Molecular dynamics study of dynamic contact and separation between tip and disk surface

Molecular dynamics simulations were performed to study contact and separation between tip and lubricants on disk surface. The effects of contact indentation depth, indentation velocity, separation velocity, adhesive energy, lubricant molecular structure and lubricating film thickness on interacting force were analyzed. The results indicate that the tip force exerted by lubricants is velocity-dependent. The tip force increases with increasing indentation velocity and separation force reduces with increasing separation velocity. The damping of branched molecule and thick lubricating film is high. The high adhesive energy of tip material can produce high separation force which reduces bouncing vibration.     

Computer simulation of sliding hydroxylated alumina surfaces

A molecular dynamics simulation is performed to investigate the frictional force and energy transfer dynamics associated with sliding hydroxylated alumina surfaces. The calculated coefficient of friction is in good agreement with a recent experimental study. The dynamics of energy transfer from the interface of the sliding surface is investigated by calculating the surface–surface intermolecular potential and the energy in surface hydroxyl groups. The simulations indicate the experimental friction force arises from energy relaxation. A transition from stick–slip to smooth sliding is observed as the sliding velocity is increased. This revised version was published online in September 2006 with corrections to the Cover Date.     

The behaviour of friction modifiers under boundary and mixed EHD conditions

The behaviour of a range of model and commercial friction modifiers (FMs) has been evaluated under elastohydrodynamic (EHD) and boundary lubrication conditions. Using a series of long‐chain carboxylic acids, it has been shown that measured boundary friction coefficients (BFCs) decrease with increasing chain length, unsaturation level, temperature, and concentration. Base oil polarity was found to have no effect under these conditions. Commercial oleate esters in synthetic base fluids gave lower BFCs than nitrogen‐containing compounds under the same conditions. This difference was observed over a range of concentrations and temperatures. The friction performance of formulated oils under mixed and full‐film EHD conditions was found to be dependent on FM, base oil, and detergent type. Under boundary conditions, friction was found to vary with FM type, but the effect of changing the base oil and the detergent system was negligible.     

Energetically and pressure driven phase transitions in molecularly thin films of n-alkanes

Molecular dynamics simulations were carried out on molecularly thin films of n-octane confined between topographically smooth solid surfaces. We focused on determining the effect of increasing solid surface-methylene unit energetic affinity and the effect of increasing pressure (normal load) of the film in inducing liquid-solid phase transitions. Simulations of films wide enough to accomodate three segmental layers showed an abrupt transition in the structural features at a critical value of the characteristic energy that quantified the affinity between solid surfaces and methylene units. This energetically driven transition was evident from the discontinuous increase of intermolecular order, a precipitous extension of the octane molecules and freezing of molecular migration and rotation. Increasing pressure had a similar effect in inducing a liquid-solid phase transition. The characteristics of the transition showed that it is a mild first-order transition from a highly ordered liquid to a poorly organized solid. These findings demonstrate that the solidification of nanoscopically thin films of linear alkanes is a general phenomenon (driven either energetically or by increasing pressure), and does not require the aid of commensurate surface topography. Our findings on relatively wider films (5 segmental diameters wide) show that the interfacial layer undergoes a similar first-order phase transition with increasing solid-methylene unit energetic affinity. This energy threshold is significantly higher than the one observed in thin film simulations.     

Transition from elastic to plastic deformation as asperity contact size is increased

Contacts between a clean sodium chloride pyramidal shaped asperity and a plane NaCl surface have been investigated by molecular dynamics simulations. For small contacts, a few atoms across, the asperity jumped to contact and behaved elastically as normal load was applied. Then, when the force was reversed to detach the asperity, brittle failure occurred without any damage to the crystalline materials. However, as the contact size of the asperity was increased to 6 × 6 atoms in area, the mechanism of detachment was seen to alter. The jump to contact was elastic and damage free, but the separation could not be achieved elastically, but required plastic deformation, giving extensive energy dissipation and severe damage as edge defects propagated through the asperity. Above this contact size, plastic flow was dominant. However, there is clearly a further transition back to elastic fracture once the asperity becomes large enough for Griffith-type cracking to propagate above 1 μm in size, since large sodium chloride contacts are known to be brittle above the micrometre scale, depending on the presence of crack initiating defects.     

