WEAR

ELSEVIER Wear 2 I x ~ I,}~sb 153 lSS

Preparation of DDP-coated PbS nanoparticles and investigation of the

antiwear ability of the prepared nanoparticles as additive in liquid paraffin
Shuang C h e n *. W e i m i n Liu, Laigui Yu
Lahnratnrv orS,did Luhri.'ation. llmztum lu~tittac ,,t ('hc,mc,I Phx ~1,,. ( 'hmcw . t. ,dc,m of Sci~,m'e. Ltznrhou 7.r0¢~. China
Rccei',cd 5 Januar3, It)t)~:accepled24 \pril it!t)S

Abstract

PbS nanoparticles of average diameter ahtlut 5 nm. whic-h ~erc ~urfacc-modilicd ~ ith dialkyldithiophosphate ( D D P ) , were prepared by
chemical synthesis. The synthesized DDP-coated PbS nanopanicle,, ~ere characterized h.'. infrared spectroscopy I IR ), X-ray photoelectron
spectroscopy I XPS). transmission electron micro',copy ITEM 1. and electron diflractilm lED). The antiv.'ear ability of the coated PbS
nanopataicles as additive in liquid paraffin was investigated u,.ing a four-hall machine. The ".,.orn surfaces were analysed with XPS also. It
was found that the dispersion capacity and oxidam.e ~.tabilit3,of PbS nanoparticle, could be improved effectively by surface modification
with DDP. Meanwhile. DDP-coated PbS nanoparticles could imprm.e the anti~.ear ability of liquid paraffin even at aa extremely low
concentration. This was attributed to the fi)rmation of a chemical reaction boundary, tilm consisting of PbS. PbO, FeS, Fe_,O~, SOj" and
PO.~~ . © 1998 Elsevier Science S.A. All right,, reserved.

Keywnrds: DDP-PbS nanopanicle~,:Surlacc modilication:Additixc:XPS ,mal~,,i,

I. Introduction by surfi~ce moditication with organic compounds, similar as

Since the physical and chemical properties o f nanosized
particles are quite different from that of the bulk material or
individual molecules, thus the experimental examination on
synthesis and application of nanoparticles has been exten-
sively focused on in many areas recently I 1-31. Among
these, the synthesis of organic-inorganic composite materials
has attracted much attention 14 ]. For example, nanoparticlcs
of DDP-coated MoS_,. Mo-S compounds, and organic acid
coated TiO, were synthesized successfully, and the antiwear
ability of these nanoparticles as additives in liquid paraffin
were investigated by Zhang et al. 15 ] and Xue et al. 16.7 I-
They found that the nanoparticles, which were modified with
organic compounds, exhibited good dispersion capacity and
excellent antiwear behaviour in liquid paraffin.
Bulk lead sulfide is unsuitable for the lubrication of sliding
steel system because of the poor dispersion capacity of PbS
in lubricating medium. Similarly. nanosized PbS is not a good
candidate for such purpose either, because it is very likely to
be oxidized and agglomerated as exposed in air. not to men-
tion its poor dispersion capacity in lubricating oil.
It is anticipated that the stability and the dispersion capacity
of nanosized PbS in liquid paraffin could also be improved
* Correspondingauthor. Fax: + 86-931-84171188.
in thc case of MoSz. Therefore, DDP surface-modified PbS
nanoparticles were synthesized in this work. The structure of
the synthesized product was characterized with IR. XPS.
TEM, and E D The antiwear ability of the product as additive
in liquid paraffin was investigated on a four-ball machine.
2. Experimental details
2. I. P r e p a r a t i o n q f P b S n a n o p a r t i c l e s
The commercial products of analytically pure lead acetate
( Pbt Ac I:- 3H~OI and sodium sulfide (Na_~S-9H,O) were
used as the raw materials for synthesis. Pyridinium di-n-
hexadecyldithiophosphate (PyDDP) was synthesized and
characterized based on Ref. [8]. Analytically pure ethanol
and de-ionized water were used as solvents.
Since the structure and properties of the synthesized PbS
nanoparticles varied with the ratio of S-" ion to PyDDP, a
typical ratio of S-" :PyDDP= h I ( mole ratio) was selected
in this work. The details about the preparation procedures are
as follow: first, put 100 ml mixture ofethanoI-H,Oas solvent
into a 250-ml reaction flask, heat the mixture to 55°C under
stirring" then add 0.67 m m o l ( 0.44 g) PyDDP into the above

