Influence of Electrochemical Potentials on the Tribological Behavior of Silicon Carbide and Diamond-Coated Silicon Carbide
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Abstract
Due to their high corrosion stability in combination with advantageous tribological performance, sintered silicon carbide ceramics are widely used in industrial applications. Both the corrosion stability and the tribological behavior can be affected by electrochemical processes. Tribological investigations were carried out using an electrochemical three electrode setup. The influence of electrochemical potentials on the friction and wear behavior of different sintered SiC materials in 1 M NaCl-solution was investigated to analyze the complex interplay between mechanical, chemical, and electrochemical interactions during tribo-corrosion. The results revealed that friction and wear of SiC were decreased under cathodic electrochemical polarization depending on the material composition. In addition, tribological tests at different electrochemical potentials showed that the coefficient of friction can be switched immediately. The results indicated that the tribological behavior is strongly affected by the increased double-layer repulsion due to the electrochemical potentials, which supports the hydrodynamic lubrication.
Keywords
Potential-controlled friction Electric conductive-sintered silicon carbide Diamond-coated silicon carbide Wear analysis Friction mechanisms1 Introduction
Due to their low friction in aqueous media and high corrosion and wear resistance silicon carbide ceramics (SiC) have become standard materials for slide bearings and face seals in pumps [1, 2, 3]. However, in aggressive media chemical or electrochemical corrosion processes of these materials may occur. Celis et al. [4] discussed the complex interplay between mechanical and chemical mechanisms during tribo-corrosion. Tribochemical reactions of water with the ceramic contact surfaces are important for a stable lubrication regime [5]. It is assumed that these chemical reactions are responsible for the formation of superlubricious phases i.e., to tribological regimes with nearly zero friction [6, 7]. In an aqueous environment, the friction coefficient of SiC sliding pairs reaches values below 0.1 [8] and tribochemical reactions in the sliding contact cause a smoothening of the sliding surfaces [9, 10, 11]. These tribochemical reactions cause mild wear conditions, and the removal of surface asperities favors hydrodynamic lubrication even at very low lubricant viscosity. Knowledge of the electrochemical and tribochemical mechanisms is the key to improve the operational safety, availability, and durability of ceramic components in many applications such as pumps in the chemical industry or power plants. Recently, a detailed investigation of the electrochemical corrosion of different SiC materials were carried out using potentiodynamic polarization measurements in acidic and alkaline environments [12, 13, 14, 15, 16]. They observed the formation of a thin layer of SiO\(_{2}\) on the surface in acid (HCl, HNO\(_{3}\)) and a more pronounced active corrosion in NaOH. The electrochemical corrosion rate strongly depends on the specific electric resistance of the materials. With increasing specific electric resistance, the electrochemical reaction rate reduces. Beside this overall dependence, also deviation of the electrochemical reaction between different grains and even inside individual grains was found. In liquid phase-sintered materials (LPS SiC) and in silicon infiltrated materials (SiSiC), a core rime structure of the grains was observed with more pronounced corrosion at the rims [13, 16, 17]. This behavior is caused by the different doping levels of the core and rim resulting in different specific electric resistances and electrochemical corrosion. Additionally, the analysis of the corrosion rate of individual grains of a solid phase-sintered SiC material (SSiC) reveals that the corrosion rate of the individual grains show a large scattering [14, 15]. This scattering could not be explained by different doping levels but only by the different grain boundary resistivities. Herrmann et al. [14] investigated the electrochemical corrosion of silicon carbide ceramics in sodium hydroxide at different potentials and found under anodic potential a specific recession of certain SiC grain surfaces, which correlated with the local resistivities.
