Development of CO2 Laser-Heating for the Study of Wide Band Gap Oxide Materials

The ability to access a vast region of the pressure-temperature landscape using energy density tuning enables exotic states of matter to be probed. A well documented method for such exploration, under static conditions, is the use of the laser-heated diamond anvil cell (LH-DAC), accessing a combination of high pressure (\u3e300 GPa) and high temperature (\u3e5000 K). This thesis presents our development of direct CO2 laser heating techniques to study a series of wide band gap insulators, La2Sn2O7, ZrO2, and CeO2, under high pressure conditions. The lasing frequency of CO2 lasers is such that these wide band gap materials absorb the light directly through anharmonic polariton-phonon scattering processes in the material. In the early stages of our high pressure-temperature laboratory development, a study on the pyrochlore La2Sn2O7 was done using CO2 laser-heating. This study investigated the pressure induced amorphization, and the production of a high pressure phase through laser annealing of La2Sn2O7. This study however was carried out with a lack of in situ diagnostics, a common shortcoming for all experiments prior to this thesis. This thesis reports a series of developments for instrumentation that enabled an ensemble of in situ measurements that are used to investigate wide band gap oxides, such as La2Sn2O7, ZrO2, and CeO2. Three Raman systems were built in the UNLV laboratory. In addition, a series of CO2 laser heating systems were built. Two dedicated laser heating systems were developed for in situ measurements at Argonne National Laboratory\u27s Advanced Photon Source using synchrotron techniques that allow temporal and spatial resolved diagnostics. These are currently installed at sector 16-IDB for in situ x-ray diffraction, and at 16-BMD for in situ x-ray absorption spectroscopy. In addition, an in-house dedicated system was developed for CO2 laser-heating system, coupled with in situ Raman spectroscopy. A series of techniques were developed and implemented in these systems, such as power stabilization, pyrometry, on-axis laser-heating, mode scrambling, and peak scaling. Finally, the Clausius-Clapeyron slope of ceria (CeO2) under high pressure and temperature is mapped using in situ Raman spectroscopy to determine both phase and temperature information

Post-aragonite phases of CaCO3_{3} at lower mantle pressures

The stability, structure and properties of carbonate minerals at lower mantle conditions has significant impact on our understanding of the global carbon cycle and the composition of the interior of the Earth. In recent years, there has been significant interest in the behavior of carbonates at lower mantle conditions, specifically in their carbon hybridization, which has relevance for the storage of carbon within the deep mantle. Using high-pressure synchrotron X-ray diffraction in a diamond anvil cell coupled with direct laser heating of CaCO$_{3}$ using a CO$_{2}$ laser, we identify a crystalline phase of the material above 40 GPa $-$ corresponding to a lower mantle depth of around 1,000 km $-$ which has first been predicted by \textit{ab initio} structure predictions. The observed $sp^{2}$ carbon hybridized species at 40 GPa is monoclinic with $P2_{1}/c$ symmetry and is stable up to 50 GPa, above which it transforms into a structure which cannot be indexed by existing known phases. A combination of \textit{ab initio} random structure search (AIRSS) and quasi-harmonic approximation (QHA) calculations are used to re-explore the relative phase stabilities of the rich phase diagram of CaCO$_{3}$. Nudged elastic band (NEB) calculations are used to investigate the reaction mechanisms between relevant crystal phases of CaCO$_{3}$ and we postulate that the mineral is capable of undergoing $sp^{2}$-$sp^{3}$ hybridization change purely in the $P2_{1}/c$ structure $-$ forgoing the accepted post-aragonite $Pmmn$ structure.Comment: 12 pages, 8 figure

Thermal Behavior of Mixtures of Perlite and Phase Change Materials in a Simulated Climate

