Small-angle X-ray scattering study of gelation and aging of Eu3+-doped sol-gel-derived siloxane-poly(oxyethylene) nanocomposites

The aggregation, gelation, and aging of urea-cross-linked siloxane-poly(oxyethylene) nanohybrids [(U600)-n] containing two different amounts of europium triflate initially dissolved in an ethanol-water mixture were investigated by in situ small-angle X-ray scattering (SAXS). For both low (n = [O]/[Eu] = 80) and high (n = 25) europium contents, the SAXS intensity was attributed to the formation of siloxane clusters of about 8-11 Angstrom in size. Siloxane cluster formation and growth is a rapid process in hybrids with low Eu contents and slow in Eu-rich hybrids. An additional contribution to the scattering intensity at very low angles was attributed to the formation of a coarse structure level. At this secondary level, the structure can be described as a set of dense domains containing siloxane clusters embedded in a depleted matrix composed of unfolded polymer chains and solvent. By fitting a theoretical function for this model to the experimental SAXS curves, relevant structural parameters were determined as functions of time during the sol-gel transition and gel aging. For hybrids with low europium contents (n = 80), the size of the siloxane clusters remains essentially invariant, whereas the dense segregation domains progressively grow. In hybrids with high doping contents (n = 25), the preponderant structure variation during the first stages of the sol-gel transformation is the slow growth of siloxane clusters. For these hybrids, the segregation of siloxane clusters forming dense domains occurs only during advanced stages of the process.

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.

Montmorillonite (MMT) effect on the structure of poly(oxyethylene) (PEO)-MMT nanocomposites and silica-PEO-MMT hybrid materials

In this work we report the effects of incorporation of variable amounts (0.5-25%w/w) of montmorillonite in poly(oxyethylene) based materials in order to decrease the polymer crystallinity. Two different classes of materials were studied: silica-poly(oxyethylene)-montmorillonite hybrids prepared by the sol-gel route and poly(oxyethylene)-montmorillonite nanocomposites prepared by mixing the dry clay or the clay aqueous suspension into the melt poly(oxyethylene). The effects of monternorillonite loading on the poly(oxyethylene) crystallization control and on the nanostructural features were investigated by X-ray powder diffraction, small-angle X-ray scattering and differential scanning calorimetry. Experimental results show that free montmorillonite layers coexist with open aggregates and tactoids in the poly(oxyethylene)-montmorillonite nanocomposites, with different features depending on the filler proportion and preparation route. The intercalation of polymer chains in montmorillonite galleries markedly hinders the crystallization of the poly(oxyethylene) matrix. For hybrids materials the silica phase favors the exfoliation of montmorillonite tactoids, so that samples are predominantly constituted by dispersed platelets. (c) 2006 Elsevier B.V. All rights reserved.

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.

Effects of different treatments on purity of silica from soluble sodium silicate

Noncrystalline silica was obtained with low iron, sodium, and nitrate ions concentrations from soluble sodium silicate (water glass) and nitric acid solution. Extractions with nitric acid solution and/or deionized water and/or dialysis were carried out to eliminate soluble metal ions. Products were dried in a microwave oven and characterized by chemical analysis, XRD, and IR. Dialysis seems to be the best treatment for the elimination of sodium and nitrate ions. Silica purified by nitric acid and water extractions followed by dialysis yields the purest silica sample.

Motional heterogeneities in siloxane/poly(ethylene glycol) ormolyte nanocomposites studied by C-13 solid-state exchange NMR

C-13 exchange solid-state NMR methods were used to study two families of siloxane/poly-(ethylene glycol) hybrid materials: Types I and II, where the polymer chains interact with the inorganic phase through physical (hydrogen bonds or van der Waals forces) or chemical (covalent bonds) interactions, respectively. These methods were employed to analyze the effects of the interactions between the organic and inorganic phases on the polymer dynamics in the milliseconds to seconds time scale, which occurs at temperatures below the motional narrowing of the NMR line width and around the polymer glass transition. Motional heterogeneities associated with these interactions and evidence of both small and large amplitude motions were directly observed for both types of hybrids. The results revealed that the hindrance to the slow molecular motions of the polymer chains due to the siloxane structures depends on the chain length and the nature of the interaction between the organic and inorganic phases.

Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.

Evaluation of glass ionomer cements properties obtained from niobium silicate glasses prepared by chemical process

Glass ionomer cements (GICs) are glass and polymer composite materials. These materials currently find use in the dental field. The purpose of this work is to obtain systems based on composition 4.5SiO(2)-3Al(2)O(3)-XNb2O5-2CaO to be used in Dentistry. The systems were prepared by chemical route at 700 degrees C. The results obtained by XRD and DTA showed that all systems prepared are glasses. The structures of the obtained glasses were compared to commercial material using Al-27 and Si-29 MAS NMR. The analysis of MAS NMR spectra indicated that the systems developed and commercial material are formed by SiO4 and AlO4 linked tetrahedra. The properties of glass ionomer cements based on the glasses prepared with several niobium contents were studied. Setting and working times of the cement pastes, microhardness and diametral tensile strength were evaluated for the experimental GICs and commercial luting cements. It was concluded that setting time of the cement pastes increased with increasing niobium content of the glasses (X). The properties to the GICs such as setting time and microhardness were influenced by niobium content. (c) 2005 Elsevier B.V. All rights reserved.

