Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

Impact and energy absorption of empty and foam-filled conical tubes

Foam-filled conical tubes have recently emerged as efficient energy absorbing devices to mitigate the adverse effects of impacts. The primary aim of this thesis was to generate research and design information on the impact and energy absorption response of empty and foam-filled conical tubes, and to facilitate their application in energy absorbing systems under axial and oblique loading conditions representative of those typically encountered in crashworthiness and impact applications. Finite element techniques supported by experiments and existing results were used in the investigation. Major findings show that the energy absorption response can be effectively controlled by varying geometry and material parameters. A useful empirical formula was developed for providing engineering designers with an initial estimate of the load ratio and hence energy absorption performances of these devices. It was evident that foam-filled conical tubes enhance the energy absorption capacity and stabilise the crush response for both axial and oblique impact loading without a significant increase in the initial peak load. This is practically beneficial when higher kinetic energy needs to be absorbed, thus reducing the impact force transmitted to the protected structure and occupants. Such tubes also increase and maintain the energy absorption capacity under global bending as well as minimise the reduction of energy absorption capacity with increasing load angle. Furthermore, the results also highlight the feasibility of adding a foam-filled conical tube as a supplementary device in energy absorbing systems, since the overall energy absorption performance of such systems can be favourably enhanced by only including a relatively small energy absorbing device. Above all, the results demonstrate the superior performance of foam-filled conical tube for mitigating impact energy in impact and crashworthiness applications.

Modelling the broadband wireless channel in rural Australia

The internet infrastructure which supports high data rates has a major impact on the Australian economy and the world. However, in rural Australia, the provision of broadband services to an internet dispersed population over a large geographical area with low population densities remains both an economic and technical challenge [1]. Furthermore, the implementation of currently available technologies such as fibre-to-the-premise (FTTP), 3G, 4G and WiMAX seems to be impractical, considering the low population density that is distributed in a large area. Therefore, new paradigms and innovative telecommunication technologies need to be explored to overcome the challenges of providing faster and more reliable broadband internet services to internet dispersed rural areas. The research project implements an innovative Multi-User- Single-Antenna for MIMO (MUSA-MIMO) technology using the spectrum currently allocated to analogue TV. MUSAMIMO technology can be considered as a special case of MIMO technology, which is beneficial when provisioning reliable and high-speed communication channels. Particularly, the abstract describes the development of a novel MUSA-MIMO channel model that takes into account temporal variations in the rural wireless environment. This can be considered as a novel approach tailor-made to rural Australia for provisioning efficient wireless broadband communications.

A multicast routing scheme for efficient safety message dissemination in VANET

Vehicular ad hoc network (VANET) is a wireless ad hoc network that operates in a vehicular environment to provide communication between vehicles. VANET can be used by a diverse range of applications to improve road safety. Cooperative collision warning system (CCWS) is one of the safety applications that can provide situational awareness and warning to drivers by exchanging safety messages between cooperative vehicles. Currently, the routing strategies for safety message dissemination in CCWS are scoped broadcast. However, the broadcast schemes are not efficient as a warning message is sent to a large number of vehicles in the area, rather than only the endangered vehicles. They also cannot prioritize the receivers based on their critical time to avoid collision. This paper presents a more efficient multicast routing scheme that can reduce unnecessary transmissions and also use adaptive transmission range. The multicast scheme involves methods to identify an abnormal vehicle, the vehicles that may be endangered by the abnormal vehicle, and the latest time for each endangered vehicle to receive the warning message in order to avoid the danger. We transform this multicast routing problem into a delay-constrained minimum Steiner tree problem. Therefore, we can use existing algorithms to solve the problem. The advantages of our multicast routing scheme are mainly its potential to support various road traffic scenarios, to optimize the wireless channel utilization, and to prioritize the receivers.

Real-time image streaming over a low-bandwidth wireless camera network

In this paper we describe the recent development of a low-bandwidth wireless camera sensor network. We propose a simple, yet effective, network architecture which allows multiple cameras to be connected to the network and synchronize their communication schedules. Image compression of greater than 90% is performed at each node running on a local DSP coprocessor, resulting in nodes using 1/8th the energy compared to streaming uncompressed images. We briefly introduce the Fleck wireless node and the DSP/camera sensor, and then outline the network architecture and compression algorithm. The system is able to stream color QVGA images over the network to a base station at up to 2 frames per second. © 2007 IEEE.

Efficient clustering approach for intrusion detection in adhoc networks

Mobile ad-hoc networks (MANETs) are temporary wireless networks useful in emergency rescue services, battlefields operations, mobile conferencing and a variety of other useful applications. Due to dynamic nature and lack of centralized monitoring points, these networks are highly vulnerable to attacks. Intrusion detection systems (IDS) provide audit and monitoring capabilities that offer the local security to a node and help to perceive the specific trust level of other nodes. We take benefit of the clustering concept in MANETs for the effective communication between nodes, where each cluster involves a number of member nodes and is managed by a cluster-head. It can be taken as an advantage in these battery and memory constrained networks for the purpose of intrusion detection, by separating tasks for the head and member nodes, at the same time providing opportunity for launching collaborative detection approach. The clustering schemes are generally used for the routing purposes to enhance the route efficiency. However, the effect of change of a cluster tends to change the route; thus degrades the performance. This paper presents a low overhead clustering algorithm for the benefit of detecting intrusion rather than efficient routing. It also discusses the intrusion detection techniques with the help of this simplified clustering scheme.

