Tribology International 44 (2011) 829–833

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

Antiwear properties of carbon-coated copper nanoparticles used as an

additive to a polyalphaolefin
J.L. Viesca a,n, A. Hernández Battez a, R. González a, R. Chou b, J.J. Cabello b
a
University of Oviedo, Department of Mechanical and Civil Engineering, Ctra. de Castiello s/n, 33204 Gijon, Spain
b
University of Cienfuegos, Faculty of Mechanical Engineering, Ctra a Rodas, Cuatro Caminos, Cienfuegos, Cuba

a r t i c l e i n f o abstract

Article history: This paper studies the influence of the addition of 25 nm carbon-coated copper nanoparticles on
Received 21 November 2010 the tribological behavior of a polyalphaolefin (PAO6) and compares this behavior with the case of
Received in revised form non-coated copper nanoparticles, determining the influence of coating. A block-on-ring tribometer,
3 January 2011
a four-ball machine, SEM and EDS were used in this research. The study concludes that the addition of
Accepted 7 February 2011
carbon-coated copper nanoparticles decreases wear and increases the load-carrying capacity of PAO6.
Available online 15 February 2011
This tribological improvement is due to the deposition of nanoparticles on the rubbing surfaces and
Keywords: probably by their action as tiny bearings. The carbon-coated copper nanoparticles did not behave better
Copper nanoparticles than non-coated ones.
Carbon-coated copper nanoparticles
& 2011 Elsevier Ltd. All rights reserved.
Additives
Wear behavior

1. Introduction show that nanoparticles can improve the tribological properties

The use of nanoparticles in the lubrication of mechanical
systems has become an interesting research line. The replacement
of organic molecules by tiny particles of solid material is not
straightforward and has only been regarded as a feasible option in
recent studies. The main advantage of using nanolubricants is that
they are relatively insensitive to temperature and their tribo-
chemical reactions are limited, compared to traditional addi-
tives [1]. Another advantage of the addition of nanoparticles in
lubricant oils is that they can pass through the filters [2].
The antiwear mechanism of nanoparticles when they are used
as additives in lubricants can be explained in three different
ways: nanoparticles may be melted and welded on the rubbing
surface, reacted with the specimen to form a protective layer, or
tribo-sintered on the surface. However, some authors state that
nanoparticles can also act as small bearings on the rubbing
surfaces [1,3–8]. Chiñas-Castillo and Spikes [8] found that colloi-
dal nanoparticles penetrate into lubricated EHD contacts via a
mechanical entrapment mechanism to form a boundary film
influencing friction and wear, and these nanoparticles are
entrained into sliding contacts only when the film thickness is
smaller than the particle size contributing to the film thickness.
The above mentioned antiwear mechanisms of the nanoparticles
take place only under mixed and boundary lubrication. Results
n
Corresponding author. Tel.: +34 985182640.
E-mail address: viescajose@uniovi.es (J.L. Viesca).
of the base oil, displaying good friction and wear reduction
characteristics even at concentrations below 2 wt% [1].
With the rapid development of nanotechnology, nanolubri-
cants with metallic additives have also been studied [9]. Experi-
mental results report that the use of metallic nanoparticles as
additives to oils can improve the antiwear properties under
extreme pressure conditions. The metallic nanoparticles can also
act without any corrosive effect and can be used at high
temperatures. Therefore, they have the potential to become a
new generation of antiwear and extreme pressure additives.
The tribological behavior of lubricants with the addition of
copper nanoparticles has been studied by some authors [2,10–15].
In all these cases, when copper coated nanoparticles (none of
them was carbon-coated ones) were tested as oil additives, the
results showed that the oils with the addition of these nanopar-
ticles exhibit an excellent antifriction and antiwear performance
and high load-carrying capacity. Recently, Xu et al. [16] also used
surface-coated copper nanoparticles as oil additives. They showed
that surface-coated nano-copper additives can significantly
improve the wear resistance and load-carrying abilities of oil, as
well as reduce the friction coefficient. They related the results to a
soft copper protective film that is formed on the worn surface
lubricated with oil containing nano-copper additives, which
separates the worn surfaces, avoids their direct contact and
reduces friction and adhesive wear. On the other hand, Bin
et al. [17] used graphene encapsulated copper nanoparticles as
a lubricant additive. In this case, the additive also increased the
load-carrying capacity of the base oil, decreased the friction

