High performance all-carbon thin film supercapacitors

We fabricated high performance supercapacitors by using all carbon electrodes, with volume energy in the order of 10−3 Whcm−3, comparable to Li-ion batteries, and power densities in the range of 10 Wcm−3, better than laser-scribed-graphene supercapacitors. All-carbon supercapacitor electrodes are made by solution processing and filtering electrochemically-exfoliated graphene sheets mixed with clusters of spontaneously entangled multiwall carbon nanotubes. We maximize the capacitance by using a 1:1 weight ratio of graphene to multi-wall carbon nanotubes and by controlling their packing in the electrode film so as to maximize accessible surface and further enhance the charge collection. This electrode is transferred onto a plastic-paper-supported double-wall carbon nanotube film used as current collector. These all-carbon thin films are combined with plastic paper and gelled electrolyte to produce solid-state bendable thin film supercapacitors. We assembled supercapacitor cells in series in a planar configuration to increase the operating voltage and find that the shape of our supercapacitor film strongly affects its capacitance. An in-line superposition of rectangular sheets is superior to a cross superposition in maintaining high capacitance when subject to fast charge/discharge cycles. The effect is explained by addressing the mechanism of ion diffusion into stacked graphene sheets.

Electropolymerisation of catalytically active PEDOT from an ionic liquid on a flexible carbon cloth using a sandwich cell configuration

We report the electropolymerization of poly(3,4-ethylenedioxythiopene) (PEDOT) from an ionic liquid, butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (C4mpyrTFSI) onto flexible carbon cloth electrodes. A continuous, homogeneous and well adhered coating of the individual cloth fibres is achieved by employing a sandwich cell arrangement where the carbon cloth which is soaked with electrolyte is placed between two indium tin oxide electrodes isolated from each other by a battery separator. The resultant PEDOT modified carbon cloth electrode demonstrates excellent activity for the oxygen reduction reaction which is due to the doping level, conductivity and morphology of the PEDOT layer and is also tolerant to the presence of methanol in the electrolyte. This simple approach therefore offers a route to fabricate flexible polymer electrodes that could be used in various electronic applications.

Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH3CONH2), urea (NH2CONH2) and ammonium nitrate (NH4NO3). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step. 2-electron pathways of O-2 to H2O2 and further reduction of H2O2 to H2O. The first 2-electron reduction of O-2 to H2O2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and ROE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BOO) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide. (C) 2010 Elsevier Ltd. All rights reserved.

Synergitic Promotion of Electrooxidation of Methanol of Carbon-Supported PT-SN Catalysts

Electrooxidation of methanol in sulphuric acid on carbon-supported electrodes containing Pt-Sn bimetal catalysts prepared by an in-situ route is reported, The catalysts have been characterized employing chemical analyses, XRD, and XANES data in conjunction with electrochemistry. This study suggests that the Sn content in Pt-Sn bimetals produces: (i) a charge transfer from Sn to Pt and (ii) an increase in the coverage of adsorbed methanolic residues with the Sn content. From the electrode-kinetics data, it is inferred that while the electrodes of (3:3) Pt-Sn/C catalyst involve a 2-electron rate-limiting step akin to Pt/C electrodes, it is shifted to only 1-electron on (3:2) Pt-Sn/C, (3:3) Pt-Sn/C, and (3:4) Pt-Sn/C electrodes.

Crucible Steel in South India-Preliminary Investigations on Crucibles from Some Newly Identified Sites

European accounts from the 17th century onwards have referred to the repute and manufacture of “wootz’, a traditional crucible steel made especially in parts of southern India in the former provinces of Golconda, Mysore and Salem. Pliny's Natural History mentions the import of iron and steel from the Seres which have been thought to refer to the ancient southern Indian kingdom of the Cheras. As yet the scale of excavations and surface surveys is too limited to link the literary accounts to archaeometallurgical evidence, although pioneering exploratory investigations have been made by scholars, especially on the pre-industrial production sites of Konasamudram and Gatihosahalli discussed in 18th-19th century European accounts. In 1991–2 during preliminary surveys of ancient base metal mining sites, Srinivasan came across unreported dumps with crucible fragments at Mel-Siruvalur in Tamil Nadu, and Tintini and Machnur in Karnataka and she collected surface specimens from these sites as well as from the known site of Gatihosahalli. She was also given crucible fragments by the Tamil University, Tanjavur, from an excavated megalithic site at Kodumanal, dated to ca 2nd c. Bc, mentioned in Tamil Sangam literature (ca 3rd c. BC-3rd c. AD), and very near Karur, the ancient capital of the Sangam Cheras. Analyses of crucible fragments from the surface collection at Mel-Siruvalur showed several iron prills with a uniform pearlitic structure of high-carbon hypereutectoid steel (∼1–1.5% C) suggesting that the end product was uniformly a high-carbon steel of a structure consistent with those of high-carbon steels used successfully to experimentally replicate the watered steel patterns on ‘Damascus’ swords. Investigations indicate that the process was of carburisation of molten low carbon iron (m.p. 1400° C) in crucibles packed with carbonaceous matter. The fabric of crucibles from all the above mentioned sites appears similar. Preliminary investigations on these crucibles are thus reported to establish their relationship to crucible production of carbon steel and to thereby extend the known horizons of this technology further.

