Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

Cracking in hydrogen ion-implanted Si/Si0.8Ge0.2/Si heterostructures

We demonstrate that a controllable cracking can be realized in Si with a buried strain layer when hydrogen is introduced using traditional H-ion implantation techniques. However, H stimulated cracking is dependent on H projected ranges; cracking occurs along a Si0.8Ge0.2 strain layer only if the H projected range is shallower than the depth of the strained layer. The absence of cracking for H ranges deeper than the strain layer is attributed to ion-irradiation induced strain relaxation, which is confirmed by Rutherford-backscattering-spectrometry channeling angular scans. The study reveals the importance of strain in initializing continuous cracking with extremely low H concentrations.

Ion irradiation effects in nanocrystalline TiN coatings

Nitride materials and coatings have attracted extensive research interests for various applications in advanced nuclear reactors due to their unique combination of physical properties, including high temperature stability, excellent corrosion resistance, superior mechanical property and good thermal conductivity. In this paper, the ion irradiation effects in nanocrystalline TiN coatings as a function of grain size are reported. TiN thin films (thickness of 100 nm) with various grain sizes (8-100 nm) were prepared on Si substrates by a pulsed laser deposition technique. All the samples were irradiated with He ions to high fluences at room temperature. Transmission electron microscopy (TEM) and high resolution TEM on the ion-irradiated samples show that damage accumulation in the TiN films reduces as the grain size reduces. Electrical resistivity of the ion-irradiated films increases slightly compared with the as-deposited ones. These observations demonstrate a good radiation-tolerance property of nanocrystalline TiN films. © 2007 Elsevier B.V. All rights reserved.

Nanostructured Cu/Nb multilayers subjected to helium ion-irradiation

Helium ion-irradiation experiments have been performed in single layer Cu films, Nb films and Cu/Nb multilayer films with layer thickness varying from 2.5 nm to 100 nm each layer. Peak helium concentration approaches a few atomic percent with 6-9 displacement-per-atom in Cu and Nb. He bubbles were observed in single layer Cu and Nb films, as well as in Cu 100 nm/Nb 100 nm multilayers with helium bubbles aligned along layer interfaces. Helium bubbles are not resolved via transmission electron microscopy in Cu 2.5 nm/Nb 2.5 nm multilayers. These studies indicate that layer interface may play an important role in annihilating ion-irradiation induced defects such as vacancies and interstitials and have implications in improving the radiation tolerance of metallic materials using nanostructured multilayers. © 2007 Elsevier B.V. All rights reserved.

Increasing the fracture toughness of silicon by ion implantation

Previous studies have shown that moderate doses of radiation can lead to increased fracture toughness in ceramics. An experimental investigation was conducted to determine the effects of ion implantation on fracture toughness in silicon. Specimens implanted with Ne showed increased fracture toughness, over the entire range of implantations tested. Using ions of various energies to better distribute implantation damage further increased the fracture toughness even though the region of amorphous damage was slightly decreased. The implantation damage accumulated in a predictable manner so that fracture toughness could be optimized.

Coverage versus supply cost in facility location:physics of frustrated spin systems

A comprehensive coverage is crucial for communication, supply, and transportation networks, yet it is limited by the requirement of extensive infrastructure and heavy energy consumption. Here, we draw an analogy between spins in antiferromagnet and outlets in supply networks, and apply techniques from the studies of disordered systems to elucidate the effects of balancing the coverage and supply costs on the network behavior. A readily applicable, coverage optimization algorithm is derived. Simulation results show that magnetized and antiferromagnetic domains emerge and coexist to balance the need for coverage and energy saving. The scaling of parameters with system size agrees with the continuum approximation in two dimensions and the tree approximation in random graphs. Due to frustration caused by the competition between coverage and supply cost, a transition between easy and hard computation regimes is observed. We further suggest a local expansion approach to greatly simplify the message updates which shed light on simplifications in other problems. © 2014 American Physical Society.

Experiments in the dissociative recombination of xenon and krypton

Experiments were conducted using the Time of Flight (TOF) method to identify the final product states of the dissociative recombination reaction of krypton and xenon. In the dissociative recombination (DR) reaction the molecular ion breaks up into product atoms whose velocities can be measured. These velocities can then be used to identify the final product states. The DR of krypton had been studied by Shiu and Biondi using spectrometric techniques. They observed the 5p states. Hardy et al. using TOF techniques had observed the 5s states. Mitchell et al. studied the DR of xenon. They observed the 6p and 5d states of xenon. In this laboratory using the TOF method I have recently identified the 5s, 6p and the 4d final states of the DR of krypton. Then I was able to identify the 5d, 7s, 6d, and 6p′ final product states of the DR of xenon. The study of the DR of these heavy inert gases can shed light on the theory of the DR of heavy polyatomic gases, which is not well developed. ^

