Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-12-12T18:02:43Z No. of bitstreams: 1 JarleyFagnerSilvaDoNascimento_TESE.pdf: 4096996 bytes, checksum: e4bf3a2cdc5da6219f6237326c93f4bc (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-12-13T19:19:21Z (GMT) No. of bitstreams: 1 JarleyFagnerSilvaDoNascimento_TESE.pdf: 4096996 bytes, checksum: e4bf3a2cdc5da6219f6237326c93f4bc (MD5) / Made available in DSpace on 2017-12-13T19:19:21Z (GMT). No. of bitstreams: 1 JarleyFagnerSilvaDoNascimento_TESE.pdf: 4096996 bytes, checksum: e4bf3a2cdc5da6219f6237326c93f4bc (MD5) Previous issue date: 2017-08-25 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Neste trabalho, foi sintetizada uma s?rie de redes metalorg?nicas mistas a base de ?ons lantan?deos (MLOFs) pelo m?todo solvot?rmico, utilizando como componente org?nico o ?cido tereft?lico (1,4-H2BDC). Inicialmente foram preparadas tr?s matrizes contendo gadol?nio dopadas com 5% molar de ?ons Eu3+ (Eu/Gd-1,4-BDC). Esta etapa teve como foco o estudo dos efeitos do tempo de s?ntese (3, 5 e 7 dias) sobre as propriedades morfol?gicas e luminescentes das MLOFs. Tal estudo se torna essencial, j? que com o aumento da cristalinidade da rede, normalmente verifica-se uma diminui??o dos canais de relaxa??o n?o radioativos. Posteriormente, foram sintetizadas matrizes com diferentes percentuais molares de Eu3+ (1, 3, 5, 7 e 9%) com o intuito de determinar a concentra??o limite do dopante, assim como investigar o efeito de tal varia??o percentual, no crescimento das redes e propriedades fotof?sicas. Por fim, uma amostra co-dopada com 2,5% molar de Tb3+ e Eu3+ (Gd/Tb/Eu-1,4-BDC) foi preparada e suas propriedades luminescentes sintoniz?veis estudadas. Os materiais sintetizados na forma de p?, foram caracterizadas por Difra??o de raios-X (DRX), Espectroscopia na regi?o do Infravermelho com Transformada de Fourier por Reflet?ncia Total Atenuada (FTIR-ATR), Microscopia Eletr?nica de Varredura (MEV), An?lise termogravim?trica (TGA) e Fotoluminesc?ncia (PL). Todas as amostras apresentaram elevada estabilidade t?rmica, e o aumento do tempo de s?ntese teve significativa influ?ncia sobre a morfologia dos cristais. Com base nas an?lises de DRX, FTIR e PL, identificou-se que a partir de 7% molar de ?ons eur?pio uma segunda fase cristalina come?a a se formar. Al?m disso, observou-se a partir dos espectros de excita??o e emiss?o que ocorreu uma efetiva transfer?ncia de energia intramolecular entre o ligante e os n?veis do Eu3+, gerando luminesc?ncia vermelha caracter?stica deste ?on. Estas amostras apresentaram linhas de emiss?o caracter?sticas do Eu3+ atribu?das as transi??es 5D0 ? 7F0, 7F1, 7F2, 7F3 e 7F4. A amostra co-dopada apresentou eficiente sintoniza??o de cor oriunda da transfer?ncia de energia entre Tb3+ ? Eu3+. Nenhum mecanismo de transfer?ncia de energia no sentido inverso foi identificado. Portanto, os materiais descritos s?o promissores para diversas aplica??es ?pticas. / In this work a series of new metal-organic frameworks containing lanthanide ions (LOFs) was synthesized by a solvothermal method at 180 0C, using terephthalic acid (1,4-H2BDC) as an organic component. Initially, three samples containing gadolinium doped with 5 mol% Eu3+ ions were prepared (Eu/Gd-1,4-BDC-MOFs). The objective of this part of the work was to study the effect of synthesis time (3, 5 and 7 days) on the morphological and luminescent properties of these materials. This study is essential because it is well known that the increase in crystallinity may lead to the decrease in reticular vibrations and, consequently, a decrease of nonradioactive relaxation channels. Subsequently, samples with different Eu3+ molar percentages (1, 3, 5, 7 and 9%) were synthesized to investigate the effect of the dopant content on the structure and photophysical properties of the LOFs. Finally, a sample co-doped with 2.5 mol% of Tb3+ and Eu3+ (Gd/Tb/Eu-1,4-BDC-MOF) was prepared and its tunable luminescent properties studied. The samples in powder form, were characterized by X-ray Diffraction (PXRD), Attenuated total reflectance