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

Estudo comparativo de abordagens de inversão do fator de qualidade Q

Seismic wave dispersion and attenuation studies have become an important tool for lithology and fluid discrimination in hydrocarbon reservoirs. The processes associated to attenuation are complex and are encapsulated in a single quantitative description called quality factor (Q). The present dissertation has the objective of comparing different approaches of Q determination and is divided in two parts. Firstly, we made performance and robustness tests of three different approaches for Q determination in the frequency domain. They are: peak shift, centroid shift and spectral ratio. All these tests were performed in a three-layered model. In the suite of tests performed here, we varied the thickness, Q and inclination of the layers for propagation pulses with central frequency of 30, 40 and 60 Hz. We found that the centroid shift method is produces robust results for the entire suíte of tests. Secondly, we inverted for Q values using the peak and centroid shift methods using an sequential grid search algorithm. In this case, centroid shift method also produced more robust results than the peak shift method, despite being of slower convergence

Estimativa da profundidade do embasamento na bacia potiguar usando inversão gravimétrica

The gravity inversion method is a mathematic process that can be used to estimate the basement relief of a sedimentary basin. However, the inverse problem in potential-field methods has neither a unique nor a stable solution, so additional information (other than gravity measurements) must be supplied by the interpreter to transform this problem into a well-posed one. This dissertation presents the application of a gravity inversion method to estimate the basement relief of the onshore Potiguar Basin. The density contrast between sediments and basament is assumed to be known and constant. The proposed methodology consists of discretizing the sedimentary layer into a grid of rectangular juxtaposed prisms whose thicknesses correspond to the depth to basement which is the parameter to be estimated. To stabilize the inversion I introduce constraints in accordance with the known geologic information. The method minimizes an objective function of the model that requires not only the model to be smooth and close to the seismic-derived model, which is used as a reference model, but also to honor well-log constraints. The latter are introduced through the use of logarithmic barrier terms in the objective function. The inversion process was applied in order to simulate different phases during the exploration development of a basin. The methodology consisted in applying the gravity inversion in distinct scenarios: the first one used only gravity data and a plain reference model; the second scenario was divided in two cases, we incorporated either borehole logs information or seismic model into the process. Finally I incorporated the basement depth generated by seismic interpretation into the inversion as a reference model and imposed depth constraint from boreholes using the primal logarithmic barrier method. As a result, the estimation of the basement relief in every scenario has satisfactorily reproduced the basin framework, and the incorporation of the constraints led to improve depth basement definition. The joint use of surface gravity data, seismic imaging and borehole logging information makes the process more robust and allows an improvement in the estimate, providing a result closer to the actual basement relief. In addition, I would like to remark that the result obtained in the first scenario already has provided a very coherent basement relief when compared to the known basin framework. This is significant information, when comparing the differences in the costs and environment impact related to gravimetric and seismic surveys and also the well drillings

Síntese e caracterização estrutural, magnética e térmica da hidroxiapatita dopada com ferro

In this work, composites were prepared using high energy mechanical milling from the precursors hydroxyapatite - HAp (Ca10(PO4)6(OH)2) and metallic iron ( -Fe ). The main goal here is to study composites in order to employ them in magnetic hyperthermia for cancer therapy. The produced samples were characterized by X-ray di raction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), magnetization curves as a function of applied eld (MxH), and nally measurements of magnetic hyperthermia. The XRD patterns of the milled samples HAp/Fe revealed only the presence of precursor materials. The SEM showed clusters with irregular shapes. The magnetization curves indicated typical cases of weak ferromagnetic behavior. For samples submitted to grinding and annealing, the identi ed phases were: HAp (Ca10(PO4)6(OH)2), hematite (Fe2O3) and Calcium Iron Phosphate (Ca9Fe(PO4)7). Analyzing the results of MxH, there was a reduction of the saturation magnetization, given that the Fe was incorporated into HAp. Hysteresis curves obtained at 300 K are characteristics of samples possessing over a phase. At 77 K, the behavior of the hysteresis curve is in uenced by the presence of hematite, which is antiferromagnetic. Already at T = 4.2 K, it is observed a weak ferromagnetic behavior. Furthermore, there is the e ect of exchange bias. Regarding the magnetic hyperthermia, the results of temperature measurements as a function of the alternating eld are promising for applications in magnetic hyperthermia and other biomedical applications.

