Dynamic susceptibility of reentrant Fe-rich inhomogeneous amorphous alloys

Melt-spun amorphous alloys of Fe₉₁Zr₉, Fe₉₁Zr₇B₂, Fe₉₀Zr₇B₃ and Fe₈₈Zr₈B₄ have been characterized by AC susceptibility at frequencies between 30 Hz and 10 KHz. The measurements reflect the existence of reentrant spin glass transitions below 40 K for all cases. The transition shift per frequency decade is large compared to the observed in conventional spin-glass alloys. The shift value increases with the boron content and becomes closer to values in fine-particle systems. We find that the relaxation in Fe₉₁Zr₉ follows a critical slowing down at the reentrant transition, with exponents and . The non-linear susceptibility displays a peak at the transition in this alloy, but wider than in canonical spin glasses. A Vogel-Fulcher (VF) activation process can explain the frequency variation in all the Fe-Zr-B alloys. The reduction of the ideal glass temperature in the VF approach, found in the higher Boron content alloys, is an indication of a superparamagnetic-like behavior. The behavior shown by these alloys is intermediate between a collective freezing and superparamagnetic-like relaxation. We propose that this is arising due to a heterogeneous spin structure. The inclusion of a reduced amount of B, affects the magnetic spin structure.Received: 13 May 2003, Published online: 22 September 2003PACS: 75.50.Lk Spin glasses and other random magnets - 75.50.Kj Amorphous and quasicrystalline magnetic materials - 75.40.Gb Dynamic properties (dynamic susceptibility, spin waves, spin diffusion, dynamic scaling, etc.)J.S. Garitaonandia: Present address: Dept. Física Aplicada, F. Ciencias, Universidad del País Vasco, Bilbao 48080, Spain     

The thioacetate approach to vitamin D analogues. Part 2: Synthesis of (25S)-23-thia-1α,25,26-trihydroxyvitamin D3

(25S)-23-Thia-1α,25,26-trihydroxyvitamin D₃ (4) was prepared from alcohol 5 in 56% overall yield (five steps) using our previously developed methodology. Alcohol 5 was synthesized from commercially available vitamin D₂.     

Applications of the group-function theory to the field of materials science

The group-function theory, as proposed by McWeeny for the study of weak intermolecular interactions and developed by Huzinaga in the context of valence-electron methods, is shown to be applicable to the ab initio study of tunable solid-state laser materials made of defective ionic crystals. The applicability of the theory relies on the existence of local electronic states (to which the demonstrated/potential laser activity is ascribed), which are essentially localized in a small cluster of atoms including the defect and whose electron correlation interactions with the surrounding crystal components are negligible. According to the group-function formalism, it is possible (a) to neglect electron correlation effects beyond the defect cluster and (b) to define a quantum mechanical embedding potential which embodies the rest of the so-called host effects. Computationally, the theory becomes applicable as the embedding potential is approximated through ab initio model potentials (AIMP). The results of AIMP embedded-cluster calculations demonstrate that it is possible to calculate the local structure and spectroscopy of the active defect at an ab initio level, the attainable accuracy being comparable to the usual one in molecular ab initio studies in the gas phase. Also, in this article, we present a systematic study of the local distortions produced upon doping divalent first-series transition-metal ions in rock-salt oxides, MO:Me²⁺ (M=Mg, Ca, Sr; Me=Sc-Zn) and Tl⁺ in KMgF₃ and KF hosts. This study leads to the calculation of the local structures of the defects in these materials, which have not been measured. The results suggest that the use of the mismatch of the empirical ionic radii of the impurity and the substituted ion in order to predict local distortions in doped ionic crystals is not significant when it is smaller than 0.1 Å, and when it is larger, it should be weighted by a reduction factor depending on the host. For the first-series divalent transition-metal ion impurities, this factor is shown to be 0.15 for SrO, 0.25 for CaO, and around 0.50 for MgO. © 1996 John Wiley & Sons, Inc.     

Temperature dependence of magnetostriction in [Co1−x(FeNi)x]75Si15B10 amorphous alloys

Magnetostriction measurements as a function of temperature and composition are reported for [Co_1x(Fe_0.5Ni_0.5)_x]₇₅Si₁₅B₁₀ metallic glasses. Single-ion as well as two-ion contributions to λ_s are found in the composition range 0<x<0.5. For x=0.12 the magnetostriction changes sign with increasing temperature.     

Enantiodivergent synthesis of (+)- and (−)-isolaurepan

The enantiodivergent synthesis of (+)-and (?)-isolaurepan was achieved from a common chiral template easily available from tri-O-acetyl-d-glucal, using as key step a diastereoselective thermal Claisen rearrangement, combined with a ring expansion reaction using trimethylsilyldiazomethane.     

Grafting vinyl monomers to starch by ceric ion. I. Acrylonitrile and acrylamide

Studies were carried out on the grafting of acrylonitrile (AN) and acrylamide (AA) to starch by ceric ion. The variables affecting the grafting of AN and AA were investigated with granular wheat starch dispersed in aqueous N,N-dimethylformamide and ceric ammonium nitrate as catalyst. Results showed that the concentrations of monomer and catalyst are the major factors influencing the grafting of AN; thus the monomer content of the grafts can be regulated by these variables. The grafting of AA is also influenced by these variables, but to a much less degree. Increasing concentrations of monomer promote homopolymerization and increasing concentration of catalyst inhibit grafting. The extent of grafting of this monomer can best be controlled by reaction time. Under the most favorable conditions, maximum grafting efficiency (ratio of amount of grafted monomer to total amount of monomer converted to polymer) was 87% for AN and 43.8% for AA. Although the monomer content of the AN grafts was higher than that of AA grafts prepared under identical conditions, the number of branches in the grafts was almost the same; only the length of the branches was different. The AN-starch grafts have branches of higher molecular weight.     

Stereoselective synthesis of (22Z)-25-hydroxyvitamin D2 and (22Z)-1α,25-dihydroxyvitamin D2

Two new vitamin D₂ analogues, (22Z)-25-(OH)-D₂ and (22Z)-1α,25-(OH)₂-D₂, were serendipitously synthesized from vitamin D₂ and using the Julia-Kocienski olefination.     

Ab initio theoretical study of luminescence properties of Pr3+-doped Lu2O3

Ab initio embedded cluster calculations have been performed on $\hbox{Pr}^{3+}$ -doped $\hbox{Lu}_2\hbox{O}_3$ , in order to investigate the mechanism responsible for the highly efficient $^3P_0\rightarrow^1D_2$ non-radiative relaxation experimentally observed. $(\hbox{PrO}_6)^{9-}$ embedded clusters representing the C ₂ and S ₆ substitutional sites of Pr³⁺:Lu₂O₃ have been studied using wave function-based methods. It is found that an outward relaxation of the first coordination sphere around the impurity takes place upon doping. At the relaxed geometry of the lowest spin triplet 4f5d state, all the 4f5d states lie much higher in energy than all 4f ² states (except the ¹S multiplet). This result is in opposition to the interpretation of intersystem crossing through a low-lying 4f5d excited state of Pr³⁺ as the mechanism for the fast non-radiative ³ P ₀????¹ D ₂ relaxation proposed in the literature. Absorption to the lowest spin triplet 4f5d state is calculated to be around 4,800?cm^?1 higher for the C ₂ site than for the S ₆ site, supporting the assignment of bands in the excitation spectrum previously reported.