Molecular dynamics simulation of helium-vacancy interaction in plutonium

The formation energies of small He_nV_m clusters (n and m denote the number of He atoms and vacancy, respectively) in Pu have been calculated with molecular dynamics (MD) simulations using the embedded atom method (EAM) potential, the Mores potential and the Lennard-Jones potential for describing the interactions of Pu-Pu, Pu-He and He-He, respectively. The binding energies of an interstitial He atom, an isolated vacancy and a self-interstitial Pu atom to a He_nV_m cluster are also obtained from the calculated formation energies of the clusters. All the binding energies mainly depend on the He-vacancy ratio (n/m) of clusters rather than the clusters size. With the increase of the n/m ratio, the binding energies of a He atom and a Pu atom to a He_nV_m cluster decrease with the ratio, and the binding energy of a vacancy to a He_nV_m cluster increases. He atoms act as a catalyst for the formation of He_nV_m clusters.     

Pressure of stable He-vacancy complex in bcc iron: Molecular dynamics simulations

Molecular dynamic simulation was employed to study the stable state of He-vacancy (He-V) complex in bcc iron. The pressure of He-V complex was calculated using the concept of atomic-level stress. In the case of no initial vacancies introduced in the simulation box, self-interstitial atoms (SIAs) are emitted by the small He cluster. As the number of the He cluster is above a critical value, interstitial-type dislocation loops (I-loop) will be generated. After the interstitial-type defects (SIA or I-loop) were created, it is found that the ratio of He atoms to athermal vacancies keeps nearly constant in the He-V complex.     

Self-radiation damage in plutonium and uranium mixed dioxide

In plutonium compounds, the lattice parameter increases due to self-radiation damage by α-decay of plutonium isotopes. The lattice parameter change and its thermal recovery in plutonium and uranium mixed dioxide (MOX) were studied. The lattice parameter for samples of MOX powders and pellets that had been left in the air for up to 32 years was measured. The lattice parameter increased and was saturated at about 0.29%. The change in lattice parameter was formulated as a function of self-radiation dose. Three stages in the thermal recovery of the damage were observed in temperature ranges of below 673 K, 673-1073 K and above 1073 K. The activation energies in each recovery stage were estimated to be 0.12, 0.73 and 1.2 eV, respectively, and the corresponding mechanism for each stage was considered to be the recovery of the anion Frenkel defect, the cation Frenkel defect and a defect connected with helium, respectively.     

Applications of parametric X-rays for X-ray diffraction analysis

Until now parametric X-rays (PXR) have not had practical applications because of the lack of a modern compact accelerator providing the required beam current and consequently high X-ray photon flux. PXR sources even with the intensities achievable at present may be applied to a number of X-ray reflectometry and diffractometry measurements which are important for the characterization of crystals and multi-layer nanostructures. In the paper we present some proposals for possible PXR applications for a number of X-ray measurements based on the smooth energy tuning, high monochromaticity and directed emission of this radiation. The theoretical background and numerical evaluations for PXR applications for determining ingredient concentration in a solid solution in the range of anomalous dispersion of the defect atoms, determination of the phase structure of a crystal, and selective PXR action in organic compounds, important for medical and biological research, are considered.     

X-ray diffraction analysis of titanium tritide film during 1600 days

The generation and accumulation of ³He by tritium decay modified the physical and chemical properties of tritides. Here the evolution of lattice defects in long-aged titanium tritide films is investigated by X-ray diffraction and changes in the positions, intensities and line shapes of diffraction peaks have been determined over a period of about 1600 days (>4 years). Texture effects are also observed by biased intensities in standard θ–2θ scans. The results show that the TiT_1.5 film keeps an fcc structure during 1600 days and reveals an hkl-dependent unit-cell expansion and line width broadening which are interpreted in terms of isolated tetrahedral interstitial ³He atoms and isolated bubble growth models by dislocation loop-punching or dislocation dipole expansion combined with Krivoglaz theory. In the first 12 days of aging, isolated tetrahedral interstitial ³He atoms or ³He clusters are formed, then interstitial ³He atoms diffuse into (1 1 1) planes and precipitate into clusters. The spontaneous formation of Frenkel pairs, the self-interstitial atoms produced are built into dislocations resulting in formation platelet bubbles and dislocation dipoles between 12 and 27 days. Above 27 days, multiple stages of ³He bubbles growth appear: (1) between 27 and 85 days platelet helium bubbles growth by dislocation dipoles expansion, (2) between 85 and 231 days the transition from platelet bubbles to sphere bubbles by loop emission, (3) after 231 days sphere bubbles growth by dislocation loop-punching and probably formation of sub-grain boundaries by dislocation rearrangement.     

