Die Arbeit beschäftigt sich mit der Nutzung polymerer Ausgangsmaterialien für die Herstellung von Hochleistungsaktivkohlen mit definiert ausgeprägter Porenstruktur unter Anwendung eines neu entwickelten Pyrolysereaktors. Es werden verschiedene Produkte und deren Verhalten bei der Pyrolyse vorgestellt und auf der Grundlage anwendungsspezifischer Kriterien bewertet. Die bei der Sulfonierung als notwendige Copolymervorbehandlung wirkenden Parameter haben einen entscheidenden Einfluss auf die resultierende Koks- und Aktivkohlequalität. Dadurch ist es möglich, genau definierte Porenstrukturen herzustellen. Die Rolle der Sulfonierungs- und Pyrolyseparameter für die Aktivkohlequalität wird dargestellt. Bezüglich der technischen Umsetzung wurde ein Pyrolysereaktor entwickelt, der sich durch ein schmales Partikelverweilzeitspektrum bei gleichzeitig guter Feststoffdurchmischung auszeichnet. Durch umfangreiche Kaltversuche konnten grundlegende Abhängigkeiten zum Transport- und Verweilzeitverhalten ermittelt werden, mit deren Hilfe der Reaktor auf den jeweiligen Anwendungsfall angepasst und optimiert werden kann. Die Tauglichkeit unter Betriebsbedingungen wurde nachgewiesen.

Die Arbeit beschäftigt sich mit der Herstellung von Hochleistungsaktivkohlen mit definiert ausgeprägter Porenstruktur. Zunächst wurden Copolymere mit unterschiedlichem Vernetzungsgrad hinsichtlich ihrer Eignung zur Herstellung synthetischer Aktivkohlen im Labormaßstab untersucht. Die Rolle der Sulfonierungsparameter für die Aktivkohlequalität wird anhand ausgewählter Beispiele untersucht und dargestellt. Wichtig für die Realisierung der erforderlichen Prozessparameter ist die technische Umsetzung in einem geeigneten Reaktorsystem. Mit den im Pilotreaktor durchgeführten Sulfonierversuchen konnten die Gültigkeit des Scale-up bewiesen und die im Labormaßstab gefundenen Zusammenhänge übertragen werden.

Hyperbranched polymers (HBP) have drawn much attention and obtained intensive research activities from both industry and academia in the last three decades. They belong to a group of macromolecules called dendritic polymers, which have peculiar and often unique properties, which derive from their three-dimensional structure and the large number of functional groups. These structural characteristics provide high possibilities for controlling functional group interactions and modifications of other polymers in coatings and therefore, they are expected to result in novel materials with desired properties. They own a highly branched backbone, which gives access to many of reactive groups; their structure gives them excellent flow and processing properties, and they are characterized by lower viscosity than those of linear polymers of comparable molecular weight. Such properties make HBP extremely interesting for coatings and UV-curing applications and for this, they have attracted a great deal of attention for application, e.g. for powder coatings, high solid coatings, flame retardant coatings, barrier coatings for flexible packaging,and they have been recently suggested as a component of a dual-cure formulation based on an UV-curable epoxy resin and a functionalized alkoxysilane additive as an inorganic precursor to achieve advanced functional hybrid coatings. By pursuing this research line, we have synthesized an aliphatic–aromatic ethoxysilyl modified hyperbranched polyester system to be used in the preparation of UV-curable epoxy hybrid organic–inorganic coatings. The addition of ethoxysilyl-modified HBP could act as a coupling agent during the formation of the inorganic domains generated in-situ via sol-gel process starting from the alkoxysilane as inorganic precursors. The cured films were characterized in terms of their dynamic-mechanical properties and surface hardness: the obtained properties were discussed in relation to the achieved morphologies. In the present work, some aromatic hyperbranched polyesters (aHBP) and aliphatic-aromatic hyperbranched polyesters (aaHBP), OH terminated have been used as matrices for nanocomposites containing TiO2. The TiO2 nanoparticles were synthesized via sol-gel directly in a solution containing the HBP polyester as a stabilizer, and then the polymer/TiO2 hybrid mixtures were thermally cured by a curing agent to obtain a hard coating or a film. In order to determine the conditions in which it was possible to get the best dispersion and the properties for the final material, the starting HBP-OH was also partially modified with alkoxysilane groups by 3-isocyanatopropyltriethoxysilane (IPTES), yielding modified aliphatic-aromatic hyperbranched polyesters aaHBP(OH)-Si and modified aromatic hyperbranched polyesters aHBP(OH)-Si, enabling it to interact with the TiO2 network. Both materials obtained were then characterized, and their properties compared.

