Effect of Temperature on the Deformation Behavior of Copper Nickel Alloys under Sliding.

The microstructural evolution in the near-surface regions of a dry sliding interface has considerable influence on its tribological behavior and is driven mainly by mechanical energy and heat. In this work, we use large-scale molecular dynamics simulations to study the effect of temperature on the deformation response of FCC CuNi alloys of several compositions under various normal pressures. The microstructural evolution below the surface, marked by mechanisms spanning grain refinement, grain coarsening, twinning, and shear layer formation, is discussed in depth. The observed results are complemented by a rigorous analysis of the dislocation activity near the sliding interface. Moreover, we define key quantities corresponding to deformation mechanisms and analyze the time-independent differences between 300 K and 600 K for all simulated compositions and normal pressures. Raising the Ni content or reducing the temperature increases the energy barrier to activate dislocation activity or promote plasticity overall, thus increasing the threshold stress required for the transition to the next deformation regime. Repeated distillation of our quantitative analysis and successive elimination of spatial and time dimensions from the data allows us to produce a 3D map of the dominating deformation mechanism regimes for CuNi alloys as a function of composition, normal pressure, and homologous temperature.

Unraveling and Mapping the Mechanisms for Near-Surface Microstructure Evolution in CuNi Alloys under Sliding.

The origin of friction and wear in polycrystalline materials is intimately connected with their microstructural response to interfacial stresses. Although many mechanisms that govern microstructure evolution in sliding contacts are generally understood, it is still a challenge to ascertain which mechanisms matter under what conditions, which limits the development of tailor-made microstructures for reducing friction and wear. Here, we shed light on the circumstances that promote plastic deformation and surface damage by studying several face-centered cubic CuNi alloys subjected to sliding with molecular dynamics simulations featuring tens of millions of atoms. By analyzing the depth- and time-dependent evolution of the grain size, twinning, shear, and stresses in the aggregate, we derive a deformation mechanism map for CuNi alloys. We verify the predictions of this map against focused ion beam images of the near-surface regions of CuNi alloys that were experimentally subjected to similar loading conditions. Our results may serve as a tool for finding optimum material compositions within a specified operating range.

Reactive Molecular Dynamics Simulations of Thermal Film Growth from Di- tert-butyl Disulfide on an Fe(100) surface.

Iron sulfide films are present in many applications, including lubricated interfaces where protective films are formed through the reactions of lubricant additive molecules with steel surfaces during operation. Such films are critical to the efficiency and useful lifetime of moving components. However, the mechanisms by which films form are still poorly understood because the reactions occur between two surfaces and so cannot be directly probed experimentally. To address this, we explore the thermal contribution to film formation of di- tert-butyl disulfide-an important extreme pressure additive-on an Fe(100) surface using reactive molecular dynamics simulations, where the reactive potential parameters are validated by comparison to ab initio calculations. The reaction pathway leading to the formation of iron sulfide surfaces is characterized using the reactive simulations. Then, the film formation process is mimicked by simulations where di- tert-butyl disulfide molecules are cyclically added to the surface and subjected to temperatures comparable to those expected due to frictional heating. The use of a reactive empirical potential is a novel approach to modeling the iterative nature of thermal film growth with realistic lubricant additive molecules.

Interfacial Microstructure Evolution Due to Strain Path Changes in Sliding Contacts.

We performed large-scale molecular dynamics (MD) simulations to study the transient softening stage that has been observed experimentally in sliding interfaces subject to strain path changes. The occurrence of this effect can be of crucial importance for the energy efficiency and wear resistance of systems that experience changes in the sliding direction, such as bearings or gears in wind parks, piston rings in combustion engines, or wheel-rail contacts for portal cranes. We therefore modeled the sliding of a rough counterbody against two polycrystalline substrates of face-centered cubic (fcc) copper and body-centered cubic (bcc) iron with initial near-surface grain sizes of 40 nm. The microstructural development of these substrates was monitored and quantified as a function of time, depth, and applied pressure during unidirectional sliding for 7 ns. The results were then compared to the case of sliding in one direction for 5 ns and reversing the sliding direction for an additional 2 ns. We observed the generation of partial dislocations, grain refinement, and rotation as well as twinning (for fcc) in the near-surface region. All microstructures were increasingly affected by these processes when maintaining the sliding direction but recovered to a great extent upon sliding reversal up to applied pressures of 0.4 GPa in the case of fcc Cu and 1.5 GPa for bcc Fe. We discuss the applicability and limits of our polycrystalline MD model for reproducing well-known bulk phenomena such as the Bauschinger effect in interfacial processes.

