Tribology International 109 (2017) 519–528

Contents lists available at ScienceDirect

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

Lubricant-surface interactions of polymer-coated engine journal bearings MARK

a,c,⁎ b b b a
Martin Repka , Nicole Dörr , Josef Brenner , Christoph Gabler , Colin McAleese ,
Osamu Ishigoa, Motohiko Koshimad
a
Daido Metal Co., Ltd – organizační složka, The European Technical Center, Brno, Czechia
b
AC2T research GmbH, Wiener Neustadt, Austria
c
Brno University of Technology, Faculty of Chemistry, Brno, Czechia
d
Daido Metal Co., Ltd, Inuyama, Japan

A R T I C L E I N F O A BS T RAC T

Keywords: This work provides the methodology for the improved understanding of tribocontacts with tribolayers formed
Bearing: Journal from the interactions of an engine oil and the surface of a journal bearing under boundary lubricating
Plain Bearings: Failures conditions. In particular, advanced surface characterisation combining X-ray photoelectron spectroscopy (XPS)
Tribochemistry and high resolution mass spectroscopy (MS) contributed to integrated knowledge on tribochemical and
Surface: Chemical analysis
tribomechanical processes in the tribocontact studied. An engine connecting rod bearing lubricated with
Spectroscopy: X-ray photoelectron
commercial 0W-20 GF5 engine oil was evaluated as part of the tribosystem. Bearing material was a recently
developed polymer-based overlay which increased in popularity in the automotive market owing to the
durability and superior tribological properties. After engine bench tests and fatigue experiments, conventional
oil analyses showed only minor changes regarding oil chemistry whereas MS revealed significant additive
degradation, e.g., formation of organic phosphates from ZDDP and depletion of tris(2,4-di-tert-butylphenyl)
phosphite additive. Regarding the fatigue experiments, surface analysis by XPS showed the formation of
tribofilms with a thickness only in the range of a few nanometers and composed of P, S and Zn, i.e., mainly
elements in ZDDP. This publication reports for the first time on surface characterisation by laser desorption
ionisation MS applied to engine journal bearings: the presence of an organic phosphorus compound the origin
of which is assumed from ZDDP could be revealed by this approach.

1. Introduction dispersed in a resin binder have been developed [8,9] to comply with
the above mentioned requirements. Due to the beneficial effect of solid
Automotive industry aims at more environmentally friendly and lubricants, wear is less likely to progress compared with conventional
more efficient combustion engines by development of so-called down- Al–Sn–Si based bearing alloys. Several inorganic materials, e.g.,
sized engines. However, these developments cause higher power molybdenum disulphide (MoS2), graphite, can provide excellent solid
densities in the engines resulting in substantially increased local lubrication [10–13]. Besides the involvement of MoS2, incorporation of
contact pressures of rolling or sliding contacts. Therefore enhanced CaCO3 in the resin overlay also contributed significantly to improved
danger of seizure can be identified [1]. One of such machine compo- anti-seizure performances of the bearing.
nents affected by this trend is the engine bearing designed to carry Tribotesting offers the advantage that the effects of different loading
increasing fatigue loads but also to conform the variations in align- collectives can be systematically applied to the tribocontact to assess
ments [2]. Improvements needed of these bearings concern tribological tribological performances of surface modifications and hence to
properties including low friction, higher wear resistance, embeddability systematically investigate the interactions of such bearing surfaces
of foreign particles, anti-seizure performance, conformability as well as with the lubricant [14]. Surface modifications refer to both structural
corrosion resistance. Therefore, the development of new bearings changes of the material in contact and formed tribolayers. The latter
needs to compromise between tribological properties, mechanical can either protect against or contribute to the degradation of the
strength, and corrosion resistance of the bearing material in conjunc- material [15] as well as determines the resulting performance. It is
tion with the engine oil [3–7]. known that rough surfaces formed in sliding contacts locally increase
Recently, bearings with resin overlays composed of a solid lubricant stress [16] whereas tribochemical interactions and tribooxidation of

⁎
Corresponding author at: Daido Metal Co., Ltd – organizační složka, The European Technical Center, Brno, Czechia
E-mail address: [email protected] (M. Repka).

http://dx.doi.org/10.1016/j.triboint.2017.01.017
Received 19 October 2016; Received in revised form 11 January 2017; Accepted 13 January 2017
Available online 17 January 2017
0301-679X/ © 2017 Elsevier Ltd. All rights reserved.
M. Repka et al. Tribology International 109 (2017) 519–528

