Computational study of methyl derivatives of ammonia borane for hydrogen storage

The structures and thermodynamic properties of methyl derivatives of ammonia–borane (BH3NH3, AB) have been studied with the frameworks of density functional theory and second-order Møller–Plesset perturbation theory. It is found that, with respect to pure AB, methyl ammonia–boranes show higher complexation energies and lower reaction enthalpies for the release of H2, together with a slight increment of the activation barrier. These results indicate that the methyl substitution can enhance the reversibility of the system and prevent the formation of BH3/NH3, but no enhancement of the release rate of H2 can be expected.

Role of charge in destabilizing AlH4 and BH4 complex anions for hydrogen storage applications : Ab initio density functional calculations

NaAlH4 and LiBH4 are potential candidate materials for mobile hydrogen storage applications, yet they have the drawback of being highly stable and desorbing hydrogen only at elevated temperatures. In this letter, ab initio density functional theory calculations reveal how the stabilities of the AlH4 and BH4 complex anions will be affected by reducing net anionic charge. Tetrahedral AlH4 and BH4 complexes are found to be distorted with the decrease of negative charge. One H-H distance becomes smaller and the charge density will overlap between them at a small anion charge. The activation energies to release of H2 from AlH4 and BH4 complexes are thus greatly decreased. We demonstrate that point defects such as neutral Na vacancies or substitution of a Na atom with Ti on the NaAlH4(001) surface can potentially cause strong distortion of neighboring AlH4 complexes and even induce spontaneous dehydrogenation. Our results help to rationalize the conjecture that the suppression of charge transfer to AlH4 and BH4 anion as a consequence of surface defects should be very effective for improving the recycling performance of H2 in NaAlH4 and LiBH4. The understanding gained here will aid in the rational design and development of hydrogen storage materials based on these two systems.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Outsourcing data storage without outsourcing trust in cloud computing

The main theme of this thesis is to allow the users of cloud services to outsource their data without the need to trust the cloud provider. The method is based on combining existing proof-of-storage schemes with distance-bounding protocols. Specifically, cloud customers will be able to verify the confidentiality, integrity, availability, fairness (or mutual non-repudiation), data freshness, geographic assurance and replication of their stored data directly, without having to rely on the word of the cloud provider.

Smart coordination of energy storage units (ESUs) for voltage and loading management in distribution networks

This paper proposes a distributed control approach to coordinate multiple energy storage units (ESUs) to avoid violation of voltage and thermal constraints, which are some of the main power quality challenges for future distribution networks. ESUs usually are connected to a network through voltage source converters. In this paper, both ESU converters active and reactive power are used to deal with the above mentioned power quality issues. ESUs' reactive power is proposed to be used for voltage support, while the active power is to be utilized in managing network loading. Two typical distribution networks are used to apply the proposed method, and the simulated results are illustrated in this paper to show the effectiveness of this approach.

