Nanocrystalline TiB2 is prepared by reaction of NaBH4 and TiCl4. The initial solution-phase reaction affords an amorphous precursor powder from which 5-100 nm TiB2 crystallites are obtained upon annealing at 900-1100 °C. Crystallite sizes depend on the annealing temperature and other processing parameters. Crystallite morphology is size dependent; crystallites smaller than 12-15 nm are cuboidal, whereas crystallites larger than 12-15 nm are hexagonal platelets. The procedure affords gram quantities of the smallest available TiB2 nanocrystallites.

This paper presents neutron and ion radiation effects in the Nicalon SiC polymer precursor fiber. It is shown that the serious structural degradation of this fiber and its composites (e.g., CVD SiC/Nicalon) previously reported for the standard grade of Nicalon is primarily due to the presence of the silicon oxycarbide phase. Results supporting this interpretation include microstructural analysis as well as post irradiation mechanical property measurements. Preliminary results of the effects of irradiation on low-oxygen Nicalon fibers are presented. The reduced oxygen content fibers exhibit radiation-induced density, strength, and Weibull's and Young's moduli changes typical of monolithic ceramic materials. This contrasts sharply with the poor irradiation behavior of the standard Nicalon fiber and suggests that improved radiation resistance can be expected in SiC/SiC composites fabricated with low oxygen Nicalon fibers.

Atomistic techniques are used to study brittle fracture under opening mode and mixed mode loading conditions. The influence of the discreteness of the lattice and of the lattice-trapping effect on crack propagation is studied using an embedded atom potential for nickel to describe the crack tip. The recently developed FEAt (Finite Element-Atomistic) coupling scheme provides the atomistic core region with realistic boundary conditions. Several crystallographically distinct crack-tip configurations are studied and commonly reveal that brittle cracks under general mixed mode loading situations follow an energy criterion (G-criterion) rather than an opening-stress criterion (Kl-criterion). However, if there are two competing failure modes, they seem to unload each other, which leads to an increase in lattice trapping. Blunted crack tips are studied in the last part of the paper and are compared to the atomically sharp cracks. Depending on the shape of the blunted crack tip, the observed failure modes differ significantly and can drastically disagree with what one would anticipate from a continuum mechanical analysis.

Wide Angle X-ray Scattering (WAXS) and Small Angle X-ray Scattering (SAXS) were applied to elucidate the microstructure and morphology of two zwitterionic copolymers. The first system is a sulfobetaine derivative of poly(4-vinyl pyridine) with an ionic content of 10% (10% of the degree of quaternization). The copolymer is almost amorphous, with a small degree of crystallinity (10%). The second copolymer is a N-oxide derivative of the poly(N,N dimethyl aminoethyl methacrylate) highly crystalline (90%). The latter forms superstructures of globular shape with crystalline domains of coordinated polymer-salt systems. X-ray data are in accordance with those published by Castaño et al. [J. Mater. Res. 5, 654 (1990)]. These authors reported TEM micrographs of zwittcrionic systems, where clusters with grainy appearance were observed within the length of scale range found in this work. Models for the morphology of these copolymers are proposed for each use.

Single layer Pb(Zr0.53Ti0.47)O3 films up to 0.7 μm thick have been prepared from air-stable titanium and zirconium precursors using a diol-based sol-gel route. Information on film crystallization, surface microstructure, and electrical properties under different firing temperatures and three different heating rates including rapid thermal annealing are presented. Films exhibited (111) preferred orientation, the extent of which reduced with increasing firing temperature or heating rate. It is possible that a PbPtx interfacial reaction product was formed during the prefiring step at 350 °C and this, together with the influence of the 111 bottom platinum electrode, contributed to (111) orientation in the PZT films. Surface microstructure was also influenced by firing temperature and heating rate as well as by film thickness. The 0.4 μm thick films used for electrical measurement had a grain size of ⋚0.1 μm, whereas 0.7 μm thick films made from concentrated sols exhibited “rosette” microstructures with grain sizes up to 0.5 μm. Among the three firing schedules studied, directly inserting the gel coatings in a furnace preset at 700 °C produced films with the most favorable electrical properties. A 0.4 μm thick film gave rise to a remanent polarization, Pr, of 33 μC cm−2 coercive field, Ec, of 46 kV cm−1; relative permittivity, ∊r, of 1100; and dissipation factor, D, of 0.05. For a 0.7 μm single layer film, the respective values were 21 μC cm−2, 36 kV cm−1, 1300, and 0.05.

