The soldering reaction and interfacial microstructure formed between liquid Sn–Zn–Ag solder and Cu at the early stage of soldering at 250 °C for 15 s were studied primarily with the aid of transmission electron microscope (TEM). To achieve the early stage reaction information, the soldered specimens, 5 mm × 5 mm × 500 μm solder on 10 mm × 10 mm × 20 μm Cu, were rapidly quenched in liquid nitrogen after soldering. The results of TEM interfacial analysis show that a Cu–Zn reaction zone, consisting of β′–CuZn and γ–Cu5Zn8, formed near Cu while a Ag–Zn zone, consisting of γ–Ag5Zn8 and ϵ–AgZn3, formed near solder. The innermost layer adjacent to the Cu substrate is an amorphous Cu-Zn diffusion region that contains dispersed β′–CuZn nanocrystalline cells. The β′–CuZn also precipitates in the γ–Ag5Zn8 and ϵ–AgZn3 layer due to the supersaturation of Cu.

We grew epitaxial α–Fe2O3(1010) on TiO2(001) rutile by oxygen plasma-assisted molecular-beam epitaxy. High-resolution transmission electron microscopy (HRTEM), reflection high-energy electron diffraction (RHEED), and x-ray diffraction pole figures confirm that the film is composed of four different in-plane orientations rotated by 90° relative to one another. For a given Fe2O3 unit cell, the lattice mismatch along the parallel [0001]Fe2O3 and [100]TiO2 directions is nominally +67%. However, due to a 3-fold repetition of the slightly distorted square symmetry of anion positions within the Fe2O3 unit cell, there is a coincidental anion alignment along the [0001]Fe2O3 and [100]TiO2 directions, which results in an effective lattice mismatch of only −0.02% along this direction. The lattice mismatch is nearly 10% in the orthogonal [1120]Fe2O3 and [100]TiO2 directions. The film is highly ordered and well registered to the substrate despite a large lattice mismatch in one direction. The film grows in registry with the substrate along the parallel [0001]Fe2O3 and [100]TiO2 directions and nucleates dislocations along the orthogonal [1120]Fe2O3 [100]TiO2 directions.

The definition of a rigorous theoretical framework for the appropriate physico-chemical description of self-propagating high-temperature synthesis (SHS) processes represents the main goal of this work which is presented in two sequential articles. In this article, a novel mathematical model to simulate SHS processes is proposed. By adopting a heterogeneous approach for the description of mass transfer phenomena, the model is based on appropriate mass and energy conservation equations for each phase present during the system evolution. In particular, it takes microstructural evolution into account using suitable population balances and properly evaluating the differentdriving forces from the relevant phase diagram. The occurrence of phase transitionsis treated on the basis of the so-called enthalpy approach, while a conventional nucleation-and-growth mechanistic scenario is adopted to describe quantitatively the formation of reaction products. The proposed mathematical model may be applied to the case of combustion synthesis processes involving a low melting point reactant and a refractory one, as for the synthesis of transition metal carbides from pure metal and graphite. Thus, the model can be profitably used to gain a deeper insight into the microscopic elementary phenomena involved in combustion synthesis processes through a suitable combination of experimental and modeling investigations, as it may be seen in Part II of this work [J. Mater. Res. 20, 1269 (2005)].

Based on the general theoretical model proposed in Part I of this work [J. Mater. Res. 20, 1257 (2005)], a series of numerical simulations related to the self-propagating high-temperature synthesis in the Ti–C system is presented. A detailed and quantitative description of the various physical and chemical processes that take place during combustion synthesis processes is provided in Part II of this work. In particular, the proposed mathematical description of the system has been discussed by highlighting the relation between system macroscopic behavior obtained experimentally with the modeled phenomena taking place at the microscopic scale. Model reliability is tested by comparison with suitable experimental data being nucleation parameters adopted for the fitting procedure. The complex picture emerging as a result of the model sophistication indicates that the rate of conversion is essentially determined by the rate of nucleation and growth. In addition, comparison between model results and experimental data seems to confirm the occurrence of heterogeneous nucleation in product crystallization.

A new type of Mg–Zn–Cu–Gd-based alloy strengthened by quasicrystal and Laves phase was developed. This alloy exhibits much better creep properties compared to AE42(Mg–4 wt% Al–2 wt% rare-earth) alloy, which is the benchmark creep-resistant magnesium die-casting alloy under the compressive creep condition of 180 °C and80 MPa. The new alloy also exhibits high room-temperature mechanical properties close to that of AZ91 alloy. The good mechanical properties are attributed to the special microstructure; the thermally stable icosahedral quasicrystals phase (i-phase) and Laves phase distributed along the grain boundary as a hard skeleton, and some fine β′1 precipitates distributed homogenously on the matrix. The dislocation morphology after the creep test was studied, and the strengthening mechanism was proposed.

