Materials Chemistry and Physics 98 (2006) 183–189

Oleic acid capped PbS nanoparticles: Synthesis,

characterization and tribological properties
Shuang Chen a,∗ , Weimin Liu b
a Department of Chemical and Environmental Engineering, Wuyi University,
Jiangmen, Guangdong 529020, China
b State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics,

Chinese Academy of Science, Lanzhou 730000, China

Received 19 August 2004; received in revised form 19 August 2005; accepted 5 September 2005

Abstract
Oleic acid (OA) capped PbS nanoparticles were chemically synthesized and characterized by means of Fourier transform-infrared spectroscopy
(FT-IR), transmission electron microscopy (TEM), X-ray electron diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The triboligical
properties of the capped PbS nanoparticles as additive in liquid paraffin was investigated using a four-ball machine. The lubricating mechanisms
were discussed along with the analyses results of XPS and scanning electron microscope (SEM). Results show that OA-capped PbS nanoparticles,
with an average diameter of about 8 nm, are able to prevent water adsorption, oxidation and are capable of being dispersed stably in organic solvents
or mineral oil. OA-capped PbS nanoparticles as an additive in liquid paraffin perform good antiwear and friction-reduction properties owing to the
formation of a boundary film.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Nanoparticles; Oil additive; Capping; Tribology

1. Introduction
Nanoparticles have been intensively investigated for the
past decade because of their distinctive physical and chemi-
cal properties [1–5]. In particular, organic compound mono-
layer capped nanoparticles have attracted extensive attention
owing to their special properties and wide application areas
[6–8], especially as additives in lubricating oils [9,10]. The
dispersion capacity of inorganic nanoparticles in lubricating
oils and their stability in air can be improved effectively
by means of capped with a layer of a long hydrocarbon
chains.
It is well known that zinc dialkyldithiophosphate (ZDDP) is
a popular used oil additive, so in the previous work, we chose
DDP as the capping agent, and synthesized DDP capped PbS,
ZnS and PbO nanoparticles, respectively [11–13]. The widely
used four-ball wear tester was chosen to evaluate the tribolog-
ical behaviour of the capped nanoparticles mentioned above
∗ Corresponding author. Fax: +86 750 3299390.
E-mail address: shuangchen72@yahoo.com (S. Chen).
as oil additives, liquid paraffin (LP) was used as the base oil.
Results show that they both can effectively improve the anti-
wear ability of LP at an extremely low additive concentration.
Unfortunately, the friction coefficient is even higher than use
LP alone, which means they cannot reduce the friction of the
system.
Both the antiwear and friction-reduction ability is impor-
tant to evaluate the capacity of an oil additive. Since all the
DDP capped PbS, ZnS and PbO nanoparticles cannot lubricating
the system effectively, the surface-capping agent was changed
in this work. We chose oleic acid (OA) as the new surface-
capping agent, and synthesized OA-capped PbS nanoparticles.
The prepared product was characterized with a variety of meth-
ods, including Fourier transform-infrared spectroscopy (FT-IR),
transmission electron microscopy (TEM), X-ray powder diffrac-
tometer (XRD), and X-ray photoelectron spectroscopy (XPS).
The tribological properties of OA-capped PbS nanoparticles as
an oil additive in LP were also studied using the four-ball wear
tester. It is anticipated that the OA-capped PbS nanoparticles will
perform better tribological properties than DDP capped PbS,
ZnS and PbO nanoparticles does, especially for the friction-
reduction ability.

0254-0584/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2005.09.043
184 S. Chen, W. Liu / Materials Chemistry and Physics 98 (2006) 183–189

