Poly(1-methylpyrrol-2-ylsquaraine) (PMPS) particles are a fine blue-black insoluble powder. Scanning electron microscopy (SEM) pictures reveal that the PMPS particles are microspheres with diameters ranging from 1.3 - 4 micrometers (distribution peaking at 1.9 micrometers). The absorption capacity values of PMPS particles were studied for a large majority of the elements in the periodic table in order to establish a pattern or trend in absorption. The elements specifically targeted at the beginning of the research were the biological elements vital to sustain life and the heavy metals that pose a threat to the environment via pollution and poisoning. Fifty-four elements were investigated in total and all absorbed in varying amounts ranging from 0.01 mmol/g for caesium up to 5.66 mmol/g for phosphorous. It was found that varying the initial elemental compound, temperature and solvent concentrations vastly altered the amount of element absorbed. The majority of elements absorbed best when dissolved in hot concentrated hydrochloric acid at 50oC, some preferred cold conditions (4oC) and/or a neutral solvent (water). The freshness of the elemental compound had a huge impact on the absorption capacities, i.e. new compounds absorbed much better than old stock. A comparison between chloride salts and the hydroxides of Group 1 alkali metals revealed that the hydroxides absorbed much better than the salts, sometimes with more than a ten-fold increase. Release profiles were studied for PMPS particles containing eleven different elements when subjected to an aqueous medium. The study focused on some of the elements that are commonly utilised in industry and also the soft acids and bases primarily because they had some of the highest sorption values and the fact that the majority are known to be particularly toxic to man. The amount of ions released varied enormously ranging from 0% release for selenium up to 83% for arsenic. It was interesting to observe that arsenic had the highest percentage release despite having the lowest sorption uptake and selenium had the lowest (zero) percentage release despite having one of the highest sorption uptakes. Analysis of the release data revealed that there appears to be two types of profile emerging. In the first type of profile the metallic ions leached out of the PMPS particles slowly over a period of time until equilibrium was reached whereupon no more ions were released. This happened for the arsenic, copper, lead, mercury, cadmium, silver and gold ions. In the second type of profile all of the free ions were released as soon as water was added, in the first 2 mL aliquot. This happened for the manganese, sodium and caesium ions. It would appear that the ions that have the gradual release profile are the heavier ions on the right hand side of the periodic table, which also means that they are soft acids or bases. The ions that have the second type of profile, where release was achieved in the first aliquot are situated on the left hand side of the periodic table and were all found to be hard acids. Over-coating studies using PMPS particles containing copper and sodium were separately investigated. The results revealed that PMPS-Cu particles when overcoated with a polymer do appear to have a slow release profile.

Ces travaux de thèse consistent à formuler des nanocomposites électriquement conducteurs pour des applications micro-ondes. L’objectif principal est la mise en œuvre de matériaux absorbant les ondes radar, plus particulièrement sur la bande X (8-12 GHz). La polyaniline et les nanotubes de carbone, dispersés dans une matrice époxyde, ont été sélectionnés pour apporter les propriétés d’absorption aux fréquences visées. Différentes morphologies de polyaniline ont été synthétisées afin d’étudier leur influence sur les propriétés d’absorption des composites. L’utilisation d’une polyaniline à morphologie feuillet, présentant une forte anisotropie et un facteur de forme élevé, permet d’augmenter la conductivité et les pertes diélectriques des composites. De plus, leur association avec des nanotubes de carbone améliore significativement les propriétés d’absorption aux fréquences micro-ondes. Des écrans absorbants radar performants qui présentent des coefficients de réflexion inférieurs à -20 dB ont pu être modélisés et mis en œuvre, confirmant le potentiel de ces matériaux pour des applications de furtivité radar. / This thesis deals with the formulation of electrically conductive nanocomposites for microwave applications. The main purpose is to process radar-absorbent materials, more particularly at the X band. (8-12 GHz). Polyaniline and carbon nanotubes, dispersed in an epoxyde matrix, have been selected. Different morphologies of polyaniline have been synthesized to study its impact on the absorption properties of composites. Using flake-like polyaniline showing high anisotropy and aspect ratio increases conductivity and dielectric losses of composites. Moreover, its association with carbon nanotubes significantly improves the absorption properties at microwaves frequencies. Efficient radar absorbing screens, showing reflection losses lower than -20 dB, have been calculated and processed confirming the potential of these materials for stealth applications.

