Journal of Molecular Liquids 339 (2021) 116829

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Journal of Molecular Liquids

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

Aminoguanidine-based deep eutectic solvents as

environmentally-friendly and high-performance lubricant additives
Amzad Khan a,b, Raghuvir Singh a, Piyush Gupta a, Kanika Gupta a,b, Om P. Khatri a,b,⇑
a
Chemical and Material Sciences Division, CSIR-Indian Institute of Petroleum, Dehradun 248005, India
b
Academcy of Scientific and Innovative Research, Ghaziabad 201002, India

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

Article history: Halogen-free, environmentally-friendly, and economically viable lubricant additives, which can furnish
Received 9 May 2021 excellent miscibility with mineral lube base oils and enhance the tribological properties, are gaining
Revised 22 June 2021 increasing interest for the formulation of new generation lubricants. Herein, aminoguanidine salt-
Accepted 24 June 2021
based deep eutectic solvents (DESs) having variable mole ratios of fatty acid (as a hydrogen bond donor;
Available online 29 June 2021
HBD) are synthesized through a single-step facile approach. The detailed chemical characterizations
based on FTIR and NMR (1H and 13C) confirmed the synthesis of DESs via a hydrogen-bonding network.
Keywords:
A linear correlation between the shear stress and shear rate implied Newtonian fluidic behaviour of these
Deep eutectic solvents
Hydrogen bonding
DESs. An increasing mole ratio of octanoic acid decreased the viscosity and thermal stability of resultant
Lubricant additives DESs. The long alkyl chain of HBD furnished good compatibility of these DESs with SN 150 mineral lube
Viscosity base oil. The DESs as additives to SN 150 mineral lube oil improved the viscosity index by 12% and
Fatty acid enhanced the tribological properties for steel tribopair by decreasing the wear volume (94%) and coeffi-
Friction cient of friction (30%). The detailed analyses of worn scars revealed the formation of DESs-derived tribo-
chemical thin film. The low shear strength of DESs-derived lubricious and protective thin film between
steel tribopair facilitated the sliding and avoided the direct contact between the steel tribopair, conse-
quently, significant enhancement of tribological properties.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction
Lubricants are indispensable substances for engineering sur-
faces to minimize friction and wear, dissipate the heat from
tribo-surfaces, keep the moving parts apart, transmit the forces,
disperse the foreign particles, and improve the efficiency of engi-
nes and machines where two or more bodies are in relative motion.
The automotive/motor oils dominate the liquid lubricants market,
followed by their applications in turbines, hydraulic systems, com-
pressors, bearings, gears, metal-working, and so on [1]. The mas-
sive wastage of energy and rising level of CO2 emission can be
reduced by redefining the roles of lubricants and tribology in
industrial machinery, devices, and automotive engines. The new
developments in tribological practices and lubricant formulations
can save ~11% of the energy used by the transportation, industrial,
and utility sectors [2]. Over the recent past, several efforts have
been made to develop new generation lubricants and additives to
increase the fuel/energy efficiency and durability of engineering
⇑ Corresponding author at: Chemical and Material Sciences Division, CSIR-Indian
Institute of Petroleum, Dehradun 248005, India.
E-mail address: opkhatri@iip.res.in (O.P. Khatri).
systems. The use of low-viscosity lube base oil and variable
functional additives, which can furnish adequate lubrication to a
diversified range of engineering surfaces and minimize the envi-
ronmental footprints, are gaining immense interest. In this context,
nanostructured materials, ionic liquids, organometallic, and
organic compounds have been explored as (a) novel additives to
liquids lubricants and greases, (b) fillers to polymeric and metal-
matrix composites, and thin films/coatings to tribo surfaces for
minimizing the friction and wear [3–8].
Ionic liquids, the poorly coordinated salts, exhibit a diffused
electrostatic interaction between the bulkier organic cation and
inorganic/organic anion. Ionic liquids are considered innovative
fluids because of their unique and tunable physicochemical prop-
erties. The negligible volatility, inherent polarity, high thermal sta-
bility, wide liquid range, good conductivity, confined layering
structure, and excellent affinity towards engineering surfaces
make them promising candidates for enhancing the tribological
properties [5,9–12]. However, the high cost of precursors, multiple
reaction steps for their preparation, purification processes, and cor-
rosiveness of halogenated ionic liquids have been major bottle-
necks and hinder their applicability for several industrial
applications, including lubrication [13–15].