Atomic-scale study of friction and energy dissipation

This paper presents an analysis of the interaction energy and various forces between two surfaces, and the microscopic study of friction. Atomic-scale simulations of dry sliding friction and boundary lubrication are based on the classical molecular dynamics (CMD) calculations using realistic empirical potentials. The dry sliding of a single metal asperity on an incommensurate substrate surface exhibits a quasi-periodic variation of the lateral force with two different stick-slip stage involving two structural transformation followed by a wear. The contact area of the asperity increases discontinuously with increasing normal force. Xe atoms placed between two atomically flat Ni surfaces screen the Ni-Ni interaction, decrease the corrugation of the potential energy as well as the friction force at submonolayer coverage. We present a phononic model of energy dissipation from an asperity to the substrates.     

Frictional dynamics of perfluorinated self-assembled monolayers on amorphous SiO<Subscript>2</Subscript>

Silicon micromachines in microelectromechanical systems (MEMS) are coated with self-assembled monolayers (SAMs) in order to reduce the wear and stiction that are commonplace during operation. Recently, perfluorinated SAMs have been the focus of attention because they have better processing properties than hydrocarbon SAMs. In this study, we perform molecular dynamics simulations that model adhesive contact and friction for perfluorinated alkylsilane (Si(OH)₃(CF₂)₁₀CF₃) self-assembled monolayers (SAMs), which are commonly used in MEMS devices. Amorphous silica is used as the substrate for the SAMs in the simulations. The frictional behavior is investigated as a function of applied pressure (50 MPa–1 GPa) for a shear velocity of 2 m/s and compared to recent simulation results of hydrocarbon alkylsilane SAMs. The microscopic friction coefficient for the perfluorinated SAMs is the same as was measured for the hydrocarbon SAMs, but the shear stress is slightly larger than in the case of the hydrocarbon SAMs on amorphous silica.     

Interactive Effect between Organic Friction Modifiers and Additives on Friction at Metal Pushing V-Belt CVT Components

The interactions between organic friction modifiers (FMs) and other additives in a continuously variable transmission (CVT) fluid (CVTF) are investigated with the goal of optimizing friction management of metal pushing V-belt CVTs. Three types of FMs (oleic acid, oleyl alcohol, and glycerol mono-oleate [GMO]) were formulated in poly-α-olefin (PAO) and a fully formulated CVTF, and the friction performance was evaluated in a reciprocating test apparatus (TE77). To estimate their effect on the major frictional components in the CVTs, a steel belt–pulley and a torque converter clutch, the tribotests were carried out with both steel–steel and paper–steel sliding configurations. Then, the posttest materials were assessed by surface analysis techniques to observe the chemical nature of any reacted layers at the surface.

The results indicate that the friction on the steel surface was significantly influenced by a combination of the FMs and the CVTF additives as well as the functional group of the FMs. Although oleic acid and GMO typically present greater friction reduction than oleyl alcohol under most conditions, oleic acid did not decrease friction at the steel–steel contact with the presence of the other additives in the CVTF formulation; the friction reduction effect was impaired by the presence of other additives. Surface analysis of the posttest specimens implied that it was interactions with the calcium detergent that inactivated the FM effect of oleic acid.     

单晶铜纳米机械加工的分子动力学模拟与实验的间接对比

以单晶铜微探针纳米刻划加工为例,提出了一种分子动力学模拟与实验的间接对比方法,依次开展了工件材料的弹性常量的定量对比、工件材料机械性能的纳米压痕测量的定量对比、已加工表面形貌的定性对比。单晶铜工件压缩、剪切、拉伸和纳米压痕的分子动力学模拟显示,分子动力学模拟体系的弹性模量与实验测得值相同,压痕后工件表面材料堆积的对称特性与实验结果相符。研究结果表明,所使用的嵌入原子势能函数可以精确地描述单晶铜工件中铜原子之间的相互作用,纳米机械加工的分子动力学模拟具有较高的精度,并且可以很好地预测纳米机械加工的实验结果。     

Atomic Friction Modulation on the Reconstructed Au(111) Surface

Friction between a nanoscale tip and a reconstructed Au(111) surface is investigated both by atomic force microscopy (AFM) and molecular statics calculations. Lateral force AFM images exhibit atomic lattice stick–slip behavior with a superstructure corresponding to the herringbone reconstruction pattern. However, the superstructure contrast is not primarily due to variations in the local frictional dissipation (which corresponds to the local width of the friction loop). Rather, the contrast occurs primarily because the local centerline position of the friction loop is periodically shifted from its usual value of zero. Qualitatively, similar behavior is reproduced in atomistic simulations of an AFM tip sliding on the reconstructed Au(111) substrate. In both simulations and experiments, this centerline modulation effect is not observed on unreconstructed surfaces. Similarly, using a topographically flat surface as a hypothetical control system, the simulations show that the centerline modulation is not caused by variations in the reconstructed surface’s topography. Rather, we attribute it to the long-range variation of the local average value of the tip-sample interaction potential that arises from the surface reconstruction. In other words, surface atoms located at unfavorable sites, i.e., in the transition between face-centered-cubic (FCC) and hexagonal-close-packed (HCP) regions, have a higher surface free energy. This leads to a varying conservative force which locally shifts the centerline position of the friction force. This demonstrates that stick–slip behavior in AFM can serve as a rather sensitive probe of the local energetics of surface atoms, with an attainable lateral spatial resolution of a few nanometers.     

