High‐pressure high‐temperature synthesis of Rh2O3‐II‐type In2O3 polymorph

The metastability of the bixbyite‐ and corundum‐type In₂O₃ polymorphs up to 33 GPa (at room temperature) is shown. While compressed (in diamond anvil cells) and laser‐heated, both polymorphs undergo a phase transition to the Rh₂O₃‐II‐type structure (space group Pbcn, No. 60). The direct transition from bixbyite to Rh₂O₃‐II structure has not yet been observed for any other oxide.

     

Investigation of electrical characteristics of the In3Sb1Te2 ternary alloy for application in phase‐change memory

A simple layered phase‐change random access memory (PRAM) cell was fabricated using the In₃Sb₁Te₂ alloy. The overall resistance value of the reset state was about 70 times larger than that of the set state. The resistance difference between the amorphous and crystalline state was fairly well maintained after 10² cycles. Interestingly, the measured current–voltage (I –V) curve showed three obvious steps in the crystalline state. By means of high temperature X‐ray diffractometry (HTXRD) and differential scanning calorimetry (DSC) experiments, we confirmed that the current steps originate from successive structural transformations of the In₃Sb₁Te₂ ternary alloy. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization of Fe75Zr25 metallic glass: a two‐step process involving metastable bcc‐Fe and polymorphic transformation

The crystallization process of mechanically alloyed Fe₇₅Zr₂₅ metallic glasses is investigated by means of both thermo‐magnetization and in situ neutron powder thermo‐diffraction experiments in the temperature range 300–1073 K. It was found that the crystallization takes place in a two‐step process, involving firstly the appearance of metastable Fe and Fe₂Zr crystalline phases between 880 K and 980 K, and a subsequent polymorphic transformation into Fe₃Zr above 980 K. These findings explain the anomalous magnetization vs. temperature behaviour on heating–cooling cycles.

     

In‐situ dispersion of ZrO2 nano‐particles coated with pentacene

Stable suspensions of pentacene functionalised ZrO₂ nano‐particles were synthesised using a microwave plasma process. The particles were dispersed in‐situ in ethylene glycol. The formation of coated particles with small cores and a well defined size in the range of 3–5 nm was shown by X‐ray diffraction. In difference to resublimed pure pentacene, suspensions of the coated nano‐particles remained stable for weeks, as confirmed by the observation of a small aggregate size in dynamic light scattering. Thin films of the particles on Si based substrates were obtained by drop‐casting. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Band bending and quasi‐2DEG in the metallized β‐SiC(001) surface

We study the mechanism leading to the metallization of the β‐SiC(001) Si‐rich surface induced by hydrogen adsorption. We analyze the effects of band bending and demonstrate the existence of a quasi‐2D electron gas, which originates from the donation of electrons from adsorbed hydrogen to bulk conduction states. We also provide a simple model that captures the main features of the results of first‐principles calculations, and uncovers the basic physics of the process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In‐situ synthesis of transparent and conductive carbon nanotube networks

A method for the production of transparent carbon nanotube networks (CNTNs) over transparent substrates was developed. In this method, CNTNs were grown directly in the target surface by applying the catalyst in specific zones of the substrate through lithographic techniques. The networks can be also transferred from the original substrate to other surfaces. The newly grown carbon nanotubes have a very high aspect ratio (>50000). Thus far, networks with an optical transmittance of 94% at 550 nm and a surface resistivity of 3.6 kΩ/sq have been produced. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Early stages of decomposition in Al alloys investigated by X‐ray absorption

We demonstrate the sensitivity of X‐ray absorption fine‐structure (XAFS) measurements to the earliest stages of decomposition in Al alloys, i.e. just a few minutes after quenching. XAFS is one of the few applicable experimental approaches to this regime. Three different AlCu(Mg) samples were investigated by XAFS at the Cu K edge. Significant changes of the XAFS can be detected in the course of the decomposition in these alloys during the first 15 minutes. Actually, these changes correspond to relaxations of the nearest neighbours towards the absorbing Cu atoms. The Fourier transformation of the XAFS spectra thus leads to a pseudo radial distribution function which reflects this relaxation. In addition, XAFS measurements of the S‐phase of AlCuMg are used to decide in favour of the Perlitz and Westgren model for the S‐phase. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Layer‐by‐layer fabrication of hierarchical structures in sol–gel templated thin titania films

The fabrication of titania nanostructures with hierarchical order of different structural levels is investigated. The nanostructures are prepared with a diblock‐copolymer assisted sol–gel process. By iterative spin‐coating of the solution onto silicon substrates a thin polymer‐nanocomposite film is deposited and transformed to purely anatase titania nanostructures via calcination. In total, this procedure is repeated three times on top of the substrate. The approach is monitored with grazing incidence small angle X‐ray scattering after each fabrication step. With scanning electron microscopy the final hierarchical structure is imaged. From the characterization different structural levels are clearly identified.

