Abnormal pressure dependence of the phase boundaries in TL/PEO/P(EO-b-DMS) ternary mixtures

The cloud-point temperatures (T-cl's) of both binary poly(ethylene oxide) (PEO)-poly(ethylene oxide-b-dimethylsiloxane) [P(EO-b-DMS)] and ternary[toluene/PEO/P(EO-b-DMS)] systems were determined by light scattering measurements at atmospheric pressure. The phase separation behavior upon cooling in the ternary system has been investigated at atmospheric pressure and under high pressure and compared to the phase behavior in the binary system. The phase transition temperatures have been obtained for all of the samples. As a result, the pressure induces compatibility in the binary mixtures, but for the ternary system, pressure not only can induce mixing but also can induce phase separation.

Phase behavior of polymer blends

The present report deals with some results on phase behavior, miscibility and phase separation for several polymer blends casting from solutions. These blends are grouped as the amorphous polymer blends, blends containing a crystalline polymer or two crystalline polymers. The blends of PMMA/PVAc were miscible and underwent phase separation at elevated temperature, exhibited LCST behavior. The benzoylated PPO has both UCST and LCST nature. For the systems composed of crystalline polymer poly(ethylene oxide) and amorphous polyurethane, of two crystalline polymers poly(epsilon-caprolactone) and poly[3,3,-bis-(chloromethyl) oxetane], appear a single T-g, indicating these blends are miscible. The interaction parameter B's were determined to be -14 J cm(-3), -15 J cm(-3) respectively. Phase separation of phenolphthalein poly(ether ether sulfone)/PEO blends were discussed in terms of thermal properties, such as their melting and crystallization behavior.

MISCIBILITY AND PHASE-BEHAVIOR IN BLENDS OF POLY(HYDROXYETHER OF BISPHENOL-A) WITH POLY(ETHYLENE OXIDE-CO-PROPYLENE OXIDE)

The miscibility of poly(hydroxyether of bisphenol A) (phenoxy) with a series of poly(ethylene oxide-co-propylene oxide) (EPO) has been studied. It was found that the critical copolymer composition for achieving miscibility with phenoxy around 60-degrees-C is about 22 mol % ethylene oxide (EO). Some blends undergo phase separation at elevated temperatures, but there is no maximum in the miscibility window. The mean-field approach has been used to describe this homopolymer/copolymer system. From the miscibility maps and the melting-point depression of the crystallizable component in the blends, the binary interaction energy densities, B(ij), have been calculated for all three pairs. The miscibility of phenoxy with EPO is considered to be caused mainly by the intermolecular hydrogen-bonding interactions between the hydroxyl groups of phenoxy and the ether oxygens of the EO units in the copolymers, while the intramolecular repulsion between EO and propylene oxide units in the copolymers contributes relatively little to the miscibility.

PHASE-BEHAVIOR IN EPOXY-RESIN CONTAINING PHENOLPHTHALEIN POLY(ETHER ETHER SULFONE)

Phenolphthalein poly(ether ether sulphone) (PES-C) was found to be miscible with uncured bisphenol-A-type epoxy resin, i.e. diglycidyl ether of bisphenol A (DGEBA), as shown by the existence of a single glass transition temperature within the whole composition range. Miscibility between PES-C and DGEBA is considered to be due mainly to the entropy contribution. However, dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM) studies revealed that PES-C exhibits different miscibility with four cured epoxy resins (ER). The overall compatibility and the resulting morphology of the cured blends are dependent on the choice of cure agent. For the blends cured with amines (4,4'-diaminodiphenylmethane (DDM) and 4,4'-diaminodiphenylsulphone (DDS)), no phase separation occurs as indicated by either d.m.a. or SEM. However, for the blends cured with anhydrides (maleic anhydride (MA) and phthalic anhydride (PA)), both d.m.a. and SEM clearly show evidence of phase separation. SEM study shows that the two phases interact well in the MA-cured blend while the interface between the phases in the PA-cured blend is poorly bonded. The differences in the overall compatibility and the resulting morphology between the amine-cured and anhydride-cured systems have been discussed from the points of view of both thermodynamics and kinetics.

含AlF3和ZrF4氟化物玻璃的分相与析晶

以摩尔组成为8．7MgF2-17．4CaF2-8．7SrF2-13．3BaF2-13．0YF3-31．6．AlF3-7．3ZrF4的氟化物玻璃为对象，研究了玻璃的分相和析晶．研究表明，玻璃中同时含有AlF3和ZrF4时，玻璃产生明显的分相，玻璃在高温下对水比较敏感，容易产生表面析晶．玻璃内部的析晶主要来自稳定性较差的富Al相，受空气中水分的影响，玻璃表面的析晶首先产生于富Zr相．依据玻璃的分相和析晶表现，讨论了含AlF3和ZrF4氟化物玻璃的表面析晶机理．

Solid-state NMR study of bioactive binary borosilicate glasses

A series of binary borosilicate glasses prepared by the sol-gel method are shown to be bioactive. Tetraethyl orthosilicate (TEOS) and trimethylborate (TMB) in acidic medium are used to prepare xB(2)O(3)center dot(1-x)SiO2 glass systems for x = 0.045-0.167. The formation of a layer of apatite-like mineral on the glass surface becomes apparent after soaking in simulated body fluid for 48 h. We have measured the B-11-B-11 homonuclear second moments of the borosilicate glasses and inferred that no macroscopic phase separation occurred in our glasses. The B-11 chemical shift data also show that the formation of clustered boroxol rings is negligible in our glass system. Although the bioactivity of our borosilicate glasses is less than that of CaO-SiO2 sol-gel glasses, these simple binary systems could be taken as reference glass systems for the search of new bioactive borosilicate glasses. (C) 2008 Elsevier Ltd. All rights reserved.