Lead ion sensor with electrodes modified by imidazole-functionalized polyaniline

Glassy carbon electrodes (GCE) and carbon paste electrodes (CPE) were modified with imidazole functionalized polyaniline with the aim to develop a sensor for lead (II) in both acidic and basic aqueous solution. The electrodes were characterized by cyclic voltammetry and differential pulse adsorptive stripping voltammetry. The limit of detections obtained with glassy carbon electrode and carbon paste electrode are 20 ng mL(-1) and 2 ng mL(-1) of lead ion, respectively. An interference study was carried out with Cd(II), As(III), Hg(II) and Co(II) ions. Cd(II) ions interfere significantly (peak overlap) and As(III) has a depressing effect on the lead signal. The influence of pH was investigated indicating that bare and modified GCE and CPE show optimum response at pH 4.0 +/- 0.05.

The role of hydrogen in hardening/softening steel: Influence of the charging process

Thermal desorption spectroscopy and nanoindentation techniques were employed to elucidate the key differences in the hydrogen (H) charging methods (electrochemical versus gaseous) and their consequences on the mechanical response of a low carbon steel. While electrochemical charging enhances the hardness, gaseous charging reduces it. This contrasting behavior is rationalized in terms of the dependency of the strength on the absorbed amount of H during charging and the H concentration gradient in the specimen. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Erosion-corrosion of mild steel in a temperature gradient

Thinning of heat-exchanger tubes by erosion-corrosion has been a problem in fluidized bed combustors (FBCs), particularly at lower metal temperatures where thicker, mechanically protective oxide scales are unable to form. Many laboratory-scale tests have shown a decrease in material loss at higher temperatures, in a similar manner to FBC boilers, but also show a decrease in wastage at low temperatures (e.g. 200°C) which has not been detected in boilers. It has been suggested that this difference is due to laboratory tests being carried out isothermally whereas in a FBC boiler the fluidized bed is considerably hotter than the metal heat exchanger tubing. In this laboratory study the simulation was therefore improved by internally cooling one of the two low carbon steel specimens. These were rotated in a horizontal plane within a lightly fluidized bed with relative particle velocities of 1.3-2.5 m s-1. Tests were carried out over a range of bed temperatures (200-500°C) and cooled specimen surface temperatures (115-500°C), with a maximum temperature difference between the two of 320°C. Although specimens exposed isothermally still showed maximum wastage at intermediate temperatures (about 350°C), those which were cooled showed high levels of wastage at temperatures as low as 200°C in a similar manner to FBC boilers. Cooling may modify the isothermal erosion-corrosion curve, causing it to broaden and the maximum wastage rate to shift to lower temperatures. © 1995.

Measurement Of Fracture Toughness And Interfacial Shear Strength Of Hard And Brittle Cr Coating On Ductile Steel Substrate

The fracture toughness and interfacial adhesion properties of a coating on its substrate are considered to be crucial intrinsic parameters determining performance and reliability of coating-substrate system. In this work, the fracture toughness and interfacial shear strength of a hard and brittle Cr coating on a normal medium carbon steel substrate were investigated by means of a tensile test. The normal medium carbon steel substrate electroplated with a hard and brittle Cr coating was quasi-statically stretched to induce an array of parallel cracks in the coating. An optical microscope was used to observe the cracking of the coating and the interfacial decohesion between the coating and the substrate during the loading. It was found that the cracking of the coating initiated at critical strain, and then the number of the cracks of the coating per unit axial distance increased with the increase in the tensile strain. At another critical strain, the number of the cracks of the coating became saturated, i.e. the number of cracks per unit axial distance became a constant after this critical strain. Based on the experiment result, the fracture toughness of the brittle coating can be determined using a mechanical model. Interestingly, even when the whole specimen fractured completely under an extreme strain of the substrate, the interfacial decohesion or buckling of the coating on its substrate was completely absent. The test result is different from that appeared in the literature though the identical test method and the brittle coating/ductile metal substrate system are taken. It was found that this difference can be attributed to an important mechanism that the Cr coating on the steel substrate has a good adhesion, and the ultimate interfacial shear strength between the Cr coating and the steel substrate has exceeded the maximum shear flow strength level of the steel substrate. This result also indicates that the maximum shear flow strength level of the ductile steel substrate can be only taken as a lower bound estimate on the ultimate shear strength of the interface. This estimation of the ultimate interfacial shear strength is consistent with the theoretical analysis and prediction presented in the literature.

