Tantalum-oxide catalysed chemical vapour deposition of single- and multi-walled carbon nanotubes

Tantalum-oxide thin films are shown to catalyse single- and multi-walled carbon nanotube growth by chemical vapour deposition. A low film thickness, the nature of the support material (best results with SiO2) and an atmospheric process gas pressure are of key importance for successful nanotube nucleation. Strong material interactions, such as silicide formation, inhibit nanotube growth. In situ X-ray photoelectron spectroscopy indicates that no catalyst reduction to Ta-metal or Ta-carbide occurs during our nanotube growth conditions and that the catalytically active phase is the Ta-oxide phase. Such a reduction-free oxide catalyst can be technologically advantageous. © 2013 The Royal Society of Chemistry.

The attrition behaviour of oxygen-carriers under inert and reacting conditions

The attrition of two potential oxygen-carriers for chemical-looping, 100. wt% mechanically-mixed, unsupported iron oxide (400-600 μm diameter) and 25. wt% copper oxide impregnated on alumina (600-900 μm diameter), has been studied. The rates of attrition of batches of these particles whilst they were being fluidised and subjected to successive cycles of reduction and oxidation were determined by measuring the rate of production of fine particles elutriated from the bed, as well as progressive changes in the distribution of particle sizes retained in the bed. The ability of the particles to withstand impacts was also investigated by examining the degree of fragmentation of 1. g of reacted particles of known size on projecting them at a target at various velocities. It was found that the mechanical strength of the iron oxide particles deteriorated significantly after repeated cycles of oxidation and reduction. Thus, the rate of elutriation increased ~35-fold between the 1st and 10th cycle. At an impact velocity of 38. m/s, the amount of fragmentation in the impact test, viz. mass fraction of particles after impact having a size less than that before impact, increased from ~2.3. wt% (fresh particles) to 98. wt% after the 10th cycle. The CuO particles, in comparison, were able to withstand repeated reaction: no signs of increased rates of elutriation or fragmentation were observed over ten cycles. These results highlight the importance of selecting a durable support for oxygen-carriers. © 2011 Elsevier Ltd.

Design and simulation of SMES system using YBCO tapes for direct drive wave energy converters

The ocean represents a huge energy reservoir since waves can be exploited to generate clean and renewable electricity; however, a hybrid energy storage system is needed to smooth the fluctuation. In this paper a hybrid energy storage system using a superconducting magnetic energy system (SMES) and Li-ion battery is proposed. The SMES is designed using Yttrium Barium Copper Oxide (YBCO) tapes, which store 60 kJ electrical energy. The magnet component of the SMES is designed using global optimization algorithm. Mechanical stress, coupled with electromagnetic field, is calculated using COMSOL and Matlab. A cooling system is presented and a suitable refrigerator is chosen to maintain a cold working temperature taking into account four heat sources. Then a microgrid system of direct drive linear wave energy converters is designed. The interface circuit connecting the generator and storage system is given. The result reveals that the fluctuated power from direct drive linear wave energy converters is smoothed by the hybrid energy storage system. The maximum power of the wave energy converter is 10 kW. © 2012 IEEE.

Soft ferrite used as thermal-magnetic conversion intermedium in the flux pumping technology

Recent progress in material science has proved that high-temperature superconductors, such as bulk melt-processed yttrium barium copper oxide (YBCO) single domains, have a great potential to trap significant magnetic fields. In this paper, we will describe a novel method of YBCO magnetization that only requires the applied field to be at the level of a permanent magnet. Instead of applying a pulsed high magnetic field on the YBCO, a thermally actuated material (TAM), such as Mg0.15}hbox{Cu}0.15} hbox{Zn0.7 Ti0.04}Fe1.96boxO4, has been used as an intermedium to create a travelling magnetic field by changing the local temperature so that the local permeability is changed to build up the magnetization of the YBCO gradually after multiple pumping cycles. It is well known that the relative permeability of ferrite is a function of temperature and its electromagnetic properties can be greatly changed by adding dopants such as Mg or Ti; therefore, it is considered to be the most promising TAM for future flux pumping technology. Ferrite samples were fabricated by means of the conventional ceramic method with different dopants. Zinc and iron oxides were used as raw materials. The samples were sintered at 1100 C, 1200 C} , and 1300 C. The relative permeability of the samples was measured at temperatures ranging from 77 to 300 K. This work investigates the variation of the magnetic properties of ferrites with different heat treatments and doping elements and gives a smart insight into finding better ferrites suitable for flux pumping technology. © 2002-2011 IEEE.

