Le principe d’élaboration des mousses de silicone est basé sur une compétition entre deux réactions mettant en jeu les fonctions hydrogénosilane portées par le polymère précurseur : la première provoque le dégagement d’un gaz (à l’origine de la formation des cellules) et la deuxième, l’hydrosilylation, bien connue et maîtrisée dans les silicones, conduit à la réticulation du milieu réactionnel. De ce fait, le contrôle des propriétés finales de la mousse nécessite la maîtrise de ces deux cinétiques de synthèse du gaz et de réticulation. D’autre part, les propriétés finales des mousses (type de porosité, densité apparente,…) dépendent également de la rhéologie (propriétés élongationnelles adéquates) ainsi que des charges ajoutées à la formulation. L’étude de la nucléation et la croissance cellulaire a été faite sous microscope optique. Les résultats montrent que le phénomène fondamental contrôlant la croissance des bulles est la coalescence. Sous l’influence couplée des effets de surface et viscoélastiques, les bulles se rapprochent et se déforment pour donner naissance à une forme intermédiaire avant d’atteindre leur forme finale. D’autre part, on a montré que l’air initialement dissous dans les formulations ainsi que l’air introduit par agitation permettent de réduire l’effet de peau, d’avoir une distribution de taille homogène et une meilleure structure cellulaire. D'autres facteurs ont également été étudiés dans le but de rendre la distribution de taille plus homogène et améliorer certaines propriétés / A foam sample is assumed to be a set of bubbles embedded into a polymeric matrix with an initial gas overpressure. Silicon foams are produced by a competition between two reactions involving the hydrogenosilane functions carried by the polymer precursor: the first reaction generates gas (initiating cell formation) while the other one, hydrosilylation, well known and controlled in silicon, leads to the crosslinking of the rising foam. Thus, obtaining enhanced foam properties requires a good balance between two reactions, crosslinking and gas generation. On the other hand, the final characteristics of the foam (porosity, bulk density…) largely depend on the rheology of the mix (appropriate elongational properties) as well as the added fillers. Nucleation and cell growth were carried out under optical microscopy. The experiments show that the main phenomenon controlling cell growth is bubble coalescence. Due to the surface effects and the viscoelastic properties, bubbles approach from each other and get deformed giving birth to an intermediate shape before reaching their final geometry. Many parameters have direct effect on foam properties. In fact, dissolved gas in formulas as well as the air introduced during manual mixing, reduce the skin effect and guarantee a homogeneous cell size distribution and a better foam structure. Other factors have also been studied in order to render size distribution more homogeneous and improve certain properties

Traditional evolutionary models depict evolution as a bifurcating pattern with a single ancestor diverging to form two lineages. However, reticulate species resulting from hybridization and recombination have unique histories shared with two independent lineages, not one. Accounting for the genetic histories of reticulate species increases the power and ability to recover biologically meaningful relationships. The genus Collomia (Polemoniaceae) is used to explore issues of reticulation and the importance of accounting for gene histories in a phylogenetic analysis. The issue of reticulation within species trees is discussed with a multilabeled, network approach being explored to better represent the genus's evolutionary history. Wherry's hypotheses regarding the relationships that exist within Collomia are addressed and the need for a new intrageneric section is recognized based on support from multiple, independent genes and morphology. Sections Collomiastrum and Courtoisia remain as previously circumscribed. Section Collomia is modified with removal of two species, C. grandiflora and C. biflora from the section and by erecting a new section, Calyperona. A morphological key is included for each section and their corresponding species, followed by sectional discussions. Finally, the evolution of lifecycle duration, seed morphology, and pollen morphology are discussed based on the phylogeny of the genus.