tribolayers and debris formed can decrease the overall stress conditions
[17–21]. Concluding, the knowledge of material composition, lubricant
formulation and the proper description of their interactions under the
investigated conditions lays the foundations for the improvement of
tribological performance.
Consequently, understanding of mechanisms and kinetics of tribo-
layer formation translated into functionality and reliability of lubri-
cated contacts goes along with appropriate surface and lubricant
characterisation. Such studies were performed by applying laser
desorption ionisation mass spectrometry (LDI-MS) to identify residual
and tribochemically altered molecules inside and outside of the wear
track. And imaging techniques reveal the distribution of tribologically
relevant species on the surfaces for an improved understanding of
lubricant-surface interactions. LDI-MS was successfully applied for the
identification of organic degradation products of the applied lubricant
additives [22] or of novel lubricants such as ionic liquids [23].
Complementary information to LDI-MS about ionic liquid tribochem-
istry of the wear track and the surface chemistry of the surroundings
was gained by X-ray photoelectron spectroscopy (XPS) [23]. Thereby,
the formation of primarily inorganic tribochemical reaction products, Fig. 1. Schematic diagram of fatigue test machine.
e.g. iron fluorides, was found. It was also shown that the composition of
the tribolayers formed was significantly dependent on the local contact Table 1
situation. Test conditions of fatigue test machine.
In this study, the methodology for the joint consideration of oil and
Items Details Unit
surface chemistry was elaborated. Therefore, the selected engine oil
was characterised by conventional oil analysis, e.g., viscosity, elemental Bearing size Φ60xW18xT1.5 mm
composition, as well as MS as advanced analytical method before and (outer diameter x width x thickness) (2 bearing half shells)
after tribotesting. These data were combined with findings acquired by Revolution speed 7000 rpm
Specific load 60 MPa
scanning electron microscopy equipped with energy dispersive X-ray
Frequency 200 Hz
spectroscopy (SEM-EDS) and (XPS) from the bearing surfaces. This Duration 19.7 million cycles
publication reports for the first time on complementary surface Oil quantity 60 L
characterisation by LDI-MS applied to newly produced and tribologi- Oil inlet temperature 110 °C
cally stressed surfaces of bearing shells. This way, insight into surface- Oil pressure 0.4 MPa
Shaft material Steel JIS S55C –
lubricant interactions on the atomic and molecular scale, respectively, Shaft roughness Rz < 1.0 μm
by identification of tribolayers formed and their probable origin is
provided.
Complementary, performance experiments were carried out on the
2. Experimental fatigue test machine developed by Daido Metal which allowed the
application of more severe conditions in the tribosystem. A schematic
2.1. Materials diagram can be seen in Fig. 1, and the test parameters are summarised
in Table 1. A dynamic loading was applied to the connecting rod with a
The applied engine journal bearings were composed of 2 half shells mounted test bearing. The loading pattern was sinusoidal with a
consisting of a standard bimetal (bearing steel and conventional Al– contact pressure of 60 MPa and a frequency of 200 Hz. The shaft was
Sn–Si alloy) coated with a resin overlay that exhibits good boundary made of steel JIS S55C with roughness Rz below 0,1 µm and connected
lubricating properties, especially during start-stop events. Thereby, to the driving unit. A torque meter was installed between the shaft and
steel served as carrier and Al–Sn–Si as additional sliding layer. As resin motor to monitor torque during the test. Thermocouples were used to
overlay for the bearing shells, a patented polymer overlay of Daido measure the temperature on the outer side of the test bearing to detect
Metal Co. Ltd. [20] based on polyamide-imide (PAI) was used having seizure and fatigue on the bearing. Engine oil was pumped via an inlet
also incorporated the solid lubricant MoS2 and CaCO3 additive for above the upper bearing half shell into the tribocontact. Tests were
increased seizure resistance. The inner diameter of the bearing shell stopped when the temperature on the backside of the bearing raised
was 56 mm, and the thickness of the polymer coating was approxi- rapidly as a response to crack initiation. Otherwise, the test bearing
mately 6 µm. Before tribotesting, the bearing half shells were cleaned passes the fatigue test if no critical temperature increase happens
by use of an ultrasonic bath with commercial cleaning agent Star 50PN. within 19.7 million cycles. Bearings and the engine oils were sampled
As counterbody to the bearings, a steel shaft made of JIS S55C was and subjected to surface and lubricant analysis, respectively.
used.
For the lubrication of the engine bearing specimens, a low viscosity
oil 0W-20 GF5 was applied. Details on fresh and used oil chemistry are 2.3. Conventional oil analysis
discussed in Section 3.2.
Optical emission spectrometer with inductively coupled plasma
2.2. Tribotesting (ICP-OES) was applied for the qualitative and quantitative determina-
tion of the elemental composition of the fresh and used oil. The device
In order to produce tribologically stressed surfaces, two kinds of was a Vista MPX (Varian, Australia) optical emission spectrometer.
experiments were performed: one set of bearing specimens were Before ICP OES analysis, the samples were prepared by acidic digestion
assessed in an engine bench test, and another set was evaluated in a in a microwave device (Multiwave 3000, Anton Paar, Austria) to
fatigue test machine. The engine bench test covered short-term tests on transform the present metallic and non-metallic compounds into water
a 3.5 L V6 gasoline engine. soluble salts and to avoid undesired matrix effects of the oil which

