Received: 18 July 2016 Revised: 28 March 2017 Accepted: 28 April 2017

DOI: 10.1002/ls.1391

RESEARCH ARTICLE ‐ LS

The tribological properties of the polyurea greases based on oil‐

miscible phosphonium‐based ionic liquids

Zeyun Wang | Wei Wu

School of Chemistry and Chemical

Engineering, Ningxia University, Yinchuan
750021, China
Correspondence
Zeyun Wang, School of Chemistry and
Chemical Engineering, Ningxia University,
Yinchuan 750021, China.
Email: 1234wangzeyun@163.com
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 51465049;
Natural Science Foundation of Ningxia
Province, Grant/Award Number: NZ14042
Abstract
Oil‐miscible phosphonium‐based ionic liquids have recently been attracted much
attention. This study is to develop potentional high temperature lubricating greases
based on oil‐miscible phosphonium‐based ionic liquids.
This lubricating grease is prepared using oil‐IL blend, which was obtained by
adding 10wt% oil‐miscible phosphonium‐based ionic liquids into the PAO 40 base
oil as base stock. Compared with the traditional PAO 40 polyurea grease, this
polyurea grease has a little lower dropping point. Corrosion test results show the
polyurea grease that was prepared using phosphonium‐based ionic liquids cations
connected with longer alkyl chains that are no corrosion to brass and steel. Most
importantly, the polyurea greases demonstrate very promising tribological proper-
ties at 150°C, such as low friction coefficient, small wear volume, and high lubrica-
tion failure load. Surface characterization revealed the tribochemical film containing
iron oxide, and Fe[PO4] was formed on the worn surface.

K EY WO R D S
high temperature, oil‐IL blend, phosphonium‐based ionic liquids, polyura grease

1 | INTRODUCTION
Polyurea grease is geneally prepared using organic com-
pounds containing urea group as the thickener and mineral
or synthetic oil as base oil. Polyurea grease posses high oxi-
dation stability and thermal stability because polyurea thick-
ener is not containing metal ion, which would catalyse and
oxidise the base oil. Polyurea grease is widely used in various
industrial fields, especially for high‐temperature, high load,
wide speed range of lubrication occasions.
Antiwear (AW) additives are usually used in the lubricat-
ing grease to improve its tribological performance. Zinc
dialkyldithiophosphate is the most commonly used AW addi-
tives but is known generate deposites (“ash”) from thermal
decomposition.1 Therefore, developing ashless and effective
lubricant additive is gaining large interest for the tribological
application. Ionic liquids (ILs) are potential ideal lubricants
because of their remarkable physical properties, such as neg-
ligible vapour pressure, high viscosity index, and excellent
thermal stability.2 Over the past dozen years, the typical
imidazolium‐based ILs, for example, [NTf2]−, [BF4]−, and
[PF6]− salts, have been reported as neat lubricants, lubricant
additives, and base oil for lubricating grease under different
experimental situations.3-9 However, the hydrolyzation prod-
ucts of these anions are considered to be highly corrosive and
hazardous for the environment.10 Moreover, little or no solu-
bility in nonpolar hydrocarbon oils limited these ILs applica-
tion as lubricating oil additives. Previous studies used ILs as
lubricating grease additives to resolve the low miscibility
issue of ILs.11,12 But high concentrations of polar ILs would
destroy the structure of the lubricating grease. Therefore, it is
necessary to develop low polar ILs with good solubility in
lubricating base oils. Halogen‐free phosphonium‐based ILs
are not only fully miscible in hydrocarbon oils but also dem-
onstrated high effectiveness in reducing friction and wear
when blended into lubricating oils.13-15
Taking the advantage of the wonderful tribological per-
formance of phosphonium‐based ILs and their solubility in

