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Pollution in developing countries is generally much worse than in developed countries, and is caused by the widespread use of poor quality machines both industrial and in motor vehicles. Obviously, motorised vehicles are a major source of today's pollution. Motor vehicle emissions, whether gases, particulate matter or noise, can all be dangerous. Particulate matter, especially very fine particulates, is the major concern of this thesis, which considers their capacity for penetrating deep into the lungs and developing slowly to cause noticeable illnesses. Low-income people who live within the city centre are the most exposed to traffic pollution whether on the move or indoors. Low cost housing, whether self built or provided by government or private sectors, often exposes occupants to both lack of thermal comfort and pollutant intrusion from adjacent street traffic. Houses in warm-humid regions depend on large openings and through ventilation for thermal comfort. Openings allow air pollution and noise to penetrate these houses easily, thereby affecting the health, comfort and well-being of residents. Closing all openings and changing from natural ventilation to air conditioning is not however a practical solution for low cost housing. This study explores the effect of boundary fences, vegetation, and detailed opening design in reducing the penetration of airborne particulates and noise into the living spaces of typical low-cost urban houses. The experiments carried out for this study include computational simulation, manual calculation and field experiments. The research indicated that there are feasible and practical solutions to the reduction of fine particulate matter and street noise in such housing by using solid and massive barriers combined with vegetation and a specific window type. Solid and massive barriers were constructed to slow the progress of the pollutants by reduction of wind speeds on approaching obstructions. If the wind slows down enough, this effectively 'holds' the pollutant in place. In this case, the deposition surface was provided by vegetation with dense foliage. The surface of the vegetation was predicted to deposit particulate matter effectively, which would then be washed away naturally by rains. Some types of leaves were studied to find the relationship between the physical characteristics of leaf surfaces and their ability to deposit particulate matter. Before entering the living spaces, the particulate matter then encounters further obstruction by jalousie windows thus reducing its concentration. The solid and massive fence also created an acoustic shadow and noise was then further reduced by the jalousie windows. The resulting indoor noise level was found to be closer to the proposed Indonesian standards of 45 dBA.

Um problema importante na heveicultura é o seu longo período de imaturidade. A explotação precoce pode reduzi-lo, porém, o seu efeito a longo prazo não é bem conhecido. O objetivo do presente estudo foi de investigar a factibilidade da explotação precoce da seringueira e avaliar diferentes sistemas de explotação. Foram explotadas árvores com perímetro do tronco entre 36 e 41 cm e sua produção e crescimento comparados com daqueles em plantas sem explotação. Quando todas as plantas do experimento atingiram perímetro de tronco de aproximadamente 45 cm, foram explotadas pelo sistema convencional 1/2S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y. O delineamento experimental adotado foi inteiramente casualizado, com uma planta por parcela. O experimento 1 foi conduzido em Nhandeara-SP, com 25 repectições por tratamento, durante 17 meses de explotação precoce e três anos de explotação convencional. Os sistemas de explotação precoce foram: tratamento 1, 1/4S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, sangria matinal; tratamento 2, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, sangria matinal; tratamento 3, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, sangria vespertina; tratamento 4 6PI 70x1 d/2 6d/7 10m/y ET 5% Ga 1/1 10/y, sangria matinal. No experimento 2, conduzido em Rio Claro-SP, com 20 repetições, durante um ano de explotação precoce e um ano de convencional, repetiu-se o tratamento 1. As produções obtidas no experimento 1, na fase de explotação precoce, foram similares entre os tratamentos 1, 2 e 4, com aproximadamente 1,2 kg de borracha por árvore, porém significativamente menor no tratamento 3, com aproximadamente 0,9 kg por árvore. Durante o mesmo período as produções em g por árvore por sangria foram maiores no tratamento 2 (22,6 g) e 3 (18,82 g), do que no tratamento 1 (14,41 g) e 4 (8,97 g), diminuindo com o aumento da frequencia de sangria. A produção acumulada, nos 4,5 anos de explotação precoce e convencional, foi maior no tratamento 1 (7,92 kg) do que no controle (5,95 kg). Os outros tratamentos de explotação precoce tiveram um resultado intermediário. O incremento do perímetro do tronco durante a fase precoce foi significativamente menor nos tratamentos 3 e 4, em comparação com os outros tratamentos e o controle. Entretanto, durante a fase convencional, o