Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Melting and freezing of spherical bismuth nanoparticles confined in a homogeneous sodium borate glass

The melting temperature and the crystallization temperature of Bi nanoclusters confined in a sodium borate glass were experimentally determined as functions of the cluster radius. The results indicate that, on cooling, liquid Bi nanodroplets exhibit a strong undercooling effect for a wide range of radii. The difference between the melting temperature and the freezing temperature decreases for decreasing radius and vanishes for Bi nanoparticles with a critical radius R = 1.9 nm. The magnitude of the variation in density across the melting and freezing transitions for Bi nanoparticles with R = 2 nm is 40% smaller than for bulk Bi. These experimental results support a basic core-shell model for the structure of Bi nanocrystals consisting of a central crystalline volume surrounded by a structurally disordered shell. The volume fraction of the crystalline core decreases for decreasing nanoparticle radius and vanishes for R = 1.9 nm. Thus, on cooling, the liquid nanodroplets with R < 1.9 nm preserve, across the liquid-to-solid transformation, their homogeneous and disordered structure without crystalline core.

Effect of Mn concentration and atomic structure on the magnetic properties of Ge thin films

This work reports on the magnetic properties of Ge(100-x)Mn(x) (x=0-24 at. %) films prepared by cosputtering a Ge+Mn target and submitted to cumulative thermal annealing treatments up to 500 degrees C. Both as-deposited and annealed films were investigated by means of compositional analysis, Raman scattering spectroscopy, magnetic force microscopy, superconducting quantum interference device magnetometry, and electrical resistivity measurements. All as-deposited films (either pure or containing Mn) exhibit an amorphous structure, which changes to crystalline as the annealing treatments are performed at increasing temperatures. In fact, the magnetic properties of the present Ge(100-x)Mn(x) films are very sensitive to the Mn content and whether their atomic structure is amorphous or crystalline. More specifically: whereas the amorphous Ge(100-x)Mn(x) films (with high x) present a characteristic spin glass behavior at low temperature; after crystallization, the films (with moderate Mn contents) are ferromagnetic at room temperature. Moreover, the magnetic behavior of the films scales with their Mn concentration and tends to be more pronounced after crystallization. Finally, the semiconducting behavior of the films, experienced by previous optical studies, was confirmed through electrical measurements, which also indicate the dependence of the resistivity with the atomic composition of the films. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3520661]

Atomistic origins of the phase transition mechanism in Ge(2)Sb(2)Te(5)

The fast and reversible phase transition mechanism between crystalline and amorphous phases of Ge(2)Sb(2)Te(5) has been in debate for several years. Through employing first-principles density functional theory calculations, we identify a direct structural link between the metastable crystalline and amorphous phases. The phase transition is driven by the displacement of Ge atoms along the rocksalt [111] direction from stable octahedron to high energy unstable tetrahedron sites close to the intrinsic vacancy regions, which generates a high energy intermediate phase between metastable and amorphous phases. Due to the instability of Ge at the tetrahedron sites, the Ge atoms naturally shift away from those sites, giving rise to the formation of local-ordered fourfold motifs and the long-range structural disorder. Intrinsic vacancies, which originate from Sb(2)Te(3), lower the energy barrier for Ge displacements, and hence, their distribution plays an important role in the phase transition. The high energy intermediate configuration can be obtained experimentally by applying an intense laser beam, which overcomes the thermodynamic barrier from the octahedron to tetrahedron sites. The high figure of merit of Ge(2)Sb(2)Te(5) is achieved from the optimal combination of intrinsic vacancies provided by Sb(2)Te(3) and the instability of the tetrahedron sites provided by GeTe.

