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Master's Dissertation
DOI
https://doi.org/10.11606/D.76.2012.tde-01062012-145924
Document
Author
Full name
Elton Tadeu Montrazi
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2012
Supervisor
Committee
Bonagamba, Tito Jose (President)
Fortulan, Carlos Alberto
Maia, Leonardo Paulo
Title in Portuguese
Estudo de cerâmicas porosas de alumina através da medida de tempos de relaxação via ressonância magnética nuclear
Keywords in Portuguese
Cerâmica
Meios Porosos
RMN
Abstract in Portuguese
A medida de tempo de relaxação longitudinal (T1) e transversal (T2) de ressonância magnética nuclear (RMN) é muito utilizada para análise de meios porosos na área do petróleo. Esses tempos de relaxação estão relacionados com tamanho dos poros. As cerâmicas, dependendo da sua temperatura de sinterização, apresentam uma porosidade intrínseca, mas cerâmicas especiais para processo de filtragem e escafoldes de implantes ósseos necessitam de poros maiores e de permeabilidade para suas aplicações. Esse objetivo é alcançado introduzindo um agente porogênico, um material degradável com a temperatura, obtendo assim poros induzidos além dos intrínsecos. O agente porogênico escolhido para este trabalho foi cristais de sacarose, os tamanhos dos poros são controláveis pelo tamanho dos cristais e pela quantidade, tornado esse um meio factível nos estudos de RMN através dos tempos de relaxação. Foram selecionadas, através de peneiras, duas faixas de tamanhos de cristais de sacarose: G (grande) com limite superior de 600μm e inferior de 300μm e P (pequeno) com tamanhos na faixa de 38μm a 150μm. A cerâmica preparada com P apresentou distribuição de tamanho de poros (de 15 à 105μm) com mediana em 40μm, menor que a fabricada com G (de 20 à 125μm), media em 100μm. Distribuições de tamanho de poros com mediana intermediária foram obtidas pelas misturas de P e G na fabricação. Foram preparadas seis cerâmicas para os estudos: pura (sem adição de agente porogênico), 100% com G, 100% com P, mistura de 50% P e 50% G, mistura de 75% P e 25% G e mistura de 25% P e 75% G. As cerâmicas foram saturadas com água por um sistema de vácuo e através da sequência CPMG obtiveram-se os decaimentos multiexponenciais da relaxação transversal para os núcleos de ¹H de moléculas de água confinadas nos poros das cerâmicas. E assim, determinaram-se as distribuições de tempo de relaxação T2. A cerâmica pura apresentou apenas um pico para T2 em 0,053s, assim como obtido por Borgia e colaboradores em outros estudos, e comparando com resultados de porosimetria por intrusão de mercúrio (PIM), determinou-se o coeficiente de relaxatividade superficial de 3,7μm.s-1, valor próximo ao tabelado para a alumina (3μm.s-1) dando confiabilidade aos equipamentos utilizados. As cerâmicas preparadas com agente porogênico apresentaram dois picos na distribuição de T2 com o primeiro localizado na mesma região de tempo que corresponde à porosidade intrínseca (0,053s) e o segundo pico, referente à porosidade induzida, deslocando-se começando com a 100P com o menor tempo T2 (0,38s) e aumentando conforme o aumento da porcentagem de grânulo G (1,02s para 100G) de acordo com era esperado. A parti das imagens de microscopia eletrônica de varredura (MEV), obteve-se as distribuições de tamanho de poros induzidos e, novamente, determinou-se o coeficiente de relaxatividade, 12μm.s-1, valor maior comparado com o anterior devida as impurezas e resíduos da queima dos cristais de sacarose deixado na superfície do poro. Por fim, concluiu-se então que a RMN foi capaz de fazer a análise das cerâmicas de alumina observando poros intrínsecos da ordem de 0,1μm e poros induzidos com tamanho de dezenas a centenas de micrometros. Foram reunidos os resultados necessários para compreender como são formados os poros a partir do agente porogênico podendo fabricar cerâmicas com distribuições de tamanhos de poros conforme desejado.
Title in English
Characterization of porous alumina ceramics through measurement of nuclear magnetic resonance relaxation times
Keywords in English
Ceramic
NMR
Porous media
Abstract in English
The measurement of longitudinal (T1) and transversal (T2) nuclear relaxation times is an important method for the analysis of porous media, much used in the petroleum industry. It is possible through this technique the determination of the porosity and pore size distribution of the media. Ceramic materials already have an intrinsic porosity dependent on its sinterization temperature, but some applications such as filtering or scaffolding in bone regeneration demand for a larger porosity and permeability. To achieve this goal, a porogenic agent is introduced in the ceramics production process which is degradable in high temperatures, producing a ceramic with both induced and intrinsic porosity. The porogenic agent chosen for this project were saccharose crystals and the pores size is controlled by the crystals size and by the quantity added in the production process. Two ranges of the saccharose crystals diameters were selected using different sieves: G size, raging from 300μm to 600μm and P size ranging from 38μm to 150μm. The P size ceramic presented pore size distribution ranging from 15 to 105μm, with median in 40μm, smaller than the median found for the ceramic produced with G size saccharose crystals (100μm), for which the porosity ranged from 20 to 125μm. Pore size distribution with median between the results found in P and G ceramics were acquired by using a mixture of P and G saccharose crystals sizes in the ceramic fabrication. Six samples were prepared for this study: pure (with no addition of porogenic agent), 100% G size, 100% P size; mixtures of 50% P and 50% G sizes, 75% P and 25% G sizes, and finally 25% P and 75% G sizes. All samples were saturated with water in a vacuum bomb, and, using the CPMG pulse sequence, the multiexponencial decay of the transverse relaxation time was obtained for the ¹H nuclei of the water molecules confined in the ceramic pores. Through this measurement, the distribution of T2 of the sample was determined. The curve for the pure ceramic presented only one peak at 0,053s, the same result obtained by Borgia at al. in other studies. Comparing this result with the porosity determined by mercury intrusion porosimetry, it was possible to determine the surface relaxation coefficient (3,7μm.s-1), with a good proximity to the value found in literature for alumina (3μm.s-1), showing that the equipment used for the measurements is reliable. The ceramic fabricated with the porogenic agent presented two peaks in the T2 time distribution, with the first peak coincident with the T2 value found for the intrinsic porosity (0,053s) and the second peak, which represents the induced porosity, varying to each ceramic sample, with the 100 % P ceramic presenting the peak with the smallest T2 (0,38s) and moving to higher T2 values as the percentage of G size saccharose crystals in the ceramic increases, (1,02s for the sample with 100% G), as it was expected. Through images from scanning electron microscopy, an assessment of the pore size distribution was made and the surface relaxation coefficient recalculated, arriving at a higher value than the one found for the pure ceramic (12μm.s-1), which shows that residues of the saccharose crystals are left in the pores surface in the burning process. In conclusion, the NMR technique proved capable to characterize the ceramic materials, allowing the observation of both the intrinsic (of magnetude 0,1μm) and the artificial induced porosity (varying from tens to hundreds of micrometers) of the alumina ceramics. The union of all the results of this project encloses the knowledge necessary to comprehend how the pores are formed by the action of the porogenic agent, making it possible to develop a manufacture process of ceramics with controlled pores sizes.
 
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Publishing Date
2012-06-05
 
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