Wear 249 (2001) 172181

High temperature phase transformations under fretting conditions

Mitjan Kalin , Joe Viintin
Centre for Tribology and Technical Diagnostics, University of Ljubljana, Bogii eva 8, 1000 Ljubljana, Slovenia c

Abstract Different and sometimes contradictory assessments of the importance of thermal and mechanical effects on tribochemical reactions in fretting have been reported in the literature. In our study of fretting wear between steel and silicon nitride ceramics, tribochemical reactions were determined to play the critical role under both non-lubricated and oil-lubricated conditions. Various possible effects on the resulting tribological interfaces are discussed based on the experimental evidence of microstructural changes, phase transformations, various thermodynamic and ash temperature calculations, and interaction couple experiments in which chemical wear was isolated by controlled mechanical and thermal parameters. It is shown here that a very high temperature must be considered as the most important factor inuencing in tribochemical reactions and various phase transformations, even under conditions which are usually considered to be low speedlow temperature conditions. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Fretting; Tribochemistry; Temperature; Phase transformation

1. Introduction It has already been recognised that tribochemical reactions determine the sliding and fretting wear behaviour of silicon nitride ceramics under various conditions [19]. Nevertheless, the details of the mechanisms and chemical reactions are still not well understood. That is to say, there sometimes exists a considerable discrepancy between the reported contact temperatures and the interpretation of the inuence of mechanical and thermal effects on the observed phase transformations. Due to the simultaneous effect of thermal and mechanical parameters in every wear experiment, it is necessary to use indirect evidence of certain phenomena, observed in the subsequent surface analysis, since in situ techniques are still not broadly available and are not suitable for all material combinations. This of course always leaves some uncertainty concerning the reported hypothesis. The main reason why mechanical factors are sometimes considered as more responsible for having the major inuence in tribochemical reactions in fretting is in the low sliding speed, characteristic of fretting. Consequently, the contact temperatures should be low. However, such an assumption holds only for the overall (bulk) contact conditions, while the exact contact conditions (spot-to-spot temperatures, inuence of entrapped wear particles, i.e. third body effects, local pressures at the asperities, etc.) are not actually known. Nevertheless, a hypothesis was proposed
Corresponding author. Tel.: +386-1-425-1188; fax: +386-1-425-1188. E-mail address: mitjan.kalin@ctd.uni-lj.si (M. Kalin).

[10], which explained tribologically induced phase transformations for steels mainly by mechanical inuences. However, some of the parameters discussed cannot be applied for all materials. For example, very high shear strains possible for steels which could transform the chemical state of the contacting materials cannot be achieved in brittle ceramic materials. On the other hand, tribochemical changes observed at the interface are often the same as in chemical reactions which are much more favourable at high temperatures [9,1114]. At least, such transformations are commonly observed when high temperatures are determined by experimental set-ups [2,3,15,16], although the relative velocity is low. This suggests that temperature is an important factor, which certainly enhances creation of tribolayers and should therefore be examined more carefully. It is clear that it is extremely difcult or impossible to come to a completely denite conclusion about the most inuential factors in tribochemical reactions and about possible maximum contact temperatures which can result in tribochemical changes at the interface if both mechanical and thermal effects can simultaneously inuence the result. Moreover, different contact conditions probably imply different inuencing parameters, which should therefore be determined for every tribological situation separately. In this paper, we present some evidence for the presence of very high contact temperatures in a gross slip fretting regime which can be deduced from various experimental techniques carried out, i.e. fretting wear experiments and interaction couple experiments in which chemical wear was isolated by controlled mechanical and thermal parameters,

0043-1648/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 0 4 3 - 1 6 4 8 ( 0 1 ) 0 0 5 4 9 - X

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and by performing ash temperature and various thermodynamic calculations. The results are also supported by a literature survey. Two very different counter-materials, i.e. ceramic and steel and also two very different contact conditions, i.e. non-lubricated and oil-lubricated give quite different features and results, which allow us to investigate the phenomena from different perspectives under very similar or identical testing parameters.

