Subramanian K. R. S. Sankaranarayanan

Macroscale superlubricity enabled by graphene nanoscroll formation

Slip sliding away Many applications would benefit from ultralow friction conditions to minimize wear on the moving parts such as in hard drives or engines. On the very small scale, ultralow friction has been observed with graphite as a lubricant. Berman et al. achieved superlubricity using graphene in combination with crystalline diamond nanoparticles and diamondlike carbon (see the Perspective by Hone and Carpick). Simulations showed that sliding of the graphene patches around the tiny nanodiamond particles led to nanoscrolls with reduced contact area that slide easily against the amorphous diamondlike carbon surface. Science, this issue p. 1118; see also p. 1087 Nanodiamonds wrapped with graphene sheets lead to ultralow friction against a diamondlike carbon surface. [Also see Perspective by Hone and Carpick] Friction and wear remain as the primary modes of mechanical energy dissipation in moving mechanical assemblies; thus, it is desirable to minimize friction in a number of applications. We demonstrate that superlubricity can be realized at engineering scale when graphene is used in combination with nanodiamond particles and diamondlike carbon (DLC). Macroscopic superlubricity originates because graphene patches at a sliding interface wrap around nanodiamonds to form nanoscrolls with reduced contact area that slide against the DLC surface, achieving an incommensurate contact and substantially reduced coefficient of friction (~0.004). Atomistic simulations elucidate the overall mechanism and mesoscopic link bridging the nanoscale mechanics and macroscopic experimental observations.

Role of solvation dynamics and local ordering of water in inducing conformational transitions in poly(N-isopropylacrylamide) oligomers through the LCST.

Conformational transitions in thermo-sensitive polymers are critical in determining their functional properties. The atomistic origin of polymer collapse at the lower critical solution temperature (LCST) remains a fundamental and challenging problem in polymer science. Here, molecular dynamics simulations are used to establish the role of solvation dynamics and local ordering of water in inducing conformational transitions in isotactic-rich poly(N-isopropylacrylamide) (PNIPAM) oligomers when the temperature is changed through the LCST. Simulated atomic trajectories are used to identify stable conformations of the water-molecule network in the vicinity of polymer segments, as a function of the polymer chain length. The dynamics of the conformational evolution of the polymer chain within its surrounding water molecules is evaluated using various structural and dynamical correlation functions. Around the polymer, water forms cage-like structures with hydrogen bonds. Such structures form at temperatures both below and above the LCST. The structures formed at temperatures above LCST, however, are significantly different from those formed below LCST. Short oligomers consisting of 3, 5, and 10 monomer units (3-, 5-, and 10-mer), are characterized by significantly higher hydration level (water per monomer ~ 16). Increasing the temperature from 278 to 310 K does not perturb the structure of water around the short oligomers. In the case of 3-, 5-, and 10-mer, a distinct coil-to-globule transition was not observed when the temperature was raised from 278 to 310 K. For a PNIPAM polymer chain consisting of 30 monomeric units (30-mer), however, there exist significantly different conformations corresponding to two distinct temperature regimes. Below LCST, the water molecules in the first hydration layer (~12) around hydrophilic groups arrange themselves in a specific ordered manner by forming a hydrogen-bonded network with the polymer, resulting in a solvated polymer acting as hydrophilic. Above LCST, this arrangement of water is no longer stable, and the hydrophobic interactions become dominant, which contributes to the collapse of the polymer. Thus, this study provides atomic-scale insights into the role of solvation dynamics in inducing coil-to-globule phase transitions through the LCST for thermo-sensitive polymers like PNIPAM.

Carbon-based tribofilms from lubricating oils

Moving mechanical interfaces are commonly lubricated and separated by a combination of fluid films and solid ‘tribofilms’, which together ensure easy slippage and long wear life. The efficacy of the fluid film is governed by the viscosity of the base oil in the lubricant; the efficacy of the solid tribofilm, which is produced as a result of sliding contact between moving parts, relies upon the effectiveness of the lubricant’s anti-wear additive (typically zinc dialkyldithiophosphate). Minimizing friction and wear continues to be a challenge, and recent efforts have focused on enhancing the anti-friction and anti-wear properties of lubricants by incorporating inorganic nanoparticles and ionic liquids. Here, we describe the in operando formation of carbon-based tribofilms via dissociative extraction from base-oil molecules on catalytically active, sliding nanometre-scale crystalline surfaces, enabling base oils to provide not only the fluid but also the solid tribofilm. We study nanocrystalline catalytic coatings composed of nitrides of either molybdenum or vanadium, containing either copper or nickel catalysts, respectively. Structurally, the resulting tribofilms are similar to diamond-like carbon. Ball-on-disk tests at contact pressures of 1.3 gigapascals reveal that these tribofilms nearly eliminate wear, and provide lower friction than tribofilms formed with zinc dialkyldithiophosphate. Reactive and ab initio molecular-dynamics simulations show that the catalytic action of the coatings facilitates dehydrogenation of linear olefins in the lubricating oil and random scission of their carbon–carbon backbones; the products recombine to nucleate and grow a compact, amorphous lubricating tribofilm.

