Alpha-Recoil Effect on the Dissolution of Betafite: Rapid Natural Annealing of Radiation Damage Within A Metamict Phase

1985 ◽  
Vol 50 ◽  
Author(s):  
Y. Eyal ◽  
G. R. Lumpkin ◽  
R. C. Ewing
Keyword(s):  
Dissolution Rate ◽  
Chemical Reactivity ◽  
Pyrochlore Structure ◽  
Dissolution Behavior ◽  
Synthetic Analogue ◽  
Recoil Effect ◽  
Waste Forms ◽  
Pyrochlore Group ◽  
Aperiodic Structure ◽  
Rapid Dissolution

AbstractBetafite, a radioactive mineral, is the Ti-rich member of the pyrochlore group, A1–2B2X6Y0–1, (Fd3m, Z = 8), where A = Ca, Na, U, Th, REE (rare earth elements), Y, Ba, Sr, Bi, Pb; B = Nb, Ti, Ta, Zr, Sn, Fe: X = oxygen; Y = 0, OH and F. The pyrochlore structure (or structural derivatives, e.g. zirconolite in SYNROC) is a common constituent of polyphase, crystalline radioactive waste forms. Naturally occurring minerals with this structure often occur in the metamict state. Therefore, a principal concern is the effect of alpha-recoil damage on the structure and dissolution behavior of synthetic, analogue, waste-form phases which contain actinides.We describe the dissolution behavior of 238U, 234U, 232Th, 230Th and 228Th in betafite during leaching in a bicarbonate-carbonate solution. Results indicate enhanced leaching of recently produced alpha-recoil damage as evidenced by the more rapid dissolution rate of 228Th relative to 232Th and 230Th, and only slightly enhanced leaching of older damage as evidenced by a small increase in the dissolution rate of 234U relative to 238U. These experiments demonstrate that individual alpha-recoil tracks are preserved for some time as disordered regions of higher chemical reactivity in already fully-damaged, aperiodic structures. We estimate an annealing time for the alpha-recoil tracks of 2,000 ± 1,300 yr in the metastable, aperiodic structure. Similar alpha-recoil tracks should be formed and annealed in other aperiodic nuclear waste forms, such as borosilicate glass.

An Investigation of Metamict And Annealed Natural Pyrochlores by XRAY Absorption Spectroscopy

1984 ◽  
Vol 44 ◽  
Author(s):  
R. B. Greegor ◽  
F. W. Lytle ◽  
B. C. Chakoumakos ◽  
G. R. Lumpkin ◽  
R. C. Ewing
Keyword(s):  
Absorption Spectroscopy ◽  
Radiation Effects ◽  
Full Range ◽  
Pyrochlore Structure ◽  
Structure Type ◽  
Slight Reduction ◽  
Coordination Geometry ◽  
Waste Forms ◽  
Naturally Occurring ◽  
Pyrochlore Group

AbstractThe pyrochlore structure type, A1−2 B2 O6 Y0−1, is a common phase in polycrystalline waste forms. A principal concern has been the effect of alpharecoil events on the longterm stability of these phases. Naturally occurring minerals of the pyrochlore group provide an example of the full range of radiation effects from fully crystalline to xray diffraction amorphous (the metamict state). Xray absorption spectroscopy is used to investigate the coordination geometry of Tisites in metamict and annealed (1,000°C) pyrochlores. The principal effects in the fullydamaged material (∼4026 alpha events/m3) compared to annealed samples include an increase in the asymmetry of the Tisite and a slight reduction in bond length and coordination number.

scholarly journals The fate of Si and Fe while nuclear glass alters with steel and clay

2021 ◽  
Vol 5 (1) ◽  
Author(s):  
C. Carriere ◽  
P. Dillmann ◽  
S. Gin ◽  
D. Neff ◽  
L. Gentaz ◽  
...  
Keyword(s):  
Dissolution Rate ◽  
Protective Layer ◽  
Glass Dissolution ◽  
A Value ◽  
Waste Forms ◽  
Controlling Mechanism ◽  
Geological Repository ◽  
The Mean ◽  
High Level ◽  
Initial Dissolution Rate

AbstractThe French concept developed to dispose high-level radioactive waste in geological repository relies on glassy waste forms, isolated from the claystone host rock by steel containers. Understanding interactions between glass and surrounding materials is key for assessing the performance of a such system. Here, isotopically tagged SON68 glass, steel and claystone were studied through an integrated mockup conducted at 50 °C for 2.5 years. Post-mortem analyses were performed from nanometric to millimetric scales using TEM, STXM, ToF-SIMS and SEM techniques. The glass alteration layer consisted of a crystallized Fe-rich smectite mineral, close to nontronite, supporting a dissolution/reprecipitation controlling mechanism for glass alteration. The mean glass dissolution rate ranged between 1.6 × 10−2 g m−2 d−1 to 3.0 × 10−2 g m−2 d−1, a value only 3–5 times lower than the initial dissolution rate. Thermodynamic calculations highlighted a competition between nontronite and protective gel, explaining why in the present conditions the formation of a protective layer is prevented.

