Illuminating Pathways to Dynamic Nanotribology: Light-Mediated Active Control of Interfacial Friction with Nanosuspensions.

Active control of nanotribological properties is a challenge. Materials responsive to external stimuli may catalyze this paradigm shift. Recently, the nanofriction of a thin film is modulated by light, ushering in phototribology. This frontier is expanded here, by investigating photoactive nanoparticles in lubricants to confer similar functionality to passive surfaces. Quartz-crystal microbalance (QCM) is employed to assess the phototribological behavior of aqueous suspensions of titanium dioxide nanoparticles. A comparison of dark and illuminated conditions provides the first demonstration of tuning the interfacial friction in solid-nanosuspension interfaces by light. Cyclic tests reveal reversible transitions between higher (dark) and lower friction (illuminated) regimes. These transitions are underpinned by transient states with surface charge variations, as confirmed by Zeta potential measurements. The accumulated surface charge increases repulsion within the system and favors sliding. Upon cessation of illumination, the system returns to its prior equilibrium state. These findings impact not only nanotribology but nanofluidics and nanorheology. Furthermore, the results underscore the need to consider light-induced effects in other scenarios, including the calculation of activity coefficients of photoactive suspensions. This multifaceted study introduces a new dimension to in operando frictional tuning, beckoning a myriad of applications and fundamental insights at the nanoscale.

Nanoscale Abrasive Wear of Polyethylene: A Novel Approach To Probe Nanoplastic Release at the Single Asperity Level.

There is a growing concern that nanoplastic pollution may pose planetary threats to human and ecosystem health. However, a quantitative and mechanistic understanding of nanoplastic release via nanoscale mechanical degradation of bulk plastics and its interplay with photoweathering remains elusive. We developed a lateral force microscope (LFM)-based nanoscratch method to investigate mechanisms of nanoscale abrasive wear of low-density polyethylene (LDPE) surfaces by a single sand particle (simulated by a 300 nm tip) under environmentally relevant load, sliding motion, and sand size. For virgin LDPE, we found plowing as the dominant wear mechanism (i.e., deformed material pushed around the perimeter of scratch). After UVA-weathering, the wear mechanism of LDPE distinctively shifted to cutting wear (i.e., deformed material detached and pushed to the end of scratch). The shift in the mechanism was quantitatively described by a new parameter, which can be incorporated into calculating the NP release rate. We determined a 10-fold higher wear rate due to UV weathering. We also observed an unexpected resistance to initiate wear for UV-aged LDPE, likely due to nanohardness increase induced by UV. For the first time, we report 0.4-4 × 10-3 µm3/µm sliding distance/µN applied load as an initial approximate nanoplastic release rate for LDPE. Our novel findings reveal nanoplastic release mechanisms in the environment, enabling physics-based prediction of the global environmental inventory of nanoplastics.

Interfacial friction of vdW heterostructures affected by in-plane strain.

Interfacial properties of van der Waals (vdW) heterostructures dominate the durability and function of their booming practical and potential applications such as opoelectronic devices, superconductors and even pandemics research. However, the strain engineering modulates of interlayer friction of vdW heterostructures consisting of two distinct materials are still unclear, which hinders the applications of vdW heterostructures, as well as the design of solid lubricant and robust superlubricity. In the present paper, a molecular model between a hexagonal graphene flake and a rectangular SLMoS2sheet is established, and the influence of biaxial and uniaxial strain on interlayer friction is explored by molecular dynamics. It is found that the interlayer friction is insensitive to applied strains. Strong robustness of superlubricity between distinct layers is owed to the structure's intrinsic incommensurate characteristics and the existence of Moiré pattern. In engineering practice, it is of potential importance to introduce two distinct 2D materials at the sliding contact interface to reduce the interfacial friction of the contact pair and serve as ideal solid lubricants. Our research provides a further basis to explore the nanotribology and strain engineering of 2D materials and vdW heterostructures.

A modified multibond model for nanoscale static friction.

Several key features of nanoscale friction phenomena observed in experiments, including the stick-slip to smooth sliding transition and the velocity and temperature dependence of friction, are often described by reduced-order models. The most notable of these are the thermal Prandtl-Tomlinson model and the multibond model. Here we present a modified multibond (mMB) model whereby a physically-based criterion-a critical bond stretch length-is used to describe interfacial bond breaking. The model explicitly incorporates damping in both the cantilever and the contacting materials. Comparison to the Fokker-Planck formalism supports the results of this new model, confirming its ability to capture the relevant physics. Furthermore, the mMB model replicates the near-logarithmic trend of increasing friction with lateral scanning speed seen in many experiments. The model can also be used to probe both correlated and uncorrelated stick slip. Through greater understanding of the effects of damping and noise in the system and the ability to more accurately simulate a system with multiple interaction sites, this model extends the range of frictional systems and phenomena that can be investigated. This article is part of the theme issue 'Nanocracks in nature and industry'.

