Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-04-14T20:00:06Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) CD - Tese - Acoplamento eletroquímico de haletos alílicos e prenílicos com aldeídos e cetonas em cátodo de pó de grafita.pdf: 1538935 bytes, checksum: 24304a2a17ee9e2727b54cae82fa996a (MD5) / Made available in DSpace on 2016-04-14T20:00:06Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) CD - Tese - Acoplamento eletroquímico de haletos alílicos e prenílicos com aldeídos e cetonas em cátodo de pó de grafita.pdf: 1538935 bytes, checksum: 24304a2a17ee9e2727b54cae82fa996a (MD5) Previous issue date: 2014-12-19 / Na primeira parte do trabalho foi investigado o acoplamento eletroquímico da mistura de haletos alílicos a compostos carbonílicos adsorvidos em cátodo de pó de grafita na presença ou ausência de aditivos (AgNO3 ou TBABF4), usando um anólito aquoso em célula de cavidade. Foram utilizadas as técnicas eletroquímicas de voltametria de varredura linear e eletrólise com potencial ou corrente constante. O uso de quantidades catalíticas dos sais de AgNO3 ou TBABF4, misturados à grafita, melhoraram significativamente a formação dos álcoois homoalílicos. As eletrólises com o cloreto de alila levaram aos melhores resultados, quando comparadas às eletrólises com o brometo de alila. A reação de alilação mostrou-se sensível a efeitos estéricos e eletrônicos. Os potenciais e correntes mais negativas favoreceram o heteroacoplamento. Os aldeídos aromáticos (67 - 99%) e a 1,1,1-trifluoroacetofenona (95%) levaram aos melhores resultados, já os rendimentos na presença de aldeídos alifáticos (28%) ou cetonas (7%) não foram satisfatórios. Na segunda parte do trabalho foi investigado o acoplamento eletroquímico da mistura de haletos prenílicos ao benzaldeído, nas mesmas condições descritas na primeira parte, utilizando as técnicas eletroquímicas de voltametria de varredura linear e eletrólise com potencial constante. O uso de quantidades catalíticas dos sais de AgNO3 ou TBABF4 misturado à grafita, influenciaram na proporção dos produtos de acoplamento (isômeros α e γ). Os melhores resultados na formação do isômero α, 1-fenil-4-metil-3-penten-1-ol (28%, proporção α:γ igual 74:26 ) foram alcançados com o brometo de prenila e os melhores resultados na formação do isômero γ, 1-fenil-2,2-dimetil-3-buten-1-ol (45%, proporção α:γ igual 6:94) com o cloreto de prenila. Dentro deste estudo, também foram investigados os efeitos da variação da quantidade de reagentes, potencial, corrente, aditivos e tipo de anólito nas reações de acoplamento eletroquímico estudadas. Do ponto de vista preparativo, os resultados são comparáveis aos da literatura e apresentam-se como uma alternativa verde, visto que o cátodo de grafita elimina solventes orgânicos e ânodo sacrificial tradicional de métodos eletrossintéticos. Do ponto de vista mecanístico, deve prevalecer o mecanismo aniônico para a reação de alilação, enquanto na reação de prenilação a competição entre o mecanismo radicalar e aniônico pode ser direcionado para a formação dos isômeros α e γ. / In the first part of this work, the electrochemical coupling of a mixture of allylic halides and carbonyl compounds was investigated. The reagents were adsorbed on graphite powder cathode, in the presence or absence of additives (AgNO3 or TBABF4) using aqueous anolyte and a cavity cell. Electrochemical techniques of linear sweep voltammetry and potential or constant current electrolyses were used. The use of catalytic amounts of AgNO3 or TBABF4 added to the graphite powder, have significantly improved the formation of homoallylic alcohols. The electrolysis with allyl chloride gave to the best results when compared to the allyl bromide electrolysis. The allylation reaction was sensitive to steric and electronic effects. More negative currents or potentials favored the heterocoupling. The aromatic aldehydes led to the best results (67 - 99%) and the1,1,1-trifluoroacetofenone (95%), the yields in the presence of aliphatic aldehydes (28%) or ketones (7%) were not satisfactory. In the second part, the electrochemical coupling of a mixture of prenylic halides and benzaldehyde was investigated under the same conditions described in the first part of this work, using electrochemical techniques of linear sweep voltammetry and constant potential electrolysis. The use of catalytic amounts of AgNO3 or TBABF4, added to the graphite powder, has influenced the proportion of the coupling products (α and γ isomers). The best results for the α isomer, 4-methyl-1-phenyl-3-penten-1-ol (28%, ratio α:γ equal 74:26 ) were achieved with prenyl bromide and the best results for the γ isomer, 2,2-dimethyl-1-phenyl-3-buten-1-ol (45%, ratio α:γ equal 6:94) in the presence of prenyl chloride. The effects of the amount of reactants, potential, current, and type of additives and anolyte solution, were also investigated for all electrochemical coupling reactions studied. From the preparation point of view, the results are comparable to the literature and appear as a green alternative, since the graphite powder cathode eliminates organic solvents and sacrificial anodes of traditional electrosynthetic methods. From the mechanistic point of view, the anionic mechanism predominates for the allylation reaction, while in the prenylation reactions take place a competition between radical and anionic mechanism in the formation of α and γ isomers.

