Journal of Molecular Liquids 340 (2021) 117134

Contents lists available at ScienceDirect

Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Clay-water interaction inhibition using amine and glycol-based deep

eutectic solvents for efficient drilling of shale formations
Mukarram Beg a, Mohd Belal Haider b, Nitu Kumari Thakur c, Maen Husein d, Shivanjali Sharma a,⇑,
Rakesh Kumar b
a
Department of Petroleum Engineering and Geological Sciences, Rajiv Gandhi Institute of Petroleum Technology, Jais, Amethi, Uttar Pradesh 229304, India
b
Department of Chemical Engineering and Engineering Sciences, Rajiv Gandhi Institute of Petroleum Technology, Jais, Amethi, Uttar Pradesh 229304, India
c
Department of Petroleum Engineering & Earth Sciences, University of Petroleum and Energy Studies, Dehradun, Uttarakhand 248007, India
d
Department of Chemical & Petroleum Engineering, Center for Environmental Engineering Research & Education (CEERE), University of Calgary, Calgary, AB T2N 1N4, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Water-based muds (WBMs) are preferred over oil-based muds owing to their lower cost and environ-
Received 19 April 2021 mentally friendly nature. However, shale instability arising from clay-water interaction is a challenging
Revised 23 July 2021 concern. The current work explores the potential of deep eutectic solvents (DESs) as shale stabilizers for
Accepted 27 July 2021
WBMs. Four amine and glycol-based DESs with different chemical composition were synthesized in the
Available online 29 July 2021
laboratory. The rheological and filtration properties of WBMs showed that DES-A, which is composed of
tetrabutyl ammonium bromide and diethanol amine, and DES-B, which is composed of tetrabutyl ammo-
Keywords:
nium bromide and diethylene glycol, with less sterically hindered cationic functionality improved the
Ionic liquids
Clay-water interaction
mud functionality. Shale inhibition performance of DESs was collected from capillary suction timer, linear
Shale swelling swell meter and shale disintegration tests. These tests revealed that DES-A and DES-B are highly efficient
Drilling fluid and outperform the conventional shale inhibitor KCl and the commercially available ionic liquid 1-butyl-
Capillary suction 3-methylimidazolium chloride (BMIM[Cl]). Shale swelling in presence of 0.2 w/v% DES-A and DES-B
Mud decreased by ~54.6% and ~70.9%, respectively. Moreover, shale recovery improved by ~17.2% and
~18.2% and capillary suction time decreased by 45% and 48% in presence of 0.5 w/v% of DES-A and
DES-B, respectively. The quaternary ammonium functionality helped in shale stabilization which was fur-
ther improved due to the presence of –OH group in the hydrogen bond donor in DESs. Quick cost analysis
showed the feasibility of industry scale application of DES-A and DES-B as shale inhibitors into WBMs.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction
Instability of the wellbore is one of the major problems encoun-
tered during drilling shale formations. It is noted that more than
75% of drilled wellbores across the globe encounter shale forma-
tion at some depth [1]. Formulating a water based mud (WBM)
Abbreviations: AHR, After Hot Rolling; ATR, Attenuated Total Reflectance; AV,
Apparent Viscosity; BHR, Before Hot Rolling; BM, Base Mud; CST, Capillary Suction
Time; DEG, Diethylene Glycol; DES, Deep Eutectic Solvents; FTIR, Fourier Transform
Infrared Spectroscopy; HBA, Hydrogen Bond Acceptor; HBD, Hydrogen Bond Donor;
HEC, Hydroxyethyl Cellulose; LPLT, Low Pressure and Low Temperature; LSM,
Linear Swell Meter; MTPPhBr, Methyltriphenyl Phosphonium Bromide; NMR,
Nuclear Magnetic Resonance; PAC-RG, Polyanionic Cellulose Regular Grade; PHPA,
Partially Hydrolyzed Polyacrylamide; Psi, pounds per square inch; PV, Plastic
Viscosity; Rpm, revolutions per minute; TBAB, Tetrabutyl Ammonium Bromide;
WBM, Water Based Mud; XG, Xanthan Gum; XRD, X-Ray Diffraction; YP, Yield Point.
⇑ Corresponding author.
E-mail address: ssharma@rgipt.ac.in (S. Sharma).
with the necessary rheological, filtration and shale inhibition char-
acteristics is a major challenge. More than 70% of the wellbore
problems are, in fact, associated with shale interaction with water
present in WBM [2,3]. Alternatively, industry resorts to oil based
muds, which are costly and pose serious environmental problems,
especially in light of the stringent environment regulations [4].
Therefore, developing cost effective, shale friendly WBMs presets
an attractive alternative.
Effect of clay content, composition and reactivity of shale cut-
tings in aqueous environment is important to understand the
long-term and short-term inhibition of shales [5]. The presence
of certain clay minerals, structure, bedding and thin laminae, and
pre-existing fractures strongly affect shale instability on exposure
to water present in WBM. This understanding led to the conclusion
that with proper composition and concentration of chemical addi-
tives, desired inhibition can be achieved [6]. Accordingly, effort
involved the use of salts such as potassium chloride, sodium

