Primary creep of UO2 and the effect of amorphous grain boundary phases

Creep experiments were conducted on nearly stoichiometric UO₂ helical springs from 1000 to 1600°C and 2.1 to 80 MPa. Entirely transient behaviour was measured in all experiments with the plastic strain,ε = (Aσ/d^1.5) exp(−Q/RT)t^m, where A is a constant that depends on purity, d is the grain size, σ is the applied stress, Q is the apparent activation energy, t is the time, m is a constant, and the other terms have their usual meaning. At T > 1200°C, Q 100 kcal mol⁻¹, but at T < 1200°C, Q increased dramatically and became strain dependent. The value of m for most experiments was 0.8, but at σ > 48 MPa, m decreased, and for d < 10 μm, it increased. Amorphous or glassy grain boundary phases were observed by transmission electron microscopy in all specimens: specimens containing the largest concentrations of Fe and Si sometimes had anomalously high creep rates. The phases existed as discontinuous, lenticular bodies on grain faces and a continuous network along triple grain junctions. Some instances of precipitation of UO₂ from the phase were observed. At T > 1200°C, glassy phases may accelerate Coble creep by providing short circuit diffusion paths along the grain boundaries or may accelerate superplastic deformation by diffusion along the continuous glassy phase triple line junctions. At low temperatures the glassy phase appears to control grain-boundary sliding.     

Ion-induced electron emission – monitoring the structure transitions in graphite

The temperature dependence of ion-induced electron emission yield γ under 30 keV Ar⁺ ion impacts at incidence angles θ = 0−80° under dynamically steady-state conditions has been measured for polygranular graphite POCO-AXF-5Q. The fluencies were 10¹⁸–10¹⁹ ion/cm², the temperatures varied from the room temperature (RT) to 400 °C. The RHEED has shown that same diffraction patterns correspond to a high degree of disorder at RT. At high temperature (HT), some patterns have been found similar to those for the initial graphite surfaces. The dependence γ(T) has been found to be non-monotonic and for normal and near normal ion incidence manifests a step-like increase typical for a radiation induced phase transition. At oblique and grazing incidence (θ > 30°), a broad peak was found at T_p = 100 °C. An analysis based on the theory of kinetic ion-induced electron emission connects the behavior of γ(θ,T) to the dependence of both secondary electron path length λ and primary ion ionizing path length R_e on lattice structure that drastically changes due to damage annealing.     

Standard Gibbs energy of formation of Cs2CdI4

The vapor pressures of CdI₂ and Cs₂CdI₄ were measured below and above their melting points, employing the transpiration technique. The standard Gibbs energy of formation Δ_fG° of Cs₂CdI₄, derived from the partial pressure of CdI₂ in the vapor phase above and below the melting point of the compound could be represented by the equations Δ_fG°Cs₂CdI₄ (±6.7) kJ mol⁻¹=−1026.9+0.270 T (643 K≤T≤693 K) and Δ_fG°{Cs₂CdI₄} (±6.6) kJ mol⁻¹=−1001.8+0.233 T (713 K≤T≤749 K) respectively. The enthalpy of fusion of the title compound derived from these equations was found to be 25.1±10.0 kJ mol⁻¹ compared to 36.7 kJ mol⁻¹ reported in the literature from differential scanning calorimetry (DSC). The standard enthalpy of formation Δ_fH°_298.15 for Cs₂CdI₄ evaluated from these measurements was found to be −918.0±11.7 kJ mol⁻¹, in good agreement with the values −920.3±1.4 and −917.7±1.5 kJ mol⁻¹ reported in the literature from two independent calorimetric studies.     

Phase transition temperature in the Zr-rich corner of Zr–Nb–Sn–Fe alloys

The influence of small composition changes on the phase transformation temperature of Zr–1Nb–1Sn–0.2(0.7)Fe alloys was studied in the present work, by electrical resistivity measurements and metallographic techniques. For the alloy with 0.2 at.% Fe we have determined T_↔+β=741°C and T_+β↔β=973°C, and for the 0.7 at.% Fe the transformation temperatures were T_↔+β=712°C and T_+β↔β=961°C. We have verified that the addition of Sn stabilized the β phase.     

Investigation of in-reactor creep and irradiation growth of zirconium-2.5 wt% niobium channel tubes

We summarize the diametral creep results obtained in the MR reactor of the Kurchatov Institute of Atomic Energy on zirconium-2.5 wt% niobium pressure tubes of the type used in RBMK-1000 power reactors. The experiments that lasted up to 30 000 h cover a temperature range of 270 to 350°C, neutron fluxes between 0.6 and 4.0 ×10¹³ n/cm² · s (E > 1 MeV) and stresses of up to 16 kgf/mm². Diametral strains of up to 4.8% have been measured. In-reactor creep results have been analyzed in terms of thermal and irradiation creep components assuming them to be additive. The thermal creep rate is given by a relationship of the type ε_th = A₁ exp [(A₂ + A _3σt) T] and the irradiation component by ε_rad = A_4σtø(T − A₅), where T = temperature, σ_t = hoop stress, ø = neutron flux and a₁ to A₅ are constants. Irradiation growth experiments carried out at 280° C on specimens machined from pressure tubes showed a non-linear dependence of growth strain on neutron fluence up to neutron fluences of 5 × 10²⁰ n/cm². The significance of these results to the elongation of RBMK reactor pressure tubes is discussed.     

