Impacto ambiental associado à utilização intensive de algumas energies renováveis – Pequeno contributo

A utilização da energia hídrica, obtida em grandes barragens, é uma prática muito antiga, em Portugal. Nas ultimas décadas de anos , o seu número tem aumentado, existindo ou estando em fase de conclusão, 57 grandes barragens, no Alentejo. Os problemas associados a este tipo de barragens são conhecidos. Iremos falar de um, extremamente importante, na região. Devido à profundidade atingida, existe pouco oxigénio no fundo destes reservatórios, e a decomposição de matéria morta origina grandes quantidades de metano. Em termos de efeito de estufa o metano é 30 vezes mais potente que o CO2. O facto de não ter havido limpeza do solo antes do enchimento das albufeiras e de algumas se encontrarem com problemas de eutrofização, vem aumentar este problema. Outro tipo de energia muito utilizada é a energia solar, existindo grandes centrais fotovoltaicas em funcionamento e prevendo-se a construção de novas centrais com uma potência total de 1300 MW para o país. Em Évora, Ourique, Alcoutim e Nisa já foi anunciada a construção de novas centrais com uma potência total de 155 MW. Os problemas associados a este tipo de centrais, são de vários tipos. Iremos debruçar-nos sobre os produtos tóxicos que as células solares contêm e que variam com o tipo de célula. Estando algumas centrais já em funcionamento e outras em fase de montagem, importa refletir sobre o que fazer depois de a central deixar de funcionar. O que fazer com os resíduos tóxicos, as toneladas de aço e outros materiais envolvidos, formação de pessoal que saiba manusear os produtos tóxicos, custos associados às soluções possíveis, etc. Não se conhecendo informação relativa a estes problemas, por parte da comunicação social, importa refletir sobre a informação fornecida à população e autoridades locais envolvidas.

Impacto ambiental associado à utilização intensive de algumas energies renováveis – Pequeno contributo

A utilização da energia hídrica, obtida em grandes barragens, é uma prática muito antiga, em Portugal. Nas ultimas décadas de anos , o seu número tem aumentado, existindo ou estando em fase de conclusão, 57 grandes barragens, no Alentejo. Os problemas associados a este tipo de barragens são conhecidos. Iremos falar de um, extremamente importante, na região. Devido à profundidade atingida, existe pouco oxigénio no fundo destes reservatórios, e a decomposição de matéria morta origina grandes quantidades de metano. Em termos de efeito de estufa o metano é 30 vezes mais potente que o CO2. O facto de não ter havido limpeza do solo antes do enchimento das albufeiras e de algumas se encontrarem com problemas de eutrofização, vem aumentar este problema. Outro tipo de energia muito utilizada é a energia solar, existindo grandes centrais fotovoltaicas em funcionamento e prevendo-se a construção de novas centrais com uma potência total de 1300 MW para o país. Em Évora, Ourique, Alcoutim e Nisa já foi anunciada a construção de novas centrais com uma potência total de 155 MW. Os problemas associados a este tipo de centrais, são de vários tipos. Iremos debruçar-nos sobre os produtos tóxicos que as células solares contêm e que variam com o tipo de célula. Estando algumas centrais já em funcionamento e outras em fase de montagem, importa refletir sobre o que fazer depois de a central deixar de funcionar. O que fazer com os resíduos tóxicos, as toneladas de aço e outros materiais envolvidos, formação de pessoal que saiba manusear os produtos tóxicos, custos associados às soluções possíveis, etc. Não se conhecendo informação relativa a estes problemas, por parte da comunicação social, importa refletir sobre a informação fornecida à população e autoridades locais envolvidas.

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.

The way forward : report on the preparatory phase of prefabricated building design and construction methodology: identifying critical issues and recommending the way forward

This is an initial report of the PolyU SD part of the team to study Pre-fabricated Building Design and Construction Methodology and marks the completion of Phase 1. It follows our first notes prepared for the meeting on 2 February that identified some critical issues including future lifestyles, life expectancy of buildings, sustainability, size, flexibility and planning considerations. It is also an expansion of our presentation in Dongguan on 23 February. It is not a comprehensive survey of existing approaches or possible ways forward, but it has homed in on certain specific issues and does give specific examples to make the suggestions concrete. It is recommended that more comprehensive research be done to establish previous work and experience internationally. It is also recommended that more research be done on lifestyles as a preliminary to developing at least three concepts for evaluation before proceeding to the detailed design of one concept for full prototyping and market testing. The goal at this point is not to define a single direction but to suggest several future trajectories for further consideration. By the same token, this report is not intended as an exhaustive description of the considerable base of knowledge and ideas brought by the PolyU team to this exciting task. Before taking on an issue of this magnitude and importance in the definition of Hong Kong's future, one must carry out a thoughtful analysis of the issues at hand and an informed definition of paradigms, directions, goals and methods whereby our energies can be best used in the next steps. This report is the result of this analysis