0301-679X/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2011.02.006
830 J.L. Viesca et al. / Tribology International 44 (2011) 829–833

coefficient and enhanced the antiwear properties. However, they
did not compare the tribological behavior of coated nanoparticles
used as lubricant additives with the non-coated ones.
The objective of this paper is to evaluate the influence of the
addition of carbon-coated copper nanoparticles on the tribologi-
cal properties of a polyalphaolefin (PAO6) and to establish the
effect of coating by comparing the results obtained using the
same copper nanoparticles with (Cu25C) and without the coating
(Cu25).
2. Experimental details
2.1. Materials
A polyalphaolefin (PAO6) was chosen as the base oil due to its
consideration among the more promising synthetic lubricants
used for general purposes. The fact that PAO6 is used in industrial
bearing oils, hydraulic oils, aviation lubricants, drilling fluids, heat
transfer fluids, dielectric fluids and greases [18] was also taken
into account.
Carbon-coated copper nanoparticles (Cu25C) and non-carbon-
coated copper nanoparticles (Cu25), Fig. 1, were provided by the
Nanostructured & Amorphous Materials Inc. The nanoparticles
were dispersed in the lubricant at concentrations of 0.5 and 2 wt%
using an ultrasonic probe for 30 min. This preparation method of
suspensions was used according to the manufacturer’s specifica-
tions in order to break up the agglomeration and to help with
degassing. Due to their high surface area and their dangling
bonds, nanoparticles have a tendency to agglomerate and absorb
moisture, oxygen, nitrogen, etc. A stability study was carried out
by sedimentation with results showing that the aggregates and
flocs were not formed for equal or lower times than those used in
the wear tests. Table 1 shows the main properties of the base oil
and nanoparticles used in the experiments.
2.2. Antiwear test procedure under medium load
All test-section components—blocks and rings—(Table 1) were
cleaned ultrasonically with heptane for 5 min, rinsed in ethanol
and dried with hot air before and after the tests. Sliding wear tests
were performed using a block-on-ring tribometer (TE53SLIM). All
the tests were run for a total distance of 3066 m at a sliding speed
of 1 m/s and a load of 165 N (corresponding to a pressure of
0.1 GPa) applied via a cantilever. This load was chosen in order to
develop the tests in a mixed lubrication regime where the anti-
wear mechanism of nanoparticles can take place. This load
calculation was made using the equations of the elastohydrody-
namic lubrication [19].
After three tests were made for each suspension at this load,
wear was measured through the weight loss ( 70.1 mg) of the
block. Wear surfaces on blocks were analyzed using scanning
electron microscopy (SEM), and energy dispersive spectrometry
(EDS) was used to detect the elements present on the worn
surface of the blocks.
2.3. Experimental test procedure under extreme pressure conditions
All specimens—balls—(Table 1) were cleaned in the same form
as those of blocks and rings for the antiwear tests under medium
load (Section 2.2). A four-ball machine with a drive shaft speed of
1470 rpm was used to conduct the extreme pressure tests
according to ASTM D2783 standard [20]. Wear scar diameters
(WSDs) were measured using a Nikon PFX optical microscope,
provided with a Nikon F-301 CCD camera. Other parameters that
characterize the extreme pressure properties of oils such as the
initial seizure load (ISL), the weld load (WL) and the load-wear
index (LWI) were obtained from the WSD values [3]. The topo-
graphy and the elements present on the wear scar surfaces were
studied using SEM and EDS.

3. Results and discussion

3.1. Antiwear tests under medium load

The addition of the carbon-coated copper nanoparticles

reduced wear with respect to pure base oil (PAO6). The best
results were found for the suspensions with a nanoparticle
Fig. 1. Micrographs of nanoparticles: (a) Cu25 and (b) Cu25C. concentration of 0.5 wt%, Fig. 2. The suspensions with 0.5 wt%

Table 1
Properties of the materials.

