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Pas de résumé en français seulement en anglais / The emergence of organic electronics – a technology that relies on carbon-based semiconductors to deliver devices with unique properties – represents one of the most dramatic developments of the past two decades. A rapidly emerging new direction in the field involves the interface with biology. The “soft” nature of organics offers better mechanical compatibility with tissue than traditional electronic materials, while their natural compatibility with mechanically flexible substrates suits the non-planar form factors often required for implants. More importantly, their ability to conduct ions in addition to electrons and holes opens up a new communication channel with biology. The coupling of electronics with living tissue holds the key to a variety of important life-enhancing technologies. One example is bioelectronic implants that record neural signals and/or electrically stimulate neurons. These devices offer unique opportunities to understand and treat conditions such as hearing and vision loss, epilepsy, brain degenerative diseases, and spinal cord injury.The engineering aspect of the work includes the development of a photolithographic process to integrate the conducting polymer poly(3,4-ethylenedioxythiophene: poly(styrene sulfonate) (PEDOT:PSS) with parylene C supports to make an active device. The technology is used to fabricate electrocorticography (ECoG) probes, high-speed transistors and wearable biosensors. The experimental work explores the fundamentals of communication at the interface between conducting polymers and the brain. It is shown that conducting polymers outperform conventional metallic electrodes for brain signals recording.Organic electrochemical transistors (OECTs) represent a step beyond conducting polymer electrodes. They consist of a conducting polymer channel in contact with an electrolyte. When a gate electrode excites an ionic current in the electrolyte, ions enter the polymer film and change its conductivity. Since a small amount of ions can effectively “block” the transistor channel, these devices offer significant amplification in ion-to-electron transduction. Using the developed technology a high-speed and high-density OECTs array is presented. The dense architecture of the array improves the resolution of the recording from neural networks and the transistors temporal response are 100 μs, significantly faster than the action potential. The experimental transistor responses are fit and modeled in order to optimize the gain of the transistor. Using the model, an OECT with two orders of magnitude higher normalized transconductance per channel width is fabricated as compared to Silicon-based field effect transistors. Furthermore, the OECTs are integrated to a highly conformable ECoG probe. This is the first time that a transistor is used to record brain activities in vivo. It shows a far superior signal-to-noise-ratio (SNR) compare to electrodes. The high SNR of the OECT recordings enables the observation of activities from the surface of the brain that only a perpetrating probe can record. Finally, the application of OECTs for biosensing is explored. The bulk of the currently available biosensors often require complex liquid handling, and thus suffer from problems associated with leakage and contamination. The use of an organic electrochemical transistor for detection of lactate by integration of a room temperature ionic liquid in a gel-format, as a solid-state electrolyte is demonstrated.

The training of movement procedures to increase the skills of athletes is a fundamental part of competitive sports. A realistic training, supported by technical equipment provides athletes a better success of training and is requested by trainers and training centers all over the world. Especially in winter sports, like luge or bob, a realistic training simulation is not always possible and demands adaptations of specific training procedures. As a part of this article, a new multilayer slide-foil will be presented, which allows athletes an even more realistic training. For this purpose the structure and production process of the foil composite will be shown, as well as results of the tribological behaviour of the foil. / Das Training von Bewegungsabläufen, zur Steigerung von Fähigkeiten, ist ein fundamentaler Bestandteil im Leistungssport. Ein realistisches Training, unterstützt durch technische Systeme, ermöglicht es Athleten optimale Trainingserfolge zu erzielen und wird dementsprechend von Trainern und Leistungszentren überall auf der Welt gewünscht. Insbesondere in Wintersportarten, wie z. B. Rennrodeln oder Bobfahren, kann dies allerdings nur bedingt realisiert werden und erfordert oftmals Abstriche bei der Trainingsgestaltung. Im Rahmen dieses Beitrags wird daher eine mehrschichtige Verbundfolie vorgestellt, welche den Athleten ein realistischeres Training ermöglichen soll. Hierzu werden zum einen der Aufbau und die Herstellung des Folienverbundes erläutert sowie tribologische Untersuchungsergebnisse präsentiert.

The following paper will illustrate the development of a multiflex chain in hybrid construction. The aim of this novel chain variant is to improve the stiffness and strength in comparison to conventional plastic slide chains. A two part multiflex chain with a chain pitch of 33.5 mm and a structural width of 83 mm was used as the basis for the development of the hybrid multiflex chain. The hybrid multiflex chain is supposed to be integrated in already existing layouts of chain conveyors. The load bearing structure of the single chain links is manufactured in the metal die cast procedure while taking the constructive, production related, and operational aspects into consideration and subsequently covered in the injection molding process with plastics commonly used for multiflex chains. The evaluation of the improved stiffness and strength takes place in the course of extensive test series. / In der folgenden Abhandlung wird die Entwicklung einer Multiflex-Kette in Hybridbauweise erläutert. Mit dieser neuartigen Kettenvariante soll eine Steifigkeits- und Festigkeitssteigerung gegenüber den konventionellen Kunststoffgleitketten erzielt werden. Als Ausgangsbasis für die Entwicklung der hybriden Förderkette dient eine zweiteilig ausgeführte Multiflex-Kette mit der Teilung von 33,5 mm und einer Baubreite von 83 mm. Die hybride Förderkette soll in bestehende Layouts von Kettenförderern integriert werden können. Unter Beachtung konstruktiver, fertigungstechnischer und betrieblicher Aspekte wird die lasttragende Struktur der einzelnen Kettenglieder im Metalldruckgussprozess gefertigt und anschließend mit einem, für Multiflex-Ketten üblichen Kunststoff im Spritzgießprozess ummantelt. Die Evaluierung der Steifigkeits- bzw. Festigkeitssteigerung erfolgt im Rahmen umfangreicher Versuchsreihen.