Optical and biomechanical factors, associated with near work and myopia

Near work may play an important role in the development of myopia in the younger population. The prevalence of myopia has also been found to be higher in occupations that involve substantial near work tasks, for example in microscopists and textile workers. When nearwork is performed, it typically involves accommodation, convergence and downward gaze. A number of previous studies have examined the effects of accommodation and convergence on changes in the optics and biometrics of the eye in primary gaze. However, little is known about the influence of accommodation on the eye in downward gaze. This thesis is primarily concerned with investigating the changes in the eye during near work in downward gaze under natural viewing conditions. To measure wavefront aberrations in downward gaze under natural viewing conditions, we modified a commercial Shack-Hartmann wavefront sensor by adding a relay lens system to allow on-axis ocular aberration measurements in primary gaze and downward gaze, with binocular fixation. Measurements with the modified wavefront sensor in primary and downward gaze were validated against a conventional aberrometer using both a model eye and in 9 human subjects. We then conducted an experiment to investigate changes in ocular aberrations associated with accommodation in downward gaze over 10 mins in groups of both myopes (n = 14) and emmetropes (n =12) using the modified Shack-Hartmann wavefront sensor. During the distance accommodation task, small but significant changes in refractive power (myopic shift) and higher order aberrations were observed in downward gaze compared to primary gaze. Accommodation caused greater changes in higher order aberrations (in particular coma and spherical aberration) in downward gaze than primary gaze, and there was evidence that the changes in certain aberrations with accommodation over time were different in downward gaze compared to primary gaze. There were no obvious systematic differences in higher order aberrations between refractive error groups during accommodation or downward gaze for fixed pupils. However, myopes exhibited a significantly greater change in higher order aberrations (in particular spherical aberration) than emmetropes for natural pupils after 10 mins of a near task (5 D accommodation) in downward gaze. These findings indicated that ocular aberrations change from primary to downward gaze, particularly with accommodation. To understand the mechanism underlying these changes in greater detail, we then extended this work to examine the characteristics of the corneal optics, internal optics, anterior biometrics and axial length of the eye during a near task, in downward gaze, over 10 mins. Twenty young adult subjects (10 emmetropes and 10 myopes) participated in this study. To measure corneal topography and ocular biometrics in downward gaze, a rotating Scheimpflug camera and an optical biometer were inclined on a custom built, height and tilt adjustable table. We found that both corneal optics and internal optics change with downward gaze, resulting in a myopic shift (~0.10 D) in the spherical power of the eye. The changes in corneal optics appear to be due to eyelid pressure on the anterior surface of the cornea, whereas the changes in the internal optics (an increase in axial length and a decrease in anterior chamber depth) may be associated with movement of the crystalline lens, under the action of gravity, and the influence of altered biomechanical forces from the extraocular muscles on the globe with downward gaze. Changes in axial length with accommodation were significantly greater in downward gaze than primary gaze (p < 0.05), indicating an increased effect of the mechanical forces from the ciliary muscle and extraocular muscles. A subsequent study was conducted to investigate the changes in anterior biometrics, axial length and choroidal thickness in nine cardinal gaze directions under the actions of the extraocular muscles. Ocular biometry measurements were obtained from 30 young adults (10 emmetropes, 10 low myopes and 10 moderate myopes) through a rotating prism with 15° deviation, along the foveal axis, using a non-contact optical biometer in each of nine different cardinal directions of gaze, over 5 mins. There was a significant influence of gaze angle and time on axial length (both p < 0.001), with the greatest axial elongation (+18 ± 8 μm) occurring with infero-nasal gaze (p < 0.001) and a slight decrease in axial length in superior gaze (−12 ± 17 μm) compared with primary gaze (p < 0.001). There was a significant correlation between refractive error (spherical equivalent refraction) and the mean change in axial length in the infero-nasal gaze direction (Pearson's R2 = 0.71, p < 0.001). To further investigate the relative effect of gravity and extraocular muscle force on the axial length, we measured axial length in 15° and 25° downward gaze with the biometer inclined on a tilting table that allowed gaze shifts to occur with either full head turn but no eye turn (reflects the effect of gravity), or full eye turn with no head turn (reflects the effect of extraocular muscle forces). We observed a significant axial elongation in 15° and 25° downward gaze in the full eye turn condition. However, axial length did not change significantly in downward gaze over 5 mins (p > 0.05) in the full head turn condition. The elongation of the axial length in downward gaze appears to be due to the influence of the extraocular muscles, since the effect was not present when head turn was used instead of eye turn. The findings of these experiments collectively show the dynamic characteristics of the optics and biometrics of the eye in downward gaze during a near task, over time. These were small but significant differences between myopic and emmetropic eyes in both the optical and biomechanical changes associated with shifts of gaze direction. These differences between myopes and emmetropes could arise as a consequence of excessive eye growth associated with myopia. However the potentially additive effects of repeated or long lasting near work activities employing infero-nasal gaze could also act to promote elongation of the eye due to optical and/or biomechanical stimuli.

