The aging in plutonium is predominantly caused by its internal self irradiation. The self-irradiation in Pu-239 is by the decay process of transmuting the Pu atom into uranium atom and emitting an α-particle. Most of the lattice damage comes from the uranium recoil resulting in Frenkel type defects consisting of vacancies and self-interstitial atoms, helium in growth and defect clusters and possibly even though it is not yet observed, the generation of voids. As part of the stockpile stewardship, it is important to understand the changes in the structure and microstructures and their correlations to the physical properties. Changes in the physical properties has direct relationship to the quality of the structure, in terms of formation of defects and defect clustering, accumulation of voids, grain boundaries, phase changes and etc. which can adversely affects the stability of the material. These changes are very difficult to monitor because of the high activity of the sample, high atomic number making x-ray and synchrotron probe into the bulk very difficult (neutron probe is not feasible) and the long life time which normally requires decades to measure. In this paper we describe the development of an in-situ in-house transmission x-ray diffraction (XRD) experimental technique used to monitor the structural changes in these materials. This technique calls for a very thin sample of less that 2 μm and to accelerate the aging process due to self-irradiation, spiked alloy of 7.5 weight percent of Pu-238 is used. This is equivalent to roughly 17 times the normal rate of aging. Current results suggest that over a period of 2.8 equivalent years, an increase of 0.5% in unit cell parameter is observed. The increase appears to be an abrupt jump at about 1.1 equivalent years, brought about by the collapsing of the atoms from the interstitials to the lattice sites. Further data analysis is on the way.

An important issue in actinide science is the changing role of the 5f electrons, both when progressing across the series, as well as how experimental variables affect these roles in a particular element's chemistries and physics. The function of these 5f electrons can be changed by experimental conditions: temperature and pressure being two of many such variables. The 5f electrons of several actinide metals, their alloys and compounds are affected greatly by pressure, due to the very large decreases in interatomic distances encountered under pressure. The latter bring about significant changes in the total energy of the system and in the electronic energy levels, which in turn affect the potential for overlap/hybridization) of their orbitals, promotion of electrons to other orbitals, etc. The physical state, temperature, pressure, specific structures, magnetic interactions and spin polarization effects are all critical parameters for bonding. Often correlations of behavior with these parameters can provide unique insights and understanding into the bonding and the changes that occur in it. With the advancement of modern computation approaches using FPMTO, or other approaches, theory has enlightened greatly the understanding of not only the bonding behavior of these elements but also the understanding of changes observed experimentally. But these computational efforts have some complications and limitations, and at times experimental findings and theory are not always in full agreement. In contrast to the behaviors of the elements, changes observed with compounds often are not be linked directly to the involvement of 5f electrons, due in part to the presence and bonding role of non-actinide atoms. The latter affect both the actinide interatomic distances and the type of electronic orbtals that interact. Presented here is an overview of the pressure behavior several actinide elements, some insights into the bonding behavior of compounds under pressure and selected correlations that help explain changes occurring in electronic configurations and bonding.

In the characterisation of amorphisation or local disordering due to actinide radiation damage, nuclear magnetic resonance (NMR) spectroscopy is attractive because it is element specific and equally sensitive to local structure in crystalline and amorphous materials. Here, we have applied high-resolution solid-state NMR spectroscopy (magic-angle spinning) to radiation damaged natural minerals containing 238U/232Th to determine the ‘number fraction’ of amorphous material (fa) through spin-counting techniques. In samples with a known alpha dose, the number of atoms displaced per alpha decay may be determined from an integration of the spectrum. A protocol for performing similar radiological magic-angle spinning experiments on plutonium containing ceramic samples with an activity of > 5 GBq isp described. Results obtained have allowed data from ancient, radiation damaged mineral samples of ZrSiO4 (238U/232Th) to be compared with modern 238/239Pu doped ceramic ZrSiO4 samples. The number of atomic displacements per alpha particle from 239Pu is similar to that for 238U/232Th (4980 ± 300/α). At lower ?-doses there are significant differences in the amorphous volume fraction (observed by density and x-ray diffraction) and the number fraction of displaced atoms (as measured by NMR) as a function of cumulative dose. These differences arise from local density considerations that manifest themselves in the local structure of the amorphous and crystalline phases. Using ab initio simulations of the damaged crystalline and amorphous regions, the magnetic response of these structures and hence the NMR shifts can be compared with experiment to reveal the nature of radiation induced changes occurring at the local scale.

Single crystals of URu2-xRexSi2 have been grown via the Czochralski technique. Detailed electrical transport studies under pressure on single crystals of URu2Si2 confirm that the zero-temperature critical field is suppressed smoothly towards an extrapolated critical pressure of 15 kbar, which also corresponds to the accepted critical pressure of the hidden order phase. Improving on previous work on polycrystalline samples, studies of single crystals of URu2-xRexSi2 have provided more precise tracking of the suppression of both the hidden order phase at low doping and the ferromagnetic phase at intermediate Re concentrations.

Suitable microstructures and homogenous microspheres of actinide compounds are of interest for future nuclear fuel or transmutation target concepts to prevent the generation and dispersal of actinide powder. Sol-gel routes are being investigated as one of the possible solutions for producing these compounds. Preliminary work is described involving internal gelation to synthesize mixed compounds including minor actinides, particularly mixed actinide or mixed actinide-inert element compounds. A parameter study is discussed to highlight the importance of the initial broth composition for obtaining gel microspheres without major defects (cracks, craters, etc). In particular, conditions are defined to produce gel beads from Zr(IV)/Y(III)/Ce(III) or Zr(IV)/An(III) systems. After gelation, the heat treatment of these microspheres is described for the purpose of better understanding the formation of cracks after calcination and verifying the effective synthesis of an oxide solid-solution.