Received: 26 January 2019 Revised: 7 April 2019
DOI: 10.1002/ls.1473
RESEARCH ARTICLE
Synthesis of ionic liquids with multifunctional tribological
properties as excellent single‐component package additives
for turbine oils
Shahriyar Keshavarz1 | Mohammad R. Naimi‐Jamal1
Mohammad G. Dekamin1
1
Research Laboratory of Green Organic
Synthesis & Polymers, Department of
Chemistry, Iran University of Science and
Technology, Tehran, Iran
2
Faculty of Chemistry, University of
Tehran, Tehran, Iran
Correspondence
Naimi‐Jamal, Research Laboratory of
Green Organic Synthesis & Polymers,
Department of Chemistry, Iran University
of Science and Technology, PO Box 16846‐
13114, Tehran, Iran.
Email: naimi@iust.ac.ir
Funding information
Iran University of Science and Technology
1 | INTRODUCTION
Mineral oils have long been used as natural lubricating
oils since the 1800s.1 When in use, the lubricating oils
experience relatively high temperatures and usually are
in contact with air. Under such conditions and in the
presence of metals, a group of chemical reactions take
place, which lead to oxidation of mineral oils. Oxidation
causes increase in viscosity and propagation of acid com-
ponents in the lubrication media. This is followed by cor-
rosion of metallic segments and formation of carbon
residues.2 In some applications, such as lubrication of
gears, the friction between the contacting elements of
Lubrication Science. 2019;1–10.
Accepted: 22 July 2019
| Yahya Izadmanesh2 |
Abstract
Three benzotriazole‐bearing imidoazolium‐based ionic liquids (ILs) have been
synthesized. The ILs were identified by 1HNMR and Fourier‐transform infra-
red (FTIR) techniques. The thermogravimetric analysis showed that they are
highly nonvolatile and have extremely high flash points. The synthesized ILs
were used in turbine oil formulation, and their lubrication properties were
critically examined and compared to commercially available package additives.
The tribological tests proved that the ILs act as an effective antifriction,
antiwear (AW), and extreme pressure (EP) additives. Performance studies
indicated that the synthesized ILs impart excellent antioxidation and corrosion
protection to the lubricant with minimum acidity change. The elemental anal-
ysis proved absence of toxic and dangerous elements in the lubricant, a confir-
mation that the ILs are potential environmentally friendly lubricants. The
results also confirmed that the synthesized ILs are ideal single‐component
package additives in the lubricant industry, i.e., one molecule imparts several
favorable functionalities to the lubricant..