https://doi.org/10.1016/j.molliq.2021.117134
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
M. Beg, M.B. Haider, N.K. Thakur et al.
Nomenclature
Greek letters
U600 viscometer dial reading at 600 rpm
U300 viscometer dial reading at 300 rpm
U200 viscometer dial reading at 200 rpm
U100 viscometer dial reading at 100 rpm
chloride and divalent brines, sodium chloride/starch muds, silicate
muds, lime-muds and calcium sulfate-based gyp muds [7-9].
Highly inhibitive silicate treated WBM were developed, which
were nevertheless limited by silica precipitation during drilling
[7,10,11]. Polymeric additives such as partially hydrolyzed poly-
acrylamide (PHPA) have been used in WBM for reducing shale
instability [12-15]. A number of nanoparticles and polymer
nanocomposites have also been proposed as effective additives in
WBM to mitigate filtration loss and shale instability problems
[1,16-27]. In our previous works, we have synthesized low molec-
ular weight amine based homopolymers and copolymers for
reducing shale swelling and filtration loss of WBMs [28,29]. There
are many aspects that should be considered while optimizing dril-
ling fluids for a particular drilling program, including the safety of
drilling crew and environment, lower mud cost, efficient hole
cleaning, high rate of penetration, shale stabilization, lubrication,
minimizing fluid loss and retaining the mud properties upon circu-
lation for reuse. However, these are very complex requirements
and in many cases, they contradict each-others. Drillers, therefore,
have a large number of mud additives at their disposal to manage
these complex situations.
Ionic liquids have been also investigated as drilling fluids addi-
tives. A number of ionic liquids have been identified as potential
shale inhibitors to improve wellbore stability in WBM [30-33].
Moreover, the effectiveness of ionic liquids at reducing filtration
loss was found very helpful at minimizing shale instability [34-
36]. On the other hand, the higher cost and the complex purifica-
tion steps associated with ionic liquids have limited their industry
application.
Deep eutectic solvents (DESs) have recently gained attention as
alternative ionic liquids [37]. DESs are synthesized by the combi-
nation of hydrogen bond donor (HBD) and hydrogen bond acceptor
(HBA) in fixed molar ratios. DESs have properties similar to the
ionic liquids but do not require complex purification step, which
significantly lowers their cost. It should be noted that even though
DESs and ionic liquids are similar in properties, they fundamentally
differ in the nature of their interactions. DESs are formed via van
der Waals and hydrogen bond interactions whereas ionic liquids
results entirely due to ionic bonds [38]. Similar to ionic liquids,
DESs are designer solvents synthesized for particular application.
For example, DESs have been applied to CO2 capturing, biodiesel
production, extractive desulfurization, azeotropic separation,
enhanced oil recovery, etc. [39-44].
Jia et al. were the first to apply DESs in drilling fluids [45]. They
synthesized three different types of choline chloride based DESs
and investigated their role as shale inhibitors. DESs were found
to be effective shale inhibitors owing to their ability to interact
with the clays through electrostatic interactions as well as hydro-
gen bonding. In another work, Jia et al. showed that the DESs exhi-
bit excellent shale inhibition properties even at high temperatures
[46]. These results suggested DESs as effective drilling fluid addi-
tives to mitigate shale instability. Nevertheless, there is very lim-
ited literature on the use of DESs in WBM as shale inhibitor
which makes this work more significant to explore various insights
on the application of DESs.
2
Journal of Molecular Liquids 340 (2021) 117134
U6 viscometer dial reading at 6 rpm
U3 viscometer dial reading at 3 rpm
2h the angle between transmitted beam and reflected
beam in XRD analysis
In this work we have synthesized four different types of DESs
and investigated their use as WBMs additives to mitigate shale
instability problems. Two different types of hydrogen bond donors;
namely glycol and amine, and two different types of hydrogen
bond acceptors; namely phosphonium and ammonium, were used
to synthesize the DESs. It is noted that the ammonium-based
acceptor is less sterically hindered. The role of the DESs as WBM
additives was investigated in light of their effect on the rheological
and filtration characteristics of the mud. Then, the DESs shale inhi-
bition attributes were assessed using capillary suction timer, linear
swell meter and shale disintegration tests. Lastly, quick cost anal-
ysis was performed in order to assess the feasibility of the as-
synthesized DESs as industry scale additives to WBM for drilling
through shale.
2. Materials and methods
2.1. Materials
Bentonite powder (Bt), hydroxyethyl cellulose (HEC), xanthan
gum (XG) and potassium chloride (KCl) were all procured from
Molychem, Mumbai, India. Shale cuttings and polyanionic cellulose
regular grade (PAC-RG) was provided by Oil and Natural Gas Cor-
poration (ONGC) Ltd, Dehradun, India for research purpose. 1-
Butyl-3-methylimidazolium chloride (98% pure) is a commer-
cially available ionic liquid which was purchased from Sigma
Aldrich, India. Octan-1-ol (<0.3% H2O; >99% pure) tetrabutyl
ammonium bromide (99% pure) and diethylene glycol (99%
pure) were purchased from S D FineChem Limited, India. Methylt-
riphenyl phosphonium bromide (>98% pure) was purchased from
the Avra Synthesis Private Limited, India. Diethanol amine with
(99% pure) was purchased from ThermoFisher Scientific, India. All
chemicals were used as received without further purifications.
2.2. Synthesis of the DESs
Detailed preparation of DESs is given in our previous work
[41,47]. In brief, to prepare DES, a hydrogen bond donor and a
hydrogen bond acceptor at a proper mole ratio are vigorously stir-
red at 60 °C. In this work, tetrabutyl ammonium bromide (TBAB)
and methyltriphenyl phosphonium bromide (MTPPhBr) were used
as the hydrogen bond acceptors and diethanolamine (DEA) and
diethylene glycol (DEG) were used as the hydrogen bond donors.
Four combinations denoted as DES-A (TBAB in DEA), DES-B (TBAB
in DEG), DES-C (MTPPhBr in DEA), and DES-D (MTPPhBr in DEG)
were synthesized, as shown in Table S1. The vigorous stirring
was maintained for 2 h before the covered solution was allowed
to cool down naturally under atmospheric condition to room tem-
perature. The as-prepared DESs were clear and homogenous liq-
uids. The DESs was further dried overnight at 50 °C under vacuum.
2.3. Preparation of base mud and mud formulations containing DESs
The base mud was prepared by mixing 4.0 w/v% bentonite pow-
der in tap water using a Hamilton beach mixer for 15 min. The dis-
M. Beg, M.B. Haider, N.K. Thakur et al. Journal of Molecular Liquids 340 (2021) 117134