Subnanometre ligand-shell asymmetry leads to Janus-like nanoparticle membranes

Self-assembly of nanoparticles at fluid interfaces has emerged as a simple yet efficient way to create two-dimensional membranes with tunable properties. In these membranes, inorganic nanoparticles are coated with a shell of organic ligands that interlock as spacers and provide tensile strength. Although curvature due to gradients in lipid-bilayer composition and protein scaffolding is a key feature of many biological membranes, creating gradients in nanoparticle membranes has been difficult. Here, we show by X-ray scattering that nanoparticle membranes formed at air/water interfaces exhibit a small but significant ∼6 Å difference in average ligand-shell thickness between their two sides. This affects surface-enhanced Raman scattering and can be used to fold detached free-standing membranes into tubes by exposure to electron beams. Molecular dynamics simulations elucidate the roles of ligand coverage and mobility in producing and maintaining this asymmetry. Understanding this Janus-like membrane asymmetry opens up new avenues for designing nanoparticle superstructures.

Interface proximity effects on ionic conductivity in nanoscale oxide-ion conducting yttria stabilized zirconia: An atomistic simulation study

We present an atomistic simulation study on the size dependence of dopant distribution and the influence of nanoscale film thickness on carrier transport properties of the model oxide-ion conductor yttria stabilized zirconia (YSZ). Simulated amorphization and recrystallization approach was utilized to generate YSZ films with varying thicknesses (3-9 nm) on insulating MgO substrates. The atomic trajectories generated in the molecular dynamics simulations are used to study the structural evolution of the YSZ thin films and correlate the resulting microstructure with ionic transport properties at the nanoscale. The interfacial conductivity increases by 2 orders of magnitude as the YSZ film size decreases from 9 to 3 nm owing to a decrease in activation energy barrier from 0.54 to 0.35 eV in the 1200-2000 K temperature range. Analysis of dopant distribution indicates surface enrichment, the extent of which depends on the film thickness. The mechanisms of oxygen conductivity for the various film thicknesses at the nanoscale are discussed in detail and comparisons with experimental and other modeling studies are presented where possible. The study offers insights into mesoscopic ion conduction mechanisms in low-dimensional solid oxide electrolytes.

Vibrational Spectra of Proximal Water in a Thermo-Sensitive Polymer Undergoing Conformational Transition Across the Lower Critical Solution Temperature

The vibrational spectrum of water near a thermo-sensitive polymer poly(N-isopropylacrylamide) (PNIPAM) undergoing conformational transition through the lower critical solution temperature (LCST) is calculated using molecular dynamics simulations. The characteristic structural features observed at the atomic scale for these proximal water molecules in a solvated polymer chain while undergoing the conformational transition are strongly correlated to their vibrational densities of states. Comparison of the vibrational spectrum below LCST for the proximal water with the vibrational spectrum obtained for bulk water reveals a significant fraction of the hydrogen bonding between the proximal water molecules and the polymer side groups. Hydrogen-bonded bridges of water molecules are formed between two adjacent and alternate monomers. This network of hydrogen bonding results in formation of locally ordered water molecules at temperatures below the LCST. Analysis of the simulation trajectories confirms the presence of a quasi-stable solvation structure near the PNIPAM. The calculated vibrational spectra for proximal water above the LCST suggest significantly reduced hydrogen bonding with the polymer and indicate a reduction in the structural stability of proximal water around a collapsed polymer chain. Systematic trends in the observed peak intensities and frequency shifts at the low- and high-frequency ends of the spectrum can be correlated with the structural and dynamical changes of water molecules below and above the LCST transition, respectively, for various polymer chain lengths. The simulations reveal that, compared to bulk water, the libration bands are blue shifted and OH stretch bands red shifted for water in proximity to PNIPAM with 30 monomer units below the LCST. The simulations suggest that vibrational spectra can be used as a predictive tool for quantifying atomic-scale structural transitions in solvation of thermo-sensitive polymers such as PNIPAM.

