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.

Repetition-rate multiplication using a single all-pass optical cavity

We demonstrate a simple lossless method for the implementation of repetition-rate multiplication of a periodic pulse train. As it is showed, a single all-pass optical cavity (APOC) can increase the repetition rate of the output pulse train by factors of 2, 3, and 4. Two different APOC implementations, based on a Gires-Tournois interferometer and an all-pass ring resonator, are proposed and numerically demonstrated.

1220km propagation of 40Gbit/s single channel RZ data over dispersion managed standard (non-dispersion shifted) fibre

Error free propagation of a single polarisation optical time division multiplexed 40 Gbit/s dispersion managed pulsed data stream over dispersion (non-shifted) fibre. This distance is twice the previous record at this data rate.

Seasonal growth and growth rate-colony size relationships in six species of saxicolous lichens

The pattern of seasonal growth and the relation of growth rate to colony size were studied in four foliose and two crustose species of saxicolous lichens. A new method of measuring growth was used whereby the advance of a sample of lobes along millimetres marked on the substrate was measured under a magnification of x10. Three peaks of growth were found(in March, June and November) for the foliose species and a single peak (in May to August) for the crustose species. THe peaks of growth corresponded approximately to peaks of rainfall. Growth rate in relation to increasing colony size fell in a smooth exponential curve when expressed on a cm squared/ cm squared/ unit time basis. The result is consistent with a linear radial rate for most of the thallus sizes for the six species. There is also evidence for an exponential incresae in growth rate initially until about 1.5 cm thallus diameter in two of the sepcies when the linear radial rate is achieved.

1000 Km transmission of 40 Gbit/s single channel RZ data over dispersion managed standard (non-dispersion shifted) fibre

Error-free transmission of a single polarization optical time division multiplexed 40 Gbit/s dispersion managed pulse data stream over 1009 km has been achieved in dispersion-compensated standard (non-dispersion shifted) fibre. This distance is twice the previous record at this data rate.

The Single drop drying of heat-sensitive materials

The literature relating to the principles and practice of drying of materials, particularly those susceptible to thermal degradation or undesirable loss of volatile components, has been reviewed. Single droplets of heat-sensitive materials were dried whilst suspended in a horizontal wind tunnel from a specially-designed, rotating thermocouple which enabled direct observation of drying behaviour and continuous measurement of droplet temperature as drying progressed. The effects of drying air temperature and initial solids concentration on the potency of various antibiotics, viz. ampicillin, chloramphenicol, oxytetracycline, streptomycin and tetracycline, were assessed using a modified Drug Sensitivity Testing technique. Only ampicillin was heat-sensitive at temperatures above 100°C, e.g. at an air temperature of 115°C its zone diameter was reduced from 100% to 45%. Selected enzymes, viz. dextran sucrase and invertase, were also dried and their residual activities determined by High Performance Liquid Chromatography. The residual activity of dextran sucrase was rapidly reduced at temperatures above 65°C, and the residual activity of invertase reduced rapidly at temperatures above 65°C; but drying with short residence times will retain most of its activity. The performance of various skin-forming encapsulants, viz. rice and wheat starch, dextrin, coffee, skim milk, fructose, gelatine 60 and 150 Bloom, and gum arabic, was evaluated to determine their capabilities for retention of ethanol as a model volatile, under different operating conditions. The effects of initial solids concentration, air velocity and temperature were monitored for each material tested. Ethanol content was analysed by Gas Liquid Chromatography and in some cases dried crusts were removed for examination. Volatiles retention was concluded to depend in all cases upon the rate and nature of the skin formation and selective diffusion phenomena. The results provided further insight into the inter-relationship between temperature, residence time and thermal degradation of heat-sensitive materials. They should also assist in selection of the preferred dryer for such materials, and of the operating parameter to enable maximum retention of the required physico-chemical characteristics in the dried materials.

