We report the nonthermal synthesis of ultrafine crystalline nanoparticles of titanium oxide and titanium nitride. The nanoparticles are formed by gas phase reactions between precursor gases dissociated in the microwave plasma. For the production of titanium nitride, titanium tetraisopropoxide (TTIP) and ammonia or nitrogen precursor gases are used. For titanium oxide production TTIP and oxygen are used as precursor gases. In both cases ultrahigh purity argon serves as a carrier gas and diluent.Transmission electron microscopy (TEM) revealed that the titanium nitride powders so formed were either cubic (TiN) or tetragonal (Ti2N) depending on the operational conditions, particularly the relative nitrogen gas flow rates. Ammonia gas was found to be a much more reactive nitrogen source than molecular nitrogen gas. For the titanium oxide growth an excess of oxygen was utilized to achieve TiO2. Powders collected from the gas phase corresponded to the rutile (tetragonal) phase. However, powders collected from the cavity walls corresponded to the high temperature and pressure (orthorhombic) 13-TiO2. There was also evidence of a polytypically modulated phase of TiO2, with the observed c-periodicity double the parent c-periodicity of the rutile phase. Using a low oxygen flow rate during powder formation led to the formation of orthorhombic Ti3O5 “powders”. The powders were easily sinterable by in situ electron beam annealing in the electron microscope, with an estimated temperature of around 550°C. This is much lower than the temperatures normally required to sinter these materials.

The glycine/nitrate process (GNP) is a combustion synthesis method that is particularly useful for synthesizing ultra-fine, multi-component oxide powders. During the self-sustaining combustion, the precursor solution is rapidly converted into an oxide product with glycine serving as the fuel and nitrates providing the oxidant. This paper examines the effects of altering the fuel/oxidant ratio on the characteristics of the product. Examples discussed include La(Sr)CrO3 and La(Sr)FeO3 perovskites and NiO.

A combustion-synthesis method [Chick et al., Materials Letters 10, 6 (1990)] has been adapted for the efficient preparation of pure barium ferrite particles, BaFe12O19. Solutions of Ba(NO3)2 and Fe(NO3)3 · 9H2O were mixed in stoichiometric amounts and glycine (aminoacetic acid) was then added according to the desired glycine / nitrate ratio. The solution was heated to around 200°C, when combustion occured, yielding a highly magnetic ash, which XRD suggests consists of extremely fine-grained γ-Fe2O3 and Ba3Fe2O6. Subsequent heat-treatments of 1050°C for 1.5 hr or 1200°C for 1 hr converted the ash to pure barium ferrite, as determined by XRD and Mdssbauer spectroscopy. Single-crystal platelets of barium ferrite, identified by SEM, varied dramatically in size with heat-treatment (diameter ∼0.2 pm and 6 μm, respectively), as did coercivity, measured by VSM (∼5000 Oe and 2500 Oe, resp.), while magnetization was unaffected.

A new co-precipitation technique for the preparation of fine ceramic mixed-oxide povders using a mixture of (NH4)HCO3, triethylamine and formaline in presence of soluble polymers, like polyvinyl alcohol (PVA). The mixture is chemically equivalent to one mole of triethylamnroniumcarbonate (TEAC). The mixed-oxide ccmpositions synthesized and characterized are - MN2O4 [Spinels; where M = Ni(II), Cu(II), Zn(II), Co(II) and N = Fe(III), tr(III)]; M3Fe5O12 [Garnets; where M = Y(III), Gd(III)] and RBa2Cu3O7+δ [Ceramic superconductors; where R = rare-earths]. The final product is characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy for microanalysis (EDX) and scanning electron microscopy (SEM).

The melting of Bi2Sr2CaCu2Ox material has been studied by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) in order to study the phases that formed in the high temperature regions. Two distinct phases of (Sr1-xCax)CuO2 and (Sr1-xCax)2CuO3 have been observed in the Bi-rich matrix depending upon quenching temperatures. Crystallization from the melt by fast cooling usually produce the co-existence of Bi (2201) and these Sr-Ca-Cu-O phases.

Superconducting thin films of the two Cu-layer phase in the Pb-doped Bi- Sr-Ca-Cu-O system have been fabricated on {100} LaAlO3 single crystals by the metalorganic deposition (MOD) from ethyl hexanoate precursors. Some of the major issues pertinent to the synthesis of high quality films have been studied.