Este trabalho relata o uso de polpa etanol /água de medula em um estudo que visa obter e caracterizar carboximetilcelulose substancialmente insolúvel, destinada a aplicação como material absorvente. Em um experimento típico a reação de carboximetilação de polpa etanol / água branqueada de medula de bagaço foi realizada em suspensão de isopropanol /água de 1: 8 (mim) a 80&#176C por 4 horas empregando relação molar de celulose / hidróxido de sódio / ácido monocloroacético de 1 /5.4 / 8.8. Os produtos foram caracterizados quanto à presença de grupos funcionais característicos; grau médio de substituição (DS); solubilidade em água e em solução aquosa alcalina; capacidade de retenção de água e de solução salina; morfologia e estabilidade térmica. As técnicas instrumentais empregadas nessas caracterizações incluem as espectroscopias de ressonância magnética nuclear (RMN) e de infravermelho (i.r); microscopia eletrônica de varredura (MEV); termogravimetria (ATG) e calorimetria diferencial de varredura (DSC). O material com melhores características foi obtido quando a condição acima descrita para a reação de carboximetilação foi aplicada e corresponde a um produto muito pouco solúvel (SH20 < 2%) com características absorventes superiores às da matéria-prima. Foram realizadas outras oito sínteses empregando diferentes concentrações de ácido monocloroacético e outros tempos de reação. Todos os produtos apresentam o efeito polieletrólito, mas suas capacidades de inchamento não dependem de forma simples dos graus médios de substituição. As capacidades de\' retenção de água apresentadas pelos produtos deste trabalho parecem resultar de um compromisso entre variáveis da reação, quantidade e distribuição de grupos iônicos ao longo das cadeias e grau de intercruzamento. Nossos resultados não permitem concluir se os materiais correspondem a cadeias poliméricas intercruzadas física ou covalentemente, pois a ocorrência de ligações de intercruzamento do tipo éster não pode ser descartada, mas a confirmação de sua presença por espectroscopia de infra-vermelho é prejudicada pela extensa superposição de bandas na região de interesse. Apesar do emprego de fontes convencionais de celulose em condições semelhantes de síntese resultar em produtos com características muitos superiores àquelas apresentadas pelos produtos deste trabalho, consideramos que nossos resultados são promissores. Por um lado, devem ser consideradas a disponibilidade e abundância da matéria-prima que podem significar um custo relativamente baixo quando comparado ao de fontes convencionais de celulose. Por outro lado, o emprego de polpas de bagaço em lugar de madeiras pode ter um impacto ecológico muito positivo dada a possibilidade de preservação de reservas florestais. Finalmente é necessário ressaltar que a qualidade dos produtos obtidos depende das características da matéria-prima empregada, principalmente grau de polimerização da celulose obtida por polpação. Nesse sentido, o emprego de outros processos de polpação e branqueamento que reduzam a degradação das cadeias de celulose melhorarão as características das polpas de medula e, por consequência, as propriedades absorventes da carboximetilcelulose insolúvel obtida. / This work describes the use of ethanol / water pulps of pith in a study aiming the obtention and characterization of substantially insoluble carboxymethylcellulose for application as an absorvente material. In a typical experiment the carboxymethylation reaction of bleached ethanol / water pulp occurred at 80&#176C for 4 hours in isopropanol/ water suspension 1 : 8 (w/w) employing a cellulose / sodium hydroxide / monochloroacetic acid molar ratio of 1.0/5.4 / 8.8. Characterizations were made through the determinations of the presence of characteristic functional groups; degree of substitution (DS); solubility in pure water and alkaline aqueous solution; water and saline aqueous solution retention capacity; morphology and thermal stability of the obtained products. Infra-red (i.r.) and nuclear magnetic ressonance (NMR) spectroscopies; scanning electronic microscopy (SEM); thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were employed for these characterizations. The material with the best absorbent characteristics was obtained through the application of the condition above described for the carboxymethylation reaction. This is a very insoluble product (S IDO < 20/0) with a much higher water retention capacity than unreacted pulp employed as raw material. Other eight products were prepared through the application of different concentrations of monochloroacetic acid and variable reactions times. AlI products manifested the polyelectrolyte effect, but their water retention capacities seem to depend on the degree of substitutions in a complex way. Water retention capacities of the products of this work seem to be the result of a compromise among the parameters of the carboxymethylation reaction, the content and distribution of ionic groups and the degree of crosslinking. From our results it cannot be concluded if the materials correspond to physically or covalently crosslinked polyffiericchains since the occurrence of ester bonds as crosslinkers can not be discarded, but its detection in the infra-red spectra is difficult as a consequence of the extensive superposition of bands in the region of interest. Although the use of conventional sources of cellulose in conditions similar to those described here result in products of superior quality we believe that pith can be a good altemative raw material for the obtention of carboxyffiethyl ceIlulose with absorbent characteristics. In Brazil it is available as a very abundant and low cost raw material derived from the industries which process sugar cane for the production of ethanol and sugar and its utilization in place of wood pulps may also represent ecological advantages as forest preservation will be favoured. Finally it is worthwhile to remember that the quality of the products also depends on the raw material characteristics, mainly the degree of polyffierization of the cellulose obtained after pulping. So the use of the other pulping and bleaching processes which minimize chain degradation wiIl certainly result in better pulps from pith and as a consequence materials with better absorbent characteristics will be prepared.

