Journal of Petroleum Science and Engineering 204 (2021) 108745

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

A critical parametric review of polymers as shale inhibitors in water-based

drilling fluids
Muhammad Adeem Abbas, Asif Zamir *, Khaled Abdalla Elraies, Syed Mohammad Mahmood,
Muhammad Hammad Rasool
Department of Petroleum Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Wellbore stability is essential to be maintained during drilling operation. It is on target due to many issues among
Wellbore stabilvdity them shale hydration is most critical problem using water-based drilling fluids especially. The reactive clay
Shale hydration minerals of shale have greater affinity towards water and show swelling when interact with water and make
Shale inhibition
wellbore conditions unstable. Different inhibitors have been utilized to inhibit water invasion. Among them,
Polymers
Performance parameters
polymers proved to be efficient and biodegradable. In this paper, responsible clay minerals for hydration and
their reactivity towards water is explained. The parametric mechanism of hydration and inhibition are thor­
oughly reviewed. In this review paper, the inhibition performance parameters of polymers are presented.
Polymers utilized in WBDF are critically reviewed with respect to their inhibition ability based on the perfor­
mance parameters like electrostatic interaction, hydrogen bonding with clay minerals, thermal stability, and
their effect on drilling fluid rheology. Different researchers have explained some of the parameters. But they are
found to be insufficient to explain all the important parameters. There are other parameters to investigate the
polymer’s performance that are required to be explained for an efficient inhibition. These parameters are
electronegativity difference in the active site of polymer, hydrophobicity, concentration, and agglomeration.
These parameters are also important to discuss because they affect polymer’s performance and drilling fluid’s
rheological properties. Nanoparticles have been used for inhibition with polymers and their effectiveness to plug
nanopores is also reviewed. Some of the polymers were found to be unstable and contaminating nanoparticles.
The reason behind this problem have also been explained parametrically here. The limitations of utilized
polymers have been discussed in this paper w.r.t. performance parameters. Polymer performance and charac­
terization results are presented and evaluated w.r.t. to performance parameters. Future perspective for a better
inhibition performance is the utilization of a polymer with improved performance parameters.

1. Introduction
Wellbore stability is a critical condition to maintain during the
drilling operation. A special care is required to stabilize the borehole
condition for an optimized drilling operation. Wellbore instability is the
most challenging and consistent situation during a drilling operation. It
includes formation damage, low drilling rate, borehole collapse, pipe
stickiness, and shale hydration (Saleh and Ibrahim, 2019; Ma et al.,
2016). Wellbore instability problems lead to increased non-productive
time (NPT) and non-optimized drilling operation.
Shale hydration is the most critical problem causing wellbore
instability. Shale hydration can cause further problems during drilling
operation like tight hole, stuck pipe, collapsed hole (in severe swelling
conditions), and bit balling. The drilled shale cuttings may disperse and
disintegrate in the drilling fluid and contaminate it. An oil and gas
drilled section is 70% composed of shale formations. Due to shale hy­
dration issue, 95% of wellbore instability problems are caused during
drilling operation (Yang et al., 2019). The reasons of shale hydration are
further discussed in this paper.
1.1. Shale formation w.r.t. reactive clay minerals
Shale formations are the most abundant sedimentary rocks in the
earth crust. Shales can be source rock for hydrocarbons, reservoir
basement, and cap rock as well to trap hydrocarbons in the reservoir
rock. Shale formations have 100–130 ◦ C at the depth of 1000–5000 m in

* Corresponding author.
E-mail address: asif.zamir@utp.edu.my (A. Zamir).

https://doi.org/10.1016/j.petrol.2021.108745
Received 19 October 2020; Received in revised form 29 March 2021; Accepted 30 March 2021
Available online 1 April 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
M.A. Abbas et al.
general. Shale formation temperature is important to be known to design
the inhibitors in terms of thermal stability and inhibition performance at
the formation temperature (Ilozobhie and Obi, 2018; Pan et al., 2016).
Shale formations are generally defined as low permeable sedimentary
rocks consisting of different clays with other minerals (Wang et al.,
2020). The quality of hydrocarbons present in shale formation is esti­
mated by kerogen and amount of total organic carbon (TOC) (You et al.,
2019; Donadelli et al., 2019; Madukwe, 2014; Pan et al., 2020). Their
permeability and porosity capacity depends on the type of clay, clay
composition and minerals present. It also depends on textural charac­
teristics of natural fractures, and anisotropy of bedding planes in the
formation as well. Among all these parameters, clay composition and
minerals present are the most important. Thus, shale formations could
be highly hydrated fragile rock to a very hard brittle shale depending on
the type of clay and minerals present (Lal, 1999; Huaqing et al., 2018;
Liang et al., 1080; Chalmers et al., 2011).
Shale formations contain organic and inorganic minerals which
comes from their existing environments. Mainly shales are composed of
quartz, potassium feldspar, phosphates, pyrites, clay minerals, carbon­
ate minerals, plagioclase, and others. The clay minerals are mostly
composed of kaolinite, chlorite, smectite, and illite/smectite mixed
layer. The amounts of these minerals vary between different shale ba­
sins. Table 1 is describing the general composition of shale formation
from Turpan Hami Basin, China (Berthonneau et al., 2017; Bergaya and
Lagaly, 2013).
Clay minerals are most prone to shale swelling when they encounter
fresh water in drilling fluids. These clay minerals contain 40–45%
mineralogy of shale formations. Smectite and illite/smectite mixed
layers have the highest tendency to swell in fresh water (Al-Arfaj et al.,
2014). Due to swelling, they put wellbore stability on target. A series of
issues may happen when a shale formation is exposed to fresh water
during operation as mentioned earlier.
1.2. Reactivity of clay minerals towards water
Clay minerals in shale formation cause formation to become reactive
towards fresh water. When these reactive minerals come in contact with
water, the formation swells and cause wellbore instability issues (Boek
et al., 1995). These reactive clay minerals are phyllosilicates and contain
layers of negatively charged octahedral alumina and tetrahedral silica
sheets (Choo and Bai, 2015; Kotal and Bhowmick, 2015). In tetrahedral
sheets, one tetrahedron is comprised of one cation which is in coordi­
nation with four oxygen atoms further and is linked to other tetrahe­
drons as well to make a continuous hexagonal two-dimensional layer.
Mostly iron, aluminum, and silica cations are present in tetrahedral
sheets. In octahedral sheets, one octahedron is composed of one cation
which is in connected with six oxygen atoms further and is linked to
other octahedrons by common edge sharing. Normally, cations available
in octahedral sheets are iron, magnesium, and aluminum cations
(Brigatti et al., 2013). These tetrahedral and octahedral sheets are ar­
ranged in a specific pattern to form different types of clays.
If the clays are composed of one tetrahedral and one octahedral
sheet, it is known as 1:1 clay or T-O clay. If clay is composed of one
octahedral sheet sandwiched in two tetrahedral sheets, it is named as 2:1
clay or T-O-T clay. These reactive clay minerals gain negative charged
Table 1
Shale formation composition from turpan hami basin, China.
Shale Formation Composition Clay minerals
Quartz 25–27%
Potassium Feldspar 4–4.3% Smectite 50–80%
Phosphates 1–1.3% Illite/smectite 10–12%
Pyrite 2–2.4% Illite 4–5%
Clay minerals 40–45% Kaolinite 2–3%
Carbonate minerals 8–10%
Plagioclase 8–10%
2
Journal of Petroleum Science and Engineering 204 (2021) 108745
on tetrahedral and octahedral layers and these charges are due to the
isomorphic substitution of metal cations. The substitutions of metal
cations induce 90–95% negative charge on clay surface. 2:1 clay has
higher negative charges as compared to 1:1 clay because it has higher
tendency of exchanging cations (Al-Arfaj et al., 2014; Choo and Bai,
2015; Benchabane and Bekkour, 2006). According to literature, clay
minerals with 2:1 (T-O-T) structure i.e., smectite and illite/smectite are
more attractive towards water. Due to higher negative charges and
cation exchange capacity, this clay is vulnerable to water and cause
swelling in shale which leads to wellbore instability.
1.3. Parametric mechanism of shale hydration
The negative charges on reactive clay minerals make shale formation
reactive towards water. When these reactive clay minerals meet water,
hydration of clay minerals occurs. This hydration results in swelling of
formation due to increase in interlayer spacing. The negatively charged
clay minerals attract the cations of water and cation exchange reactions
occur between clay interlayer cations and water. Due to cation exchange
reactions, the interlayer spacing in shale formation increases which is
termed as swelling. The major reasons of hydration and swelling in shale
formation are given below:
1.3.1. Hydraulic pressure difference
The hydraulic pressure difference between wellbore and formation is
one of the reasons of water invasion in shale formation during drilling
operation. Due to this pressure difference, the water is forced to invade
and cause swelling in shale formation due to cation exchange reactions
(Du et al., 2018).
1.3.2. Spontaneous imbibition by capillary pressure
Shale formation has high saline connate water. When it meets less
saline water, a high osmotic pressure is produced due to salinity dif­
ference which cause water to seep into the shale formation and cause
swelling. This is also known as osmotic swelling in shale formation (Du
et al., 2018).
1.3.3. Crystalline swelling
Crystalline swelling (surface hydration) of clay minerals happens
when clay is exposed to water. Surface hydration occurs in step wise
manner. Then water makes either single layer or multilayer hydrates of
interlayer cations which resulted in an increase in interlayer spacings
(Ruedrich et al., 2011).
Fig. 1 is explaining the water invasion in interlayers, hydration due
to water and swelling mechanism in shale formation.
1.4. Shale inhibition mechanism
For the sake of wellbore stability, hydration and swelling in shale
formation needs to be inhibited. Inhibition can be produced by the
neutralization of reactive clay minerals charges, present on the surface
or in the interlayers. For this purpose, different inhibitors are being used
with water-based drilling fluids to inhibit the degradation in the shale
formation. These inhibitors are present as an additive for drilling fluids
working as physical, mechanical, or chemical inhibitor. These working
mechanisms are defined on the basis of their interaction with shale
formation (Rana et al., 2019; Luo et al., 2017).
1.4.1. Inhibitor’s interaction mechanisms
Shale inhibitors are used to restrict the invasion of water in the shale
formation to stop the degradation of formation in wellbore and ulti­
mately make the wellbore stable. The conventionally used inhibitors are
inorganic salts, polymers, ionic liquids, and nanoparticles. Their inter­
action with clay minerals is described below:
M.A. Abbas et al.
Fig. 1. Hydration and swelling mechanism in shale formation).
1.4.1.1. Physical and mechanical inhibitors. These inhibitors plug the
interlayer openings i.e., nanopores and microfractures physically to stop
the invasion of water in interlayers and reduce the shale hydration. For
this purpose, nanoparticles and cellulosic materials are used (Naeimavi
et al., 2019).
1.4.1.2. Chemical inhibitors. The charges on clay minerals need to be
neutralized for shale hydration inhibition. For this, chemical inhibitors
can exchange cations and make hydrogen bonds with reactive clay
minerals. They interact with reactive clay minerals chemically to
neutralize their charges. The inorganic salts have the capability to ex­
change cations and neutralize the shale surface. KCl, CaCl2 and NH4Cl
are commonly used inorganic salts as shale inhibitors. The hydrogen
bonding capability of polymers and ionic liquids is effective for shale
inhibition. Normally used polymers are hydroxyl group, amine group,
imine group, and carboxylic group-based polymers. Imidazolium based
ionic liquids are commonly used for shale inhibition (Barati et al., 2017;
Yang et al., 2017). The parameters involved in chemical inhibition are
hydrogen bonding capability, electronegativity, and suppression of
electrical double layer. These parameters are explained with respect to
their role in inhibition and discussed here in detail.
Hydrogen bonding capability is most important property of chemical
inhibitors. The cationic end inhibitors are the most efficient in making
hydrogen bonds with clay minerals and inhibit the hydration. Usually,
the hydrophobicity of back chain of inhibitors restricts the further in­
vasion of water in the clay interlayers (Huang et al., 2017; Ren et al.,
2019; Gholami et al., 2018). Electronegativity in the active site of
chemical inhibitors allows them to make bonds with clay minerals and
induce inhibition. The electrical double layer in clay interlayers is one of
key parameter to produce swelling shales. Chemical inhibitors while
making the reactive clay minerals neutralized, try to suppress this
double layer when electrical attraction is established between cationic
end of inhibitor and reactive clay minerals (Rahman et al., 2020; Zhong
et al., 2011).
2. Performance parameters for effective shale inhibition
Hydration Inhibition in shale formation with different inhibitors is a
result of many parameters’ participation. These parameters play their
role to stop the invasion of water and make borehole conditions stable
(Liew et al., 2019; Özkaya, 2019). Some of these parameters are related
to the inhibitor behavior and some are related to inhibitor-rock inter­
action. It is the need of time to maintain and improve these parameters
for better inhibition performance. The parameters important for inhi­
bition are given below:
3
Journal of Petroleum Science and Engineering 204 (2021) 108745
- Electrostatic Interaction to stabilize the shale swelling and per­
forming the inhibition, is one of the important performance param­
eters for inhibitors. The reactive clay minerals have negatively
charged surface. It is important to neutralize the charged clay min­
erals to stop their attraction towards water during drilling operation.
Inhibitors having opposite charges, try to stabilize charged minerals
electrostatically (Shi et al., 2018). By neutralizing clay minerals, the
electric double layer of charges suppresses on shale surface, inter­
calation phenomenon of water stops and shale becomes stable in the
presence of water (Wang, 2020).
- Hydrogen Bonding is the most powerful and effective parameter of
polymers. Inhibitor should be efficient in making hydrogen bonds
with clay minerals, neutralizing clay minerals charges, and inducing
inhibition against water. Inhibitor’s ability of making hydrogen
bonds depends on the activity of their functional group. It also de­
pends on the chemical nature of inhibitor that whether it makes an
ionic solution in water or not. By making an ionic solution in water,
the charges on inhibitor’s active functional group should be opposite
to reactive clay minerals and sufficient to neutralize the charged
minerals in formation. By adsorbing due to potential difference on
shale surface and hydrogen bonding, the reactive clay minerals are
neutralized to inhibit water invasion (Rahman et al., 2020; Xu et al.,
2019).
When hydrogen bonding is in place between the inhibitor and
reactive clay minerals, a layer of inhibitor adsorbs on clay interlayers
and surface. This adsorption is different from swelling caused by water
invasion. This adsorption of inhibitor ions enhances the particle size.
According to different research groups, this particle’s size increment is
an indication of potential inhibition in clay. Due to the expulsion of
water from clay interlayers, the shale becomes hard also. This phe­
nomenon has been confirmed with particle size distribution analysis
(PSA) and different clay hardness tests. After the development of
hydrogen bonds, particle size increment has been measured by PSA
which confirmed the adsorption not swelling. For swelling measure­
ment, X – Ray Diffraction (XRD) is done to measure the increment in d -
spacing (Aston and Elliott, 1994; Liu et al., 2004; Toulhoat and
Lecourtier, 1992; Bailey et al., 1994).
- Electronegativity Difference of inhibitor’s functional group is
another parameter for shale inhibition. It assists inhibitor to dissolve
in water and making an ionic solution. Polymers with less electro­
negativity difference in their functional group are more effective
comparatively. Due to lesser electronegativity difference, the atoms
of functional group are in a weak interaction with each. Because of
M.A. Abbas et al. Journal of Petroleum Science and Engineering 204 (2021) 108745

