Fabrication, patterning, and optical properties of nanocrystalline YVO4 : A (A = Eu3+, Dy3+, Sm3+, Er3+) phosphor films via sol-gel soft lithography

Nanocrystalline YVO4:A (A = Eu3+, Dy3+, Sm3+, Er3+) phosphor films and their patterning were fabricated by a Pechini sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), atomic force microscopy (AFM) and optical microscopy, UV/vis transmission and absorption spectra, photoluminescence (PL) spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 400 degreesC and the crystallinity increased with the increase of annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of grains with an average size of 90 nm. Patterned gel and crystalline phosphor film bands with different widths (5-60 mum) were obtained. Significant shrinkage and a few defects were observed in the patterned films during the heat treatment process. The doped rare earth ions (A) showed their characteristic emission in crystalline YVO4 phosphor films because of an efficient energy transfer from vanadate groups to them. The Sm3+ and Er3+ ions also showed upconversion luminescence in a YVO4 film host. Both the lifetimes and PL intensity of the rare earth ions increased with increasing annealing temperature from 400 to 800 degreesC, and the optimum concentration for Eu3+ was determined to be 7 mol % and those for Dy3+, Sm3-, and Er3+ were 2 Mol % of Y3- in YVO4 films, respectively.

Preparation, characterization and luminescent properties of MCM-41 type materials impregnated with rare earth complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.

Synthesis and luminescence properties of organic-inorganic hybrid thin films doped with Eu(III)

In this study, silica-based transparent organic-inorganic hybrid films were prepared by the sol-gel method. Tetraethoxysilane and 3-(trimethoxysilyl)propyl methacrylate were used as the inorganic and organic compounds, respectively. Lanthanide complexes [Eu(phen)(2)]Cl-3 were incorporated into the organically modified silicates (ORMOSIL) and the luminescence properties of the resultant hybrid films (ORMOSIL:[Eu(phen)(2)]Cl-3) were characterized. The relative quantum efficiency was observed higher and the lifetimes were longer in hybrid films than those in pure silica films. Furthermore, thermal stability of hybrid films incorporating various concentration of Eu(III) complex was studied. (C) 2001 Elsevier Science B.V. All rights reserved.

Synthesis, characterization, and photophysical properties of rare earth complexes of N-phenyl-2-aminobenzoic acid and 1,10-phenanthroline

Some novel binary and ternary complexes of rare earth ions (Gd, Eu, Tb) with N-phenyl-2-aminobenzoic acid and 1,10-phenanthroline were synthesized by homogenous precipitation and characterized by elemental analysis, IR spectra, UV/Vis spectra, and thermal analysis. The phosphorescence spectra and lifetimes of gadolinium complexes were measured, and the triplet state energies of N-phenyl-2-aminobenzoic acid and 1,10-phenanthroline as well as the energy transfer efficiencies between N-phenyl-2-aminobenzoic acid and 1,10-phenanthroline were determined. The photophysical properties such as luminescence and intramolecular energy transfer between the rare earth center ions and the ligands and between ligands are discussed.

Effects of the compatibilizer PP-g-GMA on morphology and mechanical properties of PP/PC blends

Effects of the compatibilizer polypropylene grafted with glycidyl methacrylate(PP-g-GMA) on the morphology, thermal, rheological and mechanical properties of polypropylene and polycarbonate blends (PP/PC) were studied. It was found that the addition of PP-g-GMA significantly changed their morphology. The mean size of domains reduced from 20 mu m to less than 5 mu m. The dispersed domain size is also strongly dependent upon the content of PP-g-GMA. The interfacial tension of PP/PC/PP-g-GMA (50/30/20) is only about one-tenth of PP/PC (70/30). The crystallization temperature of PP in PP/PC/PP-g-GMA is 5-8 degrees C higher than that of PP in PP/PC blends. Characterization studies based on mechanical properties, differential scanning calorimetry, rheology and morphological evidence obtained by using scanning electron microscopy support the hypothesis that an in-situ copolymer PP-g-PC was formed during the blending process. (C) 1997 Elsevier Science Ltd.

Morphology and mechanical properties of PP/HMWPE blends

Mechanical properties and morphology of blends of polypropylene (PP) with high molecular weight polyethylene (HMWPE) prepared by coprecipitation from xylene solution are investigated. Compared to blends of PP with commercial high-density polyethylene (HDPE), the mechanical properties of the blends of PP/HMWPE are much superior to those of PP/HDPE blends. Not only is the tensile strength stronger, but also the elongation at break is much higher than that of the PP/HDPE blends of the same composition. These differences increase with increasing HMWPE and HDPE content. Scanning electron microscopy of the fracture surface resulting from the tensile tests shows that the compatibility in PP/HMWPE blends is much better than that in PP/HDPE blends. This is most likely attributable to the enhanced chain entanglement of HMWPE with the PP in the amorphous phase due to the lower crystallinity, owing to the high molecular weight of the HMWPE, and a much more flexible chain. The thermal behavior and spherulite morphology of both blends are also investigated.

