General-domain compressible Navier-Stokes solvers exhibiting quasi-unconditional stability and high-order accuracy in space and time

This thesis presents a new class of solvers for the subsonic compressible Navier-Stokes equations in general two- and three-dimensional spatial domains. The proposed methodology incorporates: 1) A novel linear-cost implicit solver based on use of higher-order backward differentiation formulae (BDF) and the alternating direction implicit approach (ADI); 2) A fast explicit solver; 3) Dispersionless spectral spatial discretizations; and 4) A domain decomposition strategy that negotiates the interactions between the implicit and explicit domains. In particular, the implicit methodology is quasi-unconditionally stable (it does not suffer from CFL constraints for adequately resolved flows), and it can deliver orders of time accuracy between two and six in the presence of general boundary conditions. In fact this thesis presents, for the first time in the literature, high-order time-convergence curves for Navier-Stokes solvers based on the ADI strategy---previous ADI solvers for the Navier-Stokes equations have not demonstrated orders of temporal accuracy higher than one. An extended discussion is presented in this thesis which places on a solid theoretical basis the observed quasi-unconditional stability of the methods of orders two through six. The performance of the proposed solvers is favorable. For example, a two-dimensional rough-surface configuration including boundary layer effects at Reynolds number equal to one million and Mach number 0.85 (with a well-resolved boundary layer, run up to a sufficiently long time that single vortices travel the entire spatial extent of the domain, and with spatial mesh sizes near the wall of the order of one hundred-thousandth the length of the domain) was successfully tackled in a relatively short (approximately thirty-hour) single-core run; for such discretizations an explicit solver would require truly prohibitive computing times. As demonstrated via a variety of numerical experiments in two- and three-dimensions, further, the proposed multi-domain parallel implicit-explicit implementations exhibit high-order convergence in space and time, useful stability properties, limited dispersion, and high parallel efficiency.

Zn-VI/Cu2O Heterojunctions for Earth-Abundant Photovoltaics

The need for sustainable energy production motivates the study of photovoltaic materials, which convert energy from sunlight directly into electricity. This work has focused on the development of Cu₂O as an earth-abundant solar absorber due to the abundance of its constituent elements in the earth's crust, its suitable band gap, and its potential for low cost processing. Crystalline wafers of Cu₂O with minority carrier diffusion lengths on the order of microns can be manufactured in a uniquely simple fashion — directly from copper foils by thermal oxidation. Furthermore, Cu₂O has an optical band gap of 1.9 eV, which gives it a detailed balance energy conversion efficiency of 24.7% and the possibility for an independently connected Si/Cu₂O dual junction with a detailed balance efficiency of 44.3%.

However, the highest energy conversion efficiency achieved in a photovoltaic device with a Cu₂O absorber layer is currently only 5.38% despite the favorable optical and electronic properties listed above. There are several challenges to making a Cu₂O photovoltaic device, including an inability to dope the material, its relatively low chemical stability compared to other oxides, and a lack of suitable heterojunction partners due to an unusually small electron affinity. We have addressed the low chemical stability, namely the fact that Cu₂O is an especially reactive oxide due to its low enthalpy of formation (ΔH_f⁰ = -168.7 kJ/mol), by developing a novel surface preparation technique. We have addressed the lack of suitable heterojunction partners by investigating the heterojunction band alignment of several Zn-VI materials with Cu₂O. Finally, We have addressed the typically high series resistance of Cu₂O wafers by developing methods to make very thin, bulk Cu₂O, including devices on Cu₂O wafers as thin as 20 microns. Using these methods we have been able to achieve photovoltages over 1 V, and have demonstrated the potential of a new heterojunction material, Zn(O,S).

Quantum Mechanics Studies of Fuel Cell Catalysts and Proton Conducting Ceramics with Validation by Experiment

We carried out quantum mechanics (QM) studies aimed at improving the performance of hydrogen fuel cells. This led to predictions of improved materials, some of which were subsequently validated with experiments by our collaborators.