this weak interaction, they easily make ionic solution and get the major issue is their toxicity to environment and high prices. Ionic
cationic end. This cationic end is attracted towards the negatively liquids are toxic for microorganisms present in environment (Luo et al.,
charged clay minerals and defuse their charges by making hydrogen 2017; Ren et al., 2019). When the cuttings having these inhibitors
bonds (Szatyłowicz and Krygowski, 2007; Oliferenko et al., 2006). attached with them are dumped on land, their toxicity pollutes the
- Hydrophobicity of inhibitor backbone (chain) plays an important environment. The most prone pollution is land pollution, air pollution,
role to stop the further invasion of water in formation interlayers. and food cycle pollution (in case if the land is used for agriculture af­
After making hydrogen bonds and neutralizing minerals, inhibitor’s terwards) (Johnston et al., 2019; Wang et al., 2017; Ramirez, 2009).
hydrophobic backbone restricts water invasion in formation in­ Polymers of different functional groups are being used and reported
terlayers. Shale formation becomes more stable in this condition in literature to produce an effective shale inhibition as compared to
(Ahmed et al., 2019). others. But most of them were unable to inhibit efficiently because of
- Thermal Stability of inhibitors up to the temperature of formation is high temperature degradation and less efficient functional group. The
very essential parameter. Inhibitor can only be effective towards limitations of different inhibitors are summarized in Table 2.
shale inhibition if it is not degrading at high temperature. If it de­ Different polymers have been critically reviewed further on the bases
grades at high temperature, inhibitor will become inactive and of parameters stated earlier.
desorb from shale surface. The shale surface will again be available
for water intercalation, hydration will destabilize the borehole con­ 3. Critical parametric review of polymers in WBDF as shale
ditions and drilling will be non-optimized operation (Xu et al., 2017). inhibitors
- Agglomeration of inhibitors in the presence of other drilling fluid
additives also restricts the inhibition of water invasion properly. Synthetic and natural polymers have been utilized in water-based
Inhibitor should be stable with drilling fluid additives like bentonite, drilling fluid to reduce shale swelling. These polymers are efficient
barite, cellulosic additives, and others that are added for different shale inhibitors and biodegradable. Natural polymers are normally
purposes. Otherwise, these additives can deposit on the inhibitor extracted from plants that are environment friendly and rich in terms of
molecules and it will become inactive towards water invasion in the cations exchange capacity. Synthetic polymers with less environment
formation. Additionally, drilling fluid’s rheological and filtration footprints are hydroxyl group, amine group, imine group, and carboxylic
properties also get destabilized due to the formation of agglomerates group-based polymers. Now the performance of these polymers will be
of inhibitors and both become unable to perform their role during critically reviewed here with respect to their inhibition performance,
drilling operation (Jain and Mahto, 2017). their functional group activity, high temperature stability, and reasons
- Concentration also affects the inhibitor’s performance. Many in­ of their restricted performance. Various polymers employed to WBDF for
hibitor’s performance is concentration dependent i.e., if inhibitor is shale inhibition are summarized in Table 3.
used in higher concentration, its performance will get poor. Because Carlos et al checked the inhibition performance of Hydrophobically
at higher concentrations, inhibitor makes multilayers on shale in­ Modified Polyethylene Glycol (PEG) with KCl (De Souza et al., 2010).
terlayers leaving empty spaces between molecules. These empty The reported concentration is 20 wt%. Two types of shale samples were
spaces invite water molecules to invade and the formation starts to used i.e., smectite-based clay and kaolinite-based clay. The major
swell again even in the presence of inhibitors. At higher concentra­ interaction mechanisms were hydrogen bonding, van der Waals forces,
tions, inhibitors can also make agglomeration with fluid additives ion dipole forces, and electrostatic interaction. The active functional
(An and Yu, 2018). group is glycol which is given in Fig. 2. The shale samples and inhibitor
- Stability with nanoparticles is important. Since shale formation were characterized by TGA, XRD, FTIR, and NMR. The swelling inhi­
has nano pores which are unable to be plugged with conventional bition performance is measured by hot rolling cuttings recovery tests
inhibitors. Because all of the conventional inhibitors are in macro and the reported recovery is almost 75%. The reason for low inhibition
size and eventually these nanopores remain open at all times. The performance is the hydrolyzation of PEGs occurred at 120 ◦ C which
average pore size range in shale formation is 3.76 nm–8.53 nm. reduced adsorption ability. It is effective at higher concentrations and
While the macro and micro openings ranges from more than 50 nm made multilayers in clays interlayers. These multilayers of polymer
and 1 nm to 1.60 μm, respectively (Li et al., 2016; Zhang et al., 2016; increased the empty spaces between polymer layers and chances of
Kashif et al., 2019; Lei et al., 2020; Liu et al., 2020). These ranges are water invasion increases. At last, the modified PEG worked better for
helpful for nanoparticles appropriate size selection. For the plugging
of these nano openings, nanoparticles are used for inhibition (Aftab
Table 2
et al., 2017). Many inhibitors have charges on their surface. These
Limitations of shale inhibitors.
cationic ends of inhibitors can make agglomerates with anionic
nanoparticles in water. Both inhibitor and nanoparticles will become Shale Inhibitors Interaction with Limitations
Clay
unable to inhibit shale hydration. Inhibitors should be stable with
nanoparticles being used (Bayat and Shams, 2019). Salts KCl & NH4Cl Electrostatic Elongates the
Interaction fractures and
decreases the
mechanical strength
2.1. Effectiveness of shale inhibitors based on their performance Polymers Polyethyleneimine Poly Hydrogen Can’t bear high
parameters AETMAC & Poly Bonding & temperature (more
DMAPMA Polyethylene Electrostatic than 150 ◦ C)
Glycol Interaction condition and
Conventionally used shale inhibitors i.e., inorganic salts, polymers, desorbs from the
and ionic liquids, have performed and improved shale inhibition. shale surface and the
Different studies have shown the shale inhibition up to 76% only. Shale shale starts to swell
inhibition performance was restricted due to some characteristic limi­ again.
Some polymers
tations of these shale inhibitors.
reduce the
Inorganic salts when used in the drilling fluid to inhibit shale hy­ rheological
dration, it put formation mechanical strength on target because they properties of drilling
elongate the fractures in the formation (Huaqing et al., 2018; Shi et al., fluid as well
2018). Imidazolium based ionic liquids have been used in many studies Ionic Imidazolium Group Hydrogen Monomer is toxic
Liquids Bonding and expensive
for shale inhibition. Rather being efficient in inhibiting the hydration,

