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Fatty acid based phosphite ionic liquids as multifunctional lubricant additives

in mineral oil and refined vegetable oil

Article  in  Tribology International · March 2018

DOI: 10.1016/j.triboint.2018.03.028

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 Tribology International 123 (2018) 316–324

Contents lists available at ScienceDirect

Tribology International
journal homepage: www.elsevier.com/locate/triboint

Fatty acid based phosphite ionic liquids as multifunctional lubricant T

additives in mineral oil and refined vegetable oil
Ganlin Zhenga, Tongmei Dinga, Yixu Huanga, Lei Zhengb, Tianhui Rena,∗
a
School of Chemistry and Chemical Engineering, Key Laboratory for Thin Film and Microfabrication of the Ministry of Education, Shanghai Jiao Tong University,
Shanghai, 200240, PR China
b
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100039, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Ionic liquids (ILs) are highly attractive lubricant additives for their nonflammability, low vapor pressures,
Oil-dispersible ILs structural diversity and reasonable tribological properties. A convenient synthesis route to oil-dispersible ILs has
Phosphite been presented in this paper. Phosphite binds to aliphatic acid as anion and triethylbenzylammonium serve as a
Fatty acid cation, which could be applied as lubricant additives in mineral oil (5CST) and refined vegetable oil (RSO).
Surface analysis
Results demonstrated that these ILs could effectively enhance the antiwear, friction-reducing and extreme
pressure properties of 5CST and RSO. The chain length and unsaturation of fatty acid is significant in improving
the tribological properties of base oil. TEY and FY mode K-edge XANES analysis of the formed tribofilms showed
that the improvement of anti-wear and friction-reducing properties was closely related to the content of phos-
phate species on the near surface.

1. Introduction preparing procedure, high production cost, hydrolytic instability and

As one of the most widely used base oil in lubricant industry, mi-
neral oil has many advantages of high chemical stability, reasonable
thermal and oxidative stability and economical price [1]. Due to the
depleting mineral oil reserve and stringent environment regulation, it is
necessary to develop new and environmentally benign lubricants di-
rectly from renewable natural raw materials [2]. Vegetable oil is con-
sidered to be potential substitutes for mineral oil. It possesses superior
natural properties including biodegradability, reproducibility and lu-
brication properties [3]. It has been used as lubricating additive or base
oil to substitute conventional combinations [4,5]. But they are about
twice as expensive as mineral oil based lubricating oil [6]. Although the
use of mineral oil as base oil is gradually reduced [7], it is difficult to be
completely replaced in short term. Therefore, developing additive for
vegetable oil and mineral oil is very significant to alleviate the current
problems.
Ionic liquids (ILs) are promising lubricant due to their unique
properties of high thermal stability, negligible volatility, nonflamm-
ability, and low melting point [8–11]. Many groups have carried out
relevant exploration derived from cations such as pyridinium, imida-
zolium, ammonium and anions such as bis(trifluoromethylsulfonyl)
imide (TFSI) and BF4 [12–16]. However, ILs suffer from some draw-
backs, such as strong corrosion to the interacting surface, tedious
low solubility in base oil [17–19]. Recently, fully organic protic ILs, oil-
miscible and non-corrosive ILs, environmentally friendly ILs, multi-
functional ILs and water-soluble ILs are developed [20–27]. To the best
of our knowledge, few researchers use existing low cost and high per-
formance raw material to construct ILs.
Tribochemistry studies the relationship between the worn surface
chemical composition and the lubrication effectiveness [28], which
could help us to understand the effectiveness of lubrication and the
development of new additive. The current cognition focuses on the
tribochemical reaction of P, S, N, B, and Mo on the worn surface
[29–31], especially the study of P containing additives. The improve-
ment of tribological properties could be ascribed to the formation of
phosphate and polyphosphate on the worn surface [32]. However, it is
a great challenge to utilize the existing principles of tribochemistry for
molecular design because of the changes in molecular structure, leading
to great difference in the tribochemical processes during frictional
process.
Dialkyl phosphite is widely used as extreme pressure, friction-re-
ducing and antiwear additives in mineral or vegetable oil [33]. Alkyl
group could improve the adsorption and dispersion property of additive
molecule in base oil and phosphite acts as a functional group to form
phosphate or polyphosphate on the worn surface during frictional
process. Vegetable oil has long been used as a lubricant, and its acid has