persion was kept for 16 h to allow complete hydration of the clay stress vs shear rate relationship. The Bingham plastic model for
unit layers for exfoliation of bentonite. The dispersion was further non-Newtonian fluids is preferred rheology model for drilling flu-
mixed with 0.25 w/v% XG and PAC-RG using a Hamilton beach ids by oil and gas industry. The key parameters to describe the flow
mixer for 5 min for each polymeric additive. The base mud was behavior of drilling fluids are apparent viscosity (AV), plastic vis-
mixed for 10 min at speed III to ensure uniform mud before use. cosity (PV) and yield point (YP) which were calculated using Eq.
Initially the four types of DES; namely DES-A, DES-B, DES-C and S1 to S3 [29,49] (in Supporting Information). AV is ratio of the
DES-D, were used to prepare mud formulations. Base muds were shear stress to shear strain at a given shear rate. In case of petro-
modified by adding 0.50 w/v% of each DESs using Hamilton beach leum industry AV is defined at a specified shear rate of 600 rpm
mixer for 10 min. Immediately after the addition of DES to the base as recommended by API RP 13-B1. PV express the ease of drill bit
mud, 4–5 drops of a defoamer (octan-1-ol) was added to suppress penetration which can be determined by extrapolating the viscos-
foam. The mud formulation was mixed for 10 min to completely ity at infinite shear rate. YP is the measurement of the ability of
mix the DES in the base mud. The rheology and filtration results drilling fluid to carry the cutting during mud circulation and it
of these DES muds were used to screen the compatibility of a given can be defined as the shear stress at zero shear rate for Bingham
DES. DES-A and DES-B were selected for further investigation and plastic fluids. The initial and final gel strength were measured by
their concentration in the base mud was varied to prepare 10 for- reporting the viscometer dial readings at 3 rpm rotational speed
mulations, as detailed in Table 1. All these mud formulations were after 10 s and 10 min, respectively. Gel strength is the indicator
subjected to hot rolling at 110 °C for 16 h in a roller oven. The pres- of holding the cuttings in suspension while the fluid is at static
sure in the ageing cell was kept at 150 psi to suppress the evapo- condition.
ration of water during the ageing process.
2.6. Filtration loss
2.4. Characterizations
Filter Press (make – FANN, model – Series 300) was used to
X-Ray diffraction (XRD) analysis of the shale sample was carried measure the fluid loss of the mud samples at low pressure (100
out on PANalytical X’Pert PRO, Spectris plc X-ray diffractometer psi) and low temperature (25 °C), which is also termed as API LPLT
with a scan range of 2h of 5–70°. Powdered shale sample was fluid loss. Specially hardened with qualitative low-ash filter paper
mixed with 20% (w/w) of commercial bentonite to prepare repre- having 2.7 mm nominal pore size and ~9 cm diameter was used.
sentative shale pellets of highly active shale formation. The same This filter paper is the equivalent of Whatman #50 filter paper.
shale-bentonite mix was used in the shale inhibition study of this Once fitted, the filter paper is partly covered by the gasket and
work. hence has an effective filtration area of 45.8 cm2.
The FTIR spectra of the DES additives were recorded on a Perki-
nElmer Spectrum Two spectrometer. ‘‘Attenuated Total 2.7. Capillary suction timer tests
Reflectance” (ATR) mode was employed to analyze the samples
in the FTIR with the help of PIKE MIRacle single reflection horizon- OFITE capillary suction timer was used to measure the capillary
tal ATR accessory equipped with a ZnSe ATR crystal. NMR charac- suction time (CST) of bentonite in water dispersions. DES-A or DES-
terization of the DESs was performed using ECZS Series 400 MHz B was mixed in water at concentrations shown in Table 1. The
NMR SPECTROMETER (Make – JEOL, Japan). Field strength of aqueous solution of the DESs was then mixed with 4.0 w/v% ben-
400 MHz was used at a temperature of 20 °C and relaxation delay tonite using vortexer at 2500 rpm for 1 min and then a homoge-
of 5 s. nizer at 20,000 rpm for 3 min. The slurry was tested for CST
exactly after 5 min of adding the bentonite to evaluate the effect
2.5. Mud rheology of DES concentration on CST values. CST measurements represent
the water inhibition characteristic of an additive.
American Petroleum Institute (API) recommended practice 13B-
1 (API RP 13B-1) was followed for testing the rheology of the mud 2.8. Shale swelling inhibition test
formulations [48]. Rheological parameters of the drilling muds
were analyzed by a six-speed viscometer (make – FANN, Model Linear swell meter (LSM, make – FANN, model – 2100) test
35) which is frequently used in the petroleum industry across apparatus was used to perform LSM testing of five mud formula-
the globe. Different rotational speeds were used to obtain the shear tions including base mud with and without shale inhibitors. LSM
uses a reconstituted shale pellet of ~2.54 cm diameter prepared
by compressing ~20 g of shale-bentonite powder (20 w/w% ben-
tonite) using a hydraulic press at 10,000 psi. The thickness of the
Table 1
Mud formulations used in the detailed study. compact shell pellets was ~1.25 cm. These pellets were immersed
in the mud sample and the LSM instrument probe determined the
Sample Mud Formulation DES-A Concentration DES-B Concentration
change in the pellet thickness over a duration of 2 h.
# code (w/v%) (w/v%)
1 BM 0 0
2 BMA005 0.05 0 2.9. Shale dispersion test
3 BMA010 0.10 0
4 BMA025 0.25 0 Shale cuttings were sorted by passing through 6 BSS mesh sieve
5 BMA050 0.50 0
and retained on 10 mesh sieve. These cuttings were mixed into the
6 BMA075 0.75 0
7 BMA100 1.00 0 drilling fluids before hot rolling and taken out of the mud after 16 h
8 BMB005 0 0.05 of hot rolling. Cuttings dispersion during hot rolling inside a cylin-
9 BMB010 0 0.10 drical ageing cell allowed sufficient contact between the mud and
10 BMB025 0 0.25 the shale cuttings. Shale disintegration resulted in a decreased
11 BMB050 0 0.50
12 BMB075 0 0.75
weight of the cuttings [14]. The cuttings were filtered out of the
13 BMB100 0 1.00 mud using 40 mesh screen, gently washed with water and dried
in an oven for 2 h at 105 °C. After drying, the percentage decrease
3
M. Beg, M.B. Haider, N.K. Thakur et al.
in the weight of cuttings was calculated and % recovery was
reported [29].
3. Results and discussions
3.1. DES characterization
The FTIR spectra was used to understand the structure and
potential interaction between DESs, the rest of the mud compo-
nents and the shale formation. The FTIR spectra for diethylene gly-
col and diethanolamine is shown in Fig. 1. The peak around 3600–
3000 cm 1 correspond to the presence of AOH stretching in all
DESs [50]. The presence of ANH bond for diethanolamine based-
DESs is captured in the bending around 1470 cm 1 [51]. It is noted
that phosphonium (-PH) and ammonium (ANH) stretching
expected in MTPPhBr and TBAB, respectively, are probably over-
lapped by the ACH stretching around 3000–2750 cm 1 [52]. The
AOH stretching for diethylene glycol shifted from 3338 cm 1 to
lower wave numbers, 3352 cm 1 and 3383 cm 1, for DES-B and
DES-D, respectively, confirming hydrogen bond formation. Neither
of the DESs spectrum shows a new bond formation, but rather a
shift in the AOH bond is observed. This fact was also confirmed
by the HNMR spectrum which shows absence of any new peaks
and only a shift in the AOH group of DES-B and DES-D is observed,
as shown in Fig. 2 [52]. Similar, behavior is also observed in the
diethanol amine-based DESs.
3.2. XRD of bentonite and shale
XRD analysis of shale powder containing 20% (w/w) bentonite
was performed to identify the various components of the mineral
and the potential interaction with the mud. Fig. 3 reveals kaolinite,
quartz, pyrite, siderite, mica and microcline as major minerals in
the shale sample. Montmorillonite characteristic XRD peak was
observed at 2h of ~6.5° which is attributed to the bentonite [53].
The smectite-type minerals in the shale suggest a highly interac-
tive composition easily susceptible to swelling in presence of
WBMs. Furthermore, the presence of kaolinite endows a dispersive
nature on the shale owing to the fact that kaolinite is a dispersive,
non-swelling clay [54]. Upon water sorption by kaolinite, breaking
or sliding of clay lattice occurs leading to dispersion of clay mate-
rials. Siderite, a carbonate material, is significantly softer and
imparts porosity onto shale formation [54]. Quartz minerals also
Fig. 1. FTIR spectra of (a) diethnaol amine-based DESs, and (b) diethylene glycol-based DESs and their respective H-bond donors.
4
Journal of Molecular Liquids 340 (2021) 117134
increase the porosity of the shale; however, they are hard.
Increased formation porosity contributes to more fluid penetra-
tion, hence promoting shale instability in WBMs. Accordingly,
muds with high inhibition capacity which suppress swelling and
dispersion of the shale become more relevant.
3.3. Preliminary study of DESs as mud additives
Base mud and four DESs modified mud formulations containing
0.5 w/v% of each DES were tested for their rheological and filtration
behavior. The samples were first hot rolled at 100 °C for 16 h.
Table 2 summarizes the rheological parameters and LPLT filtration
results. The addition of DES-A and DES-B increased the rheological
parameters, whereas the presence of DES-C and DES-D decreased
the rheological parameters. AV of the base mud was 34.0 cP before
hot rolling which increased to 48.5 and 54.5 cP on addition of 0.5
w/v% DES-A and DES-B, respectively. AV decreased from 34.0 cP
to 27.5 and 30.5 cP with the addition of DES-C and DES-D, respec-
tively. Similar trend, with varying magnitude, was observed for the
YP and the gel strength of the base mud on addition of DESs. In
general, during hot rolling, thermal degradation of mud additives
decreases the rheological properties and increases the filtration
loss. After hot rolling of the mud formulations, the degradation
in AV due to ageing of the base mud was ~34%, which decreased
to just ~7% for DES-A and ~3% for DES-B. The corresponding degra-
dation of AV in presence of DES-C and DES-D were 32% and 8%,
respectively. Proper values of AV and YP improve wellbore cleaning
and cuttings suspension, which are the most important functions
of a drilling fluid. Gel strength of a mud assists in holding the dense
rock cuttings in suspended form during tripping and therefore a
proper in gel strength is desired[24,55]. Hence, it is safe to say that
that DES-A and DES-B are more effective in improving the rheolog-
ical properties of the mud as compared with the other two DESs.
LPLT filtration loss results in Table 2 show that DES-A and DES-B
reduced the filtration loss by ~17% and ~19%, respectively, whereas
DES-C and DES-D increased fluid loss by ~12% and ~7%, respec-
tively. The superior performance of DES-A and DES-B in improving
the mud characteristics is believed to be due to the presence of
quaternary ammonium salts as opposed to the phosphonium salt
in case of DES-C and DES-D. Quaternary ammonium salts carrying
positive charges with higher surface charge density at the nitrogen,
owing to the smaller size of the nitrogen atom as compared to
phosphorous, make them more effective for electrostatic interac-
tion with negatively charges sites in other additives, specially at
M. Beg, M.B. Haider, N.K. Thakur et al. Journal of Molecular Liquids 340 (2021) 117134

