Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu II [C 5 H 3 (SiMe 3 ) 2 ] 3 } -
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Auger electron spectroscopy (AES) was used to characterize the oxide scale formed on an ~0.5 wt. % Ga plutonium metal alloy. Analysis of changes to the characteristic Auger transitions for Pu and O during sputter depth profiles were used in combination with previously measured sputter yields to determine the thickness of the oxide scale and provide insight into its chemistry. From this data, the parabolic kinetics for the Pu-Ga alloy were determined as a function of relative humidity, RH = 14–92%, and oxygen partial pressure, p(O 2 ) = 31–157 Torr, at 25°C. For each relative humidity investigated, the parabolic rate constant was found to be independent of oxygen partial pressure. Furthermore, power-law fits to the relative humidity effect on the rate constant was found to have a power of n = 1.265, indicating the diffusion species which rate-limits the reaction isn’t molecular water, which subsequent dissociates at the oxide-metal interface, or hydroxyl from dissociation at the gas-surface interface.
Free energy curves were built for erbium and plutonium metal, their hydrides and their oxides, as well as water and hydrogen gas. The free energy curves were then used to determine the free energy for reaction between these phases. In particular, the reactions between erbium sesquioxide and hydrogen, plutonium metal, and plutonium hydride were studied. The findings indicated that erbium sesquioxide is inert to reaction with hydrogen gas (for all realistic ranges of water partial pressure) and plutonium metal, but that the erbium sesquioxide is predicted to be reactive with plutonium hydride. Note that this latter point indicates a thermodynamic tendency, with no particular reference to the kinetics of the actual process.
Between 1944 and 1989, 54.5 metric tons of the United States’ weapons-grade plutonium and an additional 12.9 metric tons of fuel-grade plutonium were produced and separated from irradiated fuel at the Hanford Site. Acidic high-activity wastes containing around 600 kg of plutonium were made alkaline and discharged to underground storage tanks from separations, isolation, and recycle processes to yield average plutonium concentration of about 0.003 grams per liter (or ~0.0002 wt%) in the ~200 million liter tank waste volume. The plutonium is largely associated with low-solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g., iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO2∙xH2O, could undergo sufficient crystal growth through dissolution and reprecipitation in the alkaline tank waste to potentially become separable from neutron absorbing constituents by settling or sedimentation. Thermodynamic considerations and laboratory studies of systems chemically analogous to tank waste show that the plutonium formed in the alkaline tank waste by precipitation through neutralization from acid solution probably entered as 2–4-nm PuO2∙xH2O crystallite particles that, because of their low solubility and opposition from radiolytic processes, grow from that point at exceedingly slow rates, thus posing no risk of physical segregation.
The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.
High temperature engineering test reactor (HTTR) is one of high temperature gas cooled reactor (HTGR) types which has been developed by Japanese Atomic Energy Research Institute (JAERI). The HTTR is a graphite moderator, helium gas coolant, 30 MW thermal output and 950 °C outlet coolant temperature for high temperature test operation. Original HTTR uses UO{sub 2} fuel. In this study, we have evaluated the use of UO{sub 2} and PuO{sub 2} in form of mixed oxide (MOX) fuel in HTTR. The reactor cell calculation was performed by using SRAC 2002 code, with nuclear data library was derived from JENDL3.2. The result shows that HTTR can obtain its criticality condition if the enrichment of {sup 235}U in loaded fuel is 18.0% or above.
