Submitted by Silvana Teresinha Dornelles Studzinski (sstudzinski) on 2015-07-01T13:48:29Z No. of bitstreams: 1 MarieleLunkes.pdf: 2185395 bytes, checksum: 0e139b106b90af719386462d648c9ec7 (MD5) / Made available in DSpace on 2015-07-01T13:48:29Z (GMT). No. of bitstreams: 1 MarieleLunkes.pdf: 2185395 bytes, checksum: 0e139b106b90af719386462d648c9ec7 (MD5) Previous issue date: 2013-03 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / CNPQ – Conselho Nacional de Desenvolvimento Científico e Tecnológico / FAPERGS - Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul / FINEP - Financiadora de Estudos e Projetos / A utilização de resíduos perigosos em produtos construtivos, técnica denominada estabilização por solidificação (E/S), requer um conhecimento aprofundado de sua composição, viabilidade técnica e econômica, além de uma avaliação ambiental ao longo do uso e pós-uso do produto. Quando se trata da avaliação de um produto da E/S durante a fase de uso, o Brasil não dispõe de um procedimento adequado que considere a integridade física da amostra e as características do cenário onde o resíduo encapsulado se encontra. O objetivo geral desta pesquisa é avaliar a lixiviação de cromo total em monólitos de cerâmica vermelha durante a fase de uso, por imersão e irrigação. Foram confeccionados corpos de prova com adição de 0,05% de óxido de cromo III (Cr2O3), além de corpos de provas referência (sem adição Cr2O3). Com base no regime pluviométrico da região metropolitana de Porto Alegre/RS desenvolveram-se dois testes de lixiviação para a avaliação da efetividade da E/S: imersão e irrigação. O primeiro com o propósito de simular um ambiente hostil em situação de prolongado contato da cerâmica com o lixiviante e o segundo para uma condição de exposição à chuva ácida ou ciclos de molhagem e secagem, possibilitando a avaliação do desempenho ambiental do material. A E/S do Cr na cerâmica vermelha foi acima de 99,90%. Nos corpos de prova com Cr2O3 a concentração de Cr lixiviado foi de 0,1243 ppm no teste de imersão, 0,01183ppm no teste de irrigação e 0,023 ppm no teste de lixiviação da norma ambiental brasileira para resíduos sólidos. As duas formas de avaliação da lixiviação de cromo total em monólitos de cerâmica vermelha, durante a fase de uso, propostas nesta pesquisa, apresentaram baixo coeficiente de variação e resposta técnica em 28 dias, representaram o fenômeno da difusão e se diferenciaram em seus cenários. / The use of hazardous waste in products constructive, technique known as stabilization by solidification (E/S), requires a thorough knowledge of its composition, technical and economic viability, and environmental assessment along the use and post-use of the product. When it comes to assessment of E/S product's during the phase of use, Brazil does not have an appropriate procedure to consider the physical characteristics of the sample and the scenario that encapsulated residue is exposed. The objective of this research is to evaluate the leaching of total chromium (Cr) in red ceramic monoliths during the use phase, by immersion and irrigation. Samples were prepared with addition of 0.05% chromium III oxide (Cr2O3), besides samples reference (without addition Cr2O3). Based on the pluviometric regime in the metropolitan area of Porto Alegre/RS, it was developed two methods for leaching to assess the effectiveness of E/S: immersion test and irrigation test. The first was carried out in order to simulate a hostile environment in a situation of long contact between the ceramic and the leachant and the second to a condition of exposure to acid rain or cycles of wetting and drying, allowing the assessment of the environmental performance of the material. A E/S Cr in red ceramic was above 99.90%. In samples with addition of Cr2O3 was leached 0.1243 ppm total Cr from immersion test, 0,01183 ppm from the irrigation test and 0.023 ppm in the standard leaching test of the Brazilian environmental standard for solid waste. The two forms of assessment the leachingin of total chromium in red ceramic monoliths during the use phase, proposal in this study, showed low coefficient of variation e technical answer in 28 days, exhibited the phenomenon of diffusion and differentiated themselves in their scenarios.

L’efficacité des cellules solaires peut être améliorée en exploitant pleinement la partie UV-bleue du spectre solaire, par un mécanisme de conversion de fréquence de type down-conversion. Ce processus utilisant des transferts d’énergie entre ions de terre rare (TR) ou métal de transition 3d (paires TR3+/Yb3+ avec TR = Pr, Tm,… et Cr3+/Yb3+) requiert des matrices à basse énergie de phonon pour réduire les relaxations non radiatives.Jusqu’à présent, les matériaux étudiés sont principalement sous forme de poudre polycristalline, ce qui limite leur utilisation à cause de la diffusion, ou de monocristaux dont le coût de fabrication est élevé.Dans le cadre de cette thèse, les verres fluorés à base de fluorozirconate ZLAG (ZrF4-LaF3-AlF3-GaF3) et ZBLA (ZrF4-BaF2-LaF3-AlF3) ont été préparés par la technique de fusion-coulée. Ces derniers sont adaptés du fait de leurs propriétés intrinsèques de transparence et de leur faible énergie de phonon. Les matériaux obtenus ont ensuite été caractérisés par, analyse thermique, diffraction des rayons X, microscopie électronique à transmission et luminescence.Des études par dynamique moléculaire et fluorescence par affinement de raies ont été effectuées sur la matrice ZLAG afin de suivre les modifications structurales lors du passage du verre à la vitrocéramique.La luminescence de l’ion Yb3+ a été observée dans l’infra-rouge à 980 nm sous excitation bleue dans toutes les séries étudiées, signature d’un transfert d’énergie. ans le verre ZLAG, l’efficacité atteint 92% pour le transfert d’énergie Pr3+ → Yb3+ et 65% pour le transfert d’énergie Tm3+ → Yb3+. L’efficacité est plus faible dans le verre ZBLA et la vitrocéramisation du verre ZLAG n’améliore pas les performances. / The efficiency of solar cells can be improved by fully exploiting the UV-blue portion of the solar spectrum, through a frequency converting mechanism of type downconversion. This process using energy transfer between rare earth ions (RE) or 3d transition metal (pairs RE3+/Yb3+ with TR = Pr, Tm,… and Cr3+/Yb3+) requires a matrix with low phonon energy to reduce non radiative relaxation.So far, the studied materials are mainly in the form of polycristalline powder, which limits their use due to diffusion or single crystals which manufacturing cost is high.As part of this thesis, fluoride glasses based on fluorozirconate ZLAG (ZrF4-LaF3-AlF3-GaF3) and ZBLA (ZrF4-LaF2-LaF3-AlF3) have been prepared by the melting-casting technique. These are suitable because of their intrinsic properties of transparency and low phonon energy. The resulting materials were then characterized by thermal analysis, X-ray diffraction, transmission electron microscopy and luminescence.Molecular Dynamics simulation and Fluorescence line narrowing of ZLAG matrix have been performed in order to investigate the structural modification during the transformation of the glass into the glass-ceramic.Luminescence of Yb3+ ion was observed in the near IR at 980 nm under blue excitation in all studied series, which is the signature of energy transfer. In the ZLAG glass, the efficiency reaches 92% for Pr3+ → Yb3+ energy transfer and 65% for Tm3+ → Yb3+ energy transfer. The efficiency is lower in the ZBLA glass and the ZLAG ceramisation does not improve the performances.