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1995[X]
41Author    P. LamparterRequires cookie*
 Title      
 Abstract    The partial pair correlation functions of amorphous NixNb100-x alloys (x = 40, 50, 56, and 63) were simulated by computer modelling. A Cluster Relaxation procedure yielded reasonable agree­ ment with the experimental functions when non-additive pair potentials with preference for Ni-Nb atomic pairs were applied. With the use of the Reverse Monte Carlo method perfect agreement could be achieved. The impact of the chemical effect on the short range order is discussed by comparison with a statistical reference cluster. The analysis of the model clusters showed that the chemical short range order effect in amorphous Ni-Nb alloys, increasing with the Ni concentration, does not in­ volve specific stereochemical atomic arrangements. There is no correspondence to the short range order in crystalline Ni3Nb. The structure of Ni-Nb metallic glasses can be described as a polytetra-hedral packing with preferred hetero-coordination. 
  Reference    Z. Naturforsch. 50a, 329—336 (1995); received January 9 1995 
  Published    1995 
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 Identifier    ZNA-1995-50a-0329 
 Volume    50 
42Author    W. Alexander, Van HookRequires cookie*
 Title     
 Abstract    h e r m o d y n a m ic A n a ly s is o f I s o to p e E f f e c ts o n T rip le P o in ts a n d / o r M e ltin g T e m p e r a tu r e s Available literature information on triple point or melting point isotope effects (and related physical properties) is subjected to thermodynamic analysis and consistency checks. New values for the melting point isotope effects for C6H6/CgD6 and c-C6H1?/c-C6D12 are reported. 6Li/7Li melting point isotope effects reported recently by Hidaka and Lunden (Z. Naturforsch. 49 a, 475 (1994)) for various inorganic salts are questioned. 
  Reference    Z. Naturforsch. 50a, 337—346 (1995); received October 11 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0337 
 Volume    50 
43Author    L. Kisiel, PszczółkowskiRequires cookie*
 Title      
 Abstract    The b-type rotational spectrum of 1,1-dichloroethylene was investigated up to 450 GHz and was found to be dominated by type-II R-type bands. All constants in the sextic Hamiltonian for the ground states of the common isotopic species and of the 37C1 isotopomer were determined from measurements on transitions with J up to 95. Quartic and sextic planarity defects were evaluated and are compared and discussed with those for several recently investigated planar molecules. Key words: mm-wave rotational spectroscopy, band spectra, sextic constants. T h e H ig h -F re q u e n c y R o ta tio n a l S p e c tr u m o f 1,1 -D ic h lo ro e th y le n e 
  Reference    Z. Naturforsch. 50a, 347—351 (1995); received October 31 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0347 
 Volume    50 
44Author    H.-G Köhne, M. StockhausenRequires cookie*
 Title     
 Abstract    o m p u te r S im u la tio n o f a S im p le M o d e l f o r R o ta tio n a l M o m e n t F lu c tu a tio n s in a n A s s o c ia tin g L iq u id Dedicated to Professor Dr. W . Müller-Warmuth With regard to the interpretation of dielectric relaxation spectra of associating liquids such as al­ cohols, a two state model for the rotational tumbling motion of a dipole is considered: The moment (of constant magnitude) is assumed to undergo stochastic tumbling during a "free" state, alternating with an "associated" state where for a certain residence time the rotational motion can be neglected. One particle autocorrelation functions according to that model are calculated numerically. In any case, they can well be described as sum of (at most) two exponentials. The corresponding parameters are given as function of "association" probability and residence time. 
  Reference    Z. Naturforsch. 50a, 352—356 (1995); received September 29 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0352 
 Volume    50 
45Author    Volkmar LeuteRequires cookie*
 Title     
 Abstract    h e rm o d y n a m ic E x c e s s F u n c tio n s f o r Q u a s ite r n a r y S o lid S o lu tio n s o f T y p e M (X , Y, Z) I. T h e S y s te m P b (S , T e , S e) Dedicated to Prof. Dr. W . Müller-Warmuth on the occasion of his 65th birthday The excess free enthalpy of quasiternary systems of type M (X, Y, Z) with two sublattices, a mixed one (X, Y,Z) and a pure one (M), will be described in two ways: (1) by the interaction parameters of the three subregularly treated quasibinary subsystems and by one ternary parameter, and (2) by the cluster energies of 10 pyramidal clusters. It is shown that, for the spinodal miscibility gap in the special system Pb (S, Te, Se), both versions yield satisfying accordance of experiments and calculated results. 