The measurement of uranium and plutonium holdup in plants during process activity and for decommissioning is important for nuclear safeguards and material control. The amount of plutonium and uranium holdup in glove-boxes, pipes, ducts, and other containers has been measured for several decades using both neutron and gamma-ray techniques. For the larger containers such as hot cells and glove-boxes that contain processing equipment, the gamma-ray techniques are limited by self-shielding in the sample as well as gamma absorption in the equipment and associated shielding. The neutron emission is more penetrating and has been used extensively to measure the holdup for the large facilities such as the MOX processing and fabrication facilities in Japan and Europe. In some case the totals neutron emission rates are used to determine the holdup mass and in other cases the coincidence rates are used such as at the PFPF MOX fabrication plant in Japan. The neutron emission from plutonium and MOX has 3 primary source terms: 1) Spontaneous fission (SF) from the plutonium isotopes, 2) The (α,n) reactions from the plutonium alpha particle emission reacting with the oxygen and other impurities, and 3) Neutron multiplication (M) in the plutonium and uranium as a result of neutrons created by the first two sources. The spontaneous fission yield per gram is independent of thickness, whereas, the above sources 2) and 3) are very dependent on the thickness of the deposit. As the effective thickness of the deposit becomes thin relative to the alpha particle range, the (α,n) reactions and neutrons from multiplication (M) approach zero. In any glove-box, there will always be two primary modes of holdup accumulation, namely direct powder contact and non-contact by air dispersal. These regimes correspond to surfaces in the glove-box that have come into direct contact with the process MOX powder versus surface areas that have not had direct contact with the powder. The air dispersal of PuO{sub 2} particles has been studied for several decades by health physicists, because the primary health hazard of plutonium is breathing the airborne particles. The air dispersal mechanism results from the smaller particles in the top layer of powder that are lifted into the air by the electrostatic charge buildup from the alpha decay process, and the air convection carries the particles to new more distant locations. If there is open plutonium powder in a glove-box, the surfaces at more distant locations will become contaminated over time. The range of an alpha particle in a solid or powder is a function of the particle energy, the material density, and the atomic number A of the material. The average energy of a plutonium alpha particle is ∼5.2 MeV and the range in air is ∼37 mm. The range in other materials can be estimated via the Bragg-Kleenman equation. For plutonium, A is 94, and the typical density for a single particle is ∼11.5 g/cm{sup 3}, but for a powder, the density would be less because of the air packing fraction. The significance of the small diameter is that the range of the alpha particle is ∼50 μm for powder density 2.5 and significantly less for a single particle with density 11.5, so the thin deposit of separate small particles will have a greatly reduced (α,n) yield. The average alpha transit length to the surface in the isolated MOX particle would be < 2.5 μm; whereas, the range of the alpha particle is much longer. Thus, most of the alpha particles would escape from the MOX particle and be absorbed by the walls and air. The air dispersal particles will have access to a large surface area that includes the walls, whereas, the powder contact surface area will be orders of magnitude smaller. Thus, the vast majority of the glove-box surface area does not produce the full (α,n) reaction neutron yield, even from the O{sub 2} in the PuO{sub 2} as well as any impurity contamination such as H{sub 2}O. To obtain a more quantitative estimate of the neutron (α,n) yields as a function of holdup deposit thickness, we have used MCNPX calculations to estimate the absorption of alpha particles in PuO{sub 2} holdup deposits. The powder thickness was varied from 0.1 μm to 5000 μm and the alpha particle escape probability was calculated. As would be expected, as the thickness approaches zero, the escape probability approaches 1.0, and as the thickness gets much greater than the alpha particle range (∼50 μm), the escape probability becomes small. Typically, the neutron holdup calibration measurement are performed using sealed containers of thick MOX that has all 3 sources of neutrons [SF, (α,n), and M], and no significant impurities. Thus, the calibration counting rates need to include corrections for M and (α,n) yields that are different for the holdup compared with the calibration samples. If totals neutron counting is used for the holdup measurements, the variability of the (α,n) term needs to be considered.
In the framework of the WPNCS Expert Group on Uncertainty Analysis for Criticality Safety Assessment, we propose a blind numerical benchmark. Since the WPNCS Expert Group on Experimental Needs had highlighted the poor database of representative experiments of low-moderated MOX powders, this blind benchmark is focused on MOX wet powders Three PuO{sub 2} contents are proposed: 100%, 30% and 12.5%. Two Pu isotopic vectors are considered: a conservative one (0%, 71%, 17%, 11%, 1% for {sup 238}Pu up to {sup 242}Pu) and a realistic one obtained from reprocessed LWR 30 GWd/T fuels. For these 6 cases the powder moisture rate is 3%. The MOX fissile medium is a sphere surrounded by 20 cm water reflector. The required results are the calculated k{sub eff} and the associated prior uncertainty. Using benchmarks experiments, contributors should provide the projected-k{sub eff} and the corresponding posterior uncertainty. CRISTAL-V2 results based on JEFF3.1.1 nuclear data are presented. As an example, in the 30% PuO{sub 2} challenging case, the calculation uncertainty is decreased from 1160 pcm (1 σ) down to 450 pcm using EOLE and MASURCA critical Pu experiments. This uncertainty depends slightly on 'conservative' or 'realistic' Pu because the representativity factor does not vary significantly with the Pu vector. (authors)
The ARIES Program at the Los Alamos National Laboratory removes plutonium metal from decommissioned nuclear weapons, and converts it to plutonium dioxide in a specially-designed Direct Metal Oxidation furnace. The plutonium dioxide is analyzed for specific surface area, particle size distribution, and moisture content. The purpose of these analyses is to certify that the plutonium dioxide powder meets or exceeds the specifications of the end-user, and the specifications for the packaging and transport of nuclear materials. Analytical results from plutonium dioxide from ARIES development activities, from ARIES production activities, from muffle furnace oxidation of metal, and from metal that was oxidized over a lengthy time interval in air at room temperature, are presented. The processes studied produce plutonium dioxide powder with distinct differences in measured properties, indicating the significant influence of oxidation conditions on physical properties.