Solidification and superlubricity with molecular alkane films.

Hydrocarbon films confined between smooth mica surfaces have long provided an experimental playground for model studies of structure and dynamics of confined liquids. However, fundamental questions regarding the phase behavior and shear properties in this simple system remain unsolved. With ultrasensitive resolution in film thickness and shear stress, and control over the crystallographic alignment of the confining surfaces, we here investigate the shear forces transmitted across nanoscale films of dodecane down to a single molecular layer. We resolve the conditions under which liquid-solid phase transitions occur and explain friction coefficients spanning several orders of magnitude. We find that commensurate surface alignment and presence of water at the interfaces each lead to moderate or high friction, whereas friction coefficients down to [Formula: see text] are observed for a single molecular layer of dodecane trapped between crystallographically misaligned dry surfaces. This ultralow friction is attributed to sliding at the incommensurate interface between one of the mica surfaces and the laterally ordered solid molecular film, reconciling previous interpretations.

Roughness-dependent tribology effects on discontinuous shear thickening.

Surface roughness affects many properties of colloids, from depletion and capillary interactions to their dispersibility and use as emulsion stabilizers. It also impacts particle-particle frictional contacts, which have recently emerged as being responsible for the discontinuous shear thickening (DST) of dense suspensions. Tribological properties of these contacts have been rarely experimentally accessed, especially for nonspherical particles. Here, we systematically tackle the effect of nanoscale surface roughness by producing a library of all-silica, raspberry-like colloids and linking their rheology to their tribology. Rougher surfaces lead to a significant anticipation of DST onset, in terms of both shear rate and solid loading. Strikingly, they also eliminate continuous thickening. DST is here due to the interlocking of asperities, which we have identified as "stick-slip" frictional contacts by measuring the sliding of the same particles via lateral force microscopy (LFM). Direct measurements of particle-particle friction therefore highlight the value of an engineering-tribology approach to tuning the thickening of suspensions.

Squeezing and stick-slip friction behaviors of lubricants in boundary lubrication.

The fundamental questions of how lubricant molecules organize into a layered structure under nanometers confinement and what is the interplay between layering and friction are still not well answered in the field of nanotribology. While the phase transition of lubricants during a squeeze-out process under compression is a long-standing controversial debate (i.e., liquid-like to solid-like phase transition versus amorphous glass-like transition), recent different interpretations to the stick-slip friction of lubricants in boundary lubrication present new challenges in this field. We carry out molecular dynamics simulations of a model lubricant film (cyclohexane) confined between molecularly smooth surfaces (mica)--a prototypical model system studied in surface force apparatus or surface force balance experiments. Through fully atomistic simulations, we find that repulsive force between two solid surfaces starts at about seven lubricant layers (n = 7) and the lubricant film undergoes a sudden liquid-like to solid-like phase transition at n < 6 monolayers thickness. Shear of solidified lubricant films at three- or four-monolayer thickness results in stick-slip friction. The sliding friction simulation shows that instead of shear melting of the film during the slip of the surface, boundary slips at solid-lubricant interfaces happen, while the solidified structure of the lubricant film is well maintained during repeated stick-slip friction cycles. Moreover, no dilation of the lubricant film during the slip is observed, which is surprisingly consistent with recent surface force balance experimental measurements.

On the debris-level origins of adhesive wear.

Every contacting surface inevitably experiences wear. Predicting the exact amount of material loss due to wear relies on empirical data and cannot be obtained from any physical model. Here, we analyze and quantify wear at the most fundamental level, i.e., wear debris particles. Our simulations show that the asperity junction size dictates the debris volume, revealing the origins of the long-standing hypothesized correlation between the wear volume and the real contact area. No correlation, however, is found between the debris volume and the normal applied force at the debris level. Alternatively, we show that the junction size controls the tangential force and sliding distance such that their product, i.e., the tangential work, is always proportional to the debris volume, with a proportionality constant of 1 over the junction shear strength. This study provides an estimation of the debris volume without any empirical factor, resulting in a wear coefficient of unity at the debris level. Discrepant microscopic and macroscopic wear observations and models are then contextualized on the basis of this understanding. This finding offers a way to characterize the wear volume in atomistic simulations and atomic force microscope wear experiments. It also provides a fundamental basis for predicting the wear coefficient for sliding rough contacts, given the statistics of junction clusters sizes.