∗
Corresponding author.
E-mail address: thren@sjtu.edu.cn (T. Ren).

https://doi.org/10.1016/j.triboint.2018.03.028
Received 4 January 2018; Received in revised form 26 March 2018; Accepted 26 March 2018
Available online 27 March 2018
0301-679X/ © 2018 Elsevier Ltd. All rights reserved.
G. Zheng et al.
been reported as a lubricant additive recently [34]. Fatty acid can
produce metal soap and avoid the direct contact of asperities, but its
tribological properties could not meet the requirement of severe lu-
brication conditions. Quaternary ammonium base has good phase
transfer, adsorption and dispersion characteristics over a wide range of
base liquids [35].
Combined with the benefits of ILs, fatty acid and phosphite, we
report the synthesis, characterization, tribo-evaluation and lubrication
mechanism of phosphite-based halogen-free ILs additives for vegetable
oil and mineral oil. We focus on the influence of ILs concentration on
tribological properties of the base oil. The tribological performance of
ILs as lubricant additive was evaluated using a four-ball tester. A
KEYENCE vk-x200 laser scanning microscope (CLSM) was used to ex-
amine the morphology and wear volume of steel ball surface. XANES
analysis was carried out to examine the chemical composition on the
wear scar and the possible tribochemical changes involved in the fric-
tional process.
2. Materials and experimental details
2.1. Materials
Oleic acid, linoleic acid, stearic acid, and palmitic acid were pur-
chased from KLK OLEO and used to synthesize four ILs without further
treatment. RSO (trade name Arawana 1:1:1) was commercially avail-
able from Xi'an Jiali Oil and Grease Factory of China. A commercial
mineral oil (referred to 5CST), was provided by Petro China Lanzhou
Lubricating Oil R&D Institute in Lanzhou, China. T308B were obtained
from Zibo Hui Hua Chemical Corporation and used without further
purification. Other chemicals utilized in this article were all analytical
grade and procured commercially. The steel balls used in experiments
were obtained from Shanghai Ningxing steel ball Co., Ltd. and had the
following specifications:φ12.7 mm; HRC59-61; GCr15 (chemical com-
position: 0.95–1.05 wt % C; 0.15–0.35 wt % Si; 0.20–0.40 wt % Mn;
0.027 wt % P; 0.020 wt % S; 1.30–1.65 wt % Cr; 0.30 wt % Ni; 0.25 wt
% Cu).
2.2. Preparation of additives
Four ILs with quaternary ammonium group, OAPN, LAPN, SAPN
and PAPN, were synthesized in three steps (Fig. 1). The desired mixture
1 was obtained from a slight excess of epoxy propane and aliphatic acid
with triethylamine as the catalyst, and toluene as the solvent at 60 °C
after 8 h. The mixture 2 was prepared by mixing l and dimethyl phos-
phite stirring at about 120 °C until no CH3OH formed. In the third se-
quence of reactions, mixture 3 was obtained by neutralization with
quaternary ammonium base at 70 °C for 4 h. Finally it was obtained by
filtration and reduced pressure distillation. Additionally, a commercial
additive was also provided for compare and its chemical structure was
shown in Fig. 1.
2.3. Characterization
The structure of ILs was characterized by 1H, 13C NMR spectroscopy,
Fourier transform infrared (FT-IR) spectroscopy (see Fig. 2 and Table 1)
and Elemental Analysis (EA) (see Table 2). In order to estimate the
decomposition behavior of synthesized ILs under thermal conditions
(oxygen free), Tonset (thermal decomposition temperature) was de-
termined on a Perkin Elmer TGA 7 thermo-gravimetric analysis device.
OAPN: 1H NMR (500 MHz, CDCl3) δ 0.85–0.93 (t, 6H), 1.22–1.28
(m, 44H), 1.29–1.35 (t, 9H), 1.46–1.51 (t, 6H), 1.56–1.66 (m, 4H),
2.25–2.35 (m, 4H), 3.35–3.41 (t, 6H), 3.67–3.69 (s, 4H),4.65–4.70 (s,
2H), 4.85–5.1 (s,2H), 7.44–7.53 (m, 5H). 13C NMR (100 MHz, CDCl3) δ
8.25, 14.04, 22.66, 24.91, 29.50, 31.93, 34.13, 35.08, 51.45, 52.86,
61.15, 127.16, 129.27, 130.6, 130.83,132.39, 174.40, 177.87.
