ࡱ> IKFGHSD1}5@08bjbj22{XX/t&&&&D&'''J(4~(&72):P)(x)x))Q.o. {.87:7:7:7:7:7:7$8R=;b^7.-|Q...^7&&x))s7i1i1i1.&x))87i1.87i1i1/2 5645) ) -2'#/N$5T5707,5<q0<45&&&&&&<45 ..i1.....^7^7&&!' 1^&&'Otimizao das propriedades mecnicas e texturais de aluminas utilizadas em micropropulsores de satlites Fernandes, F. A. P*., Monteiro, W. R., Rodrigues, J. A. J., Zacharias, M. A. *Aluno de Iniciao Cientfica Laboratrio Associado de Combusto e Propulso - Instituto Nacional de Pesquisas Espaciais. Rodovia Presidente Dutra, km 40 - CEP: 12630-000 Cachoeira Paulista - SP - Brasil. Telefone: (0xx12) 3186-9214 Fax: 3101-1992 e-mail: marisa@lcp.inpe.br RESUMO - As aluminas assumiram uma grande importncia como suporte e/ou catalisador em inmeras reaes catalticas heterogneas. Sistemas micropropulsivos utilizam a alumina como suporte do catalisador de decomposio de hidrazina (N2H4). O principal objetivo deste trabalho o de apresentar os avanos alcanados durante o desenvolvimento das metodologias de sntese e de moldagem do precursor de uma alumina (gibsita), que aps tratamento trmico (calcinao), resulte em um suporte adequado ao uso no setor aeroespacial. A sntese deste precursor foi realizada a partir da decomposio cida do aluminato de sdio por CO2. Aps filtrao e secagem, o material foi tratado hidrotermicamente na presena e na ausncia de um agente ligante (boehmita) e com auxlio de agentes dispersantes. Em seguida, o p tratado seguiu para uma etapa de moldagem por extruso, os pellets cilndricos obtidos foram tratados termicamente com e sem fluxo de oxignio e finalmente caracterizados por diversas tcnicas. A rea especfica do material foi avaliada por volumetria de nitrognio (N2), a resistncia mecnica aferida pela compresso individual dos pellets por dinamometria, a fase cristalina, dos precursores secos em estufa e calcinados, obtida por difratometria de raios-X e a morfologia das partculas observada com o auxlio da tcnica de microscopia eletrnica de varredura (MEV). INTRODUO As aluminas so amplamente empregadas na indstria e em diversas reaes catalticas heterogneas, tanto como suporte e/ou catalisador. Sistemas micropropulsivos de correo de rbita e atitude de satlites utilizam este material com propriedades mecnicas, trmicas e texturais controladas, como suporte do catalisador de decomposio da hidrazina (N2H4). Os trihidrxidos e oxihidrxidos de alumnio so freqentemente utilizados como precursores, na obteno de aluminas de alto desempenho para fins catalticos. Sendo a decomposio da hidrazina extremamente rpida e exotrmica, torna-se importante o uso de hidrxidos precursores altamente cristalinos, os quais gerem aluminas com alta resistncia compresso, com capacidade de troca trmica rpida e porosidade adequada para facilitar a liberao dos gases desenvolvidos durante o acionamento do micropropulsor. Portanto, utilizou-se neste trabalho, um trihidrxido Al(OH)3 de alta cristalinidade (gibsita), que aps um tratamento hidrotrmico em presena de um oxihidrxido - AlOOH de baixa cristalinidade (boehmita), fornea, aps conformao e tratamento trmico, pellets com valores elevados de resistncia mecnica e rea especfica. Este trabalho teve como objetivo otimizar as propriedades mecnicas e texturais das aluminas preparadas, avaliando agentes dispersantes, a etapa de tratamento trmico e a adio de um agente ligante (boehmita). Parte Experimental Durante as etapas experimentais do processo utilizaram-se os seguintes reagentes: -Aluminato de sdio (Riedel de Hen); -Boehmita comercial, fornecida pelo CENPES; -CO2 (Air Liquide, 70%, balano em N2); -cido ntrico (10%) Merck; -cido actico (5%) Merck. Sntese do precursor (gibsita): Inicialmente preparou-se uma soluo aquosa, homognea, contendo 162g de aluminato de sdio em 600ml de gua, em seguida, esta soluo de pH entre 12 e 13 foi transferida para um reator encamisado de vidro. A soluo foi aquecida e mantida a aproximadamente 75C, com o auxlio