incremento de perímetro de tronco de todos os tratamentos foi comparável ao do controle. O índice de colheita teve valores similares em todos os sistemas de explotação precoce, porém o tratamento 1 resultou em um valor para o \"fator de perda de biomassa\" (k) muito menor do que o dos outros tratamentos (entre 0,109 e 0,1794). No experimento 2, a produção obtida durante a explotação precoce foi de aproximadamente 0,85 kg por árvore. Durante o mesmo período, a produção por árvore por corte foi de 13,31 g e comparável com aquela do experimento 1. As produções obtidas durante o primeiro ano de explotação convencional no tratamento 1 (1,52 kg) e no controle (1,15 kg) foram bastante similares àquelas dos mesmos tratamentos no experimento 1, respectivamente, 1,53 kg e 1,08 kg. Durante as fases precoce e convencional, o incremento de perímetro de tronco foi igual no tratamento 1 e no controle. O coeficiente de colheita no tratamento 1 foi similar àquele observado no experimento 1, enquanto que o \"fator de perda de biomassa\" (k) foi maior. As principais conclusões foram: 1. O sistema de explotação precoce do tratamento 1 possibilita uma produção prévia de borracha, a níveis satisfatórios, mantendo um crescimento adequado das plantas. Pela sua capacidade, em ambientes diferentes, de produção precoce sem prejuízo permanente para as plantas, pode ser recomendado para uso em seringais comerciais. 2. Os sistemas de explotação precoce dos tratamentos 2, 3 e 4 possibilitam uma produção prévia de borracha, a níveis satisfatórios, porém reduzem o crescimento das plantas. / One major problem of rubber cultivation is the long immature period. Premature exploitation may reduce it, however, its long term effects are not fully understood. The aim of this study was to investigate the feasibility of premature exploitation of rubber, and evaluate different exploitation systems. Trees of about 36 to 41 cm of girth were tapped with premature exploitation systems, and their yield and growth were compared to untapped control trees. When all experimental trees reached approximately 45 cm of girth, they were converted to conventional tapping 1/2S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y. The experiments were arranged in a complete randomized design, with one tree per plot. Experiment 1 was carried out in Nhandeara-SP, with 25 replications for each treatment, during 17 months of premature and three years of conventional exploitation. The premature systems included: treatment 1, 1/4S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, morning tapping; treatment 2, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, morning tapping; treatment 3, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, afternoon tapping; treatment 4 6PI 70x1 d/2 6d/7 10m/y ET 5% Ga 1/1 10/y, morning tapping. In experiment 2, carried out in Rio Claro-SP, with 20 replications, during one year of premature and one year of conventional tapping, treatment 1 was repeated. In experiment 1, yield obtained during premature exploitation, was similar between treatment 1, 2 and 4, with about 1.2 kg of rubber per tree, but significantly lower in treatment 3 with approximately 0.9 kg per tree. During the same period, yield in terms of g per tree per tapping, was higher in treatment 2 (22.6 g) and 3 (18.82 g), than in treatment 1 (14.41 g) and 4 (8.97 g), declining with increased tapping frequency. Cumulative yield obtained over 4,5 years of premature and conventional exploitation was higher in treatment 1 (7.92 kg) than in the control (5.95 kg). The other treatments with premature exploitation had an intermediate result. The girth increment during premature phase was significantly lower in treatment 3 and 4, compared to other treatments and control. However, during the conventional phase, girth increment of all treatments was comparable to the control. Harvest index values were similar in all premature exploitation systems, but treatment 1 resulted in a much lower value (0.019) for the \'factor of biomass loss\' (k) than the other treatments (0.109 to 0.1794). In experiment 2, yield obtained during premature exploitation in treatment 1 was approximately 0.85 kg per tree. During the same period, yield per tree per tapping was 13.31 g thus comparable to that in experiment 1. Yields obtained during the first year of conventional exploitation in treatment 1 (1.52 kg) and in control (1.15 kg) were very similar to the yields in those treatments in experiment 1, respectively 1.53 kg and 1.08 kg. During premature and conventional phases girth increment was equal in treatment 1 and control. Harvest index in treatment 1 was similar to that in experiment 1, whereas the \'factor of biomass loss\' (k) was higher (0.098). The main conclusions were: 1. The premature exploitation system of treatment 1 gives a reasonable yield and maintains appropriate tree growth. Because its capacity, in different environments, to antecipate yield without permanent damage to the trees, this system may be recommended for use in commercial rubber plantations. 2. The premature exploitation systems of treatments 2, 3 and 4 give reasonable yield, but cause growth retardation.

