Die vorliegende Arbeit befasst sich mit neuartigen Kupfer(I)- und Ruthenium(II)-komplexen und deren Verwendung als CVD-/ALD-Precursoren. Die Synthese Lewis-Basen-stabilisierter Kupfer(I)-β-Diketonat- bzw. -Carboxylat-Komplexe des Typs [LnMX] (M = Cu(I), X = Acetylacetonat, Iminopentenolat, Carboxylat; L = Phosphan PR3, Phos-phit P(OR)3; R = einbindiger, organischer Rest) standen hierbei im Vordergrund. Verbin-dungen des Typs [(PR3)MX] dienten als Ausgangsverbindungen zur Darstellung einkerni-ger Komplexe mit σ Donorliganden. Durch die Wahl der Lewis-Base sowie des β-Diketonato- bzw. Carboxylato-Fragmentes war es möglich, Einfluss auf die Eigenschaften der erhaltenen Komplexe zu nehmen. Somit waren auch die Untersuchung der thermischen Eigenschaften sowie das Abscheideverhalten der Komplexe während der MOCVD zu ana-lysieren. Thermogravimetrische Untersuchungen bzw. MOCVD-Versuche liessen Rück-schlüsse auf die Eignung der Komplexe des Typs [(PR3)MX] zur Abscheidung elementa-ren Kupfers zu. Des Weiteren wurde die Eignung von Ruthenium-Komplexen des Typs RuX2 (X = substituierte Cyclopentadienyle, 2,4-Dimethylpentadienyl, 4-Methylpent-3-en-2-on-yl) zur Erzeugung von elementaren bzw. oxidierten Rutheniums während MOCVD-Versuchen untersucht. Vorhergehende thermische Untersuchungen an den synthetisierten Komplexen liessen erste Rückschlüsse auf deren Eigenschaften zu. Da der Dampfdruck der für CVD-Zwecke eingesetzten Precursoren besonders interessant ist, wurden diese für die verwendeten Ruthenium-Komplexe bestimmt und sowohl untereinander als auch mit Lite-raturwerten verglichen. Ausgewählte Ruthenium-Komplexe wurden zur Erzeugung metal-lischer oder oxidischer Schichten während MOCVD-Versuchen eingesetzt.

La formulation des lubrifiants utilisés dans l'automobile est complexe du fait du nombre important d'additifs mélangés aux huiles de base. Pour orienter le choix des formulateurs, il est non seulement nécessaire de connaître le mécanisme d'action de chaque additif mais aussi les interactions entre ces additifs. Pour mieux appréhender ces mécanismes, une démarche originale a été mise en place dans cette étude. Celle-ci consiste à simuler expérimentalement la lubrification en régime limite par la lubrification en phase gazeuse. Pour cela, des molécules de faible poids moléculaire modélisant les différents constituants d'un lubrifiant ont été introduites sous ultravide. Ce type d'expérience a pu être réalisé grâce au développement d'un nouveau Tribomètre à Environnement Contrôlé (TEC) connecté à un système d'analyse de surface. Cette technique permet de simplifier le système tribologique et d'étudier in situ les tribofilms formés en phase gazeuse par des analyses de surface (XPS/AES). Différentes molécules ont été étudiées : triméthylborate (TMB), triméthylphosphite (TMPi) et triméthylphosphate (TMPa) modélisant respectivement les additifs boratés et phosphorés des lubrifiants de transmission. Cette simulation expérimentale a pu être validée en comparant les résultats en phase gazeuse avec ceux obtenus en phase liquide. Des observations en microscopie optique et des analyses chimiques ont mis en évidence la formation de tribofilms. Les expériences réalisées en présence de TMB ont permis de confirmer les résultats de la littérature sur la formation d'un tribofilm non sacrificiel de borates de type « minéral ». Les expériences réalisées avec les molécules phosphorées ont permis de montrer la différence entre les phosphates et les phosphites, notamment la formation d'un composé de type phosphure de fer en présence de TMPi. Les analyses in situ sur les tribofilms obtenus en présence de TMPi ont permis de déterminer le mécanisme de formation du composé phosphure de fer. La réalisation de mélanges de gaz a permis également de mettre en avant les effets de synergie et d'antagonisme entre les additifs