Gold nanocrystals were formed and grown in simultaneously polymerizing hybrid organic–inorganic films. For the preparation of Au containing films, tetraethyl orthosilicate and methacryloxypropyltrimethoxysilane were separately hydrolyzed and the resulting sols were mixed, followed by the addition of a photoinitiator and a NaAuCl4 solution in methanol. The resulting solutions were spin-coated onto glass-substrates, and the so-formed films were irradiated with a solar simulator at powers ranging from 200 to 800 W. The irradiation resulted in simultaneous polymerization of the films and formation of gold nanoparticles. The irradiated films were characterized by x-ray diffraction measurements, ultraviolet–visible optical absorption spectroscopy and transmission electron microscopy studies. After irradiation at 800 W, the transmission electron microscopy experiments showed the presence of homogeneously distributed Au nanoparticles with a size distribution ranging from 2 to 12 nm. The interpretation of the results indicates that the Au particle growth depends on the matrix polymerization rate; enhancing the rate by increasing the irradiation power or the photoinitiator concentration results in smaller particle domains. This result is explained referring to influence of the polymerization rate on the diffusion of gold species through the host.

Oxygen uptake and conductivity were measured by nuclear-reaction analysis and alternating current impedance technique at the intermediate temperature range on sol-gel grown nanocrystalline ceria films with average grain-sizes 7 nm and 38 nm synthesized at 723 and 1173 K, respectively. Higher oxygen uptake and lower ionic conductivity were observed in ceria films with ∼7-nm grain size. High permeation-assisted oxygen diffusion in nanocrystallites combined with oxygen trapping in the disordered region contributed to higher oxygen uptake. However, the lower ionic conductivity in the film resulted from the absence of long-range lattice ordering and inactive grain-boundary/surface oxygen vacancy sites due to oxygenation. The relationship between oxygen uptake and conductivity in ceria is discussed in details by considering grain-size dependent defect density, related surface area, and enhanced oxygen mobility.

The stability of interfaces with germanium, which has recently been discussed as a replacement for silicon in ultra-large-scale integrated circuits (ULSIs), was studied. Interfacial oxygen diffusion from high-permittivity gate dielectrics (ZrO2 and HfO2) into germanium substrates must be suppressed to prevent the formation of interfacial layers between the gate dielectrics and the germanium substrates. Oxygen diffusion was simulated through a molecular-dynamics technique that takes into account many-body interactions and charge transfer between different elements. The simulation results show that the addition of yttrium is effective in suppressing interfacial oxygen diffusion at the ZrO2/germanium interfaces. On the other hand, the addition of yttrium is not effective in suppressing interfacial oxygen diffusion at the HfO2/germanium interfaces. The results also show that the diffusion at the ZrO2/Ge(111) and HfO2/Ge(111) interfaces is much more suppressed than the diffusion at the ZrO2/Ge(001) and HfO2/Ge(001) interfaces.

A titania-based self-standing film with high transparency and flexibility was successfully prepared via a sol-gel process, in which a titanium tetraisopropoxide/isostearate complex (precursor), n-hexylammonium isostearate (catalyst), and o-xylene (solvent) were used. The sol obtained by the sol-gel reaction was floated on a water surface to form an unsupported film. This film was composed of a titania/isostearate nanocomposite with ordered layer structure. The basal spacings of the nanocomposites depended on the chain length of the carboxylate modifier.

Glass composition 39PbO–1BaO–25TiO2–9.8Al2O3–24.2SiO2–1B2O3 (mol%) crystallized on heat treatment at ≥600 °C to form glass-ceramics whose majority phase was PbTiO3 (PT). At 600 °C, nano-size PT crystals (∼20–50 nm) with a c/a ratio of 1.000(1) were observed, but as heat-treatment temperature increased to 1000 °C, the crystal size and c/a ratio increased to ∼1.2 μm and 1.056(4), respectively. Permittivity measurements as a function of temperature revealed a broad peak at ∼400 °C associated with the nanocrystalline PT crystals, but it sharpened and increased in temperature as heat treatment temperature increased to 1000 °C. The causes of peak broadening and shift of Tc are believed to be due to either clamping of PT crystals by glass matrix, finite size effects due to their intrinsically small size, or the incorporation of dopant impurities such as Al, Si, or Ba ions in the PT phase.

