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1992[X]
141Author    Gerhard Raabe, Wolfgang Karl, Dieter Enders, Jörg FleischhauerRequires cookie*
 Title    Conformational Aspects of Substituents in Enamines. X-Ray Structure Analyses and Quantum Chemical Calculations  
 Abstract    X-ray structure determination of the enamine (Z)-4-(6'-t-butoxycarbonyl-2',2'-dimethyl-5'-phenyl-3'-hexen-3'-yl)morpholine (1) reveals that certain bulky groups may enforce a relative orientation of the molecular subunits without conjugative interaction between the nitrogen lone pair and the olefinic double bond. According to the results of quantum chemical ab initio calculations the experimentally found arrangement would be the least favourable one in the absence of such sub-stituents. A careful analysis of the molecular structure of 1 shows that this unusual arrangement is due to the presence of both, the a-and the ^-substituent. In (£)-4-(3'-t-butoxycarbonylmethyl-l'-phenyl-r-penten-r-yl)morpholine (2) rather the nitrogen lone pair than the phenyl n system is in conjugation with the olefinic double bound. The results of ab initio calculations on model compounds show that conjugation of the double bond with the nitrogen lone pair is by 2-6 kcal/mol more favourable than conjugative interaction between the phenyl group and the C = C bond. Closer examination of the molecular structure of 2, however, led to the conclusion that it is predominantly the ^-substituent which forces the phenyl ring in a position where conjugation with the enamine double bond is not possible. 
  Reference    Z. Naturforsch. 47a, 869—876 (1992); received March 18 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0869 
 Volume    47 
142Author    Karl-Dietrich Gundermann, Elke Romahn, Maximilian ZanderRequires cookie*
 Title    A Photophysical Study of Tri-chromophoric Systems Containing Two Naphthalene Moieties: Intramolecular Excimer Fluorescence, Energy Transfer, Phosphorescence, and Delayed Fluorescence  
 Abstract    Photophysical properties of 9,10-di[(l-naphthyl)-methyl]-9,10-dihydro-9,10-phenanthrenediol (1), 9,10-di(l-naphthyl)phenanthrene (2), 9,10-di(2-naphthyl) phenanthrene (3), 10,10-di(1 -naphthyI)-9,10-dihydro-9-phenanthrone (5 a) and 10,10-di(2-naphthyl)-9,10-dihydro-9-phenanthrone (5 b) have been studied. In contrast to l,4-di(l-naphthyl)butane compound 1 shows strong (intramolecular) excimer fluorescence in dilute solution at room temperature. As a result of intramolecular triplet-triplet energy transfer the phosphorescence of 2, 3, 5 a and 5 b stems from the naphthalene moieties. The increase (compared to naphthalene) of the rate constant of the radiative deactivation of the lowest triplet state is probably due in the case of 2 and 3 to the non-planarity of the molecules, which is expected to increase spin-orbit coupling, while in compounds 5 a and 5 b intramolecular charge-transfer interaction between the carbonyl group and the naphthalene moieties may be responsible for this effect. Delayed fluorescence (from the phenanthrene moiety) of 2 has been observed in fluid solution at room temperature, and an excitation mechanism is proposed. 
  Reference    Z. Naturforsch. 47a, 877—881 (1992); received April 28 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0877 
 Volume    47 
143Author    A. Wendt, W. PreetzRequires cookie*
 Title    Luminescence Spectra of the Mixed Chloro-Bromo-Technetates(IV), lTcCl"Br 6 _"] 2 -,«=l-5  
 Abstract    The F 7 (2 T 2) r 8 (4 A 2g) luminescence spectra of mixed Cs 2 [TcCl n Br 6 _J, n= 1-5, in various host crystals have been measured between 14 000 and 12 800 cm -* at 10 K. For the first time host lattices have been doped with purely isolated chloro-bromo-technetates(IV), including the geometrical isomers with n = 2, 3, 4. The assignments of the electronic transitions and their extensive vibronic structure are discussed. 