Open-framework inorganic materials constitute an important area of study in materials chemistry, because of their potential applications in areas such as sorption and catalysis. After the discovery of nanoporous aluminium phosphates by Flanigen et al in 1982, there has been a tremendous growth in the area of porous solids. Most of them are based upon oxygen containing materials especially phosphates, and they exhibit fascinating architectures with unusual bonding and coordination environment. Besides metal phosphates and phosphites, inorganic-organic hybrids constitute an important family of open-framework structures. In this thesis, results of investigations of a variety of open-framework metal phosphates, metal phosphites, as well as a new family of phosphite-oxalates are presented. More importantly, studies directed towards the synthesis and understanding of the magnetic properties of various transition metal phosphates, phosphites, phosphite-oxalates and the upconversion behavior of uranium phosphites are discussed at length. In Chapter 1 of the thesis an overview of inorganic open-framework materials is presented. In Chapter 2 and 3, the synthesis, structure of open-framework zinc (Part A of both Chapters) and synthesis, structure and magnetic properties of open-framework iron (Part B of both Chapters) are presented. Some of these compounds show unusual structure and interesting properties. For example, two-dimensional iron phosphate exhibits ferrimagnetism whereas three-dimensional iron phosphate with SBU-6 and SBU-2 is antiferromagnetic. The three-dimensional iron phosphite exhibits small polarization at low field. In Chapter 4, we present a new family of organically templated hybrid materials synthesized by partially substituting the phosphite by the oxalate ion in manganese, iron and cobalt phosphites. These exhibit a wide range of structures in which the oxalates play an unusual dual role. Some of these compounds show interesting magnetic properties. For example, manganese phosphite-oxalate shows magnetic polarizations on application of high field at low temperatures and iron phosphite-oxalate exhibit ferromagnetism at very low temperature. While a large number of organically templated transition and main-group element phosphites have been synthesized, research on lanthanide and actinide phosphites has been rare. Most of the reported open-framework phosphate and phosphite compounds of uranium possess uranium in +6 oxidation state. The possibility of building open architectures of uranium phosphites has been explored in Chapter 5. The results have been rewarding and both layered and three-dimensional structures have been prepared. Two of them contain uranium in +4 state and exhibit upconversion behavior.

Made available in DSpace on 2016-08-12T19:15:23Z (GMT). No. of bitstreams: 1 Norma Danielle Silva Barreto ok.pdf: 1964752 bytes, checksum: f7fb43203346f0133b607e44e7c44b7c (MD5) Previous issue date: 2008-02-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Despite the high technology utilized in the melon crop at the Assú-Mossoró fruit producer area, state of Rio Grande do Norte, with respect to most of the nutrients, chiefly the micronutrients, the doses applied are the same as those utilized in regions of completely different edaphoclimatic characteristics, and most of the time defined by the supplier companies. Considering this fact, a study was aimed at to evaluate the response of the melon crop to foliar applied ferlizers containing fosfito and micronutrients. The experiment was carried out on a Red Latossolo Eutrophic soil, at Santa Júlia farm, municipality of Mossoró, utilizing a factorial scheme in randomized complete blocks design with four replications. The tratments were the combinations of fertilizers (Fosfitotal®, Fosfitototal Multielementos® and MicroUFERSA) and doses (0, 0.75, 1.5, 2.25 and 3.0 kg ha-1). The fertilizers were foliar applied prior to the beginning of flowering, through three sprayings at ten days interval. The traits evaluated were number, mean weight, and yield of marketable fruits (domestic and export markets), refuse and total, as well as pulp firmness and thickness, shape ratio, soluble solids content, titratable acidity, and laef nutrient content. Soluble solids content was higher in fruits of plants sprayed with Fosfitotal®, however the contents of P, Mg, Cu, Zn, and Fe decreased with increasing doses of the fertilizer. Plants that received the MicroUFERSA fertilizer had higher Mg, K, P,Cu, Mn, and Zn contents in leaves, which might have caused their higher yields. The highest net income was obtained with MicroUFERSA applied at the rate of 1.50 kg ha-1 / Apesar da alta tecnologia utilizada na cultura do melão, no que diz respeito à maioria dos nutrientes, principalmente micronutrientes, as doses aplicadas no pólo fruticultor Assú-Mossoró, estado do Rio Grande do Norte, são as mesmas utilizadas em regiões com características edafoclimáticas completamente diferentes, sendo muitas vezes definidas pelas empresas comercializadoras dos insumos. Em razão disso, foi conduzido um estudo para avaliar a utilização de fertilizantes