Benzothiazoliumsalze als Photoinitiatoren für kationische Epoxidpolymerisationen

In dieser Arbeit wurden neuartige substituierte N-Benzylbenzothiazoliumhexa-fluorophosphate und –antimonate synthetisiert und hinsichtlich ihre Wirksamkeit als photo- und thermolatente Initiatoren für Epoxidpolymerisationen untersucht. Zur Synthese der Benzothiazoliumderivate wurden zunächst substituierte Benzothiazole nach verschiedenen Verfahren hergestellt, diese mit den entsprechenden Benzylbromiden quaternisiert und die N-quaternären Bromide zu den Hexafluorophosphaten bzw. –antimonaten umgesalzt. Neben den niedermolekularen Benzothiazoliumsalzen wurden auch Copolymere mit dieser Struktur in der Seitenkette durch radikalische Copolymerisation vinylsubstituierter N-quaternärer Benzothiazoliumsalze mit MMA hergestellt. Sowohl die niedermolekularen als auch die polymergebundenen Benzothiazoliumhexafluorophosphate erwiesen sich als effektive direkte kationische Photo- und Thermoinitiatoren für die Polymerisation von Epoxiden. Durch die Einführung auxochromer Ethergruppierungen konnte eine bathochrome Verschiebung der UV-Absorptionswellenlänge des energieärmsten elektronischen Überganges erreicht werden. Kinetische IR-Studien der kationischen Polymerisation von Glycidylphenylether (GPE) im Nassfilm unter Bestrahlung in Gegenwart der hergestellten Benzothiazoliumsalze als Photoinitiatoren zeigten dass durch die so erreichte verbesserte Ausnutzung der einwirkenden Strahlung die kationische Photoinitiatoreffektivität deutlich gesteigert werden konnte. Der Zusatz eines photolytischen Radikalbildners führte zu einer weiteren Steigerung der Photopolymerisationsgeschwindigkeit und zu einer Umkehr der beobacheteten Initiatoreffektivitäten. UV-, 1H NMR-, sowie MALDI-TOF- Untersuchungen, sowie die vollständige Unterdrückung der Photopolymerisation durch den Protonenfänger DBP deuten auf die photolytische Generierung von Protonen als initiierende Spezies der photokationischen Polymerisation und DSC- und 1H-NMR Ergebnisse auf die thermische Generierung von Benzylkationen als initiierende Spezies der thermischen Polymerisation hin.

Cambios en el uso del suelo de las tierras del ingenio Las Palmas, provincia de Chaco, en los años 1987 y 2001

En el departamento Bermejo, provincia de Chaco, a fines del siglo XIX se origina uno de los ingenios azucareros más importantes del país: Las Palmas del Chaco Austral S.A. En la década de los noventa es víctima de las políticas de privatización imperantes del momento. Como consecuencia, se produce su cierre y posterior desaparición, lo que supuso la eliminación de la principal fuente de trabajo de la localidad. Las tendencias actuales y novedosas en teledetección, cartografía digital y Sistemas de Información Geográfica (SIG) son una forma útil e importante de ofrecer conocimientos actualizados para el diagnóstico, monitoreo y su aplicación en la gestión e investigación de recursos presentes en los distintos lugares de nuestro país. En el presente trabajo se pretende analizar los cambios producidos en el uso de suelo en las tierras del ex Ingenio a partir del cierre del mismo, mediante el uso de imágenes satelitales de los años 1987 y 2001, y de sistemas de información geográfica (SIG). El análisis multiespectral y multitemporal de las mismas permitirá discriminar los tipos de cobertura del suelo sobre la base de su respuesta espectral.