In the past two decades, it has been reported in several works that the friction behavior of metal–metal and metal–ceramic contacts in surfactant-containing solutions can be actively influenced by the application of electrochemical potentials [18, 19, 20, 21]. This mechanism was named potential-controlled friction (PCF) from Chang et al. [22] and Meng et al. [23]. However, most of these studies are focused on metals that have high electric conductivity. There have also been some investigations on the influence of electrochemical potentials on the tribological behavior of steel–ceramic sliding pairs [23, 24] and steel in contact with hard coatings (e.g., TiN-coatings [25]). In addition, it was shown that there is a clear influence of electrochemical potentials on the tribological and corrosion damage behavior of ceramic components in technical systems [26]. Potential-dependent changes in the coverage and stability of an adsorbed lubricating layer on a steel surface lead to different tribological behaviors [27]. Brandon et al. found the lowest wear at a electrochemical potential of \(-\)1000 mV against standard hydrogen electrode (SHE). A maximum wear was measured at anodic potentials due to the competing effects of oxidative corrosion and protective film formation. In addition, Kalin et al. [28] investigated how electrochemical parameters affect the properties of the surface layer, the physico–chemical and load-carrying properties of the lubricating film. They showed that the wear of alumina and zirconia can be strongly affected by electrochemical parameters. It is suggested that the surface charge, the associated pH value and the zeta-potential influence the result of tribological tests. Due to the rolling of a cylinder, the charge distribution in the electric double layer (EDL), and also the friction force, changes [29].
In these tribological systems, which are influenced by electrochemical potentials, electrokinetic interactions between the sliding surfaces are suggested as important tribological mechanism [30]. Kelsall et al. [18] suggested that increased double-layer repulsion could reduce the friction coefficient and wear because the interfacial potential of a material surface is closely related to the tribological performance. Bai et al. [31] and other researchers [32, 33] noted that the electric double layer at very thin lubricating films lead to an electrokinetic effect by which the surface near viscosity is increased [34]. As consequence, hydrodynamic lubrication is partly ensured and the friction coefficient is reduced. A mathematical model of electro-viscosity is described by Zuo et al. [35]. They discussed the hydrodynamic and elastohydrodynamic water lubrication cases and showed that the apparent viscosity depends on the sum of two zeta potentials. Therefore, the electric double layer leads to an increase of the viscosity of very thin films. By analogy, Zhang and Umehara [36] and Chen et al. [37] suggested that the electric double layer generates a repulsive force and thus promotes hydrodynamic surface separation in sliding contacts. More details about the effect of the electric double layer on the friction properties were described by Kelsall et al. [18] and Zhu [38]. Electric double layer and boundary slip are coupled effects which influence the apparent viscosity and one-dimensional slide-bearing performance [39]. The electric double layer is influenced in the presence of electrochemical potentials and at high shear rates the charge movement in the diffuse layer causes a significant increase of the viscosity, which in consequence stabilizes hydrodynamic conditions [40].
As part of preliminary investigations of the authors, evidence was found that under certain electrochemical conditions friction, wear and corrosion performance can be significantly influenced by electrochemical potentials using electrically semiconductive ceramics [41, 42]. These preliminary investigations resulted in a patent for an apparatus and a method for operating a tribologically stressed component under the influence of electrochemical potentials [43]. But the fundamental understanding of the tribological behavior of SiC in aqueous solutions is still deficient, because of the complex interplay between mechanical, chemical, and electrochemical interactions during tribo-corrosion [44]. In addition, the demand for higher energy efficiency of technical systems leads to increasing requirements for ceramic bearings. Therefore the aim of this work is to carry out a fundamental study to investigate the influence of electrochemical potentials on friction and wear. In particular, different electric conductive SiC materials were used to study the influence of electrochemical potentials on the tribological behavior. In addition, wear analysis was conducted after the friction tests to analyze the tribological mechanisms.
2 Experimental
2.1 Electrochemical Characterization
The electrochemical measurements of the SiC materials were conducted using three electrode setup. At first, the electrochemical window (ECW) was measured for 1 M NaCl-solution using cyclic voltammetry (CV) with a scan rate of 100 mV/s. In addition, the open circuit potential (OCP) of the material was measured for 1000 s and subsequently the corrosion potential (\(E_{\text{corr}}\)) was determined using linear scan voltammetry (LSV) with a scan rate of 1 mV/s. The measurements were performed using an Ag/AgCl-reference electrode, a platinum counter electrode and a pin as working electrode. The surface area of the pin was 116.2 mm\(^2\) and the measurements were carried out without rotation or loading. The LSV measurements were conducted immediately after immersion of the pins.
