Two-phase Flow in Fuel Cells in Short-term Microgravity Condition

A visual observation of liquid-gas two-phase flow in anode channels of a direct methanol proton exchange membrane fuel cells in microgravity has been carried out in a drop tower. The anode flow bed consisted of 2 manifolds and 11 parallel straight channels. The length, width and depth of single channel with rectangular cross section was 48.0 mm, 2.5 mm and 2.0 mm, respectively. The experimental results indicated that the size of bubbles in microgravity condition is bigger than that in normal gravity. The longer the time, the bigger the bubbles. The velocity of bubbles rising is slower than that in normal gravity because buoyancy lift is very weak in microgravity. The flow pattern in anode channels could change from bubbly flow in normal gravity to slug flow in microgravity. The gas slugs blocked supply of reactants from channels to anode catalyst layer through gas diffusion layer. When the weakened mass transfer causes concentration polarization, the output performance of fuel cells declines.

Proton transfers at the air-water interface

Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes.

Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H₃O⁺(g), can protonate most (non-alkane) organic species, whereas H₃O⁺(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the ‘function’ of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided valuable information regarding the structure of aqueous interfaces, but structure alone is inadequate to decipher the function. By similar analogy, theoretical predictions based on classical molecular dynamics have remained limited in their scope.

Recently, we have adapted an analytical electrospray ionization mass spectrometer (ESIMS) for probing reactions at the gas-liquid interface in real time. This technique is direct, surface-specific,and provides unambiguous mass-to-charge ratios of interfacial species. With this innovation, we have been able to investigate the following:

1. How do anions mediate proton transfers at the air-water interface?

2. What is the basis for the negative surface potential at the air-water interface?

3. What is the mechanism for catalysis ‘on-water’?

In addition to our experiments with the ESIMS, we applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the molecular scale. Our results unambiguously demonstrated the role of electrostatic-reorganization of interfacial water during proton transfer events. With our experimental and theoretical results on the ‘superacidity’ of the surface of mildly acidic water, we also explored implications on atmospheric chemistry and green chemistry. Our most recent results explained the basis for the negative charge of the air-water interface and showed that the water-hydrophobe interface could serve as a site for enhanced autodissociation of water compared to the condensed phase.

Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Direct simulation of proton-coupled electron transfer reaction dynamics and mechanisms

Proton-coupled electron transfer (PCET) reactions are ubiquitous throughout chemistry and biology. However, challenges arise in both the the experimental and theoretical investigation of PCET reactions; the rare-event nature of the reactions and the coupling between quantum mechanical electron- and proton-transfer with the slower classical dynamics of the surrounding environment necessitates the development of robust simulation methodology. In the following dissertation, novel path-integral based methods are developed and employed for the direct simulation of the reaction dynamics and mechanisms of condensed-phase PCET.

Phase-space analysis of wavefront coding imaging systems

We explore the use of the Radon-Wigner transform, which is associated with the fractional Fourier transform of the pupil function, for determining the point spread function (PSF) of an incoherant defocused optical system. Then we introduce these phase-space tools to analyse the wavefront coding imaging system. It is shown that the shape of the PSF for such a system is highly invarient to the defocous-related aberrations except for a lateral shift. The optical transfer function of this system is also investigated briefly from a new understanding of ambiguity function.

I. The effect of droplet solidification upon two-phase flow in a rocket nozzle. II. A kinetic theory investigation of some condensation-evaporation phenomena by a moment method

Part I:

The perturbation technique developed by Rannie and Marble is used to study the effect of droplet solidification upon two-phase flow in a rocket nozzle. It is shown that under certain conditions an equilibrium flow exists, where the gas and particle phases have the same velocity and temperature at each section of the nozzle. The flow is divided into three regions: the first region, where the particles are all in the form of liquid droplets; a second region, over which the droplets solidify at constant freezing temperature; and a third region, where the particles are all solid. By a perturbation about the equilibrium flow, a solution is obtained for small particle slip velocities using the Stokes drag law and the corresponding approximation for heat transfer between the particle and gas phases. Singular perturbation procedure is required to handle the problem at points where solidification first starts and where it is complete. The effects of solidification are noticeable.

Part II:

When a liquid surface, in contact with only its pure vapor, is not in the thermodynamic equilibrium with it, a net condensation or evaporation of fluid occurs. This phenomenon is studied from a kinetic theory viewpoint by means of moment method developed by Lees. The evaporation-condensation rate is calculated for a spherical droplet and for a liquid sheet, when the temperatures and pressures are not too far removed from their equilibrium values. The solutions are valid for the whole range of Knudsen numbers from the free molecule to the continuum limit. In the continuum limit, the mass flux rate is proportional to the pressure difference alone.

Energy and momentum transfer in one-dimensional trapped gases by stimulated light scattering

In ultracold atoms settings, inelastic light scattering is a preeminent technique to reveal static and dynamic properties at nonzero momentum. In this work, we investigate an array of one-dimensional trapped Bose gases, by measuring both the energy and the momentum imparted to the system via light scattering experiments. The measurements are performed in the weak perturbation regime, where these two quantities-the energy and momentum transferred-are expected to be related to the dynamic structure factor of the system. We discuss this relation, with special attention to the role of in-trap dynamics on the transferred momentum.

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications.

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range -125 to 125 °C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular.