Fourier transform infrared spectroscopy (FTIR-ATR), Scanning Electronic Microscopy (SEM), Thermogravimetric Analysis (TGA) and Photoluminescence (PL). Based on the analyzes of DXRP, FTIR and PL, it was identified that materials containing up to 7 mol% of europium ions presented a single-phase. In addition, it was observed from the excitation and emission spectra that an effective intramolecular energy transfer occurred between the ligand and the Eu3+ levels, generating characteristic red luminescence of this ion. These samples emission spectra exhibited characteristic emission lines of the Eu3+ ion ascribed to the 5D0 ? 7F0, 7F1, 7F2, 7F3 and 7F4 transitions. The co-doped sample presented efficient luminescent tuning resulting from the transfer of energy between Tb3+ ? Eu3+. Therefore, the described materials are promising for various optical applications.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-06-14T19:53:37Z No. of bitstreams: 1 AnaKarinaPereiraLeite_DISSERT.pdf: 3134726 bytes, checksum: 98310bd9f7d887f28ee1f7167205ada0 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-06-15T22:28:23Z (GMT) No. of bitstreams: 1 AnaKarinaPereiraLeite_DISSERT.pdf: 3134726 bytes, checksum: 98310bd9f7d887f28ee1f7167205ada0 (MD5) / Made available in DSpace on 2016-06-15T22:28:23Z (GMT). No. of bitstreams: 1 AnaKarinaPereiraLeite_DISSERT.pdf: 3134726 bytes, checksum: 98310bd9f7d887f28ee1f7167205ada0 (MD5) Previous issue date: 2014-01-24 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / As redes metalorg?nicas (MOFs) s?o h?bridos, normalmente cristalinos, constitu?dos de subunidades inorg?nicas, metais ou clusters met?licos, conectados por ligantes org?nicos polit?picos de forma repetitiva originando estruturas em duas ou tr?s dimens?es, geralmente porosas. Neste trabalho foram sintetizadas MOFs com ?ons lantan?deos (La3+ e Gd3+) e ligantes tipo dicarboxilatos (?cidos isoft?lico e o tereft?lico) pelos m?todos hidrot?rmico, solvot?rmico e hidro(solvo)t?rmico. Os efeitos da rota sint?tica sobre a estrutura e propriedades das MOFs foram estudados, bem como do tipo de aquecimento, convencional ou por microondas. As amostras obtidas na forma de p?s foram caracterizadas por difra??o de raios-X, espectroscopia de infravermelho, analises t?rmicas e microscopia eletr?nica de varredura. Os resultados sugerem a necessidade de uma base, org?nica ou inorg?nica, para promover a desprotona??o do ligante, uma vez que nas amostras preparadas pelo m?todo hidrot?rmico, sem o aux?lio de uma base, n?o houve forma??o de uma rede metalorg?nica. Por outro lado, a presen?a de DMF, como solvente ou co-solvente, proporcionou a desprotona??o do ligante com consequente forma??o das MOFs. Pelo menos duas estruturas cristalinas diferentes foram identificadas para as amostras preparadas com ?cido tereft?lico. Estas amostras apresentam isoestruturas semelhantes ?s reportadas para as fases Eu(1,4-BDC)DMF e Tb(1,4-BDC)H2O. A presen?a de ?gua no meio reacional, m?todo hidro(solvo)t?rmico, direcionou o crescimento da estrutura de maneira diferente da observada quando em sua aus?ncia. Isto pode ser justificado pela diferen?a na forma de coordena??o dos ?ons lantan?deos por ?gua e por DMF. Apesar de n?o terem sido identificadas por DRX, as amostras preparadas com ?cido isoft?lico tamb?m apresentam estruturas metalorg?nicas, confirmadas pelo deslocamento da banda referente ao estiramento do grupo carbonila em rela??o a ligante puro, nos espectros de infravermelho. Este deslocamento tamb?m foi observado nas amostras preparadas com ?cido tereft?lico. As analises de microscopia eletr?nica de varredura sugerem que a morfologia dos p?s e significativamente dependente do tipo de aquecimento usado, convencional ou micro-ondas. / Metal Organic Frameworks (MOFs) are hybrids materials, often crystalline, consisting of metal or metal clusters, connected by polytopic organic ligands repetitively, leading to structures, usually porous. In this work, MOFs based on lanthanide ions (La3+ and Gd3+) and dicarboxylate type of ligands (isophthalic and terephthalic