Nonmonotonic Friction due to Water Capillary Adhesion and Hydrogen Bonding at Multiasperity Interfaces.

Capillary adhesion due to water adsorption from the air can contribute to friction, especially for smooth interfaces in humid environments. We show that for multiasperity (naturally oxidized) Si-on-Si interfaces, the friction coefficient goes through a maximum as a function of relative humidity. An adhesion model based on the boundary element method that takes the roughness of the interfaces into account reproduces this nonmonotonic behavior very well. Remarkably, we find the dry friction to be significantly lower than the lubricated friction with macroscopic amounts of water present. The difference is attributed to the hydrogen-bonding network across the interface. Accordingly, the lubricated friction increases significantly if the water is replaced by heavy water (D_{2}O) with stronger hydrogen bonding.

Molecular Probing of the Stress Activation Volume in Vapor Phase Lubricated Friction.

When two solid objects slide over each other, friction results from the interactions between the asperities of the (invariably rough) surfaces. Lubrication happens when viscous lubricants separate the two surfaces and carry the load such that solid-on-solid contacts are avoided. Yet, even small amounts of low-viscosity lubricants can still significantly lower friction through a process called boundary lubrication. Understanding the origin of the boundary lubricating effect is hampered by challenges in measuring the interfacial properties of lubricants directly between the two surfaces. Here, we use rigidochromic fluorescent probe molecules to measure precisely what happens on a molecular scale during vapor-phase boundary lubrication of a polymer bead-on-glass interface. The probe molecules have a longer fluorescence lifetime in a confined environment, which allows one to measure the area of real contact between rough surfaces and infer the shear stress at the lubricated interfaces. The latter is shown to be proportional to the inverse of the local interfacial free volume determined using the measured fluorescence lifetime. The free volume can then be used in an Eyring-type model as the stress activation volume, allowing to collapse the data of stress as a function of sliding velocity and partial pressure of the vapor phase lubricant. This shows directly that as more boundary lubricant is applied, larger clusters of lubricant molecules become involved in the shear process thereby lowering the friction.

Local Shearing Force Measurement during Frictional Sliding Using Fluorogenic Mechanophores.

When two macroscopic objects touch, the real contact typically consists of multiple surface asperities that are deformed under the pressure that holds the objects together. Application of a shear force makes the objects slide along each other, breaking the initial contacts. To investigate how the microscopic shear force at the asperity level evolves during the transition from static to dynamic friction, we apply a fluorogenic mechanophore to visualize and quantify the local interfacial shear force. When a contact is broken, the shear force is released and the molecules return to their dark state, allowing us to dynamically observe the evolution of the shear force at the sliding contacts. We find that the macroscopic coefficient of friction describes the microscopic friction well, and that slip propagates from the edge toward the center of the macroscopic contact area before sliding occurs. This allows for a local understanding of how surfaces start to slide.

Semiconductor nanochannels in metallic carbon nanotubes by thermomechanical chirality alteration.

Carbon nanotubes have a helical structure wherein the chirality determines whether they are metallic or semiconducting. Using in situ transmission electron microscopy, we applied heating and mechanical strain to alter the local chirality and thereby control the electronic properties of individual single-wall carbon nanotubes. A transition trend toward a larger chiral angle region was observed and explained in terms of orientation-dependent dislocation formation energy. A controlled metal-to-semiconductor transition was realized to create nanotube transistors with a semiconducting nanotube channel covalently bonded between a metallic nanotube source and drain. Additionally, quantum transport at room temperature was demonstrated for the fabricated nanotube transistors with a channel length as short as 2.8 nanometers.

Realization and direct observation of five normal and parametric modes in silicon nanowire resonators by in situ transmission electron microscopy.