2.2. Chemical wear experiments The materials for the static interaction couples, i.e. for the isolated chemical wear experiments, were the same as those used in the fretting wear experiments, prepared by electrical discharge machining (EDM) and cut from the original specimens used in the fretting experiments. A chemical wear investigation employing interaction couple experiments was performed by pressing together polished slices of steel and ceramic. Before putting the specimens into the pressing apparatus of the machine, they were ultrasonically cleaned and prepared as a sandwich-type specimen set-up, having a ceramic specimen between two steel specimens [17]. In order to compare the fretting wear results over the whole range of possible testing contact conditions with the results of the interaction couples, a broad range of pressures and temperatures had to be selected for the static interaction couple experiments. Plastic deformation is another factor inuencing the tribochemical reactions. To be able to evaluate qualitatively the inuence of plastic deformation in our experiments, the relevant tests were performed in both the elastic and plastic regions of the steel, which were experimentally determined [18]. The experimental data and a scheme of the conditions are presented in Table 1 and Fig. 1, respectively. The selected temperaturepressure test conditions were achieved using two different testing machines, one with the ability to apply very high loads at relatively low temperatures (LTHP) and another in which only high temperatures could be obtained at low loads (HTLP). Furthermore, in order to study the effect of oxygen on the chemical

2. Experimental For the purposes of this paper, only basic information on the materials, experimental procedures and techniques of analysis are given, while the details are comprehensively presented elsewhere for fretting experiments [79], chemical wear experiments [9,17,18] and ash temperature calculations [9,19]. 2.1. Fretting wear experiments All fretting wear experiments were performed using a commercially available high frequency fretting machine having ball-on-at testing contact geometry. The lower, at specimens made from bearing steel (DIN100Cr6) were xed in the base, while the upper specimens, i.e. silicon nitride balls (NBD-l00), were xed in the oscillating holder [7]. Experiments were performed in non-lubricated conditions (ambient, RH about 50%) and in oil-lubricated conditions. A small amount of mineral oil (ISO VG 220) was spread on the surface of the at specimen in lubricated conditions. During the test, no additional oil was supplied to the contact. A normal force of 88 N resulting in an initial Hertzian stress of about 2 GPa was applied through the loading cell at each contact. The frequency of oscillation was constant for all experiments at 210 Hz. The displacement amplitude was increased in ve steps from 5 to 50 m. Due to the constant frequency of oscillation, the maximum sliding velocity increased with increasing amplitude from 0.0067 to 0.067 m/s. Before and after the test, the specimens were ultrasonically cleaned. The worn surfaces of the at and the ball were examined by means of light microscopy, stylus tip prolometry, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Auger electron spectroscopy (AES) and transmission electron microscopy (TEM).
Table 1 Experimental conditions of the static interaction couples Testing machine LTHP 20 C Pressure (MPa) Elastic region Elastic limit Plastic region 2400 2864 4000 300 C 1414 1725 3000 500 C 613 687 750

Fig. 1. Schematic presentation of pressure and temperature variations in the static interaction couple experiments.

HTLP 700 C 97 113 120 1000 C 3.6 360 1100 C 3.5 130 1150 C 4 145 1200 C 4 123

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Table 2 Pre-set and/or measured parameters from fretting wear experiments Environment Displacement amplitude ( m) Maximum stroke velocity (m/s) Coefcient of friction Frequency of oscillation (Hz) Normal force (N) Non-lubricated 5 0.0067 0.68 210 88 25 0.0336 1.18 50 0.0672 1.2 Lubricated 5 0.0067 0.58 210 88 25 0.0336 0.85 50 0.0672 0.7