Periodicities in the properties associated with the friction of model self-assembled monolayers

The classical molecular dynamics simulations presented here examine the periodicities associated with the sliding of a diamond counterface across a monolayer of hydrocarbon chains that are covalently bound to a diamond substrate. Periodicities observed in a number of system quantities are a result of the tight packing of the monolayer and the commensurate structure of the diamond counterface. The packing and commensurability of the system force synchronized motion of the chains during sliding contact. This implies that the size of the simulations for this special case can be reduced so that the simulations can be conducted with sliding speeds and time durations that may bridge the gap between theory and experiment.     

Formation and Oxidation of Linear Carbon Chains and Their Role in the Wear of Carbon Materials

The atomic-scale processes taking place during the sliding of diamond and diamond-like carbon surfaces are investigated using classical molecular dynamics simulations. During the initial sliding stage, diamond surfaces undergo an amorphization process, while an sp ³ to sp ² conversion takes place in tetrahedral amorphous carbon (ta-C) and amorphous hydrocarbon (a-C:H) surface layers. Upon separation of the sliding samples, the interface fails. A rather smooth failure occurs for a-C:H, where the hydrogen atoms present in the bulk passivate the chemically active carbon dangling bonds. Conversely, sp-hybridized carbon chains are observed to form on diamond and ta-C surfaces. These carbynoid structures are known to undergo a fast degradation process when in contact with oxygen. Using quantum-accurate density functional theory simulations, we present a possible mechanism for the oxygen-induced degradation of the carbon chains, leading to oxidative wear of the sp phase on diamond and ta-C surfaces upon exposure to air. Oxygen molecules chemisorb on C–C bonds of the chains, triggering the cleavage of the chains through concerted O–O and C–C bond-breaking reactions. A similar reaction caused by adsorption of water molecules on the carbon chains is ruled out on energetic grounds. Further O₂ adsorption causes the progressive shortening of the resulting, O-terminated, chain fragments through the same O–O and C–C bond breaking mechanism accompanied by the formation of CO₂ molecules.     

A cohesive surface separation potential

This paper presents a form of the cohesive surface separation potential, which can produce potential curves by varying a single dimensionless parameter. Results show that a partial modification of Xu and Needleman’s (1994) cohesive surface separation potential makes it possible to present the other potential curves as a special case as long as the normal separation is concerned. The proposed potential may describe interfacial debonding-crack initiation and growth-character of materials and, through numerical simulation, provide an insight for the effect of different cohesive surface separation potentials on the interfacial debonding.     

High-Performance Heterocyclic Friction Modifiers for Boundary Lubrication

The demand for increased energy efficiency continuously drives the development of new lubricants. Here we report the design and synthesis of hexahydrotriazine, triazine, and cyclen derivatives as friction modifiers (FMs) for enhanced fuel economy. This series of sulfur- and phosphorus-free oil-soluble heterocyclic ring-based molecules exhibits differing thermal and chemical stability depending on the degree of aromatization and number of linking spacers within the central heterocyclic ring. Thermally stable triazine and cyclen FMs significantly increase friction performance in the boundary lubrication regime. Cyclens in particular reduce friction by up to 70% over a wide temperature range. Detailed experimental investigations of the newly synthesized FMs at elevated temperatures demonstrate their favorable tribological performance under four operating conditions: variable-temperature sliding, linear speed ramping, reciprocating sliding, and rolling–sliding contact. These latest experimental findings suggest the potential of the application of “designer” heterocyclic FMs for reducing frictional loss in motor vehicles.     

FRET analysis of transmembrane flipping of FM4-64 in plant cells: is FM4-64 a robust marker for endocytosis?