In part I, the challenge was to find a replacement for the Pt cathode that would lead to improved performance for the Oxygen Reduction Reaction (ORR) while remaining stable under operational conditions and decreasing cost. Our design strategy was to find an alloy with composition Pt3M that would lead to surface segregation such that the top layer would be pure Pt, with the second and subsequent layers richer in M. Under operating conditions we expect the surface to have significant O and/or OH chemisorbed on the surface, and hence we searched for M that would remain segregated under these conditions. Using QM we examined surface segregation for 28 Pt₃M alloys, where M is a transition metal. We found that only Pt₃Os and Pt₃Ir showed significant surface segregation when O and OH are chemisorbed on the catalyst surfaces. This result indicates that Pt₃Os and Pt3Ir favor formation of a Pt-skin surface layer structure that would resist the acidic electrolyte corrosion during fuel cell operation environments. We chose to focus on Os because the phase diagram for Pt-Ir indicated that Pt-Ir could not form a homogeneous alloy at lower temperature. To determine the performance for ORR, we used QM to examine all intermediates, reaction pathways, and reaction barriers involved in the processes for which protons from the anode reactions react with O₂ to form H₂O. These QM calculations used our Poisson-Boltzmann implicit solvation model include the effects of the solvent (water with dielectric constant 78 with pH 7 at 298K). We found that the rate determination step (RDS) was the O_ad hydration reaction (O_ad + H₂O_ad -> OH_ad + OH_ad) in both cases, but that the barrier for pure Pt of 0.50 eV is reduced to 0.48 eV for Pt₃Os, which at 80 degrees C would increase the rate by 218%. We collaborated with the Pu-Wei Wu’s group to carry out experiments, where we found that the dealloying process-treated Pt2Os catalyst showed two-fold higher activity at 25 degrees C than pure Pt and that the alloy had 272% improved stability, validating our theoretical predictions.

We also carried out similar QM studies followed by experimental validation for the Os/Pt core-shell catalyst fabricated by the underpotential deposition (UPD) method. The QM results indicated that the RDS for ORR is a compromise between the OOH formation step (0.37 eV for Pt, 0.23 eV for Pt_2ML/Os core-shell) and H₂O formation steps (0.32 eV for Pt, 0.22 eV for Pt_2ML/Os core-shell). We found that Pt_2ML/Os has the highest activity (compared to pure Pt and to the Pt₃Os alloy) because the 0.37 eV barrier decreases to 0.23 eV. To understand what aspects of the core shell structure lead to this improved performance, we considered the effect on ORR of compressing the alloy slab to the dimensions of pure Pt. However this had little effect, with the same RDS barrier 0.37 eV. This shows that the ligand effect (the electronic structure modification resulting from the Os substrate) plays a more important role than the strain effect, and is responsible for the improved activity of the core- shell catalyst. Experimental materials characterization proves the core-shell feature of our catalyst. The electrochemical experiment for Pt_2ML/Os/C showed 3.5 to 5 times better ORR activity at 0.9V (vs. NHE) in 0.1M HClO₄ solution at 25 degrees C as compared to those of commercially available Pt/C. The excellent correlation between experimental half potential and the OH binding energies and RDS barriers validate the feasibility of predicting catalyst activity using QM calculation and a simple Langmuir–Hinshelwood model.

In part II, we used QM calculations to study methane stream reforming on a Ni-alloy catalyst surfaces for solid oxide fuel cell (SOFC) application. SOFC has wide fuel adaptability but the coking and sulfur poisoning will reduce its stability. Experimental results suggested that the Ni4Fe alloy improves both its activity and stability compared to pure Ni. To understand the atomistic origin of this, we carried out QM calculations on surface segregation and found that the most stable configuration for Ni₄Fe has a Fe atom distribution of (0%, 50%, 25%, 25%, 0%) starting at the bottom layer. We calculated that the binding of C atoms on the Ni4Fe surface is 142.9 Kcal/mol, which is about 10 Kcal/mol weaker compared to the pure Ni surface. This weaker C binding energy is expected to make coke formation less favorable, explaining why Ni₄Fe has better coking resistance. This result confirms the experimental observation. The reaction energy barriers for CHx decomposition and C binding on various alloy surface, Ni₄X (X=Fe, Co, Mn, and Mo), showed Ni₄Fe, Ni₄Co, and Fe₄Mn all have better coking resistance than pure Ni, but that only Ni₄Fe and Fe₄Mn have (slightly) improved activity compared to pure Ni.

