Light ion irradiation effects on stuffed Lu2(Ti2−xLux)O7−x/2 (x = 0, 0.4 and 0.67) structures

We have recently synthesized “stuffed” (i.e., excess Lu) Lu₂(Ti_2−xLu_x)O_7−x/2 (x = 0, 0.4 and 0.67) compounds using conventional ceramic processing. X-ray diffraction measurements indicate that stuffing more Lu³⁺ cations into the oxide structure leads eventually to an order-to-disorder (O-D) transition, from an ordered pyrochlore to a disordered fluorite crystal structure. At the maximum deviation in stoichiometry (x = 0.67), the Lu³⁺ and Ti⁴⁺ ions become completely randomized on the cation sublattices, and the oxygen “vacancies” are randomized on the anion sublattice. Samples were irradiated with 400 keV Ne²⁺ ions to fluences ranging from 1 × 10¹⁵ to 1 × 10¹⁶ ions/cm² at cryogenic temperatures (∼77 K). Ion irradiation effects in these samples were examined by using grazing incident X-ray diffraction. The results show that the ion irradiation tolerance increases with disordering extent in the non-stoichiometric Lu₂(Ti_2−xLu_x)O_7−x/2.     

Modeling the thermochemical behavior of AmO2−x

A thermochemical representation of the fluorite structure AmO_2−x phase was developed using the compound energy formalism approach assuming constituents of (Am⁴⁺)₁(O²⁻)₂, (Am⁴⁺)₁(Va)₂, (Am³⁺)₁(O²⁻)₂, and (Am³⁺)₁(Va)₂. The Gibbs free energies for the constituents and a set of interaction parameters were determined using reported oxygen potential-temperature-composition data. A good fit to the experimental information was obtained which well-reproduces the behavior. The representation is also in a format that will allow incorporation of other dissolved metals and thus will be useful in generating multi-component compound energy formalism representations for complex oxide nuclear fuel and waste systems. A full assessment relating the fluorite structure phase to the phase equilibria for Am-O, however, must await adequate data for the remainder of the system.     

Oxygen potential measurements of Am0.5Pu0.5O2−x by EMF method

The dependence of the oxygen potentials on oxygen non-stoichiometry and temperature of Am_0.5Pu_0.5O_2−x has been obtained by the electromotive force (EMF) method with the cell: (Pt) air |Zr(Ca)O_2−x| Am_0.5Pu_0.5O_2−x (Pt). The x value of Am_0.5Pu_0.5O_2−x was changed at 1333 K over 0.02 < x ? 0.25 by the coulomb titration method. The temperature dependence of the oxygen potential was also measured over the range of 1173-1333 K. It was found that the oxygen potential decreased from −80 to −360 kJ mol⁻¹ with increasing x from 0.021 to 0.22 at 1333 K and that it remained almost constant at −360 kJmol⁻¹ around x = 0.23. It was concluded that Am_0.5Pu_0.5O_2−x should be composed of the single fluorite-type phase over 0.02 < x ? 0.22 and the mixed phases of fluorite-type and (Am, Pu)₉O₁₆ at around x = 0.23.     

Band gap controlled H loss from passivated Hg1−xCdxTe (MCT) wafers under intense electronic excitations

We report here loss of H monitored by on-line elastic recoil detection analysis (ERDA) technique from passivated Hg_1−xCd_xTe (MCT) wafers due to irradiation by 80 MeV Ni⁹⁺, 120 MeV Au¹⁵⁺ and 200 MeV Ag¹⁰⁺. The loss of H is more in case of the wafer irradiated by Ag ions as compared to other two because of higher electronic energy loss (S_e). For same S_e value, H loss is more in case of the wafer having x = 0.29 as compared to the one having x = 0.204. This is due to higher band gap of the former as compared to the later, which is an important data for proper use of these materials as IR detector in intense radiation zone. These results are explained on the basis of thermal spike model of ion-solid interaction.     