foliares contendo fosfito e micronutrientes na cultura do melão. O experimento foi conduzido em solo Latossolo Vermelho Eutrófico, em área pertencente à fazenda Santa Júlia, município de Mossoró, utilizando-se um esquema fatorial em blocos completos casualizados com quatro repetições. Os tratamentos consistiram das combinações de fertilizantes (Fosfitotal®, Fosfitototal Multielementos® e MicroUFERSA) e doses (0; 0,75; 1,5; 2,25 e 3,0 kg ha 1). Os fertilizantes foram aplicados via foliar antes do florescimento, através de três pulverizações espaçadas de dez dias. As características avaliadas foram número, peso médio e produtividade de frutos comercializáveis (mercados interno e externo), refugos e totais, bem como firmeza e espessura de polpa, relação de formato, teor de sólidos solúveis, acidez titulável e teor de nutrientes nas folhas. O teor de sólidos solúveis foi maior nos frutos das plantas pulverizadas com Fosfitotal®, mas os teores de P, Mg, Cu, Zn e Fe diminuíram com o aumento das doses deste fertilizante. As plantas de melão submetidas à aplicação de MicroUFERSA apresentaram maiores teores de Mg, K, P, Cu, Mn e Zn, resultando em maiores produtividades. A maior renda líquida foi obtida com a dose 1,50 kg ha-1 de MicroUFERSA

Made available in DSpace on 2016-08-12T19:18:44Z (GMT). No. of bitstreams: 1 Norma Danielle Silva Barreto ok.pdf: 1964752 bytes, checksum: f7fb43203346f0133b607e44e7c44b7c (MD5) Previous issue date: 2008-02-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Despite the high technology utilized in the melon crop at the Assú-Mossoró fruit producer area, state of Rio Grande do Norte, with respect to most of the nutrients, chiefly the micronutrients, the doses applied are the same as those utilized in regions of completely different edaphoclimatic characteristics, and most of the time defined by the supplier companies. Considering this fact, a study was aimed at to evaluate the response of the melon crop to foliar applied ferlizers containing fosfito and micronutrients. The experiment was carried out on a Red Latossolo Eutrophic soil, at Santa Júlia farm, municipality of Mossoró, utilizing a factorial scheme in randomized complete blocks design with four replications. The tratments were the combinations of fertilizers (Fosfitotal®, Fosfitototal Multielementos® and MicroUFERSA) and doses (0, 0.75, 1.5, 2.25 and 3.0 kg ha-1). The fertilizers were foliar applied prior to the beginning of flowering, through three sprayings at ten days interval. The traits evaluated were number, mean weight, and yield of marketable fruits (domestic and export markets), refuse and total, as well as pulp firmness and thickness, shape ratio, soluble solids content, titratable acidity, and laef nutrient content. Soluble solids content was higher in fruits of plants sprayed with Fosfitotal®, however the contents of P, Mg, Cu, Zn, and Fe decreased with increasing doses of the fertilizer. Plants that received the MicroUFERSA fertilizer had higher Mg, K, P,Cu, Mn, and Zn contents in leaves, which might have caused their higher yields. The highest net income was obtained with MicroUFERSA applied at the rate of 1.50 kg ha-1 / Apesar da alta tecnologia utilizada na cultura do melão, no que diz respeito à maioria dos nutrientes, principalmente micronutrientes, as doses aplicadas no pólo fruticultor Assú-Mossoró, estado do Rio Grande do Norte, são as mesmas utilizadas em regiões com características edafoclimáticas completamente diferentes, sendo muitas vezes definidas pelas empresas comercializadoras dos insumos. Em razão disso, foi conduzido um estudo para avaliar a utilização de fertilizantes foliares contendo fosfito e micronutrientes na cultura do melão. O experimento foi conduzido em solo Latossolo Vermelho Eutrófico, em área pertencente à fazenda Santa Júlia, município de Mossoró, utilizando-se um esquema fatorial em blocos completos casualizados com quatro repetições. Os tratamentos consistiram das combinações de fertilizantes (Fosfitotal®, Fosfitototal Multielementos® e MicroUFERSA) e doses (0; 0,75; 1,5; 2,25 e 3,0 kg ha 1). Os fertilizantes foram aplicados via foliar antes do florescimento, através de três pulverizações espaçadas de dez dias. As características avaliadas foram número, peso médio e produtividade de frutos comercializáveis (mercados interno e externo), refugos e totais, bem como firmeza e espessura de polpa, relação de formato, teor de sólidos solúveis, acidez titulável e teor de nutrientes nas folhas. O teor de sólidos solúveis foi maior nos frutos das plantas pulverizadas com Fosfitotal®, mas os teores de P, Mg, Cu, Zn e Fe diminuíram com o aumento das doses deste fertilizante. As plantas de melão submetidas à aplicação de MicroUFERSA apresentaram maiores teores de Mg, K, P, Cu, Mn e Zn, resultando em maiores produtividades. A maior renda líquida foi obtida com a dose 1,50 kg ha-1 de MicroUFERSA

