Avaliação da estabilidade térmica e oxidativa dos biodieseis de algodão, girassol, dendê e sebo bovino

The search for new sources of environmentally friendly energy is growing every day. Among these alternative energies, biodiesel is a biofuel that has had prominence in world production. In Brazil, law 11.097, determine that all diesel sold in the country must be made by mixing diesel/biodiesel. The latter called BX, , where X represents the percent volume of biodiesel in the diesel oil, as specified by the ANP. In order to guarantee the quality of biodiesel and its mixtures, the main properties which should be controlled are the thermal and oxidative stability. These properties depend mainly of the chemical composition on the raw materials used to prepare the biodiesel. This dissertation aims to study the overall thermal and oxidative stability of biodiesel derived from cotton seed oil, sunflower oil, palm oil and beef tallow, as well as analyze the properties of the blends made from mineral oil and biodiesel in proportion B10. The main physical-chemical properties of oils and animal fat, their respective B100 and blends were determined. The samples were characterized by infrared and gas chromatography (GC). The study of thermal and oxidative stability were performed by thermogravimetry (TG), pressure differential scanning calorimeter (PDSC) and Rancimat. The obtained biodiesel samples are within the specifications established by ANP Resolution number 7/2008. In addition, all the blends and mineral diesel analyzed presented in conformed withthe ANP Regularion specifications number 15/2006. The obtained results from TG curves data indicated that the cotton biodiesel is the more stable combustible. In the kinetic study, we obtained the following order of apparent activation energy for the samples: biodiesel from palm oil > sunflower biodiesel > tallow biodiesel > cotton biodiesel. In terms of the oxidative stability, the two methods studied showed that biodiesel from palm oil is more stable then the tallow. Within the B100 samples studied only the latter were tound to be within the standard required by ANP resolution N° 7. Testing was carried out according to the EN14112. This higher stability its chemical composition

Estudo da estabilidade térmica de adoçantes naturais e artificiais

Sweeteners provide a pleasant sensation of sweetness that helps the sensory quality of the human diet, can be divided into natural sweeteners such as fructose, galactose, glucose, lactose and sucrose, and articial sweeteners such as aspartame, cyclamate and saccharin. This work aimed to study the thermal stability of natural and artificial sweeteners in atmospheres of nitrogen and syntetic air using thermogravimetry (TG), derivative thermogravimetry (DTG), Differential Thermal Analysis (DTA) and Differential Scanning Calorimetry (DSC). Among the natural sweeteners analyzed showed higher thermal stability for the lactose and sucrose, which showed initial decomposition temperatures near 220 ° C, taking advantage of the lactose has a higher melting point (213 ° C) compared to sucrose (191 ° C). The lower thermal stability was observed for fructose, it has the lowest melting point (122 °C) and the lower initial decomposition temperature (170 °C). Of the artificial sweeteners studied showed higher thermal stability for sodium saccharin, which had the highest melting point (364 ° C) as well as the largest initial decomposition temperature (466 ° C under nitrogen and 435 ° C in air). The lower thermal stability was observed for aspartame, which showed lower initial decomposition temperature (158 ° C under nitrogen and 170 ° C under air). For commercial sweeteners showed higher thermal stability for the sweeteners L and C, which showed initial temperature of thermal decomposition near 220 ° C and melting points near 215 ° C. The lower thermal stability was observed for the sweetener P, which showed initial decomposition temperature at 160 ° C and melting point of 130 °C. Sweeteners B, D, E, I, J, N and O had low thermal stability, with the initial temperature of decomposition starts near 160 °C, probably due to the presence of aspartame, even if they have as the main constituent of the lactose, wich is the most stable of natural sweeteners. According to the results we could also realize that all commercial sweeteners are in its composition by at least a natural sweeteners and are always found in large proportions, and lactose is the main constituent of 60% of the total recorded

Avaliação da estabilidade térmica e oxidativa do biodiesel de algodão e do efeito da adição de antioxidantes (α-tocoferol e BHT)

This work aims to study the effects of adding antioxidants, such as, α- tocopherol and BHT on the thermal and oxidative stability of biodiesel from cottonseed (B100). The Biodiesel was obtained through the methylical and ethylical routes. The main physical and chemical properties of cotton seed oil and the B100 were determined and characterized by FTIR and GC. The study of the efficiency of antioxidants, mentioned above, in concentrations of 200, 500, 1000, 1500, 2000ppm, to thermal and oxidative stability, was achieved by Thermogravimetry (TG), Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC), Differential Scanning Calorimetry - Hi-Pressure (P-DSC) and Rancimat. The Biodiesel obtained are within the specifications laid down by Resolution of ANP No7/2008. The results of TG curves show that the addition of both antioxidants, even in the lowest concentration, increases the thermal stability of Biodieseis. Through the DTA and DSC it was possible to study the physical and chemical transitions occurred in the process of volatilization and decomposition of the material under study. The initial time (OT) and temperature (Tp) of oxidation were determined through the P-DSC curve and they showed that the α-tocopherol has a pro-oxidant behavior for some high concentrations. The BHT showed better results than the α-tocopherol, with regard to the resistance to oxidation