KEYWORDS
ionic liquids, package additive, tribology, turbine oils
the system under lubrication causes substantial damage
to the rolling elements which leads to wear and failure
of the machine. These drawbacks were not serious until
the middle of the 20th century, which a boost in techno-
logical advances demanded newer lubricants. For exam-
ple, In World War II, advances in aviation, in particular,
the discovery of the gas turbine and the development of
rocket motors and space vehicles demanded lubricants
with higher performance.3 The moving components of
these newer technologies were usually exposed to greater
extremes of temperatures and there was the fire hazards
concern. The lubricants' volatility was another serious
concern. The need to enhance lubrication reliability
wileyonlinelibrary.com/journal/ls © 2019 John Wiley & Sons, Ltd. 1
2 KESHAVARZ ET AL.

promoted the present growing interest in synthetic lubri-
cants. But even with the development of synthetic base
oils such as group IV and group V base oils, the concern
was not over yet.4 The need for newer lubricants with
higher performance characteristics led to the synthesis
and use of performance enhancing additives in the lubri-
cants. These additives included oxidation inhibitors, rust
inhibitors, corrosion inhibitors, VI group improvers, anti-
wear (AW) and extreme pressure (EP) additives, and
dispersers.2
Ionic liquids (ILs) are molten salts at relatively low
temperatures (below 100°C), composed of ion pairs con-
taining bulky, asymmetric cations and anions.5 ILs were
first reported as very promising high‐performance lubri-
cants in 2001 and since then have attracted considerable
attention as high‐performance lubricants6 or as additives
with remarkable lubrication capabilities.7-9 This may be
attributed to the dipolar structure of ILs and excellent
physical properties such as extremely low volatility, non-
flammability, the ability to form tribofilms, high thermal
stability, high melting points, environmental friendliness,
and adaptability to various applications.10-12 The melting
point and the viscosity of ILs are two important parame-
ters for lubricating oils and strongly depend on molecular
structure, cation type, anions type, and alkyl chains
length.9 The good lubricating properties of the ILs are
also linked to their high polarity13 and the adsorbed
tribofilms formed on the metal surfaces, which contribute
to reducing friction and wear.14,15 The other advantages
of ILs over conventional lubricants lie in their better
ability to form tribofilms, higher thermal stability, envi-
ronmental friendliness, and adaptability to various appli-
cations.8 A remarkable reduction in friction and wear
has been observed after the addition of ILs in oil‐ or
water‐based media and in grease, suggesting that ILs are
promising candidate materials as neat lubricants as well
as lubricant additives.16
This study aims to synthesise benzotriazole‐bearing
imidazolium‐based ILs, which can be used as additive to
improve AW/EP,17 antiabrasive, antioxidative, and anti-
corrosive properties of the lubricant.18 The ILs were used
in turbine oil formulations, and a thorough investigation
has been made on the tribological properties of the lubri-
cants ,and their performance levels are compared with
turbine oils containing commercially available additive
IRGALUBE 2030A. The results confirmed that the under-
study ILs can act as an excellent single component multi-
functional oil additive. The synthesised ILs consists of a
single backbone that chemical compounds can be
implanted on it in a way that each one imparts a certain
performance‐enhancing property to the oil, providing the
possibility of tailor‐made design of lubricants. The details
of the study are given in the following sections.
2 | EXPERIMENTAL
2.1 | Materials and methods
All reagents including 1‐methyl‐imidazole, isopropyl alco-
hol, sodium tetra fluoroborate, bis(trifluoromethylsulfo-
nyl)amide (TFSA), 1,6‐dibromohexane, potassium
hexafluorophosphate, benzotriazole, dichloromethane,
acetonitrile, acetone, and ethyl acetate, to be used for syn-
thesis of ILs, were purchased from commercially available
sources such as Sigma‐Aldrich and Merck and were used
without further purification. IRGALUBE 2030A and ISO
VG 32 (ISO viscosity classification) base oil were kindly
provided by Pars Oil Company. The tribological properties
of base oil is given in Table 1. IRGALUBE 2030A is a

TABLE 1 The physical, chemical, and performance properties of understudy turbine oil formulations [Colour table can be viewed at
wileyonlinelibrary.com]

Characteristics Method ISO VG32 base oil 0.5% IL1 0.5% IL2 0.5% IL3 0.5% IRGALUB 2030

Viscosity at 40°C ASTM D445 33.3 33.8 34.1 33.95 33.03

Copper corrosion ASTM D130 1b 1a 1a 1a 1a
TAN (mg KOH/g) ASTM D664 0.07 0.08 0.08 0.08 0.09
Water separability, 40‐37‐3 (min) ASTM D1401 5 7 7 8 12
4‐ball weld point (kg) ASTM D4172 80 200 160 160 160
FZG load ASTM D5182 5 11 11 11 8
SG (15°C) ASTM D4052 0.86 0.88 0.89 0.89 0.85
RBOT test (min) ASTM D2272 100 380 330 303 180
Air release (min) ASTM D3427 5 6 7 7 9
Sulfated ash (wt%) ASTM D874 0.01 0.01 0.01 0.01 0.01

Abbreviations: FZG, Forschungstelle für Záhnräder und Getriebebau; IL, ionic liquid.
KESHAVARZ ET AL.
premium ashless package containing antioxidants, corro-
sion inhibitors, and metal deactivators. It is ideal for for-
mulating cost‐effective long service life turbine and
circulating oils for high‐temperature applications.