LAPN: 1H NMR (500 MHz, CDCl3) δ 0.86–0.91 (t, 6H), 1.20–1.40
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Tribology International 123 (2018) 316–324
(m, 32H), 1.46–1.50 (t, 4H), 1.55–1.67 (m, 2H), 2.24–2.37 (m, 2H),
3.38–3.43 (t, 3H), 3.67–3.69 (s, 4H), 4.70–4.75 (s, 2H), 4.85–5.1
(s,2H), 7.42–7.56 (m, 5H). 13C NMR (100 MHz, CDCl3) δ 8.27, 14.12,
22.63, 24.91, 29.36, 31.97, 34.12, 51.48, 127.17, 129.50, 130.77,
132.43, 174.37, 177.22.
PAPN: 1H NMR (500 MHz, CDCl3) δ 0.88–0.92 (t, 6H), 1.26–1.39 (t,
40H), 1.60–1.68 (m, 4H), 1.95–2.10 (m, 8H), 2.32–2.38 (m, 4H),
2.60–2.85 (m, 6H), 3.61–3.65 (m, 4H), 3.66–3.69 (t, 6H), 3.70–3.73 (t,
6H), 3.73–3.80 (m, 4H), 4.22–4.28 (m, 4H), 7.41–7.49 (m, 5H). 13C
NMR (100 MHz, CDCl3) δ 14.08, 22.42, 24.59, 24.90, 27.22, 29.12,
31.53, 34.20, 61.65, 63.35, 69.27, 70.53, 72.55, 127.78, 130.22,
174.10.
SAPN: 1H NMR (500 MHz, CDCl3) δ 0.88–0.93 (t, 6H), 1.26–1.39 (t,
60H), 1.47–1.51 (t, 4H), 1.58–1.68 (m,4H), 1.96–2.12 (m, 4H),
2.28–2.37 (m, 4H), 2.72–2.84 (m, 2H), 3.37–3.42 (m, 2H), 3.67–3.90
(s, 2H), 4.03–4.20 (m, 2H), 7.46–7.54 (m, 5H). 13C NMR (100 MHz,
CDCl3) δ 8.21, 14.13, 22.56, 24.95, 25.64, 27.23, 29.16, 31.54, 31.85,
34.07, 51.46, 52.78, 127.90, 128.04, 129.52, 174.44.
The measured values of C, H, P, N elements are close to their cal-
culated values. The NMR, EA and FT-IR results confirmed that the de-
signed molecules were successfully synthesized.
2.4. Lubricant preparation and oil solubility of ILs
The additives were mixed with RSO or 5CST at a fixed concentra-
tion, and the solution was stirred at fixed temperature (60 °C) for
10 min. And the solubility data of the synthesized ILs for both blends
was measured at highest concentration (3 wt %)
2.5. Tribological evaluation
The tribological properties of ILs as additives in RSO and 5CST were
evaluated using a MS-10J four-ball tester manufactured by Xia men
tenkey automation Co. Ltd, China. Four-ball tester consists of a mobile
ball bearing that is rotated in contact with three fixed ball bearings
which are immersed in the test lubricant, as shown in Fig. 3. The an-
tiwear and friction-reducing test were conducted on four-ball tester at a
speed of 1450 rpm, load 40 Kg and room temperature (25 °C) for
30 min. The wear scar diameters (WSDs) were collected by an optical
microscope with accuracy of ± 0.01 mm. The friction coefficient (COF)
was automatically calculated from measured torque and load data. The
extreme pressure (EP) performance was conducted following GB12583-
98 test procedure: speed, 1760 rpm; temperature, ambient; load, vari-
able; test duration, 10 s, which was similar to ASTMD-2783 method. EP
tests were conducted with increasing loads until welding of steel balls is
occurred. The load before which welding occurs is called the maximum
nonseized load (PB value), and the load is an EP property of the test
lubricant. For each sample, three identical tests were performed so as to
minimize data scattering. After the tribological evaluation, the steel
balls were gently rinsed in acetone and dried with tissue paper.
2.6. Analysis of the worn surface morphology and chemical composition
The morphology of the worn surface was obtained using a KEYENCE
vk-x200 laser scanning microscope (CLSM). Chemical composition
measurement on the worn surface was carried out on an X-ray ab-
sorption near edge structure spectroscopy (XANES) which was located
at the Institute of High-Energy Physics (IHEP), Chinese Academy of
Science [36]. Sample spectra were collected in partial fluorescence
yield (FY) mode for bulk information or total electron yield (TEY) mode
for near surface information. All spectras were recorded from 2140 to
2165eV with a step size of 1.0eV on the region of 2140–2145 eV,
0.50 eV in pre-edge region of 2145–2150 eV, and 0.20 eV in near edge
region of 2150–2165 eV.
G. Zheng et al. Tribology International 123 (2018) 316–324

