The implementation of polymer membranes in gas separation applications has been investigated to a great extent. Nevertheless, only a few types of polymers are used in commercial applications, disclosing the need for new materials with superior membrane performance to make membrane processes a more competitive technology over the conventional ones. Based on this context, this work focuses on the development of new polymeric membranes. Polyaniline (PANI), a multifaceted polymer that can change its structural properties upon various modification procedures, was chosen as membrane material. PANI membranes possess attractive O2/N2 selectivities, wherefore it is an interesting candidate for the use in gas separation applications, such as generation of oxygen-enriched air or inert gas generation. However, membranes made from neat PANI are suffering from brittleness and thus create leak paths through the membrane. Therefore PANI was blended with polybenzimidazole (PBI), a temperature stable polymer with good film-forming properties facilitating the preparation of thin, stable polymer films. Furthermore, several techniques were investigated including acid-doping, thermal treatment, and addition of titanate nanotubes (TiNTs) to enhance the separation properties. The materials that have been prepared are: 1)...

(EN) This dissertation thesis is focused on physicochemical and chromatographic characterization of polyaniline-coated stationary phases. In the first part, surfaces of bare silica and octadecyl silica sorbents were modified by in-situ chemical polymerization of aniline hydrochloride and their subsequent systematic characterization was performed by using the linear solvation energy relationship approach in the HILIC mode of capillary LC. In addition, several common physicochemical techniques were used to characterize properties of these altered materials. The modified sorbents were then packed into capillary columns. The retention interactions taking place between solute and the separation system were evaluated on the basis of retention data of a number of various solutes. The results showed that polyaniline coating had a significant effect on the retention promoting interactions of both polyaniline-coated stationary phases. The assumed mixed-mode retention mechanism was proven for both the stationary phases. The second part dealt with investigation of the separation potential of polyaniline- coated silica stationary phase in different chromatographic modes. The retention factor curves of structurally similar solutes were constructed as a function of organic modifier portion in the mobile phase....

In the first part of this work, silica nanoparticles and alternative or additional filler phases were incorporated into hydrogels based on the temperature-sensitive poly(N- isopropylacrylamide) (PNIPAm). Nano-SiO2-filled porous PNIPAm hydrogels with an enhanced force response (up to 100 g) to temperature stimuli were obtained by increasing several times the pore wall thickness, which was achieved via reducing the solvent (porogen) content during the gels' cryo-synthesis. A similar optimization of the force response was also carried out for analogous gels reinforced by nano-TiO2, in which the reinforcing effect of the filler is weaker. Partial intercalation of amylopectin starch into divinyl-crosslinked bulk as well as porous PNIPAm gels several times improved their extensibility. In case of starch-rich bulk gels, a very fast and extensive one-way deswelling in response to increased temperature was achieved (re-swelling upon cooling is much slower), which is attributed to specific properties of the starch-PNIPAm interface. In doubly-filled bulk PNIPAm/nano-SiO2/starch gels, a very strong synergic reinforcing effect of both fillers is observed, due to specific hydrogen bridging between the three phases. Highly porous cryogels based on PNIPAm/nano- SiO2/starch displayed a highly improved extensibility...