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The objectives of this work were divided in two experiments phases. In the first phase, it was studied the presence of trans-resveratrol in temperate climate fruits and the variation of their concentration in these fruits during storage period, as well the amount of total phenols and total anthocyanins. It was evaluated total phenols, total anthocyanins and trans-resveratrol, before and after cold storage and under controlled atmosphere; and after five days shelf-life at 20°C in Bruno kiwifruit; Araza and Yvahe strawberries; Black mulberry; Galaxi , Gala and Fuji apples; persimmon Fuyu ; Bleugem blueberry, Isabel , Merlot and Niagara Pink grapes. It was detected trans-resveratrol in natura in flesh Bruno kiwifruit; Araza and Yvahe strawberries; Black mulberry. In other fruits, it was detected transresveratrol in natura in the skin. The cold storage stimulated trans-resveratrol synthesis in Bleugem blueberry, and Isabel and Merlot grapes. In the second phase, it was evaluated the induction of trans-resveratrol synthesis and its possible action as phytoalexin in Gala and Fuji apples stored in controlled atmosphere were evaluated. Experiments were with the application of abiotic elicitors: ultraviolet irradiation, phosphite and acibenzolar-S-methyl, applied before controlled atmosphere storage, and intermittent ozone applied during storage of to Gala and Fuji apples. Rot was controlled in another experiment with the same elicitors. In fruit bark it was analyzed trans-resveratrol; total phenols and total anthocyanins, as well as the diameter of injury after inoculation of Penicillium sp. The abiotic elicitors were induced in 'Fuji' apples trans-resveratrol synthesis in the following sequence: Acibenzolar-Smethyl > phosphite ³ UV-C irradiation ³ ozone, but it wasn t effective on 'Gala' apple. There was no correlation between the syntheses of trans-resveratrol and rotting control, with exception of phosphite was control of rot in 'Gala'. / Os objetivos deste trabalho foram alcançados em duas etapas. Na primeira etapa, o objetivo foi avaliar a presença de trans-resveratrol em frutos de clima temperado e a sua variação de concentração nesses frutos durante o período de armazenamento, assim como a evolução dos polifenóis totais e antocianinas totais. Avaliou-se o conteúdo de polifenóis totais, antocianinas totais e trans-resveratrol antes e após o armazenamento refrigerado e em atmosfera controlada, e após cinco dias de exposição a 20°C em kiwi Bruno , morangos Araza e Yvahe , amora (Morus nigra), maçãs Galaxi , Gala e Fuji , caqui Fuyu , mirtilo Bleugem , uvas Isabel , Merlot e Niágara Rosada . Detectou-se o trans-resveratrol in natura em polpa de kiwi Bruno , morangos Araza e Yvahe e amora Preta . Nos demais fruto, detectou-se in natura trans-resveratrol na casca. O armazenamento refrigerado estimulou a síntese de trans-resveratrol em mirtilo Bleugem , uvas Isabel e Merlot . Na segunda etapa, o objetivo foi avaliar a indução da síntese de trans-resveratrol e sua possível ação como fitoalexina em maçãs Gala e Fuji , armazenadas em atmosfera controlada. Realizaram-se experimentos com aplicação de elicitores abióticos: irradiação ultravioleta, fosfito e acibenzolar-S-metil, aplicados antes do armazenamento em atmosfera controlada, e ozônio aplicado de forma intermitente durante o armazenamento de maçãs Gala e Fuji . Realizou-se o controle de podridão em outro experimento com os mesmos elicitores. Na casca dos frutos analisaram-se trans-resveratrol, polifenóis totais e antocianinas totais, e o diâmetro de lesão após inoculação por Penicillium sp. Os elicitores abióticos induziram a síntese de trans-resveratrol em maçã Fuji na seguinte ordem: Acibenzolar-S-metil > Fosfito ³ irradiação UV-C ³ ozônio, mas não apresentaram efeito em maçãs Gala , durante o armazenamento em atmosfera controlada. Os elicitores abióticos não apresentaram efeito no controle de podridão, com exceção do fosfito que controlaram a podridão em maçã Gala . Não houve correlação entre a síntese de trans-resveratrol e o controle de podridão.

