Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces: Part 1. -- A Fourier-transform infrared study of formic acid and formaldehyde adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

Fourier-transform infrared (FTIR) spectra are reported of formic acid and formaldehyde on ZnO/SiO2, reduced Cu/ZnO/SiO2 and reoxidised Cu/ZnO/SiO2 catalyst. Formic acid adsorption on ZnO/SiO2 produced mainly bidentate zinc formate species with a lesser quantity of unidentate zinc formate. Formic acid on reduced Cu/ZnO/SiO2 catalyst resulted not only in the formation of bridging copper formate structures but also in an enhanced amount of formate relative to that for ZnO/SiO2 catalyst. Formic acid on reoxidised Cu/ZnO/SiO2 gave unidentate formate species on copper in addition to zinc formate moieties. The interaction of formaldehyde with ZnO/SiO2 catalyst resulted in the formation of zinc formate species. The same reaction on reduced Cu/ZnO/SiO2 catalyst gave bridging formate on copper and a remarkable increase in the quantity of formate species associated with the zinc oxide. Adsorption of formaldehyde on a reoxidised Cu/ZnO/SiO2 catalyst produced bridging copper formate and again an apparent increase in the concentration of zinc formate species. An explanation in terms of the adsorption of molecules at special sites located at the interface between copper and zinc oxide is given.

A combined temperature-programmed reaction spectroscopy and Fourier-transform infrared spectroscopy study of CO2/H2 and CO/CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol-synthesis catalysts

The reaction of CO2 and H2 with ZnO/SiO2 catalyst at 295 K gave predominantly hydrogencarbonate on zinc oxide and a small quantity of formate was evolved after heating at 393 K. Elevation of the reaction temperature to 503 K enhanced the rate of formation of zinc formate species. Significantly these formate species decomposed at 573 K almost entirely to CO2 and H2. Even after exposure of CO2-H2 or CO-CO2-H2 mixtures to highly defected ZnO/SiO2 catalyst, the formate species produced still decomposed to give CO2 and H2. It was concluded that carboxylate species which were formed at oxygen anion vacancies on polar Zn planes were not significantly hydrogenated to formate. Consequently it was proposed that the non-polar planes on zinc oxide contained sites which were specific for the synthesis of methanol. The interaction of CO2 and H2 with reduced Cu/ZnO/SiO2 catalyst at 393 K gave copper formate species in addition to substantial quantities of formate created at interfacial sites between copper and zinc oxide. It was deduced that interfacial formate species were produced from the hydrogenation of interfacial bidentate carbonate structures. The relevance of interfacial formate species in the methanol synthesis reaction is discussed. Experiments concerning the reaction of CO2-H2 with physical mixtures of Cu/SiO2 and ZnO/SiO2 gave results which were simply characteristic of the individual components. By careful consideration of previous data a detailed proposal regarding the role of spillover hydrogen is outlined. Admission of CO to a gaseous CO2-H2 feedstock resulted in a considerably diminished amount of formate species on copper. This was ascribed to a combination of over-reduction of the surface and site-blockage.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 3. -- Fourier-transform infrared study of methyl formate adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methyl formate adsorbed at 295 K on ZnO/SiO2, reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methyl formate on ZnO/SiO2 gave adsorbed zinc formate species and strongly physisorbed molecular methanol on silica. The comparable reaction of methyl formate with reduced Cu/ZnO/SiO2 catalyst produced bridging formate species on copper and a diminished quantity of zinc formate relative to that formed on ZnO/SiO2 catalyst. This effect is explained in terms of site blockage on the ZnO surface by small copper clusters. Addition of methyl formate to a reoxidised Cu/ZnO/SiO2 catalyst produced a considerably greater amount of formate species on zinc oxide and methoxy groups on copper were detected. The increase in concentration of zinc formate species was rationalised in terms of rearrangement of unidentate copper formate species to become bonded to copper and zinc oxide sites located at the interface between these two components.

A fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO2 and COi/Hi on a silica-supported caesium-doped copper catalyst. Adsorption of COj on a "caesium"/silica surface resulted in the formation of COj and complexed CO species. Exposure of CO2 to' a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm"1. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and U.2, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.

Nonlinear actuator fault detection for small-scale UAS

This paper presents a recursive strategy for online detection of actuator faults on a unmanned aerial system (UAS) subjected to accidental actuator faults. The proposed detection algorithm aims to provide a UAS with the capability of identifying and determining characteristics of actuator faults, offering necessary flight information for the design of fault-tolerant mechanism to compensate for the resultant side-effect when faults occur. The proposed fault detection strategy consists of a bank of unscented Kalman filters (UKFs) with each one detecting a specific type of actuator faults and estimating corresponding velocity and attitude information. Performance of the proposed method is evaluated using a typical nonlinear UAS model and it is demonstrated in simulations that our method is able to detect representative faults with a sufficient accuracy and acceptable time delay, and can be applied to the design of fault-tolerant flight control systems of UASs.

