LiBH4/Al mixtures with various mol ratios were prepared by ball milling. The hydrogen storage properties of the mixtures were evaluated by differential scanning calorimetry/thermogravimetry analyses coupled with mass spectrometry measurements. The phase compositions and chemical state of elements for the LiBH4/Al mixtures before and after hydrogen desorption and absorption reactions were assessed via powder x-ray diffraction, infrared spectroscopy, and x-ray photoelectron spectroscopy. Dehydrogenation results revealed that LiBH4 could react with Al to form AlB2 and AlLi compounds with a two-step decomposition, resulting in improved dehydrogenation. The rehydrogenation experiments were investigated at 600 °C with various H2 pressure. It was found that intermediate hydride was formed firstly at a low H2 pressure of 30 atm, while LiBH4 could be reformed completely after increasing the pressure to 100 atm. Absorption/desorption cycle results showed that the dehydrogenation temperature increased and the hydrogen capacity degraded with the increase of cycle numbers.

An Sn-patch formed in Ni(V)-based under bump metallization during reflow and aging. To elucidate the evolution of the Sn-patch, the detailed compositions and microstructure in Sn–Ag–Cu and Ti/Ni(V)/Cu joints were analyzed by a field emission electron probe microanalyzer (EPMA) and transmission electron microscope (TEM), respectively. There existed a concentration redistribution in the Sn-patch, and its microstructure also varied with aging. The Sn-patch consisted of crystalline Ni and an amorphous Sn-rich phase after reflow, whereas V2Sn3 formed with amorphous an Sn-rich phase during aging. A possible formation mechanism of the Sn-patch was proposed.

Instrumented indentation experiments on a Zr-based bulk metallic glass (BMG) in as-cast, shot-peened and structurally relaxed conditions were conducted to examine the dependence of plastic deformation on its structural state. Results show significant differences in hardness, H, with structural relaxation increasing it and shot peening markedly reducing it, and slightly changed morphology of shear bands around the indents. This effect is in contrast to uniaxial compressive yield strength, σy, which remains invariant with the change in the structural state of the alloys investigated. The plastic constraint factor, C = H/σy, of the relaxed BMG increases compared with that of the as-cast glass, indicating enhanced pressure sensitivity upon annealing. In contrast, C of the shot-peened layer was found to be similar to that observed in crystalline metals, indicating that severe plastic deformation could eliminate pressure sensitivity. Microscopic origins for this result, in terms of shear transformation zones and free volume, are discussed.

The effects of the catalysts on the evolution of in-plane stress during heating were studied for silica gel coatings prepared from alkoxide solutions. Tetramethylorthosilicate was hydrolyzed in the presence of nitric acid, acetic acid, and ammonia as catalysts. Gel films were deposited on Si(100) wafers by spin coating, and heated at a constant rate of 5 °C/min up to 500 °C. During heating, in situ measurement of the in-plane stress was conducted by measuring the radius of curvature of the substrate. In-plane, tensile stress increased up to 560 and 370 MPa in the films prepared with HNO3 and CH3COOH, respectively. However, the stress was much smaller at 30–40 MPa, which remained almost constant during heating, for the films prepared with NH3. The much smaller stress resulted from the much lower degrees of the progress of densification during heating, which was revealed in the changes in thickness and infrared absorption spectra during heating. The low degrees of the progress of densification were caused by the colloidal nature of the gel films.

An in situ bulk ultrafine bimodal eutectic Al–Cu–Si composite was synthesized by solidification. This heterostructured composite with microstructural length scale hierarchy in the eutectic microstructure, which combines an ultrafine-scale binary cellular eutectic (α-Al + Al2Cu) and a nanometer-sized anomalous ternary eutectic (α-Al + Al2Cu + Si), exhibits high fracture strength (1.1 ± 0.1 GPa) and large compressive plastic strain (11 ± 2%) at room temperature. The improved compressive plasticity of the bimodal-nanoeutectic composite originates from homogeneous and uniform distribution of inhomogeneous plastic deformation (localized shear bands), together with strong interaction between shear bands in the spatially heterogeneous structure.

