The crystal structure of VOBDC (BDC = 1,4-benzenedicarboxylate) has a 1-dimensional channel system with apertures of ∼8 Å, and shows remarkable flexibility upon adsorption/desorption of various guest molecules in the channels. VOBDC can selectively and rapidly adsorb organic molecules containing sulfur on exposure to a 5% CH4/He stream with different contents of thiophene or dimethyl sulfide at ambient temperature. Selective uptake of thiophene from liquid octane with thiophene concentrations from 2000 ppmw down to 100 ppmw is also observed. X-ray crystallographic data show that the adsorbed thiophene molecules adopt a herringbone packing arrangement within the channels of VOBDC while adsorbed dimethyl sulfide molecules are disordered among several positions in the channels with the sulfur atoms pointing toward the channel walls. The observed adsorptive capacities for thiophene and dimethyl sulfide are 155 mg and 208 mg sulfur per gram of VOBDC, respectively, consistent with the crystal structure data.

Current semiconductor technology demands the use of compliant substrates for flexible integrated circuits. However, the maximum total strain of such devices is often limited by the extensibility of the metallic components. Although cracking in thin films is extensively studied theoretically, little experimental work has been carried out thus far. Here, we present a systematic study of the cracking behavior of 34- to 506-nm-thick Cu films on polyamide with 3.5-to 19-nm-thick Ta interlayers. The film systems have been investigated by a synchrotron-based tensile testing technique and in situ tensile tests in a scanning electron microscope. By relating the energy release during cracking obtained from the stress-strain curves to the crack area, the fracture toughness of the Cu films can be obtained. It increases with Cu film thickness and decreases with increasing Ta film thickness. Films thinner than 70 nm exhibit brittle fracture, indicating an increasing inherent brittleness of the Cu films.

The electrical resistivity ρ of palladium (Pd) films prepared by using magnetron sputtering at different pressures φ ranging from 2 to 15 mTorr showed very different hydrogen (H)-induced response. This reaction is because the mean free path of the particles in vacuum changes substantially with φ, such that the structure of the deposits is altered accordingly. A film prepared at a moderate φ value of 6 mTorr has a moderate strength. After a few hydrogenation-dehydrogenation cycles, some cracks are generated because of the great difference in the specific volumes of the metal and hydride phases. Breathing of the cracks in subsequent switching cycles occurred, which led to the response gain of ρ, defined as the resistivity ratio of the dehydrogenated-to-hydrogenated states during a cycle, to increase to 17. This result demonstrates the attractiveness of using the Pd films in H2 detection application. The H-induced resistive response of the films prepared at other φ values was found to be much smaller.

The structure and the response of the effective electrical resistivity 〈ρ〉 in hydrogenation–dehydrogenation processes of palladium-coated/magnesium-nickel (Pd/Mg–Ni) films were investigated as functions of Mg-to-Ni ratio, substrate temperature, and thickness of Pd overcoat. Films of noncrystalline structures with various Mg-to-Ni ratios showed prominent hydrogen-(H-)induced switching effect of 〈ρ〉. A film is supposed to contain segregated noncrystalline regions of different Mg-to-Ni ratios. The regions of an Mg-to-Ni ratio close to 2 are responsible for the switching processes. At room temperature, a dehydrogenation process is much slower than a hydrogenation process. Crystallization hindered the H-induced switching effect of 〈ρ〉. The use of a thicker Pd overcoat accelerated the change of 〈ρ〉 in the initial hydrogenating process but diminished the contrast. Results led to some discussions on the mechanisms governing the switching effects.

The effect of Li3N additive on the Li-Mg-N-H system was examined with respect to the reversible dehydrogenation performance. Screening study with varying Li3N additions (5, 10, 20, and 30 mol%) demonstrates that all are effective for improving the hydrogen desorption capacity. Optimally, incorporation of 10 mol% Li3N improves the practical capacity from 3.9 wt% to approximately 4.7 wt% hydrogen at 200 °C, which drives the dehydrogenation reaction toward completion. Moreover, the capacity enhancement persists well over 10 de-/rehydrogenation cycles. Systematic x-ray diffraction examinations indicate that Li3N additive transforms into LiNH2 and LiH phases and remains during hydrogen cycling. Combined structure/property investigations suggest that the LiNH2 “seeding” should be responsible for the capacity enhancement, which reduces the kinetic barrier associated with the nucleation of intermediate LiNH2. In addition, the concurrent incorporation of LiH is effective for mitigating the ammonia release.

