High-Temperature Superlubricity in MoS2/Graphene van der Waals Heterostructures.

Achieving high-temperature superlubricity is essential for modern extreme tribosystems. Solid lubrication is the sole viable alternative due to the degradation of liquid ones but currently suffers from notable wear, instability, and high friction coefficient. Here, we report robust superlubricity in MoS2/graphene van der Waals heterostructures at high temperatures up to ∼850 K, achieved through localized heating to enable reliable friction testing. The ultralow friction of the MoS2/graphene heterostructure is found to be notably further reduced at elevated temperature and dominantly contributed by the MoS2 edge. The observation can be well described by a multi-contact model, wherein the thermally activated rupture of edge-contacts facilitates the sliding. Our results should be applicable to other van der Waals heterostructures and shed light on their applications for superlubricity at elevated temperature.

Superlubric Graphullerene.

Graphullerene (GF), an extended quasi-two-dimensional network of C60 molecules, is proposed as a multicontact platform for constructing superlubric interfaces with layered materials. Such interfaces are predicted to present very small and comparable sliding energy corrugation regardless of the identity of the underlying flat layered material surface. It is shown that, beyond the geometrical effect, covalent interlinking between the C60 molecules results in reduction of the sliding energy barrier. For extended GF supercells, negligible sliding energy barriers are found along all sliding directions considered, even when compared to the case of the robust superlubric graphene/h-BN heterojunction. This suggests that multicontact architectures can be used to design ultrasuperlubric interfaces, where superlubricity may persist under extreme sliding conditions.

Why is Superlubricity of Diamond-Like Carbon Rare at Nanoscale?

Hydrogenated diamond-like carbon (HDLC) is a promising solid lubricant for its superlubricity which can benefit various industrial applications. While HDLC exhibits notable friction reduction in macroscale tests in inert or reducing environmental conditions, ultralow friction is rarely observed at the nanoscale. This study investigates this rather peculiar dependence of HDLC superlubricity on the contact scale. To attain superlubricity, HDLC requires i) removal of ≈2 nm-thick air-oxidized surface layer and ii) shear-induced transformation of amorphous carbon to highly graphitic and hydrogenated structure. The nanoscale wear depth exceeds the typical thickness of the air-oxidized layer, ruling out the possibility of incomplete removal of the air-oxidized layer. Raman analysis of transfer films indicates that shear-induced graphitization readily occurs at shear stresses lower than or comparable to those in the nanoscale test. Thus, the same is expected to occur at the nanoscale test. However, the graphitic transfer films are not detected in ex-situ analyses after nanoscale friction tests, indicating that the graphitic transfer films are pushed out of the nanoscale contact area due to the instability of transfer films within a small contact area. Combining all these observations, this study concludes the retention of highly graphitic transfer films is crucial to achieving HDLC superlubricity.

Superlubric Sliding of Graphene Auto-Kirigami with Interfaces Containing Self-Assembled Stripe-Pattern Adsorbates.

Van der Waals heterostructures formed by stacked 2D materials show exceptional electronic, mechanical, and optical properties. Superlubricity, a condition where atomically flat, incommensurate planes of atoms result in ultra-low friction, is a prime example enabling, for example, self-assembly of optically visible graphene nanostructures in air via a sliding auto-kirigami process. Here, it is demonstrated that a subtle but ubiquitous adsorbate stripe structure found on graphene and graphitic surfaces in ambient conditions remains stable within the interface between twisted graphene layers as they slide over each other. Despite this contamination, the interface retains an exceptional superlubricious state with an estimated upper bound frictional shear strength of 10 kPa, indicating that direct atomic incommensurate contact is not required to achieve ambient superlubricity for 2D materials. The results suggest that any phenomena depending on 2D heterostructure interfaces such as exotic electronic behavior may need to consider the presence of stripe adsorbate structures that remain intercalated.

Self-Adaptive Macroscale Superlubricity Based on the Tribocatalytic Properties of Partially Oxidized Black Phosphorus.

The high-flash heat generated by direct contact at asperity tips under high contact stress and shear significantly promotes the tribocatalytic reaction between a lubricating medium and a friction interface. Macroscale superlubricity can be achieved by using additives with good lubrication properties to promote the decomposition and transformation of a lubricating medium to form an ultralow shear interface during the friction process. This paper proposed a way to achieve self-adaptive oil-based macroscale superlubricity on different tribopairs, including steel-steel and steel-DLC (diamond-like carbon), which is based on the excellent lubricating performance of black phosphorus with active oxidation and the catalytic cleavage behavior of oil molecules on the surface of oBP. This work potentially expands the industrial application of superlubricity.

