An Overview of the Crystal Chemistry, Durability, and Radiation Damage Effects of Natural Pyrochlore

2000 ◽  
Vol 663 ◽  
Author(s):  
G.R. Lumpkin ◽  
R.C. Ewing ◽  
C.T. Williams ◽  
A.N. Mariano

ABSTRACTNumerous studies of pyrochlore group minerals have been completed over the previous 15 years, providing researchers in the field of nuclear waste disposal with a large body of data relevant to the behavior of these minerals in natural systems. The information obtained from studies of natural pyrochlore is applicable to the formulation of diverse waste form compositions and provides data for the assessment of the long-term behavior. Although resistant to dissolution, pyrochlore is subject to chemical alteration by ion exchange with hydrothermal fluids and low temperature ground water; however, Th and U are generally immobile and are retained in the structure. X-ray diffraction, TEM, EXAFS-XANES, and other techniques have been employed in studies of radiation damage. These studies reveal the classic sequence of damage microstructures with increasing dose and provide details about the structure of the amorphous state. Furthermore, the radiation damage studies are now complemented by data relating to the thermal histories of some of the host rocks.

2004 ◽  
Vol 824 ◽  
Author(s):  
Boris E. Burakov ◽  
Maria A. Yagovkina ◽  
Vladimir M. Garbuzov ◽  
Alexander A. Kitsay ◽  
Vladimir A. Zirlin

AbstractTo investigate the behavior of monazite during accelerated radiation damage, which simulates effects of long term storage, 238Pu-doped polycrystalline samples of (La,Pu)PO4 and PuPO4 were synthesized for the first time ever and studied using powder X-ray diffraction (XRD) analysis and optical microscopy. The starting precursor materials were obtained by precipitation of La and (or) Pu from their aqueous nitrate solutions followed by calcination in air at 700°C for 1 hour, cold pressing, and sintering in air at 1200-1250°C for 2 hours. The 238Pu contents in ceramic samples measured using gamma spectrometry were (in wt.% el.): 8.1 for (La,Pu)PO4 and 7.2 for PuPO4. The (La,Pu)PO4 monazite remained crystalline at ambient temperature up to a cumulative dose of 1.19 × 1025 alpha decays/m3. In contrast, the PuPO4 monazite became nearly completely amorphous at a relatively low dose of 4.2 × 1024 alpha decays/m3. Swelling and crack formation due to the alpha decay damage was observed in the PuPO4 ceramic. Also, under self-irradiation this sample completely changed color from initial deep blue to black. The (La,Pu)PO4 monazite was characterized by a similar change in color from initial light blue to gray, however, no swelling or crack formation have so far been observed. The results of this study allow us to conclude that the radiation damage behavior of monazite strictly depends on the chemical composition. The justification of monazite-based ceramics as actinide waste forms requires additional investigation.


2015 ◽  
Vol 79 (6) ◽  
pp. 1455-1466 ◽  
Author(s):  
W. R. Bower ◽  
C. I. Pearce ◽  
G. T. R. Droop ◽  
J. F. W. Mosselmans ◽  
K. Geraki ◽  
...  

AbstractA detailed understanding of the response of mineral phases to the radiation fields experienced in a geological disposal facility (GDF) is currently poorly constrained. Prolongued ion irradiation has the potential to affect both the physical integrity and oxidation state of materials and therefore may alter a structure's ability to react with radionuclides. Radiohalos (spheres of radiation damage in minerals surrounding radioactive (α-emitting) inclusions) provide useful analogues for studying long term α-particle damage accumulation. In this study, silicate minerals adjacent to Th- and U-rich monazite and zircon were probed for redox changes and long/short range disorder using microfocus X-ray absorption spectroscopy (XAS) and high resolution X-ray diffraction (XRD) at Beamline I18, Diamond Light Source. Fe3+ → Fe2+ reduction has been demonstrated in an amphibole sample containing structural OH– groups – a trend not observed in anhydrous phases such as garnet. Coincident with the findings of Pattrick et al. (2013), the radiolytic breakdown of OH– groups is postulated to liberate Fe3+ reducing electrons. Across all samples, high point defect densities and minor lattice aberrations are apparent adjacent to the radioactive inclusion, demonstrated by micro-XRD.


Antioxidants ◽  
2019 ◽  
Vol 8 (11) ◽  
pp. 520 ◽  
Author(s):  
Guibeth Morelo ◽  
Begoña Giménez ◽  
Gloria Márquez-Ruiz ◽  
Francisca Holgado ◽  
Patricio Romero-Hasler ◽  
...  

The effect of the physical state of flavonoid-inulin microparticles (semi-crystalline/amorphous) on the oxidative stability of lipid matrices was studied. Epicatechin (E) and quercetin (Q) microparticles with inulin were formulated at two infeed temperatures (15 °C and 90 °C) by spray drying. X-ray diffraction analyses showed that flavonoid-inulin microparticles obtained at feed temperature of 15 °C were semi-crystalline (E-In-15, 61.2% and Q-In-15, 60%), whereas those at 90 °C were amorphous (Q-In-90, 1.73 and Q-In-90 2.30%). Semi-crystalline state of flavonoid-inulin microparticles enhanced the EE (68.8 and 67.8% for E and Q, respectively) compared to amorphous state (41.6 and 51.1% for E and Q, respectively). However, amorphous Q-microparticles showed the highest antioxidant activity both in methyl linoleate and sunflower oil, increasing the induction period and decreasing the polar compounds and polymer triglyceride formation during long-term oxidation study. Therefore, the physical state of spray-dried flavonoid-inulin microparticles may determine their antioxidant activity in lipid matrices.