Compliance in peritoneal dialysis : a qualitative study of renal nurses

End-stage renal failure is a life-threatening condition, often treated with home-based peritoneal dialysis (PD). PD is a demanding regimen, and the patients who practise it must make numerous lifestyle changes and learn complicated biomedical techniques. In our experience, the renal nurses who provide mostPDeducation frequently express concerns that patient compliance with their teaching is poor. These concerns are mirrored in the renal literature. It has been argued that the perceived failure of health professionals to improve compliance rates with PD regimens is because ‘compliance’ itself has never been adequately conceptualized or defined; thus, it is difficult to operationalize and quantify. This paper examines how a group of Australian renal nurses construct patient compliance with PD therapy. These empirical data illuminate how PD compliance operates in one practice setting; how it is characterized by multiple and often competing energies; and how ultimately it might be pointless to try to tame ‘compliance’ through rigid definitions and measurement, or to rigidly enforce it in PD patients. The energies involved are too fractious and might be better spent, as many of the more experienced nurses in this study argue, in augmenting the energies that do work well together to improve patient outcomes.

Estimating total cross sections from neutron-nucleus collisions using a simple functional form

Total cross sections for neutron scattering from nuclei, with energies ranging from 10 to 600 MeV and from many nuclei spanning the mass range 6Li to 238U, have been analyzed using a simple, three-parameter, functional form. The calculated cross sections are compared with results obtained by using microscopic (g-folding) optical potentials as well as with experimental data. The functional form reproduces those total cross sections very well. When allowance is made for Ramsauer-like effects in the scattering, the parameters of the functional form required vary smoothly with energy and target mass. They too can be represented by functions of energy and mass.

Optical absorption and EPR studies on tenorite mineral

Optical absorption and EPR studies of the mineral tenorite, a cupric oxide, which originated from Mexico and contains 54.40 wt% of CuO. EPR spectral results indicate two Cu(II) closely interacting ions to give a d2 type structure. The calculated spin Hamiltonian at Rt and LNT are g = 2.160 and D = 125 G . The intensity of resonance line is not the same in low and high field regions. The optical absorption spectrum is due to Cu(II) which three sets of energies indicating Cu(II) in two independent tetragonal C4v symmetry, in addition to d2 structure of octahedral coordination. The octahedral and tetragonal field parameters are compared with those reported for several other copper containing minerals.

Effects of collimator backscatter in an Elekta linac by Monte Carlo simulation

The effects of radiation backscattered from the secondary collimators into the monitor chamber in an Elekta linac (producing 6 and 10 MV photon beams) are investigated using BEAMnrc Monte Carlo simulations. The degree and effects of this backscattered radiation are assessed by evaluating the changes to the calculated dose in the monitor chamber, and by determining a correction factor for those changes. Additionally, the fluency and energy characteristics of particles entering the monitor chamber from the downstream direction are evaluated by examining BEAMnrc phase-space data. It is shown that the proportion of particles backscattered into the monitor chamber is small (<0.35 %), for all field sizes studied. However, when the backscatter plate is removed from the model linac, these backscattered particles generate a noticeable increase in dose to the monitor chamber (up to approximate to 2.4 % for the 6 MV beam and up to 4.4 % for the 10 MV beam). With its backscatter plate in place, the Elekta linac (operating at 6 and 10 MV) is subject to negligible variation of monitor chamber dose with field size. At these energies, output variations in photon beams produced by the clinical Elekta linear accelerator can be attributed to head scatter alone. Corrections for field-size-dependence of monitor chamber dose are not necessary when running Monte Carlo simulations of the Elekta linac operating at 6 and 10 MV.

