The flow of water in carbon nanochannels has defied understanding thus far, with accumulating experimental evidence for ultra-low friction, exceptionally high water flow rates, and curvature-dependent hydrodynamic slippage. These unique properties have raised considerable interest in carbon-based membranes for desalination, molecular sieving and energy harvesting. However, the mechanism of water-carbon friction remains unknown, with neither current theories, nor classical or ab initio molecular dynamics simulations providing satisfactory rationalisation for its singular behaviour. Here, we develop a quantum theory of the solid-liquid interface, which reveals a new contribution to friction, due to the coupling of charge fluctuations in the liquid to electronic excitations in the solid. We expect that this quantum friction, which is absent in Born-Oppenheimer molecular dynamics, is the dominant friction mechanism for water on carbon-based materials. As a key result, we demonstrate a dramatic difference in quantum friction between the water-graphene and water-graphite interface, due to the coupling of water Debye collective modes with a thermally excited plasmon specific to graphite. This suggests an explanation for the radius-dependent slippage of water in carbon nanotubes, in terms of the nanotubes' electronic excitations. Our findings open the way to quantum engineering of hydrodynamic flows through the confining wall electronic properties.
The physics of sliding friction is gaining impulse from nanoscale and mesoscale experiments, simulations, and theoretical modeling. This Colloquium reviews some recent developments in modeling and in atomistic simulation of friction, covering open-ended directions, unconventional nanofrictional systems, and unsolved problems.
Developing the non-equilibrium thermodynamics of friction is required for systematic design of low friction surfaces for a broad range of technological applications. Intuitively, the thermodynamic work done by a material sliding along a surface is expected to be partially dissipated as heat and partially transformed into the change of the internal energy of the system. However, general non-equilibrium thermodynamic principles governing this separation are presently unknown. We develop a theoretical framework based on the transition state theory combined with the conventional Prandtl-Tomlinson …
Ti$_3$C$_2$T$_X$ nano-sheets (MXenes) are an emerging class of two-dimensional materials with outstanding potential to be employed in energy storage, catalysis, and triboelectric applications, on length scales ranging from the nano- to macroscopic. Despite rapidly accelerating interest in this new class of materials, their nanoscale frictional properties and in particular, their potential for solid lubrication on the nanoscale, have not been explored in detail yet. In this short communication, we present the first results on the nanoscale frictional characteristics of MXenes, in the form of a …
Nanomechanical devices can operate at much higher speeds than their macroscopic analogues, due to low inertia. For example, peak speeds >100m/s have been predicted for carbon nanotube devices. This stimulates our interest in the atomic-scale physics of friction at high velocity. Here we study a model nanosystem consisting of a graphene flake moving freely on a graphite substrate at >100m/s. Using molecular dynamics we discover that ultra-low friction, or superlubricity, is punctuated by high-friction transients as the flake rotates through successive crystallographic alignments with the substr…
A macroscopically nominal flat surface is rough at the nanoscale level and consists of nanoasperities. Therefore, the frictional properties of the macroscale-level rough surface are determined by the mechanical behaviors of nanoasperity contact pairs under shear. In this work, we first used molecular dynamics simulations to study the non-adhesive shear between single contact pairs. Subsequently, to estimate the friction coefficient of rough surfaces, we implemented the frictional behavior of a single contact pair into a Greenwood-Williamson-type statistical model. By employing the present mult…
The kinetic friction and wear at high sliding speeds is investigated using the head-disk interface of hard disk drives, wherein, the head and the disk are less than 10 nm apart and move at sliding speeds of 5-10 m/s relative to each other. While the spacing between the sliding surfaces is of the same order of magnitude as various AFM based fundamental studies on friction, the sliding speed is nearly six orders of magnitude larger, allowing a unique set-up for a systematic study of nanoscale wear at high sliding speeds. In a hard disk drive, the physical contact between the head and the disk le…
