Development of metal - SiO2 nanocomposites in a single-step process by the polymerizable complex method

This work presents the synthesis and characterization of SiO2:metal (Ni, Co, Ag, and Fe) nanocomposites processed by the polymerizable complex method. The polymeric precursor solutions obtained were characterized by means of FT-Raman and C-13 NMR spectroscopy. The results show the formation of a hybrid polymer with carbon and silicon in the macromolecule chain and the transition metal cation arrested within this polymeric chain. The nanocomposites are formed during the controlled polymeric precursor pyrolysis. The reduction of the metal cation is promoted by the CO/CO2 atmosphere resulting from the pyrolysis of the organic material. Microstructural characterization, performed by TEM and X-ray diffraction (XRD), showed that the nanocomposites are formed by metal nanoparticles embedded in a amorphous matrix formed by SiO2 and carbon. In the SiO2:Fe system, Fe3C was also detected by XRD.

The effects of bacterial leaching on metal partitioning in sewage sludge

The partitioning of Mn, Al, Zn, Cu and Ti ions in municipal sewage sludge was investigated before and after bioleaching processes effectuated by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. Oxidation reduction potential increase and pH decrease were obtained as a result of bacterial activity. A less pronounced and constant decrease was obtained with A. ferrooxidans, whereas A. thiooxidans presented a lag phase before a steep pH decrease. Metal solubilization was accomplished in experimental systems supplemented with energy source, Fe2+ for A. ferrooxidans and S-0 for A. thiooxidans. Solubilization efficiency differed for each metal except for Al, and was relatively similar for either organism. Metal partitioning was conducted using five-step sequential extraction procedure before and after the bioleaching. The results indicated that Zn and Mn ions were mostly associated with the organic fraction, whereas Cu, Al and Ti ions with the sulphide/ residue fraction. The bioleaching process caused prompt solubilization of metals mostly associated with the more labile fractions (exchangeable, adsorbed and organically bound metals), whereas those associated to the less labile ones (EDTA and sulphide/residue fractions) were exchanged towards more labile fractions.

Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange - an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators ( diethylenetetraaminepentaacetic acid ( DTPA), ethylendiaminetetraacetic acid ( EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake ( Venner Moor, Munsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC ( dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES ( inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species ( Fe, Mn, Zn) could be characterized. Conditional exchange constants K ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu( II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.

Extraction and exchange behavior of metal species in therapeutically applied peat

The binding and availability of metals (Al, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Zn) in therapeutically applied peat (GroBes Gifhorner Moor, Sassenburg/North Germany) was characterized by means of a versatile extraction approach. Aqueous extracts of peat were obtained by a standardized batch equilibrium procedure using high-purity water (pH 4.5 and 5.0), 0.01 mol l(-1) calcium chloride solution, 0.0 1 mol l(-1) ethylenediaminetetraacetic acid (EDTA) and 0.01 mol l(-1) diethylenetriarnine pentaacetic acid (DTPA) solution as metal extractants. In addition, the availability of peat-bound metal species was kinetically studied by collecting aliquots of extracts after different periods of extraction time (5, 10, 15, 30, 60 and 120 min). Metal determinations were performed by atomic spectrometry methods (AAS, ICP-OES) and dissolved organic matter (DOM) was characterized by UV/Vis measurements at 254 and 436 nm, respectively. of the extractants studied Ca, Mg and Mn were the most available metals, in contrast to peat-bound Fe and Al. The relative standard deviation s(r) of the developed extraction procedures was mostly in the range of 4 to 20%, depending on the metal and its concentration in peat. A pH increase favored the extraction of metals and DOM from peat revealing complex extraction kinetics. Moreover, a competitive exchange between peat-bound metal species and added Cu(II) ions showed that > 100 mg of Cu(II) per 50 g wet peat was necessary to exchange the maximum of bound metals (e.g. 21.8% of Al, 3.9% of Fe, 79.0% of Mn, 81.9% of Sr, related to their total content). (C) 2002 Elsevier B.V. B.V. All rights reserved.

