Synthesis and Luminescence Properties of Sheaflike TbPO4 Hierarchical Architectures with Different phase Structures

Sheaflike terbium phosphate hydrate hierarchical architectures composed of filamentary nanorods have been fabricated by a hydrothermal method. The X-ray diffraction patterns and thermogravimetric/differential thermal analysis investigations reveal that the obtained terbium phosphate hydrate has a structural formula of TbPO4 center dot H2O, which can be readily indexed to the hexagonal phase GdPO4 center dot nH(2)O in JCPDS file 39-0232. The evolution of the morphology of the products has been investigated in detail. It is found that the addition of CTAB and Na2H2L (disodium ethylenediamine tetraacetate) plays an important role in controlling the final morphology of the products. A possible formation mechanism of the sheaflike architectures was proposed according to the experimental results and analysis. In addition, the phase structure of the product changes to monoclinic phase when it is annealed at 750 degrees C for 2 h in N-2-H-2 atmosphere. Tetragonal chase TbPO4 can be obtained when annealed temperature increases to 1150 degrees C.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Chalcogenide-halides of niobium (V). 1. Gas-phase structures of NbOBr3, NbSBr3, and NbSCl3. 2. Matrix infrared spectra and vibrational force fields of NbOBr3, NbSBr3, NbSCl3, and NbOCl3

The molecular structures of NbOBr3, NbSCl3, and NbSBr3 have been determined by gas-phase electron diffraction (GED) at nozzle-tip temperatures of 250 degreesC, taking into account the possible presence of NbOCl3 as a contaminant in the NbSCl3 sample and NbOBr3 in the NbSBr3 sample. The experimental data are consistent with trigonal-pyramidal molecules having C-3v symmetry. Infrared spectra of molecules trapped in argon or nitrogen matrices were recorded and exhibit the characteristic fundamental stretching modes for C-3v species. Well resolved isotopic fine structure (Cl-35 and Cl-37) was observed for NbSCl3, and for NbOCl3 which occurred as an impurity in the NbSCl3 spectra. Quantum mechanical calculations of the structures and vibrational frequencies of the four YNbX3 molecules (Y = O, S; X = Cl, Br) were carried out at several levels of theory, most importantly B3LYP DFT with either the Stuttgart RSC ECP or Hay-Wadt (n + 1) ECP VDZ basis set for Nb and the 6-311 G* basis set for the nonmetal atoms. Theoretical values for the bond lengths are 0.01-0.04 Angstrom longer than the experimental ones of type r(a), in accord with general experience, but the bond angles with theoretical minus experimental differences of only 1.0-1.5degrees are notably accurate. Symmetrized force fields were also calculated. The experimental bond lengths (r(g)/Angstrom) and angles (angle(alpha)/deg) with estimated 2sigma uncertainties from GED are as follows. NbOBr3: r(Nb=O) = 1.694(7), r(Nb-Br) = 2.429(2), angle(O=Nb-Br) = 107.3(5), angle(Br-Nb-Br) = 111.5(5). NbSBr3: r(Nb=S) = 2.134(10), r(Nb-Br) = 2.408(4), angle(S=Nb-Br) = 106.6(7), angle(Br-Nb-Br) = 112.2(6). NbSCl3: Nb=S) = 2.120(10), r(Nb-Cl) = 2.271(6), angle(S=Nb-Cl) = 107.8(12), angle(Cl-Nb-Cl) = 111.1(11).

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Effects of zirconia phase on the synthesis of higher alcohols over zirconia and modified zirconia

The catalytic performances of ZrO2-based catalysts were evaluated for the synthesis of higher alcohols from synthesis gas. The crystal phase structures were characterized by X-ray diffraction (XRD) and UV Raman. The results indicated that ZrO2 and Pd modified ZrO2 catalysts were effective catalysts in the synthesis of ethanol or isobutanol, and their selectivities basically depended on the crystal phase of ZrO2 surface. The ZrO2 with surface tetragonal crystal phase exhibited a high activity to form ethanol, while the ZrO2 with surface monoclinic crystal phase exhibited a high activity to form isobutanol. Temperature-programmed desorption (TPD) experiment indicated that the high activity of isobutanol formation from synthesis gas over monoclinic zirconia was due probably to the strong Lewis acidity of Zr4+ cations and the strong Lewis basicity of O2- anions of coordinative unsaturated Zr4+-O2- pairs on the surface of monoclinic ZrO2. (C) 2003 Elsevier B.V. All rights reserved.

