Síntese de zeólitas utilizando cátions orgânicos a base de um anel imidazólio como agentes direcionadores de estruturas em meio fluorídrico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES

Materiais zeolíticos de estrutura MWW: síntese e caracterização

In this paper a synthesis parameters study was conducted in order to optimize the obteinment of MCM-22 (MWW structure) and increase its accessibility, getting higher external surface and generating mesopores. Syntheses with Si / Al = 15 and Si / Al = 50 ratios were performed under static conditions at different temperatures and with seeds induction, which resulted in MCM-22 pure and crystalline (Si / Al ratio = 15) after 3 days and Si / Al = 50 after 11 days. The reduction of hexamethyleneimine content (HMI) was studied in the stirring synthesis and a HMI reduction of 47% was possible through the mother liquor reuse, in addition, a specific area of 481 m² / g has been obtained in the fourth synthesis day. Regarding the increase of accessibility of the MCM-22 zeolite skeins of MCM-22 plates with about 2 μm were obtained, through the use of dissolved silica, addition of seeds, increased temperature and synthesis time of 2 days. A significant value of specific area was found for this material, around 500 m² / g. Also with respect to the increase of MCM-22 accessibility, treatment with oxalic acid concentration of 0.5 mol / L and silanization of proto-zeolitic units resulted in the mesopores formation . Furthermore, silanization still favored reduction of 70 % in crystal size and a specific area of 566 m² / g.

Petrologia e geologia estrutural do plutão granítico Barcelona, província Borborema, NE do Brasil

The Dissertation aimed to advance the geological knowledge of the Barcelona Granitic Pluton (BGP). This body is located in the eastern portion of the Rio Grande do Norte Domain (RND), within the São José do Campestre subdomain (SJC), NE of the Borborema Province. The main goal was to understand the geological evolution of the rocks of the pluton and the tectonic setting of magma generation and its emplacement. The BGP has an assumed Ediacaran age and outcropping area of approximately 260 km2, being composed of three varied petrographic/textural facies: (a) porphyritic biotite monzogranite; (b) dykes and sheets of biotite microgranite; (c) dioritic to quartz-dioritic enclaves. The rocks of the BGP have the following structures: (i) a NE-SW and NW-SE directed magmatic fabric (Sγ), accompanied by a magmatic lineation (Lγ) with gentle dip to NE-SW and NW-SE. In the southern portion, there is the concentric pattern of this foliation with medium to high dip, and (ii) a solid state foliation, in part mylonitic (S3+), mainly on the eastern edge with slightly plunging to west. The integration of structural and gravity data permitted to interpret the emplacement of the BGP as controlled by the transcurrent shear zones systems Lajes Pintadas (LPSZ) and Sítio Novo (SNSZ), both of dextral strike-slip kinematics. Mineral chemistry data show that the amphibole form the porphyritic biotite monzogranite facies is hastingsite with moderate Mg / (Mg + Fe) ratios, indicating crystallization under moderate to high ƒO2 and cristallization pressure of around 5.0-6.0 kbar. The biotite tends to be slightly richer in annite molecule and plots in the transitional field from primary biotite to reequilibrated biotite. In discriminant diagrams of magmatic series, the biotite behave like those of subalkaline affinity, consistent with the potassium calc-alkaline / sub-alkaline geochemical affinity of the hosting rock. The opaque minerals are primarily magnetite, with some crystals martitized to hematite indicating relatively oxidizing conditions during magma evolution that originated the BGP. Zoning in plagioclase, K-feldspar and allanite crystals suggest fractional crystallization process. Lithogeochemical data suggest that the facies described for the BGP have similar magma source, usually plotting in the fields and trends of the subalkaline / high potassium calc-alkaline series.

Petrologia e geocronologia U-Pb do plúton granítico Serra da Rajada, porção central do domínio Rio Piranhas - Seridó, Província Borborema, NE do Brasil