Characteristics of the synthesised materials were deter-
mined by (infrared) IR and 1HNMR. 1HNMR spectra
were recorded in DMSO‐d6 on a Bruker 300 MHz spec-
trometer using TMS (Tetramethylsilane) as an internal ref-
erence. IR spectra were recorded with a Shimadzu 8400s
Fourier‐transform infrared (FTIR) spectrometer using
potassium bromide pellets. Forschungstelle für Záhnräder
und Getriebebau (FZG) test machine (STRAMA‐MPS
Maschinenbau GmbH & Co., Germany) was used for
FZG testing of lubricants according to ASTM D5182
(American Society for Testing and Materials). Anton‐Paar
automatic viscometer (model SVM 3001) was used for vis-
cosity and density measurements according to ASTM
D445 and ASTM D2270, respectively. Flash point mea-
surements were done using Pensky Martins tester
(Herzog) according to ASTM D92. Pour point measure-
ments were done using semi‐automatic ISL trademark
(France) tester according to ASTM D97. Total acidity num-
ber (TAN) measurements were done using Metrohm semi-
automatic TAN tester according to ASTM D664. Four‐ball
measurements were done according to ASTM D2596 using
STANHOPE‐SETA test rig. Mitotoyo TM microscope (×30
magnification) was used for observing and measuring
wear diameter of balls. Water separability measurements
were done using SCVAVINI tester (Baveno, Italy) accord-
ing to ASTM D1401. The FZG gear tests were performed
SCHEME 1 General overview of ionic
liquids syntheses [Colour figure can be
viewed at wileyonlinelibrary.com]
3
Starma‐MPS test rig. Copper corrosion tests were done
according to ASTM D130. The S.D.M RBOT test rig
(Torino, Italy) was used for oxidation stability testing
according to ASTM D943 test procedure. Air release test
was measured by STANHOPE‐SETA test rig according to
ASTM D3427. TGA (Thermal gravimetric analyzer) 4000
(Perkin Elmer) equipped to a ceramic furnace was used
for thermal analysis of ILs with the heating rate of
10°C/min. Thermo Scientific iCAP 7400 ICP‐OES (induc-
tively coulpled plasma‐ optical emission spectroscopy) was
used for elemental analysis according to ASTM D5185.
2.2 | Synthesis procedure and
identification data of ILs
The ILs have been synthesised in three general steps1:
synthesis of imidazolium cation,2 converting it to benzo-
triazole bearing imidazolium cation,3 and anion exchange
to obtain final product. Scheme 1 shows the general syn-
thesis procedure of the ILs.6,19-21
2.2.1 | Synthesis of imidazolium cation
A 0.075 mole (36.6 g) of 1,6‐dibromohexane was weighed
in a 50‐ml three‐necked flask, and then 0.02 mole (1.42 g)
of 1‐methyl imidazole was added drop‐wise to the flask
content. This mixture was refluxed under neutral atmo-
spheric conditions (nitrogen gas) at 150°C for 12 hours,
which gave a white residue. Afterwards, the flask was
4 KESHAVARZ
cooled to room temperature and then its contents were
washed with 7 ml of ethyl acetate. The residue was solved
in 5 ml of isopropyl alcohol and 15ml of acetone and fil-
tered by micron‐sized filter paper. The filtrate solution
was kept in fridge for 24 hours, and then isopropyl alco-
hol and acetone were evaporated by rotary evaporator,
which gave a white to yellow coloured oily liquid with
87% yield. This product is named Precursor A in Scheme 1
and was used for benzotriazole bearing cation synthesis.
2.2.2 | Synthesis of benzotrazole bearing
cation
Five millimole (0.6 g) of benzotriazole and 5 mmole of
Precursor A (Scheme 1) were weighed and added to a
50‐ml three‐necked flask, followed by 10 ml of acetoni-
trile. The reaction mixture was refluxed under neutral
atmospheric conditions (nitrogen gas) at 70°C for 24 hours,
which gave a yellow‐coloured residue. The residue was
rinsed three times with 5 ml batches of cold acetonitrile to
separate raw unreacted material and consequently filtered
each time with filter paper. This product is named Precursor
B in Scheme 1 and was used for understudy ILs synthesis.
The yield was 89%.
2.2.3 | Synthesis of understudy ILs
Thirty‐seven millimole (10.518 g) of Precursor B and
37 mmole (6.81 g) of potassium hexafluorophosphate
were weighed in a 100‐ml three‐necked flask. Afterwards,
7 ml of water was added and mixed with it at room tem-
perature for 2 hours. Then, 10 ml of dichloromethane was
added and the flask contents were introduced into a 100‐
ml separating funnel. After thoroughly mixing, the mate-
rials were allowed to settle and form a two‐layer system.
The water layer was removed. Then dichloromethane
was evaporated by rotary evaporator. The residue with
94% yeild was named IL1 and used as the first IL for fur-
ther tribological studies.
Thirty‐seven millimole (10.51 g) of Precursor B and
37 mmole (4.07 g) of sodium tetrafluoroborate were
weighed in a 100‐ml three‐necked flask. Afterwards,
7 ml of water was added and mixed at room temperature
for 2 hours. Then 10 ml of dichloromethane was added
and the flask contents were introduced into a 100‐ml sep-
arating funnel. After thoroughly mixing, the materials
were allowed to settle and form a two‐layer system. The
water layer was removed. The dichloromethane was
evaporated by rotary evaporator. The residue with 90%
yield was named IL2 and used as the second IL for further
tribological studies.
ET AL.
