THE EFFECT OF FILM-FORMING CONDITIONS FOR TAPCUPC LANGMUIR-BLODGETT-FILMS ON MORPHOLOGY AND PROPERTIES

The dependence of morphology and properties on film-forming conditions is described for the symmetrically substituted copper tetra-4-(2, 4-di-t-amylphenoxy) phthalocyanine (tapCuPc) Langmuir-Blodgett (LB) films. The effects of LB film-forming conditions (such as the surface pressure, pH value and the concentrations of spreading solutions) on film quality were studied with the help of a UV-visible spectrophotometer and a transmission electron microscope. Transmission electron microscopy photographs of the surface morphology of tapCuPc LB films show that a smooth and homogeneous surface structure can be obtained under optimum film-forming conditions.

Specification of optimum holistic building environmental and energy performance information to support informed decision making

Political drivers such as the Kyoto protocol, the EU Energy Performance of Buildings Directive and the Energy end use and Services Directive have been implemented in response to an identified need for a reduction in human related CO2 emissions. Buildings account for a significant portion of global CO2 emissions, approximately 25-30%, and it is widely acknowledged by industry and research organisations that they operate inefficiently. In parallel, unsatisfactory indoor environmental conditions have proven to negatively impact occupant productivity. Legislative drivers and client education are seen as the key motivating factors for an improvement in the holistic environmental and energy performance of a building. A symbiotic relationship exists between building indoor environmental conditions and building energy consumption. However traditional Building Management Systems and Energy Management Systems treat these separately. Conventional performance analysis compares building energy consumption with a previously recorded value or with the consumption of a similar building and does not recognise the fact that all buildings are unique. Therefore what is required is a new framework which incorporates performance comparison against a theoretical building specific ideal benchmark. Traditionally Energy Managers, who work at the operational level of organisations with respect to building performance, do not have access to ideal performance benchmark information and as a result cannot optimally operate buildings. This thesis systematically defines Holistic Environmental and Energy Management and specifies the Scenario Modelling Technique which in turn uses an ideal performance benchmark. The holistic technique uses quantified expressions of building performance and by doing so enables the profiled Energy Manager to visualise his actions and the downstream consequences of his actions in the context of overall building operation. The Ideal Building Framework facilitates the use of this technique by acting as a Building Life Cycle (BLC) data repository through which ideal building performance benchmarks are systematically structured and stored in parallel with actual performance data. The Ideal Building Framework utilises transformed data in the form of the Ideal Set of Performance Objectives and Metrics which are capable of defining the performance of any building at any stage of the BLC. It is proposed that the union of Scenario Models for an individual building would result in a building specific Combination of Performance Metrics which would in turn be stored in the BLC data repository. The Ideal Data Set underpins the Ideal Set of Performance Objectives and Metrics and is the set of measurements required to monitor the performance of the Ideal Building. A Model View describes the unique building specific data relevant to a particular project stakeholder. The energy management data and information exchange requirements that underlie a Model View implementation are detailed and incorporate traditional and proposed energy management. This thesis also specifies the Model View Methodology which complements the Ideal Building Framework. The developed Model View and Rule Set methodology process utilises stakeholder specific rule sets to define stakeholder pertinent environmental and energy performance data. This generic process further enables each stakeholder to define the resolution of data desired. For example, basic, intermediate or detailed. The Model View methodology is applicable for all project stakeholders, each requiring its own customised rule set. Two rule sets are defined in detail, the Energy Manager rule set and the LEED Accreditor rule set. This particular measurement generation process accompanied by defined View would filter and expedite data access for all stakeholders involved in building performance. Information presentation is critical for effective use of the data provided by the Ideal Building Framework and the Energy Management View definition. The specifications for a customised Information Delivery Tool account for the established profile of Energy Managers and best practice user interface design. Components of the developed tool could also be used by Facility Managers working at the tactical and strategic levels of organisations. Informed decision making is made possible through specified decision assistance processes which incorporate the Scenario Modelling and Benchmarking techniques, the Ideal Building Framework, the Energy Manager Model View, the Information Delivery Tool and the established profile of Energy Managers. The Model View and Rule Set Methodology is effectively demonstrated on an appropriate mixed use existing ‘green’ building, the Environmental Research Institute at University College Cork, using the Energy Management and LEED rule sets. Informed Decision Making is also demonstrated using a prototype scenario for the demonstration building.