A new class of molecular composites of carbon black and an electronically conducting polymer, namely polypyrrole, has been synthesized by chemically polymerizing pyrrole in an aqueous dispersion of carbon black. The carbon black content of these composites can be varied from ∼5% to ∼85% (by weight). The surface area and density of these composites were compared to corresponding mixtures of carbon black and polypyrrole. The influence of carbon black on the efficiency of polymerization of pyrrole is described. The effect of carbon black content on the electronic conductivity of the composite has been mapped, and compared with the corresponding behavior of a mixture of carbon black and polyvinylchloride. The influence of the parent black characteristics (porosity, void volume, surface area) on the electronic conductivity of the resultant composite has been probed by comparing the behavior of composites derived from six commercial and experimental blacks. The temperature dependence of the composites has been studied as a function of the carbon black content. Finally, the application of these new materials is an environmental remediation scenario is demonstrated for Cr(vi) as a model pollutant.

Improving wettability of the polycarbonate (PC) surface to triple distilled water has been carried out by Ar+ ion irradiation with blowing oxygen gas. The amount of Ar+ was changed from 1014 to 5 × 1016 ions/cm2 at 1 keV energy by a Kaufman-type ion source. Contact angle of the water to PC has been reduced from 78°to 50°with Ar+ irradiation, and to 12°with Ar+ irradiation in various vacuum pressures adjusted by oxygen gas flow rate (0-4 sccm). Strong O-H stretching vibration peaks at about 3370 cm−1 on FT-IR spectra of the polymer appeared after the surface treatments, and the wetting angle of the treated PC was returned to its value (78°) when the PC was exposed in air environment. The minimum contact angles were maintained with the same value when the irradiated polymers were kept in dilute HCl solution. The improved wettability and surface chemical reaction by Ar+ ion irradiation with oxygen was explained by the formation of a hydrophilic functional group. Enhanced adhesion between aluminum and PC was confirmed by the scotch tape test, and was discussed with relation between the hydrophilic group on the polymer surface and the deposited metal.

Thin films of polytetrafluoroethylene have been deposited on amorphous substrates by the pulsed-laser deposition technique. By transmission electron microscopy, the polymer films were shown to consist of both amorphous and crystalline components. The data for the crystalline component are consistent with it being highly ordered with the long helical molecular chains aligned parallel to the film substrate interface plane. The fraction of crystalline material in the films was found to be related to the substrate temperature during deposition with the maximum amount of crystalline material occurring when the substrate temperature was close to the melting temperature of the polymer.

Nanocrystalline CoxCu100−x (4 ⋚ x ⋚ 49 at. %) powders were prepared by the reduction of metal acetates in a polyol. The structure of powders was characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), extended x-ray absorption fine structure (EXAFS) spectroscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy, and vibrating sample magnetometry (VSM). As-synthesized powders were composites consisting of nanoscale crystallites of face-centered cubic (fcc) Cu and metastable face-centered cubic (fcc) Co. Complementary results of XRD, HRTEM, EXAFS, NMR, and VSM confirmed that there was no metastable alloying between Co and Cu. The NMR data also revealed that there was some hexagonal-closed-packed (hcp) Co in the samples. The powders were agglomerated, and consisted of aggregates of nanoscale crystallites of Co and Cu. Upon annealing, the powders with low Co contents showed an increase in both saturation magnetization and coercivity with increasing temperature. The results suggested that during preparation the nucleation of Cu occurred first, and the Cu crystallites served as nuclei for the formation of Co.

