Homeotropic surface anchoring and the layer-thinning transition in free-standing films

In this work, we investigate the interplay between surface anchoring and finite-size effects on the smectic-isotropic transition in free-standing smectic films. Using an extended McMillan model, we study how a homeotropic anchoring stabilizes the smectic order above the bulk transition temperature. In particular, we determine how the transition temperature depends on the surface ordering and film thickness. We identify a characteristic anchoring for which the transition temperature does not depend on the film thickness. For strong surface ordering, we found that the thickness dependence of the transition temperature can be well represented by a power-law relation. The power-law exponent exhibits a weak dependence on the range of film thicknesses, as well as on the molecular alkyl tail length. Our results reproduce the main experimental findings concerning the layer-thinning transitions in free-standing smectic films.

Growth and capping of InAs/GaAs quantum dots investigated by x-ray Bragg-surface diffraction

An x-ray diffraction method, based on the excitation of a surface diffracted wave, is described to investigate the capping process of InAs/GaAs (001) quantum dots (QDs). It is sensitive to the tiny misorientation of (111) planes at the surface of the buffer layer on samples with exposed QDs. After capping, the misorientation occurs in the cap-layer lattice faceting the QDs and its magnitude can be as large as 10 degrees depending on the QDs growth rates, probably due to changes in the size and shape of the QDs. A slow strain release process taking place at room temperature has also been observed by monitoring the misorientation angle of the (111) planes.

In-field Mossbauer study of disordered surface spins in core/shell ferrite nanoparticles

Magnetization and Mossbauer spectroscopy measurements are performed at low temperature under high field, on nanoparticles with a nickel ferrite core and a maghemite shell. These nanoparticles present finite size and surface effects, together with exchange anisotropy. High field magnetization brings the evidences of a monodomain ordered core and surface spins freezing in disorder at low temperature. Mossbauer spectra at 4.2 K present an extra contribution from the disordered surface which is field dependent. Field and size dependences of this latter show a progressive spin alignment along the ferrite core which is size dependent. The weak surface pinning condition of the nanoparticles confirms that the spin disorder is localized in the external shell. The underfield decrease in the mean canting angle in the superficial shell is then directly related to the unidirectional exchange anisotropy through the interface between the ordered core and the disordered shell. The obtained anisotropy field H(Ea) scales as the inverse of the nanoparticle diameter, validating its interfacial origin. The associated anisotropy constant K(Ea) equals 2.5 x 10(-4) J/m(2). (C) 2009 American Institute qf Physics. [doi: 10.1063/1.3245326]

Transition-metal 13-atom clusters assessed with solid and surface-biased functionals

First-principles density-functional theory studies have reported open structures based on the formation of double simple-cubic (DSC) arrangements for Ru(13), Rh(13), Os(13), and Ir(13), which can be considered an unexpected result as those elements crystallize in compact bulk structures such as the face-centered cubic and hexagonal close-packed lattices. In this work, we investigated with the projected augmented wave method the dependence of the lowest-energy structure on the local and semilocal exchange-correlation (xc) energy functionals employed in density-functional theory. We found that the local-density approximation (LDA) and generalized-gradient formulations with different treatment of the electronic inhomogeneities (PBE, PBEsol, and AM05) confirm the DSC configuration as the lowest-energy structure for the studied TM(13) clusters. A good agreement in the relative total energies are obtained even for structures with small energy differences, e. g., 0.10 eV. The employed xc functionals yield the same total magnetic moment for a given structure, i.e., the differences in the bond lengths do not affect the moments, which can be attributed to the atomic character of those clusters. Thus, at least for those systems, the differences among the LDA, PBE, PBEsol, and AM05 functionals are not large enough to yield qualitatively different results. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3577999]

Surface effects in the magnetic properties of crystalline 3 nm ferrite nanoparticles chemically synthesized

We have systematically studied the magnetic properties of ferrite nanoparticles with 3, 7, and 11 nm of diameter with very narrow grain size distributions. Samples were prepared by the thermal decomposition of Fe (acac)(3) in the presence of surfactants giving nanoparticles covered by oleic acid. High resolution transmission electron microscopy (HRTEM) images and XRD diffraction patterns confirms that all samples are composed by crystalline nanoparticles with the spinel structure expected for the iron ferrite. ac and dc magnetization measurements, as well in-field Mossbauer spectroscopy, indicate that the magnetic properties of nanoparticles with 11 and 7 nm are close to those expected for a monodomain, presenting large M(S) (close to the magnetite bulk). Despite the crystalline structure observed in HRTEM images, the nanoparticles with 3 nm are composed by a magnetically ordered region (core) and a surface region that presents a different magnetic order and it contains about 66% of Fe atoms. The high saturation and irreversibility fields in the M(H) loops of the particles with 3 nm together with the misalignment at 120 kOe in the in-field Mossbauer spectrum of surface component indicate a high surface anisotropy for the surface atoms, which is not observed for the core. For T < 10 K, we observe an increase in the susceptibility and of the magnetization for former sample, indicating that surface moments tend to align with applied field increasing the magnetic core size. (C) 2010 American Institute of Physics. [doi:10.1063/1.3514585]

