Temperature-agile and structure-tunable optical properties of VO 2/Ag thin films

By integrating together VO2’s unique near-room-temperature (RT) semiconductor–metal (S–M) phase transition with a thin silver (Ag) layer’s plasmonic properties, VO2/Ag multilayers could present a much enhanced optical transmission change when increasing the temperature from RT to over VO2’s S–M phase-transition temperature. Changing VO2 and Ag layer thicknesses can also significantly tune their transmission and absorption properties, which could lead to a few useful designs in optoelectronic and energy-saving industries.

Ion conduction and phase morphology in sulfonate copolymer ionomers based on ionic liquid–sodium cation mixtures

A series of sulfonate based copolymer ionomers based on a combination of ionic liquid and sodium cations have been prepared in different ratios. This system was designed to improve the ionic conductivity of ionomers by partially replacing sodium cations with bulky cations that are less associated with anion centres on the polymer backbone. This provides more conduction sites for sodium to ‘hop’ to in the ionomers. Characterization showed the glass transition and 15N chemical shift of the ionomers did not vary significantly as the amount of Na+ varied, while the ionic conductivity increased with decreasing Na+ content, indicating conductivity is increasingly decoupled from Tg. Optical microscope images showed phase separation in all compositions, which indicated the samples were inhomogeneous. The introduction of low molecular weight plasticizer (PEG) reduced the Tg and increased the ionic conductivity significantly. The inclusion of PEG also led to a more homogeneous material.

Effect of temperature on mechanical behaviour of high manganese TWIP steel

The aim of the present study was to investigate the role of deformation temperature on the active deformation mechanisms in a 0.6C-18Mn-1.5Al (wt%) TWIP steel. The tensile testing was performed at different temperatures, ranging from ambient to 400°C at a constant strain rate of 10-3 S-1. The microstructure characterization was carried out using a scanning electron microscopy. The deformation temperature revealed a significant effect on the active deformation mechanisms (i.e. slip versus twinning), resulting in different microstructure evolution and mechanical properties. At the room temperature, the mechanical twinning was the dominant deformation mechanism, enhancing both the strength and ductility. Dynamic strain aging (DSA) effect was observed at different deformation temperatures, though it was more pronounced at higher temperatures. The volume fraction of deformation twins significantly reduced with an increase in the deformation temperature, deteriorating the mechanical behavior. There was a transition temperature (~300°C), above which the mechanical twinning was hardly observed in the microstructure even at fracture, resulting in low ductility and strength. The current observation can be explained through the change in the stacking fault energy with the deformation temperature. © (2014) Trans Tech Publications, Switzerland.

Effect of strontium addition on ferroelectric phase transition of PZT thin films prepared by chemical route

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

Vesicle-micelle transition in mixtures of dioctadecyldimethylammonium chloride and bromide with nonionic and zwitterionic surfactants

We have investigated the effect of mixing spontaneously formed dispersions of the cationic vesicle-forming dioctadecyldimethylammonium chloride and bromide (DODAX, with X being anions Cl- (C) or Br- (B)) with solutions of the micelle-forming nonionic ethylene oxide surfactants penta-, hepta-, and octaethyleneglycol mono-n-dodecyl ether, C12En (n = 5, 7, and 8), and the zwitterionic 3-(N-hexadecyl-N,N-dimethylammonio)propane sulfonate (HPS). We used for this purpose differential scanning calorimetry (DSC), turbidity, and steady-state fluorescence spectroscopy to investigate the vesicle-micelle (V-M) transition yielded by adding C12En and HPS to 1.0 mM vesicle dispersions of DODAC and DODAB. The addition of these surfactants lowers the gel-to-liquid crystalline phase transition temperature (T-m) of DODAC and DODAB, and the transition becomes less cooperative, that is, the thermogram transition peak shifts to lower temperature and broadens to disappear when the V-M transition is complete, the vesicle bilayer becomes less organized, and the T., decreases, in agreement with measurements of the fluorescence quantum yield of trans-diphenylpolyene (t-DPO) fluorescence molecules incorporated in the vesicle bilayer. Turbidity data indicate that the V-M transition comes about in three stages: first surfactants are solubilized into the vesicle bilayer; after saturation, the vesicles are ruptured, and, finally, the vesicles are completely solubilized and only mixed micelles are formed. The critical points of bilayer saturation and vesicle solubilization were obtained from the turbidity and fluorescence curves, and are reported in this communication. The solubility of DODAX is stronger for C12En than it is for HPS, meaning that C12En solubilizes DODAX more efficiently than does HPS. The surfactant solubilization depends slightly on the counterion, and varies according to the sequence C12E5 > C12E7 > C12E8 > HPS.

