Submitted by Daniele Amaral (daniee_ni@hotmail.com) on 2016-09-23T18:23:03Z No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T18:32:57Z (GMT) No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T18:33:07Z (GMT) No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) / Made available in DSpace on 2016-09-26T18:33:15Z (GMT). No. of bitstreams: 1 TesePCS.pdf: 3241758 bytes, checksum: ebda7b5367de3466e33fdbfe4e54c028 (MD5) Previous issue date: 2015-03-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Horticultural crops are an important food source for global population. However, crops still show high rates of postharvest losses, due to its high perishability. Ethylene is a plant hormone that regulates aspects such as growth, development, maturation and senescence of plants and their organs. Ethylene production varies between crops and its control can extend the life of fruits and vegetables. Many technologies have been developed in order to control the synthesis and reduce ethylene produced by plants. Oxidation through potassium permanganate (KMnO4) has application in storage, transportation and marketing. Typically, KMnO4 is impregnated in porous platforms displaying high specific surface are, which are aimed at removing ethylene within packaging. Ethylene can be oxidized by KMnO4, which subproducts (after subsequent oxidation), can be converted into water (H2O) and carbon dioxide (CO2). The use of platforms based on mesoporous nanoparticles (with diameters of 5-110 nm) impregnated with KMnO4 allows ethylene oxidation to be carried out more efficiently, once it increases the contact surface area. In this context, this study aimed at developing ethylene absorbers based on nanometric platforms (nanosilica and nanoalumina), associated with potassium permanganate (KMnO4), to remove ethylene produced during postharvest and use color changes during ethylene oxidation as a colorimetric indicator. The performance of nanometric platforms was compared to conventional silica and alumina. The following KMnO4 concentrations impregnated in the platforms were tested: 0; 2.5; 5 to 10%, which values are, respectively, half, equal and twice the values found in commercial ethylene removers. Since relative humidity is a factor that influences ethylene oxidation by KMnO4, the following UR were tested: 45, 60, 75, and 90%. The platforms impregnated with different KMnO4 concentrations and subjected to several RH in closed system, were exposed to a standardized amount of ethylene produced in the laboratory. After 1h and 24h of exposition, injection aliquots were collected for analysis by gas chromatography. The color was measured before placing samples in the closed system and after 24 hours. The silica nanoparticles, synthesized silica and alumina showed superior performance for ethylene absorption, especially when aliquots removal was evaluated in 1h. Among the tested nanoparticles, alumina nanoparticles showed to be the most effective, being able to completely remove the ethylene after 1h, under a greater variety of RH conditions and KMnO4 concentrations. The most suitable combinations, in accordance with the highest color difference and high ethylene absorption performance were synthesized nano-silica + 10% KMnO4 and nano-alumina + 10 % KMnO4 for RH = 45%; nanosilica + 10% KMnO4 and nano-alumina + 10% KMnO4 for RH= 60%; nano-silica + 10% of KMnO4, nano-alumina + 5% KMnO4 and nano-alumina + 10% KMnO4 for RH= 75 and 90%. / Os produtos hortícolas são uma importante fonte de alimentação para população global. Todavia, ainda são registrados elevados índices de perdas desses alimentos, devido a sua alta perecibilidade após a colheita. O etileno é um hormônio vegetal que regula aspectos como o crescimento, desenvolvimento, maturação e senescência de plantas e seus órgãos. A produção de etileno varia de acordo com o tipo de fruta e hortaliça, sendo que seu controle pode prolongar a vida útil dos produtos hortícolas. Muitas tecnologias já foram desenvolvidas afim de controlar a síntese e reduzir o etileno produzido pelos frutos. Por exemplo, a oxidação do etileno por meio do uso de permanganato de potássio (KMnO4) apresenta aplicação no armazenamento, transporte e comercialização. Geralmente o KMnO4 é impregnado em plataformas porosas acondicionadas em sachês, visando a remoção do etileno dentro de embalagens. O etileno oxidado gera subprodutos, que após novas oxidações, será convertido em água (H2O) e gás carbônico (CO2). A utilização de nanopartículas mesoporosas, com diâmetros da ordem de 5 a 110 nm, como plataformas para adsorção de KMnO4 permite que a oxidação do etileno seja realizada com maior eficiência, devido a maior área superficial de