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Materials Today: Proceedings 4 (2017) S75–S80 www.materialstoday.com/proceedings

NRW 2016

Tribological Performance of TiO2-Nanostructured Particles as Oil-

Lubricant Additives for Different Iron-Carbon Alloys
Alexander Beel1,3*, Martin Gottschalk2,3, Andreas Huetten2,3, Katja Toensing1,3, and
Dario Anselmetti1,3
1
Experimental Biophysics and Applied Nanoscience, Faculty of Physics, Bielefeld University, Universitaetsstrasse 25, 33613 Bielefeld, Germany
2
Thin Films and Physics of Nanostructures, Faculty of Physics, Bielefeld University, Universitaetsstrasse 25, 33613 Bielefeld, Germany
3
Bielefeld Institute for Nanoscience (BINAS)

Abstract

We evaluated the tribological performance of a dispersion of titanium dioxide (TiO2) nanostructured particles in car engine base
oil for three different iron-carbon alloy materials (bearing steel, carbon steel and cast iron) in a disc–disc tribometer. The
lubrication, friction and wear performance of the nanostructured particles was measured by testing three different configurations:
1) pure base oil, 2) base oil with additive package and 3) nanodispersion formulation. For the bearing steel – carbon steel
configuration we found that the oil additive package reduces the coefficient of friction from µ = 0.12 to µ = 0.03. Upon adding
TiO2-nanostructured particles to this formulation a further friction reduction by a factor of 3 to a superior frictional coefficient of
µ < 0.01 could be measured. This effect, however, could not be verified for the other two alloy material combinations, where the
frictional coefficient was not affected by the nanostructured particle addition. Since carbon steel is characterized by the lowest
Brinell hardness of the three tested alloy materials and exhibited the lowest surface roughness after the test procedure, we
attribute the observed friction reduction to a lubricating titanium (dioxide) overlayer that builds up on the carbon steel surface but
not on bearing steel and cast iron. This is supported by element-specific energy dispersive X-Ray analysis (EDX). Further
attempts to optimize and predict nanotribological formulations for industrial applications are under way.

© 2017 Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/ licenses/by-
nc-nd/3.0/).
Selection and Peer-review under responsibility of 7th North Rhine-Westphalian Nano-Conference.


This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial-ShareAlike License, which
permits non-commercial use, distribution, and reproduction in any medium, provided the original author and source are credited.
* Alexander Beel. Tel.: +49 (0) 521 1065384; fax: +49 (0) 521 1062959.
E-mail address: abeel@physik.uni-bielefeld.de

2214-7853© 2017 Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/ licenses/by-nc-
nd/3.0/).
Selection and Peer-review under responsibility of 7th North Rhine-Westphalian Nano-Conference.
S76 A. Beel et al. / Materials Today: Proceedings 4 (2017) S75–S80

Keywords: Nanostructured particles; nanoparticle additives; titanium dioxide; friction; lubrication; dispersion

1. Introduction

In industrialized countries approximately 1 % to 1.4 % of the gross national product can be saved by the
application of tribological principles [1]. The reduction of friction and wear between two moving parts can be seen
as the most important purpose of lubricants. In 2015, the global lubrication market accounted for 144.45 Billion
USD [2]. On the lubrication market engine oils account for more than 60 % [3]. In general the formulations of
engine oils contain base oils and additives [4].
Previous studies have reported that nanoparticles which are dispersed in lubricants led to a remarkable reduction
of friction properties [5,6]. The tribological properties of various types of nanoparticles were examined e.g. silicon
dioxide [5,7], titanium dioxide [5,8–12], aluminum oxide [12–14], and combinations of nanodiamonds and graphene
[15]. An extraordinary friction and wear reduction could be achieved with titanium dioxide nanoparticles [5,6].
In this work titanium dioxide nanostructured particles dispersed in engine base oil are used as an additional oil
additive. The tribological performance is evaluated and quantified with a disc-disc tribometer. By using cast iron
carbon steel and bearing steel discs a material dependence was found in respect of the nanostructured particle
performance.

