Modelagem do Equilíbrio de Fases entre Hidrocarbonetos Leves e Pesados

O comportamento de fases para sistemas binários com um hidrocarboneto leve e um pesado é muito importante tanto para o projeto real de um processo quanto para o desenvolvimento de modelos teóricos. Para atender a crescente demanda por informação experimental de equilíbrio de fases a altas pressões, o objetivo deste estudo é obter uma metodologia que substitua parcialmente ou maximize a pouca informação experimental disponível. Para isto propõe-se a modelagem do equilíbrio de fases em misturas de hidrocarboneto leve com um pesado, sem o conhecimento da estrutura molecular do pesado, inferindo-se os parâmetros do modelo a partir da modelagem de dados de ponto de bolha obtidos na literatura. Esta metodologia implica não só na descrição do equilíbrio de fases de um sistema como na estimação das propriedades críticas do pesado, de difícil obtenção devido ao craqueamento destes a altas temperaturas. Neste contexto, este estudo apresenta uma estratégia que estima indiretamente as propriedades críticas dos compostos pesados. Para isto, foram correlacionados dados experimentais de ponto de bolha de misturas binárias contendo um hidrocarboneto leve e um pesado, usando-se dois modelos: o de Peng-Robinson e o TPT1M (Teoria da Polimerização Termodinâmica de primeira ordem de Wertheim modificada). Os parâmetros ajustados com o modelo de Peng-Robinson correspondem diretamente às propriedades críticas do composto pesado, enquanto os ajustados com o modelo TPT1M foram usados para obtê-las. Esta estratégia fornece parâmetros dependentes do modelo, porém permite o cálculo de outras propriedades termodinâmicas, como a extrapolação da temperatura dos dados estudados. Além disso, acredita-se que a correlação dos parâmetros obtidos com as propriedades críticas disponíveis ajudará na caracterização de frações pesadas de composição desconhecida

Estudo físico-químico de copoliéteres por viscosimetria

A viscosimetria é um procedimento experimental simples e pouco oneroso, que pode fornecer informações valiosas sobre o volume hidrodinâmico e a conformação de macromoléculas em solução, num determinado solvente, em uma dada temperatura. Os parâmetros viscosimétricos podem ser matematicamente calculados por extrapolação gráfica, cuja execução experimental é mais demorada. Em contrapartida, é possível que a determinação seja feita por um único ponto. Neste trabalho, os dois métodos de cálculo, empregando uma série de seis equações: Huggins, Kraemer e Schulz-Blaschke, por extrapolação gráfica, e Schulz-Blaschke, Solomon-Ciuta e Deb-Chanterjee por um único ponto, foram utilizados em soluções de poli(glicol propilênico) (PPG) e copolímeros em bloco à base de poli(glicol propilênico) e poli(glicol etilênico) (EG-b-PG), com diferentes teores de poli(glicol etilênico), tendo isopropanol, tetra-hidrofurano (THF) e tolueno como solventes puros, além das misturas em proporções iguais de THF/ isopropanol e THF/ tolueno, a 25C. Os valores de viscosidade intrínseca e de algumas constantes indicaram que os solventes puros e as misturas se apresentaram no limite entre o bom e o mau solvente. Verificou-se também que o método de cálculo por um único ponto foi válido, especialmente quando a equação de Schulz-Blaschke foi empregada, apresentando um baixo percentual de erro sendo possível assim reduzir o tempo de análise para a maioria dos sistemas estudados

Dielectric recovery of short A-C arcs between low-boiling-point electrodes

The re-ignition characteristics (variation of re-ignition voltage with time after current zero) of short alternating current arcs between plane brass electrodes in air were studied by observing the average re-ignition voltages on the screen of a cathode-ray oscilloscope and controlling the rates of rise of voltage by varying the shunting capacitance and hence the natural period of oscillation of the reactors used to limit the current. The shape of these characteristics and the effects on them of varying the electrode separation, air pressure, and current strength were determined.

