Preparation of ferromagnetic γ - Fe2O3 nanocrystallites by oxidative co-decomposition of PEG 6000 and ferrocene

Highly crystalline and ferromagnetic γ-Fe₂O₃ nanocrystallites were prepared by controlled oxidative co-decomposition of PEG 6000 and ferrocene at a temperature of 450 ^°C under air atmosphere. The morphology, crystalline structure and preliminary magnetic properties of the as-synthesized nanocrystallites have been characterized by using transmission electron microscope (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The highly crystalline γ-Fe₂O₃ nanocrystallites are in quasi-cubic shape with an average size of 30 nm and exhibit room-temperature ferromagnetism. The capping effect of PEG 6000 has also been investigated by thermogravimetry analysis (TGA) and Fourier transform infrared (FTIR) regarding controlling the size of the nanocrystallites and preventing the volatilization of ferrocene and thus raising the yield of the products. This simple method has a high yield of over 80% as well as low cost.     

Study on B2 structure epitaxial Fe/Co superlattice

The B2 structure Fe₅₀Co₅₀ alloy is very attractive material as a large spin conductance asymmetry. In this study, we have tried to fabricate epitaxial Fe/Co superlattice with B2 structure. In order to investigate the relationship between the film structure and the substrate temperature, the films were prepared at different substrate temperature. The film structure of Fe/Co was evaluated by reflection high energy electron diffraction (RHEED). The in-plane lattice spacing gradually decreased to that of a bulk Fe₅₀Co₅₀ as increase in the number of layers. The B2 structure ordered phase of Fe/Co superlattice was successfully confirmed by RHEED and X-ray diffraction (XRD).     

Evidence of the hexagonal columnar liquid-crystal phase of hard colloidal platelets by high-resolution SAXS

A vast majority of compounds with bent core or banana shaped molecules exhibit the phase sequence B₆-B₁-B₂ as the chain length is increased in a homologous series. The B₆ phase has an intercalated fluid lamellar structure with a layer spacing of half the molecular length. The B₁ phase has a two dimensionally periodic rectangular columnar structure. The B₂ phase has a monolayer fluid lamellar structure with molecules tilted with respect to the layer normal. Neglecting the tilt order of the molecules in the B₂ phase, we have developed a frustrated packing model to describe this phase sequence qualitatively. The model has some analogy with that of the frustrated smectics exhibited by highly polar rod like molecules.     

Ab initio study of Fe-doped SnO: Local structure and hyperfine interactions at the Fe nucleus

In this work we perform an ab initio study of the electric field gradient (EFG) at the nucleus of Fe impurities in crystalline SnO. The Augmented Plane Waves plus Local Orbitals method is used to obtain the electronic structure of the doped system and the atomic relaxations introduced by the impurities in the SnO host in a fully self-consistent way. Most calculations are performed assuming that Fe ions replace the Sn atoms of the structure, in some cases including oxygen vacancies in order to discuss their role in the hyperfine interactions and in determining the local structure around Fe impurities. The case of interstitial Fe sites is also considered. Our predictions are compared with available Müssbauer spectroscopy results and also with theoretical and experimental results obtained for rutile SnO₂ and TiO₂.     

Mössbauer spectrometric study of nonstoichiometric perovskite,A (Co0.8Fe0.2) O3−° (A=Ba,Sr, Ca), for oxidative coupling of methane

Nonstoichiometric perovskites. A(Co_0.8Fe_0.2)O₃₋₆, were prepared by a pyrolysis of mixed metal citrates, and the catalytic property and structure of these perovskites were investigated. The efficiency of an oxidative coupling of methane increases with the order of Ba. Sr, and Ca substituted in A site and decreases with the amounts of deficient oxygens. The mixed valence of B site ions in the disordering of deficient oxygen is considered to contribute mainly to the oxidative coupling of methane.     