by Man-Wai Woo. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 77-81). / Abstracts in English and Chinese. / ABSTRACT --- p.i / ACKNOWLEDGMENT --- p.iii / CONTENTS --- p.iv / LIST OF FIGURES --- p.vi / LIST OF TABLES --- p.ix / ABBREVIATIONS --- p.x / Chapter 1. --- INTRODUCTION / Chapter 1.1 --- General Background of Phthalocyanines --- p.1 / Chapter 1.2 --- Previous Examples of Phthalocyanine-containing Polymers --- p.5 / Chapter 1.2.1 --- Poly(phthalocyanines) Linked Via Peripheral Substituents --- p.5 / Chapter 1.2.2 --- Poly(phthalocyanines) Linked Via Axial Ligation --- p.7 / Chapter 1.2.3 --- Poly(phthalocyanines) Attached Laterally to a Polymer Backbone --- p.11 / Chapter 1.3 --- Ring Opening Metathesis Polymerization (ROMP) --- p.15 / Chapter 1.4 --- ROMP of Norbornene Substituted Porphyrazine --- p.18 / Chapter 2. --- RESULTS AND DISCUSSION / Chapter 2.1 --- Phthalocyanines Substituted with Four Poly(norbornene)s --- p.20 / Chapter 2.1.1 --- Preparation of Tetra(norbornene) Phthalocyanines --- p.20 / Chapter 2.1.2 --- Polymerization of Tetra(norbornene) Phthalocyanines --- p.30 / Chapter 2.1.3 --- Characterization of Polymers --- p.39 / Chapter 2.1.4 --- Photophysical Properties of the Polymers --- p.43 / Chapter 2.2 --- Phthalocyanines Substituted with One Poly(norbornene) --- p.49 / Chapter 2.2.1 --- Preparation and Polymerization of Mono(norbornene) Phthalocyanines --- p.49 / Chapter 2.2.2 --- Characterization of the Polymers 41 - 44 --- p.56 / Chapter 2.2.3 --- Fluorescence Quenching of 40 Polymers 41 -44 --- p.61 / Chapter 2.2.4 --- Preparation of Water-soluble Poly(7-oxanorbornene) --- p.63 / Chapter 2.3 --- Conclusion --- p.65 / Chapter 3 --- EXPERIMENTAL SECTION --- p.66 / Chapter 3.1 --- General Methods --- p.66 / Chapter 3.2 --- Photophysical Measurements --- p.67 / Chapter 3.3 --- Synthesis of Phthalocyanines with Four Poly(norbornene) Substituents --- p.68 / Chapter 3.4 --- Synthesis of Phthalocyanines with One Poly(norbornene) Substituent --- p.74 / Chapter 4. --- REFERENCES --- p.77

No description available.

