Transformações estruturais em xerogéis de sílica tratados termicamente
Carregando...
Data
2005-03-08
Autores
Castro, Wadley Calegaro de [UNESP]
Título da Revista
ISSN da Revista
Título de Volume
Editor
Universidade Estadual Paulista (Unesp)
Resumo
Xerogéis monolíticos de sílica foram preparados pelo processo sol-gel a partir da hidrólise ácida do TEOS sob estimulação ultrasônica. A evolução da estrutura de poros de xerogéis foi estudada isotermicamente pelas técnicas de adsorção de nitrogênio e espalhamento de raios-X à baixo ângulo (SAXS). Os xerogéis apresentam em temperaturas intermediárias uma estrutura de poros, que ocupa cerca de 29% do volume, com os poros distribuídos na faixa de tamanhos abaixo de cerca de 5 nm e o volume de poros crescendo exponencialmente na região de microporos. A superfície específica da estrutura é de cerca de 390 m2/g e o diâmetro médio de poro de cerca de 1,9 nm. A eliminação da nanoporosidade nos xerogéis é prontamente acelerada em temperaturas acima de cerca de 1173 K pela ação de um mecanismo de sinterização por fluxo viscoso. O processo de eliminação dos nanoporos se dá de tal modo que o volume de poros e a superfície específica diminuem enquanto que o tamanho médio dos poros permanece constante. A distribuição relativa dos poros também se mantém constante durante o processo de eliminação, uma vez que as curvas de distribuição de tamanho de poros normalizadas pelo volume total de poros podem ser todas sobrepostas, independente do tratamento térmico. Os valores do tamanho médio de poros e da superfície específica obtidos por adsorção de nitrogênio são concordantes com os valores obtidos por SAXS. Um estudo cinético não isotérmico da eliminação de poros foi conduzido medindo-se a contração linear em ensaios dilatométricos, realizados com diferentes taxas de aquecimento, em amostras cilíndricas monolíticas de xerogéis previamente tratados a 1023 K por 10 horas. O estudo cinético não isotérmico por contração linear pôde ser aplicado a uma faixa de até cerca de 60% da fração de volume de poros eliminada (a)...
Monolithic silica xerogels were prepared by sol-gel process from acid hydrolysis of TEOS stimulated by ultrasound. The pore structure evolution was studied isothermally by means of nitrogen adsorption and small-angle x-ray scattering (SAXS). The xerogels exhibit at intermediary temperatures a pore structure, which occupy about 29% of the sample volume, formed by pores with size bellow about 5nm with the pore volume increasing exponentially in the micropore region. The specific surface of the structure is about 390 m2/g and the pore mean diameter is about 1.9 nm. The elimination of the nanoporosity is readily accelerated at temperatures above about 1173 K by the action of a viscous flux sintering mechanism. The nanopore elimination process takes place in such a way that the pore volume and the specific surface area are reduced while the mean pore size remains constant. The relative pore size distribution also remains constant during the elimination process, since the curves of the pore size distribution when normalized by the total pore volume can be matched on a unique curve, independent of the thermal treatment. The values of the pore mean size and the specific surface obtained from nitrogen adsorption are in agreement with those obtained from SAXS. A nonisothermal study of the kinetic of the pore elimination was carried out measuring the linear shrinkage using dilatometric tests, performed with different heating rates, in cylindrical monolithic xerogel samples previously treated at 1023 K for 10 hours. The study could be applied up to almost 60% of the volume fraction a of eliminated pores. The activation energy was found increasing from about 3.2þ102 kJ/mol for a ~ 6% up to about 4.4þ102 kJ/mol for a ~ 44% of the volume fraction of eliminated pores. The sintering process accompanying the nanopore elimination in this set of xerogels is in agreement with a viscous flux sintering ... (Complete abstract, access undermentioned eletronic address)
Monolithic silica xerogels were prepared by sol-gel process from acid hydrolysis of TEOS stimulated by ultrasound. The pore structure evolution was studied isothermally by means of nitrogen adsorption and small-angle x-ray scattering (SAXS). The xerogels exhibit at intermediary temperatures a pore structure, which occupy about 29% of the sample volume, formed by pores with size bellow about 5nm with the pore volume increasing exponentially in the micropore region. The specific surface of the structure is about 390 m2/g and the pore mean diameter is about 1.9 nm. The elimination of the nanoporosity is readily accelerated at temperatures above about 1173 K by the action of a viscous flux sintering mechanism. The nanopore elimination process takes place in such a way that the pore volume and the specific surface area are reduced while the mean pore size remains constant. The relative pore size distribution also remains constant during the elimination process, since the curves of the pore size distribution when normalized by the total pore volume can be matched on a unique curve, independent of the thermal treatment. The values of the pore mean size and the specific surface obtained from nitrogen adsorption are in agreement with those obtained from SAXS. A nonisothermal study of the kinetic of the pore elimination was carried out measuring the linear shrinkage using dilatometric tests, performed with different heating rates, in cylindrical monolithic xerogel samples previously treated at 1023 K for 10 hours. The study could be applied up to almost 60% of the volume fraction a of eliminated pores. The activation energy was found increasing from about 3.2þ102 kJ/mol for a ~ 6% up to about 4.4þ102 kJ/mol for a ~ 44% of the volume fraction of eliminated pores. The sintering process accompanying the nanopore elimination in this set of xerogels is in agreement with a viscous flux sintering ... (Complete abstract, access undermentioned eletronic address)
Descrição
Palavras-chave
Física aplicada, Fisica
Como citar
CASTRO, Wadley Calegaro de. Transformações estruturais em xerogéis de sílica tratados termicamente. 2005. 47 f. Dissertação (mestrado) - Universidade Estadual Paulista, Instituto de Geociências e Ciências Exatas, 2005.