520
M. Repka et al. Tribology International 109 (2017) 519–528

could disrupt the measurement. The obtained aqueous solutions were elements was obtained by XPS using the Theta Probe (Thermo Fisher
directly introduced to the ICP OES device for analysis. Scientific, East Grinstead, UK) with a monochromatic Al Kα X-ray
Infrared spectra in the mid-infrared range (400–4000 cm−1) were source (hν =1486.6 eV). The base pressure during the measurements
obtained by a Fourier Transform infrared spectrometer (FTIR) Tensor was consistently at 3×10−9 mbar. Analytical spot resolution for the
27 (Bruker, Germany). Transmission spectra were prepared with a survey spectra was 400 µm at a pass energy of 200 eV. For the detail
ZnSe cuvette having a path length of 100 µm. Spectrum comparison of spectra, the pass energy was reduced to 50 eV. For the investigation of
fresh and used oil was based on the interpretation of absorption bands smaller surface features, the spot resolution was set to 50 µm. Depth
specific for base oil, additives, and degradation products. profiles were acquired by Ar+ etching. An area of 2×2 mm2 was
Chemical degradation by oxidation of the oil samples was deter- sputtered with an acceleration voltage of 3 kV at a sputter current of
mined according to DIN 51453. Therein, the extinction is determined 1 µA. The surface was sputtered for 0, 10, 20, 50, 80, 110, 210 and
at the wavelength of 1710 cm−1 with baseline endpoints at 1970 and 260 s. The depth was calculated according to the average sputter rate of
580 cm−1. Similarly, nitration was determined by the extinction 0.2 nm/s/µA/mm2. All acquired spectra were referenced to the C1s
measured at the wavelength of 1630 cm−1 with baseline endpoints at peak at 284.6 eV. The resulting analytical data were processed with the
1645 and 1615 cm−1 as also stipulated in DIN 51453. Per definition, Avantage Data System software (Thermo Fisher Scientific, East
fresh oils have no oxidation and no nitration. Grinstead, UK) using Gaussian/Lorentzian peak fitting.
Viscometrical data according to ASTM D7042 and densities accord-
ing to ASTM D4052 were determined by a Stabinger viscometer (SVM 2.5.3. Laser desorption ionisation mass spectrometry (LDI-MS)
3000 Anton Paar, Austria) using a sample volume of 3 mL. Kinematic The cut specimens for XPS analysis were further analysed by LDI-
viscosities and densities were measured at 40 °C and 100 °C. The MS based on a procedure elaborated in a previous research work [22].
viscosity indices (VI) according to ISO 2909 and densities at 15 °C were The atmospheric pressure (AP) matrix assisted laser desorption
calculated from the measured data at 40 and 100 °C. ionisation (MALDI) and LDI mass spectrometric measurements were
performed on a LTQ Orbitrap XLTM hybrid tandem mass spectrometer
2.4. Advanced oil analysis (Thermo Fisher, Bremen, Germany). AP MALDI/LDI MS experiments
were conducted using an AP MALDI PDF+ ion source from MassTech
High-resolution and accurate mass spectroscopic measurements of (Columbia, MD, USA). The wavelength of the all-solid-state triple
the fresh and used oil samples – the latter obtained from the fatigue frequency Nd: YAG laser source was 355 nm operated at a repetition
test machine – were performed in positive and negative ion mode using rate of 10 Hz. Laser pulse width was 3–5 ns (FWHM) with pulse energy
a LTQ Orbitrap XL™ hybrid tandem mass spectrometer (Thermo of 200 µJ. Pulse delay for pulsed dynamic focusing (PDF) was set to
Fisher, Bremen, Germany) equipped with an IonMax atmospheric 25 µs to optimize ion signals. Temperature of the transfer capillary was
pressure interface (API) ion source that carries the electro-spray set to 275 °C, and the automatic gain control (AGC) of the LTQ
ionisation (ESI) probe and the atmospheric pressure chemical ionisa- Orbitrap XL was turned off to secure equal acquisition time for each
tion (APCI) probe (Thermo Fisher scientific, Germany). For qualitative single scan event. Overall acquisition time for all AP MALDI experi-
analyses, a methodology proposed by Pisarova et al. has been modified ments was set to 0.5 min. The samples were analysed without (LDI)
[24]: the oil samples were dissolved in a 7:3 chloroform-methanol and with matrix (MALDI) applied onto the surface where the matrix
mixture, with a dilution factor of 1:1000 and injected via direct served as promotor of ionisation. For MALDI measurements, the
infusion into the mass spectrometer using the ESI and APCI probe. matrix solution was prepared of α-cyano-4-hydroxycinnamic acid
Selected additives were semi-quantified by normal phase liquid (CHCA) with a concentration of 10 mg/mL in a mixture of acetonitrile
chromatography (NPLC) that was performed using an Accela pump and water (1:1, v/v).
(Thermo Fisher scientific) coupled with APCI and the LTQ Orbitrap XL
tandem mass spectrometer. The mobile phase was a mixture of n- 3. Results and discussion
hexane, ethyl acetate and 2-propanol in the ratio 93:5:2 applied with a
flow rate of 400 µL/min. As stationary phase, a Luna NH2 5 µm 3.1. Tribotesting
150×2.00 mm from Phenomenex was selected. Before injection, the oil
samples were diluted in n-hexane with a dilution factor 1:1000. The The bearing set which was assessed in the engine bench test passed
resulting chromatograms were processed with Xcalibur 2.0.7 software without any difficulties and significant damage as can be seen in Fig. 2C
(Thermo Fisher scientific). and D. Although considerable surface modifications, compared to the
newly produced bearing half shells (Fig. 2A and B), were observable, no
2.5. Surface characterisation complete removal of the coating of these bearings occurred.
Accordingly, the presence of abrasive wear scars did not negatively
2.5.1. Conventional surface characterisation influence reliability of the coating.
For the documentation of the general condition of the cleaned A complete loss of the coating was observed on samples from
bearing half shells, a stereomicroscope with a large working distance fatigue test where 19.7 million cycles running according to conditions
was applied to evaluate the cleaned specimens without prior cutting. described in Section 2.2. (see Fig. 2E and F). Wear observed is
Morphology and elemental composition was provided by high attributed to the mainly loaded area where the bearing surface is
resolution scanning electron microscope (HR-SEM) Supra VP40 (Carl operating in the boundary lubrication regime. Under such conditions,
Zeiss AG, Germany) equipped with an electron field emission gun abrasive wear on the surface can often be observed [25]. Worn surfaces
(Schottky thermal field emitter) and an energy-dispersive X-ray are discussed in more details in Section 3.3.
spectroscopy (EDS) detector for elemental analysis. The cleaned
bearing half shells were analysed without the need of prior cutting by 3.2. Oil analysis
application of a sufficiently high counting rate.
3.2.1. Conventional oil analysis
2.5.2. X-ray photoelectron spectroscopy (XPS) As to the proper interpretation of the surface chemistries, prior
For XPS characterisation, bearing half shells were cut by rotary jars compilation of oil analytical data was necessary. The differences
in 2 cm wide specimens and cleaned with petroleum ether by 10 min between the fresh oil compared to the one from fatigue experiment
ultrasonication (see Fig. 9 and 10). Detailed analysis of the surface were already detectable visually: the used oil showed indication of
chemistries regarding elemental composition and binding states of the darkening, hence signs of degradation. Minor differences between the