A study of the relationship between process conditions and mechanical strength of mineralized red algae in the preparation of a marine-derived bone void filler

Bone void fillers that can enhance biological function to augment skeletal repair have significant therapeutic potential in bone replacement surgery. This work focuses on the development of a unique microporous (0.5-10 mu m) marine-derived calcium phosphate bioceramic granule. It was prepared fro Corallina officinalis, a mineralized red alga, using a novel manufacturing process. This involved thermal processing, followed by a low pressure-temperature chemical synthesis reaction. The study found that the ability to maintain the unique algal morphology was dependent on the thermal processing conditions. This study investigates the effect of thermal heat treatment on the physiochemical properties of the alga. Thermogravimetric analysis was used to monitor its thermal decomposition. The resultant thermograms indicated the presence of a residual organic phase at temperatures below 500 degrees C and an irreversible solid-state phase transition from mg-rich-calcite to calcium oxide at temperatures over 850 degrees C. Algae and synthetic calcite were evaluated following heat treatment in an air-circulating furance at temperatures ranging from 400 to 800 degrees C. The highest levels of mass loss occurred between 400-500 degrees C and 700-800 degrees C, which were attributed to the organic and carbonate decomposition respectively. The changes in mechanical strength were quantified using a simple mechanical test, which measured the bulk compressive strength of the algae. The mechanical test used may provide a useful evaluation of the compressive properties of similar bone void fillers that are in granular form. The study concluded that soak temperatures in the range of 600 to 700 degrees C provided the optimum physiochemical properties as a precursor to conversion to hydroxyapatite (HA). At these temperatures, a partial phase transition to calcium oxide occurred and the original skeletal morphology of the alga remained intact.

An Investigation into the Optimum Thickness of Titanium Dioxide Thin Films Synthesized by Using Atmospheric Pressure Chemical Vapour Deposition for Use in Photocatalytic Water Oxidation

Twenty eight films of titanium dioxide of varying thickness were synthesised by using atmospheric pressure chemical vapour deposition (CVD) of titanium(IV) chloride and ethyl acetate onto glass and titanium substrates. Fixed reaction conditions at a substrate temperature of 660 degrees C were used for all depositions, with varying deposition times of 5-60 seconds used to control the thickness of the samples. A sacrificial electron acceptor system composed of alkaline sodium persulfate was used to determine the rate at which these films could photo-oxidise water in the presence of 365 nm light. The results of this work showed that the optimum thickness for CVD films on titanium substrates for the purposes of water oxidation was approximate to 200 nm, and that a platinum coating on the reverse of such samples leads to a five-fold increase in the observed rate of water oxidation.

Wetting of compacted clays under laterally restrained conditions: Initial state, overburden pressure and mineralogy

Compacted clay fills are generally placed at the optimum value of water content and, immediately after placement, they are unsaturated. Wetting might subsequently occur due, for example, to rainfall infiltration, which can cause volumetric deformation of the fill (either swell or collapse) with associated loss of shear strength and structural integrity. If swelling takes place under partially restrained deformation, due for example to the presence of a buried rigid structure or a retaining wall, additional stresses will develop in the soil and these can be detrimental to the stability of walling elements and other building assets. Factors such as dry density, overburden pressure, compaction water content and type of clay are known to influence the development of stresses. This paper investigates these factors by means of an advanced stress path testing programme performed on four different clays with different mineralogy, index properties and geological histories. Specimens of kaolin clay, London Clay, Belfast Clay and Ampthill Clay were prepared at different initial states and subjected to ‘controlled’ wetting, whereby the suction was reduced gradually to zero under laterally restrainedconditions (i.e. K0 conditions). The results showed that the magnitude of the increase in horizontal stresses (and therefore the increase of K0) is influenced by the overburden pressure, compaction water content, dry density at the time of compaction and mineralogy.