The ediacaran plutonic activity related to the Brasilian/Pan-African orogeny is one of the most important geological features in the Borborema Province, represented along its extension by numerous batholiths, stocks, and dikes.The object of this study, the Serra Rajada Granitic Pluton (SRGP), located in the central portion of the Piranhas-Seridó River Domain is an example of this activity. This pluton has been the subject of cartographic, petrographic, geochronological and lithogeochemical studies and its rocks were characterized by two facies. First, the granitic facies were described as monzogranites consisting of K-feldspar, plagioclase (oligoclase - An23-24%), quartz and biotite (main mafic) and opaque minerals such as titanite, allanite, apatite, and zircon as accessories. Alteration minerals are chlorite, white mica and carbonate. Second, the dioritic facies consist of rocks formed by quartz diorite containing plagioclase (dominant mineral phase), quartz and K-feldspar. Biotite and amphibole are the dominant mafic minerals; and titanite, opaque minerals, allanite, zircon and apatite are the accessories. However, previous geological mapping work in the region also identified the presence of other lithostratigraphic units. These were described as gneisses and migmatites with undifferentiated amphibolite lenses related to the Caicó Complex (Paleoproterozoic) and metasedimentary rocks of the Seridó Group (Neoproterozoic) composed of paragneiss with calc-silicate lenses, muscovite quartzite and biotite schist (respectively, the Jucurutu formations, Equador and Seridó), the host rocks for the SRGP rocks. Leucomicrogranite and pegmatite dikes have also been identified, both related to the end of the Ediacaran magmatism and colluvial- eluvial and alluvial deposits related to Neogene and Quaternary, respectively. Lithogeochemical data on the SRGP granite facies, highlighted quite evolved rocks (SiO2 69% to 75%), rich in alkalis (Na2O+K2O ≥ 8.0%), depleted of MgO (≤ 0.45%), CaO (≤ 1.42%) and TiO2 (≤ 0.36%) and moderate levels of Fe2O3t (2.16 to 3.53%). They display transitional nature between metaluminous and peraluminous (predominance of the latter) with sub-alkaline/monzonitic (High K calcium-alkali) affinity. Harker diagrams show negative correlations for Fe2O3t, MgO, and CaO, indicating mafic and plagioclase fractionation. REE spectrum shows enrichment of LREE relative to heavy REE (LaN/YbN = 23.70 to 10.13), with negative anomaly in the Eu (Eu/Eu* = 0.70 to 0.23), suggesting fractionation or accumulation in the feldspars source (plagioclase). Data integration allows to correlate the SRGP rocks with those described as Calcium-Alkaline Suite of equigranular High K. The crystallization conditions of the SRGP rocks were determined from the integration of petrographic and lithogeochemical data. These data indicated intermediate to high conditions of ƒO2 (mineral paragenesis titanite + magnetite + quartz), parent magma saturated in H2O (early biotite crystallization), tardi-magmatic processes of fluids rich in ƒCO2, H2O and O2 causing part of the mineral assembly to change (plagioclase carbonation and saussuritization, biotite chloritization and opaques Sphenitization). Thermobarometrical conditions were estimated based on geochemical parameters (Zr and P2O5) and CIPW normative minerals, with results showing the liquidus minimum temperature of about800°C and the solidus temperature of approximately 700°C. The final/minimum crystallization pressure are suggested to be between 3 and 5 Kbar. The presence of zoned minerals (plagioclase and allanite) associated with lithogeochemical data in bi-log diagrams for Rb vs. Ba and Rb vs. Sr suggest the role of fractional crystallization as the dominant process in the magmatic evolution of SRGP. U-Pb Geochronological and Sm-Nd isotope studies indicated, respectively, the crystallization age of biotite monzogranite as 557 ± 13 Ma, with TDM model age of 2.36 Ga, and εNd value of -20.10 to the crystallization age, allowing to infer paleoproterozoic crustal source for the magma.

Petrologia e geocronologia U-Pb do plúton granítico Serra da Rajada, porção central do domínio Rio Piranhas - Seridó, Província Borborema, NE do Brasil