reactivity of selected materials, and to compare it with the fretting results, interaction couple experiments were performed in which oxygen was introduced into the interaction zone. Both furnaces used for the static experiments only operate under vacuum or inert gas conditions. Therefore, oxygen was introduced by pre-oxidation of the steel. The steel was oxidised in air at the same temperature as used in the interaction couple experiment. 2.3. Flash temperature calculations For the purposes of this work, we present here the results of the Greenwood-Greiner model [20], which was developed especially for fretting conditions. However, in our extensive study on ash temperatures in fretting contacts, we performed calculations based on 10 different theoretical models and three different methods for real contact area determination [9,19]. The results presented here are in accordance with the overall results from the above-mentioned investigation. The parameters used in the calculations are based on the results from fretting wear experiments [7]. Some of these were pre-set as machine-controlled parameters, and some are experimentally obtained values (Table 2). Since the maximum possible temperature rise was of special interest, the highest coefcient of friction measured in the experiments under each fretting condition was used in the calculations. The real contact area was calculated by rather simple, but broadly accepted and used criteria, which determine the real contact area by dividing the normal force by the hardness of the softer material. Flash temperatures are calculted for non-lubricated and also for comparitive purposes for lubricated conditions. Although, the validity of the calculations from lubricated experiments can be debated, it should be pointed out that our pre-test oil-drop lubricating conditions were far from providing a continuous lubricating oil lm. Instead, a well-dened tribolayer was formed in the contact, and a combination of mixed and boundary lubrication was obtained with many dry contacts, as shown in [8,9]. Therefore, it is not reasonable to differentiate between our tribochemical layer and any other tribochemical layers obtained under non-lubricated conditions, because in both cases the interface has unknown and different properties from the ideal properties assumed in models, and a continuous lubricating lm was not provided.

3. Results 3.1. Fretting wear experiments Wear behaviour in our experiments was investigated in terms of lubrication conditions and displacement amplitudes, which were selected to vary from partial slip to a gross slip regime. The transition between the two regimes was determined using Mindlins theory [21]. For the compliance of the system used and measured values of the coefcient of friction, the critical amplitude was calculated to be around 15 m [9] (Fig. 2a). This was also conrmed by wear scar analysis, as suggested in [22]. Comparison between the wear loss under lubricated and non-lubricated conditions indicates signicantly different wear behaviours (Fig. 2b). While the wear volume increased almost linearly with increasing amplitude in non-lubricated conditions, an obvious peak value at 25 m amplitude was detected in lubricated fretting. Therefore, a transition occurred in the gross slip regime in lubricated fretting. The wear volume in non-lubricated conditions was about two orders of magnitude higher than in lubricated conditions (Fig. 2b). In lubricated conditions, the coefcient of friction was high in the rst stage of fretting, but remained high (about 0.6) only at an amplitude of 5 m (Fig. 3a). At higher

Fig. 2. (a) Critical displacement amplitude for the transition from a partial to gross slip regime; (b) wear loss as a function of displacement amplitude in lubricated and non-lubricated fretting.

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Fig. 4. Concentration of carbon in iron as a function of sputter time, obtained from AES spectra across the tribolayer created on a steel plate in lubricated fretting. Scale: 150 min of sputter time 1.5 m.

Fig. 3. Coefcient of friction as a function of testing time at different displacement amplitudes under (a) lubricated and (b) non-lubricated fretting.

amplitudes, it decreased sharply to a value of approximately 0.2. On the other hand, there were no changes or transitions in the coefcient of friction during the tests in non-lubricated conditions. At 25 and 50 m displacement amplitude, the coefcient of friction was higher than under lubricated fretting, even at the beginning of the test, i.e. 1.01.3, and remained high throughout the test (Fig. 3b). A somewhat lower but still constant value throughout the test (about 0.7) was obtained only at an amplitude of 5 m. The friction results are therefore consistent with a continuous increase of wear in non-lubricated conditions and with the observed wear transition in the gross slip regime under lubricated fretting. Such behaviour can also be explained by the SEM analysis. In lubricated fretting, mechanically dominated wear by fracture of the interface layer was observed at lower displacement amplitudes, i.e. in the partial slip regime, while in the gross slip regime, the surface layer plastically deformed and smeared [7,9]. AES and TEM analysis conrmed that a tribochemical reaction took place under these conditions [8]. The AES results show that there is an about 200300 nm thick layer close to the surface (neglecting the rst 150 nm due to cleaning of the surface) in which the concentration of carbon is about 10 wt.% (Fig. 4). In addition to this, the curve of carbon content across the tribolayer, gradually decreasing to the original steel composition of about 1 wt.% after approximately 1 m, shows points

