We briefly review our recent modeling of crystal nucleation and polycrystalline growth using a phase field theory. First, we consider the applicability of phase field theory for describing crystal nucleation in a model hard sphere fluid. It is shown that the phase field theory accurately predicts the nucleation barrier height for this liquid when the model parameters are fixed by independent molecular dynamics calculations. We then address various aspects of polycrystalline solidification and associated crystal pattern formation at relatively long timescales. This late stage growth regime, which is not accessible by molecular dynamics, involves nucleation at the growth front to create new crystal grains in addition to the effects of primary nucleation. Finally, we consider the limit of extreme polycrystalline growth, where the disordering effect due to prolific grain formation leads to isotropic growth patterns at long times, i.e., spherulite formation. Our model of spherulite growth exhibits branching at fixed grain misorientations, induced by the inclusion of a metastable minimum in the orientational free energy. It is demonstrated that a broad variety of spherulitic patterns can be recovered by changing only a few model parameters.

Powders of Zr, ZrO2, and ZrN were mixed and pressed to produce samples with different bulk stoichiometries in the ternary Zr–O–N systems. The samples were laser heated above melting, maintained at a high temperature, and quenched. The processed samples were cross-sectioned and studied using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray diffraction. The results pointed to the location of the ternary invariant point Liquid + Gas + ZrO2 + ZrN on the high-temperature portion of the Zr–ZrO2–ZrN phase diagram. The ternary liquidus in the Zr–O–N system was further constrained based on the comparison of the results obtained in this work with composition histories of zirconium particles burning in air reported earlier. Elemental analysis of nitrogen-rich inclusions found in the samples showed the existence of an extended compositional range for ternary solid Zr–O–N solutions. X-ray diffraction analysis of the quenched samples indicated that these solutions are likely to be derived from the ZrN phase. A preliminary outline of the subsolidus ternary Zr–ZrO2–ZrN phase diagram is constructed based on these findings and the interpretations of the well-known binary Zr–O and Zr–N phase diagrams.

An Al–Mg–Si alloy was annealed to various solutionized and aged states and was then severely plastically deformed by equal channel angular pressing (ECAP). These materials were subsequently annealed for a range of times and temperatures to induce precipitation, dislocation recovery, and grain growth, with changes of mechanical behavior followed by tensile testing. Precipitation of excess solute was seen to occur in all cases, independent of the initial heat treated state, but the particles present appear to play only a small role in stabilizing the deformation substructure, at least until significant particle and grain coarsening has occurred, when discontinuous grain coarsening can be provoked. The strength of materials is examined, and the respective contributions of loosely arranged dislocations, many grain boundaries, and dispersed particles are deduced. It is shown that dislocation strengthening is significant in as-deformed, as well as lightly annealed materials, with grain boundary strengthening providing the major contribution thereafter.

In this paper, we show for the first time that by using sodium gluconate-assisted solution route, fine, uniform, and single-crystalline tellurium nanorods and nanowires can be synthesized. Sodium gluconate is a green and safe chemical with strong chelating function, and this property may be useful in the fabrication of nanomaterials, especially one-dimensional (1D) nanomaterials. The sodium gluconate acts as both reducing agent and morphology-directing agent and by adjusting the experimental parameters, the lengths and the diameters of the tellurium nanorods could be further controlled in a certain range. This method is a simple and economical route for 1D nanostructure fabrication and might bring about a novel concept for the synthesis of 1D nanostructures with bio-ligand, sodium gluconate.

Smooth and uniform Ag/AgO nanoshells (about 3–4 nm) on carboxylated polystyrene latex particles were prepared by electrostatic attraction between negatively charged –COO− on the surface of carboxylated polystyrene latex particles and positively charged Ag(NH3)2+ in the solution, and subsequent decomposition of the silver complex. The resultant nanoparticles were characterized with Fourier transform infrared, transmission electron microscopy, scanning electron microscopy, and x-ray diffraction. The effects of reducing agents, the amount of NaOH and temperature on the morphology of hybrid latex particles were discussed.

