Electrochemical studies of kerosene-pyrolysedcarbon films

Polycrystalline thin films of conducting carbon are deposited on alumina substrates by the pyrolysis of kerosene vapour at 1000C for 2h in argon atmosphere. Preliminary structural analysis is done by XRD, laser-Raman, FTIR and SEM studies. The electrochemical behaviour of as-grown conducting carbon films was investigated in various electrolytes at different pH and the performance was compared with that of platinum and glassy electrodes. The electrochemical window of the kerosene carbon electrode in 100mm H2SO4 was found to be 2.91V which is greater than that of glassy carbon (2.79V) and platinum (2.02V). Cyclic voltammetry reveals that Pt electrode has almost an equal tendency towards hydrogen and oxygen evolution, whereas glassy carbon favours hydrogen evolution and kerosene carbon favours oxygen evolution. It is suggested that the kerosene carbon electrode can be used as an oxygen electrode more efficiently. Unlike diamond films or glassy electrodes, kerosene carbon thin films are of low cost and good stability; they are also easy to grow on various ceramic substrates of any size. Moreover, these electrodes are very economical and promising for application in chlor-alkali industry.     

Electrochemical preparation and characterization of poly(1-amino-9,10-anthraquinone) films

Poly(1-amino-9,10-anthraquinone), PAAQ, films were prepared by electrochemical oxidation of the monomer, AAQ, in acetonitrile using LiClO₄ as supporting electrolyte. The influence of scan repetition, scan rate and monomer concentration on the formation of polymer film was studied. The electrochemical behavior of the formed polymer films was investigated in both non-aqueous and aqueous media. The prepared films were found to be more stable in organic solvents than in aqueous solutions. The investigated organic solvents are methanol, ethanol, acetone, carbon tetrachloride, benzene, and chloroform. The polymer film shows electrochemical response in both non-aqueous and aqueous media. In non-aqueous solutions it has a wide potential range of electroactivity (from −1.5 to +1.3 V). In aqueous media the polymer film shows electrochemical response in the potential range between −0.3 and +1.3 V only. The presence of quinone units suggests potential applications in diverse areas such as electrocatalytic processes and lithium ion batteries.     

The effect of CVD-diamond film thickness on the electrochemical properties of synthetic diamond thin-film electrodes

The electrochemical behavior of polycrystalline diamond films of different thickness (0.5–7 μm), grown by hot-filament CVD method, was studied by electrochemical impedance spectroscopy and cyclic voltammetry. The differential capacitance, background current, and potential window were measured in supporting electrolyte solution; the electrochemical kinetics, in [Fe(CN)₆]^3−/4− model redox system. With the increasing of the films thickness, the crystallite size increased; both the differential capacitance and background current in the indifferent electrolyte, as well as the transfer coefficients in the redox system, decreased; thus, the diamond electrode becomes as if less reversible. The effect of the films’ thickness is reduced to that of nondiamond (amorphous) carbon contribution from intercrystalline boundaries on the electrochemical behavior of the polycrystalline diamond electrodes.     

Solvent effects on electrochemical behavior of poly(ferrocenylsilane) films

The electrochemical behaviors of poly(ferrocenylsilane) (PFS) films in organic solutions were investigated by means of cyclic voltammetry (CV) and electrochemical quartz crystals microbalance (EQCM). The influences of solvent on the electrochemical behavior of the films were discussed. In “good” solvents, the supporting electrolytes dissociated completely, the films were solvent-swollen moderately which provided a favorable condition for the electrolyte ions penetrating through, and the CV behavior of the films exhibited reversible or nearly reversible features. With increasing the carbon chain length of solvent molecule, however, the polarity of solvent reduced, which conduced to decrease the dissociation of electrolyte and the swelling of the polymer film. The efficiency of electrochemical reaction in the film was depressed, and the CV behavior of the film exhibited low reversibility. The solvent effects on the oxidation process of films exhibited more noticeable than the reduction process. The results supported the viewpoint that penetration of the electrolyte anions played an important role on the charge balance and transfer in the films during the CV process. The different electrochemical behaviors of the two PFS films in various organic solutions indicated that molecular structure of polymer had important influence on the electrochemical properties of the PFS.     

