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At least 343 records · Page 19

Thermophysical Properties of Zirconium at High Temperature

Six thermophysical properties of both the solid and liquid zirconium measured using the high-temperature electrostatic levitator at JPL are presented. These properties are: density, thermal expansion coeffiecient, constant pressure heat capacity, hemispherical total emissivity, surface tension and viscosity.

thermophysical↗

Additive Manufacture of Porous Zirconium Carbide for Nuclear Thermal Propulsion In-Core Insulators

Nuclear Thermal Propulsion (NTP) requires the use of in-core insulators to manage to thermal environment between high temperature fuel elements and lower temperature structural components. The unforgiving in-core operating conditions severely limit potential material candidates. Zirconium Carbide (ZrC) is a promising candidate due to a high melting temperature, high compressive strength, hardness, wear resistance, hydrogen compatibility, and low neutron absorption cross sections. However, fully dense ZrC is not an insulator but it has been found that the thermal conductivity of ZrC decreases by increasing porosity to approximately 60 % theoretical density (%TD). Previous methods for generating porous ZrC were difficult, expensive, and time consuming. Binder jet additive manufacture (AM) can print ceramic materials to near net shape. Binder jet AM is not utilized in many applications due to an inherently low post-sintering density on the order of 60 %TD. For this specific application the inherent lower density is leveraged as an advantage in production porous ZrC in order to control the thermal conductivity. A feasibility study was conducted to investigate binder jet AM parameter development for ZrC, heat treatment optimization (burn-out and sinter), microstructural characterization, mechanical testing, and thermal testing to generate near-net shape ZrC components with ~60 %TD with the desired thermal conductivity and mechanical strength.

Zirconium Carbide Additive Manufacture↗

Additive Manufacture of Porous Zirconium Carbide for Nuclear Thermal Propulsion In-Core Insulators

Nuclear Thermal Propulsion (NTP) requires the use of in-core insulators to manage to thermal environment between high temperature fuel elements and lower temperature structural components. The unforgiving in-core operating conditions severely limit potential material candidates. Zirconium Carbide (ZrC) is a promising candidate due to a high melting temperature, high compressive strength, hardness, wear resistance, hydrogen compatibility, and low neutron absorption cross sections. However, fully dense ZrC is not an insulator but it has been found that the thermal conductivity of ZrC decreases by increasing porosity to approximately 60 % theoretical density (%TD). Previous methods for generating porous ZrC were difficult, expensive, and time consuming. Binder jet additive manufacture (AM) can print ceramic materials to near net shape. Binder jet AM is not utilized in many applications due to an inherently low post-sintering density on the order of 60 %TD. For this specific application the inherent lower density is leveraged as an advantage in production porous ZrC in order to control the thermal conductivity. A feasibility study was conducted to investigate binder jet AM parameter development for ZrC, heat treatment optimization (burn-out and sinter), microstructural characterization, mechanical testing, and thermal testing to generate near-net shape ZrC components with ~60 %TD with the desired thermal conductivity and mechanical strength.

Zirconium Carbide Additive Manufacture↗

Thermodynamic Properties of Uranium-Zirconium Carbide Solid Solutions with Oxygen

Uranium-zirconium carbide solid solutions are potential candidates for fuel in space nuclear reactors. To support development of advanced robust fuels for space applications, (U y Zr 1-y )C x O z solid solutions were synthesized via carbothermic reduction with uranium, carbon, and oxygen contents raging from y=0.05 – 0.3, x=0.95 – 0.98, and z = 0.02 – 0.07. These solid solutions were subsequently characterized by X-ray diffraction and elemental combustion analysis. High-temperature oxidative drop solution calorimetry in molten sodium molybdate solvent at 1073 K was employed to determine the formation, oxidation, and mixing enthalpies of (U y Zr 1-y )C x O z solid solutions, and thereby for evaluating their thermodynamic stability. The solid solutions are enthalpically less stable than the UC and ZrC end members. They also become less stable and more reactive towards oxidation with increasing uranium content. Incorporation of oxygen into solid solutions increases their solid solution-stability and improves their oxidation resistance.

Calorimetry↗

Pressure and Temperature effects on the High Pressure Phase Transformation in Zirconium

At high pressure zirconium is known to undergo a phase transformation from the hexagonal close packed (HCP) alpha phase ({alpha}) to the simple hexagonal omega phase ({omega}). Under conditions of shock loading, the high-pressure omega phase is retained upon release. However, the hysteresis in this transformation is not well represented by equilibrium phase diagrams. For this reason, the influence of peak shock pressure and temperature on the retention of omega phase in Zr is explored in this study. In situ VISAR measurements along with post-mortem metallographic and neutron diffraction characterization of soft recovered specimens have been utilized to quantify the volume fraction of retained omega phase, morphology of the shocked alpha and omega phases, and qualitatively understand the kinetics of this transformation. This understanding of the role of peak shock stress will be utilized to address physics to be encoded in our present macro-scale models.

