Shape-controllable synthesis and upconversion properties of lutetium fluoride (doped with Yb3+/Er3+) microcrystals by hydrothermal process

Lutetium fluorides with different compositions, crystal phases, and morphologies, such as beta-NaLuF4 hexagonal microprisms, microdisks, mirotubes, alpha-NaLuF4 submicrospheres, LuF3 octahedra, and NH4Lu2F7 icosahedra, prolate ellipsoids and spherical particles have been successfully synthesized via a facile hydrothermal route. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, and photoluminescence spectra were used to characterize the samples. The intrinsic structural feature of lutetium fluorides, the solution pH values, F- sources, and organic additives (Cit(3-) and EDTA) account for the ultimate shape evolutions of the final products. The possible formation mechanisms for products with various architectures have been presented. Additionally, we investigated the upconversion luminescence properties of beta-NaLuF4: 20% Yb3+/2% Er3+ with different morphologies.

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.

Synthesis of REF3 (RE = Nd, Tb) nanoparticles via a solvent extraction route

NdF3 and TbF3 nanoparticles were successfully synthesized via a solvent extraction route using Cynex923 (R3P=O). X-ray diffraction (XRD) study showed that pure hexagonal phase NdF3 and pure orthorhombic phase TbF3 could be obtained under the current synthetic conditions. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations indicated that as-obtained NdF3 nanoplates have a diameter of 50-80 nm and thickness of 10-20 nm and TbF3 products have sphere morphologies with diameter from 70 to 170 nm. The driving force for the growth of NdF3 nanoplates could be attributed to the hexagonal crystal structure. The luminescence properties of NdF3 and TbF3 nanoparticles were investigated, which indicated that NdF3 nanoparticles showed typical emission at 888,1064, and 1328 nm and TbF3 nanoparticles showed characteristic emission of Tb3+ (f-f).

Different microstructures of ss-NaYF4 fabricated by hydrothermal process: Effects of pH values and fluoride sources

beta-NaYF4 microcrystals with a variety of morphologies, such as microrod, hexagonal microprism, and octadecahedron, have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra were used to characterize the samples. The intrinsic structural feature of beta-NaYF4 seeds and two important external factors, namely, the pH values in the initial reaction solution and fluoride sources, are responsible for shape determination of beta-NaYF4 microcrystals. It is found that the organic additive trisodium citrate (Cit(3-)) as a shape modifier has the dynamic effect by adjusting the growth rate of different facets under different experimental conditions, resulting in the formation of the anisotropic geometries of various beta-NaYF4 microcrystals. The possible formation mechanisms for products with various architectures have been presented. A systematic study on the photoluminescence of Tb3+-doped beta-NaYF4 samples with rod, prism, and octadecahedral shapes has shown that the optical properties of these phosphors are strongly dependent on their morphologies and sizes.

Crystal structures and elastic properties of superhard IrN2 and IrN3 from first principles

First principles calculations were performed to investigate the structural, elastic, and electronic properties of IrN2 for various space groups: cubic Fm-3m and Pa-3, hexagonal P3(2)21, tetragonal P4(2)/mnm, orthorhombic Pmmn, Pnnm, and Pnn2, and monoclinic P2(1)/c. Our calculation indicates that the P2(1)/c phase with arsenopyrite-type structure is energetically more stable than the other phases. It is semiconducting (the remaining phases are metallic) and contains diatomic N-N with the bond distance of 1.414 A. These characters are consistent with the experimental facts that IrN2 is in lower symmetry and nonmetallic. Our conclusion is also in agreement with the recent theoretical studies that the most stable phase of IrN2 is monoclinic P2(1)/c. The calculated bulk modulus of 373 GPa is also the highest among the considered space groups. It matches the recent theoretical values of 357 GPa within 4.3% and of 402 GPa within 7.8%, but smaller than the experimental value of 428 GPa by 14.7%. Chemical bonding and potential displacive phase transitions are discussed for IrN2. For IrN3, cubic skutterudite structure (Im-3) was assumed.