https://doi.org/10.1016/j.molliq.2021.116829
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
A. Khan, R. Singh, P. Gupta et al.
Deep eutectic solvents (DESs), also known as green analogous to
ionic liquids, exhibit several similar physicochemical properties to
ionic liquids. The DESs are prepared by synergistic blending of the
hydrogen bond donors (HBD; amines, alcohols, fatty acids, etc.)
and the hydrogen bond acceptors (HBA; ammonium, phospho-
nium, choline, alkyl phosphate, etc.). The charge delocalization
via hydrogen bonding between the HBD and HBA reduces the melt-
ing point of resultant DESs. The DESs have shown immense interest
because of their low volatility, moderate conductivity, cost-
effectiveness, and solvation. DESs are acknowledged over the ionic
liquids for several applications because of their environmental and
economic viability, low cytotoxicity and phytotoxicity, good
biodegradability, and ease of preparation [16–18]. The DESs are
still in their infancy stage, particularly for tribological applications.
The polarity of DESs enhances their affinity towards the engineer-
ing surfaces and makes them potential candidates as alternatives
to ionic liquids for the improvement of tribological properties.
Abbott et al. demonstrated the choline-based DESs for lubrica-
tion of steel tribopair. The choline chloride-urea and choline
chloride-ethylene glycol DESs formed a thin film, which enhanced
the lubrication of tribo interfaces by reducing friction and wear.
The quality of the lubricious thin film is governed by the composi-
tion of DESs [19]. The choline chloride-based DESs having urea,
maleic acid, and ethylene glycol as HBD showed a significantly
lower friction coefficient for steel tribopair than PAO6 lube oil
[20]. The water-miscible choline chloride-based DESs with urea,
ethylene glycol, oxalic acid, and glycerol displayed low corrosion
rates for steel, aluminium, and nickel. Moreover, these DESs fur-
nished a low coefficient of friction for iron-based materials com-
pared to mineral lube base oil [21]. The DESs of sulfur-containing
ionic liquids and polyethylene glycol formed the tribo thin film,
which extended the lubrication of silicon substrate by decreasing
the friction and protecting the tribo-surfaces against undesirable
wear [22]. The ultrathin film of choline chloride-ethylene glycol
DES between two mica surfaces furnished the structured layers
of quantized frictional properties, which are highly sensitive to
water content. The quantized layer of DES offered the superlubric
(l < 0.01) behaviour under the load of 0 to 50 lN [23]. These find-
ings suggest the potential of DESs for lubrication enhancement.
However, not much work has been carried out, particularly with
halogen-free DESs for tribological applications.
Fig. 1. Synthesis of Ag-C8 DESs using aminoguanidine bicarbonate salt and octanoic acid as HBA and HBD, respectively.
2
Journal of Molecular Liquids 339 (2021) 116829
The present work addresses the aminoguanidine salt-octanoic
acid (Ag-C8)-based DESs as an additive to SN 150 lube oil for the
enhancement of tribological properties of steel tribopair. The Ag-
C8 DESs showed good miscibility and improved the viscosity index
of SN 150 mineral lube base oil. The surface analyses of worn steel
balls are carried out to understand the role of Ag-C8 DESs in the
formation of tribochemical thin film and reduction of friction and
wear. The ease of preparation, low cost of precursors, and environ-
mental compatibility make DESs greener alternatives to ionic liq-
uids for the development of new generation lubricants.
2. Experimental section
2.1. Chemicals and materials
Aminoguanidine bicarbonate (98%, Fluka) and octanoic acid
(caprylic acid, 99%, Loba Chemie) were used without further purifi-
cation for the preparation of Ag-C8 DESs.
2.2. Synthesis of DESs
Ag-C8 DESs having variable molar ratios of aminoguanidine
bicarbonate salt as an HBA and caprylic acid as an HBD (1:2, 1:4,
and 1:8) were synthesized by their blending at 60 °C under the
uninterrupted stirring as shown in Fig. 1. The synthesized homoge-
nous liquid phase of Ag-C8 DES was kept in the vacuum oven for
24 h. These DESs having mole ratios of 1:2, 1:4, and 1:8 of
aminoguanidine bicarbonate salt and caprylic acid are coined as
AG-C8-(1:2), AG-C8-(1:4), and AG-C8-(1:8) throughout the manu-
script. The syntheses of these DESs were confirmed by NMR and
FTIR spectroscopic measurements. The chemical structure of AG-
C8 DES and the plausible hydrogen linkages are shown in Fig. 1.
2.3. Chemical and physicochemical characterizations of DESs
Vibrational spectra of all samples were collected using an FTIR
spectroscope (Spectrum-Two, Perkin Elmer) in a transmittance
mode. The NMR (1H and 13C) spectra of DESs were measured using
the Bruker Avance III 500 MHz spectroscope. A blend of 20% DES
sample in the deuterated solvent, i.e., CDCl3, was used for collect-
ing the NMR spectra. The thermal stability of these DESs was
A. Khan, R. Singh, P. Gupta et al.
measured by a thermogravimetric analyzer (TGA; Model: Dia-
mond, PerkinElmer) under the N2 flow in a temperature range of
30–300 °C. The kinematic viscosity of DESs and their blend in
SN-150 mineral lube base oil was measured using the Stabinger
viscometer (SVM 3000; Anton Paar). The viscosity index of 1.5%
DESs in SN-150 lube oil was estimated based on viscosity at 40
and 100 °C as per the ASTM D2270 standard method. The flow
characteristics of DESs were measured using a modular compact
rheometer (Anton Paar GmbH MCR 102) equipped with CP40
cone-plate geometry.
2.4. Tribo-evaluation of DESs
The AG-C8 DESs were used as additives to SN 150 mineral base
oil and evaluated the tribo-performance for steel tribopair. All tri-
bological tests were carried out using the four-ball tribo-test
machine (M/s. Ducom India). The steel balls (/ = 12.7 mm) were
thoroughly cleaned with the aid of ultrasound using n-hexane sol-
vent. Three steel balls were fixed in a sample pot. The lubricant
sample was filled in a sample pot, and a fourth steel ball was
rotated over the three stationary balls under the desired load
(392 N), temperature (75 °C), and speed (1200 rpm). Each tribolog-
ical test was carried out for one hour as per the ASTM D4172B stan-
dard test method. The coefficient of friction data was collected
with a function of time. After completing the tribo-test, the three
stationary balls were removed from the sample holder and cleaned
with n-hexane. The worn scar developed on the stationary balls
was measured by an optical microscope and reported values are
based on the wear scar diameter (WSD) of six balls (from two inde-
pendent tests of each sample). The microscopic features of worn
scars of steel balls were probed using a field-emission scanning
electron microscope (FESEM, FEI Quanta 200F). An energy-
dispersive X-ray spectroscope (EDS) integrated with the FESEM
was used for analyzing the elemental distribution over the worn
scars.
Fig. 2. FTIR spectra of (a) aminoguanidine bicarbonate, (b) octanoic acid, (c) AG-C8-(1:2), (d) AG-C8-(1:8), (e) AG-C8-(1:4), and AG-C8-(1:2) DESs.
3
Journal of Molecular Liquids 339 (2021) 116829
3. Results and discussion
Fig. 2 displays vibrational spectra of aminoguanidine bicarbon-
ate salt and octanoic acid. The FTIR spectrum (Fig. 2a) of
aminoguanidine bicarbonate exhibits multiple peaks in the spec-
tral range of 3410–3150 cm 1, revealing the N-H stretches due to
primary and secondary amine functionalities in the aminoguani-
dine. The N-H stretches due to protonated amine group in
aminoguanidine salt are vibrated at lower wavenumbers (3050–
2900 cm 1) [24]. The C@O stretch (1690 cm 1) along with asym-
metric (1499 cm 1) and symmetric (1353 cm 1) stretches of car-
bonate group revealed the presence of bicarbonate in
aminoguanidine salt. A bending mode at 1633 cm 1 along with a
shoulder toward lower wavenumber (1611 cm 1) signified the
NAH based anime functionalities in aminoguanidine bicarbonate
salt [25,26]. A strong and broad vibrational peak spanning from
3400 to 2800 cm 1 due to OAH stretch (Fig. 2b) signified the inter-
molecular hydrogen-bonded carboxylic group in octanoic acid [27].
Moreover, it is overlapped with CAH stretching modes of methy-
lene and methyl units of octyl chains. An intense vibrational mode
due to C@O stretch at 1712 cm 1 further confirmed the carboxylic
group in the octanoic acid. As demonstrated in the molecular struc-
ture of AG-C8 DESs (Fig. 1), the AOAH and AC@O linkages of a car-
boxylic group formed the hydrogen bonding network with NAH
linkages of aminoguanidine; consequently, the vibrational features
due to OAH and NAH became very intense and broad in a range of
3400–2800 cm 1 (Fig. 2d-f). The overlapping of intense and broad
vibrational peaks of NAH and OAH stretches due to the hydrogen
bonding network in AG-C8 DESs makes it very difficult to reveal
their vibrational shift precisely. Interestingly the C@O stretch
(1712 cm 1) in octanoic acid red-shifted to 1700–1706 cm 1 in
the AG-C8 DESs having variable molar ratios of octanoic acid. Like-
wise, the N-H bending mode in aminoguanidine salt is red shifted
to 1535–1540 cm 1 in the AG-C8 DESs because of their participa-
tion in hydrogen bonding. The OAH bending mode of the
A. Khan, R. Singh, P. Gupta et al. Journal of Molecular Liquids 339 (2021) 116829

