Fuel 251 (2019) 187–217

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Polymeric and low molecular weight shale inhibitors: A review T

a b,⁎ a,⁎
Hafiz Mudaser Ahmed , Muhammad Shahzad Kamal , Mamdouh Al-Harthi
a
Department of Chemical Engineering, King Fahd University of Petroleum & Minerals, 31261 Dhahran, Saudi Arabia
b
Center for Integrative Petroleum Research, King Fahd University of Petroleum & Minerals, 31261 Dhahran, Saudi Arabia

ARTICLE INFO ABSTRACT

Keywords: Water-based drilling fluids (WBDFs) are widely used for drilling oil and gas wells. Water-based drilling fluids are
Drilling fluids considered economical and environmentally friendly compared to synthetic and oil-based drilling fluids. Water
Polymers is one of the major constituents of WBDFs but causes the swelling of clay minerals in wellbore formations. Clay
Clay swelling swelling in the wellbore has detrimental impacts on drilling operations and it leads to excessive costs of drilling
Inhibitors
operations and oil well construction. During drilling operations, the interactions of drilling fluid and clay
Oil and gas exploration
swelling can be prevented by using various inhibiting agents that reduce the interactions of water contents with
the wellbore. To develop high-performance shale inhibitors that can significantly reduce clay swelling, drilling
operation costs, and environmental impacts, a significant amount of research on the industrial and academic
level has been done. The available literature lacks a comprehensive understanding of polymeric, amine-based,
ionic liquids, and surfactant-based shale inhibitors for the oil field applications. This review explains the me-
chanisms of clay swelling, techniques used for the measurement of clay swelling, and various inhibitors used to
prevent clay swelling. Additionally, the effects on the process for various polymer-based inhibitors, nitrogen-
based inhibitors, ionic liquids, and surfactants based shale inhibitors have been studied in detail.

1. Introduction
Oil and gas well drilling require different drilling fluids to perform
various functions: to maintain the rheology of fluids [1–6], manage the
hydrostatic pressure in the wellbore, lubricate the drilling bit, prevent
the invasion of fluid loss into formations, transport rock cuttings to the
surface, and prevent the swelling of shale formations [7–12]. Drilling
fluids are broadly classified as oil-based drilling fluids (OBDFs) or
water-based drilling fluids (WBDFs). Oil-based drilling fluids have su-
perior inhibition properties, excellent lubricity, and high-temperature
stability. However, the increasing demands for environmental legisla-
tion and excessive costs restrict OBDFs in drilling applications. Water-
based drilling fluids are widely employed for drilling operations be-
cause of their environmentally friendly nature, remarkable rheological
properties, and excellent performance [13–24].
However, the use of WBDFs for reactive shale formations may result
in detrimental impacts to wellbore stability. An oil and gas drilling
section composed of 75% shale formations caused 90% wellbore in-
stability problems during the drilling process [25]. The primary issue of
WBDFs is shale swelling, which causes instability problems in the
wellbore during the drilling process such as sloughing, bit balling,
caving, high drag and torque, stuck pipe, and disintegration of shale
cuttings due to the water adsorption of sensitive shales [26,27]. The
shale swelling occurs due to the presence of various clay minerals in the
shale. Clay swelling and wellbore instability also affect hole cleaning
efficiency due to the agglomeration of shale cuttings. The worst-case
scenario of wellbore instability includes the loss of drilling assembly,
lost circulation, and the chances of losing part of the hole or the com-
plete well. All wellbore instability problems seriously affect the drilling
rate and contribute to the increased exploration and production costs
[28]. Numerous studies reveal that wellbore instability problems are
10% higher in cost compared to the well costs which are usually greater
than $1 billion per annum [29]. Therefore, the development of a green
shale swelling inhibitor with enhanced inhibiting capacity is desired for
effective drilling fluid properties and to overcome the cost issues of
wellbore instability.
Traditionally used shale inhibitors include various electrolytes such
as sodium chloride, potassium chloride, and divalent brine electrolyte
for water sensitive shale formations. These electrolytes are used in
various concentrations based on the type of shale formation and the
additives of WBDFs. The high concentration of these electrolytes pre-
vents the hydration and swelling of water sensitive shale formation.
However, a high concentration of these electrolytes in drilling fluids
results in flocculation of clay minerals which affects the properties of

⁎
Corresponding authors.
E-mail addresses: shahzadmalik@kfupm.edu.sa (M.S. Kamal), mamdouh@kfupm.edu.sa (M. Al-Harthi).

https://doi.org/10.1016/j.fuel.2019.04.038
Received 14 January 2019; Received in revised form 16 March 2019; Accepted 5 April 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
H.M. Ahmed, et al.
Fig. 1. Classification of shale inhibitors.
the drilling fluid causing high fluid loss volume and loss of thixotropy.
A high concentration of salts also affects the rheological properties of
bentonite based drilling fluids, marine environment, and shale cutting
lifting capacity of drilling fluids [30]. Therefore, polymer/salt systems
are widely utilized to overcome the issues related to the high con-
centration of electrolytes in WBDFs. Polymers are employed to modify
the rheological properties such as viscosity, yield stress and gel
strength. High molecular weight and salt resistant polymers are used in
the formulation of drilling fluids that retain the rheological properties
[31–33]. Over the past few decades, a wide range of methodologies has
been proposed with high concentrations of organic salts, inorganic
salts, and various kinds of polymer-based additives for shale inhibition
[34–38]. However, these methodologies have not been effective for
inhibiting the sensitive shale formations and have many other limita-
tions.
Among these approaches, when potassium chloride is combined
with polyglycol, silicates and partially hydrolyzed polyacrylamide
(PHPA), superior inhibition results are obtained with synergistic effects.
Nitrogen-based derivatives were introduced recently with effective
shale inhibition characteristics. Among these, ammonium chloride was
the simplest nitrogen-based derivative and has been used for several
years as a shale inhibitor. Recently employed low molecular mass
polyether diamine has significant shale inhibition properties in WBDFs
compared to the oil-based drilling fluids. Recently, a new amine ter-
minated polyether (ATPE) shale inhibitor was synthesized in the la-
boratory for the inhibition of shale in water-based drilling fluid. The
shale inhibition performance of ATPE was evaluated and compared
with conventionally used shale inhibitors such as potassium chloride,
polymeric alcohol, methane siliconic acid and potassium formate. Hot
rolling dispersion test showed the superior inhibition capacity of ATPE
compared to the conventionally used shale inhibitors [39]. In another
study, a bio-surfactant was extracted from Korean red Ginseng root and
used as potential additive in water-based drilling muds for the inhibi-
tion of shale swelling and hydration. The inhibition performance of bio-
surfactant was compared to the potassium chloride and Cetrimonium
bromide cationic surfactant. Shale inhibition tests showed that bio-
surfactant was superior shale inhibitor compared to the Cetrimonium
bromide and potassium chloride. The bio-surfactant produced the
bigger size aggregates in relatively less time with less hydrophilicity
and shale recovery which indicated the enhanced shale inhibition
properties of extracted bio-surfactant [40]. Similarly, another bio-sur-
factant was extracted from mulberry leaf and evaluated as potential
environmental friendly shale inhibitor. The inhibition results showed
188
Fuel 251 (2019) 187–217
that bio-surfactant has excellent inhibition properties in the drilling
fluids [41].
In the past few years, other alternatives have also been developed
for high-performance shale inhibitions such as surfactants, copolymers,
ionic liquids, and modified nanoparticles [42–44]. Few studies have
been reported in the last decade related to the swelling of clays, bore-
hole stability, and shale inhibitors. Anderson et al. has studied the
swelling of clays based on experimental and theoretical techniques
emphasizing on the swelling of minerals under crystalline regime,
nature of charge and charge density [45]. Another recent study pre-
sented the borehole instability issues that lead to the shale swelling and
hydration. The effect of various types of water-based drilling muds are
employed to conventional drilling operations and high-temperature/
high-pressure drilling wells [27]. The available literature lacks the
comprehensive understanding of polymeric and amine-based, ionic li-
quids and surfactant-based shale inhibitors for the oil field applications.
An extensive amount of literature is available for describing shale
swelling, shale inhibition and field applications of shale inhibitors
[46,47]. In this review, a comprehensive critical analysis of the avail-
able information in the literature is presented to address the swelling
and inhibition mechanism of clays and related issues of oilfield geo-
chemistry. The first section discusses the composition, structure, and
chemistry of clay minerals followed by the experimental and analytical
techniques commonly used to investigate and characterize the perfor-
mance of shale inhibitors. The classification of various shale inhibitors
is discussed in detail which includes amine-based shale inhibitors,
polymer-based shale inhibitors and other alternatives which have re-
cently been employed for shale inhibition such as surfactants, and ionic
liquids, the purpose of discussing various classes of shale inhibitors is to
enlighten the performance evaluation pros and cons under different
drilling conditions. Finally, we discuss challenges and prospects in the
development of environmentally friendly and cost-effective shale in-
hibitors. The classification of different shale inhibitors is shown in the
Fig. 1
2. Chemistry & types of clay minerals
Clay minerals are phyllosilicates which consist of a layered structure
of negatively charged octahedral sheets of alumina and tetrahedral
sheets of silica [48,49]. In tetrahedral sheets, each tetrahedron com-
prises of a cation which is coordinated with four oxygen atoms and
linked with other tetrahedrons by sharing three corners to make a
continuous two-dimensional, hexagonal layer. The commonly found
H.M. Ahmed, et al.
Fig. 2. Sketches (a) Octahedral sheet (b) Tetrahedral sheet [54]. ©Elsevier.
Reproduced by permission of Elsevier.
cations in the tetrahedral sheets include Fe+3, Al+3 or Si+4. In octa-
hedral sheets, each octahedron contains one cation which is co-
ordinated with six oxygen atoms and attached with the adjoining oc-
tahedrons by sharing the common edges. The commonly found cations
in the octahedron are Fe+2, Fe+3, Mg+2 or Al+3. The specific ar-
rangement of tetrahedral and octahedral sheets in the clay minerals
produces several types of clay [50]. If the clay is made up of one oc-
tahedral layer and one tetrahedral layer, it is designated as 1:1 clay (or
T-O clay). If the clay is made up of two tetrahedral layers and one oc-
tahedral layer and they are arranged so that one octahedral layer is
sandwiched between two tetrahedral layers, it is designated as 2:1 clay
(or T-O-T clay) [48,51].
The clay minerals have negatively charged tetrahedral and octahe-
dral layers which are due to the isomorphic substitution of metal ca-
tions. In the case of the tetrahedral layer, Si+4 ions are replaced with
Fe+3 or Al+3 ions, while in case of the octahedral layer, the Al+3 ions
are substituted with Fe+2 or Mg+2 ions as shown in Fig. 2 [52]. The
isomorphic substitution of metal cations in the layers structure of clay
induces a 90–95% negative charge [53]. The interlayer metal cations of
clay minerals are responsible for balancing the negative charge induced
by the isomorphic substitution. The cation exchange capacity of clay
minerals is the ability to exchange interlayer cations from solution. The
physiochemical properties of clay minerals are affected by cation ex-
change capacity, the morphology of clay minerals, particle size, pH of
the solution, dispersion, hydration, aggregation properties and swelling
characteristics of clay minerals. The negative charge on the layers of
Table 1
Clay minerals and properties [55]
Clay minerals Layer Arrangement Cation Exchange Capacity Surface Area (m2/g)
Smectite 2:1 60–100 700
Illite 2:1 20–40 100
Chlorite 2:1 10–30 100
Kaolinite 1:1 3–15 20
189
Fuel 251 (2019) 187–217
clay minerals is balanced by exchanging cations with the solution and
cation exchange in the clay minerals according to the following: (i) is
controlled by the rate of diffusion of metal cations (ii) follows stoi-
chiometric rule (iii) is a reversible process (iv) is a selective process for
cation and depends on the size of exchangeable cation. The chemical
composition shows that clay minerals having a 1:1 layered structure of
tetrahedral layer and octahedral layers show fewer interlayer cations,
so the cation exchange capacity of these minerals is very small. Simi-
larly, the chemical composition of clay minerals having a 2:1 layered
structure of tetrahedral layers and octahedral layers contain a sub-
stantial negative charge on the layers which are attached to a sub-
stantial number of interlayer cations, so these clay minerals show high
cation exchange capacity. A wide range of natural minerals exists which
differ in chemical composition, layered arrangements, and type of in-
terlayer cations. A general classification of clay minerals based on the
structure, swelling properties, cation exchange capacity, and SEM
images are given below, for example, see the smectite, illite, kaolinite,
and chlorite in Table 1 and Fig. 3.
Studies show that clay minerals with a 2:1 layered structure
(smectite) are more susceptible to swelling and offer considerable
wellbore instability problems during drilling operations. Fig. 4 shows
the layered structure of smectite clay. The main component of smectite
clay is montmorillonite with chemical formula (Na,-
Ca)0,3(Al,Mg)2Si4O10(OH)2·nH2O. When the smectite clay swells its
swelled volume is many times higher than the original volume. Water
molecules adsorb on the interlayers and increase the basal spacing
which results in the large swelling of clay minerals. Smectite clay exists
in various forms based on chemical compositions such as hectorite,
beidellite, and montmorillonite. Montmorillonite can be further clas-
sified as Na-montmorillonite or Ca-montmorillonite and these two dif-
ferent forms have a different swelling index. The smectite clay which
contains sodium ions between the interlayers shows the maximum
potential of swelling compared to all other clay minerals. The swelling
of smectite clay can be reduced by replacing sodium and calcium ions
with potassium ions or other cationic ammonium ions.
Illite has a layered structure in which an octahedral alumina sheet is
sandwiched between two tetrahedral silica sheets. Chemically illite is
depicted as (K,H3O)Al2(Si3Al)O10(H2O,OH)2 which predominantly oc-
curs in most shales and clay sediments. Illite is formed in hydrothermal
environments and extreme weathering conditions by the modification
of muscovite and feldspar. Strong interlayer interactions exist between
tetrahedral sheets of silica and octahedral sheets of alumina due to high
charge density on silica sheets. Tetrahedral and octahedral sheets are
connected by the tips of tetrahedral layers and the hydroxyl group of
octahedral layers. Illite has less tendency to swell upon interacting with
water because its lattice has a non-expanding nature and therefore the
ability of water to migrate into the layers is less. The presence of po-
tassium ions in the interlayer spaces prevents the hydration and swel-
ling of illite.
Chlorite clay has the chemical formula (Mg, Fe2+)5Al(AlSi3O10)
(OH)8, which consists of a group of phyllosilicate minerals classified as
nimite, chamosite, pennantite, and clinochlore. It has a layered struc-
ture comprised of an octahedral sheet of alumina sliced between tet-
rahedral sheets of silica. The interlayers interact with each other
Density (g/cm3) Layer Thickness (Å) Chemical Formula
2–2.7 12–14 (Na, Ca)0.3(Al, Mg)2
(Si4O10) (OH)2∙ n (H2O)
2.6–2.9 10 (K, H3O) (Al, Mg, Fe)2
(Si, Al)4O10[(OH)2 ∙ (H2O)]
2.6–2.8 14 (Mg, Fe2+)5Al(AlSi3O10) (OH)8
2.5–2.7 7 Al2Si2O5(OH)4
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Fig. 3. SEM images of different clay minerals (a) smectite (b) chlorite (c) illite (d) kaolinite [56–58].

Fig. 4. Structure of smectite clay minerals [59]. ©Elsevier. Reproduced by permission of Elsevier.

