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Tribochemistry, which is another name of mechanochemistry driven by shear, deals with complex and dynamic interfacial processes that can lead to facilitation of surface wear or formation of beneficial tribofilms. For better mechanistic understanding, we investigated the reactivity of tribopolymerization of organic molecules with different internal ring strain energy (methylcyclopentane, cyclohexane, and cyclohexene) on a stainless steel (SS) surface in inert (N2), oxidizing (O2), and reducing (H2) environments. On the clean SS surface, precursor molecules were found to physisorb with a broad range of molecular orientations. In inert and reducing environments, the strain-free cyclohexane showed the lowest tribochemical activity among the three tested. Compared to the N2 environment, the tribochemical activity in H2 was suppressed. In the O2 environment, only cyclohexene produced tribofilms and methylcyclopentane and cyclohexane did not. When tribofilms were analyzed with Raman spectroscopy, the spectral features of diamond-like carbon (DLC) or amorphous carbon (a-C) were observed due to photochemical degradation of triboproducts. Based on infrared spectroscopy, tribofilms were found to be organic polymers containing oxygenated groups. Whenever polymeric tribrofilms were produced, wear volume was suppressed by orders of magnitudes but not completely to zero. These results supported the previously suggested mechanisms which involved surface oxygens as a reactant species of the tribopolymerization process.

While it is well established that nanoparticle shape can depend on equilibrium thermodynamics or growth kinetics, recent computational work has suggested the importance of thermal energy in controlling the distribution of shapes in populations of nanoparticles. Here, we used transmission electron microscopy to characterize the shapes of bare platinum nanoparticles and observed a strong dependence of shape distribution on particle size. Specifically, the smallest nanoparticles (

Reactive molecular dynamics simulations of Ti3C2Tx with three different surface terminations were used to understand friction and failure of MXenes during sliding at normal pressures from 2–20 GPa and temperatures from 300–1100 K. The O-terminated MXene had the smallest shear stress at low pressures and temperatures, but failed at more severe conditions due to interlayer bonding and the formation of Ti–O–Ti bridges between MXene layers. Failure was not observed for the OH-terminated MXene or a heterostructure combining O- and OH-terminations. For these, at less severe operating conditions, shear stress was smaller for the OH-terminated MXene, while the opposite was observed at higher temperatures and pressures. These trends were explained in terms of adhesion and the complex effect of hydrogen atoms that can either facilitate or hinder sliding, depending on the termination and conditions. Results show that friction and failure are affected by and potentially tunable via MXene surface termination.

Many previous studies of tribofilms have interpreted D- and G-bands in Raman spectra as evidence that diamond-like carbon (DLC) was formed during sliding. DLC and other amorphous-carbon films are produced by high-energy processes or high-temperature pyrolysis. Since neither of these conditions commonly occurs in a sliding interface, it seems unlikely that such materials could be produced during simple frictional sliding. To understand this apparent contradiction, we systematically analyzed tribofilms produced from vapor and liquid lubrication experiments using Raman spectroscopy with varied laser power and wavelength. The results provide evidence that DLC-like features in Raman spectra of tribofilms formed from organic molecules originate, not by tribochemical synthesis in situ during the tribo-testing as suggested previously, but rather from post-synthesis photochemical degradation of carbonaceous organic matter during the Raman analysis.

Mechanochemical activation has created new opportunities for applications such as solvent-free chemical synthesis, polymer processing, and lubrication. However, mechanistic understanding of these processes is still limited because the mechanochemical response of a system is a complex function of many variables, including the direction of applied stress and the chemical features of the reactants in non-equilibrium conditions. Here, we studied shear-activated reactions of simple cyclic organic molecules to isolate the effect of chemical structure on reaction yield and pathway. Reactive molecular dynamics simulations were used to model methylcyclopentane, cyclohexane, and cyclohexene subject to pressure and shear stress between silica surfaces. Cyclohexene was found to be more susceptible to mechanochemical activation of oxidative chemisorption and subsequent oligomerization reactions than either methylcyclopentane or cyclohexane. The oligomerization trend was consistent with shear-driven polymerization yield measured in ball-on-flat sliding experiments. Analysis of the simulations showed the distribution of carbon atom sites at which oxidative chemisorption occurred and identified the double bond in cyclohexene as being the origin of its shear susceptibility. Lastly, the most common reaction pathways for association were identified, providing insight into how the chemical structures of the precursor molecules determined their response to mechanochemical activation.

