Applications of TOF neutron diffraction in archaeometry

Neutron radiation meets the demand for a versatile diagnostic probe for collecting information from the interior of large, undisturbed museum objects or archaeological findings. Neutrons penetrate through coatings and corrosion layers deep into centimetre-thick materials, a property that makes them ideal for non-destructive examination of objects for which sampling is impractical or unacceptable. A particular attraction of neutron techniques for archaeologists and conservation scientists is the prospect of locating hidden materials and structures inside objects. Time-of-flight (TOF) neutron diffraction allows for the examination of mineral and metal phase contents, crystal structures, grain orientations, and microstructures as well as micro- and macro strains. A promising application is texture analysis which may provide clues to the deformation history of the material, and hence to specific working processes. Here we report on instructive examples of TOF neutron diffraction, including phase analyses of medieval Dutch tin-lead spoons, texture analyses of bronze specimens as well as of 16th-century silver coins. PACS 61.12.-q; 81.05.Bx; 81.70.Jd     

Short-range and medium-range order in amorphous barium germanate

Amorphous barium germanate of composition BaGe_2.55O_6.10 was prepared by ultra-rapid quenching using a double-roller melt-spinning device. The short-range and medium-range order was investigated by high-energy synchrotron X-ray diffraction, resonant scattering at the Ba K-absorption edge and by electron diffraction. There are indications that 6-fold coordinated germanium exists in the structure of the present amorphous alkaline earth germanate, i.e. both GeO₄ tetrahedra and GeO₆ octahedra are supposed to be basic building units. The ratio of 6-fold coordinated Ge to 4-fold coordinated Ge is approximately 1:3. A structure model is proposed which favours the existence of barium chains and/or barium layers, similar to the structure of barium silicate glasses.     

Crystal structure of a newly oxidized aristolane sesquiterpenes,C15H22O3, from aristolochia debilis

M_r = 250, orthorhombic, P 2₁2₁2₁, a = 9.583(6), b = 11.786(8), c = 12.298(9) Å, V = 1389.0 ų, Z = 4, D_x = 1.20 g cm⁻³, F(000) = 544, MoK_α, λ = 0.71069 Å, μ = 0.88 cm⁻¹. Final R = 0.023 for 1006 observed reflections, T = 293 K. The structure was solved by direct methods and refined by full-matrix least squares. It is an α, β unsaturated carbonyl compound with a trisubstituted double bonds. No significant variation in aromatic bond lengths. The strain affecting the molecule is largely due to angular deformation which is partly due to the fusion of the rings and partly due to substitution of H-atoms by methyl groups and oxygen atoms.     

Structural study of amorphous tellurium(II) halides TeCl2-xIx (x = 0.5, 0.1): X-ray diffraction and reverse Monte Carlo simulations

The addition of small amounts of iodine to thermodynamically instable TeCl2 yields amorphous, glassy tellurium(II) halides TeCl2-xIx (0.1 < x < 0.5), which were prepared by rapid quenching of melts with the respective compositions. At ambient temperature, these glassy solids are sufficiently stable to be handled and investigated by analytical methods. High-energy X-ray diffraction and reverse Monte Carlo simulations of two compositions TeCl2-xIx, x = 0.1 and 0.5, show that these glasses are made up of structural fragments that are present in both tellurium tetrahalides and in low-valent tellurium subhalides. In both glasses, the Te-Te bonding shows narrow coordination distribution with a mean total coordination number for the Te atoms of 4.1 +/- 1.3 and a mean Te-Te coordination number of 0.7 +/- 0.7. Accordingly, the mean Cl-Te coordination number is 1.7 +/- 0.8 and the mean I-Te coordination number is 1.6 +/- 0.7. The medium-range order increases with increasing iodine content.     

Linear Forms in Finite Sets of Integers

Let A_1, ..., A_r be finite, nonempty sets of integers, and let h_1,..., h_r be positive integers. The linear formh_1A_1 + ··· + h_rA_r is the set of all integers of the form b_1 + ··· + b_r, where b_i is an integer that can be represented as the sum ofh_i elements of the set A_i. In this paper, the structure of the linear form h_1A_1 + ··· + h_rA_r is completely determined for all sufficiently large integersh_i .     

Neutron diffraction and electrochemical studies on LiIrSn4

Large quantities of single phase, polycrystalline LiIrSn₄ have been synthesised from the elements by melting in sealed tantalum tubes and subsequent annealing. LiIrSn₄ crystallises with an ordered version of the PdGa₅ structure: I4/mcm, a=655.62(8), . The lithium atoms were clearly localised from a neutron powder diffraction study: R_P=0.147 and R_F=0.058. Time-dependent electrochemical polarisation techniques, i.e. coulometric titration, chronopotentiometry, chronoamperometry and cyclic voltammetry were used to study the kinetics of lithium ion diffusion in this stannide. The range of homogeneity (Li_1+ΔδIrSn₄, −0.091?δ?+0.012) without any structural change in the host structure and the chemical diffusion coefficient (∼10⁻⁷-10⁻⁹ cm²/s) point out that LiIrSn₄ is a first example of a large class of intermetallic compounds with lithium and electron mobility. Optimised materials from these ternary lithium alloys may be potential electrode material for rechargeable lithium batteries.     

MBE growth of SiGe with high Ge content for optical applications

The molecular beam epitaxy is a powerful technology for integrating optoelectronic devices in standard Si microelectronics. The MBE growth of high speed germanium detectors is discussed. The necessary lattice accommodation between Si and Ge is realized by an ultra thin virtual substrate. Contact layers with very high doping concentration and very sharp transitions are grown with special doping strategies. As special growth method the differential epitaxy allows the growth of epitaxial layers in oxide windows.