carboxylic group in octanoic acid at 1415 cm 1 is downshifted to 100

1402–1409 cm 1 in the AG-C8 DESs. The NAH, C@O, OAH groups
of HBA and HBD participated in hydrogen bonding (NAH. . ...OA),
(C@O. . ..HA), (OAH. . ..NA); consequently, the bond lengths of
75
these linkages increased, and their vibrational peaks are red
shifted, signifying the preparation of AG-C8 DESs [28–32]. The FTIR

peaks in a range of 2800–3000 cm 1 are assigned to asymmetric
and symmetric stretching modes of CH2 and CH3 units of octyl
chain in AG-C8 DESs. Moreover, the bending mode of C-H at
1465 cm 1 confirmed the alkyl chain in AG-C8 DESs.
1
H and 13C NMR spectra further confirmed the chemical struc-
ture and synthesis of AG-C8 DESs. Table 1 presents the chemical
structure of AG-C8 DESs along with the assignment of chemical
shifts associated with 1H NMR spectra of AG-C8 DESs. The protons
of terminal CH3 (He) in octanoic acid exhibited a chemical shift at a
shielded range of 0.6–0.9 ppm with respective 13C shift at 12–
15 ppm (Figs. S1-S3; Electronic Supplementary Information). The
1
H and 13C chemical shifts at 1.2–1.4 ppm and 25–35 ppm, respec-
tively, are assigned to methylene units (Hd) of octanoic acid in the
AG-C8 DESs. The CH2 unit adjacent to the carboxylic group of fatty
acid (Hc) showed chemical shifts at 2.3–2.5 ppm (1H) and the cor-
responding 13C shifts at 55 ppm. The unsaturated ammonium and
carboxylic protons (Hb) are highly deshielded and showed chemi-
cal shifts at 9.9–13.1 ppm with a corresponding 13C shifts at
160–175 ppm. The protons of the amine groups in AG-C8 DESs
are appeared at the downfield region because of the higher elec-
tronegativity of nitrogen and exhibited chemical shifts at 6.6–
8.6 ppm. The chemical shifts based on 1H and 13C confirmed the
preparation of AG-C8 DESs.
Thermal stability of DESs is governed by chemical composition,
size, and structure of HBA and HBD, hydrogen bonding sites and
interactions, charge delocalization in the salt, polarity of HBA/
HBD, and so on [28,33–35]. Fig. 3 presents the thermal degradation
patterns of aminoguanidine bicarbonate salt and its DESs with
octanoic acid, i.e., AG-C8-(1:2), AG-C8-(1:4), and AG-C8-(1:8).
The DESs showed significantly higher thermal stability compared
to aminoguanidine bicarbonate salt. The electronegative elements
(N and O) based ample functionalities (NAH, OAH, C@O) make the
aminoguanidine bicarbonate salt and octanoic acid to be net-
worked with each other via hydrogen-based interaction as shown
in Fig. 1; consequently, the AG-C8 DESs showed higher thermal
stability than aminoguanidine bicarbonate salt. The higher thermal
stability of AG-C8-(1:2) DES could be attributed to a higher degree
of hydrogen interaction between the HBA and HBD. The higher
mole ratios of octanoic acid (HBD) in AG-C8-(1:4) and AG-C8-
(1:8) DESs plausibly lead to steric hindrance induced by a higher
degree of longer alkyl chain (octanoic acid) and decrease the
hydrogen-based interaction. Therefore, the thermal stability of
AG-C8 DESs gradually reduced with an increasing mole ratio of
Weight, %
50
25 AG-C8-(1:2)
AG-C8-(1:4)
AG-C8-(1:8)
AG
0
60 120 180 240 300
Temperature, °C
Fig. 3. Thermal decomposition patterns of AG-C8-(1:2), AG-C8-(1:4), AG-C8-(1:8)
DESs, and the aminoguanidine bicarbonate salt under the N2 flow.
octanoic acid, and the AG-C8-(1:2) showed the highest thermal
stability among all AG-C8 DESs.
The viscosity of DESs plays a vital role in lubricant formulation.
The viscosity and thin film formation capability of liquid lubricants
are governed by the chemical composition of lube base oil and the
blended additives. The size, charge, and composition of HBA and
HBD, along with the interactive forces viz., hydrogen linkages,
van der Waals, dipole–dipole interactions, etc., control the viscos-
ity of DESs [36,37]. Fig. 4 shows the viscosity of octanoic acid
and its DESs with a function of temperature. The viscosity of all
samples gradually decreased with the rising of temperature, and
it is attributed to the increasing of thermal kinetic energy, which
loosens the interactive forces. The viscosity of AG-C8-(1:2) DES is
noted to be significantly higher, and it gradually decreased with
the increasing mole ratio of octanoic acid. These results suggest a
higher degree of hydrogen-based interactions when AG-C8-(1:2)
DES is prepared using 1 mol of aminoguanidine bicarbonate salt
with 2 mol octanoic acid. The octanoic acid contains a long alky
chain. The higher mole ratios of octanoic acids in AG-C8-(1:4)
and AG-C8-(1:8) DESs is understood to furnish a larger degree of
steric hindrance by longer alky chains of octanoic acid, which
might reduce the H-based interaction with aminoguanidine
bicarbonate salt; consequently, the viscosity of the AG-C8
DESs decreased with increasing of mole ratio of HBD, i.e., octanoic
acid [38].
Rheological measurements examine the fluidic characteristics
of aminoguanidine bicarbonate salt-based DESs. Fig. 5a shows no
measurable changes in viscosity of AG-C8-(1:4) and AG-C8-(1:8)

Table 1
Assignment of 1H chemical shifts of aminoguanidine based-DESs.