521
M. Repka et al. Tribology International 109 (2017) 519–528

Fig. 2. Appearance (A) and stereomicroscopic image (B) of a newly produced engine bearing. Appearance (C) and stereomicroscopic image (D) of the loaded bearing half shell after the
engine bench test. Appearance (E) and stereomicroscopic image (F) of the loaded bearing half shell after the fatigue experiment.

Table 2 Oxidation and nitration level of the used oil were also determined by
Elemental composition of the fresh and used engine oil. processing the respective FTIR spectra according to DIN 51453. In the
case of the oxidation level, a moderate increase was elucidated for the
Sample Concentration (ppm)
used oil. For the nitration, no change compared to the fresh oil was
B Ca Cu Fe Mo P S Si Zn observable as expected because nitration can be found in engine oils
stressed to combustion processes but not in tribometers due to lack of a
Fresh oil 240 1970 <5 1 690 710 1960 < 10 640
combustion process.
Used oil 240 1880 < 10 32 680 710 1860 < 10 630
Furthermore, the base oil could be elucidated as a group 3
hydrocrack oil. As VI improver, polymethylacrylate (PMMA) can be
fresh and the used oil are also observable for the carried out elemental suggested by means of the FTIR spectra (‘Ester’ in Fig. 3). It is noted
analysis by ICP-OES, see Table 2. The used oil from fatigue experiment that ICP-OES and FTIR provide substantial information about the
contained iron in a concentration of 32 ppm which can be assigned to composition of fresh and used lubricants. However, elements by ICP-
wear particles. Elements from additives can be attributed to the OES and functional groups by FTIR cannot evidence the exact structure
antiwear additive zinc dialkyldithiophosphate (ZDDP), an additive of the lubricant components as it is possible by mass spectrometry (see
based on molybdenum acting as antioxidant, friction modifier and/or Section 3.2.2).
wear protecting additive, a detergent based on calcium and a boron- As a consequence of tribological stress, the viscosity has signifi-
containing additive. Copper typically found in non-ferrous bearing cantly changed. The results of the measurements with the Stabinger
materials and silicon typically found in antifoam additives appeared viscometer are shown in Table 3. The used oil viscosity at 40 and
only in very low concentrations. The decrease of Ca, Mo, S and Zn are 100 °C decreased significantly in comparison with the fresh oil.
not necessarily related to additive degradation, because these changes Accordingly, the viscosity index which is 218 for the fresh oil decreased
are in the range of measuring inaccuracy. to 193 for the used oil. VI decrease can be explained by higher shear
The presence of ZDDP was also confirmed by the FTIR spectra of stress in the fatigue experiment that causes substantial degradation of
the oils (Fig. 3), which shows a significant absorption band at 900– the VI improver polymer added to achieve lower temperature depen-
1100 cm−1. Further absorption bands characteristic to phenolic and dency of the engine oil viscosity. As shown in Fig. 10, the bearing-shaft
aminic antioxidants (‘Phenolic AO’ and ‘Aminic AO’) could be assigned tribosystem is predominately operating in boundary lubrication regime
as well as salicylates (detergents) and succinimides (dispersants). in the fatigue test machine. Thus, the effect of viscosity decrease on

522
M. Repka et al. Tribology International 109 (2017) 519–528

Fig. 3. Evaluation of the FTIR spectra of the fresh (black) and used (grey) oil.