Thirty‐seven millimole (10.51 g) of Precursor B and
37 mmole (5.52 g) of TFSA were weighted in a 100‐ml
three‐necked flask. Afterwards, 7 ml of water was added
and mixed with flask contents at room temperature for
2 hours. Then, 10 ml of dichloromethane was added,
and the flask contents were introduced into a 100‐ml sep-
arating funnel. After thoroughly mixing, the materials
were allowed to settle and form a two‐layer system. The
water layer was discarded. The dichloromethane was
evaporated by rotary evaporator, and the residue having
101% yield was named IL3 and used as the third IL for
further tribological studies.
2.3 | Spectral data and identification of
synthetized compounds
The synthesised ILs were identified by 1HNMR and FTIR.
The identification data are given below. The FTIR and
HNMR spectra of the synthesised ILs are given in supple-
mentary materials.
• Precursor A: 1HNMR (300 MHz, DMSO‐d6): δ (ppm),
9.29 (1H, N─CH─N), 7.85 (1H, CH, imidazolium
ring), 7.74 (1H, CH, imidazolium ring), 4.17 (t, 2H,
N─CH2), 3.85 (s, 3H, CH3), 3.65 (t, 2H, CH2─Br),
2.20‐0.80 (m, aliphatic CH2).
• FTIR (KBr pellet, cm−1): 3432 (imidazole ring), 3145
(CH aromatic), 2938 (CH alkane), 1569.7 (C═C aro-
matic), 1458 (CH alkane), 1379 (C─N aromatic),
1167 (CH2X alkyl halide), 620 (C‐Br alkyl halide).
• Precursor B: 1HNMR (300 MHz, DMSO‐d6): δ (ppm),
9.32 (s, 1H, N─CH‐N), 7.9‐7.8 (3H, Ar H), 7.8 (1H,
CH, imidazolum ring), 7.39 (2H, Ar CH), 4.1 (3H,
N─CH3), 3.85 (4H, 2NCH2), 2.10‐0.70 (m, aliphatic
CH2).
• FTIR (KBr pellet, cm−1): 3442 (imidazole ring), 3145
(CH aromatic), 2936 (CH alkane), 1631 (C═C aro-
matic), 1459 (CH alkane).
3 | R ES U L T A N D DI S C U S S I O N S
3.1 | Thermal stability of ILs
Thermal analysis is the most well‐known technique to
determine lifetime of chemicals.22 Thermal behaviour
of synthesised ILs was measured by thermogravimetric‐
differential thermal analysis (TG‐DSC). Figure 1 shows
the TGA curves of the synthesised ILs. According to this
figure, the synthesised ILs does not exhibit any signifi-
cant weight loss and decomposition below 280°C. Above
this temperature, the decomposition starts and total
KESHAVARZ ET AL.
FIGURE 1 Thermal TGA analysis of the synthesised ionic
liquids (ILs) in air atmosphere [Colour figure can be viewed at
wileyonlinelibrary.com]
decomposition occurs at higher than 700°C, indicating
satisfying thermal stability. The decomposition of IL3
happens faster at temperatures higher than 280°C, while
IL1 and IL2 are more resistant. These observations are
not consistent with the observation that benzotriazole
has very low sublimation temperature (approximately
100°C) leading to conclusion that, by incorporating ben-
zotriazole into IL structure, its thermal volatility has sig-
nificantly decreased.
Pure benzotriazole decomposes around 200°C to
250°C,23 which is close to the three T‐onsets in Figure 1.
1,3‐Dialkylimidazolium ILs with BF4−, PF6− and TFSI
anions usually show T‐Onsets around 400°C and more.
In conclusion, the thermal decomposition of IL1, IL2,
and IL3 is limited by the benzotriazole moiety at a tem-
perature close to normal Benzotriazole. This finding is
to be expected due to the instability of the triazole ring.23
3.2 | Tribological studies
The synthesised ILs were used at 0.5% treat level in ISO
VG 32 base oil, and their performance properties were
explored with the lubricant containing 0.5 wt% of the
commercially available turbine oil package additive,
IRGALUBE 2030A. IRGALUBE 2030A is a premium
ashless package containing antioxidants, corrosion
inhibitors, and metal deactivators. Together, five oil
formulations were prepared. One of the formulations
was the ISO VG 32 base oil without any additives
(virgin base oil) to be used as an indicator for under-
standing the effect of additives in the lubricants. Three
formulations were made by addition of 0.5 wt% of each
of the three synthesised ILs to the ISO VG 32 base oil.
One formulation was prepared with 0.5 wt% treat level
of IRGALUBE 2030A to ISO VG32 base oil (reference
5
formulation). Table 1 shows the physical, chemical,
and measured tribological properties of the five
formulations.