Carefully controlled and well documented experiments have been done for two candidate configurations to control the heat load on a conditioned space. The 2:1 PCM/perlite mixture and the 6:1 PCM/perlite mixture, both on a weight basis, accomplished thermal control. The 2:1 system seemed to have enough PCM to be effective and involve a much larger fraction of its PCM in diurnal freezing and melting than the 6:1 system. It is a good starting point for engineering design of an optimum thermal control system. The results from the 2:1 system were reproduced with the computer program HEATING to prove that we know the relevant mechanisms and thermophysical properties of the PCM used in the system. Even without a model for the supersaturation and hysteresis that this material exhibited, HEATING reproduced the heat fluxes to the conditioned space in the experiments accurately enough to mirror the good thermal control performance of the system. The modified sensible heat capacity that was used in HEATING is a handy way to account for phase change effects and could be used in a subroutine to compute hourly phase change effects for whole building models like DOE-2. The experiments were done with PCM/perlite mixtures sealed in small methylmethacrylate boxes and covered top and bottom by XPS. The boxes allowed precise placement of the instrumentation used to follow the phase change effects. The XPS gave high R-value per unit thickness. A more practical prototype configuration such as PCM/perlite hermetically sealed in plastic pouches between layers of batts or blown-in insulation should be tested over a larger cross section. A good candidate is the whole attic cavity of the manufactured home test section used in the present work. Use of a PCM that does not exhibit supersaturation and hysteresis would make interpretation of the results easier. If the results of the larger scale test areas are as encouraging as the test cell results, a whole house model with a phase change algorithm should be constructed to optimize the configuration for the climate in which it will perform

Thermal behavior of mixtures of perlite and phase change material in a simulated climate

A new concept for use of phase change material (PCM) in building envelopes has been investigated. The concept is called a RCR system in analogy to an electrical circuit with a capacitor between two resistors. Here, the thermal capacitance of the PCM is sandwiched between the thermal resistance of conventional insulation. The PCM used was hydrated calcium chloride dispersed in perlite and contained in watertight test cells. One cell had a PCM/perlite ratio of 2:1 by weight; the other had a 6:1 mixture. Extruded polystyrene (XPS) was the insulation below and above the PCM. Heat-flux transducers on the top and bottom of each cell as well as thermocouples from the top to the bottom of each cell allowed them to follow closely the progression of freezing and melting in the PCM as the authors subjected the cells to both steady and diurnally varying simulated outside temperatures. Computer modeling with a transient heat conduction program was successful in proving that they understood the relevant energy transfer mechanisms and thermophysical properties. For the diurnal cycles, with twice the amount of XPS below as above the PCM, much of the energy stored during daytime by melting PCM flowed to the outside at night when it froze again. Comparisons were made to the behavior of conventional insulation. With PCM, the total daily energy flow into the conditioned space below the test cells was lower and the peak flow rate was delayed in time and decreased in magnitude

Radiation control coatings on rough-surfaced roofs at a federal facility: Two summers of monitoring plus roof and whole building modeling

Support of the federal New Technology Demonstration Program (NTDP) allowed the authors to learn the effect of radiation control coatings on roofs at a federal facility in the Panhandle of Florida. Two rough-surfaced, moderately well-insulated, low solar reflectance built-up roofs (BURs) were spray coated with a white, latex-based product with ceramic beads. Samples of the coated roofs were brought periodically to the laboratory to measure the solar reflectance as the coatings weathered. The authors monitored the power demand of the all-electric buildings that the roofs covered and temperatures and heat fluxes for two instrumented areas on each roof. Average decreases in the sunlit temperatures of the coated vs. the uncoated surfaces show weathering effects. They also show that the shading enhanced the effect of the coating on the significantly shaded roof because the coated instrumented area on it was preferentially shaded near noon of sunny days. Whole building models were constructed for DOE 2.1E and model predictions were compared to measurements of total electrical power for each all-electric building. The building with the significantly shaded roof had very high internal loads. The effect of the shading on annual energy use for cooling was twice that of the coating but the coating decreased annual cooling energy needs only by 0.5%. The building with the heavyweight concrete-decked roof had small internal loads. For it, the DOE 2.1E model predicted a 7.4% decrease in annual cooling energy use due to the coating and a comparatively small effect of the less extensive shading

The effect of air infiltration on the thermal performance of a small metal-framed assembly

Innovative construction materials and systems have generated a need for laboratory scale tests to quantify the effect of air leakage on thermal and moisture performance of building assemblies. Some construction materials and systems are inherently more air tight than others. It is desirable to do laboratory scale measurements on alternative systems so as to rank them with respect to air tightness just as they can be ranked with respect to system R-value. Participants in summer 1995 and 1996 workshops for elementary and secondary school science teachers in the Buildings Technology Center (BTC) at the Oak Ridge National Laboratory sought a way to illustrate basic principles of building science in the classroom. They decided to build a small metal-framed assembly with internal volume of 44 ft{sup 3} (1.25 m{sup 3}) and removable wall sheathing. The assembly included a door and window. Although the door and window were made from 4-in. (10.2-cm) thick foam insulation, the requisite framing for them detracted from the thermal performance of the walls and occupied a disproportionately large fraction of the wall area. The floor and roof of the assembly were also well-insulated so that the walls dominated the conduction heat loss through the assembly. The plan was to test thermal performance of the assembly with the sheathing and without it. Thereby the teachers hoped to show the effects of thermal bridges with metal framing as well as practical yet insightful way to reduce their effects

