Surface Depassivation via B-O Dative Bonds Affects the Friction Performance of B-Doped Carbon Coatings.

Boron doping of diamond-like carbon coatings has multiple effects on their tribological properties. While boron typically reduces wear in cutting applications, some B-doped coatings show poor tribological performance compared with undoped films. This is the case of the tribological tests presented in this work in which an alumina ball is placed in frictional contact with different undoped and B-doped amorphous carbon coatings in humid air.

Superlubricity of Silicon-Based Ceramics Sliding against Hydrogenated Amorphous Carbon in Ultrahigh Vacuum: Mechanisms of Transfer Film Formation.

Tribological interfaces between silicon-based ceramics, such as SiN or SiC, are characterized by high friction and wear in unlubricated conditions. A solution to this problem is to use them in combination with a hydrogenated amorphous carbon (a-C:H) countersurface from which a passivating carbon film is transferred onto the ceramic surface. However, the mechanisms underlying a stable film transfer process and the conditions that favor it remain elusive.

Toward a continuum description of lubrication in highly pressurized nanometer-wide constrictions: The importance of accurate slip laws.

The Reynolds lubrication equation (RLE) is widely used to design sliding contacts in mechanical machinery. While providing an excellent description of hydrodynamic lubrication, friction in boundary lubrication regions is usually considered by empirical laws, because continuum theories are expected to fail for lubricant film heights ≪ 10 nm, especially in highly loaded tribosystems with normal pressures ≫ 0.1 GPa.

Mechanochemical Activation of Anthracene [4+4] Cycloadducts.

Controlled formation and breaking of weak chemical bonds is a versatile method for modifying the properties of materials. Anthracene [4+4] cycloadducts are a prime example that can be formed by light and opened by external forces. We address the theoretical description of mechanochemistry of these cycloadducts, where the standard constraint geometry simulates forces approach fails due to the lack of consideration of temperature.

Humidity-dependent lubrication of highly loaded contacts by graphite and a structural transition to turbostratic carbon.

Graphite represents a promising material for solid lubrication of highly loaded tribological contacts under extreme environmental conditions. At low loads, graphite's lubricity depends on humidity. The adsorption model explains this by molecular water films on graphite leading to defect passivation and easy sliding of counter bodies.

Low-Energy Hydrogen Ions Enable Efficient Room-Temperature and Rapid Plasma Hydrogenation of TiO Nanorods for Enhanced Photoelectrochemical Activity.

Hydrogenation is a promising technique to prepare black TiO (H-TiO ) for solar water splitting, however, there remain limitations such as severe preparation conditions and underexplored hydrogenation mechanisms to inefficient hydrogenation and poor photoelectrochemical (PEC) performance to be overcome for practical applications. Here, a room-temperature and rapid plasma hydrogenation (RRPH) strategy that realizes low-energy hydrogen ions of below 250 eV to fabricate H-TiO nanorods with controllable disordered shell, outperforming incumbent hydrogenations, is reported. The mechanisms of efficient RRPH and enhanced PEC activity are experimentally and theoretically unraveled.

Relating Dry Friction to Interdigitation of Surface Passivation Species: A Molecular Dynamics Study on Amorphous Carbon.

Friction in boundary lubrication is strongly influenced by the atomic structure of the sliding surfaces. In this work, friction between dry amorphous carbon (a-C) surfaces with chemisorbed fragments of lubricant molecules is investigated employing molecular dynamic simulations. The influence of length, grafting density and polarity of the fragments on the shear stress is studied for linear alkanes and alcohols.

Solid-Phase Silicon Homoepitaxy via Shear-Induced Amorphization and Recrystallization.

We study mechanically induced phase transitions at tribological interfaces between silicon crystals using reactive molecular dynamics. The simulations reveal that the interplay between shear-driven amorphization and recrystallization results in an amorphous shear interface with constant thickness. Different shear elastic responses of the two anisotropic crystals can lead to the migration of the amorphous interface normal to the sliding plane, causing the crystal with lowest elastic energy density to grow at the expense of the other one.