Um problema importante na heveicultura é o seu longo período de imaturidade. A explotação precoce pode reduzi-lo, porém, o seu efeito a longo prazo não é bem conhecido. O objetivo do presente estudo foi de investigar a factibilidade da explotação precoce da seringueira e avaliar diferentes sistemas de explotação. Foram explotadas árvores com perímetro do tronco entre 36 e 41 cm e sua produção e crescimento comparados com daqueles em plantas sem explotação. Quando todas as plantas do experimento atingiram perímetro de tronco de aproximadamente 45 cm, foram explotadas pelo sistema convencional 1/2S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y. O delineamento experimental adotado foi inteiramente casualizado, com uma planta por parcela. O experimento 1 foi conduzido em Nhandeara-SP, com 25 repectições por tratamento, durante 17 meses de explotação precoce e três anos de explotação convencional. Os sistemas de explotação precoce foram: tratamento 1, 1/4S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, sangria matinal; tratamento 2, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, sangria matinal; tratamento 3, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, sangria vespertina; tratamento 4 6PI 70x1 d/2 6d/7 10m/y ET 5% Ga 1/1 10/y, sangria matinal. No experimento 2, conduzido em Rio Claro-SP, com 20 repetições, durante um ano de explotação precoce e um ano de convencional, repetiu-se o tratamento 1. As produções obtidas no experimento 1, na fase de explotação precoce, foram similares entre os tratamentos 1, 2 e 4, com aproximadamente 1,2 kg de borracha por árvore, porém significativamente menor no tratamento 3, com aproximadamente 0,9 kg por árvore. Durante o mesmo período as produções em g por árvore por sangria foram maiores no tratamento 2 (22,6 g) e 3 (18,82 g), do que no tratamento 1 (14,41 g) e 4 (8,97 g), diminuindo com o aumento da frequencia de sangria. A produção acumulada, nos 4,5 anos de explotação precoce e convencional, foi maior no tratamento 1 (7,92 kg) do que no controle (5,95 kg). Os outros tratamentos de explotação precoce tiveram um resultado intermediário. O incremento do perímetro do tronco durante a fase precoce foi significativamente menor nos tratamentos 3 e 4, em comparação com os outros tratamentos e o controle. Entretanto, durante a fase convencional, o incremento de perímetro de tronco de todos os tratamentos foi comparável ao do controle. O índice de colheita teve valores similares em todos os sistemas de explotação precoce, porém o tratamento 1 resultou em um valor para o \"fator de perda de biomassa\" (k) muito menor do que o dos outros tratamentos (entre 0,109 e 0,1794). No experimento 2, a produção obtida durante a explotação precoce foi de aproximadamente 0,85 kg por árvore. Durante o mesmo período, a produção por árvore por corte foi de 13,31 g e comparável com aquela do experimento 1. As produções obtidas durante o primeiro ano de explotação convencional no tratamento 1 (1,52 kg) e no controle (1,15 kg) foram bastante similares àquelas dos mesmos tratamentos no experimento 1, respectivamente, 1,53 kg e 1,08 kg. Durante as fases precoce e convencional, o incremento de perímetro de tronco foi igual no tratamento 1 e no controle. O coeficiente de colheita no tratamento 1 foi similar àquele observado no experimento 1, enquanto que o \"fator de perda de biomassa\" (k) foi maior. As principais conclusões foram: 1. O sistema de explotação precoce do tratamento 1 possibilita uma produção prévia de borracha, a níveis satisfatórios, mantendo um crescimento adequado das plantas. Pela sua capacidade, em ambientes diferentes, de produção precoce sem prejuízo permanente para as plantas, pode ser recomendado para uso em seringais comerciais. 2. Os sistemas de explotação precoce dos tratamentos 2, 3 e 4 possibilitam uma produção prévia de borracha, a níveis satisfatórios, porém reduzem o crescimento das plantas. / One major problem of rubber cultivation is the long immature period. Premature exploitation may reduce it, however, its long term effects are not fully understood. The aim of this study was to investigate the feasibility of premature exploitation of rubber, and evaluate different exploitation systems. Trees of about 36 to 41 cm of girth were tapped with premature exploitation systems, and their yield and growth were compared to untapped control trees. When all experimental trees reached approximately 45 cm of girth, they were converted to conventional tapping 1/2S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y. The experiments were arranged in a complete randomized design, with one tree per plot. Experiment 1 was carried out in Nhandeara-SP, with 25 replications for each treatment, during 17 months of premature and three years of conventional exploitation. The