Fabrication of hollow nanoclusters by ion implantation

Ag ions with four kinds of energies were implanted into silica to doses of 5 × 10¹⁶ and 1 × 10¹⁷ ions/cm², respectively. Hollow Ag nanoclusters were observed in the 1 × 10¹⁷ Ag⁺ ions/cm² implanted samples with energies of 150 and 200 keV. The evolution of hollow nanoclusters during annealing was carried out by in situ transmission electron microscopy observation. The energy dependence for the formation of hollow nanoclusters is studied. A potential mechanism for the formation of irradiation-induced nanovoids in nanoclusters is discussed.     

Fabrication of hollow Ag nanoclusters in silica by irradiation with Ar ions

Ion irradiation is an effective method to control the morphology, size and distribution of metal nanoclusters in substrates. In this work, Ag nanoclusters embedded in silica by 200 keV Ag⁺ ion implantation were irradiated at room temperature with Ar⁺ ions at 200 keV and 500 keV to different fluences. After irradiation, a transmission electron microscopy (TEM) study revealed that nanovoids are formed in the larger Ag nanoclusters. With the increase of fluence and energy of the Ar⁺ ions, the number and average size of the nanovoids grow combining with increases in the average size of the larger Ag nanoclusters within a projected range. During the ion irradiation process, the electronic energy and nuclear energy loss of the Ar⁺ ions determine the size of the hollow Ag nanoclusters and the change of the size and distribution of Ag nanoclusters in silica, leading to changes in the optical absorption spectra.     

Theory of He trapping, diffusion, and clustering in UO2

We have performed ab initio total energy calculations to investigate the behavior of helium and its diffusion properties in uranium dioxide (UO₂). Our investigations are based on the density functional theory within the generalized gradient approximation (GGA). The trapping behavior of He in UO₂ has been modeled with a supercell containing 96-atoms as well as uranium and oxygen vacancy trapping sites. The calculated incorporation energies show that for He a uranium vacancy is more stable than an oxygen vacancy or an octahedral interstitial site (OIS). Interstitial site hopping is found to be the rate-determining mechanism of the He diffusion process and the corresponding migration energy is computed as 2.79 eV at 0 K (with the spin-orbit coupling (SOC) included), and as 2.09 eV by using the thermally expanded lattice parameter of UO₂ at 1200 K, which is relatively close to the experimental value of 2.0 eV. The lattice expansion coefficient of He-induced swelling of UO₂ is calculated as 9 × 10⁻². For two He atoms, we have found that they form a dumbbell configuration if they are close enough to each other, and that the lattice expansion induced by a dumbbell is larger than by two distant interstitial He atoms. The clustering tendency of He has been studied for small clusters of up to six He atoms. We find that He strongly tends to cluster in the vicinity of an OIS, and that the collective action of the He atoms is sufficient to spontaneously create additional point defects around the He cluster in the UO₂ lattice.     

Thermal transport properties of uranium dioxide by molecular dynamics simulations

The thermal conductivities of single crystal and polycrystalline UO₂ are calculated using molecular dynamics simulations, with interatomic interactions described by two different potential models. For single crystals, the calculated thermal conductivities are found to be strongly dependent on the size of the simulation cell. However, a scaling analysis shows that the two models predict essentially identical values for the thermal conductivity for infinite system sizes. By contrast, simulations with the two potentials for identical fine polycrystalline structures yield estimated thermal conductivities that differ by a factor of two. We analyze the origin of this difference.     

Defect characterization in boron implanted silicon after flash annealing

Flash-assisted rapid thermal processing (fRTP) has gained considerable interests for fabrication of ultra-shallow junction in silicon. fRTP can significantly reduce boron diffusion, while attaining boron activation at levels beyond the limits of traditional rapid thermal annealing. The efficiency of fRTP for defect annealing, however, needs to be systematically explored. In this study, a (1 0 0) silicon wafer was implanted with 500 eV boron ions to a fluence of 1 × 10¹⁵ cm⁻². fRTP was performed with peak temperatures ranging from 1100 °C to 1300 °C for approximately one milli-second. High resolution transmission electron microscopy and secondary ion mass spectrometry were performed to characterize as-implanted and annealed samples. The study shows that fRTP at 1250 °C can effectively anneal defects without causing boron tail diffusion.     

