Tailoring texture of γ-Y2Si2O7 by strong magnetic field alignment and two-step sintering

In this study, a well-dispersed γ-Y2Si2O 7 ethanol-based suspension with 30 vol% solid loading was prepared by adding 1 dwb% polyethylene imine dispersant, which allows feeble magnetic γ-Y2Si2O7 particles with anisotropic magnetic susceptibility to rotate in a 12 T strong magnetic field during slip casting, resulting in the development of a strong texture in green bodies. Pressureless sintering gives rise to more pronounced grain growth in the textured sample than in the untextured sample prepared without the magnetic field due to the rapid migration of the grain boundaries of the well-oriented grains, which was revealed by constant-heating-rate sintering kinetics. It was found that the use of two-step sintering is very efficient not only for inhibiting the grain growth but also for enhancing the texture. This implies that controlled grain growth is crucial for enhancing texture development in γ-Y2Si2O7.

Thermal properties and thermal shock resistance of γ-Y 2Si2O7

Thermal properties, namely, Debye temperature, thermal expansion coefficient, heat capacity, and thermal conductivity of γ-Y 2Si2O7, a high-temperature polymorph of yttrium disilicate, were investigated. The anisotropic thermal expansions of γ-Y2Si2O7 powders were examined using high-temperature X-ray diffractometer from 300 to 1373 K and the volumetric thermal expansion coefficient is (6.68±0.35) × 10-6 K-1. The linear thermal expansion coefficient of polycrystalline γ-Y2Si2O7 determined by push-rod dilatometer is (3.90±0.4) × 10-6 K-1, being very close to that of silicon nitride and silicon carbide. Besides, γ-Y2Si2O7 displays a low-thermal conductivity, with a κ value measured below 3.0 W·(m·K) -1 at the temperatures above 600 K. The calculated minimum thermal conductivity, κmin, was 1.35 W·(m·K) -1. The unique combination of low thermal expansion coefficient and low-thermal conductivity of γ-Y2Si2O7 renders it a very competitive candidate material for high temperature structural components and environmental/thermal-barrier coatings. The thermal shock resistance of γ-Y2Si2O7 was estimated by quenching dense materials in water from various temperatures and the critical temperature difference, ΔTc, was determined to be 300 K.

A numerical study of the effect of loading conditions on tubular hydroforming

In this work, the mechanics of tubular hydroforming under various types of loading conditions is investigated. The main objective is to contrast the effects of prescribing fluid pressure or volume flow rate, in conjunction with axial displacement, on the stress and strain histories experienced by the tube and the process of bulging. To this end, axisymmetric finite element simulations of free hydroforming (without external die contact) of aluminium alloy tubes are carried out. Hill’s normally anisotropic yield theory along with material properties determined in a previous experimental study [A. Kulkarni, P. Biswas, R. Narasimhan, A. Luo, T. Stoughton, R. Mishra, A.K. Sachdev, An experimental and numerical study of necking initiation in aluminium alloy tubes during hydroforming, Int. J. Mech. Sci. 46 (2004) 1727–1746] are employed in the computations. It is found that while prescribed fluid pressure leads to highly non-proportional strain paths, specified fluid volume flow rate may result in almost proportional ones for the predominant portion of loading. The peak pressure increases with axial compression for the former, while the reverse trend applies under the latter. The implication of these results on failure by localized necking of the tube wall is addressed in a subsequent investigation.

Effect of diffusion-layer porosity on the performance of polymer electrolyte fuel cells

The gas-diffusion layer (GDL) influences the performance of electrodes employed with polymer electrolyte fuel cells (PEFCs). A simple and effective method for incorporating a porous structure in the electrode GDL using sucrose as the pore former is reported. Optimal (50 w/o) incorporation of a pore former in the electrode GDL facilitates the access of the gaseous reactants to the catalyst sites and improves the fuel cell performance. Data obtained from permeability and porosity measurements, single-cell performance, and impedance spectroscopy suggest that an optimal porosity helps mitigating mass-polarization losses in the fuel cell resulting in a substantially enhanced performance.