A dual-particle imager with sensitivity to both neutrons and photons has been developed for the detection of special nuclear material. This system has the capability to provide spectral information on detected sources that is useful for safeguard applications. In nuclear facilities with high photon background rates, neutron detection can aid in identification and verification capabilities. The dual-particle imager creates a reconstructed neutron spectrum by correlating neutron counts in pairs of liquid scintillators. The reconstructed spectrum, a combination of energy deposited and time-of-flight, contains resolution effects that blur the true, emitted source-spectrum. To reduce the impact of resolution effects, the reconstructed spectrum can be unfolded to create an estimated source spectrum. A statistical technique, maximum-likelihood expectation-maximization, has been shown to produce an unfolded result for Cf-252 and Am-Be. This technique requires a system response-matrix that contains reconstructed spectra for single neutron energies. Since measuring mono-energetic neutrons is difficult, the system-response-matrix is simulated. Monte Carlo modeling with MCNPX-PoliMi has been show to produce an accurate system response. This work expands on previous neutron unfolding results by showing results for mixed-oxide fuel and plutonium metal measured with the dual-particle imager. Furthermore these results also demonstrate the ability of the dual-particle imager to discrimination between spontaneous fission neutrons and (α,n) reaction neutrons.
The oxidation of an ~1.5 at% Ga plutonium metal alloy in dry air as a function of time was studied using a combination of FIB-SEM, AES, and XRD. Analysis of SEM images of FIB cross-sections of the oxide allowed for direct measurement of the oxide thickness as well as determination of heterogeneity in the extent of the oxide. AES analysis performed on cross-sections of the oxide allowed for quantitative analysis of the atomic composition and semi-quantitative analysis of the chemical composition. Initial preparation of the sample was found to induce a martensitic transformation to α' - Pu with an average thickness of 233 nm. Electropolishing was found to be sufficient to fully remove the α' layer with creation of only a minimum oxide layer. Growth of the oxide in dry air was found to initially follow parabolic kinetics, with a parabolic rate constant orders of magnitude higher than expected for δ-Pu but in-line with values extrapolated to room temperature for α-Pu. Following complete oxidation of the initial α` layer, further regions of plutonium metal depleted in gallium were observed to form at the oxide / metal interface. However, gallium, as Ga 2 O 3 , was found to be enriched at the surface and present in the oxide in an amount comparable to the relative Ga:Pu ratio of the bulk metal alloy. Finally, the results presented here serve to bridge a diverse array of previous experimental and theoretical data and provide the first comprehensive view of the fate of the δ-stabilizer during formation of an oxide.
The Plutonium Science and Manufacturing Directorate provides world-class, safe, secure, and reliable special nuclear material research, process development, technology demonstration, and manufacturing capabilities that support the nation's defense, energy, and environmental needs. We safely and efficiently process plutonium, uranium, and other actinide materials to meet national program requirements, while expanding the scientific and engineering basis of nuclear weapons-based manufacturing, and while producing the next generation of nuclear engineers and scientists. Actinide Process Chemistry (NCO-2) safely and efficiently processes plutonium and other actinide compounds to meet the nation's nuclear defense program needs. All of our processing activities are done in a world class and highly regulated nuclear facility. NCO-2's plutonium processing activities consist of direct oxide reduction, metal chlorination, americium extraction, and electrorefining. In addition, NCO-2 uses hydrochloric and nitric acid dissolutions for both plutonium processing and reduction of hazardous components in the waste streams. Finally, NCO-2 is a key team member in the processing of plutonium oxide from disassembled pits and the subsequent stabilization of plutonium oxide for safe and stable long-term storage.
