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At least 73 records · Page 4

Corrosion Tests with Developmental Iron Phosphate Glass Waste Forms

Corrosion tests are in progress to assess the dissolution behavior of developmental iron phosphate waste forms for salt waste from electrochemical separation operations. Specimens cut from materials made at PNNL to represent a range of waste salt loadings in prototype composition DPF-5 and a range of iron oxide loadings in prototype composition DPF-3 were subjected to modified ASTM C1308 tests to assess the compositional effects on the relative durabilities and retention of immobilized salt cations. The materials were composed of different amounts of glass and crystalline phases. The test results show both the intrinsic durability of the material and the salt cation retention decrease as the total amount of salt cations added to the material is increased. The results of ASTM C1220 and ASTM C1285 tests conducted with materials DPF5-280 and DPF5-336, which contained about 28% and 34% salt cations (on a mass oxide basis) and bounded the durabilities of the other materials, show that solution feedback does not attenuate the dissolution rate. This suggests the degradation of iron phosphate waste forms can be modelled by using a constant rate that probably depends on the composition and volume fraction of the glass phase. A reference composition should be formulated and used in tests to determine those dependencies. The ASTM C1220 and ASTM C1285 tests with DPF5-280 and DPF5-336 remain in progress to corrode the specimens enough to distinguish the relative extents of glass and crystalline phase corrosion by microscopic examinations. Those results are expected to provide insights regarding the relative dissolution rates of crystalline and glass phases and impact on durability to inform the formulation of the reference composition.

Ebert, W. L.↗

Spectroscopic and dielectric response of zinc bismuth phosphate glasses as a function of chromium content

Graphical abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. The optical absorption spectra of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. - Highlights: • ZnF{sub 2}–Bi{sub 2}O{sub 3}–P{sub 2}O{sub 5}:Cr{sub 2}O{sub 3} glasses were prepared by melt quenching and annealing. • Spectroscopic and dielectric properties of chromium ions were investigated. • ESR and optical absorption spectra indicate the co-existence of Cr{sup 6+} ions with Cr{sup 5+} ions and Cr{sup 3+} ions. • Cr{sup 3+} ions act as modifiers and influence the semiconducting nature of the glass system. - Abstract: 20ZnF{sub 2}–(20 − x)Bi{sub 2}O{sub 3}–60P{sub 2}O{sub 5}:xCr{sub 2}O{sub 3} (0 ≤ x ≤2 mol%) glasses are prepared by melt quenching technique. Amorphous nature of these samples is confirmed by X-ray diffraction (XRD) analysis. FTIR study reveals bands due to CrO{sub 6}(o{sub d}) and CrO{sub 4}{sup 2−}(T{sub d}) units along with conventional phosphate groups. The optical absorption and ESR studies of present glasses are analyzed as a function of chromium content. The absorption bands are assigned to {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 1g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 4}T{sub 2g}(F), {sup 4}A{sub 2g}(F) ⟶ {sup 2}T{sub 1g}(G) and {sup 4}A{sub 2g}(F) ⟶ {sup 2}E{sub g}(G) transitions of Cr{sup 3+} ions. The highest concentration of Cr{sup 3+} ions (in octahedral sites, with network modifying positions) is found in the sample with 2.0 mol% of Cr{sub 2}O{sub 3}. The analysis of dielectric properties indicates a gradual increase in semiconducting character with increase in the concentration of Cr{sub 2}O{sub 3} from 0.2 to 2.0 mol%. The studies on dielectric breakdown strength identify the highest insulating strength for lowest mol% of Cr{sub 2}O{sub 3} in the present samples.

36 MATERIALS SCIENCE↗

EPR and magnetic susceptibility investigation of iron-zinc-phosphate glass ceramics

(Fe{sub 2}O{sub 3}){sub x}⋅(P{sub 2}O{sub 5}){sub 40}⋅(ZnO){sub 60−x} glass ceramics containing different concentrations of Fe{sub 2}O{sub 3} ranging from 1 to 20 mol% were obtained by heat treatment of glass samples at 650 °C for 2 h. The structural and magnetic properties of these glass ceramics were investigated by means of electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. The EPR spectra of the studied samples revealed absorptions centered at g ≈ 2.0 and 4.3. The compositional variations of the intensity and line width of these absorption lines was interpreted in terms of the variation in Fe{sup 3+} and Fe{sup 2+} ions concentration in the glass ceramics as well as the interaction between the iron ions. The magnetic susceptibility data evidenced the presence of both Fe{sup 3+} and Fe{sup 2+} ions, with their relative content depending on the Fe{sub 2}O{sub 3} concentration. Dipolar and superexchange interactions involving iron ions were revealed depending on the iron content of the sample.

