A novel strategy for fabrication of responsive functional polymer films is based on grafting of several different functional polymers onto a solid substrate at high grafting density, resulting in varied types of polymer brushes. Such an arrangement suggests many interesting applications of the multicomponent polymer brushes, regarding their versatile adaptive surfaces, capable for responding to changes of solvent polarity, pH, temperature, electromagnetic field and other stimuli, generally by reversible swelling. Mixed amphiphilic polystyrene-poly(2-vynil pyridine) (PS-P2VP) brushes are an example for responsive class of smart materials, which can switch between hydrophilic and hydrophobic energetic state upon changes in the quality of surrounding media. The switching of wettability was found to operate in a broad range and was selectively controlled in organic solvents and in aqueous solutions. Another example for an adaptive/switching behavior is addressed to a polymer brush with a remarkable response to the pH and the ionic strength variations of the aqueous solutions. Combination of weak polyacrylic acid, PAA, and weak polybase, P2VP, in the anchored layer allowed one with a small shift of the pH, to obtain a significant effect on the surface and the interfacial properties of the material. Both type of polymer brushes were examined as adsorbing materials for nanoparticles and charged synthetic- and bio-macromolecules. Their adaptive properties were successively linked to the results of the adsorption experiments. The simplest case was adsorption of nano-particles, functionalised with strong ionic groups, onto binary, PAA-P2VP, polyelectrolyte brushes. Maintaining a constant charge density of the adsorbing component (strong polyelectrolyte effect), allowed one to cause and manipulate a privileged swelling of one of the weak polyelectrolyte brush layers, without affecting the adsorbate properties, and to regulate the thickness of adsorbed layer only by the pH signal. In the case of adsorption of macromolecules with tuneable electrical charge (polyampholytes and proteins), the system became more complicated, regarding their environmentally responsive properties, similar to that exhibited by the polymer brushes. The driving forces were regulated by the switching performance of the brush, simply by adjusting the pH and/or ionic strength conditions. The adsorbed amount and morphological changes of polyampholyte layers were investigated as function of pH and was performed on mixed amphiphilic and binary polyelectrolyte brushes. A special emphasis was set on the binary brush capability to take the control over the interfacial performance of attaching proteins. It was found, that the sharp environmental response of the adsorbent (the polymer brush) strongly influences the morphology of adsorbed protein layers, their thickness and properties. Changing the polarity of the substrate allowed one to regulate the adsorption processes qualitatively and quantitatively. The significant aggregation of protein molecules on PS-P2VP brush and their disassembly on PAA-P2VP brush at the same solvent conditions, we devote to the hydrophobic-hydrophilic transition, occurred at the surface by replacing PS with PAA. The protein aggregates, monitored on the surface of PS-P2VP, sufficiently decrease their size, when switching the brush energetic state from hydrophobic to hydrophilic by adjusting the pH of the media. This effect was found to be well controlled by the brush switching phenomenon in hydrophilic-hydrophobic direction and vice versa. In conclusion, we showed how the structural reorganization in thin polymer brush layers of different type may dramatically affect their surface properties. The adaptive behavior in response of external stimuli was found to be a basis for highly specific interactions, depending on geometric factors, conformational state and environment.

No description available.

