Oxides supported carbon air-electrodes for alkaline solution power devices

Porous carbon oxygen-reducing electrodes incorporated with perovskite oxide catalysts are reported. It has been possible to fabricate high-performance oxygen-reducing electrodes by introducing La0.5Sr0.5CoO3 and La0.99Sr0.01NiO3 with the activated coconut-shell charcoal; these electrodes could sustain load currents as high as 1 A cm−2 without serious degradation. A model to explain oxygen-reducing activity of these oxides has been proposed.

On an analytical-numerical procedure for the analysis of cylindrical-shells with arbitrarily oriented cracks

An analytical-numerical procedure for obtaining stress intensity factor solutions for an arbitrarily oriented crack in a long, thin circular cylindrical shell is presented. The method of analysis involves obtaining a series solution to the governing shell equation in terms of Mathieu and modified Mathieu functions by the method of separation of variables and satisfying the crack surface boundary conditions numerically using collocation. The solution is then transformed from elliptic coordinates to polar coordinates with crack tip as the origin through a Taylor series expansion and membrane and bending stress intensity factors are computed. Numerical results are presented and discussed for the pressure loading case.

Out-of-plane deformation and failure of masonry walls with various forms of reinforcement

Out-of-plane behaviour of mortared and mortarless masonry walls with various forms of reinforcement, including unreinforced masonry as a base case is examined using a layered shell element based explicit finite element modelling method. Wall systems containing internal reinforcement, external surface reinforcement and intermittently laced reinforced concrete members and unreinforced masonry panels are considered. Masonry is modelled as a layer with macroscopic orthotropic properties; external reinforcing render, grout and reinforcing bars are modelled as distinct layers of the shell element. Predictions from the layered shell model have been validated using several out-of-plane experimental datasets reported in the literature. The model is used to examine the effectiveness of two retrofitting schemes for an unreinforced masonry wall.

Finite element analysis of bimodulus composite stiffened thin shells of revolution

This paper is a sequel to the work published by the first and third authors[l] on stiffened laminated shells of revolution made of unimodular materials (materials having identical properties in tension and compression). A finite element analysis of laminated bimodulus composite thin shells of revolution, reinforced by laminated bimodulus composite stiffeners is reported herein. A 48 dot doubly curved quadrilateral laminated anisotropic shell of revolution finite element and it's two compatible 16 dof stiffener finite elements namely: (i) a laminated anisotropic parallel circle stiffener element (PCSE) and (ii) a laminated anisotropic meridional stiffener element (MSE) have been used iteratively. The constitutive relationship of each layer is assumed to depend on whether the fiberdirection strain is tensile or compressive. The true state of strain or stress is realized when the locations of the neutral surfaces in the shell and the stiffeners remain unaltered (to a specified accuracy) between two successive iterations. The solutions for static loading of a stiffened plate, a stiffened cylindrical shell. and a stiffened spherical shell, all made of bimodulus composite materials, have been presented.

An explicit finite element modelling method for masonry walls under out-of-plane loading

An explicit finite element modelling method is formulated using a layered shell element to examine the behaviour of masonry walls subject to out-of-plane loading. Masonry is modelled as a homogenised material with distinct directional properties that are calibrated from datasets of a “C” shaped wall tested under pressure loading applied to its web. The predictions of the layered shell model have been validated using several out-of-plane experimental datasets reported in the literature. Profound influence of support conditions, aspect ratio, pre-compression and opening to the strength and ductility of masonry walls is exhibited from the sensitivity analyses performed using the model.

Threshold photoproduction of charged pions on14N

Pion photoproduction processes14Ngs(gamma, pgr +)14C and14Ngs(gamma, pgr –)14O have been studied in the threshold region. These processes provide an excellent tool to study the corrections to soft pion theorems and Kroll-Ruderman limit as applied to nuclear processes. The agreement with the available experimental data for these processes is better with the empirical wave functions while the shell-model wave functions predict a much higher value. Detailed experimental studies of these reactions at threshold, it is shown, are expected to lead to a better understanding of the shell-model inputs and radial distributions in the 1p state. We thank Dr. S.C.K. Nair for a helpful discussion during the initial stages of this work. One of us (MVN) thanks Dr. J.M. Laget for sending some unpublished data on pion photoproduction. He is also thankful to Dr. J. Pasupathy and Dr. R. Rajaraman for their interest and encouragement.