Boiling is the out-of-equilibrium transition which occurs when a liquid is heated above its vaporization temperature. At the nanoscale, boiling may be triggered by irradiated nanoparticles immersed in water or nanocomposite surfaces and often results in micro-explosions. It is generally believed that nanoscale boiling occurs homogeneously when the local fluid temperature exceeds its spinodal temperature, around 573 K for water. Here, we employ molecular dynamics simulations to show that nanoscale boiling is an heterogenous phenomenon occuring when water temperature exceeds a wetting dependent …
We study the effect of atomic scale surface-lubricant interactions on nanoscale boundary-lubricated friction, by considering two example surfaces - hydrophilic mica and hydrophobic graphene - confining thin layers of water in molecular dynamics simulations. We observe stick-slip dynamics for thin water films confined by mica sheets, involving periodic breaking-reforming transitions of atomic scale capillary water bridges formed around the potassium ions of mica. However, only smooth sliding without stick-slip events is observed for water confined by graphene, as well as for thicker water layer…
Negative quantum friction in nanoscale water flows: the Wigner picture
Istituto per le Applicazioni del Calcolo, Consiglio Nazionale delle Ricerche（计算应用研究所，意大利国家研究委员会）；INFN Tor Vergata（托尔维加塔国立核物理研究所）；Department of Physics, Harvard University（哈佛大学物理系）；School of Engineering & Applied Sciences, Harvard University（哈佛大学生物工程与应用科学学院）；Center for Life Nano- & Neuro-Science, Fondazione Istituto Italiano di Tecnologia（意大利理工大学生命纳米与神经科学中心）
Like-charge attraction, driven by ionic correlations, challenges our understanding of electrostatics both in soft and hard matter. For two charged planar surfaces confining counterions and water, we prove that even at relatively low correlation strength, the relevant physics is the ground-state one, oblivious of fluctuations. Based on this, we derive a simple and accurate interaction pressure, that fulfills known exact requirements and can be used as an effective potential. We test this equation against implicit-solvent Monte Carlo simulations and against explicit-solvent simulations of cement…
Friction is one of the main sources of dissipation at liquid water/solid interfaces. Despite recent progress, a detailed understanding of water/solid friction in connection with the structure and energetics of the solid surface is lacking. Here we show for the first time that \textit{ab initio} molecular dynamics can be used to unravel the connection between the structure of nanoscale water and friction for liquid water in contact with graphene and with hexagonal boron nitride. We find that whilst the interface presents a very similar structure between the two sheets, the friction coefficient …
Graphene monolayers are known to display domains of anisotropic friction with twofold symmetry and anisotropy exceeding 200 percent. This anisotropy has been thought to originate from periodic nanoscale ripples in the graphene sheet, which enhance puckering around a sliding asperity to a degree determined by the sliding direction. Here we demonstrate that these frictional domains derive not from structural features in the graphene, but from self-assembly of atmospheric adsorbates into a highly regular superlattice of stripes with period 4 to 6 nm. The stripes and resulting frictional domains a…
While there are a number of models that tackle the problem of calculating friction forces on the atomic level, providing a completely parameter-free approach remains a challenge. Here we present a quasi-static model to obtain an approximation to the nanofrictional response of dry, wearless systems based on quantum mechanical all-electron calculations. We propose a mechanism to allow dissipative sliding, which relies on atomic relaxations. We define two different ways of calculating the mean nanofriction force, both leading to an exponential friction-versus-load behavior for all sliding directi…
Compared to nanoscale friction of translational motion, the mechanisms of rotational friction have received less attention. Such motion becomes an important issue for the miniaturization of mechanical machineries which often involve rotating gears. In this study, molecular dynamics simulations are performed to explore rotational friction for solid-state gears rotating on top of different substrates. In each case, viscous damping of the rotational motion is observed and found to be induced by the pure van-der-Waals interaction between gear and substrate. The influence of different gear sizes an…