Non-conductive adhesive (NCA) flip chip interconnects are emerging as attractive alternatives to lead or lead-free solder interconnects due to their environmental friendliness, lower processing temperatures, and extendability to fine pitch applications. The electrical connectivity of a NCA interconnect relies solely on the pure mechanical contact between the integrated circuit bump and the substrate pad; the electrical conductivity of the contact depends on the mechanical contact pressure, which in turns depends to a large extend on cure shrinkage characteristic of the NCA. In addition, to reduce the cost and increase the output, NCA is usually ramped up to 200 °C and cured for 1 min during the assembly process. However, fast cure reaction poses a great challenge for the accurate measurement of cure shrinkage. In this paper, to precisely determine the cure shrinkage at high temperature, cure shrinkage was first measured at lower temperatures with slow reaction rate by means of thermomechanical analyzer and then extrapolated to high temperatures. With the increase of cure temperature, the maximum of degree of cure will increase, but the maximum cure shrinkage reduces due to the expansion of materials at higher cure temperature. Furthermore, the slopes of the linear relationship between the cure shrinkage and the degree of cure at different cure temperatures after gelation were found to be similar and independent of the cure temperature. The cure shrinkage from gel-point to complete curing was determined to be 4.275%.

A model explaining the variability of oxygen solubility in the transition metals is proposed in this article. It assumes that the energy of solution can be represented as the sum of the work required to embed an oxygen atom in the electron gas of the host lattice, plus the energy generated through the formation of an oxygen anion. The latter term is treated as nearly constant across the transition metal series, leaving the work term to account for the observed variations in oxygen solubility. This work, we argue, can be approximated by the ratio of the number of metal electrons excluded from the region around the oxygen atom to the Fermi energy density of states. In turn, the number of electrons excluded by oxygen is assumed to be proportional to the charge density at the octahedral interstitial site. These assumptions allow us to define a solubility parameter that is easily determined with first-principles methods. This parameter is shown to correlate well with experimental findings regarding oxygen solubility in transition metals. Supported by these findings, we use first principle methods to identify alloying elements likely to reduce the solubility of oxygen in niobium.

Silica/titania composite particles were prepared by co-oxidation of titanium-tetra-isopropoxide and hexamethyldisiloxane in a co-flow diffusion flame reactor. The influence of precursor composition on product powder characteristics was studied by x-ray diffraction, nitrogen adsorption, electron microscopy, elemental mapping, and energy-dispersive x-ray analysis. The flame temperature was measured by Fourier transform infrared spectroscopy. The evolution of composite particle morphology from ramified agglomerates to spot- or fully coated particles was investigated by thermophoretic sampling and transmission/scanning electron microscopy. At 40–60 wt% TiO2, particles with segregated regions of silica and titania were formed, while at 80 wt% TiO2 rough silica coatings were obtained. Rapid flame-quenching with a critical flow nozzle at 5 cm above the burner nearly halved the product particle size, changed its crystallinity from pure anatase to mostly rutile and resulted in smooth silica coatings on particles containing 80 wt% TiO2.

Colloidally stable suspensions are required to fabricate dense samples with uniform microstructure by colloidal processing methods, which necessitate dispersion of ceramic powders in a liquid medium. Aqueous nano ZrO2 suspensions were prepared using polyethylenimine (PEI) as a dispersant. PEI adsorption on nano ZrO2 surfaces was promoted with increasing initial PEI content and suspension pH. Isoelectric point was shifted from pH 7 at 0 wt% PEI to pH 10.4 at 3 wt% PEI. Stable suspensions had mean particle sizes in the range of 100 to 150 nm and sedimentation rates less than0.4 mm/h, as compared to 2–5.5 μm and 10–50 mm/h for unstable suspensions. Samples with 98% relative density were fabricated after sintering at 1300 °C for 4 h from colloidally stable suspensions.

W–Si–N films were deposited by reactive sputtering in a Ar + N2 atmosphere from a W target encrusted with different number of Si pieces and followed by a thermal annealing at increasing temperatures up to 900 °C. Three iron-based substrates with different thermal expansion coefficients, in the range of 1.5 × 10−6 to 18 × 10−6 K−1 were used. The chemical composition, structure, residual stress, hardness (H), and Young’s modulus (E) were evaluated after all the annealing steps. The as-deposited film with low N and Si contents was crystalline whereas the one with higher contents was amorphous. After thermal annealing at 900 °C the amorphous film crystallized as body-centered cubic α–W. The crystalline as-deposited film presented the same phase even after annealing. There were no significant changes in the properties of both films up to 800 °C annealing. However, at 900 °C, a strong decrease and increase in the hardness were observed for the crystalline and amorphous films, respectively. It was possible to find a good correlation between the residual stress and the hardness of the films. In several cases, particularly for the amorphous coating, H/E higher than 0.1 was reached, which envisages good tribological behavior. The two methods (curvature and x-ray diffraction) used for calculation of the residual stress of the coatings showed fairly good agreement in the results.

After this article appeared in the February 2005 issue of Journal of Materials Research, the authors noticed that Eq. (14) was incorrect.