Hydrogen-Enhanced Catalytic Conversion of Amorphous Carbon to Graphene for Achieving Superlubricity.

The solid-state conversion of amorphous carbon into graphene is extremely difficult, but it can be achieved in the friction experiments that induce macroscale superlubricity. However, the underlying conversion mechanisms remain elusive. Here, the friction experiments with Cu nanoparticles and (non-hydrogen (H) or H) a-C in vacuum, show the H-induced conversion of mechanical to chemical wear, resulting in the a-C's tribosoftening and nanofragmentating that produce hydrocarbon nanoclusters or molecules. It is such exactly hydrocarbon species that yield graphene at hydrogen-rich a-C friction interface, through reaction of them with Cu nanoparticles. In comparison, graphene isn't formed at Cu/non-H a-C friction interface. Atomistic simulations reveal the hydrogen-enhanced tribochemical decomposition of a-C and demonstrate the energetically favorable graphitization transformation of hydrocarbons on Cu substrates. The findings are of importance to achieve solid-state transformation between different carbon allotropes and provide a good strategy to synthesize other graphitic encapsulated catalysts with doped elements.

Friction properties of black phosphorus: a first-principles study.

Based on the first-principle, the friction anisotropy, structural super-lubricity and oxidation induced ultra-low friction of black phosphorus at atomic scale under different loads have been studied. The results show that the interface friction of black phosphorus is anisotropic, that is, the friction along the armchair direction is greater than that along the zigzag direction. Moreover, the friction between the black phosphorus interfaces shows a structural superlubricity property, and the incommensurate interface friction is approximately one thousandth of the commensurate interface friction, which is mainly due to the less electronic charge and the smaller amplitude of electronic charge change between the incommensurate interfaces during the friction process. In addition, the oxidation of black phosphorus is beneficial for lubrication between interfaces.

Load-induced dynamical transitions at graphene interfaces.

The structural superlubricity (SSL), a state of near-zero friction between two contacted solid surfaces, has been attracting rapidly increasing research interest since it was realized in microscale graphite in 2012. An obvious question concerns the implications of SSL for micro- and nanoscale devices such as actuators. The simplest actuators are based on the application of a normal load; here we show that this leads to remarkable dynamical phenomena in microscale graphite mesas. Under an increasing normal load, we observe mechanical instabilities leading to dynamical states, the first where the loaded mesa suddenly ejects a thin flake and the second characterized by peculiar oscillations, during which a flake repeatedly pops out of the mesa and retracts back. The measured ejection speeds are extraordinarily high (maximum of 294 m/s), and correspond to ultrahigh accelerations (maximum of 1.1×1010 m/s2). These observations are rationalized using a simple model, which takes into account SSL of graphite contacts and sample microstructure and considers a competition between the elastic and interfacial energies that defines the dynamical phase diagram of the system. Analyzing the observed flake ejection and oscillations, we conclude that our system exhibits a high speed in SSL, a low friction coefficient of 3.6×10-6, and a high quality factor of 1.3×107 compared with what has been reported in literature. Our experimental discoveries and theoretical findings suggest a route for development of SSL-based devices such as high-frequency oscillators with ultrahigh quality factors and optomechanical switches, where retractable or oscillating mirrors are required.

Velocity Dependence of Moiré Friction.

Friction force microscopy experiments on moiré superstructures of graphene-coated platinum surfaces demonstrate that in addition to atomic stick-slip dynamics, a new dominant energy dissipation route emerges. The underlying mechanism, revealed by atomistic molecular dynamics simulations, is related to moiré ridge elastic deformations and subsequent relaxation due to the action of the pushing tip. The measured frictional velocity dependence displays two distinct regimes: (i) at low velocities, the friction force is small and nearly constant; and (ii) above some threshold, friction increases logarithmically with velocity. The threshold velocity, separating the two frictional regimes, decreases with increasing normal load and moiré superstructure period. Based on the measurements and simulation results, a phenomenological model is derived, allowing us to calculate friction under a wide range of room temperature experimental conditions (sliding velocities of 1-104 nm/s and a broad range of normal loads) and providing excellent agreement with experimental observations.

Tuning friction to a superlubric state via in-plane straining.