Thin films of composition Bi1.8Pb0.3Sr1.6CaCu2Ox given heat treatments in air at 850–860 °C for several hours had sharp resistive transitions with a Tc of 85–89 K. The zero-field transport critical current densities were in the range of 1–4×105 A.cm−2 at 77 K and 106 A.cm−2 at 45 K in 200–300 nm thick films. In contrast to caxis oriented films grown on (100) MgO, X-ray pole figures show that the polycrystalline films grown on (100) LaAlO3 are epitaxial, a result confirmed by electron channeling patterns.

Superconducting Ba2YCu3O7-x films 0.1-0.2 gim thick were prepared by spin coating a methanol solution of Ba, Y and Cu acrylates on (100)LaAlO3 and firing to 800°C in a total pressure of 1 mm O2. X-ray diffraction showed that these films were epitaxial with the c-axis normal to the substrate. Zero resistance was achieved above 90 K and transport DC critical current densities as high as 125,000 A/cm2 were measured at 77 K in zero applied field.

Textured superconducting films of YbBa2Cu3O7-δ supported on single and polycrystalline substrates were prepared by oxidation of a liquid precursor alloy. The substrates were coated by dipping them into a molten alloy (YbBa2Cu3, m.p. ∼870°C), withdrawing them from the melt, then oxidizing the adhering liquid alloy layer to the corresponding oxide phase, i.e., YbBa2Cu3O7-δ. Samples prepared in this way exhibited a superconducting transition at ∼80 K following annealing in pure O2 at 500°C. With SrTiO3 (100) and MgO (100) substrates, evidence was seen for the epitaxial growth of YbBa2Cu3O7-δ crystals having their c-axis parallel to the [100] direction of the substrate. For polycrystalline MgO, x-ray diffraction and microstructural examination showed that the high-Tc crystallites in the films were also oriented with their c-axis perpendicular to the substrate surface, but the a and b axes directions were randomly oriented rather than epitaxial.

We demonstrate the homoepitaxial growth of SrTiO3 prepared by the method of metallo-organic decomposition (MOD). Thin films of SrTiO3 are prepared by spin-coating and thermal decomposition of a solution of metallo-organic compounds, on single crystal, <100> oriented, SrTiO3 substrates and subsequently heat treated at temperatures ranging from 650°C to 1100°C for 30 minutes. Heat treatment at 1100°C results in the formation of single-crystal SrTiO3, perfectly aligned with respect to the underlying substrate.

Ion-channeling analysis shows that the transformation to singlecrystal material proceeds epitaxially from the coating-substrate interface towards the surface of the sample. Transmission electron microscopy (TEM) studies of partially regrown samples reveal two distinct phases: an epitaxially aligned single-crystal phase, adjacent to the substrate, and a polycrystalline phase on top. On the basis of these observations, it is proposed that the crystallization of the MOD films involves the competition between two processes: layer-by-layer solid phase epitaxy and random nucleation and growth of crystallites. Layerby- layer epitaxy is the predominant crystallization mechanism unless it is inhibited by extrinsic factors like the contamination of the interface between the MOD film and the single-crystal substrate.

Crystalline aluminum nitride thin films (∼ 1200 Å) were prepared via nitridation of amorphous aluminum oxide and characterized by XRD, SEM, TEM, oxygen resonance, Auger depth-profile analysis and ellipsometry. Precursor chemistry, heating rate, nitridation temperature and nitridation time were varied to explore the competition between densification, crystallization and nitridation. Oxygen content in the films decreased with increasing nitriding temperature or nitriding time. Heating rate was determined to have minimal effect on the oxygen content for the parameters evaluated. A modified Kissinger analysis of DTA data for the crystallization of α-Al2O3 yielded an effective activation energy of ∼104 kcal/mol.

Coating of SiC (BP-SIGMA) fibers with alumina by a sol-gel process did not cause degradation even after heating to 1000°C in air for 24 h. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Auger electron spectroscopy (AES) and scanning electron microscopy (SEM ) methods were used to study the coating fiber interface.

Carbon fiber tows have been impregnated by ethanolic solutions of organo-silicon chlorides, and fired at temperatures up to 900°C to form silicon based coatings. Fired tows were subsequently examined by X-ray photoelectron spectroscopy and scanning electron microscopy to characterize the coated material. A uniform silicon oxycarbide is formed at temperatures upwards of 400°C, which provides an oxidation barrier in carbon fiber reinforced metals.

A process involving dip coating of ceramic fibers in H3BO3 solution followed by reaction with NH3 has resulted in the formation of a BN coating on Nicalon and a carbon coated Nicalon fiber. BN coated C-Nicalon fiber maintained its strength during the coating process, while the BN coated Nicalon did not.