Interplay of mechanics and chemistry governs wear of diamond-like carbon coatings interacting with ZDDP-additivated lubricants.

Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils. Our experiments show that DLC's tribological behaviour in ZDDP-additivated oils can be optimised by tailoring its stiffness, surface nano-topography and hydrogen content. An optimal combination of ultralow friction and negligible wear is achieved using hydrogen-free tetrahedral amorphous carbon (ta-C) with moderate hardness.

Nonempirical Free Volume Viscosity Model for Alkane Lubricants under Severe Pressures.

Viscosities η and diffusion coefficients D_{s} of linear and branched alkanes at pressure 0 View Article and Find Full Text PDF

Steric Effects Control Dry Friction of H- and F-Terminated Carbon Surfaces.

A stable passivation of surface dangling bonds underlies the outstanding friction properties of diamond and diamond-like carbon (DLC) coatings in boundary lubrication. While hydrogen is the simplest termination of a carbon dangling bond, fluorine can also be used as a monoatomic termination, providing an even higher chemical stability. However, whether and under which conditions a substitution of hydrogen with fluorine can be beneficial to friction is still an open question.

Ab Initio Wavelength-Dependent Raman Spectra: Placzek Approximation and Beyond.

We analyze how to obtain non-resonant and resonant Raman spectra within the Placzek as well as the Albrecht approximation. Both approximations are derived from the matrix element for light scattering by application of the Kramers, Heisenberg, and Dirac formula. It is shown that the Placzek expression results from a semi-classical approximation of the combined electronic and vibrational transition energies.

Experimental and theoretical 2p core-level spectra of size-selected gas-phase aluminum and silicon cluster cations: chemical shifts, geometric structure, and coordination-dependent screening.

We present 2p core-level spectra of size-selected aluminum and silicon cluster cations from soft X-ray photoionization efficiency curves and density functional theory. The experimental and theoretical results are in very good quantitative agreement and allow for geometric structure determination. New ground state geometries for Al, Si, Si, and Si are proposed on this basis.

Mechano-chemical decomposition of organic friction modifiers with multiple reactive centres induces superlubricity of ta-C.

Superlubricity of tetrahedral amorphous carbon (ta-C) coatings under boundary lubrication with organic friction modifiers is important for industrial applications, but the underlying mechanisms remain elusive. Here, combined experiments and simulations unveil a universal tribochemical mechanism leading to superlubricity of ta-C/ta-C tribopairs. Pin-on-disc sliding experiments show that ultra- and superlow friction with negligible wear can be achieved by lubrication with unsaturated fatty acids or glycerol, but not with saturated fatty acids and hydrocarbons.

Friction Regimes of Water-Lubricated Diamond (111): Role of Interfacial Ether Groups and Tribo-Induced Aromatic Surface Reconstructions.

Large-scale quantum molecular dynamics of water-lubricated diamond (111) surfaces in sliding contact reveals multiple friction regimes. While water starvation causes amorphization of the tribological interface, small H_{2}O traces are sufficient to preserve crystallinity. This can result in high friction due to cold welding via ether groups or in ultralow friction due to aromatic surface passivation triggered by tribo-induced Pandey reconstruction.

Molecular Dynamic Simulation of Collision-Induced Third-Body Formation in Hydrogen-Free Diamond-Like Carbon Asperities.

The collision of two cylindrical hydrogen-free diamond-like carbon (DLC) asperities with approximately 60 % sp hybridization has been studied using classical molecular dynamics. The severity of the collision can be controlled by the impact parameter that measures the width of the projected overlap of the two cylinders. For a cylinder radius of  = 23 nm, three collisions with  = 0.

Insights into Interfacial Changes and Photoelectrochemical Stability of In(x)Ga(1-x)N (0001) Photoanode Surfaces in Liquid Environments.