Fig. 2. H-NMR spectra of (a) diethnaol amine-based DESs, and (b) diethylene glycol-based DESs.

the basal surfaces of bentonite crystals. Another factor which ways due to resonance. This charge distribution significantly
reduces the surface charge density of the MTPPhBr is the fact that reduces the surface charge density resulting in weaker electrostatic
a positive charge is distributed over 4 atoms in three different attraction with negatively charged sites of other additives such as

5
M. Beg, M.B. Haider, N.K. Thakur et al. Journal of Molecular Liquids 340 (2021) 117134

Fig. 3. XRD analysis of a 20% (w/w) bentonite into shale powder mixture.

Table 2
Rheological and LPLT filtration performance of base mud and different mud formulations modified with 0.5 w/v% DESs before (BHR) and after (AHR) hot rolling.

Sample # Parameter BM BM + DES-A BM + DES-B BM + DES-C BM + DES-D

BHR AHR BHR AHR BHR AHR BHR AHR BHR AHR
1 U600 68 45 97 90 109 106 55 37 61 56
2 U300 54 33 79 74 88 86 37 24 45 40
3 U200 48 28 69 64 78 76 29 18 37 32
4 U100 39 21 55 50 60 58 20 12 28 24
5 U6 21.5 8.5 30 25 31 26 6 4 12 7
6 U3 19 7 27 21 28 22 5 3 10 5
7 AV*(cP) 34.0 22.5 48.5 45.0 54.5 53.0 27.5 18.5 30.5 28.0
8 PV*(cP) 14.0 12.0 18.0 16.0 21.0 20.0 18.0 13.0 16.0 16.0
9 YP*(lb/100ft2) 40.0 21.0 61.0 58.0 67.0 66.0 19.0 11.0 29.0 24.0
10 Gel 0 (lb/100ft2) 20.5 10 21 19 21 19 7 3 14 5
11 Gel 10 (lb/100ft2) 31 16 30 32 30 32 29 9.5 21 13
15 LPLT fluid loss (mL) – 11.4 – 9.5 – 9.2 – 12.8 – 12.2

UN is the dial reading at N rpm speed of viscometer rotor.

*Details on the calculation of these parameters are provided in the supporting document.

negatively charged basal surfaces of bentonite platelets and ACOO– (BMA005) are almost overlapping (Fig. 4a), whereas that is not
group of PAC. These electrostatic interactions are responsible for the case for BM and BMB005 (Fig. 4b). Higher values of shear
the increase in viscosity as well as other rheological properties of stress were obtained for muds containing DES-B compared with
the mud systems. Therefore, DES-A and DES-B were selected for DES-A after hot rolling. This can be attributed to the presence
further investigation. of DEG in case of DES-B. DEG has higher relative polarity that
of DEA owing to the higher electronegativity of the AOA atom
at the center of molecule (Fig. 5). Accordingly, DEG is more effec-
3.4. Effect of DES-A and DES-B concentration on mud rheology
tive in forming hydrogen bonds with water as well as other DEG
molecules. An increase in the attractive intermolecular interac-
Shear stress vs shear rate curves of all the mud formulations
tions increases the viscosity of the fluid.
before and after hot rolling are shown in supporting information
Fig. 6 represents the values of AV, PV and YP before (BHR) and
(Fig. 4). As the concentration of both DESs increased, an improve-
after (AHR) hot rolling for muds containing different concentra-
ment in rheology captured by the higher shear stress at a given
tions of DES-A or DES-B. The increase in AV of the base mud before
shear rate is observed. Fig. 4a, a’ shows the rheology curves of
hot rolling due to the addition of 1.0 w/v% of DES-A was ~65% and
DES-A containing mud formulations before and after hot rolling,
that for 1.0 w/v% DES-B was ~82% (Fig. 6). The reduction in AV of
respectively. Similarly, Fig. 4b, b’ shows the shear stress vs shear
the base mud (BM) due to hot rolling was ~34%, which limited to
rate graphs of drilling fluids containing DES-B before and after
~7% on addition of 0.5 w/v% DES-A (BMA050) and to ~3% on addi-
ageing, respectively. Overall, ageing (or hot rolling) resulted in a
tion of 0.5 w/v% DES-B (BMB050) and the degradation was found to
reduction in the shear stress for all mud formulations at any
be negligible at the highest concentration. This suggests a tangible
given shear rate. However, this reduction is significantly higher
advantage of using DES-A and DES-B for reducing the effects of
for the base mud. Furthermore, a comparison between mud for-
long-term heat exposure. Before hot rolling, PV also increased with
mulations with DES-A and those with DES-B suggests that DES-
increasing the concentration of either DESs and remained under 26
B is more effective in improving the rheology of WBMs. Even at
cP for all the mud formulations (Fig. 6c and d). After hot rolling, PV
the lowest concentration (0.05 w/v%) of DESs, shear stress vs
decreased by only 1 or 2 cP for all the mud formulations. Lower
shear rate curves for BM and the DES-A-containing mud
6
M. Beg, M.B. Haider, N.K. Thakur et al.
Fig. 4. Shear stress vs shear rate curves of all the mud formulations listed in Table 1. (a) and (b) before (BHR); (a’) and (b’) after (AHR) hot rolling.
Fig. 5. Schematic showing the difference in relative polarity of O–H bonds present
in DEA and DEG molecules.
values of PV, preferably <30 cP, are helpful in drilling at a faster
rate of penetration [14]. Accordingly, DES-A and DES-B are excel-
lent rheology modifiers, especially since they increase AV with
minimal increase in PV. The cuttings carrying capacity of drilling
fluids depends on YP. Mud formulations containing the DESs por-
trayed higher YP than base mud. Increasing the concentration of
DESs before hot rolling (BHR) resulted in higher YP values for both
the DESs (Fig. 6e and f). Even at lowest DESs concentration tested
7
Journal of Molecular Liquids 340 (2021) 117134
(0.05 w/v%), only ~17.0% and 9.3% reduction in YP was encountered
for DES-A and DES-B, respectively. Again, these results confirm the
excellent ability of the DESs in controlling the thermal degradation
of the mud.
Cuttings suspension ability of the mud, especially during inter-
rupted operation, is crucial for drilling operations [56]. The ability
of the mud to suspend the cuttings is controlled by the gel strength
of the mud. Fig. 7 shows the initial and final gel strengths of mud
samples with different concentrations of DES-A and DES-B before
(BHR) and after (AHR) hot rolling. Fig. 7 shows that DESs did not
affect gel strength of freshly prepared mud, i.e. BHR, significantly.
However, the reduction in the initial and the final gel strength of
base mud (BM) due to hot rolling decreased progressively as the
concentration of DESs increased. For example, for DES concentra-
tion higher than 0.5 w/v%, the values of the final gel strength
AHR were even higher than the BHR values (Fig. 7c, d), but
remained close to 30 lb/100 ft2 which is close to the BHR final
gel strength of base mud.
3.5. Filtration loss control
While drilling, the mud should be prevented from seeping
into formation causing formation damage. The results of the
LPLT fluid loss are shown in Fig. 8 for muds containing different
concentrations of DES-A or DES-B. Fluid loss of the based mud
was 11.4 mL, which decreased with increasing DES-A or DES-B
concentration. Fig. 8 depicts high initial rate of filtration, which
decreases with time. During filtration, driven by the flow the
solid content of the mud deposits onto the filter paper to form
M. Beg, M.B. Haider, N.K. Thakur et al. Journal of Molecular Liquids 340 (2021) 117134

