Die vorliegende Arbeit beschreibt zwei Verfahren zur Herstellung von submikronen Ionenaustauscherpartikeln. Im ersten Verfahren, der Miniemulsionspolymerisation, liegt der Schwerpunkt auf dem energetisch sehr aufwendigen Schritt der Herstellung einer stabilen Miniemulsion. Dabei werden Prozessparameter optimiert und Destabilisierungsmechanismen analysiert. Im zweiten Teil der Arbeit wird ein neues kostengünstiges und ressourcenschonendes Herstellungsverfahren vorgestellt. Dabei werden kommerziell erhältliche Ionenaustauscherpartikel auf Polymerbasis in Kugelmühlen zerkleinert.

The work in this thesis demonstrates whether resins are better than conventional soil extractants at predicting plant metal concentrations, and whether low-cost soil treatments can effectively reduce metal content and concentrations in lettuce leaves. / Researchers have shown that ion exchange resins can simulate root metal uptake behaviour by acting as ion sinks. Chemical extractants on the other hand, generally do not behave in this manner. Thus, we would expect resins (in either bead or membrane form) to predict plant metal concentrations better than conventional extractants. For the first study, a procedure using anion exchange resin membranes (AEM) treated with either EDTA or DTPA chelators was chosen, since previous studies showed this method to be effective at predicting plant metal uptake, and practical for routine laboratory use. In addition, several conventional extractants were selected for comparison. / For the second part of the thesis, a study was undertaken to test the effectiveness of various food processing byproducts to stabilize metal contaminants in soils, and compare the results with those of a Na-based aluminosilicate (zeolite). (Abstract shortened by UMI.)

Conductive paper materials consisting of conductive polymers and cellulose are promising for high-tech applications (energy storage and biosciences) due to outstanding aspects of environmental friendliness, mechanical flexibility, electrical conductivity and efficient electroactive behavior. Recently, a conductive composite paper material was developed by covering the individual nanofibers of cellulose from the green algae Cladophora with a polypyrrole (PPy) layer. The PPy-Cladophora cellulose composite paper is featured with high surface area (80 m2 g-1), electronic conductivity (~2 S cm-1), thin conductive layer (~50 nm) and easily up-scalable manufacturing process. This doctoral thesis reports the development of the PPy-Cladophora composite as an electrode material in electrochemically controlled solid phase ion-exchange of biomolecules and all-polymer based energy storage devices. First, electrochemical ion-exchange properties of the PPy-Cladophora cellulose composite were investigated in electrolytes containing three different types of anions, and it was found that smaller anions (nitrate and chloride) are more readily extracted by the composite than lager anions (p-toluene sulfonate). The influence of differently sized oxidants used during polymerization on the anion extraction capacity of the composite was also studied. The composites synthesized with two different oxidizing agents, i.e. iron (III) chloride and phosphomolybdic acid (PMo), were investigated for their ability to extract anions of different sizes. It was established that the number of absorbed ions was larger for the iron (III) chloride-synthesized sample than for the PMo-synthesized sample for all four electrolytes studied. Further, PPy-Cladophora cellulose composites have shown remarkable electrochemically controlled ion extraction capacities when investigated as a solid phase extraction material for batch-wise extraction and release of DNA oligomers. In addition, composite paper was also investigated as an electrode material in the symmetric non-metal based energy storage devices. The salt and paper based energy storage devices exhibited charge capacities (38−50 mAh g−1) with reasonable cycling stability, thereby opening new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems. Finally, micron-sized chopped carbon fibers (CCFs) were incorporated as additives to improve the charge-discharge rates of paper-based energy storage devices and to enhance the DNA release efficiency. The results showed the independent cell capacitances of ~60-70 F g-1 (upto current densities of 99 mA cm2) and also improved the efficiency of DNA release from 25 to 45%.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2000. / Härtill 4 uppsatser.

