Wallace Gregory Sawyer

Bio: Wallace Gregory Sawyer is an academic researcher from University of Florida. The author has contributed to research in topics: Tribometer & Contact area. The author has an hindex of 27, co-authored 91 publications receiving 2386 citations. Previous affiliations of Wallace Gregory Sawyer include Georgia Tech Research Institute.

A Raman Spectroscopic Study of MoS2 and MoO3: Applications to Tribological Systems

Abstract: Molybdenum disulfide (MoS2) and molybdenum trioxide are investigated using Raman spectroscopy with emphasis on the application to tribological systems. The Raman vibrational modes were investigated for excitation wavelengths at 632.8 and 488 nm using both micro-crystalline MoS2 powder and natural MoS2 crystals. Differences are noted in the Raman spectra for these two different wavelengths, which are attributed to resonance effects due to overlap of the 632.8 nm source with electronic absorption bands. In addition, significant laser intensity effects are found that result in laser-induced transformation of MoS2 to MoO3. Finally, the transformation to molybdenum trioxide is explored as a function of temperature and atmosphere, revealing an apparent transformation at 375 K in the presence of oxygen. Overall, Raman spectroscopy is an useful tool for tribological study of MoS2 coatings, including the role of molybdenum trioxide transformations, although careful attention must be given to the laser excitation parameters (both wavelength and intensity) when interpreting Raman spectra.

Influence of surface passivation on the friction and wear behavior of ultrananocrystalline diamond and tetrahedral amorphous carbon thin films

Abstract: Highly $s{p}^{3}$-bonded, nearly hydrogen-free carbon-based materials can exhibit extremely low friction and wear in the absence of any liquid lubricant, but this physical behavior is limited by the vapor environment. The effect of water vapor on friction and wear is examined as a function of applied normal force for two such materials in thin film form: one that is fully amorphous in structure (tetrahedral amorphous carbon, or ta-C) and one that is polycrystalline with $l10$ nm grains [ultrananocrystalline diamond (UNCD)]. Tribologically induced changes in the chemistry and carbon bond hybridization at the surface are correlated with the effect of the sliding environment and loading conditions through ex situ, spatially resolved near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. At sufficiently high relative humidity (RH) levels and/or sufficiently low loads, both films quickly achieve a low steady-state friction coefficient and subsequently exhibit low wear. For both films, the number of cycles necessary to reach the steady-state is progressively reduced for increasing RH levels. Worn regions formed at lower RH and higher loads have a higher concentration of chemisorbed oxygen than those formed at higher RH, with the oxygen singly bonded as hydroxyl groups (C-OH). While some carbon rehybridization from $s{p}^{3}$ to disordered $s{p}^{2}$ bonding is observed, no crystalline graphite formation is observed for either film. Rather, the primary solid-lubrication mechanism is the passivation of dangling bonds by OH and H from the dissociation of vapor-phase H${}_{2}$O. This vapor-phase lubrication mechanism is highly effective, producing friction coefficients as low as 0.078 for ta-C and 0.008 for UNCD, and wear rates requiring thousands of sliding passes to produce a few nanometers of wear.

Friction coefficient of soft contact lenses: measurements and modeling

Abstract: Tribological conditions for contact lenses have very low contact pressures in the range 3–5 kPa and sliding speeds around 12 cm/s. Using a microtribometer a series of experiments was run on commercially available contact lenses made from Etafilcon-A. These tests were run using 10–50 mN of normal load at speeds from 63 to 6280 μm/s using a 1-mm radius glass sphere as a pin. The resulting contact pressures are believed to be nearly an order of magnitude larger than the targeted 3–5 kPa. It is hypothesized that the viscoelastic nature of the hydrogel, viscous shearing of the packaging solution, and interfacial shear between the glass sphere and the contact lens all contribute to the friction forces. A model that includes all three of these contributors is developed and compared to the experimental data. The experimental friction coefficients vary from μ = 0.025 to 0.075. The calculated fluid film␣thicknesses were between 1 and 30 nm. The average surface roughness of the lens and the glass sphere are Ra=15 nm and Ra=8 nm, respectively, suggesting that the contact is not in full elastohydrodynamic lubrication. Finally, the largest contributors to the friction force in these experiments were found to be viscous dissipation within the hydrogel and interfacial shear within the contact zone.

Frictional anisotropy of oriented carbon nanotube surfaces

Abstract: This report examines highly anisotropic tribological behavior of multi-walled nanotube films oriented in mutually orthogonal directions. The average values of coefficient of friction varied from extremely high values (μ=0.795) for vertically aligned nanotubes grown on rigid substrates to very low values (μ=0.090) for nanotubes dispersed flat on the same substrates. The results were insensitive to humidity, in contrast to graphite materials, and indicate that nanotubes could be utilized as both low and high frictional surfaces.

Addressing Practical Challenges of Low Friction Coefficient Measurements

Abstract: A friction coefficient is defined as the ratio of the friction force to the applied normal force. Despite the disarming simplicity of its calculation, there are practical challenges that make low values of friction coefficient difficult to accurately quantify. The connections of imperfect parts in friction measurement devices (called tribometers) produce small misalignments between the transducer and counterface axes. According to Schmitz et al. (J Tribol Trans ASME 127:673–678, 2005), “…the measurement of friction coefficient is extremely sensitive to misalignments” and “for materials with friction coefficients below 0.05 the alignment becomes hopelessly difficult if the goal is to have uncertainties below 1%.” This method article reviews the challenges of low friction measurements and presents a robust reversal technique that eliminates misalignment bias. Experiments with controlled misalignment angles demonstrate the bias sensitivity and validate its elimination using a low uncertainty tribometer in conjunction with the described reversal technique.