The ediacaran plutonic activity related to the Brasilian/Pan-African orogeny is one of the most important geological features in the Borborema Province, represented along its extension by numerous batholiths, stocks, and dikes.The object of this study, the Serra Rajada Granitic Pluton (SRGP), located in the central portion of the Piranhas-Seridó River Domain is an example of this activity. This pluton has been the subject of cartographic, petrographic, geochronological and lithogeochemical studies and its rocks were characterized by two facies. First, the granitic facies were described as monzogranites consisting of K-feldspar, plagioclase (oligoclase - An23-24%), quartz and biotite (main mafic) and opaque minerals such as titanite, allanite, apatite, and zircon as accessories. Alteration minerals are chlorite, white mica and carbonate. Second, the dioritic facies consist of rocks formed by quartz diorite containing plagioclase (dominant mineral phase), quartz and K-feldspar. Biotite and amphibole are the dominant mafic minerals; and titanite, opaque minerals, allanite, zircon and apatite are the accessories. However, previous geological mapping work in the region also identified the presence of other lithostratigraphic units. These were described as gneisses and migmatites with undifferentiated amphibolite lenses related to the Caicó Complex (Paleoproterozoic) and metasedimentary rocks of the Seridó Group (Neoproterozoic) composed of paragneiss with calc-silicate lenses, muscovite quartzite and biotite schist (respectively, the Jucurutu formations, Equador and Seridó), the host rocks for the SRGP rocks. Leucomicrogranite and pegmatite dikes have also been identified, both related to the end of the Ediacaran magmatism and colluvial- eluvial and alluvial deposits related to Neogene and Quaternary, respectively. Lithogeochemical data on the SRGP granite facies, highlighted quite evolved rocks (SiO2 69% to 75%), rich in alkalis (Na2O+K2O ≥ 8.0%), depleted of MgO (≤ 0.45%), CaO (≤ 1.42%) and TiO2 (≤ 0.36%) and moderate levels of Fe2O3t (2.16 to 3.53%). They display transitional nature between metaluminous and peraluminous (predominance of the latter) with sub-alkaline/monzonitic (High K calcium-alkali) affinity. Harker diagrams show negative correlations for Fe2O3t, MgO, and CaO, indicating mafic and plagioclase fractionation. REE spectrum shows enrichment of LREE relative to heavy REE (LaN/YbN = 23.70 to 10.13), with negative anomaly in the Eu (Eu/Eu* = 0.70 to 0.23), suggesting fractionation or accumulation in the feldspars source (plagioclase). Data integration allows to correlate the SRGP rocks with those described as Calcium-Alkaline Suite of equigranular High K. The crystallization conditions of the SRGP rocks were determined from the integration of petrographic and lithogeochemical data. These data indicated intermediate to high conditions of ƒO2 (mineral paragenesis titanite + magnetite + quartz), parent magma saturated in H2O (early biotite crystallization), tardi-magmatic processes of fluids rich in ƒCO2, H2O and O2 causing part of the mineral assembly to change (plagioclase carbonation and saussuritization, biotite chloritization and opaques Sphenitization). Thermobarometrical conditions were estimated based on geochemical parameters (Zr and P2O5) and CIPW normative minerals, with results showing the liquidus minimum temperature of about800°C and the solidus temperature of approximately 700°C. The final/minimum crystallization pressure are suggested to be between 3 and 5 Kbar. The presence of zoned minerals (plagioclase and allanite) associated with lithogeochemical data in bi-log diagrams for Rb vs. Ba and Rb vs. Sr suggest the role of fractional crystallization as the dominant process in the magmatic evolution of SRGP. U-Pb Geochronological and Sm-Nd isotope studies indicated, respectively, the crystallization age of biotite monzogranite as 557 ± 13 Ma, with TDM model age of 2.36 Ga, and εNd value of -20.10 to the crystallization age, allowing to infer paleoproterozoic crustal source for the magma.

Petrologia do Plutão Bom Jardim de Goiás (PBJG): implicação na evolução neoproterozoica da Província Tocantins

The Bom Jardim de Goiás Pluton (PBJG) is a semi-circular body, located in the central portion of the Tocantins Province, intrusive into orthogneisses and metassupracrustals of the Arenópolis Magmatic Arc. These metasupracrustals present a low to moderate dipping banding or schistosity, have a low to moderate angle of banding / foliation, defined by mica, andalusite and sillimanite and cordierite, which characterize an amphibolite facies metamorphism. This structure is crosscut by the emplacement of the PBJG rocks. The abrupt nature of the contacts and the absence of ductile structures indicate that the intrusion took place in a relatively cold crust. Under petrographic grounds, the pluton consists mainly of monzodiorites, tonalite and granodiorite, following the low to medium-K calk-alkaline alkaline trend. Rocks of the PBJG have hornblende and biotite as the main mafic phases, besides subordinate clinopyroxene, titanite, epidote and opaque. Late dikes of leucogranite contain only mineral biotite as relevant accessory mineral. One U-Pb zircon dating of a monzodiorite yielded an age of 550 ± 12 Ma (MSWD = 1.06). Whole-rock and mineral chemistry suggest that the studied rocks are calc-alkaline, having evolved by fractional crystallization of Ca- and Fe-Mg minerals under high oxygen fugacity. Using the amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer, we calculate temperatures and pressures of, respectively, 692-791 °C e 2.4-5.0 kbar for the intrusion of the PBJG, which is corroborated by previous metamorphic assemblages in the country rocks. The geological, geochemical and geochronological features of PBJG demonstrate their post-tectonic or post-collisional nature, with emplacement into an already uplifted and relatively cool crust at the end of brasiliano orogeny in this portion of the Tocantins Province.