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range-125 to 125°C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular. © 2012 Macmillan Publishers Limited. All rights reserved.

Finite element analysis of compressor disc heat transfer using the transient conduction method with sparse boundary collocation points

Surface temperature measurements from two discs of a gas turbine compressor rig are used as boundary conditions for the transient conduction solution (inverse heat transfer analysis). The disc geometry is complex, and so the finite element method is used. There are often large radial temperature gradients on the discs, and the equations are therefore solved taking into account the dependence of thermal conductivity on temperature. The solution technique also makes use of a multigrid algorithm to reduce the solution time. This is particularly important since a large amount of data must be analyzed to obtain correlations of the heat transfer. The finite element grid is also used for a network analysis to calculate the radiant heat transfer in the cavity formed between the two compressor discs. The work discussed here proved particularly challenging as the disc temperatures were only measured at four different radial locations. Four methods of surface temperature interpolation are examined, together with their effect on the local heat fluxes. It is found that the choice of interpolation method depends on the available number of data points. Bessel interpolation gives the best results for four data points, whereas cubic splines are preferred when there are considerably more data points. The results from the analysis of the compressor rig data show that the heat transfer near the disc inner radius appears to be influenced by the central throughflow. However, for larger radii, the heat transfer from the discs and peripheral shroud is found to be consistent with that of a buoyancy-induced flow.

Sol-gel method for the preparation of solid-phase microextraction fibers

A novel sol-gel method is applied for the preparation of solid-phase microextraction (SPME) fibers. Scanning electron microscopy experiments suggested a porous structure for the poly(dimethylsiloxane) (PDMS) coating. SPME-GC analysis provided evidence that the sol-gel fibers have some advantages, such as high thermal stability, efficient extraction rates, high velocities of mass transfer, and spacious range of application.

Quantum phase transitions in the S=1/2 distorted diamond chain

By means of the second derivative of the ground-state and first-excited energy, the quantum phase transitions (QPTs) for the distorted diamond chain (DDC) with ferromagnetic and antiferromagnetic frustrated interactions and the trimerized case are investigated, respectively. Our results show the plentiful quantum phases owing to the spin interaction competitions in the model. Meanwhile, by using the transfer-matrix renormalization-group technique, we study the two-site thermal entanglement of the DDC model in the thermodynamic limit for a further understanding of the QPTs.

Direct observation of coherent spin transfer processes in an InGaAs/GaAs quantum well via two-color time-resolved Kerr rotation measurements

A two-color time-resolved Kerr rotation spectroscopy system was built, with a femtosecond Ti:sapphire laser and a photonic crystal fiber, to study coherent spin transfer processes in an InGaAs/GaAs quantum well sample. The femtosecond Ti:sapphire laser plays two roles: besides providing a pump beam with a tunable wavelength, it also excites the photonic crystal fiber to generate supercontinuum light ranging from 500 nm to 1600 nm, from which a probe beam with a desirable wavelength is selected with a suitable interference filter. With such a system, we studied spin transfer processes between two semiconductors of different gaps in an InGaAs/GaAs quantum well sample. We found that electron spins generated in the GaAs barrier were transferred coherently into the InGaAs quantum well. A model based on rate equations and Bloch-Torrey equations is used to describe the coherent spin transfer processes quantitatively. With this model, we obtain an effective electron spin accumulation time of 21 ps in the InGaAs quantum well.

A novel hybrid phase-locked-loop frequency synthesizer using single-electron devices and CMOS transistors

This paper proposes a novel phase-locked loop (PLL) frequency synthesizer using single-electron devices (SEDs) and metal-oxide-semiconductor (MOS) field-effect transistors. The PLL frequency synthesizer mainly consists of a single-electron transistor (SET)/MOS hybrid voltage-controlled oscillator circuit, a single-electron (SE) turnstile/MOS hybrid phase-frequency detector (PFD) circuit and a SE turnstile/MOS hybrid frequency divider. The phase-frequency detection and frequency-division functions are realized by manipulating the single electrons. We propose a SPICE model to describe the behavior of the MOSFET-based SE turnstile. The authors simulate the performance of the PILL block circuits and the whole PLL synthesizer. Simulation results indicated that the circuit can well perform the operation of the PLL frequency synthesizer at room temperature. The PILL synthesizer is very compact. The total number of the transistors is less than 50. The power dissipation of the proposed PLL circuit is less than 3 uW. The authors discuss the effect of fabrication tolerance, the effect of background charge and the SE transfer accuracy on the performance of the PLL circuit. A technique to compensate parameter dispersions of SEDs is proposed.

Interplay between partial incoherence, partial inelasticity, resonance, and heterogeneity in long-range electron transfer and transport

A generalized scattering matrix formalism is constructed to elucidate the interplay of electron resonance, coherence, dephasing, inelastic scattering, and heterogeneity, which play important roles in the physics of long-range electron transfer/transport. The theory consists of an extension of the standard Buttiker phase-breaking model and an analytical expression of the electron transmission coefficient for donor-bridge-acceptor systems with arbitrary length and sequence. The theory incorporates the following features: Dephasing-assisted off-resonance enhancement, inelasticity-induced turnover, resonance enhancement and its dephasing-induced suppression, dephasing-induced smooth superexchange-hopping transition, and heterogeneity effects. (C) 2002 American Institute of Physics.