Engineering topics

Rawn, Claudia J

Publications and source records attributed to Rawn, Claudia J.

7 records

DOE OSTI2014

Mayenite Synthesized Using the Citrate Sol-Gel Method

A citrate sol-gel method has been used to synthesize mayenite (Ca12Al14O33). X-ray powder diffraction data show that the samples synthesized using the citrate sol-gel method contained CaAl2O4 and CaCO3 along with mayenite when fired ex-situ in air at 800 C but were single phase when fired at 900 C and above. Using high temperature x-ray diffraction, data collected in-situ in air at temperatures of 600 C and below showed only amorphous content; however, data collected at higher temperatures indicated the first phase to crystallize is CaCO3. High temperature x-ray diffraction data collected in 4% H2/96% N2 does not show the presence of CaCO3, and Ca12Al14O33 starts to form around 850 C. In comparison, x-ray powder diffraction data collected ex-situ on samples synthesized using traditional solid-state synthesis shows that single phase was not reached until samples were fired at 1350 C. DTA/TGA data collected either in a nitrogen environment or air on samples synthesized using the citrate gel method suggest the complete decomposition of metastable phases and the formation of mayenite at 900 C, although the phase evolution is very different depending on the environment. Brunauer-Emmett-Teller (BET) measurements showed a slightly higher surface area of 7.4 0.1 m2/g in the citrate gel synthesized samples compared to solid-state synthesized sample with a surface area of 1.61 0.02 m2/g. SEM images show a larger particle size for samples synthesized using the solid-state method compared to those synthesized using the citrate gel method.

Ude, Sabina N↗

DOE OSTI2013

Scalable economic extracellular synthesis of CdS nanostructured particles by a non-pathogenic thermophile

We report microbially facilitated synthesis of cadmium sulfide (CdS) nanostructured particles (NP) using anaerobic, metal-reducing Thermoanaerobacter sp. The extracellular CdS crystallites were <10 nm in size with yields of ~3 g/L of growth medium/month with demonstrated reproducibility and scalability up to 24 L. During synthesis, Thermoanaerobacter cultures reduced thiosulfate and sulfite salts to H2S, which reacted with Cd2+ cations to produce thermodynamically favored NP in a single step at 65oC with catalytic nucleation on the cell surfaces. Photoluminescence (PL) analysis of dry CdS NP revealed an exciton-dominated PL peak at 440 nm, having a narrow full width at half maximum of 10 nm. A PL spectrum of CdS NP produced by dissimilatory sulfur reducing bacteria was dominated by features associated with radiative exciton relaxation at the surface. High reproducibility of CdS NP PL features important for scale-up conditions was confirmed from test tubes to 24L batches at a small fraction of the manufacturing cost associated with conventional inorganic NP production processes.

Moon, Ji Won↗

DOE OSTI2013

Kinetics of Methane Hydrate Decomposition Studied via in Situ Low Temperature X-ray Powder Diffraction

Gas hydrates are known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice termed self-preservation or anomalous preservation. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Two regions of slowed decomposition for methane hydrate, 180 200 K and 230 260 K, were observed, and the kinetics were studied by in situ low temperature x-ray powder diffraction. The kinetic constants for ice formation from methane hydrate were determined by the Avrami model within each region and activation energies, Ea, were determined by the Arrhenius plot. Ea determined from the data for 180 200 K was 42 kJ/mol and for 230 260 K was 22 kJ/mol. The higher Ea in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions.

anomalous preservation↗

DOE OSTI2012

Interpreting Temperature Strain Data from Meso-Scale Clathrate Experiments

Gas hydrates are important in global climate change, carbon sequestra- tion, and seafloor stability. Currently, formation and dissociation pathways are poorly defined. We present a new approach for processing large amounts of data from meso-scale experiments, such as the LUNA distributed sensing system (DSS) in the seafloor process simulator (SPS) at Oak Ridge National Laboratory. The DSS provides a proxy for temperature measurement with a high spatial resolution allowing the heat of reaction during gas hydrate formation/dissociation to aid in locating clathrates in the vessel. The DSS fibers are placed in the sediment following an Archimedean spiral design and then the position of each sensor is solved by iterating over the arc length formula with Newtons method. The data is then gridded with 1 a natural neighbor interpolation algorithm to allow contouring of the data. The solution of the sensor locations is verified with hot and cold stimulus in known locations. An experiment was preformed with a vertically split column of sand and silt. The DSS system clearly showed hydrate forming in the sand first, then slowly creeping into the silt. Similar systems and data processing techniques could be used for monitoring of hydrates in natural environments or in any situation where a hybrid temperature/strain index is useful. Further ad- vances in fiber technology allow the fiber to be applied in any configuration and the position of each sensor to be precisely determined making practical applications easier.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2012

