Authors:J. Santos, I. Santos, M. Conceiçăo, S. Porto, M. Trindade, A. Souza, S. Prasad, V. Fernandes, and A. Araújo
Thermoanalytical, kinetic and rheological parameters of commercial edible oils were evaluated. The thermal decomposition of
the oils occurred in three steps, due to polyunsaturated, monounsaturated and saturated fatty acids decomposition, respectively.
According to the temperature of the beginning of the decomposition, the following stability order was observed: corn (A)>corn>sunflower
(A)>rice>soybean>rapeseed (A)>olive>rapeseed>sunflower (A - artificial antioxidants). Kinetic parameters were obtained using
Coats-Redfern and Madhusudanan methods and presented good correlation. According to the activation energy of the first thermal
decomposition event, obtained of Coats-Redfern' method, the following stability order is proposed: sunflower>corn>rice>soybean>rapeseed>olive.
In relation to rheological properties, a Newtonian behavior was observed and no degradation occurred in the temperature range
Authors:J. Maul, A. S. Brito, A. L. M. de Oliveira, S. J. G. Lima, M. A. M. A. Maurera, D. Keyson, A. G. Souza, and I. M. G. Santos
Copper monoxide (CuO) was successfully obtained by microwave-assisted hydrothermal method, using different conditions—in a solution without base, in a solution alkalinized with NaOH or with NH4OH. The powders were analyzed by thermal analysis (TG/DTA), X-ray diffraction (XRD), infrared spectroscopy, UV–Visible spectroscopy, and scanning electronic microscopy. XRD results showed that CuO was obtained with monoclinic structure and without secondary phases. Thermal analysis and infrared spectra indicated the presence of acetate groups on the powder surface. TG curves also showed a mass gain assigned to the Cu(I) oxidation indicating that a reduction possibly occurred during synthesis. The high and broad absorption band in the UV–Vis spectroscopy from 250 to 750 nm indicated the coexistence of Cu(II) and Cu(I), confirming the Cu(II) reduction, inside the CuO lattice. It was also possible to confirm the Cu(II) reduction by a displacement of the Me–O vibration bands observed in the IR spectra at around 500 cm−1.
Authors:M. C. D. Silva, L. M. da Silva, N. A. Santos, M. M. Conceição, A. G. Souza, and A. O. dos Santos
Nowadays the growing fuel deficit requires the development of alternative fuel sources. Biodiesel is a good substitute to the conventional diesel because it is quite similar to the fossil fuel in its main characteristics. However, there are some obstacles, as the properties of cold-flow, to the development of a more useful alternative fuel. In this work we use the X-ray diffraction and differential calorimetry scanning to study low temperature properties of ethylic Babassu biodiesel. Our results show that the nucleation of crystals starts below −8 °C and the crystallization temperature does not change significantly when the sample was submitted to a winterization process. The higher concentrations of ethyl esters from saturated fat acid are probably responsible for this characteristic. The X-ray diffraction, combined with DSC measurements, was efficiently employed in the characterization of cold-flow biodiesel properties, showing to be very helpful techniques.
Authors:R. A. Candeia, F. S. M. Sinfrônio, T. C. Bicudo, N. Queiroz, A. K. D. Barros Filho, L. E. B. Soledade, I. M. G. Santos, A. L. Souza, and A. G. Souza
Biodiesel oxidation is a complex process widely influenced by the chemical composition of the biofuel and storage conditions. Several oxidation products can be formed from these processes, depending on type and amount of the unsaturated fatty acid esters. In this work, fatty acid methyl and ethyl esters were obtained by base-catalyzed transesterification of soybean oil and physicochemically characterized according to standards from ASTM, EN, and ABNT. The thermal and oxidative stabilities of biodiesel samples were investigated during the storage process by pressure differential scanning calorimetry (PDSC) and by viscosity measurements. Absolute viscosities of biodiesels after accelerated aging were also determined. The viscosity increased as the aging temperature and time were raised. The results showed that oxidation induction can occur during storage, decreasing the biodiesel stability. PDSC analysis showed that during storage under climate simulation the values of high-pressure oxidative induction times (HPOIT) were reduced for both FAEE and FAME.
Authors:M. L. A. Tavares, N. Queiroz, I. M. G. Santos, A. L. Souza, E. H. S. Cavalcanti, A. K. D. Barros, R. Rosenhaim, L. E. B. Soledade, and A. G. Souza
The higher is the degree of unsaturation in ester chain of a biodiesel, the smaller is its oxidation stability. Sunflower biodiesel obtained by the ethyl route possesses a high amount of unsaturated fatty acids, mainly oleic acid (C18:1) and linoleic acid (C18:2), thus being more prone to the oxidation process. In Brazil, with the purpose of meeting the specifications of the Brazilian National Agency of Petroleum, Natural Gas and Biofuels (ANP), antioxidant additives, from synthetic and natural origins, have been added to the biofuel. Antioxidants are an alternative to prevent the oxidative deterioration of the fatty acid derivatives, as they are substances able to reduce the oxidation rate. In this study, the oxidative stability of sunflower biodiesel, obtained by the ethyl route and additivated with different concentrations of the antioxidants butylated hydroxytoluene (BHT) and t-butylhydroquinone (TBHQ), was evaluated by means of Pressure differential scanning calorimetry (P-DSC) and the Accelerated oxidative stability test (Rancimat, Method EN 14112). The results obtained by the two techniques showed the same oxidation tendency. Thus, P-DSC can be used as an alternative to determine the oxidative stability of biodiesel. The antioxidant TBHQ, added to biodiesel at the concentrations of 2000 and 2500 mg kg−1, raised the oxidation induction time to a value higher than 6 h, the limit established by the Resolution ANP number 7/2008, thus being the best alternative among the studied antioxidants.
Authors:M. B. Dantas, A. R. Albuquerque, L. E. B. Soledade, N. Queiroz, A. S. Maia, I. M. G. Santos, A. L. Souza, E. H. S. Cavalcanti, A. K. Barro, and A. G. Souza
Even not being described in the EN 14112 standard, PDSC has been used for the determination of the biodiesel oxidative stability, by OIT and OT measurements. In this study, biodiesel blends were obtained by mixing soybean (BES) and castor (BEM) ethyl esters and its induction periods were measured by Rancimat and PDSC. The blends (BSMX) showed intermediate values of OSI, OT, and OIT, compared with BES and BEM. Although, the molar fraction of the components varied linearly in BSMX, OSI, OT, and OIT values increased exponentially in relation to the castor biodiesel amount in the blends. Introduction of castor oil biodiesel increased the blend stability, so the BSM30 blend reached the OSI limit of 6 h. OSI, OIT, and OT showed a high-linear correlation, pointing out that PDSC can be used in the analysis of this kind of biodiesel, with a smaller sample and analysis time, as compared to Rancimat. The use of biodiesel blends was a good alternative in the correction of the oxidative stability of the final product without the need of antioxidant addition.