<p dir="ltr">Tailorable energetics are energetic materials that can be modified to alter their performance and sensitivity. Examples of tailoring energetic materials include additive manufacturing, manufactured hot spots, switchable energetics, and cocrystallization. Developing novel energetic material is a difficult and cost intensive process, because of this, tailoring the performance and sensitivity of existing energetic materials is critical for continued improvement. Additive manufacturing has provided new methods for generating complex geometries of composite materials. Additive manufacturing of composite materials through direct-ink-write (DIW) experiences extrusion limitations due to the high viscosities of highly solids loaded mixtures; the limitations being more severe with smaller syringe tip diameter. A novel printing technique called vibration-assisted printing (VAP) was developed as a method to extend the extrudability limits and extrusion speeds observed with direct-ink-write systems. Printability envelopes were shown in previous work to extend extrudability of monomodal glass bead composites in VAP systems over conventional DIW systems. This study compares the mass flowrates and extrudability limits for bimodal mixtures of glass beads suspended in a hydroxyl-terminated polybutadiene (HTPB) binder for both VAP and DIW printing as a function of volume percent solids loading. The bimodal glass bead mixtures showed a linear response in extrusion rate versus solids loading for both VAP and DIW systems. The VAP system was able to print higher volume loadings than the direct-ink-write system. In addition to extending the extrudability limits, the mass flowrate for the VAP system was significantly higher at all volume loadings tested compared to the DIW. Interestingly, bimodal mixtures were shown to extrude quicker than the monomodal mixtures at all volume loadings and across both printing systems.</p><p><br></p><p dir="ltr">Inhomogeneities within explosives affect the sensitivity and detonation wave shape of energetic materials. The influence of voids on explosive initiation has been well documented; however, the effects that voids between 0.1 mm and 10 mm have on a propagating detonation wave remains largely unexplored. The effect of single cylindrical voids on detonation wave shape and re-initiation was examined here using manufactured voids in a rubberized 1,3,5-trinitro-1,3,5-triazinane (RDX) explosive. Two streak imaging techniques were fielded to investigate void influence. For the first, back-surface streak imaging, the location of the void on the samples was changed and the resulting change in detonation wave shape at the downstream breakout was captured using a streak camera in cut-back experiments. The results from this experiment showed the effects of an initial jet form for short cut-back distances and as shock propagation progressed, the jet formation was absorbed by the unaffected portions of the wave front. The second method, top-surface streak imaging, was used to investigate the re-initiation/downstream propagation of the detonation front and the detonation velocity of the rubberized explosive. These experiments were compared to similar experimental results from machined voids in PBX 9501, a 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX)-based explosive, to investigate the interaction of a detonation wave with a 0.5 mm void for different explosives. The experiments were also compared to simulations using a multi-dimensional and multi-material hydrodynamic code (CTH). These results showed the influence that small features can have on detonation wave shaping and how explosive properties play a key role in that interaction. In addition to air-filled voids, this study examined the effects of 0.5 mm diameter voids filled with different inert metals on the detonation wave shape for an RDX-based rubberized explosive. The metals selected for experiments were 1066 aluminum, brass, copper, and tungsten. Experimental results showed that the extent of detonation wave shaping was closely tied to the density differential between the bulk explosive and metal insert. Simulations were performed using CTH to further analyze material inclusions. Forty-four different filler materials were simulated to isolate the driving factors for wave shaping of the detonation front. The main factors of interest were bulk sound speed, shock impedance, and filler material density. Understanding the influence of material inclusions on detonation performance and wave shape allows for tailoring of detonations as well as characterizing how unintentional defects will alter the explosive.</p><p><br></p><p dir="ltr">Improving the safety of explosive materials through the synthesis of insensitive explosives has been studied extensively. However, little work has focused on creating switchable explosives. A switchable explosive is normally insensitive to detonation, and therefore safe to handle and transport, but can be sensitized when needed to create a functional explosive. Similarly, it may be desired to desensitize an explosive to prevent its function. This study examined the ability to create a switchable RDX-based rubberized explosive using thermally-expandable microspheres (TEMs). The addition of TEMs to the explosive formulation allowed for microstructural changes and potential hot spot locations such as voids to form as the microspheres expanded. Small voids (less than about 10 µm) are more likely to be critical hot spots when shocked, and likewise larger voids are less likely to ignite successfully (sub-critical) when shocked. Consequently, both sensitization and desensitization are possible. The rubberized explosive considered here with unexpanded microspheres was unable to sustain a detonation for the size used, but after specific heating followed by cooling to produce small voids, a detonation was achieved. That is, the TEMs addition to the RDX-based rubberized explosive resulted in an explosive that is detonation insensitive when unheated but becomes a functional explosive after it is sensitized through heating. This paves the way to create insensitive explosive formulations with on-demand switchable detonation function through the incorporation of thermally-expandable microspheres. Desensitization was also demonstrated with specific heating of TEMs in an initially detonable explosive charge. And finally, we also demonstrated that deflagration can be affected by heating TEMs.</p><p><br></p><p dir="ltr">Energetic cocrystallization is a technique that produces a cocrystal that is formed using two known explosives to potentially gain the benefits of one or both without the drawbacks for a particular application. A comparison of cocrystals to a physical mixture of the same coformers can be considered. Cocrystals have unique material properties and crystal structure, whereas a physical mixture is just a mixed combination of the known materials at the same molar ratio. This study used photon Doppler velocimetry (PDV) to compare the particle velocity for 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and 1-methyl-3,5-dinitro-1,2,4-triazole (MDNT) at a 1:1 molar ratio for both a cocrystal and a physical mixture of the two energetic materials. This cocrystal was previously shown to detonate faster than a physical mixture. However, the PDV results here were not consistent with this result. In addition to measuring output particle velocity with PDV, the cocrystal was characterized to examine phase purity and possible signs of deterioration of the material over time. Evaluating the cocrystal with Fourier-transform infrared spectroscopy (FT-IR), bomb calorimetry, and powder X-ray diffraction (PXRD) allowed for more accurate comparison and greater confidence in the particle velocity measurements obtained in these experiments. The most significant difference in the material characterization results was the difference in enthalpy of formation, as the material tested in this study had a substantially lower enthalpy of formation than previously measured for a CL-20/MDNT cocrystal.</p>