Lubrication Science. 2017;1–7. wileyonlinelibrary.com/journal/ls Copyright © 2017 John Wiley & Sons, Ltd. 1
2 WANG AND WU
hydrocarbon oils, we add 10 wt% oil‐miscible into the PAO
40 base oil and use the oil‐IL blends as base stock to prepare
polyurea greases. Lubricating greases are composed of base
stock and thickener. Polyurea thickener, PAO 40 base oil,
and IL comprised 27 wt%, 65.7 wt%, and 7.3 wt% of the
polyurea grease, respectively. The phosphonium‐based are
fully miscible in PAO 40 oil. Furthermore, the ILs would
be swathed in the thickener. Therefore, relatively large
amounts of ILs are put in the base stock to prepare the
polyurea greases. Meanwhile, the physical and tribological
properties of the IL blend polyurea greases were
characterised. Morphology examination and chemical analy-
sis were conducted on selected tribofilms.16
2 | E X P E R IM E N TA L
2.1 | General synthesis procedures for ILs
The molecular structures of phosphonium‐based ILs used in
this paper are shown in Figure 1. The [P8881][DEHP] was syn-
thesised using a simple and halide‐free route.14 The materials,
including trioctylphosphine, trimethyl phosphite, bis(2‐
ethylhexyl) phosphate, and triethylamine, were from Aladdin
company. The synthesis procedures are as follows: A mixture
of trioctylphosphine and trimethyl phosphite was stirred at
135°C under nitrogen for 24 hours. After the reaction was
complete, the excess feed stocks were removed by vacuum dis-
tillation. Then the dimethylphosphate anion is exchanged by
bis(2‐ethylhexyl) phosphate in the presence of triethylamine.
The [P88810][DEHP] and [P88814][DEHP] were synthe-
sised according to the literature reported.17 The 1‐
bromodecane and 1‐bromotetradecane were also from Alad-
din company. The synthesis of [P88810][DEHP] is described
here specifically, and similar method is applied to the synthe-
sis of [P88814][DEHP]. In the first step, the [P88810]Br was
synthesised by stirring the mixture of trioctylphosphine and
1‐bromodecane at 160°C under nitrogen for 24 hours. In
the second step, The [P88810]Br was dissolved in hexane
and the bromine anion is exchanged by bis(2‐ethylhexyl)
phosphate in the presence of NaOH.
Thermogravimeter analysis was performed with a
SETSYS ‐1750 CS Evol. at a 10°C/min heating rate in air
from room temperature to 800°C. The viscosities of ILs and
PAO 40 were measured on a SVM3000 Stabinger viscometer
at 40°C and 100°C.
2.2 | Synthesis of the polyurea greases
PAO 40 (supplied by Lanzhou refinery company) was chosen
as the base stock. The oil‐IL blends were prepared by adding
10 wt% ILs into the PAO 40 base oil. The polyurea greases
were prepared following the patent CN1408825 reported.
The materials, including dodecylamine, p‐toluidine, and
2,4‐tolylene diisocyanate (TDI), were from energy chemical.
First, the mixture of 20 wt% base oil, dodecylamine, and p‐
toluidine was added into the vessel and heated to 70°C. Then
the TDI dissolved in 20 wt% base oil was adding into it,
allowing the monoamine to react with the TDI at 80°C for
1 hour. The mixture in the vessel was then heated to 100°C,
and 2‐ml distilled water was added to react with residual
TDI. When the residual TDI was completely reacted, the
mixture was heated to 140°C to evaporate the water. A total
of 30 wt% base oil was added when the water was completely
evaporated. Then the mixture was heated to 180°C, allowing
saponification for 1 hour. Finally, the residual base oil was
added and stop heating.18 When the mixture was cooled to
60°C, the polyurea grease was obtained after 3 grinding steps
in a 3‐roller mill.
The physical properties, including dropping point and
penatration of the polyurea greases, were, respectively,
characterised according to the national standards7 GB/T
3498 and GB/T 269. The corrosivity of polyurea grease
was investigated by the GB/T 7326‐87 procedure.
2.3 | Friction and wear tests
The friction and wear tests of the polyurea greases were
conducted on an Optimal SRV‐IV oscillating reciprocating
friction and wear tester with a ball‐on‐block configuration.
The upper balls are 10 mm in diameter and made of AISI
52100 steel with 710HV hardness. The lower disc
isφ24 × 7.9 mm in size and made of AISI 52100 steel with
600 to 700HV hardness. The details of measure parameter
are shown in Table 1.
Prior to the friction and wear test, about 1 g grease was
added to the ball and disk contact area. The friction cofficient
was recorded auomatically by a computer linked to Optimal
SRV‐IV oscillating reciprocating friction and wear tester. The
wear volume was measured using a MicroXAM‐3D surface
mapping microscope profilometer. The morphology of worn
surface was examined using JSM‐5600LV scanning electron
FIGURE 1 Molecular structures of
phosphonium‐based ionic liquids
WANG AND WU 3