190
H.M. Ahmed, et al.
Fig. 5. Mechanism of swelling (a) Osmotic swelling (b) Crystalline swelling [198]. Open access article published by Springer-Verlag.
through hydrogen bonding and electrostatic force attractions. Chlorites
have variable chemical and physical properties depending on a wide
range of temperature, pressure, and composition.
Kaolinite clay has the chemical formula Al2Si2O5(OH)4, which has a
layered structure consisting of one layer of octahedral alumina and one
layer of tetrahedral silica. It is formed by the weathering of alumino-
silicates such as feldspar and physically it is a white and soft clay.
Kaolinite has a low swelling capacity and ion exchange capacity
(1–15 meq/100 g) compared to the smectite clay. When it interacts with
water, kaolinite shows dispersion instead of swelling. The presence of
kaolinite in shale is a great subject of interest and it also important in
deciding wellbore mechanical strength.
In summary, clay swelling is mainly related to clay minerals having
a 2:1 structure due to their extensive swelling potential. The smectite
clay (saturated sodium bentonite) can swell several times in volume
compared to the un-hydrated clay and is considered as the main cause
of shale instability in the drilling operations of oil and gas wells.
Kaolinite has the least swelling potential due to its 1:1 structure.
3. Mechanism of clay swelling
Hydration of clay minerals results in swelling which causes an in-
crease of interlayer spacing and is mainly related to the type and con-
centration of interlayer cations. Interlayer cations of clay minerals can
be hydrated in the presence of water and, as a result, the interlayer
space of clay minerals increases which causes swelling. Experimental
studies have shown that swelling of clay minerals can be explained in
two separate ways: osmotic swelling and crystalline swelling. The
schematic diagram of osmotic and crystalline swelling is given in Fig. 5.
Osmotic swelling of clay minerals occurs due to the high con-
centrations of interlayer cations compared to the concentration of ca-
tions in the bulk solution. When the interlayer cation concentration is
higher compared to the concentration of the surrounding solution,
water molecules migrate between the interlayer spaces which results in
an increase in interlayer spacing. Although there is no semipermeable
membrane in the clay minerals, this mechanism of migration of water
molecules is considered as osmotic due to the difference in the con-
centration of cations. Osmotic swelling of clay minerals is only attrib-
uted to certain classes of clays which contain exchangeable cations
between the interlayer spaces.
After hydrating, the osmotic swelling of clay minerals significantly
191
Fuel 251 (2019) 187–217
increases clay volume. Typical osmotic swelling of clay minerals results
in the increase in interlayer spaces from > 20 Ã to 30 Ã, which is
usually higher than crystalline swelling of clay minerals. The smectite
clay minerals saturated with sodium ions (also known as Na-mon-
tmorillonite) mostly show osmotic swelling in the drilling operations of
oil and gas wells which leads to wellbore instability issues and in severe
cases, the wellbore may collapse. Compared to sodium saturated
smectite clay minerals, potassium smectite clay minerals do not show
osmotic swelling in the presence of water and potassium ions are used
to minimize the swelling of sodium saturated smectite clay in the
wellbore.
Crystalline swelling (surface hydration) of clay minerals occurs
when clay interacts in an aqueous solution containing high concentra-
tions of monovalent, divalent and multivalent ions. Cations in the in-
terlays of clay minerals have a significant impact on the magnitude of
crystalline swelling. Crystalline swelling of clay minerals occurs in a
stepwise manner like the formation of the single layer, double layer and
multilayer hydrates of cations in between the interlayer spaces. Quasi-
crystalline structures are formed by multiple layers of water molecules
in the interlayer of clay minerals which results in the increase in in-
terlayer spacing. Almost all types of clay minerals show crystalline
swelling in the presence of aqueous solutions. Experiments have shown
that smectite clay adsorbs water molecules and forms one, two, three
and four layers of cation hydrates with the increase in relative hu-
midity. Simulation results have also shown that the crystalline swelling
of clay minerals occurs in a stepwise fashion and forms specific layers in
between the interlayers which increase the interlayer spacing. Specific
results of interlayer spacing for a crystalline swelling show that inter-
layer spacing ranges from 9 Ã to 20 Ã. The magnitude of clay swelling is
also affected by the size, type, and charge of cations present in inter-
layers of clay minerals. The swelling of clay minerals starts with the
hydration of interlayer cations and is affected by cation charge density.
Clay minerals which contain monovalent cations and higher hydration
energies have a high potential of swelling compared to the cations
which have low hydration energies. In various simulation studies car-
ried out to study the swelling behavior of montmorillonite clay, it has
been observed that by increasing the concentration of water, clay mi-
nerals having lithium and sodium ions form one layer, two layers and
three layers of cation hydrates. While in the case of potassium mon-
tmorillonite only one layer of cation hydrate was observed.
In general, there are many variables that affect the swelling of clays,
H.M. Ahmed, et al.
such as the nature of interlayer cations, the concentration of cations,
and the type of clay minerals. The swelling of clays can be inhibited by
replacing the interlayer cations with other cations that have less affinity
towards water and by coating the clay minerals with polymers which
prevent the interactions of water with the clays. The subsequent section
will explain the techniques of clay swelling and inhibition and various
types of inhibitors.
4. Techniques for characterizing shale swelling and inhibition
Shale stability is primarily affected by the swelling of clay minerals
in the wellbore, and it is one of the main issues in drilling operations.
Various experimental and analytical techniques are employed to study
the swelling and inhibition of clay minerals. This section describes the
various techniques to determine shale swelling and to evaluate the
performance of different inhibitors.
4.1. Shale particle disintegration test
The shale particle disintegration test describes the hydration and
disintegration of a shale sample when immersed in drilling fluid. In this
test, a cylindrical real field shale sample, of specific dimensions, is
obtained after compressing the powder sample of shale in a shale
compactor. The cylindrical shale sample is then placed in a steel jar and
filled two-thirds full of drilling fluid. The jar is then placed on the
rollers of a heating oven and the time is measured for the complete
disintegration of the shale sample in the drilling fluid. The inhibitors
are evaluated based on the resistance of the shale sample to disin-
tegration. A good inhibitor is one which increases the time of complete
shale disintegration [60].
4.2. Hot rolling dispersion test
The hot rolling dispersion test is employed to study the inhibition
performance of drilling fluid to prevent the hydration, disintegration,
and dispersion of a shale cutting sample. In this test, a shale sample is
ground to a fine powder and sieved with 20–30 mesh screens. The
weighed shale sample (50 g) is placed in a steel cell along with 350 ml
of WBDFs and the lid tightly screwed shut. The cell is then placed in the
hot rolling oven at 95 °C for 16 h for aging according to API standards.
After 16 h, the shale sample is gently washed with water and passed
through 50 mesh screens. The shale sample retained over the screen is
then dried at 60 °C in the oven. The final sample is weighed and com-
pared with the original weight of the shale sample [44,60,61]. If the
percentage is high, the dispersion of shale is less and the inhibitor is
considered good.
4.3. Linear swelling test
The linear shale swelling test is also performed to evaluate the
characteristics of inhibitors. In this test, the linear swelling of a shale
pellet is determined as a function of time and an inhibitor which gives
minimum swelling of the shale sample is considered superior. In this
test, a 5-gram shale sample is ground to a fine powder and placed into a
pressure compactor by applying a pressure of 10 MPa for 5 min. Then
the cylindrical disc of the shale sample is placed in a linear swelling
meter in the presence of a prepared drilling fluid. The shale inhibition
capacity depends on the reactivity of shale and the drilling fluid. The
mineral composition of the shale sample is determined before per-
forming the linear swelling experiment. Then drilling fluid additives
and their quantities are added to the drilling fluid to minimize the
swelling of the shale sample. The linear swelling meter measures the
linear height for a specific period. The shale inhibitor which results in
minimum linear swelling of shale sample is considered as good shale
inhibitor [62–64].
192
Fuel 251 (2019) 187–217
4.4. Bulk hardness test
The bulk hardness test evaluates the hardness of a shale cutting after
immersing in drilling fluid. Shale can imbibe liquid from drilling fluids
and become softer which increases the chances of wellbore instability
during drilling operations [65]. Inhibitive properties and hardness of
shale cuttings are inter-related. Therefore, a hardness test of a definite
size shale cutting is performed after hot rolling the shale cuttings in the
drilling fluid at 65 °C for 16 h. After that, the shale sample is sieved over
40 mesh screens, washed with brine and placed in the hardness tester. A
torque wrench is used to extrude the cutting from the perforated plate.
The wrench is rotated in a clockwise direction at a steady rate. The
overall torque and number of rotations are measured as the hardness of
a cutting is expressed in terms of the number of turns and torque re-
quired to extrude the cuttings from the perforated plate. The hardness
of a shale sample depends on its recovery after the hot rolling. If the
shale recovery is high, then the shale is considered hard and less prone
to hydration and swelling [66].
4.5. Pore pressure transmission test
The pore pressure transmission test is an important technique to
evaluate the performance of shale inhibitors by blocking the pores of
the shale sample. In this test, a shale sample (shale core) is placed in the
core holder of a pore pressure transmission (PPT) device and drilling
fluid is injected into the core through an upstream inlet. The upstream
pressure of PPT is maintained at the value of 2 MPa while the down-
stream pressure is maintained at 1 MPa. The result of this experiment
shows the rising curves between time and downstream pressure. The
PPT device produces the curves that depict the shale sealing perfor-
mance of drilling fluid and the curves are used to evaluate the change in
downstream pressure over time [67]. The adsorption of inhibitors on
the surface of clay minerals makes a more hydrophobic clay surface
which is favorable to diminish pore pressure transmission.
4.6. Shale immersion test
In this test, the shale sample is placed in freshly prepared drilling
fluid for 24 h to study shale stability and fracture development in the
sample. Usually, a shale sample immersed in water results in the ero-
sion, cracks and macro pores. While, in the presence of an inhibitor, the
shale sample is less likely to have erosion, cracks, and pores due to the
formation of a protective layer on the shale sample [60,68].
4.7. Measurement of interlayer spacing
XRD analysis is one of the important techniques to determine the
inhibition capacity of a material by measuring its interlay spacing (d-
spacing) [69–72]. Inhibitor performance is determined by mixing it
with montmorillonite in the presence of deionized water. The mixture
of inhibitor and montmorillonite is stirred thoroughly for 24 h and then
centrifuged at 8000 revolutions per minutes for 30 min and washed
with deionized water three times to remove the unreacted inhibitor.
After the centrifuging, the sediment of modified montmorillonite is then
collected and divided in to two parts. One part is used to measure the
XRD of the wet sample while another part is dried at 105 °C and after
grinding to fine powder XRD analysis is carried out [69–73]. In the
presence of shale inhibitor, the wet part of the clay sample indicates the
decrement of interlayer spacing which implies that a shale inhibitor can
expel the water from interlayers and results better adsorption capacity.
While the dry part of clay sample shows an increment of interlayer
spacing which indicates a superior ability of intercalation of clay mi-
nerals.
H.M. Ahmed, et al.
4.8. Zeta potential measurement
Zeta potential is used to measure electro kinetic properties of shale
inhibitors in the colloidal dispersion of shale. The various concentra-
tions of shale inhibitors were added to the colloidal dispersions and
stirred for 24 h before measuring the zeta potential at 25 °C. The shale
inhibitors in the drilling fluid adsorb on the negatively charged surface
of clay minerals in the shale and affect the colloidal stability and sur-
face charge density. The reduction of the colloidal stability of clay leads
to the increase in the endurance of shale disintegration and hydration
[74]. The shale inhibitors adsorb on the surface of clay minerals which
reduce the overall charge on clay minerals and making their surface
hydrophobic in nature. Research has shown that if a surface charge of
clay minerals is decreased by 20% then hydration and swelling of clay
minerals can be inhibited [75].
4.9. Wettability alteration test
Shale inhibitors or stabilizers react with clay minerals in the shale
and alter the wettability properties from a hydrophilic to a hydrophobic
surface. To measure the hydrophobicity of shale reacted with the shale
stabilizer, a wettability alteration test is employed. The test involves the
formation of bentonite dispersions with different concentrations of
shale inhibitors. Dispersions are stirred for 24 h. When an inhibitor is
completely adsorbed on the clay particles and equilibrium reaches then
a thin layer of dispersion is placed on the glass sheet and air dried.
Upon drying, the dispersion forms a thin layer on the glass sheet. After
that, about 5 μL droplet is placed on the thin layer with a syringe and
the contact angle is measured using a contact angle goniometer high
resolution camera. The shale inhibitor in the clay dispersion turns the
clay particles hydrophobic by reacting with the shale inhibitor which
further prevents the hydration and swelling of clays in the formations
[71,76].
4.10. Fracture development test
The fracture development test analyzes facture developments in the
shale when it interacts with the drilling fluid. This test mainly em-
phasizes low reactivity and hard shale formations where stability issues
are associated with the development of new fractures or the propaga-
tion of existing fractures. There are two techniques involved in the
evaluation of fracture development when a shale sample interacts with
different drilling fluid formulations. First, the shale sample is examined
by microscope to determine the fracture development and other
changes in the shale sample. Various microscopic measurements are
taken to compare the parameters of the shale sample such as typical
fracture width, number of fractures and maximum fracture width.
Second, a time-lapsed photographic (TLP) technique is utilized to vi-
sualize the apparent changes in the shale sample. The fracture devel-
opment test reflects the stability and fracture of the shale sample in the
presence of diverse drilling fluids containing shale inhibitors [77].
4.11. Capillary suction test
A capillary suction test (CST) is performed by a device that mea-
sures the time of clay slurry or shale to travel across a filter paper. The
capillary suction test results can be utilized to study the reactivity of
shale samples with a single drilling fluid or to study the inhibition
characteristics of different drilling fluids with a single shale sample. In
this experiment, 5 ml of clay dispersion containing an inhibitor is
placed inside the cylinder having filter paper of a specific thickness and
two electrodes (both connected to a timer) are attached to the cylinder
at the position of 0.5 and 1 cm from one edge of the cylinder. The
electrodes measure the time required to travel through the free water
from one electrode to the other. A short capillary time indicates the
presence of a large amount of free water available in the system and less
193
Fuel 251 (2019) 187–217
attraction between water and clay minerals. High capillary suction time
indicates that a large amount of water is attached to the clay minerals
and less amount of free water available in the system. Shale inhibitors
with less capillary suction time are considered good materials to pre-
vent the hydration of clay minerals and inhibit the swelling of clay
minerals. Capillary suction tests can be performed immediately after
preparing the dispersion with a shale inhibitor or they can also be
performed after 24 h or 48 h [78]. Shale inhibitors with less capillary
suction time are considered good materials to prevent the hydration of
clay minerals and inhibit the swelling of clay minerals [78].
4.12. Scanning electron microscope
A scanning electron microscope (SEM) is an important instrument to
perform high-resolution magnification analysis of a shale sample. The
SEM analysis exhibits the presence of pores and embedded minerals in
the shale sample. The compactness orientation and texture of the shale
surface can be seen by SEM analysis. The presence of organic matter can
be identified by the presence of oxygen and carbon in the shale sample.
The shale inhibition is investigated by blocking the pores using shale
inhibitors in the formulation. The presence of polymeric inhibitors in
the water-based drilling fluid encapsulate the shale microstructure and
pores and prevent the migration of drilling fluid in the pores of shale
[79–81]. The formation of a thin layer of shale inhibitor on the shale
sample is investigated by high magnification SEM analysis [63,70,82].
4.13. Water adsorption test
The water adsorption test describes the reactivity of shale and the
measurement is taken by a hydrometer which depicts the relative hu-
midity of a shale sample [83]. The relative humidity of the shale sample
is expressed percentage to give water adsorption [84]. Another way to
measure water adsorption is to put the shale sample in water for a
specific period of time. The weight of the shale sample is measured
before and after the water adsorption test. The reactive shales have a
high affinity to adsorb large amounts of water compared to the less
reactive shales [85].
4.14. Cation exchange capacity
The cation exchange capacity of shale is a measure of the ex-
changeable cation present in the clay minerals of the shale sample. The
most commonly available cations include sodium, potassium, calcium,
iron, and magnesium. These cations are present in the interlayers of
clay minerals and neutralize the negative charge of clay minerals pro-
duced by the isomorphic substitution of cations. The reactive clays such
as montmorillonite and bentonite show high cation exchange capacity
which is expressed as milliequivalent per 100 g of clay. The cation ex-
change capacity of clay minerals is determined by API standards using
the methylene blue test (MBT). Shale is ground to a fine powder and a
small quantity of powder (2 g) is mixed in the water along with sulfuric
acid and hydrogen peroxide. The mixture is then boiled for a few
minutes and cooled to room temperature. The mixture is then titrated
against the methylene blue solution. The endpoint of the titration is
determined by putting a drop of the mixture on filter paper which re-
sults in a light green or blue color halo sphere around the droplet. The
reactive clays show high cation exchange capacity which also depict the
affinity of hydration and swelling upon interacting with water. The clay
minerals which show low cation exchange capacity values are less re-
active but brittle. The less reactive clays in the shale sample are more
susceptible to dispersion upon interacting with water. The cation ex-
change capacity range of various clay minerals is mentioned in the
above section [86–88].
H.M. Ahmed, et al.
5. Classification of shale inhibitors
Several inhibitors have been developed in the last few decades to
address shale swelling. Potassium chloride (KCl) is one of the earliest
known shale inhibitors that has been used in a concentration ranging
from 2% to 20%. However, water-based drilling fluids containing po-
tassium chloride (KCl) concentration more than 1 wt% severely affect
the microorganisms and have failed the mysid-shrimp bioassay test
[89]. Therefore, water-based drilling fluids having potassium ions are
less often considered for offshore deep-water drilling operations due to
the toxicity of potassium ions for marine life. Potassium chloride was
later used in combination with partially hydrolyzed polyacrylamide
(PHPA) in the1960s to minimize clay swelling in water-based drilling
fluids. The presence of PHPA in water-based drilling fluids serves as an
inhibiting agent by forming a protective layer on the clay and pre-
venting the interaction of water with the clay minerals. The calcium
chloride-based drilling fluid was also used for the inhibition of shale
formation by encapsulation and ion exchange mechanisms. The pre-
sence of calcium ions (Ca2+) in the drilling fluid displaces the mono-
valent cations from interlayers of clay and prevents the swelling of clay
platelets. The polymer present in the calcium chloride-based drilling
fluid shows an affinity for clay minerals and consequently, physical
adsorption (encapsulation) of polymer on the surfaces of clay minerals
reduces the water activity in shale formations. The presence of calcium
ions helps in the encapsulation of polymer on clay minerals [90].
The dispersions and swelling of clay can be effectively inhibited
either by intercalating the interlayers of clay minerals with inhibiting
agents or covering the shale formation with high molecular weight
polymers and preventing the interaction of water with reactive shale
formations. In the last few years, several shale inhibitors have been
developed. These inhibitors can be polymeric inhibitors, ionic liquids,
and surfactants. The following section discusses the recent progress and
advancement in developing shale inhibitors.
5.1. Polymeric inhibitors
Polymers are used as water-based drilling fluid additives and per-
form various functions in the drilling process. Polymers are added to
control the viscosity, suspension ability of a fluid, and inhibition of
shale formations [91,92]. The viscoelastic properties such as yield stress
and linear viscoelastic range of polymer-based drilling fluid is an im-
portant characteristic that describe shale cutting transport capacity
from downhole to surface of well and well cleaning efficiency [19].
Polymeric shale inhibitors not only enhance the inhibition properties of
drilling fluids but also modify the rheological and filtration properties
[87,93,94]. In this section, inhibition properties of polymer additives in
drilling fluids will be discussed in detail. Polymer-based inhibitors are
used to prevent clay swelling in water-based drilling fluids. Inhibition
properties are mainly related to the concentration, structure, and
charge of polymeric additives in the drilling fluids. Polymer-based in-
hibitors consist mainly of three categories, namely anionic polymers,
cationic polymers, and non-ionic polymers. Each class of polymer in-
hibitors has a certain capacity to inhibit clay swelling based on the type
of clay minerals in the wellbore.
5.1.1. Non-ionic polymers and derivatives
Non-ionic polymers including, mainly, polypropylene oxide (PPO),
polyethylene glycol (PEG) [95], and their derivatives with nano-
particles are also used for shale inhibition applications. Polyglycols are
considered as effective shale inhibitors in water-based drilling fluid
systems and are replacing the use of oil-based drilling muds due to the
superior inhibition properties. The extraordinary benefits of using
glycol as shale inhibitor include good lubrication, low cost, easy
handling, and environmental friendliness. Various experimental tech-
niques are employed (shale dispersion and shale swelling) to study the
shale inhibition due to shale hardening. Shale hardening is a process in
194
Fuel 251 (2019) 187–217
which shale becomes harder after interacting with inhibitor molecules
and as a result of shale hardening shale dispersion and swelling is re-
duced [96]. Glycols, ranging from a simple ethylene glycol to a very
complex polyhydroxy glycols are used for shale inhibition applications,
including other polymers such as polyethylene and poly propylene
oxide which are used to enhance shale inhibition capacity. Glycols have
diverse molecular structures with different molecular weights but for
shale inhibition applications low molecular weight glycols are pre-
ferred. Low molecular weight glycols are liquids which mix easily with
water-based drilling fluids. Also, low molecular weight glycols can
penetrate the matrix of shale while high molecular weight glycols are
only adsorbed on the surface of the shale matrix.
The mechanism of shale inhibition by glycols can be explained by
intermolecular forces (hydrogen bonding) between the water/glycol
and shale matrix. The shale matrix has a high propensity to adsorb
water which further leads to the swelling and ultimately to the dis-
persion in the shale matrix. The water molecules in the shale matrix
form hydrogen bonds with the aluminate and silicate groups and when
glycols interact with the shale matrix it is believed that glycols and poly
glycols beak down the hydrogen bonding of water molecules with
aluminates and silicates of the clay minerals [97]. The PEG molecules
compete with water molecules in the interlayer spaces and attach with
the aluminates and silicates of clay minerals through hydrogen bonding
and prevent the further interaction of water with clay minerals [98].
Polyethylene glycol with a molecular weight less than 1000 is used
as shale inhibitor in the water-based drilling fluid. Freshwater showed
zero percent shale recovery in the shale dispersion experiment while
polyethylene glycol systems only show a 20% shale recovery. On the
other hand, the PHPA/KCl drilling fluid system showed 50% and the
glycol/PHPA/KCl system showed an 80% recovery in the shale sample.
The shale hardening test with glycol-based drilling fluid showed that
the shale matrix becomes harder after interacting with the glycol-based
fluid compared to the original shale sample which behaves as a softer
shale sample [96].
An effective shale inhibition system was produced by the combi-
nation of salt (KCl) and glycol in the water-based drilling fluid. Both salt
and glycol adsorb on the clay surfaces which minimizes the interaction
of the water and shale matrix resulting in reduced clay swelling. The
water in the hydration of potassium cations in the shale is replaced with
the glycol which has larger molecules than water and adsorbs at mul-
tiple positions with shale samples through hydrogen bonding. The
glycol adsorption on the surfaces of clay minerals with aluminates and
silicates was also observed and resulted in the hardening of the shale
sample. The inhibition of shale is not only due to the glycol but also the
presence of salt (KCl) plays an important role to enhance shale inhibi-
tion [96]. Similarly, another study of 600 molecular weight poly-
ethylene glycol showed that a 3% PEG solution offers better inhibition
properties compared to water. Also, the addition of 7% KCl salt into a
3% PEG solution showed improved inhibition properties but very si-
milar to the inhibition properties of a 7% KCl solution. In the presence
of salt (KCl) solution, PEG shows little impact on inhibition properties.
Particle size distribution is another technique to determine the inhibi-
tion characteristics of PEG and salt solutions. The higher particle size
distribution indicates better inhibition characteristics for a shale in-
hibitor. The potassium chloride solution with 0.5% showed 21.41 μm
while the addition of 3% PEG to the system increased the particles size
distribution to 31.57 μm. This indicates that a lower concentration of
salt and PEG has a synergic effect on shale inhibition. The copolymer of
ethylene oxide with ethylene glycol (PG-1) and propylene oxide with
ethylene glycol (PG-2) is also used to determine the capability of shale
inhibition. The copolymer (PG-1) measured 45.03 μm while (PG-2)
measured a 51.52 μm particle size distribution and this greater particle
size distribution was attributed to enhanced aggregation due to the
hydrophobic contents in the copolymer. The author concludes that
copolymers having hydrophobic contents showed enhanced aggrega-
tion capabilities compared to the PEG only. Significantly, particle size
H.M. Ahmed, et al.
distribution should be the criteria to determine the inhibition capacity
of shale inhibitors rather than conventionally used linear swelling ex-
periments [99].
A recent approach has been adopted to introduce the hydrophobic
groups in non-ionic polymers (polyethylene glycols) to enhance the
inhibition performance of shale inhibitors. For this purpose, hydro-
phobically modified polyethylene glycols were synthesized using dif-
ferent synthesis routes and the influence of lipophilic (aliphatic groups)
units and hydrophilic units (ethylene oxide units) on the performance
of inhibition characteristics were determined. The basic mechanism
that explains the inhibition of shales is that modified and unmodified
polyethylene glycols penetrate and adsorbs into the interlayers of
smectite enriched clays and prevent the swelling of shales. However,
the hydrophobically modified polyethylene glycol has water repellent
groups attached to its molecules, which prevents the seeping of water
into the shale surface and swelling by making a preventive barrier
against the shale matrix. The adsorption of non-ionic polymers on the
surface of shale is a very important phenomenon and is affected by the
structure, the presence of salt (KCl, NaCl, LiCl) and hydrophobic con-
tents in the polymer structure. There are a few studies that explain the
shale cutting recovery and stability of shale formations using these
polymers in the literature [100,101].
De Souza et al. have synthesized hydrophobically modified poly-
ethylene glycol (diesters of PEG’s) by reacting 400 g/mol molecular
weight PEG. The inhibition performance of synthesized hydrophobic
molecules such as PEG400C2 and PEG400C12 was compared to the
PEG400 molecules by adsorption and by shale recovery experiments.
The adsorption measurements were taken for different molecular
weights of PEG and the adsorption capacity on clay surface was as-
sessed. The adsorption isotherm experiment showed that the adsorbed
amount of PEG on bentonite increases with increases of the molar mass
of PEG from 400 to 1500 g/mol. But higher molecules of PEG adopt
random conformation and decrease the polarity of polymer chains
which adsorb at the clay surfaces randomly with tails and loops. This
random structure of PEG at higher molar mass and abnormal adsorption
on the clay surface brings the clay platelets together by bridging with
each other and the PEG adsorption amount on the clay surface is re-
duced.
To compare the adsorption performance of PEG400 with hydro-
phobic PEG’s, adsorption isotherm experiments were performed.
PEG400C2 showed similar adsorption to the adsorption of PEG400
because the former has OH terminal hydroxyl group attached in the
structure that can be used for hydrogen bonding. The PEG400 also has
no hydroxyl group in the structure but the adsorption takes place due to
the ethylene oxide group in the structure. The structure of PEG400C12
was considered superior for adsorption of clay surfaces compared to all
other structures due to the presence of long aliphatic chains which
successfully adsorb on the clay surface and form additional layers by
hydrophobic groups and protect the clay from interacting with water.
These long chains are kept on the outside of clay surface interlayers and
prevent the water from interacting with clay minerals [35].
Ferreira et al. have introduced hyperbranched poly glycols with
remarkable structures which are obtained from glycidol or glycol car-
bonate are considered superior shale inhibitors. Experimental studies
show that hyperbranched structures have superior inhibition properties
compared to the linear structures of polyethylene glycol. The inhibition
of reactive shale formations can be done by enhancing the hydro-
phobicity of hyperbranched structures of poly glycols [104]. The
synthesis of hyperbranched polyglycerol partially hydrophobized was
prepared by reacting the polyglycerol and dodecyl tetradecyl glycidyl
ether in different molar ratios 1:1, 1:2 and 1:4 and named HPG11,
HPG12, and HPG14, respectively. The synthesis route of final hyper-
branched polyglycerol partially hydrophobized is mentioned below in
Figs. 6 and 7.
Hot rolling dispersion experiments were carried out with HPG11
and HPG12 and recovery of the shale sample was similar to the
195
Fuel 251 (2019) 187–217
recovery measured by poly-DADMAC, which is a commercially used
shale inhibitor. The shale recovery of HPG systems was higher com-
pared to the PEG (400 g/mol) fluid system. The HPG systems show
superior inhibition performance in the presence of KCl salt probably
due to the formation of complex structures between the polymer and
potassium cation. The complex structure favors the adsorption of
polymer on negatively charged layers of shale and similar results of
polymer adsorption have been mentioned in the literature [102,103].
The hot rolling dispersion experiments showed that partially hydro-
phobized molecules of HPG are considered superior inhibitors com-
pared to the polyglycerols due to the lower solubility of HPG in water
compared to the polyglycerols and increased adsorption on negatively
charged shale surfaces.
The HPG solubility in the aqueous phase and adsorption mechanism
of the negatively charged clay surface is explained by adsorption iso-
therms. It is believed that HPG11 and HPG 12 have similar inhibition
characteristics while HPG12 follows an abnormal trend which suggests
that inhibition characteristics depend on the degree of hydrophobic
contents in the non-ionic polymer systems. The aqueous systems con-
taining HPG11 and HPG12 and KCl salt showed superior shale recovery
results of up to 80% and these interesting results suggest that its ap-
plications can be applied to real field applications. The bentonite in-
hibition test was performed with HPG14 and inhibition results showed
that it has maximum inhibition properties compared to all other non-
ionic polymer systems even in the absence of KCl salt. The mechanism
that explains the best inhibition performance of HPG14 is that when it
was mixed with bentonite powder and after aging of the sample, ben-
tonite platelets get flocculated with the molecules of HPG14 and these
flocculates remain intact even after the vigorous mixing with the mixer.
These flocculate prevent bentonite from making clay swell and in the
presence of KCl salt these flocculate were not observed [104].
5.1.2. Ionic polymers
Ionic polymers and their derivatives with structural modifications
are considered superior shale inhibitors for the inhibition of shale re-
servoirs. Ionic polymers are further classified as cationic polymers and
anionic polymers, and both are considered effective shale inhibitors in
the formulations of water-based drilling fluids. There are different in-
hibition mechanisms of polymeric based shale inhibitors which involve
the adsorption of polymers on the surface of shale and the formation of
hydrogen bonding of shale inhibitors with the surface of shale. The
prime purpose of shale inhibition using ionic polymeric inhibitors is to
prevent the dispersion of drilled cuttings and to protect the borehole
surface. In the following section, two different classes of shale inhibitors
will be discussed. First, acrylamide-based polymers and its derivatives
(copolymers and terpolymer); second, amine-based shale inhibitors
with their properties and their effect on shale inhibition.
5.1.2.1. Acrylamide based polymers. Polyacrylamide (PAM) and
partially hydrolyzed polyacrylamide (HPAM) are considered potential
additives for water-based drilling fluids. They have long chain
molecules which adsorb on the surface of clays and are specifically
used to prevent the hydration and dispersion of clays in the wellbore
[79–81]. In recent decades, many water-soluble polymers have been
used for shale stabilization and to inhibit hydration and swelling. But
most of the polymers have less ability to stabilize shale under high
salinity and in high-temperature environments [105,106].
Several water-soluble copolymers are employed in the drilling fluid
industry to modify drilling fluid rheological, filtration, and shale in-
hibition properties [108–112]. Recently, a copolymer was synthesized
using acrylamide (AM), N,N-diallyl benzylamine (NAPA), acrylic acid
(AA), and 2-(acrylamide)-2-methylpropane-1-sulfonic acid (AMPS)
through a radical copolymerization technique and called as PANAA.
This copolymer has structural diversity due to the presence of carboxyl
groups, heterocycles and benzene rings which impart high temperature
and high salinity tolerance. The structure of PANAA copolymer is given
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Fig. 6. Synthesis route for hyperbranched polyglycerol [104]. ©Elsevier. Reproduced by permission of Elsevier.