Nanoparticles Properties

Cu25C Morphology: nearly spherical, purity: 99.8%, APS: 25 nm, real density/apparent: 8.94/0.15–0.35 g/cm3, SSA: 30–50 m2/g
Cu25 Morphology: nearly spherical, purity: 99.8%, APS: 25 nm

Base oil Physical properties

PAO6 Density (15.6 1C): 0.826 g/cm3 Viscosity: 31.0 cSt (40 1C)
Viscosity index: 135 5.90 cSt (100 1C)

Specimens Properties

Rings Steel—AISI D3, hardness—280 HV500 g, d ¼60 mm, Ra ¼0.1 mm, E ¼200 GPa, n ¼ 0.3
Blocks Steel—AISI 1045, hardness—266 HV500 g, dimensions—12.7  12.7  14 mm3, Ra ¼0.12 mm, E¼ 200 GPa, n ¼ 0.3
Balls Steel—AISI 52100, hardness—65 HRC, d ¼ 12.7 mm, Ra ¼ 0.035 mm

APS: average particle size; SSA: specific size area.

 J.L. Viesca et al. / Tribology International 44 (2011) 829–833
of Cu25 and Cu25C exhibited 50% and 31% of wear reduction,
respectively. On the other hand, the suspensions with 2 wt% of
Cu25 and Cu25C showed a wear reduction of 16% and 11%,
respectively. In both the cases, the increase in the concentration
of nanoparticles diminished their positive effect on the tribological
behavior of the base oil. In addition, coating the nanoparticles does
not improve the capacity of nanoparticles as antiwear additive.
After the wear tests with pure PAO6, the worn surfaces on the
blocks were analyzed by SEM and EDS to conclude that only those
chemical elements present in steel could be found. However, in
tests made with the suspensions, copper appeared on the wear
surface (Fig. 3). The percentage of deposited copper is given in
Table 2; it can be observed that the higher the copper concentra-
tion in the suspension, the higher the deposition on the wear
surface. It is also noteworthy to mention that the deposition of
non-coated nanoparticles on the wear surface is higher than that of
Fig. 2. Wear reduction of the nanoparticles suspension with regard to base oil.
Fig. 3. Micrographs and EDS of the worn surface on the blocks: (a) 0.5 wt% Cu25C and (b) 2.0 wt% Cu25C.
831
the coated nanoparticles and this phenomenon is directly related
to the comparative antiwear behavior of the tested suspensions.
The favorable results of the wear tests using the suspensions
are closely related to the presence of copper nanoparticles on the
wear surface (this fact was verified with energy dispersive
spectrometry). According to the mechanism of action of colloidal
solid dispersions proposed by Chiñas-Castillo and Spikes [8] and
taking into account that the lubricant film thickness for mixed
and boundary lubrication regimes is thinner ( o0.025 mm) [21]
than the nanoparticles diameter (25 nm), it can be stated that in
our case the nanoparticles have been dragged into contact and
have interacted with the surface causing an improvement on the
tribological behavior of the base oil. The most likely antiwear
mechanism of nanoparticulate additives is the tribosinterization
of nanoparticles on the wear surface. Zhou et al. [22] showed that,
when very fine metallic particles are employed, sintering starts as
soon as the temperature increases above the room temperature.
Besides the tribosinterization, nanoparticles can also behave as
tiny bearings, increasing the load carrying capacity of the lubri-
cant and leaving the contact surface later on. However, it is quite
difficult to establish the proportion of nanoparticles that behave
as tiny bearings or those deposited on the wear surface by
tribosinterization.
Table 2
Percentage of Cu on the wear scar surface.
Suspensions Percentage of Cu (%)
PAO6 + 0.5% Cu25C 0.17
PAO6 + 0.5% Cu25 0.58
PAO6 + 2.0% Cu25C 0.77
PAO6 + 2.0% Cu25 2.19
832 J.L. Viesca et al. / Tribology International 44 (2011) 829–833

