High‐Valent Technetium Fluorides. Does TcF7 Exist?

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Nondestructive analysis of single rapeseeds by means of Raman spectroscopy

The value of different vegetable oils can be correlated with the content of polyunsaturated fatty acids, especially omega‐3‐fatty acids such as linolenic acid, because of their contribution to healthy nutrition. One expression for the degree of unsaturation is the iodine value normally measured with gas chromatography. The use of Raman spectroscopy allows a rapid calculation of the iodine value and, in addition, only in a minimal sample volume. Therefore, this method can be used in single rapeseeds in order to predict the iodine value before harvesting. Additionally, the method can also be used for breeding investigations. Here, the lipid content and composition of a plant can be predicted by measuring the seedling without destruction. Copyright © 2006 John Wiley & Sons, Ltd.     

Kinetic Study of the Copolymerisation of Ethylene with a Single Site Catalyst in Propane Slurry Polymerisation

Summary: The kinetic behaviour of a supported metallocene catalyst in slurry polymerisation of ethylene with 1-hexene under industrially relevant reaction conditions has been studied. Polymerisation experiments were carried out in a 5-litre stirred tank reactor in a temperature range from 60 to 80 °C and ethylene partial pressures from 5 to 15 bar. Comonomer and hydrogen amounts were varied as well. The catalyst showed pronounced activation and slow deactivation during runtimes of about 1 hour. Strong influences of 1-hexene (“hexene effect”) and hydrogen (“hydrogen effect”) on the activity profiles were observed. Based on the experimental results, a kinetic model has been derived in order to describe and predict important polymerisation data such as activity profile, comonomer content and molecular weight distributions with respect to the reaction conditions. The presented kinetic model is able to describe the observed effects of 1-hexene and hydrogen on the activity profiles, as well as the comonomer incorporation across a broad range of polymerisation conditions. The molecular weight distributions can be simulated with good qualitative agreement to the experimental data.     

Modeling of a vehicle seat suspension system with pneumatic spring and viscous dampers

The paper contains physical and mathematical model of the passive system of seat suspension, used in trucks and buses. Spring force in this system is performed by air spring, whereas damping force is generated by two viscous dampers. Based on the experimental research of characteristic parts of the suspension system, the parameters of mathematical model are determined. Both results of computer simulations and experiments are presented as power spectral density of acceleration courses, measured on seat, in comparison with courses measured on excitation platform in laboratory. Transmissibility of real system and its model are also presented in the paper. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

COMPLIS experiments: COllaboration for spectroscopy Measurements using a Pulsed Laser Ion Source

Laser spectroscopy measurements have been carried out on very neutron-deficient isotopes of Au, Pt and Ir, produced as daughter elements from a Hg ISOLDE beam. For these transitional region nuclides, the hyperfine structure (HFS) and isotope shift (IS) were measured by Resonance Ionization Spectroscopy (RIS). Magnetic moments μ, spectroscopic quadrupole moments Q_s and changes of the nuclear mean square charge radius δ〈r_c ²〉along isotopic series have been extracted. For some results, a detailed comparison with theoretical predictions is presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

MOVPE growth of AlGaAs/GaInP diode lasers

GaAs-based diode lasers for emission wavelengths between 800 nm and 1060 nm with AlGaAs-cladding and GaInP-waveguide layers were grown by MOVPE. For wavelengths above 940 nm broad area devices with InGaAs QWs show state-of-the-art threshold current densities. Ridge-waveguide lasers fabricated by selective etching achieve 200 mW CW monomode output powers. (In)GaAsP QW-based diode lasers with an emitting wavelengths around 800 nm suffer from problems at the upper GaInP/AlGaAs interface. Asymmetric structures with a lower AlGaAs/GaInP and an upper AlGaAs/AlGaAs waveguide not only avoid this interface but also offer better carrier confinement. Such structures show very high slope efficiencies and a high T₀. Maximum output powers of 7 W CW are obtained from 4 mm long devices.     

Jahn–Teller Driven Electronic Instability in Thermoelectric Tetrahedrite

Tetrahedrite, Cu₁₂Sb₄S₁₃, is an abundant mineral with excellent thermoelectric properties owing to its low thermal conductivity. The electronic and structural origin of the intriguing physical properties of tetrahedrite, including its metal‐to‐semiconductor transition (MST), remains largely unknown. This work presents the first determination of the low‐temperature structure of tetrahedrite that accounts for its unique properties. Contrary to prior conjectures, the results show that the trigonal–planar copper cations remain in planar coordination below the MST. The atomic displacement parameters of the trigonal–planar copper cations, which have been linked to low thermal conductivity, increase by 200% above the MST. The phase transition is a consequence of the orbital degeneracy of the highest occupied 3d cluster orbitals of the copper clusters found in the cubic phase. This study reveals that a Jahn–Teller electronic instability leads to the formation of “molecular‐like” Cu₅⁷⁺ clusters and suppresses copper rattling vibrations due to the strengthening of direct copper–copper interactions. First principles calculations demonstrate that the structural phase transition opens a small band gap in the electronic density of states and eliminates the unstable phonon modes. These results provide insights on the interplay between phonon transport, electronic properties, and crystal structure in mixed‐valence compounds.     

Asymmetric first‐order transition and interlocked particle state in magnetocaloric La(Fe,Si)13

In‐situ synchrotron XRD measurements of the magnetocaloric material LaFe_11.8Si_1.2 are used to understand virgin effects and asymmetry of the underlying first order magnetovolume transition. A remarkable change of the transition kinetics occurs after the first cycle, which we attribute to the formation of cracks originating from the volume change. Tomographic imaging revealed that the bulk material disintegrates via an interlocked state where fragments are loosely connected. Though cracks have opened between the fragments, the transition is sharp, which we attribute to magnetostatic interactions. In the cycled sample we find a strong asymmetry between the transition interval upon heating and cooling, which we explain by isostatic pressure acting on parts of the sample during the cooling transition. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)