Isothermal sections in the Ni–Al–Ga–N quaternary phase diagram were calculated to provide a greater understanding of interfacial reactions between Ni contacts and AlxGa1−xN. The calculations were performed employing a thermodynamic database of the Ni–Al–Ga–N system that was constructed by combining the six binary systems of the four component system. The model of the Ga–N binary system was created in this work. The models of the Ni–Ga and Ni–Al systems, both of which were taken from the literature, were modified to be compatible with one another. Thermodynamic data and phase boundaries for other binary systems were taken from the literature, as was information on portions of the Al–Ga–N and Ni–Al–Ga phase diagrams. The calculated sections reveal that during reaction between Ni and AlxGa1−xN, Ni is favored to react with the GaN component of the semiconductor alloy, leaving an Al-enriched AlxGa1−xN. These predictions are consistent with a recent analysis of the Ni, Al, and Ga elemental distributions across the interface between a Ni thin film and an Al0.47Ga0.53N epitaxial layer following annealing at 850 °C. Consideration of the thermodynamic driving forces suggests that this may be a general phenomenon existing in other metal–Al–Ga–N systems.

Separation by implemented oxygen (SIMOX)(111) substrates have been formed by oxygen-ion (16O+) implantation into Si(111), showing that a so-called “dose-window” at 16O+-implantation into Si differs from Si(100) to Si(111). In SIMOX(100), an oxygen dose of 4 × 1017/cm2 into Si(100) is widely recognized as the dose-window when the acceleration energy is 180 keV. For the first time, our work shows that an oxygen dose of 5 × 1017/cm2 into Si(111) is the dose-window for the formation of SIMOX(111) substrates when the acceleration energy is 180 keV. The difference between dose-windows is caused by anisotropy of the crystal orientation during growth of the faceted buried SiO2. We also numerically analyzed the data at different oxidation velocities for each facet of the polyhedral SiO2 islands. Numerical analysis results show good agreement with the experimental data.

The influence of uniaxial prestress on dielectric and piezoelectric performance was studied for soft lead zirconate titanate piezoceramics. High electric field induced polarization and longitudinal/transverse strain were measured at different compression preload levels of up to −400 MPa. The parameters evaluated included polarization/strain outputs, dielectric permittivity, piezoelectric constants, and dissipation energy as a function of the mechanical preload and electric-field strength. The results indicate a significant enhancement of the dielectric and piezoelectric performance within a certain prestress loading range. At much higher stress levels, the predominant mechanical depolarization effect makes the material exhibit hardly any piezoeffect. However, the enhanced performance achieved by a small stress preload is accompanied by an unfavorable increased hysteresis, and consequently, increased energy loss, which is attributed to a larger extrinsic contribution due to more non-180° domain switching induced by the combined electromechanical load.

Interfacial structures of c-axis-oriented YBa2Cu3O7–y (Y123) and Nd1+xBa2–xCu3O7–y (Nd123) films were investigated by high-resolution transmission electron microscopy (HRTEM) in conjunction with geometrical lattice matching and molecular orbital calculations. These films were formed on MgO(001) substrates by liquid-phase epitaxy. Despite the similarity in lattice constants between Y123 and Nd123, the in-plane orientation relationship (OR) to the substrates is different: [100]film//[100]substrate(I) for Y123 and [110]film//[100]substrate(II) for Nd123. From the results of HRTEM observations and image simulations, it was found that the Y123 and Nd123 films are terminated by BaO and CuO-chain layers at the interfaces, respectively. For both the Y123/MgO and Nd123/MgO systems, the OR(I) is assessed to be the most favorable in point of geometrical matching and the OR(II) is the second among the rotational misorientations on the [001]film and [001]MgO. The molecular orbital calculations reveal that the interface with the OR(II) and the CuO-chain layer termination is preferable in terms of covalent bonding for both the systems. Consequently, we suggest that the preferential interfacial structures are delicately determined by a balance of the geometrical and chemical factors at the interfaces, resulting in making the lowest interfacial free energies.

