Waspaloy specimens aged at 800°C from 0.5h to 88.5h were evaluated via small angle neutron scattering (SANS), ultra small angle X-ray scattering (USAXS), electrical resistivity, and SEM. The average γ' precipitate size and volume fraction, obtained from modeling the small angle scattering data, was used to calculate a figure of merit of electron scattering. This figure of merit is designed to correlate the electron scattering ability of the material to the precipitate microstructure. The USAXS data shows a secondary precipitate population at smaller diameters that is absent from the SANS data, since the SANS measurements were not obtained at high enough values of Q. It is believed that this secondary population makes the USAXS-derived figure of merit more sensitive to the actual measured resistivity response than the SANS-derived values; however, the SANS derived primary precipitate sizes are believed to more accurate due to a larger sample volume.

Dynamic local structural change of Pd nanoparticles on alumina surface during hydrogen absorption process was directly observed by x-ray absorption fine structure spectroscopy with dispersive mode. Main four parameters of x-ray absorption spectroscopy were determined even in the case of 50 Hz observation. It is clearly revealed that Pd nanoparticles directly change to the hydride phase in 50 ms at 200 kPa of hydrogen pressure. Although large lattice expansion was observed, significant structural distortion was not investigated in the results of the change of Debye-Waller factor.

Electron tomography and high-resolution transmission electron microscopy were used to characterize the unique 3-dimensional (3D) structures of twinned Zn3P2 (tetragonal) and InAs (zinc blende) nanowires synthesized by the vapor transport method. The Zn3P2 nanowires adopt a unique superlattice structure that consists of twinned octahedral slice segments having alternating orientations along the axial [111] direction of a pseudocubic unit cell. The apices of the octahedral slice segment are indexed as six equivalent <112> directions at the [111] zone axis. At each 30 degrees turn, the straight and zigzagged morphologies appear repeatedly at the <112> and <011> zone axes, respectively. The 3D structure of the twinned Zn3P2 nanowires is virtually the same as that of the twinned InAs nanowires. In addition, we analyzed the 3D structure of zigzagged CdO (rock salt) nanowires and found that they include hexahedral segments, whose six apices are matched to the <011> directions, linked along the [111] axial direction. We also analyzed the unique 3D structure of rutile TiO2 (tetragonal) nanobelts; at each 90 degree turn, the straight morphology appears repeatedly, while the in-between twisted form appears at the [011] zone axis. We suggest that the TiO2 nanobelts consist of twinned octahedral slices whose six apices are indexed by the <011>/<001> directions with the axial [010] direction.

Understanding the high-pressure kinetics associated with the formation of methane hydrates is critical to the practical use of the most abundant energy resource on earth. In this study, we have studied, for the first time, the compression rate dependence on the formation of methane hydrates under pressures, using dynamic-Diamond Anvil Cell (d-DAC) coupled with a high-speed microphotography and a confocal micro-Raman spectroscopy. The time-resolved optical images and Raman spectra indicate that the pressure-induced formation of methane hydrate depends on the compression rate and the peak pressure. At the compression rate of around 5 to 10 GPa/s, methane hydrate phase II (MH-II) forms from super-compressed water within the stability field of ice VI between 0.9 GPa and 2.0 GPa. This is due to a relatively slow rate of the hydrate formation below 0.9 GPa and a relatively fast rate of the water solidification above 2.0 GPa. The fact that methane hydrate forms from super-compressed water underscores a diffusion-controlled growth, which accelerates with pressure because of the enhanced miscibility between methane and super-compressed water.

Inorganic borohydrides have a high gravimetric hydrogen density but release H2 only under energetically unfavorable conditions. Surface chemistry may help in lowering thermodynamic barriers, but inclusion of inorganic borohydrides in porous silica materials has proved hitherto difficult or impossible. We show that borohydrides with a large organic cation are readily adsorbed inside mesoporous silicates, particularly after surface treatment. Thermal analysis reveals that the decomposition thermodynamics of tetraalkylammonium borohydrides are substantially affected by inclusion in MCM-48. Inelastic neutron scattering (INS) data show that the compounds adsorb on the silica surface. Evidence of pore loading is supplemented by DSC/TGA, XRD, FTIR, and BET isotherm measurements. Mass spectrometry shows significant hydrogen release at lower temperature from adsorbed borohydrides in comparison with the bulk borohydrides. INS data from partially decomposed samples indicates that the decomposition of the cation and anion is likely simultaneous. These data confirm the formation of Si-H bonds on the silica surface upon decomposition of adsorbed tetramethylammonium borohydride.

First principles density functional calculations and inelastic neutron scattering measurements have been used to study the variations of the phonon density of states of PbTiO3 and SrTiO3 as a function of temperature. The phonon spectra of the quantum paraelectric SrTiO3 is found to be fundamentally distinct from those of ferroelectric PbTiO3 and BaTiO3. SrTiO3 has a large 70-90 meV phonon band-gap in both the low temperature antiferrodistortive tetragonal phase and in the high temperature cubic phase.

