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

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.

1984 ◽  
Vol 44 ◽  
Author(s):  
Bryan C. Chakoumakos ◽  
Rodney C. Ewing

AbstractThe pyrochlore structure type, A1−2 B2 O6Y0−1 Fd3m Z=8, is a common constituent of polyphase, crystalline waste forms. Naturally occurring minerals with the same structure often occur in the radiation damaged, electron-diffraction amorphous, “metamict” state; and therefore, a principal concern with phases of this structure type is the effect of alpha-recoil damage associated with the presence of actinides. In this paper we outline crystal chemical constraints on the formation of novel actinide pyrochlores.


2018 ◽  
Vol 83 (1) ◽  
pp. 107-113 ◽  
Author(s):  
Gregory Yu. Ivanyuk ◽  
Victor N. Yakovenchuk ◽  
Taras L. Panikorovskii ◽  
Nataliya Konoplyova ◽  
Yakov A. Pakhomovsky ◽  
...  

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.


Author(s):  
G. R. Lumpkin ◽  
R. C. Ewing

The pyrochlore structure type occurs as a constituent of crystalline nuclear waste form assemblages proposed for the long term isolation of actinides. Betafite, the Ti-rich end-member of the pyrochlore group, is a natural analogue similar in composition to waste form pyrochlores. This study examines the effects of alpha-recoil damage and geochemical alteration on a specimen of betafite from Antanifotsy, Madagascar (Harvard no. 87876, UNM no. 205).Electron microprobe analyses were performed using a JEOL 733 Superprobe operated at 15 kV and 20 nA sample current crushed fragments of the sample were dispersed on holey-carbon grids and examined with a JEOL 2000 EX TEM operated at 200 kV. Phase compositions were checked using a Tracor TN5500 EDS.The 1.5 cm diameter betafite crystal displays an unusual zonal sequence of alteration. The core consists of relatively unaltered betafite containing ca. 27 wt.% U02 and 2.5 wt.% CaO (TABLE 1, analysis 1).


1984 ◽  
Vol 44 ◽  
Author(s):  
Gregory R. Lumpkin ◽  
Rodney C. Ewing

AbstractSignificant amounts of the pyrochlore structure type, and derivative structures like zirconolite, have been reported to occur in crystalline, polyphase, nuclear waste forms [1,2,3,4]. Pyrochlore has abundant and chemically diverse natural analogues. Many of these contain U and Th and have been transformed to the electron-diffraction amorphous, “metamict” state by alpha-recoil nuclei. A variety of geochemical alteration processes may occur before, during, and after reaching the final saturation level for alpha-recoil damage (∼1026 alpha-events/m3 ). The purpose of this paper is to examine these alteration effects in radiation-damaged natural pyrochlores.


1985 ◽  
Vol 50 ◽  
Author(s):  
Y. Eyal ◽  
G. R. Lumpkin ◽  
R. C. Ewing

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.


1985 ◽  
Vol 50 ◽  
Author(s):  
R. B. Greegor ◽  
F. W. Lytle ◽  
B. C. Chakoumakos ◽  
G. R. Lumpkin ◽  
R. C. Ewing

AbstractThe uranium site in naturally occurring metamict minerals of the pyrochlore group (A1–2B2O6Y0–1) has been investigated using x-ray absorption spectroscopy (XAS). Pyrochlore structures are common phases in proposed polycrystalline waste forms. Betafite, a member of the pyrochlore group (B = 2Ti ≥ Nb+Ta), exhibits U-O bond lengths of 1.94 and 2.37 A for the metamict state, and 2.03 and 2.51 A for the crystalline (annealed) state. The U-O bond lengths decrease (∼0.1 A) and there is a disruption in the second nearest neighbor periodicidy as material is converted from the crystalline to the metamict state.


1981 ◽  
Vol 11 ◽  
Author(s):  
J.W. Wald ◽  
P. Offemann

Radiation effects studies in both glass and glass ceramic nuclear waste forms have identified a rare-earth titanate phase of the general formula (RE) 2Ti207 which is capable of acting as a host phase for actinides.1,2 Ringwood and co-workers3 have also proposed a structurally similar phase, zirconolite (CaZrTi2 07), as one of the primary host phases in the SYNROC waste form. Data from these and other previous studies, as well as mineralogical information available on these titanate phases, have not provided an unambiguous interpretation of the effects of radiation damage relative to nuclear waste forms. This paper reports new laboratory data concerning radiation damage effects in both of these phases.


2004 ◽  
Vol 19 (5) ◽  
pp. 1575-1580 ◽  
Author(s):  
Jie Lian ◽  
Rodney C. Ewing ◽  
L.M. Wang ◽  
K.B. Helean

Ceramics with III-IV pyrochlore compositions, A3+2B4+2O7 (A = Y and rare earth elements; B = Ti, Zr, Sn, or Hf), show a wide range of responses to ion-beam irradiation. To evaluate the role of the B-site cations on the radiation stability ofthe pyrochlore structure-type, Gd2Sn2O7 and Gd2Hf2O7 have been irradiated by1 MeV Kr+. The results are discussed in terms of the ionic size and type ofbonding of Sn4+ and Hf4+ and compared to previous results for titanate andzirconate pyrochlores. Gd2Sn2O7 is sensitive to ion beam–induced amorphizationwith a critical amorphization dose of approximately 3.4 displacements per atom(dpa) (2.62 × 1015 ions/cm2) at room temperature and a critical amorphization temperature of approximately 350 K. Gd2Hf2O7 does not become amorphous at adose of approximately 4.54 displacement per [lattice] atom (3.13 × 1015 ions/cm2) at room temperature, but instead is transformed to a disordered fluorite structure upon ion-beam irradiation. Although the radius ratio of the A- to B-site cations provides a general indication of the type of radiation response of different pyrochlore compositions, the results for Gd2Sn2O7 emphasize the importance of bond type, particularly the covalency of the 〈Sn–O〉 bond in determining the radiation response.


2015 ◽  
Vol 1744 ◽  
pp. 61-66 ◽  
Author(s):  
M. R. Gilbert

ABSTRACTSodalite (Na8[AlSiO4]6Cl2), a naturally occurring Cl-containing mineral, has long been regarded as a potential immobilization matrix for the chloride salt wastes arising from pyrochemical reprocessing operations, as it allows for the conditioning of the waste salt as a whole without the need for any pre-treatment. Here the consolidation and densification of Sm-doped sodalite (as an analogue for AnCl3) has been investigated with the aim of producing fully dense (i.e. > 95 % t.d.) ceramic monoliths via conventional cold-press-and-sinter techniques at temperatures of < 1000 °C. Microstructural analysis of pressed and sintered sodalite powders under these conditions is shown to produce poorly sintered, porous, inhomogeneous pellets. However, by the addition of a sodium aluminophosphate glass sintering aid, fully dense Sm-sodalite ceramic monoliths can successfully be produced by sintering at temperatures as low as 800 °C.


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