Diplomová práce se zabývá problematikou volby grafitového materiálu využívaného pro výrobu nástrojových elektrod při elektroerozivní obrábění. Práce je rozdělena do třech částí. Teoretická rešerše nekonvenční technologie elektroerozivního obrábění vypracovaná dle uvedených zdrojů se nachází v první části práce. Dále je v práci proveden cenový průzkum EDM grafitových materiálů nabízených v České republice a na Slovensku. Čtyři odlišné stupně kvality grafitu (od stávajícího dodavatele firmy GAMARTIS TRADE s.r.o.) a jeden měděný materiál byly podrobeny experimentu, jehož účelem bylo zjištění závislosti mezi kvalitou grafitového materiálu (cena) a přesností vyhloubené kavity, opotřebením nástrojové elektrody, časem obrábění nebo také drsností povrchu.

This work deals with carbon materials and using them in electrochemical energy sources. Object of this work was to prepare carbon materials and investigate their electrical properties. The theoretical part objects of the carbon materials, their properties, application in electrochemical energy sources and measurement methods used in experimental part. Experimental part describes the preparation of the electrodes with various carbon materials and summarizes the results of measurements.

Natural graphite from cheap and abundant natural sources is an attractive anode material for lithium ion batteries. We report on modifications of such a common natural graphite, whose electrochemical performance is very poor, with solutions of (NH4)2S2O8, concentrated nitric acid, and green chemical solutions such of e.g. hydrogen peroxide and ceric sulfate. These treatments resulted in markedly im-proved electrochemical performance (reversible capacity, coulombic efficiency in the first cycle and cycling behavior). This is attributed to the effective removal of active defects, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. These changes inhibit the decomposition of electrolyte solution, pre-vent the movement of graphene planes along a-axis direction, and provide more passage and storage sites for lithium. The methods are mild, and the uniformity of the product can be well controlled. Pilot experiments show promising results for their application in industry.

One main reason for the use of Fe-Cu-C system in PM industry is the presence of liquid phase (copper) at the start of sintering (1120oC). The diffusion of liquid copper into iron causes swelling in the structure. This in turn can cause high dimensional change and, if not controlled properly, may cause distortion. So it is of paramount importance to control the copper diffusion. Carbon, added as graphite, reduces the swelling of copper by changing the dihedral angle. The affect of graphite on copper diffusion depends on the graphite type, particle size of graphite and heating rate. The aim of this work was to find the influence of graphite type and particle size of graphite on copper diffusion. Water Atomized iron (ASC100.29) produced in Höganäs AB was taken as the base powder.  Two types of graphite were used each with two different particle sizes. Two different graphite quantities (0.2% & 0.8%) for each type was taken. Natural fine graphite (UF4), Natural coarse graphite (PG44), Synthetic fine graphite (F10) and  Synthetic coarse graphite (KS44) were the graphites used in this work. Powders were compacted at 600 Mpa and the sintering was done at 1120oC for 30 minutes in 90/10 N2/H2. Dilatometry and metallographic investigation of the samples sintered in the production furnace were used to understand the graphite influence.   The investigation showed that at low graphite levels (0.2%), the affect of graphite type or graphite size was not significant on copper diffusion. At high graphite levels (0.8%),  synthetic graphites were more effective in reducing the swelling of copper. Influence of  particle size of synthetic graphites on Cu diffusion was not significant compared to the influence of particle size of natural graphite. There was also a considerable affect of heating rate on graphite dissolution and copper swelling.

