Ab Initio Calculations of Pristine and Doped Zirconia Σ5 (310)/[001] Tilt Grain Boundaries

The structure of the cubic-ZrO₂ symmetrical tilt Σ5 (310)/[001] grain boundary is examined using density functional theory within the local density and pseudopotential approximations. Several pristine stoichiometric grain-boundary structures are investigated and compared with Z-contrast scanning transmission electron microscopy and electron energy loss spectroscopy results. The lowest-energy grain-boundary structure is found to agree well with the experimental data. When Y³⁺ is substituted for Zr⁴⁺ at various sites in the lowest-energy grain-boundary structure, the calculations indicate that Y³⁺ segregation to the grain boundary is energetically preferred to bulk doping, in agreement with experimental results.     

Solid Yttria-Stabilized Zirconia Films by Pulsed Chemical Vapor Deposition from Metal-organic Precursors

A pulsed chemical vapor deposition from metal-organic precursors (MOCVD) system was used to produce solid zirconia, and yttria-stabilized zirconia (YSZ) films. A total of six candidate metal-organic precursors for zirconia and three for yttria were investigated. Three precursor solutions for YSZ proved suitable for pulsed-MOCVD processing. Layers were deposited on metal, alumina, and porous nickel cermet substrates. Under optimal deposition conditions, precursor conversion efficiency of 90% was achieved using a solution of 3.74 vol% zirconium 2-methyl-2-butoxide + 0.42% yttium methoxyethoxide in toluene. The film growth rate was 7.5 μm·h⁻¹ at 525°C deposition temperature. Two alkoxide precursors produced YSZ layers with material costs under $0.50/(μm·cm²).     

First year growth of preterm infants fed standard compared to marine oil n−3 supplemented formula

Very low birth weight (VLBW) infants (748–1390 g, n=65) were randomly assigned to receive control or marine oil-supplemented formula when they achieved intakes >454 kJ (110 kcal)/kg/d of a formula designed for VLBW infants. Study formulas with or without marine oil were provided until 79 wk of postconceptional age (PCA), first in a formula designed for preterm infants followed by a formula designed for term infants. Infants were studied at regular intervals through 92 wk PCA. Weight, length, and head circumference were determined by standardized prodedures and normalized to the National Center for Health Statistics figures for growth of infants born at term of the same age and gender. Mean normalized weight, weight-to-length, and head circumference were greatest at 48 wk and decreased thereafter. The decline in normalized weight was greater in infants fed the marine oil-supplemented formula. Beginning at 40 wk, marine oil-supplemented infants compared to controls had significantly poorer Z-scores for weight, length and head circumference. In addition, birth order (negatively) and maternal height (positively) influenced weight and length achievement in infancy as shown previously in infants born at term. Based on a paper presented at the Symposium on Milk Lipids held at the AOCS Annual Meeting, Baltimore, MD, April 1990.     

The introduction of alkyl,ester, carboxylate,amino, hydroxyl,and phosphate functional groups to the surface of polyethylene

The surface of polyethylene was derivatized with ester, carboxylate, amino, hydroxyl, and phosphate functional groups. α, ω bifunctional alkanes, containing on one end a primary amine, were coupled to oxidized polyethylene through an amide linkage. Polyethylene was first oxidized with chromic acid, the carboxylate groups were converted to the acyl chloride with phosphorus pentachloride, and then reacted with a primary amine to give the covalently bound amide. The copposing ends of the bifunctional alkanes were the methyl, tertiary amine, ester, and hydroxyl groups. The ester was converted to the carboxylate by acid cleavage and the hydroxyl group converted to the phosphate by treatment first with phosphorus oxychloride and then aqueous base. Attenuated total reflection FTIR, XPS, and pH-dependent contact angle wetting were used to characterize the surfaces. The FTIR data were used to confirm the formation of the amide and to detect an undesired carboxylate/ammonium ion complex formed in the presence of trace amounts of water. XPS data were used to confirm expected changes in elemental composition and to provide quantitative estimates of the yields. Oxidation of the polyethylene introduced 5 × 10¹⁴ carboxylate groups/cm² in the 25 Å XPS sampling depth. Of these, up to 98% could be converted to the amide. The advancing contact angle data confirmed the acid/base behavior of the functional groups.     

