Decreasing the carbon footprint through use of renewable materials has environmental and societal impact. Foams are a valuable constituent in buildings by themselves or as a core in sandwich composites. Kenaf is a Southeast USA plant that provides renewable filler. The core of the kenaf is porous with a cell size in a 5-10 micrometer range. The use of kenaf core in foams represents a novel multiscalar cellular structural composite. Rigid polyurethane foams were made using free foaming expansion with kenaf core as filler with loadings of 5, 10 and 15 %. Free foaming was found to negatively affect the mechanical properties. An innovative process was developed to introduce a constraint to expansion during foaming. Two expansion ratios were examined: 40 and 60 % (decreasing expansion ratio). MicroCT and SEM analysis showed a varying structure of open and closed cell pores. The mechanical, thermal insulation, acoustic properties were measured. Pure PU foam showed improved cell size uniformity. Introducing kenaf core resulted in decreasing the PU performance in the free expansion case. This was reversed by introducing constraints. To understand the combined impact of having a mixed close cell and open cell architecture, finite element modeling was done using ANSYS. Models were created with varying percentages of open, closed, and bulk cells to encompass entire range of foam porosities. Net zero energy building information modelling was conducted using EnergyPlus was conducted using natural fiber composite skins. Environmental impacts for instance global warming potential, acidification, eutrophication, fossil fuel consumption, ozone depletion, and smog potential of the materials used in construction was studied using life cycle assessment. The results showed improvement on energy consumption and carbon footprint.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19234号 / 工博第4069号 / 新制||工||1628(附属図書館) / 32233 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 渡辺 宏, 教授 古賀 毅, 教授 金谷 利治 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Marine biofouling has troubled mankind, both environmentally and economically, since they set sail, resulting in many undesired consequences such as increased drag, reduced maneuverability, increased fuel consumption and greenhouse gas emissions, and heightened maintenance costs. This problem is highly complex as it involves more than 4000 marine organisms with varying modes of adhesion and surface preferences as well as many aquatic environments. The common state-of-the-art approaches to contend with marine biofouling on the submerged surfaces of ships in seawater has antifouling (AF) and fouling-release (FR) surfaces. As AF coating systems utilize biocides which are often toxic to the environment to prevent settlement of biofoulants, the endeavors have been shifted towards non-toxic FR marine system. Many FR systems take advantage of low surface energy and modulus polydimethylsiloxane (PDMS) on their surface, while the recent attempts explored the simultaneous effect of PDMS and hydrophilic moieties (i.e. polyethylene glycol (PEG) or zwitterionic polymers) on an FR surface, known as amphiphilic surfaces. Thus, the work in this dissertation focused on attaining amphiphilic surfaces with desirable FR performance. The studies in this dissertation were investigated to deliver two goals: 1) Enhancing the (FR) fouling-release performance of previously developed coating systems; 2) Introducing novel fouling-release marine coatings with set criteria. To address the former, a series of amphiphilic additives containing PDMS and hydrophilic polymers (zwitterionic-based or PEG) were prepared in chapters two-five. These additives were incorporated in several previously developed FR coating systems in order to modify their surfaces and enhance their FR performance. To address the latter, two amphiphilic marine coating systems were explored for accessing durable, non-toxic, and effective FR surfaces using epoxy-amine crosslinking chemistry. Overall, the studies in this dissertation not only demonstrated viable FR surfaces with desirable performance against several representative marine organisms such as N. incerta, U. linza, C. lytica, barnacles, and mussels but also contributed a deeper understanding about the effect of amphiphilicity concentration/balance on surface and FR properties.

