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The sliding behavior of an amorphous silica sample between two rigid surfaces is in the focus of the present paper. Molecular Dynamics using a classical Tersoff’s potential and a recently developed ReaxFF potential was applied for simulating sliding within a thin film corresponding to a tribofilm formed from silica nanoparticles. The simulations were performed at different temperatures corresponding to moderate and severe tribological stressing conditions. Simulations with both potentials revealed the need of considering different temperatures in order to obtain a sound interpretation of experimental findings. The results show the striking differences between the two potentials not only in terms of magnitude of the resistance stress (about one order of magnitude) but also in terms of friction mechanisms. The expected smooth sliding regime under high temperature conditions was predicted by both simulations, although with Tersoff’s potential smooth sliding was obtained only at the highest temperature. On the other hand, at room temperature Tersoff-style calculations demonstrate stick-slip behavior, which corresponds qualitatively with our experimental findings. Nevertheless, comparison with a macroscopic coefficient of friction is not possible because simulated resistance stresses do not depend on the applied normal pressure.
The sliding behaviors of two simplified tribofilms with amorphous structure consisting either of SiO₂ molecules or C atoms were simulated by molecular dynamics modeling. The objective was to identify mechanisms explaining the experimentally observed lubricating properties of the two amorphous films. The impacts of layer thickness, normal pressure, temperature and different substrate materials were studied systematically, while the sliding velocity was kept constant at 30 m/s. While the layer thickness was not critical, all the other parameters showed special effects under certain conditions. Normal pressure impeded void formation and could even eliminate voids if applied at high temperature. Stick-slip sliding was changed to smooth sliding at high temperature due to void healing. Considering the carbon film, high friction forces and shearing of the entire film was observed with diamond substrates, whereas interface sliding at low friction forces and an amorphous layer of iron mixed with carbon was observed if the supporting substrates consisted of α-Fe. Both films show a decrease of friction forces and smooth sliding behavior at elevated temperature, corresponding well to the tribological behavior of and advanced nanocomposite sliding against a steel disc under severe stressing conditions when high flash temperatures can be expected.
Copper is one of the most important components in brake pads and its amount can reach up to 14%. In spite of a number of positive features copper usage in brake pad formulations has recently become the subject of considerable discussions, primarily due to concerns about potential risks related to environmental impacts of copper particles. So, for developing new pad formulations with possible replacements of copper content, it is very important to understand the functionality of copper additions to brake friction materials. In the paper theoretical investigation of the role of copper as a pad ingredient was carried out on the basis of modelling by the method of movable cellular automata (MCA). Our previous studies show that copper as a constituent of the tribofilm formed during braking provides smooth sliding by forming a granular layer of mechanically mixed materials from the friction layers. In the present study the concentration of copper particles in a Fe3O4-matrix was varied systematically in the range 5.5-28 vol. % and compared to mixtures with the same amount of graphite nanoparticles. The sliding simulations were performed while assuming material properties at 500°C in order to assess the beneficial role of copper during severe braking conditions corresponding to fading cycles during dynamometer testing.
Reference nanomaterials
(2016)
This chapter reviews relevant aspects of the still less explored field of RNMs. In the first part, definition of RMs according to different metrological levels was presented as well as the general strategy on their development. In the second part, the importance of RNMs in material science and nanotoxicology is explained and considerations on the use of silica nano-objects as potential future reference material was discussed. Overall, several points should be highlighted from this chapter: Definition of a reference material depends on the level of standardization. Certified reference material represents the highest level of traceability. Different types of reference materials, standard materials and certified reference materials are available, as shown in Table 3.1. The preparation of nano-objects with well-defined mechanical properties is still an unsolved issue and thus needs further R&D activities. Nevertheless, amorphous silica seems to be a promising candidate for reaching this objective. Traceable properties of nanomaterials are still limited to few cases such as primary particle size and thickness measurements of very thin films. In general, developed RMs are monoparametric thus, only one characteristic of the nano-objects is reported. In nanotoxicology, the challenge is in the development of suitable RNM that bears similarities to the measurements made on the sample analysed.
Besides carbon, metal sulphides are used in every standard brake pad formulation as friction stabilisers. In order to investigate their impact, various powder mixtures were tribologically stressed in a pin-on-disc device in order to produce and test artificial third bodies. containing the three main components of a real friction film, namely magnetite, graphite and a metal sulphide of interest. Since the sliding behaviour is influenced by the relative humidity the powder mixtures are tested at low, medium and high moisture levels. The tests revealed that the presence of graphite dominates the friction behaviour as well as the humidity sensitivity.