     

Epitaxy of m ‐plane ZnO on (112) LaAlO3 substrate

Heteroepitaxial growth of non‐polar m ‐plane (10 0) ZnO has been demonstrated on (112) LaAlO₃ single crystal substrates using the pulsed laser deposition method. X‐ray diffraction, reflection high energy electron diffraction, and cross‐sectional transmission electron microscopy with selected‐area diffraction, have been used to characterize the structural properties of deposited ZnO films. The epitaxial relationship between ZnO and LAO is shown to be (10 0)_ZnO ∥ (112)_LAO, (11 0)_ZnO ∥ ( 1)_LAO and [0001]_ZnO ∥ [ 10]_LAO. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoelectric properties of p‐type Mg2Si0.6Ge0.4 fabricated by bulk mechanical alloying and hot pressing

Bulk mechanical alloying (BMA) followed by hot pressing (HP) was used to prepare Mg₂Si_0.6Ge_0.4 thermoelectric material with high densification. Starting from the elemental power mixture, the Mg₂Si_0.6Ge_0.4 solid solution was solid‐state synthesized via BMA. In fact, the peaks for the cubic‐structured Mg₂Si_0.6Ge_0.4 solid solution phase were detected after 300 cycles in BMA. The single phase of Mg₂Si_0.6Ge_0.4 was synthesized at 600 cycles in BMA. Mg₂Si_0.6Ge_0.4 showed p‐type semiconduction without doping. Effects of hot pressing conditions on thermoelectric properties were investigated. With increasing hot pressing temperature from 673 to 773 K and pressure from 500 MPa to 1 GPa, the electrical conductivity increased and the Seebeck coefficient decreased. The maximum figure of merit was obtained with the processing parameter of 600 cycles BMA and hot pressing at 773 K, 1 GPa for 1 h. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spatial and temporal distribution of γH2AX fluorescence in human cell cultures following synchrotron‐generated X‐ray microbeams: lack of correlation between persistent γH2AX foci and apoptosis

Formation of γH2AX foci (a marker of DNA double‐strand breaks), rates of foci clearance and apoptosis were investigated in cultured normal human fibroblasts and p53 wild‐type malignant glioma cells after exposure to high‐dose synchrotron‐generated microbeams. Doses up to 283 Gy were delivered using beam geometries that included a microbeam array (50 µm wide, 400 µm spacing), single microbeams (60–570 µm wide) and a broad beam (32 mm wide). The two cell types exhibited similar trends with respect to the initial formation and time‐dependent clearance of γH2AX foci after irradiation. High levels of γH2AX foci persisted as late as 72 h post‐irradiation in the majority of cells within cultures of both cell types. Levels of persistent foci after irradiation via the 570 µm microbeam or broad beam were higher when compared with those observed after exposure to the 60 µm microbeam or microbeam array. Despite persistence of γH2AX foci, these irradiation conditions triggered apoptosis in only a small proportion (<5%) of cells within cultures of both cell types. These results contribute to the understanding of the fundamental biological consequences of high‐dose microbeam irradiations, and implicate the importance of non‐apoptotic responses such as p53‐mediated growth arrest (premature senescence).     

Pressure study of monoclinic ReO2 up to 1.2 GPa using X‐ray absorption spectroscopy and X‐ray diffraction

The crystal and local atomic structure of monoclinic ReO₂ (α‐ReO₂) under hydrostatic pressure up to 1.2 GPa was investigated for the first time using both X‐ray absorption spectroscopy and high‐resolution synchrotron X‐ray powder diffraction and a home‐built B₄C anvil pressure cell developed for this purpose. Extended X‐ray absorption fine‐structure (EXAFS) data analysis at pressures from ambient up to 1.2 GPa indicates that there are two distinct Re—Re distances and a distorted ReO₆ octahedron in the α‐ReO₂ structure. X‐ray diffraction analysis at ambient pressure revealed an unambiguous solution for the crystal structure of the α‐phase, demonstrating a modulation of the Re—Re distances. The relatively small portion of the diffraction pattern accessed in the pressure‐dependent measurements does not allow for a detailed study of the crystal structure of α‐ReO₂ under pressure. Nonetheless, a shift and reduction in the (011) Bragg peak intensity between 0.4 and 1.2 GPa is observed, with correlation to a decrease in Re—Re distance modulation, as confirmed by EXAFS analysis in the same pressure range. This behavior reveals that α‐ReO₂ is a possible inner pressure gauge for future experiments up to 1.2 GPa.     