Storage - the necessity for a Smart-Grid

Energy policy is driving renewable energy deployment with most of the developed countries having some form of renewable energy portfolio standard and emissions reduction target. To deliver upon these ambitious targets, those renewable energy technologies that are commercially available, such as wind and solar, are being deployed, but inherently have issues with intermittency of supply. To overcome these issues, storage options will need to be introduced into the distribution network with benefits for both demand management and power systems quality. How this can be utilised most effectively within the distribution network will allow for an even greater proportion of our energy demand to be met through renewable resources and meet the aspirational targets set. The distribution network will become a network of smart-grids, but to work efficiently and effectively, power quality issues surrounding intermittency must be overcome, with storage being a major factor in this solution.

Selection of energy storage system for a regenerative dynamic dynamometer

This paper presents a design technique of a fully regenerative dynamic dynamometer. It incorporates an energy storage system to absorb the energy variation due to dynamometer transients. This allows the minimum power electronics requirement at the grid to supply the losses. The simulation results of the full system over a driving cycle show the amount of energy required to complete a driving cycle, therefore the size of the energy storage system can be determined.

Migrating to a sustainable energy system : distributed generation and storage, fuel cells and hypercars

This paper examines a number of issues in sustainable energy generation and distribution, and explores avenues that are available for integration of our society’s energy supplies. In particular, the paper presents a way in which transport vehicle energy supplies could be integrated with distributed generation schemes to achieve synergistic and beneficial outcomes. The worldwide energy system contains fundamental problems that result directly from the use of unsustainable fuels and a lack of energy system integration. There is a need to adopt an integrated, sustainable energy system for our society. The adoption of distributed generation could result in beneficial restructuring of the energy trade, and a change in the role of energy providers. Inherent benefits in distributed generation schemes would directly combat barriers to installation of renewable generation facilities, which might prove distributed renewable energy sources to be more feasible. The presence of fuel cells, batteries, power electronic inverters and intelligent controls in vehicles of the future provides many opportunities for the integration of vehicle energy supplies into a distributed generation scheme. In such a system, vehicles could play a major role in power generation and storage.

Migrating to a sustainable energy system : distributed generation and storage, fuel cells and hypercars

This paper examines a number of issues in sustainable energy generation and distribution, and explores avenues that are available for integration of our society’s energy supplies. In particular, the paper presents a way in which transport vehicle energy supplies could be integrated with distributed generation schemes to achieve synergistic and beneficial outcomes. The worldwide energy system contains fundamental problems that result directly from the use of unsustainable fuels and a lack of energy system integration. There is a need to adopt an integrated, sustainable energy system for our society. The adoption of distributed generation could result in beneficial restructuring of the energy trade, and a change in the role of energy providers. Inherent benefits in distributed generation schemes would directly combat barriers to installation of renewable generation facilities, which might prove distributed renewable energy sources to be more feasible. The presence of fuel cells, batteries, power electronic inverters and intelligent controls in vehicles of the future provides many opportunities for the integration of vehicle energy supplies into a distributed generation scheme. In such a system, vehicles could play a major role in power generation and storage.

Non-invasive assessment of corneal crosslinking changes using polarization sensitive optical coherence tomography

Collagen crosslinking (CXL) has shown promising results in the prevention of the progression of keratoconus and corneal ectasia. However, techniques for in vivo and in situ assessment of the treatment are limited. In this study, ex vivo porcine eyes were treated with a chemical CXL agent (glutaraldehyde), during which polarization sensitive optical coherence tomography (PS-OCT) recordings were acquired simultaneously to assess the sensitivity of the technique to assess changes in the cornea. The results obtained in this study suggest that PS-OCT may be a suitable technique to measure CXL changes in situ and to assess the local changes in the treated region of the cornea.