The results show that short arc spaces recover dielectric strength in two distinct stages. The first stage agrees in shape and magnitude with a previously developed theory that all voltage is concentrated across a partially deionized space charge layer which increases its breakdown voltage with diminishing density of ionization in the field-tree space. The second stage appears to follow complete deionization by the electric field due to displacement of the field-free region by the space charge layer, its magnitude and shape appearing to be due simply to increase in gas density due to cooling. Temperatures calculated from this second stage and ion densities determined from the first stage by means of the space charge equation and an extrapolation of the temperature curve are consistent with recent measurements of arc value by other methods. Analysis or the decrease with time of the apparent ion density shows that diffusion alone is adequate to explain the results and that volume recombination is not. The effects on the characteristics of variations in the parameters investigated are found to be in accord with previous results and with the theory if deionization mainly by diffusion be assumed.

π+ photoproduction at angles from 6° to 90° C.M. and energies from 589 to 1269 MeV

The differential cross section for the reaction γp → π⁺n was measured at 32 laboratory photon energies between 589 and 1269 MeV at the Caltech Synchrotron. At each energy, data have been obtained at typically fifteen π⁺ c.m. angles between 6° and 90°. A magnetic spectrometer was used to detect the π⁺ photo-produced in a liquid hydrogen target. Two Cherenkov counters were used to reject the background of positrons and protons. The data clearly show the presence of a pole in the production amplitude due to the one pion exchange. Moravcsik fits to the 32 angular distributions, including data from another experiment, are presented. The extrapolation of these fits to the pole gives a value for the pion-nucleon coupling constant of 14.5 which is consistent with the accepted value. The second and third pion-nucleon resonances are evident as peaks in the total cross section and as changes in the shape of the angular distributions. At the third resonance there is evidence for both a D5/2 and an F5/2 amplitude. The absence of large variations in the 0° and 180° cross sections implies that the second and third resonances are mostly produced from an initial state with helicity ± 3/2.

Spin wave resonance in ferromagnetic films

The objective of this investigation has been a theoretical and experimental understanding of ferromagnetic resonance phenomena in ferromagnetic thin films, and a consequent understanding of several important physical properties of these films. Significant results have been obtained by ferromagnetic resonance, hysteresis, torque magnetometer, He ion backscattering, and X-ray fluorescence measurements for nickel-iron alloy films.

Taking into account all relevant magnetic fields, including the applied, demagnetizing, effective anisotropy and exchange fields, the spin wave resonance condition applicable to the thin film geometry is presented. On the basis of the simple exchange interaction model it is concluded that the normal resonance modes of an ideal film are expected to be unpinned. The possibility of nonideality near the surface of a real film was considered by means of surface anisotropy field, inhomogeneity in demagnetizing field and inhomogeneity of magnetization models. Numerical results obtained for reasonable parameters in all cases show that they negligibly perturb the resonance fields and the higher order mode shapes from those of the unpinned modes of ideal films for thicknesses greater than 1000 Å. On the other hand for films thinner than 1000 Å the resonance field deviations can be significant even though the modes are very nearly unpinned. A previously unnoticed but important feature of all three models is that the interpretation of the first resonance mode as the uniform mode of an ideal film allows an accurate measurement of the average effective demagnetizing field over the film volume. Furthermore, it is demonstrated that it is possible to choose parameters which give indistinguishable predictions for all three models, making it difficult to uniquely ascertain the source of spin pinning in real films from resonance measurements alone.

Spin wave resonance measurements of 81% Ni-19% Fe coevaporated films 30 to 9000 Å thick, at frequencies from 1 to 8 GHz, at room temperature, and with the static magnetic field parallel and perpendicular to the film plane have been performed. A self-consistent analysis of the results for films thicker than 1000 Å, in which multiple excitations can be observed, shows for the first time that a unique value of exchange constant A can only be obtained by the use of unpinned mode assignments. This evidence and the resonance behavior of films thinner than 1000 Å strongly imply that the magnetization at the surfaces of permalloy films is very weakly pinned. However, resonance measurements alone cannot determine whether this pinning is due to a surface anisotropy, an inhomogeneous demagnetizing field or an inhomogeneous magnetization. The above analysis yields a value of 4πM=10,100 Oe and A = (1.03 ± .05) x 10^-6 erg/cm for this alloy. The ability to obtain a unique value of A suggests that spin wave resonance can be used to accurately characterize the exchange interaction in a ferromagnet.