Focused ion beam manufacturing of magnetic nanostructures

A number of patterning methods including conventional photo-lithography and E-beam lithography have been employed to pattern devices with critical dimensions of submicrometer levels. The methods of device fabrication by lithography and multilevel processing are usually specific to the chemical and physical properties of the etchants and materials used, and require a number of processing steps. As an alternative, focused ion beam (FIB) lithography is a unique and straightforward tool to rapidly develop nanomagnetic prototyping devices. This feature of FIB is critical to conduct the basic study necessary to advance the state-of-the-art in magnetic recording. ^ The dissertation develops a specific design of nanodevices and demonstrates FIB-fabricated stable and reproducible magnetic nanostructures with a critical dimension of about 10 nm. The project included the fabrication of a patterned single and multilayer magnetic media with areal densities beyond 10 Terabit/in 2. Each block had perpendicular or longitudinal magnetic anisotropy and a single domain structure. The purpose was to demonstrate how the ability of FIB to directly etch nanoscale patterns allowed exploring (even in the academic environment) the true physics of various types of nanostructures. ^ Another goal of this study was the investigation of FIB patterned magnetic media with a set of characterization tools: e.g. Spinstand Guzik V2002, magnetic force microscopy, scanning electron microscopy with energy dispersive system and wavelength dispersive system. ^ In the course of this work, a unique prototype of a record high density patterned magnetic media device capable of 10 terabit/in 2 was built. The read/write testing was performed by a Guzik spinstand. The readback signals were recorded and analyzed by a digital oscilloscope. A number of different configurations for writing and reading information from a magnetic medium were explored. The prototype transducers for this work were fabricated via FIB trimming of different magnetic recording heads. ^

Degree of conversion of different composite resins photo-activated with light-emitting diode and argon ion laser

This study evaluated the degree of conversion (DC%) of one experimental and different brands of composite resins light-cured by two light sources (one LED and one argon laser). The percentage of unreacted C = C was determined from the ratio of absorbance intensities of aliphatic C = C (peak at 1637 cm−1) against internal standards before and after curing: aromatic C–C (peak at 1610 cm−1) except for P90, where %C = C bonds was given for C–O–C (883 cm−1) and C–C (1257 cm−1). ANOVA and Tukey’s test revealed no statistically significant difference among Z350 (67.17), Z250 (69.52) and experimental (66.61 ± 2.03) with LED, just among them and Evolu-X (75.51) and P90 (32.05) that showed higher and lower DC%, respectively. For the argon laser, there were no differences among Z250 (70.67), Z350 (69.60), experimental (65.66) and Evolu-X (73, 37), however a significant difference was observed for P90 (36.80), which showed lowest DC%. The light sources showed similar DC%, however the main difference was observed regarding the composite resins. The lowest DC% was observed for the argon laser. P90 showed the lowest DC% for both light-curing sources.

Gamma-ray and neutrino fluxes from Heavy Dark Matter in the Galactic Center

We present a study of the Galactic Center region as a possible source of both secondary gamma-ray and neutrino fluxes from annihilating dark matter. We have studied the gamma-ray flux observed by the High Energy Stereoscopic System (HESS) from the J1745-290 Galactic Center source. The data are well fitted as annihilating dark matter in combination with an astrophysical background. The analysis was performed by means of simulated gamma spectra produced by Monte Carlo event generators packages. We analyze the differences in the spectra obtained by the various Monte Carlo codes developed so far in particle physics. We show that, within some uncertainty, the HESS data can be fitted as a signal from a heavy dark matter density distribution peaked at the Galactic Center, with a power-law for the background with a spectral index which is compatible with the Fermi-Large Area Telescope (LAT) data from the same region. If this kind of dark matter distribution generates the gamma-ray flux observed by HESS, we also expect to observe a neutrino flux. We show prospective results for the observation of secondary neutrinos with the Astronomy with a Neutrino Telescope and Abyss environmental RESearch project (ANTARES), Ice Cube Neutrino Observatory (Ice Cube) and the Cubic Kilometer Neutrino Telescope (KM3NeT). Prospects solely depend on the device resolution angle when its effective area and the minimum energy threshold are fixed.