  Reference    Z. Naturforsch. 50a, 357—367 (1995); received December 8 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0357 
 Volume    50 
46Author    U. Häcker3, D. Michel3, K.-P Hölzer, J. PeterssonbRequires cookie*
 Title    2H a n d 14N N M  
 Abstract    R S tu d ie s o f th e D y n a m ic s in th e I n c o m m e n s u r a te P h a s e s o f B e ta in e C a lc iu m c h lo rid e D ih y d r a te Dedicated to Professor Dr. W . Müller-Warmuth on the occasion of his 65th birthday 2H and 14N NMR spin-lattice relaxation rates were measured in the structurally incommensu-rately (IC) modulated phases of deuterated and undeuterated betaine calciumchloride dihydrate, respectively. The results are related to the elementary excitations of these phases. The presence of low-frequency phase fluctuations of the modulation wave leads to higher spin-lattice relaxation rates compared with the high-temperature normal phase and the commensurate (C) phases. The corre­ sponding "phason" contributions are found to be nearly constant in the whole IC phases. In the IC phases near the transitions to the C phases the relaxation rates decrease due to the formation of the soliton lattice. This interpretation is in agreement with the results of previous dielectric measure­ ments. 
  Reference    Z. Naturforsch. 50a, 368—372 (1995); received November 8 1994 
  Published    1995 
  Keywords    Nuclear-spin-lattice relaxation, Betaine calciumchloride dihydrate, Incommensurate phases, Phason modes, Incommensurate-commensurate phase transitions 
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 Identifier    ZNA-1995-50a-0368 
 Volume    50 
47Author    Z. T. Lalowicz3, R. Serafin3, M. Punkkinenb, A. H. Vuorimäkib, E. E. YlinenbRequires cookie*
 Title      
 Abstract    Dedicated to Professor W . Müller-Warmuth on the occasion of his 65th birthday Deuteron NMR spectra of slowly tunneling ND4 ions are analysed. Spectra are calculated as functions of the tunneling parameters which are the tunneling frequencies about the symmetry axes C2 and C3 of the tetrahedral ion. The structure and splittings within the ground torsional level (GTL) are obtained by fitting the spectra of (ND4)2SnBr6. Comparison with the GTL structure obtained before for NH4 in the same compound gives the isotope reduction factor of the tunneling frequency about 200. 
  Reference    Z. Naturforsch. 50a, 373—380 (1995); received September 26 1994 
  Published    1995 
  Keywords    Tunneling rotation, Ammonium ion, 2H-NMR spectroscopy, Molecular dynamics PACS number 7660 
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 Identifier    ZNA-1995-50a-0373 
 Volume    50 
48Author    Jürgen Kintrup, Harald ZüchnerRequires cookie*
 Title    X P S I n v  
 Abstract    e s tig a tio n s o n S o lid a n d V a c u u m D e p o s ite d , O x id iz e d a n d N o n -o x id iz e d P a lla d iu m Dedicated to Professor W . Müller-Warmuth on the occasion of his 65th birthday X-ray photoelectron spectroscopy (XPS) has been carried out to study the reaction of differently prepared palladium samples (solid and film Pd) with atmospheric oxygen. A careful curve fitting of the measured Pd-3ds/2 peak allows to separate the Pd-3d5/2 peak for Pd in surface PdO from the dominant Pd-3d5,2 peak of the non-oxidized bulk palladium and to determine the chemical shift of the "oxidized" Pa line with high accuracy. Differences in the chemical shifts for the surface PdO on solid and film palladium are explained by a different charging caused by the photoelectric effect in XPS measurements. The smaller charging effect observed for film palladium as compared to solid palladium indicates a stronger oxygen bonding to the (rougher) film palladium. The strong Pd-O bonding seems to be an essential reason for the reduced hydrogen-permeability of film palladium compared to solid palladium. 