In an effort to resolve the ambiguity of the source of pinning of the magnetization, a correlation of the ratio of magnetic moment and X-ray film thickness with the value of effective demagnetizing field 4πNM as determined from resonance, for films 45 to 300 Å has been performed. The remarkable agreement of both quantities and a comparison with the predictions of five distinct models, strongly imply that the thickness dependence of both quantities is related to a thickness dependent average saturation magnetization, which is far below 10,100 Oe for very thin films. However, a series of complementary experiments shows that this large decrease of average saturation magnetization cannot be simply explained by either oxidation or interdiffusion processes. It can only be satisfactorily explained by an intrinsic decrease of the average saturation magnetization for very thin films, an effect which cannot be justified by any simple physical considerations.

Recognizing that this decrease of average saturation magnetization could be due to an oxidation process, a correlation of resonance measurements, He ion backscattering, X-ray fluorescence and torque magnetometer measurements, for films 40 to 3500 Å thick has been performed. On basis of these measurements it is unambiguously established that the oxide layer on the surface of purposefully oxidized 81% Ni-19% Fe evaporated films is predominantly Fe-oxide, and that in the oxidation process Fe atoms are removed from the bulk of the film to depths of thousands of angstroms. Extrapolation of results for pure Fe films indicates that the oxide is most likely α-Fe₂O₃. These conclusions are in agreement with results from old metallurgical studies of high temperature oxidation of bulk Fe and Ni-Fe alloys. However, X-ray fluorescence results for films oxidized at room temperature, show that although the preferential oxidation of Fe also takes place in these films, the extent of this process is by far too small to explain the large variation of their average saturation magnetization with film thickness.

Copolímeros à base de estireno e anidrido maleico: caracterização e estudo viscosimétrico

Copolímeros à base de estireno e anidrido maleico (SMA) são materiais sintéticos comercialmente disponíveis, obtidos pela reação dos dois monômeros citados em diferentes proporções, resultando em materiais versáteis, e disponíveis em diferentes graus de massas e porcentagens molares de anidrido maleico. São considerados polímeros funcionais devido à reatividade do grupamento anidrido maleico presente na cadeia polimérica. Por este motivo, esses materiais possuem vasta gama de aplicações, e elevada importância em diversas áreas, principalmente por terem baixa toxicidade, boa resistência térmica e boa estabilidade dimensional. Dessa forma, para melhor aplicação desses copolímeros, é muito importante o conhecimento dos parâmetros relativos ao seu comportamento em solução. A viscosimetria, em especial, é um método simples, útil e apropriado para fornecer essas informações. Os parâmetros viscosimétricos podem ser matematicamente calculados por extrapolação gráfica, entretanto a geração dos dados experimentais é mais demorada. Em contrapartida, é possível que a determinação experimental seja feita de forma mais rápida, por um único ponto, procedimento esse que desperta tanto o interesse acadêmico quanto o industrial. Neste trabalho, foram empregados os dois métodos de cálculo, utilizando solventes puros, misturas de solventes e três amostras de copolímeros à base de SMA. As determinações foram conduzidas a 40C. Os copolímeros utilizados possuiam teores de anidrido maleico de 50%, 45% e 40%, sendo os dois últimos esterificados com butil-metil-éster e sec-butil-metil-éster, respectivamente. Os solventes utilizados foram: N-metil-pirrolidona (NMP), tetrahidrofurano (THF) e suas respectivas misturas 1:1 com metil-etil-cetona (MEK), ou seja, (NMP:MEK) e THF:MEK, sendo a MEK um não solvente para o copolímero não esterificado. As equações utilizadas para extrapolação gráfica foram as de Huggins, Kraemer e Schulz-Blaschke. As equações empregadas em um único ponto foram as de Solomon-Ciuta, Deb-Chanterjee e novamente Schulz-Blaschke. Os resultados obtidos foram comparados e avaliou-se a possibilidade da utilização do método mais rápido, por um único ponto, para os sistemas estudados através dos desvios percentuais tendo como padrão os resultados da equação de Huggins. A equação de Deb-Chanterjee foi a mais adequada aos sistemas em NMP, que foi também o melhor solvente para as amostras. Os resultados obtidos na mistura NMP:MEK sugeriram que a viscosimetria pode ter sido um método sensível às pequenas diferenças estruturais entre os grupos pendentes nas amostras esterificadas. Paralelamente, realizou-se análises de espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e ensaios dinâmico-mecânicos (DMA) para a caracterização estrutural e térmica das amostras. Somente os resultados obtidos a partir de DMA indicaram diferenças entre as amostras esterificadas

