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1
Mazzeo, Paolo Pio <1986>. "Crystal Engineering of bright luminescent copper iodide clusters with phosphorus and nitrogen-based ligands." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2014. http://amsdottorato.unibo.it/6389/1/TesiDottoratoMazzeo.pdf.
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Copper(I) halide clusters are recently considered as good candidate for optoelectronic devices such as OLEDs . Although the copper halide clusters, in particular copper iodide, are very well known since the beginning of the 20th century, only in the late ‘70s the interest on these compounds grew dramatically due their particular photophysical behaviour. These complexes are characterized by a dual triplet emission bands, named Cluster Centred (3CC) and Halogen-to-Ligand charge transfer (3XLCT), the intensities of which are strictly related with the temperature. The CC transition, due to the presence of a metallophylic interactions, is prevalent at ambient temperature while the XLCT transition, located preferentially on the ligand part, became more prominent at low temperature. Since these pioneering works, it was easy to understand the photophysical properties of this compounds became more interesting in solid-state respect to solution with an improvement in emission efficiency. In this work we aim to characterize in SS organocopper(I)iodide compounds to valuate the correlation between the molecular crystal structure and the photophysical properties. It is also considered to hike new strategies to synthesize CuI complexes from the wet reactions to the more green solvent free methods. The advantages in using these strategies are evident but, obtain a single crystal suitable for SCXRD analysis from these batches is quite impossible. The structure solution still remains the key point in this research so we tackle this problem solving the structure by X-ray powder diffraction data. When the sample was fully characterized we moved to design and development of the associated OLED-device. Since copper iodide complexes are often insoluble in organic solvents, the high vacuum deposition technique is preferred. A new non-conventional deposition process have also been proposed to avoid the low complex stability in this practice with an in-situ complex formation in a layer-by layer deposition route.
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Mazzeo, Paolo Pio <1986>. "Crystal Engineering of bright luminescent copper iodide clusters with phosphorus and nitrogen-based ligands." Doctoral thesis, Alma Mater Studiorum - Università di Bologna, 2014. http://amsdottorato.unibo.it/6389/.
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Copper(I) halide clusters are recently considered as good candidate for optoelectronic devices such as OLEDs . Although the copper halide clusters, in particular copper iodide, are very well known since the beginning of the 20th century, only in the late ‘70s the interest on these compounds grew dramatically due their particular photophysical behaviour. These complexes are characterized by a dual triplet emission bands, named Cluster Centred (3CC) and Halogen-to-Ligand charge transfer (3XLCT), the intensities of which are strictly related with the temperature. The CC transition, due to the presence of a metallophylic interactions, is prevalent at ambient temperature while the XLCT transition, located preferentially on the ligand part, became more prominent at low temperature. Since these pioneering works, it was easy to understand the photophysical properties of this compounds became more interesting in solid-state respect to solution with an improvement in emission efficiency. In this work we aim to characterize in SS organocopper(I)iodide compounds to valuate the correlation between the molecular crystal structure and the photophysical properties. It is also considered to hike new strategies to synthesize CuI complexes from the wet reactions to the more green solvent free methods. The advantages in using these strategies are evident but, obtain a single crystal suitable for SCXRD analysis from these batches is quite impossible. The structure solution still remains the key point in this research so we tackle this problem solving the structure by X-ray powder diffraction data. When the sample was fully characterized we moved to design and development of the associated OLED-device. Since copper iodide complexes are often insoluble in organic solvents, the high vacuum deposition technique is preferred. A new non-conventional deposition process have also been proposed to avoid the low complex stability in this practice with an in-situ complex formation in a layer-by layer deposition route.
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Gove, Lindsey. "Effects of biosolid application to agricultural land on the potential for transport of nutrients (N & P) and heavy contaminants (Cd, Cu, Pb & Zn) in soils." Thesis, Imperial College London, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.271314.
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Natheer, Adel Mohsin. "Interactions between vesicular-arbuscular mycorrhizal fungi, phosphorus, zinc and copper in some crops of semi-arid regions." Thesis, University of Leeds, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.278200.
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Hopkins, W. A. "Chemistry and applications in lubricating fluids of complexes of iron, copper and zinc with organo-phosphorus and sulphur ligands." Thesis, University of Reading, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.370119.
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Caniatto, Amanda Raquel de Miranda. "Minerais orgânicos e fitase como redutores do poder poluente de dejetos suínos." Universidade de São Paulo, 2011. http://www.teses.usp.br/teses/disponiveis/74/74131/tde-12052011-081909/.
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Este estudo teve como objetivo avaliar a utilização da enzima fitase e de minerais orgânicos (Cu e Zn) na dieta de suínos visando a redução do poder poluente dos dejetos. Foram utilizados 16 suínos com idade média de 68 dias, alocados na câmara climática, em gaiolas de metabolismo para coleta de fezes e urina. Os animais foram mantidos em duas faixas de temperaturas ambientais: conforto térmico e estresse térmico, e submetidos aos tratamentos: controle (T1); suplementação com minerais orgânicos (T2); suplementação com fitase (T3); suplementação com minerais orgânicos e fitase (T4). As fezes e a urina foram analisadas quanto à concentração de P, N, Na, K, Cu, Zn, Ca. Mensurou-se também temperatura retal e superficial dos animais, volume de fezes e urina excretadas, assim como o consumo de água e ração. Observou-se que o estresse térmico afetou a temperatura retal e superficial, além do volume de fezes excretadas (P<=0,05). A excreção de Zn e Ca foram reduzidas com a utilização da enzima fitase, enquanto que o Cu e Zn orgânicos beneficiaram o Zn, Ca e P (P<=0,05). O estresse térmico aumentou significativamente a excreção de Cu, enquanto a de Na foi reduzida (P<=0,05). Embora não tenha ocorrido interação na atuação da enzima fitase e dos minerais orgânicos, estes aditivos contribuíram com a redução da excreção de minerais.This study aimed to evaluate the use of phytase and organic minerals (Cu and Zn) in pig diets in order to reduce the power of polluting waste. Sixteen pigs at the age of 68 days, were allocated in metabolism studies cages for collection of feces and urine, in a climatic chamber. The animals were kept in two tracks of ambient temperatures: thermal comfort and heat stress, and subjected to the treatments: control (T1); organic minerals supplementation (T2); phytase supplementation (T3); organic minerals and phytase supplementation (T4). Feces and urine were analyzed for P, N, Na, K, Cu, Zn and Ca concentrations. It was also measured rectal temperature, body surface temperature, feces and urine volume and the food and water consumption. The results had shown that heat stress affected the rectal and superficial temperature, and excreted feces volume (P<=0,05). The Zn and Ca excretion were reduced with the phytase use, whereas organic Cu and Zn benefited Zn, Ca and P (P<=0,05). The heat stress significantly increased Cu excretion, while Na was reduced (P<=0,05). Although there was no interaction on the activity of phytase and organic minerals, these additives contributed to the excretion reduction of minerals.
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Koehorst, Robin Russell. "The influence of phosphorous, copper, zinc and arbuscular mycorrhiza on growth, photosynthetic processes and financial viability of artemisia afra grown in a simulated marginial soil of the Western Cape." Thesis, Cape Peninsula University of Technology, 2013. http://hdl.handle.net/20.500.11838/2025.
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Thesis (MTech (Horticulture))--Cape Peninsula University of Technology, 2013.This study evaluated the effects of supplementary phosphorus, copper and zinc alone and in conjunction with arbuscular mycorrhiza on Artemisia afra grown in a simulated soil medium. The treatments consisted two groups. Group A had no mycorrhizal inoculation and 1) no supplementary fertilization, 2) supplementary zinc application, 3) supplementary copper 4) supplementary phosphorus 5) supplementary zinc and copper, 6) supplementary zinc and phosphorus, 7) supplementary copper and phosphorus, 8) supplementary zinc, copper, and phosphorus. Group B had mycorrhizal inoculation in combination with 9) no supplementary fertilization, 10) supplementary zinc application, 11) supplementary copper 12) supplementary phosphorus 13) supplementary zinc and copper, 14) supplementary zinc and phosphorus, 15) supplementary copper and phosphorus, 16) supplementary zinc, copper, and phosphorus. There was also a pilot study into the pH range most suitable for the cultivation of A. afra in a hydroponic system, which was used to refine the mycorrhizal investigation, as pH has influences with regards to nutrient uptake of plants.
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Lawrence, Christophe L. "Effects of Feeding Phytase Enzyme and HAP Corn on Solubility of Phosphorus, Copper, and Zinc in Turkey Manure and Manure-Amended Soils." Thesis, Virginia Tech, 2000. http://hdl.handle.net/10919/33718.
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Manure from turkey poults on five diets were extracted both fresh (wet) and after drying. Soils amended with wet manure were also extracted. Phosphorus, Cu, and Zn were extracted with 0.01 M CaCl2 and acidic Mehlich III extractant (Zn in soil extracts was not evaluated). Dietary treatments were (1) normal phytic acid (NPA) corn and 0.135% inorganic P (NPA diet); (2) NPA corn, 600 units phytase enzyme, and 0.135% inorganic P (NPA+Phyt diet); (3) High available phosphorus (HAP) corn and 0.135% inorganic P (HAP diet); (4) HAP corn, 600 units phytase, and 0.135% inorganic P (HAP+Phyt diet); (5) NPA corn and 0.345% inorganic P (NPA+P diet). The NPA+P diet was similar to conventional diets being fed commercially. The NPA+Phyt diet was similar to alternative, phytase-amended diets being fed commercially.
Feeding the alternative NPA+Phyt, HAP, and HAP+Phyt diets instead of the NPA+P diet reduced total P in manures by 40%, but increased the percentage of total manure P extracted with 0.01 M CaCl2 from fresh excreta (P < 0.05). Soils amended with wet NPA+Phyt, HAP, and HAP+Phyt manures released 29 to 49% more water-soluble P than soils amended with NPA+P manure on an equal-P basis (P < 0.05). Feeding the NPA+Phyt diet instead of the NPA+P diet did not affect the percentage of total P manure extracted by Mehlich III from wet excreta, while feeding the HAP and HAP+Phyt diets increased the percentage of total manure P soluble in Mehlich III (P < 0.05). Soils amended with wet NPA+Phyt manure did not release more Mehlich III-extractable P than soils amended with NPA+P manure on an equal-P basis. Soils amended with wet HAP and HAP+Phyt manures released more Mehlich III-extractable P than soils amended with NPA+P manure on an equal-P basis (P < 0.05). Treatment-induced differences in extractability of manure and soil P appeared to be caused by a higher proportion of P in calcium phosphate form in the NPA+P manure. Drying manures prior to extraction generally heightened differences in solubility of P between the NPA+P and other manures.
