Crack mechanical failure in lithium niobate crystal under ion irradiation; novel simulation by extended finite elements

Swift heavy ion irradiation (ions with mass heavier than 15 and energy exceeding MeV/amu) transfer their energy mainly to the electronic system with small momentum transfer per collision. Therefore, they produce linear regions (columnar nano-tracks) around the straight ion trajectory, with marked modifications with respect to the virgin material, e.g., phase transition, amorphization, compaction, changes in physical or chemical properties. In the case of crystalline materials the most distinctive feature of swift heavy ion irradiation is the production of amorphous tracks embedded in the crystal. Lithium niobate is a relevant optical material that presents birefringence due to its anysotropic trigonal structure. The amorphous phase is certainly isotropic. In addition, its refractive index exhibits high contrast with those of the crystalline phase. This allows one to fabricate waveguides by swift ion irradiation with important technological relevance. From the mechanical point of view, the inclusion of an amorphous nano-track (with a density 15% lower than that of the crystal) leads to the generation of important stress/strain fields around the track. Eventually these fields are the origin of crack formation with fatal consequences for the integrity of the samples and the viability of the method for nano-track formation. For certain crystal cuts (X and Y), these fields are clearly anisotropic due to the crystal anisotropy. We have used finite element methods to calculate the stress/strain fields that appear around the ion-generated amorphous nano-tracks for a variety of ion energies and doses. A very remarkable feature for X cut-samples is that the maximum shear stress appears on preferential planes that form +/-45º with respect to the crystallographic planes. This leads to the generation of oriented surface cracks when the dose increases. The growth of the cracks along the anisotropic crystal has been studied by means of novel extended finite element methods, which include cracks as discontinuities. In this way we can study how the length and depth of a crack evolves as function of the ion dose. In this work we will show how the simulations compare with experiments and their application in materials modification by ion irradiation.

Crack mechanical failure in ceramic materials under ion irradiation: case of lithium niobate crystal

Swift heavy ion irradiation (ions with mass heavier than 15 and energy exceeding MeV/amu) transfer their energy mainly to the electronic system with small momentum transfer per collision. Therefore, they produce linear regions (columnar nano-tracks) around the straight ion trajectory, with marked modifications with respect to the virgin material, e.g., phase transition, amorphization, compaction, changes in physical or chemical properties. In the case of crystalline materials the most distinctive feature of swift heavy ion irradiation is the production of amorphous tracks embedded in the crystal. Lithium niobate is a relevant optical material that presents birefringence due to its anysotropic trigonal structure. The amorphous phase is certainly isotropic. In addition, its refractive index exhibits high contrast with those of the crystalline phase. This allows one to fabricate waveguides by swift ion irradiation with important technological relevance. From the mechanical point of view, the inclusion of an amorphous nano-track (with a density 15% lower than that of the crystal) leads to the generation of important stress/strain fields around the track. Eventually these fields are the origin of crack formation with fatal consequences for the integrity of the samples and the viability of the method for nano-track formation. For certain crystal cuts (X and Y), these fields are clearly anisotropic due to the crystal anisotropy. We have used finite element methods to calculate the stress/strain fields that appear around the ion- generated amorphous nano-tracks for a variety of ion energies and doses. A very remarkable feature for X cut-samples is that the maximum shear stress appears on preferential planes that form +/-45º with respect to the crystallographic planes. This leads to the generation of oriented surface cracks when the dose increases. The growth of the cracks along the anisotropic crystal has been studied by means of novel extended finite element methods, which include cracks as discontinuities. In this way we can study how the length and depth of a crack evolves as function of the ion dose. In this work we will show how the simulations compare with experiments and their application in materials modification by ion irradiation.

The influence of antiferroelectric compounds on helical pitch of orthoconic W-1000 mixture

The influence of six antiferroelectric compounds on the helical pitch of mixture W-1000, which was reported as long pitch orthoconic antiferroelectric liquid crystalline mixture, was checked by spectrophotometry and polarimetry methods. The electro-optical properties for the mixture with the longest pitch were measured. An improvement in electro-optical response due to the long pitch is reported. The novelty in electro-optical properties is the good symmetry response.

