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In this review, we provide a perspective on the science and technology of vitrification of waste. First, we provide a background on the general classes of wastes for which vitrification is currently used for immobilization or is proposed, including nuclear and industrial hazardous wastes. Next, we summarize the issues surrounding solubility of waste ions and resulting uncontrolled crystallization or phase separation. Some newer waste form designs propose a controlled crystallization, resulting in a glass-ceramic. A summary of glass systems and glass-ceramic systems is given, with the focus on immobilizing waste components at high waste loading. Throughout, design and processing considerations are given, and the difference between uncontrolled undesirable and controlled desirable crystallization is offered.

In this work, a systematic photoluminescence (PL) study on three series of gallium oxide/aluminum gallium oxide films and bulk single crystals is performed including comparing doping, epitaxial substrates, and aluminum concentration. It is observed that blue/green emission intensity strongly correlates with extended structural defects rather than the point defects frequently assumed. Bulk crystals or Si-doped films homoepitaxially grown on (010) β-Ga2O3 yield an intense dominant UV emission, while samples with extended structural defects, such as gallium oxide films grown on either (-201) β-Ga2O3 or sapphire, as well as thick aluminum gallium oxide films grown on either (010) β-Ga2O3 or sapphire, all show a very broad PL spectrum with intense dominant blue/green emission. PL differences between samples and the possible causes of these differences are analyzed. This work expands previous reports that have so far attributed blue and green emissions to point defects and shows that in the case of thin films, extended defects might have a prominent role in emission properties.

Optical and electrical properties of Hf- and Zn-doped β-Ga2O3 samples, which are n-type and insulating, respectively, were altered via high-energy electron irradiation at 2.5 or 0.5 MeV. The β-Ga2O3:Hf samples irradiated with 2.5 MeV electrons experienced a color change from blue to yellow and a large drop in conductivity, attributed to the creation of gallium vacancies, which compensate donors. This irradiation resulted in the absence of free carrier absorption and the presence of Cr3+ photoluminescence (PL). PL mapping prior to irradiation revealed optically active ZnO precipitates that formed during the growth of β-Ga2O3:Zn. These precipitates have a 384 nm (3.23 eV) stacking fault emission in the core; in the outer shell of the precipitate, the PL blue-shifts to 377 nm (3.29 eV) and a broad defect band is observed. After 0.5 MeV electron irradiation, the defect band broadened and increased in intensity. The blue PL band (435 nm) of β-Ga2O3 was enhanced for both Hf- and Zn-doped samples irradiated with 0.5 MeV. This enhancement is correlated with an increase in oxygen vacancies. [ABSTRACT FROM AUTHOR]

Though not often discussed explicitly in literature, sample handling and preparation for advanced characterization techniques is a significant challenge for radiological materials. In this contribution, a detailed description is given of method development associated with characterization of highly radioactive and, in some cases, hygroscopic oxides of technetium. Details are given on developed protocols, fixtures, and tooling designed for x-ray and neutron diffraction, x-ray absorption, Raman spectroscopy, magic angle spinning nuclear magnetic resonance, and electron paramagnetic resonance. In some cases, multiple iterations of improved sample holder design are described. Lessons learned in handling Tc compounds for these and similar characterization methods are discussed.

Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4-. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similar vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant.

The local chemistry of technetium-99 (99Tc) in oxide glasses is important for understanding the incorporation and long-term release of Tc from nuclear waste glasses, both those for legacy defense wastes and fuel reprocessing wastes. Tc preferably forms Tc(VII), Tc(IV), or Tc(0) in glass, depending on the level of reduction of the melt. Tc(VII) in oxide glasses is normally assumed to be isolated pertechnetate TcO4 - anions surrounded by alkali, but can occasionally precipitate as alkali pertechnetate salts such as KTcO4 and NaTcO4 when Tc concentration is high. In these cases, Tc(VII) is 4-coordinated by oxygen. A reinvestigation of the chemistry of alkali-technetium-oxides formed under oxidizing conditions and at temperatures used to prepare nuclear waste glasses showed that higher coordinated alkali Tc(VII) oxide species had been reported, including those with the TcO5 - and TcO6 - anions. The chemistry of alkali Tc(VII) and other alkali-Tc-oxides is reviewed, along with relevant synthesis conditions. Additionally, we report attempts to make 5- and 6-coordinate pertechnetate compounds of K, Na, and Li, i.e. TcO5 - and TcO6 -. It was found that higher coordinated species are very sensitive to water, and easily decompose into their respective pertechnetates. It was difficult to obtain pure compounds, but mixtures of the pertechnetate and other phase(s) were frequently found, as evidenced by x-ray absorption spectroscopy (XAS), neutron diffraction (ND), and Raman spectroscopy. Low temperature electron paramagnetic resonance (EPR) measurements showed the possibility of Tc(IV) and Tc(VI) in Na3TcO5 and Na5TcO6 compounds. It was hypothesized that the smaller counter cation would result in more stable pertechnetates. To confirm the synthesis method, LiReO4 and Li5ReO6 were prepared, and their Raman spectra match those in the literature. Subsequently, the Tc versions LiTcO4 and Li5TcO6 were synthesized and characterized by ND, Raman spectroscopy, XANES, and EXAFS. The Li5TcO6 was a marginally stable compound that appears to have the same structure as that known for Li5ReO6. Implications of the experimental work on stability of alkali technetate compounds and possible role in the volatilization of Tc are discussed.

The effects of pressure on single crystals of Cr-doped gallium oxide (β-Ga2O3:Cr3+) and aluminum gallium oxide [(Al0.1Ga0.9)2O3] were examined by measuring the wavelength shift in the spectral R lines. Photoluminescence (PL) spectra of these materials were collected from samples in diamond anvil cells at pressures up to 9 GPa. The β-Ga2O3:Cr3+R lines were found to shift linearly under hydrostatic pressure. The (Al0.1Ga0.9)2O3R lines also show a linear shift but the R1 line shifted less than for β-Ga2O3:Cr3+. The ratio of R2 to R1 peak areas vs pressure is dominated by nonradiative recombination. X-ray diffraction measurements of (Al0.1Ga0.9)2O3 indicate that its equation of state is similar to that of β-Ga2O3. β-Ga2O3:Cr3+ was examined under non-hydrostatic conditions by using mineral oil as a pressure transmitting medium. Similar to the case in ruby, the R1 line is much more sensitive to non-hydrostatic stress than R2. Spatially resolved PL of a sample at 8 GPa in mineral oil showed significant variations in the R1 emission wavelength. These results suggest that the R1 line can serve as a sensitive probe of alloy composition and non-hydrostatic stress, while the R2 line is insensitive to these perturbations. [ABSTRACT FROM AUTHOR]

This Review summarizes a range of analytical techniques that can be used to detect, quantify, and/or distinguish between isotopes of iodine (e.g., long-lived 129I, short-lived 131I, stable 127I). One reason this is of interest is that understanding potential radioiodine release from nuclear processes is crucial to prevent environmental contamination and to protect human health as it can incorporate into the thyroid leading to cancer. It is also of interest for evaluating iodine retention performances of next-generation iodine off-gas capture materials and long-term waste forms for immobilizing radioiodine for disposal in geologic repositories. Depending upon the form of iodine (e.g., molecules, elemental, and ionic) and the matter state (i.e., solid, liquid, and gaseous), the available options can vary. In addition, several other key parameters vary between the methods discussed herein, including the destructive vs nondestructive nature of the measurement process (including in situ vs ex situ measurement options), the analytical data collection times, and the amount of sample required for analysis. [ABSTRACT FROM AUTHOR]