Wurtzite-to-tetragonal structure phase transformation and size effect in ZnO nanorods

The deformation of [0001]-oriented ZnO nanorods with hexagonal cross sections under uniaxial tensile loading is analyzed through molecular statistical thermodynamics (MST) simulations. The focus is on the size dependence of mechanical behavior in ZnO nanorods with diameters ranging from 1.95 to 17.5 nm. An irreversible phase transformation from the wurtzite (P6(3)mc space group) structure to a tetragonal structure (P4(2)/mnm space group) occurs during the tensile loading process. Young's modulus before the transformation demonstrates a size dependence consistent with what is observed in experiments. A stronger size dependence of response is seen after the transformation and is attributed to the polycrystalline nature of the transformed structure. A comparison of the MST and molecular dynamics (MD) methods shows that MST is 60 times faster than MD and yields results consistent with the results of MD.

Self-assembled 3D Architectures of LuBO3 : Eu3+: Phase-selective synthesis, growth mechanism, and tunable luminescent properties

Rhombohedral-calcite and hexagonal-vaterite types of LuBO:Eu3+ microparticles with various complex self-assembled 3D architectures have been prepared selectively by an efficient surfactant- and template-free hydrothermal process for the first time. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, photoluminescence, and cathodoluminescence spectra as well as kinetic decays were used to characterize the samples.

Selective synthesis of hexagonal and monoclinic LaPO4:Eu3+ nanorods by a hydrothermal method

The hexagonal and monoclinic LaPO4:Eu3+ nanorods can be selectively synthesized through a simple hydrothermal method by only adjusting the reaction temperature. Hexagonal and monoclinic LaPO4:Eu3+ nanorods can be prepared at 120 and 180 degrees C, respectively. The phase conversion of LaPO4:Eu3+ under different temperatures is investigated in detail. Moreover, the influence of the temperature on the intensity and the shift of the peaks of the excitation and emission spectra is discussed, and the decay lifetime of the Eu3+ ions of the sample obtained at different temperature also have been investigated in this paper.

Highly uniform and monodisperse beta-NaYF4 : Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: Hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size 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 as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu(3+) (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to D-5(0-3) -> F-7(J) (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively.

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.

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.

Tunable ordered droplets induced by convection in phase-separating P2VP/PS blend film

Ordered hexagonal droplets patterns in phase-separating polymeric blend films of polystyrene and poly(2-vinylpyridine) (PS/PVP) formed due to the convection effect by solvent evaporation. The influences of PS molecular weight, solvent evaporation rate, and the weight ratio of PS to PVP on the PVP-rich domains pattern formation and distributions were investigated by atomic force microscope (AFM). Only in an appropriate range of molecular weight of PS, can the ordered pattern form. Too low or too high molecular weight of PS led no ordered pattern due to the viscosity effects. The increase of solvent evaporation rate decreased the mean radius of the PVP-rich domains and the intervals between the centers of the domains due to the enhancement of the viscosity on the top layer of the fluid film. The increase of the weight ratio of PS to PVP decreased mean radius of the PVP-rich domains whereas the intervals between the centers of droplets remained constant. Therefore, the size and the distributions of ordered patterns can be tuned by the polymer molecular weight, the weight ratio of the two components and the solvent evaporation rate.

Comparing the morphology and phase diagram of H-shaped ABC block copolymers and linear ABC block copolymers

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymers, we have investigated the morphology of H-shaped ABC block copolymers (A(2)BC(2)) and compared them with those of the linear ABC block copolymers. By changing the ratios of the volume fractions of two A arms and two C arms, one can obtain block copolymers with different architectures ranging from linear block copolymer to H-shaped block copolymer. By systematically varying the volume fractions of block A, B, and C, the triangle phase diagrams of the H-shaped ABC block copolymer with equal interactions among the three species are constructed. In this study, we find four different morphologies ( lamellar phase ( LAM), hexagonal lattice phase ( HEX), core-shell hexagonal lattice phase (CSH), and two interpenetrating tetragonal lattice (TET2)). Furthermore, the order-order transitions driven by architectural change are discussed.

