Using an additive to control the electrospinning of fibres of poly(epsilon-caprolactone)

Electrospinning is a route to polymer fibres with diameters considerably smaller than available from most fibre-producing techniques. We explore the use of a low molecular weight compound as an effective control additive during the electrospinning of poly(epsilon-caprolactone). This approach extends the control variables for the electrospinning of nanoscale fibres from the more usual ones such as the polymer molecular weight, solvent and concentration. We show that through the use of dual solvent systems, we can alter the impact of the additive on the electrospinning process so that finer as well as thicker fibres can be prepared under otherwise identical conditions. As well as the size of the fibres and the number of beads, the use of the additive allows us to alter the level of crystallinity as well as the level of preferred orientation of the poly(epsilon-caprolactone) crystals. This approach, involving the use of a dual solvent and a low molar mass compound, offers considerable potential for application to other polymer systems. (C) 2010 Society of Chemical Industry

Origin of the Parry arc

Laboratory experiments to determine the preferred orientation of free-falling hexagonal prisms were performed at Reynolds numbers appropriate to falling ice crystals in the atmosphere. Hexagonal plates orient with their c axis vertical for aspect ratios < 0.9, whilst hexagonal columns fall with their c axis horizontal. A secondary alignment is also observed: regular hexagonal columns fall preferentially with two prism facets aligned vertically and not horizontally – the latter scenario was previously assumed to be responsible for the rare Parry arc. However, if the column is made scalene in its cross-section, it can orient such that a pair of prism facets is horizontal. This finding indicates that the development of scalene crystals may be key to the production of certain ice-crystal optical phenomena

Memory effects in liquid crystal elastomers

Free-standing monodomain liquid crystal elastomer samples are shown to have a complete memory of the orientational configuration at the time of cross-linking. This memory is demonstrated through samples in which the parent polymer system is first aligned in a magnetic field prior to cross-linking. These films show reversible nematic-isotropic phase transitions and x-ray scattering patterns characteristic of nematic phases. The liquid crystal elastomer films exhibit a remarkable memory effect, in that the sample may be held at temperatures well above the nematic-isotropic transition for extended periods ( > 2 weeks), but on cooling into the liquid crystal phase region, both the original director alignment and the degree of preferred orientation are recovered. It is demonstrated that these novel memory effects are equilibrium in nature. The origins of this phenomena in terms of coupling between the mesogenic side-chains and the polymer network are discussed.

Coupling between mesogenic units and polymer backbone in side-chain liquid crystal polymers and elastomers

The levels of alignment of the mesogenic units and of the polymer backbone trajectory for polyacrylate based nematic side-chain liquid crystal polymers and elastomers were evaluated by using wide angle X-ray and small angle neutron scattering procedures. The X-ray scattering measurements show that substantial levels of preferred orientation of the mesogenic units may be introduced through magnetic fields for uncrosslinked polymers and through mechanical extension for liquid crystal elastomers. Small angle neutron scattering measurements show that for highly aligned samples an anisotropic polymer backbone trajectory is observed in which the envelope is slightly extended by ∼ 10% in the direction parallel to the axis of alignment of the mesogenic units. The sense of this coupling differs from that recorded for other uncrosslinked side-chain liquid crystal polymers. Possible mechanisms to account for this anisotropy and its relationship to the properties of liquid crystal elastomers are discussed. The observed deformation behaviour of the liquid crystal elastomer is non-affine and this appears to confirm the dominating influence of the liquid crystal order of the side chains on the mechanical properties of these novel networks.

Biaxial optical properties of thermotropic random copolyesters

The optical microstructures of thin sections of two liquid crystalline polymers are examined in the polarizing microscope. The polymers are random copolyesters based on hydroxybenzoic and hydroxynaphthoic acids (B-N), and hydroxybenzoic acid and ethylene terephthalate (B-ET). Sections cut from oriented samples, so as to include the extrusion direction, show microstructures in which there is no apparent preferred orientation of the axes describing the local optical anisotropy. The absence of preferred orientation in the microstructure, despite marked axial alignment of molecular chain segments as demonstrated by X-Ray diffraction, is interpreted in terms of the polymer having biaxial optical properties. The implication of optical biaxiality is that, although the mesophases are nematic, the orientation of the molecules is correlated about three (orthogonal) axes over distances greater than a micron. The structure is classified as a multiaxial nematic.

