Silica glass plates (Corning 7940 excimer grade) were implanted sequentially with N+ at 52 keV to different doses, ranging from 0 to 1.2 × 1017 ions cm−2, and then with Fe+ at 160 keV to 6 × 1016 ions cm−2 at room temperature and 4 µA cm−2. The intensity of ferromagnetic magnetic resonance (FMR) absorption and the magnetization calculated by the angular dependence of the FMR field reach maxima at an N/Fe atomic ratio ∼0.2. Two peaks due to Fe 2p3/2 electron are observed at 707.2 ± 0.2 and 710.9 ± 0.2 eV in the x-ray photoelectron spectra. The intensity of the former relative to the latter decreases with increasing the N dose. The conversion electron Mössbauer spectrum reveals the formation of superparamagnetic iron nitride as well as the existence of Fe2+ and Fe3+ in silica when implanting N+ to 7.5 × 1015 ions cm−2 and then Fe+ to 6 × 1016 ions cm−2 at N/Fe = 0.125. These results suggest that sequential ion-implantation of N+ and Fe+ produces iron nitride in silica glasses.

Grain boundary structure was examined in 0.1 mol% TiO2-excess BaTiO3 by high-resolution electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS). Their grain boundaries were mostly faceted with {210} type habit. The faceted boundaries were characterized to be associated with an extra Ti–O2 bond with the rutile-like structure. The grain growth behavior in a small TiO2-excess BaTiO3 is discussed from the viewpoint of grain boundary structure.

Metallo-organic thin film decomposition (MOD) was used in forming barium strontium titanate (BST) thin film capacitors on phosphorus doped polysilicon films deposited on 4 in. silicon wafers. A single step deposition process yielded highly uniform, crack-free BST films ranging up to 0.25 εm in thickness and having various step heights and dimensional area. Scanning electron microscopy (SEM) showed very good step coverage and planarization of the BST. The capacitors had capacitance densities above 200 nF/cm2, leakage current densities less than 1.55 εA/cm2 at a bias voltage of 10 V, and a dielectric breakdown field above 1 MVycm. Small temperature coefficients of capacitance and dissipation (tan δ) were also observed. Frequency response measurements were made using the BST capacitors and on-chip resistors in low pass and high pass circuit configurations. A plot of relative gain and phase angle versus frequency showed excellent agreement with predicted results.

The structural and electrochemical properties of the Ti–Ru–Fe–O system have been studied over the whole ternary metal compositional range, keeping constant the oxygen content at 30 at.%. The phase diagram was explored systematically by varying the composition of the material along one of the following axes: (i) constant Ru content of 16 at. %; (ii) constant Ti/Ru ratio of 2; (iii) constant Ti/Fe ratio of 1.6. For O/Ti ratios equal or below unity, the most prominent peaks observed in the x-ray diffraction patterns belong to a B2 structure. For O/Ti ratio larger than unity, stable titanium oxide phases are formed, which coexist with a cubic Fe-like or hcp-Ru like phases depending on the Fe/Ru ratio. Powder compositions with stoichiometry close to Ti2RuFeO2 are of interest due to good electrocatalytic properties, long-term stability, and low Ru content.

Force-strain curves were measured for 1.0 μm and 1.5 μm thick Cu0.57Ni0.42Mn0.01 films on 8 μm thick polyimide foils by tensile testing. By separating the force working on the polyimide foil from that working on the metal-polyimide compound, stress-strain curves for the CuNi(Mn) films were obtained. Young's modulus and tensile strength were determined for as-deposited and annealed [350 °C, 1 h, N2/H2(5 vol%) atmosphere] films by this method. Crack propagation starts at the end of the elastic region at 0.2 to 0.7% strain, depending on the film thickness and the thermal treatment. The cracking behavior is described by a steady-state approximation.