Phase transition in dioctadecyldimethylammonium bromide and chloride vesicles prepared by different methods

The gel to liquid crystalline phase transition of the double-chained cationic dioctadecyldimethylammonium chloride and bromide (DODAX, X = Cl- or Br-) in aqueous vesicle dispersions prepared by non-sonication, sonication and extrusion has been investigated using high-sensitivity differential scanning calorimetry (DSC). The transition temperature (T-m) is a function of the preparation method, amphiphile concentration, vesicle curvature and nature of the counterion. DSC thermograms for DODAB and DODAC non-sonicated vesicle dispersions exhibit a single endothermic peak at T-m roughly independent of concentration up to 10 mM. Extrusion broadens the transition peak and shifts T-m downwards. Sonication, however, broadens slightly the transition peak and tends to shift T-m upwards suggesting that extrusion and sonication form vesicles with different characteristics. DODAC always exhibits higher T-m than DODAB irrespective of the preparation method. T-m changes as follows: T-m (sonicated) greater than or equal to T-m (non-sonicated) > T-m (extruded). Hysteresis of about 7 degrees C was observed for DODAB vesicle dispersions. (C) 2000 Elsevier B.V. Ireland Ltd. All rights reserved.

The effect of chain length on the melting temperature and size of dialkyldimethylammonium bromide vesicles

Differential scanning calorimetry (DSc) and dynamic light scattering (DLS) were used to obtain the gel to liquid-crystalline phase transition temperature (T-m) and the apparent hydrodynamic radius (R-h) of spontaneously formed cationic vesicles of dialkyldimethylammonium bromide salts (CnH2n+1)(2)(CH3)(2)N+center dot Br-, with varying chain lengths. The preparation of cationic vesicles from aqueous solution of these surfactants, for n = 12, 14, 16 and 18 (DDAB, DTDAB, DHDAB and DODAB, respectively), requires the knowledge of the surfactant gel to liquid-crystalline phase transition temperature, or melting temperature (T-m) since below this temperature these surfactants are poorly or not soluble in water. That series of cationic surfactants has been widely investigated as vesicle-forming surfactants, although C-12 and C-18, DDAB and DODAB are by far the most investigated from this series. The dependence of T-m of these surfactants on the number n of carbons in the surfactant tails is reported. The T-m obtained by DSC increases non-linearly with n, and the vesicle apparent radius R-h is about the same for DHDAB and DODAB, but much smaller for DDAB. (c) 2006 Elsevier B.V.. All rights reserved.

Critical temperature for first-order phase transitions in confined systems

We consider the Euclidean D-dimensional -lambda vertical bar phi vertical bar(4)+eta vertical bar rho vertical bar(6) (lambda,eta > 0) model with d (d <= D) compactified dimensions. Introducing temperature by means of the Ginzburg-Landau prescription in the mass term of the Hamiltonian, this model can be interpreted as describing a first-order phase transition for a system in a region of the D-dimensional space, limited by d pairs of parallel planes, orthogonal to the coordinates axis x(1), x(2),..., x(d). The planes in each pair are separated by distances L-1, L-2, ... , L-d. We obtain an expression for the transition temperature as a function of the size of the system, T-c({L-i}), i = 1, 2, ..., d. For D = 3 we particularize this formula, taking L-1 = L-2 = ... = L-d = L for the physically interesting cases d = 1 (a film), d = 2 (an infinitely long wire having a square cross-section), and for d = 3 (a cube). For completeness, the corresponding formulas for second-order transitions are also presented. Comparison with experimental data for superconducting films and wires shows qualitative agreement with our theoretical expressions.