No description available.

New Jersey, Georgia, and the Eastern Shore of Virginia (ESV) are important snap bean (Phaseolus vulgaris L.) growing regions, but profitability is threatened by Pythium blight. Causal agents of Pythium blight on snap bean were identified using morphological characterization and sequence analysis of the rDNA-internal transcribed spacer (ITS) regions of 100 isolates. Most isolates were Pythium aphanidermatum (Edson) Fitzp. (53%), and also included Pythium deliense Meurs (31%; all from Georgia), Pythium ultimum Trow (12%), Pythium myriotylum Drechsler (2%), Pythium catenulatum Matthews (1%), and unknown Pythium sp. (1%). To our knowledge, this is the first report of P. deliense in Georgia and on common bean and squash (Cucurbita pepo L.); as well as the first report of P. catenulatum on lima bean (Phaseolus lunatus L.) and in New Jersey. Fungicide labeling and cultivar selection for Pythium blight management is hindered by difficulties associated with conducting successful trials, because the disease occurs sporadically and clustered in the field. Three P. aphanidermatum-infested inoculum substrates were evaluated at three concentrations. The vermiculite/V8 juice (5:3 weight to volume) inoculum (10,000 ppg/0.3 m) consistently caused at least 50% disease in 3 field trials. Sensitivity of the Pythium blight pathogens was determined in vitro against five fungicides. Twenty-two Pythium isolates representing P. aphanidermatum, P. deliense, P. ultimum, and P. myriotylum were inoculated to media amended with each active ingredient at 0, 100μg/ml, the concentration equivalent to the field labeled rate if applied on succulent beans at 187 L/ha, and the equivalent if applied at 374 L/ha. All isolates were completely sensitive (100% growth reduction, or GR) to all active ingredients at the labeled rates, except azoxystrobin. At 100μg/ml azoxystrobin, one P. deliense isolate had 8.9% GR. All isolates had 100% GR to copper hydroxide at 100μg/ml, and the lowest GR on mefenoxam-amended medium was 91.9%. At 100μg/ml cyazofamid, all P. deliense isolates were completely sensitive and variation was observed in P. aphanidermatum isolates. At 100μg/ml potassium phosphite, significant GR similarities were recorded within isolates of the same species, and less than 50% GR was observed in all P. deliense isolates. / Ph. D.