Ce travail a porté sur la préparation et l'étude de matériaux magnétiques fonctionnels en couches dans l'optique d'une utilisation dans des micro-systèmes magnétiques. Deux systèmes de matériaux ont été étudiés: le FePt, qui est un matériau magnétique dur, et le FeRh, qui a une transition antiferromagnétique-ferromagnétique proche de la température ambiante. Dans le cas du FePt, les influences de la concentration en Pt, de l'ajout de Cu et des traitements thermiques, sur la transition de la phase A1 désordonnée, de faible anisotropie, à la phase L10 ordonnée, de forte anisotropie, ont été étudiées. Les dépendances en température de l'aimantation spontanée et du champ d'anisotropie de la phase L10 ont été déduites de l'analyse des courbes d'aimantation. Le pic d'Hopkinson qui est lié aux processus d'aimantation de la phase L10 à l'approche de la température de Curie a été modélisé. Dans le cas du FeRh, les influences de la concentration en Rh et des traitements thermiques ont été étudiées. Une analyse thermodynamique des mesures d'aimantation et des mesures de calorimétrie différentielle a été effectuée. Enfin, des couches hybrides de FePt-FeRh ont été déposées sur des substrats pré-gravés, pour démontrer la potentialité d'utiliser le FeRh pour contrôler thermiquement le champ de fuite généré par le FePt. / The aim of this work was the preparation and study of thin films of functional magnetic materials of interest for use in magnetic micro-systems. Two material systems have been studied: FePt, which is a hard magnetic material, and FeRh, which has an antiferromagnetic - ferromagnetic transition near room temperature. For the case of FePt, the influence of the film composition, the addition of Cu, and the annealing conditions, on the transition from the disordered, low anisotropy A1 phase to the ordered, high anisotropy L10 phase has been studied. The temperature dependence of the spontaneous magnetisation and the anisotropy field of the L10 phase were deduced from an analysis of magnetisation curves. The Hopkinson peak which characterises the susceptibility of the demagnetized L10 phase close to its Curie temperature has been modelled. In the case of FeRh, the influence of film composition and annealing conditions on the antiferromagnetic - ferromagnetic transition was studied. A thermodynamic analysis of magnetisation measurements and differential calorimetry measurements has been carried out. Finally, hybrid FePt-FeRh films have been deposited on patterned wafers, to demonstrate the potential use of FeRh for the thermal control of the stray field generated by the FePt.

The goal of this project is the development of artificial ion channels that can be actuated by light and thus controlled efficiently. Our artificial system is composed of two regions: the gate and the body part. The gate part is based on light-responsive azo groups while the body part is formed by calix[4]resorcinarene. Key of controlling mechanism is the conformational change between cis and trans isomers, which is translated into movement of the gate. Light-gated artificial ion channels are aimed at eliminating of the stochastic mechanism of artificial ion channels. Such a reversible photocontrol should be a powerful tool for using artificial ion channels as the basis for the development of new pharmaceuticals and drug delivery systems, as photoswitches, and in the field of microfluidics.

