populärwissenschaftlicher Abstract:<br /> Kristallisation, Biomimetik und halbleitende Polymere in räumlich begrenzten Systemen:<br /> Öl und Wasser mischen sich nicht, man kann aber aus beiden Flüssigkeiten Emulsionen herstellen, bei denen Tröpfchen der einen Flüssigkeit in der anderen Flüssigkeit vorliegen. Das heißt, es können entweder Öltröpfchen in Wasser oder Wassertröpfchen in Öl erzeugt werden. Aus täglichen Erfahrungen, z.B. beim Kochen weiß man jedoch, dass sich eine Emulsion durch Schütteln oder Rühren herstellen lässt, diese jedoch nicht besonders stabil ist. Mit Hilfe von hohen Scherenergien kann man nun sehr kleine, in ihrer Größe sehr einheitliche und außerdem sehr stabile Tröpfchen von 1/10000 mm erhalten. Eine solche Emulsion wird Miniemulsion genannt. <br /> In der Dissertation wurden nun z.B. Miniemulsionen untersucht, die aus kleinen Wassertröpfchen in einem Öl bestehen. Es konnte gezeigt werden, dass das Wasser in diesen Tröpfchen, also in den räumlich begrenzten Systemen, nicht bei 0 &#176;C, sondern bei -22 &#176;C kristallisierte. Wie lässt sich das erklären? Wenn man einen Eimer Wasser hat, dann bildet sich normalerweise bei 0 &#176;C Eis, da nämlich in dem Wasser einige (manchmal ganz wenige) Keime (z.B. Schutzteilchen, ein Fussel etc.) vorhanden sind, an denen sich die ersten Kristalle bilden. Wenn sich dann einmal ein Kristall gebildet hat, kann das Wasser im gesamten Eimer schnell zu Eis werden. Ultrareines Wasser würde bei -22 &#176;C kristallisieren. Wenn man jetzt die Menge Wasser aus dem Eimer in kleine Tröpfchen bringt, dann hat man eine sehr, sehr große Zahl, nämlich 1017 Tröpfchen, in einem Liter Emulsion vorliegen. Die wenigen Schmutzpartikel verteilen auf sehr wenige Tröpfchen, die anderen Tröpfchen sind ultrarein. Daher kristallisieren sie erst bei -22 &#176;C.<br /> <br /> Im Rahmen der Arbeit konnte auch gezeigt werden, dass die Miniemulsionen genutzt werden können, um kleine Gelatine-Partikel, also Nanogummibärchen, herzustellen. Diese Nanogummibärchen quellen bei Erhöhung der Temperatur auf ca. 38 &#176;C an. Das kann ausgenutzt werden, um zum Beispiel Medikamente zunächst in den Partikeln im menschlichen Körper zu transportieren, die Medikamente werden dann an einer gewünschten Stelle freigelassen. In der Arbeit wurde auch gezeigt, dass die Gelatine-Partikel genutzt werden können, um die Natur nachzuahnen (Biomimetik). Innerhalb der Partikel kann nämlich gezielt Knochenmaterial aufgebaut werden kann. Die Gelatine-Knochen-Partikel können dazu genutzt werden, um schwer heilende oder komplizierte Knochenbrüche zu beheben. Gelatine wird nämlich nach einigen Tagen abgebaut, das Knochenmaterial kann in den Knochen eingebaut werden.<br /> <br /> LEDs werden heute bereits vielfältig verwendet. LEDs bestehen aus Halbleitern, wie z.B. Silizium. Neuerdings werden dazu auch halbleitende Polymere eingesetzt. Das große Problem bei diesen Materialien ist, dass sie aus Lösungsmitteln aufgebracht werden. Im Rahmen der Doktorarbeit wurde gezeigt, dass der Prozess der Miniemulsionen genutzt werden kann, um umweltfreundlich diese LEDs herzustellen. Man stellt dazu nun wässrige Dispersionen mit den Polymerpartikeln her. Damit hat man nicht nur das Lösungsmittel vermieden, das hat nun noch einen weiteren Vorteil: man kann nämlich diese Dispersion auf sehr einfache Art verdrucken, im einfachsten Fall verwendet man einfach einen handelsüblichen Tintenstrahldrucker. / The colloidal systems are present everywhere in many varieties such as emulsions (liquid droplets dispersed in liquid), aerosols (liquid dispersed in gas), foam (gas in liquid), etc. Among several new methods for the preparation of colloids, the so-called miniemulsion technique has been shown to be one of the most promising. Miniemulsions are defined as stable emulsions consisting of droplets with a size of 50-500 nm by shearing a system containing oil, water, a surfactant, and