A study of the drying of single droplets in free-flight

The literature relating to evaporation from single droplets of pure liquids and the drying of solution and slurry droplets, and of droplet sprays has been reviewed. The heat and mass transfer rates for individual droplets suspended in free-flight, were investigated using a specially-designed vertical wind tunnel, to simulate conditions in a spray drier. The technique represented a unique alternative method for investigating evaporation from unrestrained single droplets with variable residence times. The experiments covered droplets of pure liquid allowbreak (water, isopropanol) allowbreak and of significantly different solutions (sucrose, potassium sulphate) over a range of temperatures of 37oC to 97oC, initial concentrations of 5 to 40wt/wt% , and initial drop sizes of 2.8 to 4.6mm. Drop behaviour was recorded photographically and dried particles were examined by Scanning Electron Microscopy. Correlations were developed for mass transfer coefficients for pure water droplets in free-flight; (i) experiencing oscillations, rotation and deformation, Sh = -105 + 3.9 [Ta - Td/Tamb]0.18Re0.5Sc033 for Re approx. > 1380 (ii) when these movements had ceased or diminished, Sh = 2.0 + 0.71 [Ta - Td/Tamb]0.18Re0.5Sc033 for Re approx. < 1060. Data for isopropanol drops were correlated resonably well by these equations. The heat transfer data showed a similar transition range. The drying rate curves for drops of sucrose and potassium sulphate solution exhibited three distinct stages; an initial increase in the drying rate as drop temperature reduced to the wet-bulb temperature, a short constant-rate period and a falling-rate period characterised by formation of a crust which controlled the mass transfer rate. Due to drop perturbation the rates in the high Re number region were up to 5 times greater than predicted from theory for spherical droplets. In the case of sucrose solution a `skin' formed over the drop surface prior to crust formation. This provided an additional resistance to mass transfer and resulted in extended drying times and a smooth crust of low porosity. The relevance of the results to practical spray drying operations is discussed.

Processing and rendering of Fourier domain optical coherence tomography images at a line rate over 524 kHz using a graphics processing unit

In Fourier domain optical coherence tomography (FD-OCT), a large amount of interference data needs to be resampled from the wavelength domain to the wavenumber domain prior to Fourier transformation. We present an approach to optimize this data processing, using a graphics processing unit (GPU) and parallel processing algorithms. We demonstrate an increased processing and rendering rate over that previously reported by using GPU paged memory to render data in the GPU rather than copying back to the CPU. This avoids unnecessary and slow data transfer, enabling a processing and display rate of well over 524,000 A-scan/s for a single frame. To the best of our knowledge this is the fastest processing demonstrated to date and the first time that FD-OCT processing and rendering has been demonstrated entirely on a GPU.

PMD tolerance of 288 Gbit/s Coherent WDM and transmission over unrepeatered 124 km of field-installed single mode optical fiber

Low-cost, high-capacity optical transmission systems are required for metropolitan area networks. Direct-detected multi-carrier systems are attractive candidates, but polarization mode dispersion (PMD) is one of the major impairments that limits their performance. In this paper, we report the first experimental analysis of the PMD tolerance of a 288Gbit/s NRZ-OOK Coherent Wavelength Division Multiplexing system. The results show that this impairment is determined primarily by the subcarrier baud rate. We confirm the robustness of the system to PMD by demonstrating error-free performance over an unrepeatered 124km field-installed single-mode fiber with a negligible penalty of 0.3dB compared to the back-to-back measurements. (C) 2010 Optical Society of America

Nonlinearity compensation in multi-rate 28 Gbaud WDM systems employing optical and digital techniques under diverse link configurations

Digital back-propagation (DBP) has recently been proposed for the comprehensive compensation of channel nonlinearities in optical communication systems. While DBP is attractive for its flexibility and performance, it poses significant challenges in terms of computational complexity. Alternatively, phase conjugation or spectral inversion has previously been employed to mitigate nonlinear fibre impairments. Though spectral inversion is relatively straightforward to implement in optical or electrical domain, it requires precise positioning and symmetrised link power profile in order to avail the full benefit. In this paper, we directly compare ideal and low-precision single-channel DBP with single-channel spectral-inversion both with and without symmetry correction via dispersive chirping. We demonstrate that for all the dispersion maps studied, spectral inversion approaches the performance of ideal DBP with 40 steps per span and exceeds the performance of electronic dispersion compensation by ~3.5 dB in Q-factor, enabling up to 96% reduction in complexity in terms of required DBP stages, relative to low precision one step per span based DBP. For maps where quasi-phase matching is a significant issue, spectral inversion significantly outperforms ideal DBP by ~3 dB.