Kommerziell erhältliche Ionenaustauscher basieren häufig auf funktionalisierten Cellulosemembranen, die mit CerIV und Glycidylmethacrylat (GMA) gepfropft und anschließend sulfoniert werden.  Die Untersuchung dieser Polymerisation zeigte, dass während der Pfropfung eine Vernetzung des Polymers über die Epoxidfunktion des Monomers auftritt. Daher konnte keine direkte Analyse des entstandenen Hydrogels durchgeführt werden und es wurde stattdessen Methylmethacrylat (MMA) auf der Oberfläche polymerisiert. Nach Entwicklung eines geeigneten Verfahrens zur Zersetzung der Membranen und Isolierung des Pfropfpolymers konnte dieses mit Gel-Permeations-Chromatographie (GPC) analysiert werden. Zusätzlich wurden Polymerisationen auf nicht-porösem Cellophan durchgeführt und die erhaltenen Proben mittels Rasterkraftmikroskopie (Atomic Force Microscopy, AFM) untersucht.  Die Ergebnisse zeigen, dass das gepfropfte PMMA einen Polymerisationsgrad von 2100 und eine Dichte von 0,45 Ketten pro nm2 auf der Oberfläche hat. Wird die gleiche Anzahl an Polymeren auch für Pfropfung mit PGMA angenommen und mit dem Pfropfgrad verglichen, ergibt sich damit unter Vernachlässigung der Vernetzung ein Polymerisationsgrad von etwa 800. Es konnte gezeigt werden, dass die für die Pfropfung verwendete Emulsion unter anderem aus Tröpfchen besteht, deren Größe mit der der Poren der Membran übereinstimmt. Dennoch treten bei der Polymerisation keine Ausschlusseffekte auf und die Größenverteilung der Emulsionspartikel stellt sich auch nach Filtration zügig wieder ein. Zusätzlich wurde eine Methode der Atom-Transfer radikalischen Polymerisation (ATRP) auf mikroporösen Membranen entwickelt und eingesetzt, um gezielt bestimmte Eigenschaften des Hydrogels zu variieren. Bei Versuchen mit MMA wurde der reversibel deaktivierte Charakter unter den verwendeten Bedingungen untersucht und nachgewiesen.  Die verwendete Methode erlaubt, die Kettenanzahl und –länge separat voneinander einzustellen, sodass der Einfluss dieser Größen auf die Eigenschaften des resultierenden Membranadsorbers gezielt untersucht werden konnte. Es zeigte sich, dass die Dichte der Ketten einen komplexen Einfluss sowohl auf die Permeabilität als auch auf die Bindungskapazität des Ionentauschers hat. Der Einfluss der Kettenlänge ist dagegen weniger subtil und entspricht den Erwartungen.  Aus den gewonnenen Daten wurde ein Modell für die Bindung von Proteinen an der gepfropften Oberfläche des Austauschers entwickelt und daraus die Kettenlänge und –dichte des Hydrogels abgeschätzt und mit alternativen Methoden verglichen.

