济阳坳陷及其南缘奥陶系碳酸盐岩潜山储集性及控制因素

The main research area of this thesis is Jiyang Depression in the Bohaiwan Basin and its southern margin. The object formation is Ordovician carbonate. The research is based on the outcrop observation and measurement of Ordovician carbonate and the drilling data of the oilfield. The internal reservoir characteristics of carbonate buried hill and its distribution were studied by comprehensive methods of sedimentology, reservoir geology and structural geology and technics of cathodoluminescence(CL)3electron microprobe,casting and C O isotope analysis etc. The influence depth of paleokarst facies formed during the Paleozoic is discriminated as 36-84m. The sollution porosity is well developed in paleokarst facies of Ordovician carbonate and is an important type of internal reservoir of buried hill. It may be infered that the fractures may be formed mainly during the Mesozoic and Cenozoic, they were not developed during the early Paleozoic when only micro-fractures might be created. The carbon and oxigen isotope analysis shows that the calcite cements in the fractures of Ordovician carbonate and secondary solution pores were related with meteoric water and three stages of fractures were divided. The reservoir space of Ordovician carbonate are mainly secondary porosity, cavern and fracture. The development of structural fracture was controlled by the lithology and tectonic background. More fractures exist in dolomite than that in limestone. There are also more fractures near the fault and the axis of fold. The development of porous reservoir is mainly controlled by the lithology and diagenesis, especially dolomitization and dissolution. It also results in the heterogeneity vertically. So the lithology is the basic factor for the forming of internal reservoir of buried hill and the tectogenesis and diagenesis are key factors to improve it. The porosity in carbonate might experienced solution-cementation-resolution or recementation. The porosity evolution history was a kind of historical dynamic equilibrium. The internal reservoir of Ordovician carbonate is the comprehensive result of constructive and/or destructive diagenesis. The worm's eye maps of the early Paleozoic and middle-upper Proterozoic were plotted. It was inferred that the paleostress field evoluted from NNW to NW during the Mesozoic and Cenozoic. Three types of buried hills can be divided: C-P/Pzi, Mz/ Pzi and E/ Pzi. The unconformity of the buried hill of E/ Pzi type, comparatively, was formed and reconstructed latestly, t he p orous r eservoir c ould b e w ell p reseved. T his c ondition w as v ery favorable t o t he migration and accumulation of oil and gas and could form upstanding association of source-reservoir-cap rocks. The buried hills of Mz/ Pzi and C-P/Pz] type were took second place.

多波分量地震资料处理解释方法

To deal with some key problems in multi-component seismic exploration, some methods are introduced in this thesis based on reading amounts of papers about multi-component seismic theories and methods. First, to find a solution for the detection of the fracture density and orientation in igneous, carbonate and shale reservoirs, a large amount of which exist in domestic oil fields with low exploration and development degree, a new fast and slow shear waves separation method called Ratio Method based on S-wave splitting theory is discussed in this thesis, through which the anisotropy coefficient as well as fracture parameters such as density and azimuthal angle can be acquired. Another main point in this thesis involves the application of seismic velocity ratio (Vp/Vs) to predict the Hthological parameters of subsurface medium. To deal with the unfeasibility of velocity ratio calculation method based on time ratio due to the usually low single-noise ratio of S-wave seismic data acquired on land, a new method based on detailed velocity analysis is introduced. Third, pre-stack Kirchhoff integral migration is a new method developed in recent years, through which both S and P component seismic data as well as amplitude ratio of P/S waves can be acquired. In this thesis, the research on untilizing the P and S wave sections as well as amplitude ratio sections to interpret low-amplitude structures and lithological traps is carried out. The fast and slow shear wave separation method is then be applied respectively to detect the density and azimuthal angle of fractures in an igneous rock gas reservoir and the coal formation in a coal field. Two velocity ratio-calculating methods are applied respectively in the lithological prediction at the gas and coal field after summarizing a large amount of experimental results draw domestically and abroad. P and S wave sections as well as amplitude ratio sections are used to identify low-amplitude structures and lithological traps in the slope area of a oil-bearing sedimentary basin. The calculated data concerning fracture density and azimuthal angle through the introduced method matches well with the regional stress and actual drilling data. The predicted lithological data reflects the actual drilling data. Some of the low-amplitude and lithological traps determined by Kirchhoff migration method are verified by the actual drilling data. These results indicate that these methods are very meaningful when dealing with complex oil and gas reservoir, and can be applied in other areas.