Towards trusted wireless sensor networks

This article presents the design and implementation of a trusted sensor node that provides Internet-grade security at low system cost. We describe trustedFleck, which uses a commodity Trusted Platform Module (TPM) chip to extend the capabilities of a standard wireless sensor node to provide security services such as message integrity, confidentiality, authenticity, and system integrity based on RSA public-key and XTEA-based symmetric-key cryptography. In addition trustedFleck provides secure storage of private keys and provides platform configuration registers (PCRs) to store system configurations and detect code tampering. We analyze system performance using metrics that are important for WSN applications such as computation time, memory size, energy consumption and cost. Our results show that trustedFleck significantly outperforms previous approaches (e.g., TinyECC) in terms of these metrics while providing stronger security levels. Finally, we describe a number of examples, built on trustedFleck, of symmetric key management, secure RPC, secure software update, and remote attestation.

Springbrook : Challenges in developing a long-term, rainforest wireless sensor network

We describe the design, development and learnings from the first phase of a rainforest ecological sensor network at Springbrook - part of a World Heritage precinct in South East Queensland. This first phase is part of a major initiative to develop the capability to provide reliable, long-term monitoring of rainforest ecosystems. We focus in particular on our analysis around energy and communication challenges which need to be solved to allow for reliable, long-term deployments in these types of environments.

Poster Abstract : A public key technology platform for wireless sensor networks

Communication security for wireless sensor networks (WSN) is a challenge due to the limited computation and energy resources available at nodes. We describe the design and implementation of a public-key (PK) platform based on a standard Trusted Platform Module (TPM) chip that extends the capability of a standard node. The result facilitates message security services such as confidentiality, authenticity and integrity. We present results including computation time, energy consumption and cost.

Demo Abstract: A Java compatible virtual machine for wireless sensor nodes

The Java programming language has potentially significant advantages for wireless sensor nodes but there is currently no feature-rich, open source virtual machine available. In this paper we present Darjeeling, a system comprising offline tools and a memory efficient run-time. The offline post-compiler tool analyzes, links and consolidates Java class files into loadable modules. The runtime implements a modified Java VM that supports multithreading and is designed specifically to operate in constrained execution environments such as wireless sensor network nodes and supports inheritance, threads, garbage collection, and loadable modules. We have demonstrated Java running on AVR128 and MSP430 microcontrollers at speeds of up to 70,000 JVM instructions per second.

Long-Duration Solar-powered wireless sensor networks

This paper discusses hardware design principles for long-term solar-powered wireless sensor networks. We argue that the assumptions and principles appropriate for long-term operation from primary cells are quite different from the solar power case with its abundant energy and regular charging cycles. We present data from a long-term deployment that illustrates the use of solar energy and rechargeable batteries to achieve 24x7 operation for over two years, since March 2005.

On the feasibility of using servo-mechanisms in wireless multimedia sensor network deployments

This paper considers the use of servo-mechanisms as part of a tightly integrated homogeneous Wireless Multi- media Sensor Network (WMSN). We describe the design of our second generation WMSN node platform, which has increased image resolution, in-built audio sensors, PIR sensors, and servo- mechanisms. These devices have a wide disparity in their energy consumption and in the information quality they return. As a result, we propose a framework that establishes a hierarchy of devices (sensors and actuators) within the node and uses frequent sampling of cheaper devices to trigger the activation of more energy-hungry devices. Within this framework, we consider the suitability of servos for WMSNs by examining the functional characteristics and by measuring the energy consumption of 2 analog and 2 digital servos, in order to determine their impact on overall node energy cost. We also implement a simple version of our hierarchical sampling framework to evaluate the energy consumption of servos relative to other node components. The evaluation results show that: (1) the energy consumption of servos is small relative to audio/image signal processing energy cost in WMSN nodes; (2) digital servos do not necessarily consume as much energy as is currently believed; and (3) the energy cost per degree panning is lower for larger panning angles.

Camera calibration in wireless multimedia sensor networks

Wireless Multi-media Sensor Networks (WMSNs) have become increasingly popular in recent years, driven in part by the increasing commoditization of small, low-cost CMOS sensors. As such, the challenge of automatically calibrating these types of cameras nodes has become an important research problem, especially for the case when a large quantity of these type of devices are deployed. This paper presents a method for automatically calibrating a wireless camera node with the ability to rotate around one axis. The method involves capturing images as the camera is rotated and computing the homographies between the images. The camera parameters, including focal length, principal point and the angle and axis of rotation can then recovered from two or more homographies. The homography computation algorithm is designed to deal with the limited resources of the wireless sensor and to minimize energy con- sumption. In this paper, a modified RANdom SAmple Consensus (RANSAC) algorithm is proposed to effectively increase the efficiency and reliability of the calibration procedure.

Efficient control of an autonomous underwater vehicle while accounting for thruster failure

This paper is concerned with the design and implementation of control strategies onto a test-bed vehicle with six degrees-of-freedom. We design our trajectories to be efficient in time and in power consumption. Moreover, we also consider cases when actuator failure can arise and discuss alternate control strategies in this situation. Our calculations are supplemented by experimental results.

A distributed protocol for object tracking in wireless multimedia sensor networks

We consider the problem of object tracking in a wireless multimedia sensor network (we mainly focus on the camera component in this work). The vast majority of current object tracking techniques, either centralised or distributed, assume unlimited energy, meaning these techniques don't translate well when applied within the constraints of low-power distributed systems. In this paper we develop and analyse a highly-scalable, distributed strategy to object tracking in wireless camera networks with limited resources. In the proposed system, cameras transmit descriptions of objects to a subset of neighbours, determined using a predictive forwarding strategy. The received descriptions are then matched at the next camera on the objects path using a probability maximisation process with locally generated descriptions. We show, via simulation, that our predictive forwarding and probabilistic matching strategy can significantly reduce the number of object-misses, ID-switches and ID-losses; it can also reduce the number of required transmissions over a simple broadcast scenario by up to 67%. We show that our system performs well under realistic assumptions about matching objects appearance using colour.