  Reference    Z. Naturforsch. 47a, 882—886 (1992); received May 7 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0882 
 Volume    47 
144Author    Armin Kehrer, Shi-Qi Dou, Alarieh WeissRequires cookie*
 Title    The Electric Field Gradient at the Site of the Halogen Ion and Structure of Amino Acid Hydrobromides and Hydroiodides L-Arg * HBr * H z O, L-Cys * HBr * H 2 0, L-Cys-S-S-L-Cys * 2 HBr, ethanolamine * HBr, L-Glu * HBr, L-His * HBr, L-His * 2 HBr, L-Ile HBr * H 2 0, Sar * HBr, (Sar) 2 * HBr, L-Val * HBr * H 2 0, Gly * LiBr, Gly-Gly * LiBr, ethanolamine HI, Sar * HI, (Sar) 2 * HI, (Gly) 2 * HI, (L-Val) 2 * HI, Gly-L-Leu * HI * H  
 Abstract    The 79>81 Br and 127 I NQR spectra of several hydrobromides, respectively hydroiodides, of amino acides and dipeptides were studied, mostly as functions of temperature in the range 77 < T/K <420. The investigated compounds are: 2 0. A phase transition with hysteresis was observed for L-Val • HBr • H 2 0 (T c , up = 318 K, T c . d0w " = 242 K). Two solid phases of Sar • HI have been studied by NQR, one crystallized from melt, the other one from aqueous solution. For three of the title compounds the crystal structure was determined at room temperature: L-His -2 HBr, P2 1 2 1 2 1 , Z = 4, aj pm = 1652, 6/pm = 916, c/pm = 721; L-Cys HBr H 2 0, P2 1 2 1 2 1 , Z = 4, fl/pm = 1955, 6/pm = 746, c/pm = 550; Gly-L-Leu • HI • H 2 0, P2 X , Z = 2, a/pm= 1289, b/pm = 914, c/pm = 615, ß/° = 99. In most cases the halogen ion in the studied hydrohalides is polycoordinated by hydrogen bonds of the type N-H • • • X e and O-H • • • X e , X = Br, I. The NQR frequencies and, for iodine, the nuclear quadrupole coupling constants depend on this coordination. A low frequency (coupling constant) region is found for pure N-H • • • X e coordination. Replacing one N-H • • • X e bond by O-H • • • X® rises the electric field gradient, EFG, respectively the resonance frequencies. The dependence of the EFG on the hydrogen bond coordination N-H • • • X e plus O-H • • • X e is discussed for the title compounds including information from literature. 
  Reference    Z. Naturforsch. 47a, 887—917 (1992); received January 16 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0887 
 Volume    47 
145Author    KamalK. NandiRequires cookie*
 Title    Supplement to "Some Aspects of Minimally Relativistic Newtonian Gravity"  
 Abstract    provides additional material that should be combined with the contents of that paper. The combined content then provides a model of gravita-tion which is complete in essential details. Its main features are that it (i) predicts all the local GR tests accurately but (ii) does not exhibit Schwarzschild singularity, (iii) allows the wellknown Birkhoff's theorem to hold and (iv) has well defined conservation laws in virtue of the maximal group of motions admissible on the flat background spacetime. 
  Reference    Z. Naturforsch. 47a, 918—920 (1992); received April 14 1992 This supplement to 
  Published    1992 
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 Identifier    ZNA-1992-47a-0918 
 Volume    47 
146Author    Akhlesh LakhtakiaRequires cookie*
 Title    Brewster Condition for Planar Interfaces of Natural Optically Active Media  
 Abstract    Reflection of planewaves at the planar interface of two natural optically active media has been examined in order to obtain the Brewster condition. 
  Reference    Z. Naturforsch. 47a, 921—922 (1992); received April 25 1991 
  Published    1992 
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 Identifier    ZNA-1992-47a-0921_n 
 Volume    47 
147Author    A. BanerjeeRequires cookie*
 Title    Radiation Induced Colour and Crystal Defects in Topaz  
 Abstract    Changes of the colour of Topaz on y-irradiation and corre-sponding crystal defect induced changes of X-ray transpar-ency and IR spectra are observed and discussed. 
  Reference    Z. Naturforsch. 47a, 923—924 (1992); received April 15 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0923_n 
 Volume    47 
148Author    Georg Kügerl, Ferdinand SchürrerRequires cookie*
 Title    The PN Method in the Kinetic Theory of Gases  
 Abstract    An expansion of the velocity distribution function in a series of spherical harmonics is used to transform the nonlinear Boltzmann equation into a system of moment equations. The close connec-tion between the moment equations of zeroth and first order with the transport equations for mass, momentum and energy is pointed out. By comparing the order of magnitude of the various moments it is shown that the P 2 approximation is adequate for systems with small mean free path. Simplifica-tions of the collision terms of the moment equations are discussed, where attention is payed to the conservation laws and the H theorem. 