3.2.1 | Oxidative stability and metal
deactivating properties
Oxidation stability test was done according to ASTM
D2272. In this methodology, the test oil, water, and cop-
per catalyst coil, contained in a covered glass container,
are placed in a vessel equipped with a pressure gauge.
The vessel is charged with oxygen to a gauge pressure
of 620 kPa (90 psi, 6.2 bar), placed in a constant‐
temperature oil bath set at 150°C, and rotated axially at
100 rpm at an angle of 30° from the horizontal. The
number of minutes required to reach a specific drop in
gauge pressure is the oxidation stability of the test sam-
ple. Estimation of oxidation stability is of high impor-
tance in controlling the continuity of this property for
batch acceptance of production lots having the same
operation. The pressure drop of virgin ISO VG 32 base
oil happens after 100 minutes. This indicates that the
base oil itself does not have enough resistance against
oxidation, but incorporating 0.5 wt% of IRGALUBE
2030A increases the time to 180 minutes, approximately
double in comparison to virgin base oil. This indicates
effectiveness of IRGALUBE 2030A lubricant. When
incorporating 0.5 wt% of the three synthesised ILs into
the base oil, the time increases to above 300 minutes,
providing proof of better antioxidation properties of the
synthesised ILs in comparison with IRGALUBE 2030A.
The oxidation stability time for IL1, IL2, and IL3 contain-
ing oil is 380, 330, and 303 minutes, respectively. It has
been proved that ILs having BF4−, PF6−, and TFSA as
anions and imidiazolium‐based ILs have high oxidation
stabilites.24 All of the synthesised ILs have the common
cation, but they have different anions. Therefore, their
differences in oxidation properties originate from their
anion. The probable reason for lower oxidation stability
of IL3 is the presence of the sulfur in the structure of
the TFSA anion, which reduces oxidation stability.25
The anion of IL1 and IL2 do not have sulfur atoms and
hence their oxidation stability is higher. Also, they have
fluorine in their structure, which have radical scaveng-
ing effect and prevents oxidation.24,26 The IL3 anion con-
tains phosphorous atoms, which is well‐known to have
antioxidation properties.27 In summary, better antioxida-
tion properties of the synthesised ILs in comparison with
IRGALUBE 2030A originates from the presence of aro-
matics amines in the structure of cation of ILs2,18 and
anion of ILs.
6 KESHAVARZ ET AL.

For studying metal deactivating effects of the synthe-
sised ILs, the copper strip corrosion test was carried
out according to ASTM D130. In this procedure, a
polished copper strip was immersed in a specific volume
of the sample being tested and heated under conditions
of temperature (100°C) and time (three hours). At the
end of the heating period, the copper strip was removed,
washed, and the colour and tarnish level assessed
against the ASTM Copper Strip Corrosion Standard. As
can be seen in Table 1, the virgin base oil shows the
1b level, while ILs and IRGALUBE 2030A containing
lubricants showed 1a level. This indicates that the syn-
thesised ILs have similar metal passivation properties
when compared with IRGALUBE 2030A. The metal pas-
sivation of ILs originates from imidazole and azole
groups (bezotriazole and imidazole) in its structure.28
3.2.2 | Abrasion behaviour and AW/EP
properties
The four‐ball test rig was used for evaluating the AW/EP
properties of the synthesised ILs according to ASTM
D2596 standard procedure. The tester is operated with
one steel ball under load rotating against three steel balls
held stationary in the form of a cradle. The rotating speed
is 1770 ± 60 rpm. Lubricants are brought to 27 ± 8°C
(80 ± 15°F) and then subjected to a series of tests of
10 seconds duration at increasing loads until welding
occurs. The higher load that welding occurs indicates
more effective boundary lubrication and formation of
stronger tribofilm at the contact point.29,30 According to
Table 1, the welding of virgin base oil occurs at 80 kg,
while incorporating 0.5 wt% of IRGALUBE 2030A
increases the welding point to 160 kg. The same increase
can be observed for IL containing formulations, except
that for the IL1 containing additive, the welding point
increases to 200 kg. This is probably due to the presence
of phosphorous atom in IL1, which is demonstrated to
have EP role.31 Although, IL3 have sulfur atoms in its
structure, but it is embedded in the inner structure of IL
anion and cannot contribute effectively to enhanced
boundary lubrication by film formation. From these
observations it can be concluded that synthesised ILs
act as AW/EP additives in the turbine oil, when com-
pared with conventional turbine oil package (IRGALUBE
2030A). The ILs form a protecting tribofilm on the sur-
face of the steel balls, which acts as a boundary lubrica-
tion layer and enhance AW/EP properties of the oil.