2. Materials and Methods

2.1. Experimental Setup

The tribological experiments were performed with a rotation tribometer RT8000 (Kompetenzzentrum Tribologie,
HS Mannheim, Germany) and were conducted with disc-disc contacts (Fig. 1a). An applied normal force and the
resulting friction moment were measured by a two component force sensor (Lorenz Messtechnik, Germany). The
friction coefficient was calculated by the measured friction moment and the disc dimensions (Fig. 1b and 1c).
Further instrument parameters are described in detail in [5].
All presented results were performed with the following test parameters. The tribocontact was completely
immersed in the lubricant. During the experiment a constant rotation speed with v = 0.15 m/s was maintained. The
test procedure was started with a normal load of 250 N. Every 5 min the normal force was increased by 250 N until
a load of 2500 N was reached. For the next three hours the normal force was kept constant at 2500 N resulting in a
normal pressure of 10 MPa.

Fig. 1: (a) Test set up; (b) self-designed disc (contact area A = 247mm²); (c) 100Cr6 axial bearing disc

The tribological contact consists of axial bearing discs (LS2542, Schaeffler, Germany, Fig. 1c) and self-designed
discs (Fig. 1b). The dimensions of these discs are shown in Fig. 1b. They were produced by cast iron (EN-GJL 300),
carbon steel (11SMnPb30), and bearing steel (100Cr6). In order to maintain a constant high quality level of these
discs they were lapped and cleaned prior to each experiment. The preparation is described in detail elsewhere [5].
 A. Beel et al. / Materials Today: Proceedings 4 (2017) S75–S80 S77

2.2. Formulation of Dispersion

The base oil used conforms to API/ATIEL Base Stock Group III and is commonly used for conventional 5W and
10W passenger car engine oils. To prevent agglomeration and sedimentation an additive package (surfactants) as
described in [5,6] was needed to stabilize the dispersed hydrophobized fumed titanium dioxide nanostructured
particles (Aeroxide, Evonik, Germany) in our formulation which was subsequently homogenized with an ultrasonic
device (Sonoplus HD 3200, Bandelin, Germany). With this procedure long-term stabilization was given and an
average nanostructured particle diameter of 75 nm was measured with dynamic light scattering (Horiba LB-500,
Japan).

3. Results and Discussion

In order to realize reproducible results the planarity of the two contact surfaces and the surface roughness of the
discs are significant. The planarity is responsible for a uniform load distribution. The surface roughness affects the
deformation and abrasive stress [16] which directly influences the friction [17]. These requirements could be
achieved by an in-home lapping procedure (Wentzky-3R35 GR, Peter Wolters, Germany). The surface roughness of
the discs was measured with an atomic force microscope (AFM) (BioScope, Bruker, Billerica, Massachusetts, USA)
and the Brinell hardness was determined using a hardness testing machine (Zwick/Roell 2.5S1S, Germany).

3.1. Pure Base oil

The tribo-contact was built in three material combinations – (1) bearing steel vs. carbon steel, (2) bearing steel vs.
bearing steel, and (3) bearing steel vs. cast iron. Initially, the triboexperiments were conducted with the pure base
oil. The results are shown in Fig. 2. In the run-in period where the load was increased to 2500 N (10 MPa) all
experiments exhibit an increasing coefficient of friction. Hereafter, the friction coefficient was more-or-less
constant yielding a range of 0.11 < µ < 0.14 for all tested material combinations (1-3).

Fig. 2: Disc-disc triboexperiments with pure base oil. The experiments were performed with self-designed discs consisting of carbon steel
(red), bearing steel (blue) and cast iron (green) against bearing steel, yielding steady state friction coefficients of µ = 0.11 - 0.14.
S78 A. Beel et al. / Materials Today: Proceedings 4 (2017) S75–S80

3.2. Base Oil mixed with an additive package

An additive package is necessary to stabilize the nanostructured particles in the engine oil [5,6]. In order to assess
the contribution of the additive package alone a mixture of base oil with the additive package was tribologically
investigated for the various material combinations ((1)-(3)). The contribution of an additive package to the base oil
led to a friction reduction by nearly an order of magnitude (µ ≈ 0.1 to µ ≈ 0.03 (Fig. 3a)) for the material
combination bearing steel – carbon steel (1), whereas the material combinations bearing steel (2) and cast iron (3)
against bearing steel were not influenced by the additive package.
a b

Fig. 3: (a) disc-disc triboexperiments with a formulation of base oil and an additive package; (b) disc-disc triboexperiments with a formulation
of base oil, an additive package and TiO2 nanostructured particles.