Three-dimensional organization of fenestrae labyrinths in liver sinusoidal endothelial cells

- Background/Aims Liver sinusoidal endothelial cell (LSEC) fenestrae are membrane-bound pores that are grouped in sieve plates and act as a bidirectional guardian in regulating transendothelial liver transport. The high permeability of the endothelial lining is explained by the presence of fenestrae and by various membrane-bound transport vesicles. The question as to whether fenestrae relate to other transport compartments remains unclear and has been debated since their discovery almost 40 years ago. - Methods In this study, novel insights concerning the three-dimensional (3D) organization of the fenestrated cytoplasm were built on transmission electron tomographical observations on isolated and cultured whole-mount LSECs. Classical transmission electron microscopy and atomic force microscopy imaging was performed to accumulate cross-correlative structural evidence. - Results and Conclusions The data presented here indicate that different arrangements of fenestrae have to be considered: i.e. open fenestrae that lack any structural obstruction mainly located in the thin peripheral cytoplasm and complexes of multifolded fenestrae organized as labyrinth-like structures that are found in the proximity of the perinuclear area. Fenestrae in labyrinths constitute about one-third of the total LSEC porosity. The 3D reconstructions also revealed that coated pits and small membrane-bound vesicles are exclusively interspersed in the non-fenestrated cytoplasmic arms.

Modeling of magnetostrictive materials and structures

The constitutive model for a magnetostrictive material and its effect on the structural response is presented in this article. The example of magnetostrictive material considered is the TERFENOL-D. As like the piezoelectric material, this material has two constitutive laws, one of which is the sensing law and the other is the actuation law, both of which are highly coupled and non-linear. For the purpose of analysis, the constitutive laws can be characterized as coupled or uncoupled and linear or non linear. Coupled model is studied without assuming any explicit direct relationship with magnetic field. In the linear coupled model, which is assumed to preserve the magnetic flux line continuity, the elastic modulus, the permeability and magneto-elastic constant are assumed as constant. In the nonlinear-coupled model, the nonlinearity is decoupled and solved separately for the magnetic domain and the mechanical domain using two nonlinear curves, namely the stress vs. strain curve and the magnetic flux density vs. magnetic field curve. This is performed by two different methods. In the first, the magnetic flux density is computed iteratively, while in the second, the artificial neural network is used, where in the trained network will give the necessary strain and magnetic flux density for a given magnetic field and stress level. The effect of nonlinearity is demonstrated on a simple magnetostrictive rod.

N,N′-Bis(aryl)pyridine-2,6-dicarboxamide complexes of ruthenium: Synthesis, structure and redox properties

Reaction of five N,N′-bis(aryl)pyridine-2,6-dicarboxamides (H2L-R, where H2 denotes the two acidic protons and R (R = OCH3, CH3, H, Cl and NO2) the para substituent in the aryl fragment) with [Ru(trpy)Cl3](trpy = 2,2′,2″-terpyridine) in refluxing ethanol in the presence of a base (NEt3) affords a group of complexes of the type [RuII(trpy)(L-R)], each of which contains an amide ligand coordinated to the metal center as a dianionic tridentate N,N,N-donor along with a terpyridine ligand. Structure of the [RuII(trpy)(L-Cl)] complex has been determined by X-ray crystallography. All the Ru(II) complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on the [RuII(trpy)(L-R)] complexes shows a Ru(II)–Ru(III) oxidation within 0.16–0.33 V versus SCE. An oxidation of the coordinated amide ligand is also observed within 0.94–1.33 V versus SCE and a reduction of coordinated terpyridine ligand within −1.10 to −1.15 V versus SCE. Constant potential coulometric oxidation of the [RuII(trpy)(L-R)] complexes produces the corresponding [RuIII(trpy)(L-R)]+ complexes, which have been isolated as the perchlorate salts. Structure of the [RuIII(trpy)(L-CH3)]ClO4 complex has been determined by X-ray crystallography. All the Ru(III) complexes are one-electron paramagnetic, and show anisotropic ESR spectra at 77 K and intense LMCT transitions in the visible region. A weak ligand-field band has also been shown by all the [RuIII(trpy)(L-R)]ClO4 complexes near 1600 nm.