From bulk to monolayer MoS2: evolution of Raman scattering

Abstract: Molybdenum disulfi de (MoS 2 ) is systematically studied using Raman spectroscopy with ultraviolet and visible laser lines. It is shown that only the Raman frequencies of E 1 and A1g peaks vary monotonously with the layer number of ultrathin MoS 2 fl akes, while intensities or widths of the peaks vary arbitrarily. The coupling between electronic transitions and phonons are found to become weaker when the layer number of MoS 2 decreases, attributed to the increased electronic transition energies or elongated intralayer atomic bonds in ultrathin MoS 2 . The asymmetric Raman peak at 454 cm − 1 , which has been regarded as the overtone of longitudinal optical M phonons in bulk MoS 2 , is actually a combinational band involving a longitudinal acoustic mode (LA(M)) and an optical mode ( A2u ). Our fi ndings suggest a clear evolution of the coupling between electronic transition and phonon when MoS 2 is scaled down from three- to two-dimensional geometry.

Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis

Abstract: Controlling surface structure at the atomic scale is paramount to developing effective catalysts. For example, the edge sites of MoS(2) are highly catalytically active and are thus preferred at the catalyst surface over MoS(2) basal planes, which are inert. However, thermodynamics favours the presence of the basal plane, limiting the number of active sites at the surface. Herein, we engineer the surface structure of MoS(2) to preferentially expose edge sites to effect improved catalysis by successfully synthesizing contiguous large-area thin films of a highly ordered double-gyroid MoS(2) bicontinuous network with nanoscaled pores. The high surface curvature of this catalyst mesostructure exposes a large fraction of edge sites, which, along with its high surface area, leads to excellent activity for electrocatalytic hydrogen evolution. This work elucidates how morphological control of materials at the nanoscale can significantly impact the surface structure at the atomic scale, enabling new opportunities for enhancing surface properties for catalysis and other important technological applications.

Conducting MoS2 Nanosheets as Catalysts for Hydrogen Evolution Reaction

Abstract: We report chemically exfoliated MoS2 nanosheets with a very high concentration of metallic 1T phase using a solvent free intercalation method. After removing the excess of negative charges from the surface of the nanosheets, highly conducting 1T phase MoS2 nanosheets exhibit excellent catalytic activity toward the evolution of hydrogen with a notably low Tafel slope of 40 mV/dec. By partially oxidizing MoS2, we found that the activity of 2H MoS2 is significantly reduced after oxidation, consistent with edge oxidation. On the other hand, 1T MoS2 remains unaffected after oxidation, suggesting that edges of the nanosheets are not the main active sites. The importance of electrical conductivity of the two phases on the hydrogen evolution reaction activity has been further confirmed by using carbon nanotubes to increase the conductivity of 2H MoS2.

MoS2/Graphene Composite Paper for Sodium-Ion Battery Electrodes

Abstract: We study the synthesis and electrochemical and mechanical performance of layered free-standing papers composed of acid-exfoliated few-layer molybdenum disulfide (MoS2) and reduced graphene oxide (rGO) flakes for use as a self-standing flexible electrode in sodium-ion batteries. Synthesis was achieved through vacuum filtration of homogeneous dispersions consisting of varying weight percent of acid-treated MoS2 flakes in GO in DI water, followed by thermal reduction at elevated temperatures. The electrochemical performance of the crumpled composite paper (at 4 mg cm–2) was evaluated as counter electrode against pure Na foil in a half-cell configuration. The electrode showed good Na cycling ability with a stable charge capacity of approximately 230 mAh g–1 with respect to total weight of the electrode with Coulombic efficiency reaching approximately 99%. In addition, static uniaxial tensile tests performed on crumpled composite papers showed high average strain to failure reaching approximately 2%.

Tribology of diamond-like carbon films: recent progress and future prospects

Abstract: During the past two decades, diamond-like carbon (DLC) films have attracted an overwhelming interest from both industry and the research community. These films offer a wide range of exceptional physical, mechanical, biomedical and tribological properties that make them scientifically very fascinating and commercially essential for numerous industrial applications. Mechanically, certain DLC films are extremely hard (as hard as 90 GPa) and resilient, while tribologically they provide some of the lowest known friction and wear coefficients. Their optical and electrical properties are also extraordinary and can be tailored to meet the specific requirements of a given application. Because of their excellent chemical inertness, these films are resistant to corrosive and/or oxidative attacks in acidic and saline media. The combination of such a wide range of outstanding properties in one material is rather uncommon, so DLC can be very useful in meeting the multifunctional application needs of advanced mechanical systems. In fact, these films are now used in numerous industrial applications, including razor blades, magnetic hard discs, critical engine parts, mechanical face seals, scratch-resistant glasses, invasive and implantable medical devices and microelectromechanical systems. DLC films are primarily made of carbon atoms that are extracted or derived from carbon-containing sources, such as solid carbon targets and liquid and gaseous forms of hydrocarbons and fullerenes. Depending on the type of carbon source being used during the film deposition, the type of bonds (i.e. sp 1 ,s p 2 ,s p 3 ) that hold carbon atoms together in DLC may vary a great deal and can affect their mechanical, electrical, optical and tribological properties. Recent systematic studies of DLC films have confirmed that the presence or absence of certain elemental species, such as hydrogen, nitrogen, sulfur, silicon, tungsten, titanium and fluorine, in their microstructure can also play significant roles in their properties. The main goal of this review paper is to highlight the most recent developments in the synthesis, characterization and application of DLC films. We will also discuss the progress made in understanding the fundamental mechanisms that control their very unique friction and wear behaviours. Novel design concepts and the principles of superlubricity in DLC films are also presented. (Some figures in this article are in colour only in the electronic version)