Soil structural stability plays a pivotal role in landscape preservation when a protective vegetation cover is lacking. For example, under semiarid climates seasonal rainfall cannot sustain a full vegetation cover, but still causes soil erosion. With the loss of (fertile) soil material, ecosystem productivity reduces and less C can be stored. In natural semiarid systems, soil erosion is a spatially heterogeneous process, whereby local highly erodible spots are alternated by improved soil structure under the sparse canopy cover, creating a very heterogeneous landscape. Although the physical protection by the plant canopy is well understood, the potential influence of soil archaea and bacteria on soil structural stability in relation to plants and parent material is less well known. Mainly from studies under controlled conditions, we know that certain archaeal and bacterial species have the ability to produce extracellular polymeric substances (EPS), forming an extracellular matrix. As the formed matrix connects soil particles, EPS seem to have the potential of playing a substantial role in soil aggregation, thereby controlling soil erodibility. Little is known of this gluing process by EPS and its importance under natural conditions as most evidence is derived from controlled conditions in the laboratory. This dissertation aims to unravel the role of EPS from soil archaea and bacteria in soil aggregate stabilization in semiarid grasslands by considering the potential role of plant species and parent material in this process. The sparse vegetation in semiarid grasslands provide a useful gradient in soil organic C contents to study these processes. Improved conditions for soil microbes producing EPS can be found at the root surface, while the bare canopy interspaces lack in C/resources. Two sites were selected in southeast Spain, mainly differing in graphitic C, inorganic C and nitrogen contents. On both sites, soil adjacent to the widely occurring Anthyllis cytisoides legumes shrubs and Macrochloa tenacissima grass tussocks were sampled during two campaigns. The first sampling campaign in April 2017 focused on the top soil, whereby a distance gradient from the plant stem to the bare intercanopy area was sampled. The second sampling campaign in April 2018 focused more on the effect of plant roots on soil archaeal and bacterial communities by including the rhizosphere. As the parent material of the Rambla Honda site, i.e. one of the study sites, contains a substantial amount of graphitic C, several methods were tested to quantify the different types of C in these soils to understand their role in shaping EPS contents. Furthermore, the quantification of graphitic C contents opened the possibility to study a potential interaction between graphite minerals and microbes. Although graphitic C contents explained part of the variances in microbial community, no direct link with EPS-saccharide contents was found. EPS contents were relative high in the rhizosphere, most notable at the legumes shrub Anthyllis cytisoides, and were linked to the enrichment of N-fixing bacteria. However, outside the root influenced soil, EPS contents were still substantially high, whereby the abundance of microbial species, previously associated to biofilm formation in other environments, indicated that EPS synthesis is not only restricted to the rhizosphere. Soil aggregation was linked to EPS-saccharide contents, whereby two mechanisms were hypothesized. Firstly, the strong link between soil wettability and EPS-saccharide content in the soil of the carbonate poor Rambla Honda site, indicated that aggregates become stabilized by hydrophobic bonds created by the EPS. Secondly, results from the carbonate rich Alboloduy site indicates that EPS has a facilitating role in creating stable aggregates by precipitating carbonates on the EPS structure. This likely lead to a higher soil structural stability, as carbonate bindings are more stable when prolonged drought reduces soil biological activity and thereby EPS contents. Overall, EPS play a substantial role in soil aggregate stabilization in semiarid grasslands, whereby EPS contents were increased by legume plants, by means of enriching EPS producing bacteria. / Die Stabilität der Bodenstruktur spielt eine entscheidende Rolle in der Erhaltung der Landschaft, insbesondere wenn keine schützende Vegetationsbedeckung vorhanden ist. So ist beispielsweise unter semiariden Klimabedingungen wegen der Saisonalität der Niederschläge keine vollständige Vegetationsbedeckung vorhanden, was Bodenerosion verursacht. Durch den Verlust von (fruchtbarem) Bodenmaterial verringert sich die Produktivität des Ökosystems. Dadurch kann weniger Kohlenstoff (C) im Boden gespeichert werden. In natürlichen semiariden Systemen ist die Bodenerosion ein räumlich heterogener Prozess, bei dem sich stark erosionsanfällige