acids), were synthesized by hydrothermal, solvothermal and hydro(solvo)thermal methods. The effects of the synthetic route as well as the type of heating, conventional or by microwave, on the structure and properties of MOFs were studied. The powder samples obtained were characterized by X-ray diffraction, infrared spectroscopy, thermal analysis and scanning electron microscopy. The results suggest that the addition of an organic or inorganic base is needed to promote the deprotonation of the ligand, since in the samples prepared by the hydrothermal method, without the use of a base, no formation of the metalorganic framework was observed. On the other hand, the presence of DMF as solvent or cosolvent, afforded the deprotonation of the ligand with the consequent formation of MOFs. At least two different crystalline structures were identified for the samples prepared with terephthalic acid. These samples are isostructural with those reported for phases Eu(1,3-BDC)DMF, Eu2(1,4-BDC)3 (DMF)2 and Tb(1,4-BDC)H2O. The presence of water in the reaction medium in the hydro(solvo)thermal method, provoked the growth of the structure different from that observed in the absence of water. This can be explained by the difference in the coordination mode of water and DMF to lanthanide ions. Although not identified by XRD, the samples prepared with isophthalic acid, also present metalorganic structures, which was confirmed by the presence of the characteristic displacement of the carbonyl group band in their infrared spectra, compared to the spectrum of the pure ligand. This shift was also observed in the samples prepared with terephthalic acid. Thermal analisys shows that the metal organic frameworks do not collapse occurs at a temperature below 430?C.The analysis of scanning electron microscopy suggests that the morphology of powders is highly dependent on the type of heating used, conventional or by microwave.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-02-02T11:57:41Z No. of bitstreams: 1 RosivaniaSilvaDeOliveira_DISSERT.pdf: 2954896 bytes, checksum: d9524f4e838d64f94b6283e655206857 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-02-06T20:43:09Z (GMT) No. of bitstreams: 1 RosivaniaSilvaDeOliveira_DISSERT.pdf: 2954896 bytes, checksum: d9524f4e838d64f94b6283e655206857 (MD5) / Made available in DSpace on 2017-02-06T20:43:09Z (GMT). No. of bitstreams: 1 RosivaniaSilvaDeOliveira_DISSERT.pdf: 2954896 bytes, checksum: d9524f4e838d64f94b6283e655206857 (MD5) Previous issue date: 2016-04-15 / LaPO4:Eu3+/Tb3+ hierarquicamente nanoestruturados foram sintetizados por meio da atua??o combinada do aquecimento de micro-ondas e de um solvente bi-funcional (etileno glicol), que atua n?o somente como solvente, mas tamb?m como agente estabilizante. Foram preparadas cinco amostras com diferentes concentra-??es de eur?pio e t?rbio ? La0.93Eu0.07PO4, La0.93Tb0.07PO4, La0.93Eu0.006Tb0.064PO4, La0.93Eu0.011Tb0.059PO4, La0.93Eu0.017Tb0.053PO4 ? bem como a matriz pura. Estas amostras, na forma de p?, foram caracterizadas por Difra??o de Raios-X (DRX), Es-pectroscopia de Infravermelho com Transformada de Fourier por Reflet?ncia Total Atenuada (FTIR-ATR), Microscopia Eletr?nica de Transmiss?o (MET) e Fotolumi-nesc?ncia (PL). Os resultados indicam cristaliza??o com estrutura do tipo monazita monocl?nica. Tamb?m sugerem uma organiza??o hier?rquica de agregados de na-nopart?culas formadas por cristais de semente. As amostras codopadas exibiram luminesc?ncia azul autoativada da matriz hospedeira, assim como emiss?es verme-lha e verde oriundas os ?ons Eu3+ e Tb3+, respectivamente. A an?lise espectrosc?pi-ca sugere que a transfer?ncia de energia entre os ?ons ocorre do t?rbio para o eur?