(X)43-164819815- see tYont matter~) 1998ElsevierScienceS.A. All rightsreser,,ed.

PII S0043-1648198 ) 00220-8
154 s. Chen el aL / Wear218 (1998) 153-158

mixture; after PyDDP was completely dissolved, drop the P, <0.020% S. 1.30-1.65% Cr. <0.30% Ni. and <0.25%
solution of 0.67 mmol (0.16 g) Na2S'9H20 in 5 ml de- Cu. HRc 59-61 ). The fc,ur-ball test was conducted at a speed
ionized water into the flask under stirring; finally drop the of 1450 rpm under room temperature for a test duration of 30
solution of I mmol (0.38 g) Pb(Ac)2-3H20 in 5 ml de- rain. At the end of each test, the average wear scar diameter
ionized water into the flask under vigorous stirring. Subse- on the 3 lower balls was determined using an optical
quently, a brown precipitate was produced immediately. The microscopy.
colour of the precipitate became darker with the proceeding
of the reaction in the flask under continuous stirring. At the
end of the reaction (after 3 h continuous stirring), the dark 3. Results and discussion
brown precipitate was collected by filtering. The final target
product was obtained by rinsing the precipitate in ethanol- 3. I. Characterization of PbS nanoparticles
deionized water and ethanol, respectively, and was kept in a
degassed desiccator for 48 h. Then a dark brown powder was
Figs. I and 2 show the IR spectra of PyDDP and DDP-PbS
obtained, which is the expected DDP-coated PbS
nanoparticles, respectively.
nanoparticles.
The molecular formula of the PyDDP can be expressed as:
labS nanoparticles without surface modification was pre-
(CI6H330) 2PSSHNCsH.~.
pared under the same procedures as above, except that
The structure of PyDDP is as below:
PyDDP was not used.
The DDP-coated PbS nanoparticles can be dispersed in
some organic solvents, such as chloroform, benzene, methyl
benzene, and it can be dispersed in liquid paraffin also, but
to the non-coated PbS nanoparticles, it cannot be dispersed
in the solvents above. So it is concluded that after the surface-
modification with DDP. the dispersion capacity of nanosized In Fig. I, the strongest peak near 2900 c m - ~corresponds
PbS improved.
to the long alkyl chain, which is the IR characteristic peak of
the organic compounds containing long aliphatic chains. The
2.2. Characteri:ation of the synthesized nanoparticles
sharp peak at 804 c m - ~ corresponds to the P=S stretching
band 19]. This indicates that P atom is linked to S atom by
The composition and structure of the synthesized nano-
double bond in PyDDP. in combination with the OCH2 vibra-
particles were characterized by infrared spectroscopy (IR),
tion peak at 920-980 cm - t and the displaced pyridine peak.
X-ray photoelectron spectroscopy (XPS). transmission
it was concluded that the anticipated PyDDP was successfully
electron microscopy ( TEM ), and electron diffraction ( ED ).
prepared in this work. As indicated in Fig. 2, the IR spectrum
IR analysis was carried out on a Bio-Rad FTS-165 IR spec-
of DDP-coated PbS nanoparticles has some apparent differ-
trometer. XPS analysis was conducted on a PHI-550 electron
spectrometer at a pass energy of 29.35 eV. The Mg Ka radi-
ation was used as the excitation source and the binding energy
of C ts (284.6 eV ) was used as the reference. A JEM- 1200
EX/S transmission electron micro~ope was used to examine
the morphology and crystalline structure of the nanoparticles.
For the XPS analysis, the prepared powder were pressed into ~e
a slice with diameter of 4 ram; and for the electron microscopy
study, the powder were dispersed in chloroform with an ultra-
sonic vibrator for 5 min. and then deposited on a copper grid
tlqtamura~as"(©m-t)
covered with a perforated carbon film.
Fig. I. The IR spectraof PyDDP.
2.3. Antiwear ability o]'the synthesized nanoparticles as
additive in liquid paraffin
t