On the question of whether lubricants fluidize in stick-slip friction.

Intermittent sliding (stick-slip motion) between solids is commonplace (e.g., squeaking hinges), even in the presence of lubricants, and is believed to occur by shear-induced fluidization of the lubricant film (slip), followed by its resolidification (stick). Using a surface force balance, we measure how the thickness of molecularly thin, model lubricant films (octamethylcyclotetrasiloxane) varies in stick-slip sliding between atomically smooth surfaces during the fleeting (ca. 20 ms) individual slip events. Shear fluidization of a film of five to six molecular layers during an individual slip event should result in film dilation of 0.4-0.5 nm, but our results show that, within our resolution of ca. 0.1 nm, slip of the surfaces is not correlated with any dilation of the intersurface gap. This reveals that, unlike what is commonly supposed, slip does not occur by such shear melting, and indicates that other mechanisms, such as intralayer slip within the lubricant film, or at its interface with the confining surfaces, may be the dominant dissipation modes.

Strain Discontinuity, Avalanche, and Memory in Carbon Nanotube Serpentine Systems.

This work addresses the problem of how a nano-object adheres to a supporting media. The case of study are the serpentine-like structures of single-wall carbon nanotubes (SWNTs) grown on vicinal crystalline quartz. We develop in situ nanomanipulation and confocal Raman spectroscopy in such systems, and to explain the results, we propose a dynamical equation in which static friction is treated phenomenologically and implemented as cutoff for velocities, via Heaviside step function and an adhesion force tensor. We demonstrate that the strain profiles observed along the SWNTs are due to anisotropic adhesion, adhesion discontinuities, strain avalanches, and memory effects. The equation is general enough to make predictions for various one- and two-dimensional nanosystems adhered to a supporting media.

Anisotropic Stick-Slip Frictional Surfaces via Titania Nanorod Patterning.

Nanoscale or microscale surface texturing is an effective technique to tailor the tribological properties between two surfaces that are rubbed against each other. In order to achieve the desired frictional properties by a patterned surface, one needs an in-depth understanding of the underlying mechanisms. Here, we demonstrate anisotropic stick-slip friction achieved via a nanotextured surface of tilted titania nanorods (TiNRs). The surface was developed by using the glancing angle deposition (GLAD) technique, and exhibited load-dependent variations in stick-slip friction as well as frictional anisotropy in different sliding directions. For studying the frictional properties of the newly developed surface, lateral force microscopy (LFM) was performed in three different reciprocal orientations (0° rotated, 45° rotated, 90° rotated) using a custom-made colloidal alumina atomic force microscopy (AFM) probe. The frictional behavior was found to vary significantly with the orientation. At 0° rotated position) a prominent "stick-slip" was observed when scanning opposite to the tilt direction, whereas the phenomenon reduced significantly when the nanotextured surface was scanned along the tilt direction or rotated to different angles (45 and 90°) with respect to the sliding direction of the AFM cantilever supporting the probe. The experimental findings were interpreted based on the classical solution for large deflections of tilted elastic rods. Overall, the textured surface, LFM-based frictional measurement, and the quantitative analysis presented here provide a fundamental understanding of how friction can be significantly varied on a surface patterned with tilted TiNRs at a length scale of about 1 µm, which can be comprehensively applied to nanorod patterns of other materials on different substrates.

Covalent organic frameworks in tribology - A perspective.

Two-dimensional covalent organic frameworks (2D COFs) are an emerging class of crystalline porous materials formed through covalent bonds between organic building blocks. COFs uniquely combine a large surface area, an excellent stability, numerous abundant active sites, and tunable functionalities, thus making them highly attractive for numerous applications. Especially, their abundant active sites and weak interlayer interaction make these materials promising candidates for tribological research. Recently, notable attention has been paid to COFs as lubricant additives due to their excellent tribological performance. Our review aims at critically summarizing the state-of-art developments of 2D COFs in tribology. We discuss their structural and functional design principles, as well as synthetic strategies with a special focus on tribology. The generation of COF thin films is also assessed in detail, which can alleviate their most challenging drawbacks for this application. Subsequently, we analyze the existing state-of-the-art regarding the usage of COFs as lubricant additives, self-lubrication composite coatings, and solid lubricants at the nanoscale. Finally, critical challenges and future trends of 2D COFs in tribology are outlined to initiate and boost new research activities in this exciting field.