Feeding the alternative NPA+Phyt, HAP, and HAP+Phyt diets instead of the NPA+P diet did not affect total Cu levels in manure or the percentage of total Cu extracted from manure with 0.01 M CaCl2. After soils were treated with manure on an equal-Cu and equal-N basis, soils amended with NPA+Phyt, HAP, and HAP+Phyt manures released more water-soluble Cu than NPA+P-amended soils (P < 0.05). Under P-based manure management, soils amended with the three alternative manures released 92 to 108% more water-soluble Cu than NPA+P-treated soils (P < 0.05). Extractable Cu increased so dramatically because conversion to the alternative diets boosted total manure loadings by 67%. Mehlich III extraction of soils amended with manure on an equal-N and -Cu basis indicated no effect of manure type on Cu availability.
Feeding the NPA+Phyt, HAP, and HAP+Phyt diets instead of the NPA+P diet did not affect total Zn levels in excreta, but caused at least a five-fold increase in the percentage of total manure Zn extracted by 0.01 M CaCl2 from fresh excreta (P < 0.05). Feeding the NPA+Phyt, HAP, and HAP+Phyt diets did not alter the percentage of total manure Zn extracted by Mehlich III from wet excreta.Master of Science
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Charlton, Alex. "Long-term impacts of zinc and copper on microbial biomass, phosphatase enzyme activities, and the mineralisation of organic phosphorus in sludge amended soils." Thesis, Cranfield University, 2015. http://dspace.lib.cranfield.ac.uk/handle/1826/12259.
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The agricultural demand for inorganic phosphate fertilisers needs to be reduced whilst the dependence on more sustainable sources of phosphorus, such as sewage sludge, is increased. However, the presence of heavy metals in sewage sludge pose a threat to soil microorganisms and can inhibit the action of phosphatase enzymes if present in high concentrations. The long-term impact of Zn and Cu on soil microorganisms and phosphatase enzyme activity was investigated at four field sites from the Defra ‘Long-Term Sludge Experiment’ in order to determine the overall impact on organic phosphorus mineralisation. Following the final applications of sludge in 1997, the total concentrations of Zn and Cu at each site were comparable to the UK statutory limits for sludge amended soils. Almost 20 years later 63-91 % of the applied metal loadings still remained and total concentrations of Zn and Cu were found to be significantly higher in contaminated soils, in comparison to untreated soil, and soils receiving uncontaminated sewage sludge. A significant correlation between exchangeable and total metal concentration could still be seen in soils contaminated with Zn, whereas the solubility of Cu was found to be very low (< 1 %); though a significant percent remained bound to soil organic matter. No long-term decrease in microbial biomass carbon (Cmic) could be detected in the contaminated soils at any of the sites. However analysis of ergosterol showed an increase in the proportion of microbial biomass carbon derived from fungi. Significant changes were also observed in the PLFA profiles of microbial communities within contaminated soils, indicating the microbial community has adapted and become tolerant to the heavy metal contamination. Combining results using meta-analysis indicated that Zn and Cu caused an increase in fungal biomass carbon of approximately 25-35 % in comparison to soil receiving uncontaminated sludge. Whereas overall decreases of 16 and 8 % were seen for Cmic in soils contaminated with Zn and Cu, respectively, indicating a loss of bacterial biomass from the contaminated soils. Hence, the current UK statutory limits may not be sufficient to prevent changes in soil microbial community and a reduction in the limits set for sludge amended soils is recommended in order to protect microbial diversity. No long-term decrease in the activity of phosphomonoesterase was detectable in the contaminated soils. However combining the results using meta-analysis indicated phosphomonoesterase activity per milligram of biomass carbon was greater in soils contaminated with Cu. This may be an indication that Cu is inhibiting extracellular phosphatase enzyme activity within the soil environment, though this remains undetermined. Orthophosphate, phosphomonoesters, and pyrophosphate were the predominant forms of phosphorus within the applied sludge treatments; a broad phosphodiester signal was also present. Overall, the greatest range of organic phosphorus forms was seen in the uncontaminated sewage sludge. However, no difference in the range of organic phosphorus compounds was observed between the untreated and sludge amended soils at the field sites investigated. It was therefore concluded that the organic phosphorus content of sludge amended soils is returning to that of untreated soil, with no long-term interference caused by the presence of Zn and Cu.
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Bissessar, Damien. "Synthèse de nouveaux composés phosphorés : vers de nouveaux additifs pour polymères et des complexes cuivreux luminescents innovants." Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAE029.
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Ce travail de thèse s’est inscrit dans le cadre d’un projet en relation étroite avec une industrie chimique. La problématique initiale concerne le développement de nouvelles molécules antioxydantes permettant de protéger les matériaux plastiques. Dans un premier temps, la stratégie envisagée s’appuie sur la synthèse de phosphines par hydrophosphination, réaction répondant aux principes de la chimie verte. La réaction est hautement régiosélective et la simplicité de la synthèse a permis d’obtenir de nombreuses nouvelles phosphines qui ont alors été testées pour leurs propriétés anti-oxydantes. Nous avons pu identifier plusieurs structures originales répondant au cahier des charges. Dans un second temps, nous avons étudié la faisabilité de développer de nouveaux additifs antioxydants secondaires à base de dérivés phénoliques, dont le cardanol qui est une molécule biosourcée. De nombreuses nouvelles molécules phosphorées ont été synthétisées, complètement caractérisées et évaluées pour leurs propriétés anti-oxydantes. Enfin, nous avons essayé de valoriser nos nouveaux composés pour d’autres applications. Les phosphines étant d’excellents ligands pour les métaux de transition, nous avons étudié la chimie de coordination avec le cuivre(I) en espérant former des complexes cuivreux luminescents. En effet, l’élaboration de diodes électroluminescentes stables reste un défi technologique malgré toutes les avancées actuelles. Dans ce contexte, de nombreux nouveaux complexes de type cubane ont été synthétisés et entièrement caractérisés. Ces complexes tétranucléaires sont des structures intéressantes, faciles à synthétiser, avec d’excellents rendements quantiques. Ces complexes présentent une stabilité élevée et des propriétés de luminescence qui en font de très bons candidats pour des dispositifs en optoélectroniqueThis thesis work was part of a project in collaboration with a chemical industry. The topic is the development of new antioxidant molecules to protect plastic materials. Initially, the strategy envisaged was based on the synthesis of phosphines by hydrophosphination, reaction in accordance with the green chemistry principles. The reaction is highly regioselective and the simplicity of the synthesis allowed us to obtain many new phosphines which were then tested for their antioxidant properties. We were able to identify several original structures that meet the requirements. In a second step, we studied the feasibility of developing new secondary antioxidant additives based on phenolic derivatives, including cardanol, which is a biosourced molecule. Many new phosphorus molecules have been synthesized, completely characterized and evaluated for their antioxidant properties. Finally, we tried to apply our new compounds for other applications. Since phosphines are excellent ligands for transition metals, we studied coordination chemistry with copper (I), hoping to form luminescent copper complexes. Indeed, the development of stable light-emitting diodes remains a technological challenge despite all the current advances. In this context, many new cubane-type complexes have been synthesized and fully characterized. These tetranuclear complexes are interesting structures, easy to synthesize, with excellent quantum yields. These complexes exhibit high stability and luminescence properties, which make them very good candidates for optoelectronic devices
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Wang, Chang-Sheng. "Selective catalytic C(sp²)–H and C(sp³)–H bond functionalizations for the synthesis of phosphorus and nitrogen containing molecules." Thesis, Rennes 1, 2018. http://www.theses.fr/2018REN1S106/document.
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Dans la thèse de doctorat, nous avons développé une approche efficace pour la modification rapide d'oxydes d'arylphosphines via la fonctionnalisation de liaisons C-H en position ortho du groupement P=O catalysée par le ruthénium (II) en présence des alcènes. Intéressement, l'ajustement du pH du milieu réactionnel permet de contrôler la sélectivité de la réaction à savoir alkylation or oléfination. La réduction des oxydes de phosphines fonctionnalisées permet la formation d'arylphosphines portant un carboxylate flexible. Dans le second objectif, un couplage C(sp3)–H /N-H oxydatif catalysé par le cuivre a permis l'alkylation d'hétérocycles à partir de (cyclo alcanes abordables. Ce protocole implique la formation de liaisons C (sp3)–N via une voie radicalaire générée par un clivage homolytique du peroxyde de di-tert-butyle et le piégeage du ou des radicaux par des catalyseurs au cuivre. Dans une troisième partie, nous avons utilisé ces processus radicalaires pour la fonctionnalisation le liassions C(sp3)–H benzylique d'oxyde de 2-alkylpyridines. Ces transformations impliquent un processus en cascade : estérification oxydative catalysée par le cuivre suivie d'un transfert d'atome d'oxygène. Enfin, des dérivés tosylés de pyridin-2-ylméthyl ont été obtenus avec des rendements élevés à partir des oxide de 2-alkylpyridines grâce à un réarrangement sigmatropic [3,3] du produit d'addition entre les oxides de 2-alkylpridine avec des chlorures de chlorure de benzènesulfonyles. De plus, les alkylnitrones subissent également ce réarrangement sigmatropique [3,3] pour donner des cétones α-tosylées après hydrolyseIn the first chapter, we have developed an efficient approach for the fast modification of arylphosphine oxides using ruthenium(II)-catalyzed C–H bond functionalization with alkenes. Interestingly, we have found that the selectivity of the reaction, namely alkylation versus alkenylation, is depending on the reaction pH. The reduction of the phosphine oxide allows the formation of aryl phosphines bearing a flexible pendent carboxylate. In the second objective, a copper-catalyzed oxidative C(sp3)–H/N–H coupling of NH-heterocycles with affordable (cyclo)alkanes was developed. This protocol involved C(sp3)–N bond formation via a radical pathway generated by a homolytic cleavage of di-tert-butyl peroxide and trapping of the radical(s) by copper catalyst.In a third part, benzylic C(sp3)–H acyloxylation of 2-alkylpyridine, 2-alkylpyrazine and 2-alkylthiazole compounds was achieved using simple aldehydes via a copper-catalyzed tandem reaction, involving oxidative esterification followed by O-atom transfer. Finally, pyridin-2-ylmethyl tosylate derivatives are obtained in high yields from 2-alkylpyridine N-oxides via a [3,3]-sigmatropic rearrangement of the adduct between 2-alkylpridine N-oxides with benzenesolfonyl chlorides. Moreover, alkylnitrones also underwant [3,3]-sigmatropic rearrangement to give α-tosylated ketones after hydrolysis
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ARAUJO, EDVAL G. de. "Efeito das adicoes de portadores de fosforo e da alumina na sinterizacao do aco rapido M2." reponame:Repositório Institucional do IPEN, 2000. http://repositorio.ipen.br:8080/xmlui/handle/123456789/10766.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
FAPESP:95/03947-9
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Serra, Gasa Alexandra. "Fate and effects of copper in fluvial ecosystems: the role of periphyton." Doctoral thesis, Universitat de Girona, 2009. http://hdl.handle.net/10803/7876.
