Rosickyite (monoclinic gamma-sulphur) from La Presta Asphalt Mine, Neuchatel, Switzerland: new X-ray powder diffraction data

Rosickyite, the natural monoclinic gamma -form of sulphur, exists in only a few localities around the globe. In the old asphalt mine at La Presta, Neuchatel. Switzerland, rosickyite occurs locally as small, but very well formed crystals suitable for crystallographic studies. It grows as an alteration product of pyrite-rich asphalt. Rosickyite from La Presta mine is pure molecular sulphur, as revealed by gas chromatography-mass spectrometry. The X-ray powder diffraction data of La Presta rosickyite does not match the one previously published for this species. Therefore, a single crystal study was undertaken and a new indexed X-ray powder diffraction diagram for natural rosickyite is proposed.

Catalytic and anticancer activities of sawhorse-type diruthenium tetracarbonyl complexes derived from fluorinated fatty acids

The reaction of fluorinated fatty acids, perfluorobutyric acid (C3F7CO2H), and perfluorododecanoic acid (C11F23CO2H), with dodecacarbonyltriruthenium (Ru-3(CO)(12)) under reflux in tetrahydrofuran, followed by addition of two-electron donors (L) such as pyridine, 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane, or triphenylphosphine, gives stable diruthenium complexes Ru-2(CO)(4)((2)-(2)-O2CC3F7)(2)(L)(2) (1a, L=C5H5N; 1b, L=PTA; 1c, L=PPh3) and Ru-2(CO)(4)((2)-(2)-O2CC11F23)(2)(L)(2) (2a, L=C5H5N; 2b, L=PTA; 2c, L=PPh3). The catalytic activity of the complexes for hydrogenation of styrene under supercritical carbon dioxide has been assessed and compared to the analogous triphenylphosphine complexes with non-fluorinated carboxylato groups Ru-2(CO)(4)((2)-(2)-O2CC3H7)(2)(PPh3)(2) (3) and Ru-2(CO)(4)((2)-(2)-O2CC11H23)(2)(PPh3)(2) (4). In addition, the cytotoxicities of the fluorinated complexes 1 were also evaluated on several human cancer cell lines (A2780, A549, Me300, HeLa). The complexes appear to be moderately cytotoxic, showing greater activity on the Me300 melanoma cells. Single-crystal X-ray structure analyses of 1a and 3 show the typical sawhorse-type arrangement of the diruthenium tetracarbonyl backbone with two bridging carboxylates and two terminal ligands occupying the axial positions.

The contribution of the young Cretaceous Caribbean Oceanic Plateau to the genesis of late Cretaceous arc magmatism in the Cordillera Occidental of Ecuador