Exploitation of well defined responsive polymer brushes for direct and controlled immobilization of metal/semiconductor nanoparticles on macroscopic surfaces has been demonstrated. The employed approach offers the possibility of the organization of a variety of inorganic nanoparticles by irreversible bonding and homogenous distribution on an underlying substrate. The immobilization process has been realized by chemical grafting of a variety of polymer brushes on a suitable substrate followed by the attachment of pre-/in-situ formed nanoparticles exploiting the chemical/physical interactions between surface functionalities of nanoparticles and polymer chain segments. A number of polymer brushes including poly (acrylic acid), polystyrene, poly (2-vinyl pyridine) and poly (N-isopropyl acrylamide) brushes have been prepared on silicon substrate by the “grafting to” approach. A variety of inorganic nanoparticles such as quantum dots (CdTe) noble metals (gold and silver) and magnetic (Fe3O4) were immobilized on macroscopic surfaces to impart them photo luminescent, catalytic or magnetic properties. In addition, responsiveness of grafted polymer brushes in terms of variation in thickness (due to changes in chain conformation) as a function of external stimuli such as solvent and pH allowed to use the resulting polymer brush-nanoparticles nanoassemblies in the fabrication of nanosensors. The design of fabricated nanosensors is based on the modulation in the interparticle distance of immobilized nanoparticles due to swelling/deswelling of underlined polymer brushes in response to some external trigger.

Polymer brushes provide the responsive smart surfaces which can be used for fabrication of various devices. In this thesis work, adhesion, friction, and wear of polystyrene (PS) - poly(2-vinyl pyridine) (P2VP) and polystyrene - poly(acrylic acid) (PAA) binary brushes and corresponding monobrushes were investigated in dried state under controlled environment. Spin-coated films were also investigated for comparison. The aim was to explore possibilities to control/tune adhesion, friction, and wear between inorganic or polymeric surfaces by use of polymer brushes. Atomic force microscopy (AFM) with sharp silicon nitride tip and colloidal probes was employed to investigate the nanoscale adhesion and friction forces between different inorganic and polymeric surfaces. Adhesion and friction on the polymer brushes were comparable to that on the spin-coated films. Adhesion and friction force values were correlated, and were in accordance with the wettability of the brush surfaces for most of the samples. Switching in the adhesion and friction forces was observed for the PS+P2VP and PS+PAA binary brushes on treatment with selective solvents. Maximum switching in adhesion force and friction coefficient was by a factor of 2.7 and 5.4, respectively. Furthermore, switching of friction for mixed brush surface was observed during macroscale friction measurements using nanoindenter. Friction coefficients at macroscale were higher than those at the nanoscale. Moreover, adhesion and friction forces between the surfaces were significantly influenced by the humidity, grafting density of polymer brushes, chemical composition of top of the binary brush surface, and tip scan velocity. Nanowear studies were carried out with AFM using sharp silicon nitride tip while macrowear studies were carried out using nanoindenter. Nanowear on the surfaces was affected by molecular entanglements, adhesion and friction forces as well as shape and status of the tip. It was observed that the typical wear mode for PS brushes (treated with toluene) was ripple formation. In case of P2VP brushes (treated with ethanol) and PAA brushes (treated with pH 10 water), wear occurred via removal of the polymeric material. Wear mechanism observed for the monobrushes was similar to that observed for the spin-coated thick films of the same polymeric material. However, extent of the wear on the brush surfaces significantly differed from that on the spin-coated films. In case of PS+P2VP and PS+PAA binary brush samples, change in the wear mode was observed on treatment with the different selective solvents. On treatment with toluene (PS on the top), both of these binary brushes showed the wear by formation of the ripples. On the other hand, when these binary brushes were treated with selective solvent for P2VP or PAA, wear occurred mainly via removal of the polymeric material. The amount of wear increased with the number of scans for all the polymer brush samples. Moreover, wear on the polymer brush surfaces was also increased on increase in the applied load and decrease in the scan speed. Wear behavior on macroscale was averaged due to contact between surfaces at large number of asperities. Our results show that adhesion, friction, and wear of polymer surfaces can be controlled/tuned by the use of binary polymer brushes.

