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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
61

Observation of Iron (III) and Iron (II) Chloro Species at the Air-Aqueous Interfacevia Second Harmonic Generation Spectroscopy

Ng, Ka Chon 23 September 2022 (has links)
No description available.
62

Nonlinear Optical Properties Of Organic Chromophores Calculated Within Time Dependent Density Functional Theory

Tafur, Sergio 01 January 2007 (has links)
Time Dependent Density Functional Theory offers a good accuracy/computational cost ratio among different methods used to predict the electronic structure for molecules of practical interest. The Coupled Electronic Oscillator (CEO) formalism was recently shown to accurately predict Nonlinear Optical (NLO) properties of organic chromophores when combined with Time Dependent Density Functional Theory. Unfortunately, CEO does not lend itself easily to interpretation of the structure activity relationships of chromophores. On the other hand, the Sum Over States formalism in combination with semiempirical wavefunction methods has been used in the past for the design of simplified essential states models. These models can be applied to optimization of NLO properties of interest for applications. Unfortunately, TD-DFT can not be combined directly with SOS because state-to-state transition dipoles are not defined in the linear response TD approach. In this work, a second order CEO approach to TD-DFT is simplified so that properties of double excited states and state-to-state transition dipoles may be expressed through the combination of linear response properties. This approach is termed the a posteriori Tamm-Dancoff approximation (ATDA), and validated against high-level wavefunction theory methods. Sum over States (SOS) and related Two-Photon Transition Matrix formalism are then used to predict Two-Photon Absorption (2PA) profiles and anisotropy, as well as Second Harmonic Generation (SHG) properties. Numerical results for several conjugated molecules are in excellent agreement with CEO and finite field calculations, and reproduce experimental measurements well.
63

Community empowerment and sustainable livelihoods : transforming social capital into entrepreneurship in rural Southern Ethiopia

Tefera Talore Abiche 25 July 2013 (has links)
The past decades witnessed that neither the private sector nor the government could provide an adequate socio-economic safety net for the poorest of the poor in the Third World. The community-based self-help approaches were hence widely used as alternative means to help the poor and marginalised to cope with livelihood shocks. This study examined the extent to which indigenous iddirs (local neighbourhood associations) and the externally-funded self-help groups (SHGs) could transform social capital into entrepreneurship thereby enhancing sustainable livelihoods. The study was conducted in three Southern Nation and Nationalities and People’s Region (SNNPR) rural districts, namely, Shebedeno, Wonago and Humbo. Mixed (quantitative and qualitative) methods were used to collect field data. Accordingly, closed and openended questionnaires and interview schedules were developed in English and then translated into Amharic (the national language). Instruments were field tested for validity and thereafter adjusted. A total of 220 (166 male and 54 female) people participated in the study. Data were entered into an Statistical Package for the Social Sciences (SPSS) database, and analysed by using basic descriptive statistics. Qualitative data were transcribed and analysed using Microsoft Office tools. The findings indicate that the SHGs’ members were relatively better educated than the rest of the population and some of them used this opportunity to pursue employment in government and the private sector. With regard to poverty status, iddirs members were poorer than those of SHGs (15.5% of the iddirs members reported that they are destitute compared to others in the community, as opposed to 3.3% of SHGs members). The study reveals that the livelihoods of some members of iddirs and SHG (particularly the latter) improved as a result of their involvement in these institutions although, at this point, the impact is insignificant. With regard to socio-economic decision making, more SHG members were involved in participatory decision making. However, iddirs leaders were still the dominant decision makers. The SHG level of participatory decision making could be the result of capacity building efforts by the promoting organisation, particularly, the Ethiopian Kale Heywet Church (EKHC). The study also shows that some of the iddirs and SHGs members were involved in informal rural entrepreneurial activities. However, their involvement did not indicate the utilisation of micro loan taken from the iddirs and SHGs for business purposes (97% of the iddirs and SHGs respondents utilised microcredit loans for consumption and other related purposes). On the other hand, the empirical evidence reveals that the amount of loan that iddirs and SHGs respondents received was very small. The general practice is giving small loans particularly to SHG members with repayments expected to begin as quickly and frequently as possible. Transforming social capital into entrepreneurship requires a cooperative approach, i.e. the involvement of development actors so as to enhance communities’ endeavour to achieve their livelihood objectives. Despite the wide prevalence of social capital in Ethiopia, this study indicates that its effective utilisation in community empowerment and sustainable livelihoods remains a challenge. Social capital is found to have a limited role in social entrepreneurship development and promotion not because it does not have potential, but because of the limited role of promoting organisations. The study shows lack of strong linkage between iddirs and promoting organisation (NGOs and Government). The study thus underlines the need for improving network and links with iddirs and SHGs and promoting organisations so as to create an enabling environment for sustainable livelihoods in the three rural districts under scrutiny. / Development Studies / D. Litt. et Phil. (Development Studies)
64

