using oil-based and synthetic-based drilling fluids.

However, the use of these drilling fluids

is limited due to high costs and environmental restrictions particularly for deepwater opera-
tions [16, 19]. Thus, growing environmental concerns currently require the replacement of
oil-based fluids by environmentally friendly water-based drilling fluids, which can interact
with shales promoting undesirable clay-swelling phenomena [20].

Wellbore instability problems caused by clay swelling have been widely reported: sloughing
shales, hole closure causing tight hole, cave-ins leading to fill on trips, and problems when
running casing. In addition, other important problems have been identified such as cuttings
accumulation leading to reduced hole-cleaning efficiency, buildup of thick cuttings beds,
and reduced rates of penetration arising from balling of the drill bit with sticky clay [13, 15].
Moreover, wellbore instability can result in the loss of the drilling assembly, well side-tracks
or in the worst case total abandonment of the well. Consequently, these problems can sig-
nificantly reduce drilling rates as well as increase considerably the costs of exploration and
production [15]. Therefore, minimizing and controlling shale-fluid interactions during deep-
water drilling become one of the most important challenges for the design and selection of
deepwater drilling fluids.

2.1.1. Clay mineralogy

Clay minerals account for about 50–60 wt.% of most shales; thus, physical properties and behav-
ior of shale interacting with a drilling fluid rely on the type and amount of clay in the shale. Clays
are naturally occurring minerals formed by the weathering and decomposition of igneous rocks.
They are layered minerals, classified among the phyllosilicates, consisting of stacks of negatively
charged two-dimensional aluminosilicate layers [15]. There is a great variety of different clay
minerals, which differ in their composition, layer arrangement, and substitutions. However, for
shale-stability purpose, the most relevant clay minerals are kaolinite, illite, smectite, and chlo-
rite. Their main characteristics have been reported [11, 21] and are shown in Table 1.

Clay mineral Chemical elements Morphology Surface area Typical range of Layer thickness
(m2/gm) CEC (meq/100 g) (Å)
Kaolinite Al4[Si4O10](OH)8 Stacked plate or 20 3–10 7
sheets

Chlorite (Mg, Al, Fe)12[(Si, Plates, 100 10–40 14

Al)8O20](OH)16 honeycomb,
cabbage-head
rosette, or fan

Illite (K1-1,5Al4[Si7-6,5Al1- Irregular with 100 20–40 10

, O ](OH)4)
1 5 20
elongated spines
or granules

Smectite (1/2Ca,Na)0,7(Al, Irregular, wavy, 700 80–150 12–14

Mg, Fe)4[(Si, wrinkled sheets,
Al)8O20]∙nH2O webby, or
honeycomb

Table 1. Characteristics of clay minerals involved in shale stability.

Kaolinite is commonly considered as a highly stable mineral clay, non-swelling, presenting a
relatively small surface area and a low adsorptive capacity (cation exchange ­capacity (CEC)
= 3–10 meq/100 g) as shown in Table 1. Kaolinite clay can be easily dispersed in water-base
drilling fluids [11, 18]. Chlorite mineral is generally considered as non-swelling clay. Chlorite
minerals contain a layer of alumina sandwiched between two layers of silica and a layer of
magnesium or iron oxide, and without interlayer water. Illite clay minerals are similar to chlo-
rite in reactivity, presenting a low adsorptive and swelling/shrinking capacity and proper-
ties intermediate between kaolinite and smectites as shown in Table 1. It has been reported
that some older shale rocks with a high degree of diagenesis contain only chlorite and illite as
clay components. Most of these shales are relatively unreactive but some of them can hydrate
and slough [11, 18]. Table 1 shows also properties of smectite minerals which present higher
adsorptive capacity (cation exchange capacity = 80–150 meq/100 g), indicating higher reactivity
and swelling potential as it has been widely reported in literature [11–18, 20]. Smectite miner-
als include a variety of clays such as montmorillonite, hectorite, and beidellite. In addition,
mixed-layer clay minerals, such as illite-smectite and chlorite-smectite, have also been found
and reported [11, 21]. Several experimental techniques, such as X-ray diffraction (XRD), spec-
troscopy, and microscopy, are used in order to identify and characterize mineral clays. Figure 1
shows scanning electron microscopic (SEM) photos of typical clay minerals described earlier.
Studies reported in literature about clay swelling and inhibition are most often focused upon
smectite clays due to their well-known swelling potential and the frequency with which they
are found during drilling operations [15]. However, it has been also reported [13] that kaolin-
ite and illite shales can be highly unstable when drilled promoting bit-balling problems,
suggesting that interlayer expansion cannot be considered as a universal causative mecha-
nism of shale instability. Nevertheless, the tendency of sodium-saturated smectites to swell
macroscopically has been generally identified as the principal source of shale instability that
can potentially lead to collapse of the wellbore. Therefore, a deeper understanding about
the mechanisms involved in the interactions between water-based drilling fluids and mineral
clays is a key issue to get success during deepwater drilling.

