Further Studies of Synroc Immobilization of HLW Sludges and Tc for Hanford Tank Waste Remediation

1997 ◽  
Vol 506 ◽  
Author(s):  
E.R. Vance ◽  
K.P. Hart ◽  
M.L. Carter ◽  
M.J. Hambley ◽  
R.A. Day ◽  
...  

ABSTRACTSynroc/glass composites were designed for simulated Hanford HLW sludges containing U (the current “All-Blend” formulation). The composite contained ∼ 50 wt% of simulated HLW (oxide equivalent), to which ∼ 6, 10, 10, and 24 wt% of CaO, Al2O3, TiO2 and SiO2 were added, and melted under an argon atmosphere at 1350°C. The phase assemblage consisted of zirconolite, perovskite, spinel, nepheline, whitlockite and glass as major phases. Seven-day PCT tests yielded values of < 0. 1 g/m2 for all elements studied. The PCT results were tolerant to changes of ∼ 20% of the inventories of the additives, and to variations in redox conditions.Technetium separated out during decontamination of liquid Hanford wastes can be incorporated as metal in hot-pressed Synroc prepared under reducing conditions, and its leach resistance is good (∼ 10∼3 g/m2/day at 70°C), and can be improved by alloying with iron group metals. With a choice of “neutral” (P(O2) ∼ 10−4 atm., near the Ni/NiO buffer) hot-pressing conditions, Tc can also be incorporated as Tc4+, substituting for Ti4+ in the ceramic phases, and in this form, it should be highly leach resistant also.

1996 ◽  
Vol 465 ◽  
Author(s):  
E. R. Vance ◽  
K. P. Hart ◽  
R. A. Day ◽  
M. L. Carter ◽  
M. Hambley ◽  
...  

ABSTRACTThree wt% each of Cs and Tc were mixed with the standard Synroc precursor and the ceramic was formed by hot-pressing. Attempts were made to incorporate the Tc as either metal or Tc 4+, using different redox conditions in processing. Volatile losses of Tc during calcination were < 0.1% in all cases. Short-term Tc leach rates when the Tc was present as a metal alloy were in the order of 10−4 g/m /d at 90°C with frequently changed water, and decreased with increasing leaching time. The valence of the Tc was monitored by X-ray absorption spectroscopy at the drying and calcination stages of the production. The general viability of Synroc/glass composites for immobilising the Hanford HLW sludges is further demonstrated by using further refinements of additive schemes for the inactive “All-blend” formulation and initial studies using the U-containing “All-blend” waste formulation.


We showed in this work that there is a possibility of recycling the wastes derived from iron ore concentration by using glass technology. The compositions of new glass ceramics with high technological and decorative properties were developed. The influence of Al2O3, MgO and Na2O additives to the waste from ore benefication on the parameters of the synthesized glass and its crystallization products was studied. The optimal temperatures of synthesis, annealing and crystallization of glass samples in the systems (Fe2O3–FeO)–SiO2–Al2O3–Na2O and (Fe2O3–FeO)–SiO2–Al2O3–MgO were shown to be 1450100С, 500–6000С and 700–8000C, respectively. It was established that the redox conditions of crystallization of glasses in the system (FeO–Fe2O3)–SiO2–Al2O3–Na2O strongly affect the nature of the iron-containing phases that are formed: oxidative conditions favors the formation of hematite (Fe2O3) and aegirinite (Na2OFe2O34SiO2), whereas reducing conditions contributes to the formation of wustite (FeO) and fayalite (2FeOSiO2). In the system (FeO–Fe2O3)–SiO2–Al2O3–MgO under both oxidative and reducing conditions of crystallization, the same crystalline phases appear: olivine (2(Mg,Fe)OSiO2), hercin (FeOAl2O3) and iron metasilicate (FeOSiO2). It was shown that the crystallization of samples under reducing conditions allows producing materials with higher microhardness. The surface layer of glasses and glass ceramics exhibited less microhardness than their deep layers.


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