Numerical studies on channel formation and growth during solidification: Effect of process parameters

In the present work, solidification of a hyper-eutectic ammonium chloride solution in a bottom-cooled cavity (i.e. with stable thermal gradient) is numerically studied. A Rayleigh number based criterion is developed, which determines the conditions favorable for freckles formation. This criterion, when expressed in terms of physical properties and process parameters, yields the condition for plume formation as a function of concentration, liquid fraction, permeability, growth rate of a mushy layer and thermophysical properties. Subsequently, numerical simulations are performed for cases with initial and boundary conditions favoring freckle formation. The effects of parameters, such as cooling rate and initial concentration, on the formation and growth of freckles are investigated. It was found that a high cooling rate produced larger and more defined channels which are retained for a longer durations. Similarly, a lower initial concentration of solute resulted in fewer but more pronounced channels. The number and size of channels are also found to be related to the mushy zone thickness. The trends predicted with regard to the variation of number of channels with time under different process conditions are in accordance with the experimental observations reported in the literature.

PVA-PSSA Membrane with Interpenetrating Networks and its Methanol Crossover Mitigating Effect in DMFCs

A membrane with interpenetrating networks between poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) coupled with a high proton conductivity is realized and evaluated as a proton exchange membrane electrolyte for a direct methanol fuel cell (DMFC). Its reduced methanol permeability and improved performance in DMFCs suggest the new blend as an alternative membrane to Nafion membranes. The membrane has been characterized by powder X-ray diffraction, scanning electron microscopy, time-modulated differential scanning calorimetry, and thermogravimetric analysis in conjunction with its mechanical strength. The maximum proton conductivity of 3.3×10−2 S/cm for the PVA–PSSA blend membrane is observed at 373 K. From nuclear magnetic resonance imaging and volume localized spectroscopy experiments, the PVA–PSSA membrane has been found to exhibit a promising methanol impermeability, in DMFCs. On evaluating its utility in a DMFC, it has been found that a peak power density of 90 mW/cm2 at a load current density of 320 mA/cm2 is achieved with the PVA–PSSA membrane compared to a peak power density of 75 mW/cm2 at a load current density of 250 mA/cm2 achievable for a DMFC employing Nafion membrane electrolyte while operating under identical conditions; this is attributed primarily to the methanol crossover mitigating property of the PVA–PSSA membrane.

Optimal configurations of active fiber composites based on asymptotic torsional analysis - art. no. 641413

Active Fiber Composites (AFC) possess desirable characteristics over a wide range of smart structure applications, such as vibration, shape and flow control as well as structural health monitoring. This type of material, capable of collocated actuation and sensing, call be used in smart structures with self-sensing circuits. This paper proposes four novel applications of AFC structures undergoing torsion: sensors and actuators shaped as strips and tubes; and concludes with a preliminary failure analysis. To enable this, a powerful mathematical technique, the Variational Asymptotic Method (VAM) was used to perform cross-sectional analyses of thin generally anisotropic AFC beams. The resulting closed form expressions have been utilized in the applications presented herein.

A silicon micromachined photonic band gap cell, characteristics and an application

A novel PBG cell based on micromachining of Silicon using wet anisotropic etching has been considered. Since this is based on etching of the Silicon substrate, it is amenable to fabrication with standard Silicon processes and integration with millimeter wave circuits. We characterize this kind of PBG cell by full wave simulations using a time domain code. For the purpose of characterization, the scenario of a 50 ohm microstrip line placed on a Silicon substrate which is anisotropically etched to create patterns with sloping walls is considered. This is shown to produce the well known PBG response of stop bands in certain frequency bands. We look at the variation in the transmission coefficient (S-21) response as the number of periods, length based average fill factor and depth of micromachining are varied. One application of a low pass filter has been proposed and simulated results are given.

Synthesis, sintering and microstructural characterization of nanocrystalline Hydroxyapatite Composites

Nanocrystalline hydroxyapatite (HAp) exhibits better bioactivity and biocompatibility with enhanced mechanical properties compared to the microcrystalline counterpart. In the present work, nanocrystalline hydroxyapatite was synthesized by wet chemical method. Sintering was carried out with nanocrystalline alumina as additive, the content of alumina being varied from 10 to 30 wt% in the composite. For 20 and 30 wt % Al2O3, hydroxyapatite decomposed into tricalcium phosphate (TCP) above the sintering temperature of 1100 degrees C. The fracture toughness of nano HAp-nano Al2O3 composite is anisotropic in nature and reached a maximum value of 6.9 MPa m(1/2).

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.