Effective elastic properties of piezoelectric composites with radially polarized cylinders

Effective elastic properties of piezoelectric composites containing an infinitely long, radially polarized cylinder embedded in an isotropic non-piezoelectric matrix are theoretically investigated under an external strain field. Analytical solutions of elastic displacement and electric potentials are exactly derived, and the effective elastic responses are formulated in the dilute limit. Meanwhile, a vanishing piezoelectric response mechanism is revealed in the piezoelectric composite containing radially polarized cylinders. Furthermore, it is shown that the effective elastic properties can be enhanced (or reduced) due to the increase of the piezoelectric (or dielectric) constants of the cylinders. (C) 2009 Elsevier B.V. All rights reserved.

Heat capacity enhancement and thermodynamic properties of nanostructured amorphous SiO2

The heat capacity of nanostructured amorphous SiO2 (na-SiO2) has been measured by adiabatic calorimetric method over the temperature range 9-354 K. TG and differential scanning calorimeter (DSC) were also employed to determine the thermal stability. Glass transition temperature (T-g) for the two same grain sizes with different specific surface of naSiO(2) samples and one coarse-grained amorphous SiO2 (ca-SiO2) sample were determined to be 1377, 1397 and 1320 K, respectively. The low temperature experimental results show that there are significant heat capacity (C-P) enhancements among na-SiO2 samples and ca-SiO2. Entropy, enthalpy, Gibbs free energy and Debye temperature (theta (D)) were obtained based on the low temperature heat capacity measurement of na-SiO2. The Cp enhancements of na-SiO2 were discussed in terms of configurational and vibrational entropy. (C) 2001 Elsevier Science B.V. All rights reserved.

Nanotopography-induced changes in focal adhesions, cytoskeletal organization, and mechanical properties of human mesenchymal stem cells.

The growth of stem cells can be modulated by physical factors such as extracellular matrix nanotopography. We hypothesize that nanotopography modulates cell behavior by changing the integrin clustering and focal adhesion (FA) assembly, leading to changes in cytoskeletal organization and cell mechanical properties. Human mesenchymal stem cells (hMSCs) cultured on 350 nm gratings of tissue-culture polystyrene (TCPS) and polydimethylsiloxane (PDMS) showed decreased expression of integrin subunits alpha2, alpha , alpha V, beta2, beta 3 and beta 4 compared to the unpatterned controls. On gratings, the elongated hMSCs exhibited an aligned actin cytoskeleton, while on unpatterned controls, spreading cells showed a random but denser actin cytoskeleton network. Expression of cytoskeleton and FA components was also altered by the nanotopography as reflected in the mechanical properties measured by atomic force microscopy (AFM) indentation. On the rigid TCPS, hMSCs on gratings exhibited lower instantaneous and equilibrium Young's moduli and apparent viscosity. On the softer PDMS, the effects of nanotopography were not significant. However, hMSCs cultured on PDMS showed lower cell mechanical properties than those on TCPS, regardless of topography. These suggest that both nanotopography and substrate stiffness could be important in determining mechanical properties, while nanotopography may be more dominant in determining the organization of the cytoskeleton and FAs.

Role of light and photophysiological properties on phytoplankton succession during the spring bloom in the north-western Mediterranean Sea

This study aimed to determine the role of light on the succession of the phytoplankton community during the spring bloom in the northwestern Mediterranean Sea. To this end, three successive Lagrangian experiments were carried out between March and April 2003. The three experiments correspond to distinct phases of the bloom development (pre-bloom, bloom peak and post-bloom, respectively) and therefore to different trophic conditions. Phytoplankton (sampled on a daily scale) was grouped in size-based classes (pico and nano+micro) each of them were characterised in terms of chemotaxonomic composition, primary production and photophysiological properties. The phytoplankton community evolved with time changing in both size-class dominance and specie/group dominance within each size class. The bloom peak was characterised by highly dynamic condition (i.e. vertical mixing) and by the dominance of both small (pico) and large (nano and micro) diatoms, as a result of their capacity to photoacclimate to changing light regimes (‘physiological plasticity’). Concluding, we suggest that the physiological adaptation to light is the main factor driving the succession of the phytoplankton community during the first phases of the bloom (until the onset of thermal stratification) in the western Mediterranean Sea.

Poly(epsilon-caprolactone) and poly(epsilon-caprolactone)-polyvinylpyrrolidone-iodine blends as ureteral biomaterials: characterisation of mechanical and surface properties, degradation and resistance to encrustation in vitro.