陆相砂泥岩层序的高精度检测方法研究及应用

Ordos Basin is a typical cratonic petroliferous basin with 40 oil-gas bearing bed sets. It is featured as stable multicycle sedimentation, gentle formation, and less structures. The reservoir beds in Upper Paleozoic and Mesozoicare are mainly low density, low permeability, strong lateral change, and strong vertical heterogeneous. The well-known Loess Plateau in the southern area and Maowusu Desert, Kubuqi Desert and Ordos Grasslands in the northern area cover the basin, so seismic data acquisition in this area is very difficult and the data often takes on inadequate precision, strong interference, low signal-noise ratio, and low resolution. Because of the complicated condition of the surface and the underground, it is very difficult to distinguish the thin beds and study the land facies high-resolution lithologic sequence stratigraphy according to routine seismic profile. Therefore, a method, which have clearly physical significance, based on advanced mathematical physics theory and algorithmic and can improve the precision of the detection on the thin sand-peat interbed configurations of land facies, is in demand to put forward.Generalized S Transform (GST) processing method provides a new method of phase space analysis for seismic data. Compared with wavelet transform, both of them have very good localization characteristics; however, directly related to the Fourier spectra, GST has clearer physical significance, moreover, GST adopts a technology to best approach seismic wavelets and transforms the seismic data into time-scale domain, and breaks through the limit of the fixed wavelet in S transform, so GST has extensive adaptability. Based on tracing the development of the ideas and theories from wavelet transform, S transform to GST, we studied how to improve the precision of the detection on the thin stratum by GST.Noise has strong influence on sequence detecting in GST, especially in the low signal-noise ratio data. We studied the distribution rule of colored noise in GST domain, and proposed a technology to distinguish the signal and noise in GST domain. We discussed two types of noises: white noise and red noise, in which noise satisfy statistical autoregression model. For these two model, the noise-signal detection technology based on GST all get good result. It proved that the GST domain noise-signal detection technology could be used to real seismic data, and could effectively avoid noise influence on seismic sequence detecting.On the seismic profile after GST processing, high amplitude energy intensive zone, schollen, strip and lentoid dead zone and disarray zone maybe represent specifically geologic meanings according to given geologic background. Using seismic sequence detection profile and combining other seismic interpretation technologies, we can elaborate depict the shape of palaeo-geomorphology, effectively estimate sand stretch, distinguish sedimentary facies, determine target area, and directly guide oil-gas exploration.In the lateral reservoir prediction in XF oilfield of Ordos Basin, it played very important role in the estimation of sand stretch that the study of palaeo-geomorphology of Triassic System and the partition of inner sequence of the stratum group. According to the high-resolution seismic profile after GST processing, we pointed out that the C8 Member of Yanchang Formation in DZ area and C8 Member in BM area are the same deposit. It provided the foundation for getting 430 million tons predicting reserves and unite building 3 million tons off-take potential.In tackling key problem study for SLG gas-field, according to the high-resolution seismic sequence profile, we determined that the deposit direction of H8 member is approximately N-S or NNE-SS W. Using the seismic sequence profile, combining with layer-level profile, we can interpret the shape of entrenched stream. The sunken lenticle indicates the high-energy stream channel, which has stronger hydropower. By this way we drew out three high-energy stream channels' outline, and determined the target areas for exploitation. Finding high-energy braided river by high-resolution sequence processing is the key technology in SLG area.In ZZ area, we studied the distribution of the main reservoir bed-S23, which is shallow delta thin sand bed, by GST processing. From the seismic sequence profile, we discovered that the schollen thick sand beds are only local distributed, and most of them are distributary channel sand and distributary bar deposit. Then we determined that the S23 sand deposit direction is NW-SE in west, N-S in central and NE-SW in east. The high detecting seismic sequence interpretation profiles have been tested by 14 wells, 2 wells mismatch and the coincidence rate is 85.7%. Based on the profiles we suggested 3 predicted wells, one well (Yu54) completed and the other two is still drilling. The completed on Is coincident with the forecastThe paper testified that GST is a effective technology to get high- resolution seismic sequence profile, compartmentalize deposit microfacies, confirm strike direction of sandstone and make sure of the distribution range of oil-gas bearing sandstone, and is the gordian technique for the exploration of lithologic gas-oil pool in complicated areas.