Fig. 1. Synthetic route of ILs and the chemical structure of T308B.

Table 2
The results of EA for ILs.
Items/(wt%) H C P N

PAPN 10.51(10.67)a 70.86(71.00)a 3.59(3.60)a 1.80(1.62)a

SAPN 11.97(11.28)a 72.44(71.58)a 3.28(3.36)a 1.56(1.52)a
OAPN 11.24(10.89)a 70.86(71.90)a 3.36(3.38)a 1.57(1.52)a
LAPN 10.89(10.50)a 71.35(72.21)a 3.37(3.39)a 1.50(1.53)a

a
Calculated value (oxygen being at balance).

Fig. 2. The main absorption peaks of IR.

Fig. 3. Four-ball tester and schematic of ball-pot assembly in four-ball tester.

Table 1
3. Results and discussion
IR spectra data of ILs.
Adsorption peaks OAPN(cm−1) LAPN(cm−1) PAPN SAPN(cm−1) 3.1. Oil solubility
(cm−1)

=CH(Ph) 3008 3009 _ _ From Fig. 4, there is almost no stratification in the container under
-CH3,-CH2, -CH 2927, 2927, 2915, 2851 2917, 2850 the highest addition, indicating that the synthesized additives could
2866,706 2855,708 disperse in the base oil commendably. The transparency of ILs blended
C=C 1638 1637 _ _ with RSO decreases with the increase of carbon chain length and the
-COO- 1739, 1212, 1742, 1243 1727, 1210, 1742, 1215,
number of “C=C”. However, the synthesized ILs in 5CST seems to be
1059 1062 1056
-C-N+ 904 916 902 905 different. SAPN and PAPN exhibits strong thickening properties in
O-P-O 830 836 850 883 5CST. The longer the carbon chain of ILs is, the better the thickening
Ph 755, 618 756, 619 736, 617 757 property is. The thickening property is obvious at room temperature
P-O 1007 1012 1009 1009
(25 °C) and is not significant at the high temperature (40–100 °C). ILs
with more “C=C” shows better transparency in 5CST. Additionally,