Host Phases for Actinide Elements in the Metallic Waste Form

2002 ◽  
Vol 757 ◽  
Author(s):  
D. E. Janney
Keyword(s):  
Stainless Steel ◽  
Electron Microscope ◽  
Electron Diffraction ◽  
Transmission Electron Microscope ◽  
Waste Form ◽  
Dissolution Behavior ◽  
Release Rates ◽  
Waste Forms ◽  
Transmission Electron ◽  
Simulated Waste

ABSTRACTArgonne National Laboratory has developed an electrometallurgical process for conditioning spent sodium-bonded metallic reactor fuel prior to disposal. A waste stream from this process consists of stainless steel cladding hulls that contain undissolved metal fission products such as Tc, Ru, Rh, Pd, and Ag; a small amount of undissolved actinides (U, Np, Pu) also remains with the hulls. These wastes will be immobilized in a waste form whose baseline composition is stainless steel alloyed with 15 wt% Zr (SS-15Zr). Scanning electron microscope (SEM) observations of simulated metal waste forms (SS-15Zr with up to 11 wt% actinides) show eutectic intergrowths of Fe-Zr-Cr-Ni intermetallic phases with steels. The actinide elements are almost entirely in the intermetallics, where they occur in concentrations ranging from 1–20 at%. Neutron- and electron-diffraction studies of the simulated waste forms show materials with structures similar to those of Fe2Zr and Fe23Zr6.Dissolution experiments on simulated waste forms show that normalized release rates of U, Np, and Pu differ from each other and from release rates of other elements in the sample, and that release rates for U exceed those for any other element (including Fe). This paper uses transmission electron microscope (TEM) observations and results from energy-dispersive X-ray spectroscopy (EDX) and selected-area electron-diffraction (SAED) to characterize relationships between structural and chemical data and understand possible reasons for the observed dissolution behavior.Transmission electron microscope observations of simulated waste form samples with compositions SS-15Zr-2Np, SS-15Zr-5U, SS-15Zr-11U-0.6Rh-0.3Tc-0.2Pd, and SS-15Zr-10Pu suggest that the major actinide-bearing phase in all of the samples has a structure similar to that of the C15 (cubic, MgCu2-type) polymorph of Fe2Zr, and that materials with this structure exhibit significant variability in chemical compositions. Material whose structure is similar to that of the C36 (dihexagonal, MgNi2-type) polymorph of Fe2Zr was also observed, and it exhibits less chemical variability than that displayed by material with the C15 structure. The TEM data also demonstrate a range of actinide concentrations in materials with the Fe23Zr6 (cubic, Mn23Th6-type) structure.Microstructures similar to those produced during experimental deformation of Fe-10 at% Zr alloys were observed in intermetallic materials in all of the simulated waste form samples. Stacking faults and associated dislocations are common in samples with U, but rarely observed in those with Np and Pu, while twins occurred in all samples. The observed differences in dissolution behavior between samples with different actinides may be related to increased defect-assisted dissolution in samples with U.

Development of the Synthetic Rock Technique for the Immobilization of Iodine: Kinetics of the Alumina Matrix Dissolution under High Alkaline Conditions

2012 ◽  
Vol 1518 ◽  
pp. 79-84 ◽  
Author(s):  
Hideaki Miyakawa ◽  
Tomofumi Sakuragi ◽  
Hitoshi Owada ◽  
Osamu Kato ◽  
Kaoru Masuda
Keyword(s):  
Dissolution Rate ◽  
Rate Constant ◽  
Base Material ◽  
Dissolution Behavior ◽  
Treatment Technique ◽  
Release Behavior ◽  
Alumina Matrix ◽  
Synthetic Rock ◽  
The Matrix ◽  
Iodine Release

