Fabrication and application of short and novel structure in-fibre Bragg gratings

This thesis presents details on progress made in the fabrication and application of short and novel structure fibre Bragg gratings. The basic theoretical concepts of in-fibre Bragg gratings and photosensitive mechanisms are introduced together with an overview of fabrication methods and applications presented to date. The fabrication of fibre Bragg gratings using a quadrupled Nd:YAG laser is presented and some of the issues of grating fabrication using a fabrication using a phasemask are investigated, including the variation of the separation of the fibre and phasemask, and other alignment issues. A new apodisation technique is presented, enabling the production of gratings with a wide range of spectral profiles. The technique is used to investigate the design and fabrication of length limited fibre Bragg gratings for use in telecommunication systems as filters. Application to devices designed for use in WDM systems is presented. The use of fibre Bragg gratings as high spatial resolution distributed sensors is investigated. Grating sensing arrays comprising very short apodised gratings are demonstrated and Chirped Moiré gratings are implemented as distributed sensors achieving high spatial resolution with miniature point sensing sub-elements. A novel grating sensing element designed to imitate an interferometer is also presented. Finally, the behaviour of gratings fabricated in Boron-Germania-co-doped fibre is investigated, revealing atypical behaviour of the Bragg wavelength during ageing.

Writing and characterisation methods for UV-photosensitivity based devices and their applications

The underlying work to this thesis focused on the exploitation and investigation of photosensitivity mechanisms in optical fibres and planar waveguides for the fabrication of advanced integrated optical devices for telecoms and sensing applications. One major scope is the improvement of grating fabrication specifications by introducing new writing techniques and the use of advanced characterisation methods for grating testing. For the first time the polarisation control method for advanced grating fabrication has successfully been converted to apodised planar waveguide fabrication and the development of a holographic method for the inscription of chirped gratings at arbitrary wavelength is presented. The latter resulted in the fabrication of gratings for pulse-width suppression and wavelength selection in diode lasers. In co-operation with research partners a number of samples were tested using optical frequency domain and optical low coherence reflectometry for a better insight into the limitations of grating writing techniques. Using a variety of different fabrication methods, custom apodised and chirped fibre Bragg gratings were written for the use as filter elements for multiplexer-demultiplexer devices, as well as for short pulse generation and wavelength selection in telecommunication transmission systems. Long period grating based devices in standard, speciality and tapered fibres are presented, showing great potential for multi-parameter sensing. One particular scope is the development of vectorial curvature and refractive index sensors with potential for medical, chemical and biological sensing. In addition the design of an optically tunable Mach-Zehnder based multiwavelength filter is introduced. The discovery of a Type IA grating type through overexposure of hydrogen loaded standard and Boron-Germanium co-doped fibres strengthened the assumption of UV-photosensitivity being a highly non-linear process. Gratings of this type show a significantly lower thermal sensitivity compared to standard gratings, which makes them useful for sensing applications. An Oxford Lasers copper-vapour laser operating at 255 nm in pulsed mode was used for their inscription, in contrast to previous work using CW-Argon-Ion lasers and contributing to differences in the processes of the photorefractive index change