Este trabalho descreve a reação de reticulação alternativa do pericárdio bovino com os acetais do glutaraldeído, preparados a partir da solução de glutaraldeído na presença do etanol em meio ácido. Os acetais difundem para dentro da matriz colagênica, e a reticulação ocorre após a desproteção dos grupos aldeídicos com uma amina terciária. O material obtido sob estas condições mostrou as propriedades biológicas e mecânicas similares ou superiores àqueles descritos para o pericárdio bovino reticulado pelo procedimento convencional com glutaraldeído, e provavelmente, com resultados de uma distribuição e natureza química mais homogênea das reticulações formadas, devido à ausência das reticulações polímeros de glutaraldeído. As biopróteses manufaturadas com pericárdio reticulado com acetais do glutaraldeído, também mostraram durabilidade superior e foi menos suscetível ao processo de calcificação, como determinado em implantes subcutâneos em ratos. Resultados preliminares de teste à fadiga e performance hidrodinâmica foram caracterizados por um comportamento similar àqueles materiais tratados convencionalmente sugerindo que, o pericárdio reticulado com acetais do glutaraldeído pode ser um procedimento alternativo e mais eficiente na manufatura das biopróteses, particularmente com respeito à calcificação, um dos maiores problemas encontrados pós-implante. / This work describes the cross-linking of bovine pericardium with glutaraldehyde acetals, which are its protected forms. The acetals, prepared from a glutaraldehyde solution in the presence of ethanol in acidic media was al/owed to diffuse within the collagen matrix, and cross-linking achieved by deprotection with a tertiary amine. The material obtained under this conditions showed biological and mechanical properties similar or superior to those described for bovine pericardium crosslinked by conventional procedure with glutaraldehyde, and probably, as a results of a more homogeneous distribution and chemical nature of the formed crosslinks, that is the absence of polymeric cross-links. Bioprostheses manufactured with glutaraldehyde acetals cross-linked bovine pericardium, also showed higher durability and was less susceptible to calcification process, as determined in subcutaneous implant in rats. Preliminary results on fatigue test and hydrodynamic performance were characterized by a behavior similar to those observed for conventional/y treated materials suggesting that, glutaraldehyde acetals crosslinked bovine pericardium may be an alternate and more efficient procedure in the manufacture of bioprostheses, particularly in respect to calcification, one of the major problems found post-implantation.

Energy shortage, escalation of energy cost and climate change have led to an increased focus on energy conservation worldwide. In order to curb the increase in electricity demand, Eskom has introduced demand-side management (DSM) to improve energy efficiency and to shift peak-time load to off-peak periods in order to postpone additional capacity requirements. In the past, several mine DSM projects have been implemented without the use of system simulations as part of the analysis of project planning. Many of these projects are characterised by contractual energy saving targets that have not been met, projects that are delayed, potential energy savings projects that have been overlooked and additional savings that have not realised. This study demonstrates the potential of simulations to plan new and correct implemented DSM solutions. This is done by allowing analysis of energy consumption in complex technical systems and quantification of the savings potential of DSM interventions to inform design changes in order to attain energy savings. In applying simulations to a well-instrumented compressed air system, it was possible to compare the theoretical and measured values for system parameters. The simulation was fine-tuned for low-pressure operation (with the system operating well within design constraints) by incorporating estimated flow losses. By simulating high-pressure operation in which the system operates closer to design limits, the constraints that were experienced, were revealed. This application exemplifies the approach that has been adopted in the case studies to follow. The value of the use of simulation models for mine DSM projects Simulations that have been applied to four case studies demonstrate the use in improving existing DSM projects as well as in planning new DSM projects. Two case studies demonstrate the use of simulations in rectifying problems that have been encountered during the implementation of existing mine DSM projects. Simulations have been employed to propose corrections to these project implementations; this demonstrates significant value for the customer. In two additional case studies, the value of simulation models is demonstrated where simulations have been developed prior to the implementation of DSM projects. It demonstrates that projects can be implemented with less effort, in a shorter time span and at a reduced cost (both capital and man-hours) by using simulations in the planning phases of DSM projects. / Thesis (MIng (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2013.

