Optimization of Organic-Inorganic Inter-phase in Hybrid Systems Based on Waterborne Polyurethanes and Silica Nanostructures

215 p.

Mechanisms in fs-laser ablation in fused silica

A theoretical model is proposed to describe the microscopic processes involved in the ablation in fused silica induced by femtosecond-laser pulse. Conduction-band electron (CBE) can absorb laser energy, the rate is calculated by quantum mechanical method and classical method. CBE is produced via photoionization (PI) and impact ionization (II). The PI and II rates are calculated by using the Keldysh theory and double-flux model, respectively. Besides the CBE production, we investigate laser energy deposition and its distribution. The equation of energy diffusion in physical space is resolved numerically. Taking energy density E-dep=54 kJ/cm(3) as the criterion, we calculate damage threshold, ablation depth, and ablation volumes. It is found that if energy diffusion is considered, energy density near sample surface is reduced to 1/10, damage threshold is enhanced more than 30%, ablation depth is increased by a factor of 10. Our theoretical results agree well with experimental measurements. Several ultrafast phenomena in fused silica are also discussed. (C) 2004 American Institute of Physics.

Study of the origins of toughness in amorphous metals

Amorphous metals that form fully glassy parts over a few millimeters in thickness are still relatively new materials. Their glassy structure gives them particularly high strengths, high yield strains, high hardness values, high resilience, and low damping losses, but this can also result in an extremely low tolerance to the presence of flaws in the material. Since this glassy structure lacks the ordered crystal structure, it also lacks the crystalline defect (dislocations) that provides the micromechanism of toughening and flaw insensitivity in conventional metals. Without a sufficient and reliable toughness that results in a large tolerance of damage in the material, metallic glasses will struggle to be adopted commercially. Here, we identify the origin of toughness in metallic glass as the competition between the intrinsic toughening mechanism of shear banding ahead of a crack and crack propagation by the cavitation of the liquid inside the shear bands. We present a detailed study over the first three chapters mainly focusing on the process of shear banding; its crucial role in giving rise to one of the most damage-tolerant materials known, its extreme sensitivity to the configurational state of a glass with moderate toughness, and how the configurational state can be changed with the addition of minor elements. The last chapter is a novel investigation into the cavitation barrier in glass-forming liquids, the competing process to shear banding. The combination of our results represents an increased understanding of the major influences on the fracture toughness of metallic glasses and thus provides a path for the improvement and development of tougher metallic glasses.

Nonlinear optics in planar silica-on-silicon disk resonators

Optical frequency combs (OFCs) provide direct phase-coherent link between optical and RF frequencies, and enable precision measurement of optical frequencies. In recent years, a new class of frequency combs (microcombs) have emerged based on parametric frequency conversions in dielectric microresonators. Micocombs have large line spacing from 10's to 100's GHz, allowing easy access to individual comb lines for arbitrary waveform synthesis. They also provide broadband parametric gain bandwidth, not limited by specific atomic or molecular transitions in conventional OFCs. The emerging applications of microcombs include low noise microwave generation, astronomical spectrograph calibration, direct comb spectroscopy, and high capacity telecommunications.

In this thesis, research is presented starting with the introduction of a new type of chemically etched, planar silica-on-silicon disk resonator. A record Q factor of 875 million is achieved for on-chip devices. A simple and accurate approach to characterize the FSR and dispersion of microcavities is demonstrated. Microresonator-based frequency combs (microcombs) are demonstrated with microwave repetition rate less than 80 GHz on a chip for the first time. Overall low threshold power (as low as 1 mW) of microcombs across a wide range of resonator FSRs from 2.6 to 220 GHz in surface-loss-limited disk resonators is demonstrated. The rich and complex dynamics of microcomb RF noise are studied. High-coherence, RF phase-locking of microcombs is demonstrated where injection locking of the subcomb offset frequencies are observed by pump-detuning-alignment. Moreover, temporal mode locking, featuring subpicosecond pulses from a parametric 22 GHz microcomb, is observed. We further demonstrated a shot-noise-limited white phase noise of microcomb for the first time. Finally, stabilization of the microcomb repetition rate is realized by phase lock loop control.

