Electrochemical properties of N-doped hydrogenated amorphous carbon films fabricated by plasma-enhanced chemical vapor deposition methods

Nitrogen-doped hydrogenated amorphous carbon thin films (a-C:N:H, N-doped DLC) were synthesized with microwave-assisted plasma-enhanced chemical vapor deposition widely used for DLC coating such as the inner surface of PET bottles. The electrochemical properties of N-doped DLC surfaces that can be useful in the application as an electrochemical sensor were investigated. N-doped DLC was easily fabricated using the vapor of nitrogen contained hydrocarbon as carbon and nitrogen source. A N/C ratio of resulting N-doped DLC films was 0.08 and atomic ratio of sp³/sp²-bonded carbons was 25/75. The electrical resistivity and optical gap were 0.695 Ω cm and 0.38 eV, respectively. N-doped DLC thin film was found to be an ideal polarizable electrode material with physical stability and chemical inertness. The film has a wide working potential range over 3 V, low double-layer capacitance, and high resistance to electrochemically induced corrosion in strong acid media, which were the same level as those for boron-doped diamond (BDD). The charge transfer rates for the inorganic redox species, Fe^2+/3+ and Fe(CN)₆^4−/3− at N-doped DLC were sufficiently high. The redox reaction of Ce^2+/3+ with standard potential higher than H₂O/O₂ were observed due to the wider potential window. At N-doped DLC, the change of the kinetics of Fe(CN)₆^3−/4− by surface oxidation is different from that at BDD. The rate of Fe(CN)₆^3−/4− was not varied before and after oxidative treatment on N-doped DLC includes sp² carbons, which indicates high durability of the electrochemical activity against surface oxidation.     

Evaluation of mixing profiles for a new micromixer design strategy

The relationship between mixing history and reaction performance in microreactors using computational fluid dynamics (CFD) simulations is identified. In the idealized, simplified mixing model, mixing proceeds linearly and only the mixing time determined the reaction performance. However, in the case of realistic models where mixing proceeds unequally, the partial rapid progression of mixing, more than the mixing time, significantly impacts the reaction. The use of the fluid segment size distribution to capture this effect is proposed. The effective Damköhler number derived from the fluid segment size distribution predicted the reaction yield well. To demonstrate the utility of the mixing profile design strategy, we fabricated a novel micromixer with multiple partial rapid mixing zones. This micromixer achieved excellent results both in a CFD simulation and an experiment. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1154–1161, 2016     

Multi-objective topology optimization of multi-component continuum structures via a Kriging-interpolated level set approach

This paper explores a framework for topology optimization of multi-component sheet metal structures, such as those often used in the automotive industry. The primary reason for having multiple components in a structure is to reduce the manufacturing cost, which can become prohibitively expensive otherwise. Having a multi-component structure necessitates re-joining, which often comes at sacrifices in the assembly cost, weight and structural performance. The problem of designing a multi-component structure is thus posed in a multi-objective framework. Approaches to solve the problem may be classified into single and two stage approaches. Two-stage approaches start by focusing solely on structural performance in order to obtain optimal monolithic (single piece) designs, and then the decomposition into multiple components is considered without changing the base topology (identical to the monolithic design). Single-stage approaches simultaneously attempt to optimize both the base topology and its decomposition. Decomposition is an inherently discrete problem, and as such, non-gradient methods are needed for single-stage and second stage of two-stage approaches. This paper adopts an implicit formulation (level-sets) of the design variables, which significantly reduces the number of design variables needed in either single or two stage approaches. The number of design variables in the formulation is independent from the meshing size, which enables application of non-gradient methods to realistic designs. Test results of a short cantilever and an L-shaped bracket studies show reasonable success of both single and two stage approaches, with each approach having different merits.     

Structural Distortion and Compositional Gradients Adjacent to Epitaxial LiMn2O4 Thin Film Interfaces

Thin film electrode materials are key components in the development of high rate, high capacity solid‐state Li‐ion batteries. Detailed knowledge of the epitaxial film/substrate(current‐collector) interface structures, which provides insights into epitaxial growth mechanisms and the effects of microstructure on electrochemical properties, is essential for efficient materials and device design. Here we report the epitaxial growth mechanism of a typical cathodic LiMn₂O₄ thin film by exploring the detailed structural and compositional variations in the vicinity of a film/substrate interface using state‐of‐the‐art scanning transmission electron microscopy. Direct observation of atom columns shows the epitaxial film forms an atomically flat and coherent heterointerface with the substrate, but that the crystal lattice is tetragonally distorted with a measurable compositional gradient from the interface to the crystal bulk. The growth mechanism is interpreted in terms of a combination of chemical and physicomechanical effects, namely a complex interplay between the internal Jahn‐Teller distortions induced by oxygen non‐stoichiometry and the lattice misfit strain.     