Petrologia do Plutão Bom Jardim de Goiás (PBJG): implicação na evolução neoproterozoica da Província Tocantins

The Bom Jardim de Goiás Pluton (PBJG) is a semi-circular body, located in the central portion of the Tocantins Province, intrusive into orthogneisses and metassupracrustals of the Arenópolis Magmatic Arc. These metasupracrustals present a low to moderate dipping banding or schistosity, have a low to moderate angle of banding / foliation, defined by mica, andalusite and sillimanite and cordierite, which characterize an amphibolite facies metamorphism. This structure is crosscut by the emplacement of the PBJG rocks. The abrupt nature of the contacts and the absence of ductile structures indicate that the intrusion took place in a relatively cold crust. Under petrographic grounds, the pluton consists mainly of monzodiorites, tonalite and granodiorite, following the low to medium-K calk-alkaline alkaline trend. Rocks of the PBJG have hornblende and biotite as the main mafic phases, besides subordinate clinopyroxene, titanite, epidote and opaque. Late dikes of leucogranite contain only mineral biotite as relevant accessory mineral. One U-Pb zircon dating of a monzodiorite yielded an age of 550 ± 12 Ma (MSWD = 1.06). Whole-rock and mineral chemistry suggest that the studied rocks are calc-alkaline, having evolved by fractional crystallization of Ca- and Fe-Mg minerals under high oxygen fugacity. Using the amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer, we calculate temperatures and pressures of, respectively, 692-791 °C e 2.4-5.0 kbar for the intrusion of the PBJG, which is corroborated by previous metamorphic assemblages in the country rocks. The geological, geochemical and geochronological features of PBJG demonstrate their post-tectonic or post-collisional nature, with emplacement into an already uplifted and relatively cool crust at the end of brasiliano orogeny in this portion of the Tocantins Province.

Petrologia e geoquímica do magmatismo ediacarano Serra do Caramuru, Rio Grande do Norte, NE do Brasil

The Serra do Caramuru and Tapuio stocks, located in the extreme NE of Rio Piranhas-Seridó Domain (RN), are representative of the Ediacaran-Cambrian magmatism, an important magmatic feature of the Brasilian / Panafrican orogeny of the Borborema Province. These bodies are lithologically similar, intrusive in paleoproterozoic gneiss embasement, being separated by a thin belt of mylonitic orthogneiss. The field relations show a magmatic stratigraphy initiated by dioritic facies that coexists with the porphyritic granitic and equigranular granitic I facies, and less frequently with equigranular granitic II facies. These rocks are crosscut by late granitic dykes and sheets with NE-SW / NNE-SSW orientation. The dioritic facies (diorite, quartz diorite, quartz monzodiorites, tonalite and granodiorite) is leucocratic to melanocratic, rich in biotite and hornblende. The granitic facies are hololeucocratic to leucocratic, and have biotite ± hornblende. Petrographic and geochemical (whole rock) data, especially from Serra do Caramuru pluton, suggest fractionation of zircon, apatite, clinopyroxene (in diorites), opaque minerals, titanite, biotite, hornblende, allanite, plagioclase, microcline and garnet (in dykes). The behavior of trace elements such as Zr, La and Yb indicates that the dioritic magma does not constitute the parental magma for the granitic facies. On the other hand, the granitic facies seems to be cogenetic to each other, displaying differentiation trends and very similar rare earth elements (REE) spectra [12.3≤(La/Yb)N≤190.8; Eu/Eu*=0.30-0.68]. Field relationships and REE patterns [6.96≤(La/Yb)N≤277.8; Eu/Eu*=0.18-0.58] demonstrate that the granitic dykes and sheets are not cogenetically related to the Serra do Caramuru magmatism. The dioritic facies is metaluminous (A/CNK = 0.88-0.74) and shoshonitic, whereas the granitic ones are metaluminous to peraluminous (A/CNK = 1.08-0.93) and high potassium calc-alkaline. Dykes and sheets are strictly peraluminous (A/CNK = 1.01-1.04). Binary diagrams relating compatible and incompatible trace elements and microtextures indicate the fractional crystallization as the dominant mechanism of magmatic evolution of the various facies. The Serra do Caramuru and Tapuio stocks have well preserved magmatic fabric, do not show metamorphic minerals and are structurally isotropic, showing crosscutting contact with the ductile fabric of the basement. These observations lead to interpretate a stage of relative tectonic stability, consistent with the orogenic relaxation period of the Brasiliano / Pan-African orogeny. Chemical plots involving oxides and trace elements indicate late to post-collisional emplacement. In this context, the assumed better mechanism to describe the stocks emplacement within an extensional T Riedel joint, with ENE-WSW extensional vector. The U-Pb zircon age of 553 ± 10 Ma allows correlating the Serra do Caramuru magmatism to the group of post-collisional bodies, equigranular high potassium calc-alkaline granites of the NE of Rio Piranhas-Seridó Domain.

