According to the Planning Act of 28th June 2006, Andra is in charge of ensuring the sustainable management of all radioactive waste generated in France, especially the high-level and long-lived vitrified waste produced from spent fuel recycling.

Since 2006, all the studies and research related to the components of HLW cells have been incorporated into a broader R&D program which aims at characterizing and modeling (i) the glass matrix dissolution, (ii) the corrosion of the overpack and the lining, and (iii) the claystone evolution in the near field, considering all the interactions between these surrounding materials. This program, coordinated by Andra, has involved up to eighteen laboratories.

After closure of disposal cells and overpack failure, glass alteration is expected to begin in partially saturated conditions due to hydrogen production resulting from carbon steel corrosion in anoxic conditions. Therefore, the glass should at least partially be hydrated by water vapor during thousands of years until complete saturation. A part of the studies aimed to determine the glass behavior in such conditions, the influence of the main parameters (temperature, relative humidity) and consequences of vapor hydration on subsequent radionuclides release by water leaching.

In addition, the major part of the work focused on the influence of the environment on glass alteration. The effect of clay pore water on glass alteration rates (initial rate, rate drop and residual rate) was determined and particularly that of pH and magnesium. The nature of steel corrosion products and their interactions with glass alteration were also investigated. All these studies relied on experiments in surface laboratories, in Andra’s underground laboratory, together with natural or archeological analogs and modeling studies.

The highlight of this work is the synthesis of copper sulfide nanocrystals by a simple one-pot colloidal process, and the study of its electrochemical, electrical and morphological properties. Nanocrystals of Cu1.8S of about 15-30 nm were obtained at a temperature of 240°C under an argon atmosphere. The colloidal solution of the nanocrystals was analyzed by cyclic voltammetry. Agreeing to the values of EOx and ERedvs. SCE, and the average of three samples the HOMO and LUMO levels are 6.16 and 4.27 eV, respectively, the calculated HOMO – LUMO (Eg) is 1.89 eV. The Eg value, differs of that value obtained from Kubelka-Munk equation (1.7 eV). The photocurrent vs. time results showed that the Cu1.8S/Cu junction is photosensitive and could be used as absorbing material. The morphology and the topography of the film were analyzed by SEM and AFM techniques. Irregular agglomeration of nanocrystals was observed and a roughness of about 194 nm.

ZrO2/Ge is potential high-k dielectric candidate to replace silicon based devices. Controlling stress in zirconia film and stabilizing high dielectric constant phase is crucial for high-k application. A precise control of stress and phase selectivity in high-k thin films is demonstrated. Thin films of ZrO2 were grown by reactive sputter deposition. Wide range of growth stress in thin films from -0.3 to -2.8 GPa can be tuned by growth rate control. Adatom incorporation into grain boundary was the dominant source of observed stress. Phase selectivity in zirconia was achieved by tuning growth parameters.

A range of optical and optoelectronic applications would benefit from high refractive index (n), dense and transparent films that guide, concentrate and couple light. However, materials with high n usually have a high optical extinction coefficient (κ) which keeps these materials from being suitable for optical components that require long optical paths. We studied titanium hafnium oxide alloy films to obtain high refractive index (n>2) with minimum optical extinction coefficients (κ < 10−5) over the visible and near IR spectrum (380-930 nm). Titanium hafnium oxide alloys were deposited using pulsed DC reactive magnetron sputtering with and without RF substrate bias on silicon dioxide. For a given deposition condition intended for a specific titanium/hafnium molar fraction ratio, the ion energy of deposition species was explicitly controlled by varying the RF substrate bias. Spectroscopic ellipsometry, transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS) and atomic force microscopy (AFM) were used to characterize the films. It appears that applying RF substrate bias reduces the nanocrystalline size, changes the surface morphology and increases the refractive index while maintaining comparable titanium/hafnium cation molar fraction. Precise control of the nanostructure of ternary metal oxides can alter their macroscopic properties, resulting in improved optical films.

A high-fidelity two-dimensional axial symmetrical multi-physics model is established to analyze and predict the performance of a recently discovered solid oxide metal-air redox battery (SOMARB). In particular for this study, the effects of the parameters used in the charge cycle including current density, depth-of-discharge and kinetic rate of Fe3O4-reduction on the performance have been systematically investigated. Three strategies are subsequently developed with goal of achieving a balanced specific energy and cycle efficiency for the best performance of SOMARB.