Table 3 side chain lengths vary from C14, C16 to C18 corresponding to
Kinematic viscosities and densities of the fresh and used engine oil. 333.24 m/z, 361.27 m/z, and 389.30 m/z. A second detergent, alkyl-
benzenesulfonic acid was identified with a main peak at 493.37 m/z
Sample Viscosity at Viscosity at VI (-) Density at
40 °C (mm2/s) 100 °C (mm2/s) 15 °C (g/cm³)
which corresponds to a side chain of C24. The side chain distribution of
this detergent ranges from C20 to C30.
Fresh oil 37.0 8.49 218 0.8451 The mass of the ion 118.04 m/z detected was assigned to benzo-
Used oil 31.4 6.97 193 0.8473 triazole which is applied as corrosion inhibitor. As antioxidant addi-
tives, four different structures were determined. From the class of
aromatic amines useful as primary antioxidant, diphenylamine was
overall tribological behaviour is considered negligible. Oxidation
identified at 422.38 m/z. Furthermore, a phosphorus-based antioxi-
typically indicates base oil degradation and is accompanied by viscosity
dant, tris(2,4-di-tertbutylphenyl) phosphite and two phenolic struc-
increase. However, as oxidation took place at a low level, oxidation-
tures, pentaerythrol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro-
induced viscosity increase can be neglected for the used oil.
pionate) and (3,5-di-tert-butyl-4-hydroxyphenyl)propionate were de-
tected in the oil. Organic phosphites are known to eliminate hydro-
3.2.2. Chemistry of fresh oil by advanced analysis peroxides, peroxy and alkoxy radicals, retard the darkening of lubri-
By applying ESI-MS and APCI-MS, several oil additives could be cants over time and also reduce photo-degradation. Antiwear proper-
determined in the engine oil 0W-20 GF5. The presence of ZDDP as ties of such phosphites are also reported [27].
antiwear additive was already confirmed by ICP-OES and FTIR
measurements. MS measurements provided more structural informa-
tion which is based on the interpretation of the mass-to-charge ratios 3.2.3. Chemistry of used oil
(m/z) that refer to molar masses of the charged molecules. The In the used oil, all additives detected in the fresh oil were still
characteristic main peak of ZDDP was detected at 297.11 m/z. To this present. But contrary to ICP-OES and FTIR measurements, some
ion mass, a ZDDP structure with two C6 side chains can be assigned. distinct variations between the fresh and used oil could be elucidated
Other masses detected can also be attributed to ZDDP and the by applying high resolution mass spectrometry.
differences in m/z compared to the main peak can be explained by Two degradation products could be directly related to ZDDP
variations in the alkyl side chain lengths, e.g., ZDDP with two C4 antiwear additive. In Fig. 4, the comparison between the fresh and
(butyl) side chains was detected at 241.05 m/z; the ion 213.02 m/z can used oil illustrates that additional ions were detected in used oil. These
be assigned to a ZDDP with a single alkyl chain of C6H13. As second ions 181.06 m/z, 209.09 m/z, and 265.16 m/z can be assigned to alkyl
antiwear agent, molybdenum dialkyldithiocarbamates was identified. phosphate structures. The alkyl phosphates identified in the used oil,
This finding conforms to the results obtained by ICP-OES where were also detected by LDI-MS on the surface of the bearing half shell
molybdenum was unambiguously determined. It is known that the stressed in the fatigue experiment (see Section 3.3.2). Furthermore,
combination of organic molybdenum compounds and ZDDP can lead phosphorus with a binding energy related to a phosphate structure was
to a significant reduction of the friction coefficient of the lubricant by a detected on the same surface by XPS (see Section 3.3.3). This means
synergistic mechanisms [26]. As third antiwear additive, borate esters that these alkyl phosphates which are most probably ZDDP degrada-
were identified. This finding is also in good agreement with the ICP- tion products are effective in the tribological contact. This finding
OES results. These borate esters are also known to be effective complements the commonly accepted mechanism of ZDDP degrada-
antioxidants [21]. tion [28] by an important additional “brick”, briefly: dialkyldithiopho-
Alkylsalicylic acid was detected in the oil as detergent additive. The sphates (two sulfur atoms) are converted in species of alkylated

523
M. Repka et al. Tribology International 109 (2017) 519–528

Fig. 4. Alkyl phosphates as degradation products of ZDDP by ESI-MS found in used oil after fatigue experiment. Top: mass spectra of two m/z ranges with ZDDP peaks in fresh oil,
bottom: mass spectra in the same m/z range of used oil.

thiophosphates (one sulfur atom) and – adding these findings – aids on wear has been neglected.
alkylated phosphates (no sulfur atom). Fig. 7 shows the surface modification from fatigue experiment with
By applying normal phase liquid chromatography (NPLC) APCI- different patterns of scars on the substrate material. The polymer layer
MS, it was further possible to reveal that the tris(2,4-di-tertbutylphe- was smoothly abraded. In the area of the highest strain, i.e. in the
nyl) phosphite additive was significantly depleted in the used oil middle of the bearing half shell, the layer was completely rubbed off.
compared to the fresh oil. According to the evaluation of the peak area Element analysis by EDS confirmed the substantial removal of the
of the extracted ion chromatogram at 647.45 m/z, the concentration of polymer layer. Area 1129 is characterised by an elemental composition
the phosphite antioxidant was reduced by approximately 50% in the comparable to that of the newly produced bearing whereas area 1130
fatigue experiment. indicates severe thinning of the polymer layer due to high aluminium
and tin signals.

3.3. Surface characterisation

3.3.2. XPS analysis
3.3.1. SEM-EDX analysis The specimens were also investigated by XPS to elaborate changes
SEM-EDS characterisation of the newly produced bearing shell in elemental composition and binding states of the stressed sliding side
showed a homogeneous polymer layer (Fig. 5). Nitrogen, incorporated of the bearing compared to the newly produced bearing shell. The
in the PAI structure had too weak response in the EDS to be clearly results of the reference measurements on the newly produced bearing
detected. All other elements expected were found, in particular half shell, i.e. survey spectra on the top surface, are summarised in
molybdenum (MoS2), sulfur (MoS2) and calcium (CaCO3). Table 4. Neglecting the possible content of contamination on the
On the bearing half shell after the engine bench test, wear scars surface, carbon, oxygen and nitrogen can be related to the PAI coating.
were clearly visible. EDS spot analysis inside deeper grooves as shown Regarding the newly produced bearing, calcium on the top surface
in (Fig. 6, spot 1128) clearly exhibit that depth exceeded the thickness was detected with a binding energy of 348.9 eV, which can be clearly
of the polymer coating. This can be concluded from the significant attributed to calcium carbonate (CaCO3) incorporated into the polymer
increase in aluminium and tin content referring to the Al–Sn–Si sliding coating. In the detail spectrum of carbon C1s, a binding energy of
layer. Such grooves observed had clearly defined shapes indicating that 288.8 eV was elucidated, which can be also assigned to a carbonate
wear particles were pressed into the polymer thus creating a typical binding state. For molybdenum, a binding energy of 229.3 eV was
imprint. Before and/or after release from the polymer layer, the wear detected which corresponds to MoS2. Slight oxidation of molybdenum
particles scratched over the surface thus generating wear scars. The could be elucidated by assigning the binding energy of 233.0 eV to
SiO2 particle analysed by EDS (Fig. 6, spot 1127) can be attributed to MoO3. Accordingly, two binding states were obtained for sulfur in
dirt from lapping of the cylinder liner. Due to the low silicon content in MoS2 as shown in the detail spectrum in Fig. 8: the sulfidic binding
the used oil (Table 2, < 10 ppm), the effect of such residual processing state (MoS2) with a binding energy of 162.0 eV and oxidized sulfur

524
M. Repka et al. Tribology International 109 (2017) 519–528

Fig. 5. SEM images and EDS analysis of the reference surface of a newly produced engine bearing. (A) magnification 100 ×, (B) magnification 1000 ×, and (C) magnification 5000 ×.
Bottom left chemical composition.