Fig. 6. AV, PV and YP of mud formulations with varying concentration of DES-A and DES-B before (BHR) and after (AHR) hot rolling.

a layer, which increases in thickness increases with time. The ternary ammonium group (cation) in DESs and by the hydrogen
permeability of the mud cake, which is influenced by the solid bonding between these negative sites and AOH groups present
additives, is the key to controlling fluid loss. On the other hand, in the DESs. This interaction results in a more compact filter
DESs also act as a fluid loss agent. An increase in DESs concen- cake with reduced permeability.
tration decreases the permeability the filter cake. Fig. 8c shows
that the LPLT fluid loss control ability of DES-B is a little higher
3.6. Effect on capillary suction time of aqueous bentonite dispersion
than that of DES-A. For example, the reduction in cumulative
fluid loss by addition of 1.0 w/v% of DES-A and DES-B was
Bentonite dispersions in water with varying concentrations of
~19% and ~23%, respectively. Overall, the reduction of fluid loss
DES-A or DES-B were tested for their CST values. To ensure reli-
suggests the ability of DESs to decrease water infiltration into
ability of the measurements, each experiment was replicated
different formations, including shale. Filter cake formed by the
three times and the average with standard deviation are shown
solids present in WBM also contain bentonite platelets and
in Fig. 9. Detailed analytical results of these tests are shown in
polyanionic cellulose. Both of these additives have negative sites
Table S2. The addition of DES-A and DES-B resulted in a decrease
which could be bridged by the electrostatic attraction with qua-
in the CST values. This suggests increased amount of free water
8
M. Beg, M.B. Haider, N.K. Thakur et al.
Fig. 7. (a,b) Initial (10 sec) and (c,d) final (10 min) gel strengths of mud formulations with varying concentration of DES-A and DES-B.
in the bentonite slurry as bentonite is absorbing less water in
presence of DESs. Further reduction in CST values with increas-
ing DES concentration from 0.05 to 1.00 w/v% confirms inhibi-
tion of clay-water interaction. This can be attributed to the
presence of cationic ammonium functionality which gets
adsorbed in interlayer space of clay platelets resulting in water
inhibition for causing clay swelling. The strong electrostatic
interaction between negatively charges bentonite platelets and
positively charges amine functionality of DESs helps in reducing
the c-spacing (interlayer space between two adjacent unit layers
of clay) and thus resulting in less exposure to water for sorption.
This test suggests that both DESs are capable of reducing water
absorption by clay minerals typically present in shale forma-
tions. Therefore, employing DESs in WBMs can be an effective
strategy to mitigate shale instability. Lastly, it is noted that
DES-B is comparatively more effective inhibiting clay-water
interaction than the DES-A. This difference is attributed to the
difference in the relative polarity of AOH bond as discussed in
Section 3.4 since the cationic functionality of quaternary amine
is present in both the DESs. There is a stronger attractive inter-
action between negatively charged sites in montmorillonite,
illite, kaolinite etc. minerals and the AOH groups present in
DES-B than the interaction between those sites and AOH groups
in DES-A. Once strongly attached to the negatively charges clay
mineral sites in shale formations, DES-B prevents clay hydration,
dispersion and swelling. Further discussion on the nature of this
prevention/interaction is provided below.
9
Journal of Molecular Liquids 340 (2021) 117134
3.7. Shale swelling inhibition
Shale swelling inhibition characteristics of DES-A and DES-B
were assessed using linear swell meter. Drilling fluid samples in
presence and absence of different shale inhibitors were allowed
to interact with shale pellets. Fig. 10 depicts percent shale swelling
in the base mud, base mud containing 5 w/v% KCl and base muds
containing 0.2 w/v% of DES-A, DES-B or the commercial ionic liquid
1-butyl-3-methylimidazolium chloride (BMIM[Cl]). Fig. 10 sug-
gests that DES-B is the best shale swelling inhibition reagent. In
2 h, shale pellet dispersed in base mud was swelled by 28.8% while
the addition of 5 w/v% KCl reduced the swelling to 24.4%. All three
shale stabilizers (BMIM[Cl], DES-A and DES-B) have shown better
performance at 0.2 w/v% in comparison with KCl. Percent swelling
of shale was 22.0%, 13.0% and 8.4% for BMIM[Cl], DES-A and DES-B,
respectively. This suggests that the in-house prepared DES-A and
DES-B have excellent shale swelling inhibition at low concentra-
tions. The positive charges on DES-A and DES-B (owing to presence
of TBAB) are effective in reducing the interaction of the clays (e.g.
montmorillonite) in the shale with water. It is likely that DESs are
capable of holding clay unit layers together with strong electro-
static force, which makes the spaces more hydrophobic, hence
inhibits the penetration of water molecules into the interlayer
space (c-spacing). Additionally, the presence of highly polar AOH
groups in DESs make it more efficient of hold two adjacent clay
unit layers to hold at multiple sites. A schematic of the proposed
shale inhibition mechanism by DESs is shown in Fig. 11.
M. Beg, M.B. Haider, N.K. Thakur et al. Journal of Molecular Liquids 340 (2021) 117134

Fig. 9. CST results of bentonite powder dispersion in aqueous solutions of DES-A

and DES-B.

Fig. 10. Shale pellet swelling in presence and absence of different mud additives.