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L'activitat humana és una de les majors causes d'elevades concentracions de nutrients i substàncies tòxiques en els ecosistemes fluvials. Entre la gran varietat de factors que alteren aquests ecosistemes, l'eutrofització i la contaminació per metalls pesants són dos dels principals problemes ambientals en països desenvolupats. Els biofilms fluvials (també anomenats comunitats perifítiques) representen una eina valuosa per avaluar els efectes dels contaminants (ex. nutrients i metalls) en els ecosistemes aquàtics. Aquest treball pretén investigar el destí i els efectes del Cu en els ecosistemes fluvials centrant-se en les comunitats perifítiques. Diferents metodologies han estat desenvolupades i/o adaptades per investigar específicament la dinàmica del Cu, la seva toxicitat i bioacumulació en comunitats perifítiques naturals, i la interacció entre l'eutrofització i la toxicitat del Cu en aquests ecosistemes.Human activity is one of the major causes of elevated concentrations of nutrients and toxic substances in fluvial ecosystems. Among the many ecosystem stressors, eutrophication and metal pollution are two of the major environmental problems in many developed countries. Fluvial biofilms (periphyton communities) are a useful tool for monitoring the effects of pollutants (e.g. nutrients and metals) into aquatic ecosytems. The present study aims to investigate the fate and effects of Cu in fluvial ecosystems focusing on periphyton communities. Different methodologies have been developed and/or adapted to specifically investigate the dynamics of Cu, its toxicity and bioaccumulation on natural periphyton communities, and the interaction between eutrophication and Cu toxicity in these ecosystems.
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Nordin, Andreas. "Heavy metal removal from sewage sludge by pyrolysis treatment." Thesis, Högskolan i Borås, Akademin för textil, teknik och ekonomi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:hb:diva-8807.
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Sewage sludge is the product from wastewater treatment that mostly is considered as a waste material. However, it contains several nutrients, especially phosphorus, potassium and nitrogen which are excellent fertilizers. The downside is the harmful content it also carries with pathogens, heavy metals and a variety of organic pollutants that in many cases have unknown effects on the ecosystem. A possible solution to this problem could be to pyrolyse the sewage sludge and by that decrease the levels of heavy metals and also render both pathogens and organic pollutants harmless. In this thesis project pyrolysis of dried sewage sludge has been evaluated at temperatures 650 750, 850 and 950 °C with addition of chlorine in the form of PVC and straw. An energy balance for pyrolysis and drying of dewatered sewage sludge has also been suggested. The results of the pyrolysis evaluation indicate that cadmium concentration can be reduced significantly with increasing temperature in the product char. But also other heavy metals like lead and zinc are affected at the higher temperatures evaluated. Mercury is completely removed from the char residue. The more latent volatile metals copper, chromium and nickel cannot be reduced to lower concentrations at these temperatures. They are instead enriched under these conditions. Chlorine addition to the sludge enhances the evaporation of all heavy metals but copper, nickel and chromium. The energy balance over the system indicates that the drying process requires more energy than is released from the sludge into the pyrolysis gases. The energy carried by the pyrolysis gases is however larger than what is required to drive the pyrolysis process.
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Souza, Imyra Maíra Martins de. "A influência do fósforo na toxicidade de cobre e composição bioquímica de Chlorella vulgaris." Universidade Federal de São Carlos, 2011. https://repositorio.ufscar.br/handle/ufscar/2048.
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Previous issue date: 2011-09-02Financiadora de Estudos e Projetos
Metal toxicity to microalgae is dependent on environmental conditions, evolutionary history of the microalgae, and previous exposure of the organism to the specific metal. Also, it is importantly influenced by the physiological condition of the algae in the moment of metal exposure. In this research we investigated several combinations of phosphorus (P) and copper (Cu) concentrations on the biochemical composition and Cu toxicity to Chlorella vulgaris. Due to its known toxicity, copper was considered in its free Cu2+ ions specie. Because microalgae physiology reflects the environmental conditions, but it also stores some of the inorganic nutrients, previous to Cu spike in the cultures, the algae were acclimated to each treatment s specific P concentration to be tested in combination with Cu. We considered cells were acclimated to a specific P concentration after its growth rate had been stabilized for at least four generations, always transferring the cells while in the beginning of the exponential growth phase. Biomass and physiological parameters analyzed were cell number (cell.mL-1), chlorophyll-a concentration, dry weight, lipid classes (Iatroscan TLC/FID), and total cellular proteins and carbohydrates at several combinations of P/Cu. The P concentrations tested were 5.0x10-5, 2.5x10-5, 5.0x10-6 and 1.0x10-6 mol.L-1 and the free Cu2+ ions concentrations ranged within 1x10-10 and 5x10-8 mol.L-1, and were determined through ion selective electrode (ISE). Our results showed that Cu toxicity to C. vulgaris increased at low P. Carbohydrate, protein and lipid productions were in general triggered at low P and high Cu, with some exceptions. TAG was the lipid class most affected by stressing situations. AMPL and PL were the lipid classes with the higher percent composition amog the classes; HC, WE and ST were present in minor amounts even under stressing situations.
As microalgas apresentam uma estreita relação com o meio circundante, sendo a parede e membrana celulares a via de entrada dos compostos dissolvidos. Mas, o modo como as algas interagem com os metais no ambiente, depende grandemente da especiação química do elemento. Portanto, a toxicidade de metais para microalgas relaciona-se, não somente com sua história evolutiva e condição fisiológica, mas também com a forma em que o metal é encontrado no ambiente. Nesta pesquisa, investigamos o efeito de diversas combinações de concentrações de fosfato (P) e cobre (Cu) na toxicidade do micronutriente e na composição bioquímica da microalga de água doce Chlorella vulgaris. O cobre foi analisado na forma iônica livre pois esta é uma das espécies de maior toxicidade para as algas. Antes da adição de cobre, a microalga foi aclimatada para a concentração de fosfato do respectivo tratamento experimental (P:Cu). As células foram consideradas aclimatadas para uma concentração específica de P após sua taxa de crescimento ter sido estabilizada por quatro gerações, sempre transferindo as células em fase inicial de crescimento exponencial. Para cada tratamento efetuado, os parâmetros de biomassa e fisiológicos analisados foram número de células por mL, concentração de clorofila-a, biomassa seca, classes lipídicas, através do equipamento (Iatroscan TLC/FID), proteínas e carboidratos celulares totais. As concentrações de P testadas foram 5,0x10-5, 2,5x10-5, 5,0x10-6 e 1,0x10-6 mol.L-1 e a amplitude de concentração de ions Cu2+ livres ficou entre 1x10-10 and 5x10-8 mol.L-1. Cobre livre foi determinados através de eletrodo seletivo ao íon (ISE) cobre. Nossos resultados mostraram que a toxicidade de Cu para C. vulgaris foi afetada pela concentração de fosfato no meio de cultura. Em baixas concentrações de fósforo, houve a maior toxicidade do Cu, aumento na produção de carboidratos e de lipídios. A análise das classes lipídicas revelaram que os hidrocarbonetos alifáticos (HC), ésteres de cera (WE) e esterol (ST) tiveram sua síntese ativada em concentrações tóxicas de Cu e de baixo fósforo. Similarmente, a síntese proteica aumentou sob essas condições, com a maior quantidade de síntese proteica obtida na menor concentração fósforo testada.
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Dharap, Y. V. "Facile synthesis of aziridines using copper hydrotalcite under microwave irradiation; synthesis of 3-substituted2(1h)-quinolinones catalyzed by hydrotalcite like anionic clays; rearrangement of α-pinene epoxide to campholenic aldehyde with modified beta zeolite catalyst and regioselective nitration of phenols with new phosphorus based ionic liquids." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2008. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/2633.
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Ballester, Jorge. "Nouvelles méthodes éco-compatibles : synthèse de molécules phosphorées par catalyse au cuivre ou réaction de Wittig. Application en réaction d'arylation de nucléophiles. : oxydation d'alcools catalysée par des métaux alcalins." Thesis, Montpellier, Ecole nationale supérieure de chimie, 2012. http://www.theses.fr/2012ENCM0019.
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Ce travail de thèse se divise en trois parties. Dans un premier temps, nous avons mis au point une nouvelle méthode simple et efficace de synthèse d'arylphosphonates, aryphosphinates et arylphosphines, faisant appel à un système catalytique au cuivre.Dans un second temps, nous nous sommes intéressés à la synthèse, à partir des sels de phosphonium correspondants, de diylures azotés ou carbonés du phosphore. A partir de ces derniers une méthode de synthèse de phosphines vinyliques ou butadiéniques, difficiles à obtenir par d'autres voies, a été mise au point. Ces phosphines se sont avérées être d'excellents ligands pour la réaction d'arylation de nucléophiles azotés catalysées au cuivre.Enfin, dans une dernière partie, nous avons développé un système catalytique d'oxydation d'alcools en cétones correspondantes à travers une réaction de type Oppenauer, en présence d'une quantité catalytique de base (NaOtBu). Cette découverte permet de s'affranchir des oxydants et métaux couramment utilisés dans les nombreux exemples décrits dans la littératureThis thesis is divided into three parts. At first, we developed a new simple and effective synthesis method of arylphosphonates, aryphosphinates and arylphosphines, using a new copper catalytic system. In a second step, we have been interested in the synthesis of phosphorus nitrogen and carbon diylids from their corresponding salts. From these, a method of synthesis of butadiene or vinyl phosphines, difficult to obtain by other methods described in the literature, has been developed. These phosphines were found to be excellent precursors for copper catalytic arylation reactions of nitrogen nucleophiles from halogenated aromatics.Finally, in a last part, we developed a catalytic system for oxidation of alcohols to their corresponding ketones through an Oppenauer type reaction in the presence of a catalytic amount of base (NaOtBu). This finding eliminates oxidants and metals commonly used in many examples described in the literature
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Stanley, Lori Hillman. "Influence of Phytase and High Available Phosphorous Corn Diets on Solubility and Plant Uptake of P, Cu, and Zn in Poultry Manure and Manure-Amended Soils." Thesis, Virginia Tech, 2001. http://hdl.handle.net/10919/31109.