4
 Table 3

M.A. Abbas et al.

Polymers that have been studied as shale inhibitors in Water based Drilling Fluids.
Research Polymer Parameters Affecting the Performance of Polymer Shale Limitations Recommendations
Group Inhibition
Interaction Mechanism Degradation Concen.
Temperature

Gang Xie Alkyl diammonium Electrostatic Interaction – 1 w/w % 27.60% With concentration, tilted- • Small alkyl chains are recommended for better inhibition. According
& Van Der Waals Forces monolayer was formed, which to some studies, alkyl chains with 4–7 carbon atoms are
reduced inhibition recommended for good inhibition.
Mobeen Quaternary Hydrogen Bonding & – 0.025–0.1% 20% With inhibition and concentration, • Low concentration is more effective
Murtaza Ammonium Gemini Electrostatic Attraction multilayers increase hydration • Small spacer length is recommended (small number of carbon atoms)
• Functional group of low Electronegativity can be introduced.
Qi Chu Amidocyanogen Covalent Bonding and 140 ◦ C 0.1–0.5% 37–70% Chemical inhibition is not involved. • Oligomer can be modified with other binding materials than siloxane
Silanol Adsorption High concentrations form to improve thermal resistance.
multilayers • The inhibitor can be tried with any other functional group with Less
Can’t perform at high temperatures Electronegativity and better Hydrogen Bonding ability for good
inhibition.
Xingliang Li Polyamino acids Electrostatic Interaction 215–347 2 wt% 25.8–36.9% performance is pH dependent, only • Cationic end amino acids are recommended for better Electrostatic
& Adsorption perform inhibition at pH 9. Interaction.
Anionic amino acids can’t perform • The functional groups can be changed to increase the Hydrogen
inhibition due to charges similarity. Bonding and adsorption efficiency.
• Stability studies with drilling fluid additives are required.

Research Polymer Parameters Affecting the Performance of Polymer mentioned Shale Limitations Recommendations
Group Inhibition
Interaction Degradation Concen.
Mechanism Temperature

Mukarram Poly AETMAC & Poly Electrostatic 100 ◦ C 0.125–0.625 76% Expensive • Thermal degradation should be improved using any
Beg et al. DMAPMA Interaction and wt% thermally degrade at 100 ◦ C and unable plasticizer. Polymer combination can be changed to improve
Hydrogen Bonding to improve the rheological properties the thermal performance.
• Concentration can be varied to improve rheological
5

properties.
• Electronegativity Difference in polymer combination can be
varied to improve shale inhibition.
Qi Chu et al. Hyperbranched Electrostatic 140 ◦ C 0.5 vol% 11–40% Thermally degrade at 140 ◦ C and • Shale sample can be changed because the shale used was
Polyethyleneimine modified Interaction and swelling rate increased with temperature kaolinite, which is a dispersing shale, not a swelling shale. The
with Silane Hydrogen Bonding same polymer can be used for montmorillonite-based shale.
• Polymer having less electronegativity difference can be
used to improve hydrogen bonding capability.
• Hydrophobicity of the polymer chain can be varied to

Journal of Petroleum Science and Engineering 204 (2021) 108745

improve the inhibition.
Yuxiu An Polyethyleneimine Electrostatic 120 ◦ C 0 - 4 wt% 76.20% at higher concentrations, it caused • Lower molecular weight PEI should be used to ensure good
et al. Interaction and agglomeration and affected the solubility.
Hydrogen Bonding rheological properties and caused bit • Concentration can be controlled to stabilize rheological
balling behavior of drilling fluid.
compatibility issue with other drilling • Agglomeration can be removed using ultrasonication of
fluid additives drilling fluid.
not compatible with other drilling fluid • Polymer with less electronegativity difference can be used
additives to enhance hydrogen bonding at low concentration.

Research Polymer Parameters Affecting the Performance of Polymer Shale Limitations Recommendations
Group mentioned Inhibition

Interaction Mechanism Degradation Concen.

Temperature

Xianmin Acrylamide-Styrene-Butyl-Acrylate Physical Plugging & 343 ◦ C 0 - 2 wt% 37.80% the active site of polymer is unable to • Active site of polymer can be changed to any
Zhang (ASBA) Hydrogen Bonding inhibit hydration. other functional group of low electronegativity
et al. not compatible with other drilling fluid difference.
additives
(continued on next page)
 Table 3 (continued )

M.A. Abbas et al.

Research Polymer Parameters Affecting the Performance of Polymer Shale Limitations Recommendations
Group mentioned Inhibition

Interaction Mechanism Degradation Concen.

Temperature

• Any inorganic salt can be used with it to

incorporate electrostatic interaction also. It will
improve shale inhibition also.
• Hydrophobicity of the polymer can be varied by
changing the chain length.
Gang Xie Branched Polyethyleneimine (BPEI) & Electrostatic 80 ◦ C 0 - 1 wt% 65% not compatible with other drilling fluid • the primary amine group must be reduced to
et al. Hexamethylenediamine (HMDA) Interaction and additives improve adsorption at high concentrations.
Hydrogen Bonding • Thermal stability of the polymer can be
improved using any plasticizer.
• The polymer can be replaced with less
electronegativity difference polymer with high
thermal stability.
Rajat Jain Polyacrylamide/dially dimethyl Electrostatic 95 ◦ C 0.9 wt/ 60% rheological properties got destabilized at • Shale sample must be based on swelling clay
et al. Ammonium Chloride grafted Gum Acacia Interaction and vol % 95 ◦ C due to polymer thermal degradation minerals like Na-montmorillonite.
Copolymer Hydrogen Bonding and shale swelling was enhanced. • Since it is a natural polymer so any plasticizer can
be used to improve thermal stability.
• A natural polymer with functional group of less
electronegativity difference can be utilized to
improve shale inhibition.
• Concentration can be controlled to stabilize
rheological properties of drilling fluid.
• In case of agglomeration, concentration of
polymer can be controlled or ultrasonication can
be used.
6

Research Group Polymer Parameters Affecting the Performance of Polymer Shale Limitations Recommendations
mentioned Inhibition

Interaction Degradation Concen.

Mechanism Temperature

Aghil triterpenoid saponin Electrostatic 200 ◦ C – very low high concentrations are • A natural polymer with effective functional group (less
Moslemizadeh Glycyrrhiza glabra root Interaction and required for effective inhibition electronegativity difference) having high hydrogen bond making
et al. extract (GGRE) Hydrogen Bonding rheological and filtration capability can replace this polymer which is also compatible with other
properties become unstable at drilling fluid additives.