Cambios en el uso del suelo de las tierras del ingenio Las Palmas, provincia de Chaco, en los años 1987 y 2001

En el departamento Bermejo, provincia de Chaco, a fines del siglo XIX se origina uno de los ingenios azucareros más importantes del país: Las Palmas del Chaco Austral S.A. En la década de los noventa es víctima de las políticas de privatización imperantes del momento. Como consecuencia, se produce su cierre y posterior desaparición, lo que supuso la eliminación de la principal fuente de trabajo de la localidad. Las tendencias actuales y novedosas en teledetección, cartografía digital y Sistemas de Información Geográfica (SIG) son una forma útil e importante de ofrecer conocimientos actualizados para el diagnóstico, monitoreo y su aplicación en la gestión e investigación de recursos presentes en los distintos lugares de nuestro país. En el presente trabajo se pretende analizar los cambios producidos en el uso de suelo en las tierras del ex Ingenio a partir del cierre del mismo, mediante el uso de imágenes satelitales de los años 1987 y 2001, y de sistemas de información geográfica (SIG). El análisis multiespectral y multitemporal de las mismas permitirá discriminar los tipos de cobertura del suelo sobre la base de su respuesta espectral.

Cambios en el uso del suelo de las tierras del ingenio Las Palmas, provincia de Chaco, en los años 1987 y 2001

En el departamento Bermejo, provincia de Chaco, a fines del siglo XIX se origina uno de los ingenios azucareros más importantes del país: Las Palmas del Chaco Austral S.A. En la década de los noventa es víctima de las políticas de privatización imperantes del momento. Como consecuencia, se produce su cierre y posterior desaparición, lo que supuso la eliminación de la principal fuente de trabajo de la localidad. Las tendencias actuales y novedosas en teledetección, cartografía digital y Sistemas de Información Geográfica (SIG) son una forma útil e importante de ofrecer conocimientos actualizados para el diagnóstico, monitoreo y su aplicación en la gestión e investigación de recursos presentes en los distintos lugares de nuestro país. En el presente trabajo se pretende analizar los cambios producidos en el uso de suelo en las tierras del ex Ingenio a partir del cierre del mismo, mediante el uso de imágenes satelitales de los años 1987 y 2001, y de sistemas de información geográfica (SIG). El análisis multiespectral y multitemporal de las mismas permitirá discriminar los tipos de cobertura del suelo sobre la base de su respuesta espectral.

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Ruling out the impact of defects on the below band gap photoconductivity of Ti supersaturated Si

In this study, we present a structural and optoelectronic characterization of high dose Ti implanted Si subsequently pulsed-laser melted (Ti supersaturated Si). Time-of-flight secondary ion mass spectrometry analysis reveals that the theoretical Mott limit has been surpassed after the laser process and transmission electron microscopy images show a good lattice reconstruction. Optical characterization shows strong sub-band gap absorption related to the high Ti concentration. Photoconductivity measurements show that Ti supersaturated Si presents spectral response orders of magnitude higher than unimplanted Si at energies below the band gap. We conclude that the observed below band gap photoconductivity cannot be attributed to structural defects produced by the fabrication processes and suggest that both absorption coefficient of the new material and lifetime of photoexcited carriers have been enhanced due to the presence of a high Ti concentration. This remarkable result proves that Ti supersaturated Si is a promising material for both infrared detectors and high efficiency photovoltaic devices.

Intermediate band solar cells. The transition metal supersaturated Silicon approach

Within the framework of the third solar cell generation some new ideas to enlarge the spectral response of the solar cells toward the infrared have been proposed. Among them the inclusion of an Intermediate Band (IB) seems to be very promising. This paper will deal with one of the ways to generate the IB namely the deep level center approach. We will discuss not only its existence but also the carriers lifetime recovery which is necessary to obtain the expected increase of the solar cell efficiency.

Stimulation of the blue light phototropic receptor NPH1 causes a transient increase in cytosolic Ca2+

Blue light regulates plant growth and development, and three photoreceptors, CRY1, CRY2, and NPH1, have been identified. The transduction pathways of these receptors are poorly understood. Transgenic plants containing aequorin have been used to dissect the involvement of these three receptors in the regulation of intracellular Ca2+. Pulses of blue light induce cytosolic Ca2+ transients lasting about 80 s in Arabidopsis and tobacco seedlings. Use of organelle-targeted aequorins shows that Ca2+ increases are limited to the cytoplasm. Blue light treatment of cry1, cry2, and nph1 mutants showed that NPH1, which regulates phototropism, is largely responsible for the Ca2+ transient. The spectral response of the Ca2+ transient is similar to that of phototropism, supporting NPH1 involvement. Furthermore, known interactions between red and blue light and between successive blue light pulses on phototropic sensitivity are mirrored in the blue light control of cytosolic Ca2+ in these seedlings. Our observations raise the possibility that physiological responses regulated by NPH1, such as phototropism, may be transduced through cytosolic Ca2+.