Numerical studies on CFRP strengthened steel circular members under marine environment

The durability of carbon fibre reinforced polymer (CFRP) strengthened steel circular hollow section (CHS) members has now become a real challenge to researchers. In addition, various parameters that may affect the durability of such members have not been revealed yet. This paper presents brief experimental results and the first finite element (FE) approach of CFRP strengthened steel CHS beams conditioned in simulated sea water, along with an accelerated corrosion environment at ambient (24 OC ± 4 OC) and 50 OC temperatures. The beams were loaded to failure under four-point bending. It was found that the strength and stiffness reduced significantly after conditioning in an accelerated corrosion environment. Numerical simulation is implemented using the ABAQUS static general approach. A cohesive element was utilised to model the interface element and an 8-node quadrilateral in-plane general-purpose continuum shell was used to model CFRP elements. A mixed mode cohesive law was deployed for all the three components of stresses in the proposed FE approach, which were one normal component and two shear components. The validity of the FE models was ascertained by comparing the ultimate load and load vs deflection response from experimental results. A range of parametric studies were conducted to investigate the effects of bond length, adhesive types, thickness and diameter of tubes. The results of parametric studies indicated that the adhesive with high tensile modulus performed better and durability design factors varied from section to section.

Thermal stresses around circular holes in spherical shells

The thermal stress problem of a circular hole in a spherical shell of uniform thickness is solved by using a continuum approach. The influence of the hole is assumed to be confined to a small region around the opening. The thermal stress problem is converted as usual to an equivalent boundary value problem with forces specified around the cutout. The stresses and displacement are obtained for a linear variation of temperature across the thickness of the shell and presented in graphical form for ready use.

Plastic response of orthotropic spherical shells under blast loading

The plastic response of a segment of a simply supported orthotropic spherical shell under a uniform blast loading applied on the convex surface of the shell is presented. The blast is assumed to impart a uniform velocity to the shell surface initially. The material of the shell is orthotropic obeying a modified Tresca yield hypersurface conditions and the associated flow rules. The deformation of the shell is determined during all phases of its motion by considering the motion of plastic hinges in different regimes of flow. Numerical results presented include the permanent deformed configuration of the shell and the total time of shell response for different degrees of orthotropy. Conclusions regarding the plastic behaviour of spherical shells with circumferential and meridional stiffening under uniform blast load are presented.

Syntheses and Self-Assembling Characteristics of Amphiphilic Star Diblock Copolymers

Uusien polymeeripohjaisten teknologioiden ja materiaalien myötä räätälöityjen polymeerien tarve on kasvanut. Viime vuosituhannen lopussa kehitetyt kontrolloidut polymerointimenetelmät ovat avanneet uusia mahdollisuuksia paitsi monimutkaisten polymeerien synteesiin, myös itsejärjestyvyyteen perustuvien funktionaalisten nanorakenteiden suunnitteluun ja valmistukseen. Nämä voivat jäljitellä luonnossa esiintyviä rakenteita, joita muodostavat esimerkiksi lipidit ja proteiinit. Itsejärjestyvät molekyylit ovat usein amfifiilisiä eli ne koostuvat hydrofiilisistä ja hydrofobisista osista ja polymeereissä nämä osat voivat olla omina lohkoinaan, jolloin puhutaan amfifiilisistä lohko- tai blokkikopolymeereistä. Riippuen järjestyneiden rakenteiden koostumuksesta ja muodosta, amfifiilisiä blokkikopolymeerejä on tutkittu tai jo käytetty nanoteknologiassa, elastomeereissä, voiteluaineissa, pinta-aktiivisina aineina, lääkkeenannostelussa, maaleissa, sekä elektroniikka-, kosmetiikka- ja elintarviketeollisuudessa. Tavallisimmin käytetyt amfifiiliset blokkikopolymeerit ovat olleet lineaarisia, mutta viime aikoina tutkimus on suuntautunut kohti monimutkaisempia rakenteita. Tällaisia ovat esimerkiksi tähtipolymeerit. Tähtimäisissä polymeereissä miselleille tyypillinen ydin-kuori-rakenne säilyy hyvin alhaisissakin polymeerikonsentraatioissa, koska polymeeriketjut ovat kiinni toisissaan yhdessä pisteessä. Siten ne ovat erityisen kiinnostavia tutkimuskohteita erilaisten hydrofobisten orgaanisten yhdisteiden sitomiseksi ja vapauttamiseksi. Tässä työssä on tarkasteltu amfifiilisten tähtipolymeerien itsejärjestymistä vesiliuoksissa sekä kokeellisesti ja tietokonesimulaatioin. Työ koostuu kahdesta osasta: tähtipolymeerien synteesistä makrosyklisillä initiaattoreilla ja amfifiilisten tähtimäisten blokkikopolymeerien ominaisuuksien tutkimisesta.

Charge distribution, dipole moments and molecular structure of some organogermanium compounds

Formal charge distributions in, and the electric dipole moments of, a few simple organogermanium compounds have been evaluated by the method of R. P. Smith et al. [J. Amer. Chem. Soc., 73(1951) 2263]. The difference between the experimental and calculated moments in the case of alkylhalogermanes is explained in terms of the pπ—dπ back bonding effect outweighing the electron releasing effect. In unsaturated compounds, the differences are attributed to possible mesmeric effects involving the expansion of the germanium valence shell.

