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Technetium-99 immobilization in low-temperature nuclear waste forms often relies on additives that reduce environmentally mobile pertechnetate (TcO4-) to insoluble Tc(IV) species. However, this is ...

The mixed alkaline-earth compound Ca0.84Sr0.16MoO4 has a typical CaMoO4 powellite structure. Its cell parameters fit well within the trends observed in similar powellites., A mixed alkaline-earth powellite, Ca0.84Sr0.16MoO4 (calcium strontium molybdate), was synthesized by a flux method and its crystal structure was solved using single-crystal X-ray diffraction (SC-XRD) data. The compound crystallized in the I41/a space group as with a typical CaMoO4 powellite, but with larger unit-cell parameters and unit-cell volume as a result of the partial incorporation of larger Sr cations into the Ca sites within the crystal. The unit cell and volume were well fitted with the trendline calculated from literature values, and the powder X-ray diffraction (P-XRD) pattern of the ground crystal is in good agreement with the calculated pattern from the solved structure.

A cadmium germanium arsenide compound, Cd3Ge2As4, was synthesized using a double-containment fused quartz ampoule method within a rocking furnace and a melt-quench technique. The crystal structure was determined from single-crystal X-ray diffraction (SC-XRD), scanning and transmission electron microscopies (i.e. SEM, STEM, and TEM), and selected area diffraction (SAD) and confirmed with electron backscatter diffraction (EBSD). The chemistry was verified with electron energy loss spectroscopy (EELS).

This paper details the results from two laboratory-scale (∼1 L) melter experiments where the processability was evaluated for vitrifying a simulated high-MoO3 raffinate waste from reprocessing of used commercial nuclear fuel. The target glass (CSLNTM-C-2.5) contained roughly 18 mass% waste loading (2.5 mass% MoO3). A homogeneous glass product was produced after process optimizations. Following the experiments, condensates present in the experimental apparatus were analyzed and found to be primarily composed of SiO2, Al2O3, Zr-O, rare earth, molybdate, and nitrate phases. The composition of the glassy product resulting from the second melter experiment was very similar to that of the target composition with variations noted for Al, Mo, and Zr.

This paper discusses work to develop Na2O-B2O3-SiO2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. Here, five new glasses with ∼20 mass% Na2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. These improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.

High-alumina high-level waste (HLW) glasses are prone to nepheline precipitation during canister-centerline cooling (CCC). If sufficient nepheline forms, the chemical durability of the glass will be significantly impacted. Overly conservative constraints have been developed and used to avoid the deleterious effects of nepheline formation in U.S. HLW glasses. The constraints used have been shown to significantly limit the loading of waste in glass at Hanford and therefore the cost and schedule of cleanup. A 90-glass study was performed to develop an improved understanding of the impacts of glass composition on the formation of nepheline during CCC. The CCC crystallinity data from these glasses were combined with 657 glasses found in the literature. The trends showed significant effects of Na2O, Al2O3, SiO2, B2O3, CaO, Li2O, and potentially K2O on the propensity for nepheline formation. A pseudo-ternary submixture model was proposed to identify the glass composition region prone to nepheline precipitation. This pseudo-ternary with axes of SiO2 + 1.98B2O3, Na2O + 0.653Li2O + 0.158CaO, and Al2O3 was found to divide glasses that precipitate nepheline during CCC from those that do not. Application of this constraint is anticipated to increase the loading of Hanford high-alumina HLWs in glass by roughly one-third.

Nepheline crystallizes upon slow-cooling in some melts concentrated in Na2O and Al2O3, which can result in a residual glass phase of low chemical durability. Nepheline can incorporate many components often found in high-level waste radioactive borosilicate glass, including glass network ions (e.g., Si, Al, Fe), alkali metals (e.g., Cs, K, Na, and possibly Li), alkaline-earth metals (e.g., Ba, Sr, Ca, Mg), and transition metals (e.g., Mn, and possibly Cr, Zn, Ni). When crystallized from melts of different compositions, nepheline composition varies as a function of starting melt composition. Five simulated high-level nuclear waste borosilicate glasses shown to crystallize large fractions of nepheline on slow-cooling were selected for study. These starting melt compositions contained a range of Al2O3, B2O3, CaO, Na2O, K2O, Fe2O3, and SiO2 concentrations. Compositional analyses of nepheline crystals in glass by electron probe micro-analysis (EPMA) indicate that nepheline is generally rich in silica, whereas boron is unlikely to be present in any significant concentration, if at all, in nepheline. Also, several models are presented for calculating the fraction of vacancies in the nepheline structure.