ZrO2 thin films containing silver nanoparticles were prepared using the sol-gel method with Ag to Zr molar ratios [Ag]/[Zr] = 0.11, 0.25, 0.43, 0.67, 1.00, 1.50, and 2.33. After dip coating on glass substrate, coated films were annealed at 200 and 300 °C in air. X-ray diffraction peaks corresponding to crystalline Ag were observed, but a specific peak corresponding to ZrO2 was not observed. At the molar ratio [Ag]/[Zr] = 0.25, the particle size of Ag distributed broadly centered at 17 nm for an annealing temperature of 200 °C and at 25 nm for 300 °C. The films annealed in air at 200 °C showed an absorption band centered at 450 nm because of the silver surface plasmon resonance, whereas films heated at 300 °C in air caused a red shift of the absorption to 500 nm. The absorption peak was analyzed using the effective dielectric function of Ag-ZrO2 composite films modeled with the Maxwell-Garnett expression.

Directional recrystallization of an Fe–6.5wt%Si alloy was investigated by changing hot zone temperatures and growth rates. Elongated (columnar) grains with an aspect ratio more than 10 can be produced when growth parameters are carefully adjusted. It was found that at a fixed growth rate, the grain length and aspect ratio increase with increased hot zone temperatures. At a fixed hot zone temperature, there is a critical growth rate at which columnar grains have the largest average aspect ratio. Below or above this growth rate, the aspect ratio decreases. Texture and grain orientation analysis showed that the preferentially selective growth to form columnar grains was favored by the formation of low-energy surfaces and grain boundaries.

The reinforcing effects of carbon nanotubes (CNTs) are investigated for aluminum matrix composites. The composites present a strong bonding between CNTs and the aluminum matrix using a controlled mechanical milling process, producing a network structure of aluminum atoms around CNTs. At the same time, CNTs that are dispersed during the milling process can be located inside aluminum powders, thereby providing an easy consolidation route via thermomechanical processes. A composite containing 4.5 vol% multiwalled CNTs exhibits a yield strength of 620 MPa and fracture toughness of 61 MPa·mm1/2, the values of which are nearly 15 and seven times higher than those of the corresponding starting aluminum, respectively.

Ternary Sn-In-Cu alloys are prepared and equilibrated at 250 °C for 2 to 20 weeks. The phases formed in these alloys are experimentally determined. The 250 °C Sn-In-Cu isothermal section is established according to the phase equilibrium information obtained in this study and that of the three constituent binary systems. It has eight single-phase regions, namely liquid, δ1-Cu41Sn11, ε-Cu3Sn, δ2-Cu7In3, η-(Cu6Sn5, Cu2In), Cu11In9, Cu2In3Sn, and α-(Cu) phases, 14 two-phase regions, and seven three-phase regions. In the Sn-In-Cu system at 250 °C, the η-Cu6Sn5 and η-Cu2In phases form a continuous solid solution and the ternary Cu2In3Sn compound is observed. The δ1-Cu41Sn11 phase is stabilized at 250 °C with the introduction of indium although it transforms into α-(Cu) and ε-Cu3Sn phases via a eutectoid reaction around 350 °C in the binary Sn-Cu system. Except for the Cu11In9 phase and the Cu2In3Sn ternary compound, the other binary compounds all have significant indium and tin mutual solubilities.

We investigated the epitaxial growth of CoSi2 (100) on an Si (100) substrate using a modified oxide mediated epitaxy (OME) method to overcome the disadvantages of the OME method. These disadvantages are sensitivity of Co films to contamination by oxygen and the need for reiterating the film growth process to obtain thicker films. To solve these problems, nitrogen atoms were incorporated into chemically grown oxide (SiOx) by NH3 plasma treatment prior to the deposition of a Co film on the oxynitride buffer layer using the metal organic chemical vapor deposition (MOCVD) method. Subsequently, ex situ rapid thermal annealing was performed to grow Co-silicide at a temperature between 400 °C and 700 °C for 1 min. The results show that the diffusion of Co was effectively controlled by the oxynitride buffer layer without the formation of additional SiOx in between Co and Si. Our findings indicate that by using an oxynitride buffer layer, CoSi2 films can be grown epitaxially despite the fact that the initial Co film was exposed to oxygen.

X-ray diffraction patterns, scanning electron microscopy images, and transmission electron microscopy images showed that one-dimensional GaN nanorods with [0001]-oriented single-crystalline wurtzite structures were grown on Al2O3 (0001) substrates by hydride vapor-phase epitaxy without a catalyst. The tip morphology of the GaN nanorods became flat with increasing temperature difference between the gas mixing and the substrate zones. The gas mixing temperature significantly affected the formation of the nanorods, and the substrate temperature influenced the morphology and the strain of the GaN nanorods near the GaN/Al2O3 heterointerface. The strain and the stress existing in the GaN layer near the heterointerface were decreased with increasing growth rate. The formation mechanisms of the GaN nanorods grown on the Al2O3 (0001) substrates are described on the basis of the experimental results.