High-quality GaNAs/GaAs quantum wells with light emission up to 1.44 mu m grown by molecular-beam epitaxy

High-quality GaNAs/GaAs quantum wells with high substitutional N concentrations, grown by molecular-beam epitaxy, are demonstrated using a reduced growth rate in a range of 0.125-1 mu m/h. No phase separation is observed and the GaNAs well thickness is limited by the critical thickness. Strong room-temperature photoluminescence with a record long wavelength of 1.44 mu m is obtained from an 18-nm-thick GaN0.06As0.94/GaAs quantum well. (C) 2005 American Institute of Physics.

Spatial distribution of deep level defects in crack-free AlGaN grown on GaN with a high-temperature AlN interlayer

The deep level luminescence of crack-free Al0.25Ga0.75N layers grown on a GaN template with a high-temperature grown AlN interlayer has been studied using spatially resolved cathodoluminescence (CL) spectroscopy. The CL spectra of Al0.25Ga0.75N grown on a thin AlN interlayer present a deep level aquamarine luminescence (DLAL) band at about 2.6 eV and a deep level violet luminescence (DLVL) band at about 3.17 eV. Cross-section line scan CL measurements on a cleaved sample edge clearly reveal different distributions of DLAL-related and DLVL-related defects in AlGaN along the growth direction. The DLAL band of AlGaN is attributed to evolve from the yellow luminescence band of GaN, and therefore has an analogous origin of a radiative transition between a shallow donor and a deep acceptor. The DLVL band is correlated with defects distributed near the GaN/AlN/AlGaN interfaces. Additionally, the lateral distribution of the intensity of the DLAL band shows a domainlike feature which is accompanied by a lateral phase separation of Al composition. Such a distribution of deep level defects is probably caused by the strain field within the domains. (c) 2006 American Institute of Physics.

Temperature dependence of the formation of nano-scale indium clusters in InAlGaN alloys on Si(111) substrates

The temperature dependence of the formation of nano-scale indium clusters in InAlGaN quaternary alloys, which are grown by metalorganic chemical vapour deposition on GaN/Si(111) epilayers, is investigated. Firm evidence is provided to support the existence of phase separation, or nano-scale In-rich clusters, by the combined results of high-resolution transmission electron microscopy (HRTEM), high-resolution x-ray diffraction (HRXRD) and micro-Raman spectra. The results of HRXRD and Raman spectra indicate that the degree of phase separation is strong and the number of In clusters in the InAlGaN layers on silicon substrate is higher at lower growth temperatures than that at higher growth temperatures, which limits the In and Al incorporated into the InAlGaN quaternary alloys. The detailed mechanism of luminescence in this system is studied by low temperature photoluminescence (LT-PL). We conclude that the ultraviolet (UV) emission observed in the quaternary InAlGaN alloys arises from the matrix of a random alloy, and the second emission peak in the blue-green region results from the nano-scale indium clusters.

Shape and spatial correlation control of InAs-InAlAs-InP(001) nanostructure superlattices

The control of shape and spatial correlation of InAs-InAlAs-InP(001) nanostructure superlattices has been realized by changing the As overpressure during the molecular-beam epitaxy (MBE) growth of InAs layers. InAs quantum wires (QWRs) are obtained under higher As overpressure (1x10(-5) Torr), while elongated InAs quantum dots (QDs) are formed under lower As overpressure (5x10(-6) or 2.5x10(-6) Torr). Correspondingly, spatial correlation changes from vertical anti-correlation in QWR superlattices to vertical correlation in QD superlattices, which is well explained by the different alloy phase separation in InAlAs spacer layers triggered by the InAs nanostrcutures. It was observed that the alloy phase separation in QD superlattices could extend a long distance along the growth direction, indicating the vertical correlation of QD superlattices can be kept in a wide range of spacer layer thickness.