Key bonding changes in these perovskites lead to spectacular differences in their observed phonon density of states.

In order to study magnetic states in Fe-hydride under pressure, X-ray magnetic circular dichroism (XMCD) at the Fe K-edge has been measured up to 27.5 GPa. As a result, hydrogenation from bcc-Fe to dhcp-FeH occurs within a narrow region of 3.2-3.8 GPa, which is clearly observed by the dichroic profile in dhcp-FeH differing from that in bcc-Fe. Influence of H atoms on Fe 3d and 4p electronic states is discussed using the pressure-dependent XMCD and the first-principles calculation.

Growing interest in nanomaterials has raised many questions regarding the operating mechanisms active during the deformation and failure of nanoscale materials. To address this, a simple, effective in situ TEM straining technique was developed that provides direct detailed observations of the active deformation mechanisms at a length scale relevant to most nanomaterials. The capabilities of this new straining structure are highlighted with initial results in pulsed laser deposited (PLD) Al-Al2O3 thin films of uniform thickness. The Al-Al2O3 system was chosen for investigation, as the grain size can be tailored via deposition and annealing conditions and the active mechanisms in the binary system can be compared to previous studies in PLD Ni and evaporated Al films. PLD Al-Al2O3 free-standing films of various oxide concentrations and different thermal histories were produced and characterized in terms of average grain and particle sizes. Preliminary in situ TEM straining experiments show intergranular failure for films with 5 vol% Al2O3. Further work is in progress to explore and understand the active deformation and failure mechanisms, as well as the dependence of mechanisms on processing routes.

Neutron radiography is a powerful tool for the investigation of the hydrogen uptake of zirconium alloys. It is fast, fully quantitative, non-destructive and provides a spatial resolution of 30 μm. The non-destructive character of neutron radiography provides the possibility of in-situ investigations. The paper describes the calibration of the method and delivers results of ex-situ measurements of the hydrogen concentration distribution after steam oxidation, as well as in-situ experiments of hydrogen diffusion in β-Zr and in-situ investigations of the hydrogen uptake during steam oxidation.

X-ray detection on hydrogen related events is difficult due to its extremely small scattering factor. In this report, we have used nuclear resonance vibrational spectroscopy (NRVS) to examine the nature of the Fe–H vibrational modes in several FeH model complexes, which shines light on the possible measurements on the Fe-H vibrations inside real biological systems in the future.

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C.

The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content.

Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra.

For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling.

A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides.

The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

Pressure induced magnetic phase transition of iron hydride was investigated with an in-situ Mössbauer spectrometer using synchrotron radiation (SR). The spectrometer is composed of a high resolution monochromator, an X-ray focusing device, a variable frequency nuclear monochromator and a diamond anvil cell. The optical system, advantages of the spectrometer and the observed high pressure magnetic phases of iron hydride are described.

This article underlines with examples of studies for energy related materials and processes how important and useful the technique of neutron imaging can be for our future energy supply. With the help of the particularly designed configurations for each such study it becomes possible to derive essential information for the material properties and their change in a non-invasive manner.

The four mentioned examples (PEM fuel cell, Li-battery, hydrogen storage and nuclear fuel inspection) cover a very wide range of applications and demonstrate the high potential of the various used methods in neutron imaging.

Ni-NiO 30% electrodes coated with LiMg0.05Co0.95O2 cobaltite deposited on the substrate by complex sol-gel process were investigated by neutron diffraction. The measurements were carried out at the D20 diffractometer at the High Flux Reactor of the Institut Max von Laue – Paul Langevin. As the catalytic layer is only a few microns thick, the diffracting volume of the cobaltite phase was optimised by stacking small rectangular pieces cut from the original electrode and assuming that the catalytic layer on the electrodes was homogenous. A pure cobaltite sample was used as a reference for identifying in the complete electrode the diffraction peaks of the catalytic layer. Both an as-received sample and an electrode tested for 100 h at 650 °C in a cell were measured. Despite the small diffracting volume, due to the high flux available at D20, it was possible to detect the hexagonal phase of the catalytic layer and estimate its volume fraction in the as-received sample; in the tested electrode the original crystallographic structure is completely modified but information on the phases present can be obtained.

La(Fe0.88Si0.12)13 shows peculiar magnetic properties such as the first order paramagnetic-ferromagnetic transition and magnetic-field induced metamagnetic transition accompanied by the lattice expansion. The practical application using the magnetic transition temperature controlled by hydrogen absorption is expected in this compound. Here, the electronic structure of La(Fe0.88Si0.12)13 has been investigated by photoemission spectroscopy using synchrotron soft x-rays. The Fe 3s core-level photoemission spectra below and above the Curie temperature TC exhibit a satellite structure at ~ 4.3 eV higher binding energy than the main peak, which is attributed to the exchange splitting due to the local moment of Fe. The exchange splitting of the Fe 3s photoemission spectrum with the asymmetric line shape shows that the magnetization of La(Fe0.88Si0.12)13 is derived by the exchange split Fe 3d bands like the itinerant ferromagnetism in Fe metal, while the magnetic transition of La(Fe0.88Si0.12)13 is the first order. The valence band photoemission spectrum shows temperature dependence across the TC. The temperature dependence of the photoemission spectra is discussed based on the difference between the electronic structure in the ferromagnetic phase and that in the paramagnetic phase.