Tribofilm forming is probably happening via hetro atoms

FIGURE 2 SEM (Scanning electron microscopy) micrographs of worn surfaces of balls after four‐ball wear test lubricated with understudy
lubricants: (A) virgin base oil, (B) base oil + 0.5 wt% IL1, (C) base oil + 0.5 wt% IL2, (D) base oil + 0.5wt% IL3, and (E) base oil + 0.5 wt%
IRGALUBE 2030A. Test setup: 40 kg of applied load, duration of 1 hour time, rotation speed of 1770 rpm
KESHAVARZ ET AL.
(nitrogen, prosperous or sulfur) bonding to the steel ball
surfaces.32
Figure 2 shows morphologies of the damaged and lubri-
cated steel balls after four‐ball wear test. To inspect their
wear behaviour, the balls are immersed in the understudy
lubricant, and then the wear was measured after 1 hour
rotation under 40 kg of load (1770 ± 60 rpm). As can be
seen, the wear scar of balls lubricated by ISO VG32 have
much deeper and wider grooves. But in the IL containing
lubricants, the balls are protected from wear and the
grooves are shadow and much less wide. The wear scar
of the IL1 containing oil has smaller diameter in compari-
son to IL2 containing lubricant, but the grooves are
deeper. The diameter of wear scars of the IL3 containing
oil is wider and has deeper groves than other two IL con-
taining lubricants. The IRGALUBE 2030A containing oil
has wear scars and grooves with dimensions comparable
with IL3 containing lubricants. From Figure 2, it can be
concluded that IL containing formulations provide better
AW properties than turbine oil containing commercial
additive packages.
Also, in this study, SRV test machine ((Oscillating),
Reibung (Friction), Verschleiž (Wear)) was used to
study friction and abrasive behaviour of the turbine oil
formulations. The test was performed on an SRV test
machine using a test ball oscillated under constant load
against a test disk; then, coefficient of friction is mea-
sured. Figure 3 shows the friction coefficients taken from
five lubricants at a test load of 200 N, frequency of 50 Hz,
stroke amplitude of 1.00 mm, duration of 1800 seconds,
and temperature of 80°C. Highest fiction coefficients are
obtained for virgin base oil, because it does not contain
any additives to prevent friction of the lubricated parts.
The IRGALUBE 2030A containing oil shows less friction
than virgin base oil but still shows considerable friction
because this additive is not designed to be a friction mod-
ifier additive. IL containing oils show considerable reduc-
tion in friction behaviour with negligible differences
FIGURE 3 The friction coefficient of
steel discs lubricated with virgin base oil,
ionic liquid containing lubricants, and
IRGALUBE 2030A containing lubricant.
Test load, 200 N; frequency, 25 Hz; stroke
amplitude, 1.00 mm; duration,
1800 seconds; and temperature, 80°C
[Colour figure can be viewed at
wileyonlinelibrary.com]
7
among them. This observation shows that the synthesised
ILs show considerable friction modifying and anti‐
abrasive effects alongside having good AW/EP properties.
This is due to great potential of ILs in formation of
boundary tribofilm.33,34
3.2.3 | Other properties
Other tribological properties of the formulated oils using
synthesised ILs are given in Table 1.
The FZG visual method (ASTM D5182) is used to mea-
sure the scuffing load capacity of oils used to lubricate
hardened steel gears. Scoring, a form of abrasive wear is
also included as failure criteria in this test method. It is
primarily used to assess the resistance to scuffing of mild
additive treated oils. An FZG gear test machine is oper-
ated at constant speed (1450 rpm) and temperature
(90°C) for a fixed period (21 700 revolutions, approxi-
mately 15 minutes) at successively increasing loads until
the failure criteria is reached. As can be seen, the virgin
base oil has the five load stage in the FZG test, while
incorporating IRGALUBE 2030A increases this index to
8. Addition of synthetic IL additives into the oil increases
FZG load stage to 11. These results demonstrate excellent
scuffing load capacity due to presence of ILs in the
lubricants.
TAN of the oils, given in Table 1, are measured accord-
ing to ASTM D664. This method is applicable for determi-
nation of acids whose dissociation constants are larger
than 10−9 mole L−1. This parameter must be minimum
in turbine oil, because the higher the TAN number, the
formation of acidic products is more probable, which
may lead to machine failure. The TAN number of virgin
base oil is 0.07 mg KOH/g. This parameter for
IRGALUBE 2030A containing oil is equal to 0.09 mg
KOH/g. This indicates that IRGALUBE 2030A does not
contain acidic components that can considerably affect
8 KESHAVARZ
the TAN of the final lubricant. The TAN number of IL
containing oils shows that addition of ILs to the base oil
does not negatively affect the TAN of the final lubricant.
