The kinetic/thermodynamic stabilization recent results of grain growth in nanomaterials (NMs)-based metals, alloys, and compounds are generalized. Due to their large share of interfaces which can act as the sinks for radiation defects, NMs show improved irradiation resistance such as the resistance to amorphization, hardening and swelling. Radiation defects will tend also to the nanostructure annihilation and transformation into amorphous state. Some unsolved problems are emphasized.

During neutron irradiation in nuclear power plants, uranium dioxide (UO2), the most used nuclear fuel, changes gradually its chemical composition because of the incorporation of new chemical elements which are created by fissions and named Fission Products (FP). As a consequence, the fluorine-type crystalline structure and its lattice parameters may also be modified. In order to better understand this behavior, neodymium-doped UO2 ceramics have been prepared with the aim to simulate the crystallographic matrix of irradiated fuels, since Nd is one of the most abundant FP. In a previous work, high temperature X-ray diffraction was performed on a sample (U0.72Nd0.28)O2, annealed under reducing conditions. The diffractograms evidenced, for the first time, the existence of a miscibility gap in the U-Nd-O system.

In this paper, we present the first results of a thermodynamic modeling of the ternary system U-Nd-O based on the CAlculation of PHAse Diagrams (CALPHAD) method, in order to obtain a complete description of this miscibility gap. The very first results of this modeling seem to confirm the presence of a region presenting two FCC (fluorite) phases (instead of a single solid solution, which is expected from literature). At room temperature, the gap appears from a Nd content as small as about 0.02 at. % and an O/M ratio slightly lower than 2.

Solute trapping of vacancies in a Ni host lattice is a first step to understanding how solute additions may effect ordering phase transformation in Ni-based alloys. Minor additions of solutes (<3 wt.%) may not have an appreciable effect on the thermodynamics of phase stability but strong binding between the vacancy and solute may significantly alter the kinetics of phase transformations. In this work vacancy-solute binding energies are calculated for multiple elements (Cr, Fe, Mn, Si, Ti, Nb, Ta, Cu, Al, Mo) in a pure Ni face-centered cubic lattice. These elements are common in corrosion-resistant Ni-based alloys. Binding enthalpies for the first four nearest-neighbor vacancy-solute pairs are reported for all elements. The results of this study show that Si, Ti, Nb and Ta bind to vacancies in the first nearest-neighbor position. Alloys containing these solute additions may experience delayed phase transformation due to vacancy trapping that slows diffusion.

Many theoretical predictions have suggested that the confined length scales and increased interface density of various nanostructured materials may result in desired thermal, mechanical, and radiation properties. An important aspect of this for next generation nuclear reactors is understanding the change in swelling resulting from helium evolution in tungsten alloys, as a function of grain size and grain boundary type. This study investigated this using a new ion irradiation transmission electron microscope (TEM) facility that has been developed at Sandia National Laboratories and is capable of ion implanting helium at energies up to 20 keV. It was demonstrated in this feasibility study that helium could be implanted into an ultrafine grained tungsten TEM sample produced by severe plastic deformation. The size and density of the helium bubbles formed during the experiment appear nearly constant; while the larger voids formed appear to be dependent on the local microstructure. Future work is underway to both optimize the facility, as well as better understand the evolution of ultrafine grained tungsten resulting from both helium implantation and displacement damage.

Pre-storage drying-transfer operations and early stage storage expose cladding to higher temperatures and much higher pressure-induced tensile hoop stresses relative to normal operation in-reactor and pool storage under these conditions. Radial hydrides precipitate during cooling and could provide an additional embrittlement mechanism as the cladding temperature decreases below the ductile-to-brittle transition temperature. To simulate this behavior, unirradiated Zircaloy-4 samples were hydrided by a gas charging method to levels that encompass the range of hydrogen concentrations observed in current used fuel. Mechanical testing was carried out by the ring compression test (RCT) method at various temperatures to evaluate the sample’s ductility for both as-hydrided and post-hydride reorientation treated specimens. As-hydrided samples with higher hydrogen concentration (>800 ppm) resulted in lower strain before fracture and reduced maximum load. Increasing RCT temperatures resulted in increased ductility of the as-hydrided cladding. A systematic radial hydride treatment was conducted at various pressures and temperatures for the hydrided samples with H content around 200 ppm. Following the radial hydride treatment, RCTs on the hydride reoriented samples were conducted and exhibited lower ductility compared to as-hydrided samples.

