Effect of MoO3, Nd2O3, and RuO2 on the crystallization of soda–lime aluminoborosilicate glasses

Chouard, Nolwenn; Caurant, Daniel; Majérus, Odile; Dussossoy, Jean-Luc; Климин, С. А.; Pytalev, D. S.; Baddour‐Hadjean, R.; Pereira-Ramos, J.P.

doi:10.1007/s10853-014-8581-9

Cited by 46 publications

(56 citation statements)

References 72 publications

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“…Series Vx-M2: The raw materials of SiO 2 , CaCO 3 , Al 2 O 3 , H 3 BO 3 , Na 2 CO 3 , MoO 3 , and V 2 O 5 with purity higher than 99 wt% were mixed by ball-milling for 3 h. Compositions of batches were given in table 1. The obtained samples were dissolved in nitric acid and the solution was analyzed for Si, B, Ca, Al, Na, Mo and V by inductively coupled plasma-atomic emission spectroscopy [21,30]. The obtained results showed good agreement between experimental and nominal glass compositions.…”

Section: Methodsmentioning

confidence: 83%

Effect of V₂O₅ on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Lian

Zhang

et al. 2020

Mater. Res. Express

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AbstactThe effect of V 2 O 5 addition on molybdates crystallization tendency, glass structure and chemical durability of aluminoborosilicate glass belonging to SiO 2 -B 2 O 3 -CaO-Na 2 O-Al 2 O 3 -MoO 3 system has been studied. The results confirm that V 2 O 5 addition can effectively suppress the crystallization tendency of powellite and enhance the molybdenum solubility in the glass. The MoO 3 solubility limit is found to be 2.8 mol% in the V 2 O 5 -containing aluminoborosilicate glass. Raman results reveal that V 2 O 5 addition seems to modify the local structural environment of isolated MoO 4 units and increase their chemical disorder in the glass, which is favored for molybdenum incorporation in the glass. The molar volume and glass transition temperature of samples are found to depend on V 2 O 5 content. Product consistency test (PCT) results show that the normalized leaching rates of the V 2 O 5 -containing aluminoborosilicate glass maintain at a fairly low level compared with standard borosilicate glassy waste form.

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Section: Methodsmentioning

confidence: 83%

Effect of V₂O₅ on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Lian

Zhang

et al. 2020

Mater. Res. Express

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“…In some samples there are additional bands between~910-930 cm − 1 . The peak at~910 cm − 1 is associated with symmetric stretching vibrational modes of (MoO 4 ) 2 − tetrahedral units in amorphous systems [47], while a broader peak~923 cm − 1 is assigned to symmetric SieO stretching of chains with non-bridging oxygens [39,40]. In contrast to the broad bands of the amorphous phase indicating structural disorder, the crystalline phase powellite with C 4h point symmetry exhibits several sharp peaks.…”

Section: Pristine Conditionsmentioning

confidence: 97%

Impacts of composition and beta irradiation on phase separation in multiphase amorphous calcium borosilicates

Patel

Boizot

Facq

et al. 2017

Journal of Non-Crystalline Solids

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A B S T R A C TBorosilicate glasses for nuclear waste applications are limited in waste loading by the precipitation of watersoluble molybdates. In order to increase storage efficiency, new compositions are sought out that trap molybdenum in a water-durable CaMoO 4 crystalline phase. Factors affecting CaMoO 4 combination and glass-inglass phase separation in calcium borosilicate systems as a function of changing [MoO 3 ] and [B 2 O 3 ] are examined in this study in order to understand how competition for charge balancers affects phase separation. It further examines the influence of radiation damage on structural modifications using 0.77 to 1.34 GGy of 2.5 MeV electron radiation that replicates inelastic collisions predicted to occur over long-term storage. The resulting microstructure of separated phases and the defect structure were analyzed using electron microscopy, XRD, Raman and EPR spectroscopy prior to and post irradiation. Synthesized calcium borosilicates are observed to form an unusual heterogeneous microstructure composed of three embedded amorphous phases with a solubility limit~2.5 mol% MoO 3. Increasing [B 2 O 3 ] increased the areas of immiscibility and order of (MoO 4 ) 2 − anions, while increasing [MoO 3 ] increased both the phase separation and crystallization temperature resulting in phases closer to metastable equilibrium, and initiated clustered crystallization for [MoO 3 ] > 2.5 mol%. β-irradiation was found to have favorable properties in amorphous systems by creating structural disorder and defect assisted ion migration that thus prevented crystallization. It also increased reticulation in the borosilicate network through 6-membered boroxyl ring and Si ring cleavage to form smaller rings and isolated units. This occurred alongside an increased reduction of Mo 6 + with dose that can be correlated to molybdenum solubility.In compositions with existing CaMoO 4 crystallites, radiation caused a scattering effect, though the crystal content remained unchanged. Therefore β-irradiation can preferentially prevent crystallization in calcium borosilicates for [MoO 3 ] < 2.5 mol%, but has a smaller impact on systems with existing CaMoO 4 crystallites.