Stoichiometric thin films of Y2O3 have been deposited on Si at substrate temperatures as low as 300 °C by plasma enhanced chemical vapor deposition using an electron cyclotron resonance (ECR) source. The yttrium source was an organo-metallic compound which was sublimated and fed with He carrier gas into the reactor chamber. Good capacitance-voltage characteristic curves were obtained for the dielectric film and a relative electrical permittivity of 9.9 was measured. This technique is a useful means of depositing oxide ceramic films at low substrate temperatures.

The oxidation behaviour of NiCoCrAlY-ZrO2·y2O3 coatings produced by using an ion-electron-atom beams combination technique (IEABCT) was studied after air exposure at 1100 °C for up to 300 hours. It was found that pores were dispersed in the coating, especially in the interface between coating and substrate, and no spallation or separation of the ceramic layer from the metallic bond layer were observed. The composition and morphology of the coatings before and after oxidation exposure in air at 1100 °C for 300 hours were examined by microscopy and electron microprobe analysis (EMPA).

The influence of surface charge on the dispersion aspects of the nonaqueous processing of silicon powder is explained by the relationship between the liquid medium's dielectric constant and the maximum particle size that is stabilized by colloidal forces. The effects of surface charge, derived from the chemistry of the solid-liquid pair or the adsorption of ionic processing aids, are either great, significantly increasing the maximum particle size that is stable against agglomeration from the nanometer range to the micrometer range, or virtually undetectable, contributing nothing to enhanced stability. Guidelines for the processing of silicon powder when surface charge exists are discussed.

Colloidal processing offers a way to minimize undesired heterogeneities in the fabrication of advanced ceramics. Stable dispersions can be created by manipulation of interparticle potential. Adsorption of diblock copolymer amphiphiles provides a way to obtain long range repulsive interactions between particles, at comparatively low polymer coverage, thereby enabling suspension stabilization. In this study we investigate the relationship between copolymer structure and adsorbed layer characteristics, and specifically, the nature and range of interactions. We find that the surface density and interaction range are governed by a characteristic measure of the copolymer asymmetry. In the case of copolymers where one of the blocks is ionic, and therefore water soluble, we find a hysteresis in the interaction forces, indicating a meta-stable state of the polymer layer.

A new phosphate substituted phosphazene trimer [N3P3Cl5(OP(O)Ph2)] has been synthesized and characterized by 31p NMR and Raman spectroscopy. The course of each solution-state substitution was followed with 31P NMR, and this technique was used to determine the best reaction conditions for the experiment. Information such as phosphorus to phosphorus connectivity and purity were analyzed. This paper will discuss the synthesis and characterization of phosphazene moieties which are substituted by phosphorus(V) centered substituents.

The chemical functionality of binders, dispersants, and solvents will influence competitive adsorption/desorption behavior on alumina powder, and hence will affect both slurry and ultimate green tape properties. Given that multiple competitive interactions are common to most dispersions, it is usually difficult to ascertain mechanisms from simple settling density experiments. However, this problem can be partially overcome with the choice of model systems that minimize the number of competitive processes. This criterion is met to a first approximation with a model system of toluene solvent, polystyrene binder, and a C8 aliphatic dispersant with an anchor group of variable functionality. Plateau adsorption concentrations from settling experiments in toluene show that surface coverage for efficient dispersants is typically achieved at about 6μmoles/m2. Less efficient dispersants adsorb at higher plateau concentrations, and are eventually displaced after repeated washing steps in toluene. The settling densities of dispersions prepared with C8 dispersants are consistently higher than densities achieved in toluene alone, and as seen in a case study with n-octylsilane, the settling densities are independent of the presence of polystyrene. Green bodies cast from a polystyrene/Al2O3 slurry also show increased densities in the presence of n-octylsilane dispersant. However, despite the apparent low levels of interaction between polystyrene and n-octylsilane in the dispersion state, solid state NMR and dynamic mechanical results show that the solid state molecular motional behavior of polystyrene is strongly affected by the presence of n-octylsilane dispersant.

The influence of the strength of interparticle attractions on the mechanical properties of colloidal gels is explored. As attractions increase, suspensions gel. At the gel point the zero shear rate viscosity diverges while the low frequency modulus becomes measurable. In addition at the gel point, storage and loss moduli were of the same order and displayed power law sealing on oscillation frequency. With much stronger attractions, the critical strain required to rupture the gel scales in a power law manner or elastic modulus. These observations are discussed in terns of recently developed models of gel fonnation and dynamics.