in Fig. 8. The inhibition properties of PANAA were determined by
measuring the interlayer spacing of sodium montmorillonite clay. The
neat MMT clay showed 19.04 Å and in the presence of (5000 mg/L) of
the PANAA copolymer, the interlayer spacing was reduced to 18.74 Å.
However, the pronounced effect on the reduction of interlayer spacing
was observed with the addition of 3% KCl in the solution and interlayer
spacing was reduced from 18.74 Å to 15.65 Å. The superior viscosity of
PANAA at higher concentrations of salt also indicate its salt tolerance.
The drilling of deepwater oil and gas wells with a high molecular
weight encapsulator addresses the thickening problem of drilling fluid
at low temperature, where it is difficult to control the fluid loses and
bottom hole pressure. These problems can be avoided by using a low
molecular weight encapsulator in the water-based drilling fluid rather
than conventional shale encapsulators. Recently, a zwitterionic terpo-
lymer P(AM-DMC-AMPS) with monomers containing acrylamide,
methacrylate ethyl trimethyl ammonium chloride, and 2-acrylamido-2-
methylpropane sulfonic acid was synthesized via the solution poly-
merization technique. The terpolymer was used as low molecular
weight encapsulator to study the swelling inhibition properties of a
shale sample. The molecular structure of terpolymer is shown in Fig. 9.
The efficient inhibition capacity of the low molecular weight en-
capsulator was due to the strong inhibition capacity compared to the
conventionally used encapsulators and it reduced the hydration and
dispersion of shale. The results also show that low molecular weight
encapsulator was compatible in water-based drilling fluids and the re-
covery of shale increased with the encapsulator compared to the con-
ventionally used shale encapsulators. The swelling rate of the shale
sample in fresh water was approximately 41% indicating a high hy-
dration capacity which results in severe wellbore instability problems.
The presence of a low molecular encapsulator significantly reduced the

Fig. 7. Synthesis route for hyperbranched polyglycerol hydrophobized [104]. ©Elsevier. Reproduced by permission of Elsevier.

196
H.M. Ahmed, et al.
Fig. 8. Acrylamide sulfonate copolymer PANAA [107]. ©ACS Publications. Reproduced by permission of ACS Publications.
Fig. 9. Structure of terpolymer P(AM-DMC-AMPS) [63]. Reproduced according
to terms of Creative Commons Attribution 4.0 International License (http://
creativecommons.org/licenses/by/4.0/).
swelling rate of shale compared to fresh water. It is believed that the
encapsulator adsorbs on the surface of the wellbore and wraps the
surface of shale particles through hydrogen bonding and electrostatic
force of attractions which reduce the invasion of water and maintain
the integrity of the wellbore. The superior shale inhibition and rheo-
logical properties of water-based drilling fluids containing low mole-
cular weight encapsulators endorse its potential use for deepwater
drilling compared to the use of conventionally available encapsulators.
Along with superior shale inhibition and improved rheological prop-
erties at low temperatures, low molecular weight encapsulators also
showed good salt tolerance up to 10–20% concentrations of sodium
chloride [63].
For water sensitive shale formations, a copolymer of carboxymethyl
and polyacrylamide was synthesized via the free radical polymerization
technique and the resultant carboxymethyl-grafted-polyacrylamide co-
polymer exhibited superior inhibition properties. With an increase in
the concentration of grafted copolymer from 0.3% to 0.8%, the shale
recovery was improved from 68% to 89.4%. The enhanced inhibition
properties of the copolymer are due to the pronounced encapsulation
effect on the shale sample caused by the adsorption of the copolymer on
the surface of shale making a thin film which restricts the migration of
water in the shale matrix [44].
The demand for nanomaterials has widely increased to enhance oil
and gas drilling applications. Polymer microsphere emulsion (PME)
synthesized through emulsion polymerization can be employed as high-
performance shale stabilizer for water-based drilling fluids. The sche-
matic diagram of emulsion polymerization is shown in Fig. 10. The
monomers 2-acrylamide-2-methylpropane sulfonic acid (AMPS), n-
butyl acrylate (BA) and styrene (St) were used to synthesize the mi-
crosphere emulsion in which AMPS acts as hydrophilic moiety to en-
hance the dispersion of the polymer in water-based drilling fluids while
styrene and n-butyl acrylate are hydrophobic moieties used to stabilize
the shale formations. The polymer microsphere emulsion stability was
enhanced with emulsifiers which are also used to reduce capillary
197
Fuel 251 (2019) 187–217
effects and surface tension [113]. The polymer microsphere emulsion
showed superior temperature and salt resistance at the severe condi-
tions of the bottom hole. Pore plugging of the shale sample was ob-
served analytically by taking SEM images before and after immersing
the shale sample in a polymer microsphere emulsion as shown in
Fig. 11. A natural shale sample has many micropores and nanopores
and cracks, but after interacting the shale sample with the fluid con-
taining the polymer microsphere emulsion, the pores and cracks be-
came tightly plugged with the PME, which greatly reduced the per-
meability of the shale sample. This was also confirmed using a pore
pressure transmission test in which the pressure transmission rate was
decreased with an increase in time. These results indicate the effective
plugging capacity of PME in the pores and cracks of a shale sample.
The maximum shale recovery of 88.4% was observed with a 2%
concentration of PME. The contact angle substantially increased with
the increase in the concentration of PME in water-based drilling fluid
thereby making the shale surface hydrophobic. The hydrophobic shale
surface repels water and shows a little affinity for water. The shale
formation contains a lot of micro- and nanopores with fractures and
cracks through which water molecules seep in resulting in shale hy-
dration and swelling. The schematic diagram of the wellbore stability
mechanism of PME is shown in Fig. 12. The polymer microspheres were
squeezed into these pores and cracks under the capillary pressure and
drilling differential pressure which resulted in the dense physical
plugging decreasing the pore pressure transmission and permeability in
favor of shale stability. This physical plugging of the shale surface with
PME makes the surface more hydrophobic in nature which prevents the
interactions of water with shale and increases the shale inhibition
performance [114,115].
For reactive shale formations, graft copolymers have recently been
employed as additives for water-based drilling fluids to reduce shale
hydration and swelling. Graft copolymers have many applications in
drilling oil and gas wells. They are soluble in water, provide resistance
to enzyme environments, and are mechanically and thermally stable in
high-temperature drilling applications. Polyacrylamide/diallyl di-
methyl ammonium chloride-grafted-gum acacia copolymer was syn-
thesized using the free radical polymerization technique for the in-
hibition of troublesome shale hydration and swelling. Gum acacia is a
biopolymer and consists of many species such as arabino galacto pro-
tein, polysaccharide and proteins which have diverse industrial appli-
cations. For water-based drilling fluid applications, gum acacia is often
provided for pH stability, gelling characteristics, low viscosity, water
solubility and non-toxicity [116,117]. The grafting reaction between
gum acacia and the copolymer of polyacrylamide and diallyl dimethyl
ammonium chloride resulted in grafted polymer which has special
properties and can be used as a water-based drilling fluid additive,
rheology control modifier, fluid loss control agent and shale stabilizer.
The shale recovery test was performed with 0.9 w/v% of the grafted
copolymer in the water-based drilling fluid and shale recovery was
96.4 wt%. However, the shale recovery was only 86.6 wt% with 0.9 w/
v% of PHPA concentration. The overall shale recovery results prove
that synthesized grafted copolymer provides superior shale recovery
compared to the conventionally used shale stabilizer PHPA. The slake
H.M. Ahmed, et al.
Fig. 10. Schematic diagram of the polymer microsphere emulsion polymerization system [90]. Open access article published by The Royal Society of Chemistry.
durability index in the PHPA system was 53% at 0.9 w/v% con-
centration, while in the presence of the grafted copolymer system, the
slake durability index was increased to 81% at 0.9 w/v% concentration
of grafted copolymer. These results prove that grafted copolymer has
superior inhibition properties compared to the PHPA system when used
in the water-based drilling fluid. The mechanism that protects the shale
formation explains that the hydrated sodium ions are replaced by am-
monium ions which are used to neutralize the negatively charged sur-
face of clay and form a protective layer to inhibit the hydration and
swelling of shale [118–121].
The shale formations which contain high amounts of clay required
special attention for the inhibition of swelling and to maintain the in-
tegrity of the wellbore. For this purpose, a special polyacrylamide/clay
nanocomposite was reported that was synthesized via the free radical
polymerization technique. The shale recovery experiment was per-
formed and compared with the base fluid (PHPA system). The recovery
of shale in the PHPA system was less at all concentrations compared to
the nanocomposite system. The recovery of shale was observed to be
93.2% at 0.8% concentration of the nanocomposite system. The pre-
sence of nanocomposites in the drilling fluid system prevents the dis-
integration of the shale sample by making a thin protective nano-
composite layer. The thin nanocomposite layer attached to the surface
Fig. 11. SEM images of shale core samples before and after interacting with the polymer microsphere emulsion [90]. Open access article published by The Royal
Society of Chemistry.
198
Fuel 251 (2019) 187–217
of shale through hydrogen bonding and the electrostatic force of at-
traction. This protective layer prevents the interaction of water with
shale making the shale sample more stable towards dispersion and
swelling [9].
In summary, various acrylamide-based copolymers have been re-
ported in the literature and showed better properties compared to the
conventional partially hydrolyzed polyacrylamide. The improvement
was achieved by incorporating monomers that can reduce the shale
swelling and improve disintegration of shale.
5.1.2.2. Polyamines. Nitrogen-based compounds and their derivatives
have been used for the inhibition of shale for many years. The simplest
nitrogen-based inhibitor is ammonium chloride. Properties of amine-
based compounds as shale inhibitors have been reported in the
literature [120,122,123]. The previously used potassium chloride
shale inhibitor had many disadvantages such as toxicity in marine
environments and the potassium ion causing swelling in kaolinite clay
under certain conditions leading to the instability of the wellbore. To
alleviate all the disadvantages of salt, researchers have found organic
cations which behave like potassium ions for shale inhibition and then
amine-based compounds were evaluated for the inhibition of shale
[124]. In the last few years, several amine-based compounds were
H.M. Ahmed, et al.
Fig. 12. The schematic diagram of a wellbore stability mechanism by PME [90]. Open access article published by The Royal Society of Chemistry.
Fig. 13. Chemical structures of different polyether amines [71]. ©Elsevier.
Reproduced by permission of Elsevier.
studied as shale inhibitors such as polyamine acid, lipophilic polymeric
amines, hexamethylenediamine, poly-hydroxylated alkyl ammonium
salt and dendritic amines [125].
Polyether amines have attracted great interest as shale inhibitors in
water-based drilling fluids due to their efficient shale inhibition prop-
erties. The interactions between clay particles and polyether amines
depend on several factors such as the size of molecular chains, mole-
cular weight, and a number of amine groups in the structure of poly-
ether amines. The molecular structures of various amines are men-
tioned in Fig. 13. The hot rolling dispersion test was carried out on
several polyether amines suggests that PEA-3 showed the maximum
shale recovery at approximately 75.76%, while PEA-6 showed the
minimum recovery of the shale sample. The water adsorption test
199
Fuel 251 (2019) 187–217
suggested that the montmorillonite showed the highest rate of water
adsorption due to its hydrophilic nature. The treatment of montmor-
illonite with polyether amines changes the hydrophilicity of clay which
affects the water adsorption performance. The minimum water ad-
sorption rate was observed for PEA-3 which makes the clay surface less
hydrophilic. The polyether amine interactions with the clay surface are
shown in Fig. 14. The presence of terminal amines attached with the
clay surface and polypropylene oxide polymer chains makes the clay
surface less hydrophilic and inhibits the hydration and swelling of clay.
The polyether amine (PEA-3) showed superior inhibition performance
compared to all other compounds. The PEA-3 interacts with the clay
surface through hydrogen bonding; electrostatic adsorption, which re-
sulted in the monolayer arrangement, and a hydrophobic shielding ef-
fect; making it the most suitable candidate of the polyether amines
[71].
The polyamido amines substituted with the hydrophobic group are
considered as additives in water-based drilling fluid for the inhibition of
shale hydration and swelling. Poly(oxypropylene) amidoamines were
synthesized for the inhibition of shale swelling and hydration by con-
densation reactions of diacids and polyoxypropylene diamines. The
structure of poly(oxypropylene) amidoamine is shown in Fig. 15. XRD
analysis suggested that interlayer distance increased from 1.21 nm to
1.43 nm at the 0.5 (m/v.%) the concentration of POAA. Further in-
creases in the concentration did not increase the intercalating effect on
the interlayer distance which indicates a monolayer arrangement of
POAA between the interlayer. Additionally, the use of high molecular
weight POAA further increased the interlayer distance. The shale re-
covery experiment showed that the increasing concentration resulted in
an increase in shale recovery and the addition of KCl further enhanced
the recovery of shale. The interactions such as hydrogen bonding,
electrostatic and van der Waal forces between the clay surface and
POAA compounds resulted in superior inhibition performance [126].
Another category of shale inhibitor is polyoxyalkyleneamine
(POAM) which is used for the inhibition of sensitive shale formations.
Various inhibition experiments were carried out with sodium mon-
tmorillonite to study the inhibition performance of POAM. The use of
2% POAM in the water-based drilling fluid enhanced the shale recovery
and it had superior results for the suppressing of clay hydration and
swelling in the harsh drilling environment. The polyoxyalkyleneamine
has many advantages over conventionally used shale inhibitors such as
compatibility with other water-based drilling fluid additives and low
toxicity for a marine drilling environment [127].
A recent study related to the compound of multiple primary amines
as shale inhibitors was carried out and results were compared with the
diamines. Low molecular weight branched polyethyleneimine (BPEI)
and hexamethylendiamine (HMDA) were utilized to evaluate and
compare the inhibition performance of inhibitors. The chemical struc-
tures of BPEI and HMDA are mentioned in the following Fig. 16. The
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Fig. 14. Schematic diagram of clay swelling and PEA-3 inhibition mechanism [71]. ©Elsevier. Reproduced by permission of Elsevier.

