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Kinetic studies of some solid-state reactions of metal sulfidesWang, Haipeng January 2005 (has links)
This thesis is submitted as a portfolio of peer-reviewed publications. / For many geochemical systems, reaction kinetics determines the system's current status and evolution. It might also be the key to unraveling their thermal history. In metal sulfide systems, kinetic studies have been carried out on four sets of solid-state transitions/transformations in Fe-Ni-S and Ni-S systems. In this work, a new kinetic model, the Refined Avrami method, has been developed to account for reactions involving changes in reaction mechanisms. Nonstoichiometric compounds are commonly present in these reactions. The exsolution of pentladite from the monosulfide solid solution (mss) is an important reaction in the formation of nickel ores. For near equimolar mss compositions, the reaction rate is rapid even in the low temperature ranges. For bulk composition Fe₀.₇₇ Ni₀.₁₉ S, the experimental results show the reaction rates ( mss → pentlandite ) vary from 1.6x10⁻⁵ to 5.0x10⁻⁷ s⁻¹ at 200 °C and from 9.4x10⁻⁵ to 4.1x10⁻⁷ s⁻¹ at 300 °C. The activation energy, E [subscript a], varies during the course of reaction from 49.6 kJ.mol⁻¹ at the beginning of reaction (nucleation mechanism is dominant) to 20.7 kJ.mol⁻¹ at the end (crystal growth mechanism is dominant). Monosulfide solid solution (mss) is a common intermediate phase observed during the oxidation of nickel ores, such as violarite and pentlandite. The investigation of mss oxidation is of benefit in understanding the thermal behavior of economically important metal sulfides during smelting. The oxidation products of mss vary in our samples depending on their compositions. Apart from the common oxidation products hematite and Ni₁ ₇ S₁₈, Fe₂ (SO₄) ₃ was observed during the oxidation of Fe₇ . ₉ S₈ and pentlandite for Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ . The activation energy was determined using a model-free method. The oxidation of Fe₆.₄ Ni₁.₆ S₈ exhibited a higher E [subscript a] than Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ over the course of the reaction. The E [subscript a] increases with reaction extent (y) from 67.1 to 103.3 kJ.mol⁻¹ for mss composition Fe₆ . ₁ ₅Ni₁ . ₅₄ S₈ and from 76.1 to 195.0 kJ.mol⁻¹ for Fe₆.₄ Ni₁.₆ S₈ . The kinetic study of the α - Ni₁₋ ₓ S → β - NiS transition shows that initial compositions of α - Ni₁₋ ₓ S plays an important role in the kinetics of the transition. The activation energy ( E [subscript a] ) for this α - to β - phase transition is 16.0 ( ± 0.5 ) kJ.mol⁻¹ for NiS in the temperature range 70 to 150 °C, and 13.0 (± 0.5) kJ.mol⁻¹ in the temperature range 250 to 350 °C. For Ni₀. ₉₇ S, however, E [subscript a] deceases from 73.0 ( ± 0.5 ) to 17.0 ( ± 0.5 ) kJ.mol⁻¹ over the course of the reaction in the temperature range 300 to 320 °C. The relationship between E [subscript a] and extent of transition (y) for the initial bulk Ni₀. ₉₇ S was derived using the Refined Avrami method. For Ni deficient compositions, α - Ni₁₋ₓ S, the transformation to β-NiS is accompanied by the exsolution of either a progressively more Ni deficient α-Ni₁₋ₓ S and Ni₃ S₄ , and the reactions become more sluggish for more metal deficient compositions. The study of oxidation kinetics of α-NiS is of metallurgical interest, as α-NiS related phases may occur when nickel ores are flash smelted to produce nickel matte. In an open air environment, the oxidation mechanisms of α-NiS are constant at 670 and 680 °C, dominated by the direct oxidation of α-NiS → NiO. The dominant oxidation mechanism changes to a chain reaction : α-NiS → [superscript k] ₁ Ni₃ S₂ → [superscript k] ₂ NiO at 700 °C. Therefore, different kinetic models need to be applied to these two distinct reaction mechanisms. Activation energy for the oxidation, α-NiS → NiO, in the temperature range 670 to 680 °C was calculated to be 868.2 kJ.mol⁻¹ using Avrami/Arrhenius method. Rate constant k₁ and k₂ are approximated to be 3 x 10⁻⁴ s⁻¹ and 5 x 10⁻⁴ s⁻¹ for the first part and second part of the chain reaction respectively at 700 ° C. The study of the variation in reaction rate with oxidation time illustrates the optimum oxidation time zone for each temperature, where NiO can be produced at the fastest rate. / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2005.
