authors: bishop, jessica , unger, ryan , john d. auxier ii ...-jessica-jl_inmmconfe.pdf · authors:...

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Figure 1: A ring of 99.96% pure electro-refined plutonium (LANL). Isotope Ratio Mass Spectrometry Electropolishing Heating O 0 → Water vapor and atmospheric oxygen are the most likely sources of oxygen in the oxide layer Figure 4: Total oxygen content vs. temperature for three runs. Figure 5: Oxygen fractionation vs. temperature for three runs. Figure 6: Total oxygen content and oxygen fractionation split vs. time. Equation 1: Isotopic fractionation of oxygen utilizing ratio of heavy to light isotopes in the sample as compared to International Atomic Energy Agency (IAEA) standards. Figure 7: All possible sources of oxygen in the experiment. Rainwater was collected in Knoxville, TN and is representative of water vapor. Atmospheric oxygen is a global average (Kroopnick, P., & Craig, H., “Atmospheric oxygen: isotopic composition and solubility fractionation” Science, 175(4017), 54-55, (1972).) Figure 8: Fractionation factor (derived from Eq. 1) of sample sources as compared to literature values (Bernstein). O 2- O 2- Atmospheric Oxygen Water Vapor KOH solution Oxidation States: Figure 10: Log plot of CuO growth over temperature series. Figure 9: Raman spectra of copper oxide growth with increasing temperature; Figure on left is samples from Run 1 and figure on right is samples from Runs 2 and 3. Figure 2: Electropolishing experimental set up with 2 wt%KOH solution. Figure 3: Carbolite furnace environment for accelerated aging and oxidation. Authors: Bishop, Jessica 1 , Unger, Ryan 1 , John D. Auxier II 1,2,3 , Maik Lang 1,2 , Howard L. Hall 1,2,3 1 Department of Nuclear Engineering; 2 UT Radiochemistry Center of Excellence; 3 UT Institute for Nuclear Security at the University of Tennessee, Knoxville 1. Hecker, Siegfried S., Martz, Joseph C., “Aging of Plutonium and Its Alloys,” Los Alamos Science 26, 238-243, (2000). http://permalink.lanl.gov/object/tr?what=info:lanl-repo/lareport/LA-UR-00-2619 2. M. P. Brady, et al.”Tracer Film Growth Study of Hydrogen and Oxygen from the Corrosion of Magnesium in Water,” J. Electrochem. Soc. 161(9): C395-C404, (2014); doi:10.1149/2.0821409jes 3. N. Bertrand, et al. “Iron Oxidation at Low Temperature (260 – 500°C) in Air and the Effect of Water Vapor,” Oxid Met 73:139-162, (2010); doi:10.1007/211085-009-9171-0 4. Bao, Huiming, et al. “Oxygen isotope fractionation in ferric oxide-water systems: Low temperature synthesis” Geochimica et Cosmochimica Acta, Vol. 63, No. 5, pp. 599–613, (1999). 5. Shao-Kuan Lee, et al. “Oxidation Behavior of Copper at a Temperature below 300°C and the Methodology for Passivation” Materials Research 19(1): 51-56 (2016). 6. Bernstein, Richard B., “Oxygen-18 Isotope Effect in the Reaction of Oxygen with Copper” The Journal of Chemical Physics, 23, 10, (1955).

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Page 1: Authors: Bishop, Jessica , Unger, Ryan , John D. Auxier II ...-jessica-jl_inmmconfe.pdf · Authors: Bishop, Jessica1, Unger, Ryan1 , John D. Auxier II 1,2,3, Maik Lang1,2, Howard

Figure 1: A ring of 99.96% pure electro-refined plutonium (LANL).

Isotope Ratio Mass Spectrometry

Electropolishing Heating

O0

→ Water vapor and atmospheric oxygen are

the most likely sources of oxygen in the oxide layer

Figure 4: Total oxygen content vs. temperature for three runs.

Figure 5: Oxygen fractionation vs. temperature for three runs.

Figure 6: Total oxygen content and oxygen fractionation split vs. time.

Equation 1: Isotopic fractionation of oxygen utilizing ratio of heavy to light isotopes in the sample as compared to International Atomic Energy Agency (IAEA) standards.

Figure 7: All possible sources of oxygen in the experiment. Rainwater was collected in Knoxville, TN and is representative of water vapor. Atmospheric oxygen is a global average (Kroopnick, P., & Craig, H., “Atmospheric oxygen: isotopic composition and solubility fractionation” Science, 175(4017), 54-55, (1972).)

Figure 8: Fractionation factor (derived from Eq. 1) of sample sources as compared to literature values (Bernstein).

O2-

O2-

Atmospheric Oxygen

Water Vapor

KOH solution

Oxidation States:

Figure 10: Log plot of CuO growth over temperature series.

Figure 9: Raman spectra of copper oxide growth with increasing temperature; Figure on left is samples from Run 1 and figure on right is samples from Runs 2 and 3.

Figure 2: Electropolishing experimental set up with 2 wt%KOH solution.

Figure 3: Carbolite furnace environment for accelerated aging and oxidation.

Authors: Bishop, Jessica1 , Unger, Ryan1 , John D. Auxier II 1,2,3, Maik Lang1,2, Howard L. Hall 1,2,31Department of Nuclear Engineering; 2UT Radiochemistry Center of Excellence; 3UT Institute for Nuclear Security at the University of

Tennessee, Knoxville

1. Hecker, Siegfried S., Martz, Joseph C., “Aging of Plutonium and Its Alloys,” Los Alamos Science 26, 238-243, (2000). http://permalink.lanl.gov/object/tr?what=info:lanl-repo/lareport/LA-UR-00-2619

2. M. P. Brady, et al.”Tracer Film Growth Study of Hydrogen and Oxygen from the Corrosion of Magnesium in Water,” J. Electrochem. Soc. 161(9): C395-C404, (2014); doi:10.1149/2.0821409jes

3. N. Bertrand, et al. “Iron Oxidation at Low Temperature (260 – 500°C) in Air and the Effect of Water Vapor,” Oxid Met 73:139-162, (2010); doi:10.1007/211085-009-9171-04. Bao, Huiming, et al. “Oxygen isotope fractionation in ferric oxide-water systems: Low temperature synthesis” Geochimica et Cosmochimica Acta, Vol. 63, No. 5, pp. 599–613, (1999).5. Shao-Kuan Lee, et al. “Oxidation Behavior of Copper at a Temperature below 300°C and the Methodology for Passivation” Materials Research 19(1): 51-56 (2016).6. Bernstein, Richard B., “Oxygen-18 Isotope Effect in the Reaction of Oxygen with Copper” The Journal of Chemical Physics, 23, 10, (1955).