Mechanical resonators have wide applications in sensing bio-chemical substances, and provide an accurate method to measure the intrinsic elastic properties of oscillating materials. A high resonance order with high response frequency and a small resonator mass are critical for enhancing the sensitivity and precision. Here, we report on the realization and direct observation of high-order and high-frequency silicon nanowire (Si NW) resonators. By using an oscillating electric-field for inducing a mechanical resonance of single-crystalline Si NWs inside a transmission electron microscope (TEM), we observed resonance up to the 5th order, for both normal and parametric modes at ∼100 MHz frequencies. The precision of the resonant frequency was enhanced, as the deviation reduced from 3.14% at the 1st order to 0.25% at the 5th order, correlating with the increase of energy dissipation. The elastic modulus of Si NWs was measured to be ∼169 GPa in the [110] direction, and size scaling effects were found to be absent down to the ∼20 nm level.

Mesoscopic physical removal of material using sliding nano-diamond contacts.

Wear mechanisms including fracture and plastic deformation at the nanoscale are central to understand sliding contacts. Recently, the combination of tip-induced material erosion with the sensing capability of secondary imaging modes of AFM, has enabled a slice-and-view tomographic technique named AFM tomography or Scalpel SPM. However, the elusive laws governing nanoscale wear and the large quantity of atoms involved in the tip-sample contact, require a dedicated mesoscale description to understand and model the tip-induced material removal. Here, we study nanosized sliding contacts made of diamond in the regime whereby thousands of nm3 are removed. We explore the fundamentals of high-pressure tip-induced material removal for various materials. Changes in the load force are systematically combined with AFM and SEM to increase the understanding and the process controllability. The nonlinear variation of the removal rate with the load force is interpreted as a combination of two contact regimes each dominating in a particular force range. By using the gradual transition between the two regimes, (1) the experimental rate of material eroded on each tip passage is modeled, (2) a controllable removal rate below 5 nm/scan for all the materials is demonstrated, thus opening to future development of 3D tomographic AFM.

Chirality transitions and transport properties of individual few-walled carbon nanotubes as revealed by in situ TEM probing.

Physical properties of carbon nanotubes (CNTs) are closely related to the atomic structure, i.e. the chirality. It is highly desirable to develop a technique to modify their chirality and control the resultant transport properties. Herein, we present an in situ transmission electron microscopy (TEM) probing method to monitor the chirality transition and transport properties of individual few-walled CNTs. The changes of tube structure including the chirality are stimulated by programmed bias pulses and associated Joule heating. The chirality change of each shell is analyzed by nanobeam electron diffraction. Supported by molecular dynamics simulations, a preferred chirality transition path is identified, consistent with the Stone-Wales defect formation and dislocation sliding mechanism. The electronic transport properties are measured along with the structural changes, via fabricating transistors using the individual nanotubes as the suspended channels. Metal-to-semiconductor transitions are observed along with the chirality changes as confirmed by both the electron diffraction and electrical measurements. Apart from providing an alternative route to control the chirality of CNTs, the present work demonstrates the rare possibility of obtaining the dynamic structure-properties relationships at the atomic and molecular levels.

Caging tin oxide in three-dimensional graphene networks for superior volumetric lithium storage.

Tin and its compounds hold promise for the development of high-capacity anode materials that could replace graphitic carbon used in current lithium-ion batteries. However, the introduced porosity in current electrode designs to buffer the volume changes of active materials during cycling does not afford high volumetric performance. Here, we show a strategy leveraging a sulfur sacrificial agent for controlled utility of void space in a tin oxide/graphene composite anode. In a typical synthesis using the capillary drying of graphene hydrogels, sulfur is employed with hard tin oxide nanoparticles inside the contraction hydrogels. The resultant graphene-caged tin oxide delivers an ultrahigh volumetric capacity of 2123 mAh cm-3 together with good cycling stability. Our results suggest not only a conversion-type composite anode that allows for good electrochemical characteristics, but also a general synthetic means to engineering the packing density of graphene nanosheets for high energy storage capabilities in small volumes.