The eastern part of the Cordillera Occidental of Ecuador comprises thick buoyant oceanic plateaus associated with island-arc tholeiites and subduction-related calc-alkaline series, accreted to the Ecuadorian Continental Margin from Late Cretaceous to Eocene times. One of these plateau sequences, the Guaranda Oceanic Plateau is considered as remnant of the Caribbean-Colombian Oceanic Province (CCOP) accreted to the Ecuadorian Margin in the Maastrichtien. Samples studied in this paper were taken from four cross-sections through two arc-sequences in the northern part of the Cordillera Occidental of Ecuador, dated as (Rio Cala) or ascribed to (Macuchi) the Late Cretaceous and one arc-like sequence in the Chogon-Colonche Cordillera (Las Orquideas). These three island-arcs can clearly be identified and rest conformably on the CCOP. In all four localities, basalts with abundant large clinopyroxene phenocrysts can be found, mimicking a picritic or ankaramitic facies. This mineralogical particularity, although not uncommon in island arc lavas, hints at a contribution of the CCOP in the genesis of these island arc rocks. The complete petrological and geochemical study of these rocks reveals that some have a primitive island-arc nature (MgO values range from 6 to 11 wt.%). Studied samples display marked Nb, Ta and Ti negative anomalies relative to the adjacent elements in the spidergrams characteristic of subductionrelated magmatism. These rocks are LREE-enriched and their clinopyroxenes show a tholeiitic affinity (FeO(1)-TiO(2) enrichment and CaO depletion from core to rim within a single crystal). The four sampled cross-sections through the island-arc sequences display homogeneous initial Nd, and Pb isotope ratios that suggest a unique mantellic source for these rocks resulting from the mixing of three components: an East-Pacific MORB end-member, an enriched pelagic sediment component, and a HIMU component carried by the CCOP. Indeed, the ankaramite and Mg-basalt sequences that form part of the Caribbean-Colombian Oceanic Plateau are radiogenically enriched in (206)Pb/(204)Pb and (207)Pb/(204)Pb and contain a HIMU component similar to that observed in the Gorgona basalts and Galapagos lavas. The subduction zone that generated the Late Cretaceous arcs occurred far from the continental margin, in an oceanic environment. This implies that no terrigenous detrital sediments interacted with the source at this period. Thus, the enriched component can only result from the melting of subducted pelagic sediments. We have thus defined the East-Pacific MORB, enriched (cherts, pelagic sediments) and HIMU components in an attempt to constrain and model the genesis of the studied island-arc magmatism, using a compilation of carefully selected isotopic data from literature according to rock age and paleogeographic location at the time of arc edification. Tripolar mixing models reveal that proportions of 12-15 wt.% of the HIMU component, 7-15 wt.% of the pelagic sediment end-member and 70-75 wt.% of an East-pacific MORB end-member are needed to explain the measured isotope ratios. These surprisingly high proportions of the HIMU/CCOP component could be explained by the young age of the oceanic plateau (5-15 Ma) during the Late Cretaceous arc emplacement. The CCOP, basement of these arc sequences, was probably still hot and easily assimilated at the island-arc lava source. (C) 2008 Elsevier Ltd. All rights reserved,

Third order elastic constants of bcc Cu-Al-Ni

We have measured the changes in the ultrasonic wave velocity, induced by the application of uniaxial stresses in a Cu-Al-Ni single crystal. From these measurements, the complete set of third-order elastic constants has been obtained. The comparison of results for Cu-Al-Ni with available data for other Cu-based alloys has shown that all these alloys exhibit similar anharmonic behavior. By using the measured elastic constants in a Landau expansion for elastic phase transitions, we have been able to give an estimation of the value of a fourth-order elastic constants combination. The experiments have also shown that the application of a stress in the [001] direction, reduces the material resistance to a (110)[110] shear and thus favors the martensitic transition.

Premartensitic and martensitic phase transitions in ferromagnetic Ni2MnGa

We present an experimental study of the premartensitic and martensitic phase transitions in a Ni2MnGa single crystal by using ultrasonic techniques. The effect of applied magnetic field and uniaxial compressive stress has been investigated. It has been found that they substantially modify the elastic and magnetic behavior of the alloy. These experimental findings are a consequence of magnetoelastic effects. The measured magnetic and vibrational behavior agrees with the predictions of a recently proposed Landau-type model [A. Planes et al., Phys. Rev. Lett. 79, 3926 (1997)] that incorporates a magnetoelastic coupling as a key ingredient.

Kinetics of martensitic transitions in Cu-Al-Mn under thermal cycling: Analysis at multiple length scales

In this paper we study the evolution of the kinetic features of the martensitic transition in a Cu-Al-Mn single crystal under thermal cycling. The use of several experimental techniques including optical microscopy, calorimetry, and acoustic emission, has enabled us to perform an analysis at multiple scales. In particular, we have focused on the analysis of avalanche events (associated with the nucleation and growth of martensitic domains), which occur during the transition. There are significant differences between the kinetics at large and small length scales. On the one hand, at small length scales, small avalanche events tend to sum to give new larger events in subsequent loops. On the other hand, at large length scales the large domains tend to split into smaller ones on thermal cycling. We suggest that such different behavior is the necessary ingredient that leads the system to the final critical state corresponding to a power-law distribution of avalanches.