chemical structure of BPEI shows that it is a large hyperbranched

structure with multiple primary amines attached at the end of mole-
cular chains and high solubility in water. The primary amine attached
at the ends has the ability to form interactions (hydrogen bonding) with
the clay surface. Furthermore, the compatibility of BPEI and other
components of drilling fluid, superior inhibition performance, and high
viscosity makes it a preferable candidate for water-based drilling fluids.
The design criteria for cationic shale inhibitors to inhibit the swel-
ling of clays has been reported in the literature. According to this design
criteria, the cationic shale inhibitor should be soluble in water and can
replace the interlayer cations of clay. The cationic shale inhibitor Fig. 16. Chemical structures of 1,6-hexmethylenediamine and branched poly-
should have a cationic group in the structure or primary diamines and a ethyleneimine [72]. ©Elsevier. Reproduced by permission of Elsevier.
long chain alkyl group or a hydrophobic group that can form a mono-
layer on the surface of clay and protect the clays from hydration and
swelling [128]. The linear expansivity of shale inhibitors such as po-
tassium chloride, choline chloride, polyether amine, HMDA, and BPEI
were evaluated over periods of 2 and 16 h. The results showed that BPEI
had the lowest linear expansivity which predicts a better inhibition
performance. The interlayer spacing was measured with HMDA and
BPEI and it was observed that interlayer spacing decreased sharply in
the presence of alkyl amine inhibitors; (HMDA and BPEI) however,
further increases in the concentration had no effect on interlayer spa-
cing which indicates the formation of a monolayer of inhibitors on the
clay surface. The presence of the hydrophobic group repels the water in
the interlayers and protects them from hydration and swelling [72].
The hyperbranched polymer was recently introduced as an additive
in water-based drilling fluid for the inhibition of shale from hydration
and swelling. Amine-terminated hyperbranched polymer (HBP-NH2)
was synthesized by the condensation reaction of diamines. The che-
mical structure of the hyperbranched polymer is shown in Fig. 17. The
effectiveness of hyperbranched amine terminated polymer was de-
Fig. 17. Chemical structure of hyperbranched-NH2 [133]. ©John Wiley & Sons.
termined with different experimental techniques such as the hot rolling Reproduced by permission of John Wiley & Sons.
dispersion test and linear swelling experiments. Most of the available
shale inhibitors are amine-based inhibitors and mainly diamines in

Fig. 15. Chemical structure of POAA [126].

©Elsevier. Reproduced by permission of Elsevier.

200
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Fig. 18. Adsorption mechanism of HBP-NH2 with clay [133]. ©John Wiley & Sons. Reproduced by permission of John Wiley & Sons.

which amine groups are attached at the end of linear molecular chains.
There are many shortcomings of conventionally available amines such
as the linearity of molecular structure, the number of amine groups in
the molecule, and the fact that adsorption of linear amine inhibitors on
the clay surface is irregular and uneven with few available adsorption
sites. During drilling operations at high turbulence and temperature,
the adsorption of linear diamines on the clay surface is considered
weak. Whereas, hyperbranched amine terminated polymer has quasi-
spherical structure and amine groups are attached at the terminal ends
which defines the chemical properties and effectiveness of the inhibi-
tion properties of the hyperbranched polymer molecule [129–132].
The linear expansion rate of shale was determined in the presence of
hyperbranched amine terminated polymer and it was observed that the
expansion rate decreased with an increase in concentration. The
minimum expansion rate was observed to be 11.42% at 3 wt% polymer
concentrations. It was observed that the minimum expansion rate was
for amine terminated hyperbranched polymer compared to all other
shale inhibitors. The shale recovery experiment showed that increasing
concentrations of hyperbranched polymer increased the shale recovery
and the maximum recovery of shale (68.54%) was observed at 5 wt%
concentration of HBP-NH2. The adsorption of hyperbranched amine
terminated polymer can be observed in Fig. 18. Unlike linear diamines,
the adsorption of the hyperbranched polymer can occur at high-tem-
perature environments and turbulent environments. This adsorption
was due to the highly branched structure with amine terminated ends
which attached with the clay surface and resulted in protection from
shale hydration and swelling [133].
Amine-terminated dendrimer demand has been increased in the
drilling industry as an additive to water-based drilling fluids due to the
peculiar properties and their unique hyperbranched structure. Recently,

Fig. 19. Structure of PAMAM dendrimer (G3) [70]. ©Elsevier. Reproduced by permission of Elsevier.

201
H.M. Ahmed, et al.
Fig. 20. The chemical interactions of bentonite and PAMAM dendrimers [70]. ©Elsevier. Reproduced by permission of Elsevier.
various studies have shown the unique application of dendrimers in
oilfield chemistry [125,134–140]. Amanullah et al. have developed a
high-performance drilling fluid which uses dendrimers as additives for
challenging drilling applications [125]. In a study by Zhong et al., five
different amine-terminated polyamidoamine (PAMAM) dendrimers
from G0 to G5 were evaluated by various experimental techniques; the
chemical structure of a dendrimer is shown in Fig. 19.
Shale recovery experiments carried out in the presence of various
PAMAM dendrimers, KCl and polyether amine at different pH values
showed that the shale recovery with the control sample was low while
the shale recovery with PAMAM dendrimers, PEA and KCl was com-
paratively high. The high recovery of the shale sample depicts less
dispersion of shale and enhanced inhibition properties of shale in-
hibitors. The shale recovery was determined at a pH value of 11 and the
maximum shale recovery was observed for the G5 PAMAM dendrimer
compared to all other shale inhibitors. The shale recovery was further
increased for all the shale inhibitors with a decrease of pH value and the
G5 dendrimer still shows the maximum shale recovery compare to all
other shale inhibitors.
The zeta potential of clay particles was determined in order to study
the effect of shale inhibitors on the electro kinetic properties of clay
dispersions at two different pH values. According to Garea et al., the
colloidal dispersion with a zeta potential value of 30 mV is considered
as a stable dispersion [141]. Colloidal dispersion with clay particles
having high negative values of zeta potential is prone to swelling and
dispersion in an aqueous medium. The zeta potential of bentonite clay
particles is reported as −39 mV which indicates a stable dispersion of
clay particles. The addition of PAMAM dendrimers decreased the zeta
potential of clay dispersion from −39 mV to −22.6 mV. For PEA the
zeta potential was reduced to −18.7 mV and for KCl zeta the potential
was further decreased to −11.5 mV. Mohan and Fogler have reported
in the literature that a 20% reduction in charge on the layers of clay can
completely inhibit the swelling of clay [75]. Riddick has stated in his
202
Fuel 251 (2019) 187–217
research that if the zeta potential of dispersion ranges from −16 to
−30 mV, the dispersion is considered weak. If the zeta potential is in
the range of −10 to −15 mV, then the particles of dispersion can easily
bind together in the presence of an inhibitor. It can be concluded from
the above discussion, that the PAMAM dendrimers, PEA and KCl can
significantly reduce the zeta potential and inhibit the swelling of clay
[142].
The chemical interactions of bentonite platelets and PAMAM den-
drimers are presented in Fig. 20. The presence of low concentrations of
PAMAM dendrimers forms a monolayer between the platelets of ben-
tonite and results in an intercalated structure. When the concentration
of PAMAM dendrimer is increased, the interlayer distance of bentonite
platelets increases due to the formation of a bilayer of dendrimer and
the adsorption of the PAMAM dendrimer at multiple positions between
the negatively charged bentonite platelets and protonated dendrimers.
This removes the water from interlayers of bentonite for a superior
inhibition performance. The decrease in the pH value resulted in the
enhanced protonation of amine groups of dendrimers which increased
the interactions between bentonite platelets and dendrimers. The in-
creased interaction resulted in a decrease of interlayer spacing and
enhanced the inhibition performance of PAMAM dendrimers [70].
Alkyl amines have different numbers of primary amines attached
with the alkyl chains of different lengths. The structures of various alkyl
amines are presented in Fig. 21. The rate of adsorption significantly
increased with the increase in the number of primary amines in the
shale inhibitor. The alkyl amine interacted with the clay particles and
formed a monolayer on the platelets of clay resulting in an intercalated
structure. The alkyl amine replaces the interlayer replaceable cations
from the interlayers of clay and an embedded structure was formed
which repels the water molecules and protects the clay from swelling
and hydration.
The linear expansivity of shale was determined using different alkyl
amines to investigate the inhibition performance at 2 and 16 h. The
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Fig. 21. The chemical structures of alkyl amines [143]. ©Elsevier. Reproduced by permission of Elsevier.

lower expansion rate indicates superior shale inhibitor performance.
The linear expansivity of shale was significantly reduced in the pre-
sence of alkyl amines at 2 and 16 h compared to fresh water. The linear
expansivity rapidly decreased with increasing numbers of alkyl amines
indicating better performance. The microstructure of hydrated clay was
investigated with and without the presence of alkyl amines using SEM
analysis as shown in Fig. 22. The SEM images indicate an enhanced
agglomerate of clay in the presence of alkyl amines as compared to the
simple hydrated bentonite. The surface structure and edge curl phe-
nomenon were more prominent in the alkyl amine complexes compared
to the hydrated bentonite. The clay and PD inhibitor complex showed
the presence of globule structures in the SEM photograph and the by
increasing the number of primary amines in the structure it resulted in a
well-ordered layer structure of clay. The alkyl amines having multiple
primary amine groups are promising shale inhibitors for water-based
drilling fluids [143].
Polyethyleneimine (PEI) is considered as an environmentally
friendly shale inhibitor. PEI is an alkaline water-soluble polymer con-
taining large numbers of cationic groups in its structure. Due to the
presence of many nitrogen atoms in this polymer, it has the ability to
form hydrogen bonds with other electronegative atoms. PEI has many
industrial and engineering applications such as in bioengineering, the
oil and water treatment industry, and the coating industry [144–155].
The inhibition mechanism can be explained in such a way that inter-
layer cations are replaced with the PEI molecules which repel the water
molecules to migrate to the interlayer spacing. The amino groups in the
PEI make hydrogen bonds with the hydroxyl groups of clay and result in
the adsorption of PEI on the clay surface. The electrostatic interactions

Fig. 22. SEM photographs with hydrated sodium bentonite and alkyl amines (a) hydrated sodium bentonite (b) sodium bentonite + PD inhibitor (c) sodium
bentonite + APD inhibitor (d) sodium bentonite + BAPD inhibitor [143]. ©Elsevier. Reproduced by permission of Elsevier.

203
H.M. Ahmed, et al.
Fig. 23. The schematic mechanism for the inhibition of PEI with montmorillonite [156]. ©Elsevier. Reproduced by permission of Elsevier.
and adsorption of PEI form an intercalated structure of clay. The me-
chanism of PEI adsorption and the formation of the intercalated
structure is shown in Fig. 23.
The shale recovery was minimal in the presence of fresh water
while, except for PEI1800, shale recovery was significantly increased in
the presence of increasing molecular weight PEI. The higher the re-
covery of shale for a specific shale inhibitor, the better will be its in-
hibition performance. The increasing molecular weight of PEI resulted
in the decrease of linear swelling of montmorillonite pellet and lowest
swelling was observed with PEI70000 shale inhibitor [156].
Polyether diamine (PEDA) is also used as an additive in water-based
drilling fluids for the inhibition of shale swelling and hydration. The
polyether diamines are considered remarkable shale inhibitors due to
their excellent inhibition capacity, low molecular weight and less
toxicity for drilling fluid applications including rheological modifiers,
dispersants and fluid loss modifying agents [157–160]. X-ray diffraction
analysis showed that the interlayer spacing of montmorillonite at 0.5%
concentration of PEDA increased from 1.21 nm to 1.36 nm indicating
the intercalation of PEDA. The further increase in the concentration of
diamines had no increased effect on the interlayer spacing which in-
dicates the formation of a monolayer on the platelets of montmor-
illonite and with increasing concentrations of PEDA, the interlayer
space remains unchanged. In addition, the slope for the PEDA hot rolled
cuttings was high compared to the KCl rolled cutting sample indicating
a higher bulk hardness and superior inhibition performance. For water
and KCl rolled cutting samples, the plateau regions were shown by the
extrusion of shale cuttings and the softening of the shale sample. The
decrease in the pH of PDEA resulted in an increase in the slope of bulk
hardness curves which indicates that hardness and inhibition perfor-
mance increased with lowering of the pH of PDEA containing drilling
fluid during the hot rolling experiment [94].
5.2. Low molecular weight amine inhibitors
Over the past few years, various amine inhibitors including alkyl
primary amines, alkyl secondary amines, alkyl tertiary amines, poly-
amine acid, quaternary alkyl ammonium salts, ammonium cations, li-
pophilic polymeric amines, dendritic amines, poly-hydroxylated alkyl
ammonium salt, hexamethylendiamine, and polyethoxylated diamines
have been introduced as shale inhibitors [161–163]. Various amine-
based shale inhibitors are mentioned in Table 2.
The shale inhibition efficiency of amines is evaluated by de-
termining the interlayer spacing of clay particles after the adsorption of
amines. The inhibitors containing amine groups get protonated in the
aqueous solution and turned into a cationic group. The cationic groups
of inhibitors attach with the negatively charged surfaces of clay mi-
nerals through the electrostatic force of attractions and hydrogen
bonding. The electrostatic attraction and hydrogen bonding result in
the decrease in zeta potential of clay suspensions which also reduce the
204
Fuel 251 (2019) 187–217
stability of clay suspensions [164]. The adsorption of inhibitors on the
clay surfaces with hydrophobic groups results in a shielding effect. The
shielding effect of hydrophobic groups result in the decrease in the
thickness of the electrical double layer and have restricted movements
compared to the small particles [165–168]. Interactions of the amine
group with clay particles determine the inhibition capacity of amines
and are mainly affected by hydrogen bonding, static electric interac-
tions and the hydrophobic shielding effect of inhibitors. Shale inhibi-
tion takes place by the adsorption of protonated cationic amine groups
followed by the neutralization of the negative charge on the clay par-
ticles resulting in the formation of monolayer arrangement in the in-
terlayers of clay particles. The interactions among clay particles and
amine group result in the compression of a diffuse double layer of clay
particles which results in the formation of flocculated clay particles.
Low molecular weight 4,4-methylenebis-cyclohexanamine (MBCA)
showed good inhibition characteristics for sodium bentonite [169]. The
sodium bentonite dispersion in an aqueous medium showed a −39.9-
mV zeta potential which represents suspension stability. Zeta potential
values for MBCA and sodium bentonite suspension showed a decreasing
trend and dropped to −20.8 mV with the increasing concentration up
to 2 w/v% of inhibitors. The presence of MBCA in an aqueous solution
of sodium bentonite makes the surface more hydrophobic. Clay hy-
dration and swelling could be completely inhibited if the negative
charge on the clay minerals is reduced by 20% [75]. A zeta potential
value between −30 mV and −16 mV indicates a weak dispersion. The
shale inhibitive properties of MBCA for montmorillonite using contact
angle measurements also suggests their good inhibition properties. The
water droplet made an angle of 29.8 for montmorillonite film which
shows the hydrophilicity of clay minerals (montmorillonite). The in-
creasing concentration of MBCA in the montmorillonite showed that
the contact angle increased up to 86.2. The increase in the contact angle
suggests that the wettability of the clay layer decreased, becoming more
and more hydrophobic in nature. The increased hydrophobicity oc-
curred by the addition of MBCA in the drilling fluid showing that shale
stability would be increased [64]. In summary, MBCA proved to be a
better inhibitor for sodium bentonite and montmorillonite.
5.2.1. Synergistic effect of organic and inorganic inhibitors
The synergistic effect of inorganic and organic inhibitors can also
improve inhibition properties. The synergistic effect of various organic
and inorganic shale inhibitors has been reported in the literature. The
schematic representation of clay swelling inhibition is shown in Fig. 24.
A study was conducted using organic cationic salts (quaternary am-
monium chloride salt, quaternary polyamine chloride, and cationic
polyacrylamide chloride) and inorganic salts (KCl and NaCl) using a
capillary suction time test. Longer suction times for specific clays means
that a small amount of free water is available in the interlayers of clay
and a high amount of water resides in the clay interlayers, indicating a
large degree of clay swelling. The distilled water showed a maximum
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Table 2
Amine-based shale inhibitors.
Amines Structures Refs.