Thin single crystal films of N-(4-nitrophenyl)-(L)-prolinol (NPP) were prepared using the modified shear method. The surface orientation of the single crystal films was determined by x-ray diffraction and was found to be [101]. Polarized microscopy showed uniform birefringence and complete extinction when the thin film was rotated under crossed polarization, implying single crystal thin films with uniform surface were obtained. The molecular orientation in the NPP thin film was studied by polarized UV-visible and polarized micro-FTIR spectroscopy along with x-ray diffraction. The orientation of the NPP molecules was found to be almost parallel to the plane of the film. This parallel orientation is because of the polar (hydrogen bonding) interaction of the −(OH) and the N=O groups of the NPP molecule with the hydrophilic substrate surface. The results of the second harmonic generation (SHG) measurements are consistent with such a molecular orientation. These results show that the final molecular and crystallographic orientation in the film is determined by its initial molecule-substrate interaction.

The initial dielectric aging behaviors of a Mg and Mn doped lead magnesium niobate ceramic were investigated over a wide range of direct current (dc) bias. Both the dielectric constant-log(time) and the loss tangent-log(time) were regressed in terms of a linear relationship. The dc bias is found to have a strong influence on the dielectric parameters at the start of aging and to suppress the aging of dielectric constant and loss tangent. The frequency dependence of the dielectric aging is also evidently affected by the dc bias.

Solid solutions of aluminum nitride (AlN) and silicon carbide (SiC) have been grown at 900–1300 °C on vicinal α (6H)-SiC(0001) substrates by plasma-assisted, gas-source molecular beam epitaxy. Under specific processing conditions, films of (AlN)x(SiC) 1−x with 0.2 ≤ x ≤ 0.8, as determined by Auger electron spectrometry (AES), were deposited. Reflection high-energy electron diffraction (RHEED) was used to determine the crystalline quality, surface character, and epilayer polytype. Analysis of the resulting surfaces was also performed by scanning electron microscopy (SEM). High-resolution transmission electron microscopy (HRTEM) revealed that monocrystalline films with x ≥ 0.25 had the wurtzite (2H) crystal structure; however, films with x < 0.25 had the zincblende (3C) crystal structure.

Pure tetravalent nickel in γ-type cobalt substituted nickel oxyhydroxide, Ni0.70Co0.30O2K0.30(H2O)0.42, could be obtained by the “chimie douce” reaction. The presence of tetravalent nickel is confirmed by comparing the Ni K-edge XANES spectrum of the sample with those of reference compounds having various nickel valency and similar layer structure. The Co K-edge XANES spectrum indicates that the trivalent cobalt remains unchanged regardless of the nickel valency. The structural modification during chimie douce reaction observed from XRD patterns and the result of iodometric titration are consistent with the Ni and Co K-edge XANES data.

Dense hexagonal BN processed via chemical vapor deposition (CVD) was tested with respect to damping, shear modulus, and torsional creep rate up to temperatures as high as ≈2300 °C. The microstructural characteristics of the material both before and after creep testing were studied by high-resolution electron microscopy (HREM). The CVD process yields a homogeneous nanosized microstructure with no other secondary phase detectable. Damping experiments revealed no plastic relaxation during testing up to ≈2000 °C, which is consistent with the fact that also no creep deformation could be detected below such a high temperature. Small porosity and an increased amorphization process were noted by HREM inspection after stress exposure at ≈2300 °C. These phenomena may be responsible for both the enhanced damping capacity and the creep rate of the material which, in the range of the present testing conditions, seems to follow the simple viscoelastic behavior of a Maxwell solid.

Pt-coated silicon substrates with strong (111) Pt texture were annealed in an oxidizing atmosphere at temperatures from 500 °C to 750 °C. BaTiO3 thin films were deposited by pulsed laser ablation on the substrates. Observation by transmission electron microscopy showed that the substrate anneal caused the formation of TiO2 in the Pt layer, accompanied by the formation of a high density of faceted protrusions on the Pt surface, particularly at the higher anneal temperatures. The Pt protrusions had (111) facets, parallel to the substrate surface, on which (100)-oriented BaTiO3 grains were observed. BaTiO3 grains with an epitaxial relationship to the Pt lattice were observed on inclined facets of the Pt protrusions [which were not (111) planes], and also on the nonplanar regions of the Pt surface. These epitaxial BaTiO3 grains had (111) preferred orientation relative to the substrate surface. Thus, the BaTiO3 films displayed bimodal growth behavior, with both (100) texture and (111) epitaxy. We propose a model for this behavior based on surface energy considerations.