Petrologia e geoquímica do magmatismo ediacarano Serra do Caramuru, Rio Grande do Norte, NE do Brasil

The Serra do Caramuru and Tapuio stocks, located in the extreme NE of Rio Piranhas-Seridó Domain (RN), are representative of the Ediacaran-Cambrian magmatism, an important magmatic feature of the Brasilian / Panafrican orogeny of the Borborema Province. These bodies are lithologically similar, intrusive in paleoproterozoic gneiss embasement, being separated by a thin belt of mylonitic orthogneiss. The field relations show a magmatic stratigraphy initiated by dioritic facies that coexists with the porphyritic granitic and equigranular granitic I facies, and less frequently with equigranular granitic II facies. These rocks are crosscut by late granitic dykes and sheets with NE-SW / NNE-SSW orientation. The dioritic facies (diorite, quartz diorite, quartz monzodiorites, tonalite and granodiorite) is leucocratic to melanocratic, rich in biotite and hornblende. The granitic facies are hololeucocratic to leucocratic, and have biotite ± hornblende. Petrographic and geochemical (whole rock) data, especially from Serra do Caramuru pluton, suggest fractionation of zircon, apatite, clinopyroxene (in diorites), opaque minerals, titanite, biotite, hornblende, allanite, plagioclase, microcline and garnet (in dykes). The behavior of trace elements such as Zr, La and Yb indicates that the dioritic magma does not constitute the parental magma for the granitic facies. On the other hand, the granitic facies seems to be cogenetic to each other, displaying differentiation trends and very similar rare earth elements (REE) spectra [12.3≤(La/Yb)N≤190.8; Eu/Eu*=0.30-0.68]. Field relationships and REE patterns [6.96≤(La/Yb)N≤277.8; Eu/Eu*=0.18-0.58] demonstrate that the granitic dykes and sheets are not cogenetically related to the Serra do Caramuru magmatism. The dioritic facies is metaluminous (A/CNK = 0.88-0.74) and shoshonitic, whereas the granitic ones are metaluminous to peraluminous (A/CNK = 1.08-0.93) and high potassium calc-alkaline. Dykes and sheets are strictly peraluminous (A/CNK = 1.01-1.04). Binary diagrams relating compatible and incompatible trace elements and microtextures indicate the fractional crystallization as the dominant mechanism of magmatic evolution of the various facies. The Serra do Caramuru and Tapuio stocks have well preserved magmatic fabric, do not show metamorphic minerals and are structurally isotropic, showing crosscutting contact with the ductile fabric of the basement. These observations lead to interpretate a stage of relative tectonic stability, consistent with the orogenic relaxation period of the Brasiliano / Pan-African orogeny. Chemical plots involving oxides and trace elements indicate late to post-collisional emplacement. In this context, the assumed better mechanism to describe the stocks emplacement within an extensional T Riedel joint, with ENE-WSW extensional vector. The U-Pb zircon age of 553 ± 10 Ma allows correlating the Serra do Caramuru magmatism to the group of post-collisional bodies, equigranular high potassium calc-alkaline granites of the NE of Rio Piranhas-Seridó Domain.