Catalyst-free synthesis of zinc oxide nanostructures by microheaters in the ambient environment

This paper demonstrates a catalyst-free synthesis of ZnO nanostructures using platinum microheaters under ambient environmental conditions. Different morphologies of ZnO nanostructures are synthesized from the oxidization of Zn thin film by local heating. The synthesized ZnO structures are characterized by the SEM, EDX and Raman spectra. The characterization of two shapes of Pt microheaters is investigated and the relationship between the applied heating power and ZnO nanostructures synthesis is investigated under ambient conditions. We observe that the density and morphology of ZnO nanostructures can be controlled through applied heating voltages. Furthermore, a connected composite structural (Zn-ZnO-Zn) layer is synthesized using combinative microheaters. © 2011 IEEE.

Complementary metal-oxide-semiconductor-compatible and self-aligned catalyst formation for carbon nanotube synthesis and interconnect fabrication

We have for the first time developed a self-aligned metal catalyst formation process using fully CMOS (complementary metal-oxide-semiconductor) compatible materials and techniques, for the synthesis of aligned carbon nanotubes (CNTs). By employing an electrically conductive cobalt disilicide (CoSi 2) layer as the starting material, a reactive ion etch (RIE) treatment and a hydrogen reduction step are used to transform the CoSi 2 surface into cobalt (Co) nanoparticles that are active to catalyze aligned CNT growth. Ohmic contacts between the conductive substrate and the CNTs are obtained. The process developed in this study can be applied to form metal nanoparticles in regions that cannot be patterned using conventional catalyst deposition methods, for example at the bottom of deep holes or on vertical surfaces. This catalyst formation method is crucially important for the fabrication of vertical and horizontal interconnect devices based on CNTs. © 2012 American Institute of Physics.

Observing graphene grow: catalyst-graphene interactions during scalable graphene growth on polycrystalline copper.

Complementary in situ X-ray photoelectron spectroscopy (XPS), X-ray diffractometry, and environmental scanning electron microscopy are used to fingerprint the entire graphene chemical vapor deposition process on technologically important polycrystalline Cu catalysts to address the current lack of understanding of the underlying fundamental growth mechanisms and catalyst interactions. Graphene forms directly on metallic Cu during the high-temperature hydrocarbon exposure, whereby an upshift in the binding energies of the corresponding C1s XPS core level signatures is indicative of coupling between the Cu catalyst and the growing graphene. Minor carbon uptake into Cu can under certain conditions manifest itself as carbon precipitation upon cooling. Postgrowth, ambient air exposure even at room temperature decouples the graphene from Cu by (reversible) oxygen intercalation. The importance of these dynamic interactions is discussed for graphene growth, processing, and device integration.

Diffusion and chemical reaction in the porous structures of solid oxide fuel cells

The Rolls-Royce Integrated-Planar Solid Oxide Fuel Cell (IP-SOFC) consists of ceramic modules which have electrochemical cells printed on the outer surfaces. The cathodes are the outermost layer of each cell and are supplied with oxygen from air flowing over the outside of the module. The anodes are in direct contact with the ceramic structure and are supplied with fuel from internal gas channels. Natural gas is reformed into hydrogen for use by the fuel cells in a separate reformer module of similar design except that the fuel cells are replaced by a reforming catalyst layer. The performance of the modules is intrinsically linked to the behaviour of the gas flows within their porous structures. Because the porous layers are very thin, a one-dimensional flow model provides a good representation of the flow property variations between fuel channel and fuel cell or reforming catalyst. The multi-component convective-diffusive flows are simulated using a new theory of flow in porous material, the Cylindrical Pore Interpolation Model. The effects of the catalysed methane reforming and water-gas shift chemical reactions are also considered using appropriate kinetic models. It is found that the shift reaction, which is catalysed by the anode material, has certain beneficial effects on the fuel cell module performance. In the reformer module it was found that the flow resistance of the porous support structure makes it difficult to sustain a high methane conversion rate. Although the analysis is based on IP-SOFC geometry, the modelling approach and general conclusions are applicable to other types of SOFC.