TABLE 1 Friction and wear tests parameters temperatures for ILs and PAO 40 are listed in Table 2. Evi-
Items Tribological conditions
dently, the ILs and PAO 40 all posse good thermal stability.
But the viscosity of ILs is higher than that of PAO 40.
Long‐time friction Duration 30 min
Stroke 1 mm
Frequency 25 Hz
Load 300 N 3.2 | Physical properties of the polyurea
Temperature 25°C, 150°C greases
Extreme pressure friction Duration of each step 5 min All the polyurea greases are uniform ointment (Figure 2). The
Stroke 1 mm dropping point and penetration of them are listed in Table 3.
Frequency 25 Hz
The dropping point and penetration of the IL blend
Load range 100‐1000N
polyurea greases are a little lower than that of the PAO
Temperature 25°C, 150°C
40 polyurea grease. Corrosion tests of the polyurea greases
were performed according to the GB/T 7326‐87 procedure.
microscope. X‐ray photoelectron spectroscopy (XPS) experi- The brass and steel (AISI 52100) were immersed in
ments were conducted by K‐Alpha‐surface Analysis.
TABLE 3 Dropping point and penetration of the polyurea greases
3 | RESULTS A ND DISCUSSION Sample Dropping point, °C Penetration (1/4 mm)

PAO 40 295 79
3.1 | Physical properties of the ILs and PAO
40 [P8881][DEHP] 278 66
[P88810][DEHP] 285 67
The densities at room temperature, kinematic viscosities at
[P88814][DEHP] 291 77
40°C and 100°C, and TGA‐determined decomposition

TABLE 2 Physical properties of the ILs and PAO 40

Kinematic viscosity(cSt)
Decomposition
Temperature, oC Density (g/ml 25°C) 40°C 100°C

PAO 40 293 0.8327 396 40.3

[P8881][DEHP] 265 0.9392 417 48.7
[P88810][DEHP] 310 0.9023 893 98.5
[P88814][DEHP] 310 0.8788 802 93.7

Abbreviation: ILs, ionic liquids.

FIGURE 2 Appearance of the polyurea

greases and photographs of brass (yellow)
and steel (white) samples after corrosion test
[Colour figure can be viewed at
wileyonlinelibrary.com]
4 WANG AND WU

polyurea grease at 100°C for 24 hours. The photographs of 3.3 | Friction and wear results
brass and steel samples after corrosion test are shown in
The friction coefficients recorded during 1800s tests for the
Figure 2. Similar to the PAO 40 polyurea grease, the steel
polyurea greases at room temperature are shown in Figure 3
samples immersed in IL blend polyurea greases do not
A. The friction coefficients of IL blend polyurea greases are
show visible corrosion. Also, the [P88810][DEHP] and
similar to the PAO 40 polyurea grease. The only difference
[P88814][DEHP] blend polyurea greases are no corrosive to
is small friction coefficient increased for the PAO 40
brass. However, the brass immersed in the [P8881][DEHP]
polyurea grease with the passing of time. In contrast, the
blend polyurea grease shows strong black discoloration,
indicating serious corrosion.