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Gênese dos corpos de sulfeto maciço hidrotermal e platinóides associados no depósito de Fortaleza de Minas (MG) /Almeida, Carolina Michelin de. January 2003 (has links)
Orientador: Sebastião Gomes de Carvalho / Banca: Antenor Zanardo / Banca: João Batista Moreschi / Resumo: A mineralização sulfetada de Ni-Cu-Co (PGE), associado a rochas komatiíticas, da Jazida de Fortaleza de Minas, no sudoeste do Estado de Minas Gerais é tido como de origem magmática, porém processos pós-magmáticos modificaram substancialmente a distribuição original, estrutura, textura, mineralogia e química dos minérios. Estão presentes três importantes tipos de minérios sulfetados mobilizados: brecha, formação ferrífera bandada (BIF) e minério maciço hidrotermal. O último, é o objeto de estudo desta pesquisa. O minério maciço hidrotermal está associado a zonas de falhas transversais tardias, de direção NE-SW e N-S que cortam as rochas hospedeiras, e são perpendiculares a principal zona de cisalhamento que contém o principal corpo de minério. O minério maciço hidrotermal é formado por uma matriz oxi-sulfetada, constituída por pirrotita, pentlandita, calcopirita, pirita, violarita e magnetita, contendo minerais da série cobaltita-gersdorffita, minerais do grupo da platina, minerais da série linneita-polidymita, siegenita, além de carbonatos e quartzo. Os minerais do grupo da platina ocorrem disseminados por todo minério, associados a fases silicáticas hidratadas, inclusos em grãos de magnetita e minerais da série cobaltita-gersdorffita, no contato entre o minério e as rochas encaixantes. Próximo ao contato, são observados típicas feições de alteração hidrotermal do tipo talco-carbonato-clorita-sulfeto. Ao final do evento tectono-metamórfico, durante o Neo Proterozóico, que atuou na área em condições de baixa a alta temperatura (fácies xisto verde), foram produzidas diversas soluções hidrotermais que afetaram as rochas encaixantes nas proximidades do corpo de minério, bem como do próprio minério, originando um novo tipo de minério, aqui designado como minério maciço hidrotermal. / Abstract: The komatiite-associated Ni-Cu-Co (PGE) sulphide mineralization at Fortaleza de Minas, southwestern of Minas Gerais state is believed to have a magmatic origin, but a number of post-magmatic processes significantly modified the original distribution, structure, texture, mineralogy and chemistry of the ores. Three important types of mobilized sulphide are present: breccia, banded iron formation (BIF) and hydrothermal massive ore. The last is the object of study of this research. The hydrothermal massive ore are associated to the late transversal fault zones, of N-S and NE-SW direction that cut host rocks, and are perpendicular to the principal shear zone that comprise the main ore body. The hydrothermal massive ore is formed by a massive oxi-sulphated matrix, consisted of pyrrhotite, pentlandite, chalcopyrite, pyrite, violarite and magnetite, comprising cobaltite-gersdorffite minerals series, platinum-group minerals, linnaete-polydymite minerals series, siegenite, besides carbonates and quartz. The platinum-group minerals occur disseminated over the entire ore, associated to hydrated siliceous phases, and enclosed in magnetite grains and cobaltite-gersdorffite mineral series, in the contact between the ore and enclosing rocks. Next to this contact, are observed typical hydrothermal alteration features as talc-carbonate-chlorite-sulphide. In the end of the tectonic-metamorphic event, during the Neo Proterozoic, that actuated in the area in conditions of low to medium temperatures (greenschist facies), were produced a number of hydrothermal solutions that affected enclosing rocks next to the ore body as well as the proper ore, generating a new type of ore, here designated as hydrothermal massive ore. / Mestre
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Analise da expressão de genes que codificam proteinas transportadoras em Acidithiobacillus ferrooxidans e Acidithiobacillus thioxidans na presença de sulfetos metalicos / Expression analyses of genes that encode for transporter protein in Acidithiobacillus ferrooxidans and Acidithiobacillus thioxidans maintained in contact with metal sulphiidesMadureira, Danielle Jannuzzi 20 February 2008 (has links)