Low temperature (< 100 °c) deposited P-type cuprous oxide thin films: Importance of controlled oxygen and deposition energy

With the emergence of transparent electronics, there has been considerable advancement in n-type transparent semiconducting oxide (TSO) materials, such as ZnO, InGaZnO, and InSnO. Comparatively, the availability of p-type TSO materials is more scarce and the available materials are less mature. The development of p-type semiconductors is one of the key technologies needed to push transparent electronics and systems to the next frontier, particularly for implementing p-n junctions for solar cells and p-type transistors for complementary logic/circuits applications. Cuprous oxide (Cu2O) is one of the most promising candidates for p-type TSO materials. This paper reports the deposition of Cu2O thin films without substrate heating using a high deposition rate reactive sputtering technique, called high target utilisation sputtering (HiTUS). This technique allows independent control of the remote plasma density and the ion energy, thus providing finer control of the film properties and microstructure as well as reducing film stress. The effect of deposition parameters, including oxygen flow rate, plasma power and target power, on the properties of Cu2O films are reported. It is known from previously published work that the formation of pure Cu2O film is often difficult, due to the more ready formation or co-formation of cupric oxide (CuO). From our investigation, we established two key concurrent criteria needed for attaining Cu2O thin films (as opposed to CuO or mixed phase CuO/Cu2O films). First, the oxygen flow rate must be kept low to avoid over-oxidation of Cu2O to CuO and to ensure a non-oxidised/non-poisoned metallic copper target in the reactive sputtering environment. Secondly, the energy of the sputtered copper species must be kept low as higher reaction energy tends to favour the formation of CuO. The unique design of the HiTUS system enables the provision of a high density of low energy sputtered copper radicals/ions, and when combined with a controlled amount of oxygen, can produce good quality p-type transparent Cu2O films with electrical resistivity ranging from 102 to 104 Ω-cm, hole mobility of 1-10 cm2/V-s, and optical band-gap of 2.0-2.6 eV. These material properties make this low temperature deposited HiTUS Cu 2O film suitable for fabrication of p-type metal oxide thin film transistors. Furthermore, the capability to deposit Cu2O films with low film stress at low temperatures on plastic substrates renders this approach favourable for fabrication of flexible p-n junction solar cells. © 2011 Elsevier B.V. All rights reserved.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Synthesis of zinc oxide nanostructures by microheaters in the ambient environment

A catalyst-free synthesis of ZnO nanostructures using platinum microheaters under ambient environmental conditions has been developed. Different types of ZnO nanostructures are synthesized from the oxidization of Zn thin film by local heating. The characterization of two shapes of Pt microheaters is investigated and the relationship between the applied power for heat generation and ZnO nanostructure synthesis is investigated by local heating experiments under ambient conditions. Based on the developed heating approach, synthesis area, location, and morphologies of ZnO nanostructures can be controlled through the deposited thickness of Zn layer and applied heating voltages. Furthermore, a connected multiple-structure (Zn-ZnO-Zn) layer is synthesized using combinative multimicroheaters. © 2002-2012 IEEE.

Self-assembled multilayer graphene oxide membrane and carbon nanotubes synthesized using a rare form of natural graphite

The fabrication of flexible multilayer graphene oxide (GO) membrane and carbon nanotubes (CNTs) using a rare form of high-purity natural graphite, vein graphite, is reported for the first time. Graphite oxide is synthesized using vein graphite following Hummer's method. By facilitating functionalized graphene sheets in graphite oxide to self-assemble, a multilayer GO membrane is fabricated. Electric arc discharge is used to synthesis CNTs from vein graphite. Both multilayer GO membrane and CNTs are investigated using microscopy and spectroscopy experiments, i.e., scanning electron microscopy (SEM), atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), core level photoelectron spectroscopy, and C K-edge X-ray absorption spectroscopy (NEXAFS), to characterize their structural and topographical properties. Characterization of vein graphite using different techniques reveals that it has a large number of crystallites, hence the large number of graphene sheets per crystallite, preferentially oriented along the (002) plane. NEXAFS and core level spectra confirm that vein graphite is highly crystalline and pure. Fourier transform infrared (FT-IR) and C 1s core level spectra show that oxygen functionalities (-C-OH, -CO,-C-O-C-) are introduced into the basal plane of graphite following chemical oxidation. Carbon nanotubes are produced from vein graphite through arc discharge without the use of any catalyst. HRTEM confirm that multiwalled carbon nanotube (MWNTs) are produced with the presence of some structure in the central pipe. A small percentage of single-walled nanotubes (SWNTs) are also produced simultaneously with MWNTs. Spectroscopic and microscopic data are further discussed here with a view to using vein graphite as the source material for the synthesis of carbon nanomaterials. © 2013 American Chemical Society.