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR

Histerese térmica de sistemas magnéticos nanoestruturados

We report a theoretical investigation of thermal hysteresis in magnetic nanoelements. Thermal hysteresis originates in the existence of meta-stable states in temperature intervals which may be tuned by small values of the external magnetic field, and are controlled by the systems geometric dimensions as well as the composition. Two systems have been investigated. The first system is a trilayer consisting of one antiferromagnetic MnF2 film, exchange coupled with two Fe lms. At low temperatures the ferromagnetic layers are oriented in opposite directions. By heating in the presence of an external magnetic field, the Zeeman energy induces a gradual orientation of the ferromagnets with the external field and the nucleation of spin- op-like states in the antiferromagnetic layer, leading eventually, in temperatures close to the Neel temperature, to full alignment of the ferromagnetic films and the formation of frustrated exchange bonds in the center of the antiferromagnetic layer. By cooling down to low temperatures, the system follows a different sequence of states, due to the anisotropy barriers of both materials. The width of the thermal hysteresis loop depends on the thicknesses of the FM and AFM layers as well as on the strength of the external field. The second system consists in Fe and Permalloy ferromagnetic nanoelements exchange coupled to a NiO uncompensated substrate. In this case the thermal hysteresis originates in the modifications of the intrinsic magnetic

Modelo de tempo de falha acelerado com fração de cura : uma abordagem unificada

In this work we study the accelerated failure-time generalized Gamma regression models with a unified approach. The models attempt to estimate simultaneously the effects of covariates on the acceleration/deceleration of the timing of a given event and the surviving fraction. The method is implemented in the free statistical software R. Finally the model is applied to a real dataset referring to the time until the return of the disease in patients diagnosed with breast cancer

Testes de hipóteses em modelos de sobrevivência com Fração de cura

Survival models deals with the modeling of time to event data. However in some situations part of the population may be no longer subject to the event. Models that take this fact into account are called cure rate models. There are few studies about hypothesis tests in cure rate models. Recently a new test statistic, the gradient statistic, has been proposed. It shares the same asymptotic properties with the classic large sample tests, the likelihood ratio, score and Wald tests. Some simulation studies have been carried out to explore the behavior of the gradient statistic in fi nite samples and compare it with the classic statistics in diff erent models. The main objective of this work is to study and compare the performance of gradient test and likelihood ratio test in cure rate models. We first describe the models and present the main asymptotic properties of the tests. We perform a simulation study based on the promotion time model with Weibull distribution to assess the performance of the tests in finite samples. An application is presented to illustrate the studied concepts

A distribuição F generalizada para selecionar modelos de sobrevivência com fração de cura

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Condutividade térmica de rochas: uma aplicação para granitos ornamentais