a highly water insoluble compound, the so-called hydrophobe<br /> <br /> 1. In the first part of this work, dynamic crystallization and melting experiments are described which were performed in small, stable and narrowly distributed nanodroplets (confined systems) of miniemulsions. Both regular and inverse systems were examined, characterizing, first, the crystallization of hexadecane, secondly, the crystallization of ice. It was shown for both cases that the temperature of crystallization in such droplets is significantly decreased (or the required undercooling is increased) as compared to the bulk material. This was attributed to a very effective suppression of heterogeneous nucleation. It was also found that the required undercooling depends on the nanodroplet size: with decreasing droplet size the undercooling increases.<br /> <br /> 2. It is shown that the temperature of crystallization of other n-alkanes in nanodroplets is also significantly decreased as compared to the bulk material due to a very effective suppression of heterogeneous nucleation. A very different behavior was detected between odd and even alkanes. In even alkanes, the confinement in small droplets changes the crystal structure from a triclinic (as seen in bulk) to an orthorhombic structure, which is attributed to finite size effects inside the droplets. An intermediate metastable rotator phase is of less relevance for the miniemulsion droplets than in the bulk. For odd alkanes, only a strong temperature shift compared to the bulk system is observed, but no structure change. A triclinic structure is formed both in bulk and in miniemulsion droplets.<br /> <br /> 3. In the next part of the thesis it is shown how miniemulsions could be successfully applied in the development of materials with potential application in pharmaceutical and medical fields. The production of cross-linked gelatin nanoparticles is feasible. Starting from an inverse miniemulsion, the softness of the particles can be controlled by varying the initial concentration, amount of cross-link agent, time of cross-linking, among other parameters. Such particles show a thermo-reversible effect, e.g. the particles swell in water above 37 &#176;C and shrink below this temperature. Above 37 &#176;C the chains loose the physical cross-linking, however the particles do not loose their integrity, because of the chemical cross-linking. Those particles have potential use as drug carriers, since gelatin is a natural polymer derived from collagen.<br /> <br /> 4. The cross-linked gelatin nanoparticles have been used for the biomineralization of hydroxyapatite (HAP), a biomineral, which is the major constituent of our bones. The biomineralization of HAP crystals within the gelatin nanoparticles results in a hybrid material, which has potential use as a bone repair material.<br /> <br /> 5. In the last part of this work we have shown that layers of conjugated semiconducting polymers can be deposited from aqueous dispersion prepared by the miniemulsion process. Dispersions of particles of different conjugated semiconducting polymers such as a ladder-type poly(para-phenylene) and several soluble derivatives of polyfluorene could be prepared with well-controlled particle sizes ranging between 70 - 250 nm. Layers of polymer blends were prepared with controlled lateral dimensions of phase separation on sub-micrometer scales, utilizing either a mixture of single component nanoparticles or nanoparticles containing two polymers. From the results of energy transfer it is demonstrated that blending two polymers in the same particle leads to a higher efficiency due to the better contact between the polymers. Such an effect is of great interest for the fabrication of opto-electronic devices such as light emitting diodes with nanometer size emitting points and solar cells comprising of blends of electron donating and electron accepting polymers.