  Reference    Z. Naturforsch. 47a, 925—934 (1992); received May 24 1992 
  Published    1992 
  Keywords    Kinetic theory, Nonlinear Boltzmann equation, Spherical harmonics method, Moment equations 
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 Identifier    ZNA-1992-47a-0925 
 Volume    47 
149Author    N. Marinescu, M. ApostolRequires cookie*
 Title    Quantum-Mechanical Concepts in the Waveguides Theory  
 Abstract    A Klein-Gordon-type equation is derived for the wave propagation in an ideal, uniform wave-guide, and its quantum-mechanical interpretation is given. The "cross-section" concept is introduced for a waveguide and the power transmission factor is obtained by using standard methods of quantum mechanics. The spinorial formalism is also employed for deriving the equivalent Dirac-type equation, and the perturbation theory is applied for computing the frequency shifts. The general applicability of the quantum-mechanical concepts to the waveguides theory is discussed. 
  Reference    Z. Naturforsch. 47a, 935—940 (1992); received July 19 1991 
  Published    1992 
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 TEI-XML for    default:Reihe_A/47/ZNA-1992-47a-0935.pdf 
 Identifier    ZNA-1992-47a-0935 
 Volume    47 
150Author    R. L. VianaRequires cookie*
 Title    Peripheral Stochasticity in Tokamaks. The Martin-Taylor Model Revisited  
 Abstract    We analyse the effect of an Ergodic Magnetic Limiter on the magnetic field line dynamics in the edge of a large aspect-ratio Tokamak. We model the limiter action as an impulsive perturbation and use a peaked-current model for the Tokamak equilibrium field. The theoretical analysis is made through the use of invariant flux functions describing magnetic surfaces. Results are compared with a numerical mapping of the field lines. 
  Reference    Z. Naturforsch. 47a, 941—944 (1992); received December 10 1991 
  Published    1992 
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 Identifier    ZNA-1992-47a-0941 
 Volume    47 
151Author    U. Wolf, H. SchamelRequires cookie*
 Title    Polarisation in the Temperature Equilibration of Anisotropic Plasmas  
 Abstract    The polarisation effect on the isotropisation of a magnetized bi-Maxwellian plasma is investigated in the weak coupling approximation. Based on the Rostoker collision operator, which reduces in the magnetic field free limit to the Balescu-Lenard operator, the equipartition frequency v is evaluated numerically for 0 and analytically for B-*oo, respectively. This frequency, depending non-linearly on e and B, describes the approach to thermodynamic equilibrium of the anisotropy parameter e = TJT^ via de/dt — (1 — e) v(e, B). It is found that in both limits dynamical screening makes a negligible contribution to the relaxation process. For finite B a simplified, yet unexploited expression for v(a, B) is presented, which invokes three new functions. 
  Reference    Z. Naturforsch. 47a, 945—949 (1992); received June 12 1992 
  Published    1992 
  Keywords    Coulomb collisions, Weak coupling theory, Polarisation, Collision frequency 
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 Identifier    ZNA-1992-47a-0945 
 Volume    47 
152Author    R. Krzyminiewski, A. LundRequires cookie*
 Title    ENDOR Studies of X-Irradiated Single Crystals of Sulphamethoxazole  
 Abstract    Single crystals of sulphamethoxazole were X-irradiated at 273 K. ESR and ENDOR spectra were obtained at 100 K. The free radicals stable at room temperature are formally formed by abstraction of a hydrogen atom from the methyl group of the molecule. The unpaired electron is delocalized in the isoxazole ring. The assignment is supported by comparisons of spin densities obtained experi-mentally and by semiempirical molecular orbital calculations. 
  Reference    Z. Naturforsch. 47a, 950—954 (1992); received January 27 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0950 
 Volume    47 
153Author    G. Pretzier, H. Jäger, T. Neger, H. Philipp, J. WoisetschlägerRequires cookie*
 Title    Comparison of Different Methods of Abel Inversion Using Computer Simulated and Experimental Side-On Data  
 Abstract    A recently devised new method for numerical Abel inversion is compared with four other com-monly used methods. One of them, the convolution method, is employed in computer tomography for reconstructing asymmetrical objects. It is investigated whether this method can be adapted for the case of radial symmetry. As a first approach the comparison is performed by computer simulation. Special attention is given to the propagation of errors according to their origin. The result is a recipe for minimizing errors and for choosing the optimal method for reconstruction. The second step is a comparison of experimentally obtained radial profiles with functions result-ing from Abel inversion of measured side-on data. Thus it is shown that the concept developed by computer simulation can be applied in practice. 