premature systems included: treatment 1, 1/4S d/3 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, morning tapping; treatment 2, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, morning tapping; treatment 3, 1/2S d/7 6d/7 10m/y ET 2.5% La/Pa 1/1 5/y, afternoon tapping; treatment 4 6PI 70x1 d/2 6d/7 10m/y ET 5% Ga 1/1 10/y, morning tapping. In experiment 2, carried out in Rio Claro-SP, with 20 replications, during one year of premature and one year of conventional tapping, treatment 1 was repeated. In experiment 1, yield obtained during premature exploitation, was similar between treatment 1, 2 and 4, with about 1.2 kg of rubber per tree, but significantly lower in treatment 3 with approximately 0.9 kg per tree. During the same period, yield in terms of g per tree per tapping, was higher in treatment 2 (22.6 g) and 3 (18.82 g), than in treatment 1 (14.41 g) and 4 (8.97 g), declining with increased tapping frequency. Cumulative yield obtained over 4,5 years of premature and conventional exploitation was higher in treatment 1 (7.92 kg) than in the control (5.95 kg). The other treatments with premature exploitation had an intermediate result. The girth increment during premature phase was significantly lower in treatment 3 and 4, compared to other treatments and control. However, during the conventional phase, girth increment of all treatments was comparable to the control. Harvest index values were similar in all premature exploitation systems, but treatment 1 resulted in a much lower value (0.019) for the \'factor of biomass loss\' (k) than the other treatments (0.109 to 0.1794). In experiment 2, yield obtained during premature exploitation in treatment 1 was approximately 0.85 kg per tree. During the same period, yield per tree per tapping was 13.31 g thus comparable to that in experiment 1. Yields obtained during the first year of conventional exploitation in treatment 1 (1.52 kg) and in control (1.15 kg) were very similar to the yields in those treatments in experiment 1, respectively 1.53 kg and 1.08 kg. During premature and conventional phases girth increment was equal in treatment 1 and control. Harvest index in treatment 1 was similar to that in experiment 1, whereas the \'factor of biomass loss\' (k) was higher (0.098). The main conclusions were: 1. The premature exploitation system of treatment 1 gives a reasonable yield and maintains appropriate tree growth. Because its capacity, in different environments, to antecipate yield without permanent damage to the trees, this system may be recommended for use in commercial rubber plantations. 2. The premature exploitation systems of treatments 2, 3 and 4 give reasonable yield, but cause growth retardation.

Synthesis of novel amphiphilic copolymers based on sugar moieties: development of new architectures and biomedical applications As early as in the 50’s, amphiphilic copolymers started to attract much interest in the frame of polymer science thanks to their self-assemblies as organized nano-structures in a selective solvent. The resulting micelles or vesicles have emerged as potentially useful materials in the biomedical field such as drug delivery systems when matching the specific conditions of size, coating nature and functionalization,… Moreover, active cell-targeting increases the therapeutic effect by selectively delivering the drug to the required cells. Accordingly, carbohydrates have drawn much attention due to the cell recognition processes they can mediate. Carbohydrates are thus incorporated in polymer backbones to mimic the naturally occurring substrate for the adapted cell receptors. The originality of this thesis is based on the use of sugar moieties as potential multi-hydroxylated initiators for the polymerization of various lactones. This leads to well-defined amphiphilic polymer architectures along with the development of a more facile route for the incorporation of carbohydrates in polymer chains to promote active cell-targeting of the as-obtained nano-structures. The first part of the thesis aims at describing the synthesis of novel amphiphilic brush-like polymers via two pathways. A first approach relies upon the synthesis of polyester arms initiated from the alcohol groups of pending sugars distributed along a preformed hydrophilic polymethacrylate backbone obtained by controlled radical polymerization (via ATRP). Various metal-based and organic catalysts/activators have been studied to lead to the desired architectures using this “grafting from” technique. In another synthetic strategy, the lactone polymerization using a carbohydrate initiator has been carried out, followed by end-chain derivatization reactions yielding brush-like copolymers via a “grafting through” technique. Slight modifications of the end-chain functionalities