-pio, mas o inverso n?o foi observado. Al?m disso, a varia??o da concentra??o relati-va destes ?ons permitiu o controle de cor das emiss?es. Desta forma, podemos afir-mar que a rota sint?tica escolhida ? eficiente na prepara??o de nanomateriais com propriedades ?pticas avan?adas e potencial para aplica??es em fot?nica, sensoria-mento e biorotulagem. / Hierarchically Nanostructured LaPO4:Eu3+/Tb3+ powders were synthesized by the combined action of microwave heating and a bifunctional solvent (ethylene gly-col), which act as both, solvent and capping agent. Five samples were prepared with different amounts of europium and terbium - La0.93Eu0.07PO4, La0.93Tb0.07PO4, La0.93Eu0.006Tb0.064PO4, La0.93Eu0.011Tb0.059PO4, La0.93Eu0.017Tb0.053PO4 - and the pure matrix. These samples, in powder form, were characterized by X-ray Diffraction (XRD), Attenuated total reflectance Fourier transform infrared spectroscopy (FTIR-ATR), Transmission Electron Microscopy (TEM) and Photoluminescence (PL). The results indicate the crystallization structure of the monoclinic monazite type. Also suggests a hierarchical organization of nanoparticle aggregates formed by seed crys-tals. The co-doped samples exhibited self-activated blue luminescence of the host matrix, as well as red and green emissions from Eu3+ and Tb3+ions, respectively. The spectroscopic analysis suggests that the transfer of energy between the ions occurs from terbium to europium, but the opposite was not observed. Moreover, the variation of the relative concentration of these ions enabled the tuning emissions. Thus, we can say that the chosen synthetic route is efficient in the preparation of nanomateri-als with advanced optical properties and potential applications in photonics, sensing, and biolabeling.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-09T19:05:35Z No. of bitstreams: 1 GenicksonBorgesDeCarvalho_TESE.pdf: 3453614 bytes, checksum: 743ed6733d7ceea514e2575e4ec2eabf (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-10T21:24:30Z (GMT) No. of bitstreams: 1 GenicksonBorgesDeCarvalho_TESE.pdf: 3453614 bytes, checksum: 743ed6733d7ceea514e2575e4ec2eabf (MD5) / Made available in DSpace on 2017-03-10T21:24:30Z (GMT). No. of bitstreams: 1 GenicksonBorgesDeCarvalho_TESE.pdf: 3453614 bytes, checksum: 743ed6733d7ceea514e2575e4ec2eabf (MD5) Previous issue date: 2016-07-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / No presente trabalho ? descrito a s?ntese e a caracteriza??o dos compostos de coordena??o entre os nitratos de lantan?deos (III) e a pirazinacarboxamida (PyZ), visando uma poss?vel aplica??o funcional desses novos compostos como dispositivos moleculares conversores de luz. Os complexos obtidos foram caracterizados por meio de diversas t?cnicas anal?ticas, das quais podemos destacar: an?lise elementar, condutividade eletrol?tica molar, termogravimetria (TG) e an?lise t?rmica diferencial (DTA) simult?nea, calorimetria explorat?ria diferencial (DSC), espectroscopia de absor??o no infravermelho m?dio (FT-IR), espectroscopia por energia dispersiva de raios-X (EDS), difratometria de raios-X (DRX) pelo m?todo do p?, espectroscopia de absor??o eletr?nica (UV-Vis) a 298 K e espectroscopia de luminesc?ncia a 298 K. Atrav?s dos resultados de an?lise elementar, termogravimetria e de condutividade eletrol?tica molar, foi poss?vel propor as seguintes f?rmulas moleculares: [Ln(PyZ)2(NO3)2]NO3.2H2O (Ln3+ = La?Eu) e [Ln(PyZ)2(NO3)2]NO3.H2O (Ln3+ = Gd?Dy). As curvas TG-DTA e DSC forneceram informa??es a respeito da desidrata??o, degrada??o, estabilidade e natureza dos eventos t?rmicos referentes aos processos de decomposi??o. Os dados de condutividade, tanto em nitrometano como em acetonitrila, sugeriram comportamento de eletr?lito 1:1 para todos os compostos, refor?ando os resultados dos espectros de absor??o na regi?o do infravermelho m?dio, que indicaram a presen?a de nitrato n?o coordenado aos ?ons met?licos. Nos espectros eletr?nicos no UV-Vis observou-se o deslocamento das bandas de absor??o dos complexos estudados, quando comparadas ?s bandas do ligante livre, sugerindo a coordena??o do ?on met?lico central com o ligante pirazinacarboxamida. A an?lise dos espectros de absor??o na regi?o do infravermelho (FT-IR) permitiram estabelecer que os s?tios de coordena??o do ligante PyZ com o ?on met?lico s?o o oxig?nio carbon?lico e o nitrog?nio ? do anel piraz?nico. A interpreta??o dos difratogramas de raios-X revelou a exist?ncia