Characteristics of Biodiesel Oil Atomized by a Two-Fluid Nozzle Using PDA

Drop size and velocity distribution in a spray of fuel play an important role in determining combustion efficiency. The Phase Doppler anemometer (PDA) is a well-established technique allowing simultaneous measurement of velocity and size of droplets. In this work, effect of bio-substitute component on the size and velocity of biodiesel droplets which are generated by a two-fluid nozzle are investigated comprehensively using a PDA.

From offshore to onshore: multiple origins of shallow-water corals from deep-sea ancestors.

Shallow-water tropical reefs and the deep sea represent the two most diverse marine environments. Understanding the origin and diversification of this biodiversity is a major quest in ecology and evolution. The most prominent and well-supported explanation, articulated since the first explorations of the deep sea, holds that benthic marine fauna originated in shallow, onshore environments, and diversified into deeper waters. In contrast, evidence that groups of marine organisms originated in the deep sea is limited, and the possibility that deep-water taxa have contributed to the formation of shallow-water communities remains untested with phylogenetic methods. Here we show that stylasterid corals (Cnidaria: Hydrozoa: Stylasteridae)--the second most diverse group of hard corals--originated and diversified extensively in the deep sea, and subsequently invaded shallow waters. Our phylogenetic results show that deep-water stylasterid corals have invaded the shallow-water tropics three times, with one additional invasion of the shallow-water temperate zone. Our results also show that anti-predatory innovations arose in the deep sea, but were not involved in the shallow-water invasions. These findings are the first robust evidence that an important group of tropical shallow-water marine animals evolved from deep-water ancestors.

Repeated mapping of reefs constructed by Sabellaria spinulosa Leuckart 1849 at an offshore wind farm site

Sabellaria spinulosa reefs are considered to be sensitive and of high conservation status. This article evaluates the feasibility of using remote sensing technology to delineate S. spinulosa reefs. S. spinulosa reef habitats associated with the Thanet Offshore Windfarm site were mapped using high resolution sidescan sonar (410 kHz) and multibeam echo sounder (<1 m2) data in 2005 (baseline), 2007 (pre-construction baseline) and 2012 (post-construction). The S. spinulosa reefs were identified in the acoustic data as areas of distinct irregular texturing. Maps created using acoustic data were validated using quantitative measures of reef quality, namely tube density (as a proxy for the density of live S. spinulosa), percentage cover of S. spinulosa structures (both living and dead) and associated macrofauna derived from seabed images taken across the development site. Statistically significant differences were observed in all physical measures of S. spinulosa as well the number (S) and diversity (H׳) of associated species, derived from seabed images classified according to the presence or absence of reef, validating the use of high resolution sidescan sonar to map these important biogenic habitats. High precision mapping in the early stages allowed for the micro-siting of wind turbines in a way that caused minimal damage to S. spinulosa reefs during construction. These habitats have since recovered and expanded in extent. The surveys undertaken at the Thanet Offshore Windfarm site demonstrate the importance of repeat mapping for this emerging industry, allowing habitat enhancement to be attributed to the development whilst preventing background habitat degradation from being wrongly attributed to the development.

