Electrochemical impedance spectroscopy beyond linearity and stationarity - a critical review

Electrochemical impedance spectroscopy (EIS) is a widely used experimental technique for characterising materials and electrode reactions by observing their frequency-dependent impedance. Classical EIS measurements require the electrochemical process to behave as a linear time-invariant system. However, electrochemical processes do not naturally satisfy this assumption: the relation between voltage and current is inherently nonlinear and evolves over time. Examples include the corrosion of metal substrates and the cycling of Li-ion batteries. As such, classical EIS only offers models linearised at specific operating points. During the last decade, solutions were developed for estimating nonlinear and time-varying impedances, contributing to more general models. In this paper, we review the concept of impedance beyond linearity and stationarity, and detail different methods to estimate this from measured current and voltage data, with emphasis on frequency domain approaches using multisine excitation. In addition to a mathematical discussion, we measure and provide examples demonstrating impedance estimation for a Li-ion battery, beyond linearity and stationarity, both while resting and while charging

Abstracts on Radio Direction Finding (1899 - 1995)

The files on this record represent the various databases that originally composed the CD-ROM issue of "Abstracts on Radio Direction Finding" database, which is now part of the Dudley Knox Library's Abstracts and Selected Full Text Documents on Radio Direction Finding (1899 - 1995) Collection. (See Calhoun record https://calhoun.nps.edu/handle/10945/57364 for further information on this collection and the bibliography). Due to issues of technological obsolescence preventing current and future audiences from accessing the bibliography, DKL exported and converted into the three files on this record the various databases contained in the CD-ROM. The contents of these files are: 1) RDFA_CompleteBibliography_xls.zip [RDFA_CompleteBibliography.xls: Metadata for the complete bibliography, in Excel 97-2003 Workbook format; RDFA_Glossary.xls: Glossary of terms, in Excel 97-2003 Workbookformat; RDFA_Biographies.xls: Biographies of leading figures, in Excel 97-2003 Workbook format]; 2) RDFA_CompleteBibliography_csv.zip [RDFA_CompleteBibliography.TXT: Metadata for the complete bibliography, in CSV format; RDFA_Glossary.TXT: Glossary of terms, in CSV format; RDFA_Biographies.TXT: Biographies of leading figures, in CSV format]; 3) RDFA_CompleteBibliography.pdf: A human readable display of the bibliographic data, as a means of double-checking any possible deviations due to conversion