  Reference    Z. Naturforsch. 50a, 381—387 (1995); received December 16 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0381 
 Volume    50 
49Author    H. Ernst3, M. Fechtelkord\, D. Fenzke3, D. Freude3, B. Knorr3, H. Kolley3, H. Pfeifer3Requires cookie*
 Title     
 Abstract    n h a n c e d S e n s itiv ity o f Z e r o -F ie ld N M R S p e c tro s c o p y a t H ig h M a g n e tic F ie ld s Dedicated to Professor Müller-Warmuth on the occasion of his 65th birthday After reviewing the basic principles of zero-field NMR spectroscopy at high magnetic fields (ZFHF NMR) as introduced by Robert Tycko, a 2-dimensional extension of this method is described which enhances its sensitivity by at least one order of magnitude. The essential point is a com­ bination of the original pulse program including sample rotation with a Carr-Purcell pulse se­ quence during the acquisition time. Experimental results are given for the proton resonance of meta-C6H2D4 dissolved in C6D6 at 245 K. 
  Reference    Z. Naturforsch. 50a, 388—394 (1995); received December 24 1995 
  Published    1995 
  Keywords    Zero-field NMR, High magnetic fields, 2-dimensional spectroscopy, Proton-proton distance, Benzene 
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 Identifier    ZNA-1995-50a-0388 
 Volume    50 
50Author    Robert Maxwell3, Hans Erickson3, Hellmut EckertbRequires cookie*
 Title     
 Abstract    e p o ly m e r iz a tio n K in e tic s o f G la s s -F o r m in g C h a lc o g e n id e M e lts . C o h e re n c e T r a n s f e r N M R S tu d ie s o f P h o s p h o r u s S e le n id e Dedicated to Professor Müller-Warmuth on the occasion of his 65th birthday The kinetics of the depolymerization of a glass-forming phosphorus selenide melt containing 48 at.% phosphorus have been studied using one-and two-dimensional coherence transfer spectro­ scopic methods. The depolymerization leads to the creation of molecular P4Se3. Two-dimensional spectroscopy indicates that these units are in slow exchange with the residual polymeric matrix, and corresponding rate constants are extracted from temperature dependent one-dimensional coherence transfer experiments. The results are quantitatively consistent with previous temperature-dependent NMR lineshape studies, yielding an activation energy of 109 kJ/mol. 
  Reference    Z. Naturforsch. 50a, 395—404 (1995); received November 8 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0395 
 Volume    50 
51Author    Michael Prager3, Da Zhangb, Al WeissbRequires cookie*
 Title      
 Abstract    Müller-Warmuth on the occasion of his 65th birthday Mixed PbcSn1_c(CH3)4 samples with c = 0.0, 0.1, 0.2,0.25, 0.48, 0.5, 0.75,0.85, and 1.0 and mixed [Pb(CH3)4](.[Sn(CD3)4]1_< . samples with c = 0.02 and 0.09 were investigated by high resolution inelastic neutron scattering. Rotational tunnelling transitions are observed for energy transfers h c o < m peV. The global features are interpreted in a single particle model. A strong matrix effect of the Pb component is attributed to changes of potential symmetry. Effects beyond the expectation of the single particle description are found. R o ta tio n a l T u n n e llin g in B in a ry T e tra m e th y lm e ta l M ix t u r e s 
  Reference    Z. Naturforsch. 50a, 405—412 (1995); received December 15 1994 Dedicated to Professor 
  Published    1995 
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 Identifier    ZNA-1995-50a-0405 
 Volume    50 
52Author    G. Kunath-Fandrei1, D. Ehrt2, C. Jäger3Requires cookie*
 Title     
 Abstract    r o g r e s s in S t r u c t u r a l E lu c id a tio n o f G la s s e s b y 27A1 a n d n B S a te llite T r a n s itio n N M R S p e c tr o s c o p Dedicated to Prof. Dr. W . Müller-Warmuth on the occasion of his 65th birthday The structure of Na20-A l20 3-B203 and Na20-A l20 3-P 20 5 glasses with 70 mole% B20 3 or P2Os and varied Na/Al ratio is investigated using standard 31P MAS NMR and 27A1 and UB Satellite Transition NMR spectroscopy. The role of the two network formers on the glass structure is discussed. For the A10x units and B03 and B04 groups both chemical shifts and quadrupole interaction parameters including their distribution widths are reported. Besides this, the advantages of Satellite Transition spectroscopy are demonstrated both for 27A1 and n B NMR. 
