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Lu2‐xCexTi2O7 (LCTO) pyrochlores were irradiated by 400 keV Ne2+ with fluences (dose) of up to 5 × 1015 ions/cm2 (1.875 dpa). The detailed damage process was investigated by combining grazing incident angle X‐ray diffraction (GIXRD) and transmission electron microscopy (TEM). Subsequent to the 2% volume swelling at a fluence of 1 × 1014 ions/cm2 (0.037 dpa), the initially swollen LCTO pyrochlore formed both a disordered fluorite phase and a nanocrystalline pyrochlore phase at a fluence of 5 × 1014 ions/cm2 (0.185 dpa). At higher fluences, the fluorite phase diminished as amorphous domains increased in volume when the dose reached a fluence of 1 × 1015 ions/cm2 (0.371 dpa), while the nanocrystalline pyrochlore phase persisted. At the highest fluence of 5 × 1015 ions/cm2 (1.854 dpa), the amorphous fraction decreased, meanwhile the degree of crystallinity of nanocrystalline pyrochlore phase was enhanced, as evidenced by the increased intensity of superlattice diffraction maxima. The phase transformation and recrystallization can be explained by the release of strain in irradiation‐induced swollen pyrochlore crystallites. The evolution of the damage process is mainly driven by the differences in the Gibb's free energies of fluorite phase as compared with the pyrochlore phase as a function of grain size. We have demonstrated that ion beam techniques can be used to manipulate the phase stability and crystallite size of pyrochlore. These results provide the basis for tailoring the mechanical strength and response of pyrochlores to extreme radiation environments. [ABSTRACT FROM AUTHOR]

Several different models are known to describe the structure-dependent radiation-induced damage accumulation process in materials (e.g. Gibbons Proc IEEE 60:1062-1096, 1972; Weber Nuc Instr Met Phys Res B 166-167:98-106, 2000). In the literature, two different models of damage accumulation due to α-decay events in natural ZrSiO4 (zircon) have been described. The direct impact damage accumulation model is based on amorphization occurring directly within the collision cascade. However, the double cascade-overlap damage accumulation model predicts that amorphization will only occur due to the overlap of disordered domains within the cascade. By analyzing the dose-dependent evolution of mechanical properties (i.e., Poisson’s ratios, compliance constants, elastic modulus, and hardness) as a measure of the increasing amorphization, we provide support for the double cascade-overlap damage accumulation model. We found no evidence to support the direct impact damage accumulation model. Additionally, the amount of radiation damage could be related to an anisotropic-to-isotropic transition of the Poisson’s ratio for stress along and perpendicular to the four-fold c-axis and of the related compliance constants of natural U- and Th-bearing zircon. The isotropification occurs in the dose range between 3.1 × and 6.3  × 1018 α-decays/g. [ABSTRACT FROM AUTHOR]

Radiation damage in minerals is caused by the α-decay of incorporated radionuclides, such as U and Th and their decay products. The effect of thermal annealing (400-1000 K) on radiation-damaged pyrochlores has been investigated by Raman scattering, X-ray powder diffraction (XRD), and combined differential scanning calorimetry/thermogravimetry (DSC/TG). The analysis of three natural radiation-damaged pyrochlore samples from Miass/Russia [6.4 wt% Th, 23.1·1018 α-decay events per gram (dpg)], Panda Hill/Tanzania (1.6 wt% Th, 1.6·1018 dpg), and Blue River/Canada (10.5 wt% U, 115.4·1018 dpg), are compared with a crystalline reference pyrochlore from Schelingen (Germany). The type of structural recovery depends on the initial degree of radiation damage (Panda Hill 28%, Blue River 85% and Miass 100% according to XRD), as the recrystallization temperature increases with increasing degree of amorphization. Raman spectra indicate reordering on the local scale during annealing-induced recrystallization. As Raman modes around 800 cm−1 are sensitive to radiation damage (M. T. Vandenborre, E. Husson, Comparison of the force field in various pyrochlore families. I. The A2B2O7 oxides. J. Solid State Chem. 1983, 50, 362, S. Moll, G. Sattonnay, L. Thomé, J. Jagielski, C. Decorse, P. Simon, I. Monnet, W. J. Weber, Irradiation damage in Gd2Ti2O7 single crystals: Ballistic versus ionization processes. Phys. Rev. 2011, 84, 64115.), the degree of local order was deduced from the ratio of the integrated intensities of the sum of the Raman bands between 605 and 680 cm−1 divided by the sum of the integrated intensities of the bands between 810 and 860 cm−1. The most radiation damaged pyrochlore (Miass) shows an abrupt recovery of both, its short- (Raman) and long-range order (X-ray) between 800 and 850 K, while the weakly damaged pyrochlore (Panda Hill) begins to recover at considerably lower temperatures (near 500 K), extending over a temperature range of ca. 300 K, up to 800 K (Raman). The pyrochlore from Blue River shows in its initial state an amorphous X-ray diffraction pattern superimposed by weak Bragg-maxima that indicates the existence of ordered regions in a damaged matrix. In contrast to the other studied pyrochlores, Raman spectra of the Blue River sample show the appearance of local modes above 560 K between 700 and 800 cm−1 resulting from its high content of U and Ta impurities. DSC measurements confirmed the observed structural recovery upon annealing. While the annealing-induced ordering of Panda Hill begins at a lower temperature (ca. 500 K) the recovery of the highly-damaged pyrochlore from Miass occurs at 800 K. The Blue-River pyrochlore shows a multi-step recovery which is similarly seen by XRD. Thermogravimetry showed a continuous mass loss on heating for all radiation-damaged pyrochlores (Panda Hill ca. 1%, Blue River ca. 1.5%, Miass ca. 2.9%). [ABSTRACT FROM AUTHOR]