36 MATERIALS SCIENCE↗

AI/ML-assisted Design of Phosphate Glass and Ceramic Nuclear Waste Forms

Borosilicate glass is the widely accepted waste form for immobilization of high and medium level nuclear wastes. Advances in nuclear energies and new reactor designs require the development of new waste forms. For example, wastes from molten salt reactors and reprocessing of nuclear fuels lead to salt-based wastes that are difficult to be immobilized by conventional borosilicate glasses due to limited solubility and waste loading. In designing new waste forms, machine learning (ML) and artificial intelligence (AI) based approaches are much needed and can be beneficial in enabling a more efficient design in large parameter spaces as compared to traditional Edisonian trial-and-error approaches. Here, we report in this paper the rationale and latest progress of our ML/AI-based design of phosphate-based waste forms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synthesis and characterization of novel phosphate glass matrix nanocomposites containing polyhedral oligomeric silsesquioxane with improved properties

The preparation and characterization of novel tin fluorophosphate glass (Pglass) matrix nanocomposite materials containing nanoscale trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) prepared via classical glass synthesis was investigated here to accelerate efforts to develop novel hybrid Pglass/POSS nanocomposites with enhanced benefits in suitable diverse applications. The glass transition temperatures (T g ) of the obtained nanocomposites ranged from 121.6° to 147.6 °C to an extent that depends on the nano-POSS concentrations (≤ 10 wt% POSS) in the nanocomposites. The obtained scanning electron microscopy with energy-dispersive x-ray spectroscopy and atomic force microscopy results confirmed the homogeneous molecular level dispersion of the POSS cages in the continuous Pglass matrix of the nanocomposite. Chemical reaction (or bonding) between the constituents of the nanocomposites was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance spectroscopy. The rheological (storage and loss modulus) and nanomechanical (elastic modulus) properties of the nanocomposites significantly improved with increasing nano-POSS concentrations up to 10 wt% POSS. The molecular dispersion of the POSS and its strong physicochemical interaction with the continuous Pglass matrix can be tailored to satisfy requirements of a number of optomechanical applications where the pure glass is not useable.

36 MATERIALS SCIENCE↗

Phosphate glass matrix composites incorporating trisilanol phenyl polyhedral oligomeric silsesquioxane prepared by viscous flow sintering method with enhanced benefits

The effect of mixing and sintering processes to prepare tin fluorophosphate glass (Pglass) matrix composites incorporating trisilanol phenyl polyhedral oligomeric silsesquioxane (TSP-POSS) was investigated by comparing manual and suspension mixing, one-step and stepwise sintering processes to explore the structure dynamics and physical properties in the composites as a function of the different process conditions used. Energy Dispersive X-ray analysis confirmed optimal homogeneous dispersion of the TSP-POSS molecules in the composites prepared by the suspension method. The observed increase of glass transition temperature and the reduction of non-bridging bonds in the composites are believed to be the reason for the effective dispersion of TSP-POSS molecules in the composites. The chemical reaction between the TSP-POSS and Pglass was strongly influenced by the mixing/dispersion and sintering processes investigated. 13 C cross polarized magic angle spinning (CP MAS) solid state nuclear magnetic resonance (NMR) spectroscopy confirmed the chemical stability of the TSP-POSS during the sintering process at elevated temperatures. In addition, a chemical reaction between the TSP-POSS and Pglass was evidenced by 29 Si CP MAS NMR analysis. Here, this study will provide a better fundamental understanding of the effective dispersion mechanism of the TSP-POSS molecules in the Pglass matrix that will facilitate tailoring the physicochemical properties of the composites with addition of various small concentrations of TSP-POSS for a number of applications where the pure Pglass is not applicable due to the intrinsic properties of the Pglass.

36 MATERIALS SCIENCE↗

Analyses of iron phosphate glasses for dehalogenated salt waste

Specimens cut from series of glasses made at PNNL to represent a range of salt loadings in prototype composition DPF-5 and a range of iron oxide loadings in prototype composition DPF-3 were subjected to modified ASTM C1308 tests to assess the relative durabilities and retention of salt cations. Test results show both the intrinsic durability and salt cation retention decrease as the total amount of salt cations is increased, but waste forms made with up to 34 mass % salt waste loadings on a salt-cation basis are more durable than glass-bonded sodalite waste forms made with optimal salt waste loadings (about 6% on a salt-cation basis). Other tests are in progress to assess the effect of solution feedback on the long-term durability of these materials.

Ebert, W. L.↗

Compositional effects on the chemical durabilities of aluminophosphate glasses: A review

Phosphate glasses have a range of applications including as hosts for immobilizing radioactive wastes. Studies have shown that addition of iron and/or aluminum oxides can drastically improve the chemical durability of phosphate glasses where the accurate measurement of chemical durability is one of the most important factors for determining the long-term viability of a given waste form. However, due to inconsistencies with the experimental methods used to generate chemical durability data, comparing and interpreting such data is a tedious task. These variables include the temperature of the test, the specimen form (e.g., coupon, particles), the pressure of the test (e.g., atmospheric pressure, elevated pressure in an autoclave), the exposure time, the exposure medium, and how the loss is documented (e.g., total mass lost, normalized elemental release). This review paper summarizes a large collection of chemical durability tests on aluminophosphate glasses in various studies. In addition, the effects of different oxides on the properties of phosphate glasses are summarized.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