Controlling, and in many cases minimizing, friction is a goal that has long been pursued in history. From the classic Amontons-Coulomb law to the recent nanoscale experiments, the steady-state friction is found to be an inherent property of a sliding interface, which typically cannot be altered on demand. In this work, we show that the friction on a graphene sheet can be tuned reversibly by simple mechanical straining. In particular, by applying a tensile strain (up to 0.60%), we are able to achieve a superlubric state (coefficient of friction nearly 0.001) on a suspended graphene. Our atomistic simulations together with atomically resolved friction images reveal that the in-plane strain effectively modulates the flexibility of graphene. Consequently, the local pinning capability of the contact interface is changed, resulting in the unusual strain-dependent frictional behavior. This work demonstrates that the deformability of atomic-scale structures can provide an additional channel of regulating the friction of contact interfaces involving configurationally flexible materials.

Dissipation from Interlayer Friction in Graphene Nanoelectromechanical Resonators.

A unique feature of two-dimensional (2D) materials is the ultralow friction at their van der Waals interfaces. A key question in a new generation of 2D heterostructure-based nanoelectromechanical systems (NEMS) is how the low friction interfaces will affect the dynamic performance. Here, we apply the exquisite sensitivity of graphene nanoelectromechanical drumhead resonators to compare the dissipation from monolayer, Bernal-stacked bilayer, and twisted bilayer graphene membranes. We find a significant difference in the average quality factors of three resonator types: 53 for monolayer, 40 for twisted and 31 for Bernal-stacked membranes. We model this difference as a combination of change in stiffness and additional dissipation from interlayer friction during motion. We find even the lowest frictions measured on sliding 2D interfaces are sufficient to alter dissipation in 2D NEMS. This model provides a generalized approach to quantify dissipation in NEMS based on 2D heterostructures which incorporate interlayer slip and friction.

Macroscale Superlubricity on Engineering Steel in the Presence of Black Phosphorus.

Friction and wear are the main reasons for decreasing the lifetime of moving mechanical components and causing energy loss. It is desirable to achieve macroscale superlubricity on industrial materials for minimizing friction. Herein, the two-dimensional material black phosphorus (BP) is prepared as an oil-based nanoadditive in oleic acid (OA) and shown to produce macroscale superlubricity at the steel/steel contact under high pressure. Experiments and molecular dynamics simulation reveal that BP quickly captures the carboxylic group and, as a result of the high contact pressure and heat, OA decomposes to release passivating species and recombines to form amorphous carbon giving rise to a composite solid tribofilm with BP. The OA and passivating groups adsorb onto the solid tribofilm to produce the passivating layer, thus resulting in macroscale superlubricity. The findings provide fundamental insight into the nature of tribochemical mechanisms and suggest a new approach to achieve macroscale superlubricity of industrial materials.

A New Pathway for Superlubricity in a Multilayered MoS2-Ag Film under Cryogenic Environment.

A fundamental cryogenic study in tribology from 20 to 300 K revealed that a kind of disulfide film could exhibit a superlubricity state. Inspired by this, we designed a more delicate experiment and reported an extremely low friction coefficient for a multilayered MoS2-Ag film in a cryogenic environment against a bare steel ball under a high load. The results showed that the multilayered MoS2-Ag film could undergo a pressure exceeding 2 GPa to maintain a superlow friction coefficient of below 0.001 at 170 K. The film material was transferred to the sliding contacts to form an antifriction tribofilm. The superlubricity mechanism was attributed to the formation of MoS2-wrapped Ag nanoparticles accumulated at the sliding interface through nanoparticle movement and layered-structure sliding. This new kind of multilayered MoS2-Ag film provides a novel design for a solid lubricant and broadens the application of solid lubrication films under harsh working conditions for mechanical engineering.

Unraveling the Friction Evolution Mechanism of Diamond-Like Carbon Film during Nanoscale Running-In Process toward Superlubricity.

Diamond-like carbon (DLC) films are capable of achieving superlubricity at sliding interfaces by a rapid running-in process. However, fundamental mechanisms governing the friction evolution during this running-in processes remain elusive especially at the nanoscale, which hinders strategic tailoring of tribosystems for minimizing friction and wear. Here, it is revealed that the running-in governing superlubricity of DLC demonstrates two sub-stages in single-asperity nanocontacts. The first stage, mechanical removal of a thin oxide layer, is described quantitatively by a stress-activated Arrhenius model. In the second stage, a large friction decrease occurs due to a structural ordering transformation, with the kinetics well described by the Johnson-Mehl-Avrami-Kolmogorov model with a modified load dependence of the activation energy. The direct observation of a graphitic-layered transfer film formation together with the measured Avrami exponent reveal the primary mechanism of the ordering transformation. The findings provide fundamental insights into friction evolution mechanisms, and design criteria for superlubricity.

