A method to synthesize high density Tl2Ba2Ca2Cu3O10−δ bulk superconductor with uniformity from presintered powder of the 2223 phase material was developed. With a proper annealing process, the transport critical current density and the material density of such a synthesized superconductor are much improved over those of the starting material. The critical temperature and phase purity of this material are also enhanced. In this paper, we report our systematic study on some basic parameters of this material, including the normal state resistivity, Tc, Jc, phase purity, and morphology produced under different annealing conditions. An optimum preparation technique is then derived.

We developed an x-ray microdiffractometer using synchrotron radiation with which we analyzed microcrystal structures of heterogeneities in Tl-1223 superconducting wires prepared by different processes, i.e., partial melt and solid/liquid phase reaction. Samples with the nominal composition (Tl0.5Pb0.5)1(Sr0.8Ba0.2)2Ca2Cu3O9 were irradiated by focused SR x-rays of 6 μm × 8 μm size. The diffracted x-rays were two-dimensionally detected with an imaging plate. From crystal structure analysis, we identified the heterogeneities as BaPbO3 and (CaSr)2Cu1O3 which are present in Tl-1223 superconducting wires prepared by both processes. This suggested that these heterogeneous phases coexist with the stable phase in the Tl-1223 phase diagram. Consequently, it is necessary to develop a new processing method such as low temperature annealing or a suitable O2 pressure control method.

Solid state reactions induced by high energy ball milling between Pd and Si have been studied. X-ray diffractometry and differential scanning calorimetry have been used to characterize the resulting phases. During milling, Pd and Si react by diffusion to form different phases depending on the Si content in the starting mixture. With a low Si content of 19 at. %, an amorphous phase forms of the same composition. On continued milling, this amorphous phase partially crystallizes into Pd9Si2 and Pd2Si compounds. With the Si content equal to or higher than 33 at. %, no amorphous phases were observed. Instead, the Pd2Si phase is produced. For powder composition corresponding to the stoichiometric compound Pd2Si (33 at. % Si), the Pd2Si forms and remains stable during further milling. With Si content equal to or higher than 50 at. %, the initially produced Pd2Si is destabilized by a reaction with the remaining Si to form PdSi, which is a metastable phase at the temperature of ball milling. It is very unlikely that an amorphous phase of a composition equal to or higher than 33 at. % Si could be produced by ball milling in the Pd-Si system. This is because the Pd2Si phase forms very easily through the reaction between Pd and Si, and this reaction competes effectively with glass formation.

Aluminum ions may exist in one of several different types of polynuclear species depending upon the degree to which it is hydrolyzed. The hydrolysis of aluminum can be explained by a metastable equilibrium among Al(H2O)3+6, Al(OH)(H2O)2+5, Al13O4(OH)24(H2O)7+12, and an oligomer. We have made small angle x-ray scattering and 27Al NMR measurements on 0.3 M aluminum chloride solutions over a range of OH/Al ratios. 27Al NMR shows two sharp peaks corresponding to the monomer Al(H2O)3+6 and the tetrahedrally coordinated aluminum in Al13O4(OH)24(H2O)7+12, and a broad peak due to the octahedrally coordinated aluminum in the oligomer. The observed radius of gyration (Rg) of the species in solution increases from 3.0 to 3.6 A, and the intensity at zero angle (which is proportional to the weight average molecular weight of the species) also increases as the OH/Al ratio increases from 1.0 to 2.2. The oligomer has an Rg of approximately 3.3 A, a hydrolysis ratio close to 2.0, and may be a six-membered ring with a structure similar to that of a gibbsite layer.