Understanding the size- and shape-dependent properties of platinum nanoparticles is critical for enabling the design of nanoparticle-based applications with optimal and potentially tunable functionality. Toward this goal, we evaluated nine different empirical potentials with the purpose of accurately modeling faceted platinum nanoparticles using molecular dynamics simulation. First, the potentials were evaluated by computing bulk and surface properties-surface energy, lattice constant, stiffness constants, and the equation of state-and comparing these to prior experimental measurements and quantum mechanics calculations. Then, the potentials were assessed in terms of the stability of cubic and icosahedral nanoparticles with faces in the {100} and {111} planes, respectively. Although none of the force fields predicts all the evaluated properties with perfect accuracy, one potential -- the embedded atom method formalism with a specific parameter set -- was identified as best able to model platinum in both bulk and nanoparticle forms., 20 pages, 8 figures

The adhesion between nanoscale components has been shown to increase with applied load, contradicting well-established mechanics models. Here, we use in situ transmission electron microscopy and atomistic simulations to reveal the underlying mechanism for this increase as a change in the mode of separation. Analyzing 135 nanoscale adhesion tests on technologically relevant materials of anatase TiO2, silicon, and diamond, we demonstrate a transition from fracture-controlled to strength-controlled separation. When fracture models are incorrectly applied, they yield a 7-fold increase in apparent work of adhesion; however, we show that the true work of adhesion is unchanged with loading. Instead, the nanoscale adhesion is governed by the product of adhesive strength and contact area; the pressure dependence of adhesion arises because contact area increases with applied load. By revealing the mechanism of separation for loaded nanoscale contacts, these findings provide guidance for tailoring adhesion in applications from nanoprobe-based manufacturing to nanoparticle catalysts.

The wettability of ionic liquids (ILs) is relevant to their use in various applications. However, a mechanistic understanding of how the cation-anion pair affects wettability is still evolving. Here, focusing on phosphonium ILs, wettability was characterized in terms of contact angle using experiments and classical molecular dynamics simulations. Both experiments and simulations showed that the contact angle was affected by the anion and increased as benzoate < salicylate < saccharinate. Further, the simulations showed that the contact angle decreased with increasing cation alkyl chain length for these anions paired with five different tetra-alkyl-phosphonium cations. The trends were explained in terms of adhesive and cohesive energies in the simulations and then correlated to the atomic scale differences between the anions and the cations.

Molecular dynamics simulations were performed to study nanoscale friction on hydrophilic and hydrophobic self-assembled monolayers (SAMs) immersed in water. Sliding was simulated in two different directions to capture anisotropy due to the direction of motion relative to the inherent tilted orientation of the molecules. It was shown that friction depends on both hydrophobicity and sliding direction, with the highest friction observed for sliding on hydrophobic SAM in the direction against the initial orientation of the molecules. The origins of the friction trends were analyzed by differentiating the tip-SAM and tip-water force contributions to friction. The tip-water force was higher on the hydrophilic SAM, and this was shown to be due to the presence of a dense layer of water adjacent to the surface and hydrogen bonding. In contrast, the tip-SAM force was higher on the hydrophobic SAM due to a water depletion layer, which enabled the tip to be closer to the SAM terminal group. The higher-friction cases all exhibited greater penetration of the tip below the surface of the SAM, accommodated by further tilting and reorientation of the SAM molecules.

Reactive molecular dynamics simulations of MoS2 crystallization from amorphous precursor materials showed that crystal domain size decreased because of excess S or O, relative to the stoichiometric...