Granitos Variscos do Centro Norte de Portugal

A Cadeia Varisca Europeia, formada no final do Paleozóico, estende-se desde a Europa de Leste até à Península Ibérica e inclui extensas áreas ocupadas por rochas graníticas, representando, por isso, uma das regiões do globo em que mais se têm investigado os processos de reciclagem e acreção crustal em contexto de colisão continental. O Maciço Ibérico constitui o segmento mais ocidental do orógeno varisco europeu e uma das áreas onde a actividade plutónica está mais bem expressa e mostra uma maior diversidade tipológica. No Maciço Ibérico, em particular na Zona Centro Ibérica (ZCI), a intrusão de rochas granitóides de idade varisca está preferencialmente associada com a terceira fase de deformação (D3). De acordo com as suas relações com este evento de deformação, os granitóides da ZCI foram subdivididos em dois grandes grupos: sin-D3 e tardi-pós-D3. Em termos petrográficos e geoquímicos, os maciços graníticos sin- e tardi-pós-D3 têm sido integrados em duas séries principais: (a) a série dos granitos de duas micas e dos leucogranitos fortemente peraluminosos e (b) a série dos monzogranitos e granodioritos, metaluminosos a fracamente peraluminosos, com biotite ± anfíbola. Os granitos da primeira série apresentam uma filiação de tipo S e resultam da anatexia de materiais supracrustais durante o clímax de metamorfismo regional, enquanto.os granitóides da segunda série exibem características transicionais I-S e têm sido interpretados, quer como produtos da hibridização de magmas félsicos crustais com magmas básicos de proveniência mantélica, quer como resultantes da anatexia de protólitos metaígneos da crosta inferior. O trabalho realizado no batólito das Beiras revela que o clímax de metamorfismo regional foi atingido neste sector durante um evento extensional (D2), que foi acompanhado por intensa migmatização. No ínício da D3, o volume de fundidos crustais já seria suficientemente grande (ca. 15-35%) para que pudesse ocorrer a sua separação do resíduo sólido. Assim, durante a tectónica transcorrente D3, dá-se a ascenção, diferenciação e consolidação de abundantes quantidades de magmas graníticos, fortemente peraluminosos e isotopicamente evoluídos (tipo-S), que vêm a originar enormes batólitos de leucogranitos de duas micas, com idades entre 317-312 Ma. No final da D3, com a progressiva substituição do manto litosférico pela astenosfera, mais quente, diminui a densidade da coluna litosférica e ocorre o levantamento isostático e exumação da crusta. A fusão por descompressão da astenosfera gera líquidos básicos que hibridizam com os fundidos félsicos crustais, em proporções variáveis, e produzem magmas metaluminosos a ligeiramente peraluminosos, de afinidade calco-alcalina. A ascenção destes magmas terá tido lugar nos últimos estádios da deformação transcorrente e a sua instalação no nível crustal final ocorre após a D3, dando origem aos inúmeros maciços compósitos de granitóides biotíticos híbridos tardi-pós-cinemáticos, presentes no batólito das Beiras. Os dados de campo mostram que estes granitóides são intrusivos nos plutões sin-D3, cortam as estruturas regionais e provocam metamorfismo de contacto nas sequências do Carbónico Superior. Com base nas idades U-Pb obtidas em zircões e monazites, é possível datar este importante período de plutonismo granítico com 306-294 Ma. A assinatura geoquímica e isotópica dos granitóides híbridos tardi-pós-D3 revela que, para além da mistura de componentes com proveniência distinta (manto empobrecido e crusta continental), a sua evolução foi, em grande parte, controlada por processos de cristalização fraccionada (modelo AFC).

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Concentrados de ácidos graxos insaturados obtidos a partir de óleo de carpa (cyprinus carpio) utilizando o método da complexação com uréia