Commercial Whaling, Especially for Gray Whales, Eschrichtius robustus, and Humpback Whales, Megaptera novaeangliae, at California and Baja California Shore Stations in the 19th Century (1854–1899)

Shore whaling along North America’s California and Baja California coasts during 1854–99 was ancillary to the offshore and alongshore American whale fishery, which had begun in the North Pacific in the early 1800’s and was flourishing by the 1840’s. From its inception at Monterey, Calif., in the mid 1850’s, the shore fishery, involving open boats deployed from land to catch and tow whales for processing, eventually spread from Monterey south to San Diego and Baja California and north to Crescent City near the California–Oregon border. It had declined to a relict industry by the 1880’s, although sporadic efforts continued into the early 20th century. The main target species were gray whales, Eschrichtius robustus, and humpback whales, Megaptera novaeangliae, with the valuable North Pacific right whale, Eubalaena japonica, also pursued opportunistically. Catch data are grossly incomplete for most stations; no logbooks were kept for these operations as they were for high-seas whaling voyages. Even when good information is available on catch levels, usually as number of whales landed or quantity of oil produced, it is rarely broken down by species. Therefore, we devised methods for extrapolation, interpolation, pro rationing, correction, and informed judgment to produce time series of catches. The resulting estimates of landings from 1854 to 1899 are 3,150 (SE = 112) gray whales and 1,637 (SE = 62) humpback whales. The numbers landed should be multiplied by 1.2 to account for hunting loss (i.e. whales harpooned or shot but not recovered and processed).

The By-catch From the Artisanal Shrimp Trawl Fishery, Gulf of Paria, Trinidad

Samples of shrimp trawl catches were collected from a commercial artisanal vessel fishing inside the 6-fm isobath in the Gulf of Paria, Trinidad. From August 1986 to May 1987, 34 late evening-early morning trawl trips were made and 97 hauls were sampled. Annual ratio estimates were 9 (SD 1.3) finfish:shrimp and 14.7 (SD 2.0) by-catch: shrimp, with the highest ratios observed August through December and the lowest from late January through May, the dry season. Extrapolation of ratios, using shrimp catch statistics, indicates that for 1986, 974,000 kg of finfish and 620,000 kg of crabs, Callinectes spp., were caught incidentally by artisanal shrimp trawlers fishing in the Gulf of Paria. Of this total incidental catch (1,594,000 kg), about 1,500,000 kg were discarded (94 percent). Four penaeid shrimp species are targeted: Penaeus schmitti, P. notialis, P. subtilis, and Xiphopenaeus kroyeri. Callinectes spp. were caught in large quantities from Augustto mid-January. Small (4-15 cm) pelagic and demersal species of little commercial importance dominated the finfish by-catch: Harengula spp., Cetengraulis edentulus, Chloroscombrus chrysurus, Eucinostomous spp., Diapterus rhombeus, and Cyclopsetta spp. Altogether, the monthly percentage of the species ranged from 70 to 85 percent of the total finfish by-catch.