Physical properties of silicate glasses doped with SnO2

The presence of tin in the network of silicate glasses produces changes in several of their physico-chemical properties. Glasses with the composition (mol%) 22Na(2)O (.) 8CaO (.) 70SiO(2) containing up to 5 wt% of SnO2 were analyzed under several experimental techniques. Dilatometric measurements showed an increase of the glass transition temperature with increasing tin content, while the average thermal expansion coefficient is reduced. Vickers microhardness, density, and refractive index also increase with the tin content. Diffuse reflectance spectra in the infrared (DRIFT) showed that the presence of tin, even at low concentrations, is responsible for some structural changes since there is an increase of the bridging oxygen concentration. The doped glasses present a brown color and optical absorption spectra measurements are interpreted as being due to precipitation of tin in the form of colloidal particles during cooling of the melted glass. In the Na+ <-> K+ ion exchange process the presence of tin in the glass network hinders the diffusion of these ions. The diffusion coefficients of those ions were calculated by the Boltzmann-Matano technique, after concentration profiles obtained by EDS measurements. All results obtained present evidences that Sn4+ cation acts as a glass network former. (c) 2005 Elsevier B.V. All rights reserved.

NMR study of ion-conducting organic-inorganic nanocomposites poly(ethylene glycol) - Silica - LiClO4

Hybrid organic-inorganic ionic conductors, also called ormolytes, were obtained by dissolution of LiClO4 into silica/poly(ethylene glycol) matrices. Solid-state nuclear magnetic resonance (NMR) was used to probe the inorganic phase structure (Si-29) and the effects of the temperature and composition on the dynamic behavior of the ionic species (Li-7) and the polymer chains (H-1 and C-13). The NMR results between -100 and +90 degrees C show a strong correlation with ionic conductivity and differential scanning calorimetry experiments. The results also demonstrate that the cation mobility is assisted by segmental motion of the polymer, which is in agreement with the results previously reported for pure poly(ethylene oxide), PEG, electrolytes.

Structure of luminescent mono and di-urethanesil nanocomposites doped with Eu3+ ions

A structure modeling of two families of sol-gel derived Eu3+-doped organic/inorganic hybrids based on the results of small-angle X-ray scattering experiments is reported. The materials are composed of poly(oxyethylene) chains grafted at one or both ends to siloxane groups and are called mono- and di-urethanesils, respectively. A theoretical function corresponding to a two-level hierarchical structure model fits well the experimental Scattering curves. The first level corresponds to small siloxane clusters embedded in a polymeric matrix. The secondary level is associated to the existence of siloxane cluster rich domains surrounded by a cluster-depleted polymeric matrix. Results show that increasing europium doping favors the growth of the secondary domains. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Red and blue emissions of europium doped gadolinium silicate from porous silica matrix and hydroxide carbonate with spherical shaped particles

In this work, Eu(III) and Eu(II) doped gadolinium silicates has been obtained as compact tubes starting from spherical gadolinium hydroxide carbonate using the pores of silica matrix as support and its surface as reagent. Eu(III) doped gadolinium silicate with hexagonal phase shows an interesting visible shifted charge transfer band when compared to disilicate with orthorhombic phase that was also obtained. Eu(II) gadolinium silicate has been prepared using CO atmosphere presenting an intense blue emission. The divalent europium system shows a potential application as an UV-blue converter. The samples were characterized by scanning electron microscopy (SEM), X-ray powder diffractometry (XRD) and photoluminescence spectroscopy. (C) 2002 Elsevier B.V. B.V. 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.

Structure of weakly bonded PPG-silica nanocomposites

The structure of silica-polypropyleneglycol (PPG) nanocomposites with weak physical bonds between the organic (PPG) and inorganic (silica) phase, prepared by the sol-gel process, was investigated by small angle X-ray scattering (SAXS). These nanocomposite materials are transparent, flexible, have good chemical stability and exhibit high ionic conductivity when doped with lithium salt. Their structure was studied as a function of silica weight fraction x (0.06 less than or equal to x less than or equal to 0.29) and [O]/[Li] ratio (oxygens being of ether-type). The shape of the experimental SAXS curves agrees with that expected for scattering intensity produced by fractal aggregates sized between 30 and 90 Angstrom. This result suggests that the structure of the studied hybrids consists of silica fractal aggregates embedded in a matrix of PPG. The correlation length of the fractal aggregates decreases and the fractal dimension increases for increasing silica content. The variations in structural parameters for increasing Li+ doping indicate that lithium ions favor the growth of fractal silica aggregates without modifying their internal structure and promote the densification of the oligomeric PPG matrix.

Natural gum-assisted phthalocyanine immobilization in electroactive nanocomposites: Physicochemical characterization and sensing applications

Natural gums have been traditionally applied in cosmetics and the food industry, mainly as emulsification agents. Due to their biodegradability and excellent mechanical properties, new technological applications have been proposed involving their use with conventional polymers forming blends and composites. In this study, we take advantage of the polyelectrolyte character exhibited by the natural gum Chicha (Sterculia striata), extracted in the Northeastern region of Brazil, to produce electroactive nanocomposites. The nanocomposites were fabricated in the form of ultrathin films by combining a metallic phthalocyanine (nickel tetrasulfonated phthalocyanine, NiTsPc) and the Chicha gum in a tetralayer architecture, in conjunction with conventional polyelectrolytes. The presence of the gum led to an efficient adsorption of the phthalocyanine and enhanced the electrochemical response of the films. Upon combining the electrochemical and UV-vis absorption data, energy diagrams of the Chicha/NiTsPc-based system were obtained. Furthermore, modified electrodes based on gum/phthalocyanine films were able to detect dopamine at concentrations as low as 10(-5) M.