The long-term stability of InGaN photoanodes in liquid environments is an essential requirement for their use in photoelectrochemistry. In this paper, we investigate the relationships between the compositional changes at the surface of n-type In(x)Ga(1-x)N (x ∼ 0.10) and its photoelectrochemical stability in phosphate buffer solutions with pH 7.

Fluorine-Terminated Diamond Surfaces as Dense Dipole Lattices: The Electrostatic Origin of Polar Hydrophobicity.

Despite the pronounced polarity of C-F bonds, many fluorinated carbon compounds are hydrophobic: a controversial phenomenon known as "polar hydrophobicity". Here, its underlying microscopic mechanisms are explored by ab initio calculations of fluorinated and hydrogenated diamond (111) surfaces interacting with single water molecules. Gradient- and van der Waals-corrected density functional theory simulations reveal that "polar hydrophobicity" of the fully fluorinated surfaces is caused by a negligible surface/water electrostatic interaction.

Ultralow Friction of Steel Surfaces Using a 1,3-Diketone Lubricant in the Thin Film Lubrication Regime.

Ultralow friction (coefficient of friction μ ≈ 0.005) is observed when two steel surfaces are brought into sliding contact in the presence of a particular 1,3-diketone lubricant (1-(4-ethyl phenyl) nonane-1,3-dione). We investigate the friction process of such a system both experimentally and theoretically and show that the superlubricity is caused by a novel, unique mechanism: The formation of iron-1,3-diketonato complexes during frictional contact leads to a self-limiting, tribochemical polishing process while at the same time a self-assembled monolayer of the diketone is formed on the employed steel surfaces.

Density functional theory and chromium: Insights from the dimers.

The binding in small Cr clusters is re-investigated, where the correct description of the dimer in three charge states is used as criterion to assign the most suitable density functional theory approximation. The difficulty in chromium arises from the subtle interplay between energy gain from hybridization and energetic cost due to exchange between s and d based molecular orbitals. Variations in published bond lengths and binding energies are shown to arise from insufficient numerical representation of electron density and Kohn-Sham wave-functions.

Surface softening in metal-ceramic sliding contacts: an experimental and numerical investigation.

This study investigates the tribolayer properties at the interface of ceramic/metal (i.e., WC/W) sliding contacts using various experimental approaches and classical atomistic simulations.

Atomic scale mechanisms of friction reduction and wear protection by graphene.

We study nanoindentation and scratching of graphene-covered Pt(111) surfaces in computer simulations and experiments. We find elastic response at low load, plastic deformation of Pt below the graphene at intermediate load, and eventual rupture of the graphene at high load. Friction remains low in the first two regimes, but jumps to values also found for bare Pt(111) surfaces upon graphene rupture.

A highly selective and self-powered gas sensor via organic surface functionalization of p-Si/n-ZnO diodes.

Selectivity and low power consumption are major challenges in the development of sophisticated gas sensor devices. A sensor system is presented that unifies selective sensor-gas interactions and energy-harvesting properties, using defined organic-inorganic hybrid materials. Simulations of chemical-binding interactions and the consequent electronic surface modulation give more insight into the complex sensing mechanism of selective gas detection.

Coarse graining and localized plasticity between sliding nanocrystalline metals.

Tribological shearing of polycrystalline metals typically leads to grain refinement at the sliding interface. This study, however, shows that nanocrystalline metals exhibit qualitatively different behavior. Using large-scale atomistic simulations, we demonstrate that during sliding, contact interface nanocrystalline grains self-organize through extensive grain coarsening and lattice rotation until the optimal plastic slip orientation is established.

Interactions of polymers with reduced graphene oxide: van der Waals binding energies of benzene on graphene with defects.

The interaction of benzene molecules with various defects in graphene is studied using density functional theory enhanced by two different recent dispersion corrections. Both provide the same qualitative picture: the binding strength of benzene to the various defects is governed by steric hindrance. Our first principles calculations in combination with a simple model predict reduced stabilities of polymer-graphene nanocomposites made of reduced graphene oxides depending on the defect density.