Journal of Petroleum Science and Engineering 204 (2021) 108745

higher concentrations • Concentration should be controlled to stabilize rheological properties
and remove if any agglomeration is present in the drilling fluid.
Fengjie Ma et al. Polyampholyte DAM Hydrogen Bonding 288 ◦ C 0.5–2.5 47% Its performance was very low • The functional group can be replaced with a less electronegativity
wt% because of its interaction with difference functional group with high hydrogen bonds making capability.
other additives. • Any inorganic salt can be used to incorporate electrostatic interaction for
shale inhibition.
• Concentration can be varied to stop its interaction with other drilling
fluid additives and to break agglomerations if present in the solution.
• Hydrophobicity of the polymer can be varied by increasing chain length
or introducing any other hydrophobic group to improve the water
repulsion property of polymer.

Research Polymer Parameters Affecting the Performance of Polymer Shale Limitations Recommendations
Group mentioned Inhibition

Interaction Degradation Concen.

Mechanism Temperature

Guancheng 143 ◦ C 0.1–0.5 52% Due to thermal degradation, polymer • Inhibition was tested for Illite based montmorillonite
Jiang et al. wt% started to desorb from shale surface by which is not a swelling montmorillonite. So, sodium
(continued on next page)
 Table 3 (continued )

M.A. Abbas et al.

Research Polymer Parameters Affecting the Performance of Polymer Shale Limitations Recommendations
Group mentioned Inhibition

Interaction Degradation Concen.

Mechanism Temperature

Polyacrylamide/dially dimethyl Electrostatic providing the free surface for hydration montmorillonite can be used to know the exact swelling
Ammonium Chloride/Polyvinyl Interaction and again. inhibition.
alcohol (ADVA) Hydrogen Bonding • Polymer can be used with nanoparticles to incorporate
physical plugging of pores and to improve the thermal
stability.
• Thermal stability can be improved by the use of any
plasticizer in it.
• Hydrophobicity can be improved in the polymer to
enhance its water repulsion property in shale formation.
• Polymer combination can be changed with a combination
of having less electronegativity difference.
Jiang Polyethyleneimine Hydrogen Bonding 120 C
◦
2 - 4 wt% 76% After neutralization, it could not hold the • to improve the inhibition, the functional group can be
Guancheng clay particles and they start to form replaced with a functional group having less
et al. agglomerates in the wellbore. electronegativity difference.
• Any inorganic salt can be added to the solution to diffuse
clay minerals by electrostatic interaction to improve
shale inhibition.
• An inorganic salt can be used to involve electrostatic
interaction to hold back the clay particles after
neutralization.

Research Polymer Parameters Affecting the Performance of Polymer Shale Inhibition Limitations Recommendations
Group mentioned

Interaction Degradation Concen.

7

Mechanism Temperature

Conny Cerai Partially Hydrophobized Electrostatic 200 ◦ C 0.1–3 wt without KCl - It can’t inhibit shale in the absence of KCl. At • At higher concentrations, sonication can be used to break the
Ferreira Hyperbranched Interaction and % 55% with KCl - higher concentrations, caused agglomeration agglomerations.
et al. Polyglycerols Hydrogen Bonding 70% and the rheological properties got destabilize. • the accumulation properties of polymer must be improved.
• Hydrophobicity can be improved from partially
hydrophobized to completely hydrophobized, for a better
shale inhibition performance.
Hanyi Zhong Hydroxyl Terminated Electrostatic 300 ◦ C 0.35–7 g without At high concentration, inhibitive capability • Lower generations must be used. Functional group with less
et al. Polyamidoamine Interaction and KCl:42.5% got weakened because of the formation of electronegativity difference can be introduced in these

Journal of Petroleum Science and Engineering 204 (2021) 108745

Dendrimers with KCl Hydrogen Bonding with KCl:54.3% polymer double layer in the interlayers. dendrimers, for an effective inhibition by effective
hydrogen bonding.
• Concentration of polymer can be controlled to increase the
inhibition.
• Agglomeration can be removed by sonication.
Gang Xie Primary Amine Groups Electrostatic 120 ◦ C 1.4–6 54–75% primary amine groups were degraded at • Primary amine group with high thermal stability are
et al. Interaction and CEC 120 ◦ C and desorbed from shale surface. recommended.
Hydrogen Bonding • Inhibition can be improved by adding an inorganic salt to
diffuse clay minerals by electrostatic interaction.
• Amine groups with high cation exchange capacity can be
used at low concentration.
• More hydrophobic amine groups can be used to increase
water repulsion property for a better inhibition.

Research Group Polymer Parameters Affecting the Performance of Polymer mentioned Shale Limitations Recommendations
Inhibition
Interaction Mechanism Degradation Concen.
Temperature

H. Y. Zhang et al. 70 ◦ C 3 wt% • Plasticizer can be used to improve thermal stability.

(continued on next page)
 Table 3 (continued )

M.A. Abbas et al.

Research Group Polymer Parameters Affecting the Performance of Polymer mentioned Shale Limitations Recommendations
Inhibition
Interaction Mechanism Degradation Concen.
Temperature

Polyetherdiamine & Formate Ion Exchange, Hydrogen After 70 ◦ C temperature, the polymer • Functional group with Less electronegativity can be
Salts (Na & K-formate) Bonding starts to degrade replaced with current group.
Hanyi Zhong Amine Terminated Electrostatic Interaction and 200 ◦ C 1 wt/vol 70% higher generations having high • Low generations are preferred for inhibition and pH
et al. Polyamidoamine Dendrimers Hydrogen Bonding % molecular weight can’t intercalate in of drilling fluid must be controlled for the use of low
clay interlayers generations.
higher generations work best at high pH • Terminal group can be replaced with a less
which is not recommended by API. electronegative one
• Clay minerals can be diffused by electrostatic
interaction by the addition of inorganic salts.
Seyed Reza Zizyphus spina-christi extract Adsorption, Electrostatic 82 ◦ C 3-6 30% Unstable at high temperature and • An effective natural polymer with high thermal
Shadizadeh (ZSCE) Interaction and Hydrogen mass% compatibility with drilling fluid stability can replace polymer.
et al. Bonding additives is unknown. • Compatibility study with other drilling fluid additives
is required.
• Inhibition can be improved by using any salt to
neutralize clay with electrostatic interaction.
• Or a natural polymer with less electronegativity
difference can be used to improve inhibition.

Research Polymer Parameters Affecting the Performance of Polymer mentioned Shale Inhibition Limitations Recommendations
Group
Interaction Mechanism Degradation Concen.
Temperature

Yuxiu An chitosan quaternary Electrostatic Interaction – 0.1–8 wt 72% due to high molecular weight, HTCC was • HTCC with low molecular weight can be used for
et al. ammonium salt % unable to intercalate in shale formation. inhibition which can easily intercalate with shale
Expensive and compatibility with drilling formation.
fluid additives is unknown. • A polymer with less electronegativity
8

difference functional group can be used to

Carlos et al. Hydrophobically Modified
Polyethylene Glycol with
KCl
hydrogen bonding, Van der
Waals forces, ion dipole forces,
and electrostatic interaction
stable up to 20 wt% 75% PEG Hydrolyzation occurred at 120 ◦ C
120 ◦ C which reduced adsorption ability.
at higher concentrations, it made
multilayers which produced more empty
spaces and allowed water to invade.
neutralize clay by making hydrogen bonds with
them.
• Hydrolyzation of PEG must be reduced in order
to improve inhibition.
• Hydrophobicity must be improved for a better
inhibition.
• Thermal stability can be improved for inhibition
at high temperatures.

Journal of Petroleum Science and Engineering 204 (2021) 108745

• Concentration must be controlled to reduce the
multilayers formation.
Koorosh Polyethylene Glycol (PEG) Physical Plugging and Hydrogen – 0.35 g 75% by plugging PEG contaminated MWCNT by • Polymer with low accumulation properties can be
Tookalloo with MWCNT Bonding and making accumulating on its surface and both used.
et al. hydrogen bonds couldn’t perform efficient inhibition in • Poro-Perm analysis is required for nanoparticle’s
shale size selection.

Research Inhibitor Parameters Affecting the Performance of Polymer Shale Inhibition Limitations Recommendations
Group mentioned

Interaction Mechanism Concen.

Xianbin Nanoscale Laponite Electrostatic interaction 0.5–2 wt% performed better Laponite performance is pH dependent, works best at • pH of drilling fluid can be controlled to
Huang (Sodium Magnesium between laponite and clay inhibition as compared to low pH. With higher pH values of drilling fluid, its have efficient results of inhibition.
et al. Silicate Clay) minerals PHPA (50–75%) charges are reversed. Means at high pH, it can’t inhibit • Polymer with less electronegative
the water invasion in shale formations functional group can be used to inhibit clay
by hydrogen bonding.
Jian-gen Xu Polyethylene Glycol Physical Plugging and Hydrogen 0.3–1 wt/vol% performed better PEG contaminated nano silica. Nano silica is sensitive to • A nanoparticle required that is compatible
et al. grafted n - silica Bonding inhibition at low temperature and PEG degraded at 75 ◦ C, that’s why the with PEG that will not make
temperatures (35–74%) swelling index increased at 75 ◦ C.
(continued on next page)
 M.A. Abbas et al. Journal of Petroleum Science and Engineering 204 (2021) 108745

inhibition as compared to unmodified PEG.