The indentation stress is the key and fundamental parameter in indentation delamination tests, which are widely used in characterization of the interfacial fracture toughness (or adhesion) between a thin film and its substrate. The indentation stress was analyzed in the present work by using the finite element method for microwedge indenters of different wedge angles and with various other geometrical and mechanical parameters including the penetration depth, film thickness, delamination size, Young's modulus, and yield strength of the indented film. The analysis exhibited the stress field under an indentation load and the stress field after unloading caused by plastic deformation, which resulted in the loading indentation stress and the unloading indentation stress, respectively, expressed by empirical formula in terms of the indenter geometry, the indentation depth, and the film thickness and mechanical properties. The energy release rate was also calculated for the indentation-induced interfacial crack.

In instrumented indentation tests for a thin film coating on a substrate (film/substrate composite), it is well known that the substrate-affected contact area estimated through conventional approximations includes significant uncertainties, leading to a crucial difficulty in determining the elastic modulus and the contact hardness. To overcome this difficulty, an instrumented indentation microscope that enables researchers to make an in situ determination of the contact area is applied to an elastoplastic film on substrates having various values of their elastic moduli. Using the indentation microscope, the substrate-affected indentation contact parameters including contact hardness of the film/substrate composites are determined directly as well as quantitatively without any undesirable assumptions and approximations associated with the contact area estimate. The effect of a stiffer substrate on the contact profile of impression is significant, switching the profile from sinking in to piling up during penetration, and resulting in the substrate-affected contact hardness being highly enhanced at deeper penetrations. Through the present experimental study, it is demonstrated how efficient that instrumented indentation microscopy is in determining the substrate-affected elastoplastic contact parameters of film/substrate composite systems.

In this work load–penetration curves obtained by nanoindentation were analyzed, using a spherical tip approximation and applying the stress/strain concept by Tabor. Nanoindentation experiments were done on sapphire, pure TiC, and a mixed ceramic with in situ formed TiCx layer, using a sharp cube-corner indenter at very low loads and penetration depths. With the implemented method it is possible to display the elastic to elastic–plastic transition of each investigated phase, and much more information can be extracted than by conventional analysis. Regarding the mixed ceramic, it was found that the present TiC phases exhibit slightly lower hardness than the alumina phase, but they can sustain much higher stresses during the transition from the elastic to the elastic–plastic regime. This is considered to be beneficial for the application as cutting material. No correlation was found between the nanomechanical behavior of the model materials sapphire and TiC and the corresponding phases of the mixed ceramic.

Phase transformations in (111) Si after spherical indentation have been investigated by cross-sectional transmission electron microscopy. Even at an indentation load of 20 mN, a phase transformation zone including the high-pressure crystalline Si phases was observed within the residual imprints. The volume of the transformation zone, as well as that of the crystalline phases increased with the indentation load. Below the transformation zone, slip was found to occur on {311} planes rather than on {111} planes, usually observed on indentation of (100) Si. The distribution of defects was asymmetric, and for indentation loads up to 80 mN, their density was significantly lower than that reported for (100) Si. The experimental observations correlated well with modeling of the applied stress through ELASTICA.

Recently, there is a growing interest in two-dimensional (2D) plane indentation as an imprinting method for creating nanostructures. There is also a strong interest in using 2D flat-ended, wedge, and cylindrical indenters for characterizing mechanical properties of materials. In either case the knowledge of load versus displacement of the indenter is important. However, there has been some confusion about the load–displacement relationships for 2D indentation in the literature. Concerning this confusion on the relationship between the indentation load and the indentation depth for 2D elastic indentations, the symmetric indentation of an elastic half-space is studied. Parameters are introduced in determining the semianalytical relation between the indentation load and the indentation depth for flat-ended indenters and in determining the dependence of the indentation depth on the contact size for non-flat-ended indenters. The indentation load is proportional to the indentation depth for the indentation by flat-ended indenters and is a parabolic function of the indentation depth to the first order of approximation for non-flat-ended indenters including the wedge and cylindrical indenters.