Emerging markets in electrochemical energy storage, such as stationary grid storage, coupled with future concerns over the availability of lithium, places sodium-ion battery (SIB) technologies at a unique position to enter the market as a commercially viable alternative. Current shortcomings in the performance of cathode materials in SIBs would necessarily need to be addressed if this technology is to compete with existing commercial lithium-ion battery counterparts. Prussian White (PW), a promising cathode material currently being produced by Altris AB in Uppsala, Sweden, has been shown in many regards to be a promising candidate as a cathode material. In efforts to improve the lifetime, thermal stability, and rate capability of the material, both zinc oxide (ZnO) and polyaniline (PANI) coatings were applied to the active material powder.  Scanning electron microscopy (SEM) images of the ZnO coated PW showed that the ZnO was concentrated to certain regions, resulting in a rough and compromised coating. Furthermore, the notable presence of iron 2p orbital peaks in XPS spectra for ZnO and PANI coated samples, together with the SEM images, suggests that no method resulted in a conformal coating. Crystallographic information obtained using a capillary X-ray diffractometer showed that the PANI coating process had caused the PW to transition from a monoclinic to a cubic structure. This phase transition, based on subsequent thermogravimetric analysis, is attributed to an increase in both interstitial and lattice water content.  A comparative analysis of particle size and morphology, before and after slurry homogenization, showed that the ball milling technique used resulted in a reduction in size. Moreover, the ball milling process affected the uncoated PW more than the ZnO coated PW.  Findings, based on galvanostatic cycling of both full and half cells, indicate that the ZnO coating method on average results in a 12 mAh g1 loss in discharge capacity. The PANI coated PW showed a drop in capacity of approximately half that of the uncoated reference samples. No significant differences were observed in capacity retention, coulombic efficiency, and thermal stability between ZnO coated and uncoated PW. The better rate capability of the uncoated PW is suggested to be a result of the smaller particle size. Explanations for the observed similarities in electrochemical performance include (i) the breaking up of particles and agglomerates during the ball milling process (exposing uncoated faces), and (ii) the compromised coating. / Framväxande marknader inom elektrokemisk energilagring, såsom stationär nätlagring, i kombination med framtida oro över tillgängligheten av litium, placerar natriumjonbatteriteknik (SIB) i en unik position för att komma in på marknaden som ett kommersiellt lönsamt alternativ. Nuvarande brister i prestanda av katodmaterial i SIB måste nödvändigtvis åtgärdas om denna teknik ska konkurrera med befintliga kommersiella litiumjonbatterier. Prussian White (PW), ett lovande katodmaterial som produceras av Altris AB i Uppsala, Sverige, har i många avseenden visat sig vara en lovande kandidat som katodmaterial. I försök att förbättra materialets livslängd, termiska stabilitet och cyklingshastighetsförmåga applicerades både zinkoxid (ZnO) och polyanilin (PANI) -beläggningar på PW.  Svepelektronmikroskopi (SEM) -bilder av den ZnO-belagda PW visade att ZnO koncentrerades till vissa regioner, vilket resulterade i en grov och komprimerad beläggning. Vidare antyder närvaron av järn 2p orbitaltoppar i XPS-spektra för ZnO- och PANI-belagda prover, tillsammans med SEM-bilderna, att ingen metod resulterade i en lyckad beläggning. Kristallografisk information erhållen med användning av en kapillär röntgendiffraktometer visade att PANI-beläggningsprocessen hade orsakat en fasomvandling från en monoklinisk till en kubisk struktur. Denna fasomvandling, baserad på efterföljande termogravimetrisk analys, tillskrivs en ökning av både interstitiellt och gittervatteninnehåll.  En jämförande analys av partikelstorlek och morfologi före och efter homogenisering visade att den använda kulkvarnstekniken resulterade i en minskning i storlek. Dessutom påverkade kulkvarnsprocessen den obelagda PW mer än den ZnO-belagda PW.  Resultat, baserade på galvanostatisk cykling av både hel- och halvceller, indikerar att ZnO-beläggningsmetoden i genomsnitt resulterar i en 12 mAh g-1-förlust i urladdningskapacitet. Den PANI-belagda PW uppvisade en minskning i kapacitet på ungefär hälften av de obelagda referensproverna. Inga signifikanta skillnader observerades i kapacitetsretention, coulombisk effektivitet och termisk stabilitet mellan ZnO-belagd och obelagd PW. Den bättre hastighetsförmågan hos obelagd PW föreslås vara ett resultat av den mindre partikelstorleken. Förklaringar för de observerade likheterna i elektrokemisk prestanda innefattar (i) uppbrytning av partiklar och agglomerat under kulfräsningsprocessen (exponering av obelagda ytor) och (ii) ofullständig beläggning.

Die elektronischen Transporteigenschaften von Polymerketten haengen sehr stark von deren strukturellen Eigenschaften und der Temperatur ab. Auf der Basis vorhandener Bandstrukturdaten wird ein empirischer Tight-Binding-Hamiltonoperator fuer ausgewaehlte Polyanilinstrukturen konstruiert. Mit den so erhaltenen Parametern ist es moeglich, Unordnung in die Polymerkette einzufuehren, wie sie durch Polaronen- Paarbildung und Bipolarondefekte bei niedrigen Temperaturen auftritt. Die Streukoeffizienten des Systems bestimmen die Transmission durch die Kette und damit den Leitwert des Systems im Rahmen der Landauer-Buettiker- Theorie. Der Einfluss von Dissipation auf die Transporteigenschaften des Polymers wird mit Hilfe zweier Modelle untersucht. Zum einen kann inelastische Streuung durch Kopplung des Systems an zusaetzliche Elektronenreservoire eingefuehrt werden, dies ist ein sehr phaenomenologisches Modell. Die Kopplung des zu untersuchenden Systems an Reservoire harmonischer Oszillatoren bietet die Moeglichkeit, dissipative Prozesse auf der Basis eines Hamiltonoperators einzufuehren. Beide Modelle lassen sich mit Hilfe der gleichen Greens-Funktionen-Methode loesen. Polyanilin kann sowohl in Form von einzelnen, in einer isolierenden Matrix eingebetteten Polymerketten als auch in groesseren Aggregaten von miteinander gekoppelten Ketten vorliegen. Zur Beschreibung dieser quasi-eindimensionalen Systeme wird das Tight-Binding-Modell auf drei Dimensionen erweitert und die Transporteigenschaften in Abhaengigkeit von der Systemgroesse diskutiert. Im Anschluss daran wird durch Einfuehrung dissipativer Prozesse das Material auf die Moeglichkeit eines Metall-Isolator-Ueberganges untersucht.