Electrochemical behavior of glassy carbon electrodes modified by multi-walled carbon nanotube/surfactant films in a buffer solution and an ionic liquid

The electrochemical behavior of glassy carbon (GC) electrodes coated with multi-walled carbon nanotube (MWCNT)/surfactant films was studied in an ionic liquid and a phosphate buffer solution (pH = 6.86), using cyclic voltammetry. The dispersion of MWCNTs in different media was investigated by scanning and transmission electron microscopy. Cast films of MWCNT/zwitterionic dodecyldimethylamine oxide on a GC electrode show a typical redox couple in phosphate buffer solution, which is better than that of MWCNT/anionic sodium dodecyl sulfate and cationic alkyltrimethylammonium bromide. However in the ionic liquid, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), the GC electrode modified by MWCNT/cationic surfactant films shows a well-defined irreversible reduction of MWCNTs. The cyclic voltammograms clearly show that the surfactant hydrophilic group plays an important role in the electrochemical behavior of the MWCNTs. The electrolytes also have an important effect. In an ionic liquid, the strong binding of the ionic liquid cations with the MWCNTs may change the structure of the modified films and lead to changes of electrochemical behavior.     

Semiconducting carbon films from a natural source: camphor

Thin films of carbon have been grown on alumina substrates by the pyrolysis of camphor at 900 °C for 2 h in an argon atmosphere, followed by sintering for various time periods. The effect of sintering time on the surface morphology, conductivity, carrier concentration, mobility and bandgap of camphor-pyrolyzed films is discussed. Structural characterizations are performed on the basis of XRD and SEM analyses. Electrical conductivity measurements of these films, as a function of temperature, suggest them to be semiconductors. A Hall-effect study of the as-grown films shows their carrier concentrations to be of the order of 10¹⁷ cm⁻³. The Hall mobilities of these films are found to vary from 1702 to 10263 cm² V⁻¹ s⁻¹. The thermal bandgaps of these films are found to decrease with increasing of sintering time. Thus, by controlled sintering of camphor-pyrolyzed carbon films, it is possible to obtained a semiconductor with the desired bandgap. Therefore, camphor-pyrolyzed semiconducting carbon films seem to be a promising material with which to develop a photovoltaic solar cell.     

Poly(malachite green) film: Electrosynthesis, characterization, and sensor application

Poly(malachite green) films were synthesized electrochemically on the glassy carbon electrode in the potentiodynamic mode. The characterization and growth mechanism of as-prepared films were studied with FT-IR spectroscopy, UV-vis spectroscopy, cyclic voltammetry, chronocoulometry, and electrochemical impedance spectroscopy. Charge transfer and ion transport of poly(malachite green) films were investigated in the aqueous solutions with different types of supporting electrolytes. The poly(malachite green) film coated glassy carbon electrode showed catalytic ability towards ascorbic acid and dopamine. The difference of the anodic peak potential of ascorbic acid on the poly(malachite green) film modified electrode from that of dopamine was 180 mV. Based on their voltammetric responses, the poly(malachite green) film coated glassy carbon electrode was utilized as an electrochemical sensor for the content determination of ascorbic acid and dopamine simultaneously and separately in pharmaceutical and injections.     

The strain sensing and thermal–mechanical behavior of flexible multi-walled carbon nanotube/polystyrene composite films

The strain sensing and thermal–mechanical behaviors of well dispersed multi-walled carbon nanotube/polystyrene (MWCNT/PS) composite films with different wt.% of carbon nanotubes were analyzed. The thermal–mechanical properties are studied using a dynamical mechanical analyzer and the results give their storage modulus (E′) and loss modulus (E″) as a function of temperature. We found an increase in E′ of up to 122% at 80 °C for a 6 wt.% MWCNT/PS composite compared to PS. The glass transition temperature increased significantly with an increase in MWCNTs concentration. The strain sensing behavior of the films is measured by applying an axial load over film which is attached to a brass specimen. The composite films exhibit excellent strain sensing behavior for different MWCNT contents. The result shows that an electromechanical response of the composite films varies linearly with applied strain even at high strains.     