Nanocomposite particles of anatase-type titania (TiO2) and cubic/tetragonal zirconia were synthesized from hydrothermal processing of TiCl4 and ZrOCl2·8H2O or ZrCl4 alcohol solutions at 160–200 °C. It was found that the morphologies and composition of the composite particles were mainly controlled by the precursors and the sequence by which the precursors were added. The TiO2–ZrO2 composite particles with nanoscale uniformity can be obtained by solvothermal processing of TiCl4 or a ZrO2 precursor together with preformed ZrO2 or yttria stabilized zirconia (YSZ) nanoparticles in ethanol. A novel one-step and non-template method for preparing ZrO2–TiO2 core–shell structured composite particles with hollow interior was identified, and possible reaction mechanism was suggested.

The data on the compositional dependence of glass-forming ability, glass transition, and properties of bulk metallic glasses (BMGs) are important for understanding the nature and glass-forming ability of metallic glasses and for their application. In this paper, we report the formation of rare-earth-based Pr–(Cu,Ni)–Al pseudo-ternary BMGs with a large bulk glass-forming composition range and distinct glass transition. The compositional dependence of glass-forming ability, glass transition, and properties were systematically studied. The contrasting effects of Al and Pr on glass formation and glass transition, unique elastic properties, and phonon softening of the BMGs are discussed from the structural point of view.

Growth morphologies and mechanisms of the carbide of group IVB and VB elements (MC carbide), a typical faceted crystal, were studied with an estimated cooling rate from 102 to 105 K/s. Results showed that although the growth morphologies of the MC carbide vary remarkably with solidification cooling rate, the solid/liquid interface is always atomically smooth, and the growth mechanisms are always lateral growth. The growth mechanism transition from lateral to continuous growth mode, which was predicted by the classic crystal growth theory, was not observed for the TiC type MC carbide within the estimated cooling rate range of 102–105 K/s.

Well-organized mesoporous SiO2/TiO2 materials with crystallized framework were synthesized. The resultant materials showed high surface area (180–300 m2/g), narrow pore-size distribution (3.5–6 nm), and nanocrystalline framework. The influences of aging conditions on the mesoporous 80TiO2–20SiO2 materials were investigated. The water in the initial solution is beneficial for the mesostructural organization of the as-prepared sample while air moisture (relative humidity) during the aging process plays a key role in the crystallization of the calcined sample. Low aging temperature is another decisive factor to the formation of the mesostructure.

We report on the results of a comparative study in which the mechanical response of both fully dense and porous low-κ dielectric thin films was evaluated using two different techniques: nanoindentation and the plane-strain bulge test. Stiffness values measured by nanoindentation are systematically higher than those obtained using the bulge test technique. The difference between the measurements is caused by the Si substrate, which adds significantly to the contact stiffness in the indentation measurements. Depending on the properties of the coatings, the effect can be as large as 20%, even if the indentation depth is less than 5% of the film thickness. After correction of the nanoindentation results for the substrate effect using existing models, good agreement is achieved between both techniques. The results further show that densification of porous material under the indenter does not affect stiffness measurements significantly. By contrast, nanoindentation hardness values of porous thin films are affected by both substrate and densification effects. It is possible to eliminate the effect of densification and to extract the yield stress of the film using a model for the indentation of porous materials proposed by the authors. After correcting for substrate and densification effects, the nanoindentation results are in close agreement with the bulge test measurements. The results of this comparative study validate the numerical models proposed by Chen and Vlassak for the substrate effect and by Chen et al. for the densification effect.