The purpose of this research was to identify the types of surface treatments available for use on concrete bridge decks and to determine which materials are most capable of providing long-term protection from contamination by chloride ions. The products addressed in this report primarily include urethanes, silicon-based sealers, and epoxies. An extensive literature review was conducted to document common overlay distresses, performance histories, and properties of specific surface treatment products currently available in the industry. In addition, three reports summarizing in-house experiments performed by the Utah Department of Transportation between 1995 and 2003 regarding various types of surface treatments were reviewed as part of this research. Finally, a nationwide questionnaire survey was conducted to investigate the state-of-the-practice with regard to surface treatment applications on bridge decks by state departments of transportation throughout the United States. Of the three types of materials addressed in this research, epoxy-based products have the greatest ability to protect concrete and remain uncracked with an acceptable level of skid resistance. Silicon-based products do not crack because they seep into the pores of the concrete, but they do not protect the concrete from the wearing effects of traffic or improve skid resistance. Published field studies indicate that urethane surface treatments do not resist the effects of traffic as well as epoxy-based materials, nor do they offer a substantial decrease in expense or health risk when compared to epoxy-based products. The results of the nationwide questionnaire clearly indicate that bridge deck surface treatments are valuable as both chloride barriers and skid-resistant wearing courses. No standard practice appears to exist with regard to timing of surface treatments, however. Some states arbitrarily apply surface treatments at 10 to 12 years after construction, other states wait until cracking has become fairly considerable before action is taken, and still other states apply surface treatments when the chloride content of the concrete reaches a certain level. Because concrete decks with significant cracking are not ideal substrates for polymer applications, surface treatments should be applied as preventive measures early in the service lives of bridge decks to effectively prevent chloride concentrations from reaching critical levels. This research suggests that epoxy-based surface treatments should be specified for concrete bridge decks when both a chloride barrier and improved skid resistance are desired. If a chloride barrier is all that is needed or desired, a silane surface treatment should be considered; silane treatments are less expensive and easier to apply than epoxy treatments. When a large amount of epoxy is to be mixed, automatic proportioning equipment that can precisely monitor and control the ratios of components should be employed.

No description available.

Phenol-formaldehyde (PF) resole and polymeric diphenylmethane diisocyanate (PMDI) are two commonly used exterior thermosetting adhesives in the wood-based composites industry. There is an interest in combining these two adhesives in order to benefit from their positive attributes while also neutralizing some of the negative ones. Although this novel adhesive system has been reportedly utilized in some limited cases, a fundamental understanding is lacking. This research serves this purpose by investigating some of the important aspects of this novel adhesive system. The adhesive rheological and viscometric properties were investigated with an advanced rheometer. The resole/PMDI blends exhibited non-Newtonian flow behavior. The blend viscosity and stability were dependent on the blend ratio, mixing rate and time. The adhesive penetration into wood was found to be dependent on the blend ratio and correlated with the blend viscosity. By using dynamic mechanical analysis, the blend cure speed was found to increase with the PMDI content. Mode I fracture testing of resole/PMDI hybrid adhesive bonded wood specimens indicated the dependence of bondline fracture energy on the blend ratio. The 75/25 PF/PMDI blend exhibited a high fracture energy with a fast cure speed and processable viscosity. Exposure to water-boil weathering severely deteriorated the fracture energies of the hybrid adhesive bondlines. More detailed chemistry and morphological studies were performed with cross-polarization nuclear magnetic resonance and 13C, 15N-doubly labeled PMDI. A spectral decomposition method was used to obtain information regarding chemical species concentration and relaxation behavior of the contributing components within the major nitrogen resonance. Different urethane concentrations were present in the cured blend bondlines. Water-boil weathering and thermal treatment at elevated temperatures (e.g. > 200°C) caused reduced urethane concentrations in the bondline. Solid-state relaxation parameters revealed a heterogeneous structure in the non-weathered blends. Water boil weathering caused a more uniform relaxation behavior in the blend bondline. By conducting this research, more fundamental information regarding the PF/PMDI hybrid adhesives will become available. This information will aid in the evaluation of, and improve the potential use of PF/PMDI hybrid adhesives for wood-based composites. / Ph. D.