Despite the availability of numerous two-dimensional (2D) materials with structural ordering at the atomic or molecular level, direct construction of mesoscale-ordered superstructures within a 2D monolayer remains an enormous challenge. Here, we report the synergic manipulation of two types of assemblies in different dimensions to achieve 2D conducting polymer nanosheets with structural ordering at the mesoscale. The supramolecular assemblies of amphipathic perfluorinated carboxylic acids and block co-polymers serve as 2D interfaces and meso-inducing moieties, respectively, which guide the polymerization of aniline into 2D, freestanding mesoporous conducting polymer nanosheets. Grazingincidence small-angle X-ray scattering combined with various microscopy demonstrates that the resulting mesoscale-ordered nanosheets have hexagonal lattice with d-spacing of about 30 nm, customizable pore sizes of 7–18 nm and thicknesses of 13–45 nm, and high surface area. Such template-directed assembly produces polyaniline nanosheets with enhanced π–π stacking interactions, thereby resulting in anisotropic and record-high electrical conductivity of approximately 41 S cm–1 for the pristine polyaniline nanosheet based film and approximately 188 S cm–1 for the hydrochloric acid-doped counterpart. Our moldable approach creates a new family of mesoscale-ordered structures as well as opens avenues to the programmed assembly of multifunctional materials.

In der vorliegenden Arbeit wurden stickstoffhaltige Monomere ausgehend von aromatischen Aminen oder Lactamen durch Umsetzung mit Chlorsilanen synthetisiert. Die so erhaltenen Derivate wurden mit Hilfe spektroskopischer und thermischer Analysenmethoden umfassend charakterisiert. Auf Basis der stickstoffhaltigen Monomere wurden über unterschiedliche Synthesestrategien organisch-anorganische, nanostrukturierte Hybridmaterialien hergestellt. Durch die thermisch induzierte Zwillingspolymerisation der Monomere 2,2‘-Spirobi[3,4-dihydro-1H-1,3,2-benzodiazasilin] und 1,1’,4,4‘-Tetrahydro-2,2‘-spirobi[benzo[d][1,3,2]-oxazasilin] gelang es, Hybridmaterialien bestehend aus Polyanilin-Formaldehyd-Harzen und Polysilazanen bzw. Siliciumdioxid unter Variation der Reaktionstemperatur herzustellen. Die Untersuchung der entstandenen Materialien erfolgte mittels spektroskopischer Methoden. Die Lactam-Monomere wurden durch die Zugabe von Aminocarbonsäuren zu Polyamid 6/SiO2- bzw. Polysiloxan-Kompositen umgesetzt. Hier stand die Ermittlung der molekularen Struktur, wie auch die Bestimmung des thermischen Verhaltens und der Homogenität der Materialien im Vordergrund. Es konnte gezeigt werden, dass die Synthese der thermoplastischen Kompositmaterialien auch in vergrößertem Maßstab reproduzierbar ist und die Produkte zudem zu Folien extrudierbar sind. / In the present work nitrogen-containing monomers have been synthesized by reactions of silicon tetrachloride with amines or lactames and were characterized by different spectroscopic and thermal analysis methods. The twin monomers 2,2‘-spirobi[3,4-dihydro-1H-1,3,2-benzodiazasiline] and 1,1’,4,4‘-tetrahydro-2,2‘-spirobi[benzo[d][1,3,2]¬oxazasiline] can be converted to hybrid materials containing polyaniline-formaldehyde resins and polysilazane or SiO2 by thermal induced twin polymerization under variation of the reaction temperature. The obtained nano composites were investigated by spectroscopic methods and electron microscopy. The lactam containing monomers were polymerized to polyamide 6/SiO2-composites by addition of aminocarbonic acids and -caprolactam. The analysis of the molecular structure as well as the investigation of the thermal behavior and the homogeneity of materials was emphasized. It could be shown, that the synthesis can be performed reproducible. Furthermore, it is possible to extrude the thermoplastic composite materials to films.