This study describes the physicochemical properties and in vitro resistance to encrustation of solvent cast films composed of either poly(epsilon-caprolactone) (PCL), prepared using different ratios of high (50,000) to low (4000) (molecular weight) m.wt., or blends of PCL and the polymeric antimicrobial complex, poly(vinylpyrrolidone)-iodine (PVP-I). The incorporation of PVP-I offered antimicrobial activity to the biomaterials. Films were characterised in terms of mechanical (tensile analysis, dynamic mechanical thermal analysis) and surface properties (dynamic contact angle analysis, scanning electron microscopy), whereas degradation (at 37degreesC in PBS at pH 7.4) was determined gravimetrically. The resistance of the films to encrustation was evaluated using an in vitro encrustation model. Reductions in the ratio of high:low-m.wt. PCL significantly reduced the ultimate tensile strength, % elongation at break and the advancing contact angle of the films. These effects were attributed to alterations in the amorphous content and the more hydrophilic nature of the films. Conversely, there were no alterations in Young's modulus, the viscoelastic properties and glass-transition temperature. Incorporation of PVP-I did not affect the mechanical or rheological properties of the films, indicative of a limited interaction between the two polymers in the solid state. Manipulation of the high:low m.wt. ratio of PCL significantly altered the degradation of the films, most notably following longer immersion periods, and resistance to encrustation. Accordingly, maximum degradation and resistance to encrustation was observed with the biomaterial composed of 40:60 high:low m.wt. ratios of PCL; however, the mechanical properties of this system were considered inappropriate for clinical application. Films composed of either 50:50 or 60:40 ratio of high:low m.wt. PCL offered an appropriate compromise between physicochemical properties and resistance to encrustation. This study has highlighted the important usefulness of degradable polymer systems as ureteral biomaterials

Relative energetics and structural properties of zirconia using a self-consistent tight-binding model

We describe an empirical, self-consistent, orthogonal tight-binding model for zirconia, which allows for the polarizability of the anions at dipole and quadrupole levels and for crystal field splitting of the cation d orbitals, This is achieved by mixing the orbitals of different symmetry on a site with coupling coefficients driven by the Coulomb potentials up to octapole level. The additional forces on atoms due to the self-consistency and polarizabilities are exactly obtained by straightforward electrostatics, by analogy with the Hellmann-Feynman theorem as applied in first-principles calculations. The model correctly orders the zero temperature energies of all zirconia polymorphs. The Zr-O matrix elements of the Hamiltonian, which measure covalency, make a greater contribution than the polarizability to the energy differences between phases. Results for elastic constants of the cubic and tetragonal phases and phonon frequencies of the cubic phase are also presented and compared with some experimental data and first-principles calculations. We suggest that the model will be useful for studying finite temperature effects by means of molecular dynamics.

Acoustic, volumetric, compressibility and refractivity properties and Flory’s reduction parameters of some homologous series of alkyl alkanoates from 298.15 to 333.15 K

The speeds of sound u in, densities ? and refractive indices nD of some homologous series, such as n-alkyl ethanoates, n-alkyl propionates, methyl alkanoates, ethyl alkanoates, dialkyl malonates, and alkyl haloalkanoates, were measured in the temperature range from 298.15 to 333.15 K. Molar volume V, isentropic and isothermal compressibilities ?S and ?T, molar refraction Rm, Eykman’s constant Cm, molecular radius r, Rao’s molar function R, thermal expansion coefficient a, thermal pressure coefficient ?, and Flory’s characteristic parameters image, P*, V*, and T* have been calculated from the measured experimental data. Applicability of Rao theory and Flory–Patterson–Pandey (FPP) theory have been examined and discussed for these alkanoates.

Acoustic, volumetric, compressibility and refractivity properties and reduction parameters for the ERAS and Flory models of some homologous series of amines from 298.15 to 328.15 K

The speeds of sound u, densities ? and refractive indices nD of homologous series of mono-, di-, and tri-alkylamines were measured in the temperature range from 298.15 to 328.15 K. Isentropic and isothermal compressibilities ?S and ?T, molar refraction Rm, Eykman’s constant Cm, Rao’s molar sound function R, thermal expansion coefficient a, thermal pressure coefficient ?, and reduction parameters P*, V*, and T* in frameworks of the ERAS model for associated amines and Flory model for tertiary amines have been calculated from the measured experimental data. Applicability of the Rao theory and the ERAS and Flory models have been examined and discussed for the alkyl amines.

Bond and Interfacial Properties of Reinforcement in Self-Compacting Concrete

This paper reports a study carried out to assess the impact of the use of self-compacting concrete (SCC) on bond and interfacial properties around steel reinforcement in practical concrete element. The pull-out tests were carried out to determine bond strength between reinforcing steel bar and concrete, and the depth-sensing nano-indentation technique was used to evaluate the elastic modulus and micro-strength of the interracial transition zone (ITZ) around steel reinforcement. The bond and interracial properties around deformed steel bars in different SCC mixes with strength grades of 35 MPa and 60 MPa (C35, C60) were examined together with those in conventional vibrated reference concrete with the same strength grades. The results showed that the maximum bond strength decreased when the diameter of the steel bar increased from 12 to 20 mm. The normalised bond strengths of the SCC mixes were found to be about 10-40% higher than those of the reference mixes for both bar diameters (12 and 20 mm). The study of the interfacial properties revealed that the elastic modulus and the micro-strength of the ITZ were lower on the bottom side of a horizontal steel bar than on the top side, particularly for the vibrated reference concrete. The difference of ITZ properties between top and bottom side of the horizontal steel bar appeared to be less pronounced for the SCC mixes than for the corresponding reference mixes.