Russell J. Hand

Vitrification of toxic wastes: a brief review

Abstract Whilst the vitrification of waste materials is a well established technology, hitherto it has not been economically viable on any substantial scale when applied to non-radioactive wastes. However new UK and European legislation may affect this situation. The present paper briefly reviews published work pertaining to waste vitrification in terms of legislation, waste compositions, energy, emissions and economic assessments. The focus is on vitrification of ashes arising from the incineration of municipal solid waste (MSW) and sewage sludge in terms of their composition, glass melting and reuse potential. The conclusion is that the high compositional variability of these and other wastes tends to preclude their use in many applications. However, the use of modern sorting and separation technology coupled with better control of waste treatment procedures may help to improve the range of potential uses for these wastes.

Thermodynamic parameters of bonds in glassy materials from viscosity–temperature relationships

Doremuss model of viscosity assumes that viscous flow in amorphous materials is mediated by broken bonds (configurons). The resulting equation contains four coefficients, which are directly related to the entropies and enthalpies of formation and motion of the configurons. Thus by fitting this viscosity equation to experimental viscosity data these enthalpy and entropy terms can be obtained. The non-linear nature of the equation obtained means that the fitting process is non-trivial. A genetic algorithm based approach has been developed to fit the equation to experimental viscosity data for a number of glassy materials, including SiO2, GeO2, B2O3, anorthite, diopside, xNa2O-(1-x)SiO2, xPbO-(1-x)SiO2, soda-lime-silica glasses, salol, and α-phenyl-o-cresol. Excellent fits of the equation to the viscosity data were obtained over the entire temperature range. The fitting parameters were used to quantitatively determine the enthalpies and entropies of formation and motion of configurons in the analysed systems and the activation energies for flow at high and low temperatures as well as fragility ratios using the Doremus criterion for fragility. A direct anti-correlation between fragility ratio and configuron percolation threshold, which determines the glass transition temperature in the analysed materials, was found.

Epoxy based coatings on glass: strengthening mechanisms

Glass may be strengthened by epoxy coatings although the strengthening mechanisms remain unclear. Possible strengthening mechanisms are reviewed and are used to analyse strength data for both a solvent based and a water based coating system. The coatings either fill (solvent based coatings), or partially fill (water based coatings) surface cracks and it is shown that closure stresses arising from the thermal expansion mismatch of the coating within these cracks can account for the observed degrees of strengthening. It is also demonstrated that other suggested mechanisms such as flaw healing cannot fully account for the observed degree of strengthening.

Fatigue behaviour of Fe–Cr–Si–B metallic glass wires

Abstract Cyclic compressive/tensile bending has been carried out on Fe–Cr–Si–B metallic glass wires using a controlled strain double pulley testing machine. The fatigue performance of two series of glassy alloy wires Fe 78−x Cr x Si 10 B 12 and Fe 77.5−x Cr x Si 7.5 B 15 have been compared with those of HT steel wires. Because of differences in modulus, the ranking of the materials studied changes according to whether the results are reported in terms of stress or strain. In terms of stress, the HT steel wire had a superior fatigue performance to the glassy wires; however, in terms of strain, the Fe 69.5 Cr 8 Si 7.5 B 15 glassy wire, under higher cycle conditions, had a superior fatigue performance, to HT steel wire. The fatigue performance of the glassy wires improved with the partial substitution of Fe by Cr. The short fatigue life of the glassy wires containing zero or low Cr contents in the present study was at least partly due to the necked morphology along their lengths. Fractography revealed that corrosion pits nucleated on the surface of the wires and resulted in crack initiation at these points.

Corrosion of glass contact refractories for the vitrification of radioactive wastes: a review

Abstract A key consideration for all radioactive waste vitrification technologies is the physical and chemical integrity of the melting vessel. Most melting vessels require refractory liners that can safely withstand the high-temperature, highly corrosive environment, contain molten waste mixtures during melting and provide robust and reproducible service lifetimes. In this review article the key glass contact refractory materials used in radioactive waste vitrification melters, their properties, their applications and the mechanisms by which they become corroded during service are reviewed.