The liquid paraffin ( Tientsin Chemistry Reagent Factory)

was used as the base stock, which has a boiling point of 300°C
i
abow,, density of 0.835-0.89 g/cm 3, viscosity at 50°C of i
10.28 mm-'/s, because of its simple structure and unique
tribological behaviour. The friction and wear tests were car-
tried out on a four-ball machine. The balls in a diameter of
12.7 mm are made of bearing steel ( 52100 steel; composition: ~ r ~ r (cm-O
0.95-1.05% C. 0.15-0.35% Si, 0.20-0.40% Mn. <0.027% Fig. 2. The IR spectra of DDP-PbS.
 S. ('hen et ,1. / Wear 2 I?¢ r I0(~?;~ 153-15,~ 155

ences with what is shown in Fig. I. Namely, the P = S vibration 12000

neak at 804 c m - i disappears and the shifting of wavenumber ~o~ (a)
11000
from 690 c m - ~to 650 cm - ~ is observed. The disappearance
o f the peak at 804 cm - ~ indicates that reaction occurred 10000
between the polar radical in the PyDDP molecule and the Pb
moiety. The sharp peak at 2900 cm - ~ and the broad peak of
g~
OCHz at 9 2 0 - 9 8 0 c m - i also confirm this conclusion. This
also shows that the long alkyl chain in PyDDP molecule did
not dissociate during the reaction. The shitting of waven-
umber from 690 c m - ; to 650 c m - ~ could be related to the
conjugate structure between DDP and Pb moiety on the
surface.
Figs. 3 and 4 show the XPS patterns of Pb and S in the 155 150 145 140 13S
£.e,W (eV)
DDP-PbS nanoparticles and PbS nanoparticles, respectively.
The binding energies of some typical elements are listed in
Table I. Co)
It is seen from Fig. 3 that the PbS nanoparticles without
80017
modification show a Pb.w~]., peak at 137.4 eV and a S:p peak
at 160.4 eV which are in agreement with the reported values 7500
of PbS [ I01. Besides, the spectra of Pb4,7]_, in Fig. 3 show a
peak at 138.5 eV which corresponds to the Pb+jT/-, ( 138.8
j 8~
eV) in PbO [ I I l, that of S_,p show a peak at 161.4 eV which
indicates the existence of element S by oxidation of S-" and
a peak at 168.6 eV which indicates the existence of S (Vl) 5500
112l. Fig. 4 shows that the binding energies of Pb4, and S,~,
. . . .
in the coated PbS nanoparticles shift towards higher values 175 170 I(15 160
as compared with non-modified PbS nanoparticles and with Enmgy (ev)
Fig. 4 XPS ~,pectraof DDP-PbSnanoparticles.
IsX 10+
Table I
Pb~ (a) Bindingenergies,o1 the elements in samples and rcl~renccs

Sample Bindingenergy eV)

)b.7 _- S+.~, P_,p
._~
Coaled-PbS 14().I 163.7 134.9
i Nano-PbS 137.4. 138.5 160.4. 161.4. 168.6 -
PyDDP 161.5 133.1)
PbS [101 137.6 160.8 -
PbO I 111 138+8

156 150 146 140 135

what was reported about PbS also [ I0]. At the same time,
8 ~ a e E , w W (eV)
x t0 0 some differences are also observed with the binding energies
5.5 of S_-p in the coated labS nanoparticles and in PyDDP, as
S-~ (b) shown in Table I. It was supposed that the above-mentioned
differences in the binding energies could be attributed to the
5
influence of the coordination action o f Pb moiety and the