Effect of main-chain rigidity on the phase transitional behavior of comblike polymers

The influence of the rigidity of polymer backbones on the side-chain crystallization and phase transition behavior was systematically investigated by a combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), and high-resolution solid-state nuclear magnetic resonance spectroscopy (NMR). DSC investigation indicated that the crystallization number of alkyl carbon atoms of the side chains grafted onto the rigid polymer backbone, poly(p-benzamide) (PBA), is much lower than that of the alkyl carbon atoms of the side chains grafted onto the flexible polymer backbone, poly(ethyleneimine) (PEI), implying that the conformational state of the polymer backbones has a strong effect on the side-chain crystallization behavior in comblike polymers. WAXD and FTIR results proved that these two comblike polymers pack into hexagonal (PBA18C) and orthorhombic (PEI18C) crystals, respectively, depending on the adjusting ability of the polymer backbones for particular conformational states. It was also found that the presence of the crystalline-amorphous interphase (delta = 31.6 ppm) in PBA18C detected by solid-state C-13 NMR spectroscopy can be attributed to the rigid PBA backbone, which restricts the mobility of the alkyl side chains.

Order-disorder transition in eicosylated polyethyleneimine comblike polymers

Order-disorder transition (ODT) behavior in eicosylated polyethyleneimine (PEI20C) comblike polymer obtained by grafting n-eicosyl group on polyethyleneimine backbone was systematically investigated by the combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy as well as solid-state high resolution nuclear magnetic resonance (NMR) spectroscopy. DSC investigations showed two obvious transitions, assigned to the transitions (1) from orthorhombic to hexagonal and (2) from hexagonal to amorphous phase, respectively. These transitions are induced by the variations of alkyl side chain conformation and packing structure with temperature changing, which consequently lead to the destruction of original phase equilibrium. The ODT behavior can also be confirmed by spectroscopic methods like WAXD, FTIR and NMR. The ordered structure and the transition behavior of the alkyl side chains confined by the PEI backbone are obviously different from those of pristine normal alkanes. The transition mechanism of ODT and the origin of the phase transition behavior in PEI20C comblike polymer were discussed in detail in this paper.

Rapid synthesis of hexagon-shaped gold nanoplates by microwave assistant method

The microwave (MW)-based thermal process was applied to the preparation of hexagon-shaped gold nanoplates. The fort-nation of gold nanoplates occurs rapidly in a single step, carried out by directly heating a reaction mixture of HAuCl4 with sodium citrate in an MW reactor. And the gold nanoplates were characterized by UV-visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The experimental results indicated that the sizes and morphologies of the gold nanomaterials strongly depend both on the heating methods and molar ratio of HAuCl4 to sodium citrate in the initial reaction mixture. At the molar ratio 5 : 4 (HAuCl4 to sodium citrate), hexagonal nanoplates with large Au (111) crystallographic facet were preferentially synthesized by the MW assistant method.

Extended application of edge-to-edge matching model to HCP/HCP (alpha-Mg/MgZn2) system in magnesium alloys

In the present work, the edge-to-edge matching model has been introduced to predict the orientation relationships (OR) between the MgZn2 phase which has hexagonal close packed (HCP) structure and the HCP a-Mg matrix. Based on the crystal structures and lattice parameters only, the model has predicted the two most preferred ORs and they are: (1) [1 1 2 3](alpha-Mg) vertical bar vertical bar]1 1 2 3](alpha-Mg), (0 0 0 1)(alpha-Mg) 0.27 degrees from (0 0 0 1)(MgZn2), (1 0 1 1)(alpha-Mg) 26.18 degrees from (1 1 2 2)(MgZn2), (2) [1 0 1 0](alpha-Mg),vertical bar vertical bar[1 1 2 0](MgZn2), (0 0 0 1)(alpha-Mg) vertical bar vertical bar(0 0 0 1)(MgZn2), (1 0 1 1)(alpha-Mg) 3.28 degrees from ( 1 1 2 2)(MgZn2). Four experimental ORs have been reported in the alpha-Mg/MgZn2 system, and the most frequently reported one is ideally the OR (2). The other three experimental ORs are near versions of the OR (2). The habit plane of the OR (2) has been predicted and it agrees well with the experimental results.