The microstructure and superconducting properties of Bi2Sr2CaCu2Ox (Bi-2212) during high-energy attrition milling were investigated in detail by a combination of x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and magnetization techniques. The starting superconducting powder was milled in a standard laboratory attritor using yttria-stabilized ZrO2 balls and a stainless steel tank. After selected time increments, the milling was interrupted and a small quantity of milled powder was removed for further analysis. It was found that the deformation process rapidly refines Bi-2212 into nanometer-size crystallites, increases atomic-level strains, and changes the plate-like morphology of Bi-2212 to granular submicron clusters. At short milling times, the deformation seems localized at weakly linked Bi-O double layers, leading to twist/cleavage fractures along the {001} planes. The Bi-2212 phase decomposes into several bismuth-based oxides and an amorphous phase after excessive deformation. The superconducting transition is depressed by about 10 K in the early stages of milling and completely vanishes upon prolonged deformation. A deformation mechanism is proposed and correlated with the evolution of superconducting properties. The practical implications of these results are presented and discussed.

The reconstructions of high-angle twist grain boundaries on the four densest atomic planes in fcc copper, as described by a Lennard-Jones potential, and gold, as described by an embedded-atom-method potential, are investigated using the recently developed method of grand-canonical simulated quenching. It is found that the grain boundaries on the widely spaced (111) and (100) planes do not reconstruct, while those on the less widely spaced (110) and (113) planes do reconstruct. The effect that reconstruction can have on the physical properties of an interfacial system is illustrated by comparing the elastic properties and ideal cleavage energies of reconstructed grain boundaries with those of corresponding unreconstructed grain boundaries.

C-axis LiNbO3 epitaxial films have been grown on c-plane sapphire substrates by solid source metal-organic chemical vapor deposition (MOCVD) using the tetramethylheptanedionate sources, Li(thd) and Nb(thd)4. Stoichiometric LiNbO3 films were deposited from Li(thd)-rich source compositions. Rocking curve FWHM values as low as 0.044°were measured on films grown at 710 °C. Rocking curve peak widths became broader as films were grown at progressively lower substrate temperatures. Single prism coupling experiments revealed clearly visible optical waveguiding, with optical attenuation values as low as 2 dB/cm in the best films.

Superstructuring in the new compound Fe1.89Mo4.11O7 has been elucidated by transmission electron microscopy. This compound is a member of the family M2MO4O7 and has both iron and molybdenum atoms occupying octahedrally coordinated sites in the structure, represented by Fet(Fe0.89M0.11)0Mo4O7. The superstructuring, detected only by electron diffraction, involved tripling of all three lattice parameters of the subcell. The subcell was structured by single crystal x-ray diffraction [Imma, no. 74, a = 5.9793(5) Å, b = 5.7704(4) Å, and c = 17.036(1) Å]. This structure type contains a close-packed arrangement of Mo4O7 units, which are infinite chains of trans edge-shared molybdenum octahedra running parallel to b*. Two different coordination environments are observed for the cations. Parallel to the a* direction, infinite edge-sharing MO6 (M = 89% Fe or 11% Mo) octahedra are observed. The second cation site, with nearly tetrahedral coordination by oxygen, is filled solely by iron. The superstructure can be rationalized by a regular arrangement of iron and molybdenum atoms in the octahedrally coordinated cation sites.

The microstructure of Ba1−xKxBiO3 (BKBO) thin films from three different sources has been extensively compared by transmission electron microscopy studies. The three films were prepared independently in three different laboratories on three different substrates of (100) orientation and displayed excellent superconducting properties. The observed microstructure is remarkably similar in the three films. They are epitaxial with (100) orientation through all their extension and no cracks have been observed. Their defect density is similar and the resulting extension of defect-free regions is of the order of 50–80 nm.

A high resolution transmission electron microscopy study of multilayer films prepared by magnetron sputtering shows that the morphology of the growing interface in a-Si/Nb and a-SiN/NbN multilayers is remarkably uniform and smooth; this is in contrast to the polycrystalline AlN/NbN multilayers grown under similar conditions, which exhibit columnar grain structure with rough interfaces. For proper sputtering parameters, the amorphous layers seem to periodically restore a relatively smooth initial interface condition for the successive Nb (or NbN) layer growth, consequently interrupting the tendency toward increased roughness due to mechanisms such as columnar growth. Artificial multilayers having very flat interfaces could stimulate applications based on multilayer Josephson junctions.