This is a major breakthrough in the use of benzotriazole
and imidazole in the oils. These have acidic hydrogen
on aromatic amine. Although they provide excellent
anticorrosive and antioxidation properties, but presence
of acidic hydrogen increases TAN of lubricant dramati-
cally, and hence their application in lubricants becomes
impractical. Incorporating imidazole and benzotriazole
into ILs bring the possibility of using the favourable prop-
erties of these components without negatively affecting
the TAN of turbine oils.
Water separability of formulated lubricants was mea-
sured according to ASTM D1401 test procedure. This test
method covers the measurements of ability of petroleum
oils or synthetic fluids to separate from water, and it is
specifically designed for steam turbine oils. This method
provides a guide for determination of demulsibilty char-
acteristic properties of lubricating oils that are prone to
water contamination and may encounter the turbulence
of pumping and circulation capable of producing water
in oil emulsions. In this procedure, a test specimen
consisting of a 40‐ml sample; 40 ml quantity of distilled
water was stirred for 5 minutes in a graduated cylinder
at 54°C. The time required for separation or emulsion
reduction to 3 ml or less was recorded. As can be seen
from Table 1, complete separation of virgin base oil hap-
pens after 5 minutes. While this time for IL1, IL2, IL3,
and IRGALUBE 2030A containing oils are 7, 7, 8, and
12 minutes, respectively. It is obvious that water separa-
bility in IL containing oils is much better than oil con-
taining commercial package additive.
The air release properties of the lubricants under study
are also given in Table 1. The measurements were done
according to ASTM D3427. This test method covers the
ability of turbine, hydraulic, and gear oils to separate
entrained air. Agitation of lubricating oil with air in
equipment, such as bearings, couplings, gears, pumps,
and oil return lines, may produce a dispersion of finely
divided air bubbles in the oil. If the residence time in
the reservoir is too short to allow the air bubbles to rise
to the oil surface, a mixture of air and oil will circulate
through the lubricating oil system. This may result in
an inability to maintain oil pressure (particularly with
centrifugal pumps), incomplete oil films in bearings and
gears, and poor hydraulic system performance or failure.
This test method measures the time for the entrained
air content to fall to the relatively low value of 0.2% vol-
ume under a standardised set of test conditions and hence
permits the comparison of the ability of oils to separate
entrained air under conditions where a separation time
is available. Entrained air can cause sponginess and lack
ET AL.
of sensitivity of the control of turbine and hydraulic sys-
tems. As can be seen from Table 1, the air release of the
IL containing oils is less than IRGALUBE 2030A, which
demonstrates another advantage of using ILs instead of
commonly used commercial additives.
The viscosity measurements at 40°C by ASTM D445
procedure reveals that IL containing lubricants show a
slight increase in viscosity (Table 1). This is because the
ILs are highly viscous. The special gravity (SG) measure-
ments at 15°C by ASTM D4052 shows a slight increase for
IL containing oils (Table 1), which originates from higher
SG of ILs in comparison with mineral oils.
The ASTM D874 covers the determination of the sul-
fated ash from unused lubricating oils containing addi-
tives. The oil additives usually contain one or more of
the following metals: barium, calcium, magnesium, zinc,
potassium, sodium, and tin. Measuring sulfated ash is an
indicator of the absence or presence of these metal ele-
ments in the lubricant. In this test, the sample is ignited
and burned until only ash and carbon remain. After
cooling, the residue is treated with sulfuric acid and heated
at 775°C until oxidation of carbon is complete. The ash is
then cooled, retreated with sulfuric acid, and heated at
775°C to constant weight. As can be seen, all the lubricants
show the trace amount of sulfated ash (0.01 wt%) as the
lubricant understudy in this paper are almost metal free.