Reconstruction of core and surface nanoparticles: The example of Pt(55) and Au(55)

Cuboctahedron (CUB) and icosahedron (ICO) model structures are widely used in the study of transition-metal (TM) nanoparticles (NPs), however, it might not provide a reliable description for small TM NPs such as the Pt(55) and Au(55) systems in gas phase. In this work, we combined density-functional theory calculations with atomic configurations generated by the basin hopping Monte Carlo algorithm within the empirical Sutton-Chen embedded atom potential. We identified alternative lower energy configurations compared with the ICO and CUB model structures, e. g., our lowest energy structures are 5.22 eV (Pt(55)) and 2.01 eV (Au(55)) lower than ICO. The energy gain is obtained by the Pt and Au diffusion from the ICO core region to the NP surface, which is driven by surface compression (only 12 atoms) on the ICO core region. Therefore, in the lowest energy configurations, the core size reduces from 13 atoms (ICO, CUB) to about 9 atoms while the NP surface increases from 42 atoms (ICO, CUB) to about 46 atoms. The present mechanism can provide an improved atom-level understanding of small TM NPs reconstructions.

Particle size effect on abrasion resistance of mottled cast iron with different retained austenite contents

Effects of particle abrasive sizes on wear resistance of mottled cast iron with different retained austenite contents were studied. Abrasive wear tests using a pin test on alumina paper were carried out, using abrasive sizes between 16 mu m and 192 mu m. Retained austenite content of the matrix was determined by X-ray diffraction. The wear surface of samples and the alumina paper were examined by scanning electron microscopy for identifying the wear micromechanism. The results show that at lower abrasive sizes the mass loss was similar for the iron with different austenite contents. However, at higher abrasive sizes the samples with higher retained austenite content presented higher abrasion resistance. For lower abrasive sizes tested, samples with higher and lower retained austenite content both presented microcutting. On the other hand, the main wear micromechanism for the samples with higher retained austenite content and higher abrasive sizes was microploughing. The samples with lower retained austenite content presented microcutting and wedge formation at higher abrasive sizes. Higher abrasive size induced more microcutting in samples with lower retained austenite. The iron with lower retained austenite content presented wider grooves for the different abrasive sizes measured. SEM on the abrasive paper used on samples with higher retained austenite showed continuous and discontinuous microchips and the samples with lower retained austenite showed discontinuous microchips at 66 and 141 mu m. This research demonstrates the relation between abrasive size, wear resistance, groove width and wear micromechanism for mottled cast iron with different retained austenite contents. (C) 2009 Elsevier B.V. All rights reserved.

Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO(2) nanoparticles using Raman spectroscopy

Ni-doped SnO(2) nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO(2) nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A(1g) mode with the Ni content, a solubility limit at similar to 2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above similar to 2 mol% Ni, the redshift of A(1g) mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright (C) 2010 John Wiley & Sons, Ltd.

Quantification of MgO surface excess on the SnO(2) nanoparticles and relationship with nanostability and growth

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO(2) nanoparticles plays an important role in the system`s energetics and stability. Using Xray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO(2) with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO(2) nanoparticles stability. (C) 2010 Elsevier B.V. All rights reserved.

Single step process for particles surface modification or thin film composite production

Adsorbent materials and composites are quite useful for sensor development. Therefore, the aim of this work is the surface modification of particulates and/or composite formation. The material was produced by plasma polymerization of HMDS (hexamethyldisilazane) in a single step. SEM analysis shows good surface coverage of particulates with a plasma polymerized film formed by several clusters that might increase adsorption. Particles (starch. 5 5 mu m) recovered with HMDS films show good properties for retention of medium-size Organic molecules, such as dye. Thin films formed by a mixture of particles and plasma polymerized thin film HMDS species were obtained in a single step and can be used for retention of organic compounds, in liquid or gaseous phase. (C) 2009 Elsevier B.V. All rights reserved.

Surface modification of bovine bone ash prepared by milling and acid washing process

Bovine bone ash is the main raw material for fabrication of bone china, a special kind of porcelain that has visual and mechanical advantages when compared to usual porcelains. The properties of bone china are highly dependent on the characteristics of the bone ash. However, despite a relatively common product, the science behind formulations and accepted fabrication procedures for bone china is not completely understood and deserves attention for future processing optimizations. In this paper, the influence of the preparation steps (firing, milling, and washing of the bones) on the physicochemical properties of bone ash particles was investigated. Bone powders heat-treated at temperatures varying from 700 to 1000 degrees C were washed and milled. The obtained materials were analyzed in terms of particle size distribution, chemical composition, density, specific surface area, FTIR spectroscopy, dynamic electrophoretic mobility, crystalline phases and scanning electron microscopy. The results indicated that bone ash does not significantly change in terms of chemistry and physical features at calcination temperatures above 700 degrees C. After washing in special conditions, one could only observe hydroxyapatite in the diffraction pattern. By FTIR it was observed that carbonate seems to be mainly concentrated on the surface of the powders. Since this compound can influence in the dispersion stability, and consequently in the quality of the final bone china product, and considering optimal washing parameters based on the dynamic electrophoretic mobility results, we describe a procedure for surface cleaning. (c) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Physical Stability Assessment and Sensory Optimization of a Dairy-Free Emulsion Using Response Surface Methodology