In this article, the chemical and structural changes inside soda-lime glasses induced by femtosecond (fs) laser pulsing have been reported, based on transmission electron microscopy and electron energy loss spectroscopy studies. Under fs-laser interaction, Na-rich phases are formed, and Na nanoparticles are also precipitated around the Na-rich phases. These findings demonstrate how powerful and efficient the fs-laser pulsing and interaction can be in making novel microstructures in soda-lime silicate glass, and they bridge the gap between the macroscale property changes and nanometer-scale structures.

In this work, the influence of SiO2 additions in leucite ceramics on the bulk linear thermal expansion coefficient (TEC) especially during the phase transition, has been studied. Thermal expansion and x-ray diffraction measurements at high temperatures were carried out to characterize the tetragonal-cubic phase transition. TEC for reference and SiO2-added leucite samples exhibited similar behavior as a function of temperature. Before and after the phase transition, the TEC values were similar to those observed in non-SiO2-added samples, whereas during the phase transition, a maximum TEC value was observed and it tends to decrease as the SiO2 addition increases. This behavior could be caused by the formation of an intermediate phase with an extremely high TEC (70 × 10–6 °C−1) during the phase transformation. Furthermore, the results suggest that as the intermediate phase is partially suppressed via SiO2 addition, the cubic phase can be partially stabilized at temperatures as low as 200 °C.

The growth of SrTiO3 (STO) thin films is examined using classical molecular dynamics simulations. First, a beam of alternating SrO and TiO2 molecules is deposited on the (001) surface of STO with incident kinetic energies of 0.1, 0.5, or 1.0 eV/atom. Second, deposition of alternating SrO and TiO2 monolayers, where both have incident energies of 1.0 eV/atom, is examined. The resulting thin film morphologies predicted by the simulations are compared to available experimental data. The simulations indicate the way in which the incident energy, surface termination, and beam composition influence the morphology of the thin films. On the whole, some layer-by-layer growth is predicted to occur on both SrO- and TiO2-terminated STO for both types of deposition processes, with the alternating monolayer approach yielding thin films with compositions that are much closer to that of bulk STO.

We have observed ferromagnetism in dilute cobalt-doped SnO2 nanowires at room temperatures. The Co-doped SnO2 nanowires with an average diameter of ∼50 nm were synthesized by the thermal chemical vapor transport method. High-resolution transmission electron microscopy and energy-dispersive x-ray spectroscopy analyses demonstrate that the nanowires are single-crystal structures and Co is homogeneously doped into the SnO2 lattice. The ferromagnetic hysteresis curves and temperature-dependent magnetization measurement provide evidence for ferromagnetic properties with a Curie temperature above room temperature. Oxygen annealing has been performed to study the roles played by the oxygen vacancies in determining the ferromagnetic properties of the nanowires.

High-resolution transmission electron microscopy (HRTEM) images of annealed ZnO thin films showed the domain boundaries of a (0) plane with a transition zone and a (1) plane without a transition zone. The 30° in-plane rotation domain boundaries were formed in the ZnO thin films because the angle of the c-axis was tilted 3.5° in comparison with that of neighboring 30° in-plane rotation domains to reduce the misfit strain energy. The atomic arrangement variations of 30° in-plane rotation domain boundaries in ZnO thin films grown on Si substrates due to thermal annealing are described.