Full-field electronic dispersion compensation of a 10 Gbit/s OOK signal over 4 x 124 km field-installed single-mode fibre

We experimentally demonstrate the use of full-field electronic dispersion compensation (EDC) to achieve a bit error rate of 5 x 10(-5) at 22.3 dB optical signal-to-noise ratio for single-channel 10 Gbit/s on-off keyed signal after transmission over 496 km field-installed single-mode fibre with an amplifier spacing of 124 km. This performance is achieved by designing the EDC so as to avoid electronic amplification of the noise content of the signal during full-field reconstruction. We also investigate the tolerance of the system to key signal processing parameters, and numerically demonstrate that single-channel 2160 km single mode fibre transmission without in-line optical dispersion compensation can be achieved using this technique with 80 km amplifier spacing and optimized system parameters.

Ultrafast all-optical Nth-order differentiator and simultaneous repetition-rate multiplier of periodic pulse train

The letter presents a technique for Nth-order differentiation of periodic pulse train, which can simultaneously multiply the input repetition rate. This approach uses a single linearly chirped apodized fiber Bragg grating, which grating profile is designed to map the spectral response of the Nth-order differentiator, and the chirp introduces a dispersion that, besides space-to-frequency mapping, it also causes a temporal Talbot effect.

Myopia control with orthokeratology contact lenses in Spain:a comparison of vision-related quality-of-life measures between orthokeratology contact lenses and single-vision spectacles

Purpose: To compare vision-related quality-of-life measures between children wearing orthokeratology (OK) contact lenses and distance single-vision (SV) spectacles. Methods: Subjects 6 to 12 years of age and with myopia of -0.75 to -4.00 diopters and astigmatism less than or equal to 1.00 diopters were prospectively assigned OK contact lens or SV spectacle correction. A pediatric refractive error profile questionnaire was administered at 12- and 24-month intervals to evaluate children's perceptions in terms of overall vision, near vision, far distance vision, symptoms, appearance, satisfaction, activities, academic performance, handling, and peer perceptions. The mean score of all items was calculated as the overall score. Additionally, parents/guardians were asked to rate their child's mode of visual correction and their intention to continue treatment after study completion. Results: Thirty-one children were fitted with OK contact lenses and 30 with SV spectacles. Children wearing OK contact lenses rated overall vision, far distance vision, symptoms, appearance, satisfaction, activities, academic performance, handling, peer perceptions, and the overall score significantly better than children wearing SV spectacles (all P<0.05). Near vision and handling were, respectively, rated better (P<0.001) and similar (P=0.44) for SV spectacles in comparison to OK contact lenses. No significant differences were found between 12 and 24 months for any of the subjective ratings assessed (all P>0.05). Parents/guardians of children wearing OK contact lenses rated visual correction method and intention to continue treatment higher than parents of children wearing SV spectacles (P=0.01). Conclusion: The results indicate that the significant improvement in vision-related quality of life and acceptability with OK contact lenses is an incentive to engage in its use for the control of myopia in children.

High rate growth of nanocrystalline diamond films using high microwave power and pure nitrogen/methane/hydrogen plasma

In this work, we investigate the impact of minute amounts of pure nitrogen addition into conventional methane/hydrogen mixtures on the growth characteristics of nanocrystalline diamond (NCD) films by microwave plasma assisted chemical vapour deposition (MPCVD), under high power conditions. The NCD films were produced from a gas mixture of 4% CH4/H2 with two different concentrations of N2 additive and microwave power ranging from 3.0 kW to 4.0 kW, while keeping all the other operating parameters constant. The morphology, grain size, microstructure and texture of the resulting NCD films were characterized by using scanning electron microscope (SEM), micro-Raman spectroscopy and X-ray diffraction (XRD) techniques. N2 addition was found to be the main parameter responsible for the formation and for the key change in the growth characteristics of NCD films under the employed conditions. Growth rates ranging from 5.4 μm/h up to 9.6 μm/h were achieved for the NCD films, much higher than those usually reported in the literature. The enhancing factor of nitrogen addition on NCD growth rate was obtained by comparing with the growth rate of large-grained microcrystalline diamond films grown without nitrogen and discussed by comparing with that of single crystal diamond through theoretical work in the literature. This achievement on NCD growth rate makes the technology interesting for industrial applications where fast coating of large substrates is highly desirable.

1220km propagation of 40Gbit/s single channel RZ data over dispersion managed standard (non-dispersion shifted) fibre

Error free propagation of a single polarisation optical time division multiplexed 40 Gbit/s dispersion managed pulsed data stream over dispersion (non-shifted) fibre. This distance is twice the previous record at this data rate.