Chlorosodalite has the general form of Na8(AlSiO4)6Cl2 and this paper describes experiments conducted to synthesize sodalite with a solution-based approach to immobilize a simulated spent electrorefiner salt solution containing a mixture of alkali, alkaline earth, and lanthanide chlorides. The reactants used were the salt solution, NaAlO2, and either Si(OC2H5)4 or Ge(OC2H5)4. Additionally, seven different glass sintering aids (at loadings of 5 mass%) were evaluated as sintering aids for consolidating the as-made powders using a cold-press-and-sinter technique. This process of using alkoxide additives for the Group IV component can be used to produce large quantities of sodalite at near-room temperature as compared to a method where colloidal silica was used as the silica source. However, the small particle sizes inhibited densification during heat treatments.

To understand feed-to-glass conversion for the vitrification of nuclear waste, we investigated batch reactions and phase transitions in a simulated nuclear waste glass melter feed heated at 5 K/min up to 700°C using optical microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and X-ray diffraction. To determine the content and composition of leachable phases, we performed leaching tests; the leachates were analyzed by inductively coupled plasma atomic emission spectroscopy. By 400°C, gibbsite and sodium borates lost water and converted to amorphous phase, whereas other metallic hydroxides dehydrated to oxides. Between 400°C and 700°C, carbonates decomposed before 500°C; amorphous aluminum oxide and calcium oxide reacted with the sodium borate and formed the more durable amorphous borate phase along with intermediate crystalline products; above 500°C, quartz began to dissolve, and hematite started to convert to trevorite.

About 1800 years ago a Roman Corbita sunk off the coast of Italy carrying a barrel of glass cullet to the floor of the Adriatic Sea. Samples of glass cullet and the cemented surrounding sediment have been characterized and the reaction between the glass and the sea water saturated with respect to calcite and dolomite has been modeled. Results from characterization and modeling show that the phase surrounding and cementing together the sediment grains is a high-Mg calcite. We find that the origin of this cementing phase is likely the reaction between the glass and the sea water to form a Mg–silicate, here modeled as sepiolite [Mg 4 Si 6 O 15 (OH) 2 ⋅6(H 2 O)].

Three different solution-based approaches were taken to make sodalite minerals as a host for a mixed salt simulating the waste in the electrochemical separations process of nuclear fuel reprocessing. The methods used an aqueous solution of mixed chlorides (simulated waste) but the other reactants varied: (1) Al(OH) 3 + NaOH + CS, (2) NaAlO 2 + CS, and (3) Al 2 Si 2 O 7 + NaOH, (CS = colloidal silica). The products were dried, ground, pressed into pellets, and fired at 650–950 °C. In some cases, either 5 or 10 mass% of a Si–Na–B oxide glass sintering aid was introduced at different stages in the process. Method (2) proved the most successful at producing high sodalite fractions (up to 100%) with minimal sintering aid additions and showed high consolidation potential (up to 91.4% of theoretical density) at reduced firing temperatures.

A redox-active metal-organic composite material shows improved and selective O2 adsorption over N2 with respect to individual components (MIL-101 and ferrocene). The O2 sensitivity of the composite material arises due to the formation of maghemite nanoparticles with the pore of the metal-organic framework material.

Sodalite (Na8(AlSiO4)6Cl2) and cancrinite ((Na,K)6Ca2(AlSiO4)6Cl4) are environmentally stable, chloride-containing minerals that are a logical waste form option for the mixed alkali chloride salt waste stream that is generated from a proposed electrochemical separations process during nuclear fuel reprocessing. Here, we discuss a low-temperature, solution-based process to make these phases where sodalite particles are produced in the form of a fine powder with particle sizes on the order of 1–10 μm. Due to the small particle size, these powders require additional treatment to form a monolith. In this study, the powders were pressed into pellets and fired to achieve >90% of the theoretical density of sodalite (2.27 × 10−3 kg/m3). The cancrinite structure, identified as the best candidate mineral form in terms of waste loading capacity, was only produced on a limited basis but was converted to sodalite upon firing. Here, we discuss the specifics of the solution-based approach, the chemical durability of select waste forms as well as the steps taken to maximize the chloride-containing phases, decrease chloride loss during pellet firing, and to increase pellet densities.

