Comparison of the magnetic properties of metastable hexagonal close-packed Ni nanoparticles with those of the stable face-centered cubic Ni nanoparticles

We report the first magnetic study of pure and metastable hexagonal close-packed (hcp) Ni nanoparticles (sample 1). We also produced stable face-centered cubic (fcc) Ni nanoparticles, as mixtures with the hcp Ni nanoparticles (samples 2 and 3). We compared the magnetic properties of the hcp Ni nanoparticles with those of the fcc Ni nanoparticles by observing the evolution of magnetic properties from those of the hcp Ni nanoparticles to those of the fcc Ni nanoparticles as the number of fcc Ni nanoparticles increased from sample 1 to sample 3. The blocking temperature (T(B)) of the hcp Ni nanoparticles is approximately 12 K for particle diameters ranging between 8.5 and 18 nm, whereas those of the fcc Ni nanoparticles are 250 and 270 K for average particle diameters of 18 and 26 nm, respectively. The hcp Ni nanoparticles seem to be antiferromagnetic for T < T(B) and paramagnetic for T > T(B). This is very different from the fcc Ni nanoparticles, which are ferromagnetic for T < T(B) and superparamagnetic for T > T(B). This unusual magnetic state of the metastable hcp Ni nanoparticles is likely related to their increased bond distance (2.665 angstroms), compared to that (2.499 angstroms) of the stable fcc Ni nanoparticles.     

Lamellar to inverted hexagonal mesophase transition in DNA complexes with calamitic, discotic, and cubic shaped cationic lipids

In this study, we report on the lipid tail molecular shape/size effect on the mesophase self-assembly behaviors of various cationic lipids complexed with double-stranded DNA. The molecular shape of the cationic lipids was tailored from rodlike (a cyanobiphenyl imidazolium salt) to discotic (a triphenylene imidazolium salt), and finally to cubic [a polyhedral oligomeric silsesquioxane (POSS) imidazolium salt]. An increase in the cross-sectional area of the hydrophobic tails with respect to the hydrophilic imidazolium head induced a negative spontaneous curvature of the cationic lipids. As a result, a morphological change from lamello-columnar (L(C)(alpha)) phase for the DNA-cyanobiphenyl imidazolium salt (DNA-rod) and DNA-triphenylene imidazolium salt (DNA-disk) complexes to an inverted hexagonal columnar (H(C)(II)) phase for the DNA-POSS imidazolium salt (DNA-cube) complex was observed. The DNA-rod complex had a typical smectic A (SmA) L(C)(alpha) morphology, whereas the DNA-disk complex had a double lamello-columnar liquid crystalline phase. However, when the lipid tail changed to POSS, an H(C)(II) morphology was achieved. These morphological changes were successfully characterized by X-ray diffraction and transmission electron microscopy. We expect that these liquid crystalline and crystalline DNA hybrid materials may become potential functional materials for various applications such as organic microelectronics and gene transfection.     

Electronic structure of cubic tungsten subnitride W<Subscript>2</Subscript>N in comparison to hexagonal and cubic tungsten mononitrides WN

A full potential FLAPW-GGA method is used to study for the first time the electronic structure of cubic tungsten subnitride W₂N, and its equilibrium lattice parameter, density, energy of cohesion, coefficients of low temperature heat capacity and Pauli paramagnetic susceptibility are calculated. It is discussed in comparison to the similar values of hexagonal and cubic tungsten mononitrides WN.     

Interplay between cubic and hexagonal phases in block copolymer solutions

The phase behavior of a symmetric styrene-isoprene (SI) diblock copolymer in a styrene-selective solvent, diethylphthalate, was investigated by in situ small-angle X-ray scattering on isotropic and shear-oriented solutions and by rheology and birefringence. A remarkable new feature in this phase diagram is the coexistence of both body-centered cubic (bcc) and hexagonally close-packed (hcp) sphere phases, in a region between close-packed spheres (cps) and hexagonally packed cylinders (hex) over the concentration range phi approximately 0.33-0.45. By focusing on the transitions among these various ordered phases during heating and cooling cycles, we observed a strong hysteresis: supercooled cylinders persisted upon cooling. The stability of these supercooled cylinders is quite dependent on concentration, and for phi > or = 0.40, the supercooled cylinders do not revert to spheres even after quiescent annealing for 1 month. The spontaneous formation of spheres due to the dissociation of cylinders is kinetically hindered in this case, and the system is apparently not amenable to any pretransitional fluctuations of cylinders prior to the cylinder-to-sphere transition. This contrasts with the case of cylinders transforming to spheres upon heating in the melt. The application of large amplitude shear to the supercooled cylinders is effective in restoring the equilibrium sphere phases.     