de tr?s s?ries isom?rficas: a primeira compreende os compostos de La3+ e Ce3+, a segunda os compostos de Pr3+ ao Tb3+ e a terceira ao composto de Dy3+. O estudo das bandas hipersensitivas do complexo de neod?mio no estado s?lido a 298 K permitiu determinar os par?metros espectrosc?picos, cujos valores num?ricos indicam que a intera??o metal-ligante ? essencialmente eletrost?tica. A partir dos espectros eletr?nicos obtidos em solu??o de acetonitrila e etanol calculou-se a for?a do oscilador (P), cujos valores sugerem uma maior influ?ncia do etanol na esfera de coordena??o do ?on Nd3+. O espectro de emiss?o do complexo de gadol?nio revelou que a energia do estado tripleto excitado do ligante PyZ, encontra-se acima dos n?veis emissores dos ?ons Eu e Tb, o que favorece o processo de transfer?ncia de energia metal-ligante. Baseando-se na an?lise do espectro de emiss?o do composto de eur?pio no estado s?lido a 298 K, foi poss?vel atribuir uma microssimetria aproximadamente D2d, consistente com a geometria de um dodecaedro distorcido para o composto. A an?lise de luminesc?ncia sugere que os complexos de Eu3+, Tb3+, Sm3+ e Dy3+ apresentam emiss?es caracter?sticas na regi?o dos ?ons lantan?deos, por?m, quando em solu??o de acetonitrila, apenas o complexo de sam?rio n?o apresentou emiss?o na regi?o do vis?vel por ter possivelmente sua luminesc?ncia suprimida pela presen?a do solvente. / This present work describes the synthesis and characterization of coordination compounds between lanthanide nitrate (III) and pyrazinecarboxamide (PyZ), intending a possible functional application of these new compounds as molecular light conversion devices. The obtained compounds were characterized by various analytical techniques, of which we highlight: elemental analysis, molar electrolytic conductivity, thermogravimetry (TG) and differential thermal analysis (DTA) simultaneous, differential scanning calorimetry (DSC), absorption spectroscopy in mid infrared (FT-IR) spectroscopy by energy dispersive Xray (EDS), diffraction X-ray (XRD) by the powder method spectroscopy electronic absorption (UV-Vis) at 298 K and luminescence spectroscopy at 298 K. From the results of elemental analysis, thermogravimetry and molar electrolytic conductivity, it was possible to propose the following molecular formulas: [Ln(PyZ)2(NO3)2]NO3.2H2O (Ln3+ = La-Eu) and [Ln(PyZ)2 (NO3)2]NO3.H2O (Ln3+ = Gd-Dy). The TG-DTA and DSC curves provided information about dehydration, degradation, stability and nature of thermal events related to decomposition processes. The conductivity data, both nitromethane and acetonitrile, suggested an electrolyte behavior 1:1 for all compounds, reinforcing the results of the absorption spectra in the middle infrared region, which indicated the presence of nitrate is not coordinated to the metal ions. Regarding the electronic spectra UV-Vis, it was observed displacement of the absorption bands of the studied complexes, when compared to the free ligand bands, suggesting the coordination of the central metal ion with the binder pyrazinecarboxamide. The analysis of absorption spectra in the infrared (FT-IR) leads to stabilish that sites of coordination with the PyZ binder metal ion are carbonyl oxygen and nitrogen ? pyrazine ring. The interpretation of X-ray diffraction revealed the existence of three isomorphic series: the first comprises those compounds of La3+ and Ce3+, the second compounds of the Pr3+, Tb3+ and Dy3+ to the third compound. The study of hipersensitivas bands of neodymium complex in the solid state at 298 K allowed the determination of spectroscopic parameters, numerical values which indicate that metal-ligand interaction is essentially electrostatic. The oscillator strength (P) was calculated from the electronic spectra in acetonitrile solution and ethanol. The P values suggest a greater influence of ethanol in coordination ion Nd3+ ball. The emission spectrum of the gadolinium complex showed that the energy of the excited triplet state PyZ binder is between the emitting level of the Tb ions and I, which favors the process of metal-ligand energy transfer. Based on the analysis of the europium compound emission spectrum in the solid state at 298 K, it was possible to assign a microssimetria approximately D2d, consistent with the geometry of a distorted dodecahedron for the compound. Luminescence analysis suggests that the complexes of Eu3+, Tb3+, Sm3+ and Dy3+ display characteristic emissions in the region of lanthanide ions, however, when in acetonitrile solution, only samarium complex showed no emission in the visible region, probaly because a suppression of luminescence by the presence of the solvent.