2.2 Tribological Tests
Tribological experiments were performed using a tribometer (TRM 1000, Wazau GmbH, Germany) with a rotating shaft on the upper side and a stationary setup fixed on the lower side. Two different geometries (Fig. 1) were used for the tribological tests: pin-on-disk and ring-on-disk. A three electrode test setup was used in which the stationary SiC material was set as working electrode. The pin-on-disk contact geometry was used to analyze the tribochemical effects and to select an appropriate material for the more application specific tests with the ring-on-disk geometry. The pin-on-disk tests were conducted at a load of 50 N which corresponds to an Hertzian contact pressure of 1 GPa. The initial point contact of the rounded pin-tip (radius: 5 mm) changes during the tribological test to a surface contact due to wear. The applied electrochemical potentials were \(-\)1000 and +500 mV against Ag/AgCl. These electrochemical potentials were chosen to have a maximum and comparable cathodic and anodic potential related to OCP within the electrochemical stable window for a 1 M NaCl-solution, because the adsorption and stability of a lubricating surface layer strongly depends on the electrochemical potential [27]. The ring-on-disk tests were carried out at loads of 100 and 200 N which corresponds to 0.2 and 0.4 MPa contact pressure (contact area: 552 mm\(^2\)), which was kept constant over the whole testing time. For each tribological test, new samples were used. The relative low sliding speeds of 0.1 and 0.2 m/s were chosen to analyze friction and wear in the mixed lubrication regime, because the lubricant film thickness is mostly influenced by velocity besides the constant parameters viscosity and contact pressure. The film thickness at the used test parameters is calculated to appr. 0.2 \(\upmu\)m for pin-on-disk and appr. 8 \(\upmu\)m for ring-on-disk geometry [45]. It is described in literature that the transition from hydrodynamic to mixed lubrication takes place at a ratio of film thickness to composite surface roughness of 3 [46]. The roughness (Ra) of the ceramics is between 5 and 10 \(\upmu\)m and so this ratio is much lower. To analyze the samples at higher anodic potentials, in relation to the OCP, the electrochemical potentials were slightly modified to \(-\)800 and +800 mV against Ag/AgCl. In both test setups, the lower stationary sample was set as the working electrode. The counter body (disk or ring) was made of the same material as the pin. The electrochemical potential was measured between the working electrode (WE, testing sample: SiC) and the reference electrode (RE: Ag/AgCl). The necessary current flow to maintain this potential was applied between the working electrode and the counter electrode (CE: platinum). The galvanic parameters were assessed before the test specimens were brought into contact. In a second step, the normal load was applied and the tribological test was started. In addition, it must be noticed that at tribological tests the counterbody gets in contact with the working electrode and so the electrochemically influenced area increases. The real surface area can be estimated to 700 mm\(^2\) at pin-on-disk and 2800 mm\(^2\) for ring-on-disk geometry.
Three electrode test setup for electrotribological measurements (WE: testing sample, RE: Ag/AgCl, CE: platinum): a pin-on-disk geometry; b ring-on-disk geometry
The results of the wear analysis are explained in Sect. 3.3. After the tribological tests, the surfaces were analyzed using white light interferometry to measure the wear volume and evaluate the topography of the surface. To investigate deposits and wear debris (thin SiO\(_2\)-layers) the Oxford Instruments thin film measurement tool [47, 48] was used [14]. With this tool surface layers between 1 nm and 1 \(\upmu\)m in thickness can be measured.