Phase- and size-controlled synthesis of hexagonal and cubic CoO nanocrystals

Highly crystalline, phase- and size-controlled CoO nanocrystals of hexagonal and cubic phases have been prepared by thermal decomposition of Co(acac)3 in oleylamine under an inert atmosphere. Kinetic and thermodynamic control for the precursor formation leads to two different seeds of hexagonal and cubic phases at higher temperatures. The crystal size of both CoO phases can be easily manipulated by changing the precursor concentration and reaction temperature.     

Low-frequency dielectric relaxation in columnar hexagonal and micellar inverse cubic mesophases

Dielectric measurements on four diols showing columnar hexagonal and micellar cubic phases were carried out. Besides the known fast local reorientation in theGHz-range, a new absorption in theMHz region was detected. This mechanism was interpreted as a collective motion of the molecules inside the micelles or cylindrical aggregates. The absorption was also found in the isotropic phase. Based upon the interpretation given, the molecular aggregates should also exist in the isotropic state. The electrical conductivity strongly supports the classification as inverse phases.     

Structure transition from hexagonal mesostructured rodlike silica to multilamellar vesicles

We studied the synthesis of siliceous structures by using a nonionic block copolymer (Pluronic P123) and perfluorooctanoic acid (PFOA) as cotemplates in an acid-catalyzed sol-gel process. Different siliceous structures were obtained through systematically varying the molar ratio (R) of PFOA/P123, and the resultant materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen sorption analysis, and Fourier-transform infrared spectroscopy. The results are consistent and reveal a structure transition from a highly ordered 2D hexagonal (HEX) mesostructure with a rodlike morphology to multilamellar vesicles (MLVs) with sharp edges when R is increased. The fact that the MLVs are initiated from the end of hexagonally mesostructured rods provides key evidence in such a novel structure transition. Our finding indicates that, at least in our observations, the MLVs are developed gradually from HEX structures, rather than by a direct cooperative self-assembly mechanism. It is suggested that PFOA molecules with rigid fluorocarbon chains closely interact with PEO. This interaction model may well explain (1) the "wall-thicken" effect in HEX mesostructures by enlarging the hydrophilic PEO moiety (R = 0-1.4), (2) the subsequent HEX to multilamellar structure transition by modifying the hydrophilic/hydrophobic volume ratio (R = 1.4-2.8), and (3) the formation of MLVs with sharp edges by increasing the bending energy. This model provides insight into the fabrication of novel porous materials by the use of block copolymers and fluorinated surfactant mixed templates.     

Evidence of a transition to reorientational disorder in the cubic alkali-metal dodecahydro-closo-dodecaborates

A neutron powder diffraction and differential scanning calorimetry (DSC) study indicates that Cs₂B₁₂H₁₂ undergoes a second-order phase transition near 529 K that can be described as a reorientational disordering of the B₁₂H₁₂²⁻ icosahedral anions between two lowest-energy configurations within the cubic structure. Such a disordering requires the addition of another mirror plane to the low-temperature Fm3? structural symmetry to become Fm3?m. Differential scanning calorimetry measurements suggest the possible persistence of some short-range anion order at and above the transition. Additional DSC measurements of the lighter alkali-metal cubic isomorphs, Rb₂B₁₂H₁₂ and K₂B₁₂H₁₂, also indicate second-order transitions for these compounds near 742 K and 811 K, respectively. These results are suggestive of similar order–disorder phase changes as for Cs₂B₁₂H₁₂, although confirmation of their existence requires analogous diffraction measurements.     

Redirect the assembly of hexagonal MCM-41 into cubic MCM-48 from sodium silicate without the use of an organic structure modifier

In contrast to earlier methods requiring the presence of organic modifiers for the preparation of cubic MCM-48 mesostructures from low cost sodium silicate, we show that this three dimensional framework structure can be readily assembled in the absence of co-surfactants simply by using the overall SiO2/OH- ratio as means of controlling the surfactant packing parameter.     