~
A
4.5
modifying agent DDP. Thus, it can he concluded that the PbS
nanoparticles without modification exhibits poor stability in
air. In other words, non-coated PbS nanoparticles are liable
to oxidation as exposed in atmosphere because o f the high
4 scrface energy. Contrary to the non-coated ones, the coated
PbS nanoparticles show a Pb+,-7~, peak at 140.1 eV and a
single S2p peak at 163.7 eV. indicating that the coated PbS
3,~ was not oxidized as exposed in atmosphere. Accordingly, it
175 170 165 160
Energy (eV) can he concluded that the surface modification layer could
Fig. 3. XPS spectra of PbS nanoparticle~. prevent the oxidation o f PbS nanoparticles effectively.
156 S. Chen et al. / Wear218 (1998) 153-158

Fig. 5. TEM and ED pattern of DDP-PbS nanoparlicles.

Fig. 5 show the TEM image and the electron diffraction

pattern of the DDP coated PbS nanoparticles. It is found that
the particles are fairly uniformly distributed and have an ~0.7
average size of about 5 nm. This indicates that the existence
of surface modification layer could prevent the agglomeration i 0.6
ofPbS nanoparticles effectively. The electron diffraction pat-
tern implies that these nanopanicles have the structure of PbS. '~ 0.s
According to the results of IR, XPS, TEM and ED, it is
concluded that the DDP-coated PbS nanoparticles can be 0.4

dispersed well in the organic solvents and can be protected

from oxidation in air. The modification layer of DDP stabi-
0.025 0.05 0.075 0.1
lized the PbS nanopafficles.
Concentration(%)
Fig. 6. Wear scar diameter as a function of additive concentration. ( Four-
3.2. Antiwear ability o f coated PbS nanoparticles as ball. 1450rpm. 3iX)N, 30 mini.
additive in liquid paraffin
0.9
Fig. 6 shows the wear scar diameter as a function of addi-
~0.8
tive concentration of DDP-PbS nanoparticles in liquid par-
affin under a load of 300 N and at a speed of 1450 rpm. It is O.7
seen that DDP-PbS nanoparticles as additive in liquid paraffin
O.6
is effective for increasing the antiwear ability even at a very
low concentration and the optimum concentration of DDP- ~ o.5
PbS nanoparticles is 0.05 wt.%.
~ o.4
Fig. 7 shows the variations of wear scar diameter with
applied load for base stock alone and for base stock containing o.3
0.05 wt.% DDP-PbS nanopanicles. It is seen that with the 100 200 3OO
liquid paraffin alone, the wear scar diameter is relatively AppliedLoad(N)
larger, especially at a higher load. Contrary to the above, the Fig, 7. Wear scar diameleras a functionof applied load fi~rbase oil or 0.05
wt.~ DDP-PbS. I Four-ball, 145Urpm, 30 rain ).
wear scar diameter is smaller with liquid paraffin containing
0.05 wt.% DDP-PbS nanopanicles. In the latter case, the mal alkane with a boiling point of 60-90°(=) twice, totaling
effect of load on the antiwear ability becomes relatively indis- 20 min. Fig. 8 shows the binding energies of Ph4,, S~p, P2P,
tinctive as well. Fe2e and O ~ on the worn surfaces (four-ball machine, load:
300 N, test duration: 30 min, lubricant: base stock containing
3.3. XPS analysis o f the won1 surfaces 0.05 wt.% DDP-PbS nanoparlicles).
From the results in Fig. 8, it is concluded that the boundary
Since XPS is very informative for analyzing the compo- film on the rubbed surfaces is composed of PbS( Pb4m~: 137.6
sition and chemical characteristics of the elements in a mate- eV, S,~:160.8 eV) [ IO], PbO(Pb4~7/2:138.8 eV, Ois:529.4
rial. XPS analysis of the boundary film formed on the worn eV) [ I I ] , FeS(Fe~e:710.3 eV, $2e:161.6 eV) 113,14],
surfaces was performed. The upper steel ball, after wear tests, Fe.~O.~(Fea,:710.8 eV, O~s:530.2 eV) [15], S O 4 2 -
was washed with ultrasonic waves in petroleum ether ( nor- ($2p:168.8 eV. O~s:532.4 eV) 1161 and PO43 -
 S. Chert el aL / Wear 218 f 199~ ~ 153-138 157