Pose-Invariant Facial Expression Recognition Using Variable-Intensity Templates

In this paper, we propose a method for pose-invariant facial expression recognition from monocular video sequences. The advantage of our method is that, unlike existing methods, our method uses a simple model, called the variable-intensity template, for describing different facial expressions. This makes it possible to prepare a model for each person with very little time and effort. Variable-intensity templates describe how the intensities of multiple points, defined in the vicinity of facial parts, vary with different facial expressions. By using this model in the framework of a particle filter, our method is capable of estimating facial poses and expressions simultaneously. Experiments demonstrate the effectiveness of our method. A recognition rate of over 90% is achieved for all facial orientations, horizontal, vertical, and in-plane, in the range of ±40 degrees, ±20 degrees, and ±40 degrees from the frontal view, respectively. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Performances of metal fluoride added carbon anodes with pre-electrolysis for electrolytic synthesis of NF3

Metal fluoride added carbon anodes treated by pre-electrolysis were investigated for electrolytic production of nitrogen trifluoride (NF₃) in molten NH₄F·KF·4HF at 100 °C. The conditions for pre-electrolysis were first optimized using a graphite sheet anode as a model anode. The formation of fluorine-graphite intercalation compounds (fluorine-GICs) with semi-covalent C–F bonds, (C_xF)_n, on the MgF₂ and CaF₂ added carbon anode surface was accelerated by pre-electrolysis at potentials less than 4.0 V. Critical current densities (CCD) on the MgF₂ added carbon anodes pre-electrolyzed under various conditions were determined, and the highest CCD was 290 mA cm⁻² obtained for that pre-electrolyzed at 3.5 V for 500 C cm⁻². This anode was successfully used in the electrolysis at 100 mA cm⁻² for 290 h and the maximum NF₃ current efficiency was 55%. From these results, it was concluded that the metal fluoride added carbon anode treated by pre-electrolysis has a high potential for electrolytic production of NF₃ at higher current density.     

Rate acceleration of Diels–Alder reactions utilizing a fluorous micellar system in water

A fluorous micellar system in water has been created to produce a large interfacial area between these media that retains substrates, effectively facilitating intermolecular Diels–Alder reactions due to repulsion effects from both media. Because LiFOS functioned not only as a surfactant but also as a supporting electrolyte, an electrochemical approach could be introduced to evaluate the rate acceleration effects. The measurement of the particle size distribution of the fluorous micelles clearly supported these evaluations.     

Synthesis of sulfonated organic–inorganic hybrids through the radical copolymerization of vinyl sulfonate esters and vinyl trialkoxysilanes

Novel organic–inorganic hybrids with sulfonic acid groups were prepared using random copolymers composed of vinyl sulfonate esters and vinyl trialkoxysilanes. Five vinyl sulfonate esters with different substituent groups were employed as protecting monomers for the production of the poly(vinyl sulfonic acid) component, and three vinyl trialkoxysilanes were used as cross-linkable monomers. Free radical and reversible addition-fragmentation chain transfer (RAFT) copolymerizations were performed for the production of random copolymers with two different functional groups. The selective deprotection of the sulfonate esters of the copolymers proceeded smoothly and resulted in the formation of copolymers with lithium vinyl sulfonate units and cross-linkable trialkoxysilane units. The co-condensation of the trialkoxysilane moieties in the deprotected copolymers with cross-linkers yielded transparent hybrid films that contained lithium sulfonate groups without aromatic rings or ester linkages.     

Determination of optical purity and absolute configuration of natural 12‐hydroxystearic acid by the 1H NMR anisotropy method

The enantiopure of (R)‐(?) MαNPA was allowed to react with racemic 18‐(tert‐butyldimethylsilyloxy)‐5‐octadecayne‐7‐ol which was derived from dodecane‐1,12‐diol, yielding diastereomeric esters mixture. These racemic esters were easily separated by HPLC on silica‐gel. The absolute configurations of the first‐eluted diastereomeric esters from the separated esters were determined using ¹H NMR anisotropy method. Analysis on ¹H NMR spectra and HPLC elution time of the synthesized esters and those of MαNP ester derived from natural methyl‐12‐hydroxystealate showed that the absolute configuration of natural 12‐hydroxystearic acid was R form, and the enantiomeric excess was over 99%.     

Responsiveness of electric resistance of polymer-grafted carbon black/alumina gel composite against solvent vapor and solute in solution

The carbon black/alumina gel composites were prepared by sol-gel reaction of aluminum isopropoxide in the presence of polymer-grafted carbon black. The electric resistance of the alumina gel composite from polymer-grafted carbon black was very sensitive to vapor of good solvent for grafted polymer on carbon black: the electric resistance of the alumina gel composite suddenly decreased in solvent vapor and returned to initial resistance when it was transferred into dry air. The effect of surface area and particle size of carbon black on the responsiveness was also investigated. In addition, the electric resistance of the alumina gel composite was found to respond to water and methanol in n-hexane and diethyl ether.