Tip-enhanced near-field optical microscopy

Neacsu, Corneliu Catalin 14 February 2011 (has links)
Die vorliegende Arbeit beschreibt neue Entwicklungen im Verständnis und in der Umsetzung der optischen Nahfeldmikroskopie (scattering - type scanning near-field optical microscopy, s-SNOM) für die lineare und nichtlineare optische Bildgebung mit ultrahoher Auslösung und Empfindlichkeit. Die fundamentalen Mechanismen, die der Feldverstärkung am Ende von ultrascharfen metallischen Spitzen zugrunde liegen, werden systematisch behandelt. Die plasmonischen Eigenschaften der Spitze wurden erstmalig beobachtet, und ihre Bedeutung für die optische Kopplung zwischen Spitze und Probe sowie für die sich ergebende Einengung des Nahfeldes wird diskutiert. Ein aperturloses Nahfeldmikroskop für die spitzenverstärkte Ramanspektroskopie (tip-enhanced Raman spectroscopy, TERS) wurde entwickelt. Die Grundlagen der TERS und die wesentliche Rolle des plasmonischen Verhaltens der Spitze sowie die klare Unterscheidung von Nahfeld-Ramansignatur und Fernfeld-Abbildungsartefakten werden beschrieben. Nahfeld Raman Verstärkungsfaktoren von bis zu 10 wurden erreicht, was einer Feldverstärkung von bis zu 130 entspricht und Raman-Messungen bis auf Einzel-Molekül-Niveau ermöglichte. Die optische Frequenzverdopplung (second harmonic generation, SHG) an einzelnen Spitzen wurde untersucht. Aufgrund ihrer teilweise asymmetrischen Nanostruktur erlauben die Spitzen eine klare Unterscheidung von lokalen Oberflächen und nichtlokalen Volumenbeiträgen zur nichtlinearen Polarisation sowie die Analyse ihrer Polarisations- und Emissions-Auswahlregeln. Die spitzenverstärkte Frequenzverdopplungs-Spektroskopie und die räumlich hoch aufgelöste Abbildung auf Basis des dielektrischen Kontrasts werden demonstriert. Mit Hilfe einer phasen-sensitiven, Selbst-homodyn-Frequenzverdopplungs-s-SNOM-Abbildungsmethode kann die Oberflächen-Struktur der intrinsischen 180-Domänen im hexagonal multiferroischen YMnO aufgelöst werden. / This thesis describes the implementation of scattering-type near-field optical microscopy (s-SNOM) for linear and nonlinear optical imaging. The technique allows for optical spectroscopy with ultrahigh spatial resolution. New results on the microscopic understanding of the imaging mechanism and the employment of s-SNOM for structure determination at solid surfaces are presented. The method relies on the use of metallic probe tips with apex radii of only few nanometers. The local-field enhancement and its dependence on material properties are investigated. The plasmonic character of Au tips is identified and its importance for the optical tip-sample coupling and subsequent near-field confinement are discussed. The experimental results offer valuable criteria in terms of tip-material and structural parameters for the choice of suitable tips required in s-SNOM. An near-field optical microscope is developed for tip-enhanced Raman spectroscopy (TERS) studies. The principles of TERS and the role of the tip plasmonic behavior together with clear distinction of near-field Raman signature from far-field imaging artifacts are described. TERS results of monolayer and submonolayer molecular coverage on smooth Au surfaces are presented. Second harmonic generation (SHG) from individual tips is investigated. As a partially asymmetric nanostructure, the tip allows for the clear distinction of local surface and nonlocal bulk contributions to the nonlinear polarization and the analysis of their polarization and emission selection rules. Tip-enhanced SH microscopy and dielectric contrast imaging with high spatial resolution are demonstrated. SHG couples directly to the ferroelectric ordering in materials and in combination with scanning probe microscopy can give access to the morphology of mesoscopic ferroelectric domains. Using a phase sensitive self-homodyne SHG s-SNOM imaging method, the surface topology of 180 intrinsic domains in hexagonal multiferroic YMnO is resolved.
65