2.1.2. Swelling mechanisms

Exposed to aqueous solution, clay minerals will adsorb water molecules and swell. The phe-
nomenon is also known as clay hydration. The hydration of the clays is a function of the extent

Figure 1. SEM photos of typical clay minerals involved in shale instability. From left to right: kaolinite, chlorite-illite, and
smectite (montmorillonite). Images reproduced from the “Images of Clay Archive” of the Mineralogical Society of Great Britain
& Ireland and The Clay Minerals Society (www.minersoc.org/gallery.php?id=2).
and location of layer charge, the interlayer cation species, the water activity, the temperature,
the external pressure, and the salinity of the bulk solution [22]. Crystalline and osmotic swell-
ing are the two main mechanisms reported in literature to explain clay hydration phenomena
[13–15, 20–23]. Both mechanisms are described below.
Crystalline swelling. This mechanism, also called surface hydration, can occur in all types of
clay minerals when they are exposed to concentrated brine or aqueous solutions with high
content of divalent or multivalent cations. The mechanism is carried out through the stepwise
formation of integer-layer or mixtures of integer-layer hydrates. The process is thermody-
namically comparable to phase transitions. Several water-molecules layers may line up in
order to build a quasi-crystalline structure between unit layers, resulting in an increased inter-
layer spacing [15, 18]. The principal action force of this mechanism is the adsorption energy
of water on the surface of clays. The volume and thickness of water adsorbed on the clay
surface will depend on the hydration energy of exchangeable cations and the charge density
on the surface of clay. In addition, type, size and charge of exchangeable cations present in the
interlayer have a significant impact on swelling process. It has been reported that the presence
of Ca2+, Mg2+, and H+ exchangeable cations in montmorillonite clay increases their interlayer
attractive force, resulting in a thinner hydrated film and whit a directional and regular water
molecules arrangement on the clay. On the other hand, for Na+ exchangeable cations, the
interlayer attractive force decreases, the hydrated film becomes thick, and the arrangement
of water molecules on the clay is not directional and regular [13, 15, 23]. Therefore, sodium
montmorillonite has a higher swelling capacity than calcium montmorillonite according to
the mechanism described earlier. As reported in Ref. [15], molecular simulation studies have
confirmed the stepwise mechanism of crystalline swelling described earlier observing that
adsorbed water molecules form distinct layers in the interlayer region. Typical interlayer
spacings recorded in the crystalline swelling mechanism lie in the range of 0.9–2 nm [15].
Figure 2a shows the crystalline swelling mechanism described earlier.

Figure 2. Swelling mechanisms [24]: (a) crystalline swelling and (b) osmotic swelling.
Osmotic swelling. This mechanism can occur only in clay minerals containing exchange-
able cations in the interlayer region. A sketch of the mechanism is depicted in Figure 2b. As
observed, when the concentration of cations in the interlayer is higher than that of the sur-
rounding water, water molecules diffuses into the interlayer in order to dilute its ion concen-
tration, restoring cation equilibrium [15, 23]. This phenomenon creates an osmotic repulsive
pressure between the clay particles. The osmotic pressure is mainly related to the difference
of the ion concentrations between the interlayer and surrounding water. In this way, the
distance between clay particles increases greatly, and then the clay swelling is carried out
[15, 23]. Compared with crystalline swelling, this type of swelling promotes larger volume
increases with typical interlayer spacings of 2–13 nm [15]. In fact, osmotic equilibrium of the
semipermeable membrane on clay particles is considered a key factor to influence the hydra-
tion film of clay swelling. Thus, it can be stated that osmotic hydration is the major factor of
clay swelling. It has been identified that the tendency of sodium montmorillonite clay to swell
through this osmotic mechanism is the main cause of wellbore instability that can potentially
lead to collapse of the wellbore [13–15]. On the other hand, K+-saturated smectite clay min-
erals do not swell through this mechanism and form crystalline hydrates even in aqueous
suspension. Thus, the K+ ion can be used to inhibit the swelling of sodium montmorillonite
clay minerals [15].