Tri-Orthogonal Polarisation Diverse Communications

This thesis investigates improving communication link coverage through triorthogonal polarisation diversity. Tri-orthogonal polarisation diversity exploits radiated electromagnetic energy transmission and reception in three orthogonal spatial directions with an aim to provide enhanced communication link performance. Original contributions to this branch of diversity are presented in areas of both software and hardware design. First, simulations are presented highlighting the benefit of tri-orthogonal polarisation diversity at both the transmitter and receiver over a range of terrestrial channel conditions. The results are presented in an easily understandable graphical format that results from a novel model design considering all antenna orientations. Orientation robustness at the antenna is demonstrated as a consequence of a tri-orthgonal polarisation diverse approach. Second, additional research is performed in order to extend the model into the field of satellite systems. The ionosphere is required to be modelled, and this is performed according to a novel vectorised approach using realtime ionospheric data and terrestrial magnetic field appreciation. Third, ionospheric modelling is incorporated into a non-geosynchronous satellite orbit channel model that provides an insight into the benefit of applying a tri-orthogonal polarisation diverse approach uniquely at the receiver. Novelty is provided in the form of a vectorised approach to simulation covering all antenna orientations in a field-ofview as observed from a satellite transmitter. This is extended over the orbits of three distinct satellite systems. Output is provided in graphical format and conclusions are drawn form the data which suggest that a tri-orthogonal polarisation diverse approach applied at the receiver provides an increase in reception performance. Fourth, an antenna is designed, simulated, constructed and tested that provides three orthogonal polarisations in a phase-centred differentially-fed package. Novelty is provided in the design being planar in nature, with three orthogonal modes being able to be transmitted from a single slot. Results emanating from the testing procedure demonstrate the benefits of the design in terms of diversity and extension to beamforming applications. Fifth, as an extension to the antenna design, a circularly polarised feeding arrangement is used together with an omnidirectional vertically polarised mode feed in an antenna and feed combination. This provides the possibility of a direct comparison with conventional circularly polarised techniques, such as those used in both terrestrial and satellite receive antennas. Sixth, the operational bandwidth of the omnidirectional vertically polarised mode is extended by adapting the design of the cavity wall resonating slots in a substrateintegrated monopole antenna while maintaining a planar structure. The electric monopole design demonstrates an increase in operating bandwidth from 2.5% to 56%. In the thesis, a tri-orthogonal polarisation diverse approach is shown to be beneficial to signal reception over a range of channels, both in the areas of terrestrial and satellite communications. The concept is demonstrated to be feasible in a planar structure. Triorthogonal polarisation diversity is likely to play an increasing role in the future as systems look to cope with an ever increasing data flow. The demand for content on mobile devices has forced massive growth in mobile data over the past two decades. This growth has recently reached saturation point, and so new avenues for extending growth have to be considered. A search for available bandwidth has lead research to focus on the mmWave section of the electromagnetic spectrum. The advent of the next generation of wireless connectivity, dubbed fifth generation or 5G, is now upon us (Rappaport et al. 2013b). With data traffic set to multiply by up to one thousand fold by 2020 (Qualcomm Inc. Accessed: 2014b, Qualcomm Inc. Accessed: 2014a, Li et al. 2014, Chin et al. 2014), as The Internet of Things (Ashton 2009, Cisco Inc. Accessed: 2014, Gubbi et al. 2013) enters into the fray, an overhaul of wireless design is somewhat overdue. For static point-to-point, or LoS systems, challenges exist according to the channel environment and temporal changes that may occur within. For any network that has a mobile component built in, where spatial position and alignment of transmitter and receiver change over time, signal propagation is additionally influenced by link geometry. In an increasingly mobile world, this presents challenges as increased coverage, one of the main focus points of the 5G system, will require efficient use of radiated electromagnetic energy. Conventional techniques for improving data rate have typically aimed at increasing performance at the transmitter. For terrestrial networks, a transmitter is typically stationary. Performance outweighs size constraints and so power amplification and combination may be used to excite antennas that flood a network cell with a strong linearly polarised transmitted signal. For commercial providers, this has proved a very successful technique, mainly as a result of the majority of wireless subscribers living in dense urban environments. For a linearly polarised wave, operating at conventional operating frequencies around 2 GHz, and transmitted with relatively high power, the urban environment typically provides assistance for signal reception at the receiver through diversity brought about by reflection, refraction and scattering or multipath due to the presence of buildings. Small misalignments in transmit and receive antennas are mitigated as the propagating signal wavelength is large and a relatively high transmit power establishes a relatively high signal-to-noise ratio, providing useful multipath effects over the channel. At certain receive positions, channel fading may occur when superposition of received multipath components effectively cancel each other. This may be mitigated through additional transmitters that are spaced appropriately; a concept known as spatial diversity that has been cited at mmWave frequencies (Smulders 2002, Park and Pan 2012). Diversity of signal is important in that it offers a greater possibility of a signal being received due to individuality of uncorrelated channel propagation for each diverse signal component. As more content is demanded by subscribers within an ever shrinking timeframe, a higher frequency of operation is typically required for a carrier wave capable of providing this service. Add in the context of mobility, and issues quickly appear. Beneficial effects on a linearly polarised signal operating at conventional low gigahertz frequencies arising from reflection, refraction, and scattering or multipath effects, assist