Synthesis And Investigation Of Transition Metal Oxides Towards Realization Of Novel Materials Properties

Ramesha, K 07 1900 (has links)
Transition metal compounds, especially the oxides, containing dn (0 ≤ n ≤ 10) electronic configuration, constitute the backbone of solid state/materials chemistry aimed at realization of novel materials properties of technological importance. Some of the significant materials properties of current interest are spin-polarized metallic ferromagnetism, negative thermal expansion, second harmonic nonlinear optical (NLO) susceptibility, fast ionic and mixed electronic/ionic conductivity for application in solid state batteries, and last but not the least, high-temperature superconductivity. Typical examples for each one of these properties could be found among transition metal oxides. Thus, alkaline-earth metal (A) substituted rare-earth (Ln) manganites, Lnı.xAxMnΟ3, are currently important examples for spin-polarized magnetotransport, ZrV2O7 and ZrW2O8 for negative thermal expansion coefficient, KTiOPO4 and LiNbO3 for second harmonic NLO susceptibility, (Li, La) TiO3 and LiMn2O4 for fast-ionic and mixed electronic/ionic conductivity respectively, and the whole host of cuprates typified by YBa2Cu3O7 for high Tc superconductivity. Solid state chemists constantly endeavour to obtain structure-property relations of solids so as to be able to design better materials towards desired properties. Synthesis coupled with characterization of structure and measurement of relevant properties is a common strategy that chemists adopt for this task. The work described in this thesis is based on such a broad-based chemists' approach towards understanding and realization of novel materials properties among the family of metal oxides. A search for metallic ferro/ferrimagnetism among the transition metal perovskite oxides, metallicity and possibility of superconductivity among transition-metal substituted cuprates and second order NLO susceptibility among metal oxides containing d° cations such as Ti(IV), V(V) and Nb(V) - constitute the main focus of the present thesis. New synthetic strategies that combine the conventional ceramic approach with the chemistry-based 'soft1 methods have been employed wherever possible to prepare the materials. The structures and electronic properties of the new materials have been probed by state-of-the art techniques that include powder X-ray diffraction (XRD) together with Rietveld refinement, electron diffraction, thermogravimetry, measurement of magnetic susceptibility (including magnetoresistance), Mossbauer spectroscopy and SHG response (towards 1064 nm laser radiation), besides conventional analytical techniques for determination of chemical compositions. Some of the highlights of the present thesis are: (i) synthesis of new mixed valent [Mn(III)/Mn(IV)] perovskite-type manganites, ALaMn2O6-y (A = K, Rb) and ALaBMn3O9_y (A = Na, K; B = Ca, Sr) that exhibit ferromagnetism and magnetoresistance; (ii) investigation of a variety of ferrimagnetic double-perovskites that include ALaMnRuO6 (A = Ca, Sr, Ba) and ALaFeVO6 (A = Ca, Sr) and A2FeReO6 (A = Ca, Sr, Ba) providing new insights into the occurrence of metallic and nonmetallic ferrimagnetic behaviour among this family of oxides; (iii) synthesis of new K2NiF4-type oxides, La2-2xSr2XCui.xMxO4 (M = Ti, Mn, Fe, Ru) and investigation of Cu-O-M interaction in two dimension and (iv) identification of the structural rnotif(s) that gives rise to efficient second order NLO optical (SHG) response among d° oxides containing Ti(IV), V(V), Nb(V) etc., and synthesis of a new SHG material, Ba2-xVOSi2O7 