Bend sensors with direction recognition based on long-period gratings written in D-shaped fibre

The curvature- or bend-sensing response of long-period gratings (LPGs) UV inscribed in D-shaped fiber has been investigated experimentally. Strong fiber-orientation dependence of the spectral response when such LPGs are subjected to bending at different directions has been observed and is shown to form the basis for a new class of single-device sensor with vector-sensing capability. Potential applications utilizing the linear response and unique bend-orientation characteristics of the devices are discussed.

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

Implementation of vectorial bend sensors using long-period gratings UV-inscribed in special shape fibres

We report the implementation of vector bending sensors using long-period gratings (LPGs) UV-inscribed in flat-clad, four-core and D-shaped fibres. Our experiments reveal a strong fibre-orientation dependence of the spectral response when such LPGs are subjected to dynamic bending, which provided an opportunity to realize curvature measurement with direction recognition.

The investigation of vegetation change using remote sensing to detect and monitor migration of landfill gas

Decomposition of domestic wastes in an anaerobic environment results in the production of landfill gas. Public concern about landfill disposal and particularly the production of landfill gas has been heightened over the past decade. This has been due in large to the increased quantities of gas being generated as a result of modern disposal techniques, and also to their increasing effect on modern urban developments. In order to avert diasters, effective means of preventing gas migration are required. This, in turn requires accurate detection and monitoring of gas in the subsurface. Point sampling techniques have many drawbacks, and accurate measurement of gas is difficult. Some of the disadvantages of these techniques could be overcome by assessing the impact of gas on biological systems. This research explores the effects of landfill gas on plants, and hence on the spectral response of vegetation canopies. Examination of the landfill gas/vegetation relationship is covered, both by review of the literature and statistical analysis of field data. The work showed that, although vegetation health was related to landfill gas, it was not possible to define a simple correlation. In the landfill environment, contribution from other variables, such as soil characteristics, frequently confused the relationship. Two sites are investigated in detail, the sites contrasting in terms of the data available, site conditions, and the degree of damage to vegetation. Gas migration at the Panshanger site was dominantly upwards, affecting crops being grown on the landfill cap. The injury was expressed as an overall decline in plant health. Discriminant analysis was used to account for the variations in plant health, and hence the differences in spectral response of the crop canopy, using a combination of soil and gas variables. Damage to both woodland and crops at the Ware site was severe, and could be easily related to the presence of gas. Air photographs, aerial video, and airborne thematic mapper data were used to identify damage to vegetation, and relate this to soil type. The utility of different sensors for this type of application is assessed, and possible improvements that could lead to more widespread use are identified. The situations in which remote sensing data could be combined with ground survey are identified. In addition, a possible methodology for integrating the two approaches is suggested.

Flat-top pulse generation based on a fiber Bragg grating in transmission

We propose and analyze a flat-top pulse generator based on a fiber Bragg grating (FBG) in transmission. As is shown in the examples, a uniform period FBG properly designed can exhibit a spectral response in transmission close to sinc function (in amplitude and phase) in a certain bandwidth, because of the logarithm Hilbert transform relations, which can be used to reshape a Gaussian-like input pulse into a flat-top pulse.

Vectorial bending characteristics of long-period grating written in D-shaped fibre

The curvature- or bend-sensing response of long-period gratings (LPG) UV-inscribed in D-shaped fiber has been investigated experimentally. Strong fiber orientation dependence of the spectral response when such LPGs are subjected to dynamic bending has been observed and is shown to form the basis for new vector sensors.