USING FLUORESCENT AND NON-FLUORESCENT STEROLS TO STUDY RAFTS AND INTRACELLULAR CHOLESTEROL TRANSPORT IN MAMMALIAN CELLS

Cholesterol is an essential component in the membranes of most eukaryotic cells, in which it mediates many functions including membrane fluidity, permeability and the formation of ordered membrane domains. In this work a fluorescent and a non-fluorescent cholesterol analog were characterized as tools to study cholesterol. Next, these analogs were used to study two specific cell biological processes that involve cholesterol, i.e. the structure and function of ordered membrane domains/rafts and intracellular cholesterol transport. The most common method for studying ordered membrane domains is by disrupting them by cholesterol depletion. Because cholesterol depletion affects many cellular functions besides those mediated by membrane domains, this procedure is highly unspecific. The cellular exchange of cholesterol by desmosterol as a tool to study ordered membrane domains was characterized. It turned out that the ability of desmosterol to form and stabilize membrane domains in vitro was weaker compared to cholesterol. This result was reinforced by atomistic scale simulations that indicated that desmosterol has a lower ordering effect on phospholipid acyl chains. Three procedures were established for exchanging cellular cholesterol by desmosterol. In cells in which desmosterol was the main sterol, insulin signaling was attenuated. The results suggest that this was caused by desmosterol destabilizing membrane rafts. Contrary to its effect on ordered membrane domains it was found that replacing cholesterol by desmosterol does not change cell growth/viability, subcellular sterol distribution, Golgi integrity, secretory pathway, phospholipid composition and membrane fluidity. Together these results suggest that exchanging cellular cholesterol by desmosterol provides a selective tool for perturbing rafts. Next, the importance of cholesterol for the structure and function of caveolae was analyzed by exchanging the cellular cholesterol by desmosterol. The sterol exchange reduced the stability of caveolae as determined by detergent resistance of caveolin-1 and heat resistance of caveolin-1 oligomers. Also the sterol exchange led to aberrations in the caveolar structure; the morphology of caveolae was altered and there was a larger variation in the amount of caveolin-1 molecules per caveola. These results demonstrate that cholesterol is important for caveolar stability and structural homogeneity. In the second part of this work a fluorescent cholesterol analog was characterized as a tool to study cholesterol transport. Tight control of the intracellular cholesterol distribution is essential for many cellular processes. An important mechanism by which cells regulate their membrane cholesterol content is by cholesterol traffic, mostly from the plasma membrane to lipid droplets. The fluorescent sterol probe BODIPY-cholesterol was characterized as a tool to analyze cholesterol transport between the plasma membrane, the endoplasmic reticulum (ER) and lipid droplets. The behavior of BODIPY-cholesterol was compared to that of natural sterols, using both biochemical and live-cell microcopy assays. The results show that the transport kinetics of BODIPY-cholesterol between the plasma membrane, the ER and lipid droplets is similar to that of unesterified cholesterol. Next, BODIPY-cholesterol was utilized to analyze the importance of oxysterol binding protein related proteins (ORPs) for cholesterol transport between the plasma membrane, the ER, and lipid droplets in mammalian cells. By overexpressing all human ORPs it turned out that especially ORP1S and ORP2 enhanced sterol transport from the plasma membrane to lipid droplets. Our results suggest that the increased sterol transport takes place between the plasma membrane and ER and not between the ER and lipid droplets. Simultaneous knockdown of ORP1S and ORP2 resulted in a moderate but significant inhibition of sterol traffic from the plasma membrane to ER and lipid droplets, suggesting a physiological role for these ORPs in this process. The two phenylalanines in an acidic tract (FFAT) motif in ORPs, which mediates interaction with vesicle associated membrane protein associated proteins (VAPs) in the ER, was not necessary for mediating sterol transport. However, VAP silencing slowed down sterol transport, most likely by destabilizing ORPs containing a FFAT motif.

Convergence correction in colloid scattering

The error introduced in depolarisation measurements due to the convergence of the incident beam has been investigated theoretically as well as experimentally for the case of colloid scattering, where the particles are not small compared to the wavelength of light. Assuming the scattering particles to be anisotropic rods, it is shown that, when the incident unpolarised light is condensed by means of a lens with a circular aperture, the observed depolarisation ratio ϱ u is given by ϱ u = ϱ u0 + 5/3 θ2 where ϱ u0 is the true depolarisation for incident parallel light, and θ the semi-angle of convergence. Appropriate formulae are derived when the incident beam is polarised vertically and horizontally. Experiments performed on six typical colloids support the theoretical conclusions. Other immediate consequences of the theory are also discussed.