In this study, the MnOx-FeOx binary system was measured within a temperature range of 750 to 1590°C in an atmosphere of air. Multiple measurement methods were employed to accurately measure the phase boundaries, including isothermal heat-treatments followed by rapid quenching, dilatometery, differential thermal analyses with thermogravimetric analyses, and hot-stage X-ray diffraction (XRD). Phase assemblage in each sample was determined by XRD. Data were compared with literature, and a new, self consistent phase diagram was developed. The results are reported along with background information and a comparison with previously reported data.

Cadmium germanium diarsenide glasses were synthesized in bulk form (B2.4 cm 3 ) using procedures adapted from the literature. Several issues involved in the fabrication and quenching of amorphous CdGexAs2 (x 5 0.45, 0.65, 0.85, and 1.00, where x is the molar ratio of Ge to 1 mol of Cd) are described. An innovative processing route is presented to enable fabrication of high-purity, vitreous, crack-free ingots with sizes up to 10 mm diameter, and 30–40 mm long. Specimens from selected ingots were characterized using thermal analysis, optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, particle-induced X-ray emission, Rutherford backscattering, secondary ion mass spectrometry, X-ray diffraction, density, and optical spectroscopy. Variations in properties as a function of processing conditions and composition are described. Results show that the density of defect states in the middle of the band gap and near the band edges can be decreased three ways: through suitable control of the processing conditions, by doping the material with hydrogen, and by increasing the concentration of Ge in the glass.

Liquidus temperatures (TL) were measured, and primary phases were determined for 50 (from an initial test matrix of 76) compositions within the Al2O3–B2O3–CaO–Na2O–SiO2 glass-forming system and its constituent ternary subsystems. Strong linear correlations have been found between composition and TL for melts within the same primary phase fields. The TL and primary phase data are being used to develop and refine a modified associate species model (ASM). The impacts of Fe2O3, Li2O, NiO, ZrO2, Cr2O3, ZnO, and MnO additions on the TL of two baseline glass compositions are reported. These data are intended as benchmarks for further expansion of the ASM or other silicate melt solution models of nuclear waste glasses.

iii Acknowledgments v Acronyms and Abbreviations vii 1.0 Introduction and Background 1 2.0 Quality Assurance 2 3.0 Previous Silicate Glass Formulation Efforts for CCIM Processing of U.S. Tank Wastes 3 3.1 Hanford TWRS-P HLW 3 3.2 Hanford C-106/AY-102 Formulation for Crystal Tolerant Melters 4 3.3 Idaho Sodium Bearing Waste 6 3.4 Savannah River Sludge Batch 2 Glasses 8 3.5 Savannah River Sludge Batch 3 Glasses 9 3.6 Savannah River Sludge Batch 4 Glasses 11 3.6.1 Frit 503-R4 (SIA Radon) 12 3.6.2 Frit 503-R3 (KHNP) 13 3.6.3 Frit 503-R6 (CEA) 13 3.7 Hanford AZ-101 High Level Waste Glass 14 3.8 Hanford AN-105 Low-Activity Waste Glass Formulation 16 3.9 Hanford HLW Waste Cluster Groups 18 3.10 Summary of Key Processing Related Properties for CCIM Test Glasses 19 4.0 Glass Formulation and Testing for Hanford High-Alumina and High-Iron HLWs 23 4.1 Selection of Wastes 23 4.2 Experimental Methods 25 4.2.1 Glass Fabrication and Canister Centerline Cooling Treatment 25 4.2.2 Composition Analyses 26 4.2.3 Product Consistency Test 26 4.2.4 Viscosity 26 4.2.5 Electrical Conductivity 27 4.2.6 Equilibrium Crystal Fraction and Crystal Identification After Canister Centerline Cooling 27 4.3 Glass Formulation Approaches 28 4.4 High-Al2O3 Glass Formulation and Testing for C-102 29 4.5 High-Fe2O3 Glass Formulation and Testing for 244-TX 39 4.6 Summary of Glass Formulation Results for C-102 and 244-TX 45 5.0 Evaluation of Glass Formulations for Hanford Tank Waste Using CCIM 46 5.1 High-Level Waste Melter Study Report 47 5.2 Evaluation of Hanford HLW Vitrification Process Alternatives 47 5.3 River Protection Project System Plan (Current Baseline) 48