signal reception. Relatively long wavelengths are subjected to many scatterers, and due to the relatively high transmit power involved, scattering effects provide diversity at the receiver in the form of many smaller receivable diverse signal components. These signal components are superpositioned either constructively or destructively, after diverse individual propagation through the channel, at the receiver to provide signal reception. At mmWave frequencies, due to a shrinking wavelength, the following issues arise: • increased path loss over a defined range due to spreading loss (Pozar 2011), and increased atmospheric absorption (Liebe et al. 1989). An obvious solution is to provide more transmit power at the transmitter. At higher frequencies, miniaturisation of devices limits this possibility as heat sinking becomes problematic. Amplifier non-linearity and unwanted third order intermodulation impact on system performance (Niknejad and Hashemi 2008, Hashemi and Raman 2016) • the beneficial effect of multipath fading may not exist in a mmWave terrestrial channel (Pi and Khan 2011), as a smaller wavelength typically implies a reduced beamwidth and less scatterers available for the LoS signal to scatter into useful smaller diverse signal components. Due to a relatively low transmit power involved, any scattering of a LoS signal into smaller, weaker diverse signal components may result in no received signal. As a result, cell range is reduced and more transmitters are required to provide coverage over a network • with a shrinking wavelength, relatively lower transmit power, and increased mobility, antenna misalignment becomes problematic. A drive for radiated power efficiency is paramount in providing the next generation of wireless networks. An ability to transmit signals into and receive signals from all angles is necessary (Rappaport et al. 2013b). The terahertz range, for example, offers extremely high transfer rates, although any small misalignment greatly affects rate. The use of dielectric mirrors is required to effectively steer the transmitted signal to its destination. Mitigation of misalignment becomes important in maintaining system performance. For the next generation of mobile wireless systems to operate within the mmWave section of the electromagnetic spectrum, a solution to extend range is to increase radiated energy in a direction of propagation, through beam steering techniques. Within a mobile context, this poses challenges, not least as the link geometry is variable. For terrestrial networks, conventional transmitted waveforms are mainly vertically polarised, or circularly polarised, and as such are mainly one dimensional, or two dimensional at best, in performance. To provide the next generation of wireless networks, a third dimension needs to be considered to provide efficient use of radiated electromagnetic energy. Frequency bands of interest for 5G systems differ from country to country. According to the US Federal Communications Commission (FCC), the mmWave region that will be studied ranges from 24–80 GHz (Rappaport et al. 2013b, Rappaport Accessed: 2014, Above Ground Level Media Group Accessed: 2015). One of the aims of 5G is to improve coverage (Rappaport et al. 2013b). One method that is being considered is the joining of terrestrial and satellite services into one seamless network that may be readily accessed by the subscriber at the receiver (Evans et al. 2005, Evans et al. 2015, Federal Communications Commission Accessed: 2016). Satellite networks provide their own specific challenges, as transmit power is limited to payload specifications, and coverage typically requires a satellite that is moving relative to the Earth’s surface. Once again we find ourselves facing the same three issues that we encountered within the terrestrial context of a mmWave channel. If we are to increase link performance in a satellite channel to complement any improvement in terrestrial channels then the following points need to be considered: • propagation using higher operating frequencies typically suffers from higher path losses (Liebe et al. 1989, Pozar 2011). In some circumstances this can be mitigated by higher transmit power, but not all. A satellite payload is subject to a strict payload capacity and this restricts the size of transmit power devices and hence available transmit power that can be launched into orbit • a lack of beneficial reflectors, refractors, and scatterers is observed during channel propagation as the signal is typically LoS, narrow in beamwidth, and weak due to higher path loss and lower transmit power (Pi and Khan 2011). Multipath effects may degrade system performance as signals are weak • an evolving link geometry that affects antenna alignment. Linear and circular polarised signals are only two dimensional in nature. Three dimensions need to be considered, and beam steering of radiated power to provide the required range is a requirement (Evans et al. 2005, Hong et al. 2014b). To ensure that the next generation of mobile systems are fully mobile, while providing increased data rate, we need to consider diversity in three dimensions. Beam steering of a transmitted signal with high gain in the direction of a receiver is one viable option, and in the context of full mobility, three dimensional signal transmission and reception appears a logical step to achieving this (Hong et al. 2014a). While at a terrestrial transmitter, it is suggested that size is not a constraint, it remains so for a satellite transmitter, as it is at a mobile receiver. This rules out spatial diversity as an approach to increasing system performance. One approach of increasing diversity within a confined volume is through polarisation techniques (Vaughan 1990). In this thesis, we investigate the benefit of a subset of this approach—tri-orthogonal polarisation diversity (Andrews et al. 2001). In effect, the concept provides at least one additional degree of freedom or layer of diversity over conventional techniques such as circular polarisation. Due to orthogonality in three directions, this approach has a wide field of view, and potentially offers diversity and improved system performance through beam steering in any unit direction. Tri-orthogonal polarisation diversity may be applied either at the transmitter, at the receiver, or at both. In Chapter 1 of the thesis, both novel software and hardware aspects of the research are highlighted. Overall, the research outcomes of this thesis from both simulation and measured results suggest that the concept of tri-orthogonal polarisation diversity is: • beneficial to wireless performance over a majority of antenna orientations • plausible for implementation within typical antenna volume constraints.Thesis (Ph.D.) -- University of Adelaide, School of School of Electrical and Electronic Engineering, 201