ABSTRACTIodine filters expended after nuclear fuel reprocessing contain radioactive iodine (I-129), almost all of which exists as silver iodide (AgI). The synthetic rock technique is a solidification treatment technique using hot isostatic press (HIP), in which the alumina adsorbent base material is synthesized to form a dense solidified material (synthetic rock), and I-129 is physically confined in the form of AgI in the alumina matrix. Thus, it is necessary to understand the matrix dissolution behavior to evaluate the iodine release behavior.Experiments involving the dissolution of the matrix were carried out under various temperatures (35–70 °C) and pH values (10–12.5) that reflect the disposal conditions. The results of the experiments showed that the dissolution rate of Al visibly increases with temperature and pH. The dissolution rate constant was calculated from the initial data assuming the dissolution of the matrix as a primary reaction. The logarithmic rate constant showed a good linear correlation with the pH and the reciprocal of temperature. The 27Al-NMR analysis of the solutions of the dissolved matrix showed that the major chemical species present in the solutions was Al(OH)4-. This indicated that the dissolution of the matrix can be described by the following equation: Al2O3 + 2OH- + 3H2O → 2Al(OH)4-. Subsequently, the empirical equation of the rate of dissolution of the matrix as a function of the temperature and pH was derived. It will be used to evaluate the iodine release behavior from the synthetic rock.

Improving Biomaterials from a Cellular Point of View

2006 ◽  
Vol 925 ◽  
Author(s):  
Venu Gopal Varanasi ◽  
T. Vallortigara ◽  
P. M. Loomer ◽  
E. Saiz ◽  
A. P. Tomsia ◽  
...  
Keyword(s):  
Dissolution Rate ◽  
Cell Number ◽  
Point Of View ◽  
Dissolution Behavior ◽  
Ti Alloy ◽  
Bioactive Glasses ◽  
Culture Studies ◽  
Cell Numbers ◽  
Number Increase

ABSTRACTBioactive glasses (6P55) used for coating Ti/Ti-alloy were tested for their in vitro behavior in a comparative study with commercial Bioglass™ (45S5) and commercial Ti alloy (Ti6Al4V). In vitro testing included pH and dissolution rate determination in simulated body fluid (SBF) along with in vitro cyto compatibility testing. It was seen in this work that 6P55 and 45S5 had similar dissolution behavior, demonstrating t½ dependence and maximum pH of approximately 8.1 after 10 days of immersion. This pH was reduce by 0.2 0.4 pH units when the in vitro V:A ratio was increased from 1 to 3. The dissolution rate of these glasses approached 0 after additional immersion tests after 15 days and the pH stablilized at less than 7.5. Cell culture studies showed that both glasses behaved in similar fashion after 16 hours in culture. Both glasses had an increase in cell numbers of close to 200-250%, whereas Ti6Al4V had a less pronounced cell number increase (∼ 180%)

Dissolution behavior of chemically amplified resist for advanced mask- and NIL mold-making as studied by dissolution rate monitor

2006 ◽  
Author(s):  
Kazumasa Takeshi ◽  
Kazuto Oono ◽  
Yoshiyuki Negishi ◽  
Daisuke Inokuchi ◽  
Keishi Tanaka ◽  
...  
Keyword(s):  
Dissolution Rate ◽  
Dissolution Behavior ◽  
Chemically Amplified ◽  
Chemically Amplified Resist ◽  
Mold Making

Hydroxynatropyrochlore, (Na,Сa,Ce)2Nb2O6(OH), a new member of the pyrochlore group from the Kovdor phoscorite–carbonatite pipe, Kola Peninsula, Russia

2018 ◽  
Vol 83 (1) ◽  
pp. 107-113 ◽  
Author(s):  
Gregory Yu. Ivanyuk ◽  
Victor N. Yakovenchuk ◽  
Taras L. Panikorovskii ◽  
Nataliya Konoplyova ◽  
Yakov A. Pakhomovsky ◽  
...  
Keyword(s):  
Kola Peninsula ◽  
Powder Diffraction ◽  
Diffraction Data ◽  
Pyrochlore Structure ◽  
Structure Type ◽  
Accessory Mineral ◽  
Oh Groups ◽  
Pyrochlore Group ◽  
Dominant Member ◽  
Mohs Hardness