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G. Zheng et al.
Fig. 4. The dispersion of ILs and the appearance of IL blends.
their transparency do not change significantly over time.
3.2. Thermal stability
The thermogravimetry analysis (TGA) results of four ILs are shown
in Fig. 5. The anion structure of the synthesized ILs, plays a significant
effect on thermal stability of the whole molecule. Tonset (thermal de-
composition temperature) of SAPN, PAPN, OAPN and LAPN follows the
order PAPN (310.5 °C) > SAPN (245.8 °C) > OAPN (232.5 °C) >
LAPN (211.5 °C) respectively (Fig. 5), indicating that the synthesized
ILs have a high thermal stability. The decrease of thermal stability with
the increase of “C=C” due to the increasing unsaturated double bond of
phosphite by inductive effect, promoting the breakdown of C-O bond.
3.3. Antiwear performance
WSDs of steel balls with different additive concentration in 5CST
and RSO are shown in Fig. 6. WSD decreases first and then remains
relative stable with the increase of additive concentration. The antiwear
performance of the synthesized ILs blended with 5CST decreases in the
following order: LAPN > OAPN > PAPN > SAPN > T308B (Fig. 6
(a)), while that in RSO is more obvious. The four-ball tester cannot even
start because of the poor antiwear performance of T308B at 0.25 wt%.
Fig. 5. TGA curves of the synthesized ILs.
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Tribology International 123 (2018) 316–324
The antiwear performance of SAPN is the worst at the test concentra-
tion among the synthesized ILs, while OAPN, LAPN and PAPN are si-
milar at a relative wide test range (Fig. 6(b)). This phenomenon can be
attributed to the adsorption and tribochemical reaction of the additive
on the metal surface. The free movement of anion and cation is re-
stricted by the minor polarity of base oil. The adsorption property of
additive molecule can be effectively ameliorated by polar group. ILs
with more double bonds and shorter carbon chain length are more
easily to adsorb on the metal surface. SAPN contains saturated long
carbon chain, which is not conducive to its adsorption on the metal
surface. In the friction process, the additive adsorbed on the metal
surface reacts with the metal asperity to produce a film with high
strength, which replaces the direct contact between asperities under
harsh frictional process [37]. The additive with poor adsorption capa-
city may not have enough active elements on the worn surface to
produce a similar film. This situation could gradually improve with
increase of the additive concentration. Additionally, other reports have
described that when the addition amount exceeds the optimum con-
centration, the tribological properties of additive may become worse or
even deteriorate [38]. The synthesized ILs could avoid that problem
due to the protection of quaternary ammonium salt.
3.4. Friction-reducing performance
In Fig. 7, the friction coefficient of the base oil, T308B blends and
ILs blends are shown. The friction coefficient of 5CST is slightly lower
than that of RSO. When the concentration of synthesized ILs increases
in base oil, COF decreases initially and reduces drastically to relatively
low value at a particular concentration. But the contribution of T308B
to antifriction is very small or even worse at certain concentration
(0.25 wt %). Additionally, the COF difference of the four additives can
be explained by their different alkyl length and “C=C” groups. The
shorter alkyl chain and less “C=C” group can form effective lubricating
films on the rubbing surface in 5CST, resulting in lower COF. COFs
resulting from the four kinds of ILs rank as PAPN < SAPN <
OAPN < LAPN < T308B in 5CST. OAPN with long alkyl chain and
one “C=C” group exhibits the best friction-reducing performance in
RSO. While LAPN shows reasonable antiwear property and relatively
poor friction-reducing performance in RSO. This decrement in COFs can
be attributed to the physical and/or chemical reaction film initiated by
the additive during friction process. The shearing strength of the film is
G. Zheng et al. Tribology International 123 (2018) 316–324

Fig. 6. Effects of the additive concentration on WSD (a), synthesized ILs and T308B in 5CST; (b) synthesized ILs and T308B in RSO (four-ball tester, load 392 N,
rotation speed 1450 rpm, 30 min).

less than that of the metal asperities, so asperities from one surface can
easily slide over the asperities of the other sliding surface, leading to the
decrease of COF compared to base oils [39]. The shear strength of
PAPN-tribofilm is lower than that of other synthesized ILs-tribofilm in
5CST. This may be because P content of PAPN is higher than that of
other synthesized ILs, which could form a more effective lubricating
film to avoid the direct contact of asperities. OAPN with reasonable
polarity could form an adsorption film, and then generate a layer of
reaction film induced by triboheat. The adsorption film and reaction
film might form a boundary lubricating film to alleviate COF of rubbing
surfaces in RSO. The polarity of LAPN is also large, but LAPN shows the
worst friction-reducing performance than other ILs in RSO. That is may
be because the thickness of adsorption film increases with the polarity
of RSO. The reasonable friction-reducing property of OAPN-tribofilm
may be due to the lower polymerization degree or content of phosphate
species formed by OAPN than other ILs [40].

3.5. Analysis of wear volumes
The wear volumes of steel balls lubricated by base oil containing
3 wt% of OAPN, LAPN, SAPN, PAPN and T308B under a load of 392 N
for 30 min are shown in Fig. 8. T308B can improve antiwear perfor-
mance of the base oil. But in comparison with the synthesized ILs, its
antiwear performance is not remarkable. The wear volume obviously
decreases with the addition of four additives, and the wear volume of
PAPN containing lubricants are smaller than those of OAPN, LAPN and
SAPN at the same concentration, indicating that the antiwear perfor-
mance of PAPN is better than that of OAPN, LAPN and SAPN in four-
ball tests. The wear volume for RSO blended with 3.0 wt % SAPN and
5CST blended with 3.0 wt% OAPN are also considerably smaller than
Fig. 8. Wear volume of steel balls lubricated by the base oil and the base oil
containing 3 wt% of synthesized ILs and T308B (four-ball tester, load 392 N,
rotation speed 1450 rpm, 30 min).
those of the base oil, but they are much higher than those of the other
blends. This result is basically consistent with WSD results of the four-
ball tests. The wear volume results are better than WSD data in reflect
the improvement of the wear resistance.
3.6. Extreme pressure performance
PB value of as-prepared lubricants are summarized in Fig. 9. PB
value of 5CST and RSO is 52 Kg and 40 Kg, respectively. The