Elastocaloric effect associated with the martensitic transition in shape-memory alloys

The elastocaloric effect in the vicinity of the martensitic transition of a Cu-Zn-Al single crystal has been studied by inducing the transition by strain or stress measurements. While transition trajectories show significant differences, the entropy change associated with the whole transformation (DeltaSt) is coincident in both kinds of experiments since entropy production is small compared to DeltaSt. The values agree with estimations based on the Clausius-Clapeyron equation. The possibility of using these materials for mechanical refrigeration is also discussed.

Spin filtering through ferromagnetic BiMnO3 tunnel barriers

We report on experiments of spin filtering through ultrathin single-crystal layers of the insulating and ferromagnetic oxide BiMnO3 (BMO). The spin polarization of the electrons tunneling from a gold electrode through BMO is analyzed with a counterelectrode of the half-metallic oxide La2/3Sr1/3MnO3 (LSMO). At 3 K we find a 50% change of the tunnel resistances according to whether the magnetizations of BMO and LSMO are parallel or opposite. This effect corresponds to a spin-filtering efficiency of up to 22%. Our results thus show the potential of complex ferromagnetic insulating oxides for spin filtering and injection.

Exchange bias between magnetoelectric YMnO3 and ferromagnetic SrRuO3 epitaxial films

Orthorhombic YMnO3 (YMO) epitaxial thin films were deposited on SrTiO3 (STO) single-crystal substrates. We show that the out-of-plane texture of the YMO films can be tailored using STO substrates having (001), (110), or (111) orientations. We report on the magnetic properties of the YMO(010) films grown on STO(001) substrates. The dependence of the susceptibility on the temperature indicates that the films are antiferromagnetic below the Néel temperature (around 35 K). Orthorhombic YMO(010) films were also deposited on an epitaxial buffer layer of ferromagnetic and metallic SrRuO3 (SRO). The magnetic hysteresis loops of SRO show exchange bias at temperatures below the Néel temperature of YMO. These results confirm that the YMO films are antiferromagnetic and demonstrate that magnetoelectric YMO can be integrated in functional epitaxial architectures.

Premartensitic and martensitic phase transition in ferromagnetic Ni2MnGa

We present an experimental study of the premartensitic and martensitic phase transitions in a Ni2MnGa single crystal by using ultrasonic techniques. The effect of applied magnetic field and uniaxial compressive stress has been investigated. It has been found that they substantially modify the elastic and magnetic behavior of the alloy. These experimental findings are a consequence of magnetoelastic effects. The measured magnetic and vibrational behavior agrees with the predictions of a recently proposed Landau-type model [A. Planes et al., Phys. Rev. Lett. 79, 3926 (1997)] that incorporates a magnetoelastic coupling as a key ingredient.

Microwave absorption and magnetization tunneling in Mn12-acetate molecular clusters

In this paper we study the effect of microwave absorption on the quantum relaxation rate of Mn12 molecular clusters. We have determined first the resonant frequencies of a microwave resonator containing a single crystal of Mn12-Acetate and measured initial isothermal magnetization curves while microwave power was put into the resonator. We have found that the tunneling rate changes one order of magnitude for certain frequencies. This suggests that the microwave shaking of the nuclear spin and molecular vibrational degrees of freedom is responsible for the huge increasing of the tunneling rate.

Loop bifurcation and magnetization rotation in exchange-biased Ni/FeF2

Exchange-biased Ni/FeF2 films have been investigated using vector coil vibrating-sample magnetometry as a function of the cooling field strength HFC . In films with epitaxial FeF2 , a loop bifurcation develops with increasing HFC as it divides into two sub-loops shifted oppositely from zero field by the same amount. The positively biased sub-loop grows in size with HFC until only a single positively shifted loop is found. Throughout this process, the negative and positive (sub)loop shifts maintain the same discrete value. This is in sharp contrast to films with twinned FeF2 where the exchange field gradually changes with increasing HFC . The transverse magnetization shows clear correlations with the longitudinal subloops. Interestingly, over 85% of the Ni reverses its magnetization by rotation, either in one step or through two successive rotations. These results are due to the single-crystal nature of the antiferromagnetic FeF2 , which breaks down into two opposite regions of large domains.

