mixed-
wet rocks. The results from modelling are consistent
with the behaviour observed experimentally by Freed-
man et al. (2002) and Al-Mahrooqi et al. (2003).
4.2. Experimental results
4.2.1. Synthetic samples (fractionally wet)
The T2 distributions for all the samples when fully
saturated with brine are depicted in Fig. 6A. It can be
seen that as the proportion of oil-wet sand in the sample
increases so the peak of the distribution shifts to longer
values of T2. There is a large change from the
completely water-wet sample to the sample with 75%
water-wet sand and a more gradual change thereafter. In
these cases the changes in the distribution cannot be
attributed to a change from surface to bulk relaxation as
the samples do not contain any oil. It is more likely that
the changes in the distributions are due to differences in
surface relaxivity of the oil-wet and water-wet sand. As
the sands are uniformly mixed each pore's surface will
have an effective surface relaxivity controlled by the
ratio between oil-wet and water-wet surface area. The
shift to larger values of T2 suggests that in this case the
water surface relaxivity of the oil-wet sand is smaller
than that of the water-wet sand. The T2 distributions are
thus wider for the fractional-wet samples than for the
oil-wet or water-wet samples due to the increased range
of surface relaxivities in the mixed-wet samples.
The change in the distributions in this case can be
characterised by the logarithmic mean value of the T2
distributions,
X
Ai logT2i
T2m ¼ X ; ð32Þ
Ai
i
182 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186

Fig. 4. T2 responses for the mixed-wet Case-1; A) overall distribution for water-wet: water saturated (Sw1) and at irreducible water saturation (Swi), B)
overall signal and individual contributions from water and oil after wettability alteration, C) overall signal and individual contributions from water
and oil after forced imbibition (Sw = 1–Sor = 0.9). T2w is the NMR signal from water and T2o is the NMR signal from oil.

where Ai is the signal amplitude at T2i. Fig. 6B shows
the change in T2m as a function of the percentage of
water-wet sand. It should be noted that these results
suggest that surface relaxivity is also a function of
wettability. Similar observations were reported by Bryar
and Knight (2003) despite using a different method to
alter the wettability. If this is also true in reservoir
samples, then it adds an extra level of complexity, as it
would imply that the change in NMR response with
aging is a function in the change in surface relaxivity as
well as the distribution of fluids in contact with the rock
surface.
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186 183

saturations, irreducible/residual saturations and after

spontaneous imbibition/drainage during Amott test. The
results in Fig. 7A are for sample S-4, which is a strongly
water-wet plug (AHI = 0.87). At initial water saturation
Swi, the distribution consists of a large peak more or less
coincident with the relaxation time for bulk oil and a
smaller, much wider peak between 1 and 100 ms.
Clearly the large peak can be attributed to the bulk
relaxation of the oil filling the centre of the pores,
whereas the smaller broad peak is due to the surface
relaxation of water coating the surfaces of the larger
pores and filling the smallest pores. After spontaneous
imbibition the primary peak at 1000 ms reduces as the
oil saturation decreases, whilst the smaller broader peak
increases as the volume of water coating the pore
surfaces increases. This trend continues after forced
imbibition. Furthermore there is a shift in the secondary
(water) peak to longer values of T2 (100 to 400 ms) as
the surface to volume ratio of the water increases.

Fig. 5. T2 responses Case-2 after forced imbibition, Sor A) overall

signal from water-wet and mixed-wet system, B) individual contribu-
tions to the water-wet system and C) individual contribution to the
mixed-wet system.

4.2.2. Outcrop and reservoir samples

In this section we illustrated an example of how Fig. 6. A) T2 distributions for fully water saturated synthetic samples,
wettability affected the T2 distribution at various B) T2m of the water saturated samples vs. the water-wetness.
184 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186

water saturation between spontaneous and forced

imbibition.

4.3. Wettability characterisation from T2 measurements

Both the experimental and modelling results show

that, at Swi after primary drainage, the T2 distribution is a
function of the relative amounts of water trapped in
crevices plus smaller pores (wetting the surfaces) and
the oil in contact with the pore walls plus bulk oil (oil
forced into the system). The T2 distribution at Sor is a
function of the amount of oil and water in contact with
the pore walls (spontaneously imbibed water) compared
with the amount of bulk water (water forced into the
system). Hence, the log mean T2 value (T2m) at
irreducible and residual saturation is sensitive to the
same quantities used for calculating the Amott–Harvey
index. Therefore, an improved wettability index can be
calculated using the relationship between these NMR
values:
!
Swi
T2m −T2mSor
IIC ¼
NMR
Sor
: ð33Þ
T2m