( Pzp:132.9 eV, O:s:532.8 eV) [ 17]. Compare the results in

Figs. 3, 4 and 8. it is found that the binding energy o f Pb4f in
Fig. 8 is similar to that in Fig. 3, but different to that in Fig.
4. This indicates that during the friction process, the Ph-DDP
bond fractured, namely, the long aikyl chain in DDP molecule
dissociated. Accordingly, we supposed that the excellent anti-
wear capacity of DDP coated PbS nanoparticles could be
.g- attributed to the formation of the boundary film on the steel
surface.

4. C o n c l u s i o n s
£mqlyleV)
DDP-PbS nanopanicles were prepared by a chemical sur-
face modification method. The synthesized nanol~-ticles
could be well dispersed in some organic solvents and liquid
paraffin base stock. Due to the modification effect of D D P

'=/~ "t
around the surface of PbS nanoparticles, the oxidation o f PbS
nanoparticles was thus lxevented. The results of font-ball
tests show that DDP-PbS nanoparticles as additive in liquid
paraffin increased the antiwear ability effectively. The lowest
o wear scar diameter was observed as the concentration of
175 17o 1~ ~
B~dmg Enwgy (eV) coated PbS nanoparticles in liquid paraffin was 0.05 wt.%.
XPS analysis of the worn surface indicated the formation o f

=°I"° 1 a boundary f i l m consisting o f PbS, PbO, FeS, Fe2Ch, SO42-

and PO+3 . This attributed to improving the antiwear ability

--[A /1 1 of the base stock.

AcknowledgemeBts

Professor Shangkui Qi at Laboratory o f Solid Lubrication

of Lanzhou Institute of Chemical Physics o f Chinese Acad-
x 10' emy of Sciences is gratefully acknowledged for performing
the XPS analysis. The a u t h o ~ also wish to acknowledge the
financial support from National Natural Science Foundation
°, ....... t of China and Chinese Academy of Sciences.

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mographies
Shuang Chen received her BS in Chemistry at Henan Uni-
versity of China in 1995. She has been a MSc candidate at
Lanzhou Institute of Chemical Physics of Chinese Academy
of Sciences since 1995. Her research interests include nano-
tribology and tribochemistry.
Weimin Liu received his BS in Chemistry at Shandong Nor-
mal University in 1984 and PhD in tribology at Lanzboa
Institute of Chemical Physics in 1990. He joined the Labo-
ratory of Solid Lubrication, Lanzbou Institute of Chemical
Physics, Chinese Academy of Sciences in 1990, and from
1993 to 1994 he spent one year as a visiting scientist at the
Department of Chemical Engineering, Pennsylvania State
University. His research interests include lubricant additive
interactions, lubrication of ceramic, solid lubrication, tri-
bochemistry, and fuel additives, Currently, he is an associate
professor and deputy director of the Laboratory of Solid
Lubrication.
Laigui Yu received his MSc degree and PhD degree from
Lanzhou Institute of Chemical Physics of Chinese Academy
of Sciences (CAS) in 1990 and 1997, respectively. His
research interests include tribology of thin films and coatings,
tribochemistry of rare-earth lubricating additives, and tribol-
ogy of polymers and composites. Currently he is a faculty
and Associate Research Professor at the Laboratory of Solid
Lubrication of Lanzhou Institute of Chemical Physics of
CAS.