Ammonium chloride [170]

Tetramethyl ammonium chloride [171]

Hexamethylene diamine [72]

Polyethoxylated diamine [172,173]

Polyhydroxylated alkyl ammonium salt [174]

Polyether diamine [175]

Poly oxyethylene [71]

Poly oxyethylene and poly oxypropylene

Poly(oxypropylene)-amidoamine (POAA) [73]

(continued on next page)

205
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

Table 2 (continued)

Amines Structures Refs.

Poly oxypropylene [71]

Poly oxypropylene branched

Amine tartaric salt [176]

polyethyleneimine [156]

1,5-pentanediamine [143]

3-(2-aminoethyl) pentane-1,5-diamine

3,3-Bis(2-aminoethyl)-1,5-pentanediamine

Neutral quaternary ammonium salt [177]

4,4′-methylenebis-cyclohexanamine [64]

206
H.M. Ahmed, et al.
Fig. 24. Schematic representation of clay the swelling inhibition mechanism. (a) Without cationic inhibitors (b) with cationic inhibitors [78]. ©Elsevier. Reproduced
by permission of Elsevier.
amount of clay swelling because it has maximum suction time. The
addition of inorganic salts such as NaCl and KCl sufficiently reduced the
suction time and clay swelling. The combination of KCl and cationic
polyacrylamide chloride showed the minimum suction time due to the
presence of a quaternary ammonium group and high charge density
which helps in exchanging a substantial number of exchangeable ca-
tions. The overall results indicate that the mixture of inorganic and
organic inhibitors presents better swell inhibition compared to the in-
organic inhibitor alone [78].
In another study, the synergetic effect of diamino butane and dia-
mino hexane with various hydroxides and chlorides of alkali metals,
alkaline earth metals, and transition metal was investigated. The shale
inhibition characteristics of these base fluids containing water, aquagel
and inorganic compounds were measured using the linear swelling test.
The clay minerals containing smectite group mainly showed swelling of
clay upon interacting with water compared to the other group of clay
minerals such as chlorite, and illite, etc. Of these fluids, only KCl and
CaCl2 showed a minimal percentage of linear swelling of clays which
indicates their better inhibition properties. When 1% diamino butane
and 1% diamino hexane was introduced with KCl and CaCl2, the re-
sulting combination showed less clay swelling depicting the better
performance of diamino alkanes. Diamino hexane showed superior
performance of shale inhibition in both solutions of KCl and CaCl2
compared to diamino butane. The presence of amino groups at the end
of an alkyl group becomes protonated and attached with the adjacent
negatively charged layers of clay minerals and reduces the interlayer
spacing with less shale swelling. Based on smectite inhibition experi-
ments with superior properties, five different systems of drilling fluids
were tested for Marcellus shale inhibition. Constant concentrations of
1% each of salt: LiCl, KCl, NaCl, Ca(OH)2 and Mg(OH)2 were used along
with a 0.5% of diamino hexane and 5% aquagel. From all these for-
mulations, the KCl formulation was selected as the best for overall ex-
cellent performance in Marcellus shale inhibition, filtration and rheo-
logical properties [178,179].
Chitosan quaternary ammonium salt, a biodegradable and en-
vironmentally friendly shale inhibitor was chosen to study the shale
inhibition properties compared with the conventional polyether amine
in oil and gas drilling operations. Chitosan is a naturally occurring
polysaccharide having substantial numbers of oxygen, hydrogen and
nitrogen atoms. At normal conditions, it is insoluble in water but after
207
Fuel 251 (2019) 187–217
modifying the surface of chitosan by an esterification reaction between
quaternary ammonium salt and surface hydroxyl groups of chitosan it
becomes water soluble. The zeta potential measurements show the
stability of a suspension in water. The pure montmorillonite had a
−14.3-mV zeta potential but the addition of a small percentage of
chitosan quaternary ammonium salt resulted in the increase of the zeta
potential, but further increases in the concentration of ammonium salt
up to 2% did not increase the zeta potential. The gel strength mea-
surements also revealed that up to 1% of the gel strengths of four dif-
ferent concentration of montmorillonite samples increased but the
further addition of chitosan quaternary ammonium salt did not affect
the gel strength values. The shale recovery test showed that chitosan
quaternary ammonium salt has a high shale recovery of 95% at 150 °C
compared to the polyether amines which has only a 63% shale re-
covery. The inhibition mechanism of shale could be explained by the
adsorption of chitosan quaternary ammonium salt on the negatively
charged layers of clay through hydrogen bonding and electrostatic
forces and prevent the interactions of water with clay [69].
Chen et al have studied the effect of amine tartaric salt as shale
inhibitors for montmorillonite clay. The XRD results showed that in-
terlayer spacing of montmorillonite immersed into water was 1.949 nm
whereas the interlayer spacing of montmorillonite dispersion mixed
with 0.5% amine tartaric salt decreased to 1.446 nm. This shows that
the presence of an inhibiting agent in drilling fluid has a great sig-
nificance on the inhibition of shale samples [176].
Xie et al. studied the effect of branched polyethyleneimine and 1,6-
hexamethylenediamine (HMDA) on intercalation behavior of sodium
bentonite in an aqueous solution [72]. The adsorption behavior of
polyethyleneimine and 1,6-hexamethylenediamine was determined by
the Langmuir isotherm and modified Langmuir isotherms. When the
concentration of HMDA is < 1.3 CEC, the adsorption capacity of the
inhibitor on sodium bentonite increases with the increase in HMDA
concentration. When the concentration of HMDA is > 1.5 CEC, then the
HMDA inhibitor adsorption capacity increases slowly and approaches
the saturation point where no further adsorption takes place. The in-
crease in temperature showing the decrease in adsorption of HMDA
indicates that the inhibitor has two terminal amino groups which are
strongly attached with the interlayers of sodium bentonite and offers
considerable resistance to temperature. The adsorption behavior of
BPEI showed that when the concentration of the inhibitor is 0.7 CEC,
H.M. Ahmed, et al.
Table 3
Ionic liquids used as shale inhibitors.
Ionic liquids Cations
1-vinyl-3-ethylimidazolium bromide
Homopolymer of 1-vinyl-3-ethylimidazolium bromide
1-Hexyl-3-methylimidazolium chloride
1-Butyl-3-methulimidazolium octyl sulphate
1-Butyl-3-methulimidazolium bromide
1-octyl-3-methylimidazolium tetrafluoroborate
1-butyl-3-methylimidazolium tetrafluoroborate
the adsorption of the inhibitor on sodium bentonite approaches the
saturation point. The inhibitor BPEI consists of multiple amine groups
which attach with the interlayers of sodium bentonite at multiple po-
sitions and the increase in temperature also showed the decreasing
trend for adsorption capacity of BPEI which indicates its excellent
temperature resistance. The saturated adsorbed quantity of BPEI and
HMDA on sodium bentonite is 0.74 mmol/g and 1.67 mmol/g at 30 °C,
respectively. The results revealed that the saturated adsorption capacity
decreased with the increase in a number of amines in the inhibitor. The
XRD analysis showed that interlayer spacing increased with hydrated
sodium bentonite from 1.011 nm to 1.905 nm compared to dry sodium
bentonite. The increase in interlayer spacing showed that sodium
bentonite has the ability to swell upon hydration. The intercalation of
sodium bentonite was due to the replacement of water molecules from
208
Fuel 251 (2019) 187–217
Anions Refs.
[180]
[181]
[183]
[182]
interlayers of bentonite and strong adsorption of BPEI on the interlayers
of bentonite with reduced basal spacing. Further increases in con-
centration affect interlayer spacing due to the formation of a monolayer
between the interlayers. The adsorption of inhibitors on sodium ben-
tonite interlayers involves electrostatic interaction and hydrogen
bonding between amine groups and clay sheets. The larger number of
amines present in the inhibitor molecules showed a less saturated
amount and a high rate of adsorption of inhibitors on sodium bentonite.
In summary, nitrogen-based shale inhibitors are widely used in ac-
tual field applications. Amine shale inhibitors which have multiple
amine groups perform better in terms of swelling inhibition properties.
Amines with multiple quaternary groups in the structure attach with
various layers of clay minerals and bind them together which results in
less hydration of clay minerals in the shale.
H.M. Ahmed, et al. Fuel 251 (2019) 187–217

5.3. Ionic liquids

[185]

[182]

[181]

[184]
Refs.

Ionic liquids are organic salts with a low melting temperature. Ionic
liquids are synthesized with various cations including ammonium,
potential

−22.5
−30.5
−17.2
imidazolium, piperidinium, and pyrrolidinium. The anions, such as

−8.0
+5.3
+7.1
+7.5
Zeta

bromide, chloride, and tetrafluoroborate may also vary. Ionic liquids

–7
–

–
have many industrial applications due to their peculiar properties such
as ionic conductivity, low vapor pressure, and specific solvating capa-
recovery

city. Researchers are trying to replace potassium chloride and dimethyl

Shale

(%)

ammonium chloride with ionic liquids for shale inhibition. The struc-

39
42
70
62
56
65
–

–
–
–
–
tures and characteristics of different ionic liquids are shown in Tables 3
and 4.
swelling

A recent study investigated the effects of monomer 1-vinyl-3-ethy-

Linear

(cm)

27.5
26.5
27.5
35 limidazolium bromide (VeiBr) and its homopolymer (PV) on shale hy-
–

–
–
–
–
–

–
dration properties in the presence WBDFs [180]. The homopolymer was
synthesized by free a radical polymerization process with various
d > 24.10 A
d > 24.10 A
13.2609 A
12.9501 A
12.5459 A
Interlayer

concentrations of monomers. At 2 wt% concentration, VeiBr, and its

13.63 A
13.74 A
13.77 A

14.80 A
spacing

homopolymer were tested for linear swelling with a sodium bentonite

pellet and results were compared with the 2,3- epoxy propyl trimethyl
–

ammonium chloride (EPTAC) and potassium chloride. The sodium

distribution (Dn/

bentonite pellet immersed in water showed the most swelling. The

Particle size

swelling of the pellet in the KCl and EPTAC was approximately 77%
18.4/37.5

compared to the swelling of the pellet in the deionized water. The shale
30/45.8
28/42.5

inhibitor VeiBr showed less swelling (68.6%) as compared to the EPTAC

Dw)

–
–
–

and potassium chloride.

In another study, three different ionic liquids were used to study the
suction time

inhibition characteristics by measuring the swelling properties, inter-

Capillary

test (sec)

layer spacing of bentonite, zeta potential, and particle size distribution

25.5

50.3

81.5

72.8

in the presence of ionic liquids [181]. These ionic liquids were 1- hexyl-
–
–
–
–
–
–
–
–

3-methylimidazolium chloride (IL-1), 1-butyl-3-methylimidazolium

Regain permeability with
oil is 98.6% and with gas

Regain permeability with

oil is 127% and with gas

octyl-sulphate (IL-2), and 1-butyl-3-methylimidazolium bromide (IL-3).

(retained permeability
Core flow experiment

The effects of these ionic liquids on swelling characteristics were de-

with sandstone core

termined by XRD analysis which showed that untreated bentonite had

11.74 Å interlayer spacing; while the addition of three ionic liquids
increased the interlayer spacing from11.74 Å to 12.54 Å, 12.95 Å and
is 119%.

is 129%.

13.26 Å for IL-1, IL-2, and IL-3, respectively. These results indicate that
the presence of ionic liquids intercalated the bentonite structure which
–
–
–
–
–
–
–

also shows the inhibition capability of ionic liquids. The zeta potential
measurements showed that at lower concentrations of ionic liquids the
Thermal
stability

zeta potential decreases suggesting that the intercalation and adsorp-

200 °C

200 °C

200 °C

300 °C
300 °C
300 °C
300 °C
300 °C
300 °C

tion of ionic liquids on the bentonite. While at high concentration of

–
–
–

ionic liquids, the zeta potential does not change much and reaches the
Concentration

equilibrium point which suggests maximum adsorption of ionic liquids

10 mmol/l
10 mmol/l
10 mmol/l

0.05 wt%

on the interlayers of bentonite. The results from zeta potential and

2 wt%
2 wt%
2 wt%
2 wt%
2 wt%
2 ppm

2 ppm

2 ppm

particle size analysis showed that intercalation of bentonite platelets

with ionic liquids IL-1 and IL-2 are most effective and resulted in en-
bromide and PV stands for the homopolymers of for 1-

octyl-3-methyl imidazolium tetrafluoroborate and 98%

Used for clay stabilizers and shale inhibitors. IL#1 is the

Non-flammable, non-volatile, and are thermally stable.

EPTAC stands for 2,3-epoxypropyl trimethylammonium

IL#3 are quaternary ammonium sulfonate compounds.
derivative of cyclic quaternary amine. While IL#2 and

hanced attractive forces and reduced the repulsive forces among ben-
chloride, VeiBr stands for 1-vinyl-3-ethyl imidazolium
The capability of interlayer spacing, and particle size
distribution depends on the size and type of cation.

vinyl-3-ethyl imidazolium bromide having different

tonite platelets. The comparison of ionic liquids IL-1 and IL-2 with the
swelling of bentonite showed that showed maximum swelling was ob-
molecular weights and high thermal stability.
Characteristics of ionic liquids used for shale inhibition.

served with IL-1 ionic liquids due to its capability of forming weakly
associated aggregates with each other. These aggregates are so small
and do not settle down in the presence of ionic liquids suggesting stable
dispersions.
Recently, a high thermally stable ionic liquid was tested for rheo-
logical and HTHP filtration properties at a temperature of 240 °C with a
very low concentration of 0.05 mass% [182]. Various experimental
studies such as intercalation behavior, wettability, rheology, capillary
Characterizations

suction time, and filtration were carried out. The XRD results of sodium
montmorillonite dispersion showed the interlayer spacing around
12.4 Å while with the addition of 0.02% ionic liquid in the dispersion,
pure

the interlayer spacing increased from 12.4 to 13.38 indicating the ex-
change of interlayer cations with the molecules of ionic liquid which
Materials

increased the distance of interlayers. The hydrophilic part of ionic li-

EPTAC
IL # 1

IL # 2

IL # 3

VeiBr
PV-1
PV-2
PV-3
IL–1
IL-2
IL-3

quid molecules attached with the negatively charged layer and hydro-
ILB
Table 4

philic tail of the ionic liquid acts as a barrier which prevents the in-
(1)

(2)

(3)

(4)

teraction of water with clay and hydration of clays are minimized.