Controlled pore glasses are formed through selective etching of one phase of a spinodally decomposed borosilicate glass, an old technique that is the basis of the porous Vycor synthesis technique developed in the 1920s. This technique is receiving renewed attention as these glasses find new applications as substrates for biosensing, bioreactors, precise filtration, and chromatography. Analogous techniques are being applied to crystalline ceramics, such as directed cooling of ZrO2/MgO and MgAl2O4/Al2O3 eutectics to drive phase separation with the subsequent dissolution of one phase. Pyrolytic reactive sintering is a combination of the phase separation method and the reactive sintering method to obtain a 3D porous structure network. For example, dolomite (CaMg[CO3]2) and ZrO2 yield a uniformly porous CaZrO3/MgO composite that utilizes evolved CO2 as a “pore-forming agent.” This article gives an overview of recent developments on meso- and macroporous ceramics based on phase separation and reactive sintering technologies.

In this study, the dense polycrystalline Ti2AlC was synthesized by self-propagating high-temperature combustion synthesis with the pseudo–hot isostatic pressing process (SHS/PHIP). The resultant phase purity is highly dependent on the mol ratio of raw powders. The Ti2AlC was densified by applying pressure after the SHS reaction. The resultant sample mainly contains typical plate-like nonstoichiometric Ti2AlCx (x = 0.69) with grain size of ∼6 µm. The sample shows the Vickers hardness of 5.5 GPa, highest flexural strength of 431 MPa, compressive strength of 1033 MPa, and fracture toughness of 6.5 MPa·m1/2. No indentation cracks in Ti2AlCx were observed, indicative of a damage material nature. The reaction mechanism for the formation of SHS/PHIP-derived Ti2AlC is also discussed based on differential thermal analysis and x-ray diffraction results.

Porous metals and ceramic materials are of critical importance in catalysis, sensing, and adsorption technologies and exhibit unusual mechanical, magnetic, electrical, and optical properties compared to nonporous bulk materials. Materials with nanoscale porosity often are formed through molecular self-assembly processes that lock in a particular length scale; consider, for instance, the assembly of crystalline mesoporous zeolites with a pore size of 2–50 nm or the evolution of structural domains in block copolymers. Of recent interest has been the identification of general kinetic pattern-forming principles that underlie the formation of mesoporous materials without a locked- in length scale. When materials are kinetically locked out of thermodynamic equilibrium, temperature or chemistry can be used as a “knob” to tune their microstructure and properties. In this issue of the MRS Bulletin, we explore new porous metal and ceramic materials, which we collectively refer to as “hard” materials, formed by pattern-forming instabilities, either in the bulk or at interfaces, and discuss how such nonequilibrium processing can be used to tune porosity and properties. The focus on hard materials here involves thermal, chemical, and electrochemical processing usually not compatible with soft (for example, polymeric) porous materials and generally adds to the rich variety of routes to fabricate porous materials.

In this work, the correlation between magnetic-domain structure and microstructure in combined reaction-processed equiatomic L10 FePd has been investigated using magnetic force microscopy. The microstructure consisted of approximately equiaxed grains with an average grain size of ∼1 μm and a grain size distribution ranging from below the theoretical critical domain size (Dcrit∼0.2–0.3 μm) up to approximately 5 μm in diameter. The domain structure was characterized as “mixed” in nature, consisting of smaller single-domain grains, larger multidomain grains, and a larger scale interaction domain structure encompassing many grains. The domain boundaries separating interaction domains tended to lie along grain boundaries, and it is proposed that the observed interaction domains should be considered in descriptions of the magnetization and magnetization reversal behavior of this material. In particular, pinning of interaction domain walls by intragranular features of the microstructure such as grain boundaries and single-domain grains could play a role in the measured coercivities.

The effect of fluorine termination on the stability and bonding structure of diamond (111) surfaces were studied using first-principles calculations and compared with hydrogen termination by creating mixed F- and H-containing diamond surfaces. Surface F atoms, similar to H, formed sp3-type bonding with C atoms, which resulted in a more stable 1 × 1 configuration. The surface phase diagram built showed that the F-terminated surface was more stable in a larger-phase space than H termination, because of the formation of strong ionic C–F bonds and the development of attractive forces between F atoms, resulting in close packing of large F atoms. Hence, the F-terminated diamond surface was more chemically inert. A large repulsive force was required to bring two F-terminated surfaces together, because of the negative charge on F atoms, resulting in reduced adhesion tendency between two F-terminated diamond surfaces compared with H-terminated surfaces.