The fundamentally changing nature of fracture in brittle coatings on compliant substrates with diminishing coating thickness is examined. Attention is focused on cracking induced by concentrated loading with a spherical indenter at the top surface. It is shown that the fracture mode undergoes transitions, from top-surface ring cracking around the contact (“thick-coating” region) to bottom-surface radial cracking at the lower ceramic surface (“intermediate” region) and, finally, back to surface ring cracking (“thin-coating” region). These transitions reflect a progressively changing stress field in the layer structures and highlight the differences in failure mechanism that may be anticipated at the large- and small-scale levels. Simple fracture relations are derived for each mode, expressing critical loads in terms of coating thickness relative to contact or sphere radius, coating strength and coating/substrate modulus mismatch. Data from finite element simulations and contact experiments on model ceramic/polymer bilayer systems are used to validate the basic elements of the analytical relations and to quantify deviations. Implications of the transitional behavior in relation to the strength of brittle coating/film systems are discussed.

The site-incorporation mechanism of M3+ dopants into A2+B4+O3 perovskites controls the overall defect chemistry and thus their transport properties. For charge-balance reasons, incorporation onto the A2+-site would require the creation of negatively charged point defects (such as cation vacancies), whereas incorporation onto the B4+-site is accompanied by the generation of positively charged defects, typically oxygen vacancies. Oxygen-vacancy content, in turn, is relevant to proton-conducting oxides in which protons are introduced via the dissolution of hydroxyl ions at vacant oxygen sites. We propose here, on the basis of x-ray powder diffraction studies, electron microscopy, chemical analysis, thermal gravimetric analysis, and alternating current impedance spectroscopy, that nominally B-site doped barium cerate can exhibit dopant partitioning as a consequence of barium evaporation at elevated temperatures. Such partitioning and the presence of significant dopant concentrations on the A-site negatively impact proton conductivity. Specific materials examined are BaxCe0.85M0.15O3-δ (x = 0.85 - 1.20; M = Nd, Gd, Yb). The compositional limits for the maximum A-site incorporation are experimentally determined to be: (Ba0.919Nd0.081)(Ce0.919Nd0.081)O3, (Ba0.974Gd0.026)(Ce0.872Gd0.128)O2.875, and Ba(Ce0.85Yb0.15)O2.925. As a consequence of the greater ability of larger cations to exist on the Ba site, the H2O adsorption and proton conductivities of large-cation doped barium cerates are lower than those of small-cation doped analogs.

The electromigration behavior of the composite solder composed of eutectic and high-lead SnPb was investigated with 5.7 × 104 A/cm2 current stressing. Voids and hillocks were found only within the eutectic solder, and the high-lead solder remained intact. Electromigration was accelerated dramatically at 150 °C, and Pb became the major migration species of eutectic SnPb for the microstructure change at the anode. The polarity of the opposite current direction was also studied. When electrons drift from the eutectic side to the high-lead side, voids occurred at the eutectic–Cu interface whereas hillocks accumulated at the eutectic–high-lead interface. When the current was reversed, voids occurred at the eutectic–high-lead interface whereas hillocks accumulated at the eutectic–Cu interface. The anchoring effect, which results from the attaching of the lead-rich grains in the eutectic solder to the high-lead solder, was considered to retard the electromigration damage only in this current direction.

The synthesis behavior of mullite in an aqueous system was investigated. Two kinds of aluminosilicate precursor sols were prepared by the dissolution of two kinds of salt (aluminum chloride hexahydrate, AlCl3·6H2O, and aluminum sulfate with 14–18 molecules of water, Al2[SO4]3·14–18H2O) into the mixture of colloidal silica sol. The effects of the solution pH, which was controlled by addition of ammonium hydroxide (NH4OH), and the type of aluminum salt on the mullite crystallization and the grain size and morphology in the sintered materials are discussed in this paper. It has been discovered that in an aqueous system, the mullitization temperature strongly depends on the solubility and decomposition temperature of the aluminum salt used and that the pH of the initial sol impacts the grain size and morphology of mullite, in addition to the homogeneity of mixture. Mullite is synthesized at 850 °C without resorting to the addition of an organic additive or nonaqueous solvent.

The structures of the defect perovskite Pb1−3/2xLaxTiO3 prepared by the solid-state method were investigated in the solubility range of 0.05 ⩽ x ⩽ 0.30 with 0.05 increment by x-ray Rietveld method. In the system Pb1−3/2xLaxTiO3, the atom displacements of Ti (δTi) and Pb/La (δPb/La) along the spontaneous polarization (Ps) direction (c axis) decrease nonlinearly with increasing La content, while the value of δTi/δPb/La decreases linearly. The shape of oxygen octahedron of compounds Pb1−3/2xLaxTiO3 is independent of the La content. The calculated value of Ps decreases linearly in the solubility range of 0.05 ⩽ x ⩽ 0.30. In the refinement process, the hkl dependence of diffraction line broadening was also taken into account. The anisotropy of microstrain-like broadening observed in Pb1−3/2xLaxTiO3 might be ascribed to occurrence of compositional inhomogeneity between the crystallites.