Comorbidity in severe asthma requiring systemic corticosteroid therapy: cross-sectional data from the Optimum Patient Care Research Database and the British Thoracic Difficult Asthma Registry

Objective: To determine the prevalence of systemic corticosteroid-induced morbidity in severe asthma.
Design: Cross-sectional observational study.Setting The primary care Optimum Patient Care Research Database and the British Thoracic Society Difficult Asthma Registry.
Participants: Optimum Patient Care Research Database (7195 subjects in three age- and gender-matched groups)—severe asthma (Global Initiative for Asthma (GINA) treatment step 5 with four or more prescriptions/year of oral corticosteroids, n=808), mild/moderate asthma (GINA treatment step 2/3, n=3975) and non-asthma controls (n=2412). 770 subjects with severe asthma from the British Thoracic Society Difficult Asthma Registry (442 receiving daily oral corticosteroids to maintain disease control).
Main outcome measures: Prevalence rates of morbidities associated with systemic steroid exposure were evaluated and reported separately for each group.
Results: 748/808 (93%) subjects with severe asthma had one or more condition linked to systemic corticosteroid exposure (mild/moderate asthma 3109/3975 (78%), non-asthma controls 1548/2412 (64%); p<0.001 for severe asthma versus non-asthma controls). Compared with mild/moderate asthma, morbidity rates for severe asthma were significantly higher for conditions associated with systemic steroid exposure (type II diabetes 10% vs 7%, OR=1.46 (95% CI 1.11 to 1.91), p<0.01; osteoporosis 16% vs 4%, OR=5.23, (95% CI 3.97 to 6.89), p<0.001; dyspeptic disorders (including gastric/duodenal ulceration) 65% vs 34%, OR=3.99, (95% CI 3.37 to 4.72), p<0.001; cataracts 9% vs 5%, OR=1.89, (95% CI 1.39 to 2.56), p<0.001). In the British Thoracic Society Difficult Asthma Registry similar prevalence rates were found, although, additionally, high rates of osteopenia (35%) and obstructive sleep apnoea (11%) were identified.

Conclusions: Oral corticosteroid-related adverse events are common in severe asthma. New treatments which reduce exposure to oral corticosteroids may reduce the prevalence of these conditions and this should be considered in cost-effectiveness analyses of these new treatments.

Optimization of pH and Direct Imaging Conditions of Complexed Methylene Blue Sensitized Poly(vinyl chloride) Films

Significant results of our experimental investigations on the dependence of pH on real time transmission characteristics on recording media fabricated by doping PVC with complexed methylene blue are presented. The optimum pH value for faster bleaching was found to be 4×5. In typical applications, the illumination from one side, normal to the surface of this material, initiates a chemical sequence that records the incident light pattern in the polymer. Thus direct imaging can be successfully done on this sample. The recorded letters were very legible with good contrast and no scattering centres. Diffraction efficiency measurements were also carried out on this material.

Optimization of pH and Direct Imaging Conditions of Complexed Methylene Blue Sensitized Poly(vinyl chloride) Films

Significant results of our experimental investigations on the dependence of pH on real time transmission characteristics on recording media fabricated by doping PVC with complexed methylene blue are presented. The optimum pH value for faster bleaching was found to be 4×5. In typical applications, the illumination from one side, normal to the surface of this material, initiates a chemical sequence that records the incident light pattern in the polymer. Thus direct imaging can be successfully done on this sample. The recorded letters were very legible with good contrast and no scattering centres. Diffraction efficiency measurements were also carried out on this material.