The making of the architecture of the plant cell wall: How cells exploit geometry

Cell wall deposition is a key process in the formation, growth, and differentiation of plant cells. The most important structural components of the wall are long cellulose microfibrils, which are synthesized by synthases embedded in the plasma membrane. A fundamental question is how the microfibrils become oriented during deposition at the plasma membrane. The current textbook explanation for the orientation mechanism is a guidance system mediated by cortical microtubules. However, too many contraindications are known in secondary cell walls for this to be a universal mechanism, particularly in the case of helicoidal arrangements, which occur in many situations. An additional construction mechanism involves liquid crystalline self-assembly [A. C. Neville (1993) Biology of Fibrous Composites: Development Beyond the Cell Membrane (Cambridge Univ. Press, Cambridge, U.K.)], but the required amount of bulk material that is able to equilibrate thermally is not normally present at any stage of the wall deposition process. Therefore, we have asked whether the complex ordered texture of helicoidal cell walls can be formed in the absence of direct cellular guidance mechanisms. We propose that they can be formed by a mechanism that is based on geometrical considerations. It explains the genesis of the complicated helicoidal texture and shows that the cell has intrinsic, versatile tools for creating a variety of textures. A compelling feature of the model is that local rules generate global order, a typical phenomenon of life.

High-frequency, spin-label EPR of nonaxial lipid ordering and motion in cholesterol-containing membranes

The EPR spectra of spin-labeled lipid chains in fully hydrated bilayer membranes of dimyristoyl phosphatidylcholine containing 40 mol % of cholesterol have been studied in the liquid-ordered phase at a microwave radiation frequency of 94 GHz. At such high field strengths, the spectra should be optimally sensitive to lateral chain ordering that is expected in the formation of in-plane domains. The high-field EPR spectra from random dispersions of the cholesterol-containing membranes display very little axial averaging of the nitroxide g-tensor anisotropy for lipids spin labeled toward the carboxyl end of the sn-2 chain (down to the 8-C atom). For these positions of labeling, anisotropic 14N-hyperfine splittings are resolved in the gzz and gyy regions of the nonaxial EPR spectra. For positions of labeling further down the lipid chain, toward the terminal methyl group, the axial averaging of the spectral features systematically increases and is complete at the 14-C atom position. Concomitantly, the time-averaged 〈Azz〉 element of the 14N-hyperfine tensor decreases, indicating that the axial rotation at the terminal methyl end of the chains arises from correlated torsional motions about the bonds of the chain backbone, the dynamics of which also give rise to a differential line broadening of the 14N-hyperfine manifolds in the gzz region of the spectrum. These results provide an indication of the way in which lateral ordering of lipid chains in membranes is induced by cholesterol.

Estudo da microestrutura e dinâmica molecular do Poly(3-(2\'-ethylhexyl)thiophene)(P3EHT) via ressonância magnética nuclear

O estudo da microestrutura e dinâmica molecular de polímeros conjugados é de grande importância para o entendimento das propriedades físicas desta classe de materiais. No presente trabalho utilizou-se técnicas de ressonância magnética nuclear em baixo e alto campo para elucidar os processos de dinâmica molecular e cristalização do polímero Poly(3-(2’-ethylhexyl)thiophene) - P3EHT. O P3EHT é um polímero modelo para tal estudo, pois apresenta temperatura de fusão bem inferior a sua temperatura de degradação. Esta característica permite acompanhar os processos de cristalização in situ utilizando RMN. Além disso, sua similaridade ao já popular P3HT o torna um importante candidato a camada ativa em dispositivos eletrônicos orgânicos. O completo assinalamento do espectro de 13C para o P3EHT foi realizado utilizando as técnicas de defasamento dipolar e HETCOR. Os processos de dinâmica molecular, por sua vez, foram sondados utilizando DIPSHIFT. Observou-se um gradiente de mobilidade na cadeia lateral do polímero. Além disso, os baixos valores de parametros de ordem obtidos em comparação a experimentos similares realizados no P3HT na literatura indicam um aparente aumento no volume livre entre cadeias consecutivas na fase cristalina. Isso indica que a presença do grupo etil adicional no P3EHT causa um completo rearranjo das moléculas e dificulta seu empacotamento. Constatou-se ainda pouca variação das curvas de DIPSHIFT para os carbonos da cadeia lateral como função do método de excitação utilizado, o que aponta para um polímero que apresenta cadeia lateral móvel mesmo em sua fase cristalina. Os dados de dinâmica molecular foram corroborados por medidas de T1, T1ρ e TCH. Utilizando filtros dipolares em baixo campo observou-se três temperaturas de transição para o P3EHT: 250 K, 325 K e 350 K. A cristalização desse material é um processo lento. Verificou-se que o mesmo pode se estender por até até 24h a temperatura ambiente. Mudanças no espectro de 13C utilizando CPMAS em alto campo indicam um ordenamento dos anéis tiofeno (empacotamento π – π) como o principal processo de cristalização para o P3EHT.