Enthalpy and heat capacity of LiAlO2 between 298 and 1700 K by drop calorimetry

The enthalpy of γ-LiAlO₂ was measured between 403 and 1673 K by isothermal drop calorimetry. The smoothed enthalpy curve between 298 and 1700 K results in H⁰(T) − H⁰(298 K)=−37 396 + 93.143 · T + 0.00557 · T² + 2 725 221 · T⁻¹ J/mol. The standard deviation is 2.2%. The heat capacity was derived by differentiation of the enthalpy curve. The value extrapolated to 298 K is C_p,298=(65.8 ± 2.0) J/K mol.     

Thermodynamic studies on Cs4U5O17(s) and Cs2U2O7(s) by emf and calorimetric measurements

The oxygen potentials over the phase field: Cs₄U₅O₁₇(s)+Cs₂U₂O₇(s)+Cs₂U₄O₁₂(s) was determined by measuring the emf values between 1048 and 1206 K using a solid oxide electrolyte galvanic cell. The oxygen potential existing over the phase field for a given temperature can be represented by: Δμ(O₂) (kJ/mol) (±0.5)=−272.0+0.207T (K). The differential thermal analysis showed that Cs₄U₅O₁₇(s) is stable in air up to 1273 K. The molar Gibbs energy formation of Cs₄U₅O₁₇(s) was calculated from the above oxygen potentials and can be given by, Δ_fG⁰ (kJ/mol)±6=−7729+1.681T (K). The enthalpy measurements on Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were carried out from 368.3 to 905 K and 430 to 852 K respectively, using a high temperature Calvet calorimeter. The enthalpy increments, (H⁰_T−H⁰₂₉₈), in J/mol for Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) can be represented by, H⁰_T−H⁰_298.15 (Cs₄U₅O₁₇) kJ/mol±0.9=−188.221+0.518T (K)+0.433×10⁻³T² (K)−2.052×10⁻⁵T³ (K) (368 to 905 K) and H⁰_T−H⁰_298.15 (Cs₂U₂O₇) kJ/mol±0.5=−164.210+0.390T (K)+0.104×10⁻⁴T² (K)+0.140×10⁵(1/T (K)) (411 to 860 K). The thermal properties of Cs₄U₅O₁₇(s) and Cs₂U₂O₇(s) were derived from the experimental values. The enthalpy of formation of (Cs₄U₅O₁₇, s) at 298.15 K was calculated by the second law method and is: Δ_fH⁰_298.15=−7645.0±4.2 kJ/mol.     

Recrystallization of almost fully amorphous zircon under hydrothermal conditions: An infrared spectroscopic study

Hydrothermal experiments were carried out with powder from an almost fully amorphous, natural zircon under various P–T–t conditions mainly in a 0.1 N HCl solution. Powder infrared spectroscopic measurements on the experimental products reveal that first structural changes occurred at a fluid temperature as low as 75 °C. Significant recrystallization started at 200 °C, as indicated by an increase in the absorption intensity of the zircon fundamental IR bands and the formation of sharp OH stretching bands at 3385 and 3420 cm⁻¹. Although the powder has fully reacted at 400 °C, the zircon fundamental absorption bands are not fully recovered, indicating the occurrence of significant amounts of amorphous remnants. The experimental results in neutral to acidic solutions are consistent with the idea that water (H⁺ and possibly H₂O) diffuses into the amorphous network where it ‘catalyses’ solid state recrystallization. During this process, Zr and Si were leached from the amorphous network.     

Etude des divers types de transformations structurales caracterisant l'alliage Zr-Nb a 17% poids de niobium

This study was carried out mainly by quenching followed by isothermal annealing or continuous heating. X-ray diffraction, micrography, microhardness and dilatometry during quench were employed. By stepped quenching, it was found that the high-temperature β phase decomposes in different ways —either partial decomposition into _Zr, leading finally to the (_Zr+β_Nb) mixture indicated by the phase-diagram, or a diffusion-transformation into ω', or else a diffusionless transformation into ω. A fast quench breaks down the phase into a complex (β + ω + β″) structure. During isothermal anneals the β″ phase was found to vanish, while either ω' or _Zr was formed according to temperature; meanwhile residual β became enriched in niobium. During continuous heating at rates less than 150°/h, the quench-product, ω, reverts to β; then, above 600°C, is transiently deposited but disappears again above 700°C to yield the equilibrium high-temperature phase, β containing 17 wt % niobium.     