contato. Neste contexto, o objetivo deste trabalho foi desenvolver absorvedores de etileno baseados em plataformas nanométricas (nano-sílica comercial, nano-sílica sintetizada em laboratório e nano-alumina comercial), impregnadas com permanganato de potássio (KMnO4). Estas plataformas visam à remoção de etileno produzido por frutos durante a póscolheita, as quais causam alterações de coloração do KMnO4 durante a oxidação do etileno, e podem ser empregados como indicador colorimétrico de amadurecimento. O desempenho das plataformas de sílica e alumina nanométricas (comerciais e sintetizada) foram comparadas com sílica e alumina micrométricas (comerciais). Para a impregnação do KMnO4 nas diferentes plataformas, foram utilizadas concentrações (em relação a massa das plataformas) de 0; 2,5; 5 e 10% de KMnO4, cujos valores selecionados representam a metade, o valor médio e o dobro do teor de permanganato encontrado em sachês absorvedores comerciais. Os testes foram realizados em umidades relativas de 45, 60, 75, e 90%, já que esta variável altera fortemente a oxidação do etileno pelo KMnO4. As plataformas impregnadas com diferentes concentrações de KMnO4 em distintas UR, foram submetidas, em sistema fechado, a uma quantidade padronizada de 7480 μL de etileno produzida em laboratório. Após intervalos de 1h e 24h da injeção de etileno padrão, foram retiradas alíquotas para análise por cromatografia gasosa. A coloração foi aferida antes da inserção das amostras em sistema fechado e após 24h. As nanopartículas de sílica, sílica sintetizada e alumina apresentaram desempenho superior na absorção de etileno em relação a sílica e alumina de tamanhos convencionais, especialmente quando a remoção foi avaliada em 1h. Dentre as nanopartículas testadas, a nanopartícula de alumina foi a mais eficiente, sendo capaz de eliminar o montante de etileno injetado após 1h, sob um intervalo maior de condições de UR e concentração de KMnO4. A coloração pode ser indicativa da oxidação do etileno nas plataformas testadas e de acordo com a maior diferença de coloração e melhor desempenho de absorção de etileno, as combinações mais indicadas foram: nano-sílica sintetizada + 10% de KMnO4 e nano-alumina + 10% de KMnO4 para UR=45%; nano-sílica + 10% de KMnO4 e nano-alumina + 10% de KMnO4 para UR=60%; nano-sílica + 10% de KMnO4, nano-alumina + 5 % de KMnO4 e nano-alumina + 10% de KMnO4 para UR=75 e 90%.

Alumina (Al2O3) is one of the most widely used engineering ceramic. It can be used in a wide range of applications like electrical/thermal insulation, wear resistance, structural refractories, cutting tools, abrasives, catalyst carriers and coatings. A traditional ceramic process has several steps (i.e. powder synthesis and processing, shape forming, drying, organic burnout and densification). Accessing powders with sizes in the range of a couple of micrometers down to several tens of nanometers is considered critical in attaining higher densities in the final ceramic bodies. Besides since significant shrinkage can be observed in the thermal treatment steps due to the excessive use of additives (e.g. binders, solvents and plasticizers) in the powder processing and forming steps, it is important to take remedies that would increase the solids loading in the initial mixtures. In addition, most of the conventional additives and solvents used in these steps are toxic and it is necessary to replace them with the environmentally benign aqueous-based alternatives. Alumoxanes could be used as a benign aqueous-based alternative to be used as a ceramic precursor or an agent. They are a group of compounds that have nano sized boehmite cores encapsulated with the organic groups used in its production steps. In this research work, alumoxane nano particles which can be used as precursors for nano-alumina were developed starting from aluminum trihydroxide. As a preconditioning step, grinding was applied to decrease the aluminum hydroxide particle size (&amp / #8804 / 60 &amp / #956 / m) to submicron sizes. This process was followed by the glycothermal ageing step, and organic derivative of boehmite was obtained. The amorphous particles thus obtained were further treated mechanochemically in a high energy ball mill with organic chemicals like acetic acid, methoxy acetic acid, stearic acid and L-lysine. After this step the observed sizes of the particles were as low as 10-100 nm. The effects of organic molecules used in each step were studied by FTIR spectroscopy and their effectiveness in exfoliation of hydroxide layers were identified with dynamic light scattering from processing solutions dispersed in aqueous medium. Moreover, in each step, structural analyses were carried out by XRD.