having the fresnoite structure. The thesis consists of five chapters and an appendix, describing the results of the investigations carried out by the candidate. A brief introduction to transition metaloxides, perovskite oxides in particular, is presented in Chapter 1. Attention is focused on the structure and properties of these materials. Chapter 2 describes the synthesis and investigation of two series of anion-deficient perovskite oxides, ALaMn2O6-y (A = K, Rb, Cs) and ALaBMn3O9_y (A = Na, K; B = Ca, Sr). ALaMn2O6-y (A = K, Rb, Cs) series of oxides adopt 2 ap x 2 ap superstructure for K and Rb phases and √2 av x √2 ap x 2 ap superstructure (ap = perovskite subcell) for the Cs phase. Among ALaBMn3O9-y phases, the A = Na members adopt a new kind of perovskite superstructure, ap x 3 ap, while the A = K phases do not reveal an obvious superstructure of the perovskite. All these oxides are ferromagnetic (Tc ~ 260-325 K) and metallic exhibiting a giant magnetoresistance behaviour similar to alkaline earth metal substituted lanthanum manganites, Lai_xAxMnO3. However, unlike the latter, the resistivity peak temperature Tp for all the anion-deficient manganites is significantly lower than Tc. In Chapter 3, we have investigated structure and electronic properties of double-perovskite oxides, A2FeReO6 (A = Ca, Sr and Ba). The A = Sr, Ba phases are cubic (Fm3m) and metallic, while the A = Ca phase is monoclinic (P2yn) and nonmetallic. All the three oxides are ferrimagnetic with Tcs 315-385 K as reported earlier. A = Sr, Ba phases show a negative magnetoresistance (MR) (10-25 % at 5 T), while the Ca member does not show an MR effect. 57Fe Mossbauer spectroscopy shows that iron is present in the high-spin Fe3+ (S = 5/2) state in Ca compound, while it occurs in an intermediate state between high-spin Fe2+ and Fe3+ in the Ba compound. Monoclinic distortion and high covalency of Ca-O bonds appear to freeze the oxidation states at Fe+3/Re5+ in Ca2FeRe O6, while the symmetric structure and ionic Ba-O bonds render the FeReO6 array highly covalent and Ba2FeReO6 metallic. Mossbauer data for Sr2FeReO6 shows that the valence state of iron in this compound is intermediate between that in Ba and Ca compounds. It is likely that Sr2FeReO6 which lies at the boundary between metallic and insulating states is metastable, phase-seperating into a percolating mixture of different electronic states at the microscopic level. In an effort to understand the occurrence of metallicity and ferrimagnetism among double perovskites, we have synthesized several new members : ALaMnFeO6 (A = Ca, Sr, Ba), ALaMnRuO6 (A = Ca, Sr, Ba) and ALaVFeO6 (A = Ca, Sr) (Chapter 3). Electron diffraction reveals an ordering of Mn and Ru in ALaMnRuO6 showing a doubling of the primitive cubic perovskite cell, while ALaVFeO6 do not show an ordering. ALaMnRuOs are ferrimagnetic (Tcs ~ 200-250 K) semiconductors, but ALaVFeO6 oxides do not show a long range magnetic ordering . The present work together with the previous work on double perovskites shows that only a very few of them exhibit both metallicity and ferrimagnetism, although several of them are ferrimagnetic. For example, among the series Ba2MReO6 (M = Mn, Fe, Co, Ni), only the M = Fe oxide is both metallic and ferrimagnetic, while M = Mn and Ni oxides are ferrimagnetic semiconductors. Similarly, A2CrMoO6 (A = Ca, Sr), A2CrRe06 (A = Ca, Sr), and ALaMnRuO6 (A = Ca, Sr, Ba) are all ferrimagnetic but not metallic. While ferrimagnetism of double perovskites arise from an antiferromagnetic coupling of B and B' spins through the B-O-B' bridges, the occurrence of metallicity seems to require precise