Radar scattering from ice aggregates using the horizontally aligned oblate spheroid approximation

The assumed relationship between ice particle mass and size is profoundly important in radar retrievals of ice clouds, but, for millimeter-wave radars, shape and preferred orientation are important as well. In this paper the authors first examine the consequences of the fact that the widely used ‘‘Brown and Francis’’ mass–size relationship has often been applied to maximumparticle dimension observed by aircraftDmax rather than to the mean of the particle dimensions in two orthogonal directions Dmean, which was originally used by Brown and Francis. Analysis of particle images reveals that Dmax ’ 1.25Dmean, and therefore, for clouds for which this mass–size relationship holds, the consequences are overestimates of ice water content by around 53% and of Rayleigh-scattering radar reflectivity factor by 3.7 dB. Simultaneous radar and aircraft measurements demonstrate that much better agreement in reflectivity factor is provided by using this mass–size relationship with Dmean. The authors then examine the importance of particle shape and fall orientation for millimeter-wave radars. Simultaneous radar measurements and aircraft calculations of differential reflectivity and dual-wavelength ratio are presented to demonstrate that ice particles may usually be treated as horizontally aligned oblate spheroids with an axial ratio of 0.6, consistent with them being aggregates. An accurate formula is presented for the backscatter cross section apparent to a vertically pointing millimeter-wave radar on the basis of a modified version of Rayleigh–Gans theory. It is then shown that the consequence of treating ice particles as Mie-scattering spheres is to substantially underestimate millimeter-wave reflectivity factor when millimeter-sized particles are present, which can lead to retrieved ice water content being overestimated by a factor of 4.h

Two- and three-dimensional shape fabric analysis by the intercept method in grey levels

The count intercept is a robust method for the numerical analysis of fabrics Launeau and Robin (1996). It counts the number of intersections between a set of parallel scan lines and a mineral phase, which must be identified on a digital image. However, the method is only sensitive to boundaries and therefore supposes the user has some knowledge about their significance. The aim of this paper is to show that a proper grey level detection of boundaries along scan lines is sufficient to calculate the two-dimensional anisotropy of grain or crystal distributions without any particular image processing. Populations of grains and crystals usually display elliptical anisotropies in rocks. When confirmed by the intercept analysis, a combination of a minimum of 3 mean length intercept roses, taken on 3 more or less perpendicular sections, allows the calculation of 3-dimensional ellipsoids and the determination of their standard deviation with direction and intensity in 3 dimensions as well. The feasibility of this quick method is attested by numerous examples on theoretical objects deformed by active and passive deformation, on BSE images of synthetic magma flow, on drawing or direct analysis of thin section pictures of sandstones and on digital images of granites directly taken and measured in the field. (C) 2010 Elsevier B.V. All rights reserved.

Quartz recrystallization regimes, c-axis texture transitions and fluid inclusion reequilibration in a prograde greenschist to amphibolite facies mylonite zone (Ribeira Shear Zone, SE Brazil)

The crystal-plastic behavior of quartz mylonites from the Ribeira Shear Zone (SE Brazil), a major strike-slip structure that was active during a prograde metamorphic phase related to the Neoproterozoic Brasiliano-Pan African Orogeny, was investigated using a multi-method approach. Geothermobarometry results indicate deformational conditions ranging from similar to 300 to similar to 630 degrees C and 500-700 MPa. A strong correlation between mapped metamorphic zones and a dominance of different dynamic recrystallization mechanisms of quartz occurs within the mylonite zone. Bulging recrystallization (BLG) dominates within the chlorite zone between 300 and 410 degrees C, subgrain rotation recrystallization (SGR) operates within the biotite zone from 410 to 520 degrees C, and grain boundary migration recrystallization (GBM) dominates in the garnet zone above 520 degrees C. The development of quartz c-axis textures is mainly governed by temperature and dynamic recrystallization mechanisms. Textures from BLG zone mylonites are characterized by maxima around Z; SGR zone mylonites display single girdles or asymmetric type I crossed girdles; and GBM zone mylonites comprise maxima around Y and intermediate between X and Z. The scarcity or absence of water-bearing fluid inclusions in quartz mylonites from the SGR and GBM zones, which are dominated by carbonic inclusions, suggests water-deficient conditions, whereas BLG zone mylonites are dominated by water-bearing inclusions. This evidence indicates that water was available in the protoliths but has been eliminated with increasing deformation and deformation temperature. No effect of the water content variation on the quartz microstructural and recrystallized grain size evolution was detected, and little influence on c-axis texture development was observed. Most of the fluid inclusion densities were reequilibrated during the shear zone exhumation history, recording a decompression in the range of 300-500 MPa, while microstructural reequilibration effects related to the prograde metamorphism are largely preserved. Fluid inclusion microstructures and densities from two SGR zone samples preserved evidence for a near isothermal compression within the interior of the Ribeira Shear Zone during the prograde metamorphism. (C) 2009 Elsevier B.V. All rights reserved.

Fabrics of pre- and syntectonic granite plutons and chronology of shear zones in the Eastern Borborema Province, NE Brazil

We used the fabrics of two granite plutons and U/Pb (SHRIMP) zircon ages to constrain the tectonic evolution of the E-trending Patos shear zone (Borborema Province, NE Brazil). The pre-tectonic Teixeira batholith consists of an amphibole leucogranite locally with aegirine-augite. Zircons from a syenogranite yielded crystallization ages of 591 +/- 5 Ma. The batholith fabrics were determined by anisotropy of magnetic susceptibility (AMS) and mineral shape preferred orientation. The fabrics support pre-transcurrent batholith emplacement, as evidenced by: (i) magmatic/magnetic fabrics in low susceptibility (<0.35 mSI) leucogranites highly discordant to the regional host rock structure, and (ii) concordant magnetic fabrics restricted to high susceptibility (>1 mSI) corridors connected to shear zones branching off from Patos. One of these satellite shear zones controlled the syntectonic emplacement of the Serra Redonda pluton, which yields a crystallization age of 576 +/- 3 Ma. This late shearing event marks the peak regional deformation that, south of Patos, was coupled to crustal shortening nearly perpendicular to the shear belt. The chronology of the deformational events indicates that the major shear zones of the eastern Borborema are late structures active after the crustal blocks amalgamated. (C) 2007 Elsevier Ltd. All rights reserved.