Synthesis of Chemically Stabilized Cristobalite

The synthesis of chemically stabilized cristobalite (CSC) by a wet-chemical route is described. CSC is a form of silica (containing small amounts of other oxides) which is similar in many ways to β-cristobalite, but does not invert to α-cristobalite upon cooling. The effects of changing the dopant levels and various synthetic parameters on the phases formed in the CaO-Al₂O₃-SiO₂ system have been investigated. Stabilization of cristobalite with a number of different dopant combinations has been attempted, with mixed results. The use of wet-chemical techniques has led to the synthesis of apparently phase-pure CSC in a composition region where traditional solid-state synthetic techniques yield a mixture of other phases.     

Relationship between cell morphology and impact strength of microcellular foamed high‐density polyethylene/polypropylene blends

Polymer blends, such as those resulting from recycling postconsumer plastics, often have poor mechanical properties. Microcellular foams have been shown to have the potential to improve properties, and permit higher‐value uses of mixed polymer streams. In this study, the effects of microcellular batch processing conditions (foaming time and temperature) and HDPE/PP blend compositions on the cell morphology (the average cell size and cell‐population density) and impact strength were studied. Optical microscopy was used to investigate the miscibility and crystalline morphology of the HDPE/PP blends. Pure HDPE and PP did not foam well at any processing conditions. Blending facilitated the formation of microcellular structures in polyolefins because of the poorly bonded interfaces of immiscible HDPE/PP blends, which favored cell nucleation. The experimental results indicated that well‐developed microcellular structures are produced in HDPE/PP blends at ratios of 50:50 and 30:70. The cell morphology had a strong relationship with the impact strength of foamed samples. Improvement in impact strength was associated with well‐developed microcellular morphology. Polym. Eng. Sci. 44:1551–1560, 2004. © 2004 Society of Plastics Engineers.     

Effect of water on the oxygen barrier properties of poly(ethylene terephthalate) and polylactide films

The aim of this work was to study the variations in the oxygen diffusion, solubility, and permeability coefficients of polylactide (PLA) films at different temperatures (5, 23, and 40°C) and water activities (0–0.9). The results were compared with the oxygen diffusion, solubility, and permeability coefficients obtained for poly(ethylene terephthalate) (PET) films under the same experimental conditions. The water sorption isotherm for PLA films was also determined. Diffusion coefficients were determined with the half‐sorption time method. Also, a consistency test for continuous‐flow permeability experimental data was run to obtain the diffusion coefficient with the lowest experimental error and to confirm that oxygen underwent Fickian diffusion in the PLA films. The permeability coefficients were obtained from steady‐state permeability experiments. The results indicated that the PLA films absorbed very low amounts of water, and no significant variation of the absorbed water with the temperature was found. The oxygen permeability coefficients obtained for PLA films (2–12 × 10^?18 kg m/m² s Pa) were higher than those obtained for PET films (1–6 × 10^?19 kg m/m² s Pa) at different temperatures and water activities. Moreover, the permeability coefficients for PLA and PET films did not change significantly with changes in the water activity at temperatures lower than 23°C. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1790–1803, 2004     

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.     

Circulating Tumor Cells (CTC) and Cell-Free DNA (cfDNA) Workshop 2016: Scientific Opportunities and Logistics for Cancer Clinical Trial Incorporation

Despite the identification of circulating tumor cells (CTCs) and cell-free DNA (cfDNA) as potential blood-based biomarkers capable of providing prognostic and predictive information in cancer, they have not been incorporated into routine clinical practice. This resistance is due in part to technological limitations hampering CTC and cfDNA analysis, as well as a limited understanding of precisely how to interpret emergent biomarkers across various disease stages and tumor types. In recognition of these challenges, a group of researchers and clinicians focused on blood-based biomarker development met at the Canadian Cancer Trials Group (CCTG) Spring Meeting in Toronto, Canada on 29 April 2016 for a workshop discussing novel CTC/cfDNA technologies, interpretation of data obtained from CTCs versus cfDNA, challenges regarding disease evolution and heterogeneity, and logistical considerations for incorporation of CTCs/cfDNA into clinical trials, and ultimately into routine clinical use. The objectives of this workshop included discussion of the current barriers to clinical implementation and recent progress made in the field, as well as fueling meaningful collaborations and partnerships between researchers and clinicians. We anticipate that the considerations highlighted at this workshop will lead to advances in both basic and translational research and will ultimately impact patient management strategies and patient outcomes.