Electrostatic interaction can be improved

A natural polymer, Zizyphus spina-christi extract (ZSCE), based on

Less electronegative polymer can be used

electronegative polymer to induce better

Polymer can be replaced with a new less
for better hydrogen bonding capability.
Concentration of nanoparticles must be
Polymer less electronegative and high
saponin biosurfactant has been utilized in drilling fluid for shale inhi­

Thermally stable nanoparticles can be

agglomerations and temperature bition by Seyed Reza Shadizadeh (Shadizadeh et al., 2015). Polymer

hydrogen bonding for inhibition.

controlled to stabilize shale plugs.
was extracted from leaves of Zizyphus spina-christi tree. The active sites
thermal stability can be used.
of this polymer have hydroxyl and carboxylic groups which took part in

used in place of nano silica.

resistant also, can be used.

inhibition. The active functional groups of this polymer are given in

Fig. 3. Its performance was compared with polyamine and KCl. These

with another salt.

active sites interacted with reactive clay minerals by adsorption, making
Recommendations

hydrogen bonds and electrostatic interaction. Shale samples used for the
experiments were kaolinite-based clay. This natural polymer induced
better shale inhibition as compared to polyamine and KCl. But the major
issue of its restricted performance was its instability at high tempera­
tures. The inhibition performance was characterized by cation exchange
•

capability (CEC), cuttings dispersion test and bentonite sedimentation

test. All these tests have proved the potential of ZSCE for shale inhibition
erosion along the boundaries of the shale plug and
KCl, n-silica and MWCNT muds shown cracks and

except at high temperatures.

degraded at 75 ◦ C, that’s why the swelling index
Nano silica is sensitive to temperature and PEG

Chitosan Quaternary Ammonium Salt (HTCC), another natural

reduced mechanical strength of shale plugs.

polymer, have been used as an additive in WBDF for shale inhibition by

Yuxiu An (An et al., 2015). The concentration of HTCC was 0.1–8 wt%.
The characterization of shale samples and inhibitor was done by XRD,
SEM, FTIR, and zeta potential was measured to check the dispersion of
HTCC in WBDF. The inhibition performance was investigated by linear
swelling test and cuttings recovery test. Its performance was compared
with polyether amino and KCl. Electrostatic interaction and hydrogen
increased at 75 ◦ C.

bonding are the reported inhibition mechanisms of HTCC with reactive

clay minerals. HTCC has induced a shale inhibition up to 72%. The
Limitations

mentioned reason is the forces between inhibitor and clay. The

increasing concentration of HTCC resulted in increasing intermolecular
forces among HTCC and clay. The major reason of low performance is
that the bigger molecular weight of HTCC was curl and reduces the
GNP performed inhibition
efficiently as compared to

contact with rock debris of shale. HTCC is more expensive and its
Rheological properties

compatibility with drilling fluid additives is unknown.

other nanoparticles

H. Y. Zhong reported the use of Polyether Diamine & Formate Salts

Performed better
inhibition at low
Shale Inhibition

were improved

(Sodium-formate & Potassium-formate) with concentration of 3 wt% for

temperature.

shale inhibition in WBDF (Zhong et al., 2015a). The characterization of

polymer and shale samples was done by XRD and TGA. The dispersion
quality of WBDF was measured by zeta potential analysis. The interac­
tion mechanism mentioned by the author is ion exchange, hydrogen
bonding, and electrostatic interaction. The active functional group is
0.1 ppb of NPs,
11 ppb of KCl,
Parameters Affecting the Performance of Polymer

given in Fig. 4. Shale inhibition was measured by bentonite inhibition

and 3 ppb of

0.125 wt%

test, shale hot rolling test, and particle distribution test. The inhibition
Concen.

PHPA

efficiency measured was 74.5% at 77 ◦ C because the polymer started

degrading at 77 ◦ C and desorbing from shale surface.
Hanyi Zhong has used Amine Terminated Polyamidoamine
Physical Plugging and Hydrogen

(PAMAM) Dendrimers in WBDF for shale inhibition (Zhong et al.,

Interaction by KCl Hydrogen

2015b). Different generations of this polymer were used to check their

nanoparticles Electrostatic

inhibition performance with concentration 1 w/v%. The functional

Interaction Mechanism

Physical Plugging by

group is given in Fig. 5. Shale swelling was characterized by linear

bonding by PHPA

swelling test and cuttings recovery test. For low generations of PAMAM
at lower pH, the hydrogen bonding ability is improved dramatically and
mentioned

they neutralize siloxane group in reactive clay minerals efficiently. But

Bonding

this is the only case with low generations. Because the higher the gen­
eration, the greater the size, the lesser the intercalation and shale sta­
bility. Higher generations work best at high pH values which is not
Polyacrylamide-grafted-
GNP, KCl/n-Silica, KCl/
KCl, KCl/PHPA, KCl/

PEG/n-Silica
Inhibitor

MWCNT
Table 3 (continued )

Rajat Jain
Research

A. Aftab
et al.

et al.
Group

Fig. 2. Glycol as active site in Polyethylene Glycols).