Thermochemical study of vaporization of LiTiO by a mass spectrometric Knudsen effusion method

The vaporization of Li₄TiO₄ has been studied by a mass spectrometric Knudsen effusion method in the temperature range 1082–1582 K. Identified vapors are Li(g), LiO(g), Li₂O(g) and Li₃O(g). When the vaporization proceeds, the content of Li₂O in the Li₄TiO₄ sample decreases and the condensed phase of the sample changes to β-Li₄TiO₄ plus l-Li₂TiO₃ below 1323 K, to β-Li₄TiO₄ plus h-Li₂TiO₃ in the range 1323–1473 K and to h-Li₂TiO₃ plus liquid above 1473 K. On the basis of the partial pressure data, the enthalpies of formation for β-Li₄TiO₄ from elements and from constituent oxides have been determined to be ΔH_f,298^°(β-Li₄TiO₄,s) = −2247.8 ± 14.3 kJ mol⁻¹ and Δ_fox,298^°(β-Li₄TiO₄, s) = −107.3 ± 14.3 kJ mol⁻¹, respectively.     

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr_0.53Ti_0.47O₃ (PZT), (Pb_0.90La_0.10)TiO₃ (PLT10) and (Pb_0.80La_0.20)TiO₃ (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance–voltage (C–V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C–V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 °C for 10 min. The phase transition temperature [T_c] of PLT20 increased from 115 °C to 120 °C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 °C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation.     

Mass spectrometric investigation of the vaporization of li2tio3(s)

The vaporization of Li₂TiO₃(s) has been investigated by the mass spectrometric Knudsen effusion method. Partial pressures of Li(g), LiO(g), Li₂O(g), Li₃O(g) and O₂(g) over Li₂TiO₃(s) have been obtained in the temperature range 1180–1628 K. When the vaporization of Li₂TiO₃(s) proceeds, the content of Li₂O in the Li₂TiO₃(s) sample decreases. The phase of the sample is a disordered Li₂TiO₃ solid solution above 1486 K. The enthalpies of formation and the atomization energies for LiO(g) and Li₃O(g) have been evaluated from the partial pressures to be ΔH^o_f0(LiO, g) = 65.4 ± 17.4 kJ/mol, ΔH^o_f0(Li₃O, g) = − 207.5 ± 56.6 kJ/mol, D^o₀(LiO) = 340.5 ± 17.4 kJ/mol and D^o₀(Li₃O) = 931.6 ± 56.6 kJ/mol, respectively.     

Thermoluminescence kinetic parameters of Bi4Ge3O12 single crystals

In this work, we present a detailed kinetic study of the thermoluminescence of Bi₄Ge₃O₁₂ (BGO) single crystals grown by the Czochralski technique. A single crystalline phase was confirmed through X-ray diffraction pattern analysis based on the Rietveld profile refinement method. The thermoluminescent (TL) glow curves were induced by UV or beta radiation and measured between 20 °C and 200 °C. The glow curves of BGO crystal presented two peaks at 61 °C and 90 °C for both kinds of radiation. The kinetic parameters, kinetic order (b), activation energy (E) and frequency factor (s), of the TL glow curves have been determined by four different methods. The lifetime of the peaks at room temperature was also determined and used to discuss the stability of the TL peaks at room temperature.     

Status of delayed-neutron precursor data: half-lives and neutron emission probabilities

We present in this paper a compilation of the present status of experimental delayed-neutron precursor data; i.e. β-decay half-lives (T_1/2) and neutron emission probabilities (P_n) in the fission-product region (27 ≤ Z ≤ 57). These data are compared to two model predictions of substantially different sophistication: (i) an update of the empirical Kratz-Herrmann formula (KHF), and (ii) a unified macroscopic-microscopic model within the quasi-particle random-phase approximation (QRPA). Both models are also used to calculate so far unknown T_1/2 and P_n values up to Z = 63. A number of possible refinements in the microscopic calculations are suggested to further improve the nuclear-physics foundation of these data for reactor and astrophysical applications.     

Influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in PWR primary water

The influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in simulated Pressurized Water Reactor (PWR) primary water has been investigated. A-286 microstructure was characterized by transmission electron microscopy for ageing heat treatments at 670 °C and 720 °C for durations ranging from 5 h to 100 h. Spherical γ′ phase with mean diameters ranging from 4.6 to 9.6 nm and densities ranging from 8.5 × 10²² m⁻³ to 2 × 10²³ m⁻³ were measured. Results suggest that both the γ′ phase mean diameter and density quickly saturate with time for ageing heat treatment at 720 °C while the γ′ mean diameter increases significantly up to 100 h for ageing heat treatment at 670 °C. Grain boundary η phase precipitates were systematically observed for ageing heat treatment at 720 °C even for short ageing periods. In contrast, no grain boundary η phase precipitates were observed for ageing heat treatments at 670 °C except after 100 h. Hardening by γ′ precipitation was well described by the dispersed barrier hardening model with a γ′ barrier strength of 0.23. Stress corrosion cracking behaviour of A-286 was investigated by means of constant elongation rate tensile tests at 1.5 × 10⁻⁷ s⁻¹ in simulated PWR primary water at 320 °C and 360 °C. In all cases, initiation was transgranular while propagation was intergranular. Grain boundary η phase precipitates were found to have no significant effect on stress corrosion cracking. In contrast, yield strength and to a lesser extent temperature were found to have significant influences on A-286 susceptibility to stress corrosion cracking.     

The release of fission-recoiled xenon from Zr-2.5 wt% Nb alloy

The release of fission-recoiled ¹³³Xe from Zr-2.5 wt% Nb alloy was measured in the temperature range 640–1080 K. In the range 640–880 K, where purely phase exists, a linear relationship between log D versus 1/T is observed and can be represented by the equation: D(640–880 K) = 6.24 × 10⁻⁹exp(−142.7 kJmol/RT)m²/s. The release has been attributed to the non-volume diffusion process.

In the temperature range 930–1080 K where both and β phases coexist, the linearity in the plots of log D versus 1/T is violated.

The present values of the release parameters have been compared with the corresponding values for the release of fission-recoiled ¹³³Xe from Zircaloy-2. Alloying elements seem to have very small effect on the release kinetics. The results have been presented and discussed.     

Thermal stability and brazing characteristics of Zr0.7−xMxBe0.3 (M=Ti or Nb) ternary amorphous filler metals

The effects of Ti or Nb substitution on the thermal stability and brazing characteristics of Zr_0.7−xM_xBe_0.3 (M=Ti or Nb) ternary amorphous alloys were investigated in order to improve properties of Zr–Be binary amorphous alloy as a new filler metal for joining zirconium alloy. The Zr_0.7−xM_xBe_0.3 (M=Ti or Nb; 0x0.1) ternary amorphous alloys were produced by melt-spinning method. In the selected compositional range, the thermal stability of Zr_0.7−xTi_xBe_0.3 and Zr_0.7−xNb_xBe_0.3 amorphous alloys are improved by the substitution of titanium or niobium for zirconium. As the Ti and Nb content increases, the crystallization temperatures increase from 610°C to 717°C and 610°C to 678°C, respectively. These amorphous alloys were put into practical use in joining bearing pads on zircaloy cladding sheath. Using Zr–Ti–Be amorphous alloys as filler metals, smooth interface and spherical primary particles (proeutectic phase) appear in the brazed layer, which is the similar microstructure of using Zr_0.7Be_0.3 binary amorphous alloys. In the case of Zr–Nb–Be amorphous alloys, Ni-precipitated Zr phase that may cause some degradation in ductility and corrosion-resistance is formed at both sides of the brazed layer.     

Standard Gibbs energy of formation of Mo3Te4 by emf measurements

The emf of the galvanic cells Pt, Mo, MoO₂¦8 YSZ¦‘FeO’, Fe, Pt (I) and Pt, Fe,‘FeO’ ¦8 YSZ¦MoO₂, Mo₃Te₄, MoTe₂(), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo₃Te₄/MoTe₂(), was found to be

Full-size image

. Using the literature data for the Gibbs energy of formation of MoTe₂(). the expression ΔG°_f(Mo₃Te_4,s) ± 5.97 (kj/mol) = −253.58 + 0.09214T(K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of −209 ± 10 kJ/mol for ΔH°_f.298^o of Mo₃Te₄(s).     

Contribution of uranium diffusion on creep behavior of uranium dicarbide

Compressive creep tests of uranium dicarbide (UC₂) have been conducted. The general equation best describing the creep rate over the temperature range 1200–1400°C and over the stress range 2000–15000 psi is represented by the sum of two exponential terms ge =A(σ/E)^0.9 exp(−39.6 ± 1.0/RT) + B(σ/E)^4.5 exp(−120.6 ± 1.7/RT), where pre-exponential factors are A(σ/E)^0.9 = 12.3/h at low stress region (3000 psi) and B(σ/E)^4.5 = 3.17 × 10¹³/h at high stress region (9000 psi), and the activation energy is given in kcal/mol. Each term of this experimental equation indicates that important processes occurring during the steady state creep are grain-boundary diffusion of the Coble model at low stress region and the Weertman dislocation climb model at high stress region. Both mechanisms are related to migration of uranium vacancies.