Self-organization of block copolymers becomes attractive for several branches of the current science and technology, which requires a cheap way of fabrication of well-ordered arrays of various nanoobjects. High ratio between the surface (or the interface) and the volume of the nanoobjects enables development of very efficient devices. The work within this thesis profits from the chemical dissimilarity between blocks of polystyrene-block-poly(4‑vinylpyridine) copolymers, where polystyrene forms “a body” of nanostructures and poly(4‑vinylpyridine) is “a link” for assemblies with low-molar-mass additives. Procedures and phenomena are demonstrated (observed) on few sorts of PS‑b‑P4VP copolymers with respect to their molecular weight and ratio of blocks. Although there are many kinds of nanostructures based on block copolymers, only nanotemplates are involved in the study. Their properties, like an influence of substrate roughness on microphase separation, stability of porous nanotemplates in ionized solutions, or a role of additives in their supramolecular assembly, respectively, are investigated. All of them appears to be important in development of various devices based on the nanotemplates. With respect to optoelectronic applications, electrical current transport and fluorescence are two basic phenomena studied on functionalized nanotemplates, developed in the thesis. DC transport is studied on nanostructures developed via sputtering of chromium into porous nanotemplates. Sputtering process is optimized in dependence of chromium deposition rate, composition and pressure of ambient gas. It is shown that a reactive nature of PS-b-P4VP nanotemplates enables development of resistant organometallic nanotemplates. On the other hand, suppression of the polymer reactivity is achieved by oxidation of a metal during sputtering in a reactive gas, which enables e. g. development of highly ordered TiO2 nanodots. Current-voltage characteristics are measured on “sandwich” devices (like LEDs) with various electrodes and composition. Several recent theoretical models fitting the characteristics are applied together with structural characterization techniques (like AFM or x-ray reflectivity) in order to elucidate relations among surface roughness, distribution of sputtered clusters, and carrier injection and transport. Fluorescence is studied on nanotemplates with organic low-molar-mass dyes, developed either via direct blending with the copolymer or via soaking of porous nanotemplates in dye solutions. Several relations between structure and fluorescence are observed. For instance, excimer emission in pyrene assemblies is supressed after ordering of the nanotemplate. Solvent induced orientation of fluorescein molecules in the nanotemplate results in fluorescence enhancement. Dimerization of Rhodamine 6G is dependent on the way of its impregnation in the nanotemplates (solvent, concentration, speed).

The thesis is devoted to the development of general methods of preparation of tethered polymer layers with laterally changing properties and investigation of their properties with focus on controlled adsorption and liquid flow. The temperature dependent character of the grafting reaction is used for the design of mono- and bicomponent gradient polymer grafted layers. For this purpose, a special stage providing a lateral temperature gradient is designed. The stage consists of two elements, one heating and one cooling, between which the experimental sample is situated. The versatility of these approaches for both fundamental research and practical applications is demonstrated. In general, the gradient approach is proved to be useful for the combinatorial-like investigations of ultrathin polymer films. The systematic study allowed detailed investigation of the grafting kinetics, the morphologies of the grafted polymer layers, the switching mechanism of the mixed polymer brushes, adsorption of colloid particles. The second approach for the preparation of laterally resolved tethered layers consists of a novel strategy for reversible environment-responsive lithography. This strategy implies local fixation of the morphology of mixed polymer brushes via photocrosslinking by UV irradiation. Irradiated areas lose the ability to switch. Exposure to selective and non-selective solvent allows visualization or erasing of the written information, respectively. It is demonstrated that developed approaches are promising for design of smart sensors, microfluidics devices, combinatorial study of the adsorption (separation and identification) of protein molecules and colloids and for other applications.