Chemical durability of vitrified wasteforms: effects of pH and solution composition

Abstract Vitrification is used for the immobilization and conditioning of high-level waste (HLW) arising from the reprocessing of spent nuclear fuel in the UK. Vitrification is also under consideration for the immobilization of certain intermediate-level wastes (ILW), where there may be advantages of volume reduction and removal of uncertainties in long-term waste behaviour, compared to encapsulation in a cement grout. This paper gives an overview of recent work into the chemical durability of UK vitrified wasteforms to inform the technical specification for the disposal facilities for these waste products and the treatment of their long-term behaviour in post-closure performance assessment. This has included: (1) measurements of the initial glass dissolution rates of a simulated HLW Magnox waste glass in a range of groundwater types representative of potential UK host geologies and in simulated high pH near-field porewaters relevant to potential disposal concepts, using Product Consistency Test type-B (PCT-B) at 40ºC; and (2) durability testing of three simulant ILW glasses in a saturated calcium hydroxide buffered solution to simulate conditions in cement-based disposal vaults, using PCT-B tests at 50ºC. The experimentally defined initial rate of HLW Magnox waste glass dissolution in a range of simulated groundwater compositions appears to be similar regardless of the ionic strength and major element composition of the solution. The release of caesium from HLW Magnox waste glass appears to be sensitive to solution composition. Caesium is selectively retained in the glass compared to other soluble components in the two low ionic strength solutions, but is released at similar rates to other soluble components in the three groundwaters and Ca(OH)2 solution. Whether this change in caesium retention is an ionic strength effect or is related to changes in the nature of the surface alteration layer formed on the glass, has yet to be established. For HLW Magnox waste glass, dissolution is accelerated at high pH in NaOH solution, however, the presence of calcium acts to mitigate the effects of high pH, at least initially. In Ca(OH)2 solution, calcium is found to react with all the glasses studied leading to the formation of calcium-containing alteration products. The initial dissolution behaviour in Ca(OH)2 solution varies with glass composition and in particular appears to be sensitive to the boron content.

Interpretation of standard leaching test BS EN 12457-2: is your sample hazardous or inert?

A slag sample from a lead refiner has been obtained and given to two analytical laboratories to determine the release of trace elements from the sample according to BS EN 12457-2. Samples analysed by one laboratory passed waste acceptance criteria, leading it to be classified as an inert material; samples of the same material analysed by the other laboratory failed waste acceptance criteria and were classified as hazardous. It was found that the sample preparation procedure is the critical step in the leaching analysis and that the effects of particle size on leachability should be taken into account when using this standard. The purpose of this paper is to open a debate on designing a better defined standard leaching test and making current waste acceptance criteria more flexible.

Molybdenum in Nuclear Waste Glasses - Incorporation and Redox state

The composition and structure of the mixed metal molybdates that can form in simulated high level nuclear waste (HLW) glass melts have been studied. It was found that molybdates of a tetragonal scheelite type were formed upon heat treatment of the simulated glass samples (representative of the slow cools experienced by the real vitrified product), and that these compounds are capable of incorporating the majority of the mono, di, and trivalent cations that would be present in a real HLW glass. In addition, it has been shown that altering the redox conditions prevailing upon melting can promote or suppress crystallisation in simplified model waste glasses that contain molybdenum. Experiments to investigate the effect of redox conditions during melting of simulated HLW glass on molybdate formation are also reported.

The use of surrogates in waste immobilization studies : a case study of plutonium

Surrogates are widely used in the research and development of nuclear wasteforms, providing detailed insight into the chemical and physical behaviour of the wasteform whilst avoiding the widespread (restricted and costly) use of radiotoxic elements in the laboratory. However, caution must be exercised when dealing with surrogates since no single element or compound perfectly mimics all aspects of the behaviour of another. In this paper we present a broad discussion of the use of surrogates in waste immobilization, drawing upon and highlighting our research into glass and ceramic wasteforms for the immobilization of bulk PuO2.

An Investigation into the Oxidation State of Molybdenum in Simplifies High Level Nuclear Waste Glass Compositions

The redox state of Mo in glasses containing simplified simulated high level nuclear waste (HLW) streams has been investigated using Electron Spin Resonance (ESR) and X-ray Photoelectron Spectroscopy (XPS). Melts performed in highly oxidising or neutral (air) atmospheres contained Mo 6+ , but our study indicates that the Mo can be at least partially reduced to Mo 4+ or Mo 3+ by melting in a reducing atmosphere. The implications for glasses containing a full simulated HLW stream are that the formation of detrimental crystalline phases containing Mo 6+ upon heat treatment may be avoided by reducing the oxidation state of Mo during melting.