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Poultry manure is a useful nutrient source but recently it has raised environmental concern due to possible P movement from P saturated soils to waterbodies. This study was conducted to determine the effects of using phytase and high available phosphorous corn diets on the solubility and plant uptake of P, Cu, and Zn in poultry manure and soils amended with manure. Five diet treatments were used in the study: 1) normal phytic acid corn and 0.135% inorganic P (NPA), 2) normal phytic acid corn, 600 units phytase, and 0.135% inorganic P (NPA+Phytase), 3) normal phytic acid corn and 0.345% inorganic P (NPA+P), 4) high available phosphorous corn and 0.135% inorganic P (HAP), 5) high available phosphorous corn, 600 units phytase, and 0.135% inorganic P (HAP+Phytase). The NPA+P diet and NPA+Phytase diets are most similar to the conventional and alternative phytase supplemented diets currently used commercially. Three Virginia soils (Groseclose, Cecil, Mahan) were amended with manure from the diet treatments at rates of 25 and 50 g/kg and P and Cu were extracted with 0.01 M CaCl2 and Mehlich III extractant after incubation periods of 6 and 12 months. Corn was grown in a greenhouse experiment using these same Virginia soils and sand amended with 8.96 Mg/ha poultry manure from each of the five diet treatments. Poultry manure was nonsequentially extracted for determination of P, Cu, and Zn fractions. Comparing the alternative NPA+Phytase, HAP, and HAP+Phytase treatments to the conventional NPA+P treatment on an N- (nitrogen) basis all reduced both CaCl2 and Mehlich III-soluble P concentrations (P<0.05). Comparing these same treatments on a P-basis increased P extracted with CaCl2 24, 26, and 37%, respectively, and P extracted with Mehlich III P 5, 4, and 9%, respectively (P<0.05). The alternative NPA+Phytase and HAP+Phytase treatments increased water-soluble Cu compared to the conventional NPA+P on both a N- and P-basis, while no differences were observed in Mehlich III solubility between these treatments (P<0.05). The alternative NPA+Phytase treatment did not differ in Pand Cu in corn tissue or plant uptake when compared to the NPA or NPA+P (N- or P-basis) treatments. No difference in Zn in corn tissue was observed between these treatments on a N-basis, while NPA+Phytase was higher on a P-basis. Plant uptake of Zn was higher in the NPA+Phytase treatment compared to the NPA+P treatment on both a N- and P-basis. Addition of phytase reduced P solubility from all reagents except for CaCl2 (P<0.05). Replacing the conventional NPA+P treatment for the alternative NPA+Phytase treatment resulted in higher Cu concentrations for all reagents except for K-pyrophosphate and nitric acid. This same replacement increased Zn extracted by water, CaCl2, and CaNO3, while it reduced Zn extracted by HCl, acetic acid, PbNO3, K-pyrophosphate, and NH4-oxalate in the light. The use of phytase decreased P solubility from manure amended soils when treatments are compared on an equal N-basis, and increased P solubility when compared on an equal P-basis. No effect on plant uptake of P or Cu occurredfrom the NPA+Phytase treatment.Master of Science
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Ou, Jun, and 欧军. "Asymmetric reactions induced by phase-tagged phosphoric acid organocatalysts and copper hydride-catalyzed reductions of unsaturatedthioesters." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2011. http://hub.hku.hk/bib/B47849708.
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Two syntheses of non-cross-linked polystyrene-supported TADDOL-based
phosphoric acid organocatalyst have been developed. The optimal polymer-supported
catalyst 2.29d exhibited comparable catalytic activity to its small molecule
counterpart in asymmetric Mannich-type reactions, and the syntheses of several chiral
β-amino esters were demonstrated using 2.29d as catalyst. However, when this
TADDOL-based phosphoric acid was immobilized on a polystyrene cross-linked with
1,4-bis(4-vinylphenoxy)butane, ie. JandaJelTM, the catalytic activity diminished in the
first recycling and reuse of the catalyst.
Building on the success of the immobilization of chiral phosphoric acid, a more
robust phase-tagged BINOL-based phosphoric acid organocatalyst was developed.
By taking advantage of a tetraarylphosphonium salt as a solubility-controlling group,
a widely-used BINOL-based phosphoric acid, TRIP (3.1), was introduced onto a
tetraphenylphosphonium salt to produce a phosphonium salt-tagged phosphoric acid
catalyst 3.3e. After systematic optimizations of reaction conditions, it was found that
the catalyst 3.3e with PF6
as counteranion exhibited the best performance in terms of
enantioselectivity. Catalyst 3.3e was proved to be highly effective in asymmetric
Friedel-Crafts reaction of indoles because it was shown to be recyclable and reusable
after six cycles without loss of catalytic activity.
Based on our previous studies on the reduction of unsaturated thioesters catalyzed
by (BDP)CuH, further investigation of ligand effects revealed that in addition to BDP,
dppf was also an effective ligand for the simple reduction of 5.8. In the
stoichiometric reduction of unsaturated thioester 5.8, dppe and dppf were both
efficient ligands for copper hydride that could convert 5.8 to aldehyde 5.18 in the
presence of TMSCl, without the formation of the undesired enol ester 5.17, which was
a major product when stoichiometric amounts of Stryker’s reagent was employed.
When 5.30 bearing both a saturated and unsaturated thioester was reduced under these
conditions, only the enethioate functional group underwent reaction to yield the
mono-reduced product 5.31 while the saturated thioester functional group remained
inert.
The desymmetrizing reductive aldol reactions of symmetrical keto-enethioates
6.19, 6.22, 6.24 and 6.26 catalyzed by in situ generated chiral copper hydride were
investigated. After a screening of the reaction conditions, TaniaPhos L8 was found to
be the most effective chiral ligand to achieve high ee and yields. Under the optimum
reaction condition (5 mol% Cu(OAc)-H2O and L8 with 2.0 eq. PhSiH3), a range of
keto-enethioates smoothly underwent desymmetrizing reductive aldol cyclizations,
offering bicyclic or polycyclic β-hydroxythioesters (6.28a-6.32a, 6.37a-6.47a) in 35-
84% yield and 30-97% ee with high diastereoselectivity. The addition of 5 mol% of
bipyridine as additive resulted in an accelerated reaction rate in all of the reductions of
keto-enethioates. The crystal structure of the L8-copper bromide complex allowed
the rationalization of the major enantiomer (eg. 6.48a), in which all of the substituents
are cis, to be a result of a reductively generated (Z)-thioester enolate reacting through
a Zimmerman-Traxler transition state.
This stereochemical outcome is in contrast to the reduction of the analogous
oxoesters, which yield trans β-hydroxyesters, (eg. 6.54b), as the major products.
Several proposals to explain the divergent stereochemistry, including the
predominance of a Zimmerman-Traxler transition state of (E)-enolates or subsequent
retroaldol rearrangements, were discussed. The retroaldol rearrangement has been
observed in the conversion of 6.48a to 6.57c, in which there was retention of the
configuration at C5 and a perfect conservation of enantiomeric purity.published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy
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MacNevin, David. "THE EFFECTS OF PHOSPHATE AND SILICATE INHIBITORS ON SURFACE ROUGHNESS AND COPPER RELEASE IN WATER DISTRIBUTION SYSTEMS." Doctoral diss., University of Central Florida, 2008. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/3713.
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The effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined cast iron, lined cast iron, and polyvinyl chloride was measured using pipe coupons exposed for three months. Roughness of each pipe coupon was measured with an optical surface profiler before and after exposure to inhibitors. For most materials, inhibitor did not have a significant effect on surface roughness; instead, the most significant factor determining the final surface roughness was the initial surface roughness. Coupons with low initial surface roughness tended to have an increase in surface roughness during exposure, and vice versa, implying that surface roughness tended to regress towards an average or equilibrium value. For unlined cast iron, increased alkalinity and increased temperature tended to correspond with increases in surface roughness. Unlined cast iron coupons receiving phosphate inhibitors were more likely to have a significant change in surface roughness, suggesting that phosphate inhibitors affect stability of iron pipe scales. Similar roughness data collected with new copper coupons showed that elevated orthophosphate, alkalinity, and temperature were all factors associated with increased copper surface roughness. The greatest increases in surface roughness were observed with copper coupons receiving phosphate inhibitors. Smaller increases were observed with copper coupons receiving silicate inhibitor or no inhibitor. With phosphate inhibitors, elevated temperature and alkalinity were associated with larger increases in surface roughness and blue-green copper (II) scales.. Otherwise a compact, dull red copper (I) scale was observed. These data suggest that phosphate inhibitor addition corresponds with changes in surface morphology, and surface composition, including the oxidation state of copper solids. The effects of corrosion inhibitors on copper surface chemistry and cuprosolvency were investigated. Most copper scales had X-ray photoelectron spectroscopy binding energies consistent with a mixture of Cu2O, CuO, Cu(OH)2, and other copper (II) salts. Orthophosphate and silica were detected on copper surfaces exposed to each inhibitor. All phosphate and silicate inhibitors reduced copper release relative to the no inhibitor treatments, keeping total copper below the 1.3 mg/L MCLG for all water quality blends. All three kinds of phosphate inhibitors, when added at 1 mg/L as P, corresponded with a 60% reduction in copper release relative to the no inhibitor control. On average, this percent reduction was consistent across varying water quality conditions in all four phases. Similarly when silicate inhibitor was added at 6 mg/L as SiO2, this corresponded with a 25-40% reduction in copper release relative to the no inhibitor control. Hence, on average, for the given inhibitors and doses, phosphate inhibitors provided more predictable control of copper release across changing water quality conditions. A plot of cupric ion concentration versus orthophosphate concentration showed a decrease in copper release consistent with mechanistic control by either cupric phosphate solubility or a diffusion limiting phosphate film. Thermodynamic models were developed to identify feasible controlling solids. For the no inhibitor treatment, Cu(OH)2 provided the closest prediction of copper release. With phosphate inhibitors both Cu(OH)2 and Cu(PO4)·2H2O models provided plausible predictions. Similarly, with silicate inhibitor, the Cu(OH)2 and CuSiO3·H2O models provided plausible predictions.Ph.D.
Department of Civil and Environmental Engineering
Engineering and Computer Science
Environmental Engineering PhD
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Rampazzi, Vincent. "Chimie de coordination du phosphore aux métaux du groupe 11 : progrès en catalyse de couplage C-N au Cu(I) et nouveaux complexes polyphosphines de l'Au(I)." Thesis, Dijon, 2014. http://www.theses.fr/2014DIJOS025/document.
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De nos jours et depuis quelques années maintenant, le principe de développement durable encourage les chimistes de tous horizons à développer de nouvelles méthodes de synthèse économiques et écologiques, les ressources naturelles de notre planète ne sont pas illimitées. Parmi les ressources les plus exploitées, nous trouvons le pétrole et le gaz. Outre ces derniers et le gaz, les métaux précieux sont également devenus indispensables.Cette thèse se concentre sur la valorisation de complexes de cuivre et d’or, obtenus à partir de ligands phosphorés synthétisés au sein du laboratoire. Dans un premier temps, nous verrons la mise au point d’une réaction de N-arylation de pyrazoles catalysée par un complexe de cuivre portant un ligand hybride phosphinoalcène. Dans un deuxième temps, les propriétés de coordination de l’or à différentes polyphosphines ferrocéniques seront étudiées. Plusieurs complexes innovants seront mis en évidence et pourront être utilisés dans le cadre de futures études de catalyse, ou de luminescenceNowadays, sustainable development encourages chemists to develop new economic and ecologic synthesis, because natural ressources are reducing. Most exploited ressources are gas and petroleum, but precious metals are also essential. This thesis is focusing on the enhancement of gold and copper complexes, obtained in our laboratory from phosphorous-based ligands. In the first part, we will develop a new system for the N-arylation of pyrazoles from a copper complexe coordinated by a new hybrid phosphinoalkene ligand. In the second part, coordination properties of gold to different ferrocenic polyphosphine will be studied. Several new innovative complexes will be isolated, and could be used in future catalytic or luminescent studies
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CARMO, LUCAS S. do. "Dosimetria termoluminescente de altas doses de raios gama, raios beta, feixe de prótons e de nêutrons epitérmicos utilizando minerais naturais de silicatos e dosímetros de LiF: Mg, Cu, P (MCP)." reponame:Repositório Institucional do IPEN, 2015. http://repositorio.ipen.br:8080/xmlui/handle/123456789/25192.
