Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-02-04T23:03:25Z No. of bitstreams: 1 MariaSusanaSilva_TESE.pdf: 6744977 bytes, checksum: 2a8c2506ef32d61f3992dba778ac3ec1 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-02-04T23:08:50Z (GMT) No. of bitstreams: 1 MariaSusanaSilva_TESE.pdf: 6744977 bytes, checksum: 2a8c2506ef32d61f3992dba778ac3ec1 (MD5) / Made available in DSpace on 2016-02-04T23:08:50Z (GMT). No. of bitstreams: 1 MariaSusanaSilva_TESE.pdf: 6744977 bytes, checksum: 2a8c2506ef32d61f3992dba778ac3ec1 (MD5) Previous issue date: 2015-02-02 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / O aumento da consci?ncia ambiental, maximizando a biodegradabilidade e minimizando a ecotoxicidade, ? a for?a motriz principal para os novos desenvolvimentos tecnol?gicos. Deste modo, os lubrificantes biodegrad?veis utilizados em ?reas ambientalmente sens?veis podem ser mais explorados. O objetivo desse trabalho foi obter novos biolubrificantes a base de ?leo de maracuj? (Passiflora edulis Sims f. flavicarpa Degener) e de moringa (Moringa oleifera Lamarck), in natura e epoxidados e otimizar o uso de um novo pacote de aditivos atraves da metodologia de planejamento experimental para sua utiliza??o como fluido hidr?ulico. Na primeira etapa do trabalho foi realizada a otimiza??o do processo de epoxida??o dos ?leos utilizando o planejamento experimental fracionado 24-1 , variando a temperatura, tempo de rea??o, raz?o molar de ?cido f?rmico e a raz?o molar de per?xido de hidrog?nio. Em seguida, foi investigada a seletividade, termodin?mica e a cin?tica da obten??o dos dois ep?xidos a 30, 50 e 70 ?C. Os resultados dessa primeira etapa confirmaram que para a epoxida??o do ?leo de maracuj? s?o necess?rias 3 horas de rea??o, 30 ?C e uma raz?o H2O2/C=C/HCOOH (1:1:1) e para o ?leo de moringa foram necess?rias 3 horas de rea??o, 30 ?C e uma raz?o de H2O2/C=C/HCOOH (1:1:1,5). Os resultados das convers?es finais foram iguais a 83,09% (?0,3) para o ep?xido de ?leo de maracuj? e 91,02% (?0,4) para o ep?xido do ?leo de moringa. Em seguida, foi feito o planejamento experimental fatorial 23 para avaliar quais as melhores concentra??es do inibidor de corros?o e antidesgaste (IC), antioxidante (BHA) e extrema press?o (EP). Os biolubrificantes obtidos nessa etapa foram caracterizados segundo as normas DIN 51524 (Part 2 HLP) e DIN 51517 (Part 3 CLP). O processo de epoxida??o dos ?leos foi capaz de melhorar a estabilidade oxidativa e diminuir o ?ndice de acidez total quando comparados aos ?leos in natura. Em termos de desempenho f?sico-qu?mico como lubrificantes, o melhor fluido foi o ep?xido do ?leo de moringa aditivado (EMO-ADI), seguido do ep?xido do ?leo maracuj? aditivado (EMA-ADI) e, por ?ltimo, o ?leo de maracuj? in natura sem aditivos (OMA). Para finalizar, foi feita a investiga??o de seus comportamentos tribol?gicos sob condi??es de lubrifica??o lim?trofe. O desempenho tribol?gico dos lubrificantes desenvolvidos foi analisado em um equipamento HFRR (High Frequency Reciprocating Rig) e atrav?s da medi??o do coeficiente de atrito, que ocorre durante o contato e a forma??o do filme lubrificante, durante o ensaio. O desgaste foi avaliado atrav?s de microscopia ?ptica e microscopia eletr?nica de varredura (MEV). Observou-se que, em todos os ensaios, foi formado um filme lubrificante e que a adi??o de EP e IC nas bases vegetais de ?leo de maracuj? e moringa in natura n?o ocasionou uma redu??o significativa no desgaste. Os biolubrificantes desenvolvidos a partir de ?leo de maracuj? e moringa modificados via epoxida??o apresentaram propriedades tribol?gicas superiores aos fluidos comerciais testados, mostrando serem potenciais lubrificantes para substitui??o dos fluidos comerciais de base mineral. / With the increasing environmental awareness, maximizing biodegradability and minimizing ecotoxicity is the main driving force for new technological developments. Thus, can be developed new biodegradable lubricants for use in environmentally sensitive areas. The aim of this study was to obtain new bio-lubricants from passion fruit (Passiflora edulis Sims f. flavicarpa Degener) and moringa (Moringa oleifera Lamarck) epoxidized oils and develop a new additive package using experimental design for their use as a hydraulic fluid. In the first stage of this work was performed the optimization of the epoxidation process of the oils using fractional experimental design 24-1 , varying the temperature, reaction time, ratio of formic acid and hydrogen peroxide. In the second step was investigated the selectivity, thermodynamics and kinetics of the reaction for obtaining the two epoxides at 30, 50 and 70 ?C. The result of the experimental design confirmed that the epoxidation of passion fruit oil requires 2 hours of reaction, 50 ?C and a ratio H2O2/C=C/HCOOH (1:1:1). For moringa oil were required 2 hours reaction, 50 ?C and a ratio of H2O2/C=C/HCOOH (1:1:1.5). The results of the final conversions were equal to 83.09% (? 0.3) for passion fruit oil epoxide and 91.02 (?0,4) for moringa oil epoxide. Following was made the 23 factorial design to evaluate which are the best concentrations of corrosion inhibitor and anti-wear (IC), antioxidant (BHA) and extreme pressure (EP) additives. The bio-lubricants obtained in this step were characterized according to DIN 51524 (Part 2 HLP) and DIN 51517 (Part 3 CLP) standards. The epoxidation process of the oils was able to improve the oxidative stability and reduce the total acid number, when compared to the in natura oils. Moreover, the epoxidized oils best solubilized additives, resulting in increased performance as a lubricant. In terms of physicochemical performance, the best lubricant fluid was the epoxidized moringa oil with additives (EMO-ADI), followed by the epoxidized passion fruit oil with additives (EPF-ADI) and, finally, the passion fruit in natura oil without additives (PFO). Lastly, was made the investigation of the tribological behavior under conditions of boundary lubrication for these lubricants. The tribological performance of the developed lubricants was analyzed on a HFRR equipment (High Frequency Reciprocating Rig) and the coefficient of friction, which occurs during the contact and the formation of the lubricating film, was measured. The wear was evaluated through optical microscopy and scanning electron microscopy (SEM). The results showed that the addition of extreme pressure (EP) and anti-wear and corrosion inhibitor (CI) additives significantly improve the tribological properties of the fluids. In all assays, was formed a lubricating film that is responsible for reducing the coefficient of metal-to-metal wear. It was observed that the addition of EP and IC additives in the in natura vegetable oils of passion fruit and moringa did not favor a significant reduction in wear. The bio-lubricants developed from passion fruit and moringa oils modified via epoxidation presented satisfactory tribological properties and shown to be potential lubricants for replacement of commercial mineral-based fluids.