Orientadore: Laura Maria Mariscal Ottoboni, Fernanda de Castro Reis / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-11T13:23:27Z (GMT). No. of bitstreams: 1
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Previous issue date: 2008 / Resumo: Acidithiobacillus ferrooxidans e Acidithiobacillus thiooxidans são espécies bacterianas acidofilicas, quimiolitotróficas e mesofilicas, encontradas em ambientes de biolixiviação. A. ferrooxidans utiliza íons ferrosos e compostos que contém enxofte como doadores de elétrons enquanto que A. thiooxidans utiliza apenas enxofte e compostos contendo enxofte. Ambas as espécies utilizam principalmente o oxigênio como receptor final de elétrons, contudo, podem também crescer em ambientes de anaerobiose. A. thiooxidans possui maior resistência ao pH podendo ser encontrada em ambientes com pH variando de 0,5 a 5,0, enquanto que A.ferrooxidans é encontrada em pHs que variam de 1,0 a 2,5. Devido a essas características e devido a capacidade dessas bactérias de solubilizar metais, A. ferrooxidans e A. thiooxidans vem sendo utilizadas em experimentos de biolixiviação. Este processo é utilizado na indústria para recuperação de cobre devido às vantagens oferecidas. Entretanto, pouco se sabe sobre a resposta gênica destas bactériaS a presença de sulfetos metálicos e dos metais pesados em solução proveniente do processo de oxidação. Na primeira parte deste trabalho foi analisada a resposta gênica da estirpe de A. ferrooxidans LR na presença e na ausência de covelita (CuS) por 24 horas através da técnica de RAP-PCR (Random Arbitrarily Primed Polymerase Chain Reaction). Foram obtidos 19 cDNAs com expressão diferencial, dos quais 12 foram confirmados como sendo diferencialmente expressos. Dentre estes, foram isolados sete genes que codificam: proteínas de transporte (AFE 0123, AFE ,0989, AFE 0990, AFE 0580, AFE 0671, AFE 2248 e AFE 1149), a proteína diguanilato ciclase, uma proteína de membrana, uma metiltnmsferase e uma ATPase, todas induzidas na presença da covelita. Apenas o gene infC, que codifica um fator de iniciação de tradução tipo 3, teve sua expressão reprimida na presença de covelita. Como sete dos genes diferencialmente expressos pertenciam à classe de transportadores, foram investigadas às modificações químicas presentes no meio de cultura após 24 horas. Análises de absorção atômica mostraram que a quantidade de' co1?rê em solução inicialmente zero passava para aproximadamente 1,13 g/L e medidas de pH mostraram que após este período de tempo houve mudanças de 1,8 para 4,0. Pode-se sugerir que essas alterações químicas sejam responsáveis, pelo menos em parte, pela indução dos genes que codificam proteínas de transporte. Uma análise in silico da interação entre proteínas (PPI) relacionadas com transporte, cujos genes foram diferencialmente expressos na presença de covelita e de proteínas pertencentes à mesma categoria funcional, codificadas por genes que estavam fisicamente localizados nas proximidades dos genes diferencialmente expressos, mostraram que os genes de transporte podem estar envolvidos em diferentes etapas da resposta bacteriana à presença de covelita. A segunda parte deste trabalho teve como objetivo estudar a expressão diferencial, por PCR em tempo real, de duas proteínas do tipo ABC (AFE 0123 e AFE 0125) e uma proteína do tipo RND (AFE 0993) na estirpe de A. thiooxidans FGOl na presença de calcopirita (CuFeS2), covelita e pirita (FeS2) por 24 horas. Para tal, a estirpe foi crescida na presença de enxofte e depois mantida na presença dos sulfetos metálicos por 24 horas. A expressão dos três genes foi induzida na presença de covelita e inalterada na presença de calcopirita. Na presença de pirita, a expressão de dois genes foi reprimida e do gene AFE 0993, permaneceu inalterada. Estes resultados podem ser explicados, pelo menos em parte, pelas quantidades de cobre encontradas em solução na presença de covelita (l g/L) e na presença de calcopirita (0,07 g/L). Na presença de covelita e calcopirita a medida de pH também softeu aumento de 1,8 para 4,0 e 2,5, respectivamente. Para investigar se a alteração de pH ou a presença de íons de cobre eram os responsáveis pela indução da expressão desses genes, a bactéria foi mantida na presença de sulfato de cobre (16 mM) e pH 4,0 por 24 horas. Os