Synthesis of L1(0) Fe-Pd films by electrodeposition and thermal annealing

Fe-Pd alloy films have been prepared by electrochemical deposition from an alkaline electrolyte containing Fe sulfate, Pd chloride and 5-sulfosalicylic acid onto polycrystalline titanium substrates. The as-deposited films were nanocrystalline and magnetically soft (coercivity similar to 25 Oe). L1(0) Fe-Pd films with a (111) preferred orientation were obtained by post-deposition thermal annealing of films with composition about 37 at% Fe in an (Ar + 5% H-2) gas flow at 500 degrees C. Such films exhibit hard magnetic properties, with a coercivity up to 1880 Oe, and a slightly anisotropic magnetic response, with a larger in-plane remanence. Preliminary magnetic investigations support magnetization switching through pinning of domain walls. (c) 2008 Elsevier B.V. All rights reserved.

Influence of oxygen flow on crystallization and morphology of LiNbO3 thin films

Polymeric precursor solution (Pechini method) was used to deposit LiNbO3 thin films by spin-coating on (100) silicon substrates. X-ray diffraction data of thin films showed that the increase of oxygen flow promotes a preferred orientation of (001) LiNbO3 planes parallel to the substrate surface. Surface roughness and grain size, observed by atomic force microscopy, change also with oxygen flow.

Retention Characteristics of CBTi144 Thin Films Explained by Means of X-Ray Photoemission Spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Control of retention and fatigue-free characteristics in CaBi4Ti4O15 thin films prepared by chemical method

Ferroelectric CaBi4Ti4O15 (CBTi144) thin films were deposited on Pt/Ti/SiO2/Si substrates by the polymeric precursor method. The films present a single phase of layered-structured perovskite with polar axis orientation after annealing at 700 degrees C for 2 h in static air and oxygen atmosphere. The a/b-axis orientation of the ferroelectric film is considered to be associated with the preferred orientation of the Pt bottom electrode. It is noted that the films annealed in static air showed good polarization fatigue characteristics at least up to 10(10) bipolar pulse cycles and excellent retention properties up to 10(4) s. on the other hand, oxygen atmosphere seems to be crucial in the decrease of both, fatigue and retention characteristics of the capacitors. Independently of the applied electric field, the retained switchable polarization approached a nearly steady-state value after a retention time of 10 s. (C) 2006 Elsevier B.V. All rights reserved.

Study of the growth process of in situ polyaniline deposited films

Polyaniline (PAni) thin films were deposited onto BK7 glass substrates using the in situ deposition technique. The control of the time and the aniline concentration in the PAni polymerization reaction on the film deposition allowed us to prepare films with different thickness, down to similar to 25 nm. The film growth process was monitored by measuring the UV-vis spectra and the AFM height profiles of the film surface. The curves of adsorption kinetics were analyzed with the Avrami's model, yielding an exponent it n = 3, thus indicating nucleation of spheroids at the initial stages of polymerization that grow through a diffusion process. AFM images of the surface height profiles corroborate this hypothesis, with spheroids growing with no preferred orientation during the in situ deposition. (C) 2007 Elsevier B.V. All rights reserved.

Indium tin oxide films prepared via wet chemical route

In this work, indium tin oxide (ITO) films were prepared using a wet chemical route, the Pechini method. This consists of a polyesterification reaction between an alpha-hydroxicarboxylate complex (indium citrate and tin citrate) with a polyalcohol (ethylene glycol) followed by a post annealing at 500 degrees C. A 10 at.% of doping of Sn4+ ions into an In2O3 matrix was successfully achieved through this method. In order to characterize the structure, the morphology as well as the optical and electrical properties of the produced ITO films, they were analyzed using different experimental techniques. The obtained films are highly transparent, exhibiting transmittance of about 85% at 550 nm. They are crystalline with a preferred orientation of [222]. Microscopy discloses that the films are composed of grains of 30 nm average size and 0.63 nm RMS roughness. The films' measured resistivity, mobility and charge carrier concentration were 5.8 x 10(-3) Omega cm, 2.9 cm(2)/V s and -3.5 x 10(20)/cm(3), respectively. While the low mobility value can be related to the small grain size, the charge carrier concentration value can be explained in terms of the high oxygen concentration level resulting from the thermal treatment process performed in air. The experimental conditions are being refined to improve the electrical characteristics of the films while good optical, chemical, structural and morphological qualities already achieved are maintained. (C) 2007 Elsevier B.V. All rights reserved.