This work aimed to elucidate basic aspects of the influence of chemical structure and surface topography on the surface properties of a polymer material in order to minimize the work of adhesion. End-functionalised aromatic perfluorinated oligo/polyesters have been chosen to clarify effect of chemical structure. Here, the comprehensive investigation of the influence of molecular architecture on processes of fluorine segregation in the topmost surface layer and surface properties of the end-functionalised aromatic perfluorinated linear and branched oligo-and polyesters were performed. It has been shown, that the character of the surface segregation of fluorinated moieties can be influenced by different factors i.e. conditions of preparation of polymer layers (by means of spin-coated and melt films), chemical structure of fluorinated tail and polymer backbone and slightly by molecular weight. Analysis of obtained results allows distinguishing contribution of each factor. Experimentally obtained results showed a good correlation with Scheutjens-Fleer self-consistent mean-field theory extended by Kumar and Koberstein, which corresponds to the surface segregation of various chemical functional moieties located on functional polymers of different architectures. In correlation with a self-consistent field approach, observed results confirmed that polymers with end fluorinated groups are promising for producing of low-energy surfaces.The effect of surface topography has been studied on the example of regular and irregular structured surfaces fabricated from core-shell particles. A simple and effective approach for designing regularly patterned surfaces with specifically designed surface roughness and chemistry using core-shell colloidal particles was demonstrated. The chemistry was varied by covalent grafting of polymer brushes onto silica particles or by chemisorption of fluorosilane. The modified colloidal spheres were organized into closely packed hemispherical hexagonal arrays either by a vertical deposition technique or by sedimentation on slightly inclined coated silicon wafers. In this way, an increase in the vertical roughness was achieved with increasing particle radius, but without changing the Wenzel roughness factor. Controllable variations in the surface chemistry and morphology were used for a systematic study of the wetting phenomenon on regular structured arrays. The regularity and periodicity of particle structures allowed modelling of wetting. The wetting was modelled according to WENZEL, CASSIE-BAXTER, EXTRAND theories as well as minimal and maximal possible contact angles introduced by SHUTTLEWORTH and BAILEY.It has been found that none of these theories completely describe the experimental results for all particle sizes except for the surfaces made from 0.2 Mikrometer large particles. It was revealed that wetting behaviour on fluorosilane modified particles with the diameter of 0.2 Mikrometer is close to the equilibrium contact angle described by WENZEL and CASSIE-BAXTER theories. It has been shown that the deviations contact angle from equilibrium state increase with increasing particle size, decreasing intrinsic contact angle, and increasing solid free energy of the particle ´shell´. This provides the experimental evidence for the theory proposed by JOHNSON and DETTRE. It was revealed that ultrahydrophobic surfaces couldn´t be observed on layers made from regularly packed core-shell particles. Design of fractal irregular surfaces is an appropriate way for preparation of ultrahydrophobic self-cleaning surfaces. It was demonstrated that fluorination is not an obligatory factor for design of water repellent coatings. The obtained results are of essential interest for industrial application.