Determinação da energia de ativação e pureza de medicamentos de referência, genérico e similar utilizando técnicas termoanalíticas

In this work, the reference drugs, generic and similar to the active ingredients acetylsalicylic acid, paracetamol, captopril, hydrochlorothiazide and mebendazole were purchased from local pharmacies and studied by thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). Thermal decomposition was assessed to obtain from the Ozawa method the activation energy in inert atmosphere (nitrogen), using three different heating ratios (5, 10 and 20 o C min-1). The pharmaceutical formulation of the AAS reference was the one who presented different from the others (generic and similar) Thermogravimetric profile indicating likely interaction between the active ingredient and excipients. Was observed at the heating rate of the inverse temperature that no linearity of the data, ie, there was no correlation between the percentage of mass loss and the activation energy involved in the thermal decomposition of the pharmaceutical formulation of the AAS reference log graph. The analysis by differential scanning calorimetry was performed in nitrogen atmosphere with a heating rate of 10 ° C min-1. In the analysis of these same drugs, the data curves found on the melting point were, except for hydrochlorothiazide, are consistent with the literature. Hydrochlorothiazide presented a melting point well below that found in the literature, which may be justified due to the interaction of the active ingredient with the excipient lactose. In the study of purity, using the Van't Hoff equation, the reference drugs hydrochlorothiazide and mebendazole reference generic and showed similar impurity content below the limit established that this equation must be greater than 2.5 mol%

Estimativa do fluxo de calor e da difusividade térmica do solo, baseado na solução da derivada temporal fracionária de meia ordem em ferramenta de software

The soil heat flux and soil thermal diffusivity are important components of the surface energy balance, especially in ar id and semi-arid regions. The obj ective of this work was to carry out to estimate the soil heat flux from th e soil temperature measured at a single depth, based on the half-order time derivative met hod proposed by Wang and Bras (1999), and to establish a method capable of es timating the thermal diffusivity of the soil, based on the half order derivative, from the temporal series of soil temperature at two depths. The results obtained in the estimates of soil heat flux were compared with the values of soil heat flux measured through flux plates, and the thermal di ffusivity estimated was compared with the measurements carried out in situ. The results obtained showed excellent concordance between the estimated and measured soil heat flux, with correlation (r), coeffici ent of determination (R 2 ) and standard error (W/m 2 ) of: r = 0.99093, R 2 = 0.98194 and error = 2.56 (W/m 2 ) for estimated period of 10 days; r = 0,99069, R 2 = 0,98147 and error = 2.59 (W/m 2 ) for estimated period of 30 days; and r = 0,98974, R 2 = 0,97958 and error = 2.77 (W/m 2 ) for estimated period of 120 days. The values of thermal di ffusivity estimated by the proposed method showed to be coherent and consis tent with in situ measured va lues, and with the values found in the literature usi ng conventional methods.

Avaliação térmica e desempenho do processo de secagem de misturas de graviola e leite em secador de leito de jorro

The soursop (A. muricata) is a fruit rich in minerals especially the potassium content. The commercialization of soursop in natura and processed has increased greatly in recent years. Drying fruit pulp in order to obtain the powdered pulp has been studied, seeking alternatives to ensure the quality of dehydrated products at a low cost of production. The high concentration of sugars reducing present in fruits causes problems of agglomeration and retention during fruit pulp drying in spouted bed dryers. On the other hand in relation to drying of milk and fruit pulp with added milk in spouted bed, promising results are reported in the literature. Based on these results was studied in this work drying of the pulp soursop with added milk in spouted bed with inert particles. The tests were based on a 24 factorial design were evaluated for the effects of milk concentration (30 to 50% m/m), drying air temperature (70 to 90 °C), intermittency time (10 to 14 min), and ratio of air velocity in relation to the minimum spout (1.2 to 1.5) on the rate of production, of powder moisture, yield, rate of drying and thermal efficiency of the process. There were physical and chemical analysis of mixtures, of powders and of mixtures reconstituted by rehydration powders. Were adjusted statistical models of first order to data the rate of production, yield and thermal efficiency, that were statistically significant and predictive. An efficiency greater than 40% under the conditions of 50% milk mixture, at 70 ° C the drying air temperature and 1.5 for the ratio between the air velocity and the minimum spout has been reached. The intermittency time showed no significant effect on the analyzed variables. The final product had moisture in the range of 4.18% to 9.99% and water activity between 0.274 to 0.375. The mixtures reconstituted by rehydration powders maintained the same characteristics of natural blends.