Cyclic Wear Reliability of 2D Monolayers.

Understanding wear, a critical factor impacting the reliability of mechanical systems, is vital for nano-, meso-, and macroscale applications. Due to the complex nature of nanoscale wear, the behavior of nanomaterials such as two-dimensional materials under cyclic wear and their surface damage mechanism is yet unexplored. In this study, we used atomic force microscopy coupled with molecular dynamic simulations to statistically examine the cyclic wear behavior of monolayer graphene, MoS2, and WSe2. We show that graphene displays exceptional durability and lasts over 3000 cycles at 85% of the applied critical normal load before failure, while MoS2 and WSe2 last only 500 cycles on average. Moreover, graphene undergoes catastrophic failure as a result of stress concentration induced by local out-of-plane deformation. In contrast, MoS2 and WSe2 exhibit intermittent failure, characterized by damage initiation at the edge of the wear track and subsequent propagation throughout the entire contact area. In addition to direct implications for MEMS and NEMS industries, this work can also enable the optimization of the use of 2D materials as lubricant additives on a macroscopic level.

Superlubricity and Stress-Shielding of Graphene Enables Ultra Scratch-Resistant Glasses.

Glasses, when subjected to scratch loading, incur damages affecting their optical and mechanical integrity. Here, it is demonstrated that silica glasses protected with mechanically exfoliated few-layer graphene sheets can exhibit remarkable improvement in scratch resistance. To this extent, the friction and wear characteristics of silica glasses with exfoliated graphene using atomic force microscopy (AFM) are explored. The friction forces recorded during AFM scratch tests of the graphene-glass surfaces at multiple loads exhibit ∼98% reduction compared to that of the bare silica glass, with the friction coefficient falling in the superlubricity regime. This dramatic reduction in friction achieved by the graphene sheets results in significantly lower wear of the graphene-glass surfaces postscratching. Further investigations employing atomistic simulations reveal that the stress-shielding mechanism is due to the reduced deformation of graphene-glass surfaces, thereby curtailing the overall damage. Altogether, the present work provides a new fillip toward the development of glasses with enhanced scratch resistance exploiting two-dimensional coatings.

Hierarchical adaptive nanostructured PVD coatings for extreme tribological applications: the quest for nonequilibrium states and emergent behavior.

Adaptive wear-resistant coatings produced by physical vapor deposition (PVD) are a relatively new generation of coatings which are attracting attention in the development of nanostructured materials for extreme tribological applications. An excellent example of such extreme operating conditions is high performance machining of hard-to-cut materials. The adaptive characteristics of such coatings develop fully during interaction with the severe environment. Modern adaptive coatings could be regarded as hierarchical surface-engineered nanostructural materials. They exhibit dynamic hierarchy on two major structural scales: (a) nanoscale surface layers of protective tribofilms generated during friction and (b) an underlying nano/microscaled layer. The tribofilms are responsible for some critical nanoscale effects that strongly impact the wear resistance of adaptive coatings. A new direction in nanomaterial research is discussed: compositional and microstructural optimization of the dynamically regenerating nanoscaled tribofilms on the surface of the adaptive coatings during friction. In this review we demonstrate the correlation between the microstructure, physical, chemical and micromechanical properties of hard coatings in their dynamic interaction (adaptation) with environment and the involvement of complex natural processes associated with self-organization during friction. Major physical, chemical and mechanical characteristics of the adaptive coating, which play a significant role in its operating properties, such as enhanced mass transfer, and the ability of the layer to provide dissipation and accumulation of frictional energy during operation are presented as well. Strategies for adaptive nanostructural coating design that enhance beneficial natural processes are outlined. The coatings exhibit emergent behavior during operation when their improved features work as a whole. In this way, as higher-ordered systems, they achieve multifunctionality and high wear resistance under extreme tribological conditions.

Nucleation of Frank Dislocation during the Squeeze-Out Process in Boundary Lubrication: A Molecular Dynamics Study.

Liquid-vapor molecular dynamics (LVMD) simulations are performed to reinvestigate the phase transition and solvation force oscillation behavior of a simple argon liquid film confined between two solid surfaces. Our simulations present a novel scenario in which the n → n - 1 layering transitions are accompanied by the formation, climb, and annihilation of Frank partial dislocations during the squeeze-out process under compression. This is indicated by the splitting of the repulsive peaks in the solvation force profile. The detailed analysis reveals that the formation-climb-annihilation mechanism of Frank dislocation occurs during approach and disappears during receding, which would result in force hysteresis. In combination with our recent works, this study provides new insights into the physical property of nanoconfined lubricant films in boundary lubrication.