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Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-11-12T10:02:52Z
No. of bitstreams: 0Made available in DSpace on 2015-11-12T10:02:52Z (GMT). No. of bitstreams: 0
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
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Mereshchenko, Andrey S. "ULTRAFAST PHOTOCHEMISTRY OF POLYATOMIC MOLECULES CONTAINING LABILE HALOGEN ATOMS IN SOLUTION." Bowling Green State University / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1369774991.
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Safsaf, Abdelaziz. "Etude structurale par diffraction des rayons x d'un phosphonate et de quelques hydroxydiphosphonates." Paris 13, 1989. http://www.theses.fr/1989PA132001.
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Pour les acides phosphoniques, diphosphoniques et diphosphonates organiques acides, la corrélation entre la longueur p-oh et la distance oh. . . O est linéaire. Les molécules d'éthanédiphosphonate-1,1 (hydroxy-1 "0,0,0',o'"-tetramethyl) et les molécules dérivées, possedent une relative flexibilité (corrélation linéaire entre l'angle p-c-p et le décalage des deux groupes acides phosphoniques)
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Ghribi, Abdellaziz. "Utilisation des organocuivreux, associés ou non à un acide de lewis, en synthèse asymétrique et dans la préparation des beta-cétophosphonates." Nancy 1, 1986. http://www.theses.fr/1986NAN10059.
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L'action des organocuprates associés à BF::(3) sur des acétals chiraux constitue une voie très originale de synthèse des alcools secondaires optiquement actifs. Les dianons des acides diethylphono 2 alcoiques réagissent avec les aldéhydes par réaction de wittig-horner et conduisent très stéréosélectivement aux acides alpha éthyléniques trisubstitués. L'action des organocuprates sur les chlorures d'acide diethylphosphono-2 alcanoïques, constitue une voie de synthèse très générale des beta cétiogisogibates alpha substitués
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Huang, Ya-Ling, and 黃雅玲. "Effects of copper on phosphorus utilization in Ulva fasciata Delile (Ulvales, Chlorophyta)." Thesis, 2002. http://ndltd.ncl.edu.tw/handle/18093670863891850622.
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碩士國立中山大學
海洋生物研究所
90
The effects of copper on growth and phosphorus (P) utilization were investigated in the marine chlorophyte Ulva fasciata Delile. Both the daily specific growth rate and tissue P contents decreased as increasing CuSO4 concentrations, while the contents of total tissue, intracellular and cell-wall Cu increased. Based on the relationship between daily specific growth rate and external CuSO4 concentrations, the upper limit of U. fasciata is 100 uM CuSO4. After 4-day exposure to varying CuSO4 concentrations, Pi uptake was inhibited. Analysis of P fraction in U. fasciata exposed to 100 uM CuSO4 shows that the Cu-induced decline in total tissue P contents is mainly due to a decrease in both soluble reactive P (i.e. Pi). Exposure to 100 uM of Cu caused the accumulation of total tissue Cu contents to a plateau and then rose again at day 3, and tissue P contents and daily specific growth rate decreased at day 4. IC50 (concentration of 50 % inhibition) of daily specific growth rate and tissue P contents are 9.8 and 37.8 uM of Cu concentration in the medium, respectively, and 0.76 and 1.44 mg．g-1 DW for total tissue Cu contents, respectively. Overall, Cu causes Cu accumulation in intracellular space and cell wall and decrease of growth and P contents of U. fasciata partly via Pi uptake inhibition.
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Hsu, Kuo-chung, and 許國忠. "A Study of Phosphorus Diffusion into Ruthenium as A Copper Diffusion Barrier." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/15850519889256842757.
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碩士國立成功大學
微電子工程研究所碩博士班
95
Recently, as the device scaling down, in order to meet the Moore’s law, the study of Copper Diffusion Barrier material was widely investigated. The traditional Al process was replaced to Cu dual damascene process to solve RC delay issues. Unfortunately, even the copper provides lower resistivity, but many issues such as reaction with dielectric, high mobility and poor adhesion would result in reliability failure. Therefore, adding a diffusion barrier was a very critical factor to enhance the reliability performance. Many kinds of diffusion barriers were widely investigated the property of resistant to copper penetration such as Ta/TaN, WNx and Ru. The Ru owns lower bulk resistivity and excellent adhesion with copper layer could be a potential candidate as copper diffusion barrier. Moreover, the solubility between copper and Ru was very low leading to lower inter-diffusion each other. Especially, the Ru diffusion barrier could also replace the PVD copper seed layer and directly electroplated copper layer. But, the thickness of Ru diffusion barrier was less than 5nm, the thin film present crystalline phase leading to copper penetration. The crystalline structure consists of lots of grain boundary which provided fast through path and also could not resistant to copper diffusion. In this thesis, the impurities stuffy in grain boundary of Ru could block the copper diffusing into dielectric. The impurities stuffy could enhance the thermal property of copper diffusion barrier. We focused on P doping into Ru diffusion barrier to observe its copper blocking capability. The AES depth profiling shows phosphorous doping into Ru could improve the blocking copper penetration. The impurity such as phosphorous diffusion into Ru may be a good solution for improved Ru copper barrier.
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Chris and 陳沛承. "Patent analysis and literature review of phosphorus of flame retardant on copper clad laninates." Thesis, 2010. http://ndltd.ncl.edu.tw/handle/52357279404988060791.
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碩士長庚大學
化工與材料工程學系
98
Printed circuit boards are widely used in life, industries, under the EU laws and regulations of environmental protection issues and the need to develop environmentally friendly printed circuit board material. Printed circuit board material in which the composition of one of the copper base plate, early use of halogen-containing flame agent, but for manufacturers to develop environmentally friendly use of non-halogen flame agent. Phosphorus-containing epoxy resin present their own characteristics due to processing of good, less toxic, contain a small volume of phosphorus , smoke volume is low, easy-to-synthetic resins and other advantages over widely discussed and studied. This paper is based on literature reviews to find out the Department of Phosphorus - containing flame on the copper clad laminates application. there are to add type and reaction type can achieve its effect, with the patent search to understand the current phosphorus flame agent patent application, and analyze the development status of the relevant companies.
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HSIEH, TSUNGTA, and 謝宗達. "Properties of Phosphorus-Containing Poly(imide – siloxane) Hybrid Films Applied in Flexible Copper Clad Laminate." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/58449608285677008772.
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碩士國立勤益科技大學
化工與材料工程系
100
This study is divided into two parts. First, the phosphorus-containing diamine monomer (DMA), non-phosphorus-containing diamine monomer (ODA) and the flexible dianhydride monomer (IDPA) were selected to synthesize polyimide (PI) films containing various ratios of diamines. The PI film derived from 100% of DMA (10D) showed the characteristic absorption peak of phosphorus (P-O-Ph) at 914 cm-1 from the Fourier transform infrared (FTIR) spectra. Another observed peak at 1180 cm-1 belongs to the characteristic absorption peak of P-OH on polyphosphate indicating the generation of the polyphosphate on the PI surface.The depth profile of X-ray photoelectron spectra (XPS) in the phosphorus region also shows the polyphosphate P-OH on the surface with the binding energy at 132 eV. The phosphorus PI film (10D) has the highest storage modulus of 2445 MPa and the highest glass transition temperature (Tg) of 276 oC. The coefficient of thermal expansion (CTE) of 10D film is 48 ppm/oC, compared with66 ppm/oC for the PI film containing only ODA (10O). The 5% weight loss temperature (Td5) slightly decreases with the increasing proportion of phosphorus in PI matrix. The Td5 of 10D film is 430 oC. The optical transparency at 400 nm of PI films with the thickness of 25 μm increases with the phosphorus content. The transmission of 10D film is 70% and the dielectric constant of 10D film decreases to 2.7. The adhesion test of PI films with flexible copper foil(1oz ED copper) showed that the PI film containing 80% of DMA (8D2O) has the highest peel strength of 0.51 Kg/cm. The polarizing microscope was used to compare the amount of resin flow between copper and PI after adhesion test. The amount of resin flow significantly reduces as the phosphorus content increases in PI matrix. In the second part, the ODA in the 8D2O PI film was substituted by polydimethylsiloxane (PDMS) in order to further improve the adhesion strength. The diamine monomer ODA (1 to 8 wt%) in 8D2O film was substituted by PDMS, which has the diamine functional groups, to prepare the hybrid films (8D2O-Si-x%). The FT-IR spectra confirm the presence of Si-C (1260 cm-1, 800 cm-1) and Si-O (1080 cm-1, 1020 cm-1) characteristic absorption peaks in the hybrid films. The XPS results also show Si-C (102.3 eV) and Si-O (101.1eV) peaks indicating the successful blending of PDMS in PI. The mechanical strength of hybrid films decreased with the PDMS content because PDMS is a soft monomer. For 8D2O-Si-8% hybrid film, its storage modulus is 2135 MPa, Tg is 256 oC, CTE is 82 ppm/oC and Td5 is 435 oC. The optical transmission at 400 nm of this film is only 63%. PDMS forms discontinuous phases in PI andthus the light penetration is restricted. The silicon in PDMS increases the dielectric constant of the 8D2O-Si-1% film to 3.7. In contrast, the presence of PDMS can effectively reduce the moisture absorption. Hence, the dielectric constant of the 8D2O-Si-8% film further reduces to 3.0. , The peel strength of 8D2O-Si-8% film increases to 0.95 Kg/cm.The comparison of the resin flow conditions between 8D2O-Si-8% and pure-Si-8% again confirme that less amount of resin flow is achieved by the presence of phosphorus in PI.
30
Henderson, Lucas Benjamin. "Deposition and properties of Co- and Ru-based ultra-thin films." 2009. http://hdl.handle.net/2152/7836.
Full textAbstract:
Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165 °C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350 °C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis(trimethylphosphine)cobalt(0), yields cobalt-phosphorus films without any co-reactant. However, the molecule does not contain sufficient amounts of amorphizing agents to fully eliminate grain boundaries, and the resulting film is nanocrystalline.text
31
SHARMA, VIPIN KUMAR. "PERFORMANCE STUDIES OF TEXTURED JOURNAL BEARING." Thesis, 2019. http://dspace.dtu.ac.in:8080/jspui/handle/repository/17076.
Full textAbstract:
The conventional journal bearing material contains verying amounts of lead (Pb) in it.