This study provides new insights into the relation between thermally induced structural reorganization and the macroscopic mechanical properties of radiation-damaged titanite. The natural sample contains ca. 30% amorphous fraction. Low-temperature annealing affects only slightly the sample stiffness and leads to a softening resulting from the defect annihilation in crystalline regions. In the high-temperature annealing regime, amorphous domains recrystallize and this leads to further recovery of defects, reduction of interfaces, grain growth, and, in general, an increase in the long-range order. The thermally induced recrystallization is accompanied by massive dehydration leading to considerable stiffening and hardening. This interpretation of the recrystallization process in titanite based on the correlation of new results from nanoindentation and Raman-spectroscopic measurements complementing previous investigations using thermogravimetric and gas analyses by Hawthorne et al. (1991) and infrared spectroscopy by Zhang et al. (2001). The new data combined with previous work leads to a detailed description of the annealing behavior of a radiation-damaged titanite, which is a complicated process that includes dehydration and atomic-scale structural reorganization. To minimize the influence of surface phenomena on the hardness measurements, the so-called "true" hardness was used instead of the standard hardness calculation (Oliver and Pharr 1992). A comparison shows that the Oliver and Pharr method clearly underestimates the hardness. [ABSTRACT FROM AUTHOR]

Swift heavy-ion irradiations of a wide variety of materials have been used to modify and manipulate the properties of solids at the nanoscale. Recently, these high-energy irradiations have been successfully combined with high-pressure experiments. Based on results obtained for zircon (ZrSiO4), this paper introduces this new experimental approach involving diamond anvil cells and large ion-accelerator facilities. This technique provides a wide spectrum of geoscience applications from nanoscale simulations of fission-track formation under crustal conditions to phase transitions of radiation-damaged minerals resulting from meteorite impact. [ABSTRACT FROM AUTHOR]

Zircon crystals from lateritic soils at Nsimi, Cameroon, were investigated using electron microprobe analysis (EMPA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Raman spectroscopy to determine the extent of radiation damage from alpha-decay events. The soils belong to a small watershed developed on granitic rocks of the Congo craton (2.9 Ga). Interactions with fluids are evidenced by significant CaO (up to 1.5 wt%), Al2O3(up to 2.9 wt%), and Fe2O3 (up to 2.9 wt%) concentrations in UO2rich regions (0.05 to 1 wt%) of the zircon. Regional heating up to 500 °C, related to the Pan-African orogeny about 0.6 Ga ago, has lead to the recrystallization of the radiation-damaged grains and the formation of a nanoporous microstructure. The correlation observed between the presence of dissolution features and the actual damage state of zircon shows that zircon dissolution occurs under tropical weathering conditions and with preferential dissolution of the highly radiation-damaged regions. Congruent dissolution of zircon and the limited mobility of Zr are supported by the absence of zirconium oxide precipitates in the fractures of weathered grains of zircon. [ABSTRACT FROM AUTHOR]

Reidite, a high-pressure phase of zircon, is increasingly identified at terrestrial impact sites. Despite its growing recognition, the potential applications for estimating minimum impact pressure face impediments due to existing discrepancies in the condition of zircon-reidite transformation, controversial models governing the transformation mechanism, and unclear effects of pre-existing radiation damage on reidite formation. Here, we show enhanced reidite formation by synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy analyses of zircon grains that have experienced different alpha-decay doses from U and Th impurities and subsequent pressurization in diamond anvil cells. Below ∼1 × 1018 α-decay events/g, the α-decay-induced isolated point defects in the still crystalline zircon facilitate the minor atomic readjustments required for reidite formation. However, above this dose, the loss of long-range periodicity in severely damaged or even metamict zircon inhibits the transformation. The enhanced reidite formation by minor radiation damage coincides with the more common occurrence of reidite at impact sites for which the precursor zircon has a relatively lower alpha-decay-event dose before the impact event. In addition, the detailed atomic-scale structures of twinned reidite provide unambiguous evidence for a characteristic internal stress-induced martensitic transition. These findings have important implications for interpreting the formation conditions of natural reidite due to the convergence of pressure from the static, shockwave, and natural reidite samples. • Moderate radiation damage enhances atomic adjustments for reidite formation. • Reidite preferentially occurs in craters with moderately damaged zircon. • Static, shocked, and natural reidite have similar formation mechanisms. • Atomic scale twinned reidite suggests internal stress-assisted martensitic transition. • Constraining the minimum impact pressure should consider radiation damage. [ABSTRACT FROM AUTHOR]