Halocinese e tectônica de rafts na bacia emersa de Benguela (Angola): dados de campo, modelagem física e restauração estrutural

Este trabalho foi feito com dados de campo da Bacia de Benguela, na costa sul de Angola. Nesta área aflora uma plataforma carbonática de idade albiana, análoga às formações produtoras de petróleo de mesma idade na Bacia de Campos. Duas unidades principais compõem a seção albiana na área: uma unidade inferior caracterizada por carbonatos de águas rasas com intercalações de conglomerados e arenitos na base, totalizando 300 m de espessura total, e uma unidade superior formada por sedimentos carbonáticos de águas mais profundas com espessura de 100 m. Esta seção se apresenta em dois domínios estruturais. O norte é caracterizado por uma plataforma de cerca de 5 km de largura, 35 km de comprimento na direção NE e que se encontra próxima ao embasamento. No domínio sul, essa plataforma se apresenta em fragmentos de menos de 10 km de comprimento por até 5 km de largura, alguns deles afastados do embasamento. Dado que há evaporitos sob essa plataforma, fez-se este trabalho com o objetivo de se avaliar a influência da tectônica salífera na estruturação das rochas albianas. A utilização de imagens de satélite de domínio público permitiu a extrapolação dos dados pontuais e a construção de perfis topográficos que possibilitaram a montagem das seções geológicas. Os dados de campo indicam que a estruturação na parte norte, onde há menos sal, é influenciada pelas estruturas locais do embasamento. Já na parte sul, onde a espessura de sal é maior, a deformação é descolada das estruturas do embasamento. Foi feita uma seção geológica em cada domínio e a restauração dessas duas seções mostrou que a unidade albiana na parte sul sofreu uma distensão de 1,25 (125%) e a de norte se distendeu em 1,05 (105%). Essa diferença foi causada por uma maior espessura original de sal na parte sul, que fez com que a cobertura albiana se distendesse mais em consequência da fluência do sal mergulho abaixo, em resposta ao basculamento da bacia em direção a offshore. A intensidade da deformação na parte sul foi tal que os blocos falhados perderam os contatos entre si, formando rafts. Este efeito foi reproduzido em modelos físicos, indicando que a variação na espessura original de sal tem grande influência na estruturação das rochas que o cobrem. As variações de espessura de sal são controladas por zonas de transferência do embasamento e estas mesmas estruturas controlam os limites dos blocos que sofrem soerguimento diferencial no Cenozoico.

Monolithic electro-optically modulated VCSEL suitable for radio over fibre applications to 20 GHz

An integrated EOM VCSELs is shown to offer high linearity (92dB/Hz 2/3 at 6GHz) and by extrapolation ∼90dB/Hz2/3 up to 20GHz. Successful modulation with IEEE 802.11g signals is demonstrated at 6GHz with a 12dB dynamic range. © 2011 Optical Society of America.

Integration of submersible transect data and high-resolution multibeam sonar imagery for a habitat-based groundfish assessment of Heceta Bank, Oregon

In the face of dramatic declines in groundfish populations and a lack of sufficient stock assessment information, a need has arisen for new methods of assessing groundfish populations. We describe the integration of seafloor transect data gathered by a manned submersible with high-resolution sonar imagery to produce a habitat-based stock assessment system for groundfish. The data sets used in this study were collected from Heceta Bank, Oregon, and were derived from 42 submersible dives (1988–90) and a multibeam sonar survey (1998). The submersible habitat survey investigated seafloor topography and groundfish abundance along 30-minute transects over six predetermined stations and found a statistical relationship between habitat variability and groundfish distribution and abundance. These transects were analyzed in a geographic information system (GIS) by using dynamic segmentation to display changes in habitat along the transects. We used the submersible data to extrapolate fish abundance within uniform habitat patches over broad areas of the bank by means of a habitat classification based on the sonar imagery. After applying a navigation correction to the submersible-based habitat segments, a good correlation with major boundaries on the backscatter and topographic boundaries on the imagery were apparent. Extrapolation of the extent of uniform habitats was made in the vicinity of the dive stations and a preliminary stock assessment of several species of demersal fish was calculated. Such a habitat-based approach will allow researchers to characterize marine communities over large areas of the seafloor.