9
M.A. Abbas et al.
Fig. 3. Chemical structure of Saponin based polymer; ZSCE).
recommended for drilling fluids. This polymer has produced 70% inhi­
bition. The major cause of low performance is its inactivity at high
temperatures i.e., the inhibiting amine group degraded at 200 ◦ C.
Another reason is the effect of pH. The effective low generations become
inactive to inhibit clay minerals at high pH levels i.e., pH 8–11.
Primary amine groups as shale inhibitors were used by Gang Xie et
al in WBDF (Xie et al., 2017a). Different amine groups were selected
based on their cation exchange capacity (CEC) i.e., 1.4 CEC to 6 CEC.
The amine groups selected were 1,5-pentanediamine (PA), 3-(2-ami­
noethyl) pentane-1,5-diamine (APD), and 3,3-Bis(2-aminoethyl)-1,
5-pentanediamine (BAPD). The mentioned inhibition mechanisms are
hydrogen bonding and electrostatic interaction. Shale samples and in­
hibitors were characterized by FTIR, TGA, XRD, and SEM. Shale inhi­
bition was characterized by linear shale swelling test, cation exchange
capacity, and hot rolling. The shale inhibition using primary amine
groups reported was 54–75%. The reported reason for low performance
is the degradation of amine group at 120 ◦ C. Chemical structures of
amine groups are given in Fig. 6.
Hydroxyl Terminated Polyamidoamine (PAMAM) Dendrimers with
KCl have been used by Hanyi Zhong in WBDF for shale inhibition
(Zhong et al., 2016). Different generations of this polymer were used to
check their inhibition performance with concentration 0.1–2 w/v %.
The chemical structure of Polyamidoamine is given in Fig. 7. Hydroxyl
group has been reported to be responsible for inhibition by hydrogen
bonding and electrostatic neutralization of reactive clay minerals. But its
performance is dependent on its concentration. Shale swelling was
characterized by particle size distribution test, bentonite inhibition test,
cuttings dispersion test. The shale samples and inhibitors were charac­
terized by XRD, zeta potential, and TGA. This polymer has produced
32.6–63% inhibition. The major reason of low performance is that the
inhibiting amine group degraded at 300 ◦ C. Additionally, KCl elongated
the fractures in the shale samples and reduced the mechanical strength
of shale.
Conny Cerai Ferreira et al studied the use of Partially Hydro­
phobized Hyperbranched Polyglycerols (HPG) in WBDF with concen­
tration 0.1 – 3w% (Ferreira et al., 2016). The shale used was reported as
smectite rich clay. Shale samples and inhibitor were characterized by
FTIR, NMR, TGA, XRD, and SEM. XRD confirmed the presence of
smectite up to 68%. The mentioned inhibitor was synthesized in a
Fig. 4. Chemical structure of ether diamine).
10
Journal of Petroleum Science and Engineering 204 (2021) 108745
Fig. 5. Amine group as active site in PAMAM).
chemical reactor at 125 ◦ C. The interaction mechanism of inhibitor was
reported to be electrostatic and hydrogen bonding. This inhibitor is rich
in hydroxyl group and it acted as an active site for neutralizing the
reactive clay minerals and inhibited the invasion of water. The chemical
structure of inhibitor is presented in Fig. 8. HPG is thermally stable up to
200 ◦ C but their performance depends on the concentration used. After 2
w% concentration, due to high solute-solute interaction, the agglomer­
ation started which affected the rheological properties of drilling fluid.
This polymer can’t inhibit properly in the absence of KCl.
Jiang Guancheng et al utilized PEI as shale inhibitor in WBDF at
concentration 2–4 w% (Guancheng et al., 2016). The polymer was
synthesized by ring opening polymerization of ethyleneimine. The
active site for inhibition of clay minerals is ethyleneimine group. PEI has
been tested for inhibition in montmorillonite clay (MT-clay) and
inhibited Mt-clay by hydrogen bonding and electrostatic interaction.
Shale swelling was reported to be 76.2%. The stated reason for low
performance was the molecular weight dependency of PEI for inhibition.
The higher the molecular weight, the better shale inhibition resulted.
But the higher molecular weight led to worse water solubility. PEI also
decomposed clay minerals except neutralizing them. PEI is also very
expensive as compared to the other polymers used as shale inhibitors.
Branched Polyethyleneimine (BPEI) & Hexamethylenediamine
(HDMA) were utilized for shale inhibition by Gang Xie et al. (2017b).
The concentration used was 1 w% and he tested sodium bentonite for
inhibition tests. The reported interaction mechanisms are hydrogen
bonding and electrostatic interaction. Bentonite and inhibitor were
characterized by SEM, XRD, and UV spectrometer. Shale inhibition was
measured in terms of linear shale swelling test and hot roll recovery test.
The active sites for shale inhibition were Ethyleneimine & Methyl­
enediamine. Both of inhibitors were synthesized by ring opening poly­
merization of ethyleneimine. In this study, the inhibition efficiency was
65%. The reason behind this much low efficiency was the high number
of primary amine groups. As the number of amine groups increases, the
adsorption of amine groups on bentonite was decreased. Which allowed
water to adsorb on the bentonite surface even in the presence of
inhibitors.
Rajat Jain et al reported the use of Polyacrylamide/dially Dimethyl
Ammonium Chloride Grafted Gum Acacia Copolymer in WBDF for shale
inhibition (Jain and Mahto, 2017). Kaolinite-based clay was used in this
study. The active sites for shale inhibition of the reported inhibitors are
Polyacrylamide and Dially Dimethyl Ammonium Chloride and their
chemical structures are given in Fig. 9. Inhibitor interacted with reactive
clay minerals by hydrogen bonding and electrostatic interaction at
concentration 0.9 w/v%. Shale inhibition was measured by core flood­
ing, shale dispersion test, slake durability test. Shale inhibition effi­
ciency was 60% only because the reported inhibitor degraded at 95 ◦ C.
Also, the rheological properties got destabilized after 95 ◦ C.
Fengjie Ma et al has used Polyampholyte DAM polymer as shale
inhibitor in WBDF. DAM was synthesized from three monomers dially
dimethyl ammonium chloride & methyl allyl alcohol & 2-acrylamido-2-
methylpropane sulfonic acid by aqueous polymerization method using
ammonium per sulfate as initiator (Ma et al., 2017). The chemical
structures of these monomers are presented in Fig. 10. The polymer was
used in concentration of 0.5–2.5 w%. The characterization was
completed with FTIR, TGA, SEM, and molecular weight pattern analysis.
Shale inhibition was measured by linear swelling test, hot rolling
M.A. Abbas et al.
Fig. 6. Chemical structures of primary amine groups).
Fig. 7. Chemical structure of Polyamidoamine).
Fig. 8. Chemical structure of hyperbranched polyglycerols).
dispersion test, and particle size distribution tests. DAM is thermally
stable up to 288 ◦ C but it could produce only 47% shale inhibition. The
reason of this much low efficiency is the inability of the polymer to
defuse charged clay minerals. By the analysis, it was reported that the
hydrogen bond making ability of this polymer is very poor. That it was
unable to inhibit the shale completely. It worked good in the presence of
KCl because it will also neutralize clay charges by electrostatic
interaction.
Polyacrylamide-dially Dimethyl Ammonium Chloride/Polyvinyl
alcohol (ADVA) has been utilized for shale inhibition in WBDF by
Guancheng Jiang et al. (2018). This polymer was made by chemical
reactions using mechanical mixing of Polyacrylamide, Dially Dimethyl
Ammonium Chloride, and Polyvinyl alcohol. The chemical structures
are given in Fig. 11. The illite-based montmorillonite was used in this
study. The characterization of materials was done by FTIR, TEM, SEM,
XRD, and TGA. Shale inhibition was performed by linear swelling test
and hot rolling recovery test. ADVA is a hydrophilic polymer and it
covers the surface of clay by making the hydrogen bond with oxygen
ions of clay minerals. Shale inhibition efficiency was only 52% at the
concentration of 0.1–0.5 w%. Because ADVA degraded at 143 ◦ C. Due to
this degradation, the polymer desorbs from the shale surface and shale
surface became available for water adsorption and swelling again.
11
Journal of Petroleum Science and Engineering 204 (2021) 108745
A natural polymer, triterpenoid saponin Glycyrrhiza glabra root
extract (GGRE) has been utilized for shale inhibition in WBDF by Aghil
Moslemizadeh et al. (2017). Glycyrrhiza glabra is a tree that contain a
high performance saponin which has been employed in EOR studies.
Saponin is a biosurfactant that contain both hydrophobic and hydro­
philic groups. It is synthesized by spray drier method applied on Gly­
cyrrhiza Plant. It has several functional groups such as –OH, –COOH,
and –CH3. The chemical structure of saponin is given in Fig. 12. The
characterization was done by wettability tests, FTIR and SEM on in­
hibitor and shale samples. Shale inhibition was measured by shale cut­
tings recovery test. Higher concentrations of inhibitors are required. The
disadvantage of its use is that the rheological and filtration properties of
drilling fluids are disturbed at higher concentrations.
Yuxiu An et al used Polyethyleneimine (PEI) for shale inhibition.
Ring opening polymerization of ethyleneimine was used to synthesize
PEI (An and Yu, 2018). The inhibition mechanism was described w.r.t.
hydrogen bonding and electrostatic interaction. Amino group made
hydrogen bonds with reactive clay minerals to neutralize their charges.
The concentration of PEI used was 0–4 w%. The characterization was
done by using FTIR, XRD, SEM, TEM, Zeta Potential and Particle Size
Analyzer for PEI and shale samples. Shale inhibition was reported in the
form of linear swelling test and rolling recovery test. The shale inhibi­
tion efficiency of PEI was 76.2%. Because at higher molecular weights,
PEI shown worse water solubility. Additionally, due to degradation at
120 ◦ C, PEI was unable to perform inhibition completely.
Acrylamide-Styrene-Butyl Acrylate (ASBA) was used by Xianmin
Zhang et al in WBDF for shale inhibition study in WBDF (Zhang et al.,
2018). The chemical structure is given in Fig. 13. The concentration used
was 0–2 w%. They have used sodium bentonite with 95% clay particles.
The characterization was completed by FTIR, NMR, Particle Size Dis­
tribution, TEM, SEM, Contact Angle Test, and TGA. The inhibition
mechanism described is hydrogen bonding and electrostatic interaction
with clay minerals. Instead of high thermal stability, ASBA managed to
inhibit shale swelling only by 37.8%. The reason of its inability to in­
hibition is unknown. It may be the inability of the active site to
neutralizing the reactive clay minerals. It was also not compatible with
drilling fluid additives.
Mukarram Beg et al has checked the effect of neutral polymer with
a cationic polymer on shale inhibition and compared their performance.
He has used Poly AETMAC (cationic) & Poly DMAPMA (neutral) in this
study (Beg et al., 2019). These polymers were used in concentration of
0.125–0.625 w/v% in WBDF. Kaolinite-based clay has been used and
characterized by XRD, FESEM, and SEM. Shale inhibition was measured
by hot rolling test, linear swelling test, and capillary suction time test. It
has been reported a shale inhibition of 76% but the polymer combina­
tion was degraded at the temperature of 100 ◦ C.
Qi Chu et al modified polyethyleneimine with a plasticizer. PEI was
modified with silane using Michael Addition reactions on hyper­
branched PEI (HPEI) and Methacryloxy propyl trimethoxy silane (Chu
et al., 2019). This modified polymer was stable up to 140 ◦ C and this
M.A. Abbas et al. Journal of Petroleum Science and Engineering 204 (2021) 108745

Fig. 9. Polyacrylamide & diallyl dimethyl ammonium chloride).

Fig. 10. Chemical structures of monomers of Polyampholyte DAM).

Fig. 11. Chemical structures of monomers of ADVA polymer).

increased thermal stability is due to the addition of plasticizer in it. The
mentioned inhibition mechanism is the hydrogen bonding and electro­
static interaction with clay minerals. Kaolinite-based clay was used for
shale inhibition study. Shale inhibition was measured by linear swelling
test, hot rolling cutting dispersion test, bentonite inhibition test. The
reported inhibition efficiency was 11–40% only. This low performance is
because of degradation and inability of active site to neutralize clay
reactive minerals at high temperature.
Alkyl Diammoniums has been utilized as shale inhibitor in WBDF by
Gang Xie et al. (2020). The inhibition mechanism explained is the
electrostatic interaction and van der Waals forces between inhibitor’s
ammonium ion and reactive clay minerals. The inhibitor performance
was as low as 27.6% with concentration because increased alkyl chain
length made a tilted monolayer in the clay interlayers. Which allowed
water to enter again in the clay interlayers and produce swelling in the
formation. The concentration used is 1 w/w% for all diammoniums.
Mobeen Murtaza et al have used quaternary ammonium gemini
surfactant for clay swelling inhibition and explained the mechanism and
performance evaluation in detail (Murtaza et al., 2020). The inhibition is
evaluated using linear swell meter and capillary suction timer, scanning
electron microscope (SEM), wettability and zeta potential analysis. The
interaction mechanism with clay mentioned in the study is hydrogen
bonding and attractive electrostatic forces. After the complete analysis,
it is mentioned that the inhibitor didn’t affect the rheological and
filtration properties of drilling fluid. The inhibition tests were conducted
at 0.025%–0.1% and the maximum swelling inhibition efficiency re­
ported is 20% only for sodium bentonite at 0.05% concentration. Inhi­
bition performance reduced with concentration because it can’t
intercalate in clay interlayers.
A newly developed oligomer with an amino siloxane structure,
Amidocyanogen Siloxane (ANS-1) has been utilized by Qi Chu et al for

Fig. 12. Chemical structure of Saponin based inhibitor). Fig. 13. Chemical structure of ASBA).