36 MATERIALS SCIENCE↗

Comparison of zirconium redistribution in BISON EBR-II models using FIPD and IMIS databases with experimental Post Irradiation Examination

The BISON code framework is utilized to model and analyze zirconium redistribution within UPuZr metallic fuels. The simulation results are compared against past experimental metallography data to validate the BISON code models. Various BISON models are implemented and compared to properly reflect the Zr present in past data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of Cr-coated zirconium alloy cladding for enhanced accident tolerance

In the context of the development of Enhanced Accident Tolerant Fuels (EATF), AREVA NP, along with CEA and EDF, is developing, among others, a chromium (Cr) coating (5- 20 μm thick) on zirconium alloy cladding. The coating is deposited on the cladding surface by Physical Vapor Deposition (PVD) and forms a dense and adherent protective layer. It preserves the good mechanical behavior of the current cladding in normal operating conditions while significantly improving the oxidation behavior in accidental conditions. This behavior is being evaluated through out-of-pile corrosion and mechanical tests at the AREVA NP Technical and Research Centers. The corrosion behavior was evaluated through autoclave tests in both PWR water chemistry at 360 and in 415 Celsius degrees steam to increase the corrosion kinetics. In both cases very small weight gain was measured on the order of 1 mg/dm{sup 2} and remains stable throughout the length of the tests. The mechanical behavior of Cr-coated samples was evaluated through tensile tests on Cr-coated and uncoated M5 tube samples at both room temperature and 400 Celsius degrees. The curves demonstrate that the Cr-coated samples exhibit similar mechanical behavior as uncoated samples, and for all the tests performed, the mechanical properties (yield strength 0.2%, ultimate tensile strength, and total elongation) of the Cr-coated samples all fell within the range of values for uncoated samples. In order to obtain in-pile data as early as possible on this solution, an irradiation program (called IMAGO) in the Goesgen reactor will be performed in the years to come. This will be the first irradiation of EATF solutions in a commercial reactor.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A preliminary study on irradiation growth behavior modelling of N36 zirconium alloy tube

As a new kind of Zr-Sn-Nb series alloy, N36 has not been explored in irradiation growth behavior before. In this paper, four empirical correlations including power, logarithmic, exponential and hyperbolic tangent law were used to build irradiation growth model of N36 zirconium alloy preliminarily. Before that, lengths of the fuel rods with N36 claddings from pool-side measurement were analyzed to get irradiation growth strains, which were then used to fit the four empirical correlations mentioned above. Distribution of fast fluence along axial direction of tubes was considered in all irradiation growth models. The fitting results showed that the hyperbolic tangent law fit irradiation growth strains the best, while power law did the worst. In order to improve the precision of the hyperbolic tangent model, several improvements were done. Verification and validation of the improved hyperbolic tangent irradiation growth model suggested that the size of second phase may have an influence on irradiation growth behavior of N36 tubes. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synthesis and Characterisation of Caesium Phosphomolybdate and Zirconium Molybdate found in the Highly Active Storage Tanks at Sellafield - 18154