Fig. 7. Friction-reducing performance of different ILs blends (a), ILs in 5CST; (b) ILs in RSO (four-ball tester, load 392 N, rotation speed 1450 rpm, duration 30 min).

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G. Zheng et al.
Fig. 9. PB value of base oils, base oil doped with 3 wt% the synthesized ILs and
T308B (four ball tester, rotary speed 1760 rpm, duration 10 s).
synthesized ILs display more than 2 to 5- times PB value to the base oil,
which could be explained in terms of compatibility between base oil
and additives [41]. Two kinds of base oil vary greatly in their polarity:
5CST is a nonpolar hydrocarbon whereas RSO is polar since it com-
prises multiple ester groups capable of interacting with and binding
onto metal surface. Four ILs and RSO have similar aliphatic acid
structure, so ILs could be more compatible in RSO than in 5CST.
Therefore, ILs exhibit better EP performances in RSO than in 5CST. It is
reported that in EP region, surface layer of steel ball is erased away and
nascent surface is exposed continuously. The additive can quickly react
with nascent surface to generate a dense protective film and it has a
good EP performance [42]. LAPN displays a higher PB value than other
ILs in the base oil, indicating that the increase of additive polarity is
beneficial to the adsorption properties of additive. The current results
are in line with the previous observation.
3.7. Worn surface morphology analysis
Fig. 10 shows the topographies of wear scar after lubricating with
the as-prepared lubricants at a velocity of 1450 rpm for 30min. From
Fig. 10 (a), (c), (k) and (l), there are many deep furrows and wide
grooves on the worn surfaces, and grooves are elongated and orientated
in the sliding direction. That serious wear suggests that the protective
film generated by the reference base oils is too weak to reduce WSD.
T308B exhibits more deep and wide scratches than that of the synthe-
sized ILs, indicating that the strength of T308B-tribofilm is lower than
that of the synthesized ILs. The worn surface lubricated by base oil
blended with 3 wt % of ILs is smooth with minor scratch under the same
test condition. The smoothening of the worn surface could be attributed
that the tribofilm generated by ILs could effectively prevent the direct
contact of asperities. Fig. 10 (b) and (d) show more furrows than the
other figures, which could be ascribed to high hardness of tribofilm.
The tribofilm possessing a higher hardness might induce abrasive par-
ticles with high hardness, resulting in abrasive wear with clear furrow.
3.8. XANES analysis
The detection depths of the TEY and FY mode at the K-edge are
around 50 nm and around 1–3 μm respectively [43]. Li et al. showed
the chemistry properties of anti-wear films can be investigated using K-
edge XANES based on the transition of a phosphorus 1s electron to an
empty p-like anti-bonding state and the film thickness is proportional to
the intensity of the peak [44]. Recently, Zheng et al. found that the peak
intensity of oligomeric phosphate is proportional to the improvement of
tribological properties [45]. In order to study the evolution of tribofilm
and its influence on tribological properties, the peak intensity of
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Tribology International 123 (2018) 316–324
phosphate species are applied to identify the effectiveness of lubrica-
tion.
Fig. 11 shows the P K edge spectra in TEY and FY mode of tribofilms
formed by OAPN, LAPN, SAPN and PAPN respectively. Metal asperities
on the worn surface could induce the decomposition of ILs and generate
phosphate species. There is a clear difference between the growth of
phosphate species at both bulk and near surface, which might be as-
cribed to the inhomogeneity distribution of phosphate species in the
direction perpendicular to worn surface. Phosphate species produced by
frictional process in RSO are FePO4 while phosphate species generated
in 5CST are a mixture of FePO4 and Fe2P2O7 [46,47], indicating that the
polymerization degree of phosphate induced by the additives in 5CST is
higher than RSO.
The content of phosphate species in RSO and 5CST increases with
the increase of additive concentration (0.5–3 wt %) for OAPN and PAPN
at different depths, which could be linked to the improvement of an-
tiwear and friction-reducing performance. The phosphate species con-
tent increases both on near and bulk surface. However, the relationship
between the content of phosphate species and the improvement of
antiwear properties is not very close on the bulk surface for different
additives. This may be due to the detection depth of FY mode is around
1–3 μm and the thickness of tribofilm formed by the additives on metal
surface is various. The difference in tribofilm thickness leads to the
atypism between the content of phosphate species detected by FY mode
XANES and the improvement of anti-wear and friction-reducing prop-
erties. This difference in tribofilm thickness may be more closely linked
to the improvement of EP performance.
4. Discussions
In this work, the crucial distinction of the synthesized ILs is the
number of “C=C” and the length of the alkyl chain. They have different
phosphorous content, the polarity of molecular and molecular number
are different in the same addition amount, leading to the difference of
their tribological performance. Based on the tribological test results in
Figs. 6–9 and surface analysis by CLSM and XANES in Figs. 10–11, we
deduce possible tribochemical mechanism of the worn surface lu-
bricated with different ILs combinations.
The lubricity of the reference base oil is relatively poor, so it is
unable to form a lubricating film strong enough to separate the two
rubbing surfaces under 392 N. And adhesive and abrasion wear could
occur, resulting in big WSD and high COF. Additives could make up the
inadequacies of the above base oil. First, ILs can adsorb onto the metal
surface to form an adsorption film in the reference base oil, but there
exist a competitive adsorption between polar components in the re-
ference base oil and additive on the metal surface. Meanwhile, the
friction-generated triboheat could induce the tribochemical reaction
between the metal surface and additive to form a layer of reaction film.
The thick adsorption film may lead to a relatively high COF but small
WSD, which may be the contact first occurs between adsorption film
and the subsequent contact is the contact between reaction films be-
neath adsorption film. This tribofilm is composed of inorganic sub-
stance, which act as a solid lubricant to further reduce WSD and COF on
the worn surface. XANES spectra of the worn surfaces indicated that ILs
react with the metal surface, forming FePO4/FeP2O7 at near and bulk
surface. The adsorption film and reaction film could form a boundary
lubrication film on the metal surface. When the additive concentration
was 0.5 wt %, the reaction film was thin and composed mainly of FePO4
under bulk and near surface in the reference base oil. With the increase
of ILs, the content of FePO4 increases and FeP2O7 can form on the worn
surface.
5. Conclusions
From the results and afore-mentioned discussion, the following
conclusions can be drawn:
G. Zheng et al. Tribology International 123 (2018) 316–324