The major difference between semiconductor quantum dots and bulk semiconductors is in the quantum confinement effect. It results the controllable exciton¡¦s absorption and emission spectra by tuning the size of the quantum dot. Moreover, multi-exciton states are reported to be observed in the highly symmetric quantum dot systems. In this dissertation, we use the single molecule fluorescence measurement to study the power dependence of multi-exciton state in single CdSe/ZnS semiconductor quantum dots. At low excitation fluence, anti-bunching behavior, and nearly single exponential relaxation dynamics are observed. By increasing the laser power, bi-exponential fluorescence decay dynamics as well as bunching behaviors from the same QD indicate the fast PL dynamics due to the relaxation from multi-exciton. The results indicate certain threshold energy level for multi-exciton generation. In addition, the multiple step cascade radiative relaxation processes are observed. Besides, we modulate linear polarization light to study the excitation orientation dependence. The results indicate the emission dipole of multi-exciton is similar to the single exciton, having a two dimensional transition dipole plane with c-axis symmetry. However, the absorption dipole of multi-exciton exhibits different orientation dependence from the single exciton.

The effect of single mode initial conditions at the interface of Rayleigh-Taylor(RT) mixing are experimentally examined utilizing the low Atwood number water channel facility at Texas A&M. The water channel convects two separated stratified flows and unifies them at the end of a splitter plate. The RT instability is attained by convecting a cold stream above a warmer stream. Average density calculations are based on long time average optical measurements. The water channel was modifified with a flapper fin like device at the end of the splitter plate which was actuated by a computer controlled servo motor. Other modifications to the experiment were implemented resulting in reduced uncertainty. The experiment examined five different modes in addition to the baseline: 2 cm, 3 cm, 4 cm, 6 cm, and 8 cm wavelengths. The mixing width growth rates were shown to be dependent on initial conditions. Additionally, it appears that the growth rates commence with terminal velocity and are observed to line up with the baseline case.

Near-field light confinement on scanning probe is the backbone technology for near-field imaging with subwavelength resolution that overcomes the diffraction limit by exploiting the properties of evanescent waves. The fusion of the photonics and the latest nanofabrication technology creates emerging frontier for near-field light confinement research with new design approach. The propagation of light can now be controlled by periodical structure at subwavelength scale with low loss in the artificially synthesized dielectric material. New light propagation patterns can now be implemented in subwavelength structure, such as directional free space light focus grating coupler, photonic bandgap material like photonic crystal by permitting light propagation at certain wavelength while prohibiting light outside of bandgap, and nano-slot light resonator for increased light-matter interaction at nanometer scale. Advances in this research area will have tremendous impact on electromagnetic modeling and biomedical technology for probe based subwavelength optical detection. My doctoral research focused on investigating highly efficient, nanofabrication compatible directional light coupling structure and near-field subwavelength light focus through photonic crystal material. The distinct significance of this research was placed on exploitation of the embedded metallic grating coupler of high free space directivity and subwavelength light processing circuit of enhanced near-field transmission rate, the two most dominating basic elements of the scanning optical imaging system. First, I designed a compact elliptical grating coupler based on embedded noble metal such as gold or silver that efficiently interconnects free space with dielectric rectangular waveguide. The dense system integration capability shows the application potential for on-chip interfacing subwavelength light processing circuits and near-field fluorescent biosensors with far-field detection of superb radiation directivity and coupling efficiency. Second, a novel all-dielectric light confinement probe designed by slotted photonic crystal waveguide provides a light confinement mechanism on the lateral plane. The resonating nano-cavities and the λ/4 nano-slot are used to enlarge the light throughput while as the nano-slot waveguide provides single subwavelength center lobe. The impetus of this research is the growing interests by near-field imaging researchers to obtain a low loss visible light confinement probe designs through mass production. / text

Nanostructures often possess unique properties, which may lead to the development of new microelectronic and optoelectronic devices. They also provide an opportunity to test fundamental quantum mechanical concepts such as the role of quantum confinement. Considerable effort has been made to understand the electronic and structural properties of nanostructures, but many fundamental issues remain. In this work, the electronic and structural properties of nanostructures are examined using several new computational methods. The effect of dimensional confinement on quantum levels is investigated for hydrogenated Ge <110> using the plane-wave density-functional-theory pseudopotential method. We present a real-space pseudopotential method for calculating the electronic structure of one-dimensional periodic systems such as nanowires. As an application of this method, we examine H-passivated Si nanowires. The band structure and heat of formation of the Si nanowires are presented and compared to plane wave methods. Our method is able to offer the same accuracy as the traditional plane wave methods, but offers a number of computational advantages such as the ability to handle large systems and a better ease of implementation for highly parallel platforms. Doping is important to many potential applications of nano-regime semiconductors. A series of first-principles studies are conducted on the P-doped Si <110> nanowires by the real-space pseudopotential methods. Nanowires of varied sizes and different doping positions are investigated. We calculate the binding energies of P atoms, band gaps of the wires, energetics of P atoms in different doping positions and core-level shift of P atoms. Defect wave functions of P atoms are also analyzed. In addition, we study the electronic properties of phosphorus-doped silicon <111> nanofilms using the real-space pseudopotential method. Nanofilms with varied sizes and different doping positions are investigated. We calculate the binding energies of P atoms, band gaps of the films, and energetics of P atoms in different doping positions. Quantum confinement effects are compared with P-doped Si nanocrystals and as well as nanowires. We simulate the nanofilm STM images with P defects in varied film depths, and make a comparison with the experimental measurement. / text

