978 resultados para Isothermal calorimetry


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Opalescence is an unattractive browning of the interior of the pecan kernel compared to the white interior of normal kernels. The discoloration is due to the presence of free oil, resulting from decompartmentalization in the endosperm of opalescent,pecans. Using a subjective scoring system, approximately 70% of Australian-grown pecan kernels tested were found to exhibit opalescence to some degree. Evaluation of kernels for opalescence during the harvesting-processing chain showed that opalescence first becomes evident in kernels after mechanical cracking. Opalescent kernels were found to have lower levels of calcium and higher amounts of oil compared to nonoptalescent kernels. Differential scanning calorimetry showed that kernels do not freeze at -18 degreesC.

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The characteristics of sharkskin surface instability for linear low density polyethylene are studied as a function of film blowing processing conditions. By means of scanning electron microscopy and surface profilometry, is it found that for the standard industrial die geometry studied, sharkskin only occurs on the inside of the film bubble. Previous work suggests that this instability may be due to critical extensional stress levels at the exit of the die. Isothermal integral viscoelastic simulations of the annular extrusion process are reported, and confirm that the extensional stress at the die exit is large enough to cause local melt rupture. However the extensional stress level at the outer die wall predicts melt rupture of the outside bubble surface also, which contradicts the experimental findings. A significant temperature gradient is expected to exist across the die gap at the exit of the die, due to the external heating of the die and the low conductivity, of the polymer melt. It is shown that a gradient of 20 degreesC is required to cause sharkskin to only appear on the inner bubble surface.

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The rheological behaviour of nine unprocessed Australian honeys was investigated for the applicability of the Williams-Landel-Ferry (WLF) model. The viscosity of the honeys was obtained over a range of shear rates (0.01-40 s(-1)) from 2degrees to 40 degreesC, and all the honeys exhibited Newtonian behaviour with viscosity reducing as the temperature was increased. The honeys with high moisture were of lower viscosity, The glass transition temperatures of the honeys, as measured with a differential scanning calorimeter (DSC), ranged from -40degrees to -46 degreesC, and four models (WLF. Arrhenius, Vogel-Tammann-Fulcher (VTF), and power-law) were investigated to describe the temperature dependence of the viscosity. The WLF was the most suitable and the correlation coefficient averaged 0.999 +/- 0.0013 as against 0.996 +/- 0.0042 for the Arrhenius model while the mean relative deviation modulus was 0-12% for the WLF model and 10-40% for the Arrhenius one. With the universal values for the WLF constants, the temperature dependence of the viscosity was badly predicted. From non-linear regression analysis, the constants of the WLF models for the honeys were obtained (C-1 = 13.7-21.1: C-2 = 55.9-118.7) and are different from the universal values. These WLF constants will be valuable for adequate modeling of the rheology of the honeys, and they can be used to assess the temperature sensitivity of the honeys. (C) 2002 Elsevier Science Ltd. All rights reserved.

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The dissolution of a sugar (sucrose as a model) with higher melting point was studied in a molten food polyol (sorbitol as a model) with lower melting point, both in anhydrous state. A DSC and optical examination revealed the dissolution of anhydrous sucrose crystals (mp 192 degreesC) in anhydrous sorbitol (mp 99 degreesC) liquid melt. The sucrose-sorbitol crystal mixtures at the proportions of 10, 30, 60, 100 and 150 g of sucrose per 100 g of sorbitol were heat scanned in a DSC to above melting endotherm of sorbitol but well below the onset temperature of melting of sucrose at three different temperatures 110, 130 and 150 degreesC. The heat scanning modes used were with or without isothermal holding. The dissolution of sucrose in the sorbitol liquid melt was manifested by an increase in the glass transition temperature of the melt and corresponding decrease in endothermic melting enthalpy of sucrose. At given experimental conditions, as high as 25 and 85% of sucrose dissolved in the sorbitol melt during 1 h of isothermal holding at 110 and 150 degreesC, respectively. Optical microscopic observation also clearly showed the reduction in the size of sucrose crystals in sorbitol melt during the isothermal holding at those temperatures. (C) 2003 Elsevier Science Ltd. All rights reserved.

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The absorption of fluid by unsaturated, rigid porous materials may be characterized by the sorptivity. This is a simple parameter to determine and is increasingly being used as a measure of a material's resistance to exposure to fluids (especially moisture and reactive solutes) in aggressive environments. The complete isothermal absorption process is described by a nonlinear diffusion equation, with the hydraulic diffusivity being a strongly nonlinear function of the degree of saturation of the material. This diffusivity can be estimated from the sorptivity test. In a typical test the cumulative absorption is proportional to the square root of time. However, a number of researchers have observed deviation from this behaviour when the infiltrating fluid is water and there is some potential for chemo-mechanical interaction with the material. In that case the current interpretation of the test and estimation of the hydraulic diffusivity is no longer appropriate. Kuntz and Lavallee (2001) discuss the anomalous behaviour and propose a non-Darcian model as a more appropriate physical description. We present an alternative Darcian explanation and theory that retrieves the earlier advantages of the simple sorptivity test in providing parametric information about the material's hydraulic properties and allowing simple predictive formulae for the wetting profile to be generated.

