Leaching experiments on naturally occurring, metamict betafite and samarskite minerals in a bicarbonate-carbonate solution show strongly enhanced release to the solution of short-lived 228Th relative to its parent isotope 232Th (by a factor of 3 to 6), but only slightly enhanced dissolution (by a factor of 1.2 to 2) of long-lived 234U and 230Th relative to 238U and 232Th, respectively. The betafite (a complex Ca–U–Ti–Nb oxide of the pyrochlore group, A2−mB2X6Y0−1.H2O) and samarskite (a complex Y–Fe–U–Nb oxide with varying stoichiometry between AB O4 and AB2O6) are x-ray and electron diffraction amorphous having experienced doses of 2.2–2.8 × 1017 alpha-decay events/mg (24–31 dpa) and 3.8–4.4 × 1017 alpha-decay events/mg (39–45 dpa), respectively. The isotopic fractionation is attributed to the radiation damage created by the alpha-decay events. Individual alpha-recoil tracks are preserved for some time as disordered regions of higher chemical reactivity in already fully damaged, aperiodic areas that result from the alpha-decay events. The annealing time of the alpha-recoil track within the aperiodic atomic array of the metamict state is calculated to be 29 300 ± 8100 years for samarskite and 42 700 ± 13 700 years for the betafite. These data plus data on an earlier studied betafite sample (annealing time = 2000 ± 1300 years) give an average annealing time of 25 000 ± 21 000 years. The variation in calculated annealing time is due, in part, to post-metamict alteration of the sample, particularly for the betafite. The wider range of values for the betafite is attributed to its greater degree of alteration. These results demonstrate that recoil nuclei of alpha-decay events may be selectively leached from damaged, aperiodic phases, but that these tracks are subject to low-temperature annealing in short periods of time relative to the age of the samples (∼ 500 m.y.). The same phenomena are expected in actinide-containing nuclear waste form glasses.

Nitrogen trifluoride (NF3) was recently used by others as a reactive atmosphere during the melting of heavy metal fluoride glasses. This compound fluorinates oxide impurities, dehydrates the melt, and controls the oxidation state of both glassformer and impurity cations. The reaction of NF3 with nickel, silica, platinum, and vitreous carbon between 200 and 1100°C using IR absorption spectroscopy was investigated. This is an important issue, since reaction products (impurities) from the crucible and containment vessel walls may be incorporated in the melt. All materials, except for nickel, reacted below 600°C yielding corresponding fluorides (and oxides in the case of silica). The results indicate that, directly heated, vitreous carbon crucibles are preferred for melting of fluoride glasses in a NF3 atmosphere.

The melt self-quenching technique has been used to examine the metastable solid solution extension of mullite formed from rapidly solidified Al2O3.SiO2 melts. Increasing melt cooling rates were seen to increase the Al2O3 content of mullite, decrease the amount of mullite precipitating, and decrease the melt compositional range over which mullite forms. The maximum mullite Al2O3 content achieved was 77.3 mol % for cooling rates between 103 and 105 K/s. The highest Al2O3 content mullite also exhibited very similar ao and bo lattice parameters indicating a structure close to tetragonal symmetry (equilibrium mullite is orthorhombic).

A type of solidified “pure” C–S–H (calcium silicate hydrate) has been prepared by hydrating mixtures of synthesized Ca3SiO5(C3S) and silica fume at very low water/solid (w/s) ratios (< 0.15). The mechanical properties (splitting tensile strength), stoichiometry, and microstructure of hydration products have been investigated. Results are reported here in which 12.03%−41.56% (by weight) silica fume was added to C3S. It has been found that the strength of the materials with CaO/SiO2(C/S) molar ratio of 1.5 is comparatively higher than that of the others, after curing from 1 day to 28 days. The homogeneity and rheology are of direct importance to the formation of the calcium silicate bonding, which influences greatly the mechanical properties. The hydrates are primarily C–S–H with only small amounts of Ca(OH)2. The compositions of the solidified C–S–H are (1.33–1.37) CaO·SiO2. (1.02–1.21) H2O and (1.40–1.19)CaO·SiO2.(0.68–0.91)H2O for mixtures of C/S = 1.5 and 0.83, respectively. The characterization of the chemically bonded materials by Wn (nonevaporable water), density, x-ray diffraction, and scanning electron microscopy (SEM) studies has been carried out. The relationships between these characteristics and the strength are discussed.

Two quite different types of microstructures have been detected for MgTiO3-enriched LiTaO3 ceramics corresponding either to small size grains and open porosity or to large size grains with closed porosity and appearance of microcracks. The first structure appears in short sintering processes at relatively low temperature. The textural change is explained by transitory formation of a grain boundary phase that leads to quick coalescence of the small grains.

The substitution of fluorine for oxygen in TiO2 was investigated by the reaction of Ti2O3, TiO2, and TiF3 under conditions of 4–6.5 GPa and 700–1400°C. The single phase of TiO2−x Fx solid solution was obtained in the region of 0≤x≤0.7. According to the x-ray diffraction data, the a and c axes of the rutile-type structure linearly increased with increasing fluorine content. The electrical resistivities of TiO2−x Fx were in the range from 10 Ω cm for x = 0.3 to 850 Ω cm for x = 0.7 at 300 K and the relationship between In ρ and 1000/T was linear. The activation energies were estimated to be from 0.17 eV at x = 0.3 to 0.28 eV at x = 0.7. Also, the thermoelectric powers at room temperature changed from 250μV/K to + 50 μV/K. The mechanism of electric conduction was discussed on the basis of the extended band model of rutile.