Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Computer simulation of form-roll design

Changes in modern structural design have created a demand for products which are light but possess high strength. The objective is a reduction in fuel consumption and weight of materials to satisfy both economic and environmental criteria. Cold roll forming has the potential to fulfil this requirement. The bending process is controlled by the shape of the profile machined on the periphery of the rolls. A CNC lathe can machine complicated profiles to a high standard of precision, but the expertise of a numerical control programmer is required. A computer program was developed during this project, using the expert system concept, to calculate tool paths and consequently to expedite the procurement of the machine control tapes whilst removing the need for a skilled programmer. Codifying the expertise of a human and the encapsulation of knowledge within a computer memory, destroys the dependency on highly trained people whose services can be costly, inconsistent and unreliable. A successful cold roll forming operation, where the product is geometrically correct and free from visual defects, is not easy to attain. The geometry of the sheet after travelling through the rolling mill depends on the residual strains generated by the elastic-plastic deformation. Accurate evaluation of the residual strains can provide the basis for predicting the geometry of the section. A study of geometric and material non-linearity, yield criteria, material hardening and stress-strain relationships was undertaken in this research project. The finite element method was chosen to provide a mathematical model of the bending process and, to ensure an efficient manipulation of the large stiffness matrices, the frontal solution was applied. A series of experimental investigations provided data to compare with corresponding values obtained from the theoretical modelling. A computer simulation, capable of predicting that a design will be satisfactory prior to the manufacture of the rolls, would allow effort to be concentrated into devising an optimum design where costs are minimised.

Multiterminal DC wind farm collection grid internal fault analysis and protection design

The multiterminal dc wind farm is a promising topology with a voltage-source inverter (VSI) connection at the onshore grid. Voltage-source converters (VSCs) are robust to ac-side fault conditions. However, they are vulnerable to dc faults on the dc side of the converter. This paper analyzes dc faults, their transients, and the resulting protection issues. Overcurrent faults are analyzed in detail and provide an insight into protection system design. The radial wind farm topology with star or string connection is considered. The outcomes may be applicable for VSCs in the multi-VSC dc wind farm collection grid and VSC-based high-voltage direct current (HVDC) offshore transmission systems.

Digluconate and isopropyl alcohol biocide formulation

Effective surface disinfection is a fundamental infection control strategy within healthcare. This study assessed the antimicrobial efficacy of novel biocide formulations comprising 5% and 2% eucalyptus oil (EO) combined with 2% chlorhexidine digluconate (CHG) and 70% isopropyl alcohol (IPA) contained within a wipe. The efficacy of this novel antimicrobial formulation to remove and eliminate methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli and Candida albicans from steel surfaces was investigated. Adpression studies of pre-contaminated wipes were also utilised to assess their potential to induce cross-contamination between hard surfaces. Furthermore, the bactericidal nature of the EO-formulation was established in addition to time-kill. The EO-containing formulations demonstrated bactericidal antimicrobial efficacy against all microorganisms and did not induce surface cross-contamination. There was no significant difference (p < 0.05) between the 5% and 2% EO formulations in their ability to remove microorganisms from steel surfaces, however both significantly (p < 0.05) removed more than the control formulations. Microbial biofilms were eliminated within 10 min (p < 0.05) when exposed to the EO formulations. Our novel EO-formulation demonstrated rapid antimicrobial efficacy for potential disinfection and elimination of microbial biofilms from hard surfaces and may therefore be a useful adjunct to current infection control strategies currently employed within healthcare facilities.

Directed phase separation of PFO:PS blends during spin-coating using feedback controlled in situ stroboscopic fluorescence microscopy

Uniform thin-films of polymer blends can be produced through spin-coating, which is used on an industrial scale for the production of light emitting diodes, and more recently organic photovoltaic devices. Here, we present the results of the direct observation, and control, over the phase separation of polystyrene and poly(9,9′-dioctylfluorene) during spin-coating using high speed stroboscopic fluorescence microscopy. This new approach, imaging the fluorescence, from a blend of fluorescent + non-fluorescent polymers allows for intensity to be directly mapped to composition, providing a direct determination of composition fluctuations during the spin-coating process. We have studied the compositional development and corresponding structural development for a range of compositions, which produce a range of different phase separated morphologies. We initially observe domains formed by spinodal decomposition, coarsening via Ostwald Ripening until an interfacial instability causes break-up of the bicontinuous morphology. Ostwald ripening continues, and depending upon composition a bicontinuous morphology is re-established. By observing compositional and morphological development in real-time, we are able to direct and control morphological structure development through control of the spin coating parameters via in situ feedback. © 2013 The Royal Society of Chemistry.