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Artigo original Ergoespirometria

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A cristalização e formação de depósitos parafínicos é um problema operacional crítico na indústria do petróleo em todo o mundo e provoca grandes perdas econômicas na recuperação do óleo. São muitos os estudos que têm sido realizados para desenvolver modelos termodinâmicos de predição da precipitação de parafinas, sendo que boa parte deles utilizam a ressonância magnética nuclear (RMN) em alto ou baixo campo magnético juntamente com outras técnicas como calorimetria exploratória diferencial (DSC), análise elementar e cromatografia gasosa para caracterizar a fase sólida formada a partir do petróleo. Este trabalho busca um maior entendimento da cristalização de ceras parafínicas por meio de experimentos de espectroscopia de RMN de 1H e 13C conduzidos em temperaturas variáveis, o que pode auxiliar na previsão e remediação dos problemas causados pela sua deposição nas linhas de escoamento da produção. Para isso, o estudo desse fenômeno foi conduzido inicialmente em amostras de parafina comercial e, posteriormente, em uma amostra de petróleo parafínico com variação de temperatura sem extrair a fase sólida, garantindo a não interferência de solventes que podem influenciar no processo de cristalização. A metodologia desenvolvida demonstrou ser útil para determinar a temperatura inicial de aparecimento de cristais (TIAC), sendo obtida uma boa concordância com os resultados de DSC para a parafina comercial e petróleo. O registro de espectros em diferentes temperaturas permitiu também a identificação das variações de intensidade e largura de linha dos sinais associados aos diferentes grupos químicos presentes nos materiais estudados.

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P>Reconstruction of the South Atlantic opening has long been a matter of debate and several models have been proposed. One problem in tracing properly the Atlantic history arises from the existence of a long interval without geomagnetic reversals, the Cretaceous Normal Superchron, for which ages are difficult to assign. Palaeomagnetism may help in addressing this issue if high-quality palaeomagnetic poles are available for the two drifting continental blocks, and if precise absolute ages are available. In this work we have investigated the Cabo Magmatic Province, northeastern Brazil, recently dated at 102 +/- 1 Ma (zircon fission tracks, Ar39/Ar40). All volcanic and plutonic rocks showed stable thermal and AF demagnetization patterns, and exhibit primary magnetic signatures. AMS data also support a primary origin for the magnetic fabric and is interpreted to be contemporaneous of the rock formation. The obtained pole is located at 335.9 degrees E/87.9 degrees S (N = 24; A(95) = 2.5; K = 138) and satisfies modern quality criteria, resulting in a reference pole for South America at similar to 100 Ma. This new pole also gives an insight to test and discuss the kinematic models currently proposed for the South Atlantic opening during mid-Cretaceous.

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Solution enthalpies of 1-bromoadamantane, 1-adamantanol, and 2-adamantanone in a large set of protic and aprotic solvents are reported at 298.15 K. Solvent effects on the solution processes of these solutes are analyzed in terms of a modified TAKA equation, involving delta(cav) h (s) as the cavity term. The nature and magnitude of the major interactions which influence these processes are assessed and discussed in terms of the solutes' characteristics. New insights on the solution processes under scrutiny are presented.

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Storm- and tsunami-deposits are generated by similar depositional mechanisms making their discrimination hard to establish using classic sedimentologic methods. Here we propose an original approach to identify tsunami-induced deposits by combining numerical simulation and rock magnetism. To test our method, we investigate the tsunami deposit of the Boca do Rio estuary generated by the 1755 earthquake in Lisbon which is well described in the literature. We first test the 1755 tsunami scenario using a numerical inundation model to provide physical parameters for the tsunami wave. Then we use concentration (MS. SIRM) and grain size (chi(ARM), ARM, B1/2, ARM/SIRM) sensitive magnetic proxies coupled with SEM microscopy to unravel the magnetic mineralogy of the tsunami-induced deposit and its associated depositional mechanisms. In order to study the connection between the tsunami deposit and the different sedimentologic units present in the estuary, magnetic data were processed by multivariate statistical analyses. Our numerical simulation show a large inundation of the estuary with flow depths varying from 0.5 to 6 m and run up of similar to 7 m. Magnetic data show a dominance of paramagnetic minerals (quartz) mixed with lesser amount of ferromagnetic minerals, namely titanomagnetite and titanohematite both of a detrital origin and reworked from the underlying units. Multivariate statistical analyses indicate a better connection between the tsunami-induced deposit and a mixture of Units C and D. All these results point to a scenario where the energy released by the tsunami wave was strong enough to overtop and erode important amount of sand from the littoral dune and mixed it with reworked materials from underlying layers at least 1 m in depth. The method tested here represents an original and promising tool to identify tsunami-induced deposits in similar embayed beach environments.