Tillin, H. & Tyler-Walters, H., 2014. Assessing the sensitivity of subtidal sedimentary habitats to pressures associated with marine activities. Phase 2 Report – Literature review and sensitivity assessments for ecological groups for circalittoral and offshore Level 5 biotopes. JNCC Report No. 512B, 260 pp.

Human activities within the marine environment give rise to a number of pressures on seabed habitats. Improved understanding of the sensitivity of subtidal sedimentary habitats is required to underpin the management advice provided for Marine Protected Areas, as well as supporting other UK marine monitoring and assessment work. The sensitivity of marine sedimentary habitats to a range of pressures induced by human activities has previously been systematically assessed using approaches based on expert judgement for Defra Project MB0102 (Tillin et al. 2010). This previous work assessed sensitivity at the level of the broadscale habitat and therefore the scores were typically expressed as a range due to underlying variation in the sensitivity of the constituent biotopes. The objective of this project was to reduce the uncertainty around identifying the sensitivity of selected subtidal sedimentary habitats by assessing sensitivity, at a finer scale and incorporating information on the biological assemblage, for 33 Level 5 circalittoral and offshore biotopes taken from the Marine Habitat Classification of Britain and Ireland (Connor et al. 2004). Two Level 6 sub-biotopes were also included in this project as these contain distinctive characterising species that differentiate them from the Level 5 parent biotope. Littoral, infralittoral, reduced and variable salinity sedimentary habitats were excluded from this project as the scope was set for assessment of circalittoral and offshore sedimentary communities. This project consisted of three Phases. • Phase 1 - define ecological groups based on similarities in the sensitivity of characterising species from the Level 5 and two Level 6 biotopes described above. • Phase 2 - produce a literature review of information on the resilience and resistance of characterising species of the ecological groups to pressures associated with activities in the marine environment. • Phase 3 - to produce sensitivity assessment ‘proformas’ based on the findings of Phase 2 for each ecological group. This report outlines results of Phase 2. The Tillin et al., (2010) sensitivity assessment methodology was modified to use the best available scientific evidence that could be collated within the project timescale. An extensive literature review was compiled, for peer reviewed and grey literature, to examine current understanding about the effects of pressures from human activities on circalittoral and offshore sedimentary communities in UK continental shelf waters, together with information on factors that contribute to resilience (recovery) of marine species. This review formed the basis of an assessment of the sensitivity of the 16 ecological groups identified in Phase 1 of the project (Tillin & Tyler-Walters 2014). As a result: • the state of knowledge on the effects of each pressure on circalittoral and offshore benthos was reviewed; • the resistance, resilience and, hence, sensitivity of sixteen ecological groups, representing 96 characteristic species, were assessed for eight separate pressures; • each assessment was accompanied by a detailed review of the relevant evidence; Assessing the sensitivity of subtidal sedimentary habitats to pressures associated with human activities • knowledge gaps and sources of uncertainty were identified for each group; • each assessment was accompanied by an assessment of the quality of the evidence, its applicability to the assessment and the degree of concordance (agreement) between the evidence, to highlight sources of uncertainty as an assessment of the overall confidence in the sensitivity assessment, and finally • limitations in the methodology and the application of sensitivity assessments were outlined. This process demonstrated that the ecological groups identified in Phase 1 (Tillin & Tyler-Walters 2014) were viable groups for sensitivity assessment, and could be used to represent the 33 circalittoral and offshore sediments biotopes identified at the beginning of the project. The results of the sensitivity assessments show: • the majority of species and hence ecological groups in sedimentary habitats are sensitive to physical change, especially loss of habitat and sediment extraction, and change in sediment type; • most sedimentary species are sensitive to physical damage, e.g. abrasion and penetration, although deep burrowing species (e.g. the Dublin Bay prawn - Nephrops norvegicus and the sea cucumber - Neopentadactyla mixta) are able to avoid damaging effects to varying degrees, depending on the depth of penetration and time of year; • changes in hydrography (wave climate, tidal streams and currents) can significantly affect sedimentary communities, depending on whether they are dominated by deposit, infaunal feeders or suspension feeders, and dependant on the nature of the sediment, which is itself modified by hydrography and depth; • sedentary species and ecological groups that dominate the top-layer of the sediment (either shallow burrowing or epifaunal) remain the most sensitive to physical damage; • mobile species (e.g. interstitial and burrowing amphipods, and perhaps cumaceans) are the least sensitive to physical change or damage, and hydrological change as they are already adapted to unstable, mobile substrata; • sensitivity to changes in organic enrichment and hence oxygen levels, is variable between species and ecological groups, depending on the exact habitat preferences of the species in question, although most species have at least a medium sensitivity to acute deoxygenation; • there is considerable evidence on the effects of bottom-contact fishing practices and aggregate dredging on sedimentary communities, although not all evidence is directly applicable to every ecological group; • there is lack of detailed information on the physiological tolerances (e.g. to oxygenation, salinity, and temperature), habitat preferences, life history and population dynamics of many species, so that inferences has been made from related species, families, or even the same phylum; • there was inadequate evidence to assess the effects of non-indigenous species on most ecological groups, and Assessing the sensitivity of subtidal sedimentary habitats to pressures associated with human activities • there was inadequate evidence to assess the effects of electromagnetic fields and litter on any ecological group. The resultant report provides an up-to-date review of current knowledge about the effects of pressures resulting from human activities of circalittoral and offshore sedimentary communities. It provides an evidence base to facilitate and support the provision of management advice for Marine Protected Areas, development of UK marine monitoring and assessment, and conservation advice to offshore marine industries. However, such a review will require at least annual updates to take advantage of new evidence and new research as it becomes available. Also further work is required to test how ecological group assessments are best combined in practice to advise on the sensitivity of a range of sedimentary biotopes, including the 33 that were originally examined.