Advanced fibre gratings and their applications

This thesis describes a detailed study of advanced fibre grating devices using Bragg (FBG) and long-period (LPG) structures and their applications in optical communications and sensing. The major contributions presented in this thesis are summarised below. One of the most important contributions from the research work presented in this thesis is a systematic theoretical study of many distinguishing structures of fibre gratings. Starting from the Maxwell equations, the coupled-mode equations for both FBG and LPG were derived and the mode-overlap factor was analytically discussed. Computing simulation programmes utilising matrix transform method based on the models built upon the coupled-mode equations were developed, enabling simulations of spectral response in terms of reflectivity, bandwidth, sidelobes and dispersion of gratings of different structures including uniform and chirped, phase-shifted, Moiré, sampled Bragg gratings, phase-shifted and cascaded long-period gratings. Although the majority of these structures were modelled numerically, analytical expressions for some complex structures were developed with a clear physical picture. Several apodisation functions were proposed to improve sidelobe suppression, which guided effective production of practical devices for demanding applications. Fibre grating fabrication is the other major part involved in the Ph.D. programme. Both the holographic and scan-phase-mask methods were employed to fabricate Bragg and long-period gratings of standard and novel structures. Significant improvements were particularly made in the scan-phase-mask method to enable the arbitrarily tailoring of the spectral response of grating devices. Two specific techniques - slow-shifting and fast-dithering the phase-mask implemented by a computer controlled piezo - were developed to write high quality phase-shifted, sampled and apodised gratings. A large number of LabVIEW programmes were constructed to implement standard and novel fabrication techniques. In addition, some fundamental studies of grating growth in relating to the UV exposure and hydrogenation induced index were carried out. In particular, Type IIa gratings in non-hydrogenated B/Ge co-doped fibres and a re-generated grating in hydrogenated B/Ge fibre were investigated, showing a significant observation of thermal coefficient reduction. Optical sensing applications utilising fibre grating devices form the third major part of the research work presented in this thesis. Several experiments of novel sensing and sensing-demodulating were implemented. For the first time, an intensity and wavelength dual-coding interrogation technique was demonstrated showing significantly enhanced capacity of grating sensor multiplexing. Based on the mode-splitting measurement, instead of using conventional wavelength-shifting detection technique, successful demonstrations were also made for optical load and bend sensing of ultra-high sensitivity employing LPG structures. In addition, edge-filters and low-loss high-rejection bandpass filters of 50nm stop-band were fabricated for application in optical sensing and high-speed telecommunication systems

Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.

An evaluation of thermal plasmas in pyrometallurgy

The development of reliable, high powered plasma generators has resulted in many plasma processes being proposed as alternatives to existing pyrometallurgical technologies. This work evaluates the advantages and disadvantages of plasma systems by reviewing plasma generators, their integration with reactors and the process economics. Many plasma systems were shown to be technically and economically superior to existing technologies, but some of the plasma system advantages quoted in the literature were found to be impractical because of other system constraints. Process applications were limited by the power inputs available from plasma generators compared to AC electric furnaces. A series of trials were conducted where chromite and steelplant baghouse dusts were smelted in the Tetronics' 2.0 MW transferred arc/open bath reactor to confirm the operating characteristics of the plasma system and its economics. Chromite smelting was technical superior to submerged arc furnace technology, but the economics were unfavourable because of the limited power available from the water-cooled plasma torch and the high electrical energy consumption. A DC graphite electrode plasma furnace using preheated and prereduced chromite concentrates will compete economically with the submerged arc furnace. Ni, Cr and Mo were economically recovered from high alloy content steelplant dusts for recycling. Five Electric Arc Furnace dusts were smelted to produce a non-toxic residue and recover the contained zinc to an enriched zinc oxide product for recycling. It should be possible to condense the zinc vapour directly in a zinc splash condenser to increase the value of the product. Because of the limited power available from plasma generators, plasma processes will be most suitable for treating high and medium value materials such as Au, Pt, Mo, Ni, Ti, V, Cr etc at small production rates, heating metals in tundishes and ladles and remelting superalloy scrap. The treatment of environmentally hazardous waste materials is a particularly interesting application because of the additional financial incentives. Non-transferred arc plasma generators will be used for air and gas preheating in blast furnaces to reduce metallurgical coke consumptions.

Optically tuning of chromatic dispersion compensators

We present a new tuning method for chromatic dispersion compensators, which can be optically tunable. The dispersion compensators were made in Er/Yb co-doped fiber and were pumped with 980nm laser diodes. The tunable dispersion for a chirped grating and also a uniform-period grating was successfully demonstrated in the experiment.