Evaluating Corrosion Altering Properties of Thiophene Based Copolymers

There is an important and ongoing debate on how or whether conductive polymers (CP) alter corrosion performance with some researchers reporting that CPs ultimately accelerate corrosion and others saying CPs, if understood could possibly replace the world’s best standard for corrosion prevention, i.e., chromium based inhibitors. The primary project goal was to improve our understanding of how CPs alter corrosion chemistry by 1) controlling the polymer structure and 2) in-turn the properties and then 3) targeting the best protocol for fast corrosion kinetic evaluation. We detail the copolymer synthesis results and shift in corrosion protection properties for a series of polythiophene copolymers with variation in solubility and measured onset oxidation potential. Controlled polymerization can be achieved, the properties were predictable based upon the resulting comonomer composition, and we explain how these properties affect corrosion kinetics. We confirm that the lower onset oxidation potential decreases corrosion rates over steel substrates, however performance peaks at an onset oxidation potential of 0.24 V vs Fc/Fc+. Further, we confirmed our hypothesis that CPs like polythiophenes affect corrosion primarily by a combination of differences in ion barrier properties and shifted anodic polarization of the substrate. Additionally, another hypothesis is further supported in that there is/was an optimal 3,4-ethylenedioxythiophene content for the polymer to achieve the best performance for steel. The data presented here helps improve our understanding on how CP affect corrosion, the characteristic properties that are tunable for better CP design towards anti-corrosive primers, and how to adequately evaluate the material combinations performance

Ultrasound Contrast Agents for Imaging and Therapy

The aim of this thesis is to unravel the relation between shell properties and the acoustic response of single microbubbles. Next, the most stable and acoustically best performing UCAs are also investigated in vitro for therapeutic applications by means of sonoporation, and for in vivo diagnostic imaging applications

Electronic crystals: an experimental overview

This article reviews the static and dynamic properties of spontaneous superstructures formed by electrons. Representations of such electronic crystals are charge density waves and spin density waves in inorganic as well as organic low dimensional materials. A special attention is paid to the collective effects in pinning and sliding of these superstructures, and the glassy properties at low temperature. Charge order and charge disproportionation which occur in organic materials resulting from correlation effects are analysed. Experiments under magnetic field, and more specifically field-induced charge density waves are discussed. Properties of meso- and nanostructures of charge density waves are also reviewed.Comment: 255 pages, 247 figure