Electron backscatter diffraction (EBSD) was employed to probe the structural order of a zoned radiation-damaged zircon (ZrSiO 4) on the sub-micron scale. The amorphous fraction of the growth-zones is in the range of ∼45–80%, due to variations in the amount of incorporated uranium and thorium (∼0.22–0.43 wt% UO 2 and ∼0.02–0.08 wt% ThO 2) and the resulting alpha-decay events over time. The obtained Kikuchi patterns' band contrast (bc) and band slope (bs) are indicative of the degree of atomic-scale order. The excellent correlation of both parameters with the evolution of the elastic modulus validates the methods reliability. [ABSTRACT FROM AUTHOR]

Abstract: Using a new experimental approach, fission-track formation has been simulated, for the first time, under crustal conditions by exposing natural zircon, at a pressure of 7.5 kbar and a temperature of 250 °C, to a beam of relativistic heavy ions. The latent tracks were investigated using high-resolution transmission electron microscopy, and the diameters of several hundred tracks were measured. The mean values (±σ) of the track diameters were 5.2±0.5 nm and 5.4±0.4 nm for zircon at ambient and elevated pressure-temperature, respectively. Based on the number of measurements, this represents a statistically significant difference between the tracks at ambient vs. high-pressure/temperature conditions. The slightly larger size of the tracks at elevated pressure can be understood in terms of the increased efficiency of the damage process in a strained crystal lattice. This slight variation in track diameter (~0.2 nm) at high pressure probably will not affect the dimensions of etched tracks. [Copyright &y& Elsevier]

Abstract: Zircon (ZrSiO4), the most important accessory mineral in the Earth''s crust, transforms under high pressure to reidite, a scheelite-structured polymorph. Recently, reidite was found in association with meteorite impact structures. Here, we show that the zircon-to-reidite transition, and thus the amount of reidite produced during high-pressure events, strongly depends on the microstructure of the initial zircon. Our results clearly demonstrate that radiation damage, present in natural zircon due to radioactive decay, dramatically modifies the phase stability of crystalline zircon at high pressure. By simulating this radiation damage with ion beams, we show that zircon, pre-irradiated with 1.47-GeV Xe ions, formed only minor amounts of reidite up to 36GPa; whereas, an unirradiated zircon was almost completely transformed to reidite under the same conditions. By means of Raman scattering, X-ray diffraction, and transmission electron microscopy, we confirmed that the stability field of the irradiated zircon is expanded to higher pressures as a result of the interplay between pressure, ion beam-induced amorphization, and the formation of nanoscale damage domains. These results provide insight into the formation-conditions of reidite in nature and illustrate how pressure-induced phase transitions may be affected by defects, in this case those caused by radioactive decay. [Copyright &y& Elsevier]

Abstract: Complexly zoned zircons (19 grains, ∼3.3 Ga) from a porphyritic granite in the Jack Hills, Western Australia, have been investigated using electron microprobe analysis (EMPA) and transmission electron microscopy (TEM) in order to examine the effects of radiation as a function of dose, as well as the nano-scale microstructure and composition of impurities and secondary alteration phases. In back-scattered electron (BSE) images, zones with bright contrast consist of an almost unaltered zircon with limited amounts of impurity elements. In contrast, the dark zones contain higher concentrations of trace elements: U, Th, Pb, Fe, Y, Ce, Ca and Al. The cumulative doses due to alpha-decay in the dark zones are calculated to be 0.21–1.0×1017 (alpha-decay events/mg), equivalent to 1.0–4.7 dpa (displacements per atom). These doses are much higher than the dose required for radiation-induced amorphization, as determined by ion-beam irradiation of synthetic zircon, 0.3–1.0 dpa (0–600 °C). However, based on high-resolution TEM observations, none of the zircons are fully amorphous, to the result of annealing under ambient conditions. The concentrations of Ca and Al, which was considered to indicate alteration, increase dramatically at a cumulative dose of 1.6×1016 (alpha-decay events/mg). This is the dose at which the first percolation point occurs, as amorphous domains overlap and form an interconnected network. In the altered zones, nanocrystallites of zircon are present with a random orientation, and the amorphous matrix contains the impurity elements. Although the Ce-concentration is extremely high, 1–2 wt.%, the Ce anomaly, Ce/Ce⁎, does not vary significantly as a function of dose or degree of alteration, indicating that the LREE patterns were overprinted by the fluids with a similar Ce-anomaly. The valence of Ce analyzed by EELS (electron energy loss spectroscopy) is tetravalent in the altered zone, suggesting that the altering fluids were oxidizing. [Copyright &y& Elsevier]