of non-linearity at 7.0, 4.8 and 2.1 wt.% of carbon in iron. These points consistently and almost exactly correspond to the characteristic points of phase transformations in the FeC phase diagram, appearing at 6.67, 4.3 and 1.7 wt.%. The obvious shift to values of about 0.4 wt.% higher could be explained by the presence of other alloying elements in the steel (Cr, Si, Mn and Ni). TEM analysis revealed formation of carbides during fretting, since the broadly prevailing phase in this carbon diffusion layer was found to be Fe3 C [8]. No free carbon and no microcracks were found in the layer, which suggests that the layer is a tribochemical reaction product and not a tribomechanical mixture. In distinction to lubricated fretting, under non-lubricated conditions, wear occurred primarily by the intensive creation and spalling of the brittle tribochemical layer. AES and TEM analysis revealed severe silicon nitride oxidation, resulting in a 2 m thick amorphous SiO2 -rich phase with small precipitates of iron oxides, which were between 5 and 20 nm in diameter and had almost circular shape [7]. This implies that these are indeed precipitates and not wear debris. Furthermore, neither nitrogen nor Si3 N4 were found in the layer. These ndings again suggest that the layer is a tribochemical reaction product. 3.2. Chemical wear experiments Fig. 5 shows the morphology of the cross-section of the silicon nitridesteel couple tested at the highest temperature investigated, i.e. 1200 C under elastic conditions. Three regions can be clearly distinguished from Fig. 5, i.e. A, B and Y; however, it was found that region Y is actually composed of two regions, denoted as C and D. Region A represents the original Si3 N4 ceramic. Region B is the reaction layer on the ceramic side of the interaction couple incorporating some reaction products [18], whereas region Y refers to the steel side of the interaction couple. The contact plane between regions B and Y is the initial ceramicsteel interface which was determined by an inert ZrO2 marker, as reported

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Fig. 5. Interaction couple cross-section after 5 h at 1200 C and 4 MPa: (a) SEM image; (b) schematic drawing of regions in the cross-section from (a): (A) ceramic side; (B) reaction layer on the ceramic side, B/C boundary, initial steel/ceramic interface; (C) Si diffusion layer on the steel side; (D) unchanged bulk steel.

Fig. 6. (a) Reaction layer thickness and (b) Si diffusion layer thickness under elastic and plastic conditions of steel specimens as a function of temperature.

elsewhere [23]. EDS inspection of the steel in region Y close to the region B (initial ceramic/steel interface) revealed, besides the expected presence of Fe and Cr, a high Si content. The chemical composition of this material was the same as of the matrix in region B. This nding suggested a more detailed analysis of region Y; thus Si concentration line proles were determined across region Y. The layer which incorporates Si on the steel side was therefore denoted as region C, while D is the unchanged bulk steel material. The width of the reaction layer (region B) on the ceramic side and the Si diffusion layer on the steel side (region C) were systematically measured for all temperatures and pressures used under both elastic and plastic conditions (Fig. 6). For both the elastic and plastic regions, it was found that a strong bond between the steel and ceramic was formed only at temperatures of 1100 C or higher (Fig. 6a). At lower temperatures, the interaction couple always fell apart. Additionally, the thickness of the reaction layer and thus the chemical reactivity decreased with decreasing temperature, revealing the largely dominating effect of temperature. A similar situation was found by measuring the depth of Si diffusion into the steel. This depth decreased with decreasing temperature and it is very important to note that at temperatures below 700 C there was no observable Si diffusion (Fig. 6b). Quantitative evaluation of the thicknesses obtained at high and low pressures, i.e. under elastic and plastic conditions, showed that they are practically the same, since there is no statistically relevant difference between the