3.8. Shale dispersion analysis

The recovery of shale cuttings after the shale dispersion analysis

Fig. 8. LPLT fluid loss for (a) DES-A-containing base muds; (b) DES-B-containing
base muds and (c) cumulative fluid loss (after 30 min) for the DES-A- and DES-B-
containing base muds.
is reported in Fig. 12. As can be seen, the recovery was 84.3% in the
case of the base mud, which increased to 88.6% on addition of 5 w/
v% KCl. Addition of 0.1 w/v% DES-A increased shale recovery to
94.8% which further increased to 98.8% in case of 0.5 w/v% DES-
A. The corresponding values for DES-B were found to be 95.9%
for and 99.6%, respectively. These results further confirm that
DES-B is a more effective shale stabilizer than DES-A. Nevertheless,
both of these additives have shown good performance in mitigat-
ing shale instability problems and can be used as a potential shale
inhibitor in water-base muds. Economic analysis provided in the
supporting document suggests the feasibility of industry-scale
deployment of DES-A and DES-B.

10
M. Beg, M.B. Haider, N.K. Thakur et al.
Fig. 11. Schematic showing the mechanism of shale inhibition by DESs.
Fig. 12. Recovery of dispersed shale cuttings after hot rolling.
4. Conclusions
Four DESs were screened to assess their suitability as additives
to improve shale stability in WBM. DESs having ammonium func-
tional group were more effective reducing fluid loss and improving
mud rheological parameters. Therefore, DES-A and DES-B were fur-
ther investigated for their effect on mud properties with special
focus on their shale inhibition ability. Results shows that, in addi-
tion to improving the rheological and filtration properties of the
mud, DES-A and DES-B are effective toward mending shale insta-
bility issues. Shale pellet swelling by base mud was reduced from
28.75% to 13.05% and 8.36% in presence of 0.2 w/v% DES-A and
DES-B, respectively. CST of bentonite powder, which is indicative
of shale swelling, was reduced by ~45% and by ~48% on addition
of 0.5 w/v% DES-A or DES-B, respectively. The shale recovery of
base mud increased from 84.3% to 98.8 % and 99.6% on mixing
0.5 w/v% of DES-A and DES-B, respectively. Shale recovery was
higher for the in-house synthesized DES-A and DES-B than KCl
and commercially available ionic liquid. DES-A and DES-B are
effective in reducing the clay swelling by holding the clay unit lay-
ers together by strong electrostatic interaction between the nega-
tive charges at the clay faces and the positively charged quaternary
amine functionality of DESs. DES-B showed even higher shale
recovery than DES-A. A close look at the chemical structure reveals
that DES-B has an additional AOA functionality in the DEG hydro-
gen bond donor, which helps linking the AOH group on DES-B with
11
Journal of Molecular Liquids 340 (2021) 117134
the anionic sites present in shale minerals to a higher extent than
DES-A. A quick economic calculation showed the feasibility of
using DES-B as an industry-scale additive for WBM drilling of reac-
tive shale formations.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
Authors wish to extend our sincere thanks to Dr. Munmun
Bhattacharya and Mr. Ved Prakash from Institute of Drilling Tech-
nology, Oil and Natural Gas Corporation, Dehradun, India for their
support in conducting linear swell meter tests. Indian Institute of
Technology, Kanpur is acknowledged for allowing the use of XRD
instrument for shale characterization.
References
[1] Y. Kang, J. She, H. Zhang, L. You, M. Song, Strengthening shale wellbore with
silica nanoparticles drilling fluid, Petroleum 2 (2) (2016) 189–195, https://doi.
org/10.1016/j.petlm.2016.03.005.
[2] M. Lal, Shale Stability: Drilling Fluid Interaction and Shale Strength, in: SPE Lat.
Am. Caribb. Pet. Eng. Conf., Caracas, Venezuela, 1999, pp. 1–10. https://doi.org/
10.2118/54356-MS.
[3] A. Aftab, A.R. Ismail, Z.H. Ibupoto, Enhancing the rheological properties and
shale inhibition behavior of water-based mud using nanosilica, multi-walled
carbon nanotube, and graphene nanoplatelet, Egypt, J. Pet. 26 (2) (2017) 291–
299, https://doi.org/10.1016/j.ejpe.2016.05.004.
[4] C.J. Thaemlitz, A.D. Patel, C. George, C. Lee, New environmentally safe high-
temperature water-based drilling-fluid system, SPE Drill. Complet. 14 (1999)
185–189, https://doi.org/10.2118/57715-PA.
[5] M.K. Al-Arfaj, E. Hossain, A. Sultan, M. Amanullah, O. Al-Fuwaires, T. Al-Subai,
Preliminary test results of inhibitive water-based muds used to mitigate
unconventional shale drilling problems, in: Soc. Pet. Eng. – Int. Pet. Technol.
Conf. 2014, IPTC 2014 – Innov. Collab. Keys to Afford. Energy, vol. 2, 2014, pp.
918–926.
[6] W. He, S.L. Gomez, R.S. Leonard, D.T. Li, Shale-fluid interactions and drilling
fluid designs, Int. Pet. (2014) 1–12, https://doi.org/10.2523/IPTC-17235-MS.
[7] A. Patel, E. Stamatakis, S. Young, J. Friedheim, M. Swaco, Advances in inhibitive
water-based drilling fluids—can they replace, in: SPE Int. Symp. Oilf. Chem.,
Society of Petroleum Engineers, Houston, Texas, 2007, pp. 1–8.
[8] E. van Oort, D. Ripley, I. Ward, J.W. Chapman, R. Williamson, M. Aston, Silicate-
based drilling fluids: competent, cost-effective and benign solutions to
wellbore stability problems, in: IADC/SPE Drill. Conf., New Orleans, 1996, pp.
189–203. https://doi.org/10.2118/35059-MS.
[9] D.E. O’Brien, M.E. Chenevert, Stabilizing sensitive shales with inhibited,
potassium-based drilling fluids, J. Pet. Technol. (1973) 1089–1100, https://
doi.org/10.2118/4232-PA.
[10] B. Fritz, M. Jarrett, Potassium silicate-treated water-based fluid: An effective
barrier to instability in the fayetteville shale, in: IADC/SPE Drill. Conf. Exhib.,
San Diego, 2012, pp. 1220–1225. https://doi.org/10.2118/151491-MS.
M. Beg, M.B. Haider, N.K. Thakur et al.
[11] Jiankang Guo, Jienian Yan, Weiwang Fan, Hongjing Zhang, Applications of