The influence of hard-segments on two-phase structure and shape memory properties of PCL-based segmented polyurethanes

Poly(epsilon-caprolactone)-based segmented polyurethanes (PCLUs) were prepared from poly(epsilon-caprolactone) diol, diisocyanates (DI), and 1,4-butanediol. The DIs used were 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluenediisocyanate (TDI), iso-phorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). Differential scanning calorimetry, small-angle X-ray scattering, and dynamic mechanical analysis were employed to characterize the two-phase structures of all PCLUs. It was found that HDI- and MDI-based PCLUs had higher degree of microphase separation than did IPDI- and TDI-based PCLUs, which was primarily due to the crystallization of HDI- and MDI-based hard-segments. As a result, the HDI-based PCLU exhibited the highest recovery force up to 6 MPa and slowest stress relaxation with increasing temperature. Besides, it was found that the partial damage in hard-segment domains during the sample deformation was responsible for the incomplete shape-recovery of PCLUs after the first deformation, but the damage did not develop during the subsequent deformation.

Structures and electrochemical characteristics of several kinds of alloys

The structures and the electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy, Ti0.25-xZrxV0.35Cr0.1Ni0.3 (x = 0.05-0.15) alloy and AB(3

Phase structure and transition behavior of a liquid crystal 5-{[(4 '-heptoxy-4-biphenylyl)oxy]carbonyl}-1-pentyne

The phase structures and transition behaviors of a novel liquid crystal compound containing biphenylyl mesogen, 5-{[(4'-heptoxy-4-biphenytyl) oxy]carbonyl}-1-pentyne (A3E'O7), have been investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X-ray diffraction (WAXD). In contrast to the published compound 5- {[(4'-heptoxy-4-biphenyl-yl)carbonyl]oxy}-1-pentyne (A3EO7), in which the ester bridge between the mesogenic core and the flexible spacer has different linkage order, A3E'O7 shows strikingly different phase structure and transition behaviors. Overall, A3E'O7 has better packing order and higher transition temperatures. It undergoes three enantiotropic stable liquid crystalline phases which are associated to smectic A (S-A) phase (100.2-98.2 degrees C), smectic C (S-C) phase (98.2-87.2 degrees C) and highly ordered smectic X (S-X) phase (87.2-63.3 degrees C), respectively, till eventual crystallization takes place upon cooling from isotropic state to room temperature. However, A3EO7 only shows monotropic SA (72.4-53.6 degrees C) phase and the metastable monotropic S-C phase provided that the same thermal treatment is applied.

Study on the origin of inverted phase in drying solution-cast block copolymer films

In a previous study, we reported observation of the novel inverted phase (the minority blocks comprising the continuum phase) in kinetically controlled phase separating solution-cast poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer films [Zhang et al. Macromolecules 2000, 33, 9561-7]. In this study, we adopt the same approach to investigate the formation of inverted phase in a series of solution-cast poly(styrene-b-butadiene) (SB) asymmetric diblock copolymers having nearly equal polystyrene (PS) weight fraction (about 30 wt %) but different molecular weights. The microstructure of the solution-cast block copolymer films resulting from different solvent evaporation rates, R, was inspected, from which the kinetically frozen-in phase structures at qualitatively different block copolymer concentrations and correspondingly different effective interaction parameter, chieff, can be deduced. Our result shows that there is a threshold molecular weight or range of molecular weight below which the unusual inverted phase is accessible by controlling the solvent evaporation rate. In comparing the present result with that of our previous study on the SBS triblock copolymer, we find that the formation of the inverted phase has little bearing on the chain architecture. We performed numerical calculations for the free energy of block copolymer cylinders and found that the normal phase is always preferred irrespective of the interaction parameter and molecular weight, which suggests the formation of the inverted phase to have a kinetic origin.

ENTANGLEMENT FLUCTUATION DURING PHASE-SEPARATION IN POLYMER BLENDS

For perhaps the first time, the dynamics of liquid-liquid phase separation was studied by time-resolved mechanical spectrometry in order to establish the relationship between blends' properties and the phase structures during spinodal decomposition (SD). The selected system was chlorinated polyethylene (CPE)/ethylene-vinyl acetate copolymer (EVA). It was found that in the early and intermediate stage of SD, the storage modulus (G') and the loss modulus (G'') increase with time after the initiation of the isothermal phase separation; in the later stage, G' and G'' decrease as phase separation proceeds. An entanglement fluctuation model was presented to manifest this phenomenon; it was found that the rheological behavior agrees well with the expections of the model in the early stage. For the later stage, the reduction of G' and G'' can be attributed to the increment of phase-domain size. (C) 1993 John Wiley & Sons, Inc.

