Nano-urchin: The formation and structure of high-density spherical clusters of vanadium oxide nanotubes

We report the observation of urchin-like nanostructures consisting of high-density spherical nanotube radial arrays of vanadium oxide nanocomposite, successfully synthesized by a simple chemical route using an ethanolic solution of vanadium tri-isopropoxide and alkyl amine hexadecylamine for 7 days at 180oC. The results show that the growth process of the NanoUrchin occurs in stages, starting with a radial self-organized arrangement of lamina followed by the rolling of the lamina into nanotubes. The longest nanotubes are measured to be several micrometers in length with diameters of ~120 nm and hollow centers typically measured to be ~75 nm. The NanoUrchin have an estimated density of nanotubes of ~40 sr-1. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. The interlayer distance is measured to be 2.9 ± 0.1 nm and electron diffraction identified the vanadate phase in the VOx nanocomposite as orthorhombic V2O5. These nanostructures may be used as three-dimensional composite materials and as supports for other materials.

Development of low-cost sensing and separation devices based on macro, micro and nano technology for health applications

The work presented in this thesis described the development of low-cost sensing and separation devices with electrochemical detections for health applications. This research employs macro, micro and nano technology. The first sensing device developed was a tonerbased micro-device. The initial development of microfluidic devices was based on glass or quartz devices that are often expensive to fabricate; however, the introduction of new types of materials, such as plastics, offered a new way for fast prototyping and the development of disposable devices. One such microfluidic device is based on the lamination of laser-printed polyester films using a computer, printer and laminator. The resulting toner-based microchips demonstrated a potential viability for chemical assays, coupled with several detection methods, particularly Chip-Electrophoresis-Chemiluminescence (CE-CL) detection which has never been reported in the literature. Following on from the toner-based microchip, a three-electrode micro-configuration was developed on acetate substrate. This is the first time that a micro-electrode configuration made from gold; silver and platinum have been fabricated onto acetate by means of patterning and deposition techniques using the central fabrication facilities in Tyndall National Institute. These electrodes have been designed to facilitate the integration of a 3- electrode configuration as part of the fabrication process. Since the electrodes are on acetate the dicing step can automatically be eliminated. The stability of these sensors has been investigated using electrochemical techniques with excellent outcomes. Following on from the generalised testing of the electrodes these sensors were then coupled with capillary electrophoresis. The final sensing devices were on a macro scale and involved the modifications of screenprinted electrodes. Screen-printed electrodes (SPE) are generally seen to be far less sensitive than the more expensive electrodes including the gold, boron-doped diamond and glassy carbon electrodes. To enhance the sensitivity of these electrodes they were treated with metal nano-particles, gold and palladium. Following on from this, another modification was introduced. The carbonaceous material carbon monolith was drop-cast onto the SPE and then the metal nano-particles were electrodeposited onto the monolith material

Toxicity of manufactured nano-ZnO to Lemna minor

The rapid development of nanotechnology has led to a rise in the large-scale production and commercial use of engineered nano-ZnO. Engineered/manufactured nano-ZnO are applied in a broad range of products such as drugs, paints, cosmetics, abrasive agents and insulators. This can result in the unintended exposure of human beings to nano-ZnO and will inevitably result in the release of nano-ZnO in to the environment. Thus, it is necessary to assess the risk of nano-ZnO to the environment. In this thesis the toxicity of nano-ZnO was analysed using the aquatic, primary producer lesser duckweed (Lemna minor), and the mechanism of toxicity was analysed. Both short-term (one week) and long-term (six weeks) toxicity of nano-ZnO (uncoated) were determined. Results show that the toxicity of nano-ZnO added to the aquatic growth medium increases with increasing concentration and that toxicity accumulates with exposure time. A study of nano-ZnO dissolution reveals that the main reason for nano-ZnO toxicity on Lemna minor is the release of Zn ions. Nano-ZnO dissolution is pH dependent, and toxicity matches the release of Zn2+. Functional coating materials are commonly added to nano-ZnO particles to improve specific industrial applications. To test if coating materials contribute to nano-ZnO toxicity on lesser duckweed, the effect of silane coupling agent (KH550) coated nano-ZnO on Lemma minor was investigated. Results show that coating can decrease the release of Zn ions, which reduces toxicity to Lemna minor, in contrast to uncoated particles. Another commonly hypothesized reason for nano-ZnO toxicity is the formation of Reactive Oxygen Species (ROS) on the particles surface. As part of this thesis, the ROS formation induced by nano-ZnO was studied. Results show that nano-ZnO catalyse ROS formation and this can negatively affect duckweed growth. In conclusion, this work has detailed potentially toxic effects of nano-ZnO on Lemna minor. This study has also provides references for future research, and informs regulatory testing for nanoparticle toxicity. Specifically, the outcomes of this study emphasize the importance of exposure time, environmental parameters and coating material when analysing NPs toxicity. Firstly, impacts of longer exposure time should be studied. Secondly, environmental parameters such as pH and medium-composition need to be considered when investigating NPs toxicity. Lastly, coating of NPs should always be considered in the context of NPs toxicity, and similar NPs with different coatings require separate toxicity tests.