Este trabalho relata o uso de polpa etanol /água de medula em um estudo que visa obter e caracterizar carboximetilcelulose substancialmente insolúvel, destinada a aplicação como material absorvente. Em um experimento típico a reação de carboximetilação de polpa etanol / água branqueada de medula de bagaço foi realizada em suspensão de isopropanol /água de 1: 8 (mim) a 80&#176C por 4 horas empregando relação molar de celulose / hidróxido de sódio / ácido monocloroacético de 1 /5.4 / 8.8. Os produtos foram caracterizados quanto à presença de grupos funcionais característicos; grau médio de substituição (DS); solubilidade em água e em solução aquosa alcalina; capacidade de retenção de água e de solução salina; morfologia e estabilidade térmica. As técnicas instrumentais empregadas nessas caracterizações incluem as espectroscopias de ressonância magnética nuclear (RMN) e de infravermelho (i.r); microscopia eletrônica de varredura (MEV); termogravimetria (ATG) e calorimetria diferencial de varredura (DSC). O material com melhores características foi obtido quando a condição acima descrita para a reação de carboximetilação foi aplicada e corresponde a um produto muito pouco solúvel (SH20 < 2%) com características absorventes superiores às da matéria-prima. Foram realizadas outras oito sínteses empregando diferentes concentrações de ácido monocloroacético e outros tempos de reação. Todos os produtos apresentam o efeito polieletrólito, mas suas capacidades de inchamento não dependem de forma simples dos graus médios de substituição. As capacidades de\' retenção de água apresentadas pelos produtos deste trabalho parecem resultar de um compromisso entre variáveis da reação, quantidade e distribuição de grupos iônicos ao longo das cadeias e grau de intercruzamento. Nossos resultados não permitem concluir se os materiais correspondem a cadeias poliméricas intercruzadas física ou covalentemente, pois a ocorrência de ligações de intercruzamento do tipo éster não pode ser descartada, mas a confirmação de sua presença por espectroscopia de infra-vermelho é prejudicada pela extensa superposição de bandas na região de interesse. Apesar do emprego de fontes convencionais de celulose em condições semelhantes de síntese resultar em produtos com características muitos superiores àquelas apresentadas pelos produtos deste trabalho, consideramos que nossos resultados são promissores. Por um lado, devem ser consideradas a disponibilidade e abundância da matéria-prima que podem significar um custo relativamente baixo quando comparado ao de fontes convencionais de celulose. Por outro lado, o emprego de polpas de bagaço em lugar de madeiras pode ter um impacto ecológico muito positivo dada a possibilidade de preservação de reservas florestais. Finalmente é necessário ressaltar que a qualidade dos produtos obtidos depende das características da matéria-prima empregada, principalmente grau de polimerização da celulose obtida por polpação. Nesse sentido, o emprego de outros processos de polpação e branqueamento que reduzam a degradação das cadeias de celulose melhorarão as características das polpas de medula e, por consequência, as propriedades absorventes da carboximetilcelulose insolúvel obtida. / This work describes the use of ethanol / water pulps of pith in a study aiming the obtention and characterization of substantially insoluble carboxymethylcellulose for application as an absorvente material. In a typical experiment the carboxymethylation reaction of bleached ethanol / water pulp occurred at 80&#176C for 4 hours in isopropanol/ water suspension 1 : 8 (w/w) employing a cellulose / sodium hydroxide / monochloroacetic acid molar ratio of 1.0/5.4 / 8.8. Characterizations were made through the determinations of the presence of characteristic functional groups; degree of substitution (DS); solubility in pure water and alkaline aqueous solution; water and saline aqueous solution retention capacity; morphology and thermal stability of the obtained products. Infra-red (i.r.) and nuclear magnetic ressonance (NMR) spectroscopies; scanning electronic microscopy (SEM); thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were employed for these characterizations. The material with the best absorbent characteristics was obtained through the application of the condition above described for the carboxymethylation reaction. This is a very insoluble product (S IDO < 20/0) with a much higher water retention capacity than unreacted pulp employed as raw material. Other eight products were prepared through the application of different concentrations of monochloroacetic acid and variable reactions times. AlI products manifested the polyelectrolyte effect, but their water retention capacities seem to depend on the degree of substitutions in a complex way. Water retention capacities of the products of this work seem to be the result of a compromise among the parameters of the carboxymethylation reaction, the content and distribution of ionic groups and the degree of crosslinking. From our results it cannot be concluded if the materials correspond to physically or covalently crosslinked polyffiericchains since the occurrence of ester bonds as crosslinkers can not be discarded, but its detection in the infra-red spectra is difficult as a consequence of the extensive superposition of bands in the region of interest. Although the use of conventional sources of cellulose in conditions similar to those described here result in products of superior quality we believe that pith can be a good altemative raw material for the obtention of carboxyffiethyl ceIlulose with absorbent characteristics. In Brazil it is available as a very abundant and low cost raw material derived from the industries which process sugar cane for the production of ethanol and sugar and its utilization in place of wood pulps may also represent ecological advantages as forest preservation will be favoured. Finally it is worthwhile to remember that the quality of the products also depends on the raw material characteristics, mainly the degree of polyffierization of the cellulose obtained after pulping. So the use of the other pulping and bleaching processes which minimize chain degradation wiIl certainly result in better pulps from pith and as a consequence materials with better absorbent characteristics will be prepared.