Limited Susceptibility of Chickens, Turkeys, and Mice to Pandemic (H1N1) 2009 Virus

To determine susceptibility of chickens, turkeys, and mice to pandemic (H1N1) 2009 virus, we conducted contact exposure and inoculation experiments. We demonstrated that chickens were refractory to infection. However, oculo-oronasally inoculated turkeys and intranasally inoculated mice seroconverted without clinical signs of infection

Gaussian Quantum Information

The science of quantum information has arisen over the last two decades centered on the manipulation of individual quanta of information, known as quantum bits or qubits. Quantum computers, quantum cryptography and quantum teleportation are among the most celebrated ideas that have emerged from this new field. It was realized later on that using continuous-variable quantum information carriers, instead of qubits, constitutes an extremely powerful alternative approach to quantum information processing. This review focuses on continuous-variable quantum information processes that rely on any combination of Gaussian states, Gaussian operations, and Gaussian measurements. Interestingly, such a restriction to the Gaussian realm comes with various benefits, since on the theoretical side, simple analytical tools are available and, on the experimental side, optical components effecting Gaussian processes are readily available in the laboratory. Yet, Gaussian quantum information processing opens the way to a wide variety of tasks and applications, including quantum communication, quantum cryptography, quantum computation, quantum teleportation, and quantum state and channel discrimination. This review reports on the state of the art in this field, ranging from the basic theoretical tools and landmark experimental realizations to the most recent successful developments.Comment: 51 pages, 7 figures, submitted to Reviews of Modern Physic

Sequence–structure relationships in RNA loops: establishing the basis for loop homology modeling

The specific function of RNA molecules frequently resides in their seemingly unstructured loop regions. We performed a systematic analysis of RNA loops extracted from experimentally determined three-dimensional structures of RNA molecules. A comprehensive loop-structure data set was created and organized into distinct clusters based on structural and sequence similarity. We detected clear evidence of the hallmark of homology present in the sequence–structure relationships in loops. Loops differing by <25% in sequence identity fold into very similar structures. Thus, our results support the application of homology modeling for RNA loop model building. We established a threshold that may guide the sequence divergence-based selection of template structures for RNA loop homology modeling. Of all possible sequences that are, under the assumption of isosteric relationships, theoretically compatible with actual sequences observed in RNA structures, only a small fraction is contained in the Rfam database of RNA sequences and classes implying that the actual RNA loop space may consist of a limited number of unique loop structures and conserved sequences. The loop-structure data sets are made available via an online database, RLooM. RLooM also offers functionalities for the modeling of RNA loop structures in support of RNA engineering and design efforts

Adoptive immunotherapy against allogeneic kidney grafts in dogs with stable hematopoietic trichimerism.

Dogs given nonmyeloablative conditioning and marrow grafts from 2 dog leukocyte antigen (DLA)-identical littermate donors developed stable trichimerism and stably accepted a subsequent kidney graft from one of the marrow donors without the need for immunosuppression. In this study, we used trichimeras to evaluate strategies for adoptive immunotherapy to solid tumors, using the kidney as a tumor surrogate. Three DLA-identical trichimeric recipients were established by simultaneously infusing marrow from 2 DLA-identical donor dogs into a DLA-identical recipient conditioned with 2 Gy of total body irradiation (TBI) and given a short course of postgraft immunosuppression. After stable hematopoietic engraftment was confirmed, a kidney was transplanted from 1 of the 2 marrow donors into each respective trichimeric recipient. Peripheral blood lymphocytes from each kidney donor were then used to sensitize the alternate marrow donor. The trichimeric recipients were given donor lymphocyte infusions (DLIs) from the sensitized dogs and monitored for chimerism, graft-versus-host disease (GVHD), and kidney rejection. After DLI, we observed both prompt rejection of the transplanted marrow and donor kidney and disappearance of corresponding hematopoietic chimerism. Presumably due to shared minor histocompatibility antigens, host chimerism also disappeared, and GVHD in skin, gut, and liver developed. The native kidneys, although exhibiting lymphocytic infiltration, remained functionally normal. This study demonstrates that under certain experimental conditions, the kidney--an organ ordinarily not involved in graft-versus-host reactions--can be targeted by sensitized donor lymphocytes