A quantum chemical investigation of the metal centres in cytochrome c oxidase

Quantum effects are often of key importance for the function of biological systems at molecular level. Cellular respiration, where energy is extracted from the reduction of molecular oxygen to water, is no exception. In this work, the end station of the electron transport chain in mitochondria, cytochrome c oxidase, is investigated using quantum chemical methodology. Cytochrome c oxidase contains two haems, haem a and haem a3. Haem a3, with its copper companion, CuB, is involved in the final reduction of oxygen into water. This binuclear centre receives the necessary electrons from haem a. Haem a, in turn, receives its electrons from a copper ion pair in the vicinity, called CuA. Density functional theory (DFT) has been used to clarify the charge and spin distributions of haem a, as well as changes in these during redox activity. Upon reduction, the added electron is shown to be evenly distributed over the entire haem structure, important for the accommodation of the prosthetic group within the protein. At the same time, the spin distribution of the open-shell oxidised state is more localised to the central iron. The exact spin density distribution has been disputed in the literature, however, different experiments indicating different distributions of the unpaired electron. The apparent contradiction is shown to be due to the false assumption of a unit amount of unpaired electron density; in fact, the oxidised state has about 1.3 unpaired electrons. The validity of the DFT results have been corroborated by wave function based coupled cluster calculations. Point charges, for use in classical force field based simulations, have been parameterised for the four metal centres, using a newly developed methodology. In the procedure, the subsystem for which point charges are to be obtained, is surrounded by an outer region, with the purpose of stabilising the inner region, both electronically and structurally. Finally, the possibility of vibrational promotion of the electron transfer step between haem a and a3 has been investigated. Calculating the full vibrational spectra, at DFT level, of a combined model of the two haems, revealed several normal modes that do shift electron density between the haems. The magnitude of the shift was found to be moderate, at most. The proposed mechanism could have an assisting role in the electron transfer, which still seems to be dominated by electron tunnelling.

Effect of biochar amendment on yield and photosynthesis of peanut on two types of soils

Abstract Biochar has significant potential to improve crop performance. This study examined the effect of biochar application on the photosynthesis and yield of peanut crop grown on two soil types. The commercial peanut cultivar Middleton was grown on red ferrosol and redoxi-hydrosol (Queensland, Australia) amended with a peanut shell biochar gradient (0, 0.375, 0.750, 1.50, 3.00 and 6.00 %, w/w, equivalent up to 85 t ha−1) in a glasshouse pot experiment. Biomass and pod yield, photosynthesis-[CO2] response parameters, leaf characteristics and soil properties (carbon, nitrogen (N) and nutrients) were quantified. Biochar significantly improved peanut biomass and pod yield up to 2- and 3-folds respectively in red ferrosol and redoxi-hydrosol. A modest (but significant) biochar-induced improvement of the maximumelectron transport rate and saturating photosynthetic rate was observed for red ferrosol. This response was correlated to increased leaf N and accompanied with improved soil available N and biological N fixation. Biochar application also improved the availability of other soil nutrients, which appeared critical in improving peanut performance, especially on infertile redoxihydrosol. Our study suggests that application of peanut shell derived biochar has strong potential to improve peanut yield on red ferrosol and redoxi-hydrosol. Biochar soil amendment can affect leaf N status and photosynthesis, but the effect varied with soil type.

On a finite element model for the analysis of through cracks in laminated anisotropic cylindrical shells

A finite element model for the analysis of laminated composite cylindrical shells with through cracks is presented. The analysis takes into account anisotropic elastic behaviour, bending-extensional coupling and transverse shear deformation effects. The proposed finite element model is based on the approach of dividing a cracked configuration into triangular shaped singular elements around the crack tip with adjoining quadrilateral shaped regular elements. The parabolic isoparametric cylindrical shell elements (both singular and regular) used in this model employ independent displacement and rotation interpolation in the shell middle surface. The numerical comparisons show the evidence to the conclusion that the proposed model will yield accurate stress intensity factors from a relatively coarse mesh. Through the analysis of a pressurised fibre composite cylindrical shell with an axial crack, the effect of material orthotropy on the crack tip stress intensity factors is shown to be quite significant.

Spectrally Resolved Resonance Energy Transfer from ZnO:MgO Nanocrystals

Resonance energy transfer (RET) from the visible emission of core−shell ZnO:MgO nanocrystals to Nile Red chromophores, following band gap excitation in the UV, has been investigated for four different nanocrystal sizes. With use of steady state and time-resolved fluorescence spectroscopic measurements the wavelength dependent RET efficiencies have been determined. The RET process in ZnO:MgO nanocrystals occurs from emissions involving trap state recombination. There are two such processes with different RET efficiencies for the same particle size. This is shown to be a consequence of the fact that the recombination processes giving rise to the two emissions are located at different distances from the center of the particle so that the donor−acceptor distances for the two are different, even for the same particle size.