Neste estudo, a sorção e recuperação de íons metálicos de resíduos sólidos industriais provenientes de uma indústria de galvanoplastia situada no Rio de Janeiro (Brasil) foram investigadas através da utilização de duas resinas comerciais de troca iônica: Lewatit VPOC 1800 (fortemente ácida, tipo gel) e Lewatit VPOC 1960 (fortemente básica, tipo gel), produzidas pela Lanxess-Bayer Chemicals. As características físico-quimicas das resinas e do lodo galvânico foram determinadas. Os estudos de sorção das resinas foram conduzidos em batelada e em coluna. Baseado nesses estudos, os parâmetros de sorção e das curvas de ruptura foram determinados. Os estudos de equilíbrio e cinética de sorção também foram realizados. O resíduo de galvanoplastia era composto pelos metais: Cu2+, Fe3+, Al3+, Ni2+ e Cr3+. A capacidade de sorção qe das resinas Lewatit VPOC 1800 variou entre 0,1-1,9 mg g-1 para Cu2+, 0,01-0,6 mg g-1 para Fe3+ e 0,2-0,4 mg g-1 para Al3+. Enquanto que para a resina Lewatit VPOC 1960, os valores de qe variou entre 0,01-0,4 mg g-1 para Cu2+ e 0,01 0,2 mg g-1 para Fe3+ dependendo da concentração do metal e do tempo de contato. A capacidade de sorção para a resina Lewatit VPOC 1960 foi restrita para íons Cu2+ e Fe3+ os quais formam complexos aniônicos com íons Cl-. O modelo de Freundlich foi o mais adequado para descrever o equilíbrio de troca iônica de ambas as resinas. Já em relação ao mecanismo de sorção, o modelo pseudo-segunda ordem tipo 1 foi o mais aplicável. O ponto de ruptura das resinas Lewatit VPOC 1800 e Lewatit VPOC 1960 em relação aos íons Cu2+ocorreu quando passou através da coluna, 1860 cm3 e 2220 cm3 de solução de resíduo sólido respectivamente (20 g de resina, 100 mg L-1 de íons Cu2+, vazão de 60 cm3 min-1). Os íons metálicos Cu2+, Fe3+, Al3+, foram dessorvidos em alta proporção da resina Lewatit VPOC 1800 passando pela coluna solução aquosa de H2SO4 2,4 mol L-1. Já os metais Cu2+ e Fe3+ foram eluídos da resina Lewatit VPOC 1960 com solução aquosa de HCl 2,0 mol L-1. A recuperação seletiva de Cu2+ não foi alcançada porque Cu2+ e Fe3+ precipitam na mesma faixa de pH / In the present study, the sorption and recovery of metal ions from industrial solid residues proceeding from galvanoplasty industry (Rio de Janeiro, Brazil) was investigated by using two commercial ion exchange resins Lewatit VPOC 1800 (strong acid, gel type) and Lewatit VPOC 1960 (strong basic, gel type) produced by Lanxess - Bayer Chemicals. The physical-chemical characteristics of the resins and galvanic sludge were determined. The studies of sorption of the resins were conduced under batch and column conditions. Based on these studies the sorption parameters and the breakthrough curves for both resins were determined. Studies of equilibrium and kinetic of the sorption were also performed. The electroplating residue were composed of the metals Cu2+, Fe3+, Al3+, Ni2+ and Cr3+. The sorption capacity qe of the resin Lewatit VPOC1800 varied between 0.1-1.9 mg g-1 to Cu2+, 0.01-0.6 mg g-1 to Fe3+ and 0.2-0.4 mg g-1 to Al3+. While for the resin Lewatit VPOC1960 the values of qe varied between 0.01-0.4 mg g-1 to Cu2+ and 0.01-0.2 mg g-1 to Fe3+ depending of the metal concentration and contact time. The sorption capacity for Lewatit VPOC1960 was restricted to ions Cu2+ and Fe3+ that to form anionic complexes with chloride. The Freudlich model was more adequate to describe the ion exchange equilibrium for both resins and the sorption mechanism was compliant to the kinetic model of pseudo second order type 1. The breakpoint to Cu2+ occurred after passing 1860 cm3 and 2220 cm3 of residue solution through the resins Lewatit VPOC1800 and Lewatit VPOC1960, respectively (20 g of the resin, 100 ppm of Cu2+, flow rate of 60 cm3 min-1). The metals Cu2+, Fe3+ and Al3+ were desorbed on high proportion of the Lewatit VPOC1800 through passing a aqueous solution H2SO4 2.4 mol L-1. Already the metals Cu2+ and Fe3+ were eluted to Lewatit VPOC1960 with HCl aqueous solution 2.0 mol L-1. The selective recuperation of the Cu2+ was not reach because the Cu2+ and Fe3+ precipitated on similar pH

Made available in DSpace on 2014-10-09T12:44:33Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:00Z (GMT). No. of bitstreams: 1 06867.pdf: 6383508 bytes, checksum: d78bad9ca259bf6a60dc4d98d94fc7a3 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

L’optique intégrée sur verre est une technologie mature dont les nombreuses applica-tions vont des télécommunications optiques aux capteurs. L’amélioration constante des per-formances des dispositifs réalisés est basée sur une densification des fonctions et donc uneréduction des dimensions des guides d’onde ainsi qu’une augmentation de la densité de puis-sance que ceux-ci transportent. Dans ce travail, nous avons donc étudié les performancesultimes de la technologie de l’échange d’ions argent/sodium sur verre en matière de confi-nement et de longueur de propagation. En particulier, dans le cas de la génération d’effetsnon-linéaires, nous avons mis en évidence la nécessité de trouver un compromis entre ces deuxaspects. Nous démontrons alors que les performances des guides d’onde obtenus par échanged’ions argent/sodium sont intrinsèquement limitées par les pertes optiques attribuées à laprésence d’argent métallique. Ceci se traduit par la présence d’un seuil d’endommagementà fortes densités de puissances. Pour dépasser cette limitation nous avons proposé et ini-tié alors un changement radical de technologie dont nous présentons les premiers résultatsobtenus par échange thallium/sodium sur un verre spécifiquement développé. / Glass integrated optics is a key enabling technology which applications range from opticaltelecommunications to sensors. The steady improvement of devices performances is sustainedby an increasing functions density and thus smaller waveguides supporting higher powerdensities. In this work we investigate the ultimate performances in terms of confinementand propagation length of the silver/sodium ion-exchanged waveguides fabricated on glasstechnology. In particular, a trade-off between these two features has been highlighted inthe case of nonlinear effects. We then demonstrate that the performances of silver/sodiumion-exchanged waveguides are mainly limited by optical losses introduced by metallic silveraggregates even for buried low-losses waveguides. Hence the waveguides exhibit a damagethreshold for high power densities. To overcome this limitation a major technology changehas been initiate and we present the first results obtained by thallium/sodium ion exchange.