Thermal tweezers for manipulation of adatoms and nanoparticles on surfaces heated by interfering laser pulses

We conduct the detailed numerical investigation of a nanomanipulation and nanofabrication technique—thermal tweezers with dynamic evolution of surface temperature, caused by absorption of interfering laser pulses in a thin metalfilm or any other absorbing surface. This technique uses random Brownian forces in the presence of strong temperature modulation (surfacethermophoresis) for effective manipulation of particles/adatoms with nanoscale resolution. Substantial redistribution of particles on the surface is shown to occur with the typical size of the obtained pattern elements of ∼100 nm, which is significantly smaller than the wavelength of the incident pulses used (532 nm). It is also demonstrated that thermal tweezers based on surfacethermophoresis of particles/adatoms are much more effective in achieving permanent high maximum-to-minimum concentration ratios than bulk thermophoresis, which is explained by the interaction of diffusing particles with the periodic lattice potential on the surface. Typically required pulse regimes including pulse lengths and energies are also determined. The approach is applicable for reproducing any holographically achievable surfacepatterns, and can thus be used for engineering properties of surfaces including nanopatterning and design of surface metamaterials.

Thin film deposition and characterization of pure and iron-doped electron-beam evaporated tungsten oxide for gas sensors

Pure Tungsten Oxide (WO3) and Iron-doped (10 at%) Tungsten Oxide (WO3:Fe) nanostructured thin films were prepared using a dual crucible Electron Beam Evaporation techniques. The films were deposited at room temperature in high vacuum condition on glass substrate and post-heat treated at 300 oC for 1 hour. From the study of X-ray diffraction and Raman the characteristics of the as-deposited WO3 and WO3:Fe films indicated non-crystalline nature. The surface roughness of all the films showed in the order of 2.5 nm as observed using Atomic Force Microscopy (AFM). X-Ray Photoelectron Spectroscopy (XPS) analysis revealed tungsten oxide films with stoichiometry close to WO3. The addition of Fe to WO3 produced a smaller particle size and lower porosity as observed using Transmission Electron Microscopy (TEM). A slight difference in optical band gap energies of 3.22 eV and 3.12 eV were found between the as-deposited WO3 and WO3:Fe films, respectively. However, the difference in the band gap energies of the annealed films were significantly higher having values of 3.12 eV and 2.61 eV for the WO3 and WO3:Fe films, respectively. The heat treated samples were investigated for gas sensing applications using noise spectroscopy and doping of Fe to WO3 reduced the sensitivity to certain gasses. Detailed study of the WO3 and WO3:Fe films gas sensing properties is the subject of another paper.

Adiabatic compression testing - part II : background and approach to estimating severity of test methodology

Adiabatic compression testing of components in gaseous oxygen is a test method that is utilized worldwide and is commonly required to qualify a component for ignition tolerance under its intended service. This testing is required by many industry standards organizations and government agencies; however, a thorough evaluation of the test parameters and test system influences on the thermal energy produced during the test has not yet been performed. This paper presents a background for adiabatic compression testing and discusses an approach to estimating potential differences in the thermal profiles produced by different test laboratories. A “Thermal Profile Test Fixture” (TPTF) is described that is capable of measuring and characterizing the thermal energy for a typical pressure shock by any test system. The test systems at Wendell Hull & Associates, Inc. (WHA) in the USA and at the BAM Federal Institute for Materials Research and Testing in Germany are compared in this manner and some of the data obtained is presented. The paper also introduces a new way of comparing the test method to idealized processes to perform system-by-system comparisons. Thus, the paper introduces an “Idealized Severity Index” (ISI) of the thermal energy to characterize a rapid pressure surge. From the TPTF data a “Test Severity Index” (TSI) can also be calculated so that the thermal energies developed by different test systems can be compared to each other and to the ISI for the equivalent isentropic process. Finally, a “Service Severity Index” (SSI) is introduced to characterizing the thermal energy of actual service conditions. This paper is the second in a series of publications planned on the subject of adiabatic compression testing.

