O dano por umidade à um defeito frequente e um dos principais responsÃveis pelo desgaste prematuro de pavimentos. Esta pesquisa apresenta uma avaliaÃÃo do potencial do LCC como modificador de ligante asfÃltico com relaÃÃo à resistÃncia ao dano por umidadeem misturas asfÃlticas.Propriedades fÃsico-quÃmicas do LÃquido da Castanha de Caju (LCC) mostram-se potencialmente Ãteis para conferir ao Cimento AsfÃltico de PetrÃleo (CAP) maior adesÃo com os agregados.Utilizou-se um CAP convencional classificado por penetraÃÃo como 50/70 e um CAP modificado com 2% de LCC caracterizados quÃmica e reologicamente. Os agregados foram caracterizados atravÃs da fluorescÃncia de Raio-X e com relaÃÃo à forma. Foram dosadas, segundo o mÃtodo Superpave, diferentes misturas asfÃlticas contendo como ligante: CAP, CAP modificado com LCC e CAP e cal como fÃler. A caracterizaÃÃo mecÃnica das misturas foi realizada atravÃs dos ensaios Lottman modificado, MÃdulo de ResiliÃncia (MR) e desgaste CÃntabro. Utilizou-se o Processamento Digital de Imagens (PDI) para verificar o deslocamento da pelÃcula de CAP. Constatou-se que o LCC diminuiu a viscosidade e reduziu as Temperaturas de Usinagem e CompactaÃÃo (TUC) do CAP. Ambas as amostras, CAP e CAP modificado com 2% de LCC, foram classificadas como PG 70-28. Os agregados foram classificados como granÃticos, sub-arredondados, com baixa esfericidade e de textura lisa. Os resultados mostraram que a mistura com CAP modificado com LCC apresentou menor percentual de descolamento da pelÃcula de CAP e desempenho mecÃnico satisfatÃrio se comparada Ãs outras misturas analisadas. Espera-se que o LCC possa ser utilizado como aditivo gerando misturas asfÃlticas menos suscetÃveis à aÃÃo deletÃria da Ãgua. / Moisture damage is a frequent distress on pavements and is considered a major contributor to premature deterioration. Physicochemical properties of the Cashew Nut Shell Liquid (CNSL) showed to be potentially useful to improve the adhesion between asphalt binder and aggregates.The main objective of this study is to evaluate the potential of the CNSL modified asphalt binder to increase the hot mixture asphalt (HMA) resistance to moisture damage, and as a promoter of adhesiveness between binder and aggregates.Pure and modified asphalt binders with different CNSL contents were characterized chemically and rheologically. The aggregates were characterized by X-ray fluorescence and using Aggregate Imaging Measurement System (AIMS). HMAs with binders modified with CNSL were designed using the Superpave methodology. HMA mechanical characterization consisted of modified Lottman test, Resilient Modulus and Cantabro. Results were compared with those obtained using two different HMAs: (i) one with conventional asphalt binder and natural aggregates, and (ii) another one using 2% of lime as a filer. The stripping resistance of asphalt binderswere characterizedthrough digital image processing (DIP). The findings showed the CNSL decreased the asphalt binder viscosity. Both, the pure and the modified asphalt binder, were classified as PG 70-28. The granitic aggregates were classified as sub rounded, with low sphericity and smooth texture. The findings showed that the HMA contain binder modified with CNSL had better stripping resistance and behavior mechanical performance than other evaluated HMAs. Itâs expected that the effectiveness of the CNSL can be used as an additive to prevent striping in asphalt mixtures and to provide a greater resistance to breakdown caused by water.

Currently, the production of most non-asbestos organic (NAO) friction materials depends on a long and energy intensive manufacturing process and an unsustainable supply of synthetic resins and fibres; it is both expensive and bad for the environment. In this research, a new, more energy efficient, manufacturing process was developed which makes use of a naturally derived resin and natural plant fibres. The new process is known as 'cold moulding' and is fundamentally different from the conventional method. It was used to develop a new brake pad for use in low temperature (<400 °C) applications, such as rapid urban rail transit (RURT) trains. A commercially available resin based upon cashew nut shell liquid (CNSL) was analysed and found to have properties suitable for cold moulding. In addition, hemp fibre was identified as a suitable composite reinforcement. This was processed to improve its morphology and blended with aramid to improve its thermal stability. Each stage of cold mould manufacture was thoroughly investigated and the critical process parameters were identified. The entire procedure was successfully scaled up to produce an industrially sized 250 kg batch of material and the resultant composites were found to have appropriate thermal and mechanical properties for use in a rail brake pad. The tribological performance of these composites was iteratively developed through a rigorous testing and evaluation procedure. This was performed on both sub- and full-scale dynamometers. By adding various abrasives, lubricants, and fillers to the formulation it was possible to produce a brake pad with similar friction characteristics to the current market material, but with a 60% lower wear rate. In addition, this brake pad caused 15% less wear to the brake disc. A detailed examination of both halves of the friction couple found that cold moulded composites exhibit a different wear mechanism from the current market material, which was suggested to be the reason for their superior properties. Cold moulding is 3.5x faster and uses 400% less energy than the conventional method.