Energy shortage, escalation of energy cost and climate change have led to an increased focus on energy conservation worldwide. In order to curb the increase in electricity demand, Eskom has introduced demand-side management (DSM) to improve energy efficiency and to shift peak-time load to off-peak periods in order to postpone additional capacity requirements. In the past, several mine DSM projects have been implemented without the use of system simulations as part of the analysis of project planning. Many of these projects are characterised by contractual energy saving targets that have not been met, projects that are delayed, potential energy savings projects that have been overlooked and additional savings that have not realised. This study demonstrates the potential of simulations to plan new and correct implemented DSM solutions. This is done by allowing analysis of energy consumption in complex technical systems and quantification of the savings potential of DSM interventions to inform design changes in order to attain energy savings. In applying simulations to a well-instrumented compressed air system, it was possible to compare the theoretical and measured values for system parameters. The simulation was fine-tuned for low-pressure operation (with the system operating well within design constraints) by incorporating estimated flow losses. By simulating high-pressure operation in which the system operates closer to design limits, the constraints that were experienced, were revealed. This application exemplifies the approach that has been adopted in the case studies to follow. The value of the use of simulation models for mine DSM projects Simulations that have been applied to four case studies demonstrate the use in improving existing DSM projects as well as in planning new DSM projects. Two case studies demonstrate the use of simulations in rectifying problems that have been encountered during the implementation of existing mine DSM projects. Simulations have been employed to propose corrections to these project implementations; this demonstrates significant value for the customer. In two additional case studies, the value of simulation models is demonstrated where simulations have been developed prior to the implementation of DSM projects. It demonstrates that projects can be implemented with less effort, in a shorter time span and at a reduced cost (both capital and man-hours) by using simulations in the planning phases of DSM projects. / Thesis (MIng (Mechanical Engineering))--North-West University, Potchefstroom Campus, 2013.

Please read the abstract in the section 00front of this document / Dissertation (M Eng (Electrical Engineering))--University of Pretoria, 2007. / Electrical, Electronic and Computer Engineering / unrestricted

Este trabalho descreve a reação de reticulação alternativa do pericárdio bovino com os acetais do glutaraldeído, preparados a partir da solução de glutaraldeído na presença do etanol em meio ácido. Os acetais difundem para dentro da matriz colagênica, e a reticulação ocorre após a desproteção dos grupos aldeídicos com uma amina terciária. O material obtido sob estas condições mostrou as propriedades biológicas e mecânicas similares ou superiores àqueles descritos para o pericárdio bovino reticulado pelo procedimento convencional com glutaraldeído, e provavelmente, com resultados de uma distribuição e natureza química mais homogênea das reticulações formadas, devido à ausência das reticulações polímeros de glutaraldeído. As biopróteses manufaturadas com pericárdio reticulado com acetais do glutaraldeído, também mostraram durabilidade superior e foi menos suscetível ao processo de calcificação, como determinado em implantes subcutâneos em ratos. Resultados preliminares de teste à fadiga e performance hidrodinâmica foram caracterizados por um comportamento similar àqueles materiais tratados convencionalmente sugerindo que, o pericárdio reticulado com acetais do glutaraldeído pode ser um procedimento alternativo e mais eficiente na manufatura das biopróteses, particularmente com respeito à calcificação, um dos maiores problemas encontrados pós-implante. / This work describes the cross-linking of bovine pericardium with glutaraldehyde acetals, which are its protected forms. The acetals, prepared from a glutaraldehyde solution in the presence of ethanol in acidic media was al/owed to diffuse within the collagen matrix, and cross-linking achieved by deprotection with a tertiary amine. The material obtained under this conditions showed biological and mechanical properties similar or superior to those described for bovine pericardium crosslinked by conventional procedure with glutaraldehyde, and probably, as a results of a more homogeneous distribution and chemical nature of the formed crosslinks, that is the absence of polymeric cross-links. Bioprostheses manufactured with glutaraldehyde acetals cross-linked bovine pericardium, also showed higher durability and was less susceptible to calcification process, as determined in subcutaneous implant in rats. Preliminary results on fatigue test and hydrodynamic performance were characterized by a behavior similar to those observed for conventional/y treated materials suggesting that, glutaraldehyde acetals crosslinked bovine pericardium may be an alternate and more efficient procedure in the manufacture of bioprostheses, particularly in respect to calcification, one of the major problems found post-implantation.