An extensive amount of research has been reported in previous literature on the behaviour of FRP-confined concrete subjected to concentric axial compression. However, data on the behaviour of high strength concrete confined with various types and configurations of FRP systems is still lacking and no consensus exists on the complete response of FRP-confined concrete. In addition, no appropriate design guidelines are currently available. This thesis reports results from an experimental program involving 112 cylindrical concrete specimens, 88 of which were FRP-wrapped and the remaining 24 were control specimens. All the specimens were 152 mm in diameter and 305 mm in length. Test variables included: amount of FRP materials used, strength and stiffness of FRP materials, concrete strength, and the health of concrete at the time of strengthening. Experimental results indicated that a pre-repair load of up to 77% of the unconfined concrete strength had no appreciable effect on the stress-strain response of FRP-confined concrete. With an increase of the unconfined concrete strength, the strength enhancement, energy absorption capacity, ductility factor and work (energy) index at rupture of FRP jackets all decreased remarkably. A positive correlation was found between confined concrete ductility and FRP rupture strain. In addition, a gradual post-peak failure of the specimens, observed previously from FRP-confined concrete columns tested at the University of Toronto, was also observed in some of the current tests -- owing to the high speed data acquisition system. That ductile failure can be attributed to the gradual unzipping failure of FRP jacket, which in turn is related to specimen size. A new constitutive model was developed based on material properties, force equilibrium and strain compatibility. The size effect was taken into account in the model, which is able to accommodate concrete with a wide range of strength (25 MPa to 110 MPa) confined with various types and configurations FRP systems. Design equations from CSA S806-02 and CSA S6-06 provide reasonable and conservative estimates for the FRP-confined concrete strength. To calculate the peak strain for FRP-confined concrete, an equation based on the work by Berthet et al. (2006) is proposed.

An extensive amount of research has been reported in previous literature on the behaviour of FRP-confined concrete subjected to concentric axial compression. However, data on the behaviour of high strength concrete confined with various types and configurations of FRP systems is still lacking and no consensus exists on the complete response of FRP-confined concrete. In addition, no appropriate design guidelines are currently available. This thesis reports results from an experimental program involving 112 cylindrical concrete specimens, 88 of which were FRP-wrapped and the remaining 24 were control specimens. All the specimens were 152 mm in diameter and 305 mm in length. Test variables included: amount of FRP materials used, strength and stiffness of FRP materials, concrete strength, and the health of concrete at the time of strengthening. Experimental results indicated that a pre-repair load of up to 77% of the unconfined concrete strength had no appreciable effect on the stress-strain response of FRP-confined concrete. With an increase of the unconfined concrete strength, the strength enhancement, energy absorption capacity, ductility factor and work (energy) index at rupture of FRP jackets all decreased remarkably. A positive correlation was found between confined concrete ductility and FRP rupture strain. In addition, a gradual post-peak failure of the specimens, observed previously from FRP-confined concrete columns tested at the University of Toronto, was also observed in some of the current tests -- owing to the high speed data acquisition system. That ductile failure can be attributed to the gradual unzipping failure of FRP jacket, which in turn is related to specimen size. A new constitutive model was developed based on material properties, force equilibrium and strain compatibility. The size effect was taken into account in the model, which is able to accommodate concrete with a wide range of strength (25 MPa to 110 MPa) confined with various types and configurations FRP systems. Design equations from CSA S806-02 and CSA S6-06 provide reasonable and conservative estimates for the FRP-confined concrete strength. To calculate the peak strain for FRP-confined concrete, an equation based on the work by Berthet et al. (2006) is proposed.

Density functional theory is used to study the physico-chemical effects of two metallic thin films separated by distances in a range of 4-10 amperes. In this condition, the electrons from the metallic thin film surfaces tunnel through the energy barrier existing between the separated thin films, creating an electronic distribution in the gap between films. The characteristics and features of this electronic distribution, such as energy, momentum, and number of electrons, can be traced by quantum mechanical analyses. These same features can be tuned by varying metallic thin film properties like thickness, separation between films, and film chemical nature. The possibility to tune the physical properties of the electrons located in the gap between thin films makes the studied systems promising for applications that range from catalysis to nano-electronics. Molecular oxygen, water, and ethylene were located in the gap between thin films in order to study the physical and chemical effects of having those molecules in the gap between thin films. It was observed that the electron structure in the gap modifies the geometric and electronic structure of those molecules placed in the gap. In the case of molecular oxygen, it was found that the dissociation energy can be tuned by changing the separation between thin films and changing the chemical nature of the surface and overlayer of the thin film. For water, it was found that by tuning the chemical nature of the surface and sub-surface of both metallic thin films, molecular water dissociation can occur. When ethylene was located in the gap between Ti/Pt thin films, the molecule converts in an anion radical adopting the geometry and structure of the activated monomer necessary to initiate chain polymerization. Regarding magnetism, it was found that by the surface interaction between Ti/Pt and Pt thin films, the magnetic moment of the system decreases as the separation between thin films decreases. The phenomenon was explained by changes observed in the number of electronic states at the Fermi level and in the exchange splitting as a function of separation between films. Finally, a system that resembles a p-n junction was proposed and analyzed. The system is a junction of two metallic thin films with different electronic density in the gap between surfaces. These junctions can be the building blocks for many electronic devices.