Fig. 10. CLSM image of worn surface of lower balls lubricated by base oil and base oil blended with 3 wt% of ILs and T308B (applied load 392 N, rotary speed
1450 rpm, duration 30 min).

322
G. Zheng et al.
Fig. 11. XANES spectra of tribofilms: (a) TEY P K-edge spectra of the synthesized ILs in RSO; (b) TEY P K-edge spectra of the synthesized ILs in 5CST; (c) FY P K-edge
spectra of the synthesized ILs in RSO; (d) FY P K-edge spectra of the synthesized ILs in 5CST.
(1) Four novel aliphatic acid containing phosphite–based ILs, OAPN,
LAPN, PAPN and SAPN, were prepared and were used as lubricant
additives in RSO and 5CST. The prepared ILs exhibits excellent
tribological performance with low wear volume in the reference
base oils, and the additive with long carbon chain and small po-
larity is not conductive to the improvement of antiwear properties.
The additives have reasonable compatibility with the base oil and
acquire excellent friction-reducing, extreme pressure performance.
The tribological properties of the prepared ILs are better than
T308B.
(2) Using TEY and FY mode XANES analyses, we could demonstrate
that phosphate species protective layer form on the wear traces. The
effectiveness of the antiwear and friction-reducing performance
could be attributed to the variation of phosphate species content on
the near surface. The base oil with minor polarity is more likely to
generate phosphate with high polymerization
Acknowledgements
The authors are grateful to the National Natural Science Foundation
of China (Grant No. 21272157), Beijing Synchrotron Radiation Facility
(Grant No. SR06033) for financial support of the work reported in this
article.
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