Ferroelectric layered perovskite SrBi2Nb2O9 has been successfully prepared through a new process using BiNbO4 as a precursor. The SrBi2Nb2O9 formation mechanism was investigated using a nonisothermal analysis method at constant heating rates. The weight loss recorded in thermal analysis under different heating rates was analogized to the reaction conversion. A combination of the differential and integral methods was introduced to solve the reaction mechanisms. Analysis using the differential method revealed that two kinds of diffusion-controlled models have higher linear correlation coefficients than other models. Based on the integral method principle, a new integral equation combining the Arrhenius equation and the Lobatto approximation was derived in this study. The established equation significantly simplified the conventional calculation process and improved the accuracy for predicting the reaction models. Analysis using the integral method corroborated that the SrBi2Nb2O9 formation mechanism is governed by Jander's diffusion controlled model, and the activation energy was calculated to be 192.1 kJ/mol. The proposed methods and the derived equations can be further applied to other solid-state-reaction systems to elucidate their reaction kinetics and estimate the related kinetic parameters.

The influence of grain boundaries on material deformation in Ni3Al was investigated by relating the material pile-up at grain boundaries and the propagation of slip across grain boundaries to the misorientation between the corresponding grains. Indentation tests were carried out using micro- and nanoindentation at distances shorter than the radius of indent size from a grain boundary on Ni3Al. The indents were observed using scanning electron microscopy and non-contact-mode atomic force microscopy. Repeated experimentation did not reveal a rising trend of hardness near grain boundaries, indicating that hardness is not a sensitive parameter to measure grain boundary strengthening effects. However, it was observed that the slip transfer behavior across a grain boundary has a strong dependence on a local misorientation factor m′ relating the misorientation of slip planes and slip directions on either side of the grain boundary. This result agrees with the fundamental assumption in the physical explanation of the Hall–Petch effect.

The nanoscale behavior of high-temperature flow deformation for silicate-based oxide glass ultrathin films was characterized with focus on forming a nano-patterned glass surface. The oxide glass thin films were deposited at room temperature by pulsed laser deposition onto the ultrasmooth sapphire substrates with 0.2-nm-high atomic steps. It was found from atomic force microscopy (AFM) measurements that the silicate ultrathin films (about 3 nm thick) started to deform at a temperature 50 °C lower than the glass transition point of the bulk glass. The glass thin films annealed at high temperatures exhibited the nano-stepped surface structure reflecting the sapphire substrate surface. By scanning the AFM tip on the as-deposited glass film in a contact mode and then thermal annealing the film, we could pattern the nano-stepped glass surface at a nanoscale.

Many intermetallics, such as Ag3Sn, AuSn4, Cu3Sn, Cu6Sn5 (η and η`), Ni3Sn4, and γ–Cu5Zn8 are present in modern solder interconnects as a result of solder chemistry and/or due to the interfacial reaction between solder and metallization scheme. Coarse-grained, single-phase intermetallics are produced by conventional casting followed by annealing for long time. Ambient temperature isotropic elastic moduli (bulk, Young’s, shear, and Poisson’s ratio) and selected plastic properties (hardness and indentation fracture toughness) of these intermetallics are presented. The isotropic elastic moduli of these intermetallics are determined by the pulse-echo technique. The measured bulk, Young’s and shear moduli lie in the range of 6.3 to 11.4 × 1010 N/m2, 7.1 to 12.3 × 1010 N/m2 and 2.7 to 4.5 × 1010 N/m2, respectively. The hardness and fracture toughness are determined by an indentation method. The loads used for indentation experiments were: 100–10,000 g for Ag3Sn and γ–Cu5Zn8, 10–50 g for AuSn4, 200–1000 g for Cu3Sn, 50–100 g for Cu6Sn5, and 100–200 g for Ni3Sn4. The measured Vickers hardness lies in the range of 50 to 470 Kg/mm2, and the measured indentation fracture toughness lies in the range of 2.5 to 5.7 MPa m1/2. Due to coarse grain size of the specimens, the indentation cracks were contained within one grain. In Cu3Sn, Cu6Sn5 (η and η`) and Ni3Sn4 intermetallics, the indentation cracks were found to be nearly straight and run along the indent diagonal. However, the cracks in AuSn4 showed significant zig-zag and branching phenomena, and they seemed to propagate along particular cleavage plane(s). The presence of slip bands are also observed in AuSn4, Ag3Sn, Cu3Sn, γ-Cu5Zn8, and Ni3Sn4. In the case of Ag3Sn and γ–Cu5Zn8, indentation cracks cannot be induced by applying loads up to 10 kg. Rather, extensive plastic deformation occurs resulting in the formation of a large number of shear/kink bands, and possibly twins, that spread across several grains. At a load of 5000 g or higher, Ag3Sn exhibits grain boundary decohesion near the indents. Among the intermetallics studied, Ag3Sn is shown to be the most ductile.