The powders were prepared by either manual mixing or high energy ball-milling. Interestingly, all ball-milled blends provided coefficients of friction within the desired range for braking, which was attributed to the effect of zirconia particles from wear debris of the milling balls. The zirconia particles prevent the formation of solid lubricant films on the surfaces and support a homogeneous mixture of all constituents of the powder. Optimum brake performance is gained by an optimum combination of solid lubricants and abrasives.
This review article comprises of three parts. Firstly, reports of brake manufacturers on the beneficial impact of solid lubricants for pad formulations are surveyed. Secondly, since tribofilms were identified to play a crucial role in friction stabilization and wear reduction, the knowledge about tribofilm structures formed during automotive braking was reviewed comprehensively. Finally, a model for simulating the sliding behavior of tribofilms is suggested and a review on modelling efforts with different model structures related to real tribofilms will be presented. Although the variety of friction composites involved in commercial brake systems is very broad, striking similarities were observed in respect to tribofilm nanostructures. Thus a generalization of the tribofilm nanostructure is suggested and prerequisites for smooth sliding performance and minimal wear rates have been identified. A minimum of 13 vol.% of soft inclusions embedded in an iron oxide based tribofilm is crucial for obtaining the desired properties. As long as the solid lubricants or their reaction products are softer than magnetite, the main constituent of the tribofilm, the model predicts smooth sliding and a minimum of wear.
Third bodies, also termed friction layers, tribofilms or secondary contact patches, are layers of more or less compacted wear debris between pads and rotor of a disc brake. Our approach of assessing the sliding behavior and friction properties induced by third bodies has been: i) structural characterization after AK-master test procedure, ii) sliding simulation of model structures similar to the observed ones but with simpler and well defined compositions, and iii) verification of simulation results by pin-on-disc tests with artificial third bodies showing the same microstructures and compositions as the model structures. The idea was to simulate structure formation during real braking conditions by high energy ball milling of appropriate powder blends. The final outcome of numerous parameter studies was that a third body containing 15 vol% soft ingredients and 0-20 vol % hard ingredients, both distributed homogeneously in a nanocrystalline iron oxide matrix, should be most desirable for braking. This general description of the optimum third body structure and several parameter studies performed by modelling enabled us to interpret a number of features of the AK-master test procedure, such as i) friction evolution during bedding, ii) the role of solid lubricants in respect to the initiation of smooth sliding behavior, and iii) friction evolution during a single braking event (in-stop behavior).
In order to obtain a better understanding of the role of tribofilms during automotive braking, their structures were investigated and the essential features identified.
Next, different ingredient combinations were studied by preparing some model materials with simpler compositions than real tribofilms. A test method was developed for verifying the tribological properties of the model materials and for comparison with results obtained with numerical sliding simulations of such structures. Prerequisites of good brake Performance properties were identified. Although the coefficient of friction could be varied in a wide ränge, smooth sliding conditions could only be achieved with values smaller than 0.4. Tests with artificial third body powders turned out to be useful as screening method for the selection of raw materials for brake pad formulations.
In part 1 it was shown that tribofilms usually are 100 nm thick and exhibit a multiphase nanocrystalline structure. The objective of our modelling efforts was to obtain a better understanding of the sliding behaviour and associated friction properties and to study the impact of internal and external parameters on these properties. The method of movable cellular automata (MCA) was used. The third bodies were considered as aggregates of linked nanoparticles which may decompose and form a layer of granulär material, the so-called mechanically mixed layer (MML), if certain fracture criteria are fulfilled. The basic model structure which consists of Fe3Ü4 nanoparticles with 13 % graphite inclusions was used. In order to assess the robustness of the model the following parameter studies were performed. The pressure ränge at an asperity contact was varied between 15 and 50 MPa. The mechanical properties of the oxide were varied between brittle and ductile behaviour corresponding to room temperature and high temperature behaviour. The mechanical properties of the soft ingredient were varied + 50 % of the properties of graphite. The influence
The impact of pressure, sliding velocity and property variation of constituents on the sliding behaviour of a model tribofilm was studied with the method of movable cellular automata (MCA). Whereas a clear pressure dependency of the coefficient of friction (COF) was always observed and could be correlated with the structure formation in terms of varying thickness of a mechanically mixed layer, the impact of the other parameters was either negligible or rather weak. Only if a brittle-to-ductile Transition of the oxide-based tribofilm was assumed, a significant decrease in the COF level was predicted.
Temperature-dependent property changes can be neglected during MCA modelling, unless this transition takes place. For magnetite-based tribofilms, the transition temperature is beyond 800 °C, i.e. a temperature leading to fading effects during braking anyway. Thus, it could be concluded that, except for very severe braking conditions, sliding simulations with the MCA method yield meaningful results without considering temperature-dependent mechanical properties.