INTRODUÇÃO. Estudos epidemiológicos têm demonstrado que a exposição à poluição atmosférica está associada ao aumento de doenças cardiorrespiratórias. Trabalhos experimentais anteriores, utilizaram uretana para induzir a formação de nódulos pulmonares em camundongos e expor estes animais à poluição de \"mundo real\". Ou seja, os animais foram expostos a gases e partículas da mesma forma com que a população está exposta na cidade de São Paulo. Evidenciou-se então, o papel promotor e dose dependente da atmosfera poluída na progressão dos tumores de pulmão. Sabe-se que substâncias carcinogênicas como hidrocarbonetos policíclicos aromáticos (HPA), metais, ácidos graxos e aldeídos, estão presentes na fração particulada respirável da poluição (material particulado fino - MP 2,5), e a exposição prolongada a este último vem sendo considerada um risco para o desenvolvimento do câncer de pulmão. O objetivo deste estudo é verificar se a exposição crônica ao MP2,5 concentrado, a partir do ar ambiente da cidade de São Paulo, tem potencial carcinogênico. MÉTODOS. Foram utilizados 60 camundongos machos suíços (30g); e 60 AJ (20g), com quatro a seis semanas de vida. Os camundongos suíços foram pré-tratados com um carcinógeno completo, o ácido carbâmico (uretana-U), enquanto que os AJ receberam um carcinógeno iniciador 4-(methylnitrosamino)-1-(3-pyridil)-1-butanona (NNK), por serem pré-dispostos ao desenvolvimento de tumores de pulmão. Em seguida todos os animais foram expostos no Concentrador de Partículas Atmosféricas Harvard ao MP 2,5 diariamente, por 2 horas, durante quatro meses. Cada linhagem foi dividida em quatro grupos (n=15 cada): 2 controles com salina e carcinógeno (CsS e CsU ou CajS e CajNNK) e 2 expostos com salina e carcinógeno (EsS e EsU ou EajS e EajNNK). Foi realizada a análise histopatológica dos pulmões, a contagem e classificação das lesões pulmonares encontradas. Foi feito estudo imunoistoquimico para p53 e PCNA. RESULTADOS. Os animais dos grupos expostos, em ambas as linhagens, apresentaram maior número de lesões neoplásicas. As médias de lesões (nódulos e hiperplasia) obtidas foram: CsU: 1,07( DP+ 1,54), CsSl: 0( DP+ 0), EsU: 2,57 ( DP+ 2,77) e EsS: 0,40 ( DP+ 1,12), com p < 0,001; CajNNK: 4,94( DP+ 3,54), CajS: 0,15( DP+ 0,37), EajNNK: 9,14 ( DP+ 7,70) e EajS:0,80 ( DP+ 1,93), com p<0,001. Não houve alterações para o p53 em ambas as linhagens e, apenas os grupos AJ controle e exposto NNK apresentaram diferença para o PCNA. CONCLUSÃO. A exposição crônica ao MP 2,5 proveniente da poluição atmosférica da cidade de São Paulo tem potencial para promover tumores em camundongos de duas linhagens diferentes, com ou sem o pré-tratamento por carcinógenos / INTRODUCTION. Epidemiological studies have shown that exposure to air pollution is associated with increased cardiorespiratory diseases. Previous experimental studies, we used urethane to induce lung nodule formation in mice and these animals exposed to pollution from \"real world.\" In these studies, animals were exposed to gases and particles in the same way that the population is exposed in the city of São Paulo. It was evident then, the role of promoter and dose dependent polluted atmosphere in the progression of lung tumors. It is known that carcinogens such as polycyclic aromatic hydrocarbons (PAHs), metals, aldehydes and fatty acids, are present in the respirable fraction particulate pollution (fine particulate matter - PM2.5), and prolonged exposure to the latter has been considered a risk factor for the development of lung cancer. The objective of this study is to verify whether chronic exposure to PM 2.5 concentration from the air of the city of São Paulo, has carcinogenic potential. METHODS. A total of 60 male Swiss mice (30 g) and 60 AJ (20g), with four to six weeks of life. The Swiss mice were pretreated with a carcinogen completed, the carbamic acid (urethane-U), while AJ received a carcinogen primer 4 - (methylnitrosamino) -1 - (3-pyridil)-1-butanone (NNK) as being predisposed to developing lung tumors. Then all the animals were exposed to atmospheric Harvard Particle Concentrator to PM 2.5 daily for two hours for four months. Each strain was divided into four groups (n = 15 each): 2 with saline controls and carcinogen (CsS and CsU or CajS and CajNNK) and 2 exposed to saline and carcinogen (EsS and EsS or EajS and EajNNK). After the exposure time, the animals were anesthetized and euthanized. The lungs were fixed, processed histologically and imunohistochemistry was performed on slides with tumor presence of antibodies to p53 and PCNA. Later, in histopathology of pulmonary nodules made counting and classification of lesions found. RESULTS. The animals exposed groups in both strains showed a high percentage of neoplastic lesions. Mean lesions (nodules and hyperplasia) were obtained: CsU: 1.07 (SD + 1.54), CsS: 0 (DP + 0), EsU: 2.57 (SD + 2.77) and EsS: 0.40 ( + SD 1.12), p < 0.001; CajNNK: 4.94 (SD + 3.54), CajS: 0.15 (SD + 0.37), EajNNK: 9.14 (SD + 7.70) and EajS: 0 , 80 (SD + 1.93), with p < 0.001. There were no changes to the p53 in both strains, and only groups A / J control and exposed to NNK differ PCNA. CONCLUSION. The chronic exposure to PM 2.5 air pollution from the city of São Paulo has the potential to promote tumors in mice of two different strains with or without pretreatment by carcinogens