Micro-Fabricated Surface Trap and Cavity Integration for Trapped Ion Quantum Computing

Atomic ions trapped in micro-fabricated surface traps can be utilized as a physical platform with which to build a quantum computer. They possess many of the desirable qualities of such a device, including high fidelity state preparation and readout, universal logic gates, long coherence times, and can be readily entangled with each other through photonic interconnects. The use of optical cavities integrated with trapped ion qubits as a photonic interface presents the possibility for order of magnitude improvements in performance in several key areas of their use in quantum computation. The first part of this thesis describes the design and fabrication of a novel surface trap for integration with an optical cavity. The trap is custom made on a highly reflective mirror surface and includes the capability of moving the ion trap location along all three trap axes with nanometer scale precision. The second part of this thesis demonstrates the suitability of small micro-cavities formed from laser ablated fused silica substrates with radii of curvature in the 300-500 micron range for use with the mirror trap as part of an integrated ion trap cavity system. Quantum computing applications for such a system include dramatic improvements in the photonic entanglement rate up to 10 kHz, the qubit measurement time down to 1 microsecond, and the measurement error rates down to the 10e-5 range. The final part of this thesis details a performance simulator for exploring the physical resource requirements and performance demands to scale such a quantum computer to sizes capable of performing quantum algorithms beyond the limits of classical computation.

Isotopic ratios and ion composition of massive ground ice on Herschel Island

Herschel Island in the southern Beaufort Sea is a push moraine at the northwestern-most limit of the Laurentide Ice Sheet. Stable water isotope (d18O, dD) and hydrochemical studies were applied to two tabular massive ground ice bodies to unravel their genetic origin. Buried glacier ice or basal regelation ice was encountered beneath an ice-rich diamicton with strong glaciotectonic deformation structures. The massive ice isotopic composition was highly depleted in heavy isotopes (mean d18O: -33 per mil; mean dD: -258 per mil), suggesting full-glacial conditions during ice formation. Other massive ice of unknown origin with a very large d18O range (from -39 to -21 per mil) was found adjacent to large, striated boulders. A clear freezing slope was present with progressive depletion in heavy isotopes towards the centre of the ice body. Fractionation must have taken place during closed-system freezing, possibly of a glacial meltwater pond. Both massive ground ice bodies exhibited a mixed ion composition suggestive of terrestrial waters with a marine influence. Hydrochemical signatures resemble the Herschel Island sediments that are derived from nearshore marine deposits upthrust by the Laurentide ice. A prolonged contact between water feeding the ice bodies and the surrounding sediment is therefore inferred.

Electron acoustic soliton energy of the Kadomtsev-Petviashvili equation in the Earth’s magnetotail region at critical ion density

The nonlinear properties of small amplitude electron-acoustic solitary waves (EAWs) in a homogeneous system of unmagnetized collisionless plasma consisted of a cold electron fluid and isothermal ions with two different temperatures obeying Boltzmann type distributions have been investigated. A reductive perturbation method was employed to obtain the Kadomstev-Petviashvili (KP) equation. At the critical ion density, the KP equation is not appropriate for describing the system. Hence, a new set of stretched coordinates
is considered to derive the modified KP equation. Moreover, the solitary solution, soliton energy and the associated electric field at the critical ion density were computed. The present investigation can be of relevance to the electrostatic solitary structures observed in various space plasma environments, such as Earth’s magnetotail region.

Ionization of Atoms by Slow Heavy Particles, Including Dark Matter

Atoms and molecules can become ionized during the scattering of a slow, heavy particle off a bound electron. Such an interaction involving leptophilic weakly interacting massive particles (WIMPs) is a promising possible explanation for the anomalous 9σ annual modulation in the DAMA dark matter direct detection experiment [R. Bernabei et al., Eur. Phys. J. C 73, 2648 (2013)]. We demonstrate the applicability of the Born approximation for such an interaction by showing its equivalence to the semiclassical adiabatic treatment of atomic ionization by slow-moving WIMPs. Conventional wisdom has it that the ionization probability for such a process should be exponentially small. We show, however, that due to nonanalytic, cusplike behavior of Coulomb functions close to the nucleus this suppression is removed, leading to an effective atomic structure enhancement. We also show that electron relativistic effects actually give the dominant contribution to such a process, enhancing the differential cross section by up to 1000 times.

Energy levels and radiative rates for Cr-like Cu VI and Zn VII

Energy levels and radiative rates (. A-values) for transitions in Cr-like Cu VI and Zn VII are reported. These data are determined in the quasi-relativistic approach (QR), by employing a very large configuration interaction (CI) expansion which is highly important for these ions. No radiative rates are available in the literature to compare with our results, but our calculated energies are in close agreement with those compiled by NIST and other available theoretical data, for a majority of the levels. The A-values (and resultant lifetimes) are listed for all significantly contributing E1, E2 and M1 radiative transitions among the energetically lowest 322 levels of each ion.