Microstructure evolution and degradation mechanisms of reactor internal steel irradiated with heavy ions

Structure evolution and degradation mechanisms during irradiation of 18Cr-10Ni-Ti steel (material of VVER-1000 reactor internals are investigated). Using accelerator irradiations with Cr³⁺ and Ar⁺ ions allowed studying effects of dose rate, different initial structure state and implanted ions on features of structure evolution and main mechanisms of degradation including low temperature swelling and embrittlement of the 18Cr-10Ni-Ti steel. It is shown that differences in dose rate at most irradiation temperatures mainly exert their influence on the duration of the swelling transient regime. Calculations of possible transmutation products during irradiation of this steel in a VVER-1000 spectrum were performed. It is shown that gaseous atoms (He and H), which are generated simultaneously with radiation defects, stabilize the elements of radiation microstructure and influence the swelling. The nature of deformation under different temperatures of irradiation and of mechanical testing is investigated. It is shown that the temperature sensitivity of swelling behaviour in the investigated steel, with different initial structures can be connected with the dynamic behaviour of point defect sinks.     

Selection of water-dispersible carbon black for fabrication of uranium oxicarbide microspheres

Fabrication of uranium oxicarbide microspheres, a component of TRISO fuel particles for high temperature nuclear power systems, is based on the internal gelation of uranium salts in the presence of carbon black. In order to obtain a high quality product, carbon black should remain dispersed during all phases of the gelation process. In this study, the surface and structural properties of several commercial carbon black materials, and the use of dispersing agents was examined with the goal of finding optimal conditions for stabilizing submicron-sized carbon black dispersions. Traditional methods for stabilizing dispersions, based on the use of dispersing agents, failed to stabilize carbon dispersions against large pH variations, typical for the internal gelation process. An alternate dispersing method was proposed, based on using surface-modified carbons functionalized with strongly ionized surface groups (sodium sulfonate). With a proper choice of surface modifiers, these advanced carbons disperse easily to particles in the range of 0.15-0.20 μm and the dispersions remain stable during the conditions of internal gelation.     

Atomistic simulation of point defects behavior in ceria

The cerium and oxygen threshold displacement energies and the Frenkel pair recombination in CeO₂ have been investigated with empirical potential molecular dynamics simulations. The oxygen and cerium threshold displacement energies have been evaluated to be 27 and 56 eV, respectively, in agreement with experimental results. The short-range cerium and oxygen Frenkel pair recombination processes are found to be strongly dependent on the local topology and the pathways. The oxygen Frenkel pair recombinations are either spontaneous or thermally activated unlike the standard recombination usually defined in rate equations. The lifetime of Frenkel pair recombination is in general found to be much shorter than the characteristic time for single defect diffusion.     

Uranium-molybdenum nuclear fuel plates behaviour under heavy ion irradiation: An X-ray diffraction analysis

Heavy ion irradiation has been proposed for discriminating UMo/Al specimens which are good candidates for research reactor fuels. Two UMo/Al dispersed fuels (U-7 wt%Mo/Al and U-10 wt%Mo/Al) have been irradiated with a 80 MeV ¹²⁷I beam up to an ion fluence of 2 × 10¹⁷ cm⁻². Microscopy and mainly X-ray diffraction using large and micrometer sized beams have enabled to characterize the grown interaction layer: UAl₃ appears to be the only produced crystallized phase. The presence of an amorphous additional phase can however not be excluded. These results are in good agreement with characterizations performed on in-pile irradiated fuels and encourage new studies with heavy ion irradiation.     

In-pile Xe diffusion coefficient in UO2 determined from the modeling of intragranular bubble growth and destruction under irradiation

Intragranular bubbles grow in the nuclear fuel by diffusion and precipitation of fission gases, mainly xenon; and are ultimately destroyed, under irradiation, by fission fragments. This article will attempt to determine the in-pile bubble distributions taking into account the evolution of the concentration profile around a bubble during its growth and the destruction process by fission fragments. From these distributions a relation between the bubble mean radius and the diffusion coefficient of xenon can be established, allowing the determination, from experimental measurements of intragranular bubble sizes, of the in-pile Xe diffusion coefficient in UO₂. The estimated activation energy (0.9 eV) is about one order of magnitude lower than the widely used value of 3.9 eV determined from out-of-pile experiments. This effect can be attributed to the presence of point defects created by the irradiation.     