12
M.A. Abbas et al.
shale inhibition at high temperatures (Chu et al., 2020). The molecular
structure of inhibitor is given in Fig. 14. The characterization of the
performance has been completed with XRD, adsorption, contact angle,
and TEM analysis. The inhibition performance is being measured by
linear swell meter for Na-montmorillonite wafers. The performance ef­
ficiency of ANS-1 has been reported as 37–70% for the temperature
range 20–160 ◦ C at 0.1–0.5% concentration. The performance has been
compared with KCl, HCOOK, and Ultrahib inhibitors. At and above 0.4%
concentration, the inhibition performance was stop because of no
further adsorption of ANS-1 on clay. The same phenomenon was
observed with temperature increase and confirmed with dynamic
adsorption curves and contact angle analysis. After 140 ◦ C, the
desorption phenomenon occurred which resulted in hydration again.
Xingliang Li et al investigated the utilization of polyamino acids in
WBDF for shale inhibition performance. Four different polyamino acids
with different functional groups i.e., polyglycine (PGly), polyglutamic
acid (PGlu), polylysine (PLys), and polyarginine (PArg) have been uti­
lized for inhibition study (Li et al., 2020). The characterization was
completed with TGA, NMR, and zeta potential analysis. The perfor­
mance of all four inhibitors was in the range of 25.8–36.9% measured by
linear swell meter. Thermal stability was reported to be within
215–347 ◦ C. PGly and PGlu are anionic in nature and couldn’t neutralize
the charges of reactive clay minerals. They only produced inhibition due
to intercalation because of osmotic pressure. On the other hand, PLys
and PArg are cationic in nature and they inhibited hydration more
efficiently as compared to other two amino acids.
All of the polymers that have been used are available in macro size.
They can only target the reactive clay minerals in fractures large
openings. Because of this, nanopores in shale formation always remain
open and invite water molecules to invade in the formation and cause
hydration (Akhtarmanesh et al., 2013). For a better inhibition process,
the physical or electrostatic plugging of nanopores is essential (Hoxha
et al., 2019; Sensoy et al., 2009) and it can be achieved only by the
application of nanoparticles with polymers. Polymers will mainly be
focusing on defusing reactive clay minerals in large openings and
nanoparticles will plug the pores in formation. In this manner, a better
inhibition can be produced in shale formation. Different nanoparticles
have been used in drilling fluid for shale inhibition as mentioned in
Table 3.
Nano-silica grafted with Hyperbranched Polyethyleneimine (HPEI)
has been used as an additive in WBDF for shale inhibition by Hanyi
Zhong et al. (2020a). Shale inhibition has been characterized by FTIR,
particle size distribution measurement, TGA, TEM, and NMR analysis
techniques. The grafted copolymer was prepared by polymerization of
PEI with nano-silica. Thermal stability of grafted copolymer improved
up to 1000 ◦ C with 25.41% mass loss only. The shale inhibition effi­
ciency was measured by linear swell meter and reported to be 59.5% for
grafted copolymer concentration 0.5 w/v %. The reported mechanism
for inhibition is the physical plugging by nano-silica and electrical
double layer suppression by HPEI due to electrostatic interaction and
hydrogen bonding with clay minerals. This behavior has been identified
by decrease in zeta potential, decrease in d-spacing of clay interlayers,
and images taken by TEM. The low inhibition efficiency of highly
effective reported inhibitor is because of increase in size of silica
nanoparticles. After grafting, the size of silica nanoparticles increased
from 12 nm to 184.3 nm. Because of this size increment, HPEI-silica
copolymer couldn’t perform the plugging properly and most of the
Fig. 14. Molecular structure of amidocyanogen silanol).
13
Journal of Petroleum Science and Engineering 204 (2021) 108745
inhibition produced was due to electrical double layer suppression by
HPEI in the copolymer.
In recent studies, different water soluble polymers used for enhanced
oil recovery (EOR) have been reported that can also be referred as shale
inhibitors in drilling fluids. Because they are reported to be having
characteristics of swelling inhibitors. Among them, alkali/surfactant/
polymers (ASP) are the most effective. Partially hydrolyzed poly­
acrylamide (HPAM) has been used with strong alkali (NaOH) and weak
alkali (Na2CO3) by Huiying Zhong et al. (2020b). The surfactants used
were alkylbenzene sulfonate (ABS) and petroleum sulfonate (DPS). This
ASP combination has been utilized to check the permeability damage
during flooding. A 15% permeability damage reduction has been re­
ported in heterogeneous cores with mudstone interlayers. Similarly,
Hollyhocks plant as a natural polymer and viscoelastic hydrophobically
associating water soluble polymers have been reported recently for ASP
flooding in EOR (Nowrouzi et al., 2020; Zhong et al., 2018). These
polymers have the hydrogen bonding ability and can be studied
regarding shale swelling inhibition.
Rajat Jain et al have studied the effect of Polyacrylamide-grafted-
PEG/n-Silica on shale inhibition in water-based drilling fluid. He stud­
ied shale inhibition for kaolinite-based clay (Jain et al., 2015). The
concentration of nano silica was 0.125 w% in the composite. The inhi­
bition was produced by the combined effect of physical plugging by
nano silica and hydrogen bonding by polyacrylamide-grafted-PEG with
reactive clay minerals. The reported inhibition efficiency is 58% at 0.9
w/v % of copolymer. The characterization was completed by XRD,
FESEM, and TGA. Hot rolling and immersed test were conducted to
measure inhibition performance. Silica nanoparticles are sensitive to
temperature. Their swelling index was increased at 75 ◦ C. Rheological
and filtration properties were improved due to nanocomposites. After
the degradation of PEG at 75 ◦ C, the swelling was initiated again.
Graphene nanoparticles (GNP), nano silica (n-silica), and Multi
Walled Carbon Nanotubes (MWCNT) have been utilized by A. Aftab et
al for-shale inhibition. GNP, n-silica, and MWCNT were used in con­
centration 0.1 ppb in WBDF (Aftab et al., 2017). He has used
kaolinite-based clay for inhibition testing and it was characterized by
XRD. These nanoparticles were used in combination with KCl and their
performance was compared with KCl/PHPA. The reported inhibition
mechanisms are physical plugging by nanoparticles, electrostatic inter­
action by KCl, and hydrogen bonding by PHPA. Shale inhibition was
measured by linear swelling test. By emersion in the inhibiting solution
for 20 h, GNP proved to be the most efficient one among other nano­
particles, KCl, and PHPA polymer. It has produced inhibition in clay
samples more than 75%. The major issue with other nanoparticles is
their contamination. Nano silica and MWCNT surface were covered with
-polymer that’s why can’t plug the pores completely and efficiently.
Polyethylene Glycol (PEG) grafted nano silica has been studied by
Jian-gen Xu et al in WBDF to check shale inhibition performance (Xu
et al., 2018). The concentration used was 0.3–1 w%. Kaolinite-based
clay has been utilized to check inhibition performance. In this study,
hydrogen bonds were made between PEG and reactive clay minerals,
and physical plugging by nano silica produced a combined inhibition
reported as 35–74%. The characterization was done by FTIR, SEM, TEM,
TGA, and particle size distribution. Hot rolling test was conducted and
the plugging efficiency was studied by the images of SEM and TEM.
Nano silica is sensitive to temperature and PEG degraded at 75 ◦ C, that’s
why the swelling index increased at 75 ◦ C.
M.A. Abbas et al.
Nanoscale Laponite has been used in shale inhibition study by
Xianbin Huang et al in WBDF (Huang et al., 2018). Laponite is a so­
dium magnesium silicate clay that is available in nano size. It has pos­
itive charges on edges. Due to these charges, they block the interlayer
space in shale formation and inhibit the swelling. A kaolinite-based clay
was used with 0.5–2 w% concentration of laponite to check inhibition
performance. The major parameter for inhibition is the electrostatic
interaction between laponite and reactive clay minerals. Immersion test,
linear swelling test, and shale recovery test were performed. The re­
ported performance efficiency is 50–75%. Laponite proved to be po­
tential inhibitor for shale swelling but it has only one disadvantage. With
higher pH values of drilling fluid, its charges are reversed. Means at high
pH, it cannot inhibit the water invasion in shale formations.
Koorosh Tookalloo et al studied the effect of Polyethylene Glycol
with multi walled carbon nanotubes (MWCNT) with 0.35 g concentra­
tion in WBDF (Tookalloo et al., 2018). Kaolinite-based clay have been
utilized for shale inhibition study. PEG inhibited shale by making
hydrogen bonds with clay minerals and MWCNT physically plugged the
pores in formation to stop the water invasion.
Immersion test and shale recovery test was employed to check in­
hibition performance. It has reported 75% shale inhibition. The reason
for low performance is the contamination of MWCNT with PEG. PEG
accumulated on MWCNT and both could not perform inhibition in shale.
Polyethylene Glycol (PEG) grafted nano silica was prepared by Pham
et al to examine its shale inhibition. Its performance was evaluated in
the presence of electrolytes NaCl and KCl. PEG grafted nano silica was
used in concentration at 0–3 w% with 21.2 w% of NaCl and KCl (Pham
and Nguyen, 2014). Montmorillonite clay was used for inhibition per­
formance. The inhibition mechanism was physical plugging by nano
silica, electrostatic interaction by NaCl and KCl, and hydrogen bonding
by polyethylene glycol. For the sake of pH control, sodium hydroxide
(NaOH) was also added in the drilling fluid. The effect of nanoparticles
concentration, electrolytes concentration, pH, and temperature were
studied.
Shale inhibition was measured by linear swelling test from 25 to
70 ◦ C. Shale inhibition efficiency was only 56%. The reasons are
explained here. When PEG grafted nano silica was used alone, inhibition
performance was very low. Because at higher concentrations, nano­
particles and montmorillonite made agglomerates and it was unable to
inhibit the swelling. When these nanoparticles were used with NaCl and
KCl, the inhibition performance was unknowingly improved. pH of
drilling fluid did not affect the shale inhibition performance of nano­
particles in the presence of NaCl and KCl. Due to the thermal degrada­
tion of PEG, the swelling index increased after 70 ◦ C and it became
unable to inhibit. After degradation of PEG, it desorbed from shale
surface and it became again available for water invasion and started
swelling.
4. Critical analysis of polymer inhibition results on the basis of
performance parameters
Inhibition induced by polymers in shale formation and its results are
being analyzed in this section. The analysis is completed on the basis of
performance parameters functional group’s electronegativity difference
(END), interaction mechanisms with reactive clay minerals i.e., elec­
trostatic interaction, physical plugging, covalent bonding, ion exchange,
or ion dipole forces. The hydrogen bonding strength is analyzed on the
bases of END and interaction of polymers with reactive clay minerals.
Electronegativity difference (END) is most important one because it
defines the ability of a molecule to attract electrons towards itself. As
much low END, the bond making ability with reactive clay minerals will
improve. The strength of hydrogen bond is also defined on the same
scale (Koizumi, 2020). The more the strong hydrogen bond, the more the
inhibition will be produced.
The characterization results are also being analyzed here and re­
ported in terms of proof of polymer inhibition efficiency. The d – spacing
14
Journal of Petroleum Science and Engineering 204 (2021) 108745
results from XRD analysis depict the reduction produced in interlayer
distance of clay formation. Zeta potential results explains the stability of
polymer in drilling fluid. Particle size distribution analysis (PSA) ex­
plains the change in particle’s size which is also a strong indication of
inhibition. Contact angle presents the wettability change and enhance­
ment of hydrophobicity in shale formation (Chu et al., 2020; Li et al.,
2020).
In this review work, it is observed that performance parameters are
playing an important role for shale inhibition. Among these parameters,
electronegativity is the most vital one because the polymer’s perfor­
mance is depending on it. It can be seen in Table 5 that with the decrease
in END, the polymer performance is getting better because it increased
the interaction of functional group towards reactive clay minerals. END
is varying from 3.04 to 1.25 for the polymers used previously where 3.04
was least efficient and 1.25 was most efficient shale inhibitor.
Interaction forces developed with reactive clay minerals include
electrostatic interaction (attraction), van der Waals forces, and ion
dipole forces. Polymers with amine, amide, imine, and hydroxyl group
have interacted electrostatically with clay and produced bonding to
neutralize it. These polymers have been reported as most efficient as
they inhibited shale hydration up to 76%. On the other side, ammonium-
based polymers produced van der Waals forces and were least efficient
in shale hydration inhibition and reported efficiency is around 25.
Polymers with high inhibition efficiencies have been endorsed by
different characterization analysis. XRD, zeta potential, PSA, TGA, and
contact angle characterization results are summarized in Table 5. The
general trend observed for an efficient inhibition in this review is given
in Table 4.
5. Conclusion and recommendations
This article has mainly described shale inhibition efficiency of
polymers and polymers along with nanoparticles in WBDF in recent
studies. This review attempt briefs on the description of shale swelling
and inhibition w.r.t. reactive clay minerals. The mechanism of shale
inhibition has been explained with respect to the parameters governing
the inhibitors performance. Based on parameters, polymers are found to
be more effective. The important aspects of these parameters w.r.t.
polymers are concluded in following points:
- Hydrogen bonding is the most important parameter for hydration
inhibition. Polymers establish bonding and neutralize reactive clay
mineral charges. Its strength depends on the lesser electronegativity
difference in functional group of inhibitors and forces developed
with reactive clay minerals.
- In this review, polymers with ammonium, amine, amide, imine, and
hydroxyl groups have been discussed with electronegativity differ­
ence in the range 3.04–1.25. It is observed that the polymers with
less electronegative groups have performed better inhibition such as
imine and hydroxyl groups till now with 1.3 and 1.25 electronega­
tivity difference, respectively.
- Interaction forces developed between polymer and reactive clay
minerals are electrostatic, Van der Waals, or ion dipole forces.
Among them electrostatic forces are the most effective. Amine,
amide, imine, and hydroxyl groups-based polymers have created
electrostatic forces and reported maximum inhibition up to 76%.
Ammonium-based polymers interacted with clay minerals by Van
der Waals forces and presented as low inhibition as 25%
approximately.
- Hydrophobicity with long alkyl chains is important but it needs to be
controlled by handling the number of carbon atoms in the side chain
of polymers. In literature, 4 to 7 carbon atoms are recommended in
alkyl chain.
- Cationic end nanoparticles utilization is important to plug nanopores
for inhibition along with polymers such as silica, laponite, graphene,
M.A. Abbas et al. Journal of Petroleum Science and Engineering 204 (2021) 108745