have also afforded the possibility to synthesize amphiphilic mikto-arm copolymers which self-assemble in aqueous medium in micelles characterized by interesting size features affording promising applications as new drug delivery systems. On the other hand this thesis also focuses on the use of carbohydrate moieties in amphiphilic diblock copolymers such as poly(ε-caprolactone)-b-poly(methacrylate-graft-poly(ethylene oxide)-co-6-O-methacryloyl-D-galactopyranose) or poly(ε-caprolactone)-b-poly(methacrylate-graft-poly(ethylene oxide)-co-1-O-methacryloyl-D-mannofuranose), using the combination of lactone ring-opening polymerization with ATRP of the respective functionalized comonomers, followed by selective post-polymerization sugar deprotection. Next to these copolymers based on polylactones and polymethacrylates, fully degradable amphiphilic block copolymers composed of a polycarbonate backbone have been originally designed. To that end, a multi-step procedure involving the synthesis of sugar-substituted cyclic carbonates, block copolymerization reactions and ultimate selective sugar deprotection, has been investigated. The self-organization of the resulting copolymers, e.g., poly(trimethylene carbonate)-b-poly(3-O-(5’-methyl,5’-carboxy-1’,3’-dioxan-2’-one)-D-glucopyranose), has been studied in aqueous medium. Interestingly, the so-formed polymeric micelles proved to display remarkable living cell-targeting properties. Fabian Suriano

The aim of this research was to prepare high performance and fully biodegradable polymer nanocomposites. The most representative polymers classified as biodegradable are poly(!-caprolactone) (PCL) (issued from petrochemistry) and polylactide (PLA) (issued from renewable bio-resources). Biodegradable nanoparticles purposely extracted from biomass were selected, namely Cellulose NanoWhiskers (CNW) and Starch NanoCrystals (SNC). CNW are rod-like nanoparticles with 2 nanometric dimensions while SNC consists in nanosheets, thus with 1 nanometric dimension. A 3 nanometric-dimension particle often considered as “silica- type nanocage” was selected to complete this study, namely Polyhedral Oligomeric Silsesquioxane (POSS). The addition of such nanoparticles was expected to enhance several properties of the filled polymer matrix, especially thermo-mechanical performances and extent of crystallinity. In this field, the quality of the nanoparticle dispersion throughout the matrix is an essential parameter to produce nanocomposite materials with largely improved properties. One of the most cited techniques to overcome nanofiller aggregation and even agglomeration relies upon the creation of strong chemical bonds between the nanoparticle and the polymer matrix, leading to the preparation of so-called nanohybrids. For that purpose, the surface of the nanoparticles was first modified by chemical grafting and polymerization reactions. The ring-opening polymerization (ROP) of e-caprolactone and L,L-lactide catalyzed by tin(II) 2- ethylhexanoate (tin octoate, Sn(Oct)2) was initiated from functional groups available on the nanoparticle surface. The grafting efficiency was demonstrated for the three investigated nanofiller/polyester systems. Different characterization techniques were approached depending on the nanofiller nature. In a second step, the so-formed nanohybrids were used as “masterbatches” and dispersed in their corresponding commercial polyester matrices, i.e. PCL and PLA, by melt-compounding using a mini-lab twin screw extruder. The nanocomposite materials were fully characterized, correlating morphological observations with thermal, mechanical and rheological properties. To highlight the beneficial effect of the surface covalent grafting, simple melt-blends, i.e., containing unmodified nanofillers and polyester matrices (PCL or PLA) were prepared. The level of property improvement was most of the time directly related to the degree of nanofiller dispersion, and proved systematically better in case of masterbatch-based materials. Keeping in mind the effect of the nanoparticle geometry, as well as its mechanical modulus, crystallinity or extent of dispersion within the polyester matrix, the rod-like 2D-nanofiller, namely cellulose nanowhiskers extracted from ramie, appeared as the most efficient candidate for polyester reinforcement. The incorporation of PCL chains surface-grafted onto CNW contributed to substantially increasing the overall thermo- mechanical properties, most likely due to the formation of a strong physical chain network between surface- grafted chains and chains composing the matrix. Additionally, CNW-based nanohybrids revealed their potential as both nucleating sites dramatically increasing the crystallization rate of PLA matrix and compatibilizing PCL/PLA immiscible blends.