Binäre Polymerbürsten bestehen aus zwei verschiedenen Polymertypen, die nebeneinander auf dem gleichen Trägermaterial verankert sind. Wenn diese Polymere unterschiedliche Benetzungseigenschaften haben, können damit schaltbare Oberflächen produziert werden. Abhängig vom Lösungsmittel, dem man die binäre Polymerbürste aussetzt, streckt sich entweder das hydrophile oder das hydrophobe Polymer zum Lösungsmittel hin, während die zweite Komponente nahe der Oberfläche verbleibt. Durch diese vertikale Phasenseparation kann temporär eine bestimmte Oberflächeneigenschaft erzeugt werden. Allerdings verschwindet diese sofort wieder, wenn ein anderes Lösungsmittel die binäre Bürste benetzt, sei es durch direkten Kontakt oder über die Gasphase. In der vorliegenden Arbeit wurde untersucht, ob es möglich ist, neuartige schaltbare binäre Polymerbürsten bestehend aus einem hydrophilen und einem hydrophoben Polymer angebunden auf Siliziumwafern herzustellen, deren Schaltfähigkeit durch photochemische Vernetzung unterbunden werden kann. Geprüft worden ist unter anderem, inwiefern sich hydrophober und hydrophiler Zustand der Schicht fixieren lassen und ob daraus resultierend, eine entsprechende Strukturierung der Oberfläche nach Bestrahlung durch eine geeignete Fotomaske oder durch fokussiertes Licht nachweisbar ist. Als hydrophobe Komponente wurden photovernetzbare Styren/2-(4’-Styryl)-inden-Copolymere verwendet, als hydrophile Komponente kam Polyvinylpyridin zum Einsatz. Mit einem speziellen Oberflächeninitiator konnten durch „Grafting from“ binäre Polymerbürsten mit bis zu 300 nm Schichtdicke erzeugt werden. Es ist gelungen, diese schaltbaren Schichten durch selektive photochemische Vernetzung einer der Bürstenkomponenten im hydrophilen oder im hydrophoben Zustand zu fixieren, was durch Kontaktwinkelmessung nachgewiesen werden konnte. Wie beabsichtigt, verlieren dabei die vernetzten Bereiche ihre Schaltfähigkeit. Es ließen sich feine Oberflächenstrukturen mittels Bestrahlung durch eine Fotomaske erzeugen, die sichtbar werden, wenn man sie mit Wasser benetzt bzw. Wasserdampf aussetzt.

The main goal of this work is design and synthesis of novel composite hydrogel-based core-shell microparticles and their application for fabrication of coatings, which provide the “inverse-switching” behaviour to the surface, namely, to become more hydrophobic in water environment. Since contact angle of heterogeneous surfaces is dependent on the nature and ratio of surface components, an increase of amount of more hydrophobic component on the surface will cause the reducing of surface wettability. It was suggested that core-shell particles having water-swellable hydrogel core and hydrophobic, but permeable for water shell when deposited on the hydrophilic substrate should increase the total amount of hydrophobic component on the surface when the cores of particles will swell in water. During the work different approaches to obtain freely dispersed and surface-immobilized core-shell particles with required structure were developed. Obtained particles were applied for preparation of coatings with ability to display “inverse-switching” behaviour. It was demonstrated that properly designed and properly prepared core-shell particles could be successfully used for creation of smart adaptive coatings having the ability to alter the surface properties upon changing of the environment.

