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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 1213-1218 
    ISSN: 0009-2940
    Keywords: Silicon ; Octahedral oxygen coordination ; Phosphorus ; NMR, 1H MAS ; NMR, 29Si MAS ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Simple Route to Silicon in Octahedral Oxygen CoordinationSyntheses and crystal structures of three new compounds Rb2SiP4O13 (1), Cs2H2Si(P2O7)2 (2), and BaH2Si(P2O7)2 (3) containing silicon in an octahedral oxygen coordination are reported. The structures have been determined by X-ray structure analyses. All three compounds are constituted of silicophosphate polyanions. The NMR chemical shifts of silicon and hydrogen are measured.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 26 (1987), S. 1098-1110 
    ISSN: 0570-0833
    Keywords: Bond theory ; Solid-state reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 36 (1997), S. 328-343 
    ISSN: 0570-0833
    Keywords: boron ; ceramics ; nitrides ; polymers ; silicon ; Boron ; Ceramics ; Nitrides ; Polymers ; Silicon ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Materials research is an interdisciplinary field in which engineers and physical scientists work together. Since the major binary oxides, nitrides, and carbides, which are currently used as high-performance ceramics, were discovered in the last century, the role of chemistry in the development of materials has become barely noticeable. This has changed only in the recent past as, for example, purity and defined morphology of starting powders were recognized as crucial parameters for enhancing the reliability of ceramic workpieces. While the application of chemical methods led to gradual-though significant-improvements, the true potential of chemistry lies rather in the exploitation of new chemical systems and the development of new preparative routes to already known materials. Such an approach is the preparation of ceramics from molecular or polymeric precursors. Herein we survey the most important contributions to those preparative routes starting from the pioneering work in the 1960s and the 1970s; a certain emphasis is placed on the concepts that we have applied to the preparation of multinary, nonoxide materials and amorphous inorganic networks. The name “amorphous high-performance ceramics” is in fact a contradiction in terms. Such materials are thermodynamically unstable with respect to the transformation or decomposition to crystalline phases, thus excluding their application in sensitive areas at high temperatures. However, the selection of element combinations for which the binding energies are derived from strong, local covalent bonds and which are therefore less dependent on a long-range crystalline order, can yield amorphous materials of remarkable thermal and mechanical durability. This is exemplified by novel quaternary ceramics in the Si/B/N/C system, for which an efficient synthesis, starting from raw materials suitable for industrial production, has been developed. For instance, a material of the composition SiBN3C remains amorphous up to 1900°C, which is unique, and, with respect to oxidation, is the most stable nonoxide ceramic known to date. Another advantage of this in several respects unsurpassed material is the simple way, in which the viscosity of the polymeric precursors can be adjusted to various methods of shaping. So far infiltrations and coatings have been realized. Most developed is the preparation of fibers, which in terms of their performance characteristics are significantly better than those currently available.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0570-0833
    Keywords: Alkali metals ; Solid-state reactions ; Ion conductors ; Conducting materials ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transport phenomena in the solid state are of equal importance in basic research and practice. In the past two decades particular interest has been directed towards so-called “fast” or “super” ionic conductors because of their attractive potential applications. We have synthesized highly conductive alkali-metal ionic conductors based on ionic crystals in which, on the one hand, high concentrations of the charge carriers can be realized by doping (point defects in the cation substructure) and, on the other, the activation energy of the interchange of sites is decreased by translationally fixed but rotationally mobile complex anions. Mixed crystals with Na3PO4 or Na3AlF6 structures have proven especially suitable in this connection. With the object of establishing a broader experimental foundation for clarifying the controversially discussed question of whether the higher free transport volume or the rotational motion of the anions is responsible for the high cation mobility in these rotary phases we have systematically varied the type of anions and concentration of defects and monitored the resulting changes in conductivity. Although the macroscopical characteristics investigated are not suitable for explaining mechanisms in detail at the atomic level, the results afford clear support for the assumption of a “paddle wheel mechanism”; but also effects of the enlarged transport volume are not to be disputed. Both these effects enhancing the cationic conductivity are concomitantly operative in amounts varying from system to system; they cannot be totally separated from each other. Seen in this light, the alternative, “volume effect” or “paddle wheel mechanism,” is not as sharply defined as was previously discussed.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 1286-1304 
    ISSN: 0570-0833
    Keywords: computer chemistry ; solid-state structures ; structure prediction ; synthesis planning ; Computer chemistry ; Solid-state reactions ; Solid-state structures ; Solid-phase synthesis ; Structure prediction ; Synthesis design ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented here that allows, in principle, the prediction of the existence and structure of (meta)stable solid compounds. It is based on a set of adjustable modules that are applied to the study of the energy function of the chemical system of interest. The main elements are a set of routines for global optimization and local minimization, as well as algorithms for the investigation of the phase space structure near local minima of the potential energy, and the analysis and characterization of the structure candidates. The current implementation focuses on ionic compounds, for which empirical potentials are used for the evaluation of the energy function in the first stage, and a Hartree-Fock algorithm for refinements. The global optimization is performed with a stochastic simulated annealing algorithm, and the local minimization employs stochastic quenches and gradient methods. The neighborhoods of the local minima are studied with the threshold algorithm. The results of this approach are illustrated with a number of examples: compounds of binary noble gases, and binary and ternary ionic compounds. These include several substances that have not been synthesized yet, but should stand a fair chance of being kinetically stable, for example further alkali metal nitrides besides Li3N, as well as Ca3SiBr2 or SrTi2O5.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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