In der vorliegenden Arbeit wurden stickstoffhaltige Monomere ausgehend von aromatischen Aminen oder Lactamen durch Umsetzung mit Chlorsilanen synthetisiert. Die so erhaltenen Derivate wurden mit Hilfe spektroskopischer und thermischer Analysenmethoden umfassend charakterisiert. Auf Basis der stickstoffhaltigen Monomere wurden über unterschiedliche Synthesestrategien organisch-anorganische, nanostrukturierte Hybridmaterialien hergestellt. Durch die thermisch induzierte Zwillingspolymerisation der Monomere 2,2‘-Spirobi[3,4-dihydro-1H-1,3,2-benzodiazasilin] und 1,1’,4,4‘-Tetrahydro-2,2‘-spirobi[benzo[d][1,3,2]-oxazasilin] gelang es, Hybridmaterialien bestehend aus Polyanilin-Formaldehyd-Harzen und Polysilazanen bzw. Siliciumdioxid unter Variation der Reaktionstemperatur herzustellen. Die Untersuchung der entstandenen Materialien erfolgte mittels spektroskopischer Methoden. Die Lactam-Monomere wurden durch die Zugabe von Aminocarbonsäuren zu Polyamid 6/SiO2- bzw. Polysiloxan-Kompositen umgesetzt. Hier stand die Ermittlung der molekularen Struktur, wie auch die Bestimmung des thermischen Verhaltens und der Homogenität der Materialien im Vordergrund. Es konnte gezeigt werden, dass die Synthese der thermoplastischen Kompositmaterialien auch in vergrößertem Maßstab reproduzierbar ist und die Produkte zudem zu Folien extrudierbar sind. / In the present work nitrogen-containing monomers have been synthesized by reactions of silicon tetrachloride with amines or lactames and were characterized by different spectroscopic and thermal analysis methods. The twin monomers 2,2‘-spirobi[3,4-dihydro-1H-1,3,2-benzodiazasiline] and 1,1’,4,4‘-tetrahydro-2,2‘-spirobi[benzo[d][1,3,2]¬oxazasiline] can be converted to hybrid materials containing polyaniline-formaldehyde resins and polysilazane or SiO2 by thermal induced twin polymerization under variation of the reaction temperature. The obtained nano composites were investigated by spectroscopic methods and electron microscopy. The lactam containing monomers were polymerized to polyamide 6/SiO2-composites by addition of aminocarbonic acids and -caprolactam. The analysis of the molecular structure as well as the investigation of the thermal behavior and the homogeneity of materials was emphasized. It could be shown, that the synthesis can be performed reproducible. Furthermore, it is possible to extrude the thermoplastic composite materials to films.

Capacitive deionization is a promising technology for purification and desalination of brackish water with great advantages over current technologies due to its low operating cost and high-water recovery ratio. Most of the system studied relies on the adsorption/desorption capacity of activated carbon electrodes due to its high surface area. However, its specific adsorption capacity is limited since the adsorption is predominantly on the surface of the electrodes. In this thesis we propose the use of polyaniline as a chloride-ion adsorption material. Polyaniline is a redox polymer able to accommodate anions in several of its three states when subjected to an external voltage. To this end, we synthesized polyaniline by electrodeposition technique and its electrochemical behavior was studied. A hybrid CDI system was assembled, using PANI as anode material and activated carbon cloth as cathode, showing outstanding adsorption of 37.26 mg/g Cl at current densities of 250 A/g. The energy consumption of this system was of 0.4979 kWh/m3. Its stability was evaluated over 50 cycles with negligible capacity loss. Along with its use in a CDI system, the aim of this thesis was to understand the mechanisms of operation of this material, by means of its physical and electrochemical characterization, as well as its efficiency and stability through the use of this material in capacitive deionization cells. / Kapacitiv avjonisering är en lovande teknik för rening och avsaltning av bräckt vatten med stora fördelar jämfört med nuvarande teknik på grund av dess låga driftskostnader och höga vattenåtervinningsgrad. De flesta av de studerade systemen bygger på adsorptions/desorptionskapaciteten hos elektroder av aktivt kol på grund av dess stora yta. Dess specifika adsorptionskapacitet är dock begränsad eftersom adsorptionen huvudsakligen sker på elektrodernas yta. I den här avhandlingen föreslår vi att polyanilin används som adsorptionsmaterial för kloridjoner. Polyanilin är en redoxpolymer som kan ta emot anjoner i flera av sina tre tillstånd när den utsätts för en extern spänning. För detta ändamål syntetiserade vi polyanilin genom elektrodepositionsteknik och dess elektrokemiska beteende studerades. Ett hybrid CDI-system monterades med PANI som anodmaterial och aktiverad kolduk som katod, vilket visade en enastående adsorption av 37,26 mg/g Cl vid en strömtäthet på 250 A/g. Energiförbrukningen för detta system var 0,4979 kWh/m3. Systemets stabilitet utvärderades över 50 cykler med försumbar kapacitetsförlust. Förutom användningen i ett CDI-system var syftet med denna avhandling att förstå detta materials funktionsmekanismer genom fysisk och elektrokemisk karakterisering samt dess effektivitet och stabilitet genom användning av detta material i kapacitiva avjoniseringsceller.