Pb provides the anti-wear and anti-friction properties. However, Pb has hazardous effects on health and the environment and disposal of lead contained bearing and lubricant having lead particles from the bearing surface is an important issue which needs to be dealt with. Surface texturing of the bearing surface, the material of bearing surface, use of better lubricating conditions are some of the methods which could be utilized to reduce the wear and friction coefficient of the bearing material.
32
Lin, Jyun-Yen, and 林俊延. "Impacts of the Heavy Metals Copper Invasion on Enzymatic Kinetic Reaction in Biological Phosphorus Removal under Different Temperature Conditions." Thesis, 2009. http://ndltd.ncl.edu.tw/handle/48754861170060006403.
Full textAbstract:
碩士國立暨南國際大學
土木工程學系
97
The purpose of this study mainly investigated the effects of heavy metals copper invasion on phosphorus release/uptake, polyhydroxyalkanoates（PHAs）synthesis/ degradation, and intercellular enzymatic activity of Acetyl-CoA Synthetase and Polyphosphate Kinase of the activated sludge during the anaerobic/aerobic reactions under short-term temperature conditions. The efficiency of the activated sludge of B-SBR system which was acclimated until steady state basing on the condition of sludge retention time（SRT）10 days showed that the removal ratio of COD and PO43--P could be maintained above 90%. In order to realize the optimal operation in EBPR system when heavy metal invaded, this study focused on the mechanism of phosphate release/uptake, PHAs synthesis/degradation to investigate the effects of microorganism suffering from different copper concentrations (0～4 mgl-1) and temperatures (10℃~30℃）. Experimental results showed that under none added heavy metals, the specific substrate utilization rate, specific release/uptake phosphorus rates, PHAs synthesis / degradation rates, and enzymatic activity of Acetyl-CoA Synthetase and Polyphosphate Kinase significantly increased from 10℃ to 20℃ while none of heavy metal was adding; but there was no significant difference bewteen 20℃ and 30℃. In addition, specific substrate utilization rate, specific phosphorus uptake rate, PHAs synthesis/degradation rates, and enzymatic activity of Acetyl-CoA Synthetase and Polyphosphate Kinase were distinctly decreased while concentration of heavy metals increased. However, the addition of copper metal did not influence the mechanism of phosphorus release. This research also discovered two strong relationships between PHAs synthesis rate and enzymatic activity of Acetyl-CoA Synthetase, and between specific uptake phosphorus rate and Polyphosphate Kinase. It was illustrated that the inhibition of PHAs synthesis rate resulted from the temperature or toxicity effect on Acetyl-CoA Synthetase activity. Also, the phenomenon was similar to the relation between specific uptake phosphorus rate and Polyphosphate Kinase activity. In addition, applied of Lineweaver-Burk equation and coefficient of inhibition, it was demonstrated that the type of inhibition was mix-competitive inhibition, and the inhibitor mainly combined with free enzyme when the copper invaded. Thus, it could be known that the low temperature caused the metabolism in organism decreased; and the copper ions occupied the sites for combing enzyme. Besides, polyphosphate in intercellular could carry out the detoxification process when the inhibitor existed. It caused the phosphate continuously released even at aerobic stage. Consequently, this study proved that the mechanism of enhanced biological phosphate removal fluctuated easily by toxic inhibitors invasion.
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Soesanto, Meiyu, and 林美茹. "The Effects of Poultry Litter Biochar Application on the Availabilities of Phosphorus, Copper and Zinc in Paddy Soil and Rice Growth." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/25972323526403385850.
Full textAbstract:
碩士國立臺灣大學
農業化學研究所
104
The poultry industry generates many kinds of litters which can cause environmental problems. Direct land application of poultry litter made a risk of excessive phosphorus (P) releasing into surrounding water. On the other hand, rice straws are major agricultural wastes after harvested, the residual straws are often left in the field and burned. A potential approach to utilize this poultry litter and rice straw is to transform it into poultry litter biochar (PLB) and rice straw biochar (RS) through pyrolysis, which may provide an environmental and economic benefits. Application of RS biochar to soil can increase nutrients, which can efficiently reduce the need for basalt fertilizer. Some mineral elements especially P of poultry litter are significantly concentrated in the PLB and turn into potentially available slow release nutrient source for crops. However, the containing of heavy metal ions of PLB would also be concentrated through high temperature pyrolysisprocess. Moreover, the effects of PLB amendment on the soil as the fertilizer to the rice still remain unclear. Therefore, the purposes of this study in this research are (i) to investigate the effects of different additional dosage and the different pyrolysis temeperature on the growth of rice plants and (ii) to study the maximum PLBs dosage which would have no negative effect on the growth of rice plants and accumulation of heavy metals. Poultry litter and PLB obtained under different pyrolysis temperature (350oC and 550oC) and RS biochar obtained with traditional burning method were conducted physical and chemical analysis. Biochar were applied as nitrogen (N) and P fertilizer and as soil amendement (0.5, 1.0, 2.5, 5.0%). The experiment results show that higher pyrolysis temperature could increase total carbon but decrease hydrogen and oxygen. Decreasing index of H/C and (O+N)/C means that changes the structure of PLB. FTIR results showed increasing pyrolysis temperature will increase aromatic C signals. The dominance P speciation in PLBispyrophosphate in 31P-NMR spectrum. The experimental results suggested that the pH of biocahrrange from 8.29 – 10.89. The total P concentrations of in PLBs were increased by increasing pyrolysis temperature, although this concentration remain low in RS biochar. Compared to the control, the data of crop height, numbers of tillering, and dry weight of root, shoot, and rice were significantly increased by the biochar treatment and the optimaltreatment obtain at 350oC with dosage 2.5% but plant dead with 5% biochar application. The effects of PLB application as N and P fertilizer and RS biochar showed had no effects with plant growth, biomass productivity and plant P concentration compared to control and chemical fertilizer (CF) treatment. Biochar treatment cause a miner increases of the P, Cu, and Zn concentrations in plants. P availability in soil increased with increasing biochar dosage compared to control. Biochar obtained at 550oC have lower P availability compared to biochar obtained at 350oC. It explainthe reasonthat biochar treatment at 550oC had lower plant growth and biomass productivity than biochar obtain at 350oC. P, Cu, and Zn release to soil solution is very low and generally decreased during plant growth. The availability of Cu and Zn in soil increased with increasing dosages of biochar but the concentration is under safe conditions. It was concluded that PLB produced 350ºC are better to improve paddy rice growth and productivity.
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Wolff, Alexander. "Untersuchungen zur Aktivierung von elementarem Phosphor für die Synthese anorganischer Verbindungen in ionischen Flüssigkeiten." 2018. https://tud.qucosa.de/id/qucosa%3A32756.
Full textAbstract:
Die vorliegende Arbeit befasst sich mit der Synthese phosphorhaltiger anorganischer Verbindungen in ionischen Flüssigkeiten (engl. ionic liquids, ILs) und legt einen Schwerpunkt auf die Untersuchung der grundlegenden mechanistischen Abläufe, insbesondere auf die Aktivierung von elementarem Phosphor in ILs. Durch die Kombination spektroskopischer und theoretischer Methoden wurde ausführlich das chemische Verhalten von Phosphorhalogeniden in halogenidhaltigen ILs analysiert. Es konnte gezeigt werden, dass nach der Auflösung von rotem Phosphor mit Iod ein Gleichgewicht in der Lösung vorliegt, welches zu der Bildung von Tetrachlorophosphat führt. Insgesamt weist der beobachtete, dynamische Koordinationsprozess der Liganden Ähnlichkeiten zu einer strukturellen Diffusion bzw. Grotthuss-Diffusion auf. Diese Mischungen könnten somit potenziell als kostengünstige Elektrolyte verwendet werden. In weiteren Untersuchungen gelang es, aus Cu und rotem Phosphor in halogenidhaltigen ILs reproduzierbar und in hoher Reinheit Cu3−xP (x = 0,05) zu synthetisieren. Die Optimierung der Reaktion ermöglichte dabei Ausbeuten von über 99 %. Während der Reaktion kommt es zu einer IL-induzierten nukleophilen Aktivierung des roten Phosphors, wodurch hochreaktive P4-Moleküle gebildet werden. Durch die direkte Verwendung von P4 in ILs konnte nachfolgend erstmals kupferarmes Cu3−xP (0,1 < x < 0,7) gezielt synthetisiert werden, ohne das phosphorreiche Nebenprodukte gebildet wurden. Die elektrochemische Charakterisierung unterschiedlicher Cu3−xP-Phasen als Anodenmaterial in Lithium-Ionen-Akkumulatoren zeigte, dass sich das chemische Verhalten gegen Li mit der Zusammensetzung des Materials ändert. Da sich kupferarmes Cu3−xP durch eine höhere Kapazität und kupferreiches Material durch eine bessere Zykelnstabilität auszeichnet, erlauben die Ergebnisse dieser Arbeit die weitere Optimierungen dieses Materials für den Einsatz in Akkumulatoren.:1. Motivation und Einleitung 1
1.1. Klassische Flussmittel in der Materialsynthese 2
1.2. Ionische Flüssigkeiten 4
1.2.1. Struktur und Eigenschaften 4
1.2.2. Anwendung in der Synthese von anorganischen Materialien 6
1.3. Reaktionen mit elementarem Phosphor in ionischen Flüssigkeiten 8
1.3.1. Struktur und Eigenschaften der Phosphormodifikationen 8
1.3.2. Synthetische Verwendung in ionischer Flüssigkeit 10
1.4. Zielstellung der Arbeit 11
2. Allgemeiner experimenteller Teil 12
2.1. Schutzgasatmosphäre 12
2.2. Verwendeten Chemikalien 12
2.2.1. Anorganische Ausgangsverbindungen 12
2.2.2. Ionische Flüssigkeiten 13
2.2.3. Lösungsmittel 14
2.2.4. Präparationsvorschriften 14
2.3. Charakterisierungsmethoden 15
2.3.1. Röntgenpulverdiffraktometrie 15
2.3.2. Einkristall-Röntgenstrukturanalyse 15
2.3.3. Rasterelektronenmikroskopie 15
2.3.4. Energiedispersive Röntgenspektroskopie 16
2.3.5. Elementaranalyse 16
2.3.6. Kernspinresonanzspektroskopie 17
2.3.7. Raman-Spektroskopie 17
2.3.8. Röntgenabsorptionsspektroskopie 18
2.3.9. Elektronenspinresonanz-Spektroskopie 18
2.3.10. Elektrische Transportmessungen 18
2.3.11. Elektrochemische Charakterisierung 19
2.3.12. Wärmekapazitätsmessungen 20
2.3.13. Quantenchemische Berechnungen 20
3. Untersuchungen zur Bildung von Phosphorhalogeniden aus rotem Phosphor 22
3.1. Einleitung 22
