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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Obtaining, characterization and application of additives antioxidants derivatives of the main shareholders of the constituents of the bark cashew nuts / ObtenÃÃo, caracterizaÃÃo e aplicaÃÃo de aditivos antioxidantes derivados dos principais constituintes do lÃquido da casca da castanha de caju

Francisco Jonas Nogueira Maia 23 June 2015 (has links)
CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Organic substrates derived from petroleum such as gasoline, diesel, lubricants, polymers and natural organic products, such as biofuels are, in most cases, susceptible to oxidation process that occurs initially through formation of free radicals, which modifies the chemical characteristics and alters the properties of these materials. Aiming the inhibition or reduction of the oxidative process, many works have been directed to the development of additives that prevent the formation and the action of radical species, called antioxidant additives. From this perspective, the studies carried out in this work relates the application of phenolic compounds obtained from Cashew Nut Shell Liquid (cardanol and cardol), as well as their alkylated, nitrated and phosphorated derivatives in the inhibition of the oxidation processes of organic substrates and the investigation of the mechanism of action these compounds, providing useful information about the relationship between antioxidant activity and the structural composition of these substances. The evaluation of the antioxidant capacity of cardanol, cardol and tert-butylated cardanol was initially developed by electrochemical study and accelerated oxidation tests, which allowed, respectively, the determination of the anodic peak potential (Epa) and induction time (IT). In these experiments, special emphasis was given to cardol and tert-butylated derivative of cardanol, which had the lowest values of Epa (0,66 e 0,68 V, respectively) and provide higher IT values (7,87 e 7,02 h respectively), characterized as the best phenolic antioxidants tested. These tests also showed that unsaturated compounds exhibit antioxidant action superior to their saturated analogues (cardol, cardanol, and tert-butylated cardanol unsaturated had mean values of IT approximately 0.42 hours higher than its analogs saturated). The superiority of cardol and tert-butylated cardanol was also observed in comparison to nitro compounds derived from saturated cardanol, showing that groups donor of electrons has a positive effect on the action of these compounds as antioxidants. The performance of phosphorous compounds derived from cardanol was, in turn, confirmed by thermogravimetric analysis, obtained from biodiesel samples doped with these compounds in ratios ranging from 500 to 2000 ppm. In this study, it was observed that the phosphorous compounds promoted a maximum increase of 18,5 ÂC in the initial degradation temperature of the tested biodiesel sample. Thermogravimetric analysis of cardanol, cardol, tert-butylated cardanol and phosphorus compounds also showed that these compounds exhibited thermo-oxidative resistance larger than commercial antioxidants as butylated hydroxytoluene (BHT). In general, the results, presented in this work, demonstrated the antioxidant activity of compounds derived from the CNSL, presenting useful means of determining its performance and practical application as antioxidant additive for biodiesel. / Substratos orgÃnicos derivados do petrÃleo como a gasolina, o diesel, lubrificantes, polÃmeros e, produtos orgÃnicos de origem natural como os biocombustÃveis, sÃo, na sua maioria, suscetÃveis ao processo de oxidaÃÃo, o qual ocorre, inicialmente, pela formaÃÃo de radicais livres, que atuam modificando as caracterÃsticas quÃmicas e provocando alteraÃÃes nas propriedades desses materiais. Com o objetivo de inibir ou retardar a oxidaÃÃo, muitas pesquisas tÃm se dedicado ao desenvolvimento de aditivos que combatem a formaÃÃo e a atuaÃÃo das espÃcies radicalares, chamados de aditivos antioxidantes. Nessa perspectiva, os estudos desenvolvidos nesse trabalho referem-se à aplicaÃÃo de compostos fenÃlicos obtidos a partir do LÃquido da Casca da Castanha de Caju (cardanol e cardol), bem como de seus derivados alquilados, nitrados e fosforados, na inibiÃÃo do processo oxidativo de substratos orgÃnicos e na investigaÃÃo do mecanismo de aÃÃo desses compostos, oferecendo informaÃÃes sobre a relaÃÃo entre a atividade e a composiÃÃo estrutural dessas substÃncias. A avaliaÃÃo da capacidade antioxidante do cardanol, cardol e do cardanol terc-butilado foi inicialmente desenvolvida a partir de estudos eletroquÃmicos e testes de oxidaÃÃo acelerada, que permitiram a determinaÃÃo do potencial de pico anÃdico (Epa) e do tempo de induÃÃo (TI), respectivamente. Nesses experimentos, destaque especial foi dado ao cardol e ao derivado terc-butilado do cardanol, que apresentaram os menores valores de Epa, (0,66 e 0,68 V, respectivamente) e proporcionaram os maiores tempos de induÃÃo (7,87 e 7,02 horas, respectivamente), caracterizando-se como os melhores antioxidantes fenÃlicos testados. Esses testes mostraram tambÃm que os compostos insaturados apresentam aÃÃo antioxidante superior aos seus anÃlogos saturados (cardol, cardanol terc-butilado e cardanol insaturados apresentaram valores mÃdios de TI cerca de 0,42 horas superior a seus anÃlogos saturados). A superioridade do cardol e do cardanol terc-butilado foi tambÃm observada em comparaÃÃo aos compostos nitrados derivados do cardanol saturado, mostrando que grupos doadores de elÃtrons tem efeito positivo na aÃÃo desses compostos como antioxidantes. O desempenho dos compostos fosforados obtidos a partir do cardanol foi, por sua vez, comprovado por anÃlises termogravimÃtricas, pelo emprego de amostras de biodiesel dopadas com esses compostos em proporÃÃes que variaram de 500 a 2000 ppm. Nesse estudo, foi possÃvel observar que os compostos fosforados promoveram um aumento mÃximo de 18,5 ÂC na temperatura inicial de degradaÃÃo da amostra de biodiesel testada. As anÃlises termogravimÃtricas do cardanol, cardol, cardanol terc-butilado e dos compostos fosforados mostraram tambÃm que esses compostos apresentaram resistÃncia ao processo termo-oxidativo superior a antioxidantes comercias como o butilhidrixitolueno (BHT). De forma geral, os resultados apresentados nesse trabalho comprovam a aÃÃo antioxidante de compostos derivados do LCC, apresentando meios Ãteis para a determinaÃÃo de seu desempenho e aplicaÃÃo prÃtica como aditivo antioxidante para biodieseis.

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