The effect of mechanical deformation via high-energy ball milling on the structure of the Fe40Ni40P14B6 metallic glass was studied by means of x-ray diffactometry, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). After 5 h of milling, TEM observations indicated that some nanocrystallites with a diameter of about 6 nm precipitated from surface layers of the amorphous ribbons, whereas the bulk remained amorphous. When milling time was increased to 11 h, bulk crystallization occurred. The amorphous Fe40Ni40P14B6 alloy crystallized into a mixture of γ–(Fe, Ni) and (Fe, Ni)3(P, B). To understand the microstructural changes occurring in the amorphous ribbons before the onset of bulk crystallization, the isothermal crystallization behavior of as-deformed amorphous ribbons was studied. Compared with as-quenched amorphous ribbons, the local value of the Avrami exponent, derived from isothermal DSC data, increased from 3.5 to 4.1 for bulk crystallization. The thermal crystallization mechanism of deformed amorphous Fe40Ni40P14B6 ribbons changed from an eutectic-type reaction with simultaneous precipitation of γ–(Fe, Ni) and (Fe, Ni)3(P,B) from the amorphous matrix to a primary-type reaction with precipitation of α–Fe(P,B) preceding the formation of γ–(Fe,Ni) and (Fe,Ni)3(P,B). Our results suggest that several hours of mechanical milling cause surface crystallization and some atomic rearrangements in the amorphous alloy. The latter effect may be responsible for the observed primary-type reaction for crystallization of the deformed amorphous alloy

A significant difference of strength was noted in alumina ceramics made through the powder compaction process with spray dryers of two sizes. The origin of the change was examined by new characterization methods involving optical microscopy. The granules were found to have irregular shape. Defects in compacts were formed from these dimples and also from the nonuniform packing of powder particles at the granule boundaries. These defects are responsible for major defects in sintered bodies. The change of strength in the ceramics can be explained by the change of granule size with the spray dryer. The size of granules was found to directly affect the size of defects in the green and sintered bodies. The size of granules, defects in granules, green bodies, and sintered bodies were approximately 20–30% smaller for granules made with the small spray drier. There was a direct correlation between the size of defect and the strength of ceramics.

Interfacial reactions of Co/Si0.76Ge0.24 and Co(Si0.76Ge0.24)/Si0.76Ge0.24 by pulsed KrF laser annealing as a function of energy density and pulse number were studied. For the Co/Si0.76Ge0.24 samples annealed at an energy density of 0.2–0.6 J/cm2, three germanosilicide layers, i.e., amorphous structure and/or nanocrystal, Co(Si1−xGex), and Co(Si1−xGex)2, were successively formed along the film-depth direction. At 0.3 J/cm2 Ge segregated to the underlying Si0.76Ge0.24 film, inducing strain relaxation in the residual Si0.76Ge0.24 film. At 0.8 J/cm2 the reacted region was mostly transformed to a single layer of Co(Si1−xGex)2, whereas Ge further diffused to the Si substrate. At 1.0 J/cm2, constitutional supercooling appeared. Even the Co(Si0.76Ge0.24) film used as the starting material for laser annealing could not prevent the occurrence of constitutional supercooling at energy densities >1.6 J/cm2. The energy densities at which Co(Si1−xGex) transformation to Co(Si1−xGex)2, Ge segregation to the underlying Si, and constitutional supercooling occurred were higher for the Co(Si0.76Ge0.24)/ Si0.76Ge0.24 system than for the Co/Si0.76Ge0.24 system. Higher energy density and/or pulse number enhanced the growth of Co(Si1−xGex)2 film. In the present study, the Co/Si0.76Ge0.24 samples subjected to annealing at 0.2 J/cm2 for 20 pulses produced a smooth Co(Si0.76Ge0.24)2 film without inducing Ge segregation out of the germanosilicide and strain relaxation in the unreacted Si0.76Ge0.24 film.

Intercalated domains on stage 4 MoCl5–graphite intercalation compounds (MoCl5–GIC’s) were observed by atomic force microscopy (AFM) and scanning tunneling microscopy (STM). On large intercalated domains, a superstructure was found, in relation with a modulation of the electronic properties of the first layer of carbon. From that, the structure of the chloride ions layer was discussed and a model including dimer molecules was proposed. At the boundaries between large intercalated and nonintercalated domains, corrugations were observed along certain crystallographic directions of graphite. Their morphology was studied in detail at atomic scale and formation mechanisms were proposed. Small intercalated domains were also observed. Their shapes were irregular but their boundaries were clear cut.