Damage creation in ion irradiated Si1−xGex/Si structures

Strained SiGe/Si structures have been proposed as substrates for fabrication of high speed metal oxide semiconductor transistors. However, influence of strain and/or presence of Ge atoms on damage creation during ion irradiation have not been explored to a significant extent. In this study, Rutherford backscattering spectrometry (RBS) was used to characterize Si_1−xGe_x/Si structures irradiated by 140 keV He⁺ ions at room temperature. When compared with pure Si, strained samples show enhanced damage accumulation as a function of He fluence. Channeling angular scans did not reveal any specific configuration of displacements. Possible mechanisms for enhanced damage in strained Si are discussed.     

Thermodynamic properties of ThxU1−xO2 (0 < x < 1) based on quantum-mechanical calculations and Monte-Carlo simulations

Th_xU_1−xO_2+y binary compositions occur in nature, uranothorianite, and as a mixed oxide nuclear fuel. As a nuclear fuel, important properties, such as the melting point, thermal conductivity, and the thermal expansion coefficient change as a function of composition. Additionally, for direct disposal of Th_xU_1−xO₂, the chemical durability changes as a function of composition, with the dissolution rate decreasing with increasing thoria content. UO₂ and ThO₂ have the same isometric structure, and the ionic radii of 8-fold coordinated U⁴⁺ and Th⁴⁺ are similar (1.14 nm and 1.19 nm, respectively). Thus, this binary is expected to form a complete solid solution. However, atomic-scale measurements or simulations of cation ordering and the associated thermodynamic properties of the Th_xU_1−xO₂ system have yet to be determined. A combination of density-functional theory, Monte-Carlo methods, and thermodynamic integration are used to calculate thermodynamic properties of the Th_xU_1−xO₂ binary (ΔH_mix, ΔG_mix, ΔS_mix, phase diagram). The Gibbs free energy of mixing (ΔG_mix) shows a miscibility gap at equilibration temperatures below 1000 K (e.g., E_exsoln = 0.13 kJ/(mol cations) at 750 K). Such a miscibility gap may indicate possible exsolution (i.e., phase separation upon cooling). A unique approach to evaluate the likelihood and kinetics of forming interfaces between U-rich and Th-rich has been chosen that compares the energy gain of forming separate phases with estimated energy losses of forming necessary interfaces. The result of such an approach is that the thermodynamic gain of phase separation does not overcome the increase in interface energy between exsolution lamellae for thin exsolution lamellae (10 Å). Lamella formation becomes energetically favorable with a reduction of the interface area and, thus, an increase in lamella thickness to >45 Å. However, this increase in lamellae thickness may be diffusion limited. Monte-Carlo simulations converge to an exsolved structure [lamellae || ] only for very low equilibration temperatures (below room temperature). In addition to the weak tendency to exsolve, there is an ordered arrangement of Th and U in the solid solution [alternating U and Th layers || {1 0 0}] that is energetically favored for the homogeneously mixed 50% Th configurations. Still, this tendency to order is so weak that ordering is seldom reached due to kinetic hindrances. The configurational entropy of mixing (ΔS_mix) is approximately equal to the point entropy at all temperatures, indicating that the system is not ordered.     

Oxygen non-stoichiometries in (Th0.7Ce0.3)O2−x

Oxygen non-stoichiometry in (Th_0.7Ce_0.3)O_2−x oxide solid solutions was investigated from the viewpoint of Ce reduction. The oxygen non-stoichiometry was experimentally determined by means of thermogravimetric analysis as a function of oxygen potential at 1173, 1273 and 1373 K. Features of the isotherms of oxygen non-stoichiometry in (Th_0.7Ce_0.3)O_2−x similar to those in oxygen non-stoichiometric actinide and lanthanide dioxides were observed. The oxygen non-stoichiometry in (Th_0.7Ce_0.3)O_2−x was compared with those of CeO_2−x and (U_0.7Ce_0.3)O_2−x. It was concluded that the Ce reduction has some relation to defect forms and their transformations in the solid solutions.     