Thermostat Influence on the Structural Development and Material Removal during Abrasion of Nanocrystalline Ferrite.

We consider a nanomachining process of hard, abrasive particles grinding on the rough surface of a polycrystalline ferritic work piece. Using extensive large-scale molecular dynamics (MD) simulations, we show that the mode of thermostating, i.e., the way that the heat generated through deformation and friction is removed from the system, has crucial impact on tribological and materials related phenomena. By adopting an electron-phonon coupling approach to parametrize the thermostat of the system, thus including the electronic contribution to the thermal conductivity of iron, we can reproduce the experimentally measured values that yield realistic temperature gradients in the work piece. We compare these results to those obtained by assuming the two extreme cases of only phononic heat conduction and instantaneous removal of the heat generated in the machining interface. Our discussion of the differences between these three cases reveals that although the average shear stress is virtually temperature independent up to a normal pressure of approximately 1 GPa, the grain and chip morphology as well as most relevant quantities depend heavily on the mode of thermostating beyond a normal pressure of 0.4 GPa. These pronounced differences can be explained by the thermally activated processes that guide the reaction of the Fe lattice to the external mechanical and thermal loads caused by nanomachining.

Density Functional Investigation of the Adsorption of Isooctane, Ethanol, and Acetic Acid on a Water-Covered Fe(100) Surface.

The presence of water in biofuels poses the question of how it affects the frictional performance of additives in fuels containing organic substances. To investigate the effect of water on the adsorption of molecules present in fuel and its additives we simulated within the framework of density functional theory the adsorption of ethanol, isooctane (2,2,4-trimethylpentane), and acetic acid on a bare and a water-covered Fe(100) surface. Van der Waals interactions are taken into account in our computations. In those molecules, where dispersion forces contribute significantly to the binding mechanism, the water layer has a stronger screening effect. Additionally, this effect can be enhanced by the presence of polar functional groups in the molecule. Thus, with the introduction of a water layer, the adsorption energy of isooctane and ethanol is reduced but it is increased in the case of the acetic acid. The adsorption configuration of ethanol is changed, while the one of acetic acid is moderately, and for isooctane only very slightly altered. Therefore, the effect of a water layer in the adsorption of organic molecules on an Fe(100) surface strongly depends on the type of bond and consequently, so do the tribological properties.

Effects of van der Waals Interactions in the Adsorption of Isooctane and Ethanol on Fe(100) Surfaces.

van der Waals (vdW) forces play a fundamental role in the structure and behavior of diverse systems. Because of development of functionals that include nonlocal correlation, it is possible to study the effects of vdW interactions in systems of industrial and tribological interest. Here we simulated within the framework of density functional theory (DFT) the adsorption of isooctane (2,2,4-trimethylpentane) and ethanol on an Fe(100) surface, employing various exchange-correlation functionals to take vdW forces into account. In particular, this paper discusses the effect of vdW forces on the magnitude of adsorption energies, equilibrium geometries, and their role in the binding mechanism. According to our calculations, vdW interactions increase the adsorption energies and reduce the equilibrium distances. Nevertheless, they do not influence the spatial configuration of the adsorbed molecules. Their effect on the electronic density is a nonisotropic, delocalized accumulation of charge between the molecule and the slab. In conclusion, vdW forces are essential for the adsorption of isooctane and ethanol on a bcc Fe(100) surface.

On the Derjaguin offset in boundary-lubricated nanotribological systems.

We performed molecular dynamics simulations of boundary-lubricated sliding, varying the boundary lubricant type, its molecular surface coverage, the substrate roughness, and the load. The resulting load versus friction behavior was then analyzed to study how changes in lubricant type, coverage, and roughness affect the extrapolated friction force at zero load, the so-called Derjaguin offset. A smooth-particle-based evaluation method by the authors, applied here for the first time to visualize the sliding interface between the two layers of boundary lubricant, allowed the definition and calculation of a dimensionless normalized sliding resistance area, which was then related to the Derjaguin offset. This relationship excellently reflects the molecular surface coverage, which determines the physical condition of the lubricant, and can differentiate between some lubricant-specific frictional properties.