A nonlinear position controller for maritime operations of Rotary-wing UAVs

This paper presents a disturbance attenuation controller for horizontal position stabilization for hover and automatic landings of a Rotary-wing Unmanned Aerial Vehicle (RUAV) operating in rough seas. Based on a helicopter model representing aerodynamics during the landing phase, a nonlinear state feedback H-infinity controller is designed to achieve rapid horizontal position tracking in a gusty environment. The resultant control variables are further treated in consideration of practical constraints (flapping dynamics, servo dynamics and time lag effect) for implementation purpose. The high-fidelity closed-loop simulation using parameters of the Vario helicopter verifies performance of the proposed position controller. It not only increases the disturbance attenuation capability of the RUAV, but also enables rapid position response when gusts occur. Comparative studies show that the H-infinity controller exhibits great performance improvement and can be applied to ship/RUAV landing systems.

Analysis of nonlinear sequences and streamciphers

Streamciphers are common cryptographic algorithms used to protect the confidentiality of frame-based communications like mobile phone conversations and Internet traffic. Streamciphers are ideal cryptographic algorithms to encrypt these types of traffic as they have the potential to encrypt them quickly and securely, and have low error propagation. The main objective of this thesis is to determine whether structural features of keystream generators affect the security provided by stream ciphers.These structural features pertain to the state-update and output functions used in keystream generators. Using linear sequences as keystream to encrypt messages is known to be insecure. Modern keystream generators use nonlinear sequences as keystream.The nonlinearity can be introduced through a keystream generator's state-update function, output function, or both. The first contribution of this thesis relates to nonlinear sequences produced by the well-known Trivium stream cipher. Trivium is one of the stream ciphers selected in a final portfolio resulting from a multi-year project in Europe called the ecrypt project. Trivium's structural simplicity makes it a popular cipher to cryptanalyse, but to date, there are no attacks in the public literature which are faster than exhaustive keysearch. Algebraic analyses are performed on the Trivium stream cipher, which uses a nonlinear state-update and linear output function to produce keystream. Two algebraic investigations are performed: an examination of the sliding property in the initialisation process and algebraic analyses of Trivium-like streamciphers using a combination of the algebraic techniques previously applied separately by Berbain et al. and Raddum. For certain iterations of Trivium's state-update function, we examine the sets of slid pairs, looking particularly to form chains of slid pairs. No chains exist for a small number of iterations.This has implications for the period of keystreams produced by Trivium. Secondly, using our combination of the methods of Berbain et al. and Raddum, we analysed Trivium-like ciphers and improved on previous on previous analysis with regards to forming systems of equations on these ciphers. Using these new systems of equations, we were able to successfully recover the initial state of Bivium-A.The attack complexity for Bivium-B and Trivium were, however, worse than exhaustive keysearch. We also show that the selection of stages which are used as input to the output function and the size of registers which are used in the construction of the system of equations affect the success of the attack. The second contribution of this thesis is the examination of state convergence. State convergence is an undesirable characteristic in keystream generators for stream ciphers, as it implies that the effective session key size of the stream cipher is smaller than the designers intended. We identify methods which can be used to detect state convergence. As a case study, theMixer streamcipher, which uses nonlinear state-update and output functions to produce keystream, is analysed. Mixer is found to suffer from state convergence as the state-update function used in its initialisation process is not one-to-one. A discussion of several other streamciphers which are known to suffer from state convergence is given. From our analysis of these stream ciphers, three mechanisms which can cause state convergence are identified.The effect state convergence can have on stream cipher cryptanalysis is examined. We show that state convergence can have a positive effect if the goal of the attacker is to recover the initial state of the keystream generator. The third contribution of this thesis is the examination of the distributions of bit patterns in the sequences produced by nonlinear filter generators (NLFGs) and linearly filtered nonlinear feedback shift registers. We show that the selection of stages used as input to a keystream generator's output function can affect the distribution of bit patterns in sequences produced by these keystreamgenerators, and that the effect differs for nonlinear filter generators and linearly filtered nonlinear feedback shift registers. In the case of NLFGs, the keystream sequences produced when the output functions take inputs from consecutive register stages are less uniform than sequences produced by NLFGs whose output functions take inputs from unevenly spaced register stages. The opposite is true for keystream sequences produced by linearly filtered nonlinear feedback shift registers.

Separable and non-separable discrete wavelet transform based texture features and image classification of breast thermograms

Highly sensitive infrared cameras can produce high-resolution diagnostic images of the temperature and vascular changes of breasts. Wavelet transform based features are suitable in extracting the texture difference information of these images due to their scale-space decomposition. The objective of this study is to investigate the potential of extracted features in differentiating between breast lesions by comparing the two corresponding pectoral regions of two breast thermograms. The pectoral regions of breastsare important because near 50% of all breast cancer is located in this region. In this study, the pectoral region of the left breast is selected. Then the corresponding pectoral region of the right breast is identified. Texture features based on the first and the second sets of statistics are extracted from wavelet decomposed images of the pectoral regions of two breast thermograms. Principal component analysis is used to reduce dimension and an Adaboost classifier to evaluate classification performance. A number of different wavelet features are compared and it is shown that complex non-separable 2D discrete wavelet transform features perform better than their real separable counterparts.