resultados mostraram que a presença de cobre em solução induz a expressão destes genes, enquanto que a alteração do pH não / Abstract: Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans are acidophilic, chemolitotrophic and mesophilic bacteria found in bioleaching environments. A. ferrooxidans uses ferrous iron and sulphur compounds as an e1ectron donor and A. thiooxidans uses on1y sulphur and sulphur compounds. Both species are aerobic using oxygen as final e1ectron acceptor. However, these bacteria are also able to grow in anaerobic environments. A. thiooxidans is able to survive in pHs ranging from 0.5 to 5.0 while A. ferrooxidans grows in pHs from 1.0 to 2.5. Due to these characteristics and the ability of these bacteria to solubilize metal sulphides, A. ferrooxidans and A. thiooxidans are used in bioleaching. This process has several advantages over the traditional methods and has been used with success in industrial operations to recover main1y copper. However, little is known about the genetic response of these bacteria to the presence of metal sulphides and heavy metal in solution. Therefore, in the first part of this study the A. ferrooxidans LR 'response to covellite was investigated. This bacterium was maintained in contact with covellite for 24 hours and the differentially expressed cDNAs were identified by RAP-PCR (Random Arbitrarily Primed Polymerase Chain Reaction) technique. Nineteen cDNAs showed a differential expression and twe1ve had their differential expression confirmed by real time PCR. Among these cDNAs, seven codified for transporter proteins (AFE 0123, AFE 0989, AFE 0990, AFE 0580, AFE 0671, AFE 2248 and AFE 1149), one codified for a putative diguanylate cyc1ase, one for a membrane. protein, one for a methyltransferase and one for an A TPase. With the exception of infC whose expression was down regulated, all the oDNAs had their expression up regulated in the presence of covellite. Since most of the differentially expressed genes are involved in transport, chemical modifications on the culture medium after 24 hours were investigated. The atomic absorption analysis showed that the copper amount in solution was 1.13 g/L and pH changed from 1.8 to 4.0 suggesting that these changes are responsible, at least in part, for the induction,"?f1he expression of transport gene. An in si/ico ana1ysis of protein-protein interaction (PPI) between the transport proteins codified by the genes differentially expressed in the presence of covellite and those codified by genes that were physically located around the differentially expressed ones showed that these transport proteins could be involved in different steps of the bacterial response to covellite. The goal of the second part of this study was to analyse the differential expression, by real time PCR, of two ABC proteins (AFE 0123 andAFE 0125) and one RND protein (AFE 0993) inA. thiooxidans FGOl in the presence of chalcopyrite, covellite and pyrite for 24 hours. This strain was maintained in contact with the metal sulphides for 24 hours. The expression ofthe three genes was up regulated in the presence of covellite and unchanged in the presence of chalcopyrite. In the presence of pyrite two genes hOO their expression down regulated and in one (AFE 0993) the expression was unchanged. These results can be explained, at least in part, by the quantities of copper found in solution in covellite (1 g/L) and in chalcopyrite (0.07 g/L). In the presence of covellite and chalcopyrite the pH changed from l'.8 to 4.0 and 2.5, respectively. To investigate if the changes in pH or the presence of copper ions in solution were responsible for the induction of the gene expressions, the bacteria were maintained in the presence of copper sulphate (16 mM) and pH 4.0 for 24 hours. The results showed that the presence of copper in solution was the responsible for the up regulation ofthese genes / Mestrado / Biologia Celular / Mestre em Genética e Biologia Molecular
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Étude de la matte sulfo-oxydante de la mangrove de Guadeloupe : caractérisation des micro-organismes principaux des familles Beggiatoaceae et Oscillatoriaceae / Study of the sulfo-oxidant mat from the mangrove swamp of Guadeloupe : Characterization of the main micro-organisms from the Beggiatoaceae and Oscillatoriaceae familyJean, R.N. Maïtena 24 June 2013 (has links)