Monte Carlo modelling of X-ray absorptiometry and its application to body composition studies

This thesis applies Monte Carlo techniques to the study of X-ray absorptiometric methods of bone mineral measurement. These studies seek to obtain information that can be used in efforts to improve the accuracy of the bone mineral measurements. A Monte Carlo computer code for X-ray photon transport at diagnostic energies has been developed from first principles. This development was undertaken as there was no readily available code which included electron binding energy corrections for incoherent scattering and one of the objectives of the project was to study the effects of inclusion of these corrections in Monte Carlo models. The code includes the main Monte Carlo program plus utilities for dealing with input data. A number of geometrical subroutines which can be used to construct complex geometries have also been written. The accuracy of the Monte Carlo code has been evaluated against the predictions of theory and the results of experiments. The results show a high correlation with theoretical predictions. In comparisons of model results with those of direct experimental measurements, agreement to within the model and experimental variances is obtained. The code is an accurate and valid modelling tool. A study of the significance of inclusion of electron binding energy corrections for incoherent scatter in the Monte Carlo code has been made. The results show this significance to be very dependent upon the type of application. The most significant effect is a reduction of low angle scatter flux for high atomic number scatterers. To effectively apply the Monte Carlo code to the study of bone mineral density measurement by photon absorptiometry the results must be considered in the context of a theoretical framework for the extraction of energy dependent information from planar X-ray beams. Such a theoretical framework is developed and the two-dimensional nature of tissue decomposition based on attenuation measurements alone is explained. This theoretical framework forms the basis for analytical models of bone mineral measurement by dual energy X-ray photon absorptiometry techniques. Monte Carlo models of dual energy X-ray absorptiometry (DEXA) have been established. These models have been used to study the contribution of scattered radiation to the measurements. It has been demonstrated that the measurement geometry has a significant effect upon the scatter contribution to the detected signal. For the geometry of the models studied in this work the scatter has no significant effect upon the results of the measurements. The model has also been used to study a proposed technique which involves dual energy X-ray transmission measurements plus a linear measurement of the distance along the ray path. This is designated as the DPA( +) technique. The addition of the linear measurement enables the tissue decomposition to be extended to three components. Bone mineral, fat and lean soft tissue are the components considered here. The results of the model demonstrate that the measurement of bone mineral using this technique is stable over a wide range of soft tissue compositions and hence would indicate the potential to overcome a major problem of the two component DEXA technique. However, the results also show that the accuracy of the DPA( +) technique is highly dependent upon the composition of the non-mineral components of bone and has poorer precision (approximately twice the coefficient of variation) than the standard DEXA measurements. These factors may limit the usefulness of the technique. These studies illustrate the value of Monte Carlo computer modelling of quantitative X-ray measurement techniques. The Monte Carlo models of bone densitometry measurement have:- 1. demonstrated the significant effects of the measurement geometry upon the contribution of scattered radiation to the measurements, 2. demonstrated that the statistical precision of the proposed DPA( +) three tissue component technique is poorer than that of the standard DEXA two tissue component technique, 3. demonstrated that the proposed DPA(+) technique has difficulty providing accurate simultaneous measurement of body composition in terms of a three component model of fat, lean soft tissue and bone mineral,4. and provided a knowledge base for input to decisions about development (or otherwise) of a physical prototype DPA( +) imaging system. The Monte Carlo computer code, data, utilities and associated models represent a set of significant, accurate and valid modelling tools for quantitative studies of physical problems in the fields of diagnostic radiology and radiography.

Electron interaction with gel dosimeters : effective atomic numbers for collisional, radiative and total interaction processes

The effective atomic number is widely employed in radiation studies, particularly for the characterisation of interaction processes in dosimeters, biological tissues and substitute materials. Gel dosimeters are unique in that they comprise both the phantom and dosimeter material. In this work, effective atomic numbers for total and partial electron interaction processes have been calculated for the first time for a Fricke gel dosimeter, five hypoxic and nine normoxic polymer gel dosimeters. A range of biological materials are also presented for comparison. The spectrum of energies studied spans 10 keV to 100 MeV, over which the effective atomic number varies by 30 %. The effective atomic numbers of gels match those of soft tissue closely over the full energy range studied; greater disparities exist at higher energies but are typically within 4 %.