Structural and photoluminescent properties of ternary Zn1-xCdxO crystal films grown on Si(111) substrates

The ternary Zn1-xCdxO (0less than or equal toxless than or equal to0.6) alloying films with highly c-axis orientation have been deposited on Si(111) substrates by direct current reactive magnetron sputtering method. X-ray diffraction measurement indicates that the wurtzite-type structure of ZnO can be stabilized up to nominal Cd content x similar to 0.6 without cubic CdO phase separation. The lattice parameter c of Zn1-xCdxO increases almost linearly from 5.229 Angstrom (x = 0) to 5.247 Angstrom (x = 0.6), indicating that Cd substitution takes place on the Zn lattice sites. The photoluminescence spectra of the Zn1-xCdxO thin films measured at 12 K display a substantial red shift (similar to0.3 eV) in the near-band-edges (NBEs) emission of ZnO: from 3.39 eV of ZnO to 3.00 eV of Zn0.4Cd0.6O. The direct modulation of band gap caused by Zn/Cd substitution is responsible for the red shift effect in NBE emission of ZnO. (C) 2003 Elsevier Science B.V. All rights reserved.

GaN1-xPx ternary alloys with high P composition grown by metal-organic chemical vapor deposition

GaN1-xPx ternary alloys with high P compositions were deposited on sapphire substrates by means of metal-organic chemical vapor deposition. Depth profiles of the elements indicate that the maximum P/N composition ratio is about 17% and a uniform distribution of the P atoms in the alloys is achieved. 2theta/omega XRD spectra demonstrate that the (0002) peak of the GaN1-xPx alloys shifts to smaller angle with increasing P composition. From the photoluminescence (PL) spectra, the red shifts to the bandedge emission of GaN are determined to be 73, 78, 100 and 87 meV for the GaN1-xPx alloys with the P/N composition ratios of 3%, 11%, 15% and 17%, respectively. No PL peak related to GaP is observed, indicating that the phase separation between GaN and GaP is well suppressed in our GaN1-xPx samples. (C) 2003 Elsevier Science B.V. All rights reserved.

Effect of rapid thermal annealing and hydrogen plasma treatment on the microstructure and light-emission of silicon-rich oxide film

Silicon-rich silicon oxide (SRSO) films are prepared by plasma-enhanced chemical vapor deposition method at the substrate temperature of 200degreesC. The effect of rapid thermal annealing and hydrogen plasma treatment on tire microstructure and light-emission of SRSO films are investigated in detail using micro-Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and photoluminescence (PL) spectra. It is found that the phase-separation degree of the films decreases with increasing annealing temperature from 300 to 600degreesC, while it increases with increasing annealing temperature from 600 to 900degreesC. The light-emission of the films are enhanced with increasing annealing temperature up to 500degreesC, while it is rapidly reduced when the annealing temperature exceeds 600degreesC. The peak position of the PL spectrum blueshifts by annealing at the temperature of 300degreesC, then it red-shifts with further raising annealing temperature. The following hydrogen plasma treatment results in a disproportionate increase of the PL intensity and a blueshift or redshift of the peak positions, depending on the pristine annealing temperature. It is thought that the size of amorphous silicon clusters, surface structure of the clusters and the distribution of hydrogen in the films can be changed during the annealing procedure. The results indicate that not only cluster size but also surface state of the clusters plays an important role in the determination of electronic structure of the amorphous silicon cluster and recombination process of light-generated carriers.

Metalorganic chemical vapor deposition of GaNAs alloys using different Ga precursors

The GaNAs alloys have been grown by metalorganic chemical vapor deposition (MOCVD) using dimethylhydrazine (DMHv) as the nitrogen precursor, triethylgallium (TEGa) and trimethylgallium (TMGa) as the gallium precursors, respectively. Both symmetric (004) and asymmetric (1 1 5) high-resolution X-ray diffraction (HRXRD) were used to determine the nitrogen content in GaNAs layers. Secondary ion mass spectrometry (SIMS) was used to obtain the impurity content. T e influence of different Ga precursors on GaNAs quality has been investigated. Phase separation is observed in the < 1 1 5 > direction when using TMGa as the Ga precursor but not observed when using TEGa. This phenomenon should originate from the parasitic reaction between the Ga and N precursors. Furthermore. samples grown with TEGa have better quality and less impurity contamination than those with TMGa. Nitrogen content of 5.742% has been achieved using TEGa and no phase separation observed in the sample. (C) 2002 Elsevier Science B.V. All rights reserved.

Strain and photoluminescence characterization of cubic (In,Ga)N films grown on GaAs(001) substrates

Cubic InxGa1-xN films were successfully grown on GaAs(001) substrates by metalorganic chemical-vapor deposition. The values of x content ranging from 0.10 to 0.24 obtained at different growth conditions were measured by double-crystal x-ray diffraction (XRD). The perpendicular and parallel elastic strain of the In0.2Ga0.8N layer, epsilon(perpendicular to)=0.4% and epsilon(parallel to)=-0.4% for GaN and epsilon(perpendicular to)=0.37% and epsilon(parallel to)=-0.37% for InGaN, respectively, were derived using the XRD measurements. The inhomogeneous strain and the average grain size of the In0.2Ga0.8N/GaN films were also studied by XRD. Photoluminescence spectra were used to measure the optical characterization of the InxGa1-xN thin films with different In composition, and the near-band-edge emission dependence of cubic InxGa1-xN on the x value is nearly linear with In content x less than or equal to 0.24. (C) 2000 American Institute of Physics. [S0021-8979(00)03908-6].