Structural superlubricity in 2D van der Waals heterojunctions.

Structural superlubricity is a fundamentally important research topic in the area of tribology. Van der Waals heterojunctions of 2D materials are an ideal system for achieving structural superlubricity and possessing potentially a wide range of applications in the future due to their ultra-flat and incommensurate crystal interfaces. Here we briefly introduce the origin and mechanism of structural superlubricity and summarize the representative experimental results, in which the coefficient of friction has achieved the order of 10-5. Furthermore, we analyze the factors affecting structural superlubricity of 2D materials, including dynamic reconstruction of interfaces, edge effects, interfacial adsorption, etc, and give a perspective on how to realize the macroscopic expansion and where it can be applied in practice.

Structural Superlubricity Based on Crystalline Materials.

Herein, structural superlubricity, a fascinating phenomenon where the friction is ultralow due to the lateral interaction cancellation resulted from incommensurate contact crystalline surfaces, is reviewed. Various kinds of nano- and microscale materials such as 2D materials, metals, and compounds are used for the fabrication. For homogeneous frictional pairs, superlow friction forces exist in most relative orientations with incommensurate configuration. Heterojunctions bear no resemblance to homogeneous contact, since the lattice constants are naturally mismatched which leads to a robust structural superlubricity with any orientation of the two different surfaces. A discussion on the perspectives of this field is also provided to meet the existing challenges and chart the future.

Generalized Scaling Law of Structural Superlubricity.

Structural superlubricity, which promises an ultralow sliding friction due to the cancellation of the lateral force between two incommensurate interfaces, is a fundamental phenomenon in modern tribology. Achieving macroscale superlubricity is critical to its practical application, and the key is understanding how friction scales with real contact area, that is, the scaling law, especially for kinetic friction which accounts for most of the energy dissipation during sliding. Here, inspired by extensive molecular dynamics simulations we introduce an analytical general theory for the scaling law of structural superlubricity, which could well explain existing experimental measurements on the nanoscale. On the microscale, the scaling law is validated by measuring the friction of several microscale superlubric graphite/hexagonal boron nitride heterojunctions. The proposed theory predicts a characteristic size D = O(100 nm) above which the scaling transits from sublinear to linear. Our results provide insights in the origin of friction for structural superlubricity and benefit its application on macroscale.

A Hybrid Two-Axis Force Sensor for the Mesoscopic Structural Superlubricity Studies.

Structural superlubricity (SSL) is a state of nearly zero friction and zero wear between two directly contacted solid surfaces. Recently, SSL was achieved in mesoscale and thus opened the SSL technology which promises great applications in Micro-electromechanical Systems (MEMS), sensors, storage technologies, etc. However, load issues in current mesoscale SSL studies are still not clear. The great challenge is to simultaneously measure both the ultralow shear forces and the much larger normal forces, although the widely used frictional force microscopes (FFM) and micro tribometers can satisfy the shear forces and normal forces requirements, respectively. Here we propose a hybrid two-axis force sensor that can well fill the blank between the capabilities of FFM and micro tribometers for the mesoscopic SSL studies. The proposed sensor can afford 1mN normal load with 10 nN lateral resolution. Moreover, the probe of the sensor is designed at the edge of the structure for the convenience of real-time optical observation. Calibrations and preliminary experiments are conducted to validate the performance of the design.

Interwall Friction and Sliding Behavior of Centimeters Long Double-Walled Carbon Nanotubes.

Here, we studied the interwall friction and sliding behaviors of double-walled carbon nanotubes (DWCNTs). The interwall friction shows a linear dependence on the pullout velocity of the inner wall. The axial curvature in DWCNTs causes the significant increase of the interwall friction. The axial curvature also affects the sliding behavior of the inner wall. Compared with the axial curvature, the opening ends of DWCNTs play tiny roles in their interwall friction.

Hyperdislocations in van der Waals Layered Materials.

Dislocations are one-dimensional line defects in three-dimensional crystals or periodic structures. It is common that the dislocation networks made of interactive dislocations be generated during plastic deformation. In van der Waals layered materials, the highly anisotropic nature facilitates the formation of such dislocation networks, which is critical for the friction or exfoliation behavior for these materials. By transmission electron microscopy analysis, we found the topological defects in such dislocation networks can be perfectly rationalized in the framework of traditional dislocation theory, which we applied the name "hyperdislocations". Due to the strong pinning effect of hyperdislocations, the state of exfoliation can be easily triggered by 1° twisting between two layers, which also explains the origin of disregistry and frictionlessness for all of the superlubricants that are widely used for friction reduction and wear protection.