beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid

(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10 4-fold faster than its spontaneous hydrolysis, and monoanionic LHA - is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate. © 2009 American Chemical Society.

Thermal stability of ionene polymers

Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer-clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na+ and little Ca2+. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol-1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol-1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Thermal investigation and infrared evolved gas analysis of solid trivalent lanthanide and yttrium alpha-hydroxyisobutyrates in N-2 and CO2 atmospheres

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Enhancement of voltammetric determination of quinizarine based on the adsorption at surfactant-adsorbed-layer in disposable electrodes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Surfactant-assisted intercalation of high molecular weight poly(ethylene oxide) into vanadyl phosphate di-hydrate

A high molecular weight poly(ethylene oxide)/layered vanadyl phosphate di-hydrate intercalation compound was synthesized via the surfactant-assisted approach. Results confirmed that surfactant molecules were replaced with the polymer, while the lamellar structure of the matrix was retained, and that the material presents high specific surface area. In addition, intercalation produced a more thermally stable polymer as evidenced by thermal analysis. (C) 2011 Elsevier Ltd. All rights reserved.

Formation of oxysulfide LnO(2)S(2) and oxysulfate LnO(2)SO(4) phases in the thermal decomposition process of lanthanide sulfonates (Ln = La, Sm)

This study investigates two lanthanide compounds (La(3+) and Sm(3+)) obtained in water/ethyl alcohol solutions employing the anionic surfactant diphenyl-4-amine sulfonate (DAS) as ligand. Both sulfonates were characterized through IR, TG/DTG (O(2) and N(2)). The thermal treatment of both compounds at 1273 K under air leaves residues containing variable percentages of lanthanide oxysulfide/oxysulfate phases shown by synchrotron high-resolution XRD pattern including the Rietveld analysis. The phase distributions found in the residues evidence the differences in the relative stability of the precursors.

beta-ZnMoO4 microcrystals synthesized by the surfactant-assisted hydrothermal method: Growth process and photoluminescence properties

In this communication, we investigate the effect of different surfactants: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP-K40) on the growth process of zinc molybdate (beta-ZnMoO4) microcrystals synthesized under hydrothermal conditions at 140 degrees C for 8 h. These microcrystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) measurements. XRD patterns proved that these crystals are monophasic and present a wolframite-type monoclinic structure. FE-SEM images revealed that the surfactants modified the crystal shapes, suggesting the occurrence of distinct crystal growth processes. The CTAB cationic surfactant promotes the hindrance of small nuclei that leads to the formation of rectangle-like crystals, SDS anionic surfactant induces a growth of irregular hexagons with several porous due to considerable size effect of counter-ions on the crystal facets, PVP-K40 non-ionic surfactant allows a reduction in size and thickness of plate-like crystals, while without surfactants have the formation of irregular plate-like crystals. Finally, the PL properties of beta-ZnMoO4 microcrystals were explained by means of different shape/size, surface defects and order-disorder into lattice. (C) 2011 Elsevier B.V. All rights reserved.

Layered silicate nanocomposites based on various high-functionality epoxy resins: The influence of an organoclay on resin cure

The influence of an organically modified clay on the curing behavior of three epoxy systems widely used in the aerospace industry and of different structures and functionalities, was studied. Diglycidyl ether of bisphenol A (DGEBA), triglycidyl p-amino phenol (TGAP) and tetraglycidyl diamino diphenylmethane (TGDDM) were mixed with an octadecyl ammonium ion modified organoclay and cured with diethyltoluene diamine (DETDA). The techniques of dynamic mechanical thermal analysis (DMTA), chemorheology and differential scanning calorimetry (DSC) were applied to investigate gelation and vitrification behavior, as well as catalytic effects of the clay on resin cure. While the formation of layered silicate nanocomposite based on the bifunctional DGEBA resin has been previously investigated to some extent, this paper represents the first detailed study of the cure behavior of different high performance, epoxy nanocomposite systems.

Remoção de corantes têxteis em solução aquosa utilizando bentonita natural e organofílica

Searches using organoclays have been the subject of great interest due to its wide application in industry and removal of environmental pollutants. The organoclays were obtained using bentonite (BEN) and cationic surfactants: hexadecyltrimethyl ammonium bromide (HDTMA-Br) and trimethyloctadecyl ammonium bromide (TMOA-Br) in ratios of 50 and 100 % of its ion exchange capacity. The materials were characterized by the techniques of X-ray diffraction (DRX), infrared spectroscopy (IR), X-ray fluorescence (FRX), thermal analysis (TA) and scanning electron microscopy (SEM). The bentonite and organobentonite were used on the adsorption of dyes, Remazol Blue RR (AZ) and Remazol Red RR (VM) in aqueous solution. The adsorption models of Langmuir and Freundlich were used for mathematical description of sorption equilibrium data and obtain the constants of the isotherms. The Freundlich model fit to the data for adsorption equilibrium of bentonite, on the other hand both the model fit to the Langmuir adsorption test of organoclays. The adsorption processes using adsorbents with both dyes interspersed with HDTMA-Br show endothermic and exothermic nature, respectively.