In situ synchrotron X‐ray diffraction analysis of deformation behaviour in Ti–Ni‐based thin films

Deformation mechanisms of as‐deposited and post‐annealed Ti_50.2Ni_49.6, Ti_50.3Ni_46.2Cu_3.5 and Ti_48.5Ni_40.8Cu_7.5 thin films were investigated using the in situ synchrotron X‐ray diffraction technique. Results showed that initial crystalline phases determined the deformation mechanisms of all the films during tensile loading. For the films dominated by monoclinic martensites (B19′), tensile stress induced the detwinning of 〈011〉 type‐II twins and resulted in the preferred orientations of (002)_B19′ parallel to the loading direction (∥ LD) and (020)_B19′ perpendicular to the LD (⊥ LD). For the films dominated by austenite (B2), the austenite directly transformed into martensitic variants (B19′) with preferred orientations of (002)_B19′ ∥ LD and (020)_B19′ ⊥ LD. For the Ti_50.3Ni_46.2Cu_3.5 and Ti_48.1Ni_40.8Cu_7.5 films, martensitic transformation temperatures decreased apparently after post‐annealing because of the large thermal stress generated in the films due to the large differences in thermal expansion coefficients between the film and substrate.     

In‐situ X‐ray diffraction study of an electric field induced phase transition and giant strain in Na0.5Bi0.5TiO3–x %BaTiO3 lead‐free single crystals

A giant electric field (E) induced strain of ε = 0.60% has been observed for Na_0.5Bi_0.5TiO₃–5.6%BaTiO₃ single crystals under E = 20 kV/cm at 130 °C. In‐situ X‐ray diffraction (XRD) revealed that this induced transition was between pseudocubic and tetragonal structures. Our work provides a potential alternative to lead‐based piezoelectric materials. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mechano‐Chemical Changes of Nano Sized α‐Al2O3 During Wet Dispersion in Stirred Ball Mills

The mechano‐chemical changes in synthetic α‐Al₂O₃ during wet dispersion in a stirred ball mill, are studied. It is shown that a second phase is generated which can be identified as an aluminum hydroxide (Bayerite) by use of dynamic scanning calorimetry (DSC), X‐ray diffraction (XRD), thermogravimetry (TG), Fourier transformed infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). The amount of the Bayerite phase produced increases with milling time. A comparison of the evaluated amounts from TG‐ and DSC‐measurements are in reasonable agreement. Furthermore, the measured BET surface area shows a strong dependence on the temperature of sample preparation. Depending on the temperature, the bayerite phase is seen to convert to the α‐phase again and also forms meso‐ and possibly micro‐pores, leading to a high BET surface area. In this paper, we highlight the necessity for using different methods to characterize the dispersion process, and for a correct interpretation of the measurement results.     

Inhomogeneity of a highly efficient InGaN based blue LED studied by three‐dimensional atom probe tomography

The InGaN based multiple quantum well (MQW) structure in a commercially available white light emitting diode (LED) was studied by transmission electron microscopy (TEM) and three‐dimensional atom probe tomography (APT). The average In mole fraction by three‐dimensional (3D) APT was found to be about 18% in the InGaN well which is consistent with the secondary ion mass spectrometry (SIMS) analysis. The In distribution in the InGaN well layer was analyzed by the iso curve mapping of 3D APT and found to be non‐uniform in the InGaN active layer. In clustering or In rich regions in the range of 2–3 nm size were found, in contrast to recent reports. Our results thus indicate that In clustering is essential for high‐brightness InGaN based LEDs. We have also observed a discontinuity in the range of 50–100. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A new method for functionalizing α,γ‐dinitro compounds at the β‐position: application to the cyclization of β‐alkoxy‐α,γ‐dinitro compounds