Spark plasma sintering (SPS) of MgAl2O4 powder was investigated at temperatures between 1200 and 1300 °C. A significant grain growth was observed during densification. The densification rate always exhibits at least one strong minimum, and resumes after an incubation period. Transmission electron microscopy investigations performed on sintered samples never revealed extensive dislocation activity in the elemental grains. The densification mechanism involved during SPS was determined by anisothermal (investigation of the heating stage of a SPS run) and isothermal methods (investigation at given soak temperatures). Grain-boundary sliding, accommodated by an in-series {interface-reaction/lattice diffusion of the O2− anions} mechanism controlled by the interface-reaction step, governs densification. The zero-densification-rate period, detected for all soak temperatures, arise from the difficulty of annealing vacancies, necessary for the densification to proceed. The detection of atomic ledges at grain boundaries and the modification of the stoichiometry of spinel during SPS could be related to the difficulty to anneal vacancies at temperature soaks.

High temperature plasma nitriding of yttria-partially-stabilized zirconia in atmospheric pressure microwave plasma was investigated. The morphological, mechanical, and physicochemical characteristics of the resulting nitrided layer were characterized by different methods, such as optical and scanning electron microscopy, microindentation, x-ray diffraction, narrow resonant nuclear reaction profiling, secondary neutral mass spectrometry, and x-ray photoelectron spectroscopy, aiming at investigating the applicability of this highly efficient process for nitriding of ceramics. The structure of the plasma nitrided layer was found to be complex, composed of tetragonal and cubic zirconia, as well as zirconium nitride and oxynitride. The growth rate of the nitrided layer, 4 µm/min, is much higher than that obtained by any other previous nitriding process, whereas a typical 50% increase in Vickers hardness over that of yttria-partially-stabilized zirconia was observed.

Relaxor ferroelectrics of Pb(Zn1/3Nb2/3)0.5(Zr0.47Ti0.53)0.5O3 (0.5PZN-0.5PZT) were prepared using the conventional oxide mixing method. Both x-ray diffraction analysis and Raman spectroscopy indicate that the amounts of rhombohedral phase are close to tetragonal phase, implying the presence of the morphotropic phase boundary (MPB) in the system of 0.5PZN-0.5PZT, and this result was further confirmed by transmission electron microscopy (TEM) micrographs. At MPB composition, the excellent piezoelectric properties, such as kp (0.66) and d33 (425pC/N), were obtained due to the more possible polarization directions of domains and high dc resistivity of 6.5 × 1010 Ω·cm. Meanwhile, the dielectric studies revealed that the indicator of the degree of diffuseness γ value is 1.73, implying that the relaxor nature of the 0.5PZN-0.5PZT is ceramic. The activation energy related to the dc conductivity was estimated from a linear fitting of the Arrhenius law. The value of 0.09 and 1.04 eV for low and high temperature range corresponds well to the activation energies of migration and first ionization of the oxygen vacancies.

A set of Bragg peaks consistent with a hexagonal Bravais lattice was observed in the x-ray powder diffraction pattern of cubic pyrochlore rubidium tungstoniobate (RbNbWO6) subjected to high-energy ball milling. The calculated lattice parameters for this hexagonal phase are similar to those of compounds with tungsten bronze structure. In fact, the powder pattern of the hexagonal phase could be refined with a structural model based on the tungsten bronze structure. The hexagonal phase produced by high-energy ball milling of RbNbWO6 transforms back to the pyrochlore structure upon heating to 773 K in air. A similar phase was obtained by ball milling the mixture RbNbWO6 + WO3, but, in this case, the stoichiometric hexagonal tungsten bronze compound thus obtained remained stable up to 1273 K.

Bulk NaYF4:Yb,Er particles (∼1.4 μm particle size) were synthesized using a hydrothermal method. As-synthesized particles were subsequently ball milled to three average particle sizes, namely, ∼260 nm, 160 nm, and 100 nm. The x-ray diffraction pattern showed an hcp phase for as-synthesized and ball-milled particles with a predominant (100) peak. Room temperature emission spectra showed no size dependent peak shifts or peak broadening. The intensities of both green and red emissions decreased with increasing milling time. Segregation of Er ions was detected on the surfaces of milled particle that reduced the sensitizer-activator transition probability, resulting in decreased emission intensities. The green-to-red emission ratio was correlated to the surface enrichment of Er, which affected the cross-relaxation of luminescence dynamics.