AbstractHydroxynatropyrochlore, (Na,Сa,Ce)2Nb2O6(OH), is a new Na–Nb–OH-dominant member of the pyrochlore supergroup from the Kovdor phoscorite–carbonatite pipe, Kola Peninsula, Russia. It is cubic, Fd$\bar{3}$m, a = 10.3211(3) Å, V = 1099.46(8) Å3 and Z = 8 (from powder diffraction data) or a = 10.3276(5) Å, V = 1101.5(2) Å3 and Z = 8 (from single-crystal diffraction data). Hydroxynatropyrochlore is a characteristic accessory mineral of the low-carbonate phoscorite in the contact zone of the phoscorite–carbonatite pipe with host foidolite as well as in the carbonate-rich phoscorite and carbonatite of the pipe axial zone. It usually forms zonal cubic or cubooctahedral crystals (up to 0.5 mm in diameter) with irregularly shaped relics of amorphous U–Ta-rich hydroxykenopyrochlore inside. Characteristic associated minerals include rock-forming calcite, dolomite, forsterite, hydroxylapatite, magnetite and phlogopite, accessory baddeleyite, baryte, barytocalcite, chalcopyrite, chamosite–clinochlore, galena, gladiusite, juonniite, ilmenite, magnesite, pyrite, pyrrhotite, quintinite, spinel, strontianite, valleriite and zirconolite. Hydroxynatropyrochlore is pale brown, with an adamantine to greasy lustre and a white streak. The cleavage is average on {111} and the fracture is conchoidal. Mohs hardness is ~5. In transmitted light, the mineral is light brown, isotropic and n = 2.10(5) (λ = 589 nm). The calculated and measured densities are 4.77 and 4.60(5) g cm−3, respectively. The mean chemical composition determined by electron microprobe is: F 0.05, Na2O 7.97, CaO 10.38, TiO2 4.71, FeO 0.42, Nb2O5 56.44, Ce2O3 3.56, Ta2O5 4.73, ThO2 5.73, UO2 3.66, total 97.65 wt.%. The empirical formula calculated on the basis of Nb + Ta + Ti = 2 apfu is (Na1.02Ca0.73Ce0.09Th0.09 U0.05${\rm Fe}_{{\rm 0}{\rm. 02}}^{2 +} $)Σ2.00(Nb1.68Ti0.23Ta0.09)Σ2.00O6.03(OH1.04F0.01)Σ1.05. The simplified formula is (Na,Ca,Ce)2Nb2O6(OH). The mineral dissolves slowly in hot HCl. The strongest X-ray powder-diffraction lines [listed as (d in Å)(I)(hkl)] are as follows: 5.96(47)(111), 3.110(30)(311), 2.580(100)(222), 2.368(19)(400), 1.9875(6)(333), 1.8257(25)(440) and 1.5561(14)(622). The crystal structure of hydroxynatropyrochlore was refined to R1 = 0.026 on the basis of 80 unique observed reflections. The mineral belongs to the pyrochlore structure type A2B2O6Y1 with octahedral framework of corner-sharing BO6 octahedra with A cations and OH groups in the interstices. The Raman spectrum of hydroxynatropyrochlore contains characteristic bands of the lattice, BO6, B–O and O–H vibrations and no characteristic bands of the H2O vibrations. Within the Kovdor phoscorite–carbonatite pipe, hydroxynatropyrochlore is the latest hydrothermal mineral of the pyrochlore supergroup, which forms external rims around grains of earlier U-rich hydroxykenopyrochlore and separated crystals in voids of dolomite carbonatite veins. The mineral is named in accordance with the pyrochlore supergroup nomenclature.

scholarly journals The Effect of PVP Molecular Weight on Dissolution Behavior and Physicochemical Characterization of Glycyrrhetinic Acid Solid Dispersions

2020 ◽  
Vol 2020 ◽  
pp. 1-13
Author(s):  
Xiaoyu Sui ◽  
Yan Chu ◽  
Jie Zhang ◽  
Honglian Zhang ◽  
Huiyu Wang ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Dissolution Rate ◽  
Solid Dispersions ◽  
Physicochemical Characterization ◽  
Dissolution Behavior ◽  
Enhancement Effect ◽  
Glycyrrhetic Acid ◽  
Equilibrium Solubility ◽  
Drug Molecules ◽  
Pvp K30