Alkaline hydrothermal treatment of titanate nanostructures

Since its initial proposal in 1998, alkaline hydrothermal processing has rapidly become an established technology for the production of titanate nanostructures. This simple, highly reproducible process has gained a strong research following since its conception. However, complete understanding and elucidation of nanostructure phase and formation have not yet been achieved. Without fully understanding phase, formation, and other important competing effects of the synthesis parameters on the final structure, the maximum potential of these nanostructures cannot be obtained. Therefore this study examined the influence of synthesis parameters on the formation of titanate nanostructures produced by alkaline hydrothermal treatment. The parameters included alkaline concentration, hydrothermal temperature, the precursor material‘s crystallite size and also the phase of the titanium dioxide precursor (TiO2, or titania). The nanostructure‘s phase and morphology was analysed using X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy (XPS), dynamic light scattering (non-invasive backscattering), nitrogen sorption, and Rietveld analysis were used to determine phase, for particle sizing, surface area determinations, and establishing phase concentrations, respectively. This project rigorously examined the effect of alkaline concentration and hydrothermal temperature on three commercially sourced and two self-prepared TiO2 powders. These precursors consisted of both pure- or mixed-phase anatase and rutile polymorphs, and were selected to cover a range of phase concentrations and crystallite sizes. Typically, these precursors were treated with 5–10 M sodium hydroxide (NaOH) solutions at temperatures between 100–220 °C. Both nanotube and nanoribbon morphologies could be produced depending on the combination of these hydrothermal conditions. Both titania and titanate phases are comprised of TiO6 units which are assembled in different combinations. The arrangement of these atoms affects the binding energy between the Ti–O bonds. Raman spectroscopy and XPS were therefore employed in a preliminary study of phase determination for these materials. The change in binding energy from a titania to a titanate binding energy was investigated in this study, and the transformation of titania precursor into nanotubes and titanate nanoribbons was directly observed by these methods. Evaluation of the Raman and XPS results indicated a strengthening in the binding energies of both the Ti (2p3/2) and O (1s) bands which correlated to an increase in strength and decrease in resolution of the characteristic nanotube doublet observed between 320 and 220 cm.1 in the Raman spectra of these products. The effect of phase and crystallite size on nanotube formation was examined over a series of temperatures (100.200 �‹C in 20 �‹C increments) at a set alkaline concentration (7.5 M NaOH). These parameters were investigated by employing both pure- and mixed- phase precursors of anatase and rutile. This study indicated that both the crystallite size and phase affect nanotube formation, with rutile requiring a greater driving force (essentially �\harsher. hydrothermal conditions) than anatase to form nanotubes, where larger crystallites forms of the precursor also appeared to impede nanotube formation slightly. These parameters were further examined in later studies. The influence of alkaline concentration and hydrothermal temperature were systematically examined for the transformation of Degussa P25 into nanotubes and nanoribbons, and exact conditions for nanostructure synthesis were determined. Correlation of these data sets resulted in the construction of a morphological phase diagram, which is an effective reference for nanostructure formation. This morphological phase diagram effectively provides a .recipe book�e for the formation of titanate nanostructures. Morphological phase diagrams were also constructed for larger, near phase-pure anatase and rutile precursors, to further investigate the influence of hydrothermal reaction parameters on the formation of titanate nanotubes and nanoribbons. The effects of alkaline concentration, hydrothermal temperature, crystallite phase and size are observed when the three morphological phase diagrams are compared. Through the analysis of these results it was determined that alkaline concentration and hydrothermal temperature affect nanotube and nanoribbon formation independently through a complex relationship, where nanotubes are primarily affected by temperature, whilst nanoribbons are strongly influenced by alkaline concentration. Crystallite size and phase also affected the nanostructure formation. Smaller precursor crystallites formed nanostructures at reduced hydrothermal temperature, and rutile displayed a slower rate of precursor consumption compared to anatase, with incomplete conversion observed for most hydrothermal conditions. The incomplete conversion of rutile into nanotubes was examined in detail in the final study. This study selectively examined the kinetics of precursor dissolution in order to understand why rutile incompletely converted. This was achieved by selecting a single hydrothermal condition (9 M NaOH, 160 °C) where nanotubes are known to form from both anatase and rutile, where the synthesis was quenched after 2, 4, 8, 16 and 32 hours. The influence of precursor phase on nanostructure formation was explicitly determined to be due to different dissolution kinetics; where anatase exhibited zero-order dissolution and rutile second-order. This difference in kinetic order cannot be simply explained by the variation in crystallite size, as the inherent surface areas of the two precursors were determined to have first-order relationships with time. Therefore, the crystallite size (and inherent surface area) does not affect the overall kinetic order of dissolution; rather, it determines the rate of reaction. Finally, nanostructure formation was found to be controlled by the availability of dissolved titanium (Ti4+) species in solution, which is mediated by the dissolution kinetics of the precursor.