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A utilização de novos materiais aplicados aos processos de separação por membranas tem sido objeto de constante pesquisa acadêmica e tecnológica. Na permeação de gases petroquímicos, a modificação de estruturas poliméricas e o uso de membranas de transporte facilitado por adição de sais contendo metais ou nanopartículas destacam-se dentre as opções disponíveis. Os objetivos deste trabalho foram avaliar alterações químicas, estruturais e térmicas na matriz polimérica de poli(uretano-ureia) (PUU) provocadas pela adição de nanopartículas de prata (AgNps) e obter dados de pemeabilidade de gases petroquímicos (C2H4, C2H6, CO2 e N2) para avaliar a influência das AgNps no transporte desses gases através do filme polimérico. Alterações nos espectros de FTIR nas bandas de estiramento das ligações C-O-C e C=O (uretânica e ureica), e deslocamentos nos picos de difração, demonstram que houve interação entre as AgNps e o oxigênio éter do PUU. A interação com as AgNps diminuiu a estabilidade térmica dos domínios flexíveis do polímero, região onde são encontrados os grupos éteres. As imagens de TEM mostraram que houve baixa dispersão das Nps na matriz polimérica. A interação das AgNps com o grupo éter diminuiu a permeabilidade de todos os gases, porém a redução da permeabilidade do CO2 e do C2H4 foi muito mais significativa, mostrando a interferência das AgNps na sorção desses dois gases. O transporte facilitado de olefinas através dos filmes poliméricos não foi observado, em parte, causado pela baixa dispersão das AgNps na matriz polimérica. Apesar da interação, não foi possível responder se a superfície das Nps estava ativada para o transporte facilitado. Contudo, através dos resultados do trabalho foi possível propor um mecanismo de interação entre as AgNps e o PUU, e verificar como a presença das Nps pode alterar a interação da matriz polimérica com gases petroquímicos / The use of new materials applied to processes of membrane separation has been the target of constant academic and technological researches. In permeation of petrochemical gases, the modification of polymeric structure to form facilitated transport membranes are one of the worthy available options. In this sense, the goal of this work is, not only evaluate the influence of the addition of silver nanoparticles (AgNps) in the chemical, morphological and thermal properties of poly(urethane urea) (PUU) films, but also obtain permeability data for some petrochemical gases (C2H4, C2H6, CO2 e N2). FTIR spectra exhibited changes in the C-O-C and C=O stretching bands profile of (from urethane and urea groups) and XRD analyses exhibited shifts in peaks. These results demonstrate the AgNps interacted with the ether oxygen of PUU. The interaction with AgNps reduced the thermal stability of polymer soft segments, where the ether linkages are located. TEM images showed a lower dispersion of Np in the polymer matrix. The interaction between AgNps and ether groups also decreased the permeability of all gases. Reduction of CO2 and C2H4 permeability were clear, demonstrating the hindrance of AgNps in the sorption of both gases. The olefin transport facilitated through the polymeric films was not verified. . This is partially caused by the lower dispersion of AgNps in the polymer matrix. Although an interaction between the AgNps and ether oxygen was observed, it was not possible to confirm if the Nps surface was really activated to facilitated transport. However, considering the results obtained it was possible to propose the interaction mechanism between AgNps and PUU; and also to indicate how the presence of Nps can change the interaction between the polymeric matrix and the petrochemical gases