and surface modified MWCNT. Laponite and polyethylene glycol Table 5

grafted nano silica have given the maximum inhibition up to 74%. Characterization analysis discussion; general trend.
Polymers Analysis Observed Inhibition
Even being convenient in performing inhibition in shale formations, Indication
polymers were unable to inhibit hydration completely and shale Amine, Amide, Imine, Hydroxyl, X-Rays Decrease in d-spacing (d001)
swelling problem is still putting wellbore stability on target. Some and Ammonium base Polymers Diffraction
important recommendations to improve the performance are: Zeta Potential Stability range for polymer is
− 35 to 25 normally
Particle Size Particle size increases as
- In most of the studies, polymers were unable to inhibit hydration Analysis inhibition occurs
because of their low activity towards reactive clay minerals and Contact Angle Contact angle increases
making hydrogen bonds with them. Here comes the role of electro­ because of wettability
negativity in the active site of polymers. Other than hydroxyl groups, changes
polymers with electronegativity difference less than 1.25 are rec­
ommended for better inhibition.
inhibit hydration problem by neutralizing the reactive clay minerals
- Highly thermal stable polymers are recommended for inhibition
and plugging the pores as well.
because at high temperatures, the previous polymers were unable to
inhibit the swelling.
Author contributions
- Porosity-Permeability analysis of shale formation must be included
in further research work to select the exact size of nanoparticles.
Muhammad Adeem Abbas: Conceptualization, Writing the original
With appropriate size, nanoparticles can plug the pores efficiently.
draft and revisions. Asif Zamir: Supervision, Review & Editing. Khaled
- A biodegradable solution with polymer and nanoparticle hybrid with
Abdalla Elraies: Supervision, Review & Editing. Syed Mohammad
low environment footprints is the need of time. This solution will
Mahmood: Review & Editing. Muhammad Hammad Rasool: Review

Table 4
Critical Analysis of Polymer Inhibition Results on the bases of Performance Parameters.
Research Article Parametric Analysis Characterization Results Analysis

END Interaction Discussion XRD ζ - Potential PSA TGA Contact

Angle

nm mV oC degree

Gang Xie et al. (2020) 3.04 Van der Waals forces poor hydrogen bond due to 1.41 – – – –
high END
Murtaza et al. (2020) 3.04 Electrostatic Interaction poor hydrogen bond due to – − 23.38 – – –
high END
Qi Chu et al. (2020) 3.04 Covalent Bonding poor hydrogen bonds but good 1.28 − 20.36 – 140 80.16
adsorption
Xingliang et al. 3.04 Electrostatic Interaction poor hydrogen bonds due to – − 15.9 15.15–22.41 215–347 –
(2020) charges similarity μm
Qi Chu et al. (2019) 1.4 Electrostatic Interaction good hydrogen bonds due to 1.25 – – 140 –
low END
Yuxiu et al. (2018) 1.4 Electrostatic Interaction good hydrogen bonds due to 1.38 0–2.5 52–100 nm 120 –
low END
Xianmin et al. (2018) 1.4 Physical Plugging good hydrogen bonds due to – – 92–955 nm 343 62.16
low END
Gang Xie et al. (2017) 1.4 Electrostatic Interaction good hydrogen bonds due to 1.328–1.385 – 0.43–0.45 nm 80 –
low END
Rajat Jain et al. 1.4 Electrostatic Interaction good hydrogen bonds due to – – – 95 –
(2017) low END
Moslemizadeh et al. 1.3 Electrostatic Interaction better hydrogen bonds as 20-130 Å – – 200 High
(2017) compared to others
Fengjie Ma et al. 1.3 Electrostatic Interaction better hydrogen bonds as – − 19 to − 16 5.94–8.84 μm 288 –
(2017) compared to others
Guancheng et al. 1.4 Electrostatic Interaction good hydrogen bonds due to 1.32 − 34.5 – 143 37.73–51.23
(2017) low END
Guancheng (2017) 1.4 Covalent Bonding good hydrogen bonds due to 1.39–1.42 − 8 to 8 – 120 –
low END
Conny et al. (2016) 1.24 Electrostatic Interaction better hydrogen bonds as 1.47–1.49 – 50–80 nm 200 –
compared to others
Zhong et al. (2016) 1.4 Electrostatic Interaction good hydrogen bonds due to 1.29–1.44 − 33.15 to 10.5–15 μm 300 –
low END 15.42
Gang Xie et al. (2016) 1.4 Electrostatic Interaction good hydrogen bonds due to 1.32–1.36 – – 120 –
low END
Zhang et al. (2015) 1.4 Ion Exchange & good hydrogen bonds due to 1.39–1.47 − 20.4 2–4.5 μm 70 –
Electrostatic Interaction low END
Zhong et al. (2015) 1.4 Electrostatic Interaction good hydrogen bonds due to 1.32–1.38 – – 200 –
low END
Shadizadeh et al. 1.25 Adsorption & Electrostatic better hydrogen bonds as – – – 82 –
(2015) Interaction compared to others
Yuxiu et al. (2015) 3.04 Electrostatic Interaction poor hydrogen bond due to 1.46 31.6–38 – – –
high END
Carlos et al. (2009) 1.25 Ion Dipole Forces better hydrogen bonds as 14.7–22.7 Å – – 120 –
compared to others

15
M.A. Abbas et al. Journal of Petroleum Science and Engineering 204 (2021) 108745

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