Protection schemes for meshed VSC-HVDC transmission systems for large-scale offshore wind farms

This chapter discusses network protection of high-voltage direct current (HVDC) transmission systems for large-scale offshore wind farms where the HVDC system utilizes voltage-source converters. The multi-terminal HVDC network topology and protection allocation and configuration are discussed with DC circuit breaker and protection relay configurations studied for different fault conditions. A detailed protection scheme is designed with a solution that does not require relay communication. Advanced understanding of protection system design and operation is necessary for reliable and safe operation of the meshed HVDC system under fault conditions. Meshed-HVDC systems are important as they will be used to interconnect large-scale offshore wind generation projects. Offshore wind generation is growing rapidly and offers a means of securing energy supply and addressing emissions targets whilst minimising community impacts. There are ambitious plans concerning such projects in Europe and in the Asia-Pacific region which will all require a reliable yet economic system to generate, collect, and transmit electrical power from renewable resources. Collective offshore wind farms are efficient and have potential as a significant low-carbon energy source. However, this requires a reliable collection and transmission system. Offshore wind power generation is a relatively new area and lacks systematic analysis of faults and associated operational experience to enhance further development. Appropriate fault protection schemes are required and this chapter highlights the process of developing and assessing such schemes. The chapter illustrates the basic meshed topology, identifies the need for distance evaluation, and appropriate cable models, then details the design and operation of the protection scheme with simulation results used to illustrate operation. © Springer Science+Business Media Singapore 2014.

Protection issue discussion of DC network development:circuit breaker or fault-tolerant converter

This paper provides a discussion on future direct current (DC) network development in terms of system protection under DC-side fault scenarios. The argument between appropriate DC circuit breaker and new DC fault-tolerant converters is discussed after a review on DC technology development and bottleneck issues that require proper solutions. The overcurrent/cost curve of power-electronic DC circuit breakers (CB) superimposed to voltage-source converter (VSC) systems is derived and compared with other possible fault-tolerant power conversion options. This in-advance planning of protection capability is essential for the future development of DC networks.

Design of a modular, high step-up ratio DC–DC converter for HVDC applications integrating offshore wind power

High-power and high-voltage gain dc-dc converters are key to high-voltage direct current (HVDC) power transmission for offshore wind power. This paper presents an isolated ultra-high step-up dc-dc converter in matrix transformer configuration. A flyback-forward converter is adopted as the power cell and the secondary side matrix connection is introduced to increase the power level and to improve fault tolerance. Because of the modular structure of the converter, the stress on the switching devices is decreased and so is the transformer size. The proposed topology can be operated in column interleaved modes, row interleaved modes, and hybrid working modes in order to deal with the varying energy from the wind farm. Furthermore, fault-tolerant operation is also realized in several fault scenarios. A 400-W dc-dc converter with four cells is developed and experimentally tested to validate the proposed technique, which can be applied to high-power high-voltage dc power transmission.

Hydrological dynamics between a coastal aquifer and the adjacent estuarine system, Biscayne Bay, South Florida

Geochemical and geophysical approaches have been used to investigate the freshwater and saltwater dynamics in the coastal Biscayne Aquifer and Biscayne Bay. Stable isotopes of oxygen and hydrogen, and concentrations of Sr2+ and Ca2+ were combined in two geochemical mixing models to provide estimates of the various freshwater inputs (precipitation, canal water, and groundwater) to Biscayne Bay and the coastal canal system in South Florida. Shallow geophysical electromagnetic and direct current resistivity surveys were used to image the geometry and stratification of the saltwater mixing zone in the near coastal (less than 1km inland) Biscayne Aquifer. The combined stable isotope and trace metal models suggest a ratio of canal input-precipitation-groundwater of 38%–52%–10% in the wet season and 37%–58%–5% in the dry season with an error of 25%, where most (20%) of the error was attributed to the isotope regression model, while the remaining 5% error was attributed to the Sr2+/Ca2+ mixing model. These models suggest rainfall is the dominate source of freshwater to Biscayne Bay. For a bay-wide water budget that includes saltwater and freshwater mixing, fresh groundwater accounts for less than 2% of the total input. A similar Sr 2+/Ca2+ tracer model indicates precipitation is the dominate source in 9 out of 10 canals that discharge into Biscayne Bay. The two-component mixing model converged for 100% of the freshwater canal samples in this study with 63% of the water contributed to the canals coming from precipitation and 37% from groundwater inputs ±4%. There was a seasonal shift from 63% precipitation input in the dry season to 55% precipitation input in the wet season. The three end-member mixing model converged for only 60% of the saline canal samples possibly due to non-conservative behavior of Sr2+ and Ca2+ in saline groundwater discharging into the canal system. Electromagnetic and Direct Current resistivity surveys were successful at locating and estimating the geometry and depth of the freshwater/saltwater interface in the Biscayne Aquifer at two near coastal sites. A saltwater interface that deepened as the survey moved inland was detected with a maximum interpreted depth to the interface of 15 meters, approximately 0.33 km inland from the shoreline. ^