Process modeling; injection molding; long-fiber thermoplastic; fiber orientation; fiber lengt This report provides a summary of the effects of aging on and the expected forms of plutonium in Tank 18 waste residues. The findings are based on available information on the operational history of Tank 18, reported analytical results for samples taken from Tank 18, and the available scientific literature for plutonium under alkaline conditions. These findings should apply in general to residues in other waste tanks. However, the operational history of other waste tanks should be evaluated for specific conditions and unique operations (e.g., acid cleaning with oxalic acid) that could alter the form of plutonium in heel residues. Based on the operational history of other tanks, characterization of samples from the heel residues in those tanks would be appropriate to confirm the form of plutonium. During the operational period and continuing with the residual heel removal periods, Pu(IV) is the dominant oxidation state of the plutonium. Small fractions of Pu(V) and Pu(VI) could be present as the result of the presence of water and the result of reactions with oxygen in air and products from the radiolysis of water. However, the presence of Pu(V) would be transitory as it is not stable at the dilute alkaline conditions that currently exists in Tank 18. Most of the plutonium that enters Savannah River Site (SRS) high-level waste (HLW) tanks is freshly precipitated as amorphous plutonium hydroxide, Pu(OH) 4(am) or hydrous plutonium oxide, PuO 2(am,hyd) and coprecipitated within a mixture of hydrous metal oxide phases containing metals such as iron, aluminum, manganese and uranium. The coprecipitated plutonium would include Pu 4+ that has been substituted for other metal ions in crystal lattice sites, Pu 4+ occluded within hydrous metal oxide particles and Pu 4+ adsorbed onto the surface of hydrous metal oxide particles. The adsorbed plutonium could include both inner sphere coordination and outer sphere coordination of the plutonium. PuO 2(am,hyd) is also likely to be present in deposits and scales that have formed on the steel surfaces of the tank. Over the operational period and after closure of Tank 18, Ostwald ripening has and will continue to transform PuO 2(am,hyd) to a more crystalline form of plutonium dioxide, PuO 2(c) . After bulk waste removal and heel retrieval operations, the free hydroxide concentration decreased and the carbonate concentration in the free liquid and solids increased. Consequently, a portion of the PuO 2(am,hyd) has likely been converted to a hydroxy-carbonate complex such as Pu(OH) 2 (CO 3 ) (s) . or PuO(CO 3 ) · xH 2 O (am) . Like PuO 2(am,hyd) , Ostwald ripening of Pu(OH) 2 (CO 3 ) (s) or PuO(CO 3 ) · xH 2 O (am) would be expected to occur to produce a more crystalline form of the plutonium carbonate complex. Due to the high alkalinity and low carbonate concentration in the grout formulation, it is expected that upon interaction with the grout, the plutonium carbonate complexes will transform back into plutonium hydroxide. Although crystalline plutonium dioxide is the more stable thermodynamic state of Pu(IV), the low temperature and high water content of the waste during the operating and heel removal periods in Tank 18 have limited the transformation of the plutonium into crystalline plutonium dioxide. During the tank closure period of thousands of years, transformation of the plutonium into a more crystalline plutonium dioxide form would be expected. However, the continuing presence of water, reaction with water radiolysis products, and low temperatures will limit the transformation, and will likely maintain an amorphous Pu(OH) 4 or PuO 2(am,hyd) form on the surface of any crystalline plutonium dioxide produced after tank closure. X-ray Absorption Spectroscopic (XAS) measurements of Tank 18 residues are recommended to confirm coordination environments of the plutonium. If the presence of PuO(CO 3 ) (am,hyd) is confirmed by XAS, it is recommended that experiments be conducted to determine if plutonium carbonates are transformed back into PuO 2(am,hyd) upon contact with grout.