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Magma flow in dykes is still not well understood; some reported magnetic fabrics are contradictory and the potential effects of exsolution and metasomatism processes on the magnetic properties are issues open to debate. Therefore, a long dyke made of segments with different thickness, which record distinct degrees of metasomatism, the Messejana-Plasencia dyke (MPD), was studied. Oriented dolerite samples were collected along several cross-sections and characterized by means of microscopy and magnetic analyses. The results obtained show that the effects of metasomatism on rock mineralogy are important, and that the metasomatic processes can greatly influence anisotropy degree and mean susceptibility only when rocks are strongly affected by metasomatism. Petrography, scanning electron microscopy (SEM) and bulk magnetic analyses show a high-temperature oxidation-exsolution event, experienced by the very early Ti-spinels, during the early stages of magma cooling, which was mostly observed in central domains of the thick dyke segments. Exsolution reduced the grain size of the magnetic carrier (multidomain to single domain transformation), thus producing composite fabrics involving inverse fabrics. These are likely responsible for a significant number of the 'abnormal' fabrics, which make the interpretation of magma flow much more complex. By choosing to use only the 'normal' fabric for magma flow determination, we have reduced by 50 per cent the number of relevant sites. In these sites, the imbrication angle of the magnetic foliation relative to dyke wall strongly suggests flow with end-members indicating vertical-dominated flow (seven sites) and horizontal-dominated flow (three sites).

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We present a palaeomagnetic study on 38 lava flows and 20 dykes encompassing the past 1.3 Myr on S. Jorge Island (Azores ArchipelagoNorth Atlantic Ocean). The sections sampled in the southeastern and central/western parts of the island record reversed and normal polarities, respectively. They indicate a mean palaeomagnetic pole (81.3 degrees N, 160.7 degrees E, K= 33 and A95= 3.4 degrees) with a latitude shallower than that expected from Geocentric Axial Dipole assumption, suggesting an effect of non-dipolar components of the Earth magnetic field. Virtual Geomagnetic Poles of eight flows and two dykes closely follow the contemporaneous records of the Cobb Mountain Subchron (ODP/DSDP programs) and constrain the age transition from reversed to normal polarity at ca. 1.207 +/- 0.017 Ma. Volcano flank instabilities, probably related to dyke emplacement along an NNWSSE direction, led to southwestward tilting of the lava pile towards the sea. Two spatially and temporally distinct dyke systems have been recognized on the island. The eastern is dominated by NNWSSE trending dykes emplaced before the end of the Matuyama Chron, whereas in the central/western parts the eruptive fissures oriented WNWESE controlled the westward growth of the S. Jorge Island during the Brunhes Chron. Both directions are consistent with the present-day regional stress conditions deduced from plate kinematics and tectonomorphology and suggest the emplacement of dykes along pre-existing fractures. The distinct timing and location of each dyke system likely results from a slight shift of the magmatic source.

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Solution enthalpies of adamantan-1-ol, 2-methyl- butan-2-ol, and 3-methylbutan-1-ol have been measured at 298.15 K, in a set of 16 protogenic and non-protogenic solvents. The identification and quantification of solvent effects on the solution processes under study were performed using quantitative-structure property relationships. The results are discussed in terms of solute-solvent-solvent interactions and also in terms of the influence of compound's size and position of its hydroxyl group.

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Storm- and tsunami-deposits are generated by similar depositional mechanisms making their discrimination hard to establish using classic sedimentologic methods. Here we propose an original approach to identify tsunami-induced deposits by combining numerical simulation and rock magnetism. To test our method, we investigate the tsunami deposit of the Boca do Rio estuary generated by the 1755 earthquake in Lisbon which is well described in the literature. We first test the 1755 tsunami scenario using a numerical inundation model to provide physical parameters for the tsunami wave. Then we use concentration (MS. SIRM) and grain size (chi(ARM), ARM, B1/2, ARM/SIRM) sensitive magnetic proxies coupled with SEM microscopy to unravel the magnetic mineralogy of the tsunami-induced deposit and its associated depositional mechanisms. In order to study the connection between the tsunami deposit and the different sedimentologic units present in the estuary, magnetic data were processed by multivariate statistical analyses. Our numerical simulation show a large inundation of the estuary with flow depths varying from 0.5 to 6 m and run up of similar to 7 m. Magnetic data show a dominance of paramagnetic minerals (quartz) mixed with lesser amount of ferromagnetic minerals, namely titanomagnetite and titanohematite both of a detrital origin and reworked from the underlying units. Multivariate statistical analyses indicate a better connection between the tsunami-induced deposit and a mixture of Units C and D. All these results point to a scenario where the energy released by the tsunami wave was strong enough to overtop and erode important amount of sand from the littoral dune and mixed it with reworked materials from underlying layers at least 1 m in depth. The method tested here represents an original and promising tool to identify tsunami-induced deposits in similar embayed beach environments.

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The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.