Gerbstoffe stabilisieren die Kollagenmatrix der Haut, in dem sie auf unterschiedlichste Art und Weise chemische Quervernetzungen herstellen. Es bleibt jedoch bis heute weitgehend unbeantwortet, auf welcher hierarchischen Ebene der Kollagenstruktur diese Wechselwirkung stattfindet und wie stringent eine solche Bindung mindestens sein muss, um einer Substanz den Charakter eines Gerbstoffes zu verleihen. Im Rahmen der vorliegenden Arbeit wurde ein Modellsystem entwickelt, das es gestattet, Aussagen darüber zu treffen, auf welcher Strukturebene des Kollagens diese Wechselwirkung stattfindet. Dazu wurde auf ein „bottom-up“ Verfahren zurückgegriffen, bei dem der Gerbstoff nicht auf Haut aufgebracht, sondern die Fibrillen in Anwesenheit von verschiedenen Wirkstoffen neu gebildet werden. Für die Untersuchungen wurden Vertreter aus der Substanzklasse der Polymere ausgewählt. Es kam Polyacrylsäure zum Einsatz, die als Fettungsmittel genutzt wird, und Polymethacrylsäure, welche in der Produktion als Nachgerbstoff verwendet wird. Vertreter ungeladener Polymere waren Ethylen-, Diethylen- und Polyethylenglycol, wobei hier die unterschiedlichen Molekülgrößen im Vergleich von Bedeutung waren. Des Weiteren wurde Glutaraldehyd als Vertreter eines gerbenden kovalenten Vernetzers untersucht. Kollagen Typ I Fibrillen wurden in vitro ausgehend von der Monomerform assembliert, und mit UV/Vis-Spektroskopie wurde verfolgt, ob und gegebenenfalls wie die Polymere die Kinetik der in vitro Fibrillogenese verändern. Dabei wurde beobachtet, dass bis auf Polyethylenglycol alle eingesetzten Substanzen auf unterschiedlichste Art schon auf der kleinsten Kollageneinheit - der Tripelhelix wirken. Diese Daten wurden mittels eines mathematischen Modells ausgewertet, das es ermöglicht, die Fibrillogenese in Teilreaktionen zu gliedern und die geschwindigkeitsbestimmenden Schritte zu evaluieren. So konnte ermittelt werden, dass trotz ähnlich erscheinender Fibrillenbildungskinetiken große Unterschiede zwischen Polyacrylsäure und Polymethacrylsäure bezüglich ihres Hauptwirkortes in den hierarchischen Strukturebenen des Kollagens auftreten. Während der Nachgerbstoff Polymethacrylsäure schon in geringen Konzentrationen in großem Maße in alle Teilprozesse der Fibrillogenese eingreift, zeigt Polyacrylsäure die größten Effekte auf mikrofibrillärer Ebene - einer Fibrillensubstruktur. Dieser Einfluss spiegelt sich in Morphologieänderungen in Form von so genannten gesplitteten Fibrillen wider, welche mittels atomkraftmikroskopischen Untersuchungen beobachtet werden konnten. Zusätzlich scheint Polymethacrylsäure ab einer kritischen Konzentration die Fibrillenbildung über einen alternativen Weg ablaufen zu lassen, was sich in der morphologischen Betrachtung in Form von langen, dünnen Fibrillen äußert, welche nicht mehr in der Lage sind zu höheren Strukturen zu verdrillen. Um zusätzlich die Art der Bindung näher zu charakterisieren, wurde ein weiteres Verfahren entwickelt, welches die Umkehrreaktion der in vitro Fibrillogenese beschreibt. Diese Methode der so genannten Deassemblierung ermöglicht eine Unterscheidung zwischen elektrostatischen Wechselwirkungen und kovalenten Bindungen zwischen Kollagen und Polymer, indem die Fibrille wieder in ihre nativen Monomeruntereinheiten zerlegt und gleichzeitig studiert wird, ob sich die Polymere vom Kollagen durch Ladungseintrag lösen lassen. Polyethylenglycol und seine niedermolekularen Äquivalente lassen sich in saurem Milieu problemlos von Kollagen abwaschen, was für sehr schwache Wechselwirkungen spricht. Kovalente Bindungen, wie etwa zwischen Kollagen und Glutaraldehyd lassen sich mit dieser Methode nicht lösen. Polyacrylsäure und Polymethacrylsäure lassen sich nur zu einem geringen Anteil von Kollagen lösen, was auf unterschiedlich affine Bindungsplätze der Polymere an Kollagen deutet. Beeindruckender Weise ist es für ausschließlich mit Polymethacrylsäure vernetztes Kollagen nicht möglich, dieses wieder in seine Untereinheiten zu zerlegen. Polymethacrylsäure ist demnach in der Lage die Kollagenmatrix auch ohne die Ausbildung kovalenter Bindungen ausreichend zu stabilisieren. Damit können die eingesetzten und entwickelten Verfahren als Screeningmethoden gesehen werden, welche schon vor dem eigentlichen Gerbversuch weit reichende Auskünfte über ein mögliches Gerbverhalten der zu Untersuchung eingesetzten Substanz liefern. Die vorliegenden Ergebnisse erlauben Aussagen über den molekularen Charakter der Kollagen - Polymer Wechselwirkung und stellen somit einen Beitrag zum Verständnis der Gerbung dar.

Gegenstand der vorliegenden Arbeit ist der Entwurf und die Realisierung kristalliner organisch-anorganischer Festkörper mit wohldefinierten Hohlraumstrukturen auf der Grundlage von Metallkoordinationen. Basierend auf generellen Prinzipien des Crystal Engineering wurden anhand von drei Typen oligofunktioneller Liganden und ausgewählter koordinationschemischer Synthesemethoden neue polymere Komplexverbindungen hergestellt, die im Hinblick auf Koordinationsgeometrie und Liganddimensionalität strukturspezifische Unterschiede aufweisen. Diese sind durch Anwendung von strukturanalytischen Methoden belegt. Untersuchungsergebnisse der polymeren Komplexe als Rezeptoren für leichtflüchtige Lösungsmittel lassen erkennen, dass sich die erzeugten Koordinationspolymere potentiell als Beschichtungen in massensensitiven Sensoren eignen. Weiterhin konnte durch strukturgeometrische Untersuchungen an Modellkomplexen eine strukturelle Grundlage für den zukünftigen Entwurf von Koordinationspolymeren geschaffen werden.