The kinetics of constrained-film sintering were studied in a borosilicate glass (BSG) + silica system because of their applications in microelectronic packaging technologies. Samples with a silica content by 20% by volume were prepared from slurries of powder mixtures in a commercial polyvinyl butyral (PVB) binder solution. Constrained films about 0.2 mm thick were formed by doctor-blade casting the slurries on silicon wafers. Free-standing films about 0.6 mm thick were also produced by casting the slurries on a treated mylar sheet for easy lift-off. Sintering experiments were carried out in a hot stage at temperatures between 715 °C and 775 °C. Shrinkage profiles of the free and constrained (shrinkage in thickness only) films were determined in situ using a custom-designed optical system. The densification rates measured in the constrained films were slower than those in the free films. However, the substrate constraint had no effect on the activation energy of densification which was found equal to 385 ± 10 kJ/mol, the same for both free and constrained films. A relation between the constrained-film and free-film densification profiles was derived using the viscous analogy for the constitutive equations of a porous sintering body.

The deposition of Cu, Zn, Pt, and Co precursor particles from solution onto a flat silicon wafer using a spin coater was studied. Homogeneously distributed monodisperse particles can be obtained. The dependence of particle size and number density on solution concentration and rotation frequency was investigated. Different solvents and support modifications were studied. The particles were analyzed using dark-field microscopy, scanning electron microscopy, and atomic force microscopy.

The primary focus of this paper is on the axial compression behavior of high performance polymeric and carbon fibers. Seven test methods used for determining the compressive strength of single fibers have been reviewed. Various micromechanical models proposed in the literature to understand the compressive failure in single filaments and in other anisotropic systems have been discussed and analyzed. The results of various approaches to influence the compressive strength of polymeric fibers have been summarized. Possible reasons for the variation in the compressive strength of pitch and PAN-based carbon fibers have also been addressed.

This paper describes a process for uniformly enhancing the nucleation density of diamond films on silicon (Si) substrates via dc-biased hot filament chemical vapor deposition (HFCVD). The Si substrate was negatively biased and the tungsten (W) filaments were positively biased relative to the grounded stainless steel reactor wall. It was found that by directly applying such a negative bias to the Si substrate in a typical HFCVD process, the enhanced diamond nucleation occurred only along the edges of the Si wafer. This resulted in an extremely nonuniform nucleation pattern. Several modifications were introduced to the design of the substrate holder, including a metal wire-mesh inserted between the filaments and the substrate, in the aim of making the impinging ion flux more uniformly distributed across the substrate surface. With such improved growth system designs, uniform enhancement of diamond nucleation across the substrate surface was realized. In addition, the use of certain metallic wire mesh sizes during biasing also enabled patterned or selective diamond deposition.

Materials with nanocrystalline features are expected to have improved or unique properties when compared to those of conventional materials. Methods for the practical and economical production of nanoparticles in large quantities are not presently available. A method based on combustion synthesis for preparing nanocrystalline powders was investigated in this work. Yttria-doped zirconia powders with an average crystallite size of 10 nm were synthesized. The characteristics of the powder (e.g., surface area and phase content) were found to depend strongly on the fuel content in the starting mixture and on the ignition temperature used in the process. The method is expected to be suitable for commercial fabrication of nanocrystalline multicomponent oxide ceramic powders.

Five kinds of uniform metal oxide particles (α-Fe2O3, CeO2, CuO, NiO, and SiO2) were coated with polypyrrole by reacting the dispersed solids with pyrrole in a water/ethanol medium without the use of a soluble oxidant. When the process was carried out in air, all particles were coated with the polymer, although the thickness of the layer varied on different cores. In CuO dispersions, independent polypyrrole particles were produced in addition to coated spheres. While oxygen is the major oxidant that initiates the polymerization of pyrrole, some metal oxides may also affect the reaction both in terms of the amount and the composition of the shell. Thus, α-Fe2O3 and SiO2 were found to be inactive in the polymerization, while CeCh and CuO react with the adsorbed pyrrole molecules through a reductive-dissolution process, in which the monomers are oxidized, causing a release of reduced metal ions.