This dissertation focuses on rock thermal conductivity and its correlations with petrographic, textural, and geochemical aspects, especially in granite rocks. It aims at demonstrating the relations of these variables in an attempt to enlighten the behavior of thermal effect on rocks. Results can be useful for several applications, such as understanding and conferring regional thermal flow results, predicting the behavior of thermal effect on rocks based upon macroscopic evaluation (texture and mineralogy), in the building construction field in order to provide more precise information on data refinement on thermal properties emphasizing a rocky material thermal conductivity, and especially in the dimension stone industry in order to open a discussion on the use of these variables as a new technological parameter directly related to thermal comfort. Thermal conductivity data were obtained by using Anter Corporation s QuicklineTM -30 a thermal property measuring equipment. Measurements were conducted at temperatures ranging between 25 to 38 OC in samples with 2cm in length and an area of at least 6cm of diameter. As to petrography data, results demonstrated good correlations with quartz and mafics. Linear correlation between mineralogy and thermal conductivity revealed a positive relation of a quartz percentage increase in relation to a thermal conductivity increase and its decrease with mafic minerals increase. As to feldspates (K-feldspate and plagioclase) they show dispersion. Quartz relation gets more evident when compared to sample sets with >20% and <20%. Sets with more than 20% quartz (sienogranites, monzogranites, granodiorites, etc.), exhibit to a great extent conductivity values which vary from 2,5 W/mK and the set with less than 20% (sienites, monzonites, gabbros, diorites, etc.) have an average thermal conductivity below 2,5 W/mK. As to textures it has been verified that rocks considered thick/porphyry demonstrated in general better correlations when compared to rocks considered thin/medium. In the case of quartz, thick rocks/porphyry showed greater correlation factors when compared to the thin/medium ones. As to feldspates (K-feldspate and plagioclase) again there was dispersion. As to mafics, both thick/porphyry and thin/medium showed negative correlations with correlation factor smaller than those obtained in relation to the quartz. As to rocks related to the Streckeisen s QAP diagram (1976), they tend to fall from alcali-feldspates granites to tonalites, and from sienites to gabbros, diorites, etc. Thermal conductivity data correlation with geochemistry confirmed to a great extent mineralogy results. It has been seen that correlation is linear if there is any. Such behavior could be seen especially with the SiO2. In this case similar correlation can be observed with the quartz, that is, thermal conductivity increases as SiO2 is incremented. Another aspect observed is that basic to intermediate rocks presented values always below 2,5 W/mK, a similar behavior to that observed in rocks with quartz <20%. Acid rocks presented values above 2,5 W/mK, a similar behavior to that observed in rocks with quartz >20% (granites). For all the other cases, correlation factors are always low and present opposite behavior to Fe2O3, CaO, MgO, and TiO2. As to Al2O3, K2O, and Na2O results are not conclusive and are statistically disperse. Thermal property knowledge especially thermal conductivity and its application in the building construction field appeared to be very satisfactory for it involves both technological and thermal comfort aspects, which favored in all cases fast, cheap, and precise results. The relation between thermal conductivity and linear thermal dilatation have also shown satisfactory results especially when it comes to the quartz role as a common, determining phase between the two variables. Thermal conductivity studies together with rocky material density can function as an additional tool for choosing materials when considering structural calculation aspects and thermal comfort, for in the dimension stone case there is a small density variation in relation to a thermal conductivity considerable variation

Obstrução nasolacrimal congênita: fatores relacionados com a possibilidade de cura

OBJETIVO: Avaliar a chance de cura da obstrução nasolacrimal congênita de acordo com a idade em que se deu o início da epífora e o tratamento efetuado. MÉTODOS: Quarenta crianças portadoras de obstrução nasolacrimal congênita, atendidas no período de 1997 a 1999, foram estudadas retrospectivamente, avaliando-se: idade do início da epífora, tratamento efetuado e possibilidade de cura. Os dados foram submetidos à análise estatística e usou-se o teste de proporções binomiais para contrastes entre e dentro de populações. RESULTADOS: A proporção de cura foi menor quando a epífora se iniciou em idade superior a 4 meses de vida, havendo possibilidade de cura com massagem e/ou sondagem em mesmas proporções, sendo possível obter cura também em crianças com idade superior a 3 anos de vida. CONCLUSÃO: Os resultados mostram que a possibilidade de cura sofre a influência da época do início da epífora e que o tratamento com massagem ou sondagem pode ser efetivo, mesmo em crianças com idade superior a 3 anos de idade.

Violência simbólica no campo da saúde: relato de um caso de cura espiritual em um espaço terapêutico híbrido

À luz da teoria social de Pierre Bourdieu, saliento a violência simbólica concebida das relações de forças entre agentes e práticas médicas e religiosas no interior de uma instituição filantrópica voltada à assistência à saúde de portadores de deficiências múltiplas. do trabalho etnográfico, descrevo detalhes do acordo entre administradores religiosos espíritas e profissionais de saúde durante a implementação de um projeto que incluía especificamente assistência espiritual. Um caso de cura aparece como bem simbólico e sobre ele concorreram duas versões explicativas sobre a abrupta recuperação do paciente assistido durante meses na UTI por caquexia: a versão religiosa, que entendeu a reabilitação como cura espiritual, e a versão médica, que compreendeu o restabelecimento do paciente como resultado das atividades e gerência médica.

A influência do fator de vibração térmica na densidade eletrônica de cristais bidimensionais

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Biomateriais: deposição de hidroxiapatita sobre superfície de Ti-cp modificada por aspersão térmica

The osseointegrated titanium implants are reliable and safe alternatives to treatments for long periods of time. For surface modification, thermal aspersion of TiO2 was used. The samples with and without TiO2 were treated with NaOH and SBF in order to obtain a layer of HA. Characterization was done by SEM and FTIR. The images of HA obtained by SEM show a uniform morphology and a porous structure with spherical particles. The IR spectra show that the surface of Ticp/ TiO2 is more favorable for the HA deposit, as can be seen by the increase of the crystalline structure and the very intense and defined bands of the OH group of HA that is verified about 3571 and 630 cm-1. Thus the Ticp/ TiO2 surface presents a satisfactory nucleation of HA when compared to Ticp.

Efeito da concentração do catalisador acetilacetonato férrico na cura de poliuretano à base de polibutadieno líquido hidroxilado (PBLH) e diisocianato de isoforona (IPDI)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)