Interference with Hemozoin Formation Represents an Important Mechanism of Schistosomicidal Action of Antimalarial Quinoline Methanols

Background: The parasitic trematode Schistosoma mansoni is one of the major causative agents of human schistosomiasis, which afflicts 200 million people worldwide. Praziquantel remains the main drug used for schistosomiasis treatment, and reliance on the single therapy has been prompting the search for new therapeutic compounds against this disease. Our group has demonstrated that heme crystallization into hemozoin (Hz) within the S. mansoni gut is a major heme detoxification route with lipid droplets involved in this process and acting as a potential chemotherapeutical target. In the present work, we investigated the effects of three antimalarial compounds, quinine (QN), quinidine (QND) and quinacrine (QCR) in a murine schistosomiasis model by using a combination of biochemical, cell biology and molecular biology approaches. Methodology/Principal Findings: Treatment of S. mansoni-infected female Swiss mice with daily intraperitoneal injections of QN, and QND (75 mg/kg/day) from the 11(th) to 17(th) day after infection caused significant decreases in worm burden (39%-61%) and egg production (42%-98%). Hz formation was significantly inhibited (40%-65%) in female worms recovered from QN- and QND-treated mice and correlated with reduction in the female worm burden. We also observed that QN treatment promoted remarkable ultrastructural changes in male and female worms, particularly in the gut epithelium and reduced the granulomatous reaction to parasite eggs trapped in the liver. Microarray gene expression analysis indicated that QN treatment increased the expression of transcripts related to musculature, protein synthesis and repair mechanisms. Conclusions: The overall significant reduction in several disease burden parameters by the antimalarial quinoline methanols indicates that interference with Hz formation in S. mansoni represents an important mechanism of schistosomicidal action of these compounds and points out the heme crystallization process as a valid chemotherapeutic target to treat schistosomiasis.

Composites from Brazilian natural fibers with polypropylene: mechanical and thermal properties

Brazil has a well established ethanol production program based on sugarcane. Sugarcane bagasse and straw are the main by-products that may be used as reinforcement in natural fiber composites. Current work evaluated the influence of fiber insertion within a polypropylene (PP) matrix by tensile, TGA and DSC measurements. Thus, the mechanical properties, weight loss, degradation, melting and crystallization temperatures, heat of melting and crystallization and percentage of crystallinity were attained. Fiber insertion in the matrix improved the tensile modulus and changed the thermal stability of composites (intermediary between neat fibers and PP). The incorporation of natural fibers in PP promoted also apparent T(c) and Delta H(c) increases. As a Conclusion, the fibers added to polypropylene increased the nucleating ability, accelerating the crystallization process, improving the mechanical properties and consequently the fiber/matrix interaction.

Rapid solidification and phase stability evaluation of Ti-Si-B alloys

Ti-rich Ti-Si-B alloys can be considered for structural applications at high temperatures (max. 700 degrees C), however, phase equilibria data is reported only for T = 1250 degrees C. Thus, in this work the phase stability of this system has been evaluated at 700 degrees C. In order to attain equilibrium conditions in shorter time, rapid solidified samples have been prepared and carefully characterized. The microstructural characterization of the produced materials were based on X-ray diffraction (XRD), scanning electron microscopy (SEM-BSE), high resolution transmission electron microscopy (HRTEM), High Temperature X-ray diffraction with Synchrotron radiation (XRDSR) and Differential Scanning Calorimetry (DSC). Amorphous and amorphous with embedded nanocrystals have been observed after rapid solidification from specific alloy compositions. The values of the crystallization temperature (Tx) of the alloys were in the 509-647 degrees C temperature range. After Differential Scanning Calorimetry and High Temperature X-ray Diffraction with Synchrotron radiation, the alloys showed crystalline and basically formed by two or three of the following phases: alpha Ti, Ti(6)Si(2)B; Ti(5)Si(3); Ti(3)Si and TiB. It has been shown the stability of the Ti(3)Si and Ti(6)Si(2)B phases at 700 degrees C and the proposition of an isothermal section at this temperature. (C) 2011 Elsevier B.V. All rights reserved.

