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Ludwig-Maximilians-Universität München

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  1. 01/01/1994

    Compressibility of titanosilicate melts

    The effect of composition on the relaxed adiabatic bulk modulus (K0) of a range of alkali- and alkaline earth-titanosilicate [X 2 n/n+ TiSiO5 (X=Li, Na, K, Rb, Cs, Ca, Sr, Ba)] melts has been investigated. The relaxed bulk moduli of these melts have been measured using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz in the temperature range of 950 to 1600°C (0.02 Pa s s 5 Pa s). The bulk moduli of these melts decrease with increasing cation size from Li to Cs and Ca to Ba, and with increasing temperature. The bulk moduli of the Li-, Na-, Ca- and Ba-bearing metasilicate melts decrease with the addition of both TiO2 and SiO2 whereas those of the K-, Rb- and Cs-bearing melts increase. Linear fits to the bulk modulus versus volume fraction of TiO2 do not converge to a common compressibility of the TiO2 component, indicating that the structural role of TiO2 in these melts is dependent on the identity of the cation. This proposition is supported by a number of other property data for these and related melt compositions including heat capacity and density, as well as structural inferences from X-ray absorption spectroscopy (XANES). The compositional dependence of the compressibility of the TiO2 component in these melts explains the difficulty incurred in previous attempts to incorporate TiO2 in calculation schemes for melt compressibility. The empirical relationship KV-4/3 for isostructural materials has been used to evaluate the compressibility-related structural changes occurring in these melts. The alkali metasilicate and disilicate melts are isostructural, independent of the cation. The addition of Ti to the metasilicate composition (i.e. X2TiSiO5), however, results in a series of melts which are not isostructural. The alkaline-earth metasilicate and disilicate compositions are not isostructural, but the addition of Ti to the metasilicate compositions (i.e. XTiSiO5) would appear, on the basis of modulus-volume systematics, to result in the melts becoming isostructural with respect to compressibility.

  2. 01/01/1994

    Coverage-dependent adsorption sites for K/Cu(001) and Cs/Cu(001) determined by surface X-ray diffraction

    Surface X-ray diffraction has been used to analyze in situ the room-temperature adsorption behaviour and the structure of K and Cs on Cu(100) at submonolayer coverages. Adsorption of K takes place in fourfold hollow sites up to coverages of about 0.25 monolayers (ML), where 1 ML corresponds to 1.53 × 1015 atoms/cm2. At higher coverages the formation of a quasi-hexagonal incommensurate adlayer is observed. In contrast, for Cs adsorption we observe from the very beginning the formation of the quasi-hexagonal structure up to the completion of the adlayer at about 0.30 ML. For K adsorption in the hollow sites we determine an adsorption height, d = 2.25(15) Å, corresponding to an effective K radius of reff = 1.6(1) Å close to the ionic radius of 1.33 Å. We do not observe a change in the effective radius as a function of coverage. For the quasi-hexagonal Cs structure we find an (average) adsorption height d = 2.94 Å corresponding to an effective radius of reff = 2.18 and 1.93 Å, for the limiting ca hollow- and bridge-site adsorption, respectively. The analysis of the superlattice reflections corresponding to the quasi-hexagonal incommensurate structures indicated that the K adlayer is strongly modulated. The first Fourier component of the substrate-induced modulation was determined to u01 = 1.29(3) Å. In contrast, for Cs/Cu(001) static modulation is much less important (u01 0.2 Å). Variation of the Cs adlayer density by changing the substrate temperature allows continuous expansion and contraction of the adsorbate unit cell. No commensurate-incommensurate transition has been observed.

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Die Universitätsbibliothek (UB) verfügt über ein umfangreiches Archiv an elektronischen Medien, das von Volltextsammlungen über Zeitungsarchive, Wörterbücher und Enzyklopädien bis hin zu ausführlichen Bibliographien und mehr als 1000 Datenbanken reicht. Auf iTunes U stellt die UB unter anderem eine Auswahl an elektronischen Publikationen der Wissenschaftlerinnen und Wissenschaftler an der LMU bereit.

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