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.

Für die Behandlung von Knochendefekten unterschiedlicher Defektgeometrien besteht ein zunehmender Bedarf an geeigneten in-situ aushärtbaren Knochenersatzmaterialien, die nach Auffüllung des Defektes formstabil, biokompatibel, mechanisch hinreichend belastbar und biodegradierbar sind. In der vorliegenden Arbeit wurden kompakte und poröse, in-situ härtende Polymer/Apatit-Kompositmaterialien auf Basis eines hydrolytisch degradierbaren Methacrylatmakromers und nanokristallinen Apatiten hergestellt. Die entwickelten Makromer/Apatit-Gemische sind bis zur vollständigen Polymerisation des Makromers von pastöser Konsistenz und können in variable Geometrien verarbeitet werden. Durch Variation der Gemischzusammensetzung können die Verarbeitungszeiten und mechanischen Eigenschaften der Komposite gezielt eingestellt werden. Die In-vitro-Kultivierungen von MC3T3-E1-Zellen auf den Kompositen zeigen, dass die Komposite nach geeigneten Nachbehandlungsschritten cytokompatibel und vielversprechende Materialien zur Auffüllung von Knochendefekten sind.

In der vorliegenden Dissertation wurden mittels kontrolliert radikalischer Polymerisationstechniken alkinhaltige Blockcopolymere synthetisiert. In effizienten Cu(I)-katalyisierten 1,3-dipolaren Cycloadditionen (Click-Chemie) wurde diese modifiziert. Insbesondere durch die Addition dendritischer Verbindungen gelang die Darstellung nanosopischer Objekte. Darüber hinaus konnten dünne Filme phasenseparierten Blockcopolymere selektiv und ortsaufgelöst funktionalisiert werden. Die Arbeit liefert somit Beiträge zur Entwicklung neuartiger Nanomaterialien sowie ihrer Modifizierung.

This work is a numerical examination of a semiflexible polymer exposed to a disorder landscape consisting of hard disks. For a small parameter range and simple constraints it is known that disorder leads to structural transitions of the equilibrium properties of polymers. The scope of this work strongly extends this range by going to both high disorder densities and large stiffnesses of the polymers. The competing length scales of polymer stiffness and average distance between the obstacles of the potential along with the way of assembling the disorder lead to a wide range of effects such as crumpling and stretching of polymer configurations due to the disorder or a modulation of the polymer’s characterizing observables with the correlation function of the potential. The high accuracy results presented in this work have been obtained by means of sophisticated Monte Carlo simulations. The refinement of a rarely applied but highly promising method to a state of the art algorithm in connection with latest numerical techniques made it possible to investigate the impact of hard-disk disorder on semiflexible polymer conformations on a broad scale.

Composites based on ICP with conductive (SWCNT and Te) and insulating fillers (TiO2 and CuO and insulating polymers with conducting fillers (rGO, modified rGO, and SWCNT) were prepared and their thermoelectric properties were investigated. Attempts to enhance the thermoelectric properties of PEOT:PSS composites did not bring about a significant change. But, the attempts to modify rGO brought about a considerable improvement in the thermoelectric properties. At the end, the use of SWCNT provided the maximum ZT in case of insulating polymer composites. Eventually, SEBS/4 wt% SWCNT with a ZT of 0.0017 and SBS/0.5 wt% SWCNT with a ZT 6  10-6 stood out as the best p-type and n-type thermoelectric material, respectively, in this work. This success paved the way to build 2 modules of thermoelectric generators which generated a maximum potential of 93.2 mV at a temperature difference of 40 K.

The search for the ideal, environmentally friendly and preferably cheap solvent has been a persistent topic in general chemistry. Hence, the effort in the development of “green” solvents and processes skyrocketed in the recent past. However, a replacement of solvents does not deal with the problem at hand – it is just a small fix, not a big innovation. Taking this into consideration, what is the big innovation needed in chemistry? If one considers solvents as the problem, then the logical step is to simply get rid of them altogether. One approach to conduct reactions in the absence of solvents is mechanochemistry. Initiated and/or sustained by mechanical energy, mechanochemical reactions offer a sustainable alternative to many wet-chemical methods. Innovative uses thereof have made their way into the fields of pharmaceuticals, material synthesis and, foremost, organic chemistry, where the vast potential of this rediscovered field has been demonstrated. In this context, I have dedicated this thesis to establish mechanochemical protocols for the fields of polymers and nanographenes. Both of those topics are, at the moment, dominated by solution-based synthesis, although the compounds produced are hardly soluble.