Mechanical and tribological properties of a sintered glass-ceramic compared to granite and porcelainized stoneware

Mechanical and tribological properties of a partially crystallized sintered glass-ceramic were compared to two commercial floor tiles: black granite and porcelainized stoneware. Mechanical properties, hardness and elastic modulus were evaluated by instrumented indentation. Friction coefficient and wear characterization were evaluated using a reciprocating ball-on-flat tribometer in two controlled environments: air with relative humidity of 53% and under running water at 23 degrees C. The sintered glass-ceramic and porcelainized stoneware presented similar mechanical and tribological properties. Regarding the mechanical and tribological properties, the results suggest that this glass-ceramic is suitable to be used as industrial tile. (C) 2011 Elsevier B.V. All rights reserved.

Blocked diisocyanates as reactive coupling agents: Application to pine fiber-polypropylene composites

In this paper, composites from polypropylene and Kraft pulp (from Pinus radiata) were prepared. Phenyl isocyanate, unblocked and phenol blocked derivatives of 4,4`-methylenebis (phenyl isocyanate) (MDI) were used as coupling agents and the mechanical properties of the obtained composites analyzed. The results showed that the addition of such compatibilizers readily improved the tensile and flexural strengths of the composites. However, no significant variation in the mechanical properties was observed for composite formulations comprising different isocyanate compounds. Accordingly, the chemical structure of isocyanate derivatives did not affect extensively the mechanical properties of MDI-coupled pine fiber reinforced composites. These results were similar to those obtained in previous studies regarding the efficiency of organosilane coupling agents. In comparison to monoreactive isocyanates, the addition of MIDI increased considerably the mechanical properties of pine fiber-polypropylene composites. The mechanical anchoring of polymeric PP chains onto the irregular reinforcement surface supported this result. Non-isothermal DSC analysis showed a slowing effect of MDI on the crystallization kinetics of the coupled composites. This may have been the result of diminished polymer chain mobility in the matrix due to mechanical anchoring onto the fiber surface. Considering these results, the occurrence of strong bonds between the composite components was stated, rather than the unique existence of Van der Waals interactions among the non-polar structures. (c) 2008 Elsevier Ltd. All rights reserved.

Influence of the Solvent Evaporation Rate on the Crystalline Phases of Solution-Cast Poly(Vinylidene Fluoride) Films

The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N-dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 785-791, 2010

Simulated annealing applied to the irregular rotational placement of shapes over containers with fixed dimensions

This work deals with the problem of minimizing the waste of space that occurs on a rotational placement of a set of irregular two dimensional polygons inside a two dimensional container. This problem is approached with an heuristic based on simulated annealing. Traditional 14 external penalization"" techniques are avoided through the application of the no-fit polygon, that determinates the collision free area for each polygon before its placement. The simulated annealing controls: the rotation applied, the placement and the sequence of placement of the polygons. For each non placed polygon, a limited depth binary search is performed to find a scale factor that when applied to the polygon, would allow it to be fitted in the container. It is proposed a crystallization heuristic, in order to increase the number of accepted solutions. The bottom left and larger first deterministic heuristics were also studied. The proposed process is suited for non convex polygons and containers, the containers can have holes inside. (C) 2009 Elsevier Ltd. All rights reserved.

Cracking formation on the surface of extruded photodegraded polypropylene plates

The cracking formation during the photodegradation of polypropylene (PP) plates (1 mm thickness), with (PPOx) and without pro-oxidant [PP), has been investigated. The plates were produced by extrusion in an industrial production line and were exposed to ultraviolet radiation in the laboratory for periods of up to 480 hr. The samples were investigated by infrared spectroscopy- FTIR, optical light microscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed that the extension of photodegradation process is more intense for PPOx than for PP samples. For both samples, cracks were formed at the surface perpendicularly to the flow-lines. However the cracks frequency was different for both samples and sides of sample. The crack frequency was correlated with chain orientation, A(110); it was shown that lower degrees of orientation resulted in lower crack frequency. POLYM. ENG. SCI., 48:365-372, 2008. (c) 2007 Society of Plastics Engineers.