Symbol Protons Chemical Shift, ppm

AG-C8-(1:2) AG-C8-(1:4) AG-C8-(1:8)

He ACH3 0.8–0.9, d, 6H 0.6–0.9, d, 12H 0.7–0.9, d, 24H
Hd ACH2 1.2–1.4, m, 16H 1.2–1.4, m, 32H 1.2–1.4, m, 64H
Hf H2CACAC@O 1.4–1.8, m, 4H 1.4–1.8, m, 8H 1.4–1.8, m, 16H
Hc H2CAC@O 2.3–2.5, m, 4H 2.3–2.5, m, 8H 2.3–2.5, m, 16H
Hb ACOOH/+NAH 9.9–13.1, s/m, 5H 9.9–13.1, s/m, 7H 9.9–13.1, s/m, 11H
Ha ANAH 6.5–8.6, m, 5H 6.5–8.6, m, 5H 6.5–8.6, m, 5H

4
A. Khan, R. Singh, P. Gupta et al. Journal of Molecular Liquids 339 (2021) 116829

800 1650

Kinematic Viscosity, mm2.s-1

(a)
-1

100 AG-C8-(1:2) 1600 AG-C8-(1:2)

700
Kinematic Viscosity, mm .s

AG-C8-(1:4)
2

1550
600 75 AG-C8-(1:8)

Viscosity, mPa.S
C8 1500
500 50

90
400 25 AG-C8-(1:4)
80
300 0
30 40 50 60 70 80 90 100
Temperature, °C
70
200
AG-C8-(1:8)
60
100
50
0
0 100 200 300 400 500 600
30 40 50 60 70 80 90 100
-1
Shear Rate, S
Temperature, °C

Fig. 4. Kinematic viscosity of AG-C8-(1:2), AG-C8-(1:4), AG-C8-(1:8) DESs, and 50

octanoic acid (HBD). (b)
1000 40

Shear Stress, Pa
30

DESs, whereas the viscosity of AG-C8-(1:2) DES marginally

800

Shear Stress, Pa
20
increased (<5%) over the shear rate of 0–600 s 1. These results sug-
gest that hydrogen-driven interaction between the aminoguani- 10

dine bicarbonate salt (HBA) and the octanoic acid (HBD) 600 0
0 100 200 300 400 500 600
remained intact even at the higher shear rate, consequently no Shear Rate, S-1
AG-C8-(1:2)
measurable changes in viscosity of AG-C8 DESs. The linear correla- AG-C8-(1:4)
400 AG-C8-(1:8)
tion between the shear stress and shear rate (Fig. 5b) further signi-
fied the Newtonian fluidic nature of aminoguanidine bicarbonate
salt-based DESs. The slope of linear correlation between the shear 200
stress and shear rate is governed by hydrogen-based interactive
forces, driven by ratios of aminoguanidine bicarbonate salt and 0
octanoic acid in these DESs. 0 100 200 300 400 500 600
The lube oil thinning effect at higher temperatures leads to -1
Shear Rate, S
direct contact between the tribopair as the thin lube oil is easily
squeezed out from the contact interfaces, particularly under the Fig. 5. Changes in (a) viscosity and (b) shear stress as a function of shear rate for
boundary and mixed lubrication regimes. The viscosity index pre- AG-C8-(1:2), AG-C8-(1:4), and AG-C8-(1:8) DESs.
sents the change in viscosity relative to temperature for lube oils.
Higher viscosity index means low thinning of lube oil at higher selected as a representative DES for dose optimization to SN 150
temperatures. The viscosity index improvers are used as additive lube base oil. Fig. 6 presents the changes in average WSD and coef-
to lube oils for minimizing the thinning of lube oil at higher tem- ficient of friction for steel tribopair while lubricated with variable
peratures. The lube oil with low viscosity index indicates the thin- doses of AG-C8-(1:4) DES. The steel balls lubricated with SN 150
ning effect at the higher temperature. In general, lube oil should lube oil showed a high average coefficient of friction and WSD,
have a viscosity index of more than 100 for its good performance, i.e., 0.11 and 743 lm. The non-polar hydrocarbon contents of SN
and it favors the lubrication performance at higher temperatures 150 lube oil show poor affinity towards steel surfaces, which could
by inhibiting the lube thinning effect. The blending of 1.5% be accountable for the lack of lubricious tribo-film between the
aminoguanidine bicarbonate salt-based DESs in SN 150 mineral steel balls under the tribo-stress. The AG-C8-(1:4) DES as an addi-
lube oil increased the viscosity index of SN 150 lube base oil by tive to SN 150 lube oil improved the tribological properties by
12% (Table 2). The improved viscosity index of SN 150 lube oil by reducing the average coefficient of friction and WSD. The 0.5% dose
1.5% AG-C8 DESs promises the applicability of resultant lubricants of AG-C8-(1:4) DES decreased the friction and WSD of SN 150 lube
at higher temperatures and the possibility to develop lubricious oil by 12% and 28%, respectively. The increasing quantity of AG-C8-
tribo thin film between the tribopair for the enhancement of lubri- (1:4) DES showed a gradual enhancement of tribological perfor-
cation effect. mance. A 1.5% AG-C8-(1:4) DES as an additive showed maximum
Tribological properties of AG-C8 DESs as additives to SN 150 reduction in the coefficient of friction (30%) and WSD (40%).
mineral lube base oil are probed using four-ball contact geometry Further increasing of dose showed no measurable change in wear.
as per the ASTM D4172B standard test method. The AG-C8-(1:4) is Therefore, a 1.5% dose of AG-C8-(1:4) DES is considered an

Table 2
Kinematic viscosity and viscosity index of SN 150 lube base oil and 1.5% blend of each DES in the SN 150 lube oil.