de um banho termostatizado, marca Nova tica. Com a temperatura controlada, iniciou-se a adio do reagente precipitante (CO2), a uma vazo constante de aproximadamente 48ml.min-1. A agitao do sistema foi mantida em 800rpm, empregando-se um agitador tipo dupla hlice da marca JK. Depois de 15h a reao foi interrompida e a soluo retirada, filtrando-se o precipitado formado a vcuo, lavando-o com 20L de gua destilada aquecida a 70C. O produto foi seco a uma faixa de temperatura entre 50 e 60C por 24h, com o auxlio de uma estufa com circulao de ar forada. Aps seleo granulometria (<37 EMBED Equation.3 ), a gibsita obtida seguiu para uma etapa de tratamento hidrotrmico. Tratamento hidrotrmico: Nesta etapa, 200g de gibsita foram submetidas a tratamentos em meio cido (AG1), em gua (AG2) e misturada com 50g de Catapal A (ACG3), todos os componentes com granulometria inferior a 37 EMBED Equation.3 . Os precursores foram colocados em um misturador do tipo V, marca TREU, por 20min, onde foram homogeneizados fisicamente. Adicionou-se, ento, 500mL de cido ntrico 10% ou 500mL de gua destilada massa, conforme mostra a Tabela 1. A seguir, um agitador mecnico do tipo dupla hlice, da marca IKA, empregando uma rotao de 1200rpm, durante 15min, transforma o meio em uma pasta gelatinosa. Esta mistura gelatinosa novamente submetida a uma etapa de disperso, durante 5min, em um dispersor da marca Marconi. O gel obtido foi colocado em uma autoclave de metal a 170C, durante 8h, e filtrado em um funil de Bchner, com o auxlio de uma bomba de vcuo. A secagem da massa resultante em cada um dos experimentos foi feita em uma estufa entre 50 e 60C por 24h. Posteriormente o material foi triturado em um moinho almofariz/pistilo, da Marconi, de forma a obter um p com granulometria inferior a 149 EMBED Equation.3 . Tabela 1 Tratamentos hidrotrmicos realizados. PrecursoresAgentesHNO3(10%)H2Ogibsita(AG1)(AG2)gibsita+Catapal A* (4:1)(ACG3)-*boehmita comercial. Peptizao/Moldagem: Os materiais em p j tratados hidrotermicamente, provenientes de cada um dos experimentos realizados (AG1, AG2 e ACG3), foram transferidos para um misturador do tipo sigma, da marca IKA modelo Duplex Kneter, submetendo-os, ento, a uma etapa de disperso, adicionando uma soluo de cido actico (5%) a uma taxa de aproximadamente 0,2mL.min-1, at se obter uma massa homognea e moldvel. A moldagem dos pellets cilndricos foi realizada por extruso, com o auxlio de um dispositivo de prensagem dotado de um orifcio de sada com 6mm. Aps a moldagem, os pellets foram secos em uma estufa de circulao forada de ar, durante 24h, a uma temperatura entre 30 e 40C. Tratamento trmico (calcinao): Os pellets obtidos nos trs experimentos foram tratados termicamente com e sem fluxo de oxignio a 600C, durante 5h, submetendo-os a um aquecimento da temperatura ambiente at 130C, a uma taxa de aquecimento de 0,40C.min-1, permanecendo nesta temperatura por 30min, e de 130C a 600C, a uma taxa de 0,75C.min-1, permanecendo nesta temperatura por 5h. Resultados e Discusso Observando-se os difratogramas de raios X, obtidos a partir de um difratmetro da marca SEISERT, modelo Isodebyeflex 1001, com radiao K( do Cu ((=1,54178 ) do trihidrxido sintetizado (gibsita) e da boehmita utilizada (Figura 1), pode-se notar o alto grau de cristalinidade da gibsita obtida e uma baixa cristalinidade da boehmita, justificando o seu emprego como ligante.  Figura 1 Difratogramas de raios X dos precursores: a) gibsita; b) boehmita. A seguir so mostrados os difratogramas de raios X, obtidos aps tratamento hidrotrmico de cada um dos experimentos realizados. A anlise dos difratogramas evidencia que ao utilizar a gua como agente dispersante se obtm um produto com alto grau de cristalinidade (AG2).  