matching of the energies of d-states of B and B' cations and a high covalency in the BB'O6 array that allows a facile electron-transfer between B and B', Bn++B’m+↔B(n+1)++B’(m-1)+ without an energy cost, just as occurs in ReO3 and other metallic ABO3 perovskites. In an effort to understand the Cu-O-M (M = Ti, Mn, Fe, Ru) electronic interaction in two dimension, we have investigated K2N1F4 oxides of the general formula La2-2xSr2XCui.xMxO4 (M = Ti, Mn, Fe or Ru). These investigations are described in Chapter 4. For M = Ti, only the x = 0.5 member could be prepared, while for M = Mn and Fe, the composition range is 0 < x < 1.0, and for M = Ru, the composition range is 0 < x ≤ 0.5. There is no evidence for ordering of Cu(II) and M(IV) in the x = 0.5 members. While the members of the M = Ti, Mn and Ru series are semiconducting/insulating, the members of the M = Fe series are metallic, showing a broad metal-semiconductor transition around 100 K for 0 < x ≤ 0.15 that is possibly related to a Cu(II)-O-Fe(IV) < > Cu(III)-O-Fe(III) valence degeneracy. Increasing the strontium content at the expense of lanthanum in La2-2xSr2XCui.xFexO4 for x ≤ 0.20 renders the samples metallic but not superconducting. In a search for inorganic oxide materials showing second order nonlinear optical (NLO) susceptibility, we have investigated several borates, silicates and phosphates containing /ram-connected MO6 octahedral chains or MO5 square-pyramids, where M = d°: Ti(IV), Nb(V) or Ta(V). Our investigations, which are described in Chapter 5, have identified two new NLO structures: batisite, Na2Ba(TiO)2Si4O12, containing trans-connectd TiO6 octahedral chains, and fresnoite, Ba2TiOSi2O7, containing square-pyramidal T1O5. Investigation of two other materials containing square-pyramidal TiO5, viz., Cs2TiOP2O7 and Na4Ti2Si8O22. 4H2O, revealed that isolated TiO5 square-pyramids alone do not cause a second harmonic generation (SHG) response; rather, the orientation of T1O5 units to produce -Ti-O-Ti-O- chains with alternating long and short Ti-0 distances in the fresnoite structure is most likely the origin of a strong SHG response in fresnoite. Indeed, we have been able to prepare a new fresnoite type oxide, Ba2.xVOSi2O7 (x ~ 0.5) that shows a strong SHG response, confirming this hypothesis. In the Appendix, we have described three synthetic strategies that enabled us to prepare magnetic and NLO materials. We have shown that the reaction CrO3 + 2 NH4X > CrO2 + 2 NH3 + H2O + X2 (X = Br, I), which occurs quantitatively at 120-150 °C, provides a convenient method for the synthesis of CrO2. Unlike conventional methods, the method described here does not require the use of high pressure for the synthesis of this technologically important material. For the synthesis of magnetic double perovskites, we have developed a method that involves reaction of basic alkali metal carbonates with the acidic oxides (e.g. Re2O7) first, followed by reaction of this precursor oxide with the required transition metal/transition metal oxide (e.g. Fe/Fe2O3). By this method we have successfully prepared single-phase perovskite oxides, A2FeReO6, ACrMoO6 and ALaFeVO6. We have prepared the new NLO material Ba2_xV0Si207 from Ba2VOSi2O7 by a soft chemical redox reaction involving the oxidation of V(IV) to V(V) using Br2 in CH3CN/CHCI3. Ba2V0Si207 + 1/2 Br2 > Bai.5V0Si207 + 1/2 BaBr2. The work presented in this thesis was carried out by the candidate as part of the Ph.D. training programme. He hopes that the studies reported here will constitute a worthwhile contribution to the solid state chemistry of transition metal oxides and related materials.
66

