Jörg Neuefeind

Short-range order of Zr62−xTixAl10Cu20Ni8 bulk metallic glasses

Abstract The short-range order and crystallization behavior of slowly cooled Zr 62− x Ti x Al 10 Cu 20 Ni 8 bulk metallic glasses have been investigated in terms of the atomic pair correlation function as a function of Ti content x (2≤ x ≤7.5). The structural parameters point to the presence of chemical short-range order in these bulk glasses. An enhanced local excess free volume around the Ti atoms is concluded from density measurements. The first stage of crystallization in Zr 62− x Ti x Al 10 Cu 20 Ni 8 bulk glasses is related to changes in the medium-range order while the first neighborhood is retained. The atomic pair correlation functions of the first crystallization products are similar for all titanium contents. There is no indication of any special atomic arrangement for the particular alloy forming quasicrystals upon heating ( x =3). In case of Zr 54.5 Ti 7.5 Al 10 Cu 20 Ni 8 an ultrafine microstructure consisting of clusters of 2 nm in size is formed as the first step of crystallization.

A green-yellow emitting oxyfluoride solid solution phosphor Sr2Ba(AlO4F)1−x(SiO5)x:Ce3+ for thermally stable, high color rendition solid state white lighting

A near-UV excited, oxyfluoride phosphor solid solution Sr1.975Ce0.025Ba(AlO4F)1−x(SiO5)x has been developed for solid state white lighting applications. An examination of the host lattice, and the local structure around the Ce3+ activator ions through a combination of density functional theory, synchrotron X-ray and neutron powder diffraction and total scattering, and electron paramagnetic resonance, points to how chemical substitutions play a crucial role in tuning the optical properties of the phosphor. The maximum emission wavelength can be tuned from green (λem = 523 nm) to yellow (λem = 552 nm) by tuning the composition, x. Photoluminescent quantum yield is determined to be 70 ± 5% for some of the examples in the series. Excellent thermal properties were found for the x = 0.5 sample, with the photoluminescence intensity at 160 °C only decreased to 82% of its room temperature value. Phosphor-converted LED devices fabricated using an InGaN LED (λmax = 400 nm) exhibit high color rendering white light with Ra = 70 and a correlated color temperature near 7000 K. The value of Ra could be raised to 90 by the addition of a red component, and the correlated color temperature lowered to near 4000 K.

In-situ study of crystallization kinetics in ternary bulk metallic glass alloys with different glass forming abilities

In-situ transmission electron microcopy and time-resolved neutron diffraction were used to study crystallization kinetics of two ternary bulk metallic glasses during isothermal annealing in the supercooled liquid region. It is found that the crystallization of Zr56Cu36Al8, an average glass former, follows continuous nucleation and growth, while that of Zr46Cu46Al8, a better glass former, is characterized by site-saturated nucleation, followed by slow growth. Possible mechanisms for the observed differences and the relationship to the glass forming ability are discussed.

Structural behavior of Zr52Ti5Cu18Ni15Al10 bulk metallic glass at high temperatures

The structural behavior of the Zr52Ti5Cu18Ni15Al10 bulk glass-forming alloy has been investigated in situ by means of high-temperature x-ray synchrotron diffraction. The dependence of the structure factor of the glass can be well described with a Debye–Waller factor and a Debye temperature θ=412 K. At the glass transition, the structure factor significantly decreases due to additional thermal excitations. The extrapolation of the structure factor of the supercooled liquid to temperatures above the liquidus curve is in agreement with experimentally determined values of the melt. The short-range order of the glass, of the supercooled liquid state, and of the equilibrium melt at T=1193 K, is found to be quite similar. The formation of complex chemically ordered clusters in the melt is proposed to be essential for the high-glass-forming ability of this alloy.