Gamma radiation induces changes in physical, optical, and structural properties in chalcogenide glasses., Previous research has focused on As{sub 2}S{sub 3} and families of glasses containing Ge. For the first time, we present composition and dose dependent data on the As-S binary glass series. Binary As{sub x}S{sub 100-x} (x = 30, 33, 36, 40, and 42) glasses were irradiated with gamma radiation using a {sup 60}Co source at 2.8 Gy/s to accumulated doses of 1, 2, 3, and 4 MGy. The irradiated samples were characterized at each dose level for density, refractive index, x-ray diffraction, and Raman spectrum. These results are compared to those of as-made and 1 year aged samples. We report an initial increase in density followed by a decrease as a function of dose that contradicts the expected compositional dependence of molar volume of these glasses. This unusual behavior is explained based on microvoid formation and nanoscale phase-separation induced by the irradiation in these glasses. XRD, Raman, and EPR data provide supporting evidence, underscoring the importance of optimally- or overly-constrained structures for stability under aging or irradiation.

The Epsilon-metal ({var_epsilon}-metal) phase was selected in FY 2009 as a potential waste form to for immobilizing the noble metals found in the undissolved solids + aqueous stream, and the soluble Tc from ion-exchange process, each resulting from proposed aqueous reprocessing. {var_epsilon}-metal phase is observed in used nuclear fuel and the natural reactors of Oklobono in Gabon, where the long-term corrosion behavior was demonstrated. This makes {var_epsilon}-metal a very attractive waste form. Last fiscal year, {var_epsilon}-metal was successfully fabricated by combining the five-metals, Mo, Ru, Rh, Pd and Re (surrogate for Tc), into pellets followed by consolidation with an arc melter. The arc melter produced fully dense samples with the epsilon structure. However, some chemistry differences were observed in the microstructure that resulted in regions rich in Re and Mo, and others rich in Pd, while Ru and Rh remained fairly constant throughout. This year, thermal stability (air), and corrosion testing of the samples fabricated by arc melting were the main focus for experimental work. Thermal stability was measured with a differential scanning calorimeter - thermogravimetric analyzer, by both ramp heating as well as step heating. There is clear evidence during the ramp heating experiment of an exothermic event +more » a weight loss peak both beginning at {approx}700 C. Step heating showed an oxidation event at {approx}690 C with minimal weight gain that occurs just before the weight loss event at 700 C. The conclusion being that the e-metal begins to oxidize and then become volatile. These findings are useful for considering the effects of voloxidation process. Three different pellets were subjected to electrochemical testing to study the corrosion behavior of the epsilon-metal phase in various conditions, namely acidic, basic, saline, and inert. Test was done according to an interim procedure developed for the alloy metal waste form. First an open circuit potential was measured, followed by linear polarization sweeps. The linear polarization sweep range was the Tafel equation was fit to the linear polarization sweep data to determine the corrosion rate of each pellet in each test solution. The average calculated corrosion rates of the three pellets according to solution conditions were: -1.91 x 10{sup -4} mm/yr (0.001 M NaOH), -1.48 x 10{sup -3} mm/yr (0.01 M NaCl), -8.77 x 10{sup -4} mm/yr (0.001 M H{sub 2}SO{sub 4}), -2.09 x 10{sup -3} mm/yr (0.001 M NaOH + 0.01 M NaCl), and -1.54 x 10{sup -3} mm/yr (0.001 M H{sub 2}SO{sub 4} + 0.01 M NaCl). Three single-pass flow through (SPFT) test were conducted at a flow rate of 10 ml/day, at 90 C, and pH of 2.5, 7.0, and 9.0 for up to 322 days. Results of the tests indicate that dissolution rates were 5 x 10{sup -4} g m{sup 2} d{sup -1} at pH 9.0, 1.2 x 10{sup -4} g m{sup -2} d{sup -1} at pH 7.0, and 2 x 10{sup -4} g m{sup -2} d{sup -1} at pH 2.5. The sample used for the pH 7.0 SPFT test contains extra Re compared to samples used for the other two SPFT test, which came from a single pellet. The corrosion data measured this year indicate that the {var_epsilon}-metal phase is chemically durable. The two chemically different phases, but structurally the same, behave differently during dissolution according to the microstructure changes observed in both the electrochemical and in SPFT test. Characterization of the test specimens after testing suggests that the dissolution is complex and involves oxidative dissolution followed by precipitation of both oxide and metallic phases. These data suggest that the dissolution in the electrochemical and SPFT tests is different; a process that needs further investigation.« less