A new europium-silicon-oxynitride compound EuSi2O2N2 was obtained by a reaction of Eu2O3, SiO2, and α–Si3N4 at 1300 °C under a nitrogen atmosphere. EuSi2O2N2 is indexed on a monoclinic unit cell with a = 13.151(5) Å, b =17.311(5) Å, c = 7.956(2) Å, β = 104.12(4)°, and V = 1756.56 Å3. EuSi2O2N2 shows a highly pure yellow color associated with a very steep drop in the reflection spectrum with an optical absorption edge at about 512 nm (2.43 eV). On the other hand, EuSi2O2N2 can be efficiently excited in the visible range 370–485 nm and shows a broad band emission peaking at about 568 nm corresponding to the Eu2+ 4f65d1 → 4f7 transition. EuSi2O2N2 shows paramagnetic Curie behavior with an experimental magnetic moment of 7.89(3) μB in accordance with 7 unpaired spins of Eu2+. Additionally, no magnetic ordering can be observed down to 5 K. The divalent nature of the Eu ions in EuSi2O2N2 is evident from both luminescence and magnetic properties.

The isothermal oxidation behavior of bulk Ti3SiC2 at intermediate temperatures from 500 to 900 °C in flowing dry air was investigated. An anomalous oxidation with higher kinetics at lower temperatures was observed. This phenomenon resulted from the formation of microcracks in the oxide scales at low temperatures. The generation of these microcracks was caused by a phase change in the oxide products, i.e., the transformation of anatase TiO2 to rutile TiO2. This phase transformation resulted in tensile stress, which provided the driving force for the formation of the microcracks during oxidation. Despite the existence of microcracks, the intermediate-temperature oxidation of Ti3SiC2 generally obeyed the parabolic rate law and did not exhibit catastrophic destruction due to the fact that cracks occurring in the oxide layers were partially filled with amorphous SiO2. Therefore, further high oxidation kinetics was prevented.

The mechanical properties of lead zirconate titanate (PZT) multilayer systems are needed to model and design micro-electromechanical systems (MEMS) devices. Nanoindentation is a promising tool for obtaining the elastic properties of thin films. However, no means exist to obtain the elastic modulus of the lead zirconate titanate (PZT) in the multilayer system. The indentation modulus versus a/t behavior of the multilayered PZT/Pt/SiO2 film system on a silicon substrate was investigated and compared with finite element models and a new analytical solution. Six different PZT film thicknesses were indented (100, 140, 400, 700, 1500, and 2000 nm), using 5-, 10-, and 20-μm radius indenters. Good agreement was shown between the finite element analysis (FEA) and analytical solutions, and the experimental data. However the behavior of multilayer systems is complex, making deconvolution of properties difficult for films of less than a micron thick.

Thermal stability studies of Co-substituted barium hexaferrites with the U-type structure are reported. Samples were prepared using solid-state reaction and high-energy milling at 1300 and 1250 °C, respectively. The influence of different annealing conditions on their compositions and magnetic properties was studied. Thermal instability of the studied compounds was observed at as low as 600 °C. Through x-ray powder diffraction, chemical analysis, and thermomagnetic measurements it was confirmed that a degradation of the U-hexaferrites occurred during the annealing at 600–800 °C. The observed changes in the samples’ phase compositions and structures did not have a significant influence on their magnetization and microwave properties.

The phase evolution of magnesium incorporated hydroxyapatite/β-tricalcium phosphate (HA/β-TCP) ceramics of high purity prepared by solid-state reaction was investigated with the aid of x-ray diffraction and infrared spectroscopy (IR) in transmittance mode analysis. The dependence of the microstructure on the phase evolution of biphasic ceramics during natural sintering was also investigated as a function of Mg content. When sintered at 1100 °C, Mg is preferentially incorporated into the β-TCP phase rather than the HA phase. This Mg incorporation into the β-TCP effectively suppresses the phase transition from β- to α-TCP. With increasing sintering temperature, the solubility limit of the Mg in the β-TCP decreases and Mg starts to be either incorporated into the HA phase or segregated as free MgO. The decreased Mg content in the β-TCP facilitates the phase transition from β- into α-TCP, at 1300 °C or higher. Different processing methods on Mg addition show that the retarded phase transition from β- to α-TCP is the inherent property of Mg-doped HA/TCP. The variations in processing parameters mainly affect the microstructure instead of the phase evolution, leading to highly densified HA/β-TCP ceramics.

