Vibrations of micro-eV energies in nanocrystalline microstructures

The phonon density of states of nanocrystalline bcc Fe and nanocrystalline fcc Ni3Fe were measured by inelastic neutron scattering in two different ranges of energy. As has been reported previously, the nanocrystalline materials showed enhancements in their phonon density of states at energies from 2 to 15 meV, compared to control samples composed of large crystals. The present measurements were extended to energies in the micro-eV range, and showed significant, but smaller, enhancements in the number of modes in the energy range from 5 to 18 microeV. These modes of micro-eV energies provide a long-wavelength limit that bounds the fraction of modes at milli-eV energies originating with the cooperative dynamics of the nanocrystalline microstructure.     

A general preparation of (Z)-1-fluorostilbene derivatives for the design of conformationally restricted peptidomimetics

The preparation of (Z)-1-fluoro-2-bromostyrenes provides a general route for the formation of (Z)-1-fluorostilbene derivatives as configurationally stable spacial linkers for the design of conformationally restricted peptidomimetics. Palladium-catalyzed aryl Suzuki and Stille cross-coupling reactions have been surveyed to proceed with complete retention of fluoroalkene geometry, and permit the direct incorporation of a variety of aryl and heteroaromatic substituents.     

Structural relationship between negative thermal expansion and quartic anharmonicity of cubic ScF3

Cubic scandium trifluoride (ScF3) has a large negative thermal expansion over a wide range of temperatures. Inelastic neutron scattering experiments were performed to study the temperature dependence of the lattice dynamics of ScF3 from 7 to 750 K. The measured phonon densities of states show a large anharmonic contribution with a thermal stiffening of modes around 25 meV. Phonon calculations with first-principles methods identified the individual modes in the densities of states, and frozen phonon calculations showed that some of the modes with motions of F atoms transverse to their bond direction behave as quantum quartic oscillators. The quartic potential originates from harmonic interatomic forces in the DO9 structure of ScF3, and accounts for phonon stiffening with the temperature and a significant part of the negative thermal expansion.     

Absence of magnetism in hcp iron-nickel at 11 K

Synchrotron M?ssbauer spectroscopy (SMS) was performed on an hcp-phase alloy of composition Fe92Ni8 at a pressure of 21 GPa and a temperature of 11 K. Density functional theoretical calculations predict antiferromagnetism in both hcp Fe and hcp Fe-Ni. For hcp Fe, these calculations predict no hyperfine magnetic field, consistent with previous experiments. For hcp Fe-Ni, however, substantial hyperfine magnetic fields are predicted, but these were not observed in the SMS spectra. Two possible explanations are suggested. First, small but significant errors in the generalized gradient approximation density functional may lead to an erroneous prediction of magnetic order or of erroneous hyperfine magnetic fields in antiferromagnetic hcp Fe-Ni. Alternately, quantum fluctuations with periods much shorter than the lifetime of the nuclear excited state would prohibit the detection of moments by SMS.     

Crystal and molecular structure of (η5)-C5H5)Co(HNC6H4NH), a cobalto-quinonediimine complex

The X-ray structure determination of (η ⁵-C₅H₅)Co(HNC₆H₄NH) (Ib) reveals that the compound crystallizes in the monoclinic space groupP2₁/n witha=12.479(3),b=8.865(2),c=17.817(5) Å, {iβ}=94.70(2)°,V=1964.4(6) ų,Z=8 (two independent molecules form the asymmetric unit). Least-squares refinement based on 1894 independent observed reflections,I≥2.5σ(I), resulted in a finalR value of 0.054. A pattern of somewhat shortened Co-N bonds (〈av〉 1.83 Å), short C-N bonds (〈av〉 1.34 Å), Co-N-C bond angles consistent with trigonally hybridized N, and a nearly planar metallocyclic ring suggest that some electron delocalization may exist in the ring. This pattern, however, may also be explicable in terms of factors other than delocalization; alternatives are discussed. The structure may best be regarded as a Co^I complex containing ano-quinonediimine ligand.     

Grain boundaries of nanocrystalline materials – their widths, compositions, and internal structures

Nanocrystalline materials contain many atoms at and near grain boundaries. Sufficient numbers of Mössbauer probe atoms can be situated in grain boundary environments to make a clear contribution to the measured Mössbauer spectrum. Three types of measurements on nanocrystalline materials are reported here, all using Mössbauer spectrometry in conjunction with X-ray diffractometry, transmission electron microscopy, or small angle neutron scattering. By measuring the fraction of atoms contributing to the grain boundary component in a Mössbauer spectrum, and by knowing the grain size of the material, it is possible to deduce the average width of grain boundaries in metallic alloys. It is found that these widths are approximately 0.5 nm for fcc alloys and slightly larger than 1.0 nm for bcc alloys. Chemical segregation to grain boundaries can be measured by Mössbauer spectrometry, especially in conjunction with small angle neutron scattering. Such measurements on Fe-Cu and Fe₃Si-Nb were used to study how nanocrystalline materials could be stabilized against grain growth by the segregation of Cu and Nb to grain boundaries. The segregation of Cu to grain boundaries did not stabilize the Fe-Cu alloys against grain growth, since the grain boundaries were found to widen and accept more Cu atoms during annealing. The Nb additions to Fe₃Si did suppress grain growth, perhaps because of the low mobility of Nb atoms, but also perhaps because Nb atoms altered the chemical ordering in the alloy. The internal structure of grain boundaries in nanocrystalline materials prepared by high-energy ball milling is found to be unstable against internal relaxations at low temperatures. The Mössbauer spectra of the nanocrystalline samples showed changes in the hyperfine fields attributable to movements of grain boundary atoms. In conjunction with SANS measurements, the changes in grain boundary structure induced by cryogenic exposure and annealing at low temperature were found to be somewhat different. Both were consistent with a sharper density gradient between the crystalline region and the grain boundary region.     

Mössbauer diffraction and interference studies of polycrystalline metals and alloys

After a review of previous work on Mössbauer diffraction and interference phenomena, the principles of the kinematical theory of Mössbauer diffraction are presented. The emphasis is on how the spectroscopic capabilities of the Mössbauer effect can be used to advantage in diffraction studies on materials and condensed matter. Experimental results from Mössbauer powder diffractometry experiments are presented. These results identify the difficulties of Mössbauer powder diffraction experiments, but also demonstrate that a unique chemical environment selectivity is possible for Mössbauer diffraction. Future experiments with Mössbauer powder diffraction require the development of efficient detectors, and some possibilities are suggested.     

An International Laboratory Comparison Study of Volumetric and Gravimetric Hydrogen Adsorption Measurements

In order to determine a material's hydrogen storage potential, capacity measurements must be robust, reproducible, and accurate. Commonly, research reports focus on the gravimetric capacity, and often times the volumetric capacity is not reported. Determining volumetric capacities is not as straight-forward, especially for amorphous materials. This is the first study to compare measurement reproducibility across laboratories for excess and total volumetric hydrogen sorption capacities based on the packing volume. The use of consistent measurement protocols, common analysis, and figure of merits for reporting data in this study, enable the comparison of the results for two different materials. Importantly, the results show good agreement for excess gravimetric capacities amongst the laboratories. Irreproducibility for excess and total volumetric capacities is attributed to real differences in the measured packing volume of the material.