Current Canadian Building Codes mandate prescribed design requirements for the protection of vertical floor openings by means of draft stops and closely spaced sprinklers. In the event that a design cannot meet the requirements, they also allow for the use of an alternative solution as long as the alternative solution can be proven to provide at least an equivalent level of performance as that prescribed in the Code. A commonly suggested alternative to the use of draft stops includes the construction of a recession at the perimeter of the floor opening; however, the performance of this design relative to that of an equivalent draft stop design has not been thoroughly evaluated. In this research, the available methods for the evaluation of ceiling recession designs are reviewed in order to identify appropriate tools with which to conduct such an analysis. While both analytical analysis and experimental testing could be used, experimental testing of the design is not considered here as this option would not commonly be pursued by design teams due to restrictions on both project budget and design timelines. From the available analytical tools, the fire modeling software Fire Dynamics Simulator (FDS) is selected for evaluation of the ceiling recession design due primarily to the ability of FDS to address complex geometries with appropriate spatial resolution to investigate details of flow and thermal profiles at the ceiling level in a larger compartment. Previous FDS studies are reviewed and an independent validation study is conducted in order to develop an analysis methodology which is appropriate for the evaluation of ceiling recession designs. A case study evaluation is conducted consisting of two dimensionally distinct ceiling recession configurations in the same compartment and two separate source fire heat release rates (HRR). Results are analyzed to evaluate the selected analysis methodology with respect to the characteristics of the simulated flow, and thermal detector response. Results show that the presence of an obstruction to the ceiling jet flow significantly improves thermal detector response where the source fire HRR is low. At higher source fire HRRs, the difference in activation time is found to be minimal amongst configurations of ceiling recession considered in the study. Predictions of thermal detector response time for a selected ceiling recession design are compared to predictions made for code-prescribed draft stop configuration as would be necessary for an alternative solution evaluation. Results indicate that ceiling recession designs provide a reduced level of performance at both low and high source fire HRRs when the thermal detector is placed at the recession ceiling level. In contrast, when the thermal detectors are located at distances greater than 80 mm below the upper ceiling, a design which is permitted by the Code, the performance of the ceiling recession appears better than that of the prescribed draft stop design. Results from the model for detectors placed at distances from the ceiling exceeding 40 mm, however, require further confirmation through experimental testing or additional modeling.

Aluminum complexes, [O3PMe]AlR(R = OtBu, OPh), containing tris-(3,5-di-tert-butyl-2-hydroxy-phenyl)phosphine ([O3P]H3) which is a novel tridentate ligand have been synthesized and characterized by NMR, X-ray diffraction and elemental analysis. Theses complexes were used as catalysts for ring-opening polymerization of £`-caprolactone. We suggested that the stereo effect of catalysts is the main factor in the ring-opening polymerization and compared the mechanism with DFT. In additional, we studied the electronic states and electronic chemistry of [O3PMe]AlR by DFT, UV and PLE. The novel ligand, bis(3,5-tert-butyl-2-phenoxy) tert-butylphosphine ([tBuOPO]H2), reacted with alkali metals such as n-BuLi, NaH and KH to form a series metal complexes, [tBuOPO]M2(Solvent)x (M = Li, Na, K). These metal complexes are all dimeric molecules characterized by X-ray diffraction, NMR and elemental analysis. Moreover, we reacted {[tBuOPO]Li2(DME)}2 with metal complexes of group 4, TiCl3 and MCl4(THF)2 (M = Ti, Zr, Hf), and we received [tBuOPO]2M and [tBuOPO]MCl2(THF) (M = Ti, Zr, Hf). We also synthesized alkoxide complexes of the series metal complexes and studied the catalytic reactivity for ring-opening polymerizations. Furthermore, tantalum complexes, [tBuOPO]2TaX (X = F, Cl) and [tBuOPO]TaCl3, have been synthesized and characterized. Especially synthesizing [tBuOPO]TaCl3 should be carefully controlled by lowering the concentration of TaCl5.