2.3 Material
Material characteristics of the SiC materials for pin-on-disk tests
| Characteristic | SSiC-1 | SiSiC | SSiC-2 |
|---|---|---|---|
| Phases | SSiC | SiC/Si | SSiC |
| Supplier | FCTa | H.C.S.b | ESKc |
| Additive types | Al, N | – | Al |
| Elastic modulus (GPa) | 406 | 343 | 440 |
| Spec. electr. res. \((\Omega \,{\text {cm})}\) | 400 | 0.01 | 250 |
| Vickers hardness (HV) | 3030 | 2716 | 2946 |
| Roughness (\(\upmu\)m) | |||
| Ra | 13.7 | 5.20 | 10.2 |
| Rz | 149.6 | 142.70 | 96.1 |
Surface analysis of the SiC-ceramics using field emission scanning electron microscope (FESEM)
Material characteristics of the SiC materials for ring-on-disk tests
| Characteristic | SSiC-3 | Diamond-coated | ||
|---|---|---|---|---|
| Ring | Disk | Ring | Disk | |
| Supplier | EagleBurgmanna | EagleBurgmannb | ||
| Electric resistance | 7 k\(\Omega\) | M\(\Omega\)-range | 0.05 k\(\Omega\) | 5 k\(\Omega\) |
3 Results
3.1 Electrochemical Characterization
Electrochemical characterization of SSiC-1-, SSiC-2-, and SiSiC-pins in 1 M NaCl-solution: a result of cyclic voltammetry for a 1 M NaCl-solution; b open circuit potential (OCP) over time; c measurement of the corrosion potential with linear scan voltammetry (LSV, scan rate: 1 mV/s)
Results of the electrochemical characterization
| Parameter | SSiC-1 | SiSiC | SSiC-2 |
|---|---|---|---|
| \(E_{\text {corr}}\) (mV versus Ag/AgCl) | \(-\)65 | \(-\)234 | \(-\)18 |
| \(i_{\text {corr}}\) (nA/cm\(^2\)) | 24.1 | 25.9 | 15.5 |
| \(\beta _{\text {c}}\) (mV/decade of current) | 70 | 120 | 79 |
| \(\beta _{\text {a}}\) (mV/decade of current) | 338 | 146 | 524 |
| Corrosion rate (\(\upmu\)m/year) | 45 | 52 | 30 |
3.2 Pin-on-Disk Tests
Friction coefficients at different electrochemical potentials that were manually switched to different values (\(-\)1000, +1000, \(-\)1000, 0 mV vs. Ag/AgCl) using pin-on-disk geometry (1 mol NaCl, 50 N; 0.1 m/s): a SSiC-1; b SiSiC; c SSiC-2
Change of the coefficient of friction of SiSiC at different electrochemical potentials and test parameters in relation to OCP
Results of the friction tests at a constant electrochemical potential with pin-on-disk geometry using SSiC-1 (1 M NaCl, 50 N; 0.1 m/s, 2 h): a at OCP without external potential; b at cathodic and anodic potential; c current measured during friction test at cathodic and anodic potential
Coefficient of friction at a constant electrochemical potential using pin-on-disk geometry (SiSiC; 1 M NaCl, 50 N; 0.1 m/s, 2 h): a test at OCP without external potential; b test at cathodic and anodic potentials; c current measured during friction test at cathodic and anodic potential
Electric charge transfer Q and change of the COF due to electrochemical potentials in relation to OCP using pin-on-disk geometry
| Material | el. potential | COF (%) | Q |
|---|---|---|---|
| SSiC-1 | \(-\)1000 mV versus Ag/AgCl | +6 | 0.027 C |
| +500 mV versus Ag/AgCl | +120 | 0.179 C | |
| SiSiC | \(-\)1000 mV versus Ag/AgCl | \(-\)15 | 0.543 C |
| +500 mV versus Ag/AgCl | \(-\)6 | 0.567 C |
3.3 Wear Analysis
Analysis of the wear scar of the disk after pin-on-disk test with constant electrochemical potential using white light interferometry (1 M NaCl, 50 N; 0.1 m/s; 2 h): (above) SSiC-1; (below) SiSiC
Wear analysis of pin-on-disk (1 M NaCl, 50 N; 0.1 m/s; 2 h): a wear volume of the pin; b wear volume of the disk
Change of wear due to electrochemical potentials in relation to OCP using pin-on-disk geometry
| Material | El. potential | Wear volume | |
|---|---|---|---|
| Disk (%) | Pin (%) | ||
| SSiC-1 | \(-\)1000 mV versus Ag/AgCl | \(-\)17 | \(-\)21 |
| +500 mV versus Ag/AgCl | +171 | +45 | |
| SiSiC | \(-\)1000 mV versus Ag/AgCl | \(-\)13 | \(-\)14 |