Caracterização mecânica, térmica e acústica de um compósito que utiliza rejeitos de mármore, granito e EPS para a fabricação de blocos para a construção civil

The use of composite materials for the construction industry has been the subject of numerous scientific papers in Brazil and in the world. One of the factors that motivate this quest is the housing deficit that countries especially the third world face. In Brazil this deficit reaches more than 6.5 million homes, around 12% of all US households . This paper presents a composite that was obtained from waste generated in processes for the production of granite and marble slabs, cement, gypsum, sand, crushed EPS and water. These wastes cause great damage to the environment and are thrown into landfi lls in bulk. The novelty of the work is in the combined study thermal, mechanical and acoustic composite obtained in real situation of rooms that are part of an experimental housing. Many blocks were made from cement compositions, plaster, foam, sand, marb le and / or granite, preliminary tests of mechanical and thermal resistance were made by choosing the most appropriate proportion. Will be given the manufacturing processes and assembly units 500 units 10 x 80 x 28 cm produced for the construction of an ex perimental home. We studied what kind of block and residue, marble or granite, made it more feasible for the intended purpose. The mechanical strength of the produced blocks were above 3.0 MPa. The thermal resistance of the blocks was confirmed by the maxi mum temperature difference between the inner and outer walls of rooms built around 8.0 ° C. The sound absorption for optimal room was around 31%. Demonstrated the feasibility of using the blocks manufactured with composite material proposed for construction.

Mapeamento da isoterma de Curie na Bacia do Parnaíba estimada através da profundidade da base das fontes magnéticas

Located on the western edge of the Brazilian northeast, the Parnaíba Basin is an intra cratonic basin with oil production. This study aims at understanding its genesis and evolution, using aeromagnetic and gravity data. We used the spectral analysis of aeromagnetic data to map the depth to the bottom of the magnetic sources in order to assimilate this depth with the depth of the Curie isotherm, and infer the geothermal gradient. Using the spectral analysis technique, we succeeded in mapping the surface of the depth to the bottom of magnetic sources (SBFM), which marks the depth that occur magnetization. In the Parnaíba Basin the SBFM presented depths around -20,5 and -28,5 , which was consistent with an inversion of the same dataset using the technique of Magnetization Vector Inversion (MVI). Furthermore, SBFM topography correlates well with Moho depth, which was estimated from satellite gravimetric data from the GOCE mission (Gravity Field and Steady-State Ocean Circulation Explorer). Assuming that SBFM coincides with the Curie isotherm of magnetite (ICM), defined as the surface at which magnetite ( ) looses its ferromagnetic properties, it was possible to estimate the geothermal gradient. The geothermal gradient in the basin showed values between 19.2 and 26.5 , allowing to estimate the heat flow for the Parnaíba basin after assuming a conductivity of 2.69 . The resulting heat flow values ranged between 51.6 and 71.3 , which is consistent with values found in other works throughout the South American continent. Lithospheric thickness using an empirical relationship, finding values between -65.8 and -89.2 . We propose that thermal structure of Parnaíba basin is influenced by a deep thermal anomaly. This anomaly has heated the lithosphere beneath the basin and has resulted in relatively thin values for the lithospheric thickness and relatively high surface heat flow values. The origin of the anomaly is not clear, but the correlation between Curie depth and Moho topography, suggests that tectonic extension processes could have played a role.

Modos projetuais de simulação: uso de ferramentas de simulação térmica no processo projetual de arquitetura

This thesis aims to describe and demonstrate the developed concept to facilitate the use of thermal simulation tools during the building design process. Despite the impact of architectural elements on the performance of buildings, some influential decisions are frequently based solely on qualitative information. Even though such design support is adequate for most decisions, the designer will eventually have doubts concerning the performance of some design decisions. These situations will require some kind of additional knowledge to be properly approached. The concept of designerly ways of simulating focuses on the formulation and solution of design dilemmas, which are doubts about the design that cannot be fully understood nor solved without using quantitative information. The concept intends to combine the power of analysis from computer simulation tools with the capacity of synthesis from architects. Three types of simulation tools are considered: solar analysis, thermal/energy simulation and CFD. Design dilemmas are formulated and framed according to the architect s reflection process about performance aspects. Throughout the thesis, the problem is investigated in three fields: professional, technical and theoretical fields. This approach on distinct parts of the problem aimed to i) characterize different professional categories with regards to their design practice and use of tools, ii) investigate preceding researchers on the use of simulation tools and iii) draw analogies between the proposed concept, and some concepts developed or described in previous works about design theory. The proposed concept was tested in eight design dilemmas extracted from three case studies in the Netherlands. The three investigated processes are houses designed by Dutch architectural firms. Relevant information and criteria from each case study were obtained through interviews and conversations with the involved architects. The practical application, despite its success in the research context, allowed the identification of some applicability limitations of the concept, concerning the architects need to have technical knowledge and the actual evolution stage of simulation tools