O presente trabalho teve como objetivo obter concentrados de ácidos graxos mono e poliinsaturados a partir do óleo branqueado de carpa (Cyprinus carpio), utilizando o método de complexação com uréia, e estabelecer as melhores condições através do estudo de seus parâmetros. Foi utilizado um planejamento experimental 23 para determinar os fatores que influenciam de forma significativa (nível de 95%) os experimentos da complexação com uréia, e verificar quais as faixas de valores desses fatores que apresentam os melhores resultados. Os fatores de estudo foram: relação de uréia-ácido graxo (2:1 e 6:1), temperatura de cristalização (4ºC e -12ºC) e tempo de cristalização (14 e 24 h). As respostas para análise estatística foram: rendimento da fração líquida (%Rend), percentual de ácidos graxos livres (%AGL) da fração líquida e o perfil de ácidos graxos. Conforme o estudo realizado, a relação uréia/AG se mostrou muito efetiva, de forma diretamente proporcional, na obtenção de concentrados de ácidos graxos monoinsaturados (AGMI) e poliinsaturados (AGPI). Pois, uma vez que ao aumentar a relação de uréia/AG resultou em um meio favorável para a inclusão dos ácidos graxos saturados (AGS) na cristalização da uréia. Por este motivo a relação (6:1) foi melhor para obter concentrados de AGMI+AGPI. A relação entre temperatura e rendimento de concentrados de ácidos graxos insaturados foi de forma inversamente proporcional, sendo que no menor valor (-12ºC) ocorreu a melhor separação de ácidos graxos saturados dos insaturados. O tempo foi significativo, porém com menor influência quando comparado com as demais variáveis de estudo. Devido a isso, o ganho em rendimento dos concentrados de ácidos graxos insaturados em relação ao custo operacional envolvidos no método de complexação com uréia não sugere que o maior tempo seja utilizado, sendo que 14 h oferece rendimentos que tendem à maior produtividade. Assim, as melhores condições para a obtenção de concentrados foram: maior relação de uréia/AG (6:1), menor temperatura (-12ºC) e menor tempo (14 h). Sendo que nestas condições as frações líquidas apresentaram rendimento em massa de até 65,4%, e seu percentual de ácidos graxos livres (%AGL) ficou em média 35,8 g/100g ácido oléico. Os ácidos graxos mono e poliinsaturados na melhor condição de complexação com uréia foram concentrados em 85,2%, e entre estes os EPA+DHA foram concentrados em 9,4%.

Estudo da influência do nevoeiro salino nas propriedades de calcários portugueses

O nevoeiro salino é um agente de meteorização importante para a maioria dos materiais de construção. Os produtos em pedra natural não são exceção. A estrutura das rochas geralmente apresenta características texturais (rede de poros, microfissuras, fissuras, planos de xistosidade, etc.), que facilitam a penetração do nevoeiro salino na pedra e a condensação no seu interior. A presença da solução salina pode conduzir à degradação da rocha e em casos extremos, à sua total desintegração, através de mecanismos físicos decorrentes da cristalização de sais, da hidratação destes, ou de distintas dilatações/retrações térmicas entre sal e rocha. Contudo, a pedra também pode ser alterada por processos químicos, dos quais a dissolução dos carbonatos é um exemplo. Entre os principais tipos de rocha explorados em Portugal, os calcários são particularmente suscetíveis ao nevoeiro salino, posto que geralmente apresentam porosidades abertas com valores elevados e uma rede de poros que permite uma penetração mais profunda do nevoeiro salino na estrutura da pedra. O estudo do comportamento dos calcários ao nevoeiro salino assume particular importância em Portugal, devido ao facto do país possuir uma orla costeira extensa, grande parte da qual sob a influência de nevoeiro salino. É o litoral que apresenta a maior densidade populacional e, consequentemente, onde se concentram as construções. Além disto, Portugal possui vastas reservas de calcários ornamentais, que são utilizados em larga escala como materiais de construção, desde tempos imemoriais e cuja procura pelo mercado externo, tem vindo a sofrer um incremento significativo. Para este estudo foram selecionados seis calcários portugueses amplamente aplicados e com propriedades físico-mecânicas diferentes. Depois de analisadas as suas características petrográficas, químicas e as principais propriedades tecnológicas, os calcários foram submetidos aos seguintes ensaios de envelhecimento: choque térmico, gelo e nevoeiro salino. A determinação de todas as características tecnológicas através de normas europeias, permitiu uma análise crítica dos respetivos métodos de ensaio e a elaboração de propostas de melhoria de alguns dos métodos. No nevoeiro salino, a avaliação deste ensaio foi complementada com as determinações e análises a seguir apresentadas, não exigidas pela norma europeia: variações na absorção de água e na resistência à flexão; comparação do ensaio em três acabamentos superficiais distintos; análises comparativas de imagens macroscópicas da superfície, de imagens através de lupa binocular e de imagens de eletrões secundários, obtidas com recurso a microssonda eletrónica. Os resultados permitiram avaliar a aptidão dos calcários para os principais tipos de aplicações e, dentro de cada uma, para condições específicas de uso. Assim, foi possível definir as utilizações recomendadas para cada calcário, com o objectivo de maximizar a sua durabilidade. Os ensaios de envelhecimento possibilitaram determinar a resistência dos calcários perante várias condições climáticas específicas, incluindo as existentes em zonas costeiras. A análise detalhada dos resultados do nevoeiro salino reforça o conhecimento de que a porosidade aberta desempenha um papel determinante no comportamento dos calcários neste ensaio de durabilidade. Verificou-se, também, que os acabamentos superficiais grosseiros são mais suscetíveis ao nevoeiro salino, mas menos sensíveis às alterações cromáticas provocadas por este ensaio. Constatou-se que o nevoeiro salino gera perda de brilho nas superfícies com acabamento polido. Por fim, concluiu-se que a perda de massa registada por todas as amostras de calcário ensaiadas, ficou a dever-se essencialmente a processos de dissolução do CaCO3.