Simultaneous observation of the magnetic and electric behavior in a correlated system near a metal-semiconductor transition: ESR in pellets of conducting polymers

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

Magnetic field induced lattice effects in a quasi-two-dimensional organic conductor close to the Mott metal-insulator transition

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

Kinetic parameters for thermal decomposition of supramolecular polymers derived from flunixin-meglumine adducts

Meglumine, (2R,3R,4R,5S)-6-methylaminohexane-1,2,3,4,5-pentol, is a carbohydrate derived from sorbitol in which the hydroxyl group in position one is replaced by a methylamine group. It forms binary adducts with substances having carboxyl groups, which have in common the presence of hydrogen bonding as the main force in the stabilization of these species. During melting, adducts of meglumine with flunixin (2-[[2-methyl-3-(trifluoromethyl)phenyl]amino]pyridine-3-carboxylic acid) polymerize or self-assemble in amorphous supramolecular structures with molecular weights around 2.0 x 10(5) kDa. DSC curves, in a first heating, show isomorphic transitions where the last one at 137 A degrees C for the flunixin-meglumine adduct originated the supramolecular amorphous polymers with glass transition around 49.5 A degrees C. The kinetic parameters for the thermal decomposition step of the polymers were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15, and 20 A degrees C min(-1), the E (alpha) and B (alpha) terms could be determined and, consequently, the pre-exponential factor, A(alpha), as well as the kinetic model, g(alpha).

Liofilização de fatias de abacaxi: avaliação da cinética de secagem e da qualidade do produto

O objetivo deste trabalho foi avaliar a cinética de secagem e os parâmetros de qualidade - conteúdo de vitamina C, reidratação e textura - de fatias de abacaxi liofilizadas em função da espessura e da temperatura de congelamento. Abacaxis do tipo Havaí, variedade Smooth Cayenne, foram fatiados transversalmente em espessuras de 0,5, 1,0 e 1,5 cm. As fatias foram congeladas nas temperaturas de -14, -24 e -34 °C, sendo, em seguida, conduzidas ao liofilizador. Uma parcela das amostras era destinada ao estudo da cinética de secagem pela pesagem periódica das mesmas, enquanto outra foi reservada para os testes de qualidade. O teor de vitamina C foi quantificado por adição de ácido oxálico na amostra e titulado com 2,6-diclorofenolindofenol. O parâmetro de textura avaliado foi a dureza, por testes de compressão em texturômetro, enquanto a reidratação foi obtida pela pesagem das amostras antes e após a imersão em água destilada por 5 min. Os resultados do presente trabalho mostraram que existe uma forte dependência da cinética de secagem e dos atributos de qualidade de fatias de abacaxi liofilizadas em função das condições utilizadas durante a etapa de congelamento, mesmo sendo este classificado como congelamento lento. Por outro lado, a taxa de congelamento não é a única variável que tem influência sobre a cinética de secagem e os atributos de qualidade. A combinação de temperatura e umidade, tanto durante a liofilização propriamente dita, quanto durante a etapa de reidratação, tem influência sobre a transição vítrea do material que, por sua vez, afeta a extensão do colapso estrutural sofrido pelo produto.

Investigation of phase transition in ferroelectric Pb0.70Sr0.30TiO3 thin films

We have carried out dielectric and Raman spectroscopy studies at the 298-623 K temperature range in polycrystalline Pb0.70Sr0.30TiO3 thin films grown by a soft chemical method. The diffuse phase-transition behavior of the thin films was observed by means of the dielectric constant versus temperature curves, which show a broad peak. Such behavior was confirmed later by Raman spectroscopy measurements up to 823 K, indicating that a diffuselike phase transition takes place at around 548-573 K. The damping factor of the E(1TO) soft mode was calculated using the damped simple harmonic oscillator model. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of a breakdown of the microscopic local cubic symmetry by chemical disorder. The lack of a well-defined transition temperature and the presence of broad bands at some temperature interval above the ferroelectric-paraelectric phase-transition temperature suggested a diffuse nature of the phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in this thin film. (C) 2004 American Institute of Physics.

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298 - 673 K temperature range in polycrystalline Pb0.50Sr0.50TiO3 thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb0.50Sr0.50TiO3 thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO3 perovskite.