Although the styryl dye FM4–64 is now used routinely to monitor endocytosis in plants, the argument about its potential to cytoplasmically and non-endocytically relocate into a selective set of vesicular compartments persists. To address this question, we determined whether fluorescence resonance energy transfer (FRET) could occur between a cytoplasmically expressed, short-wavelength excitation green fluorescent protein (GFP) and FM4–64 in Nicotiana benthaminana . After exposure to FM4–64, the root hair plasma membrane and internal organelles became labelled. Under these conditions, no FRET with cytoplasmic GFP was seen. However, if the cells were treated with a low concentration of quillajasaponin, a membrane permeabilization agent, the cells continued to stream and FRET was detected. Thereby, we demonstrate that under conditions that do not severely compromise cell viability, the FM4–64 dye becomes a suitable FRET partner for the cytoplasmically localized GFP. Under normal conditions, FM4–64 does not significantly enter the cytosolic side of the membrane, but remains at the plasma membrane or trapped in the organelles of the endocytic pathway. Hence, when the structure or permeability of the plasma membrane is unaltered, FM4–64 dye is a robust marker for endocytosis.     

Preparation of cultured cells for SEM: air drying from organic solvents.

Air evaporation from organic solvents of differing polarities and surface free energies was used in the preparation of cultured murine peritoneal macrophages for scanning electron microscopy (SEM). The surface structural features of these cells were compared to the surfaces of similar cells prepared by the critical-point procedure. In general, all organic solvents produced a marked collapse of cell structure resulting in an increase in surface irregularity. Fracture surfaces and sharply defined contours including numerous flaps and ridges were characteristic of the non-polar solvent dehydrated samples. Polar solvent dehydrated samples, including those dried from solvents of low surface free energy, exhibited a secondary flowing and settling of the cell membrane. Primary collapse was apparent but cell contours were smoothed and rounded. Overall cell shape and cell-to-cell relationships were retained regardless of solvent type. It is suggested that solvent evaporation may prove useful in certain cases, though investigators are advised to use caution when interpreting the results obtained by such procedures.     

The surface and tribological chemistry of carbon tetrachloride on iron

The thermal decomposition of carbon tetrachloride on clean iron was studied in ultrahigh vacuum using molecular beam strategies, where it is found that carbon tetrachloride thermally decomposes on the surface to deposit iron and carbon with exactly identical kinetics as found at high pressures. No gas‐phase products are detected and the activation energy for the reaction (14.2 ± 0.5 kcal/mol) is in good agreement with the value measured at high pressures. Little carbon is detected on the surface using Auger spectroscopy following reaction and it is found that this diffuses into the surface much faster when formed from CCl₄ than from CH₂Cl₂. This effect is ascribed to the effect of co‐adsorbed chlorine on the adsorbed carbon, which is proposed to decrease the activation energy for diffusion into the bulk of the sample. This effect explains the increased tendency for carbon tetrachloride to form carbides under extreme‐pressure tribological conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Molecular Simulations of Kinetic-Friction Modification in Nanoscale Fluid Layers

Molecular simulations are used to explore kinetic-friction modification in nanoscale fluid layers of oil and additive confined between sheared parallel walls. The molecules are represented by coarse-grained bead-spring models that reflect the essential solvophilic and solvophobic natures of the chemical groups. The degree of friction modification is surveyed as a function of wall separation, sliding velocity, additive molecular weight and architecture, and oil–additive composition. As a rule, the kinetic-friction coefficient is found to increase first linearly and then logarithmically with increasing sliding velocity. From the results for different additive molecules, some subtle but systematic effects are found that point towards an optimum molecular weight and architecture.     

Mechanical Response and Energy-Dissipation Processes in Oligothiophene Monolayers Studied with First-Principles Simulations

We present an extensive first-principles study of the interaction between a silicon oxide nanoasperity and a sexithiophene monolayer in order to investigate the individual molecular processes responsible for the energy dissipation during atomic force microscope (AFM) operation. Our approach includes not only ground-state calculations of the tip–sample interaction, but an extensive set of molecular dynamics simulations at room temperature to include the folding deformation modes that are necessary to describe properly the mechanical response on the molecular layer. With this large computational effort, we have characterized the complex configuration space of the combined tip–sample system in a function of the distance, position and orientation of the tip. We identify surface adhesion as the relevant short-range dissipation mechanism. The system is trapped, due to the presence of energy barriers that cannot be overcome even with the available thermal energy, in different bonding configurations corresponding to local energy minima during the approach and retraction of the tip. These energy barriers are responsible for breaking the adiabaticity and thus lead to force hysteresis and energy dissipation. The quantitative agreement between our calculations and experimental results for the mechanical strength and the dissipated energy supports the use of combined theoretical–experimental dynamic AFM studies in order to gain a fundamental understanding of the microscopic mechanisms involved in energy dissipation.