Avaliação da saúde e desempenho de bezerros leiteiros recebendo suplemento de colostro associado ao colostro materno

O objetivo deste estudo foi avaliar o efeito do suplemento de colostro (SC) associado ao colostro materno (CM) de alta ou média qualidade na saúde e desempenho de bezerros leiteiros. No primeiro experimento foram utilizados 44 machos da raça Holandesa, distribuídos nos tratamentos: 1) CM de alta qualidade fornecido em volume correspondente a 15% do peso ao nascer (PN); 2) CM de média qualidade (15%PN) e 3) CM de média qualidade (15% PN) + SC. O protocolo de colostragem afetou a concentração de proteína total nas primeiras 48 horas de vida e durante a fase de aleitamento (P<0,05). Em relação a saúde, o protocolo de colostragem não afetou o escore fecal, bem como o número de dias com diarreia, dias com febre e dias de hidratação (P>0,05); no entanto, os animais que receberam CM de alta qualidade foram medicados por um menor número de dias (P<0,05). O consumo e o desempenho não foram afetados pelos tratamentos (P>0,05), embora tenha ocorrido efeito de idade (P<0,0001). O fornecimento de suplemento de colostro associado ao CM de média qualidade não afetou a transferência de imunidade passiva, o desempenho ou o metabolismo dos animais durante o período de aleitamento. No segundo experimento foram utilizadas 80 fêmeas da raça Holandesa nos seguintes tratamentos: 1) CM de alta qualidade fornecido em volume correspondente a 15% PN; e 2) CM de alta qualidade (15% PN) + SC. Não houve diferença na qualidade do colostro ingerido pelos animais (P>0,05). Os parâmetros sanguíneos nas primeiras 24 horas não foram afetados pelos tratamentos (P>0,05). O consumo e o desempenho não foram afetados pela administração do suplemento de colostro (P>0,05), no entanto houve efeito de idade para ambos os parâmetros (P<0,0001). Em relação à saúde, o fornecimento adicional de Ig não afetou os dias com diarreia, dias com febre ou dias medicados (P>0,05). A taxa de mortalidade observada durante o experimento foi de 2,5%. O consumo adicional de Ig através do fornecimento de suplemento de colostro em associação ao colostro materno de alta qualidade não melhorou a imunidade, bem como não afetou o desempenho ou a saúde de bezerros leiteiros. No terceiro experimento, foram utilizadas 67 fêmeas da raça Holandesa ou mestiças Girolando nos seguintes tratamentos: 1) CM de alta qualidade fornecido em volume correspondente a 10% PN; e 2) CM de alta qualidade (10% PN) + SC. O consumo e o desempenho não foram afetados pelo SC (P>0,05). O escore fecal também não foi afetado (P>0,05), mas observou-se maior frequência de animais com escore de desidratação nas 2ª e 3ª semana de vida, quando os escores fecais foram mais altos para todos os tratamentos. Houve uma maior porcentagem de animais suplementados sendo medicados devido a diarreias na segunda semana de vida. Houve maior frequência dos animais do grupo não suplementado com escore 1 de descarga nasal nas semanas 3 a 7. O consumo adicional de imunoglobulinas através do fornecimento de suplemento de colostro em associação ao colostro materno de alta qualidade não afetou o desempenho ou a saúde dos animais.

Nanoarchitectures Based on Layered Titanosilicates Supported on Glass Fibers: Application to Hydrogen Storage