Partitioning of dopant cations between β-tricalcium phosphate and fluorapatite

Mixed crystalline phase composite ceramics offer the possibility of partitioning defect species between the phases as well as occupancy of specific sites within a given phase. Here we use atomic scale simulations to study the site preference of an extensive range of divalent and trivalent substitutional ions across the five cation sites in β-tricalcium phosphate (β-TCP) and the two cations sites in fluorapatite (FAp). This study indicates that in β-TCP small dopant species occupy the smaller of the five cation sites and vice versa. Conversely, in FAp, small divalent species occupy the nominally larger Ca(1) site while larger cations occupy the Ca(2) site. Partition energies between the two phases indicate that divalent species strongly segregate to β-TCP as do Al³⁺ and Ga³⁺, whereas all other (larger) trivalent ions exhibit little preference.     

Melting behavior of MgO-based inert matrix fuels containing (Pu,Am)O2−x

The melting behavior of MgO-based inert matrix fuels containing (Pu,Am)O_2−x ((Pu,Am)O_2−x-MgO fuels) was experimentally investigated. Heat-treatment tests were carried out at 2173 K, 2373 K and 2573 K each. The fuel melted at about 2573 K in the eutectic reaction of the Pu-Am-Mg-O system. The (Pu,Am)O_2−x grains, MgO grains and pores grew with increasing temperature. In addition, Am-rich oxide phases were formed in the (Pu,Am)O_2−x phase by heat-treatment at high temperatures. The melting behavior was compared with behaviors of PuO_2−x-MgO and AmO_2−x-MgO fuels.     

Analysis of oxygen potential of (U0.7Pu0.3)O2±x and (U0.8Pu0.2)O2±x based on point defect chemistry

Stoichiometries in (U_0.7Pu_0.3)O_2±x and (U_0.8Pu_0.2)O_2±x were analyzed with the experimental data of oxygen potential based on point defect chemistry. The relationship between the deviation x of stoichiometric composition and the oxygen partial pressure P_O2 was evaluated using a Kröger-Vink diagram. The concentrations of the point defects in uranium and plutonium mixed oxide (MOX) were estimated from the measurement data of oxygen potentials as functions of temperature and P_O2. The analysis results showed that x was proportional to near the stoichiometric region of both (U_0.7Pu_0.3)O_2±x and (U_0.8Pu_0.2)O_2±x, which suggested that intrinsic ionization was the dominant defect. A model to calculate oxygen potential was derived and it represented the experimental data accurately. Further, the model estimated the thermodynamic data, and , of stoichiometric (U_0.7Pu_0.3)O_2.00 and (U_0.8Pu_0.2)O_2.00 as −552.5 kJ·mol⁻¹ and −149.7 J·mol⁻¹, and −674.0 kJ · mol^-1 and −219.4 J · mol⁻¹, respectively.     

Phase diagram analysis of (U,Pu)O2−x sub-system

The high plutonium, hypo-stoichiometric fuel exists as two phase system at low temperatures. The partial phase diagram of (U,Pu)O_2−x with two coexisting cubic phases was extensively investigated in this work using theoretical models. The critical temperature of the miscibility gap varies with Pu/M and O/M of the system. Based on the similar miscibility gap behaviour observed in PuO_2−x system and the experimental data available on the phase boundaries of (U,Pu)O_2−x for various Pu/M, some semi-empirical relationships and solution models were developed. With the help of these relationships, ternary isothermal sections of the miscibility gap, O/M at different temperatures and the critical temperature of the miscibility gap of (U,Pu)_2−x for different Pu/M values were calculated. These calculated values were compared with the available literature data.     