No. Sample Detail Kinematic viscosity, mm2.s 1

Viscosity Index
At 40 °C At 100 °C
1 SN 150 Lube oil 30.55 5.28 104
2 1.5% AG-C8-(1:2) in SN 150 Lube oil 31.69 5.60 116
3 1.5% AG-C8-(1:4) in SN 150 Lube oil 30.67 5.54 113
4 1.5% AG-C8-(1:8) in SN 150 Lube oil 30.23 5.40 114

5
A. Khan, R. Singh, P. Gupta et al. Journal of Molecular Liquids 339 (2021) 116829

Average Wear Scar Diameter, µm

0.12 800
Average Coefficient of Friction

50

Wear Volume x 10-4, mm3

0.11 700
40

600
0.10 30

71.5%
500
0.09 20

90.1%
400

94.0%
0.08 10

300
0.0 0.5 1.0 1.5 2.0 0
Doping of AG-C8 (1:4) in SN-150 Lube Base Oil, % w/v 150 8) 4) 2)
SN- -(1: -(1: -(1:
G-C8 G -C8 G-C8
A A A
Fig. 6. Changes in the average coefficient of friction and wear scar diameter as a 1.5% 1.5% 1.5%
function of variable dose of AG-C8-(1:4) DES, blended in SN 150 lube oil. Load:
392 N, temperature: 75 °C, speed: 1200 rpm, test duration: 1 h. Fig. 8. Changes in wear volume of steel tribopair lubricated with SN 150 lube oil
Average Wear Scar Diameter, µm and its blend with 1.5% AG-D8 DESs having a variable mole ratio of octanoic acid.
Average Coefficient of Friction

0.12 800
(a)
0.11 700

0.10 600

0.09 500

0.08 400

0.07
300
- 1 50 :8) :4) (1:2
)
SN -C 8 (1 -C 8 (1 -C8
-AG - AG -AG
1. 5 % 1. 5 % 1.5%
Coefficient of Friction

0.12 (b)

0.10 SN-150

0.08
1.5% AG-C8-(1:4) in SN-150
0.06

0.04
600 1200 1800 2400 3000 3600
Run Time, Seconds

Fig. 7. (a) Changes in average coefficient of friction and WSD for steel tribopair
lubricated with SN 150 lube oil and its blend with 1.5% of AG-C8 DESs having a
variable mole ratio of octanoic acid. (b) Coefficient of friction between steel
tribopair in the presence of SN-150 lube oil and its blend with 1.5% AG-C8-(1:4)
DES. All tribological tests are conducted as per the ASTM D4172B standard test
method.

optimized concentration for tribo-performance evaluation. The

polar functionalities in DESs are believed to facilitate their interac-
tions with contact interfaces of steel tribopair and improve the tri-
bological performance of SN 150 lube oil [12,39].
Fig. 7a shows the average coefficient of friction and WSD of
steel balls lubricated with SN 150 lube oil and its blend with
1.5% of AG-C8 DESs having a variable mole ratio of octanoic acid.
Fig. 9. FESEM images of worn scars developed on steel balls, which were lubricated
All DESs exhibited a significantly low coefficient of friction and with (a-b) SN 150 lube oil and its blend with1.5% (c-d) AG-C8-(1:8), (e-f) AG-C8-
wear compared to SN 150 lube oil. The degrees of friction and wear (1:4), and (g-h) AG-C8-(1:2) DESs.