The understanding of water transport in graphene oxide (GO) membranes stands out as a major theoretical problem in graphene research. Notwithstanding the intense efforts devoted to the subject in the recent years, a consolidated picture of water transport in GO membranes is yet to emerge. By performing mesoscale simulations of water transport in ultrathin GO membranes, we show that even small amounts of oxygen functionalities can lead to a dramatic drop of the GO permeability, in line with experimental findings. The coexistence of bulk viscous dissipation and spatially extended molecular frict…
Calculations of friction and heat transfer at the water-multilayer graphene interface using the theories of phononic and radiative friction and heat transfer are presented. The phononic contributions to friction and heat transfer are many orders of magnitude larger than the radiative contributions. Phononic friction and heat transfer slightly increase with an increase in the number of graphene layers $N$ and reach saturation at $N>5$, which is associated with an increase in the phonon transmission coefficient through the interface and a finite phonon mean free path in the direction perpendicul…
Using a simple theoretical model of a nanoscale asymmetric particle/molecule with asymmetric structure or/and asymmetric charge distribution, here using a charge dipole as an example, we show that there is unidirectional transportation mediated by non-white fluctuations if the asymmetric orientation of the particle/molecule is constrained. This indicates the existence of an inherent equivalent force, which drives the particle/molecule itself along the orientation of the asymmetric particle in the environment of fluctuations. In practical systems, equivalent force also exist in the asymmetric m…
Water-flow in carbon nanotubes (CNT's) starkly contradicts classical fluid mechanics, with permeabilities that can exceed no-slip Haagen-Poiseuille predictions by two to five orders of magnitude. Semi-classical molecular dynamics accounts for enhanced flow-rates, that are attributed to curvature-dependent lattice mismatch. However, the steeper permeability-enhancement observed experimentally at $\sim$nm-size radii remains poorly understood, and suggests emergence of puzzling non-classical mechanisms. Here we address water-CNT friction from a quantum-mechanical perspective, in terms of water-en…
Water, when confined at the nanoscale acquires extraordinary transport properties. And yet there is no direct experimental evidence of these properties at nanoscale resolution. Here, by using 2D NMR diffusion-relaxation (D-T2) and spin-lattice - spin-spin relaxation (T1-T2) spectroscopy, we succeeded to resolve at the nanoscale water diffusion in single and double-walled carbon nanotubes (SWCNT/DWCNT). In SWCNTs, spectra display the characteristic shape of uniform water diffusion restricted in one dimension. Remarkably, in DWCNTs water is shown to split into two axial components with the inner…
The physics of dynamic friction on water molecule contaminated surfaces is still poorly understood. In line with the growing interest in hydrophobic contact for industrial applications, this paper focuses on friction mechanisms in such interfaces. As a commonly used material, contact with graphite is considered in a twin-fold approach based on experimental investigations using the circular mode atomic force microscopy technique combined with molecular dynamic simulations. We demonstrate that an intuitive paradigm, which asserts that water molecules are squeezed out of a hydrophobic contact, sh…
Using molecular dynamics simulations, we propose a novel nanoscale watermill for unidirectional transport of water molecules through a curved single-walled carbon nanotube (SWNT). In this nanoscale system, a revolving charge is introduced to drive water chain confined inside the SWNT, which is served as nano waterwheel and nano engine. A resonance-like phenomenon is found that the revolving frequency of the charge plays a key role in pumping water chain. The water flux across the SWNT increases with respect to the revolving frequency of the external charge and reaches the maximum when the freq…
Energy exchanges between orderly intertube axial motion and vibrational modes are studied for isolated systems of two coaxial carbon nanotubes at temperatures ranging from 300 K to 500 K. It is found that the excess intertube van der Waals energy, depleted from the intertube axial motion, is primarily stored in low-frequency mechanical modes of the oscillator for an extended period of time, and furthermore, such an energy exchange may be reversible. A new nanoscale tribological phenomenon of negative friction is reported for the first time in concentric cylindrical carbon nanotube oscillators.