Made available in DSpace on 2014-12-17T15:41:42Z (GMT). No. of bitstreams: 1 RoseaneSO.pdf: 1884603 bytes, checksum: 9b9e3631718ab941c6e9125f7deb26e8 (MD5) Previous issue date: 2007-08-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Films of chitosan with trivalent lanthanides ions Eu3+ and Tb3+ were respectively prepared in the ratio of 3:1 m/m (chitosan: lanthanide) and 6:1 m/m (chitosan: lanthanide). There were no formations of films in a ratio of 1:1 m/m (chitosan: lanthanides). The films of chitosan with the Tb3+ ion have the same transparent appearance than the pure chitosan films. The film of chitosan with Eu3+ ion has a muddy appearance. These films present good resistance to tear. The appearance of the compounds prepared in ratio 1:1m/m is a white powder. The films and compounds of chitosan were characterized by Elementary Analysis (CHN), Thermal Analysis (TG/DTG) and Spectroscopy of Luminescence. The CHN analysis was made only for compounds prepared in ratio 1:1m/m, suggesting that these compounds possess the formula QUILn.6H2O, where QUI = Chitosan and Ln = Lanthanide. The results of the curves TG/DTG indicated that there are strong interactions between Eu3+ or Tb3+ and chitosan, causing a lesser lost of mass in the films. The luminescence analysis showed that the films of chitosan with the ions Eu3+ and Tb3+ present emissions in the region of the visible one, with bands of the chitosan and of the Eu3+ ion. The luminescence analysis of the compounds of chitosan with the Eu3+ and Tb3+ ions suggest that the chitosan does not transfer into energy to the ions lanthanides, however the chemical neighborhood around of the ion lanthanides breaks the selection rules and, conseq?ently the 4f-4f transitions of the lanthanide ions are observed / Filmes de quitosana com os ?ons lantan?deos trivalentes Eu3+ e Tb3+ foram preparados na propor??o de 3:1 m/m (quitosana: lantan?deo) e 6:1 m/m (quitosana: lantan?deo), respectivamente. Na propor??o 1:1 m/m (quitosana: lantan?deo) n?o houve forma??o de filmes. Os filmes de quitosana com o ?on Tb3+ t?m uma apar?ncia similar ao filme de quitosana pura, mostrando-se transparente. J? o filme de quitosana com o ?on Eu3+ tem uma apar?ncia um pouco turva. Esses filmes apresentaram boa resist?ncia ao rasgo. Os compostos preparados na propor??o 1:1 formaram um s?lido em p? de cor branca. Tanto os filmes como os compostos de quitosana foram caracterizados por An?lise Elementar (CHN), An?lise T?rmica (TG/DTG) e Espectroscopia de Luminesc?ncia. As an?lise de CHN foram feitas apenas para os compostos de quitosana em p?, sugerindo que esses compostos possuem f?rmula geral QUILn.6H2O, onde QUI = Quitosana e Ln = Lantan?deo. Os resultados das curvas TG/DTG indicam que a introdu??o desses metais na estrutura da quitosana deixa suas liga??es mas fortes, tendo menor perda de massa nos filmes. A an?lise de luminesc?ncia mostrou que os filmes de quitosana com ?on Eu3+ e Tb3+ apresentam emiss?o na regi?o do vis?vel, com bandas referentes ? quitosana e ao ?on Eu3+. Para os compostos de quitosana em p? com os ?ons Eu3+ e Tb3+, a an?lise de luminesc?ncia sugere que a quitosana n?o est? transferindo energia para o ?on lantan?deo, no entanto a vizinhan?a qu?mica onde se encontra o ?on lantan?deo quebra as regras de sele??o e favorecem a emiss?o desses ?ons

