Voltammetric performance and application of a sensor for sodium ions constructed with layered birnessite-type manganese oxide

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hyperfine interaction in Zn-Al layered double hydroxides intercalated with conducting polymers

Organic-inorganic hybrid materials based on the assembly between inorganic 2D host structure and polymer have received considerable attention in the last few years. This emerging class of materials presents several applications according to their structural and functional properties. Particularly, among others, layered double hydroxides (LDHs) provide the opportunity of preparing new organically modified 2D nanocomposites. Pyrrole carboxylic acid derivatives, namely 4-(lH-pyrrol-1-yl)benzoate, 3-(pyrrol-i-yl)-propanoate,7-(pyrrol-1-yl)-heptanoate, and aniline carboxylic acid derivative, namely 3-aminobenzoic acid, have been intercalated in LDHs of intralamellar composition Zn2Al(OH)(6). The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by powder X-ray diffraction patterns (PXRD), transmission electron microscopy (TEM) thermogravimetric analysis (TGA), and electron spin resonance (ESR). The basal spacing found by the PXRD technique gives evidence of the formation of bilayers of the intercalated anions. ESR spectra present a typical signal with a superhyperfine structure with 6 + 1 lines (g = 2.005 +/- 0.0004), which is assigned to the interaction between a carboxylate radical from the guest molecules and a nearby aluminium nucleus (I = 5/2) from the host structure. Additionally, the ESR data suggest that the monomers are connected to each other in limited number after thermal treatment. (c) 2007 Elsevier Ltd. All rights reserved.

Ferroelectric and piezoelectric properties of bismuth layered thin films grown on (100) Pt electrodes

The effect of film orientation on piezoelectric and ferroelectric properties of bismuth layered compounds deposited on platinum coated silicon substrates was investigated. Piezo-force microscopy was used to probe the local piezoelectric properties of Bi(4)Ti(3)O(12), CaBi(4)Ti(4)O(15) and SrBi(4)Ti(4)O(15) films. Our measurements on individual grains clearly reveal that the local piezoelectric properties are determined by the polarization state of the grain. A piezoelectric coefficient of 65 pm/V was attained after poling in a grain with a polar axis very close to the normal direction. The piezoelectric coefficient and the remanent polarization were larger for a-b axes oriented than for c-axis-oriented films. (c) 2007 Elsevier B.V All rights reserved.

Stabilization of a light bullet in a layered Kerr medium with sign-changing nonlinearity

Using the numerical solution of the nonlinear Schrodinger equation and a variational method, it is shown that (3+1)-dimensional spatiotemporal optical solitons, known as light bullets, can be stabilized in a layered Kerr medium with sign-changing nonlinearity along the propagation direction.

Microstructural and electric properties of bismuth-layered structured ceramics - SrBi2(Ta1-xNbx)O-9

Ceramic samples of SrBi2(Nb1-xTax)O-9 (0 less than or equal to x less than or equal to 1) were prepared by the solid state reaction method in order to investigate their structural and electrical features as well as obtain useful information to improve the properties of SrBi2(Nb1-xTax)O-9 as a thin film. The X-ray diffraction patterns and the scanning electronic microscopy photomicrographs show no secondary phases but the formation of a solid-state solution for all the composition. The ac conductivity of the samples, measured at 25 degreesC and 100 kHz frequency, decreases with the increase of Ta content. Such results were explained by intrinsic conductivity of pure components.

Mechanically activating formation of layered structured bismuth titanate

Bismuth titanatc-Bi(4)Ti(3)O(12) (BIT) with wide application in the electronic industry as capacitors, memory devices and sensors is the simplest compound in the Aurivillius family, which consists of (Bi(2)O(2))(2+) sheets alternating with (Bi(2)T(i)3O(10))(2-) perovskite-like layers. The synthesis of more resistive BIT ceramics would be preferable advance in obtaining of well-densified ceramic with small grains randomly oriented to limit the conductivity along the (Bi(2)O(2))(2+) layers. Having in mind that the conventional ceramic route for the synthesis can lead to non-stoichiometry in composition, in consequence of the undesirable loss in bismuth content through volatilization of Bi(2)O(3) at elevated temperature, our efforts were addressed to preparation of BIT by mechanical activation the constituent oxides. The nucleation and phase formation of BIT, crystal structure, microstructure, powder particle size and specific surface area were followed by XRD, Rietveld refinement analysis, thermal analysis, scanning electron microscopy (SEM) and the BET specific surface area measurements. (c) 2005 Elsevier B.V. All rights reserved.