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“…The importance of RE for the stabilization of Mo in the glass matrix has been well-described, along with the effect of removing RE from the glass by crystallization of oxyapatite. [13][14][15][16][17] At the same time, when Mo does precipitate in a crystalline phase, it is desirable to avoid the formation of water-soluble alkali molybdates above the Mo solubility limit, by controlling the distribution of Na and Cs, to force the more chemically durable calcium molybdate (powellite) phase to form preferentially. [18][19][20][21][22] A key barrier to maturation and exploitation of glass-ceramic technologies for nuclear waste forms is the gap in fundamental understanding of the molecular-scale mechanisms of phase separation and crystallization leading to the development of the desired phase assemblage and microstructure, ultimately determining long-term product performance.…”

mentioning

confidence: 99%

Crystallization study of rare earth and molybdenum containing nuclear waste glass ceramics

et al. 2019

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A glass‐ceramic waste form is being developed for immobilization of waste streams of alkali (A), alkaline‐earth (AE), rare earth (RE), and transition metals generated by transuranic extraction for reprocessing of used nuclear fuel. Benefits over an alkali borosilicate waste form are realized by the partitioning of the fission product fraction insoluble in glass into a suite of chemically durable crystalline phases through controlled cooling, including (AE,A,RE)MoO4 (powellite) and (RE,A,AE)10Si6O26 (oxyapatite). In this study, a simplified 8‐oxide system (SiO2‐Nd2O3‐CaO‐Na2O‐B2O3‐Al2O3‐MoO3‐ZrO2) was melted, then soaked at various temperatures from 1450 to 1150°C, and subsequently quenched, in order to obtain snapshots into the phase distribution at these temperatures. For these samples, small angle X‐ray and neutron scattering, quantitative X‐ray diffraction, electron microscopy, 23Na nuclear magnetic resonance, Nd3+ visible absorption, and temperature‐dependent viscosity were characterized. In this composition, soak temperatures of ≲1250°C were necessary to nucleate calcium molybdate (~10‐20 nm in diameter). Further cooling produced oxyapatite and total crystallization increased with lower soak temperatures. Both Na and Nd entered the crystalline phases with lower‐temperature soak conditions. Slow cooling or long isothermal treatments at ~975°C produced significantly higher crystal fractions.

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Effect of MoO3, Nd2O3, and RuO2 on the crystallization of soda–lime aluminoborosilicate glasses

Cited by 46 publications

References 72 publications

Effect of V₂O₅ on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Effect of V₂O₅ on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Impacts of composition and beta irradiation on phase separation in multiphase amorphous calcium borosilicates

Crystallization study of rare earth and molybdenum containing nuclear waste glass ceramics

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Effect of MoO3, Nd2O3, and RuO2 on the crystallization of soda–lime aluminoborosilicate glasses

Cited by 46 publications

References 72 publications

Effect of V2O5 on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Effect of V2O5 on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Impacts of composition and beta irradiation on phase separation in multiphase amorphous calcium borosilicates

Crystallization study of rare earth and molybdenum containing nuclear waste glass ceramics

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Effect of V₂O₅ on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass

Effect of V₂O₅ on crystallization tendency and chemical durability of Mo-bearing aluminoborosilicate glass