3.2. Experimenteller Teil 23
3.3. Reaktion von rotem Phosphor mit Iod in [BMIm]X (X = Cl, I) 24
3.4. Anionenaustausch von PX3 in [HMIm]X (X = Cl, Br, I) 25
3.4.1. Reaktion von rotem Phosphor mit Iod in [HMIm]X (X = Cl, Br, I) 25
3.4.2. Phosphortrihalogenid-Referenzsystem 26
3.5. Das molekulare Verhalten von PCl3 in [HMIm]Cl 30
3.6. Quantenchemische Rechnungen 33
3.6.1. Molekulardynamische Simulationen 33
3.6.2. Statische DFT-Rechnungen 38
3.6.3. Mechanismus des Halogenaustausches 40
3.7. Zusammenfassung 41
4. Die Synthese von Cu3−xP – ein Modellsystem zur Reaktionsanalyse 43
4.1. Einleitung 43
4.2. Darstellungsmethoden – eine Literaturübersicht 45
4.3. Synthese von Cu3−xP (x = 0,05) in ionischen Flüssigkeiten 47
4.3.1. Synthesevorschrift 47
4.3.2. Produktcharakterisierung 47
4.3.3. Die Stabilität der ionischen Flüssigkeiten unter Synthesebedingungen 49
4.3.4. Analyse des Cu3−xP-Homogenitätsbereiches 50
4.4. Synthese von Cu3−xP (0,1 < x < 0,7) in ionischen Flüssigkeiten 52
4.4.1. Synthesevorschrift 52
4.4.2. Produktcharakterisierung 53
4.4.3. Analyse des Cu3−xP-Homogenitätsbereiches 55
4.5. Mechanistische Untersuchungen zur Cu3−xP-Bildung in [P66614]Cl 57
4.5.1. Experimenteller Teil 57
4.5.2. Diffusionsexperimente mit rotem Phosphor 58
4.5.3. Aktivierung von rotem Phosphor in [P66614]Cl 59
4.5.4. Mechanistische Diskussion der Cu3−xP-Phasenbildung 61
4.6. Untersuchungen zur Optimierung der Phosphoraktivierung 63
4.6.1. Donor- und Akzeptoreigenschaften ionischer Flüssigkeiten 64
4.6.2. Experimenteller Teil 66
4.6.3. Ergebnisse und Diskussion 66
4.7. Anioneneinfluss auf die Cu3−xP-Phasenbildung 69
4.7.1. Experimenteller Teil 69
4.7.2. Ergebnisse und Diskussion 70
4.8. Temperaturabhängige Kristallstrukturanalyse von Cu3−xP 72
4.8.1. Kristallzüchtung 72
4.8.2. Ergebnisse und Diskussion 73
4.9. Physikalische Charakterisierung unterschiedlicher Cu3−xP-Phasen 77
4.9.1. Elektronische Transporteigenschaften 77
4.9.2. Elektrochemische Charakterisierung 79
4.10. Zusammenfassung 82
5. Hochschmelzende ionische Flüssigkeiten in der Synthese von CuP2 84
5.1. Einleitung 84
5.2. Synthesevorschrift 85
5.3. Ergebnisse und Diskussion 85
5.4. Zusammenfassung 88
6. Fazit und Ausblick 89
A. Anhang 91
A.1. Röntgenpulverdiffraktometrie 91
A.2. Einkristall-Röntgenstrukturbestimmung 95
A.3. Rasterelektronenmikroskopie 99
A.4. Energiedispersive Röntgenspektroskopie 101
A.5. Elementaranalyse 107
A.6. Kernspinresonanzspektroskopie 108
A.6.1. Untersuchungen zur Bildung von Phosphorhalogeniden 108
A.6.2. Untersuchungen zur Bildung von Kupferphosphid 114
A.7. Raman-Spektroskopie 119
A.8. Röntgenabsorptionsspektroskopie 121
A.9. Elektronenspinresonanz-Spektroskopie 122
A.10. Elektrische Transportmessungen 123
A.11. Elektrochemische Charakterisierung 124
A.12. Wärmekapazitätsmessungen 125
A.13. Strukturbilder 126
A.14. Fotografien und Skizzen 128
A.14.1. Reaktionsapparaturen 128
A.14.2. Auflösungsversuche von elementarem Phosphor 129
B. Literaturverzeichnis 131
C. Danksagung 145
D. Liste der Publikationen 147
E. Liste der Kooperationen 149
F. Versicherung und Erklärung 151
35
Davi, Michaël. "Développement d'une nouvelle méthodologie d'oléfination catalysée par les complexes de cuivre : applications dans des réactions en tandem." Thèse, 2008. http://hdl.handle.net/1866/6553.
Full text
36
Chang, Jo Hsuan, and 張若軒. "The electropolishing behavior of copper and copper alloy in aqueous phosphoric acid solution." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/67530467522977073535.
Full textAbstract:
博士長庚大學
機械工程學系
102
The aim of this study is to investigate the electropolishing behavior of pure Cu and cartridge brass. Pure Cu specimen was electroplated on a rotating cylindrical Ti electrode in Cu-sulphate plating baths with different thiourea contents. The hardness variation, microstructures and electropolishing behavior of the Cu deposits were studied. Experimental results show that some sulphur-rich particles were identified in the Cu deposits prepared from the thiourea-containing baths. The sulphur-rich particles dissolved preferentially during electropolishing in a 40 vol.% H3PO4 solution, forming a thin amorphous phase containing P in patches on the outer surface of the Cu deposit. The Cu deposits prepared in the baths with thiourea showed higher anodic dissolution current during electropolishing and formed a brightened and levelled surface with a surface roughness (Ra) lower than 30 nm. The electropolishing behaviour of cartridge brass in a 70 vol.% H3PO4 solution was studied using a rotating disc electrode (RDE). Based on the results of an anodic polarization test, a transition peak varying from kinetic-controlled to diffusion-controlled dissolution was detected when a blue Cu2+-rich layer was developed on the RDE. The blue Cu2+-rich layer impedes the anodic dissolution rate of the brass-RDE and is essential for levelling during electropolishing. Potentiostatic polishing at different locations on the limiting-current plateau was studied. By polishing at the transition-peak potential, grain boundaries were preferentially etched. In contrast, a well-polished surface with a nanosized surface roughness (Ra) was achieved after electropolishing in the middle of the limiting-current plateau. By polishing at the end of the limiting-current plateau at a relatively low rotational speed, nipple-like and flow-streak features were observed. The formation of these features is attributed to the evolution of oxygen bubbles on the RDE surface. Mechanisms for the formation of the above-mentioned features were also proposed in this study. The electropolishing behaviour of cartridge brass in a 70 vol.% H3PO4 solution was also studied using a rotating cylinder electrode (RCE). The same results of the study with RDE, the Cu2+-rich layer is necessary for leveling the brass-RCE. The electropolishing effect on the RCE is relatively easy to achieve, because a full coverage of the Cu2+-rich layer on the RCE surface was seen during electropolishing. A rod-climbing phenomenon of the Cu2+-rich layer was observed when electropolishing the brass-RCE at a rotational speed above 100 rpm. The formation mechanism of rod-climbing was discussed and proposed in this study.
37
Tai, Chen-Chia, and 戴振家. "Electrochemical planarization mechanism of copper in phosphoric acid." Thesis, 2009. http://ndltd.ncl.edu.tw/handle/20597505236530965740.
Full textAbstract:
碩士淡江大學
化學工程與材料工程學系碩士班
97
Electrochemical planarization mechanism of copper in phosphoric acid was studied by using anodic polarization and AC impedance analysis. Several properties were changed in phosphoric acid system, and the experimental results were compared to discuss the polishing effect and mechanism. Polarization curve can be suitable for copper to find out the potential range of electropolishing. The optimum equivalent circuit was found to fit impedance results and could illustrate electrochemical planarization mechanism well. Optical microscope, atomic force microscopy, and scanning electron microscope were used to analyze the surface profiles before and after polishing. It was found that under the potential range in limiting current, copper electropolishing in 85wt.% phosphoric acid could obtain the best performance. The surface roughness before polishing was 32 nm and decreased to 1.4 nm after polishing. The effects of pH values, conductivity, viscosity and other properties on copper electrolysis in 65wt.% phosphoric acid were investigated. The experimental results showed that low water content and high viscosity would obtain the good polishing performance. In addition, salt film was found and examined after polishing. According to electrochemical characteristics of copper in phosphoric acid, an integrated electrochemical planarization mechanism is proposed, and the relation between copper electropolishing and phosphoric acid is reported.
38
Lin, Shang-Yi, and 林昇億. "Study of Phosphorous Doped Cobalt Tungsten Film as Copper Barrier." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/75508989147446646497.
Full textAbstract:
碩士國立成功大學
微電子工程研究所碩博士班
95
Signal transmission delay of IC backend is primarily caused by the parasitic resistance and capacitance (RC) in the multilevel interconnects. Furthermore, RC delay will be the dominant factor of the whole circuit in the sub-90 nm generation. To lower resistance, aluminum (2.7 μΩ-cm) was replaced by copper (1.7 μΩ-cm) for the IC interconnection system. As of decrease capacitance, low dielectric constant (low K) insulator was used. Dual damascene process was developed for these materials changes. However, copper diffuse into low-k material easier than non-low k interconnect under thermal stress and electric field caused copper interact with low-k material, which raises the leakage current and also leads to low k dielectric breakdown. Therefore, copper barrier is needed to block copper diffusion. Traditional copper barrier is Ta/TaN film and lower barrier resistivity is necessary for future generations. W and Co both have lower resistivity than Ta. This thesis studied the barrier effectiveness when phosphorous doped to WCo and W films. The AES and SIMS depth profiles show that both barriers did not fail after 30 minute 400 oC and 500oC annealing. The XRD graphs also do not have any CuSix peaks. Higher phosphorous doping caused higher barrier sheet resistance. The TEM graph indicates that the interface between Cu and WCo film become less clear or disappear. Co and Cu alloy maybe formed during the 500oC annealing. The barrier effectiveness may further deteriorate at higher temperature for the 7 nm P doped WCo film. Because it is 7 nm WCo compare to 16nm W film, phosphorous doped barrier helps blocking Cu diffusion or not is not clear and further study is needed to verify.
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Min, Lee Yuh, and 李育民. "Study of Alumina Supported Electroless Nickel Copper Phosphour Catalysts." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/50770538777113581860.
Full textAbstract:
碩士國立中央大學
化學學系
83
The addition of copper additives in Ni-Cu-P/ Al2O3 catalysts was successfully performed via electroless plating. The catalytic activities of different catalysts in the hydrogenation of at various temperatures and pressuresof hydrogen were examined and studied as well. The results showed that the catalyst containing 0.1g copper additives exhibited the highest catalytic activity toward hydrogenation. From the plots of hydrogenation rates versus temperatures, pressures of hydrogenand concentrations of α-pinene, the following rate expression was obtained: r=(633.09±32.0 ).Cp(0.9579±0.04). PH2(0.6527±0.034). e-(4707.8±17)/T Data also showed that α- form Al2O3 supproted catalyst has better activity than γ-form Al2O3 supported catalyst. The catalyst which prepared by impregnation method has lower catalytic activity which prepared by electroless plating, probably because the degree of nickel dispersion on the catalyst surface was poorer.