Treatment of 2,4‐dinitropentane with bromine and sodium methoxide in methanol, affords formation of an ether product, 2,4‐dibromo‐3‐methoxy‐2,4‐dinitropentane, in 59% yield as a mixture of three diastereomers. This observation has led to a general synthesis of 3‐alkoxy‐2,4‐dibromo‐2,4‐dinitropentanes, obtained in 75‐86% yield from 2,4‐dibromo‐2,4‐dinitropentane as the preferred reactant. 4‐Bromo‐2,4‐dinitro‐2‐pentene has been identified as an intermediate in these reactions. The nitroalkene has been isolated and undergoes conjugate addition with alkoxides to afford the same ether products after brominative work‐up. The nitroalkene undergoes conjugate addition with sodium azide to give 3‐azido‐2,4‐dibromo‐2,4‐dinitropentane in 38% yield as a mixture of two isomers in which the (R*,R*) isomer predominates. Sequential treatment of 2,4‐dibromo‐2,4‐dinitropentane with sodium methoxide followed by sodium iodide and acetic acid gives 3‐methoxy‐2,4‐dinitropentane in 63% yield, the overall product of simple methoxylation of 2,4‐dinitropentane. However, attempted complete debromination of 2,4‐dibromo‐3‐methoxy‐2,4‐dinitropentane with excess sodium iodide and acetic acid results only in monodebromination to give 2‐bromo‐3‐methoxy‐2,4‐dinitropentane in 86% yield. Likewise, 2‐bromo‐3‐ethoxy‐2,4‐dinitropentane is formed in 93% yield from the ethoxy analog. A mechanistic rationale is offered for condition‐specific removal of the second Br atom in these reactions. Treatment of 3‐methoxy‐2,4‐dinitropentane with potassium acetate/iodine in dimethyl sulfoxide affords formation of 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide in 30% yield as a single diastereomer. Conversion of 2‐bromo‐3‐methoxy‐2,4‐dinitropentane in 15% yield to 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide is also possible by using potassium acetate in dimethyl sulfoxide. The mechanistic pathways for formation of 4,5‐dihydro‐3,4‐dimethyl‐3‐methoxy‐4‐nitroisoxazole 2‐oxide apparently involve unstable 3‐methoxy‐1,2‐dimethyl‐1,2‐dinitrocyclopropane as the common intermediate. Similarly, 2‐bromo‐3‐ethoxy‐2,4‐dinitropentane affords 4,5‐dihydro‐3‐ethoxy‐3,4‐dimethyl‐4‐nitroisoxazole 2‐oxide in 13% yield. Copyright © 2013 John Wiley & Sons, Ltd.     

Investigation of a CPG‐array CdZnTe γ‐ray imaging detector with single collecting electrodes readout

The single‐electrode readout method has been applied to a coplanar grid (CPG) array CdZnTe detector in order to halve the number of preamplifiers previously needed and to facilitate imaging applications of CPG detectors. A method of predetermining the width of the optimum collecting electrodes has also been proposed, using the calculated optimum relative gain factor G. Meanwhile, a detailed process for calculating the charge induction efficiency (CIE) is presented. To simplify the calculation process, the computational formula of the CIE was deduced through the integration of the weighting potential. For performance evaluation, a 2 × 2 CPG‐array CdZnTe detector was elaborately designed and tested with ¹³⁷Cs at 662 keV. Experimental results showed the capability of using the CPG‐array CdZnTe detector with single collecting electrode readout for γ‐ray imaging applications, with the same complexity of associated readout electronics as that of the pixelated CdZnTe detectors.     

Relative stabilities and molecular structures of the isomeric enol ethers and carboxylic esters derived from α‐acetyl‐γ‐butyrolactone and α‐acetyl‐δ‐valerolactone

Recently recorded ¹⁷O NMR spectra of compounds studied in a previous work (Taskinen E. Acta Chem. Scand. 1985; B39 : 489–494) dealing with the thermodynamics of isomerization of the enol ethers of α‐acetyl‐γ‐butyrolactone reveal an error in compound identification, caused by an unexpected isomerization reaction during the synthetic procedure. Thus, acid‐catalyzed treatment of the lactone with HC(OR)₃ in the respective alcohol ROH is shown to lead initially to the desired enol ethers which, however, are gradually isomerized to a mixture of the enol ethers and an ester of 2‐methyl‐4,5‐dihydrofuran‐3‐carboxylic acid. As a result, only one of the two isomeric compounds detected in the previous equilibration study was the expected enol ether (the thermodynamically more stable E isomer) of α‐acetyl‐γ‐butyrolactone, while the other, dominating species was the respective carboxylic ester. In the present work, the evidence provided by the ¹⁷O NMR spectra is presented, and the relative stabilities of the isomeric compounds are discussed on the basis of computational enthalpy data. The treatment is also extended to the respective isomeric compounds derived from α‐acetyl‐δ‐valerolactone. Copyright © 2007 John Wiley & Sons, Ltd.