Stellen mit solchen Bereichen abwechseln, welche durch günstige Bodenstruktur unter der spärlichen Pflanzendecke gekennzeichnet sind. Hierdurch entsteht eine sehr heterogene Landschaft. Während zum physikalischen Schutz durch Vegetationsüberschirmung viele Erkenntnisse vorliegen, ist über den möglichen Einfluss von Archaeen und Bakterien auf die strukturelle Stabilität des Bodens in Bezug auf Pflanzen und Ausgangsmaterial weit weniger bekannt. Hauptsächlich aus Studien unter kontrollierten Bedingungen wissen wir, dass bestimmte Archaen- und Bakterienarten die Fähigkeit besitzen, extrazelluläre polymere Substanzen (EPS) zu produzieren, die eine extrazelluläre Matrix bilden. Da die gebildete Matrix Bodenpartikel verbindet, scheint EPS das Potenzial für eine maßgebliche Beeinflussung der Bodenaggregation zu haben und dadurch die Erosionsanfälligkeit zu steuern. Über solche Klebemechanismen von EPS und deren Bedeutung unter natürlichen Bedingungen ist aber wenig bekannt; die meisten Hinweise stammen aus kontrollierten Bedingungen im Labor. Diese Dissertation zielt darauf ab, die Bedeutung von EPS von Archaeen und Bakterien hinsichtlich der Stabilisierung von Bodenaggregaten in semiariden Graslandschaften unter Berücksichtigung der möglichen Rolle von Pflanzenarten und Ausgangsmaterial in diesem Prozess aufzuklären. Zur Untersuchung solcher Prozesse bietet die spärliche Vegetation in semiariden Graslandschaften einen zweckdienlichen Gradienten bezüglich des Gehalt an organischem C im Boden. Günstige Bedingungen für EPS-produzierende Bodenmikroorganiosmen sind an der Wurzeloberfläche zu finden, während dem unbedeckten Boden zwischen Stellen ohne Pflanzenbedeckung C / Ressourcen fehlen. Es wurden zwei Standorte in Südostspanien ausgewählt, die sich hauptsächlich in den Gehalten an graphitischem C, anorganischem C und Stickstoff unterscheiden. An beiden Standorten wurden im Rahmen von zwei Feldkampagnen Böden in unmittelbarer Nähe zu der weit verbreiteten Leguminosenart Anthyllis cytisoides-Hülsenfrüchten und Grasbüscheln von Macrochloa tenacissima beprobt. Die erste Probenahmekampagne im April 2017 konzentrierte sich auf den obersten Boden, wobei ein Abstandsgradient vom Pflanzenspross zum unbedeckten Boden zwischen der Pflanzendecke beprobt wurde. Die zweite Probenahmekampagne im April 2018 konzentrierte sich mehr auf die Wirkung von Pflanzenwurzeln auf Archaeen- und Bakteriengemeinschaften durch Beprobung der Rhizosphäre. Am Rambla Honda-Standort enthält das Ausgangsmaterial eine erhebliche Menge an graphitischem C. Deshalb wurden verschiedene Methoden getestet, um die verschiedenen Arten von C in diesen Böden zu quantifizieren und ihre Rolle bei der Gestaltung des EPS-Gehalts zu verstehen. Darüber hinaus eröffnete die Quantifizierung des graphitischen C-Gehalts die Möglichkeit, die Wechselwirkung zwischen Graphitmineralen und Mikroorganismen zu untersuchen. Obwohl der Gehalt an graphitischem C einen Teil der Varianzen in der mikrobiellen Gemeinschaft erklärte, wurde kein direkter Zusammenhang mit dem EPS-Saccharidgehalt gefunden. Die EPS-Gehalte waren in der Rhizosphäre relativ hoch - am deutlichsten bei der Leguminosenart Anthyllis cytisoides - und mit der Anreicherung von N-fixierenden Bakterien verbunden. Außerhalb des von der Wurzel beeinflussten Bodens war der EPS-Gehalt jedoch immer noch deutlich erhöht. Dabei wies die Häufigkeit von Mikroorganismenarten, die zuvor mit der Bildung von Biofilmen in anderen Umgebungen in Verbindung gebracht wurden, darauf hin, dass die EPS-Synthese nicht nur auf die Rhizosphäre beschränkt ist. Die Bodenaggregation zeigte eine Verbindung mit dem EPS-Saccharidgehalt auf, wobei zwei Mechanismen angenommen wurden: Erstens wies der starke Zusammenhang zwischen der Bodenbenetzbarkeit und dem EPS-Saccharidgehalt im Boden des karbonatarmen Rambla Honda-Standorts auf eine Aggregatstabilisierung durch EPS-erzeugte hydrophobe Bindungen hin. Zweitens zeigen die Ergebnisse des Standorts Alboloduy-Standorts mit karbonatreichem Boden, dass EPS eine unterstützende Funktion bei der Erzeugung stabiler Aggregate besitzt, indem Karbonate auf der EPS-Struktur ausgefällt werden. Dies führt wahrscheinlich zu einer höheren Stabilität der Bodenstruktur, da Karbonatbindungen stabiler sind, wenn eine längere Trockenheit zu einer Verringerung der biologischen Aktivität im Boden und damit des EPS-Gehalts führt. Insgesamt spielt EPS eine wesentliche Rolle bei der Stabilisierung von Bodenaggregaten in semiariden Graslandschaften, wobei der EPS-Gehalt durch Leguminsosen, mittels Anreicherung von EPS-produzierenden Bakterien, erhöht wurde.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23295号 / エネ博第420号 / 新制||エネ||80(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 野平 俊之, 教授 坂口 浩司 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

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