Nonlinear optics and ferroelectrics have been recognized for several decades as promising fields with important applications in the area of opto-electronics, photonics, memory devices, etc. High performance electro-optical switching elements for telecommunications and optical information processing are based on the material properties. Hence, there is always a continuous search for new and better materials. In this thesis we have investigated the growth and physical properties of four crystals viz. two NLO and two ferroelectric crystals. This thesis consists of eight chapters. The first chapter gives an overview of historical perspectives of nonlinear optical phenomenon, ferroelectricity and materials developed therein. The second chapter gives a brief description of the underlying theories of crystal growth, nonlinear optics and ferroelectricity. A major portion of this chapter consists of gist of the earlier work carried out on compounds of our interest viz. urea L-malic acid, sodium p-nitrophenolate dihydrate, glycine phosphite and lithium niobate. Synthesis, growth, crystal structure details and some physical properties of these materials are briefed. The third chapter describes the experimental techniques needed to grow as well as characterize these crystals. The experiments are performed on single crystals grown in the laboratory using the solution growth setup and Czochralski crystal puller. These growth units are described in detail. Preliminary characterization techniques like powder Xray diffraction, optical transmission, scanning electron microscopy, Vickers and Knoop hardness are described briefly. Various experimental methods viz. dielectric, polarization reversal, photoacoustic spectroscopy and laser induced damage for characterizing the grown crystals are explained. Urea L-malic acid (ULMA) is a new NLO organic material which is reported to exhibit second harmonic efficiency three times that of the widely used inorganic crystal, KDP. Hence, this material is selected for detailed investigation and the results obtained are discussed in chapter 4. This chapter contains details of single crystal growth and characterization of ULMA. The crystals are grown by slow cooling technique. The complete morphology of the crystal is evaluated using optical goniometry. The grown crystals are characterized for their optical and thermal properties. The defect content in the grown crystal is evaluated by chemical etching. As the surface damage of the crystal by high power lasers limits its performance in NLO applications, a detailed laser induced damage studies are performed on ULMA. Both single shot and multiple shot damage threshold values for 1064 nm and 532 nm laser radiation are determined and correlated with the mechanical hardness. In addition, the thermal diffusivity and thermal conductivity of ULMA along various crystallographic orientations are evaluated using laser induced photoacoustic spectroscopy and the results are interpreted in terms of crystal bonding environment. Another NLO crystal taken up for study is sodium p-nitrophenolate dihydrate (NPNa 2H2O), a semiorganic material. This crystal is a very efficient NLO material and has the advantages of both organics and inorganics. Earlier investigations on growth of NPNa.2H2O in various solvents have shown methanol as the most suitable solvent for growth. Growth from aqueous solution was discarded as it did not yield crystals which are stable. In the present investigation, stable, NLO active NPNa.2H2O crystals are obtained using aqueous solution itself by varying the crystallization conditions and exploring the suitable temperature range. The details of growth and characterization form the subject of fifth chapter. The grown crystals are characterized using optical transmission, XRD and thermo gravimetric analysis. Later, laser induced damage threshold is evaluated for both 1064 nm and 532 nm laser radiation and compared wit the methanol grown ones. A possible mechanism of damage is given. The sixth and seventh chapters deal with growth and characterization of ferroelectric materials namely glycine phosphite and lithium niobate respectively. Glycine phosphite is a low temperature ferroelectric crystal which is well studied in terms of its dielectric and ferroelectric properties. But very few radiation damage studies are reported. The effect of ionizing radiation on ferroelectrics is of considerable interest as it significantly modifies the physical properties of these materials. In the present investigation, effects of X-ray irradiation (_ = 1.5418 °A) on the lattice parameters, dielectric constant, loss tangent, polarization switching characteristics and domain dynamics of glycine phosphite are investigated. X-ray irradiation is performed in the non-polar phase of the sample. The effect as a function of duration of exposure is studied. X-ray irradiation in GPI has resulted in drastic reduction in _ values and shift in transition temperature towards lower temperatures. X-ray irradiation on polarization switching properties of the crystal are also investigated. The activation energy and threshold field of switching increase with the irradiation time. The behaviour of domain wall mobility is quite different from that exhibited by other well known ferroelectrics. These results are discussed in chapter 6 and a possible explanation for the unusual behaviour of domain wall mobility is given. The defect generated is identified as PO32− radical by electron paramagnetic measurement. Lithium niobate (LiNbO3) is an extensively studied material in terms of its NLO and ferroelectric properties. This material has high piezoelectric coupling coefficients along certain directions which makes it suitable for wide band surface acoustic wave applications. Hence there is a demand for good quality, single domain YZ-LiNbO3 substrates. Chapter 7 describes the growth of Z-pulled congruent LiNbO3 using Czochralski technique. Large single crystals of diameter 30 mm and length 80 mm are grown from congruent composition employing Czochralski technique. The grown crystals are multidomain and hence electric field poling is performed to get single domain crystals. Their subsequent characterization for SAW devices upto 200 MHz was performed and compared with the imported substrate. The general conclusions are given in chapter 8 along with possible future work that could be performed on these crystals.