Synthesis and characterisation of interfacial layers in organic solar cells

The quest for renewable energy sources has led to growing attention in the research of organic photovoltaics (OPVs), as a promising alternative to fossil fuels, since these devices have low manufacturing costs and attractive end-user qualities, such as ease of installation and maintenance. Wide application of OPVs is majorly limited by the devices lifetime. With the development of new encapsulation materials, some degradation factors, such as water and oxygen ingress, can almost be excluded, whereas the thermal degradation of the devices remains a major issue. Two aspects have to be addressed to solve the problem of thermal instability: bulk effects in the photoactive layer and interfacial effects at the photoactive layer/charge-transporting layers. In this work, the interface between photoactive layer and electron-transporting zinc oxide (ZnO) in devices with inverted architecture was engineered by introducing polymeric interlayers, based on zinc-binding ligands, such as 3,4-dihydroxybenzene and 8-hydroxyquinoline. Also, a cross-linkable layer of poly(3,4-dimethoxystyrene) and its fullerene derivative were studied. At first, controlled reversible addition-fragmentation chain transfer (RAFT) polymerisation was employed to achieve well-defined polymers in a range of molar masses, all bearing a chain-end functionality for further modifications. Resulting polymers have been fully characterised, including their thermal and optical properties, and introduced as interlayers to study their effect on the initial device performance and thermal stability. Poly(3,4-dihydroxystyrene) and its fullerene derivative were found unsuitable for application in devices as they increased the work function of ZnO and created a barrier for electron extraction. On the other hand, their parental polymer, poly(3,4-dimethoxystyrene), and its fullerene derivative, upon cross-linking, resulted in enhanced efficiency and stability of devices, if compared to control. Polymers based on 8-hydroxyquinoline ligand had a negative effect on the initial stability of the devices, but increased the lifetime of the cells under accelerated thermal stress. Comprehensive studies of the key mechanisms, determining efficiency, such as charge generation and extraction, were performed by using time-resolved electrical and spectroscopic techniques, in order to understand in detail the effect of the interlayers on the device performance. Obtained results allow deeper insight into mechanisms of degradation that limit the lifetime of devices and prompt the design of better materials for the interface stabilisation.

Hierarchical ZnO “rod like” architecture synthesized via reverse micellar route for improved photocatalytic activity

Hierarchical ZnO “rod like” architecture was successfully synthesized via reverse micellar route and characterized by various techniques. The FESEM studies show controlled decomposition of zinc oxalate into ZnO “rod like” architecture at 500 °C with slow heat rate at 1°/min. Interestingly, improved photocatalytic activity was observed for the degradation of Rhodamine B, due to the self assembly of hexagonal nanoparticles of zinc oxide forming hierarchical ZnO “rod like” architecture which can greatly enhance the light utilization rate due to its special architecture and enlarge the specific surface area, providing more reaction sites and promoting mass transfer. More importantly, the reusability studies of this architecture were most economical.

Clean hydrogen production and carbon dioxide capture methods

Fossil fuels constitute a significant fraction of the world's energy demand. The burning of fossil fuels emits huge amounts of carbon dioxide into the atmosphere. Therefore, the limited availability of fossil fuel resources and the environmental impact of their use require a change to alternative energy sources or carriers (such as hydrogen) in the foreseeable future. The development of methods to mitigate carbon dioxide emission into the atmosphere is equally important. Hence, extensive research has been carried out on the development of cost-effective technologies for carbon dioxide capture and techniques to establish hydrogen economy. Hydrogen is a clean energy fuel with a very high specific energy content of about 120MJ/kg and an energy density of 10Wh/kg. However, its potential is limited by the lack of environment-friendly production methods and a suitable storage medium. Conventional hydrogen production methods such as Steam-methane-reformation and Coal-gasification were modified by the inclusion of NaOH. The modified methods are thermodynamically more favorable and can be regarded as near-zero emission production routes. Further, suitable catalysts were employed to accelerate the proposed NaOH-assisted reactions and a relation between reaction yield and catalyst size has been established. A 1:1:1 molar mixture of LiAlH 4, NaNH2 and MgH2 were investigated as a potential hydrogen storage medium. The hydrogen desorption mechanism was explored using in-situ XRD and Raman Spectroscopy. Mesoporous metal oxides were assessed for CO2 capture at both power and non-power sectors. A 96.96% of mesoporous MgO (325 mesh size, surface area = 95.08 ± 1.5 m2/g) was converted to MgCO 3 at 350°C and 10 bars CO2. But the absorption capacity of 1h ball milled zinc oxide was low, 0.198 gCO2 /gZnO at 75°C and 10 bars CO2. Interestingly, 57% mass conversion of Fe and Fe 3O4 mixture to FeCO3 was observed at 200°C and 10 bars CO2. MgO, ZnO and Fe3O4 could be completely regenerated at 550°C, 250°C and 350°C respectively. Furthermore, the possible retrofit of MgO and a mixture of Fe and Fe3O 4 to a 300 MWe coal-fired power plant and iron making industry were also evaluated.