Desserts made with soy cream, which are oil-in-water emulsions, are widely consumed by lactose-intolerant individuals in Brazil. In this regard, this study aimed at using response surface methodology (RSM) to optimize the sensory attributes of a soy-based emulsion over a range of pink guava juice (GJ: 22% to 32%) and soy protein (SP: 1% to 3%). WHC and backscattering were analyzed after 72 h of storage at 7 degrees C. Furthermore, a rating test was performed to determine the degree of liking of color, taste, creaminess, appearance, and overall acceptability. The data showed that the samples were stable against gravity and storage. The models developed by RSM adequately described the creaminess, taste, and appearance of the emulsions. The response surface of the desirability function was used successfully in the optimization of the sensory properties of dairy-free emulsions, suggesting that a product with 30.35% GJ and 3% SP was the best combination of these components. The optimized sample presented suitable sensory properties, in addition to being a source of dietary fiber, iron, copper, and ascorbic acid.

Biophysical characterization of the recombinant merozoite surface protein-3 of Plasmodium vivax

Plasmodium vivax Merozoite Surface Protein-3 alpha and 3 beta are members of a family of related merozoite surface proteins that contain a central alanine-rich domain with heptad repeats that is predicted to form alpha-helical secondary and coiled-coil tertiary structures. Seven recombinant proteins representing different regions of MSP-3 alpha and MSP-3 beta of P. vivax were generated to investigate their structure. Circular dichroism spectra analysis revealed that some proteins are folded with a high degree of alpha-helices as secondary structure, whereas other products contain a high content of random coil. Using size exclusion chromatography, we found that the two smaller fragments of the MSP-3 alpha, named CC4 and CC5, predicted to form coiled-coil (CC) structures, eluted at volumes corresponding to molecular weights larger than their monomeric masses. This result suggests that both proteins are oligomeric molecules. Analytical ultracentrifugation experiments showed that the CC5 oligomers are elongated molecules. Together, these data may help to understand important aspects of P. vivax biology. (C) 2008 Elsevier B.V. All rights reserved.

Two novel reports of semidry stigmatic surface in Asteraceae

Research documents related to the morphology and function of style branches and stigmatic surface of Asteraceae are still rather few, and the literature reports are thus controversial. We report in the present study that the stigmatic surfaces of two non-related species of Asteraceae (Lessingianthus grandiflorus and Lucilia lycopodioides) have features of semidry stigmas. Sporodermis of both species was also analyzed so that we could understand how the stigmatic surface works during pollen deposition and rehydration. Stylar branches and pollen grains (sporodermis) were studied using scanning and transmission electron microscopy (SEM and TEM) and histochemistry techniques. The inner and marginal bands of stylar branches in these species display intermediary features between the dry and wet types of stigma: the cuticle characterizes the dry stigma and cells with secretory activity characterize the wet stigma; these showed differences from what has been described to the Asteraceae family, where stigmatic surface of species from several tribes is considered dry. Pollen grains are medium-size to large with exine ornamentation (echinate and echinolophate) and abundant secretion which latter characterizes pollenkitt. We can assume that two processes might help pollen grain hydration on stigmatic surface in Lessingianthus grandiflorus and Lucilia lycopodioides: (1) the presence of pollenkitt, as observed in the secretory content inside exine cavities and around pollen grains; and (2) the secretory activity of stigmatic surface cells, whose secretion accumulates among intercellular and subcuticular spaces and leads to cuticle disruption during the floral receptive phase. Our results suggest that ultrastructural and histochemical studies should be considered when describing stigmatic surface and that the ""semidry"" feature within Asteraceae should be investigated still more in detail, so that the taxonomic or adaptation value of this trait in the family can be verified. (C) 2010 Elsevier GmbH. All rights reserved.

Biological monitoring of a xenomaterial for grafting: an evaluation in critical-size calvarial defects

Our purpose was to evaluate the osteoconduction potential of mixed bovine bone (MBB) xenografts as an alternative for bone grafting of critical-size defects in the calvaria of rats. After surgery, in the time intervals of 1, 3, 6, and 9 months, rats were killed and their skulls collected, radiographed and histologically prepared for analysis. The data obtained from histological analysis reported that the particles of MBB did not promote an intense immunological response, evidencing its biocompatibility in rats. Our results clearly showed the interesting evidence that MBB was not completely reabsorbed at 9 months while a small amount of newly formed bone was deposited by osteoprogenitor cells bordering the defect. However, this discrete bone-forming stimulation was unable to regenerate the bone defect. Overall, our results suggest that the properties of MBB are not suitable for stimulating intense bone regeneration in critical bone defects in rats.