| +500 mV versus Ag/AgCl | +12 | \(-\)7 | |
Analysis of the wear scar of the pins after pin-on-disk friction test with scanning electron microscope (1 M NaCl, 50 N; 0.1 m/s; 2 h): a SSiC-1 (+500 mV vs. Ag/AgCl): SiO\(_{2}\) debris besides a smooth wear surface; b SiSiC (OCP): cracks in the SiC and grinding marks on the silicon; c SiSiC (\(-\)1000 mV vs. Ag/AgCl): also partially cracks in the silicon
3.4 Ring-on-Disk Tests
Friction tests with at different electrochemical potentials were started at OCP, afterward the potential was changed as shown in Fig. 12a, b. The friction values of SSiC-3 at OCP (SSiC) show that the friction coefficient reached constant value of 0.11 after a 30 min running-in period. In contrast to the subsequent cathodic polarization with nearly no change in COF, there is a strong COF change at anodic potential (Fig. 12a). This increase of the COF is reversible because after switching the potential to OCP the COF decreases to its starting level after running-in.
Influence of electrochemical potential on the coefficient of friction using ring-on-disk geometry (1 M NaCl): a SSiC-3 (100 N; 0.2 m/s); b diamond-coated SSiC (200 N; 0.2 m/s); c COF under various tribological test conditions for diamond-coated SSiC
Results of friction tests using ring-on-disk geometry (1 M NaCl; 100 N; 0.2 m/s): COF of SSiC-3 at three successive 20 h friction tests at a constant electrochemical potential
4 Discussion
In previous publications, several tribological mechanisms for water-lubricated SiC sliding contacts have been proposed [5, 7, 10, 11, 30, 32, 57, 58]. Most of them identified tribochemical reactions as a clue for the explanation of low and stable friction coefficients. The mild chemical wear may lead to the formation of very smooth surfaces and tribochemical oxidation products may act as lubricious oxides. Only few papers recognized electrochemical effects, especially electrokinetic effects a possible mechanism to significantly influence friction and wear [34, 41, 42]. As shown in this work, electrochemical potentials strongly influence the tribological behavior. Therefore the formation of an electric double layer (EDL), which consists of a compact layer (ions are strongly attracted to the wall surface and are immobile) and a diffuse double layer (ions are affected less by the electrical field and are mobile), is assumed to initiate the changed tribological behavior using electrochemical potentials. An EDL is formed on a solid surface due to an electrochemical potential. The thickness of the diffuse EDL depends upon the electric potential of the solid surface. The electrical potential at the boundary between the compact layer and the diffuse layer is called the zeta potential. In addition, shear of EDL leads to a movement of the ions in the mobile part of the EDL and this causes an electrical current (streaming current) and this sets up an electrical field which leads to an electrical potential, the streaming potential [59]. This electrokinetic effect [18, 38, 40] then leads to an increase of the surface near viscosity and causes an increase of the electrostatic repulsion, especially at a very thin lubricating film [18, 31, 32, 33, 34]. These mechanisms support the hydrodynamic lubrication, which can be observed due to the change of the coefficient of friction using electrochemical potentials. In addition, it can be assumed that the effect of EDL is the most important mechanism concerning the change of the tribological behavior, because there is also a very strong influence of electrochemical potentials visible by using diamond-coated surfaces at which tribochemical reactions on the surface can be excluded (Fig. 12).