(sulfate) with a binding energy of 169.2 eV. This finding indicates that molybdenum and sulfur on the stressed surface than on the unaffected
MoS2 on the surface exhibits some sensitivity towards oxidation even surface (reference: 0.6 at% Mo and 1.8 at% S, spot 1: 2.4 at% Mo and
without tribological stress. 5.2 at% S, spot 2: 5.1 at% Mo and 4.7 at% S) owing to the formation of
On the top surface of the bearing stressed in the engine bench test, a MoS2 film from the MoS2 particles embedded in the polymer layer
two morphologically different regions could be elucidated by visual and distributed over the bearing surface during operation. By contrast,
inspection. In these regions, two corresponding measurement spots CaCO3 seems to be less abundant on the surface supported by a lower
were defined (Fig. 9): spot 1 referring to lower impact of tribological Ca content in comparison to the reference. Interactions between the oil,
stress, and spot 2 referring to significantly worn surface. As shown in in detail with ZDDP, and the bearing surface are supported by traces of
Table 4, the amount of MoS2 has a noticeable difference between zinc found in spot 2.
surface of the newly produced engine bearing and the worn surfaces The spots for XPS measurements of the specimen obtained from
obtained by engine bench test. XPS revealed higher amounts of fatigue test machine were selected along a line with increasing wear,

Fig. 6. SEM images and EDS analyses of the worn polymer surface after the engine bench test. (A) overview at magnification 500×, (B) wear scars at magnification 1000×, and (C)
imprint possibly from a wear particle at magnification 3000×. Bottom left chemical composition of particle (spot 1127) and disruption of the polymer surface (spot 1128) shown in (A).

525
M. Repka et al. Tribology International 109 (2017) 519–528

Fig. 7. SEM images and EDS analyses of the worn polymer surface after the fatigue experiment. (A) overview at magnification 100×, (B) worn surface in the transition zone of substrate
material and polymer layer at magnification 1000×, and (C) detail view at magnification 2000×. Bottom left chemical compositions of selected spot and areas shown in (B).

Table 4
Elemental compositions by XPS on the top surface of the bearing half shells with
different surface conditions.

Element Reference Engine Bench Test Fatigue Experiment

Spot 1 Spot 2 Spot 1 Spot 2 Spot 3

at%

Al – – – – – 7.9
C 76.0 71.5 72.5 76.0 78.8 58.0
Ca 2.0 0.9 1.2 0.7 0.9 1.1
Mo 0.6 2.4 5.1 1.4 1.0 0.2
N 3.4 3.2 – 4.9 3.0 2.3
O 16.2 16.9 16.2 14.0 14.1 26.0 Fig. 9. XPS measurement spots defined on the bearing half shell obtained after the
P – – – – – 2.5 engine bench test. The dashed black line assigns the areas were the bearing was cut by
S 1.8 5.2 4.7 2.4 1.8 0.5
rotary jars.
Sn – – – – – 0.1
Zn – – 0.4 0.5 0.5 2.0

Fig. 10. XPS measurement spots defined on the bearing half shell evaluated in the
fatigue test machine. The dashed black line assigns the areas were the bearing was cut by
rotary jars.

i.e., progressive removal of the polymer layer (Fig. 10, spot 1–3).
Results comparable to the unaffected polymer layer (reference) were
found in the parts where the polymer was only partly removed (Table 4,
Fig. 8. Detail spectrum of sulfur (S2p) on the newly produced engine bearing. spot 1 and spot 2). XPS of spot 3 corresponding to the mainly loaded
area confirms that the polymer coating has been widely removed and
hence the substrate material (Al, Sn) is exposed. In addition to SEM-