In part III, we used QM to examine the proton transport in doped perovskite-ceramics. Here we used a 2x2x2 supercell of perovskite with composition Ba₈X₇M₁(OH)₁O₂₃ where X=Ce or Zr and M=Y, Gd, or Dy. Thus in each case a 4⁺ X is replace by a 3⁺ M plus a proton on one O. Here we predicted the barriers for proton diffusion allowing both includes intra-octahedron and inter-octahedra proton transfer. Without any restriction, we only observed the inter-octahedra proton transfer with similar energy barrier as previous computational work but 0.2 eV higher than experimental result for Y doped zirconate. For one restriction in our calculations is that the O_donor-O_acceptor atoms were kept at fixed distances, we found that the barrier difference between cerates/zirconates with various dopants are only 0.02~0.03 eV. To fully address performance one would need to examine proton transfer at grain boundaries, which will require larger scale ReaxFF reactive dynamics for systems with millions of atoms. The QM calculations used here will be used to train the ReaxFF force field.

Stability of Hypervelocity Boundary Layers

The early stage of laminar-turbulent transition in a hypervelocity boundary layer is studied using a combination of modal linear stability analysis, transient growth analysis, and direct numerical simulation. Modal stability analysis is used to clarify the behavior of first and second mode instabilities on flat plates and sharp cones for a wide range of high enthalpy flow conditions relevant to experiments in impulse facilities. Vibrational nonequilibrium is included in this analysis, its influence on the stability properties is investigated, and simple models for predicting when it is important are described.

Transient growth analysis is used to determine the optimal initial conditions that lead to the largest possible energy amplification within the flow. Such analysis is performed for both spatially and temporally evolving disturbances. The analysis again targets flows that have large stagnation enthalpy, such as those found in shock tunnels, expansion tubes, and atmospheric flight at high Mach numbers, and clarifies the effects of Mach number and wall temperature on the amplification achieved. Direct comparisons between modal and non-modal growth are made to determine the relative importance of these mechanisms under different flow regimes.

Conventional stability analysis employs the assumption that disturbances evolve with either a fixed frequency (spatial analysis) or a fixed wavenumber (temporal analysis). Direct numerical simulations are employed to relax these assumptions and investigate the downstream propagation of wave packets that are localized in space and time, and hence contain a distribution of frequencies and wavenumbers. Such wave packets are commonly observed in experiments and hence their amplification is highly relevant to boundary layer transition prediction. It is demonstrated that such localized wave packets experience much less growth than is predicted by spatial stability analysis, and therefore it is essential that the bandwidth of localized noise sources that excite the instability be taken into account in making transition estimates. A simple model based on linear stability theory is also developed which yields comparable results with an enormous reduction in computational expense. This enables the amplification of finite-width wave packets to be taken into account in transition prediction.

Numerical analysis and comparison of three metal-oxide-type super-resolution near field structures

Based on the Fresnel-Kirchkoff diffraction theory, we build up a Gaussian diffraction model of metal-oxide-type super-resolution near field structure (super-RENS), which can describe far field optical properties. The spectral contrast induced by refractive index and the structural changes in AgOx, PtOx and PdOx thin films, which are the key functional layers in super-RENS, are studied by using this model. Comparison results indicate that the spectral contrast intensively on laser-induced distribution and change of the refractive index in the metal-oxide films. The readout mechanism of the metal-oxide-type super-RENS optical disc is further clarified. This Gaussian diffraction model can be used as a simple and effective method for choosing proper active materials in super-RENS.

Effect of oxygen substitution by halide ions on structure, thermal stability and upconversion fluorescence in Er3(+)/Yb3(+)-codoped germanium-bismuth glasses

For the first time. effect of halide ions (F-, Cl-, Br-, and I-) introduction on structure, thermal stability, and upconversion fluorescence in Er3+/Yb3+-codoped oxide-halide germanium-bismuth glasses has been systematically investigated. The results show that halide ions modified germanium-bismuth glasses have lower maximum phonon energy and phonon density, worse thermal stability. longer measured lifetimes of I-4(l1/2) level, and stronger upconversion emission than germanium-bismuth glass. All these results indicate that halide ions play an important role in the formation of glass network, and have an important influence on the upconversion luminescence. The possible upconversion mechanisms of Er3+ ion are also evaluated. © 2005 Elsevier Ltd. All rights reserved.

