Structural Studies and Valence Band Splitting Parameters in Ordered Vacancy Compound AgGa7Se12

The threefold absorption in the fundamental absorption region of the ternary chalcopyrite AgGa₇Se₁₂, an ordered defect compound of AgGaSe₂, is analyzed to elucidate the three closely spaced band gaps in its valence band due to the lifting of degeneracy of the Γ₁₅ level. Hopfield’s quasi cubic model is employed to extract the crystal-field and spin–orbit splitting parameters and the linear hybridisation of orbitals model for evaluating the percentage contribution of Ag d-orbital and Ga and Se p-orbitals to the p–d hybridization of orbitals. The observed optical properties are correlated with the structural parameters like deformation parameter, anion displacement and anion–cation bond lengths that are deduced from X-ray diffraction data. The compound films for the studies are prepared by a modified form of Gunther’s three temperature technique and the compositional analysis was done by energy dispersive analysis of X-rays. X-ray photoelectron spectroscopy confirms the compound formation while atomic force microscopic technique was used for surface morphological analysis. The electrical resistivity of these n-type semi-conducting films is assessed to be ~5 Ωm and the films are found to be photosensitive.     

Microwave dielectric properties of flexible butyl rubber–strontium cerium titanate composites

Butyl rubber–strontium cerium titanate (BS) composites have been prepared by hot pressing. The tensile tests show that the BS composites are flexible. The dielectric properties of the composites have been investigated at 1 MHz and 5 GHz as a function of ceramic contents. The composite with volume fraction 0.43 of ceramic filler has a dielectric constant (ε_r) of 11.9 and dielectric loss (tan δ) 1.8 × 10^?3 at 5 GHz. The measured values of ε_r are compared with the effective values calculated using different theoretical models. The thermal conductivity of the composites is found to increase with ceramic contents and reaches a value of 4.5 Wm^?1 K^?1 for maximum filler loading 0.43 volume fraction. The coefficient of thermal expansion of the composites decreases gradually with filler loading and reaches a minimum value of 30.2 ppm °C^?1 at a volume fraction 0.43. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A cathode support structure for use in a magnetron oscillator experiment

A low temperature co-fired ceramic (LTCC) material system has been used to develop a protype field emission cathode structure for use in an experimental magnetron oscillator. The structure is designed for used with 30 gated field emission array (GFEA) die electrically connected through silver metal traces and electrical vias. To approximate a cylinder, the cathode structure (48 mm long and 13.7 mm in diameter) is comprised of 10 faceted plates which cover the GFEA dies. Slits in the facet plates allow electron injection. The GFEA die (3 mm × 8 mm) are placed in axial columns of 3 and spaced azimuthally around a cylindrical support structure in a staggered configuration resulting in 10 azimuthal locations. LTCC manufacturing techniques were developed in order to fabricate the newly designed cathode with seven layers wrapped to form the cylinder with electrical traces and vias. Two different cathode wrapping techniques and two different via filling techniques were studied and compared. Two different facet plate manufacturing techniques were studied. Finally, four different support stand configurations for firing the cylindrical structure were also compared with a square post stand having the best circularity and linearity measurements of the fired structure.     

An investigation of the effect of air addition during oil sand conditioning

Bitumen aeration was studied by flooding samples of medium grade oil sand with de‐ionized water under both ambient and high vacuum conditions. The samples were then agitated on a shaker table. Subsequent analysis revealed the presence or absence of an air gap in the sample container was the single most important factor in determining the overall bitumen recovery. Furthermore, samples that were flooded while under high vacuum produced slightly less bitumen compared to samples flooded at atmospheric pressure. This suggests that oil sand that is not under high vacuum when flooded with water contains some amount of indigenous air (see introduction) that would aid in bitumen flotation.     

Recycling of EPDM waste. II. Replacement of virgin rubber by ground EPDM vulcanizate in EPDM/PP thermoplastic elastomeric composition

Virgin ethylene propylene diene monomer (EPDM) rubber in a thermoplastic elastomeric blend of polypropylene (PP) and EPDM rubber was substituted by ground EPDM vulcanizate of known composition, after which the mechanical properties of the raw EPDM/waste EPDM/PP blends were determined. The ratio of the rubber content in the waste EPDM (r‐W‐EPDM) to the raw EPDM (R‐EPDM) in the blends was varied from 0 : 100 to 45 : 55. Attempts to replace higher amounts (>45%) of R‐EPDM by W‐EPDM failed because of processing difficulty. Although a drop in mechanical properties of the blends was observed at lower loadings of W‐EPDM, the properties showed improvement at intermediate W‐EPDM loadings. The R‐EPDM/W–EPDM/PP blends were found to be reprocessable. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3304–3312, 2001     