We report here partially stabilized zirconia (PSZ) matrix deposited with nanocrystalline diamond (NCD) films on its surface as an alternative material for pulverization disk with a potential of substituting high cost synthetic single crystal diamond. The deposition of NCD films on PSZ improved the characterization of the desorption-oxygen from PSZ matrix and enhanced the poor adhesion strength between NCD film and PSZ when N2 was used as doping gas. The results for X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed that with increasing N2 flow rate, nitrogen and desorption-oxygen were incorporated into film. The adhesion test and the pulverization test showed that enhancement in the adhesion strength as well as in the pulverization performance with increasing nitrogen and oxygen concentration in the NCD films. The results proposed to substitute a synthetic single crystal diamond with PSZ by coating nitrogen-doped NCD film.

Uranium-plutonium mixed oxides incorporating high amounts of plutonium are considered for future nuclear reactors. For plutonium content higher than 20%, a phase separation occurs, depending on the temperature and on the oxygen stoichiometry. This phase separation phenomenon is still not precisely described, especially at high plutonium content. Here, using an original in situ fast X-ray diffraction device dedicated to radioactive materials, we evidenced a phase separation occurring during rapid cooling from 1773 K to room temperature at the rate of 0.05 and 2 K per second for a (U0.55Pu0.45)O2-x compound under a reducing atmosphere. The results show that the cooling rate does not impact the lattice parameters of the obtained phases at room temperature but their fraction. In addition to their obvious fundamental interest, these results are of utmost importance in the prospect of using uranium-plutonium mixed oxides with high plutonium content as nuclear fuels.

We developed a new highly porous polyimide (PI) -silica composite with high flexibility, mechanical strength, and heat resistance. The composite was prepared by a new process consisting of (1) phase separation of a mixture of PI precursor (polyamic acid), solvent, and silicon alkoxide, induced by high-pressure CO2 (40 °C, 20 MPa), (2) silicate formation by sol-gel reaction, and (3) supercritical CO2 extraction of the solvent. The composite had a bimodal porous structure with micropores of 10-30 μm and nanopores of ∼50 nm. In the PI matrix, silica nanoparticles (< 100 nm in diameter) were highly dispersed. Porosity of the composite was 78%, which is higher than that of conventional porous PI prepared by physical foaming technique. Relative dielectric constant of the material was lower than 1.4 at 1 MHz. The porous PI-silica composite sheet was flexible enough to be folded without cracking. Notably, the Young’s modulus (0.80 GPa) and the onset decomposition temperature (600 °C) of the PI-silica composite were higher than those of conventional porous PI with similar porosity, respectively. The porous PI-silica composite is promising as a flexible thermal insulator for high-temperature use and as a thermal resistant low-k material.

Dielectric properties of titanium oxide ceramics are strongly influenced by the microstructural features and concentration of dopants and impurity ions. Electrical conductivity (via insulation resistance) of vanadium doped nanostructured titanium dioxide (TiO2) ceramics was measured as a function of donor concentration and temperature. In order to further clarify the effect of the dopants on the microstructural development and resultant dielectric properties of TiO2, electron paramagnetic resonance (EPR) spectroscopy was employed. Vanadium-doped TiO2 exhibited well-defined hyperfine splitting characteristics of the 51V nuclei indicating that the dopant ions are dispersed within the grains and not preferentially segregated at the grain boundaries.

One of the critical issues for development of the nuclear fusion demonstration reactor (DEMO) is the high heat flux on heat-resistant equipments, especially the blanket and divertor. Materials of such equipments require relatively high thermal conductivities. In this study, we developed iron-based composite materials with carbon nanotube (CNT) and copper, which have high thermal diffusivities, by means of Hot Pressing (HP) and Spark Plasma Sintering (SPS).

The thermal diffusivity in the iron/CNT composites was not high enough compared with that of pure iron, while iron/copper composite showed a relatively high thermal diffusivity in the joining conditions. One of the reasons not to be improved thermal diffusivity could be non-mono-dispersion of CNT by the formation of carbides in the matrix.

Precipitates of Cr at Σ3 <110> {112} GB in α-Fe have been studied using molecular dynamics with a two-band embedded atomic model potential. The accumulation and segregation of Cr atoms and the evolution of the GB depend on local Cr concentration and temperature. At the early stage, with the existence of vacancies, the strong attraction of Cr with the GB core provides a pathway for Cr atoms to quickly accumulate within the GB core. With the increase of Cr concentration, the size of Cr dilute precipitates increases dramatically. And the strong segregation of Cr at the GB is observed, when Cr concentration reach 20%. Also, the size of Cr precipitates increases with increasing the temperatures from 300 K to 1000 K. The accumulation and segregation of Cr atoms at the GB lead to significant deformation of the GB structure and the formation of GB steps, causing the displacement and broadening of the GB.