Nineteen disks of IR window grade, hot pressed magnesium fluoride (˜0% porosity, grain size ˜1 μm) previously loaded in ring-on-ring flexure tests were used to analyze the crack branching patterns. Fractal geometry was used to determine the crack branching fractal dimension which was named the crack branching coefficient or CBC. The failure stress was proportional to the CBC and the number of pieces generated during the fracture. Thus, the number of pieces was proportional to the crack branching coefficient. The crack branching coefficient is distinct from the fractal dimension obtained from the onset of mist and hackle on the fracture surface. The fractal dimension of the fracture surface is, in most cases for brittle materials, a constant and related to the crack tip stress field. The crack branching fractal dimension is a function of the stress at fracture and the far-field stress distribution, or in other words, related to both the type and magnitude of loading. The findings in this work have strong implications for many commercial processes such as comminution, attrition, grinding, and basic studies in crack branching.

Homogeneous or uniform crystalline materials are obtained following the ball milling of pure elemental powders of Fe and Zn in proportions to yield single phases Γ(Fe3Zn10), Γ1(Fe5Zn21), and Γ + Γ1 mixed phase (Fe25Zn75). Differential scanning calorimetry (DSC) measurements of the as-milled materials show characteristic stages in the temperature range of 50–600 °C prior to establishing stable equilibrium. The activation energies determined from kinetic analyses range from 49 to 189 kJ/mole in these materials. A characteristic stage at 130 °C marking the distinct evolution of the Γ and Γ1 phases from the intermediate or mixed phase composition is identified from XRD measurements. The identification of a unique Fe site with a quadrupole splitting (QS) of 1.5 mm/s in corroboration with x-ray diffraction (XRD) shows that this stage marks the onset of an in situ transformation prior to the distinct evolution of the homogeneous phases. The Mössbauer effect measurement of the as-milled materials are resolved in terms of four unique Fe sites with QS of 1.1, 0.241, 0.073, and 0.0772 mm/s.

Tantalum carbide nanorods and nanoparticles have been synthesized using a vapor-solid reaction path starting with CVD grown carbon nanotube precursors. Their structures were studied using XRD, TEM, and HRSEM. Superconducting properties were characterized using a SQUID magnetometer. For reactions at lower temperatures, carbide nanorods, which replicate the ∼14 nm diameter of the precursor carbon nanotubes, are observed. For higher temperature reactions, coarsened carbide nanoparticles (100–250 nm) are observed which have spherical or cubic-faceted morphologies. A morphological Rayleigh instability is postulated as initiating the transition from nanorod to nanoparticle morphologies. Stoichiometric bulk TaC crystallizes in the rock salt structure and has a superconducting transition temperature of 9.7 K. In TaC nanorods and nanoparticles, the superconducting properties correlate with the lattice parameter. Nanoparticles with a little higher lattice parameter than the ideal one show higher Tc and higher fields at which the superconductivity disappears than stoichiometric bulk TaC.

Phosphate ceramics were synthesized using sol-gel technique of direct reaction of P2O5 with tetraethoxy silane (TEOS) or titanium tetraethoxide (Ti(OEt)4). The reaction mechanism of P2O5 and TEOS was deduced using liquid and solid-state NMR. Hexacoordinated silicon in phosphosilicate gels was observed. A specially structured titanium phosphate-layered Ti(HPO4)2 · 2H2O was synthesized for the first time through the sol-gel method. The gelation process and phase transformations were investigated.

The durability of a specific backfilling pozzolanic cement mortar, which is employed in Spain, in concrete containers for the storage of low (LLW) and medium level wastes (MLW), has been studied by means of the Köch–Steinegger test at the temperature of 40 °C during a period of 365 days. Mortar samples were immersed in a simulated radioactive liquid waste very rich in sulphate (0.68 M), phosphate (0.89 M), and chloride (0.51 M) ions. The changes of the microstructure were followed by x-ray diffraction (XRD), mercury intrusion porosimetry (MIP), and scanning electron microscopy (SEM). Pore solution was extracted at different periods in order to see the changes of the chemical composition caused by the diffusion of those ions inside the microstructure.