The role of organic matter on the adsorption of mercury in sediments from Amazon lakes, Brazil

Gold has been exploited intensively in the Brazilian Amazon during the past 20 years, and the elemental mercury (Hg) used in amalgamating the gold has caused abnormal Hg concentrations in waterways. Since 1986 particular attention has been given to the Madeira River because it is the largest tributary of the Amazon River and gold mining was officially allowed on a 350-km sector of the river. In this paper, samples of sediments from nine lakes located in the Madeira River basin, Rondonia State, Brazil, were analysed for mercury and organic matter. The average Hg content ranged between 33 and 157 ppb, which is about 8-40 times higher than the average value corresponding to 4.4 ppb for rocks occurring in the area (regional background). Significant correlation was found between the Hg content and organic matter in the sediments, indicating its importance on the retention of this heavy metal.

Study of an organically modified clay: Selective adsorption of heavy metal ions and voltammetric determination of mercury(II)

In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexaclecyltrimethylammonium ions (HDTA), with the formulae of [(CH3)(3)N(C16H33)](+) ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded oil the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. (c) 2005 Elsevier B.V. All rights reserved.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile. (C) 2007 Elsevier B.V. All rights reserved.

Organic complexation and translocation of ferric iron in podzols of the Negro River watershed. Separation of secondary Fe species from Al species

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Reduction of dissolved oxygen in water: Hydrazine and its organic substitutes

In industrial processes using aqueous solutions, corrosion of metal surfaces may occur at various locations. Much of the damage to steam generators and boilers is caused by corrosion. Dissolved oxygen in water is one of the most potent corrosion-causing factors, and therefore oxygen should be eliminated from steam-generating systems' feedwater. Chemical reduction, by reagents such as hydrazine or organic compounds, generally is used for the deoxygenation of water. This article reviews the major oxygen scavengers currently available.

Filmes de metal-hexacianoferrato: Uma ferramenta em química analítica

Chemically modified electrodes based on hexacyanometalate films are presented as a tool in analytical chemistry. Use of amperometric sensors and/or biosensors based on the metal-hexacyanoferrate films is a tendency. This article reviews some applications of these films for analytical determination of both inorganic (e.g. As3+, S2O3 2-) and organic (e.g. cysteine, hydrazine, ascorbic acid, gluthatione, glucose, etc.) compounds.

Full-color phosphors from amine-functionalized crosslinked hybrids lacking metal activator ions

Sol-gel derived hybrids that contain OCH2CH2 (polyethylene glycol, PEG) repeat units grafted onto a siliceous backbone by urea, -NHC(=O)NH-, or urethane, -NHC(=O)O-, bridges have been prepared. It is demonstrated that the white light PL of these materials results from an unusual convolution of a longer lived emission that originates in the NH groups of the urea/urethane bridges with shorter lived electron-hole recombinations occurring in the nanometer-sized siliceous domains. The PL efficiencies reported here (maximum quantum yields at room temperature of ≈ 0.20 ± 0.02 at a 400 nm excitation wavelength) are in the same range as those for tetramethoxysilane-formic acid, and APTES-acetic acid, sol-gel derived phosphors. The high quantum yields combined with the possibility of tuning the emission to colors across the chromaticity diagram present a wide range of potential applications for these hybrid materials.

Four new metal complexes with the amino acid deoxyalliin

The solid complexes [Co(C6H10NO2S) 2], [Ni(C6H10NO2S)2], [Cu(C6H10NO2S)2] and [Fe(C 6H10NO2S)2] were obtained from the reaction of cobalt(II), nickel(II), copper(II) and iron(II) salts with the potassium salt of the amino acid deoxyalliin (S-allyl-L-cysteine). Electronic absorption spectra of the complexes are typical of octahedral structures. Infrared spectroscopy confirms the ligand coordination to the metal ions through (COO-) and (NH2) groups. EPR spectrum of the Cu(II) complex indicates a slight distortion of its octahedral symmetry. Mössbauer parameters permitted to identify the presence of iron(II) and iron(III) species in the same sample, both of octahedral geometry. Thermal decomposition of the complexes lead to the formation of CoO, NiO, CuO and Fe2O3 as final products. The compounds show poor solubility in water and in the common organic solvents. ©2005 Sociedade Brasileira de Química.