  Reference    Z. Naturforsch. 47a, 955—970 (1992); received April 23 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0955 
 Volume    47 
154Author    A. Kawski, P. Bojarski, A. KubickiRequires cookie*
 Title    The Inertial Effect in Rotational Fluorescence Depolarization  
 Abstract    The influence of the moment of inertia on the rotational fluorescence depolarization is discussed. Based on experimental results obtained for five luminescent compounds: 2,5-diphenyloxazole (PPO), 2,2'-p-phenylene-bis(5-phenyloxazole) (POPOP), p-bis[2-(5-a-naphthyloxazolyl)]-benzene (a-NOPON), 4-dimethylamino-a)-methylsulphonyl-trans-styrene (3 a) in n-parafines at low viscosity (from 0.22 x 10" 3 Pa • s to 0.993 x 10"* Pa • s) and diphenylenestilbene (DPS) in different solvents, a semi-empirical equation is proposed, yielding moments of inertia that are only two to five times higher than those estimated from the molecular geometry. 
  Reference    Z. Naturforsch. 47a, 971—973 (1992); received May 27 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0971 
 Volume    47 
155Author    B. A. Bilal, E. MüllerRequires cookie*
 Title    Thermodynamic Study of Ce 4 + /Ce 3+ Redox Reaction in Aqueous Solutions at Elevated Temperatures: 1. Reduction Potential and Hydrolysis Equilibria of Ce 4 + in HCIO4 Solutions  
 Abstract    The redox potential (E) of the couple Ce 4+ /Ce 3 + has been determined up to 368 K by means of cyclic voltammetric measurement in aqueous HC10 4 solutions with c HC104 decreasing from 7.45 to 0.023 mol kg" 1 . A constant potential of (1.741 V) 298 K , resp. (1.836 V) 368K , indicating the existence of pure unhydrolysed Ce 4+ was obtained at c Hcl04 > 6.05 m. At lower HC10 4 concentration, the potential as a function of the HC10 4 molality, as well as of the pH shows 4 further distinct steps. At 298 K, for instance, the potential became nearly constant at pH values of 0.103, 0.735,1.115, after which it drastically decreased, respectively at 1.679, just before the precipitation of Ce(OH) 4 oc-curred. The curves indicate obviously the stepwise formation of the Ce(IV) mono-, di-, tri-and tetrahydroxo complexes. The slope of the curves E vs. pH increased gradually with increasing temperature. AS and AH of the redox reaction were determined as functions of T at the different HC10 4 concentrations. AS is positive at c HC104 > 1.85 m and turns to be negative at lower concentra-tions. AH is negative at all HC10 4 concentrations studied. The cumulative formation constants ß, of the Ce(IV) hydroxo complexes and the corresponding hydrolysis constants (K h); were calculated. An unusual decrease of ß t with increasing temperature has been discussed. Key words: Redox potential of Ce 4+ /Ce 3+ ; Aqueous solutions; Thermodynamics of redox equilibria; Ce(IV) hydrolysis; Cyclic voltammetry. 
  Reference    Z. Naturforsch. 47a, 974—984 (1992); received June 26 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0974 
 Volume    47 
156Author    Hyoung-Ryun Park, Nikola GetoffRequires cookie*
 Title    Radiolysis of Aqueous Ethanol in the Presence of CO  
 Abstract    First, the following rate constants (in dm 3 mol" 1 s" 1) were reported: k(eä q + C 2 H 5 OH) = (1.2 ±0.3)x 10 3 , lc(H + C 2 H 5 OH) = (2.8 ± 0.2) x 10 7 and fc(OH + C 2 H 5 OH) = (1.85 + 0.1) x 10* The major radiolytic products resulting from aqueous 10~ 2 , 1 and 10 mol dm" 3 ethanol were studied in the absence and presence of CO as a function of dose at pH 2 and 7. Probable reaction mechanisms are presented. 
  Reference    Z. Naturforsch. 47a, 985 (1992); received June 29 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0985 
 Volume    47 
157Author    A. G. KalinichevRequires cookie*
 Title    Monte Carlo Simulations of Water under Supercritical Conditions. II. Convergence Characteristics and the System Size Effects  
 Abstract    The size dependence and convergence rates of thermodynamic averages during Monte Carlo simulations of supercritical water in a wide range of densities have been analysed and compared with simulations under normal conditions. It is shown that the fluctuations of internal energy (enthalpy) in NPT-ensemble Monte Carlo simulations of high-temperature water are strongly correlated with fluctuations of volume and the convergence of the thermodynamic averaging under such conditions depends on the frequency of volume-changing moves and may be considerably improved by increas-ing this frequency by a factor of 3-10 relative to generally accepted values. 