The simultaneous synthesis and densification of the ternary Ti3SiC2 was investigated by the field-activated, pressure-assisted combustion method. Depending on temperature and time at temperature, relatively pure and nearly fully dense materials can be synthesized by this approach. The optimum conditions to produce this phase were a reaction temperature of 1525 °C and a time at temperature of 2 h. The product contained TiC as a second phase at a level of ≤2 mol%. The resulting ternary phase has typically elongated grains which were about 25 μm in size. Within a range of applied force of 1–4 N, the microhardness of the product was relatively constant, ranging from 6 to 7 GPa. Investigations on the thermal and chemical stabilities of the ternary were also conducted. Vacuum annealing at temperatures of 1600 and 2000 °C resulted in the formation of a surface layer of TiC, while the air annealing at 1000 °C resulted in the formation of TiO2. Oxidation studies on the prepared Ti3SiC2 were made at temperatures ranging from 800 to 1100 °C. The results suggest a two-mechanism process, one dominating in the approximate range of 800–950 °C and the other in the range 950–1100 °C with corresponding activation energies of 137.7 and 312.5 kJ·mol−1. The results are explained in terms of two proposed reactions on the basis of microprobe analyses.

This paper aims to investigate the initiation and distribution of dislocations and twins in the subsurface of alumina subjected to single-point scratching and to gain a deeper understanding of the mechanisms of ductile-regime grinding of alumina. It found that there generally exist three regions of dislocation and twin systems in the scratched alumina. The first region contains five independent slip systems so that macroscopic plastic flow is possible there. In the second and third regions, not all the systems can be activated, and then microcracking in the subsurface may occur easily. The distribution of these regions varies with the grain size of alumina. In the 25 μm-grained alumina all three regions appear. Thus, in this case, microcracking is difficult to avoid. In the 1 μm-grained alumina, however, only the first region appears, indicating that the material may be scratched under a real ductile mode without microcracking. A comparison shows that theoretical predictions are in good agreement with experimental observations.

Ln(Mg1/2Ti1/2)O3 (Ln = Dy, La, Nd, Pr, Sm, Y) compositions have been prepared, and their pertinent properties for use as thin film substrates for YBa2Cu3Ox (YBCO) were measured. X-ray diffraction shows that Ln(Mg1/2Ti1/2)O3 compositions have noncubic symmetry and the GdFeO3-type structure. Dielectric constant measurements revealed values between 22 and 27, which are larger than those of the LnAlO3 family. Quality factor (=1/ tan δ) of the ceramic specimens measured at room temperature was larger than 3000 at 10 GHz. Among the compounds, La(Mg1/2Ti1/2)O3 exhibited the highest dielectric constant and the lowest dielectric loss. Chemical reaction was observed between Ln(Mg1/2Ti1/2)O3 (Ln = Dy, Sm, Y) and YBCO after annealing a 1 : 1 mixture at 950 °C. Considering dielectric and physical properties, La(Mg1/2Ti1/2)O3 and Sm(Mg1/2Ti1/2)O3 were determined to be suitable substrates for YBCO thin film used in microwave applications.

A phenomenological model of ion-beam mixing during energetic collision cascades is developed, based on the concept of a thermal spike, to correctly predict that the mixing rate Dt depends linearly on nuclear stopping power (instead of a power-law dependence), and is correlated with a heat of mixing (analogous to Darken's relation). Previous ion-beam mixing experiments from 25 different metallic bilayers agree well with the model's predictions: mixing rates (Dt)/(ion-dose) ∼ 1 nm4, and an activation enthalpy of approximately 1 eV for atomic diffusion in liquid-like cascades.

An interfacial SiO2 hampers a silicidation reaction between Co and Si. A refractory metal cap is believed to block ambient oxygen diffusing toward the Co/Si interface. However, an interfacial SiO2 can also be present prior to and/or during the annealing. This work reports on our findings of the interaction between SiO2 and Co layers capped with refractory metals. It was found that Ti diffuses through the Co layer and segregates underneath the Co, which leads to the reduction of SiO2 and the formation of free Si. The free Si in-diffuses and reaches the original Ti surface. On the other hand, TiN shows a very inert behavior compared to Ti. The results are discussed in connection with Co silicidation processes.

A micromechanical model of void nucleation in passivated metal interconnection lines is proposed. The model is based on the evolution of stress and strain fields in a two-dimensional model system, obtained from numerical modeling. Interface flaws in the form of debond between the metal and the surrounding dielectric are assumed to exist. A unique pattern of shear stress resolved on the slip systems in the metal line, due to the presence of pre-existing debond, is found. A dislocation slip model is constructed in accordance with the shear mode. The mechanism of crystallographic slip is such that lateral thinning of the metal line at the debond region together with the slip step produced at the edges of debond lead to a net transport of atoms away from the debond area, and a physical void is thus formed. The significance and implications of this proposed micromechanism are discussed.