Table 5 compares the calculated wettability numbers

Fig. 7. T2 distributions at different saturations A) for a strongly water-
wet sandstone plug, sample S-4, and B) for an aged reservoir core plug,
sample 40.
Fig. 7B shows the very different T2 response
observed in a strongly oil-wet core, sample 40
(AHI = − 0.97). At Swi, the T2 distribution is similar
to S-4 but there is a slight shift in the primary oil peak
toward lower T2 values. After aging, the oil becomes
in contact with rock surface and relaxes faster. After
spontaneous imbibition the primary oil peak decreases
slightly as only a small volume of water will imbibe
into this mainly mixed-wet core while the intermediate
peak spreads out and shifts to higher T2 due to the
increase in volume of the water although the surface
area coated by the water remains approximately
constant. The main peak also spreads out as the
signal from the water moves towards the bulk water,
larger T2 values (> 2000 ms). This spreading and
and indices for the simulation Cases 1 and 2 (water-wet
and mixed-wet scenarios) using the methods of Guan et
al. (2002) (Eqs. (4a) and (4b)), and the NMR wettability
indices, Eqs. (5) and (33).
It can be seen that the modelling results confirm the
experimental observations that T2 distributions are
sensitive to sample wettability. The methods of Guan
et al. are not normalised so they have a different range of
values that are not directly comparable to the AH or
USBM indices. The Fleury–Deflandre index gives the
best evaluation of the model wettability, but is
experimentally very time-consuming, as it requires the
determination of the relaxation times at four saturation
states and also requires that the sample be very carefully
cleaned and dried more than once. The improved index
Table 5
Wettability calculated from the pore scale model T2 distributions
Guan et al. NMR Indices
Eq. (4a) Eq. (4b) Fleury– Proposed
Deflandre INMR
IC
INMR
F & D

decrease in the main peak is even more significant Case-1 Water-wet − 37 1.04 1.0 0.04
after forced imbibition. The signal from the oil moves Mixed-wet 185 0.84 −0.36 −0.16
to lower T2 as its surface area to volume ratio Case-2 Water-wet 12.7 1.16 1.0 0.16
Mixed-wet − 7.4 0.92 −0.6 −0.08
increases. This is the result of the larger change in
 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186
proposed here is easier and faster to obtain as it only
requires NMR measurements at two end point satura-
tions and no additional cleaning is required.
The proposed index was tested using data from
synthetic samples, as shown in Fig. 8A. Sample S100
(strongly water-wet) has a large positive index, which is
consistent with the status of the sample, whereas the
strongly oil-wet sample (S00) has a large negative
index. Also, it can be seen that for porous media with
otherwise similar characteristics there is an excellent
correlation between the index and the wettability of the
samples. The results of the outcrop and reservoir data
were also used to test the index on sandstones (Fig. 8B).
The results show a very good correlation between AH
index and the proposed NMR index, especially for those
with strong wetting characteristics (strongly water and
oil-wet according to AH index). However, some of
intermediate-wet samples do not correlate very well.
This may be due to other factors, such as sample
mineralogy, pore size distribution, etc.
The index defined by Fleury and Deflandre is based
on surface area and the peaks from the T2 distribution,
thus it seems to provide a better wettability definition.
However, the index proposed in this paper uses the
mean of the T2 distribution, which includes all the
relaxation components and the amount of residual oil/
water in the rock. The use of a representative surface
area to volume ratio, or T2m, is very important because it
provides a better measure of how easy it is for oil or
water to flow. The bulk relaxation of the oil (T2Bo) and
its viscosity will affect the value of the index defined by
Eq. (33). Nevertheless this wettability index will be
valid for any oil with a T2Bo equal or larger than the
maximum T2 of the fully brine saturated sample. A
Fig. 8. Comparison of the improved NMR wettability index, defined in Eq. (33), with A) the percentage of water-wet surface of the synthetic samples
and, B) the Amott–Harvey index of the outcrop and reservoir samples.
185
better index could be defined if all the relaxation
components of the T2 distribution could be decomposed
to provide a fuller picture of the location of each fluid
within the rock. This may be possible in the near future.
5. Conclusions
• A one-dimensional pore scale model composed of a
bundle of capillary tubes with a triangular cross-
section was used to study the effects of solid/fluid
interactions on NMR T2 relaxation time. The simple
modelling technique presented allowed us to
○ Determine the relative contributions of wettabil-
ity, saturation, pore-size distribution and surface
relaxivity on the NMR T2 distribution;
○ Distinguish between the individual contributions
of water and oil relaxation to the overall T2
distribution as a function of their location within
the pore space;
○ Improve the interpretation of NMR measure-
ments in core plugs by unravelling the influence
of different parameters.This approach has en-
abled us to evaluate and compare different me-
thods of wettability characterisation from NMR
measurements.
• An improved wettability index is proposed from the
T2 relaxation distribution. This index is defined by
the following equation: IIC NMR
= (T2m,Swi − T2m,Sor) /
T2m,Sor. It has the advantage that it only requires
NMR measurements at two saturations.
• The proposed index has been successfully tested for
synthetic samples of known wettability, outcrop
cores and clean/aged reservoir core plugs. However,
more modelling and experiments, covering a wider
186 S.H. Al-Mahrooqi et al. / Journal of Petroleum Science and Engineering 52 (2006) 172–186
set of conditions, are needed to fully validate the
proposed methodology.
Acknowledgements
Sultan Al-Mahrooqi would like to thank Petroleum
Development of Oman (PDO) for the support and
encouragement during his PhD studies. The authors
would like to acknowledge EPSRC for the financial
support. The experiments were carried out in the BG
Petrophysical laboratory at the Imperial College.
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