Thermodynamic properties applied to the sorption isotherms of kiwifruit

The net isosteric heat and entropy of water sorption were calculated for kiwifruit, based on sorption isotherms obtained by the static gravimetric method at different temperatures (20 to 70 degreesC). The Guggenheim-Anderson-deBoer equation was fitted to the experimental data, using direct non-linear regression analysis; the agreement between experimental and calculated values was satisfactory. The net isosteric heat of sorption was estimated from equilibrium sorption data, using the Clausius-Clapeyron equation. Isosteric heats of sorption were found to increase with increasing temperature and could be well adjusted by an exponential relationship. The enthalpy-entropy compensation theory was applied to sorption isotherms and plots of DeltaH versus DeltaS provided the isokinetic temperature, T-B = 450.9 +/- 7.7 K, indicating an enthalpy-controlled desorption process over the whole range of moisture content considered.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Micro-Raman analysis of cubic GaN layers grown by MBE on (001) GaAs substrate

Cubic GaN layers are grown by molecular beam epitaxy on (001) GaAs substrates. Optical micrographs of the GaN epilayers intentionally grown at Ga excess reveal the existence of surface irregularities such as bright rectangular structures, dark dots surrounded by rectangles and dark dots without rectangles. Micro-Raman spectroscopy is used to study the structural properties of these inclusions and of the epilayers in greater detail. We conclude that the observed irregularities are the result of a melting process due to the existence of a liquid Ga phase on the growing surface.

Titanium and zirconium complexes containing sterically hindered hydrotris(pyrazolyl)borate ligands: synthesis, structural characterization, and ethylene polymerization studies

The synthesis, characterization and ethylene polymerization behavior of a set of Tp'MCl3 complexes (4, M = Ti, Tp' HB(3-neopentyl-pyrazolyl)(3)(-) (Tp(NP)); 5, M = Ti, Tp'= HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu)); 6, M = Ti, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(Ph)); 7, M = Zr, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(ph)); 8, M = Zr, Tp' = HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu))) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 degreesC and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 X 10(3) g of PE/mol[M](.)h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights ((M-v) over bar) of the PE's produced with these catalyst precursors varying from 3.57 to 20.23 x 10(5) gmol(-1) with melting temperatures in the range of 127-134 degreesC. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 degreesC. The viscosity-average molecular weights of the polyethylene's decreases with increasing AI/Zr molar ratio. (C) 2003 Elsevier B.V. All rights reserved.

Blue cooperative luminescence properties in Yb3+ doped GeO2-PbO-Bi2O3 vitreous system for the production of thin films

Germanate glasses are of interest for optoelectronic applications because they combine high mechanical strength, high chemical durability and temperature stability with a large transmission window (400 to 4500 nm) and high refractive index (2.0). GeO2-PbO-Bi2O3 glasses doped with Y-b(3+) were fabricated by melting powders in a crucible and then pouring them in a brass mold. Energy Dispersive Spectroscopy showed that the glass composition has a high spatial uniformity and that the Yb concentration in the solid sample is proportional to the Yb concentration in the melt, what was confirmed by absorption measurements. Intense blue emission at 507 nm was observed, corresponding to half of the wavelength of the near infrared region (NIR) emission; besides, a decay lifetime of 0.25 ms was measured and this corresponds to half of the decay lifetime in the infrared region; these are very strong indications of the presence of blue cooperative luminescence. Larger targets have been produced to be sputtered, resulting in thin films for three dimensional (3D) display and waveguide applications. (c) 2006 Elsevier B.V. All rights reserved.

Oxygen mobility in SmBa2Cu3O7-delta measured by anelastic spectroscopy

Anelastic spectroscopy has been performed on a sample of superconducting oxide SmBa2Cu3O7-delta (SBCO) using a torsion pendulum operating with frequency around 10 Hz. A thermally activated relaxation peak is observed near 500 K with the activation enthalpy of 1.55 +/- 0.03 eV and the pre-exponential factor of approximately 10(-15) s, which is attributed to the mobility of non-stoichiometric oxygen by jumps in positions O1 and O5 of the lattice. (c) 2006 Elsevier B.V. All rights reserved.