2. Experimental

Analytically pure lead acetate, sodium sulfide and oleic acid were used as
the raw materials for synthesis. Analytically pure ethanol and distilled water
were used as solvents.
Capped PbS nanoparticles were prepared by a chemical co-deposition
method using OA as a capping agent. Lead acetate and sodium sulfide were
dissolved in distilled water, respectively, to prepare the stock solution. The
preparation technique was as follows. Ethanol–water mixture was used as the
solvent to suffice the reaction system to be homogeneous. Capping agent OA
and sodium sulfide stock solution was added to the mixture solution mentioned
above in turn, and heated to 333 K with vigorous stirring, adjusting the ratio
of ethanol and distilled water to ensure the solution to be homogeneous. After
they were well mixed together, lead acetate stock solution was added drop by
drop under agitation, and black precipitate appeared immediately. After further
stirring for 3 h, the black precipitate was filtered, washed with ethanol-distilled
water, and ethanol, respectively, and dried in a degassed desiccators for 48 h.
Finally, the target product, a black powder of OA-capped PbS nanoparticles, was
obtained. Non-capped PbS nanoparticles were prepared for comparison by the
same procedures as the capped ones, except that no capping agent was added
during the preparation process.
The prepared OA-capped PbS nanoparticles can be well dispersed in several
organic solvents, including chloroform, benzene, toluene, and liquid paraffin,
whereas non-capped PbS nanoparticles cannot be dispersed in the above sol-
vents. So it is concluded that after the surface-capping with OA, the dispersion
capability of nano-sized PbS is improved. The improvement in the dispersion
capability enables the OA-capped PbS nanoparticles to be used as an additive
in lubricating oils.
FT-IR spectra were taken on a Bio-Red FTS-165 IR spectrometer, to investi-
gate the chemical structures of the capping layer on the PbS nanoparticles’ sur-
face. The morphology of the PbS nanoparticles was studied by JEM-1200 EX/S
TEM. The crystal phase of the prepared powders was identified by a D/max-RB Fig. 1. FT-IR spectra of: (a) OA, (b) OA-capped PbS nanoparticles and (c) non-
X-ray powder diffractometer (XRD) using Cu K␣ radiation (λ = 1.5418 Å). XPS capped PbS nanoparticles.
analysis was conducted on a PHI-5702 photoelectron spectrometer using a pass
energy of 29.35 eV and a Mg K␣ line excitation source with the reference of
C1s at 284.6 eV. Because a monochromator was used, the resolution for binding at 722 cm−1 . This band is typical of (CH2 )n chains with n > 3.
energy reached 0.3 eV. The band at 3006 cm−1 is assigned to the stretching vibration
The tribological properties of the OA-capped PbS nanoparticles as an addi- of C H, the strong band at 1710 cm−1 is the characteristic
tive in liquid paraffin were evaluated on a four-ball machine under a rotating stretching vibration of C O in carboxylic acid. Compare Fig. 1a
speed of 1450 r min−1 at ambient conditions. The test duration was 30 min and
and b, it was found that the peaks around 3006, 2900, 2850,
the load applied was 100, 200, 300 and 400 N, respectively. The 12.7 mm diam-
eter balls used in the test were made of GCr15 bearing steel (SAE52100 steel) 1465, and 722 cm−1 also exist in the IR spectra of OA-capped
with a HRc of 59–61. Before each test, the balls and the specimen holders were PbS nanoparticles (Fig. 1b), indicate the existence of C H
all cleaned in petroleum ether (normal alkane with a boiling point of 60–90 ◦ C). group and long alkyl chain in the OA-capped PbS nanoparticles.
For each sample, three identical tests were performed so as to minimize data This reveals that OA was successfully capped on the surface of
scattering. At the end of each test, the wear scar diameters on the three stationary
PbS nanoparticles. The characteristic band of carbonyl in car-
balls were measured on a digital-reading optical microscope to an accuracy of
0.01 mm in the direction parallel and perpendicular to the sliding motion, and boxyl acid at 1710 cm−1 was not found in Fig. 1b, but a new
the average wear scar diameter of the three identical tests was calculated as the peak at 1544 cm−1 appeared. The band at 1544 cm−1 demon-
wear scar diameter in this work. The steel ball, after wear tests, was washed strates the existence of carboxylic acid salt in OA-capped PbS
with ultrasonic waves in petroleum ether twice, totaling 20 min before surface nanoparticles. The disappearance of the peak at 1710 cm−1 for
analysis. A JSM-5600 LV scanning electron microscope (SEM) equipped with
carboxylic acid and the appearance of the peak at 1544 cm−1
KEVEX energy dispersion X-ray analyzer (EDS) was employed to examine the
morphologies and the element distributions in the worn surfaces. for carboxylic acid salt reveals that the capping agent OA does
react with PbS nanoparticles, and form carboxylic acid salt.
Namely, the surface-capping agent capped on the surface of
3. Results and discussion PbS nanoparticles not by physically adsorption, but undergoes
chemical reaction process. The broad band near 3400 cm−1 in
Fig. 1 shows the FT-IR transmission spectra of OA, OA- Fig. 1c indicates that there are large amounts of adsorbed water
capped PbS nanoparticles, and non-capped PbS nanoparticles, in non-capped PbS nanoparticles due to the high surface energy
respectively. Characteristics of OA can be clearly seen in Fig. 1a, of nanoparticles. In combination with the results in Fig. 1b, it
it relates to the long alkyl chain, the double bond between car- is subsequently concluded that the surface-capping layer can
bon atoms and the carboxylic acid group. Fig. 1a shows the effectively prevent the adsorption of water on the surface of PbS
antisymmetric and symmetric C H stretching vibration of the nanoparticles.
CH2 group around 2920 and 2850 cm−1 , respectively, the CH2 Fig. 2 shows the TEM image of non-capped PbS nanopar-
deformation vibration at 1465 cm−1 , and the rocking vibration ticles and OA-capped PbS nanoparticles, respectively. It was
 S. Chen, W. Liu / Materials Chemistry and Physics 98 (2006) 183–189 185