two conditions [9]. These experimental results are also in excellent agreement with thermodynamic predictions [9,24]. Fig. 7 shows details of the cross-section of the interaction couple tested at 1200 C in the presence of oxygen in the contact. EDS analysis revealed a number of different phases in the reaction layer which are reported in detail elsewhere [17]. Among others, a 510 m thick SiO2 -rich layer was found at the reaction front, as shown in Fig. 7. A limited amount of iron was also found in some regions of the SiO2 -rich layer, which could originate either from the matrix surrounding the layer or from iron oxides, similar

Fig. 7. Cross-section of an interaction couple tested at 1200 C in the presence of oxygen showing the SiO2 layer.

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to those that were determined by TEM analysis on the fretting specimens. This would suggest an even more direct correlation between the two types of experiments, but this was not investigated further and is therefore not conrmed. With decrease in temperature, the chemical reactivity also decreased and, exactly as in the absence of oxygen, at 500 C there were no traces of any chemical interaction between the contacting materials. Furthermore, at 1000 C or lower, no SiO2 layer was formed in the contact, while at higher temperatures clear and well-dened layers were always observed. This again conrms the critical inuence of the temperature on the formation of the SiO2 layer on silicon nitride. 3.3. Flash temperature calculations Fig. 8 represents ash temperatures calculated for non-lubricated and lubricated fretting contacts. It can be seen that the temperature increases with the displacement amplitude, and that the differences between the partial slip regime at 5 m amplitude and at the highest amplitude of 50 m in the gross slip regime are extremely high, especially for non-lubricated fretting. The temperatures under non-lubricated conditions were 57, 495 and 1010 C at 5, 25 and 50 m displacement amplitude, respectively. On the other hand, the calculated temperatures under lubricated conditions are lower, i.e. 49, 357 and 588 C at 5, 25 and 50 m displacement amplitude, respectively. However, it should be pointed out that the calculated real contact areas for the lubricated conditions are somewhat higher than that for non-lubricated ones and are between 10 and 20% of the apparent contact area [9]. Therefore, if the real area of contact decreases below 10% of the apparent contact area, the temperature at the highest amplitude used would increase rapidly and could reach values similar or higher to those under non-lubricated conditions. However, all these results should be taken as approximate due to many well-known uncertainties in such calculations [2528] and also the very large differences between various ash temperature models, as presented and extensively discussed in [9,19].

4. Discussion 4.1. Fretting wear 4.1.1. Lubricated conditions According to the results obtained under oil-lubricated fretting conditions, it is suggested here that the wear transition occurs due to the higher sliding speed at the critical amplitude of 25 m in the gross slip regime and consequently higher ash temperatures at the contact. This resulted in a tribochemical transformation of the interface which has much more benecial properties for wear and friction behaviour than the original materials. Such transformations and interfacial changes were not observed at amplitudes lower than the critical, i.e. in the partial slip regime, where mechanical wear by fracture dominated [7]. Furthermore, possible effects of better lubrication at higher amplitudes were also investigated [9], but were excluded from playing an important role in the observed transition. Critical information about the possible maximum contact temperature is provided by the TEM and AES results which conrmed the formation of carbides during fretting, while no free carbon or any mechanical damage were found in the investigated tribolayer, thus conrming the tribochemical rather than tribomechanical nature of the tribolayer. In addition, the more than 10 wt.% of carbon found in the 200300 nm thick layer close to the surface is above the equilibrium content of all the components in the binary FeC phase diagram except the melt, which implies a temperature of about 1145 C [9]. Moreover, the gradient of carbon content through the layer with points of non-linearity which almost exactly coincide with the points of the phase transformations in the binary FeC diagram suggest a temperature even higher than 1145 C. This tentative explanation is in agreement with thermodynamic models and with transitions to a low coefcient of friction (and low wear) occurring exactly at those conditions (Figs. 2 and 3). Furthermore, strong support to the suggested high temperature in the gross slip regime is also provided by the fact that the oil broke-down during the experiment, since it formed the source for carbonisation of the steel during the fretting experiments. Namely, in such experiments, it is not possible to mechanically break carbon bonds. The necessary temperature for thermal cracking of the oil used is about 400 C [29], which in this case determines the necessary minimum temperature to obtain a source for the carbonisation process. It is therefore clear that carbonisation occurs at even higher temperatures. In addition, thermal degradation of oil was also anticipated from visual inspection of the wear scars. That is to say, when the ball and at were separated after the test, the black thermally degraded oil was spread across the clean oil which surrounded the contact set-up (Fig. 9). This therefore clearly represents the lower necessary temperature at the 50 m displacement amplitude in gross slip fretting under lubricated conditions, but it does not restrict