Nanoindentation and nano-scratching of hydroxyapatite coatings for resorbable magnesium alloy bone implant applications.

The corrosion rate of Mg alloys is currently too high for viable resorbable implant applications. One possible solution is to coat the alloy with a hydroxyapatite (HA) layer to slow the corrosion and promote bone growth. As such coatings can be under severe stresses during implant insertion, we present a nano-mechanical and nano-tribological investigation of RF-sputtered HA films on AZ31 Mg alloy substrates. EDX and XRD analysis indicate that as-deposited coatings are amorphous and Ca-deficient whereas rapid thermal annealing results in c-axis orientation and near-stoichiometric composition. Analysis of the nanoindentation data using a thin film model shows that annealing increases the coating's intrinsic hardness (H) and strain at break (H/E) values, from 2.7 GPa to 9.4 GPa and from 0.043 to 0.079, respectively. In addition, despite being rougher, the annealed samples display better wear resistance; a sign that the rapid thermal annealing does not compromise their interfacial strength and that these systems have potential for resorbable bone implant applications.

Nanofriction Properties of Mono- and Double-Layer Ti3C2Tx MXenes.

Unique structure and ability to control the surface termination groups of MXenes make these materials extremely promising for solid lubrication applications. Due to the challenging delamination process, the tribological properties of two-dimensional MXenes particles have been mostly investigated as additive components in the solvents working in the macrosystem, while the understanding of the nanotribological properties of mono- and few-layer MXenes is still limited. Here, we investigate the nanotribological properties of mono- and double-layer Ti3C2Tx MXenes deposited by the Langmuir-Schaefer technique on SiO2/Si substrates. The friction of all of the samples demonstrated superior lubrication properties with respect to SiO2 substrate, while the friction force of the monolayers was found to be slightly higher compared to double- and three-layer flakes, which demonstrated similar friction. The coefficient of friction was estimated to be 0.087 ± 0.002 and 0.082 ± 0.003 for mono- and double-layer flakes, respectively. The viscous regime was suggested as the dominant friction mechanism at high scanning velocities, while the meniscus forces affected by contamination of the MXenes surface were proposed to control the friction at low sliding velocities.

Insight into the Nanotribological Mechanism of Two-Dimensional Covalent Organic Frameworks.

Two-dimensional (2D) materials are promising in reducing friction-induced energy loss and wear in automotive and electronics industries because of their superior tribological performance. As a kind of organic 2D materials, the structure and functionality of covalent organic frameworks (COFs) are much easier to tailor compared to other inorganic 2D materials, which expand their potential application in a Micro-Electro-Mechanical System (MEMS). In this manuscript, several kinds of COFs are synthesized and characterized on the surface of highly oriented pyrolytic graphite (HOPG) to investigate the nanotribological mechanism of organic 2D materials. It is surprisingly revealed that the friction coefficients of surface COFs are positively correlated with the pore sizes of honeycomb networks. The COFs with smaller pores would have a smoother potential energy surface and exhibit a lower friction coefficient. Besides, the porous structures of surface COFs make them good candidates to be host templates. The host-guest assembly structures are successfully constructed after introducing coronene molecules, and these host-guest systems display higher friction coefficients because the assembly structure of the guest molecules would be perturbed during the friction process and bring additional slip energy barriers, but the capacity of COFs to form composite assembly with functional guest molecules greatly promotes their further application in the MEMS.

Insight Into the Superlubricity and Self-Assembly of Liquid Crystals.

Liquid crystals are promising molecular materials in the application of lubrication. Herein, the microscale solid superlubricity is accomplished by the construction of uniform and ordered self-assembly of several liquid crystals. The self-assembly structures on a highly oriented pyrolytic graphite (HOPG) surface are explicitly revealed by using scanning tunneling microscopy (STM). Meanwhile, the nanotribological performance of the self-assemblies are measured by using atomic force microscopy (AFM), revealing ultralow friction coefficients lower than 0.01. The interaction energies are calculated by density functional theory (DFT) method, indicating the positive correlation between friction coefficients and interaction strength. The effort on the self-assembly and superlubricity of liquid crystals could enhance the understanding of the nanotribological mechanism and benefit the further application of liquid crystals as lubricants.