Síntese e caracterização de ligantes nitrogenados derivados de isatina, 4-benziltiossemicarbazida e seus complexos com metais d¹º

Neste trabalho são apresentadas e discutidas as estruturas cristalinas e moleculares do ligante (1), isatina-3-(toluilsulfono-hidrazona), dos complexos [bis(2-acetilpiridina-N4 - benziltiossemicarbazona-N,N,S)Cd(II)], (1), [bis (isatina-3-N4 -benziltiossemicarbazonaN,S)Hg(II)].Etanol, (2) e [bis (isatina-3-N4 -benziltiossemicarbazona-N,S,O)Zn(II)].DMF, (3). Cristais amarelos vítreos do ligante (1) foram obtidos a partir da evaporação lenta de etanol do ensaio de cristalização. Seus dados cristalográficos indicam que duas moléculas interagem através de ligações de hidrogênio do tipo N1-H···O1, formando unidades dímeras. A reação entre 2-acetilpiridina-N4 -benziltiossemicarbazona e Cd(CH3COO)2.2H2O, em presença de etanol, KOH, e após evaporação lenta da mistura de acetona e DMF(2:1), resultou em cristais amarelos do complexo (1). As interações do tipo C(10)-H(10)···S(1)···H(1)-N(4), e N(8)- H(29)⋅⋅⋅S(2) permitem a dimerização do complexo, e a formação de uma cadeia unidimensional. Os cristais laranja do complexo (2) foram obtidos da reação entre o ligante isatina-3-N4 -benziltiossemicarbazona e Hg(NO3)2.H2O, na presença de metanol, KOH, e após evaporação lenta de uma mistura de tolueno e acetona (2:1). As moléculas do complexo (2) estão associadas por ligações de hidrogênio do tipo N(63)-H(4)···O(21), essas interações centrossimétricas conduzem a formação de dímeros. A reação entre o ligante isatina-3-N4 - benziltiossemicarbazona e Zn(CH3COO)2.2H2O, em presença de etanol e KOH resultou em cristais de coloração laranja do complexo (3). A estrutura do complexo apresenta múltiplas ligações de hidrogênio, com formação de dímeros através das interações N1-H1···O1 e C3- H3···N(7). Os dímeros associam-se por interações N4-H4···O2 numa cadeia unidimensional ao longo da direção cristalográfica [100]. A polimerização bidimensional é observada 7 considerando-se as interações do tipo C20-H20···S1, N8-H8···S2 ao longo da direção cristalográfica [010], bem como das interações, N5-H5···O3DMF e C31-H31B···Car, que ocorrem através da molécula de solvente DMF.

Chemical resistance of lime-based grouts for masonry strengthening

The stone masonry walls are present in many buildings and historical monuments, with undeniable asset value, but also in old buildings housing both in Portugal and in Europe. Most of these buildings in masonry are in certain cases in a high state of degradation needing urgent intervention. This requires the identification of deficiencies and the application of appropriate intervention techniques. One of the possible techniques for structural consolidation works of stone masonry walls is the injection of fluid mortars currently called grouts. The choice of grouts is very important with regard in particular to their chemical and physical properties. In this study, carried out under the Master of Chemical Engineering, two types of lime-based grouts were used, in order to evaluate and compare their chemical resistance due to the crystallization of soluble salts. One of the grouts is a pre-dosed blend commercially available, Mape-Antique I from company Mapei (CA), and the second grout is a mixture prepared in the laboratory (LB), comprising metakaolin, cement, hydrated lime, water and superplasticizer. With the purpose of evaluating the action of sulphates on these grouts, a series of samples underwent several wetting-drying cycles using two different temperatures, 20 °C and 50 °C. During the experiment it was determined the change of weight and compressive strength in the analyzed grouts, as well as the sulphate ion concentration and pH of the solution in which the samples were dipped. The commercial grout (CA) apparently has a greater chemical resistance to sulphates. However grout LB showed to have positive results in some parameters.