Surface physics at the nano-scale via scanning probe microscopy and molecular dynamics simulations

Probe-based scanning microscopes, such as the STM and the AFM, are used to obtain the topographical and electronic structure maps of material surfaces, and to modify their morphologies on nanoscopic scales. They have generated new areas of research in condensed matter physics and materials science. We will review some examples from the fields of experimental nano-mechanics, nano-electronics and nano-magnetism. These now form the basis of the emerging field of Nano-technology. A parallel development has been brought about in the field of Computational Nano-science, using quantum-mechanical techniques and computer-based numerical modelling, such as the Molecular Dynamics (MD) simulation method. We will report on the simulation of nucleation and growth of nano-phase films on supporting substrates. Furthermore, a theoretical modelling of the formation of STM images of metallic clusters on metallic substrates will also be discussed within the non-equilibrium Keldysh Green function method to study the effects of coherent tunnelling through different atomic orbitals in a tip-sample geometry.

Numerical modelling for electromagnetic processing of materials

Electromagnetic processing of materials (EPM) is one of the most widely practiced and fast growing applications of magnetic and electric forces to fluid flow. EPM is encountered in both industrial processes and laboratory investigations. Applications range in scale from nano-particle manipulation to tonnes of liquid metal treated in the presence of various configurations of magnetic fields. Some of these processes are specifically designed and made possible by the use of the electromagnetic force, like the magnetic levitation of liquid droplets, whilst others involve electric currents essential for electrothermal or electrochemical reasons, for instance, in electrolytic metal production and in induction melting. An insight for the range of established and novel EPM applications can be found in the review presented by Asai [1] in the EPM-2003 conference proceedings.

Modelling of nano-imprint forming process for the production of miniaturised 3D structures

Nano-imprint forming (NIF) as manufacturing technology is ideally placed to enable high resolution, low-cost and high-throughput fabrication of three-dimensional fine structures and the packaging of heterogeneous micro-systems (S.Y. Chou and P.R. Krauss, 1997). This paper details a thermo-mechanical modelling methodology for optimising this process for different materials used in components such as mini-fluidics and bio-chemical systems, optoelectronics, photonics and health usage monitoring systems (HUMS). This work is part of a major UK Grand Challenge project - 3D-Mintegration - which is aiming to develop modelling and design technologies for the next generation of fabrication, assembly and test processes for 3D-miniaturised systems.

Intrinsic dielectric response in ferroelectric nano-capacitors

Measurements on 'free-standing' single-crystal barium titanate capacitors with thickness down to 75 nm show a dielectric response typical of large single crystals, rather than conventional thin films. There is a notable absence of any broadening or temperature shift of the dielectric peak or loss tangent. Peak dielectric constants of similar to25 000 are observed, and Curie-Weiss analysis demonstrates first order transformation behaviour. This is in dramatic contrast to results on conventionally deposited thin film capacitor heterostructures, which show large dielectric peak broadening and temperature shifts (e.g. Parker et al 2002 Appl. Phys. Lett. 81 340), as well as an apparent change in the nature-of the paraelectric-ferroelectric transition from first to second order. Our data are compatible with a recent model by Bratkovsky and Levanyuk (2004 Preprint cond-mat/0402100), which attributes dielectric peak broadening to gradient terms that will exist in any thin film capacitor heterostructure. The observed recovery of first order transformation behaviour is consistent with the absence of significant substrate clamping in our experiment, as modelled by Pertsev et al (1998,Phys. Rev. Lett. 80 1988), and illustrates that the second order behaviour seen in conventionally deposited thin films cannot be attributed to the effects of reduced dimensionality in the system, nor to the influence of an intrinsic universal interfacial capacitance associated with the electrode- ferroelectric interface.

Liquid source misted chemical deposition process of three-dimensional nano-ferroelectrics with substrate heating

A modification of liquid source misted chemical deposition process (LSMCD) with heating mist and substrate has developed, and this enabled to control mist penetrability and fluidity on sidewalls of three-dimensional structures and ensure step coverage. A modified LSMCD process allowed a combinatorial approach of Pb(Zr,Ti)O-3 (PZT) thin films and carbon nanotubes (CNTs) toward ultrahigh integration density of ferroelectric random access memories (FeRAMs). The CNTs templates were survived during the crystallization process of deposited PZT film onto CNTs annealed at 650 degrees C in oxygen ambient due to a matter of minute process, so that the thermal budget is quite small. The modified LSMCD process opens up the possibility to realize the nanoscale capacitor structure of ferroelectric PZT film with CNTs electrodes toward ultrahigh integration density FeRAMs.

Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior

Silver colloids prepared by reducing AgNO3 in aqueous solution with sodium citrate were embedded in alumina following two different preparation procedures resulting in samples containing 3 and 5 wt.% silver. Characterization of these materials using TEM. XPS, XAES, CP/MAS NMR, XRD, and adsorption-desorption isotherms of nitrogen showed that embedding the pre-prepared silver colloids into the alumina via the sol-gel procedure preserved the particle size of silver. However, as XAES demonstrates, the catalysts prepared in a sol-gel with a lower amount of water led to embedded colloids with a higher population of Ag+ species. The catalytic behaviors of the resultant catalysts were well correlated with the concentration of these species. Thus, the active silver species of the catalysts containing more Ag+ species selectively converts NO to N-2. However, subsequent thermal aging leads to an enhancement of the conversion of NO parallel to slight alteration of the selectivity with the appearance of low amounts of N2O despite an increase of Ag+ species. Accordingly, an optimal surface Ag-0/Ag+ ratio is probably needed, independently of the size of silver particles. It was found that this optimal ratio strongly depends on the operating conditions during the synthesis route. (C) 2010 Elsevier Inc. All rights reserved.

Atomic ordering in nano-layered FePt: Multiscale Monte Carlo simulation

Nano- and meso-scale simulation of chemical ordering kinetics in nano-layered L1(0)-AB binary intermetallics was performed. In the nano- (atomistic) scale Monte Carlo (MC) technique with vacancy mechanism of atomic migration implemented with diverse models for the system energetics was used. The meso-scale microstructure evolution was, in turn, simulated by means of a MC procedure applied to a system built of meso-scale voxels ordered in particular L1(0) variants. The voxels were free to change the L1(0) variant and interacted with antiphase-boundary energies evaluated within the nano-scale simulations. The study addressed FePt thin layers considered as a material for ultra-high-density magnetic storage media and revealed metastability of the L1(0) c-variant superstructure with monoatomic planes parallel to the (001)-oriented layer surface and off-plane easy magnetization. The layers, originally perfectly ordered in the c-variant, showed discontinuous precipitation of a- and b-L1(0)-variant domains running in parallel with homogeneous disordering (i.e. generation of antisite defects). The domains nucleated heterogeneously on the free monoatomic Fe surface of the layer, grew inwards its volume and relaxed towards an equilibrium microstructure of the system. Two

Atomic ordering in nano-layered FePt

Monte Carlo simulation of chemical ordering kinetics in nano-layered L1₀ AB binary intermetallics was performed. The study addressed FePt thin layers considered as a material for ultra-high-density magnetic storage media and revealed metastability of the L1₀ c-variant superstructure with monoatomic planes parallel to the surface and off-plane easy magnetization. The layers, originally perfectly ordered in a c-variant of the L1₀ superstructure, showed homogeneous disordering running in parallel with a spontaneous re-orientation of the monoatomic planes leading to a mosaic microstructure composed of a- and b-L1₀-variant domains. The domains nucleated heterogeneously on the surface of the layer and grew discontinuously inwards its volume. Finally, the domains relaxed towards an equilibrium microstructure of the system. Two “atomistic-scale” processes: (i) homogeneous disordering and (ii) nucleation of the a- and b-L1₀-variant domains showed characteristic time scales. The same was observed for the domain microstructure relaxation. The discontinuous domain growth showed no definite driving force and proceeded due to thermal fluctuations. The above complex structural evolution has recently been observed experimentally in epitaxially deposited thin films of FePt.

The control of porosity at nano scale in resorcinol formaldehyde carbon aerogels

Organic aerogels were synthesized by sol–gel polymerization of resorcinol (R) with formaldehyde (F) catalyzed by sodium carbonate (C) followed by vacuum drying. The influence of the resorcinol/sodium carbonate ratio (R/C) on the porous structure of the resultant aerogels was investigated. The nitrogen adsorption–desorption measurements show that the aerogels possess a well developed porous structure and mesoporosity was found to increase with increasing the R/C ratio. Carbon aerogels were obtained by carbonization of RF aerogels. The carbonization temperature impacts the microstructure of the aerogels by pore transformations during carbonization probably due to the formation of micropores and shrinkage of the gel structure. The results showed that a temperature of 1073 Kis more effective in the development of the pore structure of the gel. Activated carbon aerogels were obtained from the CO2 activation of carbon aerogels. Activation results in an increase in the number of both micropores and mesopores, indicative of pore creation in the structure of the carbon. Activation at higher temperatures results in a higher degree of burn off and increases the pore volume and the surface area remarkably without change of the basic porous structure, pore size, and pore size distribution.

Phenomenology and system engineering of micro- and nano-antenna FPA sensors for detection of concealed weapons and improvised explosive devices

The ability of millimetre wave and terahertz systems to penetrate clothing is well known. The fact that the transmission of clothing and the reflectivity of the body vary as a function of frequency is less so. Several instruments have now been developed to exploit this capability. The choice of operating frequency, however, has often been associated with the maturity and the cost of the enabling technology rather than a sound systems engineering approach. Top level user and systems requirements have been derived to inform the development of design concepts. Emerging micro and nano technology concepts have been reviewed and we have demonstrated how these can be evaluated against these requirements by simulation using OpenFx. Openfx is an open source suite of 3D tools for modeling, animation and visualization which has been modified for use at millimeter waves. © 2012 SPIE.