strongly inhibitive silicate-based drilling fluids in troublesome shale
formations in Sudan, J. Pet. Sci. Eng. 50 (3-4) (2006) 195–203, https://doi.
org/10.1016/j.petrol.2005.12.006.
[12] C.A. Sawdon, M.E. Brady, S. Cliffe, S.G. James, An integrated approach to the
development of a water-based mud with oil-based mud performance, in: SPE/IADC
Drill. Conf., Amsterdam, 1995, pp. 375–386. https://doi.org/10.2118/29375-MS.
[13] R.G. Bland, G.L. Smith, P. Eagark, Low salinity polyglycol water-based drilling
fluids as alternatives to oil-based muds, in: SPE/IADC Drill. Conf., Society of
Petroleum Engineers, Amsterdam, 1996, pp. 405–418. http://cat.inist.fr/?
aModele=afficheN&cpsidt=6345345.
[14] Mohamed Khodja, Jean Paul Canselier, Faiza Bergaya, Karim Fourar, Malika
Khodja, Nathalie Cohaut, Abdelbaki Benmounah, Shale problems and water-
based drilling fluid optimisation in the Hassi Messaoud Algerian oil field, Appl.
Clay Sci. 49 (4) (2010) 383–393, https://doi.org/10.1016/j.clay.2010.06.008.
[15] R.T. Ewy, E.K. Morton, Wellbore-stability performance of water-based mud
additives, SPE Drill. Complet 24 (2009) 390–397, https://doi.org/10.2118/
116139-PA.
[16] H. Mao, Z. Qiu, Z. Shen, W. Huang, Hydrophobic associated polymer based
silica nanoparticles composite with core-shell structure as a filtrate reducer
for drilling fluid at utra-high temperature, J. Pet. Sci. Eng. 129 (2015) 1–14,
https://doi.org/10.1016/j.petrol.2015.03.003.
[17] M.M. Barry, Y. Jung, J.K. Lee, T.X. Phuoc, M.K. Chyu, Fluid filtration and
rheological properties of nanoparticle additive and intercalated clay hybrid
bentonite drilling fluids, J. Pet. Sci. Eng. 127 (2015) 338–346, https://doi.org/
10.1016/j.petrol.2015.01.012.
[18] M. Sadeghalvaad, S. Sabbaghi, The effect of the TiO2/polyacrylamide
nanocomposite on water-based drilling fluid properties, Powder Technol.
272 (2015) 113–119, https://doi.org/10.1016/j.powtec.2014.11.032.
[19] V. Srivastava, M. Beg, S. Sharma, A.K. Choubey, Application of manganese oxide
nanoparticles synthesized via green route for improved performance of water-
based drilling fluids, Appl. Nanosci. (2021) 1–14, https://doi.org/10.1007/
S13204-021-01956-8.
[20] Xianbin Huang, Haokun Shen, Jinsheng Sun, Kaihe Lv, Jingping Liu, Xiaodong
Dong, Shaojie Luo, Nanoscale laponite as a potential shale inhibitor in water-
based drilling fluid for stabilization of wellbore stability and mechanism study,
ACS Appl. Mater. Interfaces 10 (39) (2018) 33252–33259, https://doi.org/
10.1021/acsami.8b11419.
[21] A. Parizad, K. Shahbazi, A. Ayatizadeh Tanha, Enhancement of polymeric
water-based drilling fluid properties using nanoparticles, J. Pet. Sci. Eng. 170
(2018) 813–828, https://doi.org/10.1016/j.petrol.2018.06.081.
[22] J.Y. Liu, Z.S. Qiu, W. Huang, Novel latex particles and aluminum complexes as
potential shale stabilizers in water-based drilling fluids, J. Pet. Sci. Eng. 135
(2015) 433–441, https://doi.org/10.1016/j.petrol.2015.10.003.
[23] S. Perween, M. Beg, R. Shankar, S. Sharma, A. Ranjan, Effect of zinc titanate
nanoparticles on rheological and filtration properties of water based drilling
fluids, J. Pet. Sci. Eng. 170 (2018) 844–857, https://doi.org/10.1016/j.
petrol.2018.07.006.
[24] S. Perween, N.K. Thakur, M. Beg, S. Sharma, A. Ranjan, Enhancing the properties
of water based drilling fluid using bismuth ferrite nanoparticles, Colloids
Surfaces A Physicochem. Eng. Asp. 561 (2019) 165–177, https://doi.org/
10.1016/j.colsurfa.2018.10.060.
[25] Mei-Chun Li, Qinglin Wu, Kunlin Song, Yan Qing, Yiqiang Wu, Cellulose
nanoparticles as modifiers for rheology and fluid loss in bentonite water-based
fluids, ACS Appl. Mater. Interfaces 7 (8) (2015) 5006–5016, https://doi.org/
10.1021/acsami.5b00498.
[26] Mei-Chun Li, Suxia Ren, Xiuqiang Zhang, Lili Dong, Tingzhou Lei, Sunyoung
Lee, Qinglin Wu, Surface-chemistry-tuned cellulose nanocrystals in a
bentonite suspension for water-based drilling fluids, ACS Appl. Nano Mater.
1 (12) (2018) 7039–7051, https://doi.org/10.1021/acsanm.8b0183010.1021/
acsanm.8b01830.s001.
[27] K. Song, Q. Wu, M.C. Li, A.K. Wojtanowicz, L. Dong, X. Zhang, S. Ren, T. Lei,
Performance of low solid bentonite drilling fluids modified by cellulose
nanoparticles, J. Nat. Gas Sci. Eng. 34 (2016) 1403–1411, https://doi.org/
10.1016/j.jngse.2016.08.036.
[28] Mukarram Beg, Priyanka Singh, Shivanjali Sharma, Umaprasana Ojha, Shale
inhibition by low-molecular-weight cationic polymer in water-based mud, J.
Pet. Explor. Prod. Technol. 9 (3) (2019) 1995–2007, https://doi.org/10.1007/
s13202-018-0592-7.
[29] M. Beg, S. Sharma, U. Ojha, Effect of cationic copolyelectrolyte additives on
drilling fluids for shales, J. Pet. Sci. Eng. 161 (2018) 506–514, https://doi.org/
10.1016/j.petrol.2017.12.009.
[30] Shaohua Gou, Ting Yin, Qiang Xia, Qipeng Guo, Biodegradable polyethylene
glycol-based ionic liquids for effective inhibition of shale hydration, RSC Adv. 5
(41) (2015) 32064–32071, https://doi.org/10.1039/C5RA02236C.
[31] Lili Yang, Guancheng Jiang, Yawei Shi, Xiao Yang, Application of ionic liquid
and polymeric ionic liquid as shale hydration inhibitors, Energy Fuels 31 (4)
(2017) 4308–4317, https://doi.org/10.1021/acs.energyfuels.7b00272.
[32] Z. Luo, L. Wang, P. Yu, Z. Chen, Experimental study on the application of an
ionic liquid as a shale inhibitor and inhibitive mechanism, Appl. Clay Sci. 150
(2017) 267–274, https://doi.org/10.1016/j.clay.2017.09.038.
[33] Han Jia, Pan Huang, Qiuxia Wang, Yugui Han, Shaoyan Wang, Jiajun Dai,
Jinyong Song, Fan Zhang, Hui Yan, Kaihe Lv, Study of a gemini surface active
ionic liquid 1,2-bis(3-hexylimidazolium-1-yl) ethane bromide as a high
performance shale inhibitor and inhibition mechanism, J. Mol. Liq. 301
(2020) 112401, https://doi.org/10.1016/j.molliq.2019.112401.
12