3.3. Dispersion

In Fig. 3b the results of disc-disc experiments with a formulation consisting of base oil, additive package and
0.5%wt titanium dioxide nanostructured particles are shown. In the run-in period, the coefficient of friction
increased stepwise up to µ ≈ 0.13 with the normal load for bearing steel – iron steel (3). During the next 30 min the
friction decreased to µ ≈ 0.12 which can be explained by a flattening of the surface. After this run-in period the
friction kept nearly on a constant level at µ ≈ 0.12. The experiment with a self-designed bearing steel disc (2)
showed a comparable coefficient of friction at the end of the test, as does the experiment with self-designed cast iron
discs. Using bearing steel – carbon steel discs (1) the friction coefficient was reduced from µ ≈ 0.09 to µ < 0.01.
Adding TiO2 nanostructured particles (Fig. 3b red curve) causes a friction reduction by a factor of 3 compared to the
identical experiment without nanoparticles (Fig. 3a red curve). We show that TiO2 nanostructured particles only
realize the superior friction properties when using certain material combinations.

3.4. Considerations to the mechanism

In order to investigate how the differences in surface roughness and hardness of the various materials may have a
significant impact on the friction reduction mechanism of nanostructured particles in lubricants, we analyzed these
parameters by AFM and hardness testing machine after the tribo-experiment.
Carbon steel Cast iron Bearing steel
Surface roughness Ra in nm (after the experiment) 8.9 nm 21.36 nm 14.4 nm
Hardness 185 HB 240 HB 250 HB
Table 1: disc properties for the various materials
 A. Beel et al. / Materials Today: Proceedings 4 (2017) S75–S80 S79

The surface roughness was measured for each disc after a cleaning procedure. We measured a surface roughness
of Ra(3) = 21.36 nm, Ra(2) = 14.4 nm and Ra(1) = 8.9 nm for the cast iron (3), bearing steel (2) and the carbon steel
(1) discs (Table 1), respecting the low roughness of carbon steel could be a reason for superior friction performance.
To characterize the Brinell hardness of the discs we performed indentation experiments. Interestingly, we found
that on the softest material (carbon steel) a surface titanium (oxide) layer has formed (Table 1). This was
investigated by element-specific energy dispersed X-ray analysis mapping (EDX). Prior to the EDX-experiment a
part of the surface was etched away with a focused-ion-beam-microscope (FEI Helios NanoLab Dual Beam, USA),
yielding a clear change in the titanium-concentration at the interface (Fig. 4b). In Fig. 4c is shown that titanium
(dioxide) is uniformly distributed over the surface.
In order to determine the contribution of the titanium (dioxide) layer to the friction reduction an experiment was
performed with “used” discs from a former TiO2-dispersion experiment. After a cleaning procedure with acetone
and petroleum ether the titanium (dioxide) layer could still be detected on the surface with EDX. Upon testing these
discs in pure base oil the coefficient of friction (Fig. 4a) was found again at the superior friction level of µ < 0.01,
which was also achieved in experiments with nanodispersions. In addition, the coefficient of friction in the run-in
period was also found remarkably low. With this experiment we can conclude that the titanium (dioxide) layer plays
an essential role for the superior performance in friction performance.

Fig. 4: (a) disc-disc triboexperiments with used discs in pure base oil; (b) material on disc surface was removed by a FIB. On the top surface
more titanium could be localized than on the deeper area; (c) EDX mapping of the self-designed disc surface. The green color symbolizes the
detected titanium.

4. Results and Discussion

In this work, we could show that TiO2-nanostructured particles yield a substantial friction reduction in bearing
steel- carbon steel disc-disc triboexperiments by testing a dispersion including base oil, an additive package, and
TiO2 nanostructured particles. In contrast, such an effect could not be verified for the other two alloy material
combinations (bearing steel/cast iron, bearing steel/bearing steel), where the coefficient of friction was not affected
by the nanoparticle addition.
S80 A. Beel et al. / Materials Today: Proceedings 4 (2017) S75–S80

In EDX mapping a titanium (dioxide) layer could be detected uniformly distributed over the disc surface. An
experiment performed in pure base oil with used discs, which have a titanium (dioxide) layer, also exhibited a
reduced friction, thereby proving the relevance of a surface contact layer of titanium (dioxide). Our results
demonstrate the potential to evaluate and quantify the contribution of nanostructured particle additives in engine oil
lubricant applications.

Acknowledgements

We gratefully acknowledge support and funding from Evonik Resource Efficiency GmbH, Hanau-Wolfgang,
Germany, and Prof. Dr.-Ing. Kordisch (University of Applied Science Bielefeld) for providing hardness
measurements.

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