The purpose of this study was to find compositions that increase waste loading of high-alumina wastes beyond what is currently acceptable while avoiding crystallization of nepheline (NaAlSiO4) on slow cooling. Nepheline crystallization has been shown to have a large impact on the chemical durability of high-level waste glasses. It was hypothesized that there would be some composition regions where high-alumina would not result in nepheline crystal production, compositions not currently allowed by the nepheline discriminator. Optical basicity (OB) and the nepheline discriminator (ND) are two ways of describing a given complex glass composition. This report presents the theoretical and experimental basis for these models. They are being studied together in a quadrant system as metrics to explore nepheline crystallization and chemical durability as a function of waste glass composition. These metrics were calculated for glasses with existing data and also for theoretical glasses to explore nepheline formation in Quadrant IV (passes OB metric but fails ND metric), where glasses are presumed to have good chemical durability. Several of these compositions were chosen, and glasses were made to fill poorly represented regions in Quadrant IV. To evaluate nepheline formation and chemical durability of these glasses, quantitative X-ray diffraction (XRD) analysis and the Product Consistency Test were conducted. A large amount of quantitative XRD data is collected here, both from new glasses and from glasses of previous studies that had not previously performed quantitative XRD on the phase assemblage. Appendix A critically discusses a large dataset to be considered for future quantitative studies on nepheline formation in glass. Appendix B provides a theoretical justification for choice of the oxide coefficients used to compute the OB criterion for nepheline formation.

In FY2009, PNNL performed scoping studies to qualify two waste form candidates, tellurite (TeO2-based) glasses and halide minerals, for the electrochemical waste stream for further investigation. Both candidates showed promise with acceptable PCT release rates and effective incorporation of the 10% fission product waste stream. Both candidates received reprisal for FY2010 and were further investigated. At the beginning of FY2010, an in-depth literature review kicked off the tellurite glasses study. The review was aimed at ascertaining the state-of-the-art for chemical durability testing and mixed chloride incorporation for tellurite glasses. The literature review led the authors to 4 unique binary and 1 unique ternary systems for further investigation which include TeO2 plus the following: PbO, Al2O3-B2O3, WO3, P2O5, and ZnO. Each system was studied with and without a mixed chloride simulated electrochemical waste stream and the literature review provided the starting points for the baseline compositions as well as starting points for melting temperature, compatible crucible types, etc. The most promising glasses in each system were scaled up in production and were analyzed with the Product Consistency Test, a chemical durability test. Baseline and PCT glasses were analyzed to determine their state, i.e., amorphous, crystalline, phase separated, had undissolved material within the bulk, etc. Conclusions were made as well as the proposed direction for FY2011 plans. Sodalite was successfully synthesized by the sol-gel method. The vast majority of the dried sol-gel consisted of sodalite with small amounts of alumino-silicates and unreacted salt. Upon firing the powders made by sol-gel, the primary phase observed was sodalite with the addition of varying amounts of nepheline, carnegieite, lithium silicate, and lanthanide oxide. The amount of sodalite, nepheline, and carnegieite as well as the bulk density of the fired pellets varied with firing temperature, sol-gel process chemistry, and the amount of glass sintering aid added to the batch. As the firing temperature was increased from 850 C to 950 C, chloride volatility increased, the fraction of sodalite decreased, and the fractions nepheline and carnegieite increased. This indicates that the sodalite structure is not stable and begins to convert to nepheline and carnegieite under these conditions at 950 C. Density has opposite relationship with relation to firing temperature. The addition of a NBS-1, a glass sintering aid, had a positive effect on bulk density and increased the stability of the sodalite structure in a minimal way.