Exploring new and emerging models for nonlinear performative works

This dissertation seeks to define and classify potential forms of Nonlinear structure and explore the possibilities they afford for the creation of new musical works. It provides the first comprehensive framework for the discussion of Nonlinear structure in musical works and provides a detailed overview of the rise of nonlinearity in music during the 20th century. Nonlinear events are shown to emerge through significant parametrical discontinuity at the boundaries between regions of relatively strong internal cohesion. The dissertation situates Nonlinear structures in relation to linear structures and unstructured sonic phenomena and provides a means of evaluating Nonlinearity in a musical structure through the consideration of the degree to which the structure is integrated, contingent, compressible and determinate as a whole. It is proposed that Nonlinearity can be classified as a three dimensional space described by three continuums: the temporal continuum, encompassing sequential and multilinear forms of organization, the narrative continuum encompassing processual, game structure and developmental narrative forms and the referential continuum encompassing stylistic allusion, adaptation and quotation. The use of spectrograms of recorded musical works is proposed as a means of evaluating Nonlinearity in a musical work through the visual representation of parametrical divergence in pitch, duration, timbre and dynamic over time. Spectral and structural analysis of repertoire works is undertaken as part of an exploration of musical nonlinearity and the compositional and performative features that characterize it. The contribution of cultural, ideological, scientific and technological shifts to the emergence of Nonlinearity in music is discussed and a range of compositional factors that contributed to the emergence of musical Nonlinearity is examined. The evolution of notational innovations from the mobile score to the screen score is plotted and a novel framework for the discussion of these forms of musical transmission is proposed. A computer coordinated performative model is discussed, in which a computer synchronises screening of notational information, provides temporal coordination of the performers through click-tracks or similar methods and synchronises the audio processing and synthesized elements of the work. It is proposed that such a model constitutes a highly effective means of realizing complex Nonlinear structures. A creative folio comprising 29 original works that explore nonlinearity is presented, discussed and categorised utilising the proposed classifications. Spectrograms of these works are employed where appropriate to illustrate the instantiation of parametrically divergent substructures and examples of structural openness through multiple versioning.

Self excitation in equity indices

A "self-exciting" market is one in which the probability of observing a crash increases in response to the occurrence of a crash. It essentially describes cases where the initial crash serves to weaken the system to some extent, making subsequent crashes more likely. This thesis investigates if equity markets possess this property. A self-exciting extension of the well-known jump-based Bates (1996) model is used as the workhorse model for this thesis, and a particle-filtering algorithm is used to facilitate estimation by means of maximum likelihood. The estimation method is developed so that option prices are easily included in the dataset, leading to higher quality estimates. Equilibrium arguments are used to price the risks associated with the time-varying crash probability, and in turn to motivate a risk-neutral system for use in option pricing. The option pricing function for the model is obtained via the application of widely-used Fourier techniques. An application to S&P500 index returns and a panel of S&P500 index option prices reveals evidence of self excitation.

Locally weighted learning model predictive control for nonlinear and time varying dynamics

This paper proposes an online learning control system that uses the strategy of Model Predictive Control (MPC) in a model based locally weighted learning framework. The new approach, named Locally Weighted Learning Model Predictive Control (LWL-MPC), is proposed as a solution to learn to control robotic systems with nonlinear and time varying dynamics. This paper demonstrates the capability of LWL-MPC to perform online learning while controlling the joint trajectories of a low cost, three degree of freedom elastic joint robot. The learning performance is investigated in both an initial learning phase, and when the system dynamics change due to a heavy object added to the tool point. The experiment on the real elastic joint robot is presented and LWL-MPC is shown to successfully learn to control the system with and without the object. The results highlight the capability of the learning control system to accommodate the lack of mechanical consistency and linearity in a low cost robot arm.

The velocity synchronous discrete Fourier transform for order tracking in the field of rotating machinery

Diagnostics of rotating machinery has developed significantly in the last decades, and industrial applications are spreading in different sectors. Most applications are characterized by varying velocities of the shaft and in many cases transients are the most critical to monitor. In these variable speed conditions, fault symptoms are clearer in the angular/order domains than in the common time/frequency ones. In the past, this issue was often solved by synchronously sampling data by means of phase locked circuits governing the acquisition; however, thanks to the spread of cheap and powerful microprocessors, this procedure is nowadays rarer; sampling is usually performed at constant time intervals, and the conversion to the order domain is made by means of digital signal processing techniques. In the last decades different algorithms have been proposed for the extraction of an order spectrum from a signal sampled asynchronously with respect to the shaft rotational velocity; many of them (the so called computed order tracking family) use interpolation techniques to resample the signal at constant angular increments, followed by a common discrete Fourier transform to shift from the angular domain to the order domain. A less exploited family of techniques shifts directly from the time domain to the order spectrum, by means of modified Fourier transforms. This paper proposes a new transform, named velocity synchronous discrete Fourier transform, which takes advantage of the instantaneous velocity to improve the quality of its result, reaching performances that can challenge the computed order tracking.