Characterization of the barrier layer of nanoporous alumina films prepared using two different contact configurations

We investigated the structure of the barrier layers of nanoporous alumina formed by anodization of aluminum films laid over platinum electrodes by cyclic voltammetry technique and scanning electron microscopy. Two methods of anodization were employed in this study—the conventional sub-surface anodization method and a novel pipette anodization method. Measurements of the electron transfer rate constant values at these alumina-modified electrodes demonstrated very different alumina microstructures at the barrier layer region for these two types of alumina-modified electrodes. The sub-surface anodized electrode consists of a barrier layer, which forms a kinetic barrier for the electrochemical reaction of a redox probe at the underlying platinum electrode. In contrast, the quasi-reversible electrochemical behaviour of a redox probe at the pipette-anodized electrodes closely resembles the reaction observed at a bare platinum electrode. Scanning electron microscopy revealed pore structures along the underside surface of the alumina overlayer of a pipette-anodized electrode. These results indicate alumina modified eletrodes fabricated using the pipette anodization method comprise channels which penetrate the barrier layer, giving rise to ‘barrier layer-free’ alumina films.     

Galvanic function of zinc-rich coatings facilitated by percolating structure of the carbon nanotubes. Part I: Characterization of the nano-size particles

The newly developed zinc-rich hybrid paints are composed of polypyrrole (PPy) and polystyrene-sulfonate (PSS) modified alumina hydrate and either purified or functionalized multi-walled carbon nanotubes (MWCNTs). Preparation of the nano-size particles, i.e., in situ polymerization and deposition of PPy-PSS complexes on the mixture of alumina hydrate and MWCNTs is presented. Characterization of the particles by cyclic voltammetry (CV), Fourier-transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) as well as their dispersions by rheology investigation is detailed in this part of the work. High electrochemical reversibility, increasing electrical conductivity and Coulombic efficiency of the particles with greater relative amount of the MWCNTs were evinced. Thin layer polymer deposition was found continuous on alumina and the MWCNTs and varied compactness of the PPy films and charge-delocalization over their network were witnessed depending on the proportion of incorporated PSS. Different micron-scale dispersity of the particles, compactness and ramification of particle clusters as well as their aggregation at nano-scale and flocculation at micron-scale were disclosed resulting in either kinetically three-dimensional (3D) interacting or non-percolating distribution. Corrosion protection performance of the hybrid coatings was examined whereas characteristics of the protection mechanism is substantially analysed from many perspectives, which all detailed in 2nd part of this study.     

Effects of alumina sols on the sintering of α-alumina ceramics

The effects of two kinds of alumina sols on the densification behavior of sub-micron grain sized α-alumina ceramics have been investigated. Composition of the sol-derived gels was investigated by energy dispersive spectra and Fourier transform infrared spectra. Structural evolution of the gels at different temperatures was characterized by a combination of X-ray diffraction and ²⁷Al magic angle spinning nuclear magnetic resonance spectroscopy. Results showed that the gel containing chlorine and carbon transformed to α-alumina at about 950 °C, significantly lower than the other gel which transformed at about 1050 °C. Density measurements and scanning electron microscopy analyses were used to investigate the sintering of alumina ceramics with or without alumina sols. It was found that the alumina sols had profound effects on the densification of alumina ceramics. The ceramic displayed the best densification behavior when the sol containing chlorine and carbon was added.     

Electrochemical impedance study of polyaniline electrocoated porous carbon foam

Electropolymerization of aniline on mesophase pitch based carbon foam has been studied in order to evaluate the influence of conductive polymer coating on the properties of carbon foam. The surface morphology of the coating was determined by scanning electron microscopy (SEM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of resulting modified carbon foam samples. Polyaniline (PANI) electrocoated-mesophase pitch based carbon foam showed good capacitor behavior in 0.5 M H₂SO₄. Better capacitive behavior is obtained for 100 and 150 mV/s compared to other scan rates, under these faster scan rates thinner films of PANI coatings were combined with more porous structure of carbon foam. Conductivity of the carbon foam was increased from 9.23 to 13.73 S/cm by electrocoating of PANI.     

A novel EDOT–nonylbithiazole–EDOT based comonomer as an active electrode material for supercapacitor applications

A novel EDOT–nonylbithiazole–EDOT based bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer was synthesized and was electrochemically deposited onto carbon fiber electrode as an active electrode material. An electrochemical impedance study on the prepared electrodes is reported in this paper. Capacitive behavior of the carbon fiber microelectrode/poly(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) system was investigated with cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy. Variation of capacitance values by scan rate and specific capacitance values at different potentials are presented. Specific capacitance value for a galvanostatically prepared polymer film with a charge of 5 C cm⁻² was obtained about 340 mF cm⁻². Effect of the solvent and the deposition charge on the capacitive behavior of the film was investigated using electrochemical impedance spectroscopy. An equivalent circuit model was proposed and the electrochemical impedance data were fitted to find out numerical values of the proposed components. The galvanostatic charge/discharge characteristic of a film was investigated by chronopotentiometry and the morphology of the films electrodeposited at different deposition charges were monitored using FE-SEM.     