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan (Barnes and Voke 2006). The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Hanford Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP RPP WTP 467 (Fiskum et al. 2007), eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan. • Characterizing the homogenized sample groups. • Performing parametric leaching testing on each group for compounds of interest. • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on a filtration/leaching test performed using two of the eight waste composite samples. The sample groups examined in this report were the plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR). Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, thus requiring caustic leaching. WTP RPT 167 (Snow et al. 2008) describes the homogenization, characterization, and parametric leaching activities before benchtop filtration/leaching testing of these two waste groups. Characterization and initial parametric data in that report were used to plan a single filtration/leaching test using a blend of both wastes. The test focused on filtration testing of the waste and caustic leaching for aluminum, in the form of gibbsite, and its impact on filtration. The initial sample was diluted with a liquid simulant to simulate the receiving concentration of retrieved tank waste into the UFP2 vessel (< 10 wt% undissolved solids). Filtration testing was performed on the dilute waste sample and dewatered to a higher solids concentration. Filtration testing was then performed on the concentrated slurry. Afterwards, the slurry was caustic leached to remove aluminum present in the undissolved solid present in the waste. The leach was planned to simulate leaching conditions in the UFP2 vessel. During the leach, slurry supernate samples were collected to measure the dissolution rate of aluminum in the waste. After the slurry cooled down from the elevated leach temperature, the leach liquor was dewatered from the solids. The remaining slurry was rinsed and dewatered with caustic solutions to remove a majority of the dissolved aluminum from the leached slurry. The concentration of sodium hydroxide in the rinse solutions was high enough to maintain the solubility of the aluminum in the dewatered rinse solutions after dilution of the slurry supernate. Filtration tests were performed on the final slurry to compare to filtration performance before and after caustic leaching.

This is the final report in a series of eight reports defining characterization, leach, and filtration testing of a wide variety of Hanford tank waste sludges. The information generated from this series is intended to supplement the Waste Treatment and Immobilization Plant (WTP) project understanding of actual waste behaviors associated with tank waste sludge processing through the pretreatment portion of the WTP. The work described in this report presents information on a high-iron waste form, specifically the ferrocyanide tank waste sludge. Iron hydroxide has been shown to pose technical challenges during filtration processing; the ferrocyanide tank waste sludge represented a good source of the high-iron matrix to test the filtration processing.

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.(a) The testing program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. The actual wastetesting program included homogenizing the samples by group, characterizing the solids and aqueous phases, and performing parametric leaching tests. Two of the eight defined groups—plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR)—are the subjects of this report. Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, requiring caustic leaching. Characterization of the composite Group 3 and Group 4 waste samples confirmed them to be high in gibbsite. The focus of the Group 3 and 4 testing was on determining the behavior of gibbsite during caustic leaching. The waste-type definition, archived sample conditions, homogenization activities, characterization (physical, chemical, radioisotope, and crystal habit), and caustic leaching behavior as functions of time, temperature, and hydroxide concentration are discussed in this report. Testing was conducted according to TP-RPP-WTP-467.

This report presents the results of preparation and characterization of chemical plugs based on selected Hanford Site waste simulants. Included are the results of chemical plug bench testing conducted in support of the M1/M6 Flow Loop Chemical Plugging/Unplugging Test (TP-RPP-WTP-495 Rev A). These results support the proposed plug simulants for the chemical plugging/ unplugging tests. Based on the available simulant data, a set of simulants was identified that would likely result in chemical plugs. The three types of chemical plugs that were generated and tested in this task consisted of: 1. Aluminum hydroxide (NAH), 2. Sodium aluminosilicate (NAS), and 3. Sodium aluminum phosphate (NAP). While both solvents, namely 2 molar (2 M) nitric acid (HNO3) and 2 M sodium hydroxide (NaOH) at 60°C, used in these tests were effective in dissolving the chemical plugs, the 2 M nitric acid was significantly more effective in dissolving the NAH and NAS plugs. The caustic was only slightly more effecting at dissolving the NAP plug. In the bench-scale dissolution tests, hot (60°C) 2 M nitric acid was the most effective solvent in that it completely dissolved both NAH and NAS chemical plugs much faster (1.5 – 2 x) than 2 M sodium hydroxide.more » So unless there are operational benefits for the use of caustic verses nitric acid, 2 M nitric acid heated to 60°C C should be the solvent of choice for dissolving these chemical plugs. Flow-loop testing was planned to identify a combination of parameters such as pressure, flush solution, composition, and temperature that would effectively dissolve and flush each type of chemical plug from preformed chemical plugs in 3-inch-diameter and 4-feet-long pipe sections. However, based on a review of the results of the bench-top tests and technical discussions, the Waste Treatment Plant (WTP) Research and Technology (R&T), Engineering and Mechanical Systems (EMS), and Operations concluded that flow-loop testing of the chemically plugged pipe sections would not provide any additional information or useful data. The decision was communicated through a Sub Contract Change Notice (SCN-070) that included a revised scope as follows: • Photographing the chemical plugs in the pipes before extrusion to compare the morphology of aged gels with that of fresh gels. • Setting up an extrusion apparatus and extruding the chemical plugs. • Documenting the qualitative observations on the efforts to remove the chemical plug materials from the pipe sections. • Performing X-ray diffraction (XRD) analysis of extruded gel samples to detect any crystallization of gel during storage. • Disposing of the extruded gel as a waste. • Documenting the analytical results in a test report. There were no significant morphological differences between the fresh and aged plugs except for an overgrowth of small transparent crystals on the surface of the aged NAS gel plug. An initial pressure of 15 KPa for the NAS plug and from ~2 to 6 KPa for the NAH plug. Following extrusion, the NAP plug sections were thixotropic. The bulk of all the aged gel plugs consisted of amorphous material with nitratine constituting the crystalline phase. A separate question about the whether the current in-tank waste conditions will bound the future multi-tank blended feed conditions for the Waste Treatment Plant is outside the scope of this study.« less