Delamination of oil paints from acrylic grounds

Many modern artists paint in oil or oil-modified alkyd paints over acrylic grounds. In some cases the oil based paints do not remain adhered to the ground. In a set of composite samples of oil or alkyd paints, over acrylic grounds, naturally aged for nine years, some of the samples delaminated. Samples were analyzed with X-ray fluorescence (XRF), inductively coupled plasma (ICP), Fourier transform infrared - attenuated total reflectance (FTIR-ATR), scanning electron microscopy (SEM), pyrolysis gas-chromatography mass-spectrometry (PY-GC/MS), laser desorption/ionization mass-spectrometry (LDI-MS), atomic force microscopy (AFM) and other methods, in order to find what the delaminating ones have in common. In addition, two examples of severely delaminating paintings were examined, to confirm the results from the laboratory-prepared samples. Results indicate the main cause of delamination is metal soaps in the oil paint and particularly zinc soaps. There is some evidence that metal soaps were more concentrated at the interface between the layers and this disrupted the adhesion. The ground is a minor consideration as well, rougher grounds providing better adhesion than smooth ones.

Oil on Troubled Waters-Multinational Corporations and Realising Human Rights in the Developing World with Particular Reference to Nigeria

This article examines the current state of tension in the Niger Delta of Nigeria. It locates the current unrest in the continued denial of economic, social and cultural rights to the oil-rich communities in the area. The author argues that this denial happened with the complicity and acquiescence of the international community. The Nigerian government as well as multinational corporations operating in the area have not been responsive to the development needs of the people. The article argues that, although the primary obligation for realising the economic, social and cultural rights of host communities rests on the government, multi-national corporations in developing countries, considering their awesome resources and influence on government policies, should be similarly obligated to respect, promote and protect those rights.