This work reports on the synthesis of nanosheets of layered titanosilicate JDF-L1 supported on commercial E-type glass fibers with the aim of developing novel nanoarchitectures useful as robust and easy to handle hydrogen adsorbents. The preparation of those materials is carried out by hydrothermal reaction from the corresponding gel precursor in the presence of the glass support. Because of the basic character of the synthesis media, silica from the silicate-based glass fibers can be involved in the reaction, cementing its associated titanosilicate and giving rise to strong linkages on the support with the result of very stable heterostructures. The nanoarchitectures built up by this approach promote the growth and disposition of the titanosilicate nanosheets as a house-of-cards radially distributed around the fiber axis. Such an open arrangement represents suitable geometry for potential uses in adsorption and catalytic applications where the active surface has to be available. The content of the titanosilicate crystalline phase in the system represents about 12 wt %, and this percentage of the adsorbent fraction can achieve, at 298 K and 20 MPa, 0.14 wt % hydrogen adsorption with respect to the total mass of the system. Following postsynthesis treatments, small amounts of Pd (<0.1 wt %) have been incorporated into the resulting nanoarchitectures in order to improve their hydrogen adsorption capacity. In this way, Pd-layered titanosilicate supported on glass fibers has been tested as a hydrogen adsorbent at diverse pressures and temperatures, giving rise to values around 0.46 wt % at 298 K and 20 MPa. A mechanism of hydrogen spillover involving the titanosilicate framework and the Pd nanoparticules has been proposed to explain the high increase in the hydrogen uptake capacity after the incorporation of Pd into the nanoarchitecture.

The acceptability of alcohol fuels for automobile engines

The aim of this project was to carry out an investigastion into suitable alternatives to gasoline for use in modern automobiles. The fuel would provide the western world with a means of extending the natural gasoline resources and the third world a way of cutting down their dependence on the oil producing countries for their energy supply. Alcohols, namely methanol and ethanol, provide this solution. They can be used as gasoline extenders or as fuels on their own.In order to fulfil the aims of the project a literature study was carried out to investigate methods and costs of producing these fuels. An experimental programme was then set up in which the performance of the alcohols was studied on a conventional engine. The engine used for this purpose was the Fiat 127 930cc four cylinder engine. This engine was used because of its popularity in the European countries. The Weber fixed jet carburettor, since it was designed to be used with gasoline, was adapted so that the alcohol fuels and the blends could be used in the most efficient way. This was mainly to take account of the lower heat content of the alcohols. The adaptation of the carburettor was in the form of enlarging the main metering jet. Allowances for the alcohol's lower specfic gravity were made during fuel metering.Owing to the low front end volatility of methanol and ethanol, it was expected that `start up' problems would occur. An experimental programme was set up to determine the temperature range for a minimum required percentage `take off' that would ease start-up since it was determined that a `take off' of about 5% v/v liquid in the vapour phase would be sufficient for starting. Additions such as iso-pentane and n-pentane were used to improve the front end volatility. This proved to be successful.The lower heat content of the alcohol fuels also meant that a greater charge of fuel would be required. This was seen to pose further problems with fuel distribution from the carburettor to the individual cylinders on a multicylinder engine. Since it was not possible to modify the existing manifold on the Fiat 127 engine, experimental tests on manifold geometry were carried out using the Ricardo E6 single cylinder variable compression engine. Results from these tests showed that the length, shape and cross-sectional area of the manifold play an important part in the distribution of the fuel entering the cylinder, ie. vapour phase, vapour/small liquid droplet/liquid film phase, vapour/large liquid droplet/liquid film phase etc.The solvent properties of the alcohols and their greater electrical conductivity suggested that the materials used on the engine would be prone to chemical attack. In order to determine the type and rate of chemical attack, an experimental programme was set up whereby carburettor and other components were immersed in the alcohols and in blends of alcohol with gasoline. The test fuels were aerated and in some instances kept at temperatures ranging from 50oC to 90oC. Results from these tests suggest that not all materials used in the conventional engine are equally suitable for use with alcohols and alcohol/gasoline blends. Aluminium for instance was severely attacked by methanol causing pitting and pin-holing in the surface.In general this whole experimental programme gave valuable information on the acceptability of substitute fuels. While the long term effects of alcohol use merit further study, it is clear that methanol and ethanol will be increasingly used in place of gasoline.

Hierarchical macroporous-mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis

Hierarchical macroporous-mesoporous SBA-15 silicas have been synthesised via dual-templating routes employing liquid crystalline surfactants and polystyrene beads. These offer high surface areas and well-defined, interconnecting macro- and mesopore networks with respective narrow size distributions around 300 nm and 3-5 nm for polystyrene:tetraethoxysilane ratios ≥2:1. Subsequent functionalisation with propylsulfonic acid yields the first organized, macro-mesoporous solid acid catalyst. The enhanced mass transport properties of these new bi-modal solid acid architectures confer significant rate enhancements in the transesterification of bulky glyceryl trioctanoate, and esterification of long chain palmitic acid, over pure mesoporous analogues. This paves the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion. © 2010 The Royal Society of Chemistry.