For another major nonlinear optical application of disk resonators, highly coherent, simulated Brillouin lasers (SBL) on silicon are also demonstrated, with record low Schawlow-Townes noise less than 0.1 Hz^2/Hz for any chip-based lasers and low technical noise comparable to commercial narrow-linewidth fiber lasers. The SBL devices are efficient, featuring more than 90% quantum efficiency and threshold as low as 60 microwatts. Moreover, novel properties of the SBL are studied, including cascaded operation, threshold tuning, and mode-pulling phenomena. Furthermore, high performance microwave generation using on-chip cascaded Brillouin oscillation is demonstrated. It is also robust enough to enable incorporation as the optical voltage-controlled-oscillator in the first demonstration of a photonic-based, microwave frequency synthesizer. Finally, applications of microresonators as frequency reference cavities and low-phase-noise optomechanical oscillators are presented.

A Study on iron-based amorphous alloys : alloy development, thermodynamics and soft magnetism

Metallic glass has since its debut been of great research interest due to its profound scientific significance. Magnetic metallic glasses are of special interest because of their promising technological applications. In this thesis, we introduced a novel series of Fe-based alloys and offer a holistic review of the physics and properties of these alloys. A systematic alloy development and optimization method was introduced, with experimental implementation on transition metal based alloying system. A deep understanding on the influencing factors of glass forming ability was brought up and discussed, based on classical nucleation theory. Experimental data of the new Fe-based amorphous alloys were interpreted to further analyze those influencing factors, including reduced glass transition temperature, fragility, and liquid-crystal interface free energy. Various treatments (fluxing, overheating, etc.) were discussed for their impacts on the alloying systems' thermodynamics and glass forming ability. Multiple experimental characterization methods were discussed to measure the alloys' soft magnetic properties. In addition to theoretical and experimental investigation, we also gave a detailed numerical analysis on the rapid-discharge-heating-and-forming platform. It is a novel experimental system which offers extremely fast heating rate for calorimetric characterization and alloy deformation.

Influence of composition on the structure and properties of Fe-Pd-P and Ni-Pd-P amorphous alloys

Ternary alloys of nickel-palladium-phosphorus and iron-palladium- phosphorus containing 20 atomic % phosphorus were rapidly quenched from the liquid state. The structure of the quenched alloys was investigated by X-ray diffraction. Broad maxima in the diffraction patterns, indicative of a glass-like structure, were obtained for 13 to 73 atomic % nickel and 13 to 44 atomic % iron, with palladium adding up to 80%.

Radial distribution functions were computed from the diffraction data and yielded average interatomic distances and coordination numbers. The structure of the amorphous alloys could be explained in terms of structural units analogous to those existing in the crystalline Pd₃P, Ni₃P and Fe₃P phases, with iron or nickel substituting for palladium. A linear relationship between interatomic distances and composition, similar to Vegard's law, was shown for these metallic glasses.

Electrical resistivity measurements showed that the quenched alloys were metallic. Measurements were performed from liquid helium temperatures (4.2°K) up to the vicinity of the melting points (900°K- 1000°K). The temperature coefficient in the glassy state was very low, of the order of 10^-4/°K. A resistivity minimum was found at low temperature, varying between 9°K and 14°K for Ni_x-Pd_80-x -P₂₀ and between 17°K and 96°K for Fe_x-Pd_80-x -P₂₀, indicating the presence of a Kondo effect. Resistivity measurements, with a constant heating rate of about 1.5°C/min,showed progressive crystallization above approximately 600°K.

The magnetic moments of the amorphous Fe-Pd-P alloys were measured as a function of magnetic field and temperature. True ferromagnetism was found for the alloys Fe₃₂-Pd₄₈-P₂₀ and Fe₄₄-Pd₃₆-P₂₀ with Curie points at 165° K and 380° K respectively. Extrapolated values of the saturation magnetic moments to 0° K were 1.70 µ_B and 2.10 µ_B respectively. The amorphous alloy Fe₂₃-Pd₅₇-P₂₀ was assumed to be superparamagnetic. The experimental data indicate that phosphorus contributes to the decrease of moments by electron transfer, whereas palladium atoms probably have a small magnetic moment. A preliminary investigation of the Ni-Pd-P amorphous alloys showed that these alloys are weakly paramagnetic.

Ultraviolet-infrared femtosecond laser-induced damage in fused silica and CaF2 crystals

The damage in fused silica and CaF2 crystals induced by wavelength tunable femtosecond lasers is studied. The threshold fluence is observed to increase rapidly with laser wavelength lambda in the region of 250-800 nm, while it is nearly a constant for 800