209
H.M. Ahmed, et al.
Luo et al. have studied the effect of 1-octyl-3-methylimidazolium
tetrafluoroborate on hydration and swelling characteristics of sodium
montmorillonite clay and the results were compared with the con-
ventionally used shale inhibitors such as potassium chloride and poly-
ether diamine [183]. The capillary suction time test is one of the in-
dicators of shale inhibitor capability. A good quality shale inhibitor is
considered one which protects the clay from swelling and dispersion
and contains a large amount of free water with flocculated clay parti-
cles. On the other hand, a poor-quality shale inhibitor is considered one
in which clay swells and there is less free water available in the dis-
persed system along with no flocculation of clay minerals. The capillary
suction time of shale particles in the presence of water was 215 s which
indicates the shale was highly dispersed and prone to swell upon in-
teracting with water. The capillary suction time of 5% potassium
chloride was 132 s which was less than that of the water system in-
dicating a good inhibition capacity of potassium chloride. The capillary
suction time of 0.05% of ionic liquid was only 72.8 s which was higher
than 2 wt% polyether amine system and lower than the potassium
chloride system. The lower capillary suction time with ionic liquid
compared to the potassium chloride makes it a suitable candidate as a
shale inhibitor.
In summary, ionic liquids are a new class of shale inhibitors recently
employed for shale reservoirs to prevent the hydration and swelling of
shale formations. Compared to the conventional shale inhibitors, ionic
liquids are more efficient and thermally stable for high-temperature
applications of the drilling process. The diverse nature of ionic liquids
makes them a superior shale inhibitor due to the distinctive hydro-
phobic alkyl chains which act as insulators for water in drilling appli-
cations. The presence of ionic liquids in water-based drilling fluid for-
mulations could be used for better wellbore stability and to preserve
formation integrity.
5.4. Surfactants
Surfactants (also known as wetting agents) are molecules which are
used for lowering the surface tension of water to help in wetting sur-
faces. Surfactants are composed of a hydrophilic head (affinity for
Fig. 25. Adsorption of surfactant molecules on the surface of clay [185].
©Elsevier. Reproduced by permission of Elsevier.
210
Fuel 251 (2019) 187–217
water) and a hydrophobic tail (repelling water molecules). Surfactants
are categorized into three different classes: non-ionic, cationic and
anionic, based on their active head groups. There are many industrial
applications of surfactants but in the petroleum industry, surfactants
are employed in the formulation of drilling fluids and enhanced oil
recovery techniques. In the applications of enhanced oil recovery,
surfactants are utilized to decrease the interfacial tension of water and
oil. However, surfactants have many additional applications in drilling
fluids such as to: minimize differential pipe sticking, prevent drilled
cuttings from sticking with the drilling bit, emulsify the oil and water
systems, and the most importantly, shale stability. Among the three
categories of surfactants, non-ionic and cationic surfactants are em-
ployed for inhibiting shale swelling and hydration. These cationic and
non-ionic surfactants adsorb on the surface of swelling clays due to the
presence of negative charges and silanol groups on the clay surfaces
while their long hydrophobic tails act as a water repellent and prevent
the clay minerals from swelling. A schematic diagram which shows the
adsorption of surfactant molecule on clay surfaces is shown in Fig. 25.
In the following section, the adsorption chemistry of different surfac-
tants on the surface of clay minerals will be discussed. The effect of
various surfactant concentrations on the inhibition properties of shales
using different experimental techniques such as the hot rolling disper-
sion test, linear swelling, effect of temperature, zeta potential and X-ray
analysis will be discussed.
Inhibition performance of tallow amine ethoxylate (surfactant) was
investigated by water-based drilling fluids [186]. Untreated bentonite
has a strong affinity with water molecules and adsorption of water was
determined after 11 days resulting in a 45.23% increase in the weight of
bentonite. Whereas, bentonite treated with 2 wt% tallow amine
ethoxylate showed water adsorption of only 31.5% compared to the
untreated bentonite. This indicates that the lower water adsorption
capacity of clay in the presence of surfactants leads to wellbore stabi-
lity. The wettability alteration test showed that the contact angle of
bentonite film on smeary glass was zero whereas the incorporation of
tallow amine ethoxylate increased the contact angle from zero to 22.54°
which represents enhanced hydrophobicity of bentonite droplet to-
wards the water. Shale recovery experiments were carried out using
surfactants and potassium chloride and showed that by the addition of
2 wt% of a surfactant, shale recovery was increased up to 79% com-
pared to the base fluid recovery of only 43% of the shale sample. The
overall, experimental results show that the tallow amine ethoxylate
surfactant had a better shale inhibition performance. The surfactant has
many amine groups in the structure which attach with the oxygen
atoms of silicate groups through hydrogen bonding and compete with
the water molecules to adsorb on the surface of clay minerals. The
superior inhibition performance also showed its compatibility with
other drilling fluid components for high-temperature applications
[187].
A novel approach was adopted to study the wettability of shale
powder by contact angle measurement and other experimental techni-
ques by using the two different surfactant compounds of Twelve alkyl
two hydroxyethyl amine oxide (THAO) and polyamine (PA). Contact
angle measurements of untreated shale sample and salt-treated shale
sample showed zero contact angle while shale samples treated with
1 wt% surfactant compounds showed an increase in contact angle from
zero to 48.64 for PA and from zero to 31.5 for THAO. These results
indicate that treating the shale with surfactant compounds changes the
wettability of the shale surface. The zeta potential measurements
showed that incorporation of these surfactant compounds decreased the
zeta potential and reduced the hydration of the shale sample by elec-
trostatic repulsion of particles. The surfactant concentration higher
than 0.1 wt% has little effect on zeta potential and zeta potential re-
mains unchanged with higher surfactant concentration.
The surface hydration of shale powder with water showed 32.7 mg/
g indicating easy hydration of the shale sample. While in the presence
of 0.2% of PA and 0.1% THAO, the surface hydration water of the shale
H.M. Ahmed, et al.
Fig. 26. Schematic diagram of PA and THAO adsorption on clay surfaces [188]. ©Elsevier. Reproduced by permission of Elsevier.
Fig. 27. Chemical structure of Saponins [194]. ©ACS Publications. Reproduced
by permission of ACS Publications.
sample declined to 18.31 mg/g. The surface hydration reduction was
due to the adsorption of surfactant compounds on the surface and re-
duced the interaction of water with shale. The interlayer spacing of
untreated shale power was 1.033 nm in the dry form while the treated
shale sample with 0.3% of PA and THAO, the interlayer spacing was
further reduced to 1.006 nm and 1.015 nm, respectively. The reduction
in the interlayer spacing was due to the intercalation of shale powder
with surfactant compounds and it is believed that these surfactants
were adsorbed on the clay minerals by hydrogen bonding with a
monolayer formation [188].
The schematic diagram in Fig. 26 represents the adsorption of sur-
factant molecules on negatively charged layers of clay minerals. It is
believed that PA molecules contain amine groups which make hy-
drogen bonding with the silicon-oxygen alkyl groups found on the clay
surface through irreversible adsorption [189]. The hydrophobic nature
of shale surface was improved with the alkyl groups present in the
structure of PA which prevents the interaction of water with shale. The
surfactant THAO also showed similar hydrogen bonding interactions
with the clay surface.
The demand for environmentally friendly and less toxic shale in-
hibitors is increasing due to the requirements of the drilling industry. A
newly developed shale inhibitor Zizyphus spina-christi extract (ZSCE)
was used for shale inhibitions and inhibition performance was com-
pared with the conventionally used polyamine and potassium chloride.
The non-ionic biosurfactant was extracted from trees extracted by a
spray drier method and it is believed that it contains a high con-
centration of saponins which have complex structures as shown in
Fig. 27. The saponin molecules have both hydrophilic and hydrophobic
211
Fuel 251 (2019) 187–217
structures and are connected to each other through glycoside bonds
[190–192]. The hydrophilic side of the molecules consists of saccharide
residues while the hydrophobic side consists of triterpenoid and steroid
or steroid-alkaloid [193,194]. Increasing the concentration of ZSCE
increases the inhibition capacity of the surfactant but the concentration
above the critical micelle concentration (CMC) has little effect on the
inhibition performance of a surfactant. Below the CMC concentration,
free surfactant molecules are available for the inhibition of clay but the
concentration above CMC results in the interaction of molecules and
formation of micelles with no major change in the free surfactant mo-
lecule concentration. The inhibition properties of ZSCE was determined
by performing cutting dispersion experiments on highly reactive shale.
The percentage of recovery was only 18.25% in the presence of deio-
nized water and the recovery percentage increases with the increase in
the concentration of ZSCE. The superior inhibition performance of ZSCE
is greater than the two commonly used shale inhibitors of potassium
chloride and polyamine. The ZSCE has better hydration inhibition ca-
pacity and potential to prevent a shale cutting from the dispersion. The
mechanism of the inhibition of ZSCE is explained by the interactions of
surfactant molecules with the clay surfaces. ZSCE contains saponins
with hydrophobic and hydrophilic moieties. The hydrophilic part of
ZCSE attaches with the negatively charged surfaces while hydrophobic
part of ZSCE is oriented towards the aqueous phase as shown in Fig. 28.
The ZCSE molecules attach with the clay surface through hydrogen
bonding between hydroxyl groups of ZSCE and oxygen atoms of the
clay surface. The ZSCE molecules compete with the water molecules
and increasing concentrations of ZCSE enhance the hydrophobicity of
the shale surface which prevents the hydration and swelling of shale
formations.
A combination of cationic and anionic surfactants can reduce the
surface tension and enhance the contact angle with the shale surface.
Various experimental techniques were used to study the inhibition
mechanism with 0.1 wt% sodium dodecyl benzene sulfonate (SDBS)
and 0.2 wt% cetyltrimethylammonium bromide (CTAB). The results
show that at higher temperature and salinity conditions, the perfor-
mance of the surfactant decreases. The swelling rate of shale was
slightly greater than 7% in the presence of fresh water. While the
swelling rate of shale was greatly reduced in the presence of CTAB and
SDBS surfactants to approximately 4%. The results show that higher
temperature has less effect on the swelling rate of shale and surfactant
solution has a superior temperature tolerance. The surfactant molecules
of CTAB and SDBS were used in combination to improve the inhibition
performance. The anionic surfactant was used to reduce the surface
tension and to block the pores at the shale surface [195]. The CTAB
surfactant adsorbs on the surface of shale through ionic attractions
because CTAB contains positive charge and the shale surface has ne-
gative charges and both strongly attract each other. The hydrophilic
end of CTAB is oriented toward the solid shale surface while the hy-
drophobic end of the surfactant is oriented away from the shale surface
H.M. Ahmed, et al.
Fig. 28. Schematic adsorption of ZSCE on the shale surface [199]. ©Elsevier. Reproduced by permission of Elsevier.
which reduces the surface energy of shale and increases the contact
angle as shown in Figs. 28 and 29 [196].
In summary, the non-ionic and cationic surfactant molecules are
used to enhance the wellbore stability of shale formations by altering
the surface tension and wettability of shale. Most importantly, some of
the surfactants can be used for high temperature applications. Another
important benefit of surfactants in water-based drilling fluids is lower
toxicity, especially for marine drilling applications.
6. Challenges and future prospects
Shale inhibitors are extremely important to protect the wellbore
integrity during the drilling process of shale reservoirs. Previously, oil-
based drilling fluids were frequently employed for the drilling of shale
reservoirs and to minimize the invasion of drilling fluid into the for-
mations. Oil-based drilling fluids have superior shale inhibition capa-
city compared to the water-based drilling fluids and oil molecules of the
oil-based drilling fluid cannot penetrate into the tiny non-organic and
organic pores of shale formations during the drilling process. Further,
oil-based drilling fluids have better ability to protect the shale forma-
tions with minimum efforts in the drilling process. But, due to the strict
environmental regulations and the waste disposal issues of the ex-
tremely toxic oil-based drilling fluids, they cannot be directly disposed
in the land or in the oceans, which irrespective of legal implications
could affect the environment and marine life for years to come. In
comparison to oil-based drilling fluids, water-based drilling fluids are
considered environmentally friendly, low cost and, with shale in-
hibitors, they also have good inhibition properties. Recently, the oil and
Fig. 29. Mechanism of CTAB adsorption on the surface of shale [196]. ©Elsevier. Reproduced by permission of Elsevier.
212
Fuel 251 (2019) 187–217
gas industry has shifted their interest from vertical drilling processes to
horizontal or multilateral drilling process to enhance the production of
oil and gas. There are many challenges associated with conventionally
used shale inhibitors in water-based drilling fluids which include the
ammonia-based salts, quaternary alkyl ammonium salts, polyamines,
polyhydroxylated alkyl ammonium salt, quaternary amines, poly-
hydroxy diamines, and primary diamines.
Ammonium cations from the salt have a similar radius as potassium
cations and penetrate into the interlayers and replace the conventional
sodium or calcium cation from clay and act as shale inhibitor. The main
advantages of ammonia-based salts are that they are cheap and can be
employed with acidic and basic environments and applied in chloride
free environments. The main challenge associated with ammonia-based
salts is their thermal stability. Ammonia salts are pH sensitive and
temperature sensitive. They cannot be used at high temperatures
(150°F) and high pH conditions. However, most of the drilling opera-
tions are conducted at high temperature using high pH fluids. At these
conditions, odorous ammonia is produced because of the reaction of
ammonia-based salts.
Quaternary alkyl ammonium salts are the derivatives of ammonia
and are made by replacing the hydrogen of ammonia with an alkyl
group. This class shows better inhibition properties compared to the
ammonia salt inhibitors because these inhibitors have less odor and are
more effective at low concentrations. The simplest example of this class
of inhibitors is tetramethyl ammonium chloride. Quaternary ammo-
nium alkyl salt is extremely pH dependent and it shows good properties
at low pH levels. High molecular weight salts are not compatible with
anionic drilling fluids and affect the marine environment when used in
H.M. Ahmed, et al.
the offshore drilling operations. Among all the amine-based shale in-
hibitors, polyether amines are considered as excellent shale inhibitors
due to lower marine toxicity, compatibility with most of the water-
based drilling fluids, less ammonia odor, and high temperature stabi-
lity. Furthermore, the unique structure of polyether diamine is suitable
for the best inhibition properties of shale because PEA molecules easily
migrate between the interlayer spaces and replace the interlayer ca-
tions. To get the optimum performance with PEA, a less saline en-
vironment and absence of potassium chloride effectively enhance the
shale inhibition properties. The drilling industry has shifted their in-
terest towards the new materials such as polymers and polymer nano-
composites as drilling fluid additives due to the excellent inhibition
properties and fewer environmental impacts.
Polymers and polymer nanocomposites are widely employed as
drilling fluid additives and are also used as shale inhibitors. The se-
lection of polymer additives as shale inhibitors in the water-based
drilling fluid depends on ionic charge density of polymer chains.
Polymers containing a positive charge are preferred for shale inhibition
applications rather than using a polymer having no charge or a negative
charge on polymer chains. The copolymer has recently been used as a
multipurpose additive in the water-based drilling fluid in order to
modify the rheological properties, enhance the high temperature and
high pressure applications of drilling fluids as well as to modify the
inhibition properties of drilling fluids [108–110,197]. Several polymers
have been utilized in drilling fluids as additives for shale inhibition
applications such as poly glycols, zwitterionic polymers, and a cationic
polymer. Poly glycols, zwitterionic polymers, and cationic polymers
have limited applications in shale inhibition because these polymers are
severely affected by high salinity and high-temperature conditions.
Whereas in the absence of high temperature and high salinity, cationic
polymer shows enhanced shale inhibition. The cationic part of polymer
attached with the negatively charged surface and produce large size
agglomerates which suggest superior inhibition properties. Similarly,
polymer nanocomposites are also utilized in shale inhibition applica-
tions because of the presence of nanoparticles which have good thermal
stability and plug the pores of shale. Development of polymeric in-
hibitors that are stable under high salinity and high temperature en-
vironments will resolve several issues related to different types of in-
hibitors.
Recently, a new class of shale inhibitors “ionic liquids,” has been
suggested for shale inhibition applications in water-based drilling
fluids. Ionic liquids have excellent thermal stability for high-tempera-
ture reservoir applications. Furthermore, ionic liquids show superior
shale inhibition properties compared to the polymer-based and amine-
based shale inhibitors.
In summary, the polymers, polymer nanocomposites, and ionic li-
quids with high thermal stability are considered as promising shale
inhibitors for future applications in the drilling of oil and gas reservoirs.
However, the practical implementations of ionic liquids, copolymers,
and nanocomposites as shale inhibitors in drilling fluid additives need
to be considered. The synthesis cost of copolymers and polymer nano-
composites, their toxicity, and hazard analysis for real field applications
should be considered. Although there is limited literature available on
copolymers, polymer nanocomposites, and ionic liquids as shale in-
hibitors, the lab scale analysis of shale inhibition has proven them to a
strong candidate for shale inhibition applications in water-based dril-
ling fluids.
7. Concluding remarks