Morphological control and luminescent properties of CeF3 nanocrystals

The nanocrystals of CeF3 with the hexagonal structure and different morphologies such as the disk, the rod, and the dot have been successfully synthesized via a mild ultrasound assisted route from an aqueous solution of cerium nitrate and different fluorine sources (KBF4, NaF, NH4F). The use of different fluorine sources has a remarkable effect on the morphology of the final product. The luminescence and UV-vis absorption properties of CeF3 nanocrystals with different morphologies have been investigated. Compared with other shape nanocrystals, the luminescence intensity of the disklike nanocrystals is obviously enhanced. It is suggested that the function-improved materials could be obtained by tailoring the shape of the CeF3 nanocrystals.

One-step synthesis of palladium/SBA-15 nanocomposites and its catalytic application

Well-dispersed palladium nanoparticles in mesoporous SBA- 15 SiO2 were prepared in a facile one-step approach during sol-gel route under reductive atmosphere. X-ray diffraction (XRD) results indicate that as-synthesized nanocomposites basically remain ordered two-dimensional hexagonal mesostructure while transmission electron microscopy (TEM) study exhibits a well dispersion of palladium nanoparticles within the mesoporous SBA-15 channels. The size of Pd nanoparticles is approximately in the range of 5-10nm. However, the resulting nanocomposites exhibit a highly catalytic activity and reused ability at least after five recycles without ligand in air for both the Suzuki and Heck coupling reactions.

Transformation from ordered islands to holes in phase-separating P2VP/PS blend films by adding triton X-100

Our previous investigation showed that the ordered hexagonal island pattern in the phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/P2VP) formed due to the convection effect by proper control of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to P2VP. In this paper, we further illustrate that, by adding a proper amount of the surfactant Triton X-100 to the PS/P2VP toluene solution, the ordered hexagonal island pattern can be transformed to the ordered honeycomb pattern. The effects of the amount of Triton X-100 on the surface morphology evolution and the pattern transformation are discussed in terms of the collapse of Triton X-100, phase separation between Triton X-100/P2VP and PS, the interfacial interaction between Triton X-100/P2VP and the mica substrate, and the Benard-Marangoni convection.

Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared.

Effects of crystal growth conditions on morphology of crystalline syndiotactic 1,2-polybutadiene

The crystalline syndiotatic 1,2-polybutadiene was synthesized with a catalyst consisting of iron acetylacetonate (Fe(acac)(3))-triisobutylaluminum (Al(i-Bu)(3))-diethyl phosphite (DEP), and the effects of crystal growth conditions on morphology of thin films of the polymer were investigated by transmission electron microscopy (TEM) and electron diffraction (ED) techniques. The polymer with melting point 179 degreesC was found to have 89.3% 1,2-content and 86.5% syndiotacticity by C-13 NMR measurement. The results of electron microscopic studies indicate that the solution-cast thin films of the syndiotatic 1,2-polybutadiene consist of lath-like lamellae with the c-axis perpendicular to the film plane, while a- and b-axes are in the film plane. The morphology of isothermally crystallized thin films of the polymer is temperature dependent. At lower crystallization temperatures (130 degreesC), a spherulitic structure consisting of flat-on lamellae is formed. With an increase in the crystallization temperature (e.g., at 140 degreesC), the spherulites and single faceted crystals coexist. At higher crystallization temperatures (150 degreesC), single crystals with a hexagonal prismatic shape are produced.

Synthesis, crystal structure, and density of (W1-xAlx)C

A new solid solution system of Al in WC, with the stoichiometry of (W1-xAlx)C (x = 0.10, 0.25, 0.50, 0.75, 0.86), has been synthesized by a solid-state reaction between W1-xAlx alloys and carbon at around 1673 K in vacuum. Environment scanning electron microscope, energy- dispersive analysis of X-ray, X-ray photoelectron spectroscopy, and inductively coupled plasma analyses are used to certify the formation of the products. The mechanism of the solid-state reaction is also discussed. (W1-xAlx)C is identified to crystallize in the hexagonal space group P6m2 (No. 187) and belongs to the WC structure type. The atoms of W and Al occupy the same lattice site (la site) in the cell of (W1-xAlx)C. The cell parameters for each specimen in the phase of W-AI-C are quite close to that of WC, while their densities are far lower than that of WC.