Wadge Bank trawl fishery studies. Pt. 4. An analysis of the length frequency measurements of the sea bream (Lethrinus nebulosus) made in 1949 and 1953 to 1958

Length frequency distributions of the sea bream collected during the period 1953 to 1958 have been analysed. The increase in average sizes of the sea bream with depth suggests a movement to deeper waters with increase in size. By numbers, the sea bream is more abundant between 21 and 30 fathoms than in deeper areas. The recruitment was continuous and regular. There is no sign of entry or progression of a dominant brood throughout the period under study. Length frequency distribution shows three distinct modes. The first mode occurs regularly but does not progress beyond 40cm, recruitment being balanced by natural and fishing mortality. The other two which are not regular are probably the result of fishing outside regular areas. Short sections of “growth” lines which fit into one another when extrapolated, are evident. The larger lines obtained by extrapolation are parallel to one another. These tentative "growth lines" indicate that this species which enters the fishing grounds, when 15 cm or larger in length are exploited by the trawl fishery for a period of three to four years. This species appears to be six months old when it enters the fishing grounds and increases in length by about 37.5 cm in the next 30 months. Later growth slows down. The average size of the specimens sampled continued to get smaller from 1953 till 1957. It is shown that this reduction in size is due to increased fishing effort.

Contrasting high-resolution characteristic shock-capturing methods in aeroacoustic test problems

Two shock-capturing methods are considered. One is based on a standard conservative Roe scheme with van Leer's MUSCL variable extrapolation method applied to characteristic variables and a Runge-Kutta time stepping scheme. The other is based on the novel CABARET space-time scheme, which uses two sets of staggered variables, one for the conservation step and the other for characteristic splitting into local Riemann invariants. The methods are compared in a range of 2-D inviscid compressible flow test cases. Copyright © 2008 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.

Production of freshwater giant prawn using over-wintered juveniles for enhancement of farm income and reduction of rural poverty in Bangladesh

Freshwater giant prawn, Macrobrachium rosenbergii fry produced during late season can not withstand low temperature thus the prawn culture programme during winter is hampered. To overcome this problem, late season (August-September) prawn juveniles (0.9-6.8 g) were stocked at a density of 1.43 to 3.57/square meter in 350-476 square-meter ponds in Pabna and Mymensingh districts during October 2000 and cultured till May 2001. Monthly average water temperature during the winter months (December-February) varied from 16 to 22 °C and gradually increased to 32 °C in May. The prawn fry showed fast growth rate and attained an average weight of 60-70 g within eight months including three winter months. Growth compensation was observed during summer months. Survival rate was 60-79%. After extrapolation of the present growth rate more than 1,600 kg/ha production can be achieved in better-managed ponds. Extrapolated cost of production was Tk. 268,000 and 200,000 Tk./ha in two best ponds, sale value was Tk. 644,9146 [sic] and 528,466 and gross profit was Tk. 376,000-410,000, suggesting a higher economic feasibility of farming freshwater prawn with over-wintered juveniles.

Subdivision-stabilised immersed b-spline finite elements for moving boundary flows

An immersed finite element method is presented to compute flows with complex moving boundaries on a fixed Cartesian grid. The viscous, incompressible fluid flow equations are discretized with b-spline basis functions. The two-scale relation for b-splines is used to implement an elegant and efficient technique to satisfy the LBB condition. On non-grid-aligned fluid domains and at moving boundaries, the boundary conditions are enforced with a consistent penalty method as originally proposed by Nitsche. In addition, a special extrapolation technique is employed to prevent the loss of numerical stability in presence of arbitrarily small cut-cells. The versatility and accuracy of the proposed approach is demonstrated by means of convergence studies and comparisons with previous experimental and computational investigations.