Les mattes de procaryotes constituent une niche écologique diversifiée. peu étudié!<..en mangrove et jamais décrjte dans les Antilles. L'objectif de cette thèse est de décrire les procaryotes filamenteux reposant sur le sédiment marin et de caractériser les interactions entre la matte, milieu et entre les différents micro-organismes. Nous avons d'abord caractérisé les micro-organismes majoritaires de la matte par le séquençage de l'ADNr 16S et des hybridations moléculaires (FISH). Il a ainsi été possible de décrire deux nouvelles espèces de Beggiatoaceae dont la structure a été étudiée par microscopie électronique. De plus, afin de caractériser l'environnement chimique de ces bactéries, des capteurs potentiométriques ont été utilisés. Ils ont permis de démontrer que les Beggiaotaceae oxydaient les sulfures en prélevant l'oxygène du milieu, tandis que des analyses de microscopie couplées à de l'EDX ont mis en évidence des réserves de soufre intracellulaires dans ces bactéries. Le séquençage de l'ADNr 16S des cyanobactéries filamenteuses a mis en évidence quatre nouvelles espèces de l'ord~e des Oscillatoriales. Deux d'entre elles, du genre Planktothricoides ont révélé une toxicité positive sur les Artemia sp:, les deux autres ont été identifiées comme proches d'Oscillatoria spongeliae, une espèce symbiotique d'éponge, bien que les coupes uItrafines d'une de ces souches aient montré une morphologie interne proche des Tychonema. L'analyse des données a permis d'étoffer les connaissances sur les communautés microbiennes de mangrove et constitue une base intéressante de travail sur la contribution des micro-organismes au fonctionnement de l'écosystème mangrove dans son ensemble / Procaryotic mats are ecological niches, occuring in many ecosystems. Those structures are little studied in marine mangrove sediment and have never been described in West Indies. The purpose ofthis thesis is to characterize the interactions between the mat and the environment, and between the different filamentous micro-organisms living into the mat. In a first place, we characterized the mainly micro-organisrns of the mat by sequencing 16S rDNA. We confirmed these sequences by molecular hybridization (FISH) with specific probes designed from sequences obtained. Thus, it was possible to describe two new Beggiatoaceae strains, whose structure has been studied by electronic microscopy. Furthemore, we used potentiometric captors in situ and in laboratory, by creating a mesocosm, in order to define the chemical environment where involved these bacteria. These experiences proved that the Beggiatoaceae of the mat oxidized the sulfur taking the oxygen from the medium, while the microscopic analysis coupled with EDX showed intracellular sulfur granules into the bacteria. The study of the filamentous cyanobacteria of the mat highlighted four new cyanobacteria strains, all studied by electronic rmcroscopy. Two of them belongs to Planktothrlcoides genus and showed positive toxicity on Artemia salina. The others species are close to Oscillatorla spongeliae, a sponge symbiont, nevertheless, one ofthem showed an intemal morphology close to Tychonema. The analysis of the different results adduces sorne knowledge about mangrove microbial communities. Furthermore, this study can be used as an interesting base to study the micro-organisms contribution in functioning mangrove ecosystem
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Silver Substitution into Common Metal Sulphides from Cobalt, OntarioMalcolmson, Sarah 04 1900 (has links)
<P> The occurrence of silver in galena, chalcopyrite, sphalerite, and pyrite as well as
tailings from Cart Lake, Cobalt Ontario were investigated to compare with the
undetectable ( <10^-11 g/g) Ag found in runoff water from the Cobalt area. </p> <p> Silver was detected at very low levels: 0.012 wt% ± 0.009 wt%, 0.015 wt% ±
0.01 wt%, and 0.0062 wt% ±0.02 wt% for pyrite, galena and chalcopyrite, respectively. </p> <p> Attempts to characterize the mineralogical associations of silver were not
successful. The silver sequence of pyrite> galena> chalcopyrite is contrary to results
from other studies. This may be due to the maximum thermal stabilities of the minerals