We report on the feasibility of using molybdenum silicide as a conducting barrier for integration of ferroelectric lead zirconate titanate capacitors on Si. Thin films of MoSi2 were deposited by pulsed laser-ablation deposition (PLD). The silicide films showed a structural transition from amorphous to orthorhombic to tetragonal phase as the temperature of deposition was changed from room temperature to 900 °C. The four-probe resistivity and surface roughness of the films decreased with an increase in the deposition temperature and crystallinity of the phase. Ferroelectric (La, Sr)CoO3/Pb(Nb, Zr, Ti)O3/(La, Sr)CoO3 capacitors were grown on Si/poly Si/MoSi2, and Si/poly Si/MoSi2/Pt structures. Transmission electron microscopy (TEM) studies of the MoSi2/LSCO and MoSi2/Pt/LSCO heterostructures indicated the formation of a thin layer of SiO2. In the case of Pt/MoSi2, Pt reacts with the silicide and forms PtSi, consuming the entire platinum layer and, thus, makes it unsuitable as a composite barrier. Electrical testing of the LSCO/PNZT/LSCO capacitors through capacitive coupling showed desirable ferroelectric properties on these substrates.

Magnetic and mechanical properties of Co-rich amorphous microwires of nominal compositions (Co1–xMnx)75Si10 B15 (0.08 < x < 0.11) and Co56.5Fe6.5Ni10B16Si11 with nearly zero magnetostriction constant have been studied. Drastic changes of the hysteresis loop with the decrease of x from rectangular to flat shape were observed at x < 0.1, while the Co56.5Fe6.5Ni10B16Si11 microwire showed rectangular hysteresis loops. Compositions with x ≥ 0.1 have small but positive magnetostriction constant while negative λs values have been observed at x ≤ 4 0.09, indicating rectangular character of the hysteresis loop in samples with nearly zero and even for small negative λs. External stress dependence of switching field, H*, showed an increase of H*; with s for samples with x = 0.11 and a decrease of H* with σ for x = 0.1. Besides, microwires of the same composition but with different dimensions showed different H*(σ) dependencies.

Plasticity in material is typically described as a function of strain, but recent observations from torsion and indentation experiments in metals suggested that plasticity is also dependent on strain gradient. The effects of strain gradient on plastic deformation in thermosetting epoxy and polycarbonate thermoplastic were experimentally investigated by nanoindentation and atomic force microscopy in this study. Both thermosetting and thermoplastic polymers exhibited hardening as a result of imposed strain gradients. Strain gradient plasticity theory developed on the basis of a molecular kinking mechanism has predicted strain gradient hardening in polymers. Comparisons made between indentation data and theoretical predictions correlated well. This suggests that strain gradient plasticity in glassy polymers is determined by molecular kinking mechanisms.

The possibility of stabilizing the theoretically predicted β–C3N4 phase by high-energy ball milling is investigated. Charges of graphitic carbon were milled with and without minor alloying additions under different atmospheric media, namely gas and/or liquid phases of nitrogen, air, or ammonia. Milling was performed at either of two energy levels for periods of up to 48 h. The β–C3N4 phase was found to exist as small crystallites in a matrix of primarily amorphous carbon at volume fractions estimated between 5 and 10 at.%. High-resolution electron diffraction and x-ray diffraction indicate that the crystalline nature of the C3N4 phase corresponds with a hexagonal lattice with a = 6.46 Å and c/a = 0.374, which are within 2% of the theoretically calculated lattice parameter values. Analysis of electron energy-loss spectroscopy (EELS), x-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectra verify the presence of chemically bonded carbon and nitrogen with chemical states reflecting combined sp2 and sp3 hybridization. Chemical analysis confirms nitrogen enrichment at levels consistent with the C3N4 stoichiometry and the estimated degree of stabilization. The possible mechanism(s) responsible for the stabilization of the β–C3N4 phase are briefly discussed.

Anodic spark deposition (ASD) is an advanced plasma-electrochemical coating process to prepare polycrystalline, ceramic-like conversion coatings on metal surfaces. As an example, polycrystalline barium titanate (BaTiO3) phases have been prepared by the anodic conversion of metal substrate and the metal ions in the electrolyte. By a combination of various characterization techniques, the configuration of the coating was elucidated. On the metal substrate a thin (~50 nm) passivating amorphous film of titania (TiO2) first forms, which subsequently changes to anatase and rutile structures. With increasing anodic potentials, a plasma-chemical conversion reaction starts, leading to the heterogeneous formation of BaTiO3 layers of 2–10 μm thickness. The results of this study lead to the formulation of a model describing a polycrystalline and inhomogeneous layer configuration.

