Accounting for Nanometer-Thick Adventitious Carbon Contamination in X-ray Absorption Spectra of Carbon-Based Materials

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is a powerful technique for characterizing the composition and bonding state of nanoscale materials and the top few nanometers of bulk and thin film specimens. When coupled with imaging methods like photoemission electron microscopy, it enables chemical imaging of materials with nanometer-scale lateral spatial resolution. However, analysis of NEXAFS spectra is often performed under the assumption of structural and compositional homogeneity within the nanometer-scale depth probed by this technique. This assumption can introduce large errors when analyzing the vast majority of solid surfaces due to the presence of complex surface and near-surface structures such as oxides and contamination layers. An analytical methodology is presented for removing the contribution of these nanoscale overlayers from NEXAFS spectra of two-layered systems to provide a corrected photoabsorption spectrum of the substrate. This method relies on the subtraction of the NEXAFS spectrum of the overlayer adsorbed on a reference surface from the spectrum of the two-layer system under investigation, where the thickness of the overlayer is independently determined by X-ray photoelectron spectroscopy (XPS). This approach is applied to NEXAFS data acquired for one of the most challenging cases: air-exposed hard carbon-based materials with adventitious carbon contamination from ambient exposure. The contribution of the adventitious carbon was removed from the as-acquired spectra of ultrananocrystalline diamond (UNCD) and hydrogenated amorphous carbon (a-C:H) to determine the intrinsic photoabsorption NEXAFS spectra of these materials. The method alters the calculated fraction of sp2-hybridized carbon from 5 to 20% and reveals that the adventitious contamination can be described as a layer containing carbon and oxygen ([O]/[C] = 0.11 ± 0.02) with a thickness of 0.6 ± 0.2 nm and a fraction of sp2-bonded carbon of 0.19 ± 0.03. This method can be generally applied to the characterization of surfaces and interfaces in several research fields and technological applications

Novel Metal Silicide Thin Films by Design via Controlled Solid-State Diffusion

In the quest to accelerate the discovery and deployment of new materials with ideal and tailored properties, synthesis via solid-state diffusion holds particular promise as it allows the crystal structure and stoichiometry of thin films to be controlled independently of the deposition method. However, the kinetics and the quality of the resulting materials remain relatively unexplored. Here we demonstrate both source-limited and kinetically-limited solid-state diffusion as novel routes to tune the stoichiometry of platinum silicide (PtxSi) thin films, representative of metal silicides which have attractive mechanical and electronic properties. Using in situ heating inside a transmission electron microscope (TEM) while performing electron diffraction, we show that both routes lead to stoichiometrically-controlled formation of PtxSi (x = 1, 2, 3) thin films with high phase selectivity, revealing the crystal structure and formation sequence for each phase. The PtxSi formation process from sequentially-deposited layers of platinum (Pt) and amorphous silicon (a-Si) significantly differs from the Pt/single-crystal silicon (sc-Si) case, allowing the formation of Pt3Si thin films for the first time

Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts

Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation

Understanding the hydrogen and oxygen gas pressure dependence of the tribological properties of silicon oxide-doped hydrogenated amorphous carbon coatings

Silicon oxide-doped hydrogenated amorphous carbons (a–C:H:Si:O) are amorphous thin films used as solid lubricants in a range of commercial applications, thanks to its increased stability in extreme environments, relative to amorphous hydrogenated carbons (a–C:H). This work aims to develop a fundamental understanding of the environmental impact on the tribology of a–C:H:Si:O. Upon sliding an a–C:H:Si:O film against a steel counterbody, two friction regimes develop: high friction in high vacuum and low gas pressure (oxygen pressure < 10 mbar; hydrogen pressure < 50 mbar), and a low friction regime at higher gas pressures (10 mbar < oxygen pressure < 500 mbar; 50 mbar < hydrogen pressure < 1000 mbar). Scanning electron microscopy (SEM) revealed that the tribological behavior of a–C:H:Si:O is governed by adhesive junctions at the sliding interface. At low gas pressures, material transfer from the steel pin to the a–C:H:Si:O flat occurs. At higher gas pressures, a tribofilm forms on the steel countersurface. Raman and near edge X-ray absorption spectroscopy (NEXAFS) spectroscopies demonstrate that upon sliding under the higher gas pressure, low friction regime, a surface layer with an elevated fraction of sp2-bonded carbon atoms forms. These changes indicate that these gases favor the release of the adhesive junctions by dissociatively reacting with the mechanically-stressed sp2 carbon-rich surface layer

Multiscale friction in lubricant-surface systems for high performance transmissions under mild wear

The lubricant-surface system is complex in nature and can significantly affect the frictional performance of high-performance transmission systems. The complexity stems from the coupled mechanical and chemical phenomena that occur at the interfacial tooth conjunctions. A combined analytical and precision experimental approach is presented to analyse the salient parameters of the lubricant-surface system. A multiscale procedure comprising topographical measurement, pin-on-disc tribometry, atomic force microscopy in lateral force mode, X-ray photo-electron spectroscopy and continuum contact mechanics analysis under mixed non-Newtonian thermo-elastohydrodynamics is used to describe the formation of a tribo-film, as well as wear and frictional characteristics of the lubricant-surface system. The contribution of chemisorbed and physisorbed bonded tribo-film on the boundary coefficient of friction is ascertained at different physical scales. Therefore, the paper presents a novel multiscale analysis, promoting improved understanding of the complex interactions between mechanisms of friction, wear and surface chemistry

Salt Dependence of the Tribological Properties of a Surface-Grafted Weak Polycation in Aqueous Solution

The nanoscopic adhesive and frictional behaviour of end-grafted poly[2-(dimethyl amino)ethyl methacrylate] (PDMAEMA) films (brushes) in contact with gold- or PDMAEMA-coated atomic force microscope tips in potassium halide solutions with different concentrations up to 300 mM is a strong function of salt concentration. The conformation of the polymers in the brush layer is sensitive to salt concentration, which leads to large changes in adhesive forces and the contact mechanics at the tip–sample contact, with swollen brushes (which occur at low salt concentrations) yielding large areas of contact and friction–load plots that fit JKR behaviour, while collapsed brushes (which occur at high salt concentrations) yield sliding dominated by ploughing, with conformations in between fitting DMT mechanics. The relative effect of the different anions follows the Hofmeister series, with I − collapsing the brushes more than Br − and Cl − for the same salt concentration

Hindered rolling and friction anisotropy in supported carbon nanotubes

Carbon nanotubes (CNTs) are well known for their exceptional thermal, mechanical and electrical properties. For many CNT applications it is of the foremost importance to know their frictional properties. However, very little is known about the frictional forces between an individual nanotube and a substrate or tip. Here, we present a combined theoretical and experimental study of the frictional forces encountered by a nanosize tip sliding on top of a supported multiwall CNT along a direction parallel or transverse to the CNT axis. Surprisingly, we find a higher friction coefficient in the transverse direction compared with the parallel direction. This behaviour is explained by a simulation showing that transverse friction elicits a soft 'hindered rolling' of the tube and a frictional dissipation that is absent, or partially absent for chiral CNTs, when the tip slides parallel to the CNT axis. Our findings can help in developing better strategies for large-scale CNT assembling and sorting on a surface.Comment: 8 pages, 5 figure