in relation to the ions available for replacement. </p> / Thesis / Bachelor of Science (BSc)
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Induced polarization of metallic minerals : a study of its chemical basis.Angoran, Yed Esaie January 1976 (has links)
Thesis. 1976. Ph.D.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Microfiche copy available in Archives and Lindgren. / Bibliography: leaves 182-186. / Ph.D.
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Electronics of sulfide minerals : implications for induced polarizationMorgan, Frank Dale Oliver January 1981 (has links)
Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Earth and Planetary Sciences, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND LINDGREN. / Vita. / Bibliography: leaves 133-136. / by Frank Dale Oliver Morgan. / Ph.D.
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Cerium chloride inhibition for high strength low alloy steel exposed to sulphide polluted seawaterCoimbatore Dhandayuth, Venkatesh January 2008 (has links)
[Truncated abstract] Corrosion of steel structures caused by sulphide is a common engineering problem encountered by many industries, such as the petroleum, chemical processing, mining and mineral processing industries. The control of sulphide corrosion is still a controversial topic among corrosion engineers. There is an absence of guideline for a reliable acceptable limit of sulphide level in service and each processing industry has its own empirical values. Selection of inhibitors in the sulphide environment depends on laboratory testing before its actual application in pipelines and reaction vessels. Many investigators have postulated the corrosion mechanisms due to sulphide based on operating envelopes such as pH, chloride, manganese, hydrogen sulphide, sulphate reducing bacteria levels and inhibitor concentration. It is recommended in the literature that the batch dosing of inhibitor and biocide needs to be evaluated in regards to sulphide reducing bacteria (SRB) level, which may produce sulphide concentrations up to 2000 ppm. Although sulphide scale formation may protect the base metal by providing a physical barrier, the detrimental effects of sulphide are often inevitable, such as stress corrosion cracking, hydrogen embrittlement, etc. Currently, there are many chemicals that are used as inhibitors to prevent corrosion by scavenging the sulphide from the environment. Cerium, a rare-earth element, is not used as inhibitor in the sulphide environment. Also, there are no previous research findings on the effects of compounds of rare-earth metals, such as cerium chloride (CeCl3), in sulphide environment. This research examines the corrosion behaviour of 0.4Mo-0.8Cr steel, a High Strength Low Alloy (HSLA) steel, in sulphide-polluted artificial seawater with the addition of CeCl3 and glutaraldehyde. ... It is postulated that the moderate inhibiting effect of CeCl3 is due to the scavenging effect thereby forming Ce2S3 complex. Further reaction of sulphide with steel resulted in ferrous sulphide, leading to an increased corrosion rate. It is also concluded that the CeCl3 interferes with both anodic and cathodic reactions in deaerated conditions. Addition of glutaraldehyde in the sulphide-polluted seawater was found to decrease the corrosion rate. According to the electrochemical measurements conducted, the concurrent addition of glutaraldehyde and CeCl3 appeared to have an added effect on reducing the corrosion of the steel, as evidenced by the increase of the open circuit potential during the short-term testing. From the weight loss measurements after 60 days, sulphide pollution in deaerated seawater was found to increase corrosion rate. This is attributed to the increase of sulphide activity whereby continual dissolution of steel was encountered. From the weight loss tests, it was found that the addition of CeCl3 and glutaraldehyde reduced the corrosion rate of the steel in the solutions containing 0-10 ppm sulphide. There is no noticeable corrosion rate decrease for the solution containing 100 ppm sulphide. The added effect of CeCl3 and glutaraldehyde to the SRB medium has resulted in lower corrosion rates. Further detailed experimentation is required to elucidate the corrosion reduction mechanism in glutaraldehyde-containing environments.