Fig. 8. Flash temperatures at different displacement amplitudes in non-lubricated and lubricated fretting.

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Fig. 9. Optical micrograph revealing the thermal break-down of oil.

the possibility of even higher temperatures, as implied from the TEM and AES results. In addition, ash temperature calculations based on the GreenwoodGreiner model showed temperatures of around 600 C at 50 m amplitude (Fig. 8), which is consistent with the nding of the lowest possible temperature for oil degradation. However, since the coefcient of friction at the transition was practically the same as in non-lubricated fretting, where the more reliably calculated ash temperatures are about 1000 C, this temperature could be even higher. Moreover, using other criteria for the real contact area calculation and/or another theoretical ash temperature model would give sometimes lower and sometimes higher values [9,19]. In any case, ash temperatures could serve only as an approximation of the real contact temperature conditions due to the many problems associated with such calculations, discussed in [9,19,2528]. Therefore, even the ash temperature results under lubricated fretting seem to be in good agreement with the results and conclusions on possible maximum contact temperatures based on more reliable surface analyses. Fig. 10 schematically summarises the contact conditions in lubricated fretting based on the actual results previously

presented. It can be seen that when increasing the amplitude from the partial slip to the gross slip fretting regime and approaching the critical transition amplitude, the two most important parameters for increase in temperature also increase. Namely, the relative sliding speed and the coefcient of friction increase and remain high or even increase with further increase of displacement amplitude. Such behaviour is also in accordance with the observed wear mechanism transitions. On the other hand, apparent contact pressure decreases when approaching the transition amplitude due to the increase in the wear scar. Accordingly, mechanical pressure itself cannot be responsible for the observed transformations. Moreover, at lower displacement amplitudes, the pressure was even much higher, but phase transformations did not occur at these conditions. Therefore, this suggests that thermal effects are much more important for the observed tribochemical changes under these conditions than mechanical ones. It is however true that an increased coefcient of friction results in increased shear stresses and strains in materials, but it is not reasonable to assume that this was the cause for the transition in our experiments, especially since there exists clear evidence of thermal degradation of oil and no signs of deformation, dislocations or cracks were found by TEM in the phase-transformed layer. Moreover, the maximum shear stress is located below the surface [30], and therefore the phase transformations should originate and be the most pronounced below the surface, not at the interface, as was found in our analyses. On the contrary, the thermal effect of friction is the most pronounced at the interface, which was also conrmed by the AES analysis and therefore supports the critical inuence of temperature in the observed phase transformations. 4.1.2. Non-lubricated conditions Based on the high coefcient of friction and large amounts of silica (2 m thickness, high wear loss) produced in our experiments under non-lubricated conditions [7], even higher temperatures are expected compared to lubricated fretting. Although, silica was reported to form on silicon nitride in tribological applications even at room temperature, the amount of wear loss and the layer thickness must be considered in interpretation of the results. According to the following explanation, these two parameters seem to be the critical points of contradictions in reported key governing factors for the tribochemical reactions with silicon nitride. According to many isolated oxidation studies of silicon nitride, it was realised that for engineering applications, the silicon nitride oxidation type is the passive one, which occurs at high oxygen potentials. Here, a thin protective lm of SiO2 is formed on the surface of the ceramic which limits the rate of any further oxidation. Furthermore, it was found that in both dry and wet atmospheres, the oxidation process proceeds in a strongly diffusion-controlled manner [3135], which is consistent with the parabolic behaviour of the diffusion of oxidants through the protective silica layer in the stage of passive oxidation [33,34].