Two different electron energy loss spectroscopy (EELS) quantitative analytical methods for obtaining complete compositions from interface regions are applied to ultrathin oxide-based amorphous grain boundary (GB) films of ∼ 1 nm thickness in high-purity HIPed Si3N4 ceramics. The first method, 1, is a quantification of the segregation excess at interfaces for all the elements, including the bulk constituents such as silicon and nitrogen; this yields a GB film composition of SiN0.49±1.4O1.02±0.42 when combined with the average film thickness from high resolution electron microscopy (HREM). The second method, II, is based on an EELS near-edge structure (ELNES) analysis of the Si–L2,3 edge of thin GB films which permits a subtraction procedure that yields a completeEELS spectrum, e.g., that also includes the O–K and N–K edges, explicitly for the GB film. From analysis of these spectra, the film composition is directly obtained as SiN0.63±0.19O1.44±0.33, close to the one obtained by the first method but with much better statistical quality. The improved quality results from the fewer assumptions made in method II; while in method I uniform thickness and illumination condition have to beassumed, and correction of such effects yields an extra systematic error. Method II is convenient as it does not depend on the film thickness detected by HREM, nor suffer from material lost by preferential thinning at the GB. In addition, a chemical width for these films can be deduced as 1.33 ± 0.25 nm, that depends on an estimation of film density based on its composition. Such a chemical width is in good agreement with the structural thickness determined by HREM, with a small difference that is probably due to the different way in which these techniques probe the GB film. The GB film compositions are both nonstoichiometric, but in an opposite sense, this discrepancy is probably due to different ways of treating the surface oxidation layers in both methods.

Sn–Zn binary alloys have been examined as a lead-free solder. Zn distributes in a Sn matrix as platelets. The hypoeutectic alloys show two endothermic peaks in DTA, which correspond to the eutectic and the liquidus temperatures. Three reaction layers are formed at the Sn–Zn/Cu interface without containing Sn: the thick γ–Cu5Zn8 adjacent to the solder, the thin β′–CuZn in the middle, and the thinnest layer adjacent to Cu. Although many nonwetting regions and voids are formed at the interface because of poor wetting, soldering at 290 °C can form a rigid interface, and tensile strength reaches about 40 MPa.

Pulsed electrodeposition is a simple, yet versatile method for the production of nanostructured metals. For n-nickel we determine the influence of the physical and chemical deposition parameters on the nanostructure of the deposits and demonstrate that the grain size can be tuned to values between 13 and 93 nm, with rather narrow grain size distribution. The thermal stability of our n-nickel as studied by x-ray diffraction and differential thermal analysis exhibits no detectable grain growth up to temperatures of about 380 K and an initial behavior at 503 K followed by a regime of anomalous grain growth. For nanocrystalline Ni1-x Cux (Monel-metal™) we demonstrate that alloy formation occurs at room temperature and that both chemical composition and grain size can be controlled by the pulse parameters and by appropriate organic additives.

A combustion synthesis (SHS) process developed in our previous study for the synthesis of Si3N4 has been tested for the synthesis of boron nitride (BN) powder. Boron and NaN3 powders were used as the reactants. In addition to ammonium halides, KHF2, FeCl3, NaNH2, or a mixture of 50 mol% FeCl3 and 50 mol% NaNH2 was added to the reactants to examine their catalytic effect. These powders were mixed and pressed into a cylindrical compact. The compact was wrapped up with an igniting agent (i.e., Mg + Fe3O4) and the synthesis reaction was triggered by the combustion of the igniting agent. It was found that only those reagents containing both halogen and hydrogen can exert effectively the catalytic effect. The BN powder as-synthesized is mostly in the form of agglomerated fine particles (0.1–1 μm in diameter) and is hexagonal in crystalline structure. Effects of various experimental parameters on the product yield were investigated. A possible reaction mechanism was proposed, which explains the effects of the experimental parameters on the synthesis reaction.