6
A. Khan, R. Singh, P. Gupta et al.
reduction increased with decreasing mole ratio of octanoic acid in
the AG-C8 DESs. Among all DESs, the 1.5% AG-C8-(1:2) showed a
minimum coefficient of friction and wear, i.e., 31 and 46% lower
than the SN 150 lube oil. The higher viscosity and polar compo-
nents in AG-C8-(1:2) DES are believed to furnish the good quality
lubricous thin film over the contact interfaces of steel tribopair
for lowering the friction and wear [40,41]. The DESs yielded the
tribo-induced thin film of low shear strength, which facilitated
the shearing under the tribo-stress and avoided the direct contact
between the steel tribopair. The good affinity of these DESs
towards the steel tribo surfaces and the formation of tribochemical
thin film is further supported by a low and stable friction profile of
1.5% AG-C8(1:4) DES in SN 150 lube oil (Fig. 7b).
Lubricous and protective tribo thin film by DESs over the con-
tact interfaces minimizes the wear. Fig. 8 displays the average wear
volume of steel balls lubricated with SN 150 lube oil and its blend
with 1.5% AG-D8 DESs having a variable mole ratio of octanoic acid.
The 1.5% AG-D8 DESs as a lubricious additive to SN 150 lube oil
decreased the wear volume of steel balls by 94%. The AG-C8-
(1:2) DES showed minimum wear volume, and it was attributed
to the higher polar components and viscosity of AG-C8-(1:2),
which formed the good quality protective thin film for minimizing
the wear events.
Fig. 9 displays representative electron microscopic images of
worn scars developed on steel balls during the tribo tests using
SN 150 lube oil and 1.5% AG-C8 DESs. The steel balls lubricated
with SN 150 lube oil developed a larger wear scar and showed dee-
per scratches and furrows (Fig. 9a-b) in the sliding direction. It
could be associated with the lack of the lubricous thin film by
non-polar hydrocarbon contents of SN 150 lube oil. The steel balls
lubricated with 1.5% AG-C8 DESs decreased the WSD to a signifi-
cant extent. The mole ratio of fatty acid in the DESs governed the
size of WSD. The 1.5% AG-C8-(1:2), having a minimum mole ratio
of octanoic acid and highest viscosity among all samples, devel-
oped the smallest WSD (Fig. 9g-h). The wear scar gradually
Fig. 10. Microscopic images of worn scars and elemental distribution over the corresponding area of steel balls lubricated with (a) SN 150 and 1.5% blend of (b) AG-C8-(1:2),
(c) AG-C8-(1:4), and (d) AG-C8-(1:8) DESs in SN 150 lube oil.
7
Journal of Molecular Liquids 339 (2021) 116829
increased with increasing the mole ratio of octanoic acid in the
AG-C8 DESs-based lubricant system. The EDS measurements of
worn scars of lubricated steel balls probed the role of DESs in tribo
thin film formation.
Fig. 10 displays microscopic images of worn scars and elemental
distribution of the corresponding area developed on steel balls
during the lubrication test using SN 150 lube oil and its blend with
1.5% AG-C8-(1:2), AG-C8-(1:4), and AG-C8-(1:8) DESs. The regular
distribution of carbon and nitrogen over the worn scars lubricated
with the DESs-based system as deduced from their elemental map-
ping revealed the role of DESs for developing the tribochemical
thin film. Nitrogen is a characteristic element of the AG-C8-based
lubricant system. Its regular distribution and intensification of car-
bon signified the DESs-based tribochemical thin film formation,
which is accountable for lowering the coefficient of friction and
preventing the direct contact between tribo-surfaces to minimize
the wear. Fig. 11 displays the atomic% of elements detected over
the worn scars based on EDS measurement. The steel balls lubri-
cated with SN 150 lube base oil showed no nitrogen signature,
whereas 36.5 at% carbon is detected. The lubrication of steel balls
with 1.5% AG-C8 DESs increased the carbon at% to 60.1, and the
nitrogen has emerged as a new element with 6.5 at%. The enhanced
carbon at% and emergence of nitrogen could be attributed to the
participation of octanoic acid (HBD) and aminoguanidine salt
(HBA) of DESs in the tribochemical thin film formation. The fatty
acids, having a long alkyl chain, show adequate lubrication because
of the carboxylic group-driven interaction with the steel surface.
They adhere to the tribo surfaces under the mixed and boundary
lubrication regime and form the lubricious thin film [42,43].
The affinity of DESs and ionic liquids towards the engineering
surfaces and their nanoscopic layering structure play an important
role in governing the tribological properties [23,38,44]. The struc-
ture of nanoscopic layers of DESs over the engineering surfaces is
controlled by charge distribution in the salt (HBA), hydrogen inter-
action, the chemical composition of HBA and HBD, and the charge
A. Khan, R. Singh, P. Gupta et al.
80
60.1%
70 SN-150 Oil
1.5% AG-C8 DESs
60
45.5%
50
Atomic %
36.5%
40
17.8%
30 16.6%
15.3%
20
6.5%
10 1.0%
0.3%
0 coefficient of friction (30%) and wear volume (94%). The degrees
Iron Carbon Oxygen Chromium Nitrogen
Fig. 11. Quantification of tribochemical thin film over the steel balls lubricated
with SN 150 lube base oil and its blend with 1.5% AG-C8 DESs. Atomic% of all
elements in the thin films over the worn scars is quantified based on multiple EDS
spectra.
on engineering surfaces [23]. Herein, the AG-C8-(1:2) DES exhibits
the highest degree of hydrogen interaction and maximum viscosity
among all studied samples. The higher degree of interaction might
allow the AG-C8-(1:2) DES to generate good quality quantized lay-
ering structure on the tribo interfaces, which facilitated the sliding
events and reduced the friction. The atomic force microscopic stud-
ies demonstrated the molecular layering of confined ester and
polyalphaolefins on steel surface in the nanoscale range [45].
Moreover, the carboxylic group of fatty acids and the highly polar
nature of electron-rich nitrogen in the aminoguanidine salt facili-
tated their interaction with steel surfaces, particularly under con-
tact stress, and formed a good quality tribochemical film for the
protection against the undesirable events of wear [46,47]. The
AG-C8-(1:4) and AG-C8-(1:8) DESs having a higher mole ratio of
octanoic acid probably decreased hydrogen-based interaction
because of the steric hindrance by a higher degree of longer alkyl
chain; as a result, these DESs showed lower viscosity (Fig. 4). Plau-
sibly, the lower viscosity minimized the layering structure of such