Flexible free-standing carbon nanotube films for model lithium-ion batteries

A comparative study of conductive, free-standing, binder-free flexible films made from three different types of commercial carbon nanotubes (CNTs), i.e., single-wall, double-wall, and multi-wall was carried out. The conductive CNT films were prepared by adding the CNTs to the starting dispersion of carbon black and Triton X-100, followed by a vacuum filtration technique. These films have been characterized as model free-standing, binder-free electrodes for flexible lithium-ion batteries. Our experiments revealed that films based on multi-wall CNTs (MWCNTs) are much better than single-wall and double-wall CNTs films in terms of their electrochemical performance. The flexible MWCNT electrodes show stable cycling behavior and allow up to a 10 C-rate.     

Direct electrodeposition of thin-layer (phenylene–carbazolylene) copolymers

Thin (phenylene–carbazolylene) copolymer films of controlled composition can be directly deposited onto solid cathodes such as indium tin oxide (ITO) glass or glassy carbon through a dehalogenative polycondensation of 4,4′-dibromobiphenyl and 3,6-dibromo-N-alkylcarbazole mixtures in the presence of an electrogenerated zero-valent nickel catalyst. The electrochemical and optical properties of the resulting thin films have been studied. The electrochemical behavior reveals two distinct electronic states that depend on the copolymer composition and structure. The first electronic state is characterized by either only one redox process, attributed to the presence of phenylene-disubstituted carbazolic units in the case of copolymers with the highest proportion of phenylene, or two successive redox processes, attributed to the occurrence of a radical cation and dication of carbazolic diades, in the case of copolymers with the lowest proportion of phenylene. The second electronic state shows in all cases a single redox system occurring at a higher potential than the first state and due to phenylene moieties in the copolymer. All the electrodeposited copolymer films were found to be reducible in the same manner as pure poly(p-phenylene). © 1994 John Wiley & Sons, Inc.     

Structure,electrochemical properties and functionalization of amorphous CN films deposited by femtosecond pulsed laser ablation

Amorphous carbon nitride (a-C:N) material has attracted much attention in research and development. Recently, it has become a more promising electrode material than conventional carbon based electrodes in electrochemical and biosensor applications. Nitrogen containing amorphous carbon (a-C:N) thin films have been synthesized by femtosecond pulsed laser deposition (fs-PLD) coupled with plasma assistance through Direct Current (DC) bias power supply. During the deposition process, various nitrogen pressures (0 to 10 Pa) and DC bias (0 to − 350 V) were used in order to explore a wide range of nitrogen content into the films. The structure and chemical composition of the films have been studied by using Raman spectroscopy, electron energy-loss spectroscopy (EELS) and high-resolution transmission electron microscopy (HRTEM). Increasing the nitrogen pressure or adding a DC bias induced an increase of the N content, up to 21 at.%. Nitrogen content increase induces a higher sp² character of the film. However DC bias has been found to increase the film structural disorder, which was detrimental to the electrochemical properties. Indeed the electrochemical measurements, investigated by cyclic voltammetry (CV), demonstrated that a-C:N film with moderate nitrogen content (10 at.%) exhibited the best behavior, in terms of reversibility and electron transfer kinetics. Electrochemical grafting from diazonium salts was successfully achieved on this film, with a surface coverage of covalently bonded molecules close to the dense packed monolayer of ferrocene molecules. Such a film may be a promising electrode material in electrochemical detection of electroactive pollutants on bare film, and of biopathogen molecules after surface grafting of the specific affinity receptor.     