Fig. 10. A schematic presentation of wear transition amplitude in relation to the contact and testing parameters in lubricated fretting wear experiments.

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Although, in static oxidation experiments under steady conditions, better stoichiometry can be achieved, these ndings imply that in wear experiments at room temperature a silica layer can form, but because of the limited testing time its thickness is probably very low and also its amount is very small (depending on time). Furthermore, a literature survey revealed that in order to obtain a quantitatively relevant amount of oxidation products, isolated oxidation experiments are typically performed at temperatures above 1000 C and a test duration more than 100 h. In this respect, at room temperature, very thin even transparent wear debris of silica were found [36], which seems to be very consistent with the above results and explanations. Accordingly, the large amounts and relatively thick layer of silica produced in our fretting experiments suggest that the actual ash temperature should be very high because of the diffusion-controlled nature of silicon nitride oxidation, which is a temperaturetime-dependent process. Furthermore, ash temperatures above 1000 C were calculated for the selected fretting conditions, supporting the above explanations (Fig. 8). 4.2. Chemical wear experiments Since it is very difcult to determine the effects of mechanical and thermal parameters on tribochemical changes separately due to their simultaneous action, the following method gives an opportunity to isolate chemical wear by simultaneous control of thermal and mechanical effects, thus serving as indirect evidence of the major inuences in (tribo)chemical interactions between the materials in contact. It is, however, clear that such a method can only partially explain the actual dynamic/fretting situation, but can bring important information on basic chemical wear mechanisms. For example, such experiments were successfully applied in cutting tool applications [37,38]. Comparison between the eld tests and interaction couple experiments showed very good agreement, and thus it was concluded that they are relevant for prediction of the chemical wear in dynamic cutting tool situations. Because of the even larger discrepancy between static experiments and dynamic conditions in cutting tool applications compared to fretting (practically closed contact and very slow relative velocity), it is reasonable to assume that such experiments can be successfully applied also for studying chemical behaviour in fretting wear. From our results, it can be concluded that the chemical interaction of silicon nitride with steel and oxidised steel is strongly inuenced by the temperature. Below 700 C, no evidence of any interaction was found, while at temperatures above 1100 C, the reactivity was strongly enhanced. On the other hand, increased contact pressures, resulting in extensive plastic deformation of the steel, did not enhance chemical reactivity between the selected materials at any temperature (Fig. 6).

However, one of the very important facts in this study, which strongly favours the critical inuence of temperature in silicon nitride oxidation, is the observation that in the contact between steel and silicon nitride in the presence of oxygen, silica was formed only at temperatures of 1100 C and above (Fig. 7). Although, the contact times in static interaction couple experiments were much longer than those of the contacts in fretting experiments and thus more favourable for the progression of the diffusion process, no silica was formed at lower temperatures. This is again in excellent agreement with results of isolated Si3 N4 oxidation experiments [3135] and thermodynamic calculations based on Gibbs free energy criteria [9,17]. 4.3. General considerations The very different materials (steel/ceramics) and contact conditions (air-dry/oil-lubricated) in this study allowed us to use different indirect evidence from various viewpoints in order to investigate the tribochemical reactions observed. Additionally, ash temperature calculations and various thermodynamic calculations were employed for this purpose. Results on the isolated chemical wear of silicon nitride [9,17,18] partially presented in this paper and in many other previous studies of silicon nitride oxidation [3135] together with thermodynamic calculations strongly favour temperature as the key governing factor in the oxidation of silicon nitride, at least to the extent and thickness found in our fretting experiments, i.e. in the range of micrometres. In all these studies, it was shown that a silica layer is likely to form only above 1000 C. So the question arises, which mechanical mechanism could contribute in such a manner to completely change the oxidation mechanism and drastically increase the chemical reactivity, being the equivalent of about 1000 C? It was shown here that pressure (compressive stress) and plastic deformation cannot affect these reactions under the selected conditions. Shear is another parameter which could inuence the tribochemical reactions; however, high shear strains which could accelerate transformation of the chemical state of the contacting materials such as are possible for steels cannot be achieved in silicon nitride ceramics. In addition to this, the position of the shear plane at the interface, which accommodates the relative velocity and its changes with the dynamic contact situation and third body effects, is also difcult to establish, and it is therefore rather speculative to associate shear with the specic tribochemical changes. Moreover, the increased friction which increases shear stress also increases heat generation and thus the contact temperature, which again cannot exclude the possibility of high temperatures even when shear is considered to be predominant factor in the tribochemical reactions. The results of ash temperature calculations giving more than 1000 C under gross slip conditions at a 50 m displacement amplitude evidently support the above explanation. On the other hand, in lubricated fretting, there exists clear evidence that the contact temperature was at least about

