Keywords

Alloy, diffusion, reaction, multi component diffusion, uranium alloy, nuclear fuel

Abstract

U-Mo metallic fuels with Al alloys as the matrix/cladding are being developed as low enriched uranium fuels under the Reduced Enrichment for Research and Test Reactor (RERTR) program. Significant interactions have been observed to occur between the U-Mo fuel and the Al alloy during fuel processing and irradiation. U-Zr metallic fuels with stainless steel claddings have been developed for the generation IV sodium fast reactor (SFR). The fuel cladding chemical interaction (FCCI) induced by the interdiffusion of components was also observed. These interactions induce deleterious effects on the fuel system, such as thinning of the cladding layer, formation of phases with undesirable properties, and thermal cracking due to thermal expansion mismatches and changes in molar volume. The interaction between the fuel and the cladding involves multi-component interdiffusion. To determine the ternary interdiffusion coefficients using a single diffusion couple, a new method based on regression via the matrix transformation approach is proposed in this study. This new method is clear in physical meaning and simple in mathematical calculation. The reliability and accuracy of this method have been evaluated through application to three case studies: a basic asymptotic concentration profile, a concentration profile with extrema and a smoothed concentration profile with noise. Generally, this new method works well in all three cases. In order to investigate the interdiffusion behavior in U-Mo alloys, U vs. Mo diffusion couples were assembled and annealed in the temperature range of 650 to 1000°C. The interdiffusion microstructures and concentration profiles were examined via scanning electron iv microscopy (SEM) and electron probe microanalysis (EPMA), respectively. Interdiffusion coefficients and activation energies were calculated as functions of temperature and Mo composition. The intrinsic diffusion coefficients of U and Mo at the marker composition were also determined. The activity of U and the thermodynamic factor of the U-Mo alloy have been calculated using the ideal solution, the regular solution, and the subregular solution models based on the molar excess Gibbs free energy of the U-Mo alloy. The calculated intrinsic diffusivities of U and Mo along with the thermodynamic factor of the U-Mo alloy were employed to estimate the atomic mobilities and the vacancy wind effects of U and Mo according to Manning’s description. To explore potential diffusion barrier materials for reducing the fuel cladding chemical interaction between the U-Mo fuel and the Al alloy matrix/cladding, the interdiffusion behavior between U-Mo alloys and Mo, Zr, Nb and Mg were systematically studied. U-10wt.%Mo vs. Mo, Zr and Nb diffusion couples were annealed in the temperature range from 600 to 1000°C. A diffusion couple between U-7wt.%Mo and Mg was annealed at 550°C for 96 hours. SEM and transmission electron microscopy (TEM) were applied to characterize the microstructure of the interdiffusion zone. X-ray energy dispersive spectroscopy (XEDS) and EPMA were utilized to examine the concentration redistribution and the phase constituents. For the U-Mo vs. Mo diffusion couples, the interdiffusion coefficients at high Mo concentrations ranging from 22 to 32 at.%Mo were determined for the first time. In the U-Mo vs. Zr diffusion couples, the Mo2Zr phase was found at the interface. The diffusion paths were estimated and investigated according to the Mo-U-Zr ternary phase diagram. Thermal cracks and pure U precipitates were found within the diffusion zone in the U-Mo vs. Nb system. The growth rate of the interdiffusion zone v was found to be lower by about 103 times for Zr, 105 times for Mo and 106 times for Nb compared to those observed in the U-10wt.%Mo vs. Al or Al-Si systems. For the diffusion couple of U-Mo vs. Mg, the U-Mo was bonded very well to the Mg and there was negligible diffusion observed even after 96 hours annealing at 550°C. For a more fundamental understanding of the complex diffusion behavior between U-Zr fuels and their stainless steel claddings, U vs. Fe, Fe-15wt.%Cr and Fe-15wt.%Cr-15wt.%Ni diffusion couples were examined to investigate the interdiffusion behaviors between U and Fe and the effects of the alloying elements Cr and Ni. The diffusion couples were annealed in the temperature range from 580 to 700°C for various times. Two intermetallic phases, U6Fe and UFe2, developed in all of the diffusion couples with the U6Fe layer growing faster than the UFe2 layer. For the diffusion couples of U vs. Fe, extrinsic growth constants, intrinsic growth constants, integrated interdiffusion coefficients and activation energies in each phase were calculated. The results suggest that U6Fe impeded the growth of UFe2, and the boundary condition change caused by the allotropic transformation of U played a role in the growth of the U6Fe and UFe2 layers. The reasons why U6Fe grew much faster than UFe2 are also discussed. The additions of Cr and Ni into Fe affected the growth rates of U6Fe and UFe2. The solubility of Cr and Ni in U6Fe and UFe2 were determined, and it was found that Cr diffused into U more slowly than Fe or Ni.

Notes

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Graduation Date

2012

Semester

Fall

Advisor

Sohn, Yongho

Degree

Doctor of Philosophy (Ph.D.)

College

College of Engineering and Computer Science

Department

Materials Science Engineering

Degree Program

Materials Science and Engineering

Format

application/pdf

Identifier

CFE0004548

URL

http://purl.fcla.edu/fcla/etd/CFE0004548

Language

English

Release Date

December 2012

Length of Campus-only Access

None

Access Status

Doctoral Dissertation (Open Access)

Subjects

Dissertations, Academic -- Engineering and Computer Science, Engineering and Computer Science -- Dissertations, Academic

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