a system close to engineering interfaces; as a result, AG-C8-(1:4)
and AG-C8-(1:8) DESs showed a higher coefficient of friction than
the AG-C8-(1:2)-based lubricant system. The adsorption kinetic of
the electron-rich amine group towards the steel surface governs by
steric hindrance. The faster adsorption of amine molecules forms
an effective lubricious thin film over the worn scar and dictates
the friction [46]. The wearing of steel tribo-interfaces exposes the
highly active (pristine) surfaces for the adsorption of surface-
active additives under contact stress. The layering of DESs on the
freshly prepared tribo-surfaces of steel and high contact stress
advance the tribochemical thin film formation [23,48]. The AG-
C8-(1:2)-based lubricant system having a good layering structure
via hydrogen linkages between the aminoguanidine bicarbonate
salt (HBA) and the octanoic acid (HBD) furnished good quality tribo
thin film driven by the interaction of amine-rich cation in
aminoguanidine salt. Moreover, the good chemical affinity of octa-
noic acid also facilitated the thin-film formation and yielded the
tribochemical thin film of low shear strength for enhancement of
tribological properties. The steric hindrance by a higher degree of
octyl chain in AG-C8-(1:4) and AG-C8-(1:8) DESs-based lubricant
system compromised the interfacial layering and decreased the
adsorption kinetics, consequently, poor quality tribochemical thin
film formation. It is further supported by a gradual decline in both
wear and friction coefficient in the AG-C8 DESs-based lubricant
system when the molar ratio of octanoic acid decreased.
8
Journal of Molecular Liquids 339 (2021) 116829
4. Conclusion
Aminoguanidine salt-based DESs were synthesized by a single-
step facile approach using variable mole ratios of octanoic acid as
an HBD. The AG-C8-(1:2) DES having a two-mole ratio of octanoic
acid showed the highest viscosity and thermal stability among all
samples. The increasing mole ratio of octanoic acids in AG-C8-
(1:4) and AG-C8-(1:8) DESs decreased the magnitude of
hydrogen-based interaction because of steric hindrance by a higher
degree of a longer alkyl chain; as a result, these DESs showed lower
viscosity and thermal stability. The good miscibility of these DESs
in SN 150 lube base oil and thin film formation capability make
them potential candidates for new generation lubricant formula-
tion. The AG-C8 DESs as additives to SN 150 mineral lube base
oil improved the tribological properties of steel by reducing the
of friction and wear reductions are noted to be governed by the
composition of DESs. The AG-C8-(1:2)-based lubricant system with
a higher degree of hydrogen linkages yielded a good quality tribo
thin film; consequently, low and stable coefficient of friction. The
affinity of amino-rich aminoguanidine and octanoic acid towards
iron surfaces under the tribo-stress promoted the tribochemical
thin film formation, supported by spectroscopic measurement.
Being halogen-free, economically viable, prepared by a facile
approach, good miscibility with mineral lube base oils, and signif-
icant improvement in viscosity index, friction, and wear make
these DESs potential candidates for new generation lubricant
formulation.
CRediT authorship contribution statement
Amzad Khan: Conceptualization, Data curation, Formal analy-
sis, Investigation, Methodology, Validation, Writing - original draft.
Raghuvir Singh: Formal analysis. Piyush Gupta: Formal analysis.
Kanika Gupta: Investigation, Methodology. Om P Khatri: Concep-
tualization, Data curation, Funding acquisition, Investigation, Pro-
ject administration, Supervision, Visualization, Writing - review &
editing.
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.
Acknowledgment
The authors are grateful to the Director, CSIR-Indian Institute of
Petroleum, Dehradun, for his kind permission to publish these
results. Authors are thankful to CSIR, India, for financial support
(OLP-884) and ASD, UWRD, and CMSD of CSIR-IIP, Dehradun, for
analytical support. AK and KG are grateful to CSIR and UGC for
the research fellowship support.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molliq.2021.116829.
References
[1] C.J. Reeves, P.L. Menezes, Advancements in eco-friendly lubricants for
tribological applications: past, present, and future, in: J. Davim (Ed.),
Ecotribology, Springer, 2016, pp. 41–61.
[2] R.W. Carpick, A. Jackson, W.G. Sawyer, N. Argibay, P. Lee, A. Pachon, R.M.
Gresham, The tribology opportunities study: can tribology save a quad?, Tribol.
Lubr. Techno. 72 (2016) 44.
A. Khan, R. Singh, P. Gupta et al.
[3] W. Dai, B. Kheireddin, H. Gao, H. Liang, Roles of nanoparticles in oil lubrication,
Tribol. Int. 102 (2016) 88–98.
[4] A. Chouhan, H.P. Mungse, O.P. Khatri, Surface chemistry of graphene and
graphene oxide: a versatile route for their dispersion and tribological
applications, Adv. Colloid Interface Sci. 283 (2020) 102215.
[5] Y. Zhou, J. Qu, Ionic liquids as lubricant additives: a review, ACS Appl. Mater.
Interfaces 9 (2017) 3209–3222.
[6] Z. Tang, S. Li, A review of recent developments of friction modifiers for liquid
lubricants (2007–present), Curr. Opin. Solid State Mater. Sci. 18 (2014) 119–
139.
[7] S.S. Rawat, A. Harsha, O.P. Khatri, R. Wäsche, Pristine, reduced, and alkylated
graphene oxide as additives to paraffin grease for enhancement of tribological
properties, J. Tribol. 143 (2021) 021903.
[8] H. Nautiyal, S. Kumari, R. Tyagi, U. Rao, O.P. Khatri, Evaluation of tribological
performance of copper-based composites containing nano-structural 2D
materials and their hybrid, Tribol. Int. 153 (2021) 106645.
[9] T. Torimoto, T. Tsuda, K.i. Okazaki, S. Kuwabata, New frontiers in materials
science opened by ionic liquids, Adv. Mater. 22 (2010) 1196–1221.
[10] S. Perkin, Ionic liquids in confined geometries, Phys. Chem. Chem. Phys. 14
(2012) 5052–5062.
[11] X. Gong, L. Li, Nanometer-thick ionic liquids as boundary lubricants, Adv. Eng.
Mater. 20 (2018) 1700617.
[12] R. Gusain, P. Gupta, S. Saran, O.P. Khatri, Halogen-free bis (imidazolium)/bis
(ammonium)-di [bis (salicylato) borate] ionic liquids as energy-efficient and
environmentally friendly lubricant additives, ACS Appl. Mater. Interfaces 6
(2014) 15318–15328.
[13] A.I. Siriwardana, Industrial applications of ionic liquids, Electrochemistry in
Ionic Liquids, Springer, 2015, pp. 563–603.
[14] R. Gusain, S. Dhingra, O.P. Khatri, Fatty-acid-constituted halogen-free ionic
liquids as renewable, environmentally friendly, and high-performance