Tilt model of inverted amphiphilic mesophases

We present an alternative model of structure and energetics of the inverted amphiphilic mesophases. The previous studies of the inverted hexagonal, H_II, and inverted micellar cubic, Q_II, phases considered the amphiphilic monolayers to be homogeneously bent. In contrast, we assume a unit cell of an inverted mesophase to consist of flat fragments of monolayer. Hence, the unit cells of the H_II and Q_II phases are represented by a hexagonal rod and a polyhedron, respectively. Our model is motivated by Turner and Gruner's X-ray diffraction reconstruction of structure of the H_II phase. The only deformation of the amphiphilic monolayers we consider is tilt of the hydrocarbon chains with respect to the monolayer surface, determined by the packing constraints imposed in the mesophases. Applying our recent model for the elastic energy of tilt in liquid membranes [#!ref23!#], we show that: i) tilt accounts in a natural way for the frustration energy of mesophases resulting from filling by the hydrocarbon chains the corners of the unit cells, ii) the energy of tilt variation along the membrane surface is analogous to the bending energy. We compute the energetics of the H_II, Q_IIsc and Q_IIfcc phases and obtain a hypothetical phase diagram in terms of the elastic constants of monolayers. Moreover, we calculate the structural dimensions of the mesophases. We verify the model showing that the obtained phase diagram describes the recent data for the glycolipids/water systems; the predicted dimensions of the Q_II phase are in accord with the measured values; the model treats quantitatively the structural features observed for the H_II phase. Received: 9 February 1998 / Revised: 4 June 1998 / Accepted: 3 July 1998     

NDMAP: the best material to study the Haldane's prediction

As predicted by Haldane, spin, S=1 one-dimensional (1D) Heisenberg antiferromagnet (HAF) has an energy gap between the singlet ground state and first excited triplet. On application of magnetic field, the triplet state Zeeman splits and the energy of one of the triplet state becomes zero at a critical field, H_c. Above H_c the system recovers magnetism. Then, we expect that a quasi-1D HAF will show a magnetic long-range ordering (LRO) at low temperatures due to the inter-chain coupling. This field-induced LRO has not been observed before due to complication of the crystal structure in the materials studied so far and/or technical difficulty.From a heat capacity measurement on a single crystal of an S=1 quasi-Q1D HAF, Ni(C₅H₁₄N₂)₂N₃(PF₆), we found an anomaly at a temperature in finite fields indicating a field-induced phase transition. A magnetic LRO is confirmed by a neutron diffraction measurement on the same sample. The temperature versus magnetic field phase diagram of this compound is constructed and discussed.     

Optical inhomogeneity model for evaporated Y2O3 obtained from physical thickness measurement

A multiparameter fitting with additional parameters for film inhomogeneity based on transmission results is used to get film inhomogeneity information and to compare different models for film structure. For a number of evaporated materials similar results from transmission fitting have been obtained by using a model consisting of two sublayers with a constant difference in refractive indices between them, either with a thin sublayer in the contact with a substrate or with air. As additional information, we obtained the film physical thickness result from step profile measurements for an oxygen-doped Y₂O₃ film on a fused silica and we compared it with the fit results for this coating. The result closest to the profilometry one has been achieved for a model with a thinner sublayer in contact with the substrate. The differences are great enough to assert that Y₂O₃ films on a fused silica possess a higher refractive index in the first stages of growth and then, after some transition, the main material with smaller refractive index grows on it.     

XRD and XPS analysis of laser treated vanadium oxide thin films

In this work, we present X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis of laser treated vanadium oxide sols. The films were also observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) to reveal how the original xerogel structure changes into irregular shaped, layer structured V₂O₅ due to the laser radiation. XRD revealed that above 102 W/cm² the original xerogel structure disappears and above 129 W/cm² the films become totally polycrystalline with an orthorhombic structure. XPS spectra showed O/V ratio increment by using higher laser intensities.     

First-principles prediction of half-metallic ferromagnetism in Cd(TM)O2 (TM=Cr, Mn, Fe, Co, Ni) compounds

We report the electronic structure of Cd(TM)O₂ (TM=Cr, Mn, Fe, Co, Ni) in the chalcopyrite structures. From this study we find that Cd(TM)O₂ is a half-metallic ferromagnetic compound. From the energy consideration we find that Cd(TM)O₂ is more stable in chalcopyrite structure rather than in rock salt structure. A careful analysis of the spin density reveals the ferromagnetic coupling between the p-d states and the cation dangling-bond p states, which is believed to be responsible for the stabilization of the ferromagnetic phase. The calculated heat of formation, bulk modulus and cohesive energy are reported.     

