Magnetic anisotropy of textured CrO2 thin films investigated by X-ray magnetic circular dichroism

Highly a-axis-textured CrO₂ films have been deposited on Al₂O₃ (0001) substrates by chemical vapor deposition. CrO₂ has been found to have highly a-axis (010)-oriented columnar growth on a Cr₂O₃ (0001) initial layer. The six-fold surface symmetry of the Cr₂O₃ initial layer leads to three equivalent in-plane orientations of the a-axis-oriented CrO₂ unit cell. We report Cr L_2,3 X-ray magnetic circular dichroism data along the surface normal and at 60° off-normal sample orientation. For a 60° sample alignment, a strong increase of the projected orbital moment could be observed for unoccupied majority t_2g states using moment analysis. Therefore, the c axis is identified as the intrinsic magnetic easy axis of CrO₂. In addition, a small spin moment and a very strong magnetic dipole term T_z have been found. Received: 8 January 2002 / Accepted: 8 January 2002     

Stereoselective synthetic approaches to highly substituted cyclopentanes via electrophilic additions to mono-, di-, and trisubstituted cyclopentenes

Electrophilic additions to allylically substituted alkenes are of broad synthetic utility. The control of stereoselectivity in such reactions has attracted considerable interest. However, the effect of allylic and homoallylic substituents in cyclopentenyl systems has not been investigated systematically. Studies on a series of mono, di-, and trisubstituted cyclopentenes are reported in which trans-vicinal-additions favor a syn-selective approach of electrophiles to the cyclopentene system. The formal addition of HOBr, HOCl, CH(3)SCl, and dimethyl(methylthio)sulfonium tetrafluoroborate (DMTSF)/NaN(3) with a variety of cyclopentene substrates has been carried out, and the effects of various allylic substituents on these selectivities have been examined. Additions of HOBr, HOCl, and DMTSF to highly functionalized substrates proceed predictably with syn selectivity, giving predominantly or exclusively one product. Methanesulfenyl chloride additions are less predictable, but can be tuned by suitable alteration of solvent and substrate. Results have proven useful in total syntheses of (+)-trehazolin and (+)-allosamidin.     

Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments

The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions.Received: 1 January 2003, Published online: 14 October 2003PACS: 64.70.Pf Glass transitions - 77.22.Gm Dielectric loss and relaxation - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling     

Segmental dynamics of poly(methyl phenyl siloxane) confined to nanoporous glasses

The effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). Nanoporous glasses with pore sizes of 2.5–20 nm have been used. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. For high temperatures the temperature dependence of the relaxation rates for confined PMPS crosses that of the bulk state. Besides finite states effects also the thermodynamic state of nano-confined PMPS is different from that of the bulk. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel/Fulcher/Tammann like to an Arrhenius behavior where the activation energy depends on pore size. This is in agreement with the results obtained by NS. The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale between 3 and 5 nm which can be regarded as minimal length scale for glass transition to appear in PMPS.     

Adsorption kinetics and dynamics of small organic molecules on a silica wafer: Butane, pentane, nonane, thiophene, and methanol adsorption on SiO2/Si(1 1 1)

The adsorption kinetics (by thermal desorption spectroscopy) and adsorption dynamics (by molecular beam scattering) have been determined for a number of alkanes, methanol, thiophene, and water on a silica wafer—SiO₂/Si(1 1 1). No indications for bond activation were present, i.e., all probe molecules adsorb molecularly obeying 1st order kinetics. The coverage-dependent heat of adsorption has been determined accordingly. The adsorption dynamics are precursor-mediated with Kisliuk-like shapes of the adsorption probabilities at low impact energies and adsorbate-assisted adsorption at large impact energies.     

Adsorption of water on JSC‐1A (simulated moon dust samples)—a surface science study

JSC‐1a (a simulated lunar dust sample) supported on a silica wafer (SiO₂/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x‐ray (EDX) spectroscopy, and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and in addition by collecting isothermal adsorption transients. Blind experiments on the silica support have been performed as well. JSC‐1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg, as characterized in detail in prior studies, for example, at NASA. The particle sizes span the range from a few micrometers up to 100 µm. At small exposures, H₂O TDS is characterized by broad (100–450) K structures; at large exposures, distinct TDS peaks emerge, which are assigned to amorphous solid water (ASW) (145 K) and crystalline ice (CI) (165 K). Water dissociates on JSC‐1a at small exposures but not on the bare silica support. Coadsorption TDS data (alkane–water mixtures) indicate that rather porous condensed ice layers form at large exposures, with the mineral particles acting most likely as nucleation sites. At thermal impact energies, the initial adsorption probability amounts to 0.92 ± 0.05. It is evident that the drop‐and‐dry technique, developed in studies about nanoparticles/tubes, can be extended to obtain samples for surface science studies based on powders consisting of particles with rather large diameters. Copyright © 2008 John Wiley & Sons, Ltd.     

Online monitoring of thermoset post-curing by dynamic mechanical thermal analysis DMTA

Thermosetting moulding compounds are synthetic materials which can be easily formed in the molten state and achieve high temperature stability due to a cross-linking process which takes place during manufacture. To ensure thermal and mechanical properties, post-curing of moulded phenolic resin components is necessary for high quality applications. In the industrial practice, post-curing time–temperature-programs are heuristically acquired. In this paper, dynamical mechanical thermal analysis is employed to determine optimal post-curing conditions for injection moulded parts from phenolic resin.     

Lithium-ion batteries based on vertically-aligned carbon nanotube electrodes and ionic liquid electrolytes

In conjunction with environmentally benign ionic liquid electrolytes, vertically-aligned carbon nanotubes (VA-CNTs) sheathed with and without a coaxial layer of vanadium oxide (V(2)O(5)) were used as both cathode and anode, respectively, to develop high-performance and high-safety lithium-ion batteries. The VA-CNT anode and V(2)O(5)-VA-CNT cathode showed a high capacity (600 mAh g(-1) and 368 mAh g(-1), respectively) with a high rate capability. This led to potential to achieve a high energy density (297 Wh kg(-1)) and power density (12 kW kg(-1)) for the prototype batteries to significantly outperform the current state-of-the-art Li-ion batteries.     

Fast ethylamine gas sensing based on intermolecular charge-transfer complexation

We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride(CDBF) loaded poly(acrylonitrile) nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.