The investigation of physical properties of uranium and plutonium mixed oxide (MOX) fuels is important for the development of fast reactor fuels. It is well known that MOX is a nonstoichiometric oxide, and the physical properties change drastically with the Oxygen-to-Metal (O/M) ratio. A control technique for O/M ratio was established for measurements of high temperature properties of uranium and plutonium mixed oxide fuels. Sintering behavior, thermal expansion and O/M change of (U{sub 0.7}Pu{sub 0.3})O{sub 2.00} and (U{sub 0.7}Pu{sub 0.3})O{sub 1.99} were investigated in PO{sub 2}-controlled atmosphere which was controlled by H{sub 2}/H{sub 2}O gas system. Sintering behavior changed drastically with O/M ratio, and shrinkage of (U{sub 0.7}Pu{sub 0.3})O{sub 2.00} was faster and more advanced at lower temperatures as compared with (U{sub 0.7}Pu{sub 0.3})O{sub 1.99}. Thermal expansion was observed to be slightly increased with decreasing O/M ratio. (authors)
The safe and secure management of Pu is a matter of serious international concern, with ∼250 t of separated Pu currently stockpiled worldwide. Nearly 50% of this material is in long-term storage in the UK whilst the British government develops its options for final treatment and disposition. Options for this are: (i) reuse as a fuel in modern reactors (e.g. as MOX fuel or within a fast reactor) prior to disposal; (ii) prompt immobilisation for disposal as soon as is practicable; or, (iii) continued long term storage (prior to disposition). The focus of the work presented here is options (ii) and (iii). The R and D needs of both are now pressing: in option (iii) due to it being the current default; in option (ii) because of a comparative lack of R and D on Pu conditioning and packaging due to policy uncertainty as to whether it would be disposed of in a Geologic Disposal Facility (GDF). Addressing these needs is complicated by Pu's high radioactivity, decay heat and radiotoxicity, nuclear safeguard requirements and, for some UK Pu contaminated materials targeted for disposal, poor inventory. Thus, there is also a critical requirement for underpinning research on characterisation methods for Pu bearing materials. In response to these needs, the DISTINCTIVE Consortium (Decommissioning, Immobilisation and Storage Solutions for Nuclear Waste Inventories, a multi-disciplinary collaboration of 11 universities and 3 key industry partners from across the UK's civil nuclear sector) has been seeking to: - Understand how the structure and properties of PuO{sub 2} change with time in the presence of H{sub 2}O. - Understand the roles these processes play in gaseous product evolution from PuO{sub 2} in storage. - Understand radiation-induced amorphization and dissolution kinetics of Pu waste forms. - Develop novel, fast neutron based radiometric methods for the quantification, isotopic composition assessment and remote imaging of Pu-bearing materials. This paper describes recent progress made towards achieving these objectives. (authors)
In Japan, uranium and plutonium mixed oxide (MOX) fuels has been developed for sodium-cooled fast reactors. The developing MOX fuels come in variety of O/M ratio, Pu content, minor actinide (MA) content and density. We have studied a science based fuel technology to evaluate fuel behaviors in fabrication process and irradiation condition of such various fuels. The technologies which are constructed based on experimental database can apply to mechanistic evaluation of fuel behaviors. To develop the science based fuel technology, many different varieties of basic properties have been investigated, and experimental database was constructed. And a mechanistic physical property model has been studied. The models contribute to describe various behaviors in fuel fabrication process and irradiation condition. In Japan, the researches on MOX fuel technologies have been carried out for sodium cooled fast reactor development. It is important to develop the fuel technologies on fuel fabrication process and irradiation performance model evaluation. The researches will be carried out by experimental approach and expanded in international collaboration frame works such as the CNWG and The Generation IV International Forum (GIF). (author)
The Separations Process Research Unit (SPRU) is located within the boundary of Knolls Atomic Power Laboratory (KAPL) at 2425 River Road, Niskayuna, Schenectady County, New York (Figure A-1). SPRU was designed and developed to research an efficient process to chemically separate plutonium and uranium from processed fuel. Buildings H2 and G2 were the primary research and process facilities. SPRU operated between February 1950 and October 1953 at which time the research was successful in developing useable reduction oxidation and plutonium uranium extraction processes. These processes were subsequently moved to the Hanford and the Savannah River sites for full-scale operations. Building H2 was used by KAPL after the SPRU process ceased until the late 1990s for radioactive wastewater processing and Building G2 was utilized for offices. Process areas and equipment were maintained in a safe condition under a surveillance and maintenance program.
Energy dependent electron emission between zero and 1.4 keV generated by the natural reactivity of plutonium was measured by an electrostatic spectrometer with known acceptance angle and acceptance area. The electron spectral intensity decreases continuously except for a distinctive feature of unknown origin at approximately 180eV. The spectrum was converted to energy dependent electron flux (e/cm 2 } s) using the assumption that the emission has a cosine angular distribution. The energy dependent electron mean free path in gases and literature cross sections for electron induced reactions were used to determine the number of ionization and dissociation reactions per cm 2 second, found to be about 8*10 8 /cm 2 s and 1.5*10 8 /cm 2 s, respectively, for hydrogen. These results are to be used with caution until complementary measurements can be made, e.g. independent measurement of the total emitted electron current, since the results here are based on the assumption that the electron emission has a cosine angular distribution. That is unlikely to be correct.