New layered double hydroxides intercalated with substituted pyrroles. 1. In situ polymerization of 4-(1H-pyrrol-1-yl)benzoate

The two-dimensional hybrid organic-inorganic materials Zn-2-Cr and Zn-2-Al-LDHs (Layered Double Hydroxides) containing 4-(1H-pyrrol-1yl)benzoate anions as the interlayer anions were synthesized by the co-precipitation method at constant pH followed by subsequent hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, ESR, TGA, and TEM. The basal spacing found by the X-ray diffraction technique is coincident with the formation of bilayers of the intercalated anions. Solid-state C-13 NMR and ESR data strongly suggest the partial in situ polymerization of the 4-(1H-pyrrol-1yl)benzoate anions during coprecipitation. (c) 2006 Elsevier Ltd. All rights reserved.

Nature of defects for bismuth layered thin films grown on Pt electrodes

The authors investigated the influence of defects on the piezoelectric and dielectric properties of Bi4Ti3O12 (BIT), SrBi4Ti4O15 (SBTi) and CaBi4Ti4O15 (CBTi144) thin films by x-ray photoemission spectroscopy measurements. In the SBTi film, Sr which is a nonpolarizable ion restricting the movement of Ti4+ ions and thus leads to a low piezoresponse. Meanwhile, the oxygen environment is quite different in the BIT and CBTi144 films exhibiting excellent piezoelectric properties. The piezoelectric coefficient and the dielectric behavior were larger for a-b axis oriented than for c axis-oriented films due to the defects created during the films crystallization. (c) 2007 American Institute of Physics.

Thermal decomposition of crystalline Ni-II-Cr-III layered double hydroxide: A structural study of the segregation process

A structural study of the thermal evolution of Ni0.69Cr0.31(OH)(2)(CO3)(0.155)(.)nH(2)O into NiO and tetragonal NiCr2O4 is reported. The characteristic structural parameters of the two coexisting crystalline phases, as well as their relative abundance, were determined by Rietveld refinement of powder x-ray diffraction (PXRD) patterns. The results of the simulations allowed us to elucidate the mechanism of the demixing process of the oxides. It is demonstrated that nucleation of a metastable nickel chromite within the common oxygen framework of the parent Cr-III-doped bunsenite is the initial step of the cationic redistribution. The role that trivalent cations play in the segregation of crystalline spinels is also discussed.

New layered double hydroxides intercalated with substituted pyrroles. 2. 3-(Pyrrol-1-yl)-propanoate and 7-(pyrrol-1-yl)-heptanoate LDHs

We report the synthesis and characterization of organic-inorganic hybrid materials: Zn-2-Al-LDHs (layered double hydroxides) containing 3-(1H-pyrrol-1-yl)-propanoate and 7-(1H-pyrrol-l-yl)-heptanoate as the interlayer anions. The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, TGA, and ESR. The basal spacing found by PXRD technique is coincident with the formation of bilayers of the intercalated anions. The solid state C-13 NMR showed that the interlayered anions remain identical after intercalation. ESR data suggest that the monomers connect each other in a limited number of guests when a thermal treatment is applied. The inorganic LDH sheets delay the temperature of degradation of the monomers. (c) 2006 Elsevier Ltd. All rights reserved.

Geochronology of the lpanema layered mafic-ultramafic complex, Minas gerais, Brazil: Evidence of extension at the meso-neoproterozoic time boundary

The mafic/ultramafic Ipanema Layered Complex (ILC), Minas Gerais Brazil, consists of seven individual bodies. These units crosscut polyphase orthogneisses and interlayered paragneisses of the Paleoproterozoic Juiz de Fora Complex. Intrusive granitoids tectonically related to [lie Neoproterozoie Aracuai orogen are also present in the study area.A Sm-Nd whole-rock linear array for seven samples metapyoxenites, metaperidotiles, metagabbro. and meta-anorthosite) from the Santa Cruz massif, the largest body of the ILC. suggest that it was emplaced at 1104 +/- 78 Ma the original magma was derived from a depleted mantle source (epsilon(Ndt)= +3.8). U-Pb single-grain zircon stud of a meta-anorthosite yields all upper intercept age of 1719 +/- 4 Ma, which is interpreted to represent inheritance. The lower intercept at 630+/-3 Ma indicates (hat a Neoproterozoic tectonothermal episode overprinted the ILC, this event occurred under upper-amphiolite-, to granulite-facies conditions. The 630 Ma episode is consistent with the timing of regional metamorphism and deformation of the adjacent Aracuai orogen (Brasiliano collage). Emplacement of the ILC and other coeval metamafies and meta-ultramafics (of alkaline affinity) in the re, oil is attributed to early extension tectonics, accompanying accretion of the Rodinia super- continent during the Mesoproterozoic-Neoproterozoic time boundary.