Effect of chloride ions' introduction on structural, thermal stability, and spectroscopic properties in Yb3+Er3+-codoped germanate-bismuth-lead glasses

Yb3+Er3+-codoped chloride-modified germanate-bismuth-lead glasses have been synthesized by the conventional melting and quenching method. Structural and thermal stability properties have been obtained on the basis of the Raman spectra and differential thermal analysis, which indicate that the PbCl2 addition has an important influence on the phonon density of states, maximum phonon energy, and thermal stability of host glasses. The Judd-Ofelt intensity parameters and quantum efficiencies were calculated on the basis of the Judd-Ofelt theory and lifetime measurements. For the 1.53 mu m emission band, the full widths at the half-maximum increase and peak wavelengths are blueshifted with increasing PbCl2 content. Moreover, the effect of the PbCl2 addition on the phonon density of states, OH- content, and upconversion luminescence has been discussed and evaluated. Our results reveal that, with increasing PbCl2 content, the decrease of phonon density and OH- content contributes more to the enhanced upconversion emissions than that of maximum phonon energy. (c) 2005 Optical Society of America

Study on the hydrolytic property and thermal stability of LiAlO2 substrate

The hydrolytic property and thermal stability of LiAlO2 (LAO), important factors for its application, were examined by AFM and X-ray rocking curve. We found that H2O may be deleterious for LAO surface polishing when the root mean square (RMS) value is less than 1 nm. However, when the RMS value is more than 1 nm it may be useful for LAO polishing. (100)-plane LAO substrates are annealed in the range of 850-900 degrees C in flux N-2, Slick AlN layer probably is produced on the substrate surface. M-plane GaN layer has grown on the substrate by metal-organic chemical vapor deposition (MOCVD) method. Theses results show that LiAlO2 crystal is a promising substrate of fabricating high-efficiency LEDs by MOCVD. (c) 2006 Elsevier B.V. All rights reserved.

Investigation of laser-induced damage on multi-layer dielectric gratings

We investigate mechanisms of laser induced damage thresholds (LIDTs) of multi-layer dielectric gratings (AIDG,). It is found that the laser damage thresholds of MDGs and unstructured dielectric multi-layer coatings (the substrate of MDG) are 3.15J/cm(2) and 9.32 J/cm(2), respectively, at 1064nm (12ns) with the Littrow angle 51.2 degrees and the TEM00 mode. The laser-induced damage mechanism of multi-layer dielectric is presented with the analysis of the following factors: The dominant factor is the pollution on the corrugated surface, which is induced by the complex manufacture process of multi-layer dielectric gratings; another is the electric field distribution along the corrugated surface. The third reason is due to the reduction in stoichiometry of oxide films, resulting from the manufacture process of etching.

Influence of buffer layer thickness on the structure and optical properties of ZnO thin films

A series of ZnO thin films were deposited on ZnO buffer layers by DC reactive magnetron sputtering. The buffer layer thickness determination of microstructure and optical properties of ZnO films was investigated by X-ray diffraction (XRD), photoluminescence (PL), optical transmittance and absorption measurements. XRD results revealed that the stress of ZnO thin films varied with the buffer layer thickness. With the increase of buffer layer thickness, the band gap edge shifted toward longer wavelength. The near-band-edge (NBE) emission intensity of ZnO films deposited on ZnO buffer layer also varied with the increase of thickness due to the spatial confinement increasing the Coulomb interaction between electrons and holes. The PL measurement showed that the optimum thickness of the ZnO buffer layer was around 12 nm. (c) 2005 Elsevier B.V. All rights reserved.

Investigation on thermal stability of TiO2 films for application at high temperature

The thermal stability of electron beam deposited TiO2 monolayers and TiO2/SiO2 high reflectors (HR) during 300 to 1100 degrees C annealing is studied. It is found that the optical loss of film increases with the increase in annealing temperature, due to the phase change, crystallisation and deoxidising of film. Scattering loss dominates the optical property degradation of film below 900 degrees C, while the absorption is another factor at 1100 degrees C. The increase in refractive index and decrease in physical thickness of TiO2 layer shift the spectra of HR above 900 degrees C. The possible crack mechanism on the surface of HR during annealing is discussed. Guidance for application on high temperature stable optical coatings is given.

