Scandium fluorophosphate glasses: a structural approach

A systematic investigation on glass formation in the ternary system InF3-BaF2-[Sc(PO3)(3)](n) has been carried out. Scandium polyphosphate [Sc(PO3)(3)](n) has been used as a third component in order to investigate the possibilities of obtaining new stable glasses. The above long-chain polyphosphate has been prepared using a specially elaborated cryo-technique, which allowed the preparation of high-purity product. Stable ternary compositions have been obtained within the compositions range (in mol%): 5-75 InF3, 0-80% BaF2, 0-50% [Sc(PO3)(3)](n). Glasses were characterized by Differential Scanning Calorimetry, vibrational spectroscopy (Raman) and P-31 NMR. Structural features for the glass were put forward. Isolated P(O,F)4 groups or fluoroindated metaphosphate units could be identified depending on glass compositions. (C) 2002 Academie des sciences / Editions scientifiques et medicales Elsevier SAS.

Phase transition in poly(vinylidene fluoride) investigated with micro-Raman spectroscopy

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates at 80 degrees C, while the transition to P-PVDF was monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, along with the concomitant increase in the 839 cm-1 band characteristic of the P-phase. The alpha ->beta transition in our PVDF samples could be achieved even for the sample stretched to twice (2 X -stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the a-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.

Thermal degradation of a composite solid propellant examined by DSC - Kinetic study

The thermal decomposition of ammonium perchlorate (AP)/hydroxyl-terminated-polybutadiene (HTPB), the AP/HTPB solid propellant, was studied at different heating rates in dynamic nitrogen atmosphere. The exothermic reaction kinetics was studied by differential scanning calorimetry (DSC) in non-isothermal conditions. The Arrhenius Parameters were estimated according to the Ozawa method. The calculated activation energy was 134.5 W mol(-1), the pre-exponential factor, A, was 2.04.10(10) min(-1) and the reaction order for the global composite decomposition was estimated in 0.7 by the kinetic Shimadzu software based on the Ozawa method. The Kissinger method for obtaining the activation energy value was also used for comparison. These results are discussed here.

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

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.

Preparation and thermal decomposition of solid state compounds of 4-methoxybenzylidenepyruvate with alkali earth metals, except beryllium and radium

Solid compounds of general formula ML(2) . nH(2)O [where M is Mg, Ca, Sr or Ba; L=4 methoxybenzylidenepyruvate (4-MeO-BP); n = 4, 1 or 0] have been synthetized. Thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), x-ray diffraction powder patterns and elemental analysis have been used to characterize the compounds. The thermal stability of these compounds as well as that of the decomposition products were studied using Pt or Al2O3 crucibles in an air or a CO2 atmosphere.

Salt-induced sphere-to-disk transition of octadecyltrimethylammonium bromide micelles

We have used surface tension measurements, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and cryo-transmission electron microscopy (cryo-TEM) to investigate the dynamic and structural behavior of octadecyltrimethylammonium bromide (C(18)TAB) micelles in water and NaBr solution. The surface tension data for fixed C(18)TAB concentrations of 25 mM and varied NaBr additions (0-50 mM) shows that the critical micelle concentration (cmc) increases after an initial decrease at 0.5 mM NaBr. This unusual effect has been explained using results from DSC and DLS. At low salt concentrations (below ca. 25 mM) the relaxation time distribution is bimodal with a dominant fast mode due to spherical micelles. Above ca. 35 mM NaBr disklike structures are favored and the relaxation time distribution is more closely unimodal. The postulated sphere-to-disk transition is supported by cryo-TEM micrographs. A pronounced increase in the micellar effective hydrodynamic radius (R-H) is observed as the NaBr concentration is increased above about 35 mM; below 35 mM the R-H of the spherical micelles changes Little with ionic strength.

Influence of silver additions on the thermal behavior of the Cu-8 mass% Al alloy

The influence of additions of 2, 4, 6, 8, 10 and 12 mass% Ag on the thermal behavior of the Cu-8 mass% Al alloy was studied using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicate that the presence of silver introduces new thermal events, due to the formation of a silver-rich phase and, for additions of 10 and 12 mass% Ag, it is possible to verify the formation of the gamma (1) phase (Cu9Al4) and the metastable transitions which are only observed in alloys with a minimum of 9 mass% Al.