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400 C, since the carbon bonds in oil cannot be broken by the mechanical parameters of fretting conditions, but rather this is a well-known thermal process. Furthermore, a tentative explanation which is in agreement with the thermodynamic model suggests temperatures even higher than 1145 C. Flash temperature calculations are also in good agreement with this suggestion, especially if the many uncertainties of such calculations are considered. Nevertheless, it must be explicitly stressed that high temperatures were obtained only under gross slip conditions, preferentially at the highest amplitude of 50 m. Moreover, our testing conditions with a 210 Hz oscillating frequency and 88 N normal load (initially 2 GPa) were much more severe than those typically reported in fretting. Therefore, the results are not inconsistent with most of the fretting studies reporting rather low contact temperatures, typically in partial slip regime or low amplitude gross slip fretting. The calculated ash temperatures showing only about a 50 C temperature rise in the partial slip regime (Fig. 8) and also the surface analysis under these conditions are in perfect agreement with those frequently reported general observations on contact temperatures in fretting. However, the experimental results described in this paper supported by the literature survey and ash temperature and thermodynamic calculations clearly show that very high ash temperatures resulting in phase transformations of materials must be considered even under low-speed conditions, such as fretting, which is in agreement with several previous investigations [1114]. A model explaining these processes in detail, including the discrepancy between micro- and macro-observations is however presented elsewhere [9,39]. Nevertheless, it is clearly very difcult to give a nal answer as to which are the most inuential factors for tribochemical reactions in various specic conditions, since in dynamic situations both mechanical and thermal effects act simultaneously and they also affect different materials differently. However, the results of our isolated chemical wear study showed good agreement with other experimental and theoretical approaches of this work, and with those of other previous applications [37,38]. Therefore, we believe that various isolated studies, such as our chemical wear investigation, should be used more often to provide clear evidence and better understanding of the basic mechanisms involved also in dynamic fretting wear situations. 5. Conclusions 1. The results reported in this study strongly favour temperature as the most important parameter inuencing tribochemical reactions under selected fretting conditions. Very high temperatures must therefore also be considered under conditions which are usually regarded as low speedlow temperature conditions. 2. Very high temperatures (between 400 C and possibly more than 1145 C) were obtained only in a high

amplitude gross slip fretting regime, while at lower displacement amplitudes, temperature rises of the order of a few tens of C (about 50 C) were generated. 3. Based on the present results and a literature survey, the thickness of the silica layer developed on silicon nitride during a tribological test is the most meaningful parameter for the estimation of contact temperature due to its strongly diffusion-controlled formation. 4. The results of our isolated chemical wear study were in good agreement with results of other experimental and theoretical approaches employed in this work, and therefore we suggest that similar isolated investigations should be used more often to provide clearer evidence and better understanding of the basic mechanisms involved in fretting wear. References
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