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Submitted by Milena Rubi (milenarubi@ufscar.br) on 2016-11-09T14:11:31Z No. of bitstreams: 1 ROSA_Wesley_2016.pdf: 8516860 bytes, checksum: ee5a7fd54adf8975660601cc883291f2 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2016-11-09T14:11:44Z (GMT) No. of bitstreams: 1 ROSA_Wesley_2016.pdf: 8516860 bytes, checksum: ee5a7fd54adf8975660601cc883291f2 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2016-11-09T14:11:50Z (GMT) No. of bitstreams: 1 ROSA_Wesley_2016.pdf: 8516860 bytes, checksum: ee5a7fd54adf8975660601cc883291f2 (MD5) / Made available in DSpace on 2016-11-09T14:11:57Z (GMT). No. of bitstreams: 1 ROSA_Wesley_2016.pdf: 8516860 bytes, checksum: ee5a7fd54adf8975660601cc883291f2 (MD5) Previous issue date: 2016-03-28 / Não recebi financiamento / The need to obtain biomaterials in order to reduce environmental impacts has been the focus of research groups in recent years, and cellulose, a dominant component at most forms of plants is a promising resource because of its abundance. In order to improve the ability processing, the chemical modification of cellulose has been widely studied. Among the most important reactions of cellulose are: etherification, esterification, acetylation and oxidation; being cellulose acetate, viscose, nitrocellulose and cellulose ethers, the main cellulose derivatives. The chemical modification with isocyanates presents some unique properties, such as absence of by-products and chemical stability of the urethane group. In this work we were synthesized gels obtained by modified cellulose acetate (CA) with a degree of substitution (DS) 2,5 by crosslinking, with 4,4' - Diphenylmethane diisocyanate (MDI) in stoichiometry of 1:1, in homogeneous by varying the humidity and the homogenization time. For characterization were used the following techniques and tests: vibrational infrared absorption spectroscopy (Fourier Transform Spectrometer - FTIR), size exclusion Chromatography (SEC), molecular absorption spectrophotometry UV-VIS, density determining of the gels by pycnometry, determination of the coefficient swelling, determination of cross-links by Flory-Rehner theory, thermogravimetry (TG) and scanning electron microscopy (SEM). Crosslink density results showed that the gel synthesized in the absence of moisture suffered greater crosslinking with an average number of repeat units between the crosslinking points of about 1000 times lower. The potential applications of these gels were tested, by using than as stationary phase in size exclusion chromatography, having been assessed its efficiency in the fractionation and separation of natural and synthetic polymers. Results showed the effectiveness of the gel as stationary phase on separation of polymers, opening up a range of opportunities, taking into consideration the simplicity of the process and lower costs attributed to it. / A necessidade de se obter biomateriais na tentativa de reduzir impactos ambientais tem sido o foco de grupos de pesquisa nos últimos anos e, a celulose, um componente dominante na maioria das formas de plantas, é um recurso promissor devido à sua abundância. A fim de melhorar a capacidade de processamento, a modificação química da celulose tem sido amplamente estudada. Dentre as reações mais importantes da celulose estão: eterificação, esterificação, acetilação e oxidação; sendo o acetato de celulose, viscose, nitrocelulose e éteres de celulose, os principais derivados da celulose. A modificação química com isocianatos apresenta algumas propriedades únicas, como ausência de produtos secundários e estabilidade química do grupo uretano. Nesse trabalho foram sintetizados géis obtidos por meio da modificação de Acetato de Celulose (AC) com grau de substituição (GS) 2,5 através da reticulação com 4,4' - Difenilmetano Diisocianato (MDI), na estequiometria 1:1, em meio homogêneo, variando a umidade e o tempo de homogenização. Para caracterização foram utilizadas as seguintes técnicas e ensaios: espectroscopia vibracional de absorção no infravermelho por Transformada de Fourier (FTIR), cromatografia de exclusão por tamanho (SEC), espectrofotometria de absorção molecular UV-VIS, determinação de densidade dos géis por picnometria, determinação do coeficiente de intumescimento, determinação de ligações cruzadas pela teoria de Flory-Rehner, termogravimetria (TG) e microscopia eletrônica de varredura (MEV). Resultados da densidade de ligações cruzadas mostraram que o gel sintetizado na ausência de umidade sofreu uma maior reticulação, com um número médio de unidades de repetição entre os pontos de reticulação cerca de 1000 vezes menor. As aplicações potenciais desses géis foram testadas como fase estacionária em cromatografia de exclusão por tamanho, tendo sido avaliada sua eficiência no fracionamento e separação de polímeros naturais e sintéticos. Resultados mostraram a eficácia do gel como fase estacionária na separação de polímeros, abrindo uma gama de oportunidades, levando-se em consideração a simplicidade do processo e os baixos custos a ele atribuídos.