Improved lithium storage properties of electrospun TiO2 with tunable morphology:from porous anatase to necklace rutile

Three-dimensional TiO2 with tunable morphology and crystalline phase was successfully prepared by the electrospinning technique and subsequent annealing. Porous-shaped anatase TiO2, cluster-shaped anatase TiO2, hierarchical-shaped rutile (minor) TiO2 and nano-necklace rutile (major) TiO2 were achieved at 500, 600, 700 and 800°C, respectively. The mechanism of the formation of these tailored morphologies and crystallinity was investigated. Lithium insertion properties were evaluated by galvanostatic and potentiostatic modes in half-cell configurations. By combining the large surface area, open mesoporosity and stable crystalline phase, the porous-shaped anatase TiO2 exhibited the highest capacity, best rate and cycling performance among the four samples. The present results demonstrated the usefulness of three-dimensional TiO 2 as an anode for lithium storage with improved electrode performance. © 2013 The Royal Society of Chemistry.

Probing crystallisation of a fluoro-apatite - mullite system using neutron diffraction

Real-time small angle neutron scattering and wide angle neutron scattering studies were undertaken concurrently on a glass ionomer of nominal composition 4.5(SiO2)-3(Al2O3)-1.5(P2O5)-3(CaO)-2(CaF2). Neutron studies were conducted as a function of temperature to investigate the crystallisation process. No amorphous phase separation was observed at room temperature and the onset of crystallisation was found to occur at 650°C, which is 90°C lower than previously reported. The first crystalline phase observed corresponded to fluorapatite; it was only upon further heating was the mullite phase became present. The crystallite size at 650°C was found to be ~115Å and the result was consistent across all measurements.

Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

(Table 1, Page 1046-1047) Chemical composition of iron-manganese concretions from the Indian Ocean recovered by the R/V Vityaz and the R/V Ob

The data given in this and previous communications is insufficient to assess the quantitative role of these supplementary sources in the Indian Ocean, but they do not rule out their local significance. Elucidation of this problem requires further data on the characteristics of the composition and structure of nodules in various different metallogenic regions of the ocean floor. A study of the distribution of ore elements in nodules both depthwise and over the area of the floor together with compilation of the first schematic maps based on the results of analyses of samples from 54 stations) enables us to give a more precise empirical relation between the Mn, Fe, Ni, Cu, and Co contents in Indian Ocean nodules, the manganese ratio and the values of the oxidation potential, which vary regularly with depth. This in turn also enables us to confirm that formation of nodules completes the prolonged process of deposition of ore components from ocean waters, and the complex physico-chemical transformations of sediments in the bottom layer. Microprobe investigation of ore rinds revealed the nonuniform distribution of a num¬ber of elements within them, owing to the capacity of particles of hydrated oxides of manganese and iron to adsorb various elements. High concentration of individual elements is correlated with local sectors of the ore rinds, in which the presence of todorokite, in particular, has been noted. The appearance of this mineral apparently requires elevated Ca, Mg, Na, and K concentrations, because the stable crystalline phase of this specific mineral form of the psilomelane group may be formed when these cations are incorporated into a lattice of the delta-MnO2 type.

Estudo experimental do escoamento bifásico líquido gás em golfadas com leve mudança de direção

Gas-liquid two-phase flow is very common in industrial applications, especially in the oil and gas, chemical, and nuclear industries. As operating conditions change such as the flow rates of the phases, the pipe diameter and physical properties of the fluids, different configurations called flow patterns take place. In the case of oil production, the most frequent pattern found is slug flow, in which continuous liquid plugs (liquid slugs) and gas-dominated regions (elongated bubbles) alternate. Offshore scenarios where the pipe lies onto the seabed with slight changes of direction are extremely common. With those scenarios and issues in mind, this work presents an experimental study of two-phase gas-liquid slug flows in a duct with a slight change of direction, represented by a horizontal section followed by a downward sloping pipe stretch. The experiments were carried out at NUEM (Núcleo de Escoamentos Multifásicos UTFPR). The flow initiated and developed under controlled conditions and their characteristic parameters were measured with resistive sensors installed at four pipe sections. Two high-speed cameras were also used. With the measured results, it was evaluated the influence of a slight direction change on the slug flow structures and on the transition between slug flow and stratified flow in the downward section.