Die RAFT-Polymerisation ("Reversible Addition-Fragmentation Chain Transfer") ist eine radikalische Polymerisation, die auf dem Prinzip des degenerativen Kettentransfers basiert. Es können Polymere hergestellt werden, die eine niedrige Dispersität aufweisen und komplexe makromolekulare Strukturen ausbilden. Für die Funktionalisierung von Polymerketten bietet sich die RAFT-Polymerisation ebenfalls an, da idealerweise jede auf diese Art hergestellte Polymerkette eine RAFT-Einheit trägt und so eine vollständige Funktionalisierung gewährleistet ist. Im Fokus dieser Arbeit stand die Funktionalisierung von Polybutadien und 1,3-Butadien enthaltenden Copolymeren mit gezielt eingebauten schwefelhaltigen Gruppen. Dabei wurden zwei verschiedene Ansätze verfolgt: Die α,ω-Funktionalisierung der Polymerketten mittels modifizierter RAFT-Agenzien sowie eine Funktionalisierung entlang der Polymerkette mit Hilfe von speziellen Monomeren. Da diese Polymere in technischen Anwendungen Verwendung finden sollen, standen einfache Synthesen, die sich gut auf den Technikums- und Industriemaßstab übertragen lassen, im Vordergrund. Da es sich bei der RAFT-Einheit auch um eine schwefelhaltige Gruppe handelt, wurden Strategien zur Funktionalisierung der Abgangsgruppe erarbeitet und experimentell untersucht, um so ein α,ω-funktionalisiertes Polymer zu erhalten. Neben klassischen RAFT-Agenzien wurden auch neuartige Makro-RAFT-Agenzien verwendet, bei denen die schwefelhaltige Gruppe während einer Polymerisation in situ angebunden wird. Darüber hinaus konnten erfolgreich Monomere synthetisiert werden, die wegen ihrer styrolähnlichen Struktur und der Ähnlichkeit der Monomere Styrol und 1,3-Butadien in ihrem Polymerisationsverhalten gut mit 1,3-Butadien copolymerisieren und dabei die schwefelhaltige Gruppe entlang der Polymerkette einbauen. Das Hauptaugenmerk weiterer Untersuchungen lag auf den Copolymerisationseigenschaften der Monomere. Dazu wurden umfangreiche Untersuchungen mit Styrol als Modellsystem für 1,3-Butadien durchgeführt und die gewonnenen Erkenntnisse in einer Copolymerisation der funktionalisierten Monomere mit 1,3-Butadien verifiziert. Es konnte weiterhin gezeigt werden, dass sich schaltbare RAFT-Agenzien für die Synthese von Poly(butadien)-block-poly(vinylacetat) eignen, obwohl es sich um zwei Monomere mit stark unterschiedlichen elektronischen Eigenschaften handelt, die in einer konventionellen radikalischen Polymerisation kein Copolymer bilden würden. Aufgrund der Ähnlichkeit der Monomere Vinylacetat und Ethylen eröffnet dies neue Wege in der kontrollierten radikalischen Polymerisation von Polybutadien-block-polyethylen und erweitert so das Spektrum der unpolaren Monomere in der RAFT-Polymerisation zur Herstellung von Blockcopolymeren.

The design of functional materials with complex properties is very important for different applications, such as coatings, microelectronics, biotechnologies and medicine. It is also crucial that such kinds of materials have a long service lifetime. Unfortunately, cracks or other types of damages may occur during everyday use and some parts of the material should be changed for the regeneration of the initial properties. One of the approaches to avoid the replacement is utilization of self-healing materials. The aim of this thesis was to design a self-repairable material with superhydrophobic and switchable properties using colloidal particles. Specific goals were the synthesis of colloidal particles and the preparation of functional surfaces incorporated with the obtained particles, which would exhibit a repairable switching behavior and repairable superhydrophobicity. In order to achieve these goals, first, methods of preparation of simple and functional colloidal particles were developed. Second, the behavior of particles at surfaces of easy fusible solid materials, namely, paraffin wax or perfluorodecane, was investigated.

Environmentally benign alternatives for solvents and catalysts are essential for the development of sustainable chemical processes. Toward this end, we focused our research on the design of novel solvents and catalysts that reduce the environmental impact of these important materials. In this research, we develop switchable and tunable systems that couple reaction and separation to ease the processing requirements for product isolation and catalyst recovery. The switchable solvents use a ¡°switch¡± to transition from non-volatile, polar, aprotic solvents to volatile gases that can be easily separated. This allows us to facilitate reactions within the solvent and then enable easy separation through activation of the switch. We have used these materials for numerous reaction applications, including difficult reactions involving highly immiscible compounds. We also extended the work to acid-catalyzed reactions, in which we can avoid wasteful neutralization processes that are often associated with homogeneous acid catalysis. The tunable solvents use carbon dioxide pressure to ¡°tune¡± into desired solvent properties. We enable this through the dissolution of carbon dioxide into organic solvents, which generates gas-expanded liquids with solvent properties highly dependent on the carbon dioxide pressure. We can use this effect to couple homogeneous reaction with heterogeneous separation, allowing for recovery of expensive catalysts and ligands. In this work, we assess the possibilities of using liquid polyethylene glycol in the tunable systems, studying the phase behavior and industrial applications.