Caesium phosphomolybdate (Cs{sub 3}PMo{sub 12}O{sub 40}.xH{sub 2}O, CPM) and zirconium molybdate (ZrMo{sub 2}O{sub 7}(OH){sub 2}.xH{sub 2}O, ZM) are two known fission products that precipitate out within the Highly Active Storage Tanks (HASTs) at Sellafield, potentially causing 'hot-spots' and blocking pipes. Currently, there is not enough behavioural understanding of these compounds present in the Highly Active Liquor (HAL) for effective Post Operational Clean Out (POCO) strategic planning. As the HASTs do not have an in situ monitoring system the behaviour of the HAL cannot be directly observed. Therefore, as with this research, non-radioactive simulants can be utilised to aid behavioural understanding to assist with the planning of future waste management programs. CPM, along with two different morphologies of ZM were characterised and compared to the common oxide particle material titanium dioxide (TiO{sub 2}). The study provides a detailed physical characterisation of the simulants including: particle shape, particle size, water content and crystal structure, along with zeta particle potential, suspension settling and compressive yield stress. CPM was found to be spheroidal in nature with a particle size of 275 nm and an x value of 13 H{sub 2}O which crystallises as a cubic lattice with space group Pn-3m. ZM was found to have a range of morphologies from cuboidal to wheat-sheaf, varying in size from 10 μm to 20 μm, with an x value of between 3 and 4 H{sub 2}O, which crystallise as a body-centred tetragonal lattice with space group I4{sub 1cd}. TiO{sub 2} used as a comparison simulant was found to be spheroidal in shape with particle size of 725 nm. The isoelectric points (IEPs) of the two ZM samples (ZM-A and ZM-B) with different morphologies were found to be pH 2.5, while for TiO{sub 2} it was pH 3.2. For CPM it could not be confidently identified due to its instability within the acidic environment. The settling rates and compressive yield stress of all simulants were tested in both water and 2 M nitric acid, conditions that replicate the HASTs. TiO{sub 2}, ZM-A and ZM-B all found settled faster in acid than in water. For CPM, slightly faster settling in acid was measured. For all samples it was found that as the particle concentration increased the settling rate decreased, which is a result of hindered settling. For compressive yield stress, similar trends were observed for CPM with little variation in its behaviour in acid and water, suggesting that the particles are highly aggregated in both fluids. For ZM samples little change in equilibrium volume fraction was measured with an increase in pressure (both acid and water). However, overall the sediment bed was denser in water, a result of the rapid settling in acid not allowing the non-spherical particles to pack in an ordered manner. It has been highlighted that both CPM and ZM within the acidic conditions of the HASTs, result in unstable and aggregated compounds, which settle quickly to form large open networks. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Zirconium Alloy Corrosion and Hydrogen Pickup

During operation nuclear fuel rods are immersed in the primary water, causing waterside corrosion and consequent hydrogen ingress. The mechanisms of corrosion and hydrogen pickup and the role of alloy selection in minimizing both phenomena are considered, based on two principal characteristics: the pre-transition kinetics and the loss of oxide protectiveness at transition. In zirconium alloys very small changes in composition or microstructure can cause significant corrosion differences, so that corrosion performance is strongly alloy dependent. The alloys show different, but reproducible sub-parabolic pre-transition kinetics and transition thicknesses. A mechanism for oxide growth and breakup based on a detailed study of the oxide structure can explain these results. Using the recently developed Coupled Current Charge Compensation model of corrosion kinetics and hydrogen pickup, the sub-parabolic kinetics and the hydrogen fraction can be rationalized: hydrogen pickup increases when electron transport decreases, requiring hydrogen ingress to close the reaction. (authors)

36 MATERIALS SCIENCE↗

Engineering-Scale Development/Demonstration of Zirconium Recovery from Used Duel Cladding

Recognizing that the zirconium (Zr) in used nuclear fuel (UNF) cladding is the second largest mass in UNF assemblies, process development studies for the recovery and purification of Zr were initiated and have been in progress at Oak Ridge National Laboratory (ORNL) for the last several years as a major element of waste minimization for advanced nuclear fuel recycle. Together with uranium recovery and recycle, Zr recovery would divert >90% (wt.) of the UNF assemblies from emplacement in a geologic repository by converting the Zr to low-level waste or reuse/recycle.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrode and Microstructure Dependence of Oxygen Diffusion in Ferroelectric Hafnium Zirconium Oxide Thin Films

Hafnia-based ferroelectrics hold promise to reduce energy demand for computing by enabling compute-in-memory and as non-volatile memories. The ferroelectric phase in this material system is, in part, stabilized by oxygen vacancies. While oxygen vacancies may be a necessity for phase stability, they limit device endurance through diffusion and accumulation into conducting channels. Herein, it is shown that oxygen diffusion is spatially variable within individual grains of ferroelectric hafnium zirconium oxide (HZO). Using 18 O tracers and finite difference modeling, it is shown that grain boundaries and regions near electrode interfaces allow for relatively rapid oxygen diffusion, with values as much as 10 4 larger than the grain cores. Further, the selection of electrode material affects the diffusion coefficients across all microstructural regions. HZO films in contact with TiN electrodes result in more oxygen-deficient HZO films and higher oxygen diffusion coefficients. Tungsten electrodes result in fewer vacancies and lower diffusion coefficients. Diffusion activation energy differences between the HZO with the two electrodes is reconciled by differing populations of charged and uncharged oxygen vacancies. This insight into the local vacancy populations and diffusion pathways provides a platform for designing hafnia-based films, deposition processes, and integration strategies to reduce vacancy gradients and improve performance.

36 MATERIALS SCIENCE↗