Physical oceanography during POLARSTERN cruise ANT-V/3

The work carried out by the physical oceanography group on POLARSTERN Leg ANT-V/3 concentrated on four major topics: A. A large scale survey of the eastern boundary between the Weddell gyre and the open ocean. On the way to the coastal polynya in early October 12 CTD stations were carried out between 54°30'S, 6°E and 70°30'S 8°W. Another set of 16 stations was obtained in early December on the way back north. During this transsect three current meter moorings were recovered at Maud Rise. The path between the current meter arrays was used to run an additional section to the NNE across the top of Maud Rise. B. A large scale survey of the Antarctic Coastal Current along the eastern shelf area. To obtain the water mass characteristics along the eastern Weddell shelf 36 CTD stations were carried out between Atka Bay and the Filchner Trench. Most of the stations were located on the shelf. Cross shelf sections were obtained both near Drescher Inlet and off Halley Bay, in the divergence area of the Coastal Current where the continental slope turns to the west and south of Vestkapp at Neptune's Point. A longshore section over 120 km was run north of Vestkapp. C. A mesoscale survey of the Antarctic Coastal Current off Drescher Inlet. The experimental work consisted of 37 CTD-stations and direct current measurements. The CTD-profiles were grouped into seven sections perpendicular to the coast line off Drescher Inlet extending once over 70 km but normally over 35 km. The profile depth ranged from 300 m on one section to the complete water column at two sections. Most sections consist of five stations providing highest resolution over the upper continental slope with offshore increasing spacing. The stations were chosen to represent the shelf (450 m), the shelf break (800 m), the upper slope (1600 m), the lower slope (2400 m) and the transition to the abyssal plain (3400 m). Rough topography and difficult ice conditions made it impossible to meet those requirements in all cases. D. A small scale survey of the hydrographic conditions under the sea ice. The motivation for these studies arose during the cruise. Consequently a suitable Instrumentation had to be developed at sea. This was done with a NB-Smart CTD which was inserted on an L-shaped lever through a hole in the ice. However, various water intrusions into the instrument resulted in the failure of this technique. In consequence a special lever system was built to position a NB Mark 3b weighing about 40 kg below the ice. Twenty four profiles were obtained reaching from the bottom of the ice down to 2 m below the ice surface with a maximum distance of 1 m from the entry hole. As the conductivity sensor was influenced by nearby ice platelets, salinity samples where drawn to check the sensor.

(Table 2, page 2172) Chemical analytical data on thirty-two manganese nodules and crusts

Mn, Fe, Ca, Co, Ni, Cu, Zn, Cd, Sn, Tl, Pb and Bi have been estimated in thirty-two nodules from the Pacific, Atlantic and Indian oceans. Various features about the composition of manganese nodules are discussed: element abundances, degrees of enrichment, inter-element relationships (notably between Ni and Cu, and between Zn and Cd), regional variations and some aspects of statistical distribution.

Numerical Simulations for the Design of Novel Integrated Parallel Reception, Excitation, and Shimming (iPRES) Coil Arrays

Magnetic field inhomogeneity results in image artifacts including signal loss, image blurring and distortions, leading to decreased diagnostic accuracy. Conventional multi-coil (MC) shimming method employs both RF coils and shimming coils, whose mutual interference induces a tradeoff between RF signal-to-noise (SNR) ratio and shimming performance. To address this issue, RF coils were integrated with direct-current (DC) shim coils to shim field inhomogeneity while concurrently emitting and receiving RF signal without being blocked by the shim coils. The currents applied to the new coils, termed iPRES (integrated parallel reception, excitation and shimming), were optimized in the numerical simulation to improve the shimming performance. The objectives of this work is to offer a guideline for designing the optimal iPRES coil arrays to shim the abdomen.