(Table 1) Chemical composition of a sample contaiting native aluminium, Core DM9-647, Northeast Pacific

Composition, structure and occurrence of native aluminium in bottom sediments of the Northeast Pacific at Station DM9-647 are reported.

Mechanismus der CR-Vernetzung mit Ethylenthio-harnstoff und Zinkoxid

Es wurde eine Untersuchung zum Mechanismus der Vernetzung von Polychloropren durch Ethylenthioharnstoff in Kombination mit Zinkoxid durchgeführt. Dies wurde mit einer Überprüfung der Vernetzungsmechanismen von Polychloroprenkautschuk mit Ethylenthioharnstoff und Zinkoxid getrennt bzw. gemeinsam erreicht. Dabei kamen spektroskopische und physikalische Charakterisierungsverfahren zum Einsatz, um die Vernetzungsmechanismen von  CR mit anderen Standardvulkanisationsbeschleunigern und Modellverbindungen – mit ETU-analogen Strukturen und Funktionalitäten – zu erforschen. Aus den Untersuchungen resultierte der Vorschlag zu einem neuen Mechanismus, nach dem ETU und ZnO Polychloropren synergistisch vernetzen. Zusätzlich wurden neue Hinweise gewonnen, die gleichzeitig bestehende Mechanismen, die schon zur Vernetzung von Polychloropren veröffentlicht wurden, untermauern. An investigation into the mechanism by which ethylene thiourea crosslinks polychloroprene in combination with zinc oxide was undertaken. This was achieved through an examination of the mechanisms of crosslinking polychloroprene rubber with ETU and ZnO separately and in unison. Spectroscopic and physical characterisation techniques were employed to probe the crosslinking mechanisms of CR using other standard rubber accelerators and model compounds with analogous structures and functionalities to ETU. These investigations have resulted in the proposal of a new mechanism by which ETU and ZnO can synergistically crosslink polychloroprene, in addition to providing new evidence to support concomitant mechanisms already published for crosslinking polychloroprene.

Optically pumped chirped grating for tunable chromatic dispersion compensation

We demonstrate a novel optically tunable dispersion compensator based on pumping a chirped grating made in Er/Yb co-doped fiber. The dispersion was tuned from 900 to 1900ps/nm and also from-600 to-950ps/nm in the experiment. © 2010 Optical Society of America.

Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.

(Table 3, page 264), Composition of a manganese micronodule found in a fossil red clay bed from Western Timor

Chemical analyses are presented for two Cretaceous clays from Noil Tobee, Timor. Mineralogical examination has shown that they consist principally of quartz, feldspar, illite and chlorite, together with minor amounts of montmorillonite. Both chemically and mineralogically the clays are very similar to the recent argillaceous deep-sea sediments of the Pacific and Indian Oceans, which confirms Molengraaff's theory (1921) that they are of deep-sea origin. Further confirmation of this theory is provided by comparison of the composition of micromanganese nodules, separated from one of these clays, with that of manganese nodules from the Pacific Ocean.