Intricate Short-Range Ordering and Strongly Anisotropic Transport Properties of Li1–xSn2+xAs2

A new ternary compound, Li(1-x)Sn(2+x)As2, 0.2 < x < 0.4, was synthesized via solid-state reaction of elements. The compound crystallizes in a layered structure in the R3̅m space group (No. 166) with Sn-As layers separated by layers of jointly occupied Li/Sn atoms. The Sn-As layers are comprised of Sn3As3 puckered hexagons in a chair conformation that share all edges. Li/Sn atoms in the interlayer space are surrounded by a regular As6 octahedron. Thorough investigation by synchrotron X-ray and neutron powder diffraction indicate no long-range Li/Sn ordering. In contrast, the local Li/Sn ordering was revealed by synergistic investigations via solid-state (6,7)Li NMR spectroscopy, HRTEM, STEM, and neutron and X-ray pair distribution function analyses. Due to their different chemical natures, Li and Sn atoms tend to segregate into Li-rich and Sn-rich regions, creating substantial inhomogeneity on the nanoscale. The inhomogeneous local structure has a high impact on the physical properties of the synthesized compounds: the local Li/Sn ordering and multiple nanoscale interfaces result in unexpectedly low thermal conductivity and highly anisotropic resistivity in Li(1-x)Sn(2+x)As2.

Formation of ultrafine nanostructure by crystallization of Zr52Al6Cu14Ni8Fe20 metallic glass

The short-range order and the crystallization behavior of amorphous Zr52Al6Cu14Ni8Fe20 alloys have been investigated by means of calorimetry and x-ray diffraction. The amorphous structure transforms upon annealing without formation of long-range order. An ultrafine microstructure consisting of about 60 vol % cubic NiZr2 crystal-like clusters with a size of 〈D〉≈2 nm embedded in a residual amorphous matrix phase forms as a first step of crystallization resulting from high nucleation rate combined with low growth velocity. In a second step growth of the clusters to crystals up to a mean diameter of 〈D〉≈4–5 nm takes place as a distinct process.

Structure of Zr52Ti5Cu18Ni15Al10 Bulk Metallic Glass at Elevated Temperatures

The glass transition and the phase formation during crystallization of the Zr52Ti5Cu18Ni15Al10 bulk metallic glass were followed in situ by high-temperature X-ray diffraction using synchrotron radiation at the high energy beam-line BW5 ( λ = 0.01040 nm) at the storage ring DORIS (HASYLAB, Hamburg). The experimental set-up enables to record intensities in transmission up to scattering vectors q of 200 nm -1 with a measuring time of 20 s per diagram. The crystallization starts with the formation of an extremely fine nanostructure followed by the transformation into tetragonal NiZr2-type crystals plus an unknown phase. Both phases are metastable and transform at about 1123 K into the stable equilibrium phases. The temperature dependence of the structure factor S(q) of the glass can be well described within the framework of the Debye theory. At the glass transition the first derivative dS(q)/dT changes. A Debye temperature Θ = 412 K was estimated for the glassy, and Θ = 162 K for the liquid state of the Zr52Ti5Cu18Ni15Al10 alloy. The short-range order of the glass, of the supercooled liquid state, and of the equilibrium melt at T = 1193 K is found to be quite similar.

A suite-level review of the neutron powder diffraction instruments at Oak Ridge National Laboratory

The suite of neutron powder diffractometers at Oak Ridge National Laboratory (ORNL) utilizes the distinct characteristics of the Spallation Neutron Source and High Flux Isotope Reactor to enable the measurements of powder samples over an unparalleled regime at a single laboratory. Full refinements over large Q ranges, total scattering methods, fast measurements under changing conditions, and a wide array of sample environments are available. This article provides a brief overview of each powder instrument at ORNL and details the complementarity across the suite. Future directions for the powder suite, including upgrades and new instruments, are also discussed.

Density driven structural transformations in amorphous semiconductor clathrates

The pressure induced crystalline collapse at 14.7 GPa of the semiconductor clathrate Sr8Ga16Ge30 and its polyamorphic structures are reported up to 35 GPa. In-situ total scattering measurements under pressure allow the direct microscopic inspection of the mechanisms associated with the pressure induced amorphization in these systems, as well as the structure of the recovered phase. It is observed that, between 14.7 and 35 GPa, the second peak in the structure factor function gradually disappears. Analysis of the radial distribution function extracted from those data indicates a systematic lengthening of the nearest-neighbor framework bonds. This feature is associated with gradual cage collapse and breakdown of the tetrahedral structure. This suggests a change in the local bonding in the high density amorphous form, similarly to that observed in other semiconductor clathrates and elemental silicon. Upon recovery from high pressure, the sample remains amorphous and, while there is some indication of the gue...