L’exploitation de l’énergie nucléaire pour la production d’électricité présente un défi de gestion des e˜uents radiotoxiques pour les générations présentes et futures. Face à ce constat, la communauté des chimistes recherche continument à améliorer les solutions de traitement et de recyclage du combustible usé. Dans le contrôle de ces procédés, les opérations d’analyse jouent un rôle primordial. La miniaturisation des procédés est un des enjeux principaux de la recherche en sûreté nucléaire, dans un e˙ort de réduction des risques, des délais et des coûts des activités de laboratoire. Dans ce contexte, les travaux présentés ici sont issus d’une collaboration entre le CEA de Marcoule et l’IMEP-LAHC et traitent de la mise au point d’un microsystème optofluidique sur verre, adapté à la mesure de concentration de plutonium (VI) en acide nitrique. Une source de lumière sonde est confinée dans un guide d’onde obtenu par échange d’ions et interagit par onde évanescente avec un canal microfluidique. La raie d’absorption à 832 nm du Pu(VI) dans la solution à analyser devient donc observable dans le spectre de la lumière après une certaine longueur d’interaction. Un des enjeux principaux est de fabriquer un capteur très robuste, fonctionnel en boîte à gants. L’assemblage du dispositif est e˙ectué par collage moléculaire avec un procédé permettant d’atteindre une énergie de surface > 2, 5 J·m2 suÿsante à garantir la tenue du dispositifs à des pressions testées jusqu’à 2 bars dans les canaux. Les fonctions optiques et fluidiques du dispositif sont complètement interfacées avec des fibres optiques et des capillaires fluidiques. Des mesures spectrales d’une solution de plutonium (VI) en acide nitrique ont permis de vérifier la compatibilité de la solution technologique abordée pour la manipulation d’acides forts et la résistance à l’irradiation. Le système présente une limite de détection de 1,6·10−2 mol·L−1 Pu(VI) pour un volume sondé inférieur à 1 nano-litre, au sein d’un microcanal de 21 micro-litres. Une structure permettant d’optimiser la sensibilité du capteur ainsi que le volume du canal est étudiée en perspective du travail de thèse, afin d’atteindre les performances équivalentes à des outils commerciaux pour des volumes sondés de l’ordre de quelques nano-litres. / .The use of nuclear energy for electricity production presents an important concern with radiotoxic waste management for present and future generations. In view of this fact, the chemists’ community has been searching for solutions to treat and recycle nu-clear fuel. The miniaturization of chemical processes is extensively sought out nowerdays, in an attempt to reduce laboratory acivity risks, delays and costs. The researched ana-lytical innovation requires subsequent development of appropriate analysis tools. In this respect, the work presented here addresses the development of co-integrated optofluidic micro-systems on borosilicate glass, compatible with nuclear e˜uent analysis constraints. A spectrometric sensor is designed, fabricated, interfaced and characterized in a nuclear environement. An optical waveguide and a microfluidic channel are designed adjacent to one another in order to obtain wide-spectrum absorption spectroscopy measurements by light/fluid evanescent interaction. Both ion-exchange technology and wet-etching tech-nologies were used to create the optical and fluidic planar functions. The device is assem-bled by direct molecular bonding with an optimized protocole which withstands surface energies > 2, 5 J·m2. Sensor optical and fluidic functions are interfaced with fiber optics and fluid capillaries in order for the chip to be used within a plug-and-play detection chain. Spectral measurements of a plutonium(VI) in nitric acid solution have allowed to verify the technological solution’s compatibility with harsh acid manipulation and irra-diation resistance. The system put together for the detection of plutonium(VI) displays a detection limit of 1.6×10−2 mol·L−1 for a probed volume below 1 nano-liter, inside a 21 micro-liter channel. A new sensor design is studied in the thesis work perspectives in order to optimize sensor detection limit and channel volume and reach industrial tools analytical performances with nano-liter sample volumes.

Organically overfertilization cambisoil modal after conversion to kultizem horticka was further fertilized in version P compost industry (communal) and version H compost humus (agricultural) containing 13,72% of humus and 22,78% of the primary organic matter over a period of 6 years dose 50 t / ha annually. Fertilization with an actual compost H in organically fertilized soil reflected not only by increasing the ion exchange capacity of the soil, but also a significant improvement of water regime of soil, manifested by a quarter greater ability to maintain the water in the soil and 44% lower amount of water, physiologically ineffective.