Despite extensive research on the tribological properties of MoS2, the frictional characteristics of other members of the transition-metal dichalcogenide (TMD) family have remained relatively unexplored. To understand the effect of the chalcogen on the tribological behavior of these materials and gain broader general insights into the factors controlling friction at the nanoscale, we compared the friction force behavior for a nanoscale single asperity sliding on MoS2, MoSe2, and MoTe2 in both bulk and monolayer forms through a combination of atomic force microscopy experiments and molecular dynamics simulations. Experiments and simulations showed that, under otherwise identical conditions, MoS2 has the highest friction among these materials and MoTe2 has the lowest. Simulations complemented by theoretical analysis based on the Prandtl-Tomlinson model revealed that the observed friction contrast between the TMDs was attributable to their lattice constants, which differed depending on the chalcogen. While the corrugation amplitudes of the energy landscapes are similar for all three materials, larger lattice constants permit the tip to slide more easily across correspondingly wider saddle points in the potential energy landscape. These results emphasize the critical role of the lattice constant, which can be the determining factor for frictional behavior at the nanoscale.

Atomic-scale friction measured for a single asperity sliding on 2D materials depend on the direction of scanning relative to the material's crystal lattice. Here, nanoscale friction anisotropy of wrinkle-free bulk and monolayer MoS2 is characterized using atomic force microscopy and molecular dynamics simulations. Both techniques show 180° periodicity (2-fold symmetry) of atomic-lattice stick-slip friction vs. the tip's scanning direction with respect to the MoS2 surface. The 60° periodicity (6-fold symmetry) expected from the MoS2 surface's symmetry is only recovered in simulations where the sample is rotated, as opposed to the scanning direction changed. All observations are explained by the potential energy landscape of the tip-sample contact, in contrast with nanoscale topographic wrinkles that have been proposed previously as the source of anisotropy. These results demonstrate the importance of the tip-sample contact quality in determining the potential energy landscape and, in turn, friction at the nanoscale.

Atomic resolution imaging of surfaces in liquid environments using atomic force microscopy (AFM) is challenging in terms of both reproducibility and measurement interpretation. To understand the origins of these challenges, we used molecular dynamics simulations of AFM on hydrophilic self-assembled monolayers (SAMs) in water. The force on the model AFM tip was calculated as a function of lateral and vertical position relative to the SAM surface. The contributions of the water and SAMs to the overall force were analyzed, and the former was correlated to the water density distribution. Then, dynamic AFM was modeled by oscillating the tip at a driving amplitude. It was found that the contrast between amplitudes at different lateral positions on the surface was dependent on the vertical position of the tip. Lastly, amplitude maps were produced for two vertical positions at constant height, and the ability to capture atomic resolution was related to the force on the tip. These results offer an explanation for the observed instability in atomic scale imaging using AFM and more generally provide insight into the contrast mechanisms of surface images obtained in liquid environments.

Although superlubricity is highly desirable for many engineering applications, its implementation has so far been seriously restricted due to limitations in contact size, environmental adaptability and life time. By designing superlattice films with alternating molybdenum disulfide (MoS2) and tungsten carbide (WC) layers, we show that long-term macroscale superlubricity (friction coefficient of 0.006) in low vacuum (~10-3 Pa) after a short running-in period in air. Such unusual behavior is enabled when the fine structure of the bilayer unit is rationally controlled to yield incommensurate contacts between MoS2 and metal oxides nanoparticles produced spontaneously during tribological sliding. Our analysis indicates that the WC phase is critical for superlubricity by helping stiffen the film, facilitate preferential growth of crystalline MoS2 along (002) plane parallel to substrate, and produce lubricous nanoparticles. We further demonstrate the superlattice design is generally applicable for MoS2/ceramics materials to achieve long life-time macroscale superlubricity with easy self-rejuvenation capability.

Interfacial shear-driven or shear-assisted chemical reactions play an important role in many engineering processes, including reactions between lubricant additives and the surfaces of mechanical components and fabrication of surface topographic features. Mechanistic studies of shear-driven chemical reactions often employ a mechanically assisted thermal activation model from which a so-called activation volume can be defined. Activation volume is important because it quantifies the efficiency of interfacial shear to drive the reaction. Recent advancements have enabled calculation of activation volume from both nano- and macro-scale experiments as well as simulations. However, the calculated volumes differ by orders of magnitude, even for the same reactant species, and the physical interpretations vary correspondingly. Here, we review how activation volume has been measured and interpreted for shear-driven reactions in the literature with the goal of guiding future efforts to understand and use this important parameter for engineering design through tribochemistry.