Développement de sources lasers solides innovantes pompées longitudinalement par diodes laser continues ou quasi-continues. Applications à la LIBS portable et au marquage par laser / Development of innovative solid state lasers end-pumped by continuous or quasi-continuous laser diodes. Application to portable LIBS and laser marking

Claudon, Michaël 16 October 2013 (has links)
Ce mémoire présente des travaux portant sur le développement de trois sources lasers pompées longitudinalement par diodes laser et déclenchées activement par modulateur électro-optique pour deux applications spécifiques : la LIBS et le marquage par laser. Ces travaux ont été réalisés en collaboration avec deux sociétés : Bertin Technologies et SDAE.Le premier chapitre de ce manuscrit présente le développement d’une nouvelle source laser compacte, réalisée pour la société Bertin Technologies dans le cadre d’un projet de tri de matériaux plastiques par analyse spectroscopique de plasma induit par laser (LIBS). Cette technique d’analyse ponctuelle ainsi que le contexte spécifique du projet sont détaillés dans la première partie de ce chapitre. Ensuite, les différentes étapes de recherche et de développement qui ont permis d’aboutir à cette nouvelle source laser innovante, compacte et de hautes performances seront décrites en détail. Le second chapitre présente le développement de deux sources lasers pour le marquage industriel réalisées en partenariat avec la société SDAE. Après avoir présenté les principes et techniques généraux de l’application marquage ainsi que les contraintes spécifiques au projet, les deux sources lasers développées seront décrites. Des tests de LIBS et de marquage ont été réalisés grâce aux lasers développés / This thesis deals with the development of three lasers end-pumped by laser diode and actively Q-Switched by electro-optic Pockels cells for two specific applications: Laser Induced Breakdown Spectroscopy (LIBS) and marking. This work was done in collaboration with two companies: Bertin Technologies and SDAE.In the first part, we present the development of a new compact laser source, made for Bertin Technologies as part of sorting of plastics waste by LIBS. This analysis technique and the specific context of the project will be detailed in the first part of this chapter. Then, the different steps of research and development which have resulted in this innovative, compact and high performance new laser are described in detail. The second part is devoted to the development of lasers for industrial marking accomplished in partnership with SDAE. More precisely, the general principles and techniques of laser marking are described as well as the specific constraints of this project. LIBS and laser marking tests will be done with these lasers
67

Community empowerment and sustainable livelihoods : transforming social capital into entrepreneurship in rural Southern Ethiopia

Tefera Talore Abiche 11 1900 (has links)
The past decades witnessed that neither the private sector nor the government could provide an adequate socio-economic safety net for the poorest of the poor in the Third World. The community-based self-help approaches were hence widely used as alternative means to help the poor and marginalised to cope with livelihood shocks. This study examined the extent to which indigenous iddirs (local neighbourhood associations) and the externally-funded self-help groups (SHGs) could transform social capital into entrepreneurship thereby enhancing sustainable livelihoods. The study was conducted in three Southern Nation and Nationalities and People’s Region (SNNPR) rural districts, namely, Shebedeno, Wonago and Humbo. Mixed (quantitative and qualitative) methods were used to collect field data. Accordingly, closed and openended questionnaires and interview schedules were developed in English and then translated into Amharic (the national language). Instruments were field tested for validity and thereafter adjusted. A total of 220 (166 male and 54 female) people participated in the study. Data were entered into an Statistical Package for the Social Sciences (SPSS) database, and analysed by using basic descriptive statistics. Qualitative data were transcribed and analysed using Microsoft Office tools. The findings indicate that the SHGs’ members were relatively better educated than the rest of the population and some of them used this opportunity to pursue employment in government and the private sector. With regard to poverty status, iddirs members were poorer than those of SHGs (15.5% of the iddirs members reported that they are destitute compared to others in the community, as opposed to 3.3% of SHGs members). The study reveals that the livelihoods of some members of iddirs and SHG (particularly the latter) improved as a result of their involvement in these institutions although, at this point, the impact is insignificant. With regard to socio-economic decision making, more SHG members were involved in participatory decision making. However, iddirs leaders were still the dominant decision makers. The SHG level of participatory decision making could be the result of capacity building efforts by the promoting organisation, particularly, the Ethiopian Kale Heywet Church (EKHC). The study also shows that some of the iddirs and SHGs members were involved in informal rural entrepreneurial activities. However, their involvement did not indicate the utilisation of micro loan taken from the iddirs and SHGs for business purposes (97% of the iddirs and SHGs respondents utilised microcredit loans for consumption and other related purposes). On the other hand, the empirical evidence reveals that the amount of loan that iddirs and SHGs respondents received was very small. The general practice is giving small loans particularly to SHG members with repayments expected to begin as quickly and frequently as possible. Transforming social capital into entrepreneurship requires a cooperative approach, i.e. the involvement of development actors so as to enhance communities’ endeavour to achieve their livelihood objectives. Despite the wide prevalence of social capital in Ethiopia, this study indicates that its effective utilisation in community empowerment and sustainable livelihoods remains a challenge. Social capital is found to have a limited role in social entrepreneurship development and promotion not because it does not have potential, but because of the limited role of promoting organisations. The study shows lack of strong linkage between iddirs and promoting organisation (NGOs and Government). The study thus underlines the need for improving network and links with iddirs and SHGs and promoting organisations so as to create an enabling environment for sustainable livelihoods in the three rural districts under scrutiny. / Development Studies / D. Litt. et Phil. (Development Studies)
68

Interfaces Liquides/Liquides Actives: Apport de l'Optique Non Linéaire et de la Tensiométrie.