The synthesis of Bi2−xPbxSr2Ca2Cu3O10 (Bi2223) powders from a freeze dried nitrate precursor is reported here. We examine the composition and morphology of the precursor material, describe the chemistry and kinetics of product formation, and evaluate the phase composition and superconducting properties of the products. A nitrate solution containing the appropriate ratio of cations was rapidly frozen and then freeze dried at low temperatures to form an atomic mixture of the component salts. The thermal processing of the freeze dried material consisted of three steps: (i) dehydration, (ii) denitration, and (iii) solid state reaction to form the Bi2223 superconducting product. Calcium-substituted bismuthates and strontium-substituted calcium cuprate, not Bi2201, are the intermediates between the nitrates and the superconducting products. These highly disordered phases rapidly transform into Bi2212 or Bi2223 at higher temperatures (≍790 °C). The kinetics of product formation was studied using XRD analysis and magnetic susceptibility. The kinetics were shown to follow the nucleation and growth mechanism. Bi2223 formed after only 30 min at a few degrees below the melting point, and after 37 h Bi2223 products exhibited excellent phase composition and magnetic susceptibility characteristics.

This paper reports a study of the microstructural changes that occur when BSCCO powder is processed by the powder-in-tube method. In this study the initial powder consisted of the 2212 phase plus second phases containing Ca, Cu, Sr, and Pb. When the material was drawn, there was no alignment of the 2212 phase and the second phase particles remained large and blocky. Rolling induced a small amount of alignment into the 2212 phase so that its c-axis was perpendicular to the rolling direction. Rolling also caused the second phase particles to become flatter. When these rolled samples were annealed at 828 °C, the core sintered into a platelet structure, and there was an increase in the amount of aligned material, particularly after annealing treatments of 16 and 32 h. After 8 h at 828 °C, the 2212 variant of the superconducting phase began to transform to the 2223 variant. Pressing this structure improved the alignment, and annealing after pressing allowed further conversion of the 2212 phase to the 2223 phase and apparently removed the strains produced by the pressing. Repeated pressing improved the alignment and repeated annealing allowed more conversion of 2212 to 2223. Both the improved alignment, produced by pressing, and the transformation of 2212 to 2223, produced by the anneals, caused the superconducting properties of the material to improve.

The development of passive and active electronics from high-temperature superconducting thin films depends on the development of process technology capable of producing appropriate feature sizes without degrading the key superconducting properties. We present a new class of chelating etches based on di- and tri-carboxylic acids that are compatible with positive photoresists and can produce submicron feature sizes while typically producing increases in the microwave surface resistance at 94 GHz by less than 10%. This simple etching process works well for both the Y-Ba-Cu-O and Tl-Ba-Ca-Cu-O systems. In addition, we demonstrate that the use of chelating etches with an activator such as HF allows the etching of related oxides such as LaAlO3, which is a key substrate material, and Pb(Zr0.53Ti0.47)O3 (PZT) which is a key ferroelectric material for HTS and other applications such as nonvolatile memories.

A complex-shaped TiAl turbine rotor has been uniformly aluminized by a metal-organic chemical vapor deposition under reduced pressure (RPMOCVD), and a thick TiAl3 layer, which affects the oxidation resistance, can be formed on the surface by subsequent heat treatment. The oxidation resistance has been studied with an oxidation test at 1173 K for 760 ks in static air. The microstructure has been investigated by SEM, EPMA, AES, and XRD. A heat treatment at above 933 K, which is the melting point of Al, is required to enhance the oxidation resistance of TiAl. With increasing the surface roughness of TiAl, the formation of TiAl3 increases, and consequently the oxidation resistance is more improved.