Orientador: Matthieu Tubino / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T17:54:49Z (GMT). No. of bitstreams: 1 Bastos_FlavioAdriano_D.pdf: 1277928 bytes, checksum: 9039000b025b809b99909b347545f47f (MD5) Previous issue date: 2014 / Resumo: A primeira parte deste trabalho consiste na apresentação de um novo método, seletivo e quantitativo, para a determinação de metóxido de sódio em solução metanólica, utilizando-se a termometria. O metóxido é usado como reagente em muitos processos industriais, como na indústria farmacêutica e também como catalisador na síntese de biodiesel. O método desenvolvido está baseado no aumento da temperatura da solução como consequência da reação exotérmica entre a água e o íon metóxido. Em relação ao método atualmente usado, ele apresenta vantagens como maior rapidez e simplicidade nas análises, além de custo mais baixo. Os resultados obtidos pelos dois métodos foram submetidos a testes estatísticos que comprovaram, em nível de confiança de 95%, que os resultados obtidos com os dois procedimentos não diferem entre si. Os valores de desvio padrão estão abaixo de 2,0 %. O método proposto pode ser aplicado, por exemplo, no controle da concentração de metilato de sódio em lotes do produto adquirido para fins de síntese e, também, no controle da produção industrial deste reagente. Na segunda etapa, foi realizado o estudo da influência do líquido obtido da casca de castanha de caju (LCC) na estabilidade oxidativa de biodieseis oriundos de óleos de soja, de milho, de canola e de girassol utilizando-se o método Rancimat® e variando-se a concentração do antioxidante para cada um dos tipos de biodiesel. Em todos os casos, pode-se observar que a adição do antioxidante eleva a resistência à oxidação do biodiesel, sendo que concentrações, em mol L-1, da ordem de 10-5, para o biodiesel de girassol, e de 10-3 para os demais, já se nota ação antioxidante em função da diminuição da velocidade de oxidação do biodiesel estudado. Também foram determinados parâmetros cinéticos e termodinâmicos das reações envolvendo o antioxidante / Abstract: The first part of this work presents a new and selective quantitative analytical thermometric method for sodium methoxide determination in methanol solutions in the presence of hydroxide ions. The sodium methoxide is used as a reagent or a catalyst in many industrial processes such as, for example, pharmaceuticals and biodiesel syntheses. The procedure is based on the measurement of the temperature increase of the solution caused by the exothermic reaction between water and the ion methoxide. In relation to the current method, the method proposed has advantages such as lower cost and has greater speed and simplicity analysis, besides is faster. The results obtained in this work were compared with those obtained by current method were subjected to statistical tests proved that, within certain levels of confidence, the results obtained by the proposed method does not differ significantly from the current method used by manufacturers. The observed relative standard deviations are below 2,0 %. The proposed method can be applied, for example, in incoming inspection of raw materials and in quality control of the industrial production of sodium methoxide. In the second part of this work we carried out a study of cashew nut shell liquid (CNSL) influence as antioxidant on biodiesel came from the refined vegetable oils from soybean, sunflower, canola and corn through the official Rancimat® method. The tests were performed varying the temperature and concentration of the antioxidant for each of the biodiesel. In all cases, it can be seen that the addition of antioxidant increases the oxidation resistance of biodiesel, with concentrations, in mol L-1, in the order of 10-5 for sunflower biodiesel and 10-3 for the other ones, already observed antioxidant activity due to the decrease in the rate of oxidation of biodiesel studied. Besides that, it was determined kinetics and thermodynamics parameters from the antioxidant action / Doutorado / Quimica Analitica / Doutor em Ciências

Fossils fuels are highly demanded in everyday life domestically or industrially. Fossil fuels are finite resources and they are rapidly depleting, as such alternative renewable feedstocks are sought to replace fossil fuels. Tall oil from paper processing and cashew nut shell liquid from the cashew nut industry are the two major renewable sources we studied, they are both waste byproducts, and have the potential to be converted into value-added materials. Tall oil from the paper industry mainly contained tall oil fatty acid, and under isomerising methoxycarbonylation with palladium catalyst, dimethyl 1,19-dimethyl nonadecanedioate can be obtained. This difunctional ester, dimethyl 1,19-dimethyl nonadecanedioate, is converted to diols, secondary and primary diamines by a hydrogenation reaction with ruthenium complexes of 1,1,1-tris(diphenylphosphinometyl)ethane (triphos) as catalysts in the presence of water, amine or aqueous ammonia respectively. In the case of aqueous ammonia it is necessary to use a two step reaction via diol to obtain 1,19-diaminononadecane. Diesters, diols and diamines are useful precursors for the synthesis of polyesters and polyamides. Difunctional substrates with 8-19 carbon chains are all tolerated under the reaction conditions and are successfully converted to the corresponding diols and diamines in high yields. Under similar hydrogenation conditions with the same ruthenium catalyst, cyclic products were predominantly produced with decreased chain length. N-heterocycles, which are important building blocks for the synthesis of drug molecules, were formed from the hydrogenation of diesters with 4-7 carbon chains in the presence of an amine. Another polymer precursor, ε-caprolactam, which is the precursor for Nylon 6, is obtained in a reasonable yield from both adipic acid and adipate esters together with aqueous ammonia in the presence of ruthenium catalyst. Cashew nut shell liquid was also converted into useful medical drugs, such as norfenefrine, rac-phenylephrine, etilefrine and fenoprofene in reasonable yields. Most of these drug molecules have been formed from 3-vinylphenol by catalytic hydroxyamination followed by methylation or ethylation. 3-Vinylphenol was synthesised from cardanol by ethenolysis to 3-non-8-enylphenol followed by isomerising ethenolysis, whilst the N-alkylation reactions used methyl or ethyl triflate to avoid dialkylation. Fenoprofene was formed by firstly O-phenylating cardanol then ethenolysis followed by isomerising ethenolysis to form 1-phenoxy-3-vinylbenzene. Methoxycarbonyation followed by hydrolysis formed the final product in good yield. Our methods start from renewable waste materials and avoid unpleasant reagents in the original stoichiometric synthesis of those drugs, for example, cyanide is no longer essential for the synthesis of fenoprofene.

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.