Influence of Water Content, Time, and Temperature on the Rheological Behavior of Polyethylene Terephtalate

In this work, the main factors affecting the rheological behavior of polyethylene terephtalate (PET) in the linear viscoelastic regime (water content, time delay before test, duration of experiment, and temperature) were accessed. Small amplitude oscillatory shear tests were performed after different time delays ranging from 300 to 5000 s for samples with water contents ranging from 0.02 to 0.45 wt %. Time sweep tests were carried out for different durations to explain the changes undergone by PET before and during small amplitude oscillatory shear measurements. Immediately after the time sweep tests, the PET samples were removed from the rheometer, analyzed by differential scanning calorimetry and their molar mass was obtained by viscometry analysis. It was shown that for all the samples, the delay before test and residence time within the rheometer (i.e. duration of experiment) result in structural changes of the PET samples, such as increase or decrease of molar mass, broadening of molar mass distribution, and branching phenomena. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3525-3533, 2010

Influence of the rubbery phase on the crystallinity and thermomechanical properties of poly(3-hydroxybutyrate)/elastomer blends

Poly(3-hydroxybutyrate) (PHB) is a very promising biopolymer. In order to improve its processability and decrease its brittleness, PHB/elastomer blends can be prepared. In the work reported, the effect of the addition of a rubbery phase, i.e. ethylene - propylene-diene terpolymer (EPDM) or poly(vinyl butyral) (PVB), on the properties of PHB was studied. The effects of rubber type and of changing the PHB/elastomer blend processing method on the crystallinity and physical properties of the blends were also investigated. For blends based on PHB, the main role of EPDM is its nucleating effect evidenced by a decrease of crystallization temperature and an increase of crystallinity with increasing EPDM content regardless of the processing route. While EPDM has a weak effect on PHB glass transition temperature, PVB induces a marked decrease of this temperature thank to its plasticizer that swells the PHB amorphous phase. A promising solution to improve the mechanical properties of PHB seems to be the melt-processing of PHB with both plasticizer and EPDM. In fact, the plasticizer is more efficient than the elastomer in decreasing the PHB glass transition temperature and, because of the nucleating effect of EPDM, the decrease of the PHB modulus due to the plasticizer can be counterbalanced. (C) 2010 Society of Chemical Industry

Colloidal Processing of Glass-Ceramics for Laminated Object Manufacturing

Green tapes of Li(2)O-ZrO(2)-SiO(2)-Al(2)O(3) (LZSA) parent glass were produced by aqueous tape casting as the starting material for the laminated object manufacturing (LOM) process. The rheological behavior of the powder suspensions in aqueous media, as well as the mechanical properties of the cast tapes, was evaluated. According to xi potential measurements, the LZSA glass powder particles showed acid surface characteristics and an IEP of around 4 when in aqueous media. The critical volume fraction of solids was about 72 wt% (27 vol%), which hindered the processability of more concentrated slurries. The glass particles also showed an anisometric profile, which contributed to an increase in the interactions between particles during flow. Therefore, the suspensions could not be processed at high solids loadings. Aqueous-based glass suspensions were also characterized by shear thickening after the addition of dispersants. Three slurry compositions were formulated, suitable green tapes were cast, and tapes were successfully laminated by LOM to a gear wheel geometry. A higher tensile strength of the green tapes corresponded to a higher tensile strength of the laminates. Thermal treatment was then applied to the laminates: pyrolysis at 525 degrees C, sintering at 700 degrees C for 1 h, and crystallization at 850 degrees C for 30 min. A 20% volumetric shrinkage was observed, but no surface flaws or inhomogeneous areas were detected. The sintered part maintained the curved edges and internal profile after heat treatment.