Gassin, Pierre-Marie 21 June 2013 (has links) (PDF)
Dans le cadre de la séparation sélective pour le traitement et la valorisation des combustibles nucléaires usés, l'extraction liquide/liquide est largement utilisée au niveau industriel. Néanmoins, ce procédé est encore mal compris en ce qui concerne les phénomènes physico-chimiques qui se produisent à l'interface liquide/liquide. Ce travail porte sur la compréhension de la dynamique de l'interface liquide nanométrique durant le transfert d'une espèce entre une phase aqueuse et une phase organique. Deux techniques expérimentales ont principalement été utilisées: la mesure de tension interfaciale et l'optique non linéaire. Ce travail a également donné lieu au développement d'un modèle numérique de dynamique de transfert de phase prenant en compte à la fois des phénomènes de transport diffusif proche de l'interface et une cinétique chimique sur l'interface décrivant les processus d'adsorption/désorption. Des systèmes modèles constitués de molécules surfactantes et/ou chromophores et/ou complexantes ont été étudiés aux interfaces air/liquide et liquide/liquide. L'adsorption/désorption, l'agrégation en surface, la complexation d'ion à une interface liquide et la structuration des systèmes ont ainsi pu être étudiées tant d'un point de vue des états d'équilibre que de la dynamique. Enfin, ces études ont été appliquées à un système d'intérêt industriel utilisé dans le procédé de dépollution DIAMEX.
69

Untersuchungen zur Elektrokatalyse von Hochtemperatur-Polymerelektrolytmembran-Brennstoffzellen (HT-PEMFCs) / Electrocatalytic Investigations on High Temperature Polymer Electrolyte Membrane Fuel Cells (HT-PEMFCs)

Hofmann, Constanze 14 January 2010 (has links)
No description available.
70

Growth and Physical Properties of Biaxial Nonlinear Optical Crystals of Ascorbic Acid Family

Raghavendra Rao, K January 2014 (has links) (PDF)
Saccharides, a class of organic materials, are potential candidates for nonlinear optical applications. Ascorbic acid is a sugar acid and is classified as a monosaccharide. The molecule of ascorbic acid has two chiral centers and, therefore, four stereoisomers. Among them, two are naturally occurring compounds; L-ascorbic acid and D-isoascorbic acid. From these two acids various salts and other derivatives could be synthesized. In this thesis, four compounds of the ascorbic acid family were selected for detailed study based on their nonlinearity, chemical and physical stability and their crystallization characteristics. The thesis is organized into seven chapters. The first chapter covers the theoretical background of nonlinear optics, especially, second harmonic generation. Second chapter details the experimental techniques and methodology adopted. Chapter 3 discusses the crystal structure, growth, physical and nonlinear optical properties of Lithium Disoascorbate monohydrate (LDAM). Detailed analysis of refractive index measurements employing Brewsters angle method and determination of phase matching curves, effective nonlinear coefficient, walk off angle etc are given. In Chapter 4, investigations on Sodium D-isoascorbate monohydrate (NDAM) are presented. Detailed characterization of the crystals including thermal, optical, dielectric properties are carried out. Analyses of dielectric dispersion based on Cole-Cole equation are discussed. Comprehensive studies on laser damage of the crystals are discussed. Chapter 5 discusses the nonlinear optical properties of the monoclinic D-isoascorbic acid (DIA). Chapter 6 presents studies on the triclinic Lithium L-ascorbate dihydrate (LLA) crystals. The crystals exhibit intense non-collinear second harmonic rings as they possesses large birefringence coupled with high second order nonlinear coefficients. The SHG conversion efficiency of these crystals is 15 times that of KDP. In the final chapter, a comprehensive summary of the work carried out is presented along with scope for further investigations.

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