M. A. Adel-Hadadi

Leaching of natural and nuclear waste glasses in sea water

Microtektites, some with a SiO2 content as low as 50%, exhibit a very limited extent of corrosion after having been exposed to interaction with their environment in sea-bed sediments for periods of 105a. Measurements carried out on a bottle-green microtektite glass composition in de-ionized water show that this glass has relatively high leach rates, as expected on the basis of its low SiO2 content (≈ 50%) and high modifier content (≈ 20%). However, is sea water the leach rates are smaller by at least 2 orders of magnitude, in agreement with the small extent of microtektite corrosion observed in nature (typically<5μ). Systematic studies of leachant composition effects show that the suppression of leaching in sea water is probably due to the presence of high levels of Mg. Measurements were also carried out on man-made silicate glasses related in composition to nuclear waste glasses. Although the compositions of the man-made glasses are different in many important respects from the composition of microtektites, it was found that the leach rates of the man-made glasses, too, are smaller by about 2 orders of magnitude in sea water compared with their values in de-ionized water. Surface analysis of glasses exposed to sea water shows that the predominant feature is the formation of a layer which is very rich in Mg.

Composition and particle size of superparamagnetic corrosion products in tap water

Chemical analyses, magnetization, Mössbauer spectrum, and x-ray diffraction measurements were made on solids removed from tap water by means of membrane filters. The taps from which this water was obtained had previously been unused for prolonged periods of time. When these taps were reactivated and water was first drawn, it was observed that the quantity of coarse solids in the water gradually decreased with flow, while at the same time the quantity of fine solids gradually increased. The magnetization, Mössbauer spectra, and x-ray diffraction patterns of the solids showed the presence of a significant number of superparamagnetic particles of magnetite. In the temperature range of our measurements (77 K<T<300 K), paramagnetic iron-based species, particularly lepidocrocite, were also present in the solids. Contaminants such as Pb, Cu, and As were observed to be present in significant amounts, and it is shown that these are adsorbed to the magnetic nanoparticles. It was observed that almost all of the solid particles could be removed by means of 5-microm filters. This removal process can be explained by means of a model which assumes that initial deposition of coarse aggregates of corrosion products on the filters forms a coating, rich in extremely fine iron oxides. The coating has a high capacity for sorption of very small individual particles.

Dissolution mechanism of soda-lime silicate glass and of PNL 76-68 in the presence of dissolved Mg

Leaching studies were performed on powdered PNL 76-68 glass in de-ionized water in the presence of Mg solute. The results showed that the presence of Mg in the leachant greatly reduced the rate of glass dissolution. The equation Q = kt{sup {alpha}} was used to express the experimental data. In the absence of Mg, {alpha} was about 1, i.e., the amount of glass dissolved was linear with time. In the presence of Mg, {alpha} was close to 0.5, i.e. the extracted amount was proportional to the square root of time. Therefore, the reduction of the dissolution rate of PNL 76-68 glass in the presence of Mg solute could be explained as a result of a change in the glass dissolution mechanism. Comparative leaching studies on bulk soda-lime silicate glass in a sodium borate buffered system (pH 8.1) showed the same results. The presence of Mg in the leachant reduced the rate of glass dissolution. In the absence of Mg, {alpha} was about 1, while in the presence of Mg, {alpha} was 0.5. This change in {alpha} was not caused by changes in pH, and it represents a real change in the glass dissolution mechanism.

Effects of Fluoride and other Anions on the Corrosion of Alloy 22

Samples of Alloy 22 were tested in solutions containing various anions in order to determine their effect on the corrosion of the alloy. It was found that Alloy 22 is relatively corrosion resistant in HCl and HNO 3 at pH 1 and 160°C (general corrosion rates on the order of 10 μm/year), but more susceptible to phosphoric acid, especially under reducing conditions. The presence of fluoride raised the corrosion rate of Alloy 22 to the order 1 mm/year at pH 1, and fluoride is still active towards Alloy 22 at pH levels as high as 3.5. Samples tested in solutions of 1000xJ13 in which the pH was altered during testing showed an increase in corrosion rate over solutions of constant pH. Preliminary electrochemical tests suggest that nitrate may be an effective corrosion inhibitor in fluoride containing solutions, while sulfate is not.

Effects of Volatilization on Groundwater Chemistry

Both concentrated and dilute simulated solutions of saturated J13 and unsaturated UZ pore water were concentrated through distillation of the solutions under atmospheric pressure. It was observed that condensed vapors from the pH of J13 waters steadily rose during the distillations to a value of 10, while the pH of UZ waters remained steady until 90% of the volume of the solution had been distilled, after which the pH of the condensed vapors dropped precipitously, often below 1. Residual solutions analyzed when most of the solution had been distilled away were also found to be extremely acidic. The temperature of these residual solutions was around 144°C due to their high solute content causing boiling point elevation. All experiments were performed with the condenser open to ambient air at atmospheric pressure. The pH drop during the distillation of UZ water is attributed largely to the presence of large amounts of magnesium. Specimens of Alloy 22 tested in the residual solutions of at their boiling temperature (around 144°C) showed significant rates of general corrosion over a broad range, often approaching 1 mm/year. Similarly high corrosion rates were also observed in tests on Alloy 22 specimens in condensates obtained during the late stages of the distillation. These tests were performed either in situ at 75–80°C using a Soxhlet extractor, or in separate pressure vessels at temperatures between 90 and 130°C.