Figura 2 Difratogramas de raios X das amostras tratadas hidrotermicamente: AG1; AG2; ACG3. A partir dessas observaes, pode-se afirmar que o cido ntrico promove uma transformao completa para fase desejada menos cristalina, proporcionando a formao de um material moldvel (AG1; ACG3). J o material tratado com gua (AG2) no sofreu transformao total de fase, permanecendo com alto grau de cristalinidade, conforme mostra a figura 2. Antes da etapa de moldagem, uma pequena trao de cada uma das amostras dos experimentos (AG1; AG2 e ACG3) foi calcinada, sob a forma de p, para avaliao da rea especfica, em funo do tratamento trmico com e sem fluxo de oxignio. Os resultados so apresentados na tabela 2. Tabela 2 - Resultados de rea especfica das amostras em p aps calcinao Com fluxo de oxignioSem fluxo de oxignioAG1179158AG212994ACG3204149 A partir destes resultados, fica evidente a importncia da utilizao do fluxo de oxignio durante a etapa de tratamento trmico, favorecendo a limpeza e a retirada da umidade durante a formao dos poros no material, condio que resulta em um aumento considervel no resultado de rea especfica.  Figura 3 Difratograma de raios X tpico das amostras calcinadas.  a) b) Figura 4 Microscopia Eletrnica de Varredura: a) precursor sintetizado (gibsita) e b) material com melhores propriedades mecnicas e texturais aps hidrotratamento e moldagem (ACG3), ambos calcinados a 600C por 5h. Nas micrografias apresentadas, fica evidente a presena de uma estrutura altamente cristalina no precursor gibsita. Este material, aps as etapas de hidrotratamento e moldagem, apresenta poucos cristais isolados, envolvidos por uma massa menos cristalina. Aps tratamento trmico com fluxo de oxignio, observa-se que todas as amostras se convertem a uma mistura de aluminas de transio, provavelmente (-Al2O3 e (- Al2O3, como mostra a figura 3. Aps moldagem, os pellets obtidos foram secos e ento tratados termicamente, sob fluxo de oxignio, para avaliao da resistncia mecnica compresso e da rea especfica.  Tabela 3 - Resultados de rea especfica e resistncia mecnica compresso dos pellets cilndricos calcinados. Resistncia (N/mm)rea especfica (m2/g)AG119184AG22133ACG327190 Os resultados de resistncia mecnica compresso individual dos pellets cilndricos demonstram um maior valor desta propriedade para o material que partiu da mistura de gibsita com boehmita, tratado hidrotermicamente em meio cido e calcinado sob fluxo de oxignio. Concluses - A metodologia de sntese do precursor (gibsita) resulta um material altamente cristalino; - Os testes realizados utilizando a gua como agente dispersante comprovam que h formao de um material com valores baixos de rea especfica e resistncia mecnica compresso; - A utilizao do cido ntrico como agente dispersante favorece a converso para uma fase menos cristalina; - Observa-se tambm que durante a etapa de tratamento trmico o fluxo de oxignio promove um aumento expressivo nos resultados de rea especfica das aluminas; - A adio de um agente ligante (Catapal A) torna a etapa de moldagem mais fcil, alm de aumentar a resistncia mecnica do material moldado ; Finalmente, de forma resumida, pode-se afirmar que as melhores condies para a obteno de pellets com elevada resistncia mecnica sem comprometer a rea especfica dos mesmos foram: a) adio de um agente ligante (Catapal A); b) tratamento hidrotrmico em cido ntrico e, c) tratamento trmico sob fluxo de oxignio. REFERNCIAS OBERLANDER, R. K. Aluminas for Catalysts Their Preparation and Properties. Applied Industrial Catalysis, v. 3, p. 63, Academic Press, New York, 1984. RODRIGUES, J. A. J.; ZACHARIAS, M. A. A influncia do Teor de Bicarbonato de Amnio na Estrutura Porosa das Aluminas. Qumica Nova, v.16, p. 10-14, 1993. SUTTON G. P.; ROSS, D. M., Rocket Propulsion Elements, 4th Edition, John Wiley, 1976 AGRADECIMENTOS Ao Centro de Pesquisas da Petrobrs CENPES pelo fornecimento da boehmita comercial (Catapal A). Ao CNPQ pela concesso da bolsa ao aluno Frederico Augusto Pires Fernandes, processo n 501459/2003-0.      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