Ni-Mn-Ga thin films produced by pulsed laser deposition

Polycrystalline Ni-Mn-Ga thin films have been deposited by the pulsed laser deposition (PLD) technique, using slices of a Ni-Mn-Ga single crystal as targets and onto Si (100) substrates at temperatures ranging from 673 K up to 973 K. Off-stoichiometry thin films were deposited at a base pressure of 1×10-6-Torr or in a 5 mTorr Ar atmosphere. Samples deposited in vacuum and temperatures above 823 K are magnetic at room temperature and show the austenitic {220} reflection in their x-ray diffraction patterns. The temperature dependences of both electrical resistance and magnetic susceptibility suggest that these samples exhibit a structural martensitic transition at around 260 K. The magnetoresistance ratio at low temperature can be as high as 1.3%, suggesting the existence of a granular structure in the films

Epäpuhtauksien vaikutus monokaliumfosfaattikiteen kasvuun

Työssä on tutkittu epäpuhtauksien vaikutusta kastelulannoitesuolojen monokaliumfosfaatin, kaliumnitraatin ja ureafosfaatin kiteytyksessä. Kirjallisuusosassa on käsitelty kastelulannoiteprosessit ja epäpuhtauksien vaikutus kastelulannoitteiden valmistuksessa. Kiteytys ja kiteenkasvu on esitetty perusyhtälöin, joissa on otettu epäpuhtauksien vaikutus huomioon. Tarkemmin on perehdytty monokaliumfosfaatin kiteytykseen ja kolmenarvoisten kationeiden, Al3+, Fe3+ ja Cr3+, vaikutukseen kiteiden kasvuun. Kolmenarvoiset metalli-ionit adsorboituvat kiteen pintaan haitaten kiteenkasvua, mikä vaikuttaa erityisesti kiteen prismapinnan kasvuun. Lisäksi on esitelty muita kiteenkasvuun vaikuttavia olosuhteita. Lopuksi on käsitelty kompleksinmuodostajia metalli-ionien haitallisten vaikutusten ehkäisijöinä. Kokeellisessa osassa suoritettiin liukoisuuskokeita monokaliumfosfaatin liukoisuuden selvittämiseksi eri pH-olosuhteissa. Suoritetuissa yksikidekokeissa tutkittiin pH:n ja kolmenarvoisten kationeiden; Al3+, Fe3+ ja Cr3+, vaikutus monokaliumfosfaattikiteen pituus- ja leveyskasvuun ja kidemuotoon eri ylikylläisyyksillä. Lisäksi tutkittiin voidaanko lämpötilaa ja pH muuttamalla tai pyrofosfaattia lisäämällä poistaa raudan kasvua inhiboima vaikutus. Kiteytyslämpötilaa nostamalla voidaan poistaa raudan haitallinen vaikutus kiteen kasvuun.

Large Magnetoresistance in Fe/MgO/FeCo(001) Epitaxial Tunnel-Junctions on GaAs(001).

We present tunneling experiments on Fe~001!/MgO~20 Å!/FeCo~001! single-crystal epitaxial junctions of high quality grown by sputtering and laser ablation. Tunnel magnetoresistance measurements give 60% at 30 K, to be compared with 13% obtained recently on ~001!-oriented Fe/amorphous-Al2O3 /FeCo tunnel junctions. This difference demonstrates that the spin polarization of tunneling electrons is not directly related to the density of states of the free metal surface Fe~001! in this case but depends on the actual electronic structure of the entire electrode/barrier system.