lubricant additives, Ind. Eng. Chem. Res. 55 (2016) 856–865.
[15] M. Amde, J.-F. Liu, L. Pang, Environmental application, fate, effects, and
concerns of ionic liquids: a review, Environ. Sci. Technol. 49 (2015) 12611–
12627.
[16] E.L. Smith, A.P. Abbott, K.S. Ryder, Deep eutectic solvents (DESs) and their
applications, Chem. Rev. 114 (2014) 11060–11082.
[17] M.T. Donato, R. Colaço, L.C. Branco, B. Saramago, A review on alternative
lubricants: ionic liquids as additives and deep eutectic solvents, J. Mol. Liq. 333
(2021) 116004.
[18] K. Radošević, M.C. Bubalo, V.G. Srček, D. Grgas, T.L. Dragičević, I.R.
Redovniković, Evaluation of toxicity and biodegradability of choline chloride
based deep eutectic solvents, Ecotoxicol. Environ. Saf. 112 (2015) 46–53.
[19] S. Lawes, S. Hainsworth, P. Blake, K. Ryder, A. Abbott, Lubrication of steel/steel
contacts by choline chloride ionic liquids, Tribol. Lett. 37 (2010) 103–110.
[20] I. Garcia, S. Guerra, J. de Damborenea, A. Conde, Reduction of the coefficient of
friction of steel-steel tribological contacts by novel graphene-deep eutectic
solvents (DESs) lubricants, Lubricants 7 (2019) 37.
[21] A.P. Abbott, E.I. Ahmed, R.C. Harris, K.S. Ryder, Evaluating water miscible deep
eutectic solvents (DESs) and ionic liquids as potential lubricants, Green Chem.
16 (2014) 4156–4161.
[22] M. Antunes, A.-S. Campinhas, M. de Sá Freire, F. Caetano, H.P. Diogo, R. Colaço,
L.C. Branco, B. Saramago, Deep eutectic solvents (DES) based on sulfur as
alternative lubricants for silicon surfaces, J. Mol. Liq. 295 (2019) 111728.
[23] J.E. Hallett, H.J. Hayler, S. Perkin, Nanolubrication in deep eutectic solvents,
Phys. Chem. Chem. Phys. 22 (2020) 20253–20264.
[24] M. Slaný, L’. Jankovič, J. Madejová, Structural characterization of organo-
montmorillonites prepared from a series of primary alkylamines salts: Mid-IR
and near-IR study, Appl. Clay Sci. 176 (2019) 11–20.
[25] G. Richner, G. Puxty, Assessing the chemical speciation during CO2 absorption
by aqueous amines using in situ FTIR, Ind. Eng. Chem. Res. 51 (2012) 14317–
14324.
[26] C. Karthikeyan, S. Rajeswari, S. Maruthamuthu, K. Subramanian, G. Rajagopal,
Biogenic ammonia for CO2 capturing and electrochemical conversion into
bicarbonate and formate, J. CO2 Util. 6 (2014) 53–61.
Journal of Molecular Liquids 339 (2021) 116829
[27] D.P. Arcon, F.C. Franco Jr, All-fatty acid hydrophobic deep eutectic solvents
towards a simple and efficient microextraction method of toxic industrial
dyes, J. Mol. Liq. 318 (2020) 114220.
[28] H. Ghaedi, M. Ayoub, S. Sufian, B. Lal, Y. Uemura, Thermal stability and FT-IR
analysis of Phosphonium-based deep eutectic solvents with different
hydrogen bond donors, J. Mol. Liq. 242 (2017) 395–403.
[29] D.L. Pavia, G.M. Lampman, G.S. Kriz, J.A. Vyvyan, Introduction to Spectroscopy,
Nelson Education, 2014.
[30] H. Wang, S. Liu, Y. Zhao, J. Wang, Z. Yu, Insights into the hydrogen bond
interactions in deep eutectic solvents composed of choline chloride and
polyols, ACS Sustain. Chem. Eng. 7 (2019) 7760–7767.
[31] K.-I. Takei, R. Takahashi, T. Noguchi, Correlation between the hydrogen-bond
structures and the C=O stretching frequencies of carboxylic acids as studied by
density functional theory calculations: theoretical basis for interpretation of
infrared bands of carboxylic groups in proteins, J. Phys. Chem. B 112 (2008)
6725–6731.
[32] R. Gautam, N. Kumar, J.G. Lynam, Theoretical and experimental study of
choline chloride-carboxylic acid deep eutectic solvents and their hydrogen
bonds, J. Mol. Struct. 1222 (2020) 128849.
[33] Q. Abbas, L. Binder, Synthesis and characterization of choline chloride based
binary mixtures, ECS Trans. 33 (2010) 49.
[34] F.U. Shah, I.A. Khan, P. Johansson, Comparing the thermal and electrochemical
stabilities of two structurally similar ionic liquids, Molecules 25 (2020) 2388.
[35] P.J. Carvalho, S.P. Ventura, M.L. Batista, B. Schröder, F. Gonçalves, J. Esperança,
F. Mutelet, J.A. Coutinho, Understanding the impact of the central atom on the
ionic liquid behavior: phosphonium vs ammonium cations, J. Chem. Phys. 140
(2014) 064505.
[36] R.L. Gardas, J.A. Coutinho, A group contribution method for viscosity
estimation of ionic liquids, Fluid Phase Equilib. 266 (2008) 195–201.
[37] G. Yu, D. Zhao, L. Wen, S. Yang, X. Chen, Viscosity of ionic liquids: database,
observation, and quantitative structure-property relationship analysis, AIChE
J. 58 (2012) 2885–2899.
[38] A. Khan, R. Gusain, M. Sahai, O.P. Khatri, Fatty acids-derived protic ionic liquids
as lubricant additive to synthetic lube base oil for enhancement of tribological
properties, J. Mol. Liq. 293 (2019) 111444.
[39] A. Khan, S.R. Yasa, R. Gusain, O.P. Khatri, Oil-miscible, halogen-free, and
surface-active lauryl sulphate-derived ionic liquids for enhancement of
tribological properties, J. Mol. Liq. 318 (2020) 114005.
[40] A. Westerholt, M. Weschta, A. Bosmann, S. Tremmel, Y. Korth, M. Wolf, E.
Schlücker, N. Wehrum, A. Lennert, M. Uerdingen, Halide-free synthesis and
tribological performance of oil-miscible ammonium and phosphonium-based
ionic liquids, ACS Sustain. Chem. Eng. 3 (2015) 797–808.
[41] G. Huang, Q. Yu, Z. Ma, M. Cai, Probing the lubricating mechanism of oil-
soluble ionic liquids additives, Tribol. Int. 107 (2017) 152–162.
[42] C.J. Reeves, P.L. Menezes, T.-C. Jen, M.R. Lovell, The influence of fatty acids on
tribological and thermal properties of natural oils as sustainable biolubricants,
Tribol. Int. 90 (2015) 123–134.
[43] R.R. Sahoo, S. Biswas, Frictional response of fatty acids on steel, J. Colloid
Interface Sci. 333 (2009) 707–718.
[44] R. Espinosa-Marzal, A. Arcifa, A. Rossi, N. Spencer, Microslips to ‘‘avalanches”
in confined, molecular layers of ionic liquids, J. Phys. Chem. Lett. 5 (2014) 179–
184.
[45] M.-D. Krass, G. Krämer, U. Dellwo, R. Bennewitz, Molecular layering in
nanometer-confined lubricants, Tribol. Lett. 66 (2018) 1–10.
[46] P.C. Nalam, A. Pham, R.V. Castillo, R.M. Espinosa-Marzal, Adsorption behavior
and nanotribology of amine-based friction modifiers on steel surfaces, J. Phys.
Chem. 123 (2019) 13672–13680.
[47] R. Gusain, O.P. Khatri, Fatty acid ionic liquids as environmentally friendly
lubricants for low friction and wear, RSC Adv. 6 (2016) 3462–3469.
[48] N. Gosvami, J. Bares, F. Mangolini, A. Konicek, D. Yablon, R. Carpick,
Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity
sliding contacts, Science 348 (2015) 102–106.