The results of this investigation but also show that SiC materials of different material compositions show significantly different results in both sliding geometries (i.e., pin-on disk and ring-on ring). This can be mostly explained by different electrical conductivities of the ceramics. The grain boundaries in SiC materials have an higher electrical resistivity in comparison to the grains [17, 60, 61, 62]. Therefore the current through the grain and thus the value of corrosion will be different for different grains due to the distribution of grain boundary resistivities [14]. Because of this electric behavior not only the electric conductivity of the whole test specimen is relevant, but also the microscale variation of the conductivity due to microstructural effects. As shown by Herrmann et al. [14] these local variations of electric conductivities lead to locally different electrochemical corrosion rates. But it can also be assumed that electric double layers can only be influenced by electrochemical potentials when the electric activity of the surface is sufficiently high. The formation of a SiO\(_{2}\) surface layer was provided after electrochemical corrosion experiments of SSiC in \({\text{H}}_{2}{\text{SO}}_{4}\) at different voltages [14]. The grains for which the grain boundary resistivity is low will exhibit a high current density and therefore form thicker SiO\(_2\) layers [14]. Therefore the formation of an SiO\(_{2}\) surface layer under electrochemical potentials could have a dominating influence concerning the friction behavior.
In the case of ring-on-ring sliding geometries, the contact area is rather large (552 mm\(^2\)) and the contact pressure is rather low (0.2 MPa). Under these conditions, the influence of electrochemical potentials is visible when the electric conductivity is sufficiently high. In our investigation the electrical resistance of SSiC-3 was high (7 k\(\Omega\)), but the diamond-coated surfaces had very good conductivity. As a result, the friction coefficient was varied between 0.025 and 0.06. On diamond surfaces the formation of solid oxide phases on the surface can be excluded. But it has to be discussed, if only EDL effects are responsible for this change of COF. The electrochemical potentials could also simply reduce the amount or density of dangling bonds in the sliding surfaces that are formed during tribological mechanisms. The passivation of dangling bonds may then reduce adhesion and interaction of surfaces in solid–solid contact events. These tests using ring-on-disk contact geometry show considerable benefits with electrochemical potentials, which may also be obtained in real applications like slide bearings and face seals.
The influence of electrochemical potentials on the COF also strongly depends on the tribological test parameters. At low sliding speeds a higher change of COF was observed. This is an indication for the enhancement of hydrodynamic lubrication, which are assumed to arise due to the formation of an electric double layer (increase of repulsion force, increase of surface near viscosity).
5 Conclusions and Outlook
- Pin-on-disk tests
- *
The coefficient of friction can be switched for SiSiC and SSiC-2 immediately by the application of an electrochemical potential.
- *
SSiC-1 did not show an instantaneous change of the friction value.
- *
Friction and wear can be strongly influenced with electrochemical potentials. SSiC-1 shows higher interference with electrochemical potentials as SiSiC, due to different electric conductivities of the materials.
- *
A correlation of wear volume and electric charge transfer was found. Higher wear is connected to higher electric charge transfer during the test.
- *
- Ring-on-disk tests
- *
An anodic potential leads to an increase of the coefficient of friction using SSiC-3, whereas at cathodic polarization there is no change in relation without electrochemical potential.
- *
The coefficient of friction can immediately be changed using Diamond-coated SSiC by \(-\)35 % (cathodic) and +45 % (anodic).
- *
At constant electrochemical potentials over a testing time of 60 h using SSiC-3, there was a strong decrease of the coefficient of friction at cathodic potential.
- *
Notes
Acknowledgments
The authors gratefully acknowledge the AIF (Arbeitsgemeinschaft industrieller Forschungsvereinigungen, IGF-Vorhaben 390ZBG019 Tribokorrosion) for funding this project.
Compliance with Ethical Standards
Conflict of interest
On behalf of all authors, the corresponding author states that there is no conflict of interest.
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