Author(s): Yang, Quanpeng; Li, Wenjun; Stober, Spencer T; Burns, Adam B; Gopinadhan, Manesh; Martini, Ashlie

Varnish accumulation resulting from lubricant degradation can adversely affect the efficient operation of lubricated mechanical systems. There are various chemical cleaners commercially available t...

We present atomic force microscopy experiments of wearless sliding between nanoscale tips and both bulk and monolayer $\mathrm{Mo}{\mathrm{S}}_{2}$ in ultrahigh vacuum across a wide range of temperatures (150--450 K) and scanning speeds (5 nm/s to 500 $\ensuremath{\mu}\mathrm{m}/\mathrm{s}$). Atomic lattice stick-slip behavior is consistently resolved. However, a bifurcation of behavior is seen, with some measurements showing a strong decrease in friction with increasing temperature and others showing athermal and low friction under nominally identical conditions. The difference between thermal and athermal behavior is attributed to a change in the corrugation of the potential energy surface, possibly due to trace amounts of adsorbed contaminants. While the speed dependence at a given temperature is consistent with the thermal Prandtl-Tomlinson model for atomic-scale friction, that is not the case for the temperature dependence (when it is present), nor can the temperature dependence be described by other existing models. We discuss the limitations of these models considering the measured results.

The high mechanical performance of common structural materials (e.g., metals, alloys, and ceramics) originates from strong primary bonds (i.e., metallic, covalent, ionic) between constituent atoms. However, the large formation energy of primary bonds requires high temperatures in order to process these materials, resulting in significant manufacturing costs and a substantial environmental footprint. Herein, we report a strategy to leverage secondary bonds (e.g., hydrogen bonds) to produce a high-performance and low-cost material that outperforms most existing structural compounds. By dispersing graphite flakes and nanofibrillated cellulose (NFC) in water at room temperature to form a stable and homogeneous solution with a high solid concentration (20 wt%), we demonstrate this slurry can be scalably printed to manufacture a graphite-NFC composite that exhibits a high tensile strength (up to 1.0 GPa) and toughness (up to 30.0 MJ/m3). The low density of graphite and cellulose leads to a specific strength of the composite (794 MPa/(g cm−3)) that is significantly greater than most engineering materials (e.g., steels, aluminum, and titanium alloys). We demonstrate how hydrogen bonds between the graphite flakes and NFC play a pivotal role in the superb mechanical performance of the composite, also enabling this low-cost material to be recyclable for an environmentally sustainable solution to high performance structural materials.

Ultralow friction can be achieved with 2D materials, particularly graphene and MoS2. The nanotribological properties of these different 2D materials have been measured in previous atomic force microscope (AFM) experiments sequentially, precluding immediate and direct comparison of their frictional behavior. Here, friction is characterized at the nanoscale using AFM experiments with the same tip sliding over graphene, MoS2, and a graphene/MoS2 heterostructure in a single measurement, repeated hundreds of times, and also measured with a slowly varying normal force. The same material systems are simulated using molecular dynamics (MD) and analyzed using density functional theory (DFT) calculations. In both experiments and MD simulations, graphene consistently exhibits lower friction than the MoS2 monolayer and the heterostructure. In some cases, friction on the heterostructure is lower than that on the MoS2 monolayer. Quasi-static MD simulations and DFT calculations show that the origin of the friction contrast is the difference in energy barriers for a tip sliding across each of the three surfaces.