Characterization of mechanochemically synthesized imidazolates of Ag, Zn, Cd, and Hg: Solid state reactivity of nd cations

Silver, zinc, cadmium, and mercury imidazolates have been synthesized mechanochemically by milling imidazole and the metal oxides in an agate mortar. The reaction products were characterized by FTIR and XRPD techniques. The results obtained for the mechanochemical imidazolates have been compared with those obtained by precipitation reported in the literature. The mechanochemical Ag imidazolate has the same orthorhombic crystal structure as the precipitated one. The mechanochemical Zn imidazolate has a tetragonal structure with similar crystal parameters to those of Zn(Imz)₂H₂O, but no water molecules are present in the structure. This new anhydrous form is a polymorph of the one obtained by precipitation. The mechanochemical Cd imidazolate has a monoclinic structure which is the polymorph of the precipited orthorombic form. The mechanochemical Hg imidazolate presents a hexagonal structure which is a polymorph of the orthorombic structure obtained by precipitation. The influence of the nd¹⁰ electronic configuration of the cations on the mechanochemical reaction is discussed.     

Atypical grain growth for (2 1 1) CdTe films deposited on surface reconstructed (1 0 0) SrTiO3 substrates

The (1 0 0) SrTiO₃ substrate has emerged as the oxide substrate of choice for the deposition of a wide variety of materials. The substrate's unavoidable miscut leads to a step-terrace morphology when heated to high temperatures. This morphological transition is accompanied by an atomic scale repositioning of the uppermost terrace atoms, the nature of which is strongly dependent on the substrate temperature and ambient atmosphere used. Here, we report the deposition of CdTe films on the as-received and reconstructed surfaces of (1 0 0) SrTiO₃. The as-received substrate gives rise to a [1 1 1] CdTe film with four equally distributed in-plane grain orientations. The surface reconstruction, on the other hand, gives rise to an unprecedented reorientation of the film's grain structure. For this case, a [2 1 1] CdTe film emerges having twelve unevenly distributed in-plane orientations. We attribute the film's grain structure to an atomic scale surface reconstruction, with the anisotropic distribution of grain-types arising from a preferential formation due to the step edges.     

Effective dielectric constant of two-dimensional photonic crystals in optical bands

By using the Fourier expansion method, we have developed an approach to calculate the effective dielectric index of a two-dimensional photonic crystal. The approach is very general: it can take into account various Bravais lattice structure as well as arbitrary spatial variation of the dielectric index. It has been found that near a nondegenerate frequency ω_n(Γ) at Γ point, the transverse magnetic (TM) mode is ordinary, as it is independent of the propagation direction, whereas in general the transverse electric (TE) mode depends on the propagation direction, it is extraordinary. Therefore, a two-dimensional photonic crystal can always be described by an effective dielectric index for TM mode near the nondegenerate frequency ω_n(Γ). However, the TE mode is much more complicated unless the lattice structure is highly symmetric. Moreover, a two-dimensional square photonic crystal has been identified as an effective birefringent crystal having two negative refractive indexes from the perspective of Snell's law.     

Fabrication of a nanostructured gold-polymer composite material

A facile synthesis route is described for the preparation of a poly-(o-aminophenol)-gold nanoparticle composite material by polymerization of o-aminophenol (AP) monomer using HAuCl₄ as the oxidant. The synthesis was carried out in a methanol medium so that it could serve a dual solvent role, a solvent for both the AP and the water solution of HAuCl₄. It was found that oxidative polymerization of AP leads to the formation of poly-AP with a diameter of 50±10nm, while the reduction of AuCl₄ ^- results in the formation of gold nanoparticles (∼ 2nm). The gold nanoparticles were uniformly dispersed and highly stabilized throughout the macromolecular chain that formed a uniform metal-polymer composite material. The resultant composite material was characterized by means of different techniques, such as UV-vis, IR and Raman spectroscopy, which offered the information about the chemical structure of polymer, whereas electron microscopy images provided information regarding the morphology of the composite material and the distribution of the metal particles in the composite material.     

X-ray spectroscopy of the metal-insulator transition in YbGdTe and YbLaTe

We report extended X-ray absorption fine structure (EXAFS) of Yb_1-xGd_xTe and Yb_1-xLa_xTe, two solid solutions which show an insulator-metal transition (IMT) as a function of x for a high donor concentration . The results are correlated to transport experiments and X-ray diffraction data, to analyse the IMT in relation to the structure at both a local and a macroscopic scale. A bimodal distribution is found for rare earth-Te nearest distances in these compounds crystallized in the fcc structure. In particular, we find the less rigid Yb-Te bond can be used as a local probe for the wavefunction of the electrons introduced by La or Gd donors, hence a new insight on the metal-insulator transitions which are of a different nature in the two solid solutions. Received: 23 March 1998 / Revised and Accepted: 12 July 1998     