Effect of carbon nanotubes and aluminum oxide on the properties of a plasma sprayed thermal barrier coating

To protect the structural components of a power generating unit from the corrosive environment, thermal spray coatings are applied to the components. In the present work, four different types of thermal barrier coating (TBC) viz. partially stabilised zirconia (8YSZ), zirconia-20% alumina (ZA) composite coating without carbon nanotube (CNT) reinforcement, and ZA with 1% and 3% CNT reinforcement. The coating was deposited on NiCrAlY coated P91 steel using a plasma spraying process. The coating microstructure and phases were characterised using field emission scanning electron microscope (FE-SEM) with energy dispersive spectroscopy (EDS). The phases of the coating were analyzed using X-ray diffraction technique. The effect of CNT reinforcement on the thermal conductivity, porosity, and hardness of the composite coatings was investigated. The protective behavior of the coatings was characterised by potentiodynamic polarization testing and electrochemical impedance measurements. The thermal conductivity of the composite coating was found to be increased with increasing CNT content. Hardness was found to be highest for 3% CNT reinforcement and the thermal conductivity was found to increase with decreasing porosity. The electrochemical measurements indicate that reinforcement of CNT in zirconia alumina composite coating improved its corrosion resistance.     

Electrochemically grown passive films on carbon steel (SAE 1018) in alkaline sour medium

Corrosion films were prepared by applying cyclic potential pulses to the 1018 carbon steel-sour medium interface (1 M (NH₄)₂S, 500 ppm CN⁻) for 1 min. Electrochemical behavior and surface morphology of these films were determined using electrochemical impedance spectroscopy (EIS), scanning electron microscopy, and scanning photoelectrochemical microscopy (SPECM). EIS diagrams and SPECM images show the passive properties and homogeneity of the films. Furthermore, X-ray photoelectron spectroscopy (XPS) was used to characterize their chemical nature and structure. XPS results show that different oxide and sulfur structures were developed during the electrochemical oxidation of carbon steel in concentrated sour media. The analysis of O 1s data indicated that, during film growth, H₂O and/or hydroxyl groups are incorporated into the film structure. The XPS spectra of Fe 2p show iron bonds with S as iron sulfide (FeS₂ and FeS) and the corresponding peak of O 1s shows those bonds with oxygen as Fe₂O₃ and/or FeO. XPS depth profile analyses for the film showed that the ratio of FeS and FeO increases from film surface to film-carbon steel interface. This corroborates the diffusion of iron ions through the film during its electrochemical growth. The chemical shift through the film for the peak associated with Fe 2p signal proves that transport mechanism of iron ions through the film is carried out by chemical diffusion.     

Alumina coatings on carbon bonded alumina nozzles for active filtration of steel melts

Slip casted, carbon bonded nozzles with and without alumina based active coatings have been simultaneously tested in a novel casting simulator according to their clogging behavior against endogenous as well as exogenous non-metallic inclusions. Computer tomography images as well as SEM micrographs support the investigation of the clogging areas. The nozzle with the alumina active coating leads to increased clogging phenomena based on endogenous and exogenous inclusions as well as steel clogged particles. Correlating the clogging to a type of improved “filtration efficiency”, a higher filtration of steel melts is expected with the application of alumina active coatings on carbon bonded filters.     

Highly conductive alumina/NCN composites electrodes fabricated by gelcasting and reduction-sintering—An electrochemical behavior study in aggressive environments

A novel highly conductive alumina/nano-carbon network composites (alumina/NCN composites) was fabricated by gelcasting and reduction-sintering method under argon atmosphere. The electrochemical behaviors of the alumina/NCN composites were studied systematically in some aggressive solutions (HCl, H₂SO₄, HNO₃, NaOH, and KOH), using potentiodynamic polarization and chronoamperometry and X-ray diffraction and SEM observations. The results showed that the electrochemical stability and reproducibility of the composite electrodes in these diluted acids and alkalis were very good and had, in some extent, an electro-catalytic activity toward formation of hydrogen evolution and reduction of dissolved oxygen in aqueous solutions in comparison with a commercial graphite electrode. In addition, the pyrolyzed nano-carbon contents, size, and shape in the alumina matrix, have greatly effects on the electrochemical performances and electrode reactions in these solutions. It is found that the minimal residual carbon content of 0.62 wt.% in the matrix is enough to improve electrochemical performances and avoid to loss the ceramics physical properties at the same time. When the additional potential in all the tested electrolytes was at +1700 mV (vs. SCE), alumina particles at the electrode surface were not observed to dissolve into solution in this case, indicating the material being suitable for electrodes in aggressive solutions.