Atomistic insights into aqueous corrosion of copper

Corrosion is a fundamental problem in electrochemistry and represents a mode of failure of technologically important materials. Understanding the basic mechanism of aqueous corrosion of metals such as Cu in presence of halide ions is hence essential. Using molecular dynamics simulations incorporating reactive force-field (ReaxFF), the interaction of copper substrates and chlorine under aqueous conditions has been investigated. These simulations incorporate effects of proton transfer in the aqueous media and are suitable for modeling the bond formation and bond breakage phenomenon that is associated with complex aqueous corrosion phenomena. Systematic investigation of the corrosion process has been carried out by simulating different chlorine concentration and solution states. The structural and morphological differences associated with metal dissolution in the presence of chloride ions are evaluated using dynamical correlation functions. The simulated atomic trajectories are used to analyze the charged states, molecular structure and ion density distribution which are utilized to understand the atomic scale mechanism of corrosion of copper substrates under aqueous conditions. Increased concentration of chlorine and higher ambient temperature were found to expedite the corrosion of copper. In order to study the effect of solution states on the corrosion resistance of Cu, partial fractions of proton or hydroxide in water were configured, and higher corrosion rate at partial fraction hydroxide environment was observed. When the Cl(-) concentration is low, oxygen or hydroxide ion adsorption onto Cu surface has been confirmed in partial fraction hydroxide environment. Our study provides new atomic scale insights into the early stages of aqueous corrosion of metals such as copper.

Quantitative 3D evolution of colloidal nanoparticle oxidation in solution

Watching nanomaterials transform in time Real-time analysis of chemical transformations of nanoparticles is usually done with electron microscopy of a few particles. One limitation is interference by the electron beam. Sun et al. monitored the oxidation of iron nanoparticles in solution by using small- and wide-angle x-ray scattering and molecular dynamics simulations (see the Perspective by Cadavid and Cabot). These methods revealed the formation of voids within the nanoparticles, diffusion of material into and out of the nanoparticles, and ultimately the coalescence of the voids. Science, this issue p. 303; see also p. 245 Transformation of iron nanoparticles into hollow iron oxide structures through the Kirkendall effect is observed using x-rays. Real-time tracking of the three-dimensional (3D) evolution of colloidal nanoparticles in solution is essential for understanding complex mechanisms involved in nanoparticle growth and transformation. We used time-resolved small-angle and wide-angle x-ray scattering simultaneously to monitor oxidation of highly uniform colloidal iron nanoparticles, enabling the reconstruction of intermediate 3D morphologies of the nanoparticles with a spatial resolution of ~5 angstroms. The in situ observations, combined with large-scale reactive molecular dynamics simulations, reveal the details of the transformation from solid metal nanoparticles to hollow metal oxide nanoshells via a nanoscale Kirkendall process—for example, coalescence of voids as they grow and reversal of mass diffusion direction depending on crystallinity. Our results highlight the complex interplay between defect chemistry and defect dynamics in determining nanoparticle transformation and formation.

Influence of surface orientation and defects on early-stage oxidation and ultrathin oxide growth on pure copper

We investigate oxidation and oxide growth on single-crystal copper surfaces using reactive molecular dynamics simulation. The kinetics of surface oxide growth are strongly correlated with the microstructure of the metal substrates. Simulating oxide layer growth along the (100), (110), and (111) orientations of crystalline copper, oxidation characteristics are investigated at temperatures of 300 K and 600 K. The oxidation kinetics are found to strongly depend on the surface orientation, ambient temperature, and surface defects. The effect of surface morphology on oxidation characteristics is analyzed by comparing oxygen adsorption on various sites and the structure factor. The surface oxide formed on (100) retains the initial crystal structure in the 300–600 K range. The (100) surface shows the highest oxidation rate at both temperature conditions but saturates, facilitating oxygen adsorption on hollow sites. The oxidation kinetics of the (100) orientation are found to be not significantly affected by surface defects. (110) shows modest oxidation at 300 K but the highest oxidation is observed at 600 K. By surface disorder and reconstruction, the oxide layer is produced continuously. The (111) surface is sensitive to ambient temperature and surface defects, showing that surface reconstruction is a key element for further oxidation. The charge distribution of oxidized Cu atoms indicates multiple groups of stoichiometric oxides, while the fraction of CuO-like characteristics increases significantly on the (110) and (111) orientations at higher temperature (600 K). The energetics and mechanisms of oxidation on Cu metal substrates at the nanoscale are discussed in detail, and comparisons with available experimental and other theoretical studies are presented wherever possible.

Acoustic streaming induced elimination of nonspecifically bound proteins from a surface acoustic wave biosensor: Mechanism prediction using fluid-structure interaction models

Biosensors typically operate in liquid media for detection of biomarkers and suffer from fouling resulting from nonspecific binding of protein molecules to the device surface. In the current work, using a coupled field finite element fluid-structure interaction simulation, we have identified that fluid motion induced by high intensity sound waves, such as those propagating in these sensors, can lead to the efficient removal of the nonspecifically bound proteins thereby eliminating sensor fouling. We present a computational analysis of the acoustic-streaming phenomenon induced biofouling elimination by surface acoustic-waves (SAWs) propagating on a lithium niobate piezoelectric crystal. The transient solutions generated from the developed coupled field fluid solid interaction model are utilized to predict trends in acoustic-streaming induced forces for varying design parameters such as voltage intensity, device frequency, fluid viscosity, and density. We utilize these model predictions to compute the vario...