Food additives are used by the food industry in order to enhance the aroma, flavor and texture of foods. Of all the additives used colors are the most genotoxic. The azo dyes, derived from oil, used by industries, are the tartrazine and red #40. The SMART wing test was used to verify the possible genotoxic effects of colors in somatic cells of Drosophila melanogaster. For this evaluation were used larvae of 48 hours, descendants of the Standard Cross (ST) and High Bioactivation (HB) that who were treated with tartrazine in concentrations 1.5, 2.5 and 3.0 mg / mL and 5, 10 and 20 mg / mL for the red #40. The results showed significant increase of spots in the ST descendants for tartrazine and HB for the red #40. We concluded that the artificial colors tartrazine and red #40 are genotoxic in the doses used for the study. / Os aditivos alimentares são utilizados pela indústria alimentícia com o intuito de melhorar o aroma, o sabor e a textura dos alimentos. De todos os aditivos utilizados os corantes são os mais genotóxicos. Os corantes azóicos, derivados do petróleo, utilizados pelas indústrias, são o tartrazina e vermelho 40. O teste SMART de asa foi utilizado para verificar os possíveis efeitos genotóxicos destes corantes em células somáticas de Drosophila melanogaster. Para esta avaliação foram utilizadas larvas de 48 horas, descendentes do cruzamento padrão (ST) e alta bioativação (HB) que foram tratadas com tartrazina nas concentrações 1,5, 2,5 e 3,0 mg/mL e 5, 10 e 20 mg/mL para o vermelho 40. Os resultados mostraram aumento significativo de manchas nos descendentes ST para tartrazina e HB para o vermelho 40. Concluímos que os corantes artificiais tartrazina e vermelho 40 são genotóxicos nas doses utilizadas para o estudo. / Mestre em Genética e Bioquímica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A utilização de novos materiais aplicados aos processos de separação por membranas tem sido objeto de constante pesquisa acadêmica e tecnológica. Na permeação de gases petroquímicos, a modificação de estruturas poliméricas e o uso de membranas de transporte facilitado por adição de sais contendo metais ou nanopartículas destacam-se dentre as opções disponíveis. Os objetivos deste trabalho foram avaliar alterações químicas, estruturais e térmicas na matriz polimérica de poli(uretano-ureia) (PUU) provocadas pela adição de nanopartículas de prata (AgNps) e obter dados de pemeabilidade de gases petroquímicos (C2H4, C2H6, CO2 e N2) para avaliar a influência das AgNps no transporte desses gases através do filme polimérico. Alterações nos espectros de FTIR nas bandas de estiramento das ligações C-O-C e C=O (uretânica e ureica), e deslocamentos nos picos de difração, demonstram que houve interação entre as AgNps e o oxigênio éter do PUU. A interação com as AgNps diminuiu a estabilidade térmica dos domínios flexíveis do polímero, região onde são encontrados os grupos éteres. As imagens de TEM mostraram que houve baixa dispersão das Nps na matriz polimérica. A interação das AgNps com o grupo éter diminuiu a permeabilidade de todos os gases, porém a redução da permeabilidade do CO2 e do C2H4 foi muito mais significativa, mostrando a interferência das AgNps na sorção desses dois gases. O transporte facilitado de olefinas através dos filmes poliméricos não foi observado, em parte, causado pela baixa dispersão das AgNps na matriz polimérica. Apesar da interação, não foi possível responder se a superfície das Nps estava ativada para o transporte facilitado. Contudo, através dos resultados do trabalho foi possível propor um mecanismo de interação entre as AgNps e o PUU, e verificar como a presença das Nps pode alterar a interação da matriz polimérica com gases petroquímicos / The use of new materials applied to processes of membrane separation has been the target of constant academic and technological researches. In permeation of petrochemical gases, the modification of polymeric structure to form facilitated transport membranes are one of the worthy available options. In this sense, the goal of this work is, not only evaluate the influence of the addition of silver nanoparticles (AgNps) in the chemical, morphological and thermal properties of poly(urethane urea) (PUU) films, but also obtain permeability data for some petrochemical gases (C2H4, C2H6, CO2 e N2). FTIR spectra exhibited changes in the C-O-C and C=O stretching bands profile of (from urethane and urea groups) and XRD analyses exhibited shifts in peaks. These results demonstrate the AgNps interacted with the ether oxygen of PUU. The interaction with AgNps reduced the thermal stability of polymer soft segments, where the ether linkages are located. TEM images showed a lower dispersion of Np in the polymer matrix. The interaction between AgNps and ether groups also decreased the permeability of all gases. Reduction of CO2 and C2H4 permeability were clear, demonstrating the hindrance of AgNps in the sorption of both gases. The olefin transport facilitated through the polymeric films was not verified. . This is partially caused by the lower dispersion of AgNps in the polymer matrix. Although an interaction between the AgNps and ether oxygen was observed, it was not possible to confirm if the Nps surface was really activated to facilitated transport. However, considering the results obtained it was possible to propose the interaction mechanism between AgNps and PUU; and also to indicate how the presence of Nps can change the interaction between the polymeric matrix and the petrochemical gases