Foods ◽  
2021 ◽  
Vol 10 (5) ◽  
pp. 1074
Author(s):  
Wei Zhou ◽  
Yun Zhang ◽  
Ruyi Li ◽  
Shengfeng Peng ◽  
Roger Ruan ◽  
...  

Thymol has been applied as a spice and antibacterial agent in commercial products. However, the utilization of thymol in the food and pharmaceutical field has recently been limited by its poor water solubility and stability. In this work, a caseinate-stabilized thymol nanosuspension was fabricated by pH-driven methods to overcome those limitations. Firstly, the chemical stability of thymol at different pH value conditions was investigated. The physiochemical properties of thymol nanosuspensions were then characterized, such as average particle size, zeta potential, encapsulation efficiency, and loading capacity. Meanwhile, the X-ray diffraction results showed that thymol was present as an amorphous state in the nanosuspensions. The thermal stability of thymol was slightly enhanced by encapsulation through this process, and the thymol nanosuspensions were stable during the long-term storage, and the average particle size of nanosuspensions showed that there was no aggregation of nanosuspensions during storage and high temperature. Finally, the antimicrobial activity of thymol nanosuspensions was evaluated by investigating the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) against Salmomella enterca, Staphlococcus aureus, Escherichia coli, and Listeria monocytogenes. These results could provide useful information and implications for promoting the application of thymol in food, cosmetic, and pharmaceutical commercial products.


Author(s):  
T. J. Headley ◽  
R. C. Ewing ◽  
R. F. Haaker

Ceramic waste forms are being developed as solid hosts for radioactive waste disposal, Of concern is the effect of long-term radiation damage on crystalline integrity and subsequent leachability of the waste form. In preparation for understanding radiation damage effects, we have performed a high resolution study of the metamict state in natural zircons (ZrSiO4). Metamict minerals are a class of “amorphous” minerals, originally crystalline which have suffered extensive structural degradation over time from decay of internal radioactive impurities, principally U and Th. From x-ray diffraction evidence it is widely believed that the metamict state is amorphous in the sense of an isotropic glass. However, an electron microscope study performed some 15 years ago suggested that metamict zircons possess a structure composed of slightly misoriented crystallites about 100 Å in size, a structure indistinguishable from an isotropic glass by x-ray diffraction. We felt that high resolution electron microscopy could clearly delineate between the isotropic glass and misoriented microcrystalline concepts.


1997 ◽  
Vol 506 ◽  
Author(s):  
Gregory R. Lumpkin ◽  
Katherine L. Smith ◽  
Mark G. Blackford ◽  
Reto Gieré ◽  
C. Terry Williams

ABSTRACTDose-age relationships have been determined by analytical and transmission electron microscopy (AEM and TEM) for the onset dose and critical amorphization dose of a suite of natural zirconolites. Together with a preliminary investigation of the thermal histories of the zirconolite-bearing rocks, the results indicate that valid estimates of D0 (intercept dose at t = 0) and K (annealing rate constant) are obtained and that the host rocks experienced temperatures on the order of 100-200 °C averaged over time. The natural samples are therefore best suited as radiation damage analogues for waste forms stored under deep borehole conditions where temperatures of 100-450 °C are expected. Our results indicate that the critical amorphization (or saturation) dose of zirconolite will increase by a factor of approximately 2 or more as a result of storage at elevated temperature. The effect of long-term annealing on the critical amorphization dose is only important for times in excess of 107-108 years due to the low annealing rate constant of 10−9/yr.


2020 ◽  
Vol 9 (1) ◽  
pp. 998-1008
Author(s):  
Guo Li ◽  
Zheng Zhuang ◽  
Yajun Lv ◽  
Kejin Wang ◽  
David Hui

AbstractThree nano-CaCO3 (NC) replacement levels of 1, 2, and 3% (by weight of cement) were utilized in autoclaved concrete. The accelerated carbonation depth and Coulomb electric fluxes of the hardened concrete were tested periodically at the ages of 28, 90, 180, and 300 days. In addition, X-ray diffraction, thermogravimetry, and mercury intrusion porosimetry were also performed to study changes in the hydration products of cement and microscopic pore structure of concrete under autoclave curing. Results indicated that a suitable level of NC replacement exerts filling and accelerating effects, promotes the generation of cement hydration products, reduces porosity, and refines the micropores of autoclaved concrete. These effects substantially enhanced the carbonation and chloride resistance of the autoclaved concrete and endowed the material with resistances approaching or exceeding that of standard cured concrete. Among the three NC replacement ratios, the 3% NC replacement was the optimal dosage for improving the long-term carbonation and chloride resistance of concrete.


2021 ◽  
Vol 1756 ◽  
pp. 147334
Author(s):  
Charles Budaszewski Pinto ◽  
Natividade de Sá Couto-Pereira ◽  
Felipe Kawa Odorcyk ◽  
Kamila Cagliari Zenki ◽  
Carla Dalmaz ◽  
...  

1997 ◽  
Vol 07 (11) ◽  
pp. 2487-2499 ◽  
Author(s):  
Rabbijah Guder ◽  
Edwin Kreuzer

In order to predict the long term behavior of nonlinear dynamical systems the generalized cell mapping is an efficient and powerful method for numerical analysis. For this reason it is of interest to know under what circumstances dynamical quantities of the generalized cell mapping (like persistent groups, stationary densities, …) reflect the dynamics of the system (attractors, invariant measures, …). In this article we develop such connections between the generalized cell mapping theory and the theory of nonlinear dynamical systems. We prove that the generalized cell mapping is a discretization of the Frobenius–Perron operator. By applying the results obtained for the Frobenius–Perron operator to the generalized cell mapping we outline for some classes of transformations that the stationary densities of the generalized cell mapping converges to an invariant measure of the system. Furthermore, we discuss what kind of measures and attractors can be approximated by this method.


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