Nano-sized metallic powders have advantages as fuels including faster, more complete combustion than micron-sized metal powder particles; however, the unpassivated nanoparticles of some metals of interest, such as Al, are pyrophoric and highly reactive, making them difficult to handle. Additionally, metal-hydrides are of great potential interest for a significant gravimetric energy increase without a penalty in the volumetric energy content, as the inclusion of hydrogen in the metallic matrix does not significantly decrease overall density of the material. Reactive metal amorphous powders produced by the sonochemical decomposition and dehydrogenation of an in situ-produced mixed borohydride-tetrahydroaluminate of titanium and containing hydrogen are examined in the current work and show exceptional air-stability and higher energy content than nano-Al. An aerosolized powder burner is used to investigate the combustion behavior of these powders mixed with gaseous fuels to quantify the energy density and reaction rate as compared to commercial aluminum powders in an effort to benchmark the performance of the sonochemically generated amorphous Ti-Al-B powder fuels.

We have used fluctuation electron microscopy (FEM) to measure the medium range order in the molecular packing of 40 nm thick indomethacin glass films. Vapor deposition of indomethacin can create glasses with extraordinary kinetic stability and high density. We find peaks in the FEM variance at diffraction vector magnitudes between 0.03 and 0.09 Å-1, corresponding to intermolecular packing distances of 1-3 nm. FEM experiments were performed with a 13 nm diameter electron probe, so these data are sensitive to medium-range order in intermolecular packing. The FEM variance from an indomethacin glass with normal stability cooled from the liquid is significantly smaller than the variance from the ultrastable glass, suggesting that ultrastable glass is more structurally heterogeneous at a 13 nm length scale. A dose of ∼7×105 e-/nm2 with a very low beam current of ∼ 2.5 pA at 200 kV was used to minimize electron beam damage to the sample, and the average electron diffraction from the sample is unchanged at total electron doses fourteen times larger than required for a FEM experiment. These preliminary results on medium-range order in molecular glasses suggest that we may be able to provide insight into the structural differences between the remarkable ultrastable thin films and ordinary glasses.

As the major heat carriers in dielectrics and semiconductors, phonons are strongly scattered by boundaries and interfaces at the nanoscale, which can lead to a significantly reduced lattice thermal conductivity k L . In recent years, such phonon size effects have been used to enhance the thermoelectric performance of various nanostructured materials. With dramatically reduced k L and bulk-like electrical properties, high thermoelectric performance has been demonstrated for nanoporous Si films at room temperature. Despite these encouraging results, however, challenges still exist in the theoretical explanation of the observed low k L values. Existing studies mainly attribute the observed low k L to phononic effects and/or amorphous pore edges. These two effects can be separated when the specific heat of the film can be measured along with k L to provide more insight into the phonon dispersion modification. In this work, both the specific heat and k of a suspended nanoporous Si film is extracted from the 3ω measurements. The result is compared to the reported k L values of various porous Si films. The influence of employed phonon mean free path spectrum on the data analysis is discussed.

Cellulose nanocrystals (CNCs) have emerged as a new class of renewable material for various applications due to their remarkable properties and commercialization prospect. The relative low density, expected low cost, non-toxic character, uniform nanosize distribution, high aspect ratios, high surface area, thermal properties and high modulus of elasticity make CNCs attractive nanomaterials that recently prompted the industrial production of CNCs in North America. Surface functionalization of CNCs continues to be an exciting area of research for the design of novel CNC-based materials. In this work, we report the synthesis, characterization and cytotoxicity studies of novel cationic surface modified CNC derivatives. The negative surface of CNC was rendered positive after grafting with cationic polymers via surface-initiated living radical polymerization method. The modified CNCs were characterized by both spectroscopic and microscopic techniques. Their cytotoxicity effects were evaluated using MTT assay in two cell lines such as mouse macrophages (J774.A1) and human breast cancer (MCF7). Preliminary studies indicated that only one of the modified CNCs caused significant decrease in J774.A1 cell viability (50%), at the highest concentration tested (100 µg/mL). However this concentration is well above of what would be applicable for biomedical purposes. MCF7 cells were not affected by any of the cationic CNCs at any concentration. A detailed cytotoxicity study is currently underway to fully understand the interaction of these cationic CNCs with the biological systems for possible bio-inspired applications.