1.5 mu m emission and infrared-to-visible frequency upconversion in Er+3/Yb+3-doped phosphoniobate glasses

Sodium phosphoniobate glasses with the composition (mol%) 75NaPO(3)-25Nb(2)O(5) and containing 2 mol% Yb3+ and x mol% Er3+ (0.01 <= x <= 2) were prepared using the conventional melting/casting process. Er3+ emission at 1.5 mu m and infrared-to-visible upconversion emission, upon excitation at 976 nm, are evaluated as a function of the Er3+ concentration. For the lowest Er3+ content, 1.5 mu m emission quantum efficiency was 90%. Increasing the Er3+ concentration up to 2 mol%, the emission quantum efficiency was observed to decrease to 37% due to concentration quenching. The green and red upconversion emission intensity ratio was studied as a function of Yb3+ co-doping and the Er3+-Er3+ energy transfer processes. (c) 2006 Elsevier B.V. All rights reserved.

Evaluation of the thermal shrinkage of titanium and the setting and thermal expansion of phosphate-boded investments

Statement of problem. There are few studies on titanium casting shrinkage, and phosphate-bonded investments for titanium casting have not produced appropriate marginal fit.Purpose. The purpose of this study was to determine the thermal shrinkage of titanium and the setting and thermal expansion of 3 phosphate-bonded investments.Material and methods. The thermal shrinkage between the melting temperature and room temperature was calculated using a titanium thermal expansion coefficient. The thermal and setting expansion were measured for 3 phosphate bonded investments: Rematitan Plus (RP) specific for titanium, Rema Exakt (RE), and Castorit Super C (CA), using different special liquid concentrations (100%, 75%, and 50%). Setting expansion was measured for cylindrical specimens 50 mm long x 8 mm in diameter with a transducer. The heating and cooling curves were obtained with a dilatometer (DIL 402 PC). The total expansion curve was drawn using software, and temperatures to obtain expansion equivalent to titanium casting shrinkage were determined (n=5). In addition, the total expansion of the control group (RP at 430 degrees C) was measured, as well as the temperatures at which the other groups achieved equivalent total expansion (n=5). Data were analyzed by 1-way ANOVA and the Tukey HSD test (alpha=.05).Results. Titanium casting shrinkage was estimated as 1.55%. RP did not achieve this expansion. RE achieved expansion of 1.55% only with a special liquid concentration of 100% at 594 degrees C. CA with all special liquid concentrations attained this expansion (351 degrees C to 572 degrees C). Total expansion of the control group was 0.86%, and the other groups reached that expansion within the range of 70 degrees C to 360 degrees C.Conclusions. Only RE and CA demonstrated sufficient expansion to compensate for titanium casting shrinkage. All groups reached total expansion equivalent to that of the control group at significantly lower temperatures.

New tungstate fluorophosphate glasses

\A new class of tungstate fluorophosphate glasses was identified in the NaPO3-BaF2-WO3 ternary system. The variation of several physical properties was determined with respect to chemical composition. Characteristic temperatures, density and refractive index increase as tungsten oxide content increases. The optical transmission range and specially the energy bandgap depend of the WO3 amount. No crystallization could be observed for the Most WO3 concentrated vitreous samples (greater than or equal to20% molar). Color and optical properties of the glasses depend of the melting time because of the presence of reduced tungsten species like W5+ and W4+. In addition, photodarkening is observed in tungsten rich glass samples under UV laser illumination and this phenomenon can be reversible by heat treatment near the glass transition temperature. (C) 2004 Published by Elsevier B.V.

Effects of Nd : YAG laser irradiation on root canal dentin wall: A scanning electron microscopic study

Objective: the purpose of this study was to evaluate, by scanning electron microscopy (SEM), the effects of Nd:YAG laser irradiation applied perpendicular or parallel to the root canal dentin wall. Methods: Thirty human teeth were divided into two groups: Group A (20 roots), laser application with circular movements, parallel to the dentin root surface; and Group B (10 roots), roots cut longitudinally and laser applied perpendicular to the root surface. Group A was subdivided into A1 (10 roots), laser application with 100 mJ, 15 Hz and 1.5 W; and A2 (10 roots) with 160 mJ, 15 Hz, and 2.4 W. Group B was subdivided into B1 (10 hemisections) and B2 (10 hemi-sections) with parameters similar to A I and A2. Four applications of 7-sec duration were performed, with a total exposure of 28 sec. SEM evaluations were made in the cervical, middle, and apical thirds, with 500X and 2000X magnifications. Morphological changes scores were attributed, and the results were submitted to Kruskal Wallis statistical test (5%). Results: Significant statistical differences were found between groups A and B (p = 0.001). In groups A1 and A2, few areas of dentin melting were observed. In groups B1 and B2, areas of melting dentin covering dentin surface were observed. Conclusions: It was concluded that intracanal laser application with circular movements (parallel to the surface) produces limited morphological changes in root canal dentin wall.

Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

Surface modification of Ti dental implants by Nd: YVO4 laser irradiation

Surface modifications have been applied in endosteal bone devices in order to improve the osseointegration through direct contact between neoformed bone and the implant without an intervening soft tissue layer. Surface characteristics of titanium implants have been modified by addictive methods, such as metallic titanium, titanium oxide and hydroxyapatite powder plasma spray, as well as by subtractive methods, such as acid etching, acid etching associated with sandblasting by either AlO2 or TiO2, and recently by laser ablation. Surface modification for dental and medical implants can be obtained by using laser irradiation technique where its parameters like repetition rate, pulse energy, scanning speed and fluency must be taken into accounting to the appropriate surface topography. Surfaces of commercially pure Ti (cpTi) were modified by laser Nd:YVO4 in nine different parameters configurations, all under normal atmosphere. The samples were characterized by SEM and XRD refined by Rietveld method. The crystalline phases alpha Ti, beta Ti, Ti6O, Ti3O and TiO were formed by the melting and fast cooling processes during irradiation. The resulting phases on the irradiated surface were correlated with the laser beam parameters: the aim of the present work was to control titanium oxides formations in order to improve implants osseointegration by using a laser irradiation technique which is of great importance to biomaterial devices due to being a clean and reproducible process. (c) 2007 Elsevier B.V. All rights reserved.

Linear low density polyethylene (LLDPE) from ethylene using Tp(Ms)NiCl (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and CP2ZrCl2 as a tandem catalyst system

Linear low density polyethylene (LLDPE) with different branching contents were prepared from ethylene, without the addition of alpha-olefin comonomer, using a combination of catalyst precursors {Tp(Ms)}NiCl (1) (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and Cp2ZrCl2 (2) activated with MAO/TMA (1:1) in toluene at 0degreesC and by varying the nickel loading mole fraction (x(Ni)). The polymerization results showed that the turnover frequencies are strongly dependent on the x(Ni) varying from 6.6 x 10(3) to 32.1 x 10(3) mol[C2H4]/mol[Zr] h. The C-13 NMR spectra of the copolymers showed that the branch contents of the polymers increase as the x(Ni) increase in the medium promoting the production of polymers with a wide range of melting point (T-m) (C) 2004 Elsevier B.V. All rights reserved.

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid-ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T-c). Solutions of polymers containing 10% or less of AA display a constant T-c for pH above 5.5, with 15% there is a continuous increase in T-c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I (1)/I (3) ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T-c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.

Polymerization of ethylene by the tris(pyrazolyl)borate titanium(IV) compound immobilized on MAO-modified silicas

The immobilization of soluble catalyst {Tp(Ms)}TiCl3 (Tp(Ms*)HB(3-mesityl-pyrazolyl)(2)(5-mesityl-pyrazolyl)(-)) on silica and MAO-modified silicas containing 4.0, 8.0 and 23.0 wt.% Al/SiO2 yields active supported catalysts for ethylene polymerization. Among the supported catalysts studied by XRF spectroscopy, higher titanium content was obtained using MAO-modified silica containing 8.0 wt.% Al/SiO2 as support. For the ethylene polymerization reactions carried out in hexane at 60degreesC using a combination of triisobutylaluminum (TiBA) and methylaluminoxane (MAO) (1:1), the activities varied between 24.4 and 113.5 kg of PE/mol [Ti] h. The highest activity is reached using MAO-modified silica containing 4.0 wt.% Al/SiO2 as support. The viscosity-average molecular weights ((M) over bar (v)) of the PE's produced with the supported catalysts varying from 1.44 to 9.94 x 10(5) g/mol with melting temperatures in the range of 125-140degreesC. The use of other Lewis acid cocatalysts, including TiBA, diethylaluminium chloride (DEAC), and trimethylaluminum (TMA) resulted also in the formation of active catalysts for ethylene polymerization. However, the activities are lower than that one using a combination of TiBA and MAO. The viscosity-average molecular weights (R,) of PE's are influenced by varying the cocatalysts as well as the Al/Ti molar ratio. The supported catalyst generated in situ under ethylene atmosphere is roughly four times more active than supported one containing 4.0 wt.% Al/SiO2. (C) 2003 Elsevier B.V. All rights reserved.