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The influence of continuous casting parameters on hot tensile behaviour in low carbon, niobium and boron steelsChown, Lesley H. 26 February 2009 (has links)
Abstract
This thesis studies the factors that govern transverse cracking during continuous casting
of low carbon, niobium microalloyed and boron microalloyed steels. Crack susceptibility
in the thick slab, billet and thin slab casting processes are compared by using typical
conditions in laboratory hot ductility tests.
There is limited published literature on hot ductility in aluminium-killed and siliconkilled
boron microalloyed steels and the proposed mechanisms of failure by transverse
cracking are contradictory. Few published papers specifically compare hot ductility
behaviour of any steels between thick slab, billet and thin slab continuous casting
processes. Thus, the basis of this research is to assess the influence of casting parameters
and compositional variations on hot ductility behaviour in low carbon steels, niobium
microalloyed steels, aluminium-killed boron microalloyed steels and silicon-killed, boron
microalloyed steels.
The typical temperature ranges, cooling rate and strain rate conditions of the continuous
casting processes were used in reheated and in situ melted hot tensile tests performed on
steel specimens. Solidification, transformation and precipitation temperatures were
calculated using solubility equations and modelled using the Thermo-CalcTM
thermodynamics program. Scanning electron microscopy and transmission electron
microscopy were used to determine the modes of failure in the tested specimens.
In the low carbon steels, hot ductility was improved by increasing the strain rate; by
calcium treatment, which minimises copper sulphide and iron sulphide formation; and by
maintaining a nickel to copper ratio of 1:1. It was shown that thin slab casting conditions
provided the best hot ductility results for the low carbon steels.
All the niobium steels showed poor ductility in the single-phase austenite temperature
region, indicating that intergranular precipitation of fine niobium carbonitrides was the
cause of the poor ductility. It was shown that the hot ductility was greatly improved by
calcium treatment, by decreasing the cooling rate and by increasing the strain rate. Slow
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thin slab and thick slab casting conditions provided the best hot ductility results for the
niobium steels.
Hot ductility was substantially improved in the aluminium-killed boron steels by
increasing the boron to nitrogen ratio from 0.19 to 0.75. The results showed that, at
cooling rates generally associated with thick slab, bloom and slow thin slab casting, a
boron to nitrogen ratio of ≥0.47 was sufficient to avoid a ductility trough altogether.
However, under conditions typically experienced in fast thin slab and billet casting, a
boron to nitrogen ratio of 0.75 was required to provide good hot ductility. The mechanism
of the ductility improvement with increasing boron to nitrogen ratio was found to be
enhanced precipitation of boron nitride, leading to a decrease in nitrogen available for
aluminium nitride precipitation.
In the silicon-killed boron steels, it was found that the boron to nitrogen ratio had the
overriding influence on hot ductility and hence on crack susceptibility. Excellent hot ductility
was found for boron to nitrogen ratios above 1. Additionally, analysis of industrial casting data
showed that the scrap percentage due to transverse cracking increased significantly at
manganese to sulphur ratios below fourteen. An exponential decay relationship between the
manganese to sulphur ratio and the average scrap percentage due to transverse cracking was
determined as a tool to predict scrap levels in the casting plant.