Recently unusual properties of water in single-walled carbon nanotubes (CNT) with diameters ranging from 1.05 nm to 1.52 nm were observed. It was found that water in the CNT remains in an ice-like phase even when the temperature ranges between 105 - 151 C and 87 - 117 C for CNTs with diameters 1.05 nm and 1.06 nm respectively. Apart from the high freezing points, the solid-liquid phase transition temperature was found to be strongly sensitive to the CNT diameter. In this paper we show that water in such CNT's can admit coherent nanoscale structures provided certain conditions are met. The form…
The relationship between humidity and water content in a hydrating cement paste is largely controlled by the nanostructure of the C-S-H gel. Current hydration models do not describe this nanostructure, thus sorption isotherms and self-desiccation are given as constitutive inputs instead of being predicted from microstructural evolution. To address this limitation, this work combines a C-S-H gel description from nanoscale simulations with evolving capillary pore size distributions from a simple hydration model. Results show that a progressive densification of the C-S-H gel must be considered in…
We introduce a model for zwitterionic monolayers and investigate its tribological response to changes in applied load, sliding velocity, and temperature by means of molecular-dynamics simulations. The proposed model exhibits different regimes of motion depending on temperature and sliding velocity. We find a remarkable increase of friction with temperature, which we attribute to the formation and rupture of transient bonds between individual molecules of opposite sliding layers, triggered by the out-of-plane thermal fluctuations of the molecules' orientations. To highlight the effect of the mo…
In the context of friction we use atomistic molecular-dynamics simulations to investigate water confined between graphene sheets over a wide range of pressures. We find that thermal equilibration of the confined water is hindered at high pressures. We demonstrate that, under the right conditions, square ice can form in an asperity, and that it is similar to cubic ice VII and ice X. We simulate sliding of atomically flat graphite on the square ice and find extremely low friction due to structural superlubricity. The conditions needed for square ice to form correspond to low sliding speeds, and …
Exciton-mediated optical control of liquid-solid friction
MIPT（莫斯科物理技术学院）；Russian Quantum Center, Skolkovo（俄罗斯量子中心）；Westlake University（西湖大学）；St. Petersburg State University（圣彼得堡国立大学）；Institute of Science and Technology Austria (ISTA)（奥地利科学技术研究所）
Diffusion of tracer dye molecules in water confined to nanoscale is an important subject with a direct bearing on many technological applications. It is not yet clear however, if the dynamics of water in hydrophilic as well as hydrophobic nanochannels remains bulk-like. Here, we present diffusion measurement of a fluorescent dye molecule in water confined to nanoscale between two hydrophilic surfaces whose separation can be controlled with a precision of less than a nm. We observe that the fluorescence intensities correlate over a fast($\sim$ 30 $μ$s) and slow ($\sim$ 1000 $μ$s) time component…
The main physical features and operating principles of isothermal nanomachines in microworld are reviewed, which are common for both classical and quantum machines. Especial attention is paid to the dual and constructive role of dissipation and thermal fluctuations, fluctuation-dissipation theorem, heat losses and free energy transduction, thermodynamic efficiency, and thermodynamic efficiency at maximum power. Several basic models are considered and discussed to highlight generic physical features. Our exposition allows to spot some common fallacies which continue to plague the literature, in…
Using equilibrium and non-equilibrium molecular dynamic (MD) simulations, we found that engineering the strain on the graphene planes forming a channel can drastically change the interfacial friction of water transport through it. There is a sixfold change of interfacial friction stress when the strain changes from -10% to 10%. Stretching the graphene walls increases the interfacial shear stress, while compressing the graphene walls reduces it. Detailed analysis of the molecular structure reveals the essential roles of the interfacial potential energy barrier and the structural commensuratenes…
Molecule- and solid-state gears build the elementary constituents of nanoscale mechanical machineries. Recent experimental advances in fabrication technologies in the field have strongly contributed to better delineate the roadmap towards the ultimate goal of engineering molecular-scale mechanical devices. To complement experimental studies, computer simulations play an invaluable role, since they allow to address, with atomistic resolution, various fundamental issues such as the transmission of angular momentum in nanoscale gear trains and the mechanisms of energy dissipation at such length s…