The variation of apparent hardness observed in previously reported Vickers indentation tests of metals is reexamined. Common deseriptions of the effect are shown to be inaccurate: the variation of apparent hardness is monotonic but not simple. The effect is consistent with varying size of a previously postulated “plastic hinge” at the perimeter of the indent. This complexity confers uncertainty on the estimation of characteristic macrohardness from small scale tests. Association of the indentation size effect with friction and with strain hardening is confirmed.

The observation of aerogels submitted to a pressure of mercury indicates that this porous material is compacted and not intruded by the mercury. Consequently, the classical Washburn equation cannot be applied. A relation is established between the pressure P of compaction and the size L of the largest pores. The size of pores is estimated by using the nitrogen adsorption-desorption isotherms analysis and SEM measurements. A relation is found in which P is proportional to L−4 The new relation is applied to mercury porosimetry. Finally, a mechanical model is proposed that reproduces successfully the behavior of aerogels under high pressure of mercury.

Verneuil sapphire was purified of Cr3+ by containerless melting and processing at ca. 2550 K in argon, dry air, and pure oxygen. Recovered material was examined by laser induced fluorescence and Raman spectroscopy. The Cr3+ fluorescence intensity decreased in processed specimens at rates proportional to the chromium concentration and p(O2)0.21. The initial chromium concentration was ca. 5 ppm and decreased by factors of ca. 50, 3000, and 2 × 105 after processing for 300 s in argon, air, and oxygen, respectively. Evidence is presented that the Cr3+ was removed predominantly as CrO2(g) and not by conversion to other oxidation states of chromium in the condensed phase.

The oxidation behavior of reaction-formed silicon carbide (RFSC) ceramics was investigated in the temperature range of 1100 to 1400 °C. The oxidation weight change was recorded by TGA; the oxidized materials were examined by light and electron microscopy, and the oxidation product by x-ray diffraction analysis (XRD). The materials exhibited initial weight loss, followed by passive weight gain (with enhanced parabolic rates, kp), and ending with a negative (logarithmic) deviation from the parabolic law. The weight loss arose from the oxidation of residual carbon, and the enhanced kp values from internal oxidation and the oxidation of residual silicon, while the logarithmic kinetics is thought to have resulted from crystallization of the oxide. The presence of a small amount of MoSi2 in the RFSC material caused a further increase in the oxidation rate. The only solid oxidation product for all temperatures studied was silica.

Hertzian contact damage in as-fired, peak-aged, and over-aged Mg-PSZ is studied, in single-cycle and multiple-cycle loading. Indentation stress-strain curves reveal a monotonically increasing quasi-plasticity component in the contact deformation with increasing aging time. A bonded-interface technique is used to obtain surface and subsurface views of the damage zones beneath the spherical indenter. Analytical techniques, including optical and scanning electron microscopy, acoustic emission, Raman spectroscopy, and thermal wave imaging, are used to characterize the damage. The damage patterns are fundamentally different in the three aging states: microfracture dominated in as-fired; tetragonal-monoclinic phase-transformation-dominated in peak-aged; monoclinic-phase twinning-dominated in over-aged. The damage accumulates with increasing number of cycles, most strongly in the as-fired state. It also increases with increasing test duration in the as-fired and over-aged states, but not perceptibly in the peak-aged. The results imply predominantly mechanical fatigue effects, augmented by a chemical component in the as-fired and over-aged states. Broader implications in relation to the susceptibilities of zirconia ceramics to fatigue degradation in concentrated stress configurations, with special relevance to the evolution of flaws at the microstructural level, are considered.