In this thesis work, the main field () inhomogeneity was evaluated by root mean square error (RMSE). To investigate the shimming abilities of iPRES coil arrays, a set of the human abdomen MRI data was collected for the numerical simulations. Thereafter, different simplified iPRES(N) coil arrays were numerically modeled, including a 1-channel iPRES coil and 8-channel iPRES coil arrays. For 8-channel iPRES coil arrays, each RF coil was split into smaller DC loops in the x, y and z direction to provide extra shimming freedom. Additionally, the number of DC loops in a RF coil was increased from 1 to 5 to find the optimal divisions in z direction. Furthermore, switches were numerically implemented into iPRES coils to reduce the number of power supplies while still providing similar shimming performance with equivalent iPRES coil arrays.

The optimizations demonstrate that the shimming ability of an iPRES coil array increases with number of DC loops per RF coil. Furthermore, the z direction divisions tend to be more effective in reducing field inhomogeneity than the x and y divisions. Moreover, the shimming performance of an iPRES coil array gradually reach to a saturation level when the number of DC loops per RF coil is large enough. Finally, when switches were numerically implemented in the iPRES(4) coil array, the number of power supplies can be reduced from 32 to 8 while keeping the shimming performance similar to iPRES(3) and better than iPRES(1). This thesis work offers a guidance for the designs of iPRES coil arrays.

Seawater carbonate chemistry and reproduction of a coral reef fish in a laboratory experiment

Ocean acidification is predicted to negatively impact the reproduction of many marine species, either by reducing fertilization success or diverting energy from reproductive effort. While recent studies have demonstrated how ocean acidification will affect larval and juvenile fishes, little is known about how increasing partial pressure of carbon dioxide (pCO2) and decreasing pH might affect reproduction in adult fishes. We investigated the effects of near-future levels of pCO2 on the reproductive performance of the cinnamon anemonefish, Amphiprion melanopus, from the Great Barrier Reef, Australia. Breeding pairs were held under three CO2 treatments [Current-day Control (430 µatm), Moderate (584 µatm) and High (1032 µatm)] for a 9-month period that included the summer breeding season. Unexpectedly, increased CO2 dramatically stimulated breeding activity in this species of fish. Over twice as many pairs bred in the Moderate (67% of pairs) and High (55%) compared to the Control (27%) CO2 treatment. Pairs in the High CO2 group produced double the number of clutches per pair and 67% more eggs per clutch compared to the Moderate and Control groups. As a result, reproductive output in the High group was 82% higher than that in the Control group and 50% higher than that in the Moderate group. Despite the increase in reproductive activity, there was no difference in adult body condition among the three treatment groups. There was no significant difference in hatchling length between the treatment groups, but larvae from the High CO2 group had smaller yolks than Controls. This study provides the first evidence of the potential effects of ocean acidification on key reproductive attributes of marine fishes and, contrary to expectations, demonstrates an initially stimulatory (hormetic) effect in response to increased pCO2. However, any long-term consequences of increased reproductive effort on individuals or populations remain to be determined.

Differential contributions of the mIPS and PMd in the movement planning of reaches investigated through HD-tDCS

To reach for a target, we must formulate a movement plan - a difference vector of the target position with respect to the starting hand position. While it is known that the medial part of the intraparietal sulcus (mIPS) and the dorsal premotor (PMd) activity reflects aspects of a kinematic plan for a reaching movement, it is unclear whether or how the two regions may differ. We investigated the functional roles of the mIPS and PMd in the planning of reaching movements using high definition transcranial direct current stimulation (HD-tDCS) and examined changes in horizontal endpoint error when participants were subjected to anodal and cathodal stimulation. The left mIPS and PMd were functionally localized with fMRI in each participant using an interleaved center-out pointing and saccade task and mapped onto the scalp using Brainsight. We adopted a randomized, single-blind design and applied anodal and cathodal stimulation (2mA for 20 min; 3cm radius 4x1 electrode placement) during 4 separate visits scheduled at least a week apart. Each participant performed 250 baseline, stimulation, and post-stimulation memory-guided reaches starting from one of two initial hand positions (IHPs) to one of 4 briefly flashed targets (20 cm distant, 5 cm apart horizontally) while fixating on a straight-ahead cross located at the target line. Separate 2-way repeated measures ANOVAs of horizontal endpoint error difference after cathodal tDCS at each stimulation site revealed a significant IHP by target position interaction effect at the left mIPS, and significant IHP and target main effects at the left PMd. Behaviorally, these effects corresponded to IHP-dependent contractions after cathodal mIPS tDCS and IHP-independent contractions after cathodal PMd tDCS. These results suggest that the movement vector is not yet formed at the input level of mIPS, but is encoded at the input of PMd. These results also indicate that tDCS is a viable, useful method in investigating movement planning properties through temporary perturbations of the system.