This article has mainly discussed recent progress and development
of water-based drilling fluid shale inhibitors. Various amine inhibitors,
polymer inhibitors, and ionic liquids as shale inhibitors have been
discussed in this article. There are a brief description and discussion
about the types of clays, their properties, and swelling characteristics.
The two types of clay swelling mechanisms including osmotic swelling
213
Fuel 251 (2019) 187–217
and crystalline swelling have been discussed in detail. Several techni-
ques were discussed in detail for characterizing shales and the perfor-
mance of shale inhibitors. The main literature discussed the amine-
based inhibitors, polymer-based inhibitors, and ionic liquid-based shale
inhibitors.
• The amine-based inhibitors are good compared to potassium
chloride which has been conventionally used for shale inhibition
applications.
• Ammonium compounds replace the interlayer cation and adsorb on
the negatively charged layers of shale. These amine-based inhibitors
were also useful for enhanced shale inhibition properties because
amine compounds compete with the water molecules in the shale
and prevent the shale from hydration and swelling.
• Amine inhibitors have several limitations including thermal stabi-
lity, pH sensitivity and cannot be used for marine environment ap-
plications of the drilling process.
• The polymer-based shale inhibitors are cheap, environmentally
friendly, less pH sensitive compared to the amine-based inhibitors
and have superior shale inhibition properties. Especially, cationic
polymers attach to the negatively charged layers of clay minerals in
the shale and protect them from hydration and swelling.
• The polymer also adsorbs on the shale formations in the wellbore
and makes a thin layer which prevents the invasion of drilling fluid
in shale formations.
• There are some limitations of using polymers in water-based drilling
fluids as shale inhibitors. The polymer can degrade at high-tem-
perature applications, especially cationic polymers result in the
flocculation of bentonite clay in the water-based drilling fluids
which causes the segregation of drilling fluid components.
• To avoid these limitations, high molecular weight copolymer has
recently been recommended.
Ionic liquids have evolved as a novel class of shale inhibitors and
their superior shale inhibition properties are comparable to the
amine inhibitors and polymeric shale inhibitors.
• Ionic liquids have high thermal stability up to 300 °C and have high
salt resistance in shale inhibition applications. Although there is
limited literature on ionic liquids and surfactant as shale inhibitors,
their remarkable shale inhibition properties make them a superior
class for shale inhibition applications.
• There are multiple applications of polymeric and low molecular
weight shale inhibitors. The specific application of a shale inhibitor
depends on the ionicity, molecular weight, interaction with the
shale surface and stability in the water-based drilling fluid.
• The selection of a shale inhibitor is done based on its solubility in
the drilling formulations, toxicity, and stability under high tem-
perature and pressure conditions.
References
[1] Saboorian-Jooybari H, Dejam M, Chen Z. Heavy oil polymer flooding from la-
boratory core floods to pilot tests and field applications: half-century studies. J
Petrol Sci Eng 2016;142:85–100.
[2] Saboorian-Jooybari H, Dejam M, Chen Z. Half-century of heavy oil polymer
flooding from laboratory core floods to pilot tests and field applications. SPE
Canada Heavy Oil Technical Conference. Society of Petroleum Engineers; 2015.
[3] Mashayekhizadeh V, Kord S, Dejam M. EOR potential within Iran. Special Topics &
Reviews in Porous Media. Int J 2014;5(4).
[4] Olayiwola SO, Dejam M. A comprehensive review on interaction of nanoparticles
with low salinity water and surfactant for enhanced oil recovery in sandstone and
carbonate reservoirs. Fuel 2019;241:1045–57.
[5] Olayiwola SO, Dejam M. Mathematical modelling of surface tension of nano-
particles in electrolyte solutions. Chem Eng Sci 2019;197:345–56.
[6] Olayiwola SO, Dejam M. Surface tension of nanoparticles in electrolyte solutions.
Bull Am Phys Soc 2018.
[7] Cao P-F, Mangadlao JD, Advincula RC. Stimuli-responsive polymers and their
potential applications in oil-gas industry. Polym Rev 2015;55(4):706–33.
[8] Mohammed AS. Effect of temperature on the rheological properties with shear
stress limit of iron oxide nanoparticle modified bentonite drilling muds. Egypt J
Pet 2016.
H.M. Ahmed, et al.
[9] Jain R, Mahto V. Evaluation of polyacrylamide/clay composite as a potential
drilling fluid additive in inhibitive water based drilling fluid system. J Petrol Sci
Eng 2015;133:612–21.
[10] Dias F, Souza R, Lucas E. Influence of modified starches composition on their
performance as fluid loss additives in invert-emulsion drilling fluids. Fuel
2015;140:711–6.
[11] Kelessidis VC, Tsamantaki C, Michalakis A, Christidis GE, Makri P, Papanicolaou K,
et al. Greek lignites as additives for controlling filtration properties of water–-
bentonite suspensions at high temperatures. Fuel 2007;86(7–8):1112–21.
[12] Alimohammadi N, Shadizadeh SR, Kazeminezhad I. Removal of cadmium from
drilling fluid using nano-adsorbent. Fuel 2013;111:505–9.
[13] Zhong H, Qiu Z, Huang W, Sun D, Zhang D, Cao J. Synergistic stabilization of shale
by a mixture of polyamidoamine dendrimers modified bentonite with various
generations in water-based drilling fluid. Appl Clay Sci 2015;114:359–69.
[14] Aftab A, Ismail AR, Ibupoto ZH. Enhancing the rheological properties and shale
inhibition behavior of water-based mud using nanosilica, multi-walled carbon
nanotube, and graphene nanoplatelet. Egypt J Pet 2017;26(2):291–9.
[15] Aftab A, Ismail AR, Ibupoto ZH, Akeiber H, Malghani MGK. Nanoparticles based
drilling muds a solution to drill elevated temperature wells: a review. Renew
Sustain Energy Rev 2017;76:1301–13.
[16] Baba Hamed S, Belhadri M. Rheological properties of biopolymers drilling fluids. J
Petrol Sci Eng 2009;67(3–4):84–90.
[17] Eutamene M, Benbakhti A, Khodja M, Jada A. Preparation and aqueous properties
of starch-grafted polyacrylamide copolymers. Starch – Stärke 2009;61(2):81–91.
[18] van Oort E. On the physical and chemical stability of shales. J Petrol Sci Eng
2003;38(3–4):213–35.
[19] Werner B, Myrseth V, Saasen A. Viscoelastic properties of drilling fluids and their
influence on cuttings transport. J Petrol Sci Eng 2017;156:845–51.
[20] Yuxiu A, Guancheng J, Yourong Q, Xianbin H, He S. High-performance shale
plugging agent based on chemically modified graphene. J Nat Gas Sci Eng
2016;32:347–55.
[21] Teixeira GT, Lomba RFT, Fontoura SA, Melendez VA, Ribeiro E, Francisco AD,
et al. Material for wellbore strengthening and fluid losses mitigation in deepwater
drilling scenario. SPE Deepwater Drilling and Completions Conference. Society of
Petroleum Engineers; 2014.
[22] Amirian E, Dejam M, Chen Z. Performance forecasting for polymer flooding in
heavy oil reservoirs. Fuel 2018;216:83–100.
[23] Dejam M. Advective-diffusive-reactive solute transport due to non-Newtonian fluid
flows in a fracture surrounded by a tight porous medium. Int J Heat Mass Transf
2019;128:1307–21.
[24] Dejam M. Dispersion in non-Newtonian fluid flows in a conduit with porous walls.
Chem Eng Sci 2018;189:296–310.
[25] Dzialowski A, Hale A, Mahajan S. Lubricity and wear of shale: effects of drilling
fluids and mechanical parameters. SPE/IADC Drilling Conference. Society of
Petroleum Engineers; 1993.
[26] Anderson R, Ratcliffe I, Greenwell H, Williams P, Cliffe S, Coveney P. Clay swel-
ling—a challenge in the oilfield. Earth Sci Rev 2010;98(3–4):201–16.
[27] Gholami R, Elochukwu H, Fakhari N, Sarmadivaleh M. A review on borehole in-
stability in active shale formations: interactions, mechanisms and inhibitors. Earth
Sci Rev 2018;177:2–13.
[28] Boek E, Coveney P, Skipper N. Monte Carlo molecular modeling studies of hy-
drated Li-, Na-, and K-smectites: understanding the role of potassium as a clay
swelling inhibitor. J Am Chem Soc 1995;117(50):12608–17.
[29] Ouadfeul S-A, Aliouane L. Wellbore stability in shale gas reservoirs, a case study
from the Barnett Shale. SPE North Africa Technical Conference and Exhibition.
Society of Petroleum Engineers; 2015.
[30] Sehly K, Chiew H-L, Li H, Song A, Leong Y-K, Huang W. Stability and ageing be-
haviour and the formulation of potassium-based drilling muds. Appl Clay Sci
2015;104:309–17.
[31] Su J, Chu Q, Ren M. Properties of high temperature resistance and salt tolerance
drilling fluids incorporating acrylamide/2-acrylamido-2-methyl-1-propane sul-
fonic acid/N-vinylpyrrolidone/dimethyl diallyl ammonium chloride quad-
ripolymer as fluid loss additives. J Polym Eng 2014;34(2):153–9.
[32] Ghassem A, Nickdel T. Effects of salinity, PH and temperature on CMC polymer
and XC polymer performance. Int J Eng Trans B 2007;20(3):283–90.
[33] Sepehri S, Soleyman R, Varamesh A, Valizadeh M, Nasiri A. Effect of synthetic
water-soluble polymers on the properties of the heavy water-based drilling fluid at
high pressure-high temperature (HPHT) conditions. J Petrol Sci Eng
2018;166:850–6.
[34] Caenn R, Chillingar GV. Drilling fluids: state of the art. J Petrol Sci Eng
1996;14(3):221–30.
[35] De Souza CEC, Lima AS, Nascimento RSV. Hydrophobically modified poly (ethy-
lene glycol) as reactive clays inhibitor additive in water-based drilling fluids. J
Appl Polym Sci 2010;117(2):857–64.
[36] Stamatakis E, Thaemlitz C, Coffin G, Reid W. A new generation of shale inhibitors
for water-based muds. SPE/IADC Drilling Conference. Society of Petroleum
Engineers; 1995.
[37] Van Oort E. On the physical and chemical stability of shales. J Petrol Sci Eng
2003;38(3):213–35.
[38] Zhang LM, Tan YB, Li ZM. Multifunctional characteristics of new carbox-
ymethylcellulose-based graft copolymers for oilfield drilling. J Appl Polym Sci
2000;77(1):195–201.
[39] Bai X, Zhang X, Koutsos V, Fu Z, Ning T, Luo Y, et al. Preparation and evaluation of
amine terminated polyether shale inhibitor for water-based drilling fluid. SN Appl
Sci 2019;1(1):94.
[40] Qasemi M, Moslemizadeh A, Shahbazi K, Mohammadzadeh O, Zendehboudi S,
214
Fuel 251 (2019) 187–217
Jafari S. Primary evaluation of a natural surfactant for inhibiting clay swelling. J
Petrol Sci Eng 2019.
[41] Moslemizadeh A, Samadzadeh Hafshejani K, Shahbazi K, Zaravi Dezfuli M,
Zendehboudi S. A biosurfactant for inhibiting clay hydration in aqueous solutions:
applications to petroleum industry. Canad J Chem Eng 2019;97(1):384–94.
[42] Guo W-Y, Peng B. Synthesis and characterization of starch-graft-polyacrylamide
copolymers and their application as filtration control agents in drilling fluid. J
Vinyl Add Tech 2012;18(4):261–6.
[43] Jain R, Mahto V, Mahto TK. Study of the effect of xanthan gum based graft co-
polymer on water based drilling fluid. J Macromol Sci A 2014;51(12):976–82.
[44] Jain R, Paswan BK, Mahto TK, Mahto V. Study the effect of synthesized graft co-
polymer on the inhibitive water based drilling fluid system. Egypt J Pet 2015.
[45] Anderson RL, Ratcliffe I, Greenwell HC, Williams PA, Cliffe S, Coveney PV. Clay
swelling — a challenge in the oilfield. Earth Sci Rev 2010;98(3):201–16.
[46] Zhang L, Li T, Huang L, Ye Z, Ye Z, Yan X, et al. Preparation and application of
melamine cross-linked poly ammonium as shale inhibitor. Chem Cent J
2018;12(1):44.
[47] Zhengqin Y, Zhongbin Y, Lei H, Yun B, Lili L, Jie Z, et al. Preparation and appli-
cation of a new crosslinked polyammonium as a shale inhibitor. J Appl Biomater
Funct Mater 2018;16(1_suppl):119–24.
[48] Choo KY, Bai K. Effects of bentonite concentration and solution pH on the rheo-
logical properties and long-term stabilities of bentonite suspensions. Appl Clay Sci
2015;108:182–90.
[49] Kotal M, Bhowmick AK. Polymer nanocomposites from modified clays: recent
advances and challenges. Prog Polym Sci 2015;51:127–87.
[50] Brigatti M, Galan E, Theng B. Structure and mineralogy of clay minerals.
Developments in Clay Science. Elsevier; 2013. p. 21–81.
[51] Benchabane A, Bekkour K. Effects of anionic additives on the rheological behavior
of aqueous calcium montmorillonite suspensions. Rheol Acta 2006;45(4):425–34.
[52] Avadiar L, Leong Y-K, Fourie A. Physicochemical behaviors of kaolin slurries with
and without cations—contributions of alumina and silica sheets. Coll Surf A
2015;468:103–13.
[53] Duc M, Gaboriaud F, Thomas F. Sensitivity of the acid–base properties of clays to
the methods of preparation and measurement: 1. Literature review. J Colloid
Interface Sci 2005;289(1):139–47.
[54] Murray HH. Chapter 2—structure and composition of the clay minerals and their
physical and chemical properties. Developments in Clay Science. Elsevier; 2006. p.
7–31.
[55] Alcázar-Vara LA, Cortés-Monroy IR. Drilling fluids for deepwater fields: an over-
view. Recent Insights in Petroleum Science and Engineering. InTech; 2018.
[56] Wilson M, Wilson L, Patey I. The influence of individual clay minerals on forma-
tion damage of reservoir sandstones: a critical review with some new insights. Clay
Miner 2014;49(2):147–64.
[57] Haile BG, Hellevang H, Aagaard P, Jahren J. Experimental nucleation and growth
of smectite and chlorite coatings on clean feldspar and quartz grain surfaces. Mar
Pet Geol 2015;68:664–74.
[58] Velbel MA, Barker WW. Pyroxene weathering to smectite: conventional and cryo-
field emission scanning electron microscopy, Koua Bocca ultramafic complex,
Ivory Coast. Clays Clay Miner 2008;56(1):112–27.
[59] Mondal D, Mollick MMR, Bhowmick B, Maity D, Bain MK, Rana D, et al. Effect of
poly (vinyl pyrrolidone) on the morphology and physical properties of poly (vinyl
alcohol)/sodium montmorillonite nanocomposite films. Progr Nat Sci: Mater Int
2013;23(6):579–87.
[60] Jain R, Mahto V, Sharma VP. Evaluation of polyacrylamide-grafted-polyethylene
glycol/silica nanocomposite as potential additive in water based drilling mud for
reactive shale formation. J Nat Gas Sci Eng 2015;26:526–37.
[61] Liu F, Jiang G, Peng S, He Y, Wang J. Amphoteric polymer as an anti-calcium
contamination fluid-loss additive in water-based drilling fluids. Energy Fuels
2016;30(9):7221–8.
[62] Zhao S, Yan J, Wang J, Ding T, Yang H, Gao D. Water-based drilling fluid tech-
nology for extended reach wells in Liuhua Oilfield, South China Sea. Pet Sci
Technol 2009;27(16):1854–65.
[63] Zhao X, Qiu Z, Zhang Y, Zhong H, Huang W, Tang Z. Zwitterionic polymer P(AM-
DMC-AMPS) as a low-molecular-weight encapsulator in deepwater drilling fluid.
Appl Sci 2017;7(6):594.
[64] Zhong H, Qiu Z, Tang Z, Zhang X, Xu J, Huang W. Study of 4, 4′-methylenebis-
cyclohexanamine as a high temperature-resistant shale inhibitor. J Mater Sci
2016;51(16):7585–97.
[65] Patel A, Stamatakis E, Friedheim JE, Davis E. Highly inhibitive water-based fluid
system provides superior chemical stabilization of reactive shale formations.
National Drilling Conference. 2001.
[66] Young S, Maas T. Novel polymer chemistry increases shale stability AADE 01-NC-
HO-41, Houston (TX), March 27-29. Drilling Technology, American Association of
Drilling EngineersAADE National Drilling Technical Conference. 2001.
[67] Xu J, Qiu Z, Huang W, Zhao X. Preparation and performance properties of polymer
latex SDNL in water-based drilling fluids for drilling troublesome shale formations.
J Nat Gas Sci Eng 2017;37:462–70.
[68] Al-Bazali T. A novel experimental technique to monitor the time-dependent water
and ions uptake when shale interacts with aqueous solutions. Rock Mech Rock Eng
2012;46(5):1145–56.
[69] An Y, Jiang G, Ren Y, Zhang L, Qi Y, Ge Q. An environmental friendly and bio-
degradable shale inhibitor based on chitosan quaternary ammonium salt. J Petrol
Sci Eng 2015;135:253–60.
[70] Zhong H, Qiu Z, Zhang D, Tang Z, Huang W, Wang W. Inhibiting shale hydration
and dispersion with amine-terminated polyamidoamine dendrimers. J Nat Gas Sci
Eng 2016;28:52–60.
H.M. Ahmed, et al.
[71] Zhong H, Qiu Z, Sun D, Zhang D, Huang W. Inhibitive properties comparison of
different polyetheramines in water-based drilling fluid. J Nat Gas Sci Eng
2015;26:99–107.
[72] Xie G, Luo P, Deng M, Su J, Wang Z, Gong R, et al. Intercalation behavior of
branched polyethyleneimine into sodium bentonite and its effect on rheological
properties. Appl Clay Sci 2017;141:95–103.
[73] Zhong H, Qiu Z, Huang W, Cao J. Poly (oxypropylene)-amidoamine modified
bentonite as potential shale inhibitor in water-based drilling fluids. Appl Clay Sci
2012;67–68:36–43.
[74] Koteeswaran S, Pashin JC, Ramsey JD, Clark PE. Quantitative characterization of
polyacrylamide–shale interaction under various saline conditions. Pet Sci
2017;14(3):586–96.
[75] Mohan KK, Fogler HS. Effect of pH and layer charge on formation damage in
porous media containing swelling clays. Langmuir ACS J Surf Coll
1997;13(10):2863–72.
[76] J-g Xu, Qiu Z, Zhao X, Huang W. Hydrophobic modified polymer based silica
nanocomposite for improving shale stability in water-based drilling fluids. J Petrol
Sci Eng 2017;153:325–30.
[77] Stephens M, Gomez-Nava S, Churan M. Laboratory methods to assess shale re-
activity with drilling fluids. American Association of Drilling Engineers. National
Technical Conference & Exhibition, New Orleans, Louisiana. 2009.
[78] Balaban RdC, Vidal ELF, Borges MR. Design of experiments to evaluate clay
swelling inhibition by different combinations of organic compounds and inorganic
salts for application in water base drilling fluids. Appl Clay Sci
2015;105–106:124–30.
[79] Taylor K, Burke R, Nasr-El-Din H, Schramm L. Development of a flow injection
analysis method for the determination of acrylamide copolymers in oilfield brines.
SPE International Symposium on Oilfield Chemistry. Society of Petroleum
Engineers; 1995.
[80] Clark R, Scheuerman R, Rath H, Van Laar H. Polyacrylamide/potassium-chloride
mud for drilling water-sensitive shales. J Petrol Technol 1976;28(06):719–27.
[81] McKenzie LF, McElfresh PM. Acrylamide/acrylic acid copolymers for cement fluid
loss control. SPE oilfield and geothermal chemistry symposium. Society of
Petroleum Engineers; 1982.
[82] Zhong HY, Qiu ZS, Huang WA, Qiao J, Li HB, Cao J. The development and ap-
plication of a novel polyamine water-based drilling fluid. Pet Sci Technol
2013;32(4):497–504.
[83] Ni X, Liu Z, Wei J. Quantitative evaluation of the impacts of drilling mud on the
damage degree to the permeability of fractures at different scales in coal re-
servoirs. Fuel 2019;236:382–93.
[84] Chenevert M. Shale control with balanced-activity oil-continuous muds. J Petrol
Technol 1970;22(10). 1,309–1,16.
[85] Barati P, Keshtkar S, Aghajafari A, Shahbazi K, Momeni A. Inhibition performance
and mechanism of Horsetail extract as shale stabilizer. Pet Explor Dev
2016;43(3):522–7.
[86] Erkekol S, Gucuyener IH, Kok MV. An experimental investigation on the chemical
stability of selected formation and determination of the proper type of water-base
drilling fluids. Part 1. Descriptive tests. Energy Sour A 2006;28(9):875–83.
[87] Khodja M, Canselier JP, Bergaya F, Fourar K, Khodja M, Cohaut N, et al. Shale
problems and water-based drilling fluid optimisation in the Hassi Messaoud
Algerian oil field. Appl Clay Sci 2010;49(4):383–93.
[88] Oliveira CIRd, Rocha MCG, Silva ALNd, Bertolino LC. Characterization of bento-
nite clays from Cubati, Paraíba (Northeast of Brazil). Cerâmica
2016;62(363):272–7.
[89] O'Brien DE, Chenevert ME. Stabilizing sensitive shales with inhibited, potassium-
based drilling fluids. J Petrol Technol 1973;25(09). 1,089–1,100.
[90] Caenn R, Darley HC, Gray GR. Composition and properties of drilling and com-
pletion fluids. Gulf professional publishing; 2011.
[91] Kamal MS, Sultan AS, Al-Mubaiyedh UA, Hussein IA. Review on polymer flooding:
rheology, adsorption, stability, and field applications of various polymer systems.
Polym Rev 2015;55(3):491–530.
[92] Dehghanpour H, Kuru E. A New Look at the viscoelastic fluid flow in porous
media: a possible mechanism of internal cake formation and formation-damage