3.2.4 | Elemental analysis
Table 2 shows the elemental composition of the oil for-
mulations measured by ICP‐OES according to ASTM
D5185. Elemental analysis is of great importance for con-
dition monitoring of machine oil. Also, it can provide
insight on the presence of elements harmful to environ-
ment in the lubricant, as these are increasingly important
in environmental regulations. Most of the AW/EP and
friction‐modifying additives contain phosepherous, sul-
fur, and zinc, which are under environmental resrtrictions.2
As can be seen, the IL containing oils are free from any of
those elements, except for IL3 which contain sulfur. The
base oil itself contains 223 ppm of sulfur. Other environ-
mentally harmful elements such as Pb, Ba, and molybde-
num are absolutely absent in IL additised oils. Small
amounts of Si in these oils is originating from silicon
antifoam and not from IL additives. This indicates that the
synthesised ILs increase desired lubrication properties of
the oil without having any toxic elements in their structure,
making them environmentally a friendly alternative to their
commercial cousins. This advantage gives the opportunity
to consider them as potentially environmental friendly
lubricants. However, it should be reminded that, although
there concentration of harmful elements in the IL
KESHAVARZ ET AL. 9

TABLE 2 Elemental composition of turbine oil preparations prepared with ILs, and their performance properties were
according to ADSTM D5185 [Colour table can be viewed at compared with turbine oil containing commercially avail-
wileyonlinelibrary.com] able turbine oil package additive. The oxidation stability
0.5% studies (RBOT) indicated that the ILs provide much better
Element ISO VG 0.5% 0.5% 0.5% IRGALUB oxidation resistance to the turbine oil containing commer-
(ppm) 32 IL1 IL2 IL3 2030 cial additive package (IRGALUBE 2030A). The AW/EP
Fe 0 0 0 0 0
properties of the IL containing oils were better than
IRGALUBE 2030A containing oil. The coefficient of fric-
Cr 0 0 0 0 0
tion in IL containing oils was considerably lower than
Al 0 0 0 0 0 IRGALUBE 2030A containing turbine oil. Other perfor-
Cu 0 0 0 0 0 mance properties including metal passivation, water
Pb 0 0 0 0 0 separability, air release, and acidity number were also
Sn 0 0 0 0 0 measured, which were in the acceptable range of typical
turbine lubricants. The synthesized ILs consisted of an
Ni 0 0 0 0 0
imidazole backbone containing benzotriazle, which both
Ti 0 0 0 0 0
act as antioxidation and metal passivation agents, pro-
Ag 0 0 0 0 0 viding deposit‐control properties. Also, hetroatoms in
Mo 0 0 0 0 0 the cation and anions of the ILs bind to the lubricating
Zn 0 0 0 0 0 surfaces and provide a tribofilm, which induce AW/EP
and antifriction properties in the oil. These ILs can be
P 0 246 0 0 0
assumed as ideal single component package additives.
Ca 0 0 0 0 0
The ILs design can be tailor‐made to provide special
Ba 0 0 0 0 0 lubrication performance properties to the oil. Most of
Mn 0 0 0 0 0 the systems under lubrication have elastomers, which
Mg 0 0 0 0 0 aren't compatible with the lubricants, but lubrication
media provided by ILs are chemically simple and pro-
Si 0 10 10 9.5 11.1
vide the advantage of better control of elastomer compat-
Na 0 0 0 0 2.4
ibility. The elemental analysis of lubricants indicated a
B 0 0 82 0 0 negligible amount of toxic elements, which proved the
V 0 0 0 0 0 ILs can be considered as potentially environmentally
K 0 21 19 3 0 friendly lubricants.
Sulfur 223 225 227 252 270

Abbreviations: IL, ionic liquid.

ACKNOWLEDGEMENTS

containing oils is minimum, there are reports that claim
BF4− or PF6− tend to be hydrolytically instable and release
toxic hydrogen fluoride‐ and imidazolium‐based cations
are not degradable in aqueous media.35 Also, TFSI is
reported in literature as toxic anion.36 Also, there are reports
in the literature37 claiming that benzotriazole derivatives
have toxicity in the environment and are not readily biode-
gradable. However, since the concentration of ILs in the
lubricant is rather low (0.5 wt%), the dangers to environ-
ment are minimum using synthesised ILs.
4 | CONCLUSIONS
Three imidazolium‐based ILs containing benzotriazole
having three different anions were synthesised for the
first time. The synthesized ILs showed good solubility in
mineral base oil. Three turbine oil formulations were
The authors would like to acknowledge Iran University of
Science and Technology for partial financial support of
this work.
ORCID
Mohammad R. Naimi‐Jamal https://orcid.org/0000-0002-
8305-7234
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How to cite this article: Keshavarz S, Naimi‐
Jamal MR, Izadmanesh Y, Dekamin MG. Synthesis
of ionic liquids with multifunctional tribological
properties as excellent single‐component package
additives for turbine oils. Lubrication Science. 2019;
1–10. https://doi.org/10.1002/ls.1473