Effects of modifier additions on the thermal properties, chemical durability, oxidation state and structure of iron phosphate glasses

Abstract

Modified iron phosphate glasses have been prepared with nominal molar compositions [(1−x)·(0.6P2O5-0.4Fe2O3)]·xRySO4, where x = 0-0.5 in increments of 0.1 and R = Li, Na, K, Mg, Ca, Ba, or Pb and y = 1 or 2. In most cases the vast majority or all of the sulfate volatalizes and quarternary P2O5-Fe2O3-FeO-RyOz glasses or partially crystalline materials are formed. Here we have characterized the structure, thermal properties, chemical durability and redox state of these materials. Raman spectroscopy indicates that increasing modifier oxide additions result in depolymerization of the phosphate network such that the average value of i, the number of bridging oxygens per -(PO4)-tetrahedron, and expressed as Q i , decreases. Differences have been observed between the structural effects of different modifier types but these are secondary to the amount of modifier added. Alkali additions have little effect on density; slightly increasing Tg and Td; increasing α and Tliq; and promoting bulk crystallization at temperatures of 600-700 °C.Additions of divalent cations increase density, α, Tg, Td, Tliq and promote bulk crystallization at temperatures of 700-800 °C. Overall the addition of divalent cations has a less deleterious effect on glass stability than alkali additions.57 FeMössbauer spectroscopy confirms that iron is present as Fe 2+ and Fe 3+ ions which primarily occupy distorted octahedral sites. This is consistent with accepted structural models for iron phosphate glasses. The iron redox ratio, Fe 2+/ΣFe, has a value of 0.13-0.29 for the glasses studied. The base glass exhibits a very low aqueous leach rate when measured by Product Consistency Test B, a standard durability test for nuclear waste glasses. The addition of high quantities of alkali oxide (30-40 mol% R2O) to the base glass increases leach rates, but only to levels comparable with those measured for a commercial soda-lime-silica glass and for a surrogate nuclear waste-loaded borosilicate glass. Divalent cation additions decrease aqueous leach rates and large additions (30-50 mol% RO) provide exceptionally low leach rates that are 2-3 orders of magnitude lower than have been measured for the surrogate waste-loaded borosilicate glass. The P2O5-Fe2O3-FeO-BaO glasses reported here show particular promise as they are ultra-durable, thermally stable, lowmelting glasses with a large glass-forming compositional range.

Graphite immobilisation in iron phosphate glass composite materials produced by microwave and conventional sintering routes

“…Microwave and conventional melting resulted in iron phosphate glasses with largely similar physical properties, although the microwaved samples retained slightly less phosphorus than the conventionally melted samples, which is consistent with other reported studies [31,32]. Due to the similar properties of the glasses prepared by the two methods, it is suggested that the Absorption (a.u) Fig.…”

Immobilization of simulated radioactive fluoride waste in phosphate glass

“…The good leaching durability is primarily caused by the presence of strong, hydration-resistant Fe-O-P bonds in these glasses [10,29]. Although the release of the alkali metal cations was highest for the IP glasses, their networks remain largely insensitive to the addition of cations and can solubilize them in high quantity without sacrificing leaching resistance, which is also consistent with that reported by Bingham et al [19].…”

“…The peaks in the spectra can be assigned to their vibrational mode according to known frequencies from IP glasses reported in Refs. [18][19][20], and NaAlP glasses in Refs. [21][22][23], some of which are summarized in Table 4.…”

Titanium-containing bioactive phosphate glasses

“…Of more technological interest is the development of ternary systems such as the Na 2 O−CaO−P 2 O 5 system, which has been investigated extensively [12,38,39], and also the Na 2 O-Fe 2 O 3 -P 2 O 5 system [40], an extension of the developmental work on the binary Fe 2 O 3 -P 2 O 5 system [41] as a possible system for the encapsulation of nuclear waste.…”