(A)
(A)

(B)
(B)

(C)
(C)

FIGURE 3 Friction behaviour of PAO 40 and ionic liquid blend

polyurea greases at room temperature. A, The friction coefficients and FIGURE 4 Friction behaviour of PAO 40 and IL blend polyurea
B, wear volumes in long‐time friction test. C, The friction coefficients in greases at 150°C. A, The friction coefficients and B, wear volumes in
extreme pressure friction test [Colour figure can be viewed at long‐time friction test. C, The friction coefficients in extreme pressure
wileyonlinelibrary.com] friction test [Colour figure can be viewed at wileyonlinelibrary.com]
WANG AND WU 5

IL blend polyurea greases show stable frictional behaviour
all the time. The IL blend polyurea greases have lower wear
volumes than PAO 40 polyurea grease (Figure 3B). Mean-
while, the IL cations connected with longer alkyl chains
showed better AW properties. In extreme pressure friction
test, lubrication failure for PAO 40 polyurea grease and
[P88810][DEHP] blend polyurea grease happened at 600 N.
Little change is observed for [P88814][DEHP] blend
polyurea grease whose lubrication failure happened at
700 N. However, the lubrication failure load for [P8881]
[DEHP] blend polyurea grease is increased to 900 N. This
is possibly because it is much easier for the [P8881][DEHP]
cation to lose alkyls and react with the metal surface to
form iron phosphates (a major compound in tribofilm14,17)
at higher load compared with the [P88810][DEHP] and
[P88814][DEHP].

FIGURE 5 SEM, profile images, and

EDS spectra of worn surfaces lubricated by
PAO 40 and ionic liquid blend polyurea
greases at room temperature [Colour figure
can be viewed at wileyonlinelibrary.com]

FIGURE 6 SEM, profile images, and EDS spectra of worn surfaces lubricated by ionic liquid blend polyurea greases at 150°C [Colour figure can
be viewed at wileyonlinelibrary.com]
6 WANG AND WU

Figure 4 shows the friction traces of polyurea greases at shown in Figure 7. The binding energies of O, P, and Fe of
150°C. The friction coefficient of the PAO 40 polyurea the worn surface lubricated by[P88814][DEHP] blend
grease starts around 0.1, and then quickly transitioned to polyurea grease at room temperature are similar to those of
between 0.15 and 0.22. Lubrication failure happened at the [P88814][DEHP] blend polyurea grease at 150°C, suggesting
time of 500 seconds. The friction coefficient of all IL blend
polyurea greases stabilised around 0.065 through the entire
test. The wear volumes of the IL blend polyurea greases
decrease in the following order: [P8881][DEHP] > [P88810]
[DEHP] > [P88814][DEHP]. Figure 5C shows a load ramp test
at 150°C. The friction coefficient for PAO 40 polyurea grease
fluctuates around 0.1, and it is seized at 300 N. In contrast,
the IL blend polyurea greases show stable friction coeffi-
cients around 0.65.The lubrication failure load ranking is
[P8881][DEHP] = [P88810][DEHP] (600 N) > [P88814]
[DEHP](700 N).
From these data, we can conclude that at room tempera-
ture, the ILs have little effort on the tribological properties
of the PAO 40 polyurea grease, only increase its AW prop-
erty. However, at 150°C, the IL blend polyurea greases show
lower friction coefficients and wear volumes, higher lubrica-
tion failure loads in comparison with the PAO 40 polyurea
grease. A reasonable explanation is that the ILs react with
the steel surface and form protective layer during the friction
process. At high temperature, the reactions become easy and
more stable tribochemical film is formed on the worn surface
to prohibit friction and wear.