Fabrication of diamond based schottky barrier diodes with oxide ramp termination

The paper's goal is the first demonstration of the fabrication of high power Schottky diodes on synthetic diamond using oxide ramp termination. In order to allow full activated impurities at room temperature and a high hole mobility a low boron doping of the drift layer is employed. Several aspects of the manufacturing technology are presented. A termination with a small ramp angle can be obtained using only RIE technique due to diamond wafer nonuniformity (roughness). Experimental forward and reverse characteristics measured on diamond diodes are also included. © 2007 IEEE.

Interfacial immobilization of monoclonal antibody and detection of human prostate-specific antigen.

Antibody orientation and its antigen binding efficiency at interface are of particular interest in many immunoassays and biosensor applications. In this paper, spectroscopic ellipsometry (SE), neutron reflection (NR), and dual polarization interferometry (DPI) have been used to investigate interfacial assembly of the antibody [mouse monoclonal anti-human prostate-specific antigen (anti-hPSA)] at the silicon oxide/water interface and subsequent antigen binding. It was found that the mass density of antibody adsorbed at the interface increased with solution concentration and adsorption time while the antigen binding efficiency showed a steady decline with increasing antibody amount at the interface over the concentration range studied. The amount of antigen bound to the interfacial immobilized antibody reached a maximum when the surface-adsorbed amount of antibody was around 1.5 mg/m(2). This phenomenon is well interpreted by the interfacial structural packing or crowding. NR revealed that the Y-shaped antibody laid flat on the interface at low surface mass density with a thickness around 40 Å, equivalent to the short axial length of the antibody molecule. The loose packing of the antibody within this range resulted in better antigen binding efficiency, while the subsequent increase of surface-adsorbed amount led to the crowding or overlapping of antibody fragments, hence reducing the antigen binding due to the steric hindrance. In situ studies of antigen binding by both NR and DPI demonstrated that the antigen inserted into the antibody layer rather than forming an additional layer on the top. Stability assaying revealed that the antibody immobilized at the silica surface remained stable and active over the monitoring period of 4 months. These results are useful in forming a general understanding of antibody interfacial behavior and particularly relevant to the control of their activity and stability in biosensor development.

Diffusion and chemical reaction in the porous structures of solid oxide fuel cells

The Rolls-Royce Integrated-Planar Solid Oxide Fuel Cell (IP-SOFC) consists of ceramic modules which have electrochemical cells printed on the outer surfaces. The cathodes are the outermost layer of each cell and are supplied with oxygen from air flowing over the outside of the module. The anodes are in direct contact with the ceramic structure and are supplied with fuel from internal gas channels. Natural gas is reformed into hydrogen for use by the fuel cells in a separate reformer module of similar design except that the fuel cells are replaced by a reforming catalyst layer. The performance of the modules is intrinsically linked to the behaviour of the gas flows within their porous structures. Because the porous layers are very thin, a one-dimensional flow model provides a good representation of the flow property variations between fuel channel and fuel cell or reforming catalyst. The multi-component convective-diffusive flows are simulated using a new theory of flow in porous material, the Cylindrical Pore Interpolation Model. The effects of the catalysed methane reforming and water-gas shift chemical reactions are also considered using appropriate kinetic models. It is found that the shift reaction, which is catalysed by the anode material, has certain beneficial effects on the fuel cell module performance. In the reformer module it was found that the flow resistance of the porous support structure makes it difficult to sustain a high methane conversion rate. Although the analysis is based on IP-SOFC geometry, the modelling approach and general conclusions are applicable to other types of SOFC.

Catalyst-free synthesis of zinc oxide nanostructures by microheaters in the ambient environment

This paper demonstrates a catalyst-free synthesis of ZnO nanostructures using platinum microheaters under ambient environmental conditions. Different morphologies of ZnO nanostructures are synthesized from the oxidization of Zn thin film by local heating. The synthesized ZnO structures are characterized by the SEM, EDX and Raman spectra. The characterization of two shapes of Pt microheaters is investigated and the relationship between the applied heating power and ZnO nanostructures synthesis is investigated under ambient conditions. We observe that the density and morphology of ZnO nanostructures can be controlled through applied heating voltages. Furthermore, a connected composite structural (Zn-ZnO-Zn) layer is synthesized using combinative microheaters. © 2011 IEEE.