In the presented work, we have developed VLSI technology processes for new prototype sensors based on the synthesis of boron doped nanocrystalline diamond (B-NCD) and silicon based commercial detectors. The process is based on commercial passivated implanted planar silicon (PIPS) devices of PD450 and CAM450 types (CANBERRA). A layer of B-NCD of several hundred nanometers thickness and boron concentration up to 1021 atoms/cm3 is grown on the SiOx passivation layer in an ellipsoidal plasma enhanced chemical vapor deposition (PECVD) reactor at temperatures from 520-750°C, in hydrogen atmosphere. . The diamond electrode is dry chemically structured and aluminum electrodes are realized before mounting in a three-fold housing for measurements in aqueous solution. The prototype sensors show an alpha spectroscopy resolution of 100 keV for 241Am electroprecipitated from liquid solution.

We present results of modeling and experimental characterization of thermoelectric (TE) materials built on new fabrication principles, involving the coating of three-dimensionally structured quantum well super-lattice substrates with PbTe/PbSe. A new system for wafer-scale electrochemical deposition of such structures was specifically developed and will be described in this paper. Scanning electron microscopy (SEM) was used to measure film thickness and electron diffraction spectroscopy (EDS) was used to determine film material concentration. By adjusting deposition parameters, we were able to build stoichiometric PbSe, PbTe and stacked PbSe/PbTe super-lattice films on planar and pre-structured surfaces. The films were thermoelectrically modelled using COMSOL and then characterized using an infrared Seebeck effect measurement system which measured surface heating of the film while measuring the voltage associated with the temperature gradient. We report advances in the design and fabrication of TE materials which improve cost-effectiveness and TE efficiency.

Crosslinked or non-crosslinked ultrathin semipermeable membranes based on the N-butylated and N-butylsulfonated polybenzimidazole (BPBI and BSPBI) were successfully prepared by spin-coating method. Structural characterization by FTIR and WAXD revealed that the N-substitution and the crosslinked structure of PBI suppressed the hydrogen bonding and increased the d-spacing. Furthermore, positron annihilation lifetime spectroscopy (PALS) clearly showed the pore radius change from 0.27-0.29 nm to 0.33 nm by crosslinking. As a result, the enhancement of water flux and NaCl rejection was achieved by the crosslinking of the BPBI and BSPBI. Especially, the crosslinked N-butylsulfonated PBI (CL-BSPBI) membrane significantly improved not only salt rejection but also water flux (NaCl rejection : 46 %, water flux : 22.1 L m-2 h-1) compared to those of non-crosslinked BSPBI one (NaCl rejection : 11 %, water flux : 1.88 L m-2 h-1) due to both the Donnan effect and the formation of larger pores in the membrane, respectively.

We present a strain-free, self-assembled GaAs nanodots on GaAs(001) surfaces. Nanodots are studied by atomic force microscopy and field emission scanning electron microscopy. Nanodots self-assemble on the GaAs surface when two laser pulses overlap on the surface interferentially. Their stoichiometry is characterized by energy dispersive X-ray spectroscopy in the electron microscope. For the stoichiometry study, electrons with voltages less than 5 kilovolts were used to produce the characteristic X-rays from dots in order to enhance the surface sensitivity. The stoichiometric analysis indicates that the nanodots’ relative composition ratio of Ga over As reaches to that of GaAs substrate when the dot size becomes smaller than 100 nm. The chemical analysis suggests a novel route of strain-free semiconductor nanodots.

Thin films of amorphous silicon with nanocrystalline silicon inclusions are fabricated using a dual plasma PECVD co-deposition system. Raman spectroscopy and X-ray diffraction confirmed the crystallinity of the embedded nanocrystals as well as their diameter, which is varied from 4.3 nm to 17.5 nm. The dark conductivity of the films is highly dependent on the crystal fraction, with a maximum room temperature conductivity found for a crystal concentration of 5.5%, well below the percolation threshold. Proton irradiation at energies of 217 MeV with a total fluence of 5 x1012 protons/cm2 caused no significant radiation damage. The enhancement of the conductivity, along with the absence of radiation damage suggests this material may be a candidate for use in the next generation of particle detectors in the Compact Muon Solenoid in the Large Hadron Collider at CERN.