3.2. Wear tests under extreme pressure conditions suspensions. The addition of Cu25C nanoparticles increased the
last non-seizure load for the suspensions with 0.5 wt% of nano-
The goal of this test (ASTM D2783) is to determine the load particles concentration.
carrying capacity of the tested suspensions under extreme pres- Although the suspensions with 0.5 wt% of Cu25 and 2 wt% of
sure (EP) conditions. Fig. 4 shows the results of the wear tests Cu25 and Cu25C showed identical last non-seizure load similar to
under increasing loads for the pure base oil (PAO6) and Cu25C the one presented by PAO6, Table 3, the wear scar diameters at
this load were lower for the mentioned suspensions than for
10 Compensation line PAO6. This wear behavior of the cited suspensions was similar
PAO6 from the last non-seizure load onwards. On the other hand, the
PAO6 + 0.5% Cu25C suspension with 0.5 wt% of Cu25C nanoparticles had the best
PAO6 + 2% Cu25C tribological behavior under extreme pressure conditions due to its
WSD [mm]

higher last non-seizure load. In general, all suspensions showed

1 higher last non-seizure load, weld load and load-wear index
than PAO6.
SEM and EDS analyses showed deposition of the nanoparticles
on the wear surface at initial seizure load, Fig. 5. As the results
from the tests were made under medium load (Section 3.1), the
0 presence of nanoparticles in contact is closely related to the
100 1000 10000 improvement of the tribological behavior of the suspensions with
Load [N] regard to PAO6. In this case, it was also found that non-coated
nanoparticles were deposited on the wear surface in a higher
Fig. 4. Wear scar diameter vs. load curve for the Cu25C suspensions. proportion than the coated nanoparticles. On the other hand,

Table 3
Results of tests under extreme pressure conditions.

Lubricants Last non-seizure Mean wear scar Initial seizure Weld load Load-wear
load (LNSL) (N) diameter at LNSL (mm) load (ISL) (N) (WL) (N) index (LWI) (N)

PAO6 490.50 0.369 618.03 1569.6 201.818

PAO6 + 0.5% Cu25C 618.03 0.375 784.80 1962 259.391
PAO6 + 0.5% Cu25 490.50 0.348 618.03 1962 221.279
PAO6 + 2.0% Cu25C 490.50 0.346 618.03 1962 215.842
PAO6 + 2.0% Cu25 490.50 0.347 618.03 1962 229.900

Fig. 5. Micrographs and EDS of the wear surface at initial seizure load (ISL): (a) 0.5 wt% Cu25C at 784.8 N and (b) 2 wt% Cu25C at 618.03 N.
 J.L. Viesca et al. / Tribology International 44 (2011) 829–833
Table 4
Percentage of Cu in the surface of the wear scar at initial seizure load.
Suspensions Percentage of Cu (%)
PAO6 + 0.5% Cu25C at 784.8 N 0.29
PAO6 + 0.5% Cu25 at 618.03 N 2.33
PAO6 + 2.0% Cu25C at 618.03 N 0.64
PAO6 + 2.0% Cu25 at 618.03 N 3.95
wear surface analyses showed the fact that for the suspensions
with the same type of nanoparticles at higher nanoparticles
concentration, there was higher nanoparticles deposition on the
wear surface at the same load, Table 4.
4. Conclusions
On the basis of this research, the following conclusions can be
drawn: all suspensions decreased wear with respect to PAO6
between 10% and 50% under mixed lubrication regime; under
extreme pressure conditions, the load-wear index for all studied
suspensions is higher than that of the base oil, with increments
between 7% and 29%; from the tribological point of view, the
carbon-coated copper nanoparticles did not behave better than
non-coated copper nanoparticles; and the analysis of the wear
scar by SEM and EDS showed that the tribological improvements
with the use of these suspensions are closely related to the
nanoparticles deposition on the wear surfaces and probably also
by the action of the nanoparticles as tiny bearings.
Acknowledgment
The authors want to express their gratitude to the Spanish
Ministry of Education and Science for supporting this paper
within the framework of the Research Project MAT2007-62210.
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