3.4 | Tribofilm characterization

Figure 5 shows the scanning electron microscope (SEM),
profile images, and energy dispersive X‐ray spectroscopy
(EDS) spectra of the worn surfaces at room temperature.
The SEM and profile images clearly show that there are
many scratches on the worn surface lubricated with PAO
40 polyurea grease, while there are only few furrows on
the worn surfaces lubricated with IL blend polyurea
greases.
Figure 6 shows SEM, profile images, and EDS spectra of
the worn surfaces at 150°C. The wear scar of the IL cations
with longer alkyl chains is much shallower. The SEM images
show that the worn surfaces are smooth, with only few
scratches, indicating that the IL blend polyurea greases poss
good AW property at 150°C.
All worn surface showed strong signals of O, suggesting
strong oxidation during the tribotests.16 Weak signals of P
were observed on surfaces lubricated with IL blend polyurea
greases, implying the formation of P‐containing tribo‐films.
XPS was applied to the worn surface lubricated with
[P88814][DEHP] blend polyurea grease to probe the binding FIGURE 7 XPS spectra of O1s, P2p, Fe2p of worn surface
energies of the elements that compose the tribo‐films. The lubricated by [P88814][DEHP] blend polyurea grease and neat [P88814]
XPS spectra of Fe 2p, O1s, and P2p on the worn surface [DEHP] blend polyurea grease [Colour figure can be viewed at
lubricated by [P88814][DEHP] blend polyurea grease are wileyonlinelibrary.com]
WANG AND WU
the same composition tribochemical film is formed on the
worn surface at room temperature and 150°C. Compared with
neat [P88814][DEHP] blend polyurea grease, the binding ener-
gies of O1s, P2p are all decreased, indicating new species
are formed on the worn surface. The Fe2p peaks at 710 eV
and 723.2 eV combined with the O1s peaks at 529.1 eV and
530.2 eV indicate the formation of iron oxide on the worn sur-
face. The peak position of P2p at 132.3 eV combined with the
O1s peak at 530.2 eV indicated Fe[PO4],19 likely a result of
the [P88814][DEHP] decomposition and subsequent reactions
with metallic iron.
4 | CONCLUSIONS
Three oil‐miscible phosphonium‐based ILs were synthesised
and characterised for blending into PAO 40 base oil to pre-
pare polyurea greases. Compared with the neat PAO 40
polyurea grease, the IL blend polyurea greases have a little
lower dropping point and the [P88810][DEHP] and [P88814]
[DEHP] blend polyurea greases are noncorrosive to brass
and steel. The IL blend polyurea greases demonstrated
effective fiction‐reduction, AW, and higher lubrication fail-
ure load than neat PAO 40 polyurea grease at room temper-
ature and 150°C, especially at 150°C. EDS and XPS
analysis revealed tribochemical films containing iron oxide
and Fe[PO4] are formed on the worn surfaces. The charac-
terization results suggest that the [P88810][DEHP] and
[P88814][DEHP] blend polyurea greases are promising candi-
dates of high temperature lubricating greases.
AC KN OWL ED GE M EN T
This work was supported by National Natural Science Foun-
dation of China (51465049) and Natural Science Foundation
of Ningxia Province (NZ14042).
R E F E RENC E S
1. Spikes H. The history and mechanisms of ZDDP. Tribology Letters.
2004;17:469‐489.
2. Fu XS, Sun LG, Zhou XG, Li ZP, Ren TH. Tribological study of oil‐
miscible quaternary ammonium phosphites ionic liquids as lubricant
additives in PAO. Tribology Letters. 2015;60:23