Journal of Molecular Liquids 340 (2021) 117134
[34] Z. Luo, J. Pei, L. Wang, P. Yu, Z. Chen, Influence of an ionic liquid on rheological
and filtration properties of water-based drilling fluids at high temperatures,
Appl. Clay Sci. 136 (2017) 96–102, https://doi.org/10.1016/j.clay.2016.11.015.
[35] T.N. Ofei, C.B. Bavoh, A.B. Rashidi, Insight into ionic liquid as potential drilling
mud additive for high temperature wells, J. Mol. Liq. 242 (2017) 931–939,
https://doi.org/10.1016/j.molliq.2017.07.113.
[36] Mohamed A. Betiha, Gehad G. Mohamed, Nabel A. Negm, Modather F. Hussein, Hany
E. Ahmed, Fabrication of ionic liquid-cellulose-silica hydrogels with appropriate
thermal stability and good salt tolerance as potential drilling fluid, Arab. J. Chem. 13
(7) (2020) 6201–6220, https://doi.org/10.1016/j.arabjc.2020.05.027.
[37] Alexandre Paiva, Rita Craveiro, Ivo Aroso, Marta Martins, Rui L. Reis, Ana Rita C.
Duarte, Natural deep eutectic solvents – solvents for the 21st century, ACS
Sustain. Chem. Eng. 2 (5) (2014) 1063–1071, https://doi.org/10.1021/
sc500096j.
[38] María Francisco, Adriaan van den Bruinhorst, Maaike C. Kroon, Low-
Transition-temperature mixtures (LTTMs): a new generation of designer
solvents, Angew. Chemie Int. Ed. 52 (11) (2013) 3074–3085, https://doi.org/
10.1002/anie.201207548.
[39] Mohd Belal Haider, Manas Dwivedi, Divyam Jha, Rakesh Kumar,
Balathanigaimani Marriyappan Sivagnanam, Azeotropic separation of
isopropanol-water using natural hydrophobic deep eutectic solvents, J.
Environ. Chem. Eng. 9 (1) (2021) 104786, https://doi.org/10.1016/
j.jece:2020.104786.
[40] Divyam Jha, Mohd Belal Haider, Rakesh Kumar, Marriyappan Sivagnanam
Balathanigaimani, Extractive desulfurization of fuels using diglycol based deep
eutectic solvents, J. Environ. Chem. Eng. 8 (5) (2020) 104182, https://doi.org/
10.1016/j.jece:2020.104182.
[41] Mohd Belal Haider, Rakesh Kumar, Solubility of CO2 and CH4 in sterically
hindered amine-based deep eutectic solvents, Sep. Purif. Technol. 248 (2020)
117055, https://doi.org/10.1016/j.seppur.2020.117055.
[42] A. Mohsenzadeh, Y. Al-Wahaibi, R. Al-Hajri, B. Jibril, N. Mosavat, Sequential
deep eutectic solvent and steam injection for enhanced heavy oil recovery and
in-situ upgrading, Fuel 187 (2017) 417–428, https://doi.org/10.1016/
j.fuel.2016.09.077.
[43] M. Yusuf, M. Athar, Biodiesel production using hexane as co-solvent, J.
Biofuels. 6 (2015) 88–91, https://doi.org/10.5958/0976-4763.2015.00013.6.
[44] Toktam ShenavaeiZare, Ali Khoshsima, Bahman ZareNezhad, Production of
biodiesel through nanocatalytic transesterification of extracted oils from
halophytic safflower and salicornia plants in the presence of deep eutectic
solvents, Fuel 302 (2021) 121171, https://doi.org/10.1016/j.fuel.2021.121171.
[45] H. Jia, P. Huang, Q. Wang, Y. Han, S. Wang, F. Zhang, W. Pan, K. Lv, Investigation
of inhibition mechanism of three deep eutectic solvents as potential shale
inhibitors in water-based drilling fluids, Fuel 244 (2019) 403–411, https://doi.
org/10.1016/j.fuel.2019.02.018.
[46] H. Jia, P. Huang, Y. Han, Q. Wang, K. Jia, T. Sun, F. Zhang, H. Yan, K. Lv,
Investigation for the novel use of a typical deep eutectic solvent as a potential
shale inhibitor, Energy Sources, Part A Recover. Util. Environ. Eff. (2019) 1–14,
https://doi.org/10.1080/15567036.2019.1643953.
[47] Mohd Belal Haider, Divyam Jha, Balathanigaimani Marriyappan Sivagnanam,
Rakesh Kumar, Modelling and simulation of CO2 removal from shale gas using
deep eutectic solvents, J. Environ. Chem. Eng. 7 (1) (2019) 102747, https://doi.
org/10.1016/j.jece:2018.10.061.
[48] American Petroleum Institute, Recommended Practice for Laboratory Testing
of Drilling Fluids, 5th ed., 1995. http://ballots.api.org/ecs/sc13/API_RP13B-1_
5Ed_TestingWBDF_4316.pdf.
[49] M. Beg, P. Kumar, P. Choudhary, S. Sharma, Effect of high temperature ageing
on TiO 2 nanoparticles enhanced drilling fluids : a rheological and filtration
study, Upstream Oil Gas Technol. 5 (2020) 100019, https://doi.org/10.1016/j.
upstre.2020.100019.
[50] Jing-jing Li, Huan Xiao, Xiao-dong Tang, Miao Zhou, Green carboxylic acid-
based deep eutectic solvents as solvents for extractive desulfurization, Energy
Fuels 30 (7) (2016) 5411–5418, https://doi.org/10.1021/acs.
energyfuels.6b0047110.1021/acs.energyfuels.6b00471.s001.
[51] Ghulam Murshid, Farouq S. Mjalli, Jamil Naser, Suaad Al-Zakwani, Adeeb
Hayyan, Novel diethanolamine based deep eutectic mixtures for carbon
dioxide (CO 2) capture: synthesis and characterisation, Phys. Chem. Liq. 57 (4)
(2019) 473–490, https://doi.org/10.1080/00319104.2018.1491043.
[52] Papu Kumar Naik, Sandip Paul, Tamal Banerjee, Physiochemical properties and
molecular dynamics simulations of phosphonium and ammonium based deep
eutectic solvents, J. Solution Chem. 48 (7) (2019) 1046–1065, https://doi.org/
10.1007/s10953-019-00903-0.
[53] H. Zhong, Z. Qiu, W. Huang, J. Cao, Poly (oxypropylene)-amidoamine modified
bentonite as potential shale inhibitor in water-based drilling fluids, Appl. Clay
Sci. 67–68 (2012) 36–43, https://doi.org/10.1016/j.clay.2012.06.002.
[54] D. Breeden, J. Shipman, Shale analysis for mud engineers, in: AADE Drill. Fluids
Conf., Houston, Texas, 2004, pp. 1–17.
[55] Roshan Tiwari, Saket Kumar, Maen M. Husein, Pranali M. Rane, Nitesh Kumar,
Environmentally benign invert emulsion mud with optimized performance for
shale drilling, J. Pet. Sci. Eng. 186 (2020) 106791, https://doi.org/10.1016/j.
petrol.2019.106791.
[56] Mei-Chun Li, Qinglin Wu, Kunlin Song, Corneils F. De Hoop, Sunyoung Lee, Yan
Qing, Yiqiang Wu, Cellulose nanocrystals and polyanionic cellulose as
additives in bentonite water-based drilling fluids: rheological modeling and
filtration mechanisms, Ind. Eng. Chem. Res. 55 (1) (2016) 133–143, https://doi.
org/10.1021/acs.iecr.5b0351010.1021/acs.iecr.5b03510.s001.