Powders of TiO2 doped with a metal ion and N species were prepared by a polymerized complex method and the visible-light photocatalytic activities of the products are investigated. Of the metal ions studied (K+, Ca2+, Sr2+, Ba2+, Nb5+, Fe3+, Zn2+, and Al3+), the photocatalyst prepared with Sr2+ exhibits the highest activity for acetaldehyde decomposition under visible-light irradiation. Results obtained from x-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) analyses suggest that the doped N species reside at interstitial lattice positions in the catalyst. It was also found by XPS and ESR measurements that the doped N species combine with lattice oxygen to give rise to a paramagnetic property. The visible-light response of the catalyst is driven by the formation of paramagnetic N species at interstitial positions in the TiO2 lattice.

The superconducting properties of air-processed melt-textured growth Sm–Ba–Cu–O samples with addition of small amounts (0.004 wt%, 0.4 wt%, 4 wt%) of nano-sized Sm2BaCuO5 particles (nm211) were studied. The microstructure observations show that the size distribution and morphology of the 211-particles of the nm211-doped samples are similar to that of the control (undoped) samples. However, except for the 4 wt% nm211-doped sample, both Tc (critical temperature) and Jc (H, T) (critical current density) are enhanced in nm211-doped samples, and the Jc–H curves are different from those of control samples. The effect of nm211 particles on Jc enhancement is larger at high magnetic fields (>1 T at 77 K) than at low magnetic fields (0∼1 T). The dominant pinning mechanism by analyzing the Jc (H, T) data using the scaling theory indicate that the nm211-doped samples are originated from Δκ pinning (i.e., Tc variation); on the other hand, the control samples are originated from normal pinning (i.e., nonsuperconducting crystalline defects). It is proposed that nano-sized compositional fluctuations in the RE1+x Ba2−x Cu3O y matrix, which are products of nm211 particles and liquid peritectic reaction, act as the source of Δκ pinning centers.

The determination of the mechanical properties of polymers is more complex than that of many other structural materials, because they display time-dependence in their response to load. Generally, dynamic analysis techniques, such as dynamic mechanical thermal analysis (DMTA), are used to characterize the viscoelastic properties of bulk polymers. However, polymers are increasingly being used as thin films, the properties of which are not readily determined using conventional techniques. Nanoindentation offers the possibility of determining the properties of thin films but has generally only been used to measure static properties. Dynamic nanoindentation equipment has recently become available, but its accuracy with soft polymers is unproven. This paper presents results of a comparison between dynamic nanoindentation, DMTA, and differential scanning calorimetry (DSC) for the determination of the thermal response of four different polymers. A favorable comparison is shown, indicating that dynamic nanoindentation is capable of measuring the time-dependent properties of small samples of polymers.

Using molecular dynamics to simulate behavior of polymer surfaces during scratch testing, we report the first results of computer simulations of scratch behavior of noncrystals. A previously described procedure for creating realistic polymeric materials on the computer [W. Brostow, A.M. Cunha, and R. Simoes, Mater. Res. Innovat. 7, 19 (2003)] and used until now to simulate mechanical behavior of metals [S. Blonski, W. Brostow, and J. Kubat, Phys. Rev. B 49, 6494 (1994)] and one- and two-phase polymers [W. Brostow, A.M. Cunha, J. Quintanilla, and R. Simoes, Macromol. Theory Simul. 11, 308 (2002); W. Brostow, A.M. Cunha, and R. Simoes, Proc. Ann. Tech. Conf. Soc. Plastics Engrs. 60, 3105 (2002)] was applied. While experiments provide only the macroscopic penetration depth and the recovery (healing) depth, the simulations give the behavior of each macromolecular chain segment at each moment in time. We report results for one-phase polymers and also for systems with varying concentrations of a liquid crystalline (LC) second-phase that acts as a reinforcement. We relate the local structure to scratch resistance and recovery. The orientation of the chemical bonds is a major factor. The presence of a LC phase improves the tribological properties; however, the effect is not as significant as might have been expected.