NON-GAUSSIAN STATISTICS OF OIL PRICING TIME-SERIES: A CASE STUDY

The stochastic nature of oil price fluctuations is investigated over a twelve-year period, borrowing feedback from an existing database (USA Energy Information Administration database, available online). We evaluate the scaling exponents of the fluctuations by employing different statistical analysis methods, namely rescaled range analysis (R/S), scale windowed variance analysis (SWV) and the generalized Hurst exponent (GH) method. Relying on the scaling exponents obtained, we apply a rescaling procedure to investigate the complex characteristics of the probability density functions (PDFs) dominating oil price fluctuations. It is found that PDFs exhibit scale invariance, and in fact collapse onto a single curve when increments are measured over microscales (typically less than 30 days). The time evolution of the distributions is well fitted by a Levy-type stable distribution. The relevance of a Levy distribution is made plausible by a simple model of nonlinear transfer. Our results also exhibit a degree of multifractality as the PDFs change and converge toward to a Gaussian distribution at the macroscales.

Numerical simulation of a patent technology for sealing of deep-sea oil wells using nonlinear finite element method

For over 50 years bridge plugs and cement have been used for well abandonment and work over and are still the material of choice. However the failures of cement abandonments using bridge plugs has been reported on many occasions, some of which have resulted in fatal consequences. A new patented product is designed to address the shortcomings associated with using bridge plugs and cement. The new developed tools use an alloy based on bismuth that is melted in situ using Thermite reaction. The tool uses the expansion properties of bismuth to seal the well. Testing the new technology in real field under more than 2 km deep sea water can be expensive. Virtual simulation of the new device under simulated thermal and mechanical environment can be achieved using nonlinear finite element method to validate the product and reduce cost. Experimental testing in the lab is performed to measure heat generated due to thermite reaction. Then, a sequential thermal mechanical explicit/implicit finite element solver is used to simulate the device under both testing lab and deep water conditions.

Evaluation of methodologies to determine vegetable oil species present in oil mixtures: Proposition of an approach to meet the EU legislation demands for correct vegetable oils labelling

Refined vegetable oils are widely used in the food industry as ingredients or components in many processed food products in the form of oil blends. To date, the generic term 'vegetable oil' has been used in the labelling of food containing oil blends. With the introduction of new EU Regulation for Food Information (1169/2011) due to take effect in 2014, the oil species used must be clearly identified on the package and there is a need for development of fit for purpose methodology for industry and regulators alike to verify the oil species present in a product. The available methodologies that may be employed to authenticate the botanical origin of a vegetable oil admixture were reviewed and evaluated. The majority of the sources however, described techniques applied to crude vegetable oils such as olive oil due to the lack of refined vegetable oil focused studies. Nevertheless, DNA based typing methods and stable isotopes procedures were found not suitable for this particular purpose due to several issues. Only a small number of specific chromatographic and spectroscopic fingerprinting methods in either targeted or untargeted mode were found to be applicable in potentially providing a solution to this complex authenticity problem. Applied as a single method in isolation, these techniques would be able to give limited information on the oils identity as signals obtained for various oil types may well be overlapping. Therefore, more complex and combined approaches are likely to be needed to identify the oil species present in oil blends employing a stepwise approach in combination with advanced chemometrics. Options to provide such a methodology are outlined in the current study.

