Masters Theses

Abstract

"Waste loadings of reprocessed spent nuclear fuel vitrified into borosilicate glass can be increased by precipitating environmentally stable phases concentrated with waste components in a chemically stable glass matrix. The principal objective of this thesis was to characterize the development of crystalline powellite (CaMoO4 and related phases) and oxyapatite (Ca2LN8Si6O26) in borosilicate glass-ceramics and to determine how the formation of those phases affected its chemical durability.

Borosilicate glasses provided by PNNL were re-melted and quenched at rates from over 300⁰C/s to ~0.05⁰C/s. Isothermal heat treatment experiments were conducted by quenching melts in a molten tin bath at various temperatures, holding for periods of time, and then quenching in a water bath. Analytical electron microscopy and x-ray diffraction provided information about the kinetics of the phase separation and crystallization processes responsible for microstructural development. Powellite and oxyapatite crystals formed during slower quench rates and longer isothermal times, and time-temperature-transformation (TTT) diagrams were developed from the latter experiments.

Corrosion tests were performed to understand how the individual phases in the glass-ceramic affect its overall chemical durability. Product consistency tests provided release rates of major elements from samples as a function of cooling rate, and atomic force microscopy and profilometry measurements of surface topology determined the relative corrosion rates of the residual glass and oxyapatite phases. Faster dissolution rates were measured from samples cooled more slowly and these were explained by the greater fractions of B2O3 in the residual glass phase after the formation of oxyapatite and powellite. Oxyapatite was found to be more durable than the residual glass"--Abstract, page iv.

Advisor(s)

Brow, Richard K.

Committee Member(s)

Smith, Jeffrey D.
Miller, F. Scott, 1956-

Department(s)

Materials Science and Engineering

Degree Name

M.S. in Materials Science and Engineering

Sponsor(s)

United States Department of Energy

Comments

This work was supported by the Department of Energy and the Nuclear Energy University Program (Project 15-8112).

Publisher

Missouri University of Science and Technology

Publication Date

Fall 2018

Journal article titles appearing in thesis/dissertation

  • Phase development in a complex borosilicate glass-ceramic waste form
  • The effects of microstructure on the dissolution behavior of a complex glass-ceramic waste form

Pagination

xv, 152 pages

Note about bibliography

Includes bibliographical references.

Rights

© 2018 Nicholas Stephen Roberts, All rights reserved.

Document Type

Thesis - Open Access

File Type

text

Language

English

Thesis Number

T 11437

Electronic OCLC #

1084479815

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