Microstructural evolution is directly observed when the cross-sectional film specimen of Si/SiGe/Si on insulator (Si/SiGe/SOI) is heated from room temperature (R.T., 291 K) up to 1113 K in high voltage transmission electron microscope (HVEM). The misfit dislocation at the lower interface of the SiGe layer begins to extend downwards even at 913 K. The lower interface takes the lead in roughening against the upper interface of the SiGe layer. The roughened interface is ascribed to elastic relaxation. As misfit strain is partially transferred to SOI top Si layer and misfit dislocation is prolonged at the lower interface, the roughened interface turns smooth again. Thereafter, the misfit dislocations are introduced into the upper roughened interface of the SiGe layer to release the increased misfit strain. It is suggested that the microscopic relaxation of the SiGe layer is related to dislocation behavior and strain transfer.

Light element complex hydrides (e.g. NaBH4) together with metal hydrides (e.g. MgH2) are considered two primary classes of solid state hydrogen storage materials. In spite of drawbacks such as unfavourable thermodynamics and poor kinetics, enhancements may occur in reactive hydride composites by nanostructuring of reactant phases and formation of more stable product phases (e.g. MgB2) which lower overall reaction enthalpy and allow reversibility. One potential system is based on mixing NaBH4 and MgH2 and subsequent ball milling, which in a 2:1 molar ratio can store considerable amounts of hydrogen by weight (up to 7.8 wt%). A study of the 2NaBX4 + MgX2 → MgB2 + 2NaX + 4X2 (X=D,H) reaction is assessed by means of in-situ neutron diffraction with different combinations of hydrogen and deuterium on the X position. The desorption is established to begin at temperatures as low as 250 °C, starting with decomposition of nanostructured MgX2 due to joint effects of nanostructured MgX2 and its reducing effect at NaBX4. Analyses of background profile, due to the high incoherent neutron scattering of hydrogen, as a function of temperature demonstrate direct correlation of H/D desorption reactions with relative phases amount.

Cu-Li-Mg-(H,D) was studied as an example of destabilizer of the Ti-(H,D) system. A Cu-Li-Mg alloy was prepared resulting in the formation of a system with 60.5 at% of CuLi0.08Mg1.92, 23.9 at% of CuMg2 and 15.6 at% of Cu2Mg. Titanium was added to a fraction of this mixture so that 68.2 at% (47.3 wt%) of the final mixture was Ti. The mixture was ground and kept at 200 °C/473 K for 7h under H2 or 9h under D2 at P = 34 bar. Under those conditions, neutron powder diffraction shows the formation of TiD2, as well as of the deuteride of CuLi0.08Mg1.92. Similarly inelastic neutron scattering shows that at 10 K TiH2 is present in the sample, together with the hydride of CuLi0.08Mg1.92. Interestingly, at 10 K TiH2 is very clearly detected and at 300 K TiH2 is still clearly present as indicated by the neutron vibrational spectrum, but CuLi0.08Mg1.92-H is not detected anymore. These results indicate that Ti(H,D)2 is possibly formed by diffusion of hydrogen from the Cu-Li-Mg-(H,D) alloys. This is an intriguing result since TiH2 is normally synthesized from the metal at T > 400°C/673 K (and most commonly at T ˜ 700 °C/973 K). In the presence of CuLi0.08Mg1.92, TiH2 forms at a temperature that is 300 – 400 K lower than that needed to synthesize it just from the elements.

The influence of adding InF3 as a reducing agent on the oxidation state of Eu in fluoro-chloro- (FCZ) and fluorobromozirconate (FBZ) glass ceramics was investigated using x-ray ab-sorption near edge (XANES) and photoluminescence (PL) spectroscopy. For both materials, it was found that InF3 decreases the Eu2+-to-Eu3+ ratio significantly. PL spectroscopy proved that an annealing step leads to the formation of Eu-doped BaCl2 and BaBr2 nanocrystals in the FCZ and FBZ glasses, respectively. In the case of FCZ glass ceramics the hexagonal phase of BaCl2 could be detected in indium-free and InF3-doped ceramics, but only for InF3 containing FCZ glass ceramics a phase transition of the nanoparticles from hexagonal to orthorhombic structure is observed. For the FBZ glass ceramics, the hexagonal phase of BaBr2 can be formed with and without indium doping, but only in the indium-free case a phase transition to orthorhombic BaBr2 could be found.