On the selective removal of steel by laser-assisted vortex machining

Of all laser-based processes, laser machining has received little attention compared with others such as cutting, welding, heat treatment and cleaning. The reasons for this are unclear, although much can be gained from the development of an effcient laser machining process capable of processing diffcult materials such as high-performance steels and aerospace alloys. Existing laser machining processes selectively remove material by melt shearing and evaporation. Removing material by melting and evaporation leads to very low wall plug effciencies, and the process has difficulty competing with conventional mechanical removal methods. Adopting a laser machining solution for some materials offers the best prospects of effcient manufacturing operations. This paper presents a new laser machining process that relies on melt shear removal provided by a vertical high-speed gas vortex. Experimental and theoretical studies of a simple machining geometry have identifed a stable vortex regime that can be used to remove laser-generated melt effectively. The resultant combination of laser and vortex is employed in machining trials on 43A carbon steel. Results have shown that laser slot machining can be performed in a stable regime at speeds up to 150mm/min with slot depths of 4mm at an incident CO2 laser power level of 600 W. Slot forming mechanisms and process variables are discussed for the case of steel. Methods of bulk machining through multislot machining strategies are also presented.

Optical phase modulation using a hybrid carbon nanotube-liquid-crystal nanophotonic device.

The carbon nanotube-liquid-crystal (CNT-LC) nanophotonic device is a class of device based on the hybrid combination of a sparse array of multiwall carbon nanotube electrodes grown on a silicon surface in a liquid-crystal cell. The multiwall carbon nanotubes act as individual electrode sites that spawn an electric-field profile, dictating the refractive index profile within the liquid crystal and hence creating a series of graded index profiles, which form various optical elements such as a simple microlens array. We present the refractive index and therefore phase modulation capabilities of a CNT-LC nanophotonic device with experimental results as well as computer modeling and potential applications.

Fabrication of carbon nanotubes on inter-digitated metal electrode for switchable nanophotonic devices

This paper reports the modeling and characterization of interdigitated rows of carbon nanotube electrodes used to address a liquid crystal media. Finite Element Method modeling of the nanotube arrays was performed to analyze the static electric Fields produced to Find suitable electrode geometry. A device was fabricated based on the simulation results and electro optics characteristics of the device are presented. This Finding has applications in the development of micron and submicron pixels, precise beem steering and nanotube based active back planes.

Performance comparison of Stellite 6® deposited on steel using supersonic laser deposition and laser cladding

Stellite 6® powders were deposited on carbon steel using Supersonic Laser Deposition. The microstructure and performance of the coatings were examined using SEM, optical microscopy, EDS, XRD, microhardness testing and pin-on-disc wear testing. The results showed that the microstructure and wear behaviour of the most successful SLD deposition conditions with N2 at a pressure of 30bar, a temperature of 450°C and a deposition power of 1.5kW were compared with that of optimised laser cladding. © 2012 Elsevier B.V.

The effect of carbon nanotube orientation on erosive wear resistance of CNT-epoxy based composites

Aligned carbon nanotube (CNT) polymer composites are envisioned as the next-generation composite materials for a wide range of applications. In this work, we investigate the erosive wear behavior of epoxy matrix composites reinforced with both randomly dispersed and aligned carbon nanotube (CNT) arrays. The aligned CNT composites are prepared in two different configurations, where the sidewalls and ends of nanotubes are exposed to the composite surface. Results have shown that the composite with vertically aligned CNT-arrays exhibits superior erosive wear resistance compared to any of the other types of composites, and the erosion rate reaches a similar performance level to that of carbon steel at 20° impingement angle. The erosive wear mechanism of this type of composite, at various impingement angles, is studied by Scanning Electron Microscopy (SEM). We report that the erosive wear performance shows strong dependence on the alignment geometries of CNTs within the epoxy matrix under identical nanotube loading fractions. Correlations between the eroded surface roughness and the erosion rates of the CNT composites are studied by surface profilometry. This work demonstrates methods to fabricate CNT based polymer composites with high loading fractions of the filler, alignment control of nanotubes and optimized erosive wear properties. © 2014 Elsevier Ltd. All rights reserved.

Development of durable carbon black/titanium dioxide supported macrocycle catalysts for oxygen reduction reaction

Carbon black and titanium dioxide supported iron tetraphenylporphyrin (FeTPP/TiO2/C) catalysts for oxygen reduction reaction (ORR) were prepared by sol-gel and precipitation methods followed by a heat-treatment at temperatures of 400-1000 degrees C. The FeTPP/C and TiO2/C were also studied for comparison. The FeTPP/TiO2/C pyrolyzed at 700 degrees C exhibits significantly improved stability while maintaining high activity towards ORR in comparison with the FeTPP/C counterpart. The electrochemical study combined with XRD, XPS, and SEM/EDX analyses revealed that the appropriate dispersion of TiO2 on the surface of FeTPP/TiO2/C catalysts, which depending on heat-treatment temperature, plays a crucial role in determining the activity and stability of catalysts.