Thermal studies on fluorite type ZryU1−yO2 solid solutions

Solid state reactions of UO₂ and ZrO₂ in mild oxidizing condition followed by reduction at 1673 K showed enhanced solubility up to 35 mol% of zirconium in UO₂ forming cubic fluorite type Zr_yU_1−yO₂ solid solution. The lattice parameters and O/M (M = U + Zr) ratios of the solid solutions, Zr_yU_1−yO_2+x, prepared in different gas streams were investigated. The lattice parameters of these solid solutions were expressed as a linear equation of x and y: a₀ (nm) = 0.54704 − 0.021x - 0.030y. The oxidation of these solid solutions for 0.1 ? y ? 0.2 resulted in cubic phase MO_2+x up to700 K and single orthorhombic zirconium substituted α-U₃O₈ phase at 1000 K. The kinetics of oxidation of Zr_yU_1−yO₂ in air for y = 0-0.35 were also studied using thermogravimetry. The specific heat capacities of Zr_yU_1−yO₂ (y = 0-0.35) were measured using heat flux differential scanning calorimetry in the temperature range of 334-860 K.     

Lattice parameters of (U, Pu, Am, Np)O2−x

The solid solutions of (U_{1−z−y’−y”}Pu_zAm_y’Np_y”)O_2−x (z = 0-1, y’ = 0-0.12, y” = 0-0.07) were investigated by X-ray diffraction measurements, and a database for the lattice parameters was updated. A model to calculate the lattice parameters was derived from the database. The radii of the ions present in the fluorite structure of (U, Pu, Am, Np)O_2−x were estimated from the lattice parameters measured in this work. The model represented the experimental data within a standard deviation of σ = ±0.025%.     

Optical properties of InxGa1−xP/InP grown at high fluence Ga implantation on InP using focused ion beam

Single-crystalline InP(1 0 0) substrate was implanted by 30 keV Ga⁺ ions with fluences of 1 × 10¹⁶-1.5 × 10¹⁷ cm⁻² followed by post-annealing treatment at 750 °C to recover implantation-induced structural defects and activate dopants into the lattices. The optical property, composition, and microstructure of the Ga⁺-implanted InP were studied by Raman spectroscopy and transmission electron microscopy (TEM). Raman spectra show that the In_xGa_1−xP phase is formed at a critical fluence of 7 × 10¹⁶ cm⁻². The newly grown phase was identified with the appearance of Ga rich TO_InP and In rich TO_GaP modes of a random alloy in the 1 bond-2 phonon mode configuration along with TEM structural identification.     

Influence on the structural characteristic of defect solid solution GdxZr1−xO2−x/2 with 0.18 ? x ? 0.62 under longer term annealing studied by Gd Mössbauer spectroscopy

Three kinds of defect solid solution Gd_xZr_1−xO_2−x/2 with 0.18 ? x ? 0.62, including the three single crystal samples with x = 0.21, 0.26 and 0.30, were investigated by ¹⁵⁵Gd Mössbauer spectroscopy at 12 K. Difference in the structural characteristic under longer term annealing were confirmed by comparing the ¹⁵⁵Gd Mössbauer parameters of the polycrystalline samples sintered one time and twice at 1773 K for 16 h in air, respectively. The results indicated that the polycrystalline samples sintered twice have relatively equilibrated structure by comparing with the three single crystal samples. After being sintered twice, basically the local structure around the Gd³⁺ ions does not change, but the degree of the displacements of the six 48f oxygen ions from positions of cubic symmetry becomes slightly smaller, and distribution of the Gd³⁺ ions in the system becomes more homogeneous.     