For the industrial application of silicon thin film solar cells, the current focus is on how to realize high-efficiency low-cost production process and minimize light-induced degradation effect, thus effectively reducing the balance-of-system (BOS) costs of system integration. In this paper, a brief introduction based on our development and application in this area is presented, highlighting in the achievement of some layers in a-Si:H/μc-Si:H tandem solar cell by optimizing the property of single layers, such as amorphous intrinsic layer, intermediate reflective layer and microcrystalline intrinsic layer. After transferring the process achievement to the industrial production line, we obtained the low-cost thin-film silicon solar cells with high photovoltaic conversion efficiency of 10.2%.

The junction resistance control of conducting networks is a crucial factor for high performance of the network-structured conducting film. Here, we show that silver nanowire (AgNW) networks can be stabilized by using single-walled carbon nanotubes (SWCNTs) which were functionalized with 2-ureido-4[1H]pyrimidinone (UHP) moieties. UHP-modified SWCNTs allowed us to fabricate AgNW suspension containing SWCNTs without adding additional dispersant molecules. The stabilization of AgNW networks was achieved by minimizing the joule heating at the NW-NW junction assisted by in-situ interconnection with the work function modulated SWCNTs. We propose that the electrical transportation pathway was modulated by the SWCNTs through the SWCNT-AgNW junctions, which results in a relatively lower junction resistance than the NW-NW junction in the network film.

Multimillion-atom reactive molecular dynamics (RMD) and large quantum molecular dynamics (QMD) simulations are used to investigate structural and dynamical correlations under highly nonequilibrium conditions and reactive processes in nanostructured materials under extreme conditions. This paper discusses four simulations:

1. 1. RMD simulations of heated aluminum nanoparticles have been performed to study the fast oxidation reaction processes of the core (aluminum)-shell (alumina) nanoparticles and small complexes.

2. 2. Cavitation bubbles readily occur in fluids subjected to rapid changes in pressure. We have used billion-atom RMD simulations on a 163,840-processor Blue Gene/P supercomputer to investigate chemical and mechanical damages caused by shock-induced collapse of nanobubbles in water near silica surface. Collapse of an empty nanobubble generates high-speed nanojet, resulting in the formation of a pit on the surface. The gas-filled bubbles undergo partial collapse and consequently the damage on the silica surface is mitigated.

3. 3. Our QMD simulation reveals rapid hydrogen production from water by an Al superatom. We have found a low activation-barrier mechanism, in which a pair of Lewis acid and base sites on the Al n surface preferentially catalyzes hydrogen production.

4. 4. We have introduced an extension of the divide-and-conquer (DC) algorithmic paradigm called divide-conquer-recombine (DCR) to perform large QMD simulations on massively parallel supercomputers, in which interatomic forces are computed quantum mechanically in the framework of density functional theory (DFT). A benchmark test on an IBM Blue Gene/Q computer exhibits an isogranular parallel efficiency of 0.984 on 786,432 cores for a 50.3 million-atom SiC system. As a test of production runs, LDC-DFT-based QMD simulation involving 16,661 atoms was performed on the Blue Gene/Q to study on-demand production of hydrogen gas from water using LiAl alloy particles.

Two self-assembling twin guanine-cytosine (G∧C) hybrid molecules featuring porphyrin (TPPO-(G∧C)2) and oligothiophene groups (6T-(G∧C)2) were synthesized. In organic solution, these molecules self-assemble into one-dimensional rosette nanotubes (RNTs) featuring the porphyrin or oligiothiophene groups on the outer surface. Using a combination of imaging and spectroscopic techniques we established the structure of the TPPO-(G∧C)2 and 6T-(G∧C)2 RNTs and compared the HOMO and LUMO energy levels with PC61BM, a well-known electron acceptor material. These studies, in combination with solid-state photoluminescence data of PC61BM-TPPO-(G∧C)2 RNT blended thin films, indicates that these self-assembled nanomaterials have great potential as electron donor materials for solution-processed organic photovoltaics.