Dynamic mechanical-thermal, microstructural and mechanical analysis of ultra-light polymer-metal composites: influence of forming

A really particular and innovative metal-polymer sandwich material is Hybrix. Hybrix is a product developed and manufactured by Lamera AB, Gothenburg, Sweden. This innovative hybrid material is composed by two relatively thin metal layers if compared to the core thickness. The most used metals are aluminum and stainless steel and are separated by a core of nylon fibres oriented perpendicularly to the metal plates. The core is then completed by adhesive layers applied at the PA66-metal interface that once cured maintain the nylon fibres in position. This special material is very light and formable. Moreover Hybrix, depending on the specific metal which is used, can achieve a good corrosion resistance and it can be cut and punched easily. Hybrix architecture itself provides extremely good bending stiffness, damping properties, insulation capability, etc., which again, of course, change in magnitude depending in the metal alloy which is used, its thickness and core thickness. For these reasons nowadays it shows potential for all the applications which have the above mentioned characteristic as a requirement. Finally Hybrix can be processed with tools used in regular metal sheet industry and can be handled as solid metal sheets. In this master thesis project, pre-formed parts of Hybrix were studied and characterized. Previous work on Hybrix was focused on analyze its market potential and different adhesive to be used in the core. All the tests were carried out on flat unformed specimens. However, in order to have a complete description of this material also the effect of the forming process must be taken into account. Thus the main activities of the present master thesis are the following: Dynamic Mechanical-Thermal Analysis (DMTA) on unformed Hybrix samples of different thickness and on pre-strained Hybrix samples, pure epoxy adhesive samples analysis and finally moisture effects evaluation on Hybrix composite structure.

Thermal decomposition of the synthetic hydrotalcite iowaite

The thermal stability and thermal decomposition pathways for synthetic iowaite have been determined using thermogravimetry in conjunction with evolved gas mass spectrometry. Chemical analysis showed the formula of the synthesised iowaite to be Mg6.27Fe1.73(Cl)1.07(OH)16(CO3)0.336.1H2O and X-ray diffraction confirms the layered structure. Dehydration of the iowaite occurred at 35 and 79°C. Dehydroxylation occurred at 254 and 291°C. Both steps were associated with the loss of CO2. Hydrogen chloride gas was evolved in two steps at 368 and 434°C. The products of the thermal decomposition were MgO and a spinel MgFe2O4. Experimentally it was found to be difficult to eliminate CO2 from inclusion in the interlayer during the synthesis of the iowaite compound and in this way the synthesised iowaite resembled the natural mineral.

Thermal Treatments of Fe—Mn Alkoxide of Glycerol: Infrared absorption and emission

Synthetic Fe—Mn alkoxide of glycerol samples are submitted to controlled heating conditions and examined by IR absorption spectroscopy. On the other hand, the same sample is studied by infrared emission spectroscopy (IRES), upon heating in situ from 100 to 600°C. The spectral techniques employed in this contribution, especially IRES, show that as a result of the thermal treatments ferromagnetic oxides (manganese ferrite) are formed between 350 and 400°C. Some further spectral changes are seen at higher temperatures.

Purity evaluation and influence of carbon nanotube on carbon nanotube/graphite thermal stability

High resolution thermogravimetry has been used to evaluate the carbonaceous content in a commercial sample of single-walled carbon nanotube (SWNT). The content of SWNTs in the sample was found to be at least 77mass% which was supported by images obtained with scanning and transmission electron microscopies (SEM and TEM). Furthermore, the influence of SWNT addition on the thermal stability of graphite in mixtures of SWNT/graphite at different proportions was investigated. The graphite stability decreased with the increased of SWNT content in the overall range of composition. This behavior could be due to the close contact between these carbonaceous species as determined by SEM analysis.

Thermal transition properties of spagehetti measured by Differential Scanning Calorimetry (DSC) and Thermal Mechanical Compression Test (TMCT)

Glass transition temperature of spaghetti sample was measured by thermal and rheological methods as a function of water content.