Activation energies for metastable to stable phase transition of 4,4'-di-n-heptyl- oxyazoxybenzene

Complexes of adenine, AdH, with cobalt, nickel and copper chlorides were prepared and their thermodynamic functions were determined. The complexing processes are endothermic in nature. The thermal behaviour of complexes was followed up by using TG and DTA analyses. The stoichiometry of thermal decomposition of the investigated complexes was suggested. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydrothermal hot-pressing induced phase transition in hexagonal boron nitride

The phase transition of hBN nanocrystals induced by hydrothermal hot-pressing process has been investigated by XRD, FTIR, TEM and HRTEM. It was found that a phase transition of hBN → tBN → aBN occurred with increasing hot-pressing temperature, i.e., hBN transformed into tBN at above 270 °C, and followed by another transformation from tBN to aBN at 310 °C. In addition, FTIR spectra and HRTEM images indicate that a small amount of cBN formed directly from the amorphous BN matrix at 75 MPa and 310 °C. This phenomenon is similar to what happened in conventional high temperature and high pressure method, which is believed to promote the phase transition from hBN to cBN.     

Pressure induced isostructural metastable phase transition of ammonium nitrate

The energetic material ammonium nitrate (AN, NH(4)NO(3)) has been studied under both hydrostatic and nonhydrostatic conditions using diamond anvil cells combined with micro-Raman spectroscopy and synchrotron X-ray powder diffraction. The refined powder X-ray data indicates that under hydrostatic conditions AN-IV (orthorhombic, Pmmn) is stable to above 40 GPa. In one nonhydrostatic compression experiment a volume collapse was observed, suggesting an isostructural phase transition to a "metastable" phase IV' between 17 and 28 GPa. The structures of phase IV and IV' are similar with the subtle difference in the hydrogen-bonding network; that is, a noticeably shorter N1···O1 distance seen in phase IV'. This hydrogen bond has a significant component along the b-axis, which proves to be the most compressible until cell axis over the entire pressure range. It is likely that the shear stress of the nonhydrostatic experiment drives the phase IV-to-IV' transition to occur. We compare the present isotherms of phase IV and IV' in both static and nonhydrostatic conditions with the previously obtained Hugoniot and find that the nonhydrostatic isotherm approximately matches the Hugoniot. On the basis of this comparison, we conjecture that a chemical reaction or phase transition may occur in AN under dynamic pressure conditions at 22 GPa.     

On the structure of the thermotropic cubic mesophases

Two new substances, glycosides, with an optically isotropic mesophase were investigated. Using measurements of the refractive index, the optical isotropy of the thermotropic phases was proved. X-ray diffraction experiments provided information about the structure of the cubic mesophase. Similarly to the lyotropic cubic phases, here too structures of space group la-3d are present.     

Parameterization of the hyperfine structure of metastable states in103Rh

The experimental data on the hyperfine structure of metastable even parity states in¹⁰³Rh have been analysed by means of an effective-operator formalism. The effective radial parameters of the magnetic dipole interaction are determined, using wave functions in intermediate coupling. The comparison with relativistic calculations gives an estimate of the effects due to configuration interaction.     

Self-assembly of ternary cubic, hexagonal, and lamellar mesophases using the lattice-Boltzmann kinetic method

We use a kinetic lattice-Boltzmann method to simulate the self-assembly of the cubic primitive (P), diamond (D), and gyroid (G) mesophases from an initial quench composed of oil, water, and amphiphilic particles. Here, we also report the self-assembly of the noncubic hexagonal phase and two lamellar phases, one with periodic convolutions. The periodic mesophase structures are emergent from the underlying conservation laws and quasi-molecular interactions of the lattice-Boltzmann model. We locate regions of the model's parameter space where the sequence of appearance of mesophases lamellar --> primitive --> hexagonal is in agreement with pressure jump experiments and the sequence cubic --> lamellar is in agreement with compositional variations reported in the literature. The ability of our lattice-Boltzmann model to simulate self-assembly of cubic and noncubic phases in a unified and consistent manner opens the way for further investigations into the transition pathways and kinetics of the phase transitions between these states as well as of the rheology of these phases.     

Proton ordering in cubic ice and hexagonal ice; a potential new ice phase--XIc

Ordinary water ice forms under ambient conditions and has two polytypes, hexagonal ice (Ih) and cubic ice (Ic). From a careful comparison of proton ordering arrangements in Ih and Ic using periodic density functional theory (DFT) and diffusion Monte Carlo (DMC) approaches, we find that the most stable arrangement of water molecules in cubic ice is isoenergetic with that of the proton ordered form of hexagonal ice (known as ice XI). We denote this potential new polytype of ice XI as XIc and discuss a possible route for preparing ice XIc.