Optimization of pH and direct imaging conditions of complexed methylene blue sensitized poly(vinyl chloride) films

Significant results of our experimental investigations on the dependence of pH on real time transmission characteristics on recording media fabricated by doping PVC with complexed methylene blue are presented. The optimum pH value for faster bleaching was found to be 4 . 5. In typical applications, the illumination from one side, normal to the surface of this material, initiates a chemical sequence that records the incident light pattern in the polymer. Thus direct imaging can be successfully done on this sample. The recorded letters were very legible with good contrast and no scattering centres. Diffraction efficiency measurements were also carried out on this material.

Effects of row spacing on productivity and nodulation of two soybean varieties under hot sub-moist tropical conditions in south-western Ethiopia

The objective of this study was to determine the optimum row spacing to improve the productivity of two soybean (Glycine max L.) varieties under the tropical hot sub-moist agroecological conditions of Ethiopia. A two-year split-plot design experiment was conducted to determine the effect of variety (Awasa-95 [early-maturing], Afgat [medium-maturing]) and row spacing (RS: 20, 25, 30, 35, 40, 45, 50, 55, 60 cm) on the productivity, nodulation and weed infestation of soybean. Seed and total dry matter (TDM) yield per ha and per plant, and weed dry biomass per m^2 were significantly affected by RS. Soybean variety had a significant effect on plant density at harvest and some yield components (plant height, number of seeds/pod, and 1000 seed weight). Generally, seed and TDM yield per ha and per plant were high at 40 cm RS, and weed dry biomass per m^2 was higher for RS >= 40 cm than for narrower RS. However, the results did not demonstrate a consistent pattern along the RS gradient. The medium-maturing variety Afgat experienced higher mortality and ended up with lower final plant density at harvest, but higher plant height, number of seeds per pod and 1000 seed weight than the early-maturing variety Awasa-95. The results indicate that 40 cm RS with 5 cm plant spacing within a row can be used for high productivity and low weed infestation of both soybean varieties in the hot sub-moist tropical environment of south-western Ethiopia.

Calibration and sensitivity analysis of a river water quality model under unsteady flow conditions

Water quality models generally require a relatively large number of parameters to define their functional relationships, and since prior information on parameter values is limited, these are commonly defined by fitting the model to observed data. In this paper, the identifiability of water quality parameters and the associated uncertainty in model simulations are investigated. A modification to the water quality model `Quality Simulation Along River Systems' is presented in which an improved flow component is used within the existing water quality model framework. The performance of the model is evaluated in an application to the Bedford Ouse river, UK, using a Monte-Carlo analysis toolbox. The essential framework of the model proved to be sound, and calibration and validation performance was generally good. However some supposedly important water quality parameters associated with algal activity were found to be completely insensitive, and hence non-identifiable, within the model structure, while others (nitrification and sedimentation) had optimum values at or close to zero, indicating that those processes were not detectable from the data set examined. (C) 2003 Elsevier Science B.V. All rights reserved.

Productivity and optimum plant density of pigeonpea in different environments in Tanzania

The objective of the present study was to determine the optimum plant density of four pigeonpea genotypes, representing early, medium and late maturing types, grown in five contrasting environments in Tanzania. ICPL 86005 (early), Kat 50/3 and QP 37 (medium) and Local (late) were grown at four plant densities (40 000-320 000 plants/ha) in irrigated and rainfed conditions at Ilonga and under rainfed conditions at Kibaha, Selian and Ismani. At maturity, total above-ground biomass and seed yield (SY) were measured. The highest yields were obtained in the irrigated experiment at Ilonga, where the medium/late genotypes produced 25 t biomass/ha and 5 center dot 6 t seed/ha. The lowest SY were at Kibaha, 0 58 to 1 center dot 76 t/ha, where a severe drought occurred. In nearly all cases the response to density was linear or asymptotic. The response of ICPL 86005 was significantly different from the other three genotypes. The optimum density for SY varied from 37 000 to 227 000 plants/ha in ICPL 86005, compared with 3000 to 101000 plants/ha in the medium/late genotypes. The highest optimum density was at Selian and Ismani and the lowest at Ilonga and Kibaha, where drought occurred. Optimum densities therefore varied greatly with genotype (duration) and environment, and this variation needs to be considered when planning trials.