Synthesis of new vegetable oil-based polymeric materials

A crescente procura de recursos fosseis a que se tem assistido nos ultimos anos, tem resultado num crescimento sem precedentes dos precos, com consequencias imprevisiveis e que levara, no espaco de decadas, ao seu inevitavel esgotamento. A procura de um modelo de desenvolvimento sustentavel, baseado em recursos renovaveis e o grande desafio que se coloca a civilizacao no seculo XXI. A biomassa vegetal, atraves das designadas gBio-refinarias h, e uma alternativa logica para a producao de produtos quimicos e de materiais mas tambem de combustiveis e energia. Os oleos vegetais constituem uma das fracoes da biomassa vegetal, cuja exploracao tem merecido redobrada atencao nos ultimos anos, como fonte de materiais e de combustiveis. Assim, a presente dissertacao tem por objetivo o desenvolvimento de novos materiais polimericos derivados de oleos vegetais, seguindo duas abordagens distintas, nomeadamente a preparacao de polimeros atraves de polimerizacao por etapas e polimerizacao em cadeia (Parte B e C, respetivamente). Em primeiro lugar, foram sintetizados poliesteres alifaticos de cadeia longa a partir de monomeros provenientes do oleo de colza (Capitulo III). A auto-metatese do acido erucico com catalisadores de rutenio, seguida de hidrogenacao da ligacao dupla, originou o acido 1,26-hexacosanodioico, que por sua vez foi convertido em hexacosano-1,26-diol. Subsequentemente, a policondensacao do acido ƒ¿,ƒÖ-dicarboxilico de cadeia longa com o hexacosano-1,26-diol originou o poliester 26,26. O diacido C26 foi tambem polimerizado com outros alcano-diois de cadeia curta, nomeadamente o dodecano-1,12-diol e o butano-1,2-diol, produzindo, respetivamente, os poliesteres 12,26 e 4,26. Estes poliesteres de fontes 100% renovaveis possuem valores de Mn na ordem dos 8-14 kDa e valores de PDI entre 2.1 e 2.7. As propriedades destes poliesteres alifaticos foram avaliadas atraves de varias tecnicas, revelando elevada cristalinidade (com uma estrutura cristalina como a do polietileno) e elevadas temperaturas de fusao (74-104 ‹C), cristalizacao (68-92 ‹C) e degradacao (323-386 ‹C). Em segundo lugar, foram sintetizados polimeros lineares termo-reversiveis a partir de derivados do oleo de ricinio (Capitulo IV). Para tal foram preparados monomeros que incorporam aneis furanicos inseridos atraves do acoplamento tiol-eno, e que posteriormente foram polimerizados pela reacao de Diels-Alder (DA) entre os grupos furano (dieno A) e estruturas complementares do tipo maleimida (dienofilo B). Para as polimerizacoes DA foram consideradas duas abordagens diferentes, nomeadamente (i) o uso de monomeros com dois aneis furanicos terminais em conjunto com uma bismaleimida (sistemas AA+BB) e (ii) a utilizacao de um monomero que incorpora ambos os grupos reativos, furano e maleimida, na sua estrutura (sistema AB). Este estudo demonstrou claramente que ambas as estratégias foram bem sucedidas embora com diferentes resultados em termos da natureza dos produtos obtidos. Estes polímeros lineares apresentam valores relativamente baixos de Tg (-40 to -2 °C) devido à natureza flexível dos grupos separadores das funções reativas, e de Mn (4.5-9.0 kDa) dada a observada tendência de ciclização associada a concentrações baixas de monómero. A aplicação da reação de retro-DA aos polímeros em causa confirmou o seu caráter reversível, ou seja, a possibilidade de promover, em condições controladas, a despolimerização com recuperação dos monómeros de partida. Esta particularidade abre caminhos para materiais macromoleculares originais com aplicações promissoras tais como auto-reparação e reciclabilidade. Em terceiro lugar, sintetizaram-se polímeros não-lineares termo-reversíveis a partir de derivados do óleo de ricínio (Capítulo V). Para tal foram preparados monómeros trifuncionais e posteriormente polimerizados através da reação de DA entre os grupos reativos complementares furano/maleimida. Foram consideradas três abordagens distintas para preparar estes polímeros não-lineares, nomeadamente através da utilização de (i) um monómero bisfurânico em combinação com uma trismaleimida (sistema A2+B3) e (ii) um monómero trisfurânico em conjunto com uma bismaleimida (sistema A3+B2) que originaram materiais ramificados ou reticulados, e ainda (iii) a utilização de monómeros assimetricamente substituídos do tipo A2B ou AB2 capazes de originar estruturas macromoleculares hiper-ramificadas. Todos os sistemas apresentaram valores de Tg perto de 0 °C, o que era de esperar para estes materiais não-lineares. A aplicação da reação de retro-DA comprovou mais uma vez o caráter termo-reversível das polimerizações em causa. Em quarto lugar e último lugar, foram preparados copolímeros de acetato de vinilo (VAc) com monómeros derivados de óleo de girassol (Capítulo VI). Ésteres vinílicos de ácidos gordos (FAVE) foram sintetizados por transvinilação dos ácidos oleico e linoleico com VAc catalisada por um complexo de irídio. Os monómeros vinílicos preparados foram caracterizados e posteriormente homopolimerizados e copolimerizados com VAc através do uso dos grupos vinílicos terminais como função inicial de polimerização. A variação do tipo e quantidade de monómero FAVE e da quantidade de iniciador radicalar originou copolímeros de VAc com valores de Mn na gama de 1.2-3.0 kDa e valores de Tg de -5 a 16 °C. Os copolímeros foram avaliados em testes de cura oxidativa através das insaturações nas suas cadeias alifáticas para formar materiais reticulados, e os resultados sugerem que eles podem ser sistemas efetivos de cura para aplicações como tintas, vernizes e outros tipos de revestimento. Todos os materiais poliméricos preparados ao longo deste trabalho constituem contribuições atrativas para a área dos polímeros oriundos de recursos renováveis e representam uma prova indiscutível de que os óleos vegetais são percursores promissores de materiais macromoleculares com potenciais aplicações.