Helium embrittlement poses a great threat to materials used in both fusion and fissionreactor systems due to (n,α) transmutation reactions. Because of this, materials capable of moderating the helium content reaching grain boundaries and voids must be developed and improved to prevent catastrophic failure of reactor materials. Nanostructured ferritic alloys (NFAs) have shown great promise in preventing helium embrittlement due to the large number density of nanoscale precipitates acting as trapping sites for helium clusters and helium bubbles. In this study, we present density functional theory calculations on the interaction of helium with nanoscale precipitates found in NFAs as a preliminary study to furthering our understanding of the energetic mechanisms causing the precipitates to act as trapping sites for helium.

Electrochemical Impedance Spectroscopy (EIS) and the Parallel Electrical Dielectric Response Analysis (PEDRA) application were used to describe the inner barrier oxide films on irradiated zirconium alloys. This is achieved with minimal surface preparation and without disturbing the outer porous oxide. These two distinguishable inner and outer oxide layers result from a growth-fracture oxidation mechanism. Key to success of the EIS technique in describing the barrier oxide layer are: 1) the model and procedure used to fit EIS spectra, 2) the validation of the fit, and 3) converting circuit parameters (R, C and n) into physical attributes of the barrier oxide.

The barrier oxide is defined as the inner-dense layer adjacent to the metal-oxide interface. The integrity of barrier oxide is thought to effect both oxidation (i.e. access of water to the interface), and hydrogen pickup (i.e. failure hydrogen to escape away from the interface). Using EIS and the PEDRA application, the barrier oxide is described in terms of multiple independent dielectric responses to yield a unique 'micro-macro' picture of the barrier oxide that can be used to explain observed H pickup behavior.

The MIAMI* facility at the University of Huddersfield is one of a number of facilities worldwide that permit the ion irradiation of thin foils in-situ in a transmission electron microscope. MIAMI has been developed with a particular focus on enabling the in-situ implantation of helium and hydrogen into thin electron transparent foils, necessitating ion energies in the range 1 – 10 keV. In addition, however, ions of a variety of species can be provided at energies of up to 100 keV (for singly charged ions), enabling studies to focus on the build up of radiation damage in the absence or presence of implanted gas.

This paper reports on a number of ongoing studies being carried out at MIAMI, and also at JANNuS (Orsay, France) and the IVEM / Ion Accelerator Facility (Argonne National Lab, US). This includes recent work on He bubbles in SiC and Cu; the former work concerned with modification to bubble populations by ion and electron beams and the latter project concerned with the formation of bubble super-lattices in metals.

A study is also presented consisting of experiments aimed at shedding light on the origins of the dimensional changes known to occur in nuclear graphite under irradiation with either neutrons or ions. Single crystal graphite foils have been irradiated with 60 keV Xe ions in order to create a non-uniform damage profile throughout the foil thickness. This gives rise to varying basal-plane contraction throughout the foil resulting in almost macroscopic (micron scale) deformation of the graphite. These observations are presented and discussed with a view to reconciling them with current understanding of point defect behavior in graphite.

*Microscope and Ion Accelerator for Materials Investigations

A novel atom probe tomography (APT) method has been developed that enables a full description of the orientation relationship between individual grains to be determined together with estimates of the extents of solute segregation for all elements over the surface of the grain boundary with 1 nm by 1 nm spatial resolution. This approach also enables variations in the solute excess for the elements with the habit plane and curvature of the grain boundary to be evaluated. The method has been applied to a mechanically-alloyed nanostructured ferritic alloy (NFA) after high dose heavy ion irradiation. The innovative high-resolution two-dimensional mapping of the solute segregation across the surface of grain boundaries in the NFA clearly demonstrates that the distributions of chromium and tungsten are not uniform across the grain boundaries, and the distributions correlate with changes in its local curvature and the position of the grain boundary precipitates. These features pin the grain boundary against grain growth and provide the stability for excellent creep properties.

We present a physically justified formalism for the calculation of defect formation energies in UO2. The accessible ranges of chemical potentials of the two components U and O are calculated using the U-O experimental phase diagram and a constraint on the formation energies of vacancies. We then apply this formalism to the DFT+U investigation of the monovacancies and monointerstitials in UO2.

The results of the most stable charge states of these defects are consistent with a strongly ionic system. Calculations predict similarly low formation energies for $V_U^{4 - }$ and $I_O^{2 - }$ in hyperstoichiometric UO2.