Epitaxial VO2 thin films grown on (1120) sapphire (α-Al2O3) substrates by MOCVD at 600 °C have been characterized by conventional electron microscopy and high resolution electron microscopy (HREM). Three different epitaxial relationships between the monoclinic VO2 films and sapphire substrates have been found at room temperature: I. (200) [010] monoclinic VO2 ‖ (1120) [0001] sapphire, II. (002) [010] monoclinic VO2 ‖ (1120) [0003] sapphire, and III. (020) [102] monoclinic VO2 ‖ (1120) [0001] sapphire. Expitaxial relationships II and III are equivalent to each other when the film possesses tetragonal structure at the deposition temperature; i.e., they can be described as (010) [100] tetragonal VO2 ‖ (1120) [0001] sapphire and (100) [010] tetragonal VO2 ‖ (1120) [0001] sapphire. HREM image shows that the initial nucleation of the film was dominated by the first orientation relationship, but the film then grew into the grains of the second and the third (equivalent to each other at the deposition temperature) epitaxial relationships. Successive 90°transformation rotational twins around the a-axis are commonly observed in the monoclinic films.

Observations of various metastable crystalline and amorphous polymorphs of Ll2-type intermetallics Zr3Al and Ni3Al are summarized. The difference in the tendency of these two alloys to become amorphous is obvious. Regardless of the nonequilibrium routes employed for synthesis and processing, amorphous Zr3Al is obtained easily, while amorphization of Ni3Al is rare. An analysis of thermodynamic and kinetic factors responsible for the observed polymorph selection and amorphization behavior is presented. The inadequacy of a simplified model proposed earlier is also discussed.

The main puzzle in oxidation of hexagonal SiC is the slower rate of the Si-terminated surface as compared to the C-terminated surface, which is blamed on an unknown interface compound. ARXPS is a unique method to identify minor amounts of interface compounds, especially for smooth surfaces. Our ARXPS analysis of oxidized Si-(001) and C-(001) surfaces of 6H SiC reveals the interface oxide Si4C4−xO2 (x < 2), likely a reaction product of a peroxidic O2-bond to a SiC double layer. Si4C4−xO2 occurs in larger thickness (≃1 nm) at the slowly oxidizing Si-(001) surface, whereas the C-(001) surface shows smaller amounts, diminishing fast with oxidation above 1000 K. Evidence is presented that with increasing amount of Si4C4−xO2 the oxidation of SiC to SiO2 is reduced. ARXPS is consistent with a layer of SiO2 containing less than 3% Si4C4O4 being an oxidation product of Si4C4−xO2. At the surface of SiO2, graphite and some Si4C4O4 exist, aside from standard adsorbates.

A Mg-6.5 wt. % Li alloy containing 80% hep alpha phase and 20% bcc beta phase was processed to achieve an average grain size of 5.9 μm. Strain-rate-change tests were performed in the temperature range from 398 K to 573 K. Two types of creep behavior were observed. A stress exponent of five, obtained at low temperatures and high stresses, is attributed to a diffusion-controlled dislocation creep process in the alpha matrix. A stress exponent of three, obtained at high temperatures and low stresses, is attributed to a solute-drag controlled dislocation creep process in the alpha matrix.

Epitaxial LaNiO3 thin films have been grown on SrTiO3 and several other substrates by pulsed laser deposition. The films are observed to be metallic down to 15 K, and the temperature dependence of resistivity is similar to that of bulk LaNiO3. Epitaxial, c-axis oriented YBa2Cu3O7-x films with good superconducting properties have been grown on the LaNiO3 (100) films. I-V characteristics of the YBa2Cu3O7-x-LaNiO3 junction are linear, indicating ohmic contact between them.

Thin solid films of C60 and C70 have been used as nucleating layers for the growth of diamond thin films on a variety of substrate surfaces, including metal, insulator, and semiconductors. Compared to other forms of carbon, such as graphite, amorphous carbon, soot, etc., it is found that the nucleation density on a C70 film is equivalent to that of diamond seeds themselves. On the other hand, diamond nucleation on a C60 film is less favorable. We argue from our experiments that the reason for C70 film to have such favorable nucleating properties is its chemical stability and geometry. A working model is proposed to explain the nucleation of diamond on solid C70 films. Application of this work extending to the growth of diamond on a wide range of substrates is also discussed.