Optimization models for a short sea fuel oil distribution problem

O transporte marítimo e o principal meio de transporte de mercadorias em todo o mundo. Combustíveis e produtos petrolíferos representam grande parte das mercadorias transportadas por via marítima. Sendo Cabo Verde um arquipelago o transporte por mar desempenha um papel de grande relevância na economia do país. Consideramos o problema da distribuicao de combustíveis em Cabo Verde, onde uma companhia e responsavel por coordenar a distribuicao de produtos petrolíferos com a gestão dos respetivos níveis armazenados em cada porto, de modo a satisfazer a procura dos varios produtos. O objetivo consiste em determinar políticas de distribuicão de combustíveis que minimizam o custo total de distribuiçao (transporte e operacões) enquanto os n íveis de armazenamento sao mantidos nos n íveis desejados. Por conveniencia, de acordo com o planeamento temporal, o prob¬lema e divido em dois sub-problemas interligados. Um de curto prazo e outro de medio prazo. Para o problema de curto prazo sao discutidos modelos matemáticos de programacao inteira mista, que consideram simultaneamente uma medicao temporal cont ínua e uma discreta de modo a modelar multiplas janelas temporais e taxas de consumo que variam diariamente. Os modelos sao fortalecidos com a inclusão de desigualdades validas. O problema e então resolvido usando um "software" comercial. Para o problema de medio prazo sao inicialmente discutidos e comparados varios modelos de programacao inteira mista para um horizonte temporal curto assumindo agora uma taxa de consumo constante, e sao introduzidas novas desigualdades validas. Com base no modelo escolhido sao compara¬das estrategias heurísticas que combinam três heur ísticas bem conhecidas: "Rolling Horizon", "Feasibility Pump" e "Local Branching", de modo a gerar boas soluçoes admissíveis para planeamentos com horizontes temporais de varios meses. Finalmente, de modo a lidar com situaçoes imprevistas, mas impor¬tantes no transporte marítimo, como as mas condicões meteorológicas e congestionamento dos portos, apresentamos um modelo estocastico para um problema de curto prazo, onde os tempos de viagens e os tempos de espera nos portos sao aleatórios. O problema e formulado como um modelo em duas etapas, onde na primeira etapa sao tomadas as decisões relativas as rotas do navio e quantidades a carregar e descarregar e na segunda etapa (designada por sub-problema) sao consideradas as decisoes (com recurso) relativas ao escalonamento das operacões. O problema e resolvido por um metodo de decomposto que usa um algoritmo eficiente para separar as desigualdades violadas no sub-problema.

Development of an operational tool for oil spill forecast: application to oil exposed regions

Tese de doutoramento, Ciências do Mar, da Terra e do Ambiente (Modelação), Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014