The effect of polyvinylpyrrolidone (PVP) as glycyrrhetic acid (GA) solid dispersions carrier at different molecular weights on the dissolution behavior and physicochemical properties was investigated. PVP-GA-SDs prepared with all four molecular weight PVPs displayed good enhancement of dissolution rate and equilibrium solubility compared with pure drug and corresponding physical mixtures. The results showed that the enhancement effect of molecular weight on dissolution rate and equilibrium solubility follows PVP   K 30 > PVP   K 60 > PVP   K 17 > PVP   K 15 . In addition, the dissolution rate and solubility of the SDs with a carrier-drug ratio of 8 : 1 were better than the samples of 4 : 1. The DSC and XRD patterns showed that the crystallization of GA in SDs prepared by PVP K30 and PVP K60 was significantly inhibited, and both were transformed to amorphous. Based on FTIR and Raman detection, a hydrogen-bond between PVP and drug molecules is formed. SEM results showed that there were no significant differences in the appearance of SDs prepared with four PVPs, and no crystalline morphology of GA was seen. In conclusion, the findings of this study demonstrated that the dissolution performance of the PVP-GA-SDs prepared by the solvent method is related to the molecular weight of PVP, and the change in the molecular weight of PVP does not cause a monotonic change in dissolution of GA. The samples with PVP K30 as the carrier have the best dissolution performance.

Development of an Oral Curcumin Nanocrystal Formulation

2012 ◽  
Vol 3 (4) ◽  
Author(s):  
R. Ravichandran
Keyword(s):  
The Body ◽  
Dissolution Behavior ◽  
Poorly Soluble Drugs ◽  
Solid Dosage Forms ◽  
Bioavailability Enhancement ◽  
Solid Dosage ◽  
Rapid Dissolution ◽  
Poorly Soluble ◽  
Drug Nanocrystal ◽  
Spray Dried

During the last ten years, the formulation of drugs as nanocrystals has rapidly evolved into a mature drug delivery strategy, with currently five products on the market. The major characteristic of these systems is the rapid dissolution velocity, enabling bioavailability enhancement after oral administration. This study describes the preparation of a solid dosage capsule form of spray-dried curcumin nanocrystal and compares its dissolution behavior with market capsule in different media. The aim was to obtain a stable nanocrystal loaded drug capsule with an increased drug saturation solubility and dissolution velocity. The solubility and dissolution experiments were performed to verify the obvious improvement of the dissolution behavior compared with commercial product. Improved dissolution behavior in drug nanocrystal-loaded solid dosage forms should lead to better bioavailability of poorly soluble drugs in the body.

scholarly journals Impact of HPMCAS on the Dissolution Performance of Polyvinyl Alcohol Celecoxib Amorphous Solid Dispersions

Pharmaceutics ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 541 ◽  
Author(s):  
Marius Monschke ◽  
Karl G. Wagner
Keyword(s):  
Polyvinyl Alcohol ◽  
Dissolution Rate ◽  
Solid Dispersions ◽  
Amorphous Solid ◽  
Scanning Calorimetry ◽  
Amorphous Solid Dispersions ◽  
Dissolution Studies ◽  
Rapid Dissolution ◽  
Poorly Soluble ◽  
Inhibitory Potential

Amorphous solid dispersions (ASDs) have been proven to increase the bioavailability of poorly soluble drugs. It is desirable that the ASD provide a rapid dissolution rate and a sufficient stabilization of the generated supersaturation. In many cases, one polymer alone is not able to provide both features, which raises a need for reasonable polymer combinations. In this study we aimed to generate a rapidly dissolving ASD using the hydrophilic polymer polyvinyl alcohol (PVA) combined with a suitable precipitation inhibitor. Initially, PVA and hydroxypropylmethylcellulose acetate succinate (HPMCAS) were screened for their precipitation inhibitory potential for celecoxib in solution. The generated supersaturation in presence of PVA or HPMCAS was further characterized using dynamic light scattering. Binary ASDs of either PVA or HPMCAS (at 10% and 20% drug load) were prepared by hot-melt extrusion and solid-state analytics were conducted using differential scanning calorimetry (DSC), X-ray powder diffraction (XRPD) and fourier-transformed infrared spectroscopy (FT-IR). The non-sink dissolution studies of the binary ASDs revealed a high dissolution rate for the PVA ASDs with subsequent precipitation and for the HPMCAS ASDs a suppressed dissolution. In order to utilize the unexploited potential of the binary ASDs, the PVA ASDs were combined with HPMCAS either predissolved or added as powder and also formulated as ternary ASD. We successfully generated a solid formulation consisting of the powdered PVA ASD and HPMCAS powder, which was superior in monophasic non-sink dissolution and biorelevant biphasic dissolution studies compared to the binary and ternary ASDs.

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