Gas Production from Hydrate-Bearing Sediments - Emergent Phenomena -

Even a small fraction of fine particles can have a significant effect on gas production from hydrate-bearing sediments and sediment stability. Experiments were conducted to investigate the role of fine particles on gas production using a soil chamber that allows for the application of an effective stress to the sediment. This chamber was instrumented to monitor shear-wave velocity, temperature, pressure, and volume change during CO{sub 2} hydrate formation and gas production. The instrumented chamber was placed inside the Oak Ridge National Laboratory Seafloor Process Simulator (SPS), which was used to control the fluid pressure and temperature. Experiments were conducted with different sediment types and pressure-temperature histories. Fines migrated within the sediment in the direction of fluid flow. A vuggy structure formed in the sand; these small cavities or vuggs were precursors to the development of gas-driven fractures during depressurization under a constant effective stress boundary condition. We define the critical fines fraction as the clay-to-sand mass ratio when clays fill the pore space in the sand. Fines migration, clogging, vugs, and gas-driven fracture formation developed even when the fines content was significantly lower than the critical fines fraction. These results show the importance of fines in gas production from hydrate-bearing sediments, even when the fines content is relatively low.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Magnetic properties of bio-synthesized zinc ferrite nanoparticles

The magnetic properties of zinc ferrite (Zn-substituted magnetite, Zn{sub y}Fe{sub 1-y}Fe{sub 2}O{sub 4}) formed by a microbial process compared favorably with chemically synthesized materials. A metal reducing bacterium, Thermoanaerobacter, strain TOR-39 was incubated with Zn{sub x}Fe{sub 1-x}OOH (x=0.01, 0.1, and 0.15) precursors and produced nanoparticulate zinc ferrites. Composition and crystalline structure of the resulting zinc ferrites were verified using X-ray fluorescence, X-ray diffraction, transmission electron microscopy, and neutron diffraction. The average composition from triplicates gave a value for y of 0.02, 0.23, and 0.30 with the greatest standard deviation of 0.02. Average crystallite sizes were determined to be 67, 49, and 25 nm, respectively. While crystallite size decreased with more Zn substitution, the lattice parameter and the unit cell volume showed a gradual increase in agreement with previous literature values. The magnetic properties were characterized using a superconducting quantum interference device magnetometer and were compared with values for the saturation magnetization (M{sub s}) reported in the literature. The averaged M{sub s} values for the triplicates with the largest amount of zinc (y=0.30) gave values of 100.1, 96.5, and 69.7 emu/g at temperatures of 5, 80, and 300 K, respectively indicating increased magnetic properties of the bacterially synthesized zinc ferrites.

42 ENGINEERING↗

DOE OSTI2011

Fiber Optic Sensing Technology for Detecting Gas Hydrate Formation and Decomposition

A fiber optic-based distributed sensing system (DSS) has been integrated with a large volume (72 L) pressure vessel providing high spatial resolution, time resolved, 3-D measurement of hybrid temperature-strain (TS) values within experimental sediment gas hydrate systems. Areas of gas hydrate formation (exothermic) and decomposition (endothermic) can be characterized through this proxy by time series analysis of discrete data points collected along the length of optical fibers placed within a sediment system. Data is visualized as a 'movie' of TS values along the length of each fiber over time. Experiments conducted in the Seafloor Processing Simulator (SPS) at Oak Ridge National Laboratory show clear indications of hydrate formation and dissociation events at expected P-T conditions given the thermodynamics of the CH4-H2O system. The high spatial resolution achieved with fiber optic technology makes the DSS a useful tool for visualizing time resolved formation and dissociation of gas hydrates in large-scale sediment experiments.

fiber optics↗