Phase structure and transitions in a poly(methyloctadecylsilane) oligomer

A poly(methyloctadecylsilane) oligomer was synthesized by a typical Wurtz coupling reaction. Upon cooling, three transitions were observed at temperatures of 39.9, 37.5 and 33.9 degreesC at a rate of 2.5 degreesC/min in differential scanning calorimetry (DSC). The first transition, with enthalpy change of 0.47 kT/mol and supercooling of 0.2 degreesC, was characteristic of the conformational change in the Si-Si backbone into an all-trans conformation, which was detected by temperature-dependent Fourier transform infrared (FT-FR) spectroscopy. The second and the third transitions with large supercooling were identified as the formation of two-dimensional hexagonal crystal packing and three-dimensional two-chain orthorhombic crystal packing, respectively. The crystal structure was determined by the combination of WAXD and transmission electron microscopy (TEM) experiments. (C) 2000 Elsevier Science Ltd. All rights reserved.

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.

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.

Phase identification of triphenylene-based discotic monomer and its main chain polymers

A monomer, 2,3,6,7,10,11-hexakispentyloxy triphenylene (HPT) possesses a triphenylene core as a discotic mesogen. Polymers containing this discotic mesogen have been studied using wide-angle X-ray and electron diffraction. HPT is known to show a discotic liquid crystal phase, noted as D-ho (h for hexagonal bidimensional lattice, o for ordered molecular spacing in each column). In this paper, however, HPT Liquid crystalline phases, heated up from the crystalline state and cooled down from the isotropic state, were characterized in the diameter dimensions. In addition. the diameters of the columns are close to a parameter of two separate crystals. A core orientation was, therefore, proposed in the mesophase obtained by heating the crystalline. In order to distinguish these differences, the D-ho phase was divided to include the D-hcd and D-hco phases. Molecular modeling was performed to help our understanding of the orientation. The D-hcd and D-hco phases were used to characterize the phases of the discotic polymeric analogs by comparing their column diameters to those of the monomers. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Locating hexagonal and cubic phases in boron nitride using wavelength-selective optically detected x-ray absorption spectroscopy

Locating hexagonal and cubic phases in boron nitride using wavelength-selective optically detected x-ray absorption spectroscopy, D.A. Evans, A.R. Vearey-Roberts, N.R.J. Poolton Appl Phys Lett 89, (2006) 161107

Synchrotron X-ray diffraction study of the phase transformations in titanium alloys

High-resolution synchrotron X-ray diffraction was used to study the phase transformations in titanium alloys. Three titanium alloys were investigated: Ti-6Al-4V, Ti-6Al-2Sn-4Zr-2Mo-0.08Si and beta21s. Both room and high temperature measurements were performed. The room temperature experiments were performed to study the structure of the alloys after different heat treatments, namely as received (AR), furnace cooling (FC), water quenching (WQ) and water quenching followed by ageing. The alpha, alpha', alpha'' and beta phases were observed in different combinations depending on the heat treatment conditions and the alloy studied. A multicomponent hexagonal close packed (hcp) alpha phase, with different c and the same a lattice parameters, was detected in Ti-6Al-4V after FC. High temperature synchrotron X-ray diffraction was used for 'in situ' study of the transformations on the sample surface at elevated temperatures. The results were used to trace the kinetics of surface oxidation and the concurrent phase transformations taking place under different conditions. The influence of the temperature and oxygen content on the lattice parameters of the alpha phase was derived and new data obtained on the coefficients of thermal expansion in the different directions of the hcp alpha phase, for Ti-6Al-4V and Ti-6Al-2Sn-4Zr-2Mo-0.08Si.

Discrete breathers in hexagonal dusty plasma lattices

The occurrence of single-site or multisite localized vibrational modes, also called discrete breathers, in two-dimensional hexagonal dusty plasma lattices is investigated. The system is described by a Klein-Gordon hexagonal lattice characterized by a negative coupling parameter epsilon in account of its inverse dispersive behavior. A theoretical analysis is performed in order to establish the possibility of existence of single as well as three-site discrete breathers in such systems. The study is complemented by a numerical investigation based on experimentally provided potential forms. This investigation shows that a dusty plasma lattice can support single-site discrete breathers, while three-site in phase breathers could exist if specific conditions, about the intergrain interaction strength, would hold. On the other hand, out of phase and vortex three-site breathers cannot be supported since they are highly unstable.