Distribution of some active elements in primary graphite precipitates

The distributions of cerium and oxygen in the matrix and in graphite precipitates of a pure Fe–C–Ce cast iron sample have been studied using scanning Auger microscopy. It is shown that there is no accumulation of any element at the graphite-matrix interface. Cerium was detected in some cases in spheroidal graphite precipitates, most often associated with oxygen. Various non-spheroidal graphite precipitates proved to contain cerium and oxygen suggesting a correlation between cerium content and graphite degeneracy

Role of substrate outgassing on the formation dynamics of either hydrophilic or hydrophobic wood surfaces in atmospheric-pressure, organosilicon plasmas

This work examines the influence of substrate outgassing on the deposition dynamics of either hydrophilic or hydrophobic coatings on wood surfaces in organosilicon, dielectric barrier discharges. Sugar maple and black spruce wood samples were placed on the bottom electrode and the discharge was sustained in N2–HMDSO (hexamethyldisiloxane) gas mixtures by applying a 24 kV peak-to-peak voltage at 2 kHz. Current–voltage characteristics revealed a transition from a filamentary to a homogeneous discharge with increasing plasma treatment time, t. Based on opticalemission spectroscopy, the filamentary behaviorwas ascribed to the release of air and humidity from the wood substrate following discharge exposure which produced significant quenching of N2 metastables. This effect vanished at longer treatment times due to the nearly complete “pumping” of products from the wood substrate and the progressive deposition of a “barrier” layer. Analysis of the surface wettability through static, water contact angles (WCAs) and of the surface composition through Fourier-Transform-Infra-Red-Spectroscopy and X-ray-Photoelectron-Spectroscopy indicated that for t b 10 min, the wood surface was more hydrophilic due to the formation of a SiOx layer, a typical behavior for HMDSO deposition in presence of oxygen. On the other hand, for t > 10 min, the static WCA increased up to ~140° due to the deposition of hydrophobic Si(CH3)3-O-Si(CH3)2, Si(CH3)3, and Si(CH3)2 functional groups

DFT Simulation of XPS Reveals Cu/Epoxy Polymer Interfacial Bonding

Experiments and computations are performed to assess the interfacial bonding between Cu and a poly-epoxy surface relevant to many applications. The surface of the poly-epoxy is characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy before and after ultrahigh vacuum Cu deposition. Modifications of the XPS spectra are observed, suggesting a strong interaction between specific C and O atoms of the surface with Cu. Density functional theory (DFT) calculations are then performed to simulate XPS spectra and to better understand bonding. DFT computations are performed in the framework of the uGTS methodology, which takes initial and final state effects into account, and allows to calculate chemical shifts between the different C 1s and O 1s molecular orbitals with good accuracy, for the pristine surface. DFT calculations are then set to determine the preferential adsorption sites of Cu on different sites of the polymer surface. Finally, XPS simulation of the C 1s and O 1s spectra with Cu adsorbed at these sites matches very well with the experimental spectra, indicating that Cu atoms interact preferentially with hydroxyls to form Cu−O−C bonds, stabilized by a transfer of 0.5 electrons from Cu to O; hence, Cu is partially oxidized

A poly-epoxy surface explored by Hartree-Fock ΔSCF simulations of C1s XPS spectra

Whereas poly-epoxy polymers represent a class of materials with a wide range of applications, the structural disorder makes them difficult to model. In the present work, we use good experimental model samples in the sense that they are pure, fully polymerized, flat and smooth, defect-free, and suitable for ultrahigh vacuum x-ray photoelectron spectroscopy, XPS, experiments. In parallel, we perform Hartree-Fock, HF, calculations of the binding energies, BEs, of the C1s electrons in a model molecule composed of the two constituents of the poly-epoxy sample. These C1s BEs were determined using the HF ΔSCF method, which is known to yield accurate values, especially for the shifts of the BEs, ΔBEs. We demonstrate the benefits of combining rigorous theory with careful XPS measurements in order to obtain correct assignments of the C1s XPS spectra of the polymer sample. Both the relative binding energies—by the ΔSCF method—and relative intensities—in the sudden approximation, SA, are calculated. It results in an excellent match with the experimental spectra. We are able to identify 9 different chemical environments under the C1s peak, where an exclusively experimental work would have found only 3 contributions. In addition, we observe that some contributions are localized at discrete binding energies, whereas others allow a much wider range because of the variation of their second neighbor bound polarization. Therefore, HF-ΔSCF simulations significantly increase the spectral resolution of XPS and thus offer a new avenue for the exploration of the surface of polymers

One-step synthesis of few-layered-graphene/alumina powders for strong and tough composites with high electrical conductivity

The chemical vapor deposition of carbon onto a commercial α-Al2O3 powder bed produces a pristine film of few-layered-graphene (FLG) uniformly covering the α-Al2O3 grains. This obviates both the manipulation of nanocarbons, lengthy mixing steps and the risk of damaging any pre-existing graphene platelets. The powders are consolidated to 99 % by SPS, producing samples where a FLG film is located along the grain boundaries of the submicron α-Al2O3. Compared to the pure α-Al2O3, the composites are moderately stronger and similarly tough and hard due to crack-deflection and crack-bridging and they are electrically conducting with a percolation threshold below 0.74 vol.% of carbon. The high conductivity values reflect the high quality of the thin FLG film and its continuous nature over very long distances. The samples are characterized by Raman spectroscopy, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy

A Novel Method for the Metallization of 3D Silicon Induced by Metastable Copper Nanoparticles

The development of efficient copper deposition processes in high-aspect-ratio silicon structures is still a key technological issue for the microelectronic industry. We describe here a new process for the deposition of copper thin films in three-dimensional (3D) structures induced by the decomposition of a copper amidinate precursor in solution under a moderate H2 pressure. The reduction of a metal precursor under soft conditions (3 bar, 110 °C) affords the preparation of a high-purity, conformal metallic layer. We unveil a novel deposition mechanism driven by colloidal copper nanoparticles (NPs) in solution that behave as a reservoir of metastable metallic NPs that eventually condense as a solid film on all immersed surfaces. The film growth process is characterized by time-resolved analyses of the NPs in the colloidal state (nuclear magnetic resonance NMR and UV–vis spectra) and of the NPs and metallic layer on substrates (transmission electron microscopy TEM, and scanning electron microscopy SEM). Major deposition stages of this process are proposed and the conformal metallization of 3D silicon substrates is successfully achieved. This method is transposable to other metallic layers such as silver or nickel

Bidimensional lamellar assembly by coordination of peptidic homopolymers to platinum nanoparticles

A key challenge for designing hybrid materials is the development of chemical tools to control the organization of inorganic nanoobjects at low scales, from mesoscopic (~µm) to nanometric (~nm). So far, the most efficient strategy to align assemblies of nanoparticles consists in a bottom-up approach by decorating block copolymer lamellae with nanoobjects. This well accomplished procedure is nonetheless limited by the thermodynamic constraints that govern copolymer assembly, the entropy of mixing as described by the Flory–Huggins solution theory supplemented by the critical influence of the volume fraction of the block components. Here we show that a completely different approach can lead to tunable 2D lamellar organization of nanoparticles with homopolymers only, on condition that few elementary rules are respected: 1) the polymer spontaneously allows a structural preorganization, 2) the polymer owns functional groups that interact with the nanoparticle surface, 3) the nanoparticles show a surface accessible for coordination

Alumina thin films prepared by direct liquid injection chemical vapor deposition of dimethylaluminum isopropoxide: a process-structure investigation

The development of a new process to obtain amorphous alumina thin films is presented. We show for the first time the direct liquid injection chemical vapor deposition (DLI CVD) of alumina thin films using dimethylaluminum isopropoxide (DMAI) precursor in two oxidizing atmospheres. At high process temperature (500-700 °C), the film growth takes place in the presence of O2 whereas at low temperature (150-300 °C) H2O vapor is used. The materials characteristics, such as the surface morphology and roughness (SEM and AFM), crystal structure (XRD), composition (EPMA) and chemistry (XPS) are discussed in detail. Very smooth films, with typical roughness values lower than 2.0 nm are obtained. The thin films are all composed of an amorphous material with varying composition. Supported by both EPMA and XPS results, film composition evolves from a partial oxyhydroxide to a stoichiometric oxide at low deposition temperature (150-300 °C) in the presence of H2O. At higher growth temperature (500-700 °C) in the presence of O2, the composition changes from that of a stoichiometric oxide to a mixture of an oxide with aluminum carbide. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Impedance analysis of film-forming amines for the corrosion protection of a carbon steel

Octadecylamine (ODA) is a well-known organic inhibitor for the corrosion protection of carbon steels. In the present study, electrochemical impedance data analysis was performed to extract physical parameters of the ODA thin film that formed on a P275 carbon steel surface. First, surface observations and contact angle measurements showed the steel surface modification after the ODA treatment linked to the adsorption of an organic hydrophobic thin film. X-ray photoelectron spectroscopy confirmed the presence of a very thin organic layer and revealed the presence of iron oxide/hydroxide underlying the ODA film. The impedance data analysis with a power-law distribution of resistivity in the organic film allowed the permittivity and thickness to be extracted. Finally, from the impedance results with and without ODA, the instantaneous corrosion inhibition efficiency was determined

Industrially scalable surface treatments to enhance the current density output from graphite bioanodes fueled by real domestic wastewater

Acid and electrochemical surface treatments of graphite electrode, used individually or in combination, significantly improved the microbial anode current production, by +17% to +56%, in well-regulated and duplicated electroanalytical experimental systems. Of all the consequences induced by surface treatments, the modifications of the surface nano-topography preferentially justify an improvement in the fixation of bacteria, and an increase of the specific surface area and the electrochemically accessible surface of graphite electrodes, which are at the origin of the higher performances of the bioanodes supplied with domestic wastewater. The evolution of the chemical composition and the appearance of C-O, C=O, and O=C-O groups on the graphite surface created by combining acid and electrochemical treatments was prejudicial to the formation of efficient domestic-wastewater-oxidizing bioanodes. The comparative discussion, focused on the positioning of the performances, shows the industrial interest of applying the surface treatment method to the world of bioelectrochemical systems