Fig. 2. TEM image of: (a) non-capped PbS nanoparticles and (b) OA-capped PbS nanoparticles.

found that non-capped PbS nanoparticles tended to agglomerate
and did not permit identification of a single particle (Fig. 2a)
owing to the high surface energy of nanoparticles. Unlike the
non-capped ones, the OA-capped PbS nanoparticles had a nar-
row size distribution and the average diameter was about 8 nm
(Fig. 2b). Comparing Fig. 2a and b, it can be concluded that the
existence of the surface-capping layer can effectively prevent the
agglomeration and growth of PbS particles and led to the for-
mation of fine nanoparticles. Besides, the blurry spots in Fig. 2a
indicate the existence of some surface adsorbed water around
the non-capped PbS nanoparticles, which is also confirmed by
the above-mentioned FT-IR observation. No similar observa-
tion is availed in Fig. 2b. This reveals that the existence of the
surface-capping layer cannot only effectively prevent agglom-
eration between PbS nanoparticles, but also effectively prevent
the surface adsorbed water around PbS nanoparticles.
Fig. 3 shows the XRD pattern of the OA-capped PbS nanopar-
ticles. It revealed several broad diffractions, which were in good
agreement with face-centered cubic (fcc) PbS phase (reference:
JCPDS 5-0592). The widened X-ray diffraction peaks indicate
that the synthesized product consists of very small PbS crystal-
lites. It is thus concluded that the PbS nanocore in the capped PbS
nanoparticles has fcc structure and the surface-capping agent
restrains the particle size.
Figs. 4 and 5 shows the XPS spectra of non-capped and OA-
capped PbS nanoparticles, respectively. It is seen from Fig. 4
that the PbS nanoparticles without capping show a Pb4f7/2 peak
at 137.4 eV and a S2p peak at 160.5 eV, which are in agree-
ment with the reported values of PbS (Pb4f7/2 : 137.6 eV, S2p :
160.8 eV) [14]. Besides, the spectra of Pb4f7/2 in Fig. 4 show a
shoulder peak at 138.5 eV which corresponds to PbO (Pb4f7/2 :
138.8 eV) [14], that of S2p show a peak at 168.6 eV which indi-
cates the existence of S(VI) [14]. Thus it can be concluded that
the PbS nanoparticles without capping exhibits poor stability in
air. In other words, non-capped PbS nanoparticles are liable to
oxidation as exposed in atmosphere because of the high surface
energy. OA-capped PbS nanoparticles show a Pb4f7/2 peak at
137.8 eV, which is the signals for PbS and a single S2p peak at

Fig. 3. XRD spectra of OA-capped PbS nanoparticles.

186 S. Chen, W. Liu / Materials Chemistry and Physics 98 (2006) 183–189

Fig. 4. XPS spectra of non-capped PbS nanoparticles.

Fig. 5. XPS spectra of OA-capped PbS nanoparticles.

161.2 eV (Fig. 5), a little higher than what was reported for the
signals of S2p in PbS. It was supposed that the above-mentioned
changes in the binding energies could be attributed to the influ-
ence of the coordination action of Pb moiety and the capping
agent OA. No peaks of PbO and S(VI) were found in Fig. 5,
indicating that surface-capping layer could prevent the oxida-
tion of PbS nanoparticles effectively.
According to the results of FT-IR, TEM, XRD and XPS,
the model of the monolayer OA-capped PbS nanoparticles was

Fig. 7. Tribological properties as a function of additive concentration (four-ball,

Fig. 6. Model of OA-capped PbS nanoparticles. 1450 r min−1 , 300 N, 30 min).
 S. Chen, W. Liu / Materials Chemistry and Physics 98 (2006) 183–189 187

Fig. 8. Wear scar diameter as a function of applied load with the lubrication of Fig. 9. Friction coefficient as a function of applied load with the lubrication of
LP alone or that containing 0.2 wt.% OA-capped PbS nanoparticles (four-ball, LP alone or that containing 0.2 wt.% OA-capped PbS nanoparticles (four-ball,
1450 r min−1 , 30 min). 1450 r min−1 , 30 min).

established and shown in Fig. 6. Since the PbS nanocore was
embedded in the monolayer of OA, the dispersion capacity in
the organic solvent and stability in the air was both improved,
accordingly. The repulsion between the surface-capping layers
enables the PbS nanocore away from agglomeration. Namely,
the capping layer of OA stabilized the PbS nanoparticles, and
made the OA-capped PbS nanoparticles to be a potential oil
additive.
Fig. 7 shows the tribological behaviour as a function of the
additive concentration of OA-capped PbS nanoparticles in LP