3. Ye CF, Liu WM, Chen YX, Yu LG. Room‐temperature ionic liquids:
a novel versatile lubricant. Chem Commun. 2001;21:2244‐2245.
4. Wang HZ, Lu QM, Ye CF, Liu WM, Cui ZJ. Friction and wear behav-
iors of ionic liquid of alkylimidazolium hexaflu‐orophosphates as
lubricants for steel/steel contact. Wear. 2004;256:44‐48.
5. Jin C, Ye CF, Phillips BS, Zabinski JS, Liu XQ, Liu WM. Polyeth-
ylene glycol functionalized dicat‐ionic ionic liquids with alkyl or
polyfluoroalkyl substituents ashigh temperature lubricants. J Mater
Chem. 2006;16:1529‐1535.
7
6. Yao MH, Liang YM, Xia YQ, Zhou F, Liu XQ. High‐temperature
tribological properties of 2‐substituted imidazolium ionic liquids
for Si3N4‐steel contacts. Tribology Letters. 2008;32:73‐79.
7. Suzuki A, Shinka Y, Masuko M. Tribological characteristics of
imidazolium‐based room temperature ionic liquids under high vac-
uum. Tribology Letters. 2007;27:307‐313.
8. Wang ZY, Xia YQ, Liu ZL, Wen ZZ. Conductive lubricating grease
synthesized using the ionic liquid. Tribology Letters. 2012;46:33‐42.
9. Fan XQ, Wang LP. Highly conductive ionic liquids toward high‐per-
formance space‐lubricating greases. ACS Appl Mater Interfaces.
2014;6:14660‐14671.
10. Torimoto T, Tsuda T, Okazaki K, Kuwabata S. New frontiers in
materials science opened by ionic liquids. Advance Materials.
2010;22:1196‐1221.
11. Cai MR, Zhao Z, Liang YM, Zhou F, Liu WM. Alkyl imidazolium
ionic liquids as friction reduction and anti‐wear additive in polyurea
grease for steel/steel contacts. Tribology Letters. 2010;40:215‐224.
12. Wang ZY, Xia YQ, Liu ZL. Comparative study of the tribological
properties of ionic liquids as additives of the attapulgite and bentone
greases. Lubrication science. 2012;24:174‐187.
13. Qu J, Bansal DG, Yu B, et al. Antiwear performance and mechanism
of an oil‐miscible ionic liquid as a lubricant additive. ACS Appl
Mater Interfaces. 2012;4:997‐1002.
14. Westerholt A, Weschta M, Bösmann A. Halide‐free synthesis and
tribological performance of oil‐miscible ammonium and phospho-
nium‐based ionic liquids. ACS Sustainable Chemistry &
Engineering. 2015;3:797‐808.
15. Zhang SW, Hu LT, Qiao D, Feng DP, Wang HZ. Tribological per-
formance of phosphonium‐based ionic liquids as lubricants and
lubricant additives of multialkylated cyclopentanes. Tribology Inter-
national. 2013;66:289‐295.
16. Zhou Y, Dyck J, Graham TW, Luo H, Leonard DN, Qu J. Ionic liq-
uids composed of phosphonium cations and organophosphate,
carboxylate, and sulfonate anions as lubricant antiwear additives.
Langmuir. 2014;30:13301‐13311.
17. Bradaric CJ, Downard A, Kennedy C, Robertson AJ, Zhou YH.
Industrial preparation of phosphonium ionic liquids. Green Chem.
2003;5:143‐152.
18. Wang ZY, Xia YQ, Liu ZL, Hu TC. Friction and wear behaviour of
laser‐textured surface under the lubrication of polyurea grease con-
taining various additives. Proceedings of the Institution of
Mechanical Engineers, Part J: Journal of Engineering Tribology.
2011;225:139‐150.
19. Zhang L, Feng D, Xu B. Tribological characteristics of
alkylimidazolium diethyl phosphates ionic liquids as lubricants for
steel‐steel. Tribology Letters. 2009;34:95‐101.
How to cite this article: Wang Z, Wu W. The
tribological properties of the polyurea greases based
on oil‐miscible phosphonium‐based ionic liquids.
Lubrication Science. 2017;0:1–8. https://doi.org/
10.1002/ls.1391