Local Er(III) environment in luminescent titanosilicates prepared from microporous precursors

The local environment of Er3+ ions in microporous titanosilicate ETS-10 and in synthetic narsarsukite and glassy materials obtained by calcination of ETS-10 has been investigated by EXAFS, Raman and photoluminescence spectroscopies. Er L-III-edge EXAFS studies of Er3+-doped ETS-10 support the view that the exchanged Er3+ ions reside close to the (negatively charged) TiO6 octahedra. In ETS-10, Er3+ is partially bonded to framework oxygen atoms and hydration water molecules. The Er...Ti distance (3.3 Angstrom) is similar to the Na...Ti distances (3.15-3.20 Angstrom) reported previously for Na-ETS-10. Although the exact location of the ErO6 units within the host structure of Er3+-doped synthetic narsarsukite is still an open question, it is most likely that Er3+ substitutes Ti4+ rather than Na+ ions. EXAFS spectroscopy indicates that no significant clustering of erbium atoms occurs in the titanosilicate samples studied. Evidence for the insertion of Er3+ ions in the framework of narsarsukite has been obtained by Raman spectroscopy. This is indicated by the increasing full-width at half-maximum (FWHM) of the 775 cm(-1) peak and the increasing intensity of the anatase peaks as the erbium content increases. In addition, as the narsarsukite Er3+ content increases a band at ca. 515 cm(-1) firstly broadens and subsequently a new peak appears at ca. 507 cm(-1).Er3+-doped narsarsukite exhibits a characteristic local vibrational frequency, (h) over bar omega ca. 330 cm(-1), with an electron-phonon coupling, g ca. 0.2, which constitutes additional evidence for framework Er3+ insertion. The number of lines in the infrared emission spectrum of synthetic narsarsukite indicates the presence of two optically-active erbium centres with very similar local environments and an average I-4(13/2) lifetime of 7.8 +/- 0.2 ms.

Dynamical study of ZnO nanocrystal and Zn-HDS layered basic zinc acetate formation from sol-gel route

We have pointed out that zinc based particles obtained from ethanolic solution of a zinc acetate derivative (zinc oxy-acetate, Zn4O(Ac)(6)) are a mixture of nanometer sized ZnO, zinc oxy-acetate, and zinc hydroxide double salt (Zn-HDS). The knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, and the evolution of Zn species in reaction medium was monitored in situ during 14 h by simultaneous measurements of UV-vis absorption and extended X-ray absorption fine structures (EXAFS) spectra. This spectroscopic monitoring was initialized just after the addition of an ethanolic lithium hydroxide solution ([LiOH]/[Zn] = 0. 1) to the reaction medium kept under controlled temperature (40 degrees C). This study points out the first direct evidence of the reaction between ZnO nanoparticles and unreacted zinc oxy-acetate to form a Zn-HDS phase. The dissolution of ZnO and the reprecipitation of Zn-HDS are induced by the gradual release of water mainly produced by ethanol esterification well evidenced by gas chromatography coupled to mass spectroscopy and FT-IR measurements.

Multi-layered LiNbO3 films prepared by a polymeric precursor method

The polymeric precursor method was used to prepare multi-layered LiNbO3 films. The overall process consists of preparing a coating solution from the Pechini process and the deposited film is subsequently heat-treated. Two-layered films were prepared by this process, onto (0001) sapphire substrates. Two different routes were investigated for the heat-treatment. The amorphous route consisted of performing, after each deposition, a pre-treatment at low temperature to eliminate the organic material. In this case, the crystallization heat-treatment was performed only after the two layers had been deposited. on the other hand, a process layer-after-layer crystallization was used. Both routes led to (0001) LiNbO3 oriented films. However, only the film prepared by the layer-after-layer crystallization presented an epitaxial growth and a crack-free morphology. Moreover, the layer-after-layer crystallization process led to a film exhibiting the best optical properties. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Synthesis, characterization and electrochemical study of layered double hydroxides intercalated with 2-thiophenecarboxylate anions

The synthesis, characterization, and electrochemical study of the Zn(II)-Al(III) and Zn(II)-Cr(III) Layered Double Hydroxides (LDHs) containing 2-thiopenecarboxylate as the interlayer anions are described. The LDHs were prepared by the constant pH coprecipitation technique followed by hydrothermal treatment for 72 h. The materials were analyzed by PXRD, FT-IR, C-13 CP-MAS, EDX, TEM, and CV. The presence of the organic heterocyclic anions was confirmed by FT-IR and the related solid-state C-13 NMR data strongly suggested that these were dimerised during coprecipitation. Accordingly, the basal spacing found by the X-ray technique was similar to 15.3 Angstrom, a distance coincident with the formation of bilayers of the intercalated anions. The structural organization of all the new materials was greatly enhanced by hydrothermal treatment, as shown by PXRD. The improved organization of the bilayered structures had a strong influence in the electrochemical behaviour of clay-modified electrodes produced with these materials, such as the diminished resistance to the ionic flow through the LDHs films. (C) 2003 Elsevier Ltd. All rights reserved.