Made available in DSpace on 2014-12-17T15:42:28Z (GMT). No. of bitstreams: 1 RoseaneSO_TESE.pdf: 2833413 bytes, checksum: cb4d0597d5a75ea4dc574237866165c1 (MD5) Previous issue date: 2013-07-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40? to 385?C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle / Visando um trabalho de estudos fundamentais da qu?mica, envolvendo a s?ntese e caracteriza??o estrutural, assim como uma poss?vel aplica??o futura desses novos compostos como sensores luminescentes ou agentes de prote??o solar, foram sintetizados os complexos com o ?cido 4,4-diaminoestilbeno-2,2-disulf?nico (DSD) e os ?ons lantan?deos trivalentes La3+, Nd3+, Eu3+, Gd3+ e Yb3+, preparados na propor??o de 3 mmol: 1mmol (DSD: Lantan?deos). Os complexos obtidos com esses ?ons apresentaram-se na forma de p? e foram caracterizados por: Titula??o Complexom?trica com EDTA, An?lise Elementar de CHN, Espectroscopia de Absor??o Molecular na Regi?o do Ultravioleta, Espectroscopia de Absor??o na Regi?o do Infravermelho, An?lise T?rmica (TG/DTG), Resson?ncia Magn?tica Nuclear RMN-1H e Espectroscopia de Luminesc?ncia. A titula??o complexom?trica e a an?lise de CHN, com confirma??o da TG/DTG, sugerem que esses complexos possuem as seguintes f?rmulas qu?micas gerais: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O, [Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O, [Eu2(C14H12S2O6N2)2(H2O)2Cl2].7H2O, [Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. O desaparecimento das bandas, no espectro de Infravermelho, em 2921 cm-1 e 2623 cm-1 e o deslocamento das bandas da amina nos espectros dos complexos indicam que a coordena??o ao ?on lantan?deo ocorre atrav?s dos oxig?nios dos grupos sulfonatos e pelos nitrog?nios das aminas, sugerindo a forma??o do d?mero. O desaparecimento do sinal SO2O-H e o deslocamento do sinal das aminas no espectro de RMN-1H dos complexos s?o tamb?m indicativos dessa coordena??o e da forma??o do d?mero. A an?lise t?rmica indica que o DSD ? termicamente est?vel no intervalo de 40?C at? 385?C e que os seus complexos com os ?ons lantan?deos apresentam perda de massa entre 4 e 5 etapas. Os espectros de Uv-Vis?vel indicam que DSD e os complexos apresentam isomeria cis. A an?lise de luminesc?ncia indica que os complexos n?o apresentam emiss?o na regi?o dos ?ons lantan?deos, mas sim uma emiss?o intensa da parte do ligante. Isso est? relacionado com os estados tripletos do ligante, que est?o em energia mais baixa que o estado emissor dos ?ons lantan?deos, e tamb?m com a forma??o do d?mero que suprime a luminesc?ncia do ?on Eu3+. A forma??o do d?mero tamb?m foi confirmada atrav?s do c?lculo da estrutura do complexo de eur?pio, utilizando o modelo Sparkle e hamiltoniano PM6, que mostrou um ponto de m?nimo na superf?cie de energia potencial desta esp?cie

<p>U ovom radu su sintetisani prahovi na bazi lantan-galata, citratnom sol-gel<br />metodom i hemijskom sintezom u parnoj fazi (CVS), a njihovim presovanjem<br />i sinterovanjem su dobijeni keramički uzorci kontrolisane mikrostrukture. Cilj<br />disertacije je bio dobijanje guste keramike koja bi mogla da se primeni kao<br />jonski provodni elektrolit u gorivnim ćelijama sa čvrstim elektrolitom (SOFC),<br />a koje bi radile na srednjim temperaturama od 500&ndash;700 &deg;C (IT-SOFC). Po prvi<br />put su sintetisani nanoprahovi lantan-galata u gasnoj fazi i utvrđeno je da ovako<br />dobijeni polazni prahovi, zbog svojih superiornih karakteristika omogućavaju<br />snižavanje temperature sinterovanja za 150 &deg;C, &scaron;to je veoma povoljno kako sa<br />stanovi&scaron;ta dizajniranja mikrostrukture, tako i zbog u&scaron;tede energije u procesu<br />proizvodnje gorivnih ćelija. Ipak, zbog nedovoljne kontrole hemijskog sastava<br />i stehiometrije sintetisanih prahova, &scaron;to je i najveći nedostatak CVS metode<br />dobijanja perovskitnog LaGaO₃, nije bilo moguće dobiti keramiku koja bi ispunjavala zahteve za primenu u SOFC. S druge strane, citratna sol-gel metoda<br />pruža veliku kontrolu pomenutih parametara zbog čega je bila moguća sinteza<br />čitavog niza čvrstih rastvora lantan-galata. Ovom metodom su tako sintetisani<br />čist lantan-galat (LG) i dopirani prahovi kod kojih je deo lantana