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Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas / Novel vinyl sulfides-based molecular dyes: synthesis and photophysical propertiesAraujo, Matias Monçalves January 2017 (has links)
Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This thesis describes, initially, the synthesis and photophysical characterization
of new sulfides,sulphoxides and vinyl sulfones based dyes. The compounds in question
were obtained in good yields and good diastereoselectivity through Horner-Wadsworth-
Emmons (HWE) reactions. The compounds absorb light in the UV/Vis region, with the
major transitions occurring between – * orbitals. As for the emission, the PS-1 and PS-
2 vinyl sulphides have their maximum emission bands in the blue region of the spectrum.
The oxidation to their respective sulphoxides and sulfones, and the attainment of D– –A
structure, causes the emission to undergo a bathochromic shift to the green region of the
spectrum. These effects are most pronounced in the triphenylamine derivatives (PSO-1
and PSO2-1) and in polar solvents (positive solvatocromism). With the aid of DFT and
TD-DFT calculations, it can be observed that this behaviors are related to the formation
of intramolecular charge transfer states (ICT) in the excited state.
Subsequently, the design, synthesis and characterization of new vinyl sulphides for
possible application in dye-sensitized solar cell (DSSCs) are presented. The compounds
were designed to have a D– –A structure, where the sulphides would serve as a bridge
between the donor (D) and acceptor (A) blocks. The compounds studied were obtained
by the HWE and Knoevenagel condensation, in good yields and good diastereoselectivity.
Through preliminary photophysical analysis, it has been observed that the dyes have a
wide light absorption range (250–550 nm), in particular the dyes derived from malononitrile
PCN-1, PCN-2 and PSCN. In addition to being greatly influenced by the nature
of the electron acceptor group. These characteristics are in line with that expected for
application in DSSCs and are similar to several sensitizing dyes reported in the literature. / Nesta tese descreve-se, inicialmente, a síntese e a caracterização fotofísica de novos
corantes derivados de sulfetos, sulfóxidos e sulfonas vinílicas. Os compostos em questão
foram obtidos em bons rendimentos e boa diastereosseletividade, através de reações de
Horner-Wadsworth-Emmons (HWE). As propriedades fotofísicas dos corantes estudados
mostraram-se bastante interessantes. Os compostos absorvem luz na região do UV/Vis,
sendo que as principais transições ocorrem entre orbitais – *. Quanto a emissão, os
sulfetos vinílicos PS-1 e PS-2 têm suas bandas máximas de emissão na região azul do
espectro. A oxidação para seus respectivos sulfóxidos e sulfonas, e a obtenção de estrutura
do tipo D– –A, faz com que a emissão sofra um deslocamento batocrômico para a
região verde do espectro. Estes efeitos são mais acentuados nos derivados da trifenilamina
(PSO-1 e PSO2-1) e em solvente polares (solvatocromismo positivo). Com o auxílio de
cálculos DFT e TD-DFT, pode-se constatar que estes comportamentos estão relacionados
à formação de estados de transferência de carga intramolecular (ICT) no estado excitado.
Posteriormente, são apresentados o design, síntese e caracterização de novos sulfetos
vinílicos para possível aplicação em células solares sensibilizadas (DSSCs). Os compostos
foram desenhados para possuírem estrutura do D– –A, onde os sulfetos vinílicos
serviriam como uma “ponte” -conjugada para os blocos doador (D) e aceptor (A). Os
compostos estudados foram obtidos através da reação de HWE e condensação de Knoevenagel,
em bons rendimentos e boa diastereosseletividade. Através da análise fotofísica
preliminar, observou-se que os corantes possuem uma ampla faixa de absorção de luz (250–
550 nm), sobretudo os corantes derivados da malononitrila PCN-1, PCN-2 e PSCN.
Além de serem bastante influenciados pela natureza do grupo aceptor de elétrons. Estas
características estão de acordo com o esperado para aplicação em DSSCs e, são semelhantes
a diversos corantes sensibilizadores reportados na literatura.
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