Pure and deuterated titanium thin films 140 nm thick were deposited on 〈100〉 Si wafers by electron beam evaporation, keeping the substrate temperature at 150, 300, and 450 °C. Pure Ti samples were deposited in a high-vacuum condition, while for deuterated samples, deuterium high-purity gas was introduced in the deposition chamber during the process. Film composition was studied by Rutherford backscattering spectrometry (RBS) and elastic recoil detection analysis (ERDA), whereas structural characterization of the deposited layers was carried out by x-ray diffraction (XRD) using both the traditional Bragg–Brentano geometry and a parallel beam setup for pole figure measurements. Titanium films deposited in a high vacuum showed the hexagonal Ti structure (α−Ti) and grew with a double orientation at each of the examined substrate temperatures. Deuterated titanium films deposited at 150 °C had a compositional ratio Ti: D = 1: 0.35 and grew with a [111] oriented fcc structure, suggesting the formation at low temperature of a substoichiometric δ hydride phase. Deuterated films deposited at higher substrate temperatures revealed a lower deuterium content and XRD reflections corresponding to the hexagonal Ti phase. The present results were interpreted according to a temperaturedependent D2 adsorption mechanism at the surface of the continuously growing Ti film.

A hydroxyapatite [HAp; Ca10(PO4)6(OH)2] coating layer was formed on a Ti-based alloy by the electron-beam deposition method. When pure HAp was used as a target for the deposition, an amorphous layer was formed on the metal substrate. By heat treatment in a vacuum at 630 °C, the layer was crystallized into tricalcium phosphate [Ca3(PO4)2]. The crystallization improved the dissolution rate of the layer remarkably; however, at the same time, it deteriorated the bond strength with the substrate. When extra CaO (up to 25 wt%) was added to the target and processed under the same conditions, a layer compositionally close to crystalline HAp was deposited. Before the heat treatment, even though the layer was in amorphous state, the dissolution rate in the physiological solution was extremely low. Furthermore, the bond strength increased remarkably compared to the layer formed by the pure HAp target. Compositional and structural resemblance of the layer with the crystalline HAp was attributed to these improvements in properties.

The incorporation of vacancies, H atoms, and sp2 bond defects into single-crystal homoepitaxial (100) (2 × 1)–and (111)-oriented chemical-vapor-deposited diamond was simulated by atomic-scale kinetic Monte Carlo. Simulations were performed for substrate temperatures from 600 to 1200 °C with 0.4% CH4 in the feed gas, and for 0.4–7% CH4 feeds with a substrate temperature of 800 °C. The concentrations of incorporated H atoms increased with increasing substrate temperature and feed gas composition, and sp2 bond trapping increased with increasing feed gas composition. Vacancy concentrations were low under all conditions. The ratio of growth rate to H atom concentration was highest around 800–900°C, and the growth rate to sp2 ratio was maximum around 1% CH4, suggesting that these conditions are ideal for economical diamond growth under simulated conditions.

Plastic deformation of metals is generally a function of the strain. Recently, both phenomenological and dislocation-based strain gradient plasticity laws were proposed after strain gradients were experimentally found to affect the plastic deformation of the metal. A strain gradient plasticity law is developed on the basis of molecular theory of yield for glassy polymers. A strain gradient plasticity modulus with temperature and molecular dependence is proposed and related to indentation hardness. The physics of the strain gradient plasticity in glassy polymer is then discussed in relation to the modulus.

Processing-microstructure relationships in a silica gel system, based on mixtures of colloidal sol and soluble potassium silicate, have been studied. Quantitative microstructural information regarding colloidal cluster sizes, size distributions, surface areas, and pore-size distribution from the nanopore range to the macropore range was determined via small-angle scattering and transmission electron microscopy. The colloid cluster size distribution varies systematically, with gels fabricated with the least colloidal fraction possessing the most polydisperse microstructure. It is shown that the porosity over the entire range can be tailored by selecting the appropriate starting chemistry; under the same pH conditions, the ratio of the two silicate ingredients controls the average size, the polydispersity of sizes, and the connectivity of the pores. A population of fine (2 nm) uniformly dispersed nanopores, which result from leaching, is responsible for large increases in surface area. The leaching process can be controlled by the surrounding macropore void size, which determines alkali transport. The product material consists of 85% large, open pores, with fine pores within the gel skeleton, making this gel an ideal candidate for controlled-porosity applications such as catalyst supports and magnetic composites.