control. SPE International Symposium on Oilfield Chemistry. The Woodlands.
Texas: Society of Petroleum Engineers; 2009. p. 15.
[93] Retz R, Friedheim J, Lee L, Welch O. An environmentally acceptable and field-
practical, cationic polymer mud system. Offshore Europe: Society of Petroleum
Engineers; 1991.
[94] Zhong H, Qiu Z, Huang W, Cao J. Shale inhibitive properties of polyether diamine
in water-based drilling fluid. J Petrol Sci Eng 2011;78(2):510–5.
[95] Villabona-Estupiñán S, de Almeida Rodrigues J, Nascimento RSV. Understanding
the clay-PEG (and hydrophobic derivatives) interactions and their effect on clay
hydration and dispersion: a comparative study. Appl Clay Sci 2017;143:89–100.
[96] Aston M, Elliott G. Water-based glycol drilling muds: shale inhibition mechanisms.
European petroleum conference. Society of Petroleum Engineers; 1994.
[97] Quintero L. An overview of surfactant applications in drilling fluids for the pet-
roleum industry. J Dispers Sci Technol 2002;23(1–3):393–404.
[98] Bloys B, Davis N, Smolen B, Bailey L, Houwen O, Reid P, et al. Designing and
managing drilling fluid. Oilfield Rev 1994;6(2):33–43.
[99] Liu S, Mo X, Zhang C, Sun D, Mu C. Swelling inhibition by polyglycols in mon-
tmorillonite dispersions. J Dispers Sci Technol 2004;25(1):63–6.
[100] Toulhoat H, Lecourtier J. Physical chemistry of colloids and interfaces in oil
production: proceedings of the 6th IFP exploration and production research con-
ference, Held in Saint-Raphaël, September 4–6, 1991. Editions Technip; 1992.
[101] Bailey L, Keall M, Audibert A, Lecourtier J. Effect of clay/polymer interactions on
shale stabilization during drilling. Langmuir ACS J Surf Colloids
215
Fuel 251 (2019) 187–217
1994;10(5):1544–9.
[102] Reid P, Dolan B, Cliffe S. Mechanism of shale inhibition by polyols in water based
drilling fluids. SPE International symposium on oilfield chemistry. Society of
Petroleum Engineers; 1995.
[103] Bland R, Smith GL, Eagark P, van Oort E, Dharma N. Low salinity polyglycol
water-based drilling fluids as alternatives to oil-based muds. SPE/IADC Asia
Pacific Drilling Technology. Society of Petroleum Engineers; 1996.
[104] Ferreira CC, Teixeira GT, Lachter ER, Nascimento RSV. Partially hydrophobized
hyperbranched polyglycerols as non-ionic reactive shale inhibitors for water-based
drilling fluids. Appl Clay Sci 2016;132:122–32.
[105] Kosynkin DV, Ceriotti G, Wilson KC, Lomeda JR, Scorsone JT, Patel AD, et al.
Graphene oxide as a high-performance fluid-loss-control additive in water-based
drilling fluids. ACS Appl Mater Interfaces 2011;4(1):222–7.
[106] Razali S, Yunus R, Rashid SA, Lim H, Jan BM. Review of biodegradable synthetic-
based drilling fluid: progression, performance and future prospect. Renew Sustain
Energy Rev 2018;90:171–86.
[107] < Water-Soluble Acrylamide Sulfonate Copolymer for Inhibiting Shale hydration.
pdf > .
[108] Ahmad HM, Kamal MS, Murtaza M, Al-Harthi MA. Improving the drilling fluid
properties using nanoparticles and water-soluble polymers. SPE kingdom of Saudi
Arabia annual technical symposium and exhibition. Society of Petroleum
Engineers; 2017.
[109] Ahmad HM, Kamal MS, Al-Harthi MA. High molecular weight copolymers as
rheology modifier and fluid loss additive for water-based drilling fluids. J Mol Liq
2018;252:133–43.
[110] Ahmad HM, Kamal MS, Al-Harthi MA. Rheological and filtration properties of
clay-polymer systems: impact of polymer structure. Appl Clay Sci
2018;160:226–37.
[111] Ahmad HM, Kamal MS, Al-Harthi MA. Effect of thermal aging and electrolyte on
bentonite dispersions: rheology and morphological properties. J Mol Liq
2018;269:278–86.
[112] Ahmad HM, Kamal MS, Al-Harthi MA, Elkatatny SM, Murtaza MM. Synthesis and
experimental investigation of novel CNT-polymer nanocomposite to enhance
borehole stability at high temperature drilling applications. SPE Kingdom of Saudi
Arabia Annual Technical Symposium and Exhibition. Dammam, Saudi Arabia:
Society of Petroleum Engineers; 2018. p. 17.
[113] Yousefvand HA, Jafari A. Stability and flooding analysis of nanosilica/NaCl/
HPAM/SDS solution for enhanced heavy oil recovery. J Petrol Sci Eng
2018;162:283–91.
[114] Xu J-g, Qiu Z-s, Zhao X, Zhong H-y, Li G-r, Huang W-a. Synthesis and character-
ization of shale stabilizer based on polyethylene glycol grafted nano-silica com-
posite in water-based drilling fluids. J Petrol Sci Eng 2018;163:371–7.
[115] J-g Xu, Qiu Z, Zhao X, Mou T, Zhong H, Huang W. A polymer microsphere
emulsion as a high-performance shale stabilizer for water-based drilling fluids.
RSC Adv. 2018;8(37):20852–61.
[116] Zhang X, Liu J. Effect of arabic gum and xanthan gum on the stability of pesticide
in water emulsion. J Agric Food Chem 2011;59(4):1308–15.
[117] Jayme M, Dunstan D, Gee M. Zeta potentials of gum arabic stabilised oil in water
emulsions. Food Hydrocolloids 1999;13(6):459–65.
[118] Franklin J, Chandra R. The slake-durability test. International Journal of Rock
Mechanics and Mining Sciences & Geomechanics Abstracts. Elsevier; 1972. p.
325–8.
[119] de Carvalho Balaban R, Vidal ELF, Borges MR. Design of experiments to evaluate
clay swelling inhibition by different combinations of organic compounds and in-
organic salts for application in water base drilling fluids. Appl Clay Sci
2015;105:124–30.
[120] Patel A, Stamatakis S, Young S, Friedheim J. Advances in inhibitive water-based
drilling fluids—can they replace oil-based muds? International Symposium on
Oilfield Chemistry. Society of Petroleum Engineers; 2007.
[121] Jain R, Mahto V. Formulation of a water based drilling fluid system with syn-
thesized graft copolymer for troublesome shale formations. J Nat Gas Sci Eng
2017;38:171–81.
[122] Patel AD. Design and development of quaternary amine compounds: shale in-
hibition with improved environmental profile. SPE International Symposium on
Oilfield Chemistry. Society of Petroleum Engineers; 2009.
[123] Schlemmer R. Progression of water-based fluids based on amine chemistry-can the
road lead to true oil mud replacement April 1-3, 2003 AADE National Drilling
Conference, Houston. 2003.
[124] Gomez SL, Patel A. Shale inhibition: what works? SPE International Symposium on
Oilfield Chemistry. Society of Petroleum Engineers; 2013.
[125] Amanullah M. Dendrimers and dendritic polymers-application for superior and
intelligent fluid development for oil and gas field applications. SPE Middle East Oil
and Gas Show and Conference. Society of Petroleum Engineers; 2013.
[126] Zhong H, Qiu Z, Huang W, Cao J. Poly (oxypropylene)-amidoamine modified
bentonite as potential shale inhibitor in water-based drilling fluids. Appl Clay Sci
2012;67:36–43.
[127] Qu Y, Lai X, Zou L, Yn Su. Polyoxyalkyleneamine as shale inhibitor in water-based
drilling fluids. Appl Clay Sci 2009;44(3–4):265–8.
[128] Suter J, Coveney P, Anderson R, Greenwell H, Cliffe S. Rule based design of clay-
swelling inhibitors. Energy Environ Sci 2011;4(11):4572–86.
[129] Huang M, Fang Y, Li R, Huang T, Yu Z, Xia H. Synthesis and properties of liquid
polycarbosilanes with hyperbranched structures. J Appl Polym Sci
2009;113(3):1611–8.
[130] Essawy HA, Mohamed HA, Elsayed NH. Upgrading the adhesion properties of a
fast-curing epoxy using hydrophilic/hydrophobic hyperbranched poly (amidoa-
mine) s. J Appl Polym Sci 2013;127(6):4505–14.
H.M. Ahmed, et al.
[131] Cao Q, Liao L, Xu H. Study on the influence of thermal characteristics of hyper-
branched polyurethane phase change materials for energy storage. J Appl Polym
Sci 2010;115(4):2228–35.
[132] Gao C, Yan D. Hyperbranched polymers: from synthesis to applications. Prog
Polym Sci 2004;29(3):183–275.
[133] Bai X, Wang H, Luo Y, Zheng X, Zhang X, Zhou S, et al. The structure and appli-
cation of amine-terminated hyperbranched polymer shale inhibitor for water-
based drilling fluid. J Appl Polym Sci 2017;134(46):45466.
[134] Rehim MHA, Youssef AM, Essawy HA. Hybridization of kaolinite by consecutive
intercalation: preparation and characterization of hyperbranched poly (amidoa-
mine)–kaolinite nanocomposites. Mater Chem Phys 2010;119(3):546–52.
[135] Mo Z, Niu G, Chen H, Wu Y. Synthesis and characterization of hyperbranched poly
(amine-ester)/lanthanum/montmorillonite nanocomposites. Mater Lett
2008;62(10–11):1743–6.
[136] Kaiser A. Environmentally friendly emulsion breakers: vision or reality? SPE
International Symposium on Oilfield Chemistry. Society of Petroleum Engineers;
2013.
[137] Rivers GT, Tian J, Trenery JB. Kinetic gas hydrate inhibitors in completion fluids.
2011. Google Patents.
[138] Stanciu C, Vo L, Nguyen P, Weaver J. Maintaining well productivity through
controlling fines migration and scale formation. EUROPEC 2015. Society of
Petroleum Engineers; 2015.
[139] Lai N, Qin X, Ye Z, Peng Q, Zhang Y, Ming Z. Synthesis and evaluation of a water-
soluble hyperbranched polymer as enhanced oil recovery chemical. J Chem
2013;2013.
[140] Li L, Ma C, Yuan X, Fan J, Yang Y, Li Y. Synthesis and application of dendrimers in
oilfield chemistry. Modern Chem Ind 2012;32(6):16–21.
[141] Garea SA, Ghebaur A, Vasile E. Hybrid materials based on dendritic polymer and
halloysite. Mater Plast 2014;51(1):12–6.
[142] Ritter A, Geraut R. New optimization drilling fluid programs for reactive shale
formations. SPE Annual Technical Conference and Exhibition. Society of
Petroleum Engineers; 1985.
[143] Xie G, Luo P, Deng M, Su J, Wang Z, Gong R, et al. Investigation of the inhibition
mechanism of the number of primary amine groups of alkylamines on the swelling
of bentonite. Appl Clay Sci 2017;136:43–50.
[144] Tang X, Zhang J, Wang X, Yu B, Ding W, Xiong J, et al. Shale characteristics in the
southeastern Ordos Basin, China: implications for hydrocarbon accumulation
conditions and the potential of continental shales. Int J Coal Geol 2014;128:32–46.
[145] Poghosyan AH, Arsenyan LH, Antonyan LA, Shahinyan AA, Koetz J. Molecular
dynamics simulations of branched polyethyleneimine in water-in-heptanol mi-
celles stabilized by zwitterionic surfactants. Colloids Surf A 2015;479:18–24.
[146] Neville F, Murphy T, Wanless EJ. The formation of poly-
ethyleneimine–trimethoxymethylsilane organic–inorganic hybrid particles.
Colloids Surf A 2013;431:42–50.
[147] Foundas M, Britcher LJ, Fornasiero D, Morris GE. Effects of poly-
ethyleneimine–phosphonate–carboxylic copolymers on the dispersion of boehmite
particles. Colloids Surf A 2015;466:10–7.
[148] Rajagopalan B, Oh ES, Chung JS. The effect of diethylenetriamine on the sol-
vothermal reactions of polyethyleneimine-graphene oxide/lithium titanate nano-
composites for lithium battery anode. J Power Sources 2015;275:702–11.
[149] Wang C, Bao X, Ding X, Ding Y, Abbad S, Wang Y, et al. A multifunctional self-
dissociative polyethyleneimine derivative coating polymer for enhancing the gene
transfection efficiency of DNA/polyethyleneimine polyplexes in vitro and in vivo.
Polym Chem 2015;6(5):780–96.
[150] Wang C, Fang S, Duan M, Xiong Y, Ma Y, Chen W. Synthesis and evaluation of
demulsifiers with polyethyleneimine as accepter for treating crude oil emulsions.
Polym Adv Technol 2015;26(5):442–8.
[151] Adewunmi AA, Ismail S, Sultan AS. Study on strength and gelation time of poly-
acrylamide/polyethyleneimine composite gels reinforced with coal fly ash for
water shut-off treatment. J Appl Polym Sci 2015;132(5).
[152] Zhu D, Li X, Liao X, Shi B. Polyethyleneimine-grafted collagen fiber as a carrier for
cell immobilization. J Ind Microbiol Biotechnol 2015;42(2):189–96.
[153] Li K, Jiang J, Tian S, Yan F, Chen X. Polyethyleneimine–nano silica composites: a
low-cost and promising adsorbent for CO 2 capture. J Mater Chem A
2015;3(5):2166–75.
[154] Liu J, Liu G, Liu W, Wang Y. Turn-on fluorescence sensor for the detection of
heparin based on rhodamine B-modified polyethyleneimine–graphene oxide
complex. Biosens Bioelectron 2015;64:300–5.
[155] Sunintaboon P, Duangphet S, Tangboriboonrat P. Polyethyleneimine-functiona-
lized poly (methyl methacrylate) colloidal nanoparticles for directly coating nat-
ural rubber sheet. Colloids Surf A 2009;350(1–3):114–20.
[156] Guancheng J, Yourong Q, Yuxiu A, Xianbin H, Yanjun R. Polyethyleneimine as
shale inhibitor in drilling fluid. Appl Clay Sci 2016;127–128:70–7.
[157] Guerrero M, Guerrero X. Use of amine/PHPA system to drill high reactive shales in
the Orito field in Colombia. International oil conference and exhibition in Mexico.
Society of Petroleum Engineers; 2006.
[158] Ramirez MA, Moura EM, Aragao AFL, Taira HS. HPWBM as a technical alternative
to drill challenging wells project: lessons learned in deepwater Brazil. Latin
American & Caribbean petroleum engineering conference. Society of Petroleum
Engineers; 2007.
[159] Ramirez MA, Sanchez G, Preciado Sarmiento OE, Santamaria J, Luna E.
Aluminum-based HPWBM successfully replaces oil-based mud to drill exploratory
wells in an environmentally sensitive area. SPE Latin American and Caribbean
Petroleum Engineering Conference. Society of Petroleum Engineers; 2005.
[160] Watson P, Meize B, Aldea C, Eastern Blackwell B. Gulf of Mexico: inhibitive water-
based drilling fluid sets ultra-deepwater records. IADC/SPE drilling conference.
216
Fuel 251 (2019) 187–217
Society of Petroleum Engineers; 2004.
[161] Gomez SL, He W. Fighting Wellbore Instability: Customizing Drilling Fluids Based
on Laboratory Studies of Shale-Fluid Interactions. Society of Petroleum Engineers.
[162] Amanullah M. Dendrimers and Dendritic Polymers – Application for Superior and
Intelligent Fluid Development for Oil and Gas Field Applications. Society of
Petroleum Engineers.
[163] Patel A, Stamatakis S, Young S, Friedheim J. Advances in Inhibitive Water-Based
Drilling Fluids—Can They Replace Oil-Based Muds?: Society of Petroleum
Engineers.
[164] Lin J-J, Chen Y-M, Yu M-H. Hydrogen-bond driven intercalation of synthetic
fluorinated mica by poly (oxypropylene)-amidoamine salts. Colloids Surf, A
2007;302(1–3):162–7.
[165] Takahashi T, Yamada Y, Kataoka K, Nagasaki Y. Preparation of a novel PEG–clay
hybrid as a DDS material: dispersion stability and sustained release profiles. J
Control Release 2005;107(3):408–16.
[166] Yalçın T, Alemdar A, Ece ÖI, Güngör N. The viscosity and zeta potential of ben-
tonite dispersions in presence of anionic surfactants. Mater Lett 2002;57(2):420–4.
[167] Duman O, Tunç S, Çetinkaya A. Electrokinetic and rheological properties of kao-
linite in poly (diallyldimethylammonium chloride), poly (sodium 4-styrene sul-
fonate) and poly (vinyl alcohol) solutions. Colloids Surf, A 2012;394:23–32.
[168] Wang J, Liu G, Wang L, Li C, Xu J, Sun D. Synergistic stabilization of emulsions by
poly (oxypropylene) diamine and Laponite particles. Colloids Surf, A
2010;353(2–3):117–24.
[169] Wang L, Liu S, Wang T, Sun D. Effect of poly (oxypropylene) diamine adsorption
on hydration and dispersion of montmorillonite particles in aqueous solution.
Colloids Surf, A 2011;381(1–3):41–7.
[170] Lummus J, Azar J. Drilling fluids optimization: a practical field approach. Tulsa,
EUA: PennWell Publ. Co; 1986.
[171] Himes RE, Vinson EF. Fluid additive and method for treatment of subterranean
formations. 1989. Google Patents.
[172] Brady M, Craster B, Getliff J, Reid P. Highly inhibitive, low-salinity glycol water-
base drilling fluid for shale drilling in environmentally sensitive locations. SPE
International Conference on health, safety, and environment in oil and gas ex-
ploration and production. Society of Petroleum Engineers; 1998.
[173] Gholizadeh-Doonechaly N, Tahmasbi K, Davani E. Development of high-perfor-
mance water-based mud formulation based on amine derivatives. SPE
International symposium on oilfield chemistry. Society of Petroleum Engineers;
2009.
[174] Patel AD, Thaemlitz CJ, McLaurine HC, Stamatakis E. Drilling fluid additive and
method for inhibiting hydration. 1999. Google Patents.
[175] Patel AD, Stamatakis E, Davis E. Shale hydration inhibition agent and method of
use. 2001. Google Patents.
[176] Chen G, Yan J, Lili L, Zhang J, Gu X, Song H. Preparation and performance of
amine-tartaric salt as potential clay swelling inhibitor. Appl Clay Sci
2017;138:12–6.
[177] Yu H, Hu W, Guo G, Huang L, Li L, Gu X, et al. Investigation of melamine derived
quaternary as ammonium salt potential shale inhibitor. IOP Conf Series Earth
Environ Sci 2017;69:012065.
[178] Onuoha IEO, Bilgesu HI, Ameri S. Study of drilling fluid additives and their impact
on smectite inhibition, marcellus shale inhibition, and filtration and rheological
properties of bentonite based drilling fluids. SPE eastern regional meeting. Society
of Petroleum Engineers; 2011.
[179] Srivastava A, Prasad R. Triglycerides-based diesel fuels. Renew Sustain Energy Rev
2000;4(2):111–33.
[180] Yang L, Jiang G, Shi Y, Yang X. Application of ionic liquid and polymeric ionic
liquid as shale hydration inhibitors. Energy Fuels 2017;31(4):4308–17.
[181] Nasser M, Onaizi SA, Hussein I, Saad M, Al-Marri M, Benamor A. Intercalation of
ionic liquids into bentonite: swelling and rheological behaviors. Colloids Surf, A
2016;507:141–51.
[182] Luo Z, Pei J, Wang L, Yu P, Chen Z. Influence of an ionic liquid on rheological and
filtration properties of water-based drilling fluids at high temperatures. Appl Clay
Sci 2017;136:96–102.
[183] Luo Z, Wang L, Yu P, Chen Z. Experimental study on the application of an ionic
liquid as a shale inhibitor and inhibitive mechanism. Appl Clay Sci
2017;150:267–74.
[184] Berry SL, Boles JL, Brannon HD, Beall BB. Performance evaluation of ionic liquids
as a clay stabilizer and shale inhibitor. SPE international symposium and exhibi-
tion on formation damage control. Society of Petroleum Engineers; 2008.
[185] Zhao Q, Choo H, Bhatt A, Burns SE, Bate B. Review of the fundamental geo-
chemical and physical behaviors of organoclays in barrier applications. Appl Clay
Sci 2017;142:2–20.
[186] Barati P, Shahbazi K, Kamari M, Aghajafari A. Shale hydration inhibition char-
acteristics and mechanism of a new amine-based additive in water-based drilling
fluids. Petroleum 2017.
[187] Wagner H, Luther R, Mang T. Lubricant base fluids based on renewable raw ma-
terials: their catalytic manufacture and modification. Appl Catal A
2001;221(1–2):429–42.
[188] Huang W, Li X, Qiu Z, Jia J, Wang Y, Li X. Inhibiting the surface hydration of shale
formation using preferred surfactant compound of polyamine and twelve alkyl two
hydroxyethyl amine oxide for drilling. J Petrol Sci Eng 2017;159:791–8.
[189] Alemdar A, Öztekin N, Güngör N, Ece ÖI, Erim FB. Effects of polyethyleneimine
adsorption on the rheological properties of purified bentonite suspensions.
Colloids Surf, A 2005;252(2–3):95–8.
[190] Niessen WR. Combustion and incineration processes: applications in environ-
mental engineering. CRC Press; 2010.
[191] Mujumdar AS. Handbook of industrial drying. CRC Press; 2006.
H.M. Ahmed, et al.
[192] Chiou D, Langrish T. Crystallization of amorphous components in spray-dried
powders. Drying Technol 2007;25(9):1427–35.
[193] Kjellin M, Johansson I. Surfactants from renewable resources. John Wiley & Sons;
2010.
[194] Stanimirova R, Marinova K, Tcholakova S, Denkov N, Stoyanov S, Pelan E. Surface
rheology of saponin adsorption layers. Langmuir ACS J Surf Colloids
2011;27(20):12486–98.
[195] Bi Z, Zhang Z, Xu F, Qian Y, Yu J. Wettability, oil recovery, and interfacial tension
with an SDBS–dodecane–kaolin system. J Colloid Interface Sci
1999;214(2):368–72.
217
Fuel 251 (2019) 187–217
[196] Yue Y, Chen S, Wang Z, Yang X, Peng Y, Cai J, et al. Improving wellbore stability
of shale by adjusting its wettability. J Petrol Sci Eng 2018;161:692–702.
[197] Liu X, Liu K, Gou S, Liang L, Luo C, Guo Q. Water-soluble acrylamide sulfonate
copolymer for inhibiting shale hydration. Ind Eng Chem Res 2014;53(8):2903–10.
[198] Ruedrich J, Bartelsen T, Dohrmann R, Siegesmund S. Moisture expansion as a
deterioration factor for sandstone used in buildings. Environ Earth Sci
2011;63(7–8):1545–64.
[199] Shadizadeh SR, Moslemizadeh A, Dezaki AS. A novel nonionic surfactant for in-
hibiting shale hydration. Appl Clay Sci 2015;118:74–86.