  Reference    Z. Naturforsch. 47a, 992—998 (1992); received June 30 1992 
  Published    1992 
  Keywords    Monte Carlo computer simulations, Supercritical conditions, Thermodynamic proper-ties, Convergence analysis 
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 Identifier    ZNA-1992-47a-0992 
 Volume    47 
158Author    H.-W Nicolaisen, H. Mäder, F. RohartRequires cookie*
 Title    Temperature Dependence of N 2 -Relaxation of Rotational Lines of Propionitrile  
 Abstract    The temperature dependence of the rotational relaxation of propionitrile, CH 3 CH 2 C 15 N, has been investigated by means of microwave transient emission signals. From analysis of the pressure dependence of the coherence decay rates for the rotational lines (J, K_, K +) — (2, 0, 2)-(3, 0, 3), (2,1, 2)-(3, 1, 3), and (2, 2, l)-(3, 2, 2) pressure broadening parameters have been derived for mix-tures with nitrogen in the 210-300 K range and for the pure gas at ambient temperatures. 
  Reference    Z. Naturforsch. 47a, 999—1002 (1992); received July 4 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-0999 
 Volume    47 
159Author    T. Radnai, H. OhtakiRequires cookie*
 Title    Intramolecular and Liquid Structures of Tetramethylurea Studied by Means of X-Ray Diffraction  
 Abstract    The intramolecular and liquid structures of tetramethylurea (TMU) were investigated by the liquid x-ray diffraction method. It is confirmed that in the liquid state the four methyl groups are out of the plane which is constructed by the O, C, and the two N atoms, the molecular structure being similar to what had been found in the gas phase. All structural parameters are in good agreement with those of TMU determined in the gas phase and with those of amide derivatives in the liquid phase. The liquid is characterized by a random distribution of molecules as predominant, but a weak molecular ordering characterized by approximately two intermolecular nonbonding Me • • • O dis-tances at 340 pm is proposed. 
  Reference    Z. Naturforsch. 47a, 1003—1010 (1992); received May 20 1992 
  Published    1992 
  Keywords    Tetramethylurea, Liquid x-ray diffraction, Liquid structure, Molecular structure, Non-aqueous solvent 
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 Identifier    ZNA-1992-47a-1003 
 Volume    47 
160Author    Kanchan Gaur, H. B. LaiRequires cookie*
 Title    High Ionic Conductivity of Li 2 0:B 2 0 3 : V 2 O s  
 Abstract    Lithium ion conducting solids have been of great interest in recent years [1 -5]. We have also been active in this direction [6-8]. This paper reports on the electrical transport and phase transition of Li 2 0:B 2 0 3 :V 2 0 5 . The compound was prepared by solid state reaction technique. The measurements of the electrical conductivity (er), thermoelectric power (S), dielectric constant (K) and molar magnetic suscep-tibility (x M) are performed from 500 to 1110 K. The details of these measurements are described in [9,10]. The a and S variations are shown in Fig. 1 as log a T and S vs. 1/T plots. Both the plots show three linear regions, namely, 500-850 K, 900-960 K, and 980-1110 K. The activation energy (£ a) and heat of trans-port (Q) for the third temperature range are 0.39 eV and 0.58 eV, respectively, o jumps by a factor of 180 around 855 K, and again jumps by a factor of 4 around 970 K. Thus this material seems to have two phase transition temperatures: one around 855 K and the other at 970 K. The sign of S indicates that current is carried by positive charge carriers. The time varia-tion of the dc electrical conductivity (the results are not shown) shows that o is completely ionic in the temperature range 980-1110 K. Ions are also the dominant charge carriers at lower temperatures but in general a is mixed (ionic and electronic). Lithium seems to be the mobile ion of the solid, c in the temperature range 980-1110 K is high, being 150fi _1 m _1 , and it is totally ionic, hence this is the superionic phase of the solid. The phase transitions around 855 K and 970 K are also reflected in K and VS. T plots, as shown in Figs. 2 and 3, respectively. The room temperature K value is not high, being about 30 around 300 K. It increases slowly up to 700 K but rises steeply above 855 K and becomes of the order of 3.2 x 10 7 at 900 K. It drops by a factor of 3 around 970 K and then remains almost constant. It 
  Reference    Z. Naturforsch. 47a, 1011—1012 (1992); received March 5 1992 
  Published    1992 
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 Identifier    ZNA-1992-47a-1011_n 
 Volume    47 
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