526
M. Repka et al. Tribology International 109 (2017) 519–528

Table 5 This solid but soft lubricant is smeared over the surface and remains
Elemental compositions by XPS after sputtering of the exposed substrate material there due to moderate loads. As a consequence, such bearing surfaces
(Fig. 10, spot 3) on the bearing half shell after the fatigue experiment.
are less stressed as compared to the fatigue test.
Element 0 nm 4 nm 13 nm In order to estimate the tribofilm thickness formed from engine oil
in spot 3, a depth profile was generated by Ar+ sputtering of the
at% exposed substrate material. In Table 5, three sputter levels and the
respective elements are illustrated. Sputtering clearly shows that after a
Al 8.2 45.3 57.4
C 57.8 19.1 23.2 few nanometers (~ 4 nm) of sputtering, phosphorus, sulfur and zinc (~
Ca 1.1 1.3 – 13 nm) are not anymore abundant on the surface. This suggests that no
Cu 0.0 0.2 0.6 substantially thick tribofilm is built up in the mainly loaded area during
Mo 0.3 0.6 0.7 the fatigue experiment.
O 25.7 31.0 15.1
P 4.1 – –
S 1.4 – – 3.3.3. MALDI-MS and LDI-MS analysis
Sn 0.4 1.5 2.6 For complementary information about organic molecules bound to
Zn 1.1 1.0 0.3
the surface, MALDI-MS and LDI MS were applied. It can be concluded
that the LDI-MS approach provides more comprehensive spectra from
the bearing surface than the MALDI-MS approach. In the spectra
EDS results, phosphorus and zinc were detected by XPS. Thereby, the acquired by the MALDI-MS approach, mainly CHCA matrix peaks were
chemical binding state of phosphorus was identified as phosphate observable and no information about additives on the surface could be
based on the binding energy of 134.3 eV. Zinc is present as ZnSO4, and extracted. For this reason, only spectra obtained by LDI-MS are
sulfur occurs as both sulfide and sulfate in spot 3. These three elements presented here.
can be related to engine oil additives, in particular ZDDP that reacted Measurements on the surface of the newly produced bearing shell
with the metallic substrate [28–32]. Sulfur can also originate from resulted in spectra with low intensity peaks. This finding can be
MoS2 in the polymer coating. In contrast to the engine bench test, only attributed to the fact that surface chemistry of the resin overly consists
low enrichment of MoS2 was observed in the fatigue experiment (spot mainly of polymers and solid lubricants which are hardly detectable by
1: 1.4 at% Mo and 2.4 at% S, spot 2: 1.0 at% Mo and 1.8 at% S). In spot LDI-MS which is used as a molecule analytical method. Regarding the
3, no substantial MoS2 layer was formed (0.2 at% Mo and 0.5 at% S). In bearing shell from the fatigue experiment, a mass of 233.13 m/z was
turn, tribochemical interactions with the engine oils took place in spot detected which can be related to a sum formula of C11H22O3P (Fig. 11).
3 as stated above (2.5 at% P and 2.0 at% Zn). Although the exact structure of this molecule could not be identified, it
These findings provide evidence that different wear mechanisms are is considered a degradation product of ZDDP rather than tris(2,4-di-
addressed in the engine bench test and the fatigue test machine. The tert-butylphenyl)phosphite antioxidant as characterised in engine oil
differences in wear formation are attributed to the load level and the analysis in . Similar alkyl phosphate structures were also identified as
mainly loaded area, respectively. The fatigue test machine applies ZDDP degradation products in the used engine oil. C11H22O3P
constantly high loading pattern to the central bearing position in compound was solely detected on the bearing shell stressed in the
comparison to the engine bench test where the location of the loaded fatigue test machine.
area is not fully controllable and hence is distributed axially and
radially. Once the polymer has been removed, adhesive wear was
4. Conclusions
observed on the bearing from fatigue test (Fig. 2F). Tribochemical
reactions with the engine oil, in particular with ZDDP, are not observed
For the comprehensive description of the chemical and tribochem-
as long as the polymer layer is intact (engine bench test: Fig. 9 spot 1
ical behaviour of engine oils and engine journal bearings in an engine
and 2, fatigue test: Fig. 10 spot 1 and 2) but then occur on a significant
bench test and a fatigue test machine, a joint approach of conventional
level with Al–Sn–Si which acts as additional sliding layer (fatigue test:
and advanced analytical methods for oil and surface characterisation
Fig. 10 spot 3). Furthermore, lower load is anticipated in the engine
was developed and applied to engine journal bearings lubricated with
bench test indicated by the significant amounts of MoS2 on the surface.
commercial 0W-20 GF5 engine oil.

Fig. 11. Comparison of the LDI spectra of the surface of the newly produced bearing shell (top) and the bearing shell obtained after the fatigue experiment (bottom).

527
M. Repka et al. Tribology International 109 (2017) 519–528

Conventional lubricant analysis using ICP-OES and FTIR revealed 2016;93:687–95.