Elemental analysis of mining wastes by energy dispersive X-ray fluorescence (EDXRF)

An energy dispersive X-ray fluorescence (EDXRF) tri-axial geometry experimental spectrometer has been employed to determine the concentrations of 13 different elements (K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr and Pb) in mine wastes from different depths of two mine tailings from the Cartagena-La Union (Spain) mining district. The elements were determined and quantified using the fundamental parameters method. The concentrations of Cr, Ni, Cu, Zn and Pb were compared to the values from the European and Spanish legislation to evaluate the environmental risk and to classify the wastes as inert wastes or as wastes that have to be control land-filled. The results obtained demonstrate that these wastes can be considered as inert for the considered elements, apart from the concentration levels of Zn and Pb. Whilst Zn slightly overpasses the regulatory levels, Pb mean value exceeds three to six times the value to be considered as Class I potential land-filling material.     

Simulating radiation damage in δ-plutonium

Radiation events in δ-Pu (fcc) have been simulated in an attempt to understand the fundamental mechanisms that contribute to the Pu ageing process. The Pu interactions are modelled using a potential based on the modified embedded atom method (MEAM). The energetics of point defects have been investigated using static calculations together with molecular dynamics (MD) to simulate radiation events. All MD simulations were carried out with Pu initially in the face-centred-cubic (fcc) structure, although this is not the lowest energy configuration for the pure metal.The point defect study suggests that the mono-vacancy has the lowest formation energy (0.46 eV), with interstitial defects favouring the - split orientation over occupation of the native fcc octahedral site. Displacement threshold energy calculations at room temperature give a minimum value of between 5 and 6 eV, increasing to 8-14 eV along the major crystallographic directions.Low energy collision cascades, initiated with energies in the range of 0.4-1 keV, show that the cascades form in a similar manner to other fcc metals with a vacancy rich zone at the cascade core, surrounded by isolated interstitial defects. Higher energy cascades show similar features but with occasional channelling of energetic atoms and sub-cascade branching which significantly reduces defect production. A common trait observed across all the cascades was the relatively slow annealing period, compared to cascades in other fcc metals, with simulations at energies above 5 keV requiring many 10’s of picoseconds before the ballistic phase was completed.     

Positron annihilation on the surfaces of SiO2 films thermally grown on single crystal of Cz-Si

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO₂, SiO₂ films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10⁻³m₀c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO₂ and Si without oxide film. However, for the thermally grown SiO₂-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO₂-Si system consist of a surface layer, a SiO₂ layer, a SiO₂-Si interface layer and a semi-infinite Si substrate.     

Irradiation induced dislocation loop and its influence on the hardening behavior of Fe-Cr alloys by an Fe ion irradiation

Nano indentation analysis and transmission electron microscopy observation were performed to investigate a microstructural evolution and its influence on the hardening behavior in Fe-Cr alloys after an irradiation with 8 MeV Fe⁴⁺ ions at room temperature. Nano indentation analysis shows that an irradiation induced hardening is generated more considerably in the Fe-15Cr alloy than in the Fe-5Cr alloy by the ion irradiation. TEM observation reveals a significant population of the a₀<1 0 0> dislocation loops in the Fe-15Cr alloy and an agglomeration of the 1/2a₀<1 1 1> dislocation loops in the Fe-5Cr alloy. The results indicate that the a₀<1 0 0> dislocation loops will act as stronger obstacles to a dislocation motion than 1/2a₀<1 1 1> dislocation loops.     

Breather mechanism of the void ordering in crystals under irradiation

The void ordering has been observed in very different radiation environments ranging from metals to ionic crystals. In the present paper the ordering phenomenon is considered as a consequence of the energy transfer along the close packed directions provided by self-focusing discrete breathers. The self-focusing breathers are energetic, mobile and highly localized lattice excitations that propagate great distances in atomic-chain directions in crystals. This points to the possibility of atoms being ejected from the void surface by the breather-induced mechanism, which is similar to the focuson-induced mechanism of vacancy emission from voids proposed in our previous paper. The main difference between focusons and breathers is that the latter are stable against thermal motion. There is evidence that breathers can occur in various crystals, with path lengths ranging from 10⁴ to 10⁷ unit cells. Since the breather propagating range can be larger than the void spacing, the voids can shield each other from breather fluxes along the close packed directions, which provides a driving force for the void ordering. Namely, the vacancy emission rate for “locally ordered” voids (which have more immediate neighbors along the close packed directions) is smaller than that for the “interstitial” ones, and so they have some advantage in growth. If the void number density is sufficiently high, the competition between them makes the “interstitial” voids shrink away resulting in the void lattice formation. The void ordering is intrinsically connected with a saturation of the void swelling, which is shown to be another important consequence of the breather-induced vacancy emission from voids.