This thesis is concerned with the effects of lateral confining reinforcement on the ductile behaviour of reinforced concrete columns. The contents of the chapters are summarized as follows. In Chapter one, the general problems in seismic design are discussed and earthquake design methods based on the ductile design approach are described. Japanese, New Zealand and United States design codes are compared. Finally, the scope of this research project is outlined. In Chapter two, after reviewing previous research on confined concrete, the factors which affect the effectiveness of lateral confinement are discussed. Especially the effects of the yield strength of transverse reinforcement, the compressive strength of plain concrete and the strain gradient in the column section due to bending are discussed based on tests which were conducted by the author et al at Kyoto University and Akashi Technological College, Japan. In the axial compression tests on spirally reinforced concrete cylinders (150 mm in diameter by 300 mm in height), the yield strength of transverse reinforcement and the compressive strength of plain concrete were varied from 161 MPa to 1352 MPa and from 17 MPa to 60 MPa, respectively, as experimental parameters. It is found that, when high strength spirals are used as confining reinforcement, the strength and ductility of the confined core concrete are remarkably enhanced but need to be estimated assuming several failure modes which could occur. These are based on the observations that concrete cylinders with high strength spirals suddenly failed at a concrete compressive strain of 2 to 3.5 % due to explosive crushing of the core concrete between the spiral bars or due to bearing failure of the core concrete immediately beneath the spiral bars, while the concrete cylinders with ordinary strength spirals failed in a gentle manner normally observed. In addition, eccentric loading tests were conducted on concrete columns with 200 mm square section confined by square spirals. It is found that the effectiveness of confining reinforcement is reduced by the presence of the strain gradient along the transverse section of column. In Chapter three, the effectiveness of transverse reinforcement with various types of anchorage details which simplify the fabrication of reinforcing cages are investigated. Eight reinforced concrete columns, with either 400 mm or 550 mm square cross sections, were tested subjected to axial compression loading and cyclic lateral loading which simulated a severe earthquake. The transverse reinforcement consisted of arrangements of square perimeter hoops with 135° end hooks, cross ties with 90° and 135° or 180° end hooks, and 'U' and 'J' shaped cross ties and perimeter hoops with tension splices. Conclusions are reached with regard to the effectiveness of the tested anchorage details in the plastic hinge regions of columns designed for earthquake resistance. In Chapter four, the effectiveness of interlocking spirals as transverse reinforcement is studied. Firstly, the general aspects and the related problems of interlocking spirals to provide adequate ductility in the potential plastic hinge region of columns are discussed, referring to the provisions in the New Zealand code,the CALTRANS (California Transportation Authority) code and other related codes. Secondly, based on those discussions, a design method to securely interlock the spirals is proposed. Thirdly, the effectiveness of interlocking spirals is assessed based on column tests conducted as part of this study. Three columns with interlocking spirals and, for comparison, one rectangular column with rectangular hoopsandcross ties, were tested under cyclic horizontal loading which simulated a severe earthquake. The sections of those columns were 400 mm by 600 mm. In Chapter five, analytical models to investigate the buckling behaviour of longitudinal reinforcement restrained by cross ties with 90° and 135° end hooks and by peripheral hoops are proposed. The analyzed results using the proposed models compare well with the experimental observations described in Chapter three. Using those proposed models, a method to check the effectiveness of cross ties with 90° and 135° end hooks is proposed for practical design purposes. In Chapter six, a theory for the prediction of the ultimate longitudinal compressive concrete strain at the stage of first hoop fracture referred to as the "Energy Balance Theory", which has been developed by Mander, Priestley and Park at University of Canterbury, is introduced. After discussing the problems in the "Energy Balance Theory", a modified theory for the prediction of the ultimate longitudinal compressive concrete strain at the stage of first hoop fracture is proposed. The predictions from the modified theory are found to compare well with previous experimental results.

Growth confinement techniques for multi walled carbon nanotubes on Au/SiO2 surfaces was studied and incorporated into a gas sensor design. A device framework was conceived and a sensor was built to achieve this structure. The fabrication results were analyzed using scanning electron microscopy which confirmed the achievement of highly site-selective growth of carbon nanotubes, exclusively between the interdigitated electrodes. The sensor was then evaluated for its capacitance and conductance response when exposed to NO2 gas. Variation in sensitivities with frequency and flow rate were analyzed. A mathematical model was derived for such a device structure and the predictions of the model were compared with experimental results.