40
SANGA, BHARAT. "SOME STUDIES ON ULTRASONIC JOINING OF THIN COPPER, ALUMINIUM AND PHOSPHOR BRONZE SHEETS." Thesis, 2022. http://dspace.dtu.ac.in:8080/jspui/handle/repository/19725.
Full textAbstract:
The quest to produce cost-effective, efficient, and ergonomically designed products demands
the use of assemblies fabricated with assorted materials. Because of the differences in their
physical, chemical, and metallurgical properties, joining dissimilar metals has been a difficult
task for the researchers. Ultrasonic metal welding has overcome some of these limitations due
to its unique characteristics. A number of diversified applications, ranging from small
components used in the electronics industry to aerospace and solar, are being fabricated by
Ultrasonic Spot Metal Welding (USMW). USMW uses vibrational energy to produce heat at
the interface of the faying surfaces. The sheets are subjected to combined normal and shear
loading with the help of sonotrode assembly. These combined loads disperse the oxides and
contaminants as well as remove the surface asperities so as to form pure metallic bonds in
cold conditions without filler metal, flux, or shielding gas. It’s an efficient, green process that
takes very little processing time. Since USMW is designed to join dissimilar metals/materials,
this study used both similar and dissimilar combinations of phosphor bronze (UNS C51100),
copper (UNS C10300), and aluminum (Al 3003).
It was observed through the available literature that there is a need for the optimization of the
process parameters along with the characterization of the weld joint in the case of USMW.
With these goals in mind, experiments were carried out in both 'Time Control Mode' and
'Energy Control Mode' using different experimental designs. The Analysis of Variance
(ANOVA) is utilized on the response parameters-tensile shear load and the weld area. Weld
pressure is observed as the most significant parameter, followed by weld time, and vibration
amplitude, in affecting the weld strength. A reasonably good correlation is observed between
the tensile shear load and the weld area between all the combinations of the weld metals. The
process parameters are optimized by coupling the regression model as a fitness function with
vii
the simulated annealing optimization algorithm. Finally, the confirmatory experimental
results substantiated the predicted results and validated the proposed methodology.
The modeling and simulation of the USMW process is carried out using FEM. The model is
utilized for the study and prediction of the thermal profiles at the weld interface. The heat
fluxes generated due to deformation and friction are calculated and assigned as boundary
conditions during thermal simulation. The forecast of temperature is done under various
welding conditions. The maximum temperature obtained by transient simulation at the weld
interface is 368.8℃, 369.4℃ and 296.1℃ for PB-PB, PB-Cu, and PB-Al, respectively. The
continuous reduction in the temperature is observed towards the extremes of the weld metal.
The sonotrode and the anvil achieve a lower temperature in comparison to the weld interface.
The effect of clamping force and bonding ratio on the interface temperature is observed to be
positive. The weld interface is distinguished as the weld zone, TMAZ and HAZ. The model is
validated with the maximum absolute errors within 5% for PB-PB joints, 6.26% for PB-Cu
joints, and 5.68% for PB-Al joints between the observed and predicted temperature results. A
correlation coefficient of 0.96, 0.87, and 0.86 is established between the simulated
temperature result and the weld strength for PB-PB, PB-Cu, and PB-Al, respectively. Thus, it
is clear that the interface temperature has a strong linear relationship with joint strength and is
a major deciding factor for achieving strong joints.
The effect of the weld energy on interface temperature and weld strength is also explored. It
is observed that the values of peak interface temperature and tensile-shear strength increase
with the welding energy. The failure mode changes from interfacial to nugget pull-out at a
considerably high energy level during the tensile-shear load test. There is a significant rise in
the tensile-shear load initially, but a negligible change is observed in the last stage. The
scanning electron microscopy (SEM) revealed that the joining line appears almost straight at
a low energy level but fades away at a higher energy level. The bonding region ultimately
viii
acquires the shape of a wavy, convoluted interface. Micro-bonding accompanied by
interlocking is observed as the primary joining mechanism at high energy level. Hence, it can
be concluded that joint strength in USMW was the combined result of the formation of
micro-bonds and mechanical interlocking due to the swirling of metal at the interface.
The observations and the results of the current study reflect that different combinations of
PB, Cu, and Al give very good responses to the ultrasonic spot metal welding in the given
ranges of the parameters. Hence, this joining technique can be effectively used for the
fabrication of thin components made of these metals. This study can provide useful inputs for
the industries involved in the manufacturing of battery electrical vehicles, solar panels, small
electrical and electronic products like relays, contacts, and heat sinks etc.
41
Chou, Chun-Hung, and 周俊宏. "Syntheses and structures of copper(I) dinuclear and polynuclear complexes containing phosphorous- and nitrogen- donor ligands." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/61611086692873423994.
Full textAbstract:
碩士國立中山大學
化學系研究所
93
Here we report the preparation, structure, and spectroscopic properties of an intriguing copper(I) cyclophane-like dimeric complex [Cu2(dppa)2(bpy)2][BF4]2(2)、[Cu2(dppa)2(mbpy)2][BF4]2(3)、[Cu2(dpbp)2(bpy)2][BF4]2(7)和[Cu2(dppb)2(bpy)2] [BF4]2(8), containing phenyl phosphine bridge ligands, such as diphenylphosphino acetylene (dppa), 1,4-bis(diphenylphosphino)benzene (dppb) and 4,4''-bis(diphenyl phosphino)biphenyl (dpbp). As a building unit, the complex [Cu2(dpbp)2(NCMe)4] [BF4]2(9) containing labile acetonitrile molecules those can be easily substituted by anionic ligands, is expected to combine with suitable linkers to synthesize supramolecular arrays with shapes of polygons and polyhedra.
42
Lin, Tung-Jung, and 林彤蓉. "Growth characteristics of copper nanowires and new chemical routes for the synthesis of K2SiF6:Mn4+ phosphors." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/3bmubf.
Full textAbstract:
碩士國立臺北科技大學
資源工程研究所
106
In the first part, one-dimensional copper nanowires (CuNWs) are synthesized via galvanic displacement reaction and the growth characteristics of CuNWs are studied by TEM and EDS mapping. As the reduction-oxidation reaction occurs on the solid-liquid interface, the Cu2+ ions on the Al foil surface are reduced to Cu nanoparticles which aggregate on the substrate surface during the initial reaction. The aluminum oxidizes into Al3+ ions and subsequently forms the AlOxHy interlayer between Al foil and Cu nanoparticles. By adding surfactant of CTAC, CuNWs grow on the Cu nanoparticle seeds in the [100] direction when the reaction time increases. In the second part, K2SiF6:Mn4+ powders are synthesized by co-precipitation reaction via a new chemical route. The structural, morphological and optical properties of the K2SiF6:Mn4+ powder are characterized by using powder X-ray diffraction, scanning electron microscope and photoluminescence spectroscopy, respectively. The compound is prepared by adding potassium silicate, KF and KMnO4 in an HF acidic solution following the reduction of Mn7+ to Mn4+ by using H2O2 at room temperature. By using PEG as surfactant, particles sized of K2SiF6:Mn4+ powders is about 5-10 μm. Moreover, Na2SiF6:Mn4+ powders are also successfully synthesized using this new chemical route.
43
He, Shih-Wei, and 何世偉. "Modification of waste carbon fiber using phosphoric acid heating process and studying its adsorption of aqueous copper ions." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/40940020652850745536.
Full textAbstract:
碩士國立雲林科技大學
環境與安全衛生工程系碩士班
101
Activation of waste carbon fiber by conventional heating method using phosphoric acid and adsorption of aqueous copper ions using said modified waste carbon fiber was investigated. The conventional heating temperature was 500℃ then maintained one hour and the ratio of weight between waste carbon fiber and phosphoric acid were 1:1, 1:5, 1:10 and 1:15 (named CF-1, CF-5, CF-10 and CF-15). In characteristic of original waste carbon fiber and modified waste carbon fibers for CF-1, the specific surface area was from 2 to 26 m2/g. In addition, modified waste carbon fiber of CF-15 reached 90% for preparation and was the highest ratio in all the modified waste carbon fiber. The result indicated that conventional heating method using phosphoric acid maintained high yield for preparation. In the adsorption material environment application aspect, the simulation and experimental results indicated suitable Freundlich model for equilibrium and pseudo-second order model for kinetic. The adsorption experiments at 320 K, CF-5 was the highest capacity of 5.25 mg/g. However, the original waste carbon fiber was only 0.19 mg/g, and the results showed that the capacity of adsorption increased for activation of waste carbon fiber by conventional heating method using phosphoric acid.
44
Jieratum, Vorranutch. "Iron and copper chalcogenides : photovoltaic absorber candidates and YZrF��� : a new upconversion host." Thesis, 2012. http://hdl.handle.net/1957/31352.
Full textAbstract:
The materials Fe���(Si,Ge)(S,Se)���, Cu���PS[subscript 4-x]Se[subscript x] (0 ��� x ��� 4), and Cu���PxAs[subscript 1-x]S��� (0 ��� x ��� 1) have been synthesized and studied as new earth-abundant absorbers for single and multijunction photovoltaic cells as well as solar fuel generation. The synthesis, single-crystal growth, and optical and electrical properties of these materials are described and discussed in Chapter 2, 3, and 4. Inspired by the photovoltaic absorber Cu���ZnSnS���, the new compound CuZnPS��� has been discovered; its structure and properties are discussed in Chapter 5, including a comparative analysis to Cu���PS���. The compound YZrF��� (Chapter 6) has been synthesized and evaluated for the first time as a new optical host for green up-conversion.Graduation date: 2013
45
ŽÁČKOVÁ, Klára. "Sezónní dynamika vybraných krevních parametrů u vybraných masných plemen ovcí chovaných v podhorských podmínkách." Master's thesis, 2009. http://www.nusl.cz/ntk/nusl-51260.
Full textAbstract:
Sheep breeding is nowadays a developing branch of agriculture again. There is a lot of different breed and they react distinctly on the same conditions of the enviroment. Sheep of breeds charollais, suffolk, šumavská ovce and valaška bred in similar conditions were observed in spring and autumn of years 2007 and 2008. In these seasons were taking blood samples (from {$\pm$}7{--}24) ewes and lambs and were analyzed in hematology laboratory. There were determined haemoglobin level, haematocrit indicator, erytrocytes and leucocytes levels, glucose, cholesterol, triglycerides levels, urea and plasmatic proteins, activity of ALP and GMT enzymes, phosphor, calcium, magnesium, zinc and copper levels. The main objective of this project was determine seasonal changes in observed parametres. Next objectives were determine different changes in blood parametres in different breeds and different aimes of breeds. There were recognized that all the observed breeds don`t react the same way on similar conditions. There were not provably determined seasonal changes in observed parametres, but average Hb level was higher in autumn than in spring. Urea level was conversely higher in spring season than in autumn. The demostrable fact is, that the similar conditions induce different answers not only in different breeds but also in different aimes of breeds.