Hardness and elastic modulus of micromaterials can be evaluated by analyzing instrumented sharp-tip-indentation load–depth curves. The present study quantified the effects of tip-blunting and pile-up or sink-in on the contact area by analyzing indentation curves. Finite-element simulation and theoretical modeling were used to describe the detailed contact morphologies. The ratio f of contact depth, i.e., the depth including elastic deflection and pile-up and sink-in, to maximum indentation depth, i.e., the depth measured only by depth sensing, ignoring elastic deflection and pile-up and sink-in, was proposed as a key indentation parameter in evaluating real contact depth during indentation. This ratio can be determined strictly in terms of indentation-curve parameters, such as loading and unloading slopes at maximum depth and the ratio of elastic indentation energy to total indentation energy. In addition, the value of f was found to be independent of indentation depth, and furthermore the real contact area can be determined and hardness and elastic modulus can be evaluated from f. This curve-analysis method was verified in finite-element simulations and nanoindentation experiments.

We report for the first time on load versus depth-of-indentation response of Ti3SiC2 surfaces loaded with a 13.5 μm spherical tipped diamond indenter up to loads of 500 mN. Using orientation imaging microscopy, two groups of crystals were identified; one in which the basal planes were parallel to, and the other normal to, the surface. When the load-penetration depth curves were converted to stress-strain curves the following was apparent: when the surfaces were loaded normal to the c axis, the response at the lowest loads was linear elastic—well described by a modulus of 320 GPa—followed by a clear yield point at approximately 4.5 GPa. And while the first cycle was slightly open, the next 4 on the same location were significantly harder, almost indistinguishable, and fully reversible. At the highest loads (500 mN) pop-ins due to delaminations between basal planes were observed. When pop-ins were not observed the indentations, for the most part, left no trace. When the load was applied parallel to the c axis, the initial response was again linear elastic (modulus of 320 GPa) followed by a yield point of approximately 4 GPa. Here again significant hardening was observed between the first and subsequent cycles. Each cycle resulted in some strain, but no concomitant increase in yield points. This orientation was even more damage tolerant than the orthogonal direction. This response was attributed to the formation of incipient kink bands that lead to the formation of regular kink bands. Remarkably, these dislocation-based mechanisms allow repeated loading of Ti3SiC2 without damage, while dissipating significant amounts of energy per unit volume, Wd, during each cycle. The values of Wd measured herein were in excellent agreement with corresponding measurements in simple compression tests reported earlier, confirming that the same mechanisms continue to operate even at the high (≈9 GPa) stress levels typical of the indentation experiments.

The effect of environmental exposure on the fracture characteristics of two polymer–metal interfaces was measured using a four-point bend delamination test. Films of high-molecular-weight polymethylmethacrylate (PMMA) resin were spin-cast on metal-coated silicon wafer substrates, for which the metal was either titanium or aluminum. Sandwich beam specimens were fabricated and stored in one of the following conditions prior to the bending tests: vacuum desiccator at 25 °C, vacuum desiccator at 65 °C, distilled water at 25 °C, or distilled water at 65 °C. Load–displacement behavior measured during bending revealed significant differences between the delamination characteristics of the two PMMA–metal interfaces after vacuum exposure which were eliminated after the degrading effects of water exposure. Three distinctive load–displacement behaviors were observed: plateau, fracture at a single load; R-curve, fracture at increasing load with crack extension; and stick-slip, cycles of gradual load increase and sudden load drop with crack extension. PMMA–Al samples stored in vacuum desiccator at 25 °C exhibited R-curve fracture and the largest average crack driving force, GC, 12.2 (±0.5) J/m2, of all samples tested. After storage in 25 °C water, these PMMA–Al samples exhibited stick-slip fracture and GC decreased to 7.1 (±2.6) J/m2; storage in 65 °C water further decreased GC to 2.1 (±0.7) J/m2. PMMA–Ti samples exhibited stick-slip fracture after storage in vacuum desiccator at 25 °C, with an average GC of 8.0 (±2.6) J/m2; storage in 65 °C water resulted in a transition to plateau fracture and a decrease in GC to 1.6 (±0.3) J/m2. The initial difference and subsequent similarity are interpreted in terms of surface roughness and hydrolysis, respectively.