Synthesis and characterization of iodosodalite

The effects of six process variables were investigated on the hydrothermal growth of iodosodalite, Na₈Al₆Si₆O₂₄I₂: pH (NaOH concentration), aging time, temperature, Al/Si ratio, precursors used (i.e., zeolite 4A, kaolinite, meta‐kaolin, colloidal silica, and sodium aluminate), and precursor concentration. Powder X‐ray diffraction (XRD) with Rietveld refinements, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) were performed to characterize the structures, phase fractions, chemical state, and surface morphology of the synthesized products. Iodosodalite yield increased as aging time and pH increased. The crystallization of iodosodalite was favored in the temperature range 140°C‐180°C. Decreasing the Al/Si ratio by half increased the crystallization of basic cancrinite. Lowering the precursor concentration by adding water revealed the crystallization of nepheline hydrate I and a decrease in the sodalite fraction. Among the tested precursors, zeolite 4A yielded the highest mass fraction of iodosodalite in the synthesized powders. From the aging time and temperature variation experiments, the phase transformation of zeolite A→sodalite→cancrinite was observed. XPS and FTIR results showed the presence of only iodide but not iodate in the synthesized product. The crystallization of various minerals suggests that mechanisms for transport of the ions and formation of the aluminosilicate frameworks vary with hydrothermal conditions.     

Effect of Mechanical Constraint on Domain Reorientation in Predominantly {111}‐Textured Lead Zirconate Titanate Films

Ferroelectric/ferroelastic domain reorientation was measured in 2.0 μm thick tetragonal {111}‐textured PbZr_0.30Ti_0.70O₃ thin films using synchrotron X‐ray diffraction (XRD). Lattice strain from the peak shift in the 111 Bragg reflection and domain reorientation were quantified as a function of applied electric field amplitude. Domain reorientation was quantified through the intensity exchange between the 112 and 211 Bragg reflections. Results from three different film types are reported: dense films that are clamped to the substrate (as‐processed), dense films that are partially released from the substrate, and films with 3% volume porosity. The highest amount of domain reorientation is observed in grains that are misoriented with respect to the {111} preferred (domain engineered) orientation. Relative to the clamped films, films that were released from the substrate or had porosity exhibited neither significant enhancement in domain reorientation nor in 111 lattice strain. In contrast, similar experiments on {100}‐textured and randomly oriented films showed significant enhancement in domain reorientation in released and porous films. Therefore, {111}‐textured films are less susceptible to changes in properties due to mechanical constraints because there is overall less domain reorientation in {111} films than in {100} films.     

Scaling Effects in Perovskite Ferroelectrics: Fundamental Limits and Process‐Structure‐Property Relations

Ferroelectric materials are well‐suited for a variety of applications because they can offer a combination of high performance and scaled integration. Examples of note include piezoelectrics to transform between electrical and mechanical energies, capacitors used to store charge, electro‐optic devices, and nonvolatile memory storage. Accordingly, they are widely used as sensors, actuators, energy storage, and memory components, ultrasonic devices, and in consumer electronics products. Because these functional properties arise from a noncentrosymmetric crystal structure with spontaneous strain and a permanent electric dipole, the properties depend upon physical and electrical boundary conditions, and consequently, physical dimension. The change in properties with decreasing physical dimension is commonly referred to as a size effect. In thin films, size effects are widely observed, whereas in bulk ceramics, changes in properties from the values of large‐grained specimens is most notable in samples with grain sizes below several micrometers. It is important to note that ferroelectricity typically persists to length scales of about 10 nm, but below this point is often absent. Despite the stability of ferroelectricity for dimensions greater than ~10 nm, the dielectric and piezoelectric coefficients of scaled ferroelectrics are suppressed relative to their bulk counterparts, in some cases by changes up to 80%. The loss of extrinsic contributions (domain and phase boundary motion) to the electromechanical response accounts for much of this suppression. In this article, the current understanding of the underlying mechanisms for this behavior in perovskite ferroelectrics is reviewed. We focus on the intrinsic limits of ferroelectric response, the roles of electrical and mechanical boundary conditions, grain size and thickness effects, and extraneous effects related to processing. In many cases, multiple mechanisms combine to produce the observed scaling effects.     

Current Understanding of Structure–Processing–Property Relationships in BaTiO3–Bi(M)O3 Dielectrics

As part of a continued push for high permittivity dielectrics suitable for use at elevated operating temperatures and/or large electric fields, modifications of BaTiO₃ with Bi(M)O₃, where M represents a net‐trivalent B‐site occupied by one or more species, have received a great deal of recent attention. Materials in this composition family exhibit weakly coupled relaxor behavior that is not only remarkably stable at high temperatures and under large electric fields, but is also quite similar across various identities of M. Moderate levels of Bi content (as much as 50 mol%) appear to be crucial to the stability of the dielectric response. In addition, the presence of significant Bi reduces the processing temperatures required for densification and increases the required oxygen content in processing atmospheres relative to traditional X7R‐type BaTiO₃‐based dielectrics. Although detailed understanding of the structure–processing–property relationships in this class of materials is still in its infancy, this article reviews the current state of understanding of the mechanisms underlying the high and stable values of both relative permittivity and resistivity that are characteristic of BaTiO₃‐Bi(M)O₃ dielectrics as well as the processing challenges and opportunities associated with these materials.