[3] Pratt GC. Bearing materials: plain bearings. In: Mortensen Andreas, editor.
general information about lubricant composition and has been found Encyclopedia of materials: science and technology. Oxford: Elsevier Science Ltd;
as essential base for advanced chemical analysis based on high 2004.
resolution MS to detail especially the degradation mechanism on the [4] Eastham DR, Crooks CS. Plating for bearing applications. Aston University Metals
Engineering Congress; 1981.p. 9-13.
molecular level. Overall, only low oil degradation was indicated by [5] Gebretsadik DW, et al. Tribological performance of tin-based overlay plated engine
conventional oil analysis in the fatigue experiment. However, viscome- bearing materials. Tribol Int 2015;92:281–9.
trical properties were attributed to shear stress that induced substantial [6] Katsuki H, et al. Friction and wear properties of low friction plain bearing materials
by a ball on disk test. JAST Tribology Conf. Fukui; 2010. p. 247–48.
polymer cracking during tribotesting Using high resolution MS, it could [7] Nakada M. Trends in engine technology and tribology. Tribol Int 1994;27:3–8.
be shown that ZDDP decomposed in various alkyl phosphates and a [8] Tanaka T, et al. Studies on lead-free resin overlay for engine bearings. SAE Tech
phosphite additive was significantly consumed. Pap 2006:01–1104.
[9] Kawagoe K, et al. New conceptual lead free overlays consisted of solid lubricant for
Regarding surface analysis, oil analytical data could be correlated
internal combustion engine bearings. SAE Technical Paper; 2003. 01-0244.
with surface chemistry. XPS revealed different surface chemistries in [10] Lansdown AR. Lubrication by molybdenum disulphide alone. Tribol Ser
the engine bench test and the fatigue test machine owing to different 1999;35:129–51.
tribological processes dominating in the respective tribocontacts. By [11] Sliney HE. Solid lubricant materials for high temperatures – a review. Tribol Int
1982:303–15.
LDI-MS, the main analytical findings relate to a phosphorus-containing [12] Lancaster JK. Handbook of lubrication: theory and practice of tribology, Volume II:
moiety detected in the mainly loaded area of the fatigue experiment theory and design. Boca Raton: CRC Press; 1984.
which correlates to alkyl phosphates that were also identified as [13] Kobayakawa H, et al. A study of resin overlay bearing material for recent
automotive engines. SAE Technical Paper; 2013: 01-1394.
degradation products in the used engine oil. [14] Barbosa MV, et al. Physicochemical characterisation of tribolayers by micro-Raman
The overall methodology led to promising findings although a and GDOES analyses. Tribol Int 2015;81:223–30.
significant protective tribofilm was not observed in the case of the [15] Biswas SK. Some mechanisms of tribofilm formation in metal/metal and ceramic/
metal sliding interactions. Wear 2000;245:178–89.
fatigue experiment. Advanced oil and surface analysis by high resolu- [16] Fischer TE. Tribochemistry. Annu Rev Mater Sci 1988;18:303–23.
tion MS for the identification of organic compounds in used oils and in [17] Blomberg A, Hogmark S, Lu J. An electron microscopy study of worn ceramic
tribofilms turned out as valuable tools possible to provide new insights surfaces. Tribol Int 1993;26:369–81.
[18] Fischer TE, Tomizawa H. Interaction of tribochemistry and microfracture in the
in oil degradation and lubricant-surface interactions. Furthermore, this
friction and wear of silicon nitride. Wear 1985;105:29–45.
approach can also support method development and validation of lab- [19] Dumpala R, Kumar N, Samji SK, Dash S, Ramamoorthy B, Ramachandra MS, et al.
based tribometrical procedures having more correlation to aggregate Characterization of tribo-layer formed during sliding wear of SiC ball against
nanocrystalline diamond coatings. Mater Charact 2014;95:252–8.
tests and tribosystems in applications. For the generation of more
[20] Kobayakawa H, Kawakami N, Inami S, McAleese C. Sliding Bearing. EP patent
intense MS spectra that enable unambiguous structure identification, 2762736; 2015.
method development is required for the implementation of MS [21] Ruddnick LR. Lubricant additives chemistry and applications. New York: Marcel
techniques in the field of lubrication chemistry. The developed Dekker Inc; 2003.
[22] Widder L, Ristic A, Brenner F, Brenner J, Hutter H. Modified-atmospheric
methodology lays the foundations for the identification of further pressure-matrix assisted laser desorption/ionization identification of friction
additive degradation products so far unknown and thus systematic modifier additives Oleamid and ethoxylated tallow amines on varied metal target
investigations of the influence of additive degradation products on materials and Tribologically stressed steel surfaces. Anal Chem 2015;87:11375–82.
[23] Gabler C, Pittenauer E, Dörr N, Allmaier G. Imaging of a tribolayer formed from
friction and wear, accordingly with focus on those degradation ionic liquids by laser desorption/ionization-reflection time-of-flight mass spectro-
products that are involved in tribofilm formation. Thereby, a more metry. Anal Chem 2012;87:10708–14.
complete and confirmed mechanism of ZDDP degradation is of [24] Pisarova L, Totolin V, Gabler C, Dörr N, Pittenauer E, Allmaier G, et al. Insight into
degradation of ammonium-based ionic liquids and comparison of tribological
particular interest. performance between selected intact and altered ionic liquid. Tribol Int
2013;65:13–27.
Acknowledgements [25] Kagohara Y, Takayanagi S, Haneda S, Fujita M, Iwai Y. Tribological property of
plain bearing with low frictional layer. Tribol Int 2009;42:1800–6.
[26] Hu JQ, Wei XY, Dai GL, Fei YW, Xie F, Zong ZM. Tribological behaviors and
This work was supported by Daido Metal Co., Ltd – organizační mechanism of sulfur- and phosphorus-free organic molybdate ester with zinc
složka. Parts of the work were also funded by the "Austrian COMET- dialkyldithiophosphate. Tribol Int 2008;41:549–55.
[27] Kawamura M, Fujita K. Antiwear property of lubricant additives for high silicon
Program" in the frame of K2 XTribology (project no. 849109) and
aluminium alloy under boundary lubricating conditions. Wear 1983;89:99–105.
carried out within the "Excellence Centre of Tribology" (AC2T research [28] Spikes H. The history and mechanisms of ZDDP. Tribol Lett 2004:17.
GmbH). [29] Martin JM. Antiwear mechanisms of zinc dithiophosphate: a chemical hardness
approach. Tribol Lett 1999;6:1–8.
[30] Naveira-Suarez A, Tomala A, Pasaribu R, Larsson R, Gebeshuber IC. Evolution of
References ZDDP-derived reaction layer morphology with rubbing time. Scanning
2010;5:294–303.
[1] Kobayakawa H, Tsuji H, Kawakami N, McAleese C. A study of resin overlay bearing [31] Martin JM, Onodera T, Minfray C, Dassenoy F, Miyamoto A. The origin of anti-
material for recent automotive engines. SAE Technical Paper; 2013. 01-1394. wear chemistry of ZDDP. Faraday Discuss 2012;156:311–23.
[2] Zhang Y, Tudela I, Pal M, Kerr I. High strength tin-based overlay for medium and [32] Topolovec-Miklozic K, Forbus RT, Spikes A. Film thickness and roughness of ZDDP
high speed diesel engine bearing tribological applications. Tribol Int antiwear films. Tribol Lett 2007:26.

528