supstituisan<br />stroncijumom, a deo galijuma magnezijumom: La_0,85Sr_0,15Ga_0,85Mg_0,15O_3-<br />La_1-xSr_xGa_0,8Mg_0,2O_3-, gde je x = 0,10, 0,15 ili 0,20 (LSGM). Svi ovako sintetisani</p><p>prahovi su zahtevali naknadnu kalcinaciju na 900 &deg;C, ali su potrebne<br />gustine (&gt;95% teorijske gustine) postignute sinterovanjem na temperaturi<br />od 1450 &deg;C već nakon 2 h, &scaron;to je izuzetno kratko imajući u vidu literaturne<br />podatke. Takođe, sinterovani uzorci su po faznom sastavu bili čista LSGM<br />keramika, a impedansna merenja su pokazala da je najveću provodljivost imao<br />uzorak La_0,85Sr_0,15Ga_0,8Mg_0,2O_3-. Ovaj sastav je dalje kori&scaron;ćen u cilju provere</p><p>mogućnosti za dodatno povećanje provodljivosti te su pripremljeni i uzorci kod kojih je izvr&scaron;ena parcijalna supstitucija magnezijuma sa niklom ili kobaltom:<br />La_0,85Sr_0,15Ga_0,8Mg_0,2-yMyO_3-, gde je M = Ni ili Co, a y = 0,03 ili 0,05 (LSGMN i</p><p>LSGMC). Pokazano je da dodatak male količine prelaznih metala značajno utiče<br />na mehanizam provođenja, ali da je na vi&scaron;im temperaturama jonska provodljivost<br />i dalje dominantna. Konstatovano je da se dodavanjem male količine Ni ili Co u<br />LSGM mogu dobiti materijali koji bi služili kao elektroliti u IT-SOFC, pri čemu je<br />potencijal nikla kao dopanta ne&scaron;to veći nego kobalta.</p> / <p>Powders based on lanthanum-gallate have been synthesised in this work by using citrate sol-gel method in the liquid phase and by chemical vapour synthesis (CVS). As-synthesised powders were calcined, pressed and finally sintered in order to produce ceramic samples with controlled microstructure. The main goal of this dissertation has been obtaining of dense ceramics for application in ion conducting electrolyte for solid oxide fuel cells working at 500&ndash;700 &deg;C (IT-SOFC). Lanthanum-gallate nanopowders have been synthesised in the gas phase for the first time and it has been determined that these starting powders posses superior properties which could lower down the sintering temperature for about 150 &deg;C. This is very significant considering microstructure design, but also high energy consumption during the manufacturing process of fuel cells. However, it has not been possible to obtain ceramics with exact properties needed for SOFC application using CVS due to the lack of control of chemical composition and stoichiometry of the as-synthesised powders, which are the main drawbacks of this method. On the other hand, citrate sol-gel method offered a possibility to precisely control aforementioned parameters which enabled synthesis of a whole range of lanthanum-gallate sollid solutions. So, pure perovskite lanthanum-gallate (LG) has been synthesised by using this liquid phase method, but also doped powders where part of lanthanum and gallium was supstituted with strontium and magnesium, respectively: La_0,85Sr_0,15Ga_0,85Mg_0,15O_3-and La_1-xSr_xGa_0,8Mg_0,2O_3-, where x = 0.10, 0.15 or 0.20 (LSGM). Calcination at 900 &deg;C was necessary step during the processing of these sol-gel powders but the sintering time at 1450 &deg;C was only 2 h which is quite short in comparison with available literature data. Additionaly, the sintered samples were phase pure LSGM ceramics and impedance measurement showed that the highest conductivity had sample La_0,85Sr_0,15Ga_0,8Mg_0,2O_3-. Accordingly, this composition has been used to check the possibility of further improvement of conductivity. A set of new samples has been prepared where one part of magnesium has been substituted with nickel or cobalt: La_0,85Sr_0,15Ga_0,8Mg_0,2-yMyO_3-, where M = Ni or Co and y = 0.03 or 0.05 (LSGMN i LSGMC). It has been shown that addition of small amount of transition metals significantly influences conduction mechanism, but at higher temperatures the ionic conductivity is still dominant. It has been found that electrolyte materials for IT-SOFCs could be obtained by incorporation of small quantities of Ni or Co into LSGM and that nickel is more promissing for this purpose than cobalt.</p>