A stronger, cooler wood One good way to reduce the amount of cooling a building needs is to make sure it reflects away infrared radiation. Passive radiative cooling materials are engineered to do this extremely well. Li et al. engineered a wood through delignification and re-pressing to create a mechanically strong material that also cools passively. They modeled the cooling savings of their wood for 16 different U.S. cities, which suggested savings between 20 and 50%. Cooling wood would be of particular value in hot and dry climates. Science , this issue p. 760

Parallel reactive molecular dynamics simulations were used to statistically analyze chemical reactions between tri-cresyl phosphate (TCP) and an amorphous iron oxide surface. To accurately model this system, a new parameter set for Fe/P/O interactions within the ReaxFF framework was developed. Using the new parameter set, 100 parallel simulations of a single TCP molecule on an amorphous iron oxide surface were run to capture multiple possible reactions at temperatures ranging from 300 to 700 K. The frequency of TCP–surface reactions for each atom type and each unique reaction site on the TCP was analyzed across the range of temperatures. Finally, the composition of the material chemisorbed to the surface was determined and analyzed in the context of previously reported experimental measurements of TCP films in oxygen-deficient environments. The results are specifically relevant to TCP, but the parallel reactive simulation approach and statistical analysis of reaction sites can be applied more generally to...

Conductive-atomic force microscopy (C-AFM) and molecular dynamics (MD) simulations are used to investigate time-dependent electrical contact resistance (ECR) at the nanoscale. ECR is shown to decrease over time as measured using C-AFM and estimated using two approaches from MD simulations, although the experiments and simulations explore different time scales. The simulations show that time dependence of ECR is attributable to an increase in real contact area due to atoms diffusing into the contact. This diffusion-based aging is found to be a thermally activated process that depends on the local contact pressure. The results demonstrate that contact aging, previously identified as an important mechanism for friction, can significantly affect electrical conduction at the nanoscale.Graphical Abstract

The last 25 years have seen immense changes, both in the world generally and in scientific publishing. It is now hard to imagine that our original editorial responsibilities included managing filing cabinets full of manuscripts and making frequent trips to the post office! In this first Invited Viewpoint, we have invited ourselves to highlight some of the key breakthroughs that have been made on topics that are within the scope of Tribology Letters, i.e., breakthroughs in the science of tribology. We also bring your attention to some unique, existing features of the journal, as well as new ways in which Tribology Letters will be more functional for you in the future. Finally, we share our views on publishing tribology research more generally, with the aim of encouraging publication decisions that benefit the tribology community as a whole., Tribology Letters, 69 (2), ISSN:1023-8883, ISSN:1573-2711

Phosphate esters have a wide range of industrial applications, for example in tribology where they are used as vapour phase lubricants and antiwear additives. An atomic-level understanding of phosphate ester tribofilm formation mechanisms is required to improve their tribological performance. A process of particular interest is the thermal decomposition of phosphate esters on steel surfaces, since this initiates polyphosphate film formation. In this study, reactive force field (ReaxFF) molecular dynamics (MD) simulations are used to study the thermal decomposition of phosphate esters with different substituents on several ferrous surfaces. The ReaxFF parameterisation was validated for a representative system using density functional theory (DFT) calculations. During the MD simulations on Fe 3 O 4 (001) and α-Fe(110), chemisorption interactions between the phosphate esters and the surfaces occur even at room temperature, and the number of molecule-surface bonds increases as the temperature increases from 300 to 1000 K. Conversely, on hydroxylated, amorphous Fe 3 O 4 , most of the molecules are physisorbed and some desorption occurs at high temperature. Thermal decomposition rates were much higher on Fe 3 O 4 (001) and particularly α-Fe(110) compared to hydroxylated, amorphous Fe 3 O 4. This suggests that water passivates ferrous surfaces and inhibits phosphate ester chemisorption, decomposition, and ultimately polyphosphate film formation. For the alkyl phosphates, thermal decomposition proceeds mainly through CO and C-H cleavage on Fe 3 O 4 (001). Aryl phosphates show much higher thermal stability, and decomposition on Fe 3 O 4 (001) only occurs through P-O and C-H cleavage, which require very high temperature. The onset temperature for CO cleavage on Fe 3 O 4 (001) increases as: tertiary alkyl < secondary alkyl < primary linear alkyl ≈ primary branched alkyl < aryl. This order is consistent with experimental observations for the thermal stability of antiwear additives with similar substituents. The simulation results clarify a range of surface and substituent effects on the thermal decomposition of phosphate esters on steel that should be helpful for the design of new molecules with improved tribological performance.