Reconstruction of geomagnetic activity and near-Earth interplanetary conditions over the past 167 yr - Part 4: Near-Earth solar wind speed, IMF, and open solar flux

In the concluding paper of this tetralogy, we here use the different geomagnetic activity indices to reconstruct the near-Earth interplanetary magnetic field (IMF) and solar wind flow speed, as well as the open solar flux (OSF) from 1845 to the present day. The differences in how the various indices vary with near-Earth interplanetary parameters, which are here exploited to separate the effects of the IMF and solar wind speed, are shown to be statistically significant at the 93% level or above. Reconstructions are made using four combinations of different indices, compiled using different data and different algorithms, and the results are almost identical for all parameters. The correction to the aa index required is discussed by comparison with the Ap index from a more extensive network of mid-latitude stations. Data from the Helsinki magnetometer station is used to extend the aa index back to 1845 and the results confirmed by comparison with the nearby St Petersburg observatory. The optimum variations, using all available long-term geomagnetic indices, of the near-Earth IMF and solar wind speed, and of the open solar flux, are presented; all with ±2sigma� uncertainties computed using the Monte Carlo technique outlined in the earlier papers. The open solar flux variation derived is shown to be very similar indeed to that obtained using the method of Lockwood et al. (1999).

Holocene Climatic Optimum centennial-scale paleoceanography in the NE Aegean (Mediterranean sea)

Combined micropaleontological and geochemical analyses of the high-sedimentation gravity core M-4G provided new centennial-scale paleoceanographic data for sapropel S1 deposition in the NE Aegean Sea during the Holocene Climatic Optimum. Sapropel layer S1a (10.2–8.0 ka) was deposited in dysoxic to oxic bottom waters characterized by a high abundance of benthic foraminiferal species tolerating surface sediment and/or pore water oxygen depletion (e.g., Chilostomella mediterranensis, Globobulimina affinis), and the presence of Uvigerina mediterranea, which thrives in oxic mesotrophic-eutrophic environments. Preservation of organic matter (OM) is inferred based on high organic carbon as well as loliolide and isololiolide contents, while the biomarker record and the abundances of eutrophic planktonic foraminifera document enhanced productivity. High inputs of terrigenous OM are attributed to north Aegean borderland riverine inputs. Both alkenone-based sea surface temperatures (SSTs) and δO18G. bulloides records indicate cooling at 8.2 ka (S1a) and ~7.8 ka (S1 interruption). Sapropelic layer S1b (7.7–6.4 ka) is characterized by rather oxic conditions; abundances of foraminiferal species tolerant to oxygen depletion are very low compared with the U. mediterranea rise. Strongly fluctuating SSTs demonstrate repeated cooling and associated dense water formation, with a major event at 7.4 ka followed by cold spells at 7.0, 6.8, and 6.5 ka. The prominent rise of the carbon preference index within the S1b layer indicates the delivery of less degraded terrestrial OM. The increase of algal biomarkers, labile OM-feeding foraminifera and eutrophic planktonic species pinpoints an enhanced in situ marine productivity, promoted by more efficient vertical convection due to repeated cold events. The associated contributions of labile marine OM along with fresher terrestrial OM inputs after ~7.7 ka imply sources alternative/additional to the north Aegean riverine borderland sources for the influx of organic matter in the south Limnos Basin, plausibly related to the inflow of highly productive Marmara/Black Sea waters.

Determining the Optimum Processing Parameters of Glass-like Carbon Using Weibull Analysis of its Fracture Behaviour

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)