Terahertz transmission of a chalcogenide family of glasses is reported. The glasses were processed using established methods for non-oxide glasses. Transmission through the samples was measured using a THz spectrometer. The transmission and optical properties of the glasses are summarized. The results show promise of these glasses for application as THz windows.

For about four decades, radioactive wastes have been collected and calcined from nuclear fuels reprocessing at the Idaho Nuclear Technology and Engineering Center (INTEC), formerly Idaho Chemical Processing Plant (ICPP). Over this time span, secondary radioactive wastes have also been collected and stored as liquid from decontamination, laboratory activities, and fuel-storage activities. These liquid wastes are collectively called sodium-bearing wastes (SBW). About 5.7 million liters of these wastes are temporarily stored in stainless steel tanks at the Idaho National Engineering and Environmental Laboratory (INEEL). Vitrification is being considered as an immobilization step for SBW with a number of treatment and disposal options. A systematic study was undertaken to develop a glass composition to demonstrate direct vitrification of INEEL's SBW. The objectives of this study were to show the feasibility of SBW vitrification, not a development of an optimum formulation. The waste composition is relatively high in sodium, aluminum, and sulfur. A specific composition and glass property restrictions, discussed in Section 2, were used as a basis for the development. Calculations based on first-order expansions of selected glass properties in composition and some general tenets of glass chemistry led to an additive (fit) composition (68.69 mass % SiO{sub 2}, 14.26 mass% B{sub 2}O{sub 3}, 11.31 mass% Fe{sub 2}O{sub 3}, 3.08 mass% TiO{sub 2}, and 2.67 mass % Li{sub 2}O) that meets all property restrictions when melted with 35 mass % of SBW on an oxide basis, The glass was prepared using oxides, carbonates, and boric acid and tested to confirm the acceptability of its properties. Glass was then made using waste simulant at three facilities, and limited testing was performed to test and optimize processing-related properties and confirm results of glass property testing. The measured glass properties are given in Section 4. The viscosity at 1150 C, 5 Pa{center_dot}s, is nearly ideal for waste-glass processing in a standard liquid-fed joule-heated melter. The normalized elemental releases by 7-day PCT are all well below 1 g/m{sup 2}, which is a very conservative set point used in this study. The T{sub L}, ignoring sulfate formation, is less than the 1050 C limit. Based on these observations and the reasonable waste loading of 35 mass 0/0, the SBW glass was a prime candidate for further testing. Sulfate salt segregation was observed in all test melts formed from oxidized carbonate precursors. Melts fabricated using SBW simulants suggest that the sulfate-salt segregation seen in oxide and carbonate melts was much less of a problem. The cause for the difference is likely H{sub 2}SO{sub 4} fuming during the boil-down stage of wet-slurry processing. Additionally, some crucible tests with SBW simulant were conducted at higher temperatures (1250 C), which could increase the volatility of sulfate salts. The fate of sulfate during the melting process is still uncertain and should be the topic of future studies. The properties of the simulant glass confirmed those of the oxide and carbonate glass. Corrosion tests on Inconel 690 electrodes and K-3 refractory blocks conducted at INEEL suggest that the glass is not excessively corrosive. Based on the results of this study, the authors recommend that a glass made of 35% SBW simulant (on a mass oxide and halide basis) and 65% of the additive mix (either filled or raw chemical) be used in demonstrating the direct vitrification of INEEL SBW. It is further recommended that a study be conducted to determine the fate of sulfate during glass processing and the tolerance of the chosen melter technology to sulfate salt segregation and corrosivity of the melt.