2.1.3. Shales characterization

The main methods developed for shale characterization including shale-fluid interactions and
clay-swelling inhibition deal with composition, reactivity (swelling), mechanical, and physi-
cochemical properties of shales (or clay). Some of the most important experimental methods
reported are described below.

X-ray diffraction (XRD). This is a basic tool in the mineralogical analysis of shales. This
experimental technique has been widely used to determine clay mineral composition of shale
samples, degree of crystallization and swelling profiles of clay minerals [25].

Small-angle X-ray scattering (SAXS). This technique is useful for the characterization of the
microstructural and swelling properties of clay samples [15].

Small-angle neutron scattering (SANS). This is a useful and versatile technique for the study
of in-homogeneities of both crystalline and amorphous structures on the sub-micron scale,
with capabilities to measure samples with high degree of swelling (up to interlayer d-spac-
ings of 2000 Å) [15].

X-ray fluorescence (XRF). It is an experimental method used to determine chemical composi-

tion (major and trace elements) of rocks, minerals, sediments, and fluids.

Computer tomography (CT). The technique is generally suitable for visualization from meter
to millimeter scale. Shale applications include viewing full-diameter core sections to deter-
mine orientation relative to bedding, presence of fractures and nodules, density studies for
highly interbedded interval, and quality assessment of prepared plug samples [26].
and location of layer charge, the interlayer cation species, the water activity, the temperature,
the external pressure, and the salinity of the bulk solution [22]. Crystalline and osmotic swell-
ing are the two main mechanisms reported in literature to explain clay hydration phenomena
[13–15, 20–23]. Both mechanisms are described below.
Crystalline swelling. This mechanism, also called surface hydration, can occur in all types of
clay minerals when they are exposed to concentrated brine or aqueous solutions with high
content of divalent or multivalent cations. The mechanism is carried out through the stepwise
formation of integer-layer or mixtures of integer-layer hydrates. The process is thermody-
namically comparable to phase transitions. Several water-molecules layers may line up in
order to build a quasi-crystalline structure between unit layers, resulting in an increased inter-
layer spacing [15, 18]. The principal action force of this mechanism is the adsorption energy
of water on the surface of clays. The volume and thickness of water adsorbed on the clay
surface will depend on the hydration energy of exchangeable cations and the charge density
on the surface of clay. In addition, type, size and charge of exchangeable cations present in the
interlayer have a significant impact on swelling process. It has been reported that the presence
of Ca2+, Mg2+, and H+ exchangeable cations in montmorillonite clay increases their interlayer
attractive force, resulting in a thinner hydrated film and whit a directional and regular water
molecules arrangement on the clay. On the other hand, for Na+ exchangeable cations, the
interlayer attractive force decreases, the hydrated film becomes thick, and the arrangement
of water molecules on the clay is not directional and regular [13, 15, 23]. Therefore, sodium
montmorillonite has a higher swelling capacity than calcium montmorillonite according to
the mechanism described earlier. As reported in Ref. [15], molecular simulation studies have
confirmed the stepwise mechanism of crystalline swelling described earlier observing that
adsorbed water molecules form distinct layers in the interlayer region. Typical interlayer
spacings recorded in the crystalline swelling mechanism lie in the range of 0.9–2 nm [15].
Figure 2a shows the crystalline swelling mechanism described earlier.

Figure 2. Swelling mechanisms [24]: (a) crystalline swelling and (b) osmotic swelling.