Synthesis and thermal study of the prodrug of oxamniquine

Oxamniquine polymeric prodrug with potential antischistosomal activity was prepared using dextran T-70 as a carrier, which was analysed by (HNMR)-H-1, C-13 NMR and IR spectroscopy. The formation of the oxamniquine salt was confirmed by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) which showed a different thermal behaviour when compared to the physical mixture.

Thermal studies on solid compounds of 4-chlorobenzylidenepyruvate of some alkali earth metals

Solid-state M-4-Cl-BP compounds, where M stands for bivalent Mg, Ca, Sr, Ba and 4-Cl-BP is 4-chlorobenzylidenepyruvate, have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, elemental analysis and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to informations about the composition, dehydration, thermal stability and thermal decomposition of the isolated complexes.

Morphology of poly(vinylidene fluoride) and poly(o-metoxyaniline) blends

Blends of poly(o-methoxyaniline) - POMA - and poly(vinylidene fluoride) - PVDF - of various compositions were prepared from organic solvent solutions. Flexible, free-standing and stretchable films were obtained by casting, which were characterized by conductivity measurements, electron microscopy and differential scanning calorimetry. As expected, the blends conductivity increases with increasing contents of the conducting polymer. The onset of the conductivity at low contents of conducting polymer indicates a low percolation threshold for the blends. Despite the presence of the conductive host, the blends displayed the crystalline spherulitic morphology and the beta-phase characteristic of pure PVDF. This morphology appears to be destroyed, however, if the film is stretched by zone-drawing.

Thermoanalytical study of the complexes of 4-dimethylaminocynnamylidenepyruvate with manganese (II), cobalt (II), nickel (II), cupper (II), zinc (II) and lead (II), in the solid state

Solid state compounds M-4-DMCP, where 4-DMCP is 4-dimethylaminocynnamylidenepyruvate and M represents Mn (II), Co (II), Ni (II), Cu (II), Zn (II) and Pb (II) were prepared. These compounds were studied by thermoanalytical techniques: thermogravimetry (TG), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and complexometric titration with EDTA. From the results obtained by the complexometric titration with EDTA, TG, DTG and DSC curves, was possible to establish the hydration degree, stoichiometry and thermal stability of the prepared compounds.

Solid-state chelates of ethylenediamine-tetraacetate with alkali earth metals

Solid-state M-EDTA chelates, where M represents the divalent ions Mg(II), Ca(II), Sr(II) or Ba(II) and EDTA is ethylenediaminetetraacetate anion, were synthesized. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC) and X-ray diffraction powder patterns have been used to characterize and to study the thermal behaviour of these chelates. The results provided information concerning the stoichiometry, crystallinity, thermal stability and thermal decomposition.

Effect of salt nature on structure and ionic conductivity of sodium-doped siloxane-PPO ormolytes

Siloxane-polyoxypropylene (PPO) hybrids obtained by the sol-gel process and containing short polymer chain have been doped with different sodium salts NaX (X = ClO4, BF4 or I). The effect of the counter-ion (X) on the chemical environment of the sodium ions and on the ionic conductivity of these hybrids was investigated by Na-23 NMR, small angle X-ray scattering (SAXS), complex impedance, Raman spectroscopy and differential scanning calorimetry (DSC). Results reveal that the different sodium salts have essentially the same effect on the nanoscopic structure of the hybrids. The formation of immobile Na+ cations involved in NaCl-like species could be minimized by using a low amount of HCl as hydrolytic catalyst. The differences in the ionic conductivity of hybrids doped with different sodium salts were correlated with the proportion of Na ions solvated by ether-type oxygen of the polymeric chains and by the carboxyl oxygen located in the urea groups of the PPO chain extremities. (c) 2005 Elsevier Ltd. All rights reserved.

Study of fluorine losses in oxyfluoride glasses

Glasses in PbGeO3-PbF-CdF2 and GeO2-PbO-PbF2-CdF2 systems were studied and the fluorine losses during synthesis were investigated. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and Raman scattering spectroscopy. The use of stoichiometric germanate glass, PbGeO3, instead of introducing individual oxides (GeO2 + PbO) lead to decreasing fluorine losses, as detected by a fluorine ion selective electrode. The main structural features obtained from vibrational spectroscopy could be described by a metagermanate basic structure permeating fluorine rich regions. (c) 2005 Elsevier B.V. All rights reserved.