Doctoral Dissertations


"The atomic structure, glass forming and crystallization characteristics, and the chemical durability of vitreous binary iron phosphates of approximate batch composition 40Fe2O3-60P2O5 (mol%) and those containing up to 40 wt% of one or more common nuclear waste components such as Na2O, CS2O, SrO, UO2, or Bi2O3 have been investigated. The analytical tools used are Fe-57 Mössbauer, x-ray absorption, x-ray photoelectron, and Raman spectroscopies, high energy x-ray and neutron diffraction techniques, differential thermal analysis (DTA), and the product consistancy test (ASTM C-1285-94). The excellent chemical durability of iron phosphate glasses containing nuclear waste components is indicated by dissolution rates (at 90 °C in distilled water) as low as 10-10 to 10-11 g/cm2/min. When melted in air at 1100 to 1200°C, these iron phosphate melts reach a redox equilibria corresponding to a Fe(II)/Fe(III) ratio less than 0.51. The Fe(II) content increases with increasing melting temperature and when melted in reducing atmospheres. However, the glass forming ability of the melts decreases when the Fe(II)/Fe(III) ratio exceeds ca. 0.67. Both species of iron ions are coordinated with 5 to 5.5 near neighbor oxygen ions. The phosphorous-oxygen network is dominated by (P2O7 )4- dimer units. The iron-oxygen coordination and the phosphorous-oxygen network do not appreciably depend on the type or the concentration of the waste elements. The waste ions, which are situated outside the second shell coordination environment of iron and phosphorus ions, are not a major influence on the chemistry of the iron-oxygen-phosphorus host matrix. Therefore the addition of waste components does not cause major changes in properties such as the chemical durability of the iron phosphate host matrix. Vitreous iron phosphate host matrices appear to be a low cost and effective alternative to borosilicate glasses for vitrifying selected nuclear wastes"--Abstract, page iv.


Waddill, George Daniel

Committee Member(s)

Day, D. E.
Marasinghe, Gaya K.
Parris, Paul Ernest, 1954-
Peacher, Jerry
Pringle, Oran Allan



Degree Name

Ph. D. in Physics


University of Missouri--Rolla

Publication Date

Fall 1999

Journal article titles appearing in thesis/dissertation

  • Structural features of iron phosphate glasses
  • X-ray photoelectron and Mössbauer spectroscopic studies of iron phosphate glasses containing U, Bi, and Cs
  • A high energy x-ray and neutron scattering study of iron phosphate glasses containing uranium
  • The local environment of iron and uranium ions in iron phosphate glasses studied by Fe K and U LIII-edge x-ray absorption fine structure spectroscopy
  • Investigation of the iron local environment in iron phosphate glasses with different Fe(II) concentrations
  • Vitrified iron phosphate wasteforms containing multiple waste components


xix, 228 pages

Note about bibliography

Includes bibliographical references.


© 1999 Mevlüt Karabulut, All rights reserved.

Document Type

Dissertation - Restricted Access

File Type




Thesis Number

T 7703

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Link to Catalog Record

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