Automatic segmentation of choroidal thickness in optical coherence tomography

The assessment of choroidal thickness from optical coherence tomography (OCT) images of the human choroid is an important clinical and research task, since it provides valuable information regarding the eye’s normal anatomy and physiology, and changes associated with various eye diseases and the development of refractive error. Due to the time consuming and subjective nature of manual image analysis, there is a need for the development of reliable objective automated methods of image segmentation to derive choroidal thickness measures. However, the detection of the two boundaries which delineate the choroid is a complicated and challenging task, in particular the detection of the outer choroidal boundary, due to a number of issues including: (i) the vascular ocular tissue is non-uniform and rich in non-homogeneous features, and (ii) the boundary can have a low contrast. In this paper, an automatic segmentation technique based on graph-search theory is presented to segment the inner choroidal boundary (ICB) and the outer choroidal boundary (OCB) to obtain the choroid thickness profile from OCT images. Before the segmentation, the B-scan is pre-processed to enhance the two boundaries of interest and to minimize the artifacts produced by surrounding features. The algorithm to detect the ICB is based on a simple edge filter and a directional weighted map penalty, while the algorithm to detect the OCB is based on OCT image enhancement and a dual brightness probability gradient. The method was tested on a large data set of images from a pediatric (1083 B-scans) and an adult (90 B-scans) population, which were previously manually segmented by an experienced observer. The results demonstrate the proposed method provides robust detection of the boundaries of interest and is a useful tool to extract clinical data.

Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ- monoanion. In the presence of Mx+(MeCN), reaction with TCNQ-(MeCN) leads to deposition of Mx+[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 μm in length and with diameters of less than 180 nm, and Co[TCNQ]2(H2O)2 as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal−TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.

Characterisation of two distinctly different processes associated with the electrocrystallization of microcrystals of phase I CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane)

Semi-conducting phase I CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which is of considerable interest as a switching device for memory storage materials, can be electrocrystallized from CH3CN via two distinctly different pathways when TCNQ is reduced to TCNQ˙− in the presence of [Cu(MeCN)4]+. The first pathway, identified in earlier studies, occurs at potentials where TCNQ is reduced to TCNQ˙− and involves a nucleation–growth mechanism at preferred sites on the electrode to produce arrays of well separated large branched needle-shaped phase I CuTCNQ crystals. The second pathway, now identified at more negative potentials, generates much smaller needle-shaped phase I CuTCNQ crystals. These electrocrystallize on parts of the surface not occupied in the initial process and give rise to film-like characteristics. This process is attributed to the reduction of Cu+[(TCNQ˙−)(TCNQ)] or a stabilised film of TCNQ via a solid–solid conversion process, which also involves ingress of Cu+via a nucleation–growth mechanism. The CuTCNQ surface area coverage is extensive since it occurs at all areas of the electrode and not just at defect sites that dominate the crystal formation sites for the first pathway. Infrared spectra, X-ray diffraction, surface plasmon resonance, quartz crystal microbalance, scanning electron microscopy and optical image data all confirm that two distinctly different pathways are available to produce the kinetically-favoured and more highly conducting phase I CuTCNQ solid, rather than the phase II material.

The operating schedule for battery energy storage companies in electricity market

This paper presents a series of operating schedules for Battery Energy Storage Companies (BESC) to provide peak shaving and spinning reserve services in the electricity markets under increasing wind penetration. As individual market participants, BESC can bid in ancillary services markets in an Independent System Operator (ISO) and contribute towards frequency and voltage support in the grid. Recent development in batteries technologies and availability of the day-ahead spot market prices would make BESC economically feasible. Profit maximization of BESC is achieved by determining the optimum capacity of Energy Storage Systems (ESS) required for meeting spinning reserve requirements as well as peak shaving. Historic spot market prices and frequency deviations from Australia Energy Market Operator (AEMO) are used for numerical simulations and the economic benefits of BESC is considered reflecting various aspects in Australia’s National Electricity Markets (NEM).