Deformation and fracture of a columnar-grained, ∼1.3-μm-thick TiN coating on a stainless steel substrate was investigated using a spherical tipped conical indenter of 5-μm nominal tip radius. Structural analysis, performed with the support of focused ion beam (FIB) milling and imaging techniques, revealed that the microstructure of the TiN coating had a strong influence on the deformation behavior of the coating. Intergranular sliding in the coating, as well as plastic flow in the ductile substrate, was found to be the predominant processes during the indentation. Neither plastic deformation, in the form of plastic flow, within the coating nor delamination of the interface was observed. Coating deformation was observed to be controlled by the intergranular shear cracking and thus by the interfacial columbic frictional stress between columnar grains. An indentation-energy based model was developed, which deconvolutes the coating behavior from that of the substrate, allowing quantification of the intergranular sliding stress.

Repeated deformation processing was used to produce layered aluminium titanate (ATI)-alumina composites with a corrugated microstructure. Viscous nonpolar pastes of ATI and alumina powders were prepared using paraffin oil as the dispersing medium. These pastes were rolled into tapes 1 mm thick, which were then stacked together to form starting bi-material laminates in an A-B-A sequence. The laminates were then plastically deformed by repeated folding and rolling at room temperature. After a sufficiently large true plastic deformation, composites with corrugated microstructures were successfully produced. During sintering, part of the ATI decomposed; in the alumina layers large anisotropic grains were formed. The mechanical properties of the sintered composites improved with structural refinement, in spite of extensive microcracking observed during cooling from the sintering temperature. In addition, the thermal expansion coefficient along the rolling direction did not differ from that of the reference material.

We present a detailed study of the thermal stability of organic thin films of diindenoperylene encapsulated by sputtered aluminum oxide layers. We studied the influence of capping layer thickness, stoichiometry, and heating rate on the thermal stability of capped films and their eventual breakdown. Under optimized encapsulation conditions (thick and stoichiometric capping layer), the organic films desorb only at temperatures 200 °C above the desorption of the uncapped film. Moreover, the capped organic films retain their crystalline order at these elevated temperatures, whereas they would normally (i.e., uncapped) be in the gas phase. This study therefore also shows a way of studying organic materials under temperature conditions normally inaccessible. Considering results from complementary techniques, we discuss possible scenarios for the eventual breakdown. The results have implications for the performance and long-term stability of organic devices for which stability against elevated temperatures as well as against exposure to ambient gases is crucial.

A silica-free MgO–CaO–BaO–Al2O3–ZrO2 glass was converted into glass-ceramic by adding zirconia as a nucleating agent. The crystallization and properties of the glass-ceramics were investigated. It was found that ZrO2 is an efficient nucleating agent for the present calcium aluminate glass. Addition of an appropriate amount of ZrO2 changed the crystallization behavior from surface nucleation to internal nucleation. The primary crystalline phase was Ca3Al2O6, which exhibited bulk nucleation. When the crystallizing time was increased, BaAl2O4 formed as a surface layer that grew from the surface into the interior of the sample. The hardness was increased when the parent glass was converted into glass-ceramics. The glass-ceramics without BaAl2O4 surface layer have visible-to-infrared transparency comparable with the parent glass. The transparency was substantially reduced after the development of the surface layer.

The influence of the molecular weight of poly(acrylic acid) (PAA) on chemical mechanical planarization (CMP) for shallow trench isolation (STI) was investigated. The adsorption behaviors of PAA as a function of molecular weight on deposited plasma-enhanced tetraethylorthosilicate and chemical vapor deposition Si3N4 films were analyzed by the force measurement using atomic force microscopy (AFM). The AFM results revealed that the affinity of PAA with the nitride film is higher than the affinity with the oxide film, and thus a denser adsorption layer on the nitride film is formed with higher molecular weight of PAA, which leads to higher selectivity in STI CMP. Additionally, to determine the correlation between the dispersion stability of the CeO2 resulting from the presence of PAA with different molecular weight and CMP performance, the colloidal properties of the slurry as a function of the molecular weight of PAA were examined.