Crystal structure change of Li2+xTiO3+y tritium breeder under moist air

To investigate the aging behavior of Li_2+xTiO_3+y, the materials Li_2.0TiO_3+y, Li_2.2TiO_3+y and Li_2.4TiO_3+y were stored under moist air at ambient temperature. Under these conditions the weight of Li_2.0TiO_3+y increased by only 1% in 100 days, which provides evidence for the high chemical stability of Li₂TiO₃. In comparison, under the same storage conditions the weights of Li_2.2TiO_3+y and Li_2.4TiO_3+y increased by 14% and 18%, respectively. The observed weight gain is attributed to the uptake of water, and to the reaction of a by-product of Li_2+xTiO_3+y with water and carbon dioxide. The weight gain curves were evaluated by the Jander equation. From the analysis, it was possible to obtain the diffusion coefficient of water through Li₂TiO₃ particles at ambient temperature. The determined value was 2 × 10⁻¹⁷ m²/s.     

Improvement on thermoelectric properties of multilayered Si1−xGex/Si by ion beam bombardment

We made n-type nano-scale thin film thermoelectric (TE) devices that consist of multiple periodic layers of Si_1−xGe_x/Si. The period is about 10 nm. The structure was modified by 5 MeV Si ion bombardment that formed a nano-scale cluster structure. In addition to the effect of confinement of the phonon transmission, formation of nanoclusters by the ionization energy of incident MeV Si ions further increases the scattering of phonons, increasing the chance of inelastic interaction of phonons, resulting in more annihilation of phonons. This limits phonon mean free path. Phonons are absorbed and dissipated along the layers rather than in the direction perpendicular to the layer interfaces, therefore cross plane thermal conductivity is reduced. The increase of the density of electronic states due to the formation of nanocluster minibands increases the cross plane Seebeck coefficient and increases the cross plane electric conductivity of the film. Eventually, the thermoelectric figure of merit of the TE film increases.     

Effect of oxygen potential on the sintering behavior of MgO-based heterogeneous fuels containing (Pu, Am)O2−x

The effect of oxygen potential on the sintering behavior of MgO-based heterogeneous fuels containing (Pu, Am)O_2−x was experimentally investigated. Sintering tests in various atmospheres, i.e. air, moisturized 4%H₂-Ar, and 4%H₂-Ar atmosphere, were carried out. The sintering behavior was found to be significantly affected by the oxygen potential in the sintering atmosphere. The sintered density decreased with decreasing oxygen potential. The (Pu, Am)O_2−x phase sintered in a reductive atmosphere had hypostoichiometry. The aggregates of the (Pu, Am)O_2−x phase sintered in the reductive atmosphere grew, in comparison with those in the oxidizing one. The sintering mechanism was discussed in terms of the difference in sintering behavior of (Pu, Am)O_2−x and MgO.     

Structural study of Pu1−xAmxO2 (x = 0.2; 0.5; 0.8) obtained by oxalate co-conversion

This study describes the synthesis and the characterisation of Pu_1−xAm_xO₂ (x = 0.2; 0.5; 0.8) mixed oxides obtained by oxalate co-conversion. We studied the self-irradiation effect in these compounds at the structural scale. We determined, for each composition, the initial lattice parameter and the equation describing its variation versus time and displacements per atom. Similarly to other α emitting compounds, it was observed a fast lattice parameter expansion rate, followed by a stabilisation at a maximum value. The observations also showed that the initial expansion rate varies according to the Am content and the maximum value to the Pu content. However, for all compositions, the lattice parameter relative variations are the same.     

Compactibility and sintering behavior of nanocrystalline (Th1−xCex)O2 powders synthesized by co-precipitation process

Thoria (ThO₂) based ceramic material is a versatile and very important matrix for immobilization of plutonium and other tetravalent actinides either as a burning or a deposition material for final disposal. The aim of this study was to investigate the influence of the actinide concentration (simulated with cerium), the fabrication conditions and the properties of the produced powders on the compactibility and sinterability of the final products. The (Th_1−xCe_x)O₂ powders with ceria concentration varying from 5 to 50 mol% were synthesized by co-precipitation method. The pellets were then compacted from calcined and ground powders at pressures varying from 250 to 750 MPa. The produced pellets had a homogenous grain size and sintered densities of 0.88% to 0.95% TD, respectively.