A thin polymer bilayer film was transformed into micro- and nano-tubes using strain driven self-rolling phenomena of polystyrene (PS)/poly (4-vinyl pyridine) (P4VP) film. Polymer bilayer was produced by consecutive deposition of PS and P4VP, from toluene and chloroform solutions, respectively, by dip-coating technique. The object formation proceeds from a opening in the film made by photolithography or by mechanical scratching followed by immersion of patterned sample in dodecylbenzene sulfonic acid (DBSA) solution. DBSA forms supramolecular complexes with pyridine rings of P4VP and increases the specific volume of the polymer. Since the solution is neutral to PS layer, bilayer film develops strain due to unequal swelling of polymers in solution of DBSA and hence the film bends and scrolls in order to minimize its free energy and form tubes. The length of the tubes and the direction of rolling are determined by mechanical patterning of the film. UV-photolithography is used to fabricate patterns of polymer bilayer in order to create tube in a precise manner. The kinetics of the tube formation was studied with respect to acidity of the solution and UV dose. Rate of rolling increased with the acidity of the solution. Tube diameter and rate of rolling decreased with the increase of the UV exposure time. Films with 2-dimensional gradients of layer thicknesses were prepared to study a broad range of parameters in a single experiment. Furthermore, polymer micro-toroids and triangles were also fabricated using self-rolling approach of PS/P4VP layer. Moreover, the kinetics of toroid formation is also studied in the present work. The equilibrium dimensions of toroid are determined by the balance of the bending and the stretching energies of the film. The width of the rolled-up bilayer is larger for the films with higher values of the bending modulus and smaller values of the effective stretching modulus. Moreover, self-rolling phenomena of polymer layer was also explored as a template to fabricate metal, ceramic and metal/ceramic hybrid tube. In order to fabricate metallic and V bimetallic tube, the cross-linked polymer film is capped by metallic layer. After rolling, polymer template is removed by pyrolysis resulting in pure metal microtubes. The fabrication of silica and silica/gold hybrid tubes of high aspect ratio is also demonstrated. Polydimethylsiloxane (PDMS) is used as a precursor of the silica and it is converted into silica by pyrolysis at high temperature. Entire polymer moiety is also removed at this temperature. In order to fabricate hybrid tube of silica with gold, a thin gold layer is deposited on the polymer layer by physical vapour deposition. Self-rolling of polymer bilayers is a very convenient approach for interfacing the interior of microtubes with external electrical circuits and it can be used in particular for creating devices as micro-bubble generators exploiting electrolytic decomposition of fluids. A demonstration of microbubble generation inside the polymer tube is shown in this work. Possibility to functionalize the hidden walls of the tubes is one of the major advantages of the self-rolling approach. One can modify the surface of the film prior to rolling by magnetron sputtering of metal and upon rolling, tube and toroids with metallized inner surface could be obtained. The tube and toroids with metallic inner surface are promising for the future research as IR-frequency range resonators. Polymer and metallic microtubes fabricated by self-rolling approach may find applications in such fields as IR-waveguiding, microfluidics, enzyme bi-reaction, chemical and biochemical sensing. The silica and silica/gold hybrid tubes have potential use in optoelectronic devices and in catalytic applications.

Gegenstand der vorliegenden Arbeit war es, die Grundlagen für ein mögliches technisches Verfahren zur Aromatennitrierung mit Salzhydratschmelzen (M(NO3)3 · n H2O, M = Fe, Cr, Bi, In, Al; n = 4 - 9) zu untersuchen. Es sollte geklärt werden, ob Toluol quantitativ zu Dinitrotoluol bzw. Benzol zu Nitrobenzol umgesetzt werden kann. In Screening-Versuchen wurden geeignete, nitrierend wirkende Salzhydrate ermittelt, sowie Wege untersucht, die Reaktivität der eingesetzten Salzhydratschmelzen durch Variation von Wasser- bzw. Säuregehalt, Durchmischung, verschiedenen Schmelzenzusätzen bzw. Reaktionstemperatur zu steigern. Das entstehende Verhältnis der Isomeren der Mono- und Dinitrierung wurde hinsichtlich einer möglichen Beeinflussung untersucht. Das Spektrum an Nebenprodukten wurde bestimmt, sowie Möglichkeiten aufgezeigt, diese zu vermeiden. Dabei konnte gezeigt werden, dass im Gegensatz zum etablierten Mischsäureverfahren beim Einsatz von Salzhydratschmelzen keine kresolischen Nebenprodukte gebildet werden. Weiterhin wurden Möglichkeiten zur Präparation wasserarmer Salzhydratschmelzen durch thermische Entwässerung bzw. Reaktion mit flüssigem N2O4 untersucht, die Löslichkeit der isomeren Zwischen- und Endprodukte in der Salzhydratschmelze bestimmt sowie das thermische Verhalten von Dinitrotoluol in Gegenwart der Salze betrachtet.