Study on thermoplastic-modified multifunctional epoxies : influence of heating rate on cure behaviour and phase separation

The effect of heating rate on the cure behaviour and phase separation of thermoplastic-modified epoxy systems was investigated. Polyethersulphone (PES) modified multifunctional epoxies, triglycidyl-aminophenol (TGAP) and tetraglycidyldiaminodiphenylmethane (TGDDM), as well T300/914 prepreg were used. It was shown that heating rate had a significant influence on the cure kinetics and phase structures of investigated systems. Greater heating rate causes higher epoxy conversion. The domain size of the macrophases formed from phase separation increases with the increase of heating rate. A more complete phase separation is achieved by fast heated thermoplastic-modified epoxy blends.

Phase behavior and nanomechanical mapping of block ionomer complexes

Block ionomer complexes SSEBS-c-PCL were prepared, as a consequence of proton transfer from the sulfonic acid of sulfonated polystyrene-block- poly(ethylene-ran-butylene)-block-polystyrene (SSEBS) to the tertiary amine of a tertiary amine terminated poly(?-caprolactone) (APCL). The phase behavior of SSEBS-c-PCL was thoroughly investigated and the results showed that APCL in SSEBS-c-PCL displays unique crystallization behavior owing to the influence of interactions between the amine and sulfonic acid groups as well as the effects of confinement. Further, small-angle X-ray scattering study revealed that SSEBS-c-PCL displays a less ordered micro-phase structure compared to SSEBS. A quantitative mapping of mechanical properties at the nanoscale was achieved using peak force mode atomic force microscopy. It is found that the block ionomer complex possesses a higher average elastic modulus after complexation with crystallizable APCL. Additionally, the moduli for both hard and soft phases increase and the phase with higher modulus assignable to the hard SPS component shows much more pronounced changes after complexation, confirming that APCL interacts mainly with the SPS blocks. This provides an understanding of the composition and nanomechanical properties of these new block ionomer complexes and an alternative insight into the micro-phase structures of multi-phase materials.

Phase-structure effects of electrospun TiO2 nanofiber membranes on As(III) adsorption

TiO2 nanofibers (NFs) with different phases such as amorphous, anatase, mixed anatase?rutile, and rutile have been prepared by combining the electrospinning technique with the subsequent process of heat treatment or acidic-dissolution method. The obtained NFs are characterized by a Fourier transform infrared spectrometer (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption?desorption isotherm measurements. Phase structure effects of electrospun TiO2 NFs on As(III) adsorption behaviors have been investigated. The results showed a significant effect of the phase structures of TiO2 NFs on As(III) adsorption rates and capacities. Amorphous TiO2 NFs have the highest As(III) adsorption rate and capacity in the investigated samples, which can be attributed to its higher surface area and porous volume. This research provides a simple and low-cost method for phasecontrolled fabrication of TiO2 NFs and application for effective removal of arsenic from aqueous solution.

Efficiency evaluation of ZrB2 incorporation in the MgB 2 matrix phase using high-energy milling

The present study suggests the use of high energy ball milling to mix (to dope) the phase MgB2 with the AlB2 crystalline structure compound, ZrB2, with the same C32 hexagonal structure than MgB 2, in different concentrations, enabling the maintenance of the crystalline phase structures practically unaffected and the efficient mixture with the dopant. The high energy ball milling was performed with different ball-to-powder ratios. The analysis of the transformation and formation of phases was accomplished by X-ray diffractometry (XRD), using the Rietveld method, and scanning electron microscopy. As the high energy ball milling reduced the crystallinity of the milled compounds, also reducing the size of the particles, the XRD analysis were influenced, and they could be used as comparative and control method of the milling. Aiming the recovery of crystallinity, homogenization and final phase formation, heat treatments were performed, enabling that crystalline phases, changed during milling, could be obtained again in the final product. © (2010) Trans Tech Publications.

Comparison of Experimental and Theoretical Structures of a Transition State Analogue Used for the Induction of Anti-Cocaine Catalytic Antibodies

Comparison of the crystal structure of a transition state analogue that was used to raise catalytic antibodies for the benzoyl ester hydrolysis of cocaine with structures calculated by ab initio, semiempirical, and solvation semiempirical methods reveals that modeling of solvation is crucial for replicating the crystal structure geometry. Both SM3 and SM2 calculations, starting from the crystal structure TSA I, converged on structures similar to the crystal structure. The 3-21G(*)/HF, 6-31G*/HF, PM3, and AM1 calculations converged on structures similar to each other, but these gas-phase structures were significantly extended relative to the condensed phase structures. Two transition states for the hydrolysis of the benzoyl ester of cocaine were located with the SM3 method. The gas phase calculations failed to locate reasonable transition state structures for this reaction. These results imply that accurate modeling of the potential energy surfaces for the hydrolysis of cocaine requires solvation methods.