Influence of thermal and mechanical cycling on the flexural strength of ceramics with titanium or gold alloy frameworks

Objectives: The aim of this study was to evaluate the effect of thermal and mechanical cycling alone or in combination, on the flexural strength of ceramic and metallic frameworks cast in gold alloy or titanium. Methods: Metallic frameworks (25 mm × 3 mm × 0.5 mm) (N = 96) cast in gold alloy or commercial pure titanium (Ti cp) were obtained using acrylic templates. They were airborne particle-abraded with 150 μm aluminum oxide at the central area of the frameworks (8 mm × 3 mm). Bonding agent and opaque were applied on the particle-abraded surfaces and the corresponding ceramic for each metal was fired onto them. The thickness of the ceramic layer was standardized by positioning the frameworks in a metallic template (height: 1 mm). The specimens from each ceramic-metal combination (N = 96, n = 12 per group) were randomly assigned into four experimental fatigue conditions, namely water storage at 37 °C for 24 h (control group), thermal cycling (3000 cycles, between 4 and 55 °C, dwell time: 10 s), mechanical cycling (20,000 cycles under 10 N load, immersion in distilled water at 37 °C) and, thermal and mechanical cycling. A flexural strength test was performed in a universal testing machine (crosshead speed: 1.5 mm/min). Data were statistically analyzed using two-way ANOVA and Tukey's test (α = 0.05). Results: The mean flexural strength values for the ceramic-gold alloy combination (55 ± 7.2 MPa) were significantly higher than those of the ceramic-Ti cp combination (32 ± 6.7 MPa) regardless of the fatigue conditions performed (p < 0.05). Mechanical and thermo-mechanical fatigue decreased the flexural strength results significantly for both ceramic-gold alloy (52 ± 6.6 and 53 ± 5.6 MPa, respectively) and ceramic-Ti cp combinations (29 ± 6.8 and 29 ± 6.8 MPa, respectively) compared to the control group (58 ± 7.8 and 39 ± 5.1 MPa, for gold and Ti cp, respectively) (p < 0.05) (Tukey's test). While ceramic-Ti cp combinations failed adhesively at the metal-opaque interface, gold alloy frameworks exhibited a residue of ceramic material on the surface in all experimental groups. Significance: Mechanical and thermo-mechanical fatigue conditions decreased the flexural strength values for both ceramic-gold alloy and ceramic-Ti cp combinations with the results being significantly lower for the latter in all experimental conditions. © 2007 Academy of Dental Materials.

Influence of cerium (IV) ions on the inorganic and organic phase for preparation of a siloxane-PMMA based film on tin plate substrate

Tinplate is one of the most widely used food canning materials, however, there are significant problems related to the use of tinplate cans, such as alterations in sensory features affecting food quality and corrosion phenomena of the canning material. To avoid corrosion problems different methods have been used for the passivation of tinplate such protective lacquers or different kinds of corrosion inhibitors (chromate and dichromate). However, chromates and dichromates are extremely harmful to the environment and can cause carcinogenic tumors to humans. An option, protective coatings obtained by the sol-gel process, act as a physical barrier, which isolates the surface of metal protecting from the corrosive agents. The aim of this work is to study the influence of addition of cerium (IV) ions in the inorganic and organic part of sol-gel processing in the formation of hybrid coatings based on siloxane-PMMA on tin plate. The coatings were obtained by dip-coating technique and evaluated by open circuit and impedance measurements, linear polarization and polarization curves obtained in 3.5% NaCl solution. The results have clearly shown the improvement on the protective properties of the Ce 4+ modified film when added into the organic phase, which can be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. © 2009 by NACE International.

Nanocompósito de alumina com inclusão nonométricas de zircônia para infraestruturas de próteses odontológicas livres de metal: avaliação de prosperidades mecânicas e análise microestrutural. -

Pós-graduação em Reabilitação Oral - FOAR