Deep desulfurization of model gasoline over photoirradiated titanium-pillared montmorillonite

The activity of Ti-pillared montmorillonite for photocatalytic oxidative desulfurization using 2,5-dimethylthiophene dissolved in n-octane as a model organosulfur compound in gasoline was investigated. Using Ti-pillared montmorillonite and an oil/acetonitrile two-phase extraction, deep desulfurization of sulfur-containing compounds was achieved. During this process, O₂ was used as the oxygen source and photoirradiation was achieved by UV light. Using this approach, 97.4% of the sulfur compounds were oxidized and successfully removed from the model gasoline system under mild reaction conditions. Montmorillonite was prepared by sol–gel method and characterized by XRD, N₂ absorption and UV–vis spectroscopy. The characterization indicates that Ti component enters the interlayer of montmorillonite, working as an active component in the crystal phase of anatase. Deep desulfurization experiments show that the activity of Ti-pillared montmorillonite is obviously better than P25.     

Microscale steps and micro-nano combined structures by anodizing aluminum

In this paper, we firstly present a novel microscale-step structure fabricated by anodizing aluminum in a mixture of 0.05-0.5 wt% NaCl (HCl), 2 wt% H₃PO₄ and 20 wt% ethanol under potentials of 1-40 V at room temperature. Then, we present two micro-nano combined structures by integrating the microsteps with nanopores through multi-step anodizations. The microstep-nanopore hierarchical structure was obtained by re-anodizing the sample in oxalic acid, and the regular nanopores can be realized on the microscale patterned aluminum surface. The two-layer porous structure was one layer of nanoporous anodic alumina and another layer of micropores by two-step anodization on sample's both sides. These two novel structures can be useful for surface engineering and high flux filtration, respectively. The current fabrication approach broadens the applications of aluminum anodization, and brings a new method for assembling micro-nano structures.     

Observation of magnetic domain structure in Terfenol-D by scanning electron acoustic microscopy

The magnetic domain structure in oriented Tb_0.3Dy_0.7Fe_1.92 (Terfenol-D) is investigated by scanning electron acoustic microscopy (SEAM) in a wide frequency range from 75 to 530 kHz. Both secondary electron image and electron acoustic image can be obtained in situ simultaneously. By changing the modulation frequencies, the SEAM can be used as an effective nondestructive method to observe not only the surface topography and domain structure but also the subsurface domain structure and defects. The magnetic domain structure is verified by magnetic force microscopy (MFM). Furthermore, magnetic domains can be observed in both linear and nonlinear imaging modes by SEAM. The contributions to the image contrast are related to the signal generation through the piezomagnetic coupling mechanism, magnetostrictive coupling mechanism, and thermal-wave coupling mechanism.     

First-principles studies of the electronic and elastic properties of Ti2GeC

We have performed first-principles studies on electronic structure and elastic properties of Ti₂GeC. The calculated band structure shows that this compound is electrical conductor. From the pressure dependence of elastic constants, we find that Ti₂GeC is most stable in the pressure range from 0 to 100 GPa. The strong Ti 3d, Ge 4p and C 2p hybridization may stabilize the structure of Ti₂GeC. By analyzing the ratio between the bulk and shear moduli, we conclude that Ti₂GeC is brittle in nature, and the brittleness of Ti₂GeC originated from the large value of Ti atom occupying the internal parameter z.     

Orbital correlations in doped manganites

We review our recent X-ray scattering studies of charge and orbital order in doped manganites, with specific emphasis on the role of orbital correlations in Pr_1-xCa_xMnO₃. For x=0.25, we find an orbital structure indistinguishable from the undoped structure and long-range orbital order at low temperatures. For dopings 0.3≤x≤0.5, we find scattering consistent with a charge and orbitally ordered CE-type structure. While in each case the charge order peaks are resolution limited, the orbital order exhibits only short-range correlations. We report the doping dependence of the correlation length and discuss the connection between the orbital correlations and the finite magnetic correlation length observed on the Mn³⁺ sublattice with neutron-scattering techniques. The physical origin of these domains, which appear to be isotropic, remains unclear. We find that weak orbital correlations persist well above the phase transition, with a correlation length of 1–2 lattice constants at high temperatures. Significantly, we observe similar correlations at high temperatures in La_0.7Ca_0.3MnO₃, which does not have an orbitally ordered ground state, and we conclude that such correlations are robust to variations in the relative strength of the electron–phonon coupling. Received: 22 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001