Fig. 10. SEM morphologies and element distribution of the worn surface.
188 S. Chen, W. Liu / Materials Chemistry and Physics 98 (2006) 183–189
under a load of 300 N. Results show that with the addition of
OA-capped PbS nanoparticles to the LP, the wear scar diameter
and friction coefficient both reduced remarkably. The effective
additive concentration of OA-capped PbS nanoparticles as an
additive is above 0.05 wt.%, which is much lower than the com-
mercial oil additives (usually larger than 0.5 wt.%). As the addi-
tive concentration lower than 0.05 wt.%, the wear scar diameter
and friction coefficient become larger, which means the bound-
ary lubrication film could not be completely formed with such
a low additive concentration. Further addition of OA-capped
PbS nanoparticles to LP can reduce wear but cannot reduce fric-
tion coefficient any more. The lowest wear scar diameter was
obtained at the additive concentration reach to 0.2 wt.%, under
this condition, the wear scar diameter can be reduced by 31%,
and the friction coefficient can be reduced by 30% as compared
to LP. Since the optimal additive concentration was 0.2 wt.%
according to both antiwear and friction-reduction ability, this
concentration was chosen to investigate the influence of the load.
Figs. 8 and 9 show the variation of the wear scar diameter and
friction coefficient with the applied load for LP alone and for
LP containing 0.2 wt.% OA-capped PbS nanoparticles. With LP
alone, the wear scar diameter and friction coefficient is relatively
large, and the friction system scuffs at a load higher than 300 N.
However, with LP containing 0.2 wt.% OA-capped PbS nanopar-
Fig. 11. XPS spectra of Pb4f , S2P , P2P , Fe2P and O1S in the boundary film.
ticles, a smaller wear scar diameter and friction coefficient was
generated, and the friction system could be effectively lubri-
cated even at a load of 400 N. It is concluded that OA-capped
PbS nanoparticles as an additive can effectively improved tribo-
logical properties of LP.
Fig. 10 gives the SEM morphologies and elemental distribu-
tions of Pb, S and O of the worn surfaces (four-ball machine,
load: 300 N, test duration: 30 min, lubricant: LP containing
0.2 wt.% OA–PbS nanoparticles). The distributions of Pb, S and
O thereon give strong evidence that a protective film was indeed
formed during the friction process.
Since XPS is very informative for analyzing the composi-
tion and chemical characteristics of the elements in a material,
XPS analysis of the boundary film formed on the worn surfaces
was performed. Fig. 11 shows the binding energies of some
elements on the worn surfaces. From the results in Fig. 11,
it is concluded that the boundary film on the rubbed surfaces
is composed of PbS (Pb4f7/2 : 137.6 eV, S2P : 160.8 eV), PbO
(Pb4f7/2 : 138.8 eV, O1S : 529.4 eV), FeS (Fe2P : 710.3 eV, S2P :
161.6 eV), Fe2 O3 (Fe2P : 710.8 eV, O1S : 530.2 eV) and SO4 2−
(S2P : 168.8 eV, O1S : 532.4 eV) [14]. Compare the XPS results
of Figs. 5 and 11, it is indicated that during the friction process,
the chemical bond between Pb and capping agent OA frac-
tured. Namely, the long alkyl chain in OA molecule dissociated,
 S. Chen, W. Liu / Materials Chemistry and Physics 98 (2006) 183–189
PbS nanocore became exposure and be oxidized to PbO and
S(VI). Accordingly, we supposed that the excellent antiwear
and friction-reducing capacity of OA-capped PbS nanoparticles
could be attributed to the formation of the boundary film on the
steel surface.
4. Conclusions
OA-capped PbS nanoparticles were successfully prepared by
a chemical method. The synthesized nanoparticles with an aver-
age diameter of 8 nm could be well dispersed in several organic
solvents and liquid paraffin, which enables the synthesized par-
ticles to be used as additives in lubricating oils. Surface-capping
agent capped on the PbS nanoparticles’ surface by chemical
bond, not by physically adsorption. The existence of OA capping
layer on the surface of the PbS nanoparticles restrained water
adsorption and the growth of the nanoparticles. OA-capped PbS
nanoparticles as an additive in LP can effectively reduce friction
and wear at a low additive concentration owing to the formation
of a complex boundary film.
Acknowledgments
The authors wish to acknowledge the financial support of
the National Natural Science Foundation of China (50272068,
189
50275142) and Natural Science Foundation of Guangdong
(04011772).
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