  Reference    Z. Naturforsch. 50a, 413—422 (1995); received December 16 1994 
  Published    1995 
  Keywords    NMR, Glass, Structure, Satellite Transition, 11B, 27A1, 31 P 
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 Identifier    ZNA-1995-50a-0413 
 Volume    50 
53Author    P. /., Frank Ambrosius, Elke Klaus, Torsten Schaller, Angelika SebaldRequires cookie*
 Title     
 Abstract    o f H e a v y S p in -1 /2 N u c le i a t B 0 = 2 .3 5 T Dedicated to Prof. W . Müller-Warmuth on the occasion of his 65th birthday Perspectives of CP/MAS NMR at low external magnetic field (5" = 2.35 T) are discussed. Appli­ cations are illustrated for the case of heavy spin-1/2 nuclei such as 19^Pt and Hg: 195Pt and Hg CP/MAS spectra of a variety of organometallic compounds are reported. Aspects of shielding aniso­ tropics, of 19sPt-35'37Cl interactions and of 31P-M (M = Cd, Hg, Pt) coupling in transition metal phosphine complexes will be briefly addressed. 
  Reference    Z. Naturforsch. 50a, 423—428 (1995); received November 8 1994 
  Published    1995 
  Keywords    High-resolution solid-state NMR, cross polarisation, magic angle spinning, 195Pt, 199Hg 
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 Identifier    ZNA-1995-50a-0423 
 Volume    50 
54Author    C. P., R. S. Tu D, Wolfgang Baumann, Yuri Oprunenko, Harald GüntherRequires cookie*
 Title     
 Abstract    y n a m ic B e h a v io u r o f T e tra m e th y le th y le n e D ia m in e (T M E D A) L ig a n d s in S o lid O r g a n o lith iu m C o m p o u n d s : A V a r ia b le T e m p e r a tu r e 13C a n d 15N Dedicated to Professor Dr. W . Müller-Warmuth on the occasion of his 65th birthday The dynamic behaviour of tetramethylethylene diamine (TMEDA) ligands in three organometallic complexes, dimeric phenyllithium, [Li(tmeda)/*-Ph]2 (1), lithium cyclopentadienide, [Li(tmeda)]C5H5 (2), and dilithium naphthalendiide, trans-[Li(tmeda)]2C10H8 (3), has been studied by CP/MAS 13C and 15N as well as 7Li MAS NMR spectroscopy of powdered samples. Two dynamic processes with free activation enthalpies of 40 and 68 kJ mol-1, respectively, were detected for 1. The first one can be assigned to ring inversion of the five-membered Li-TMEDA rings, while the second is caused by a complete rotation of the TMEDA ligands or a ring inversion of the central four-membered C-Li-C-Li metallacycle. Fast rotation of the ligands on the NMR time scale was found for 2, while 3 shows 180° ring flips of the Li-TMEDA groups, which are characterized by an energy barrier AG" (317) of 64 kJ mol-1. 
  Reference    Z. Naturforsch. 50a, 429—438 (1995); received November 8 1994 
  Published    1995 
  Keywords    CP/MAS NMR, 13C-NMR, 15N-NMR, 7Li NMR, dynamic processes, organometallics 
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 Identifier    ZNA-1995-50a-0429 
 Volume    50 
55Author    M. Neichel, E. U. FranckRequires cookie*
 Title     
 Abstract    r itic a l C u rv e s a n d P h a s e E q u ilib r ia o f B in a ry M e th a n o l-S y s te m s fo r H ig h P r e s s u r e s a n d T e m p e r a tu r e s The critical curves of binary systems of methanol combined with CH4, N2, H2, CO and C 02 have been determined experimentally up to 100 MPa and higher by Brunner. In the present work a rational equation of state of the perturbation type with a repulsion and an attraction term has been applied to reproduce these critical curves up to high pressures. A square well potential for inter­ molecular interaction is used. With pairwise combination rules for these potentials three adjustable parameters are needed. Values for these parameters, obtained from the fitting of the critical curves are used to calculate isotherms of the two-phase high pressure equilibrium surfaces for the four systems of methanol combined with CH4, N2, H2, and CO. Three of these have not yet been investigated experimentally. It is suggested to use this procedure for predictions of the extent of three-dimensional two-phase regions in temperature-pressure-composition spaces. 
  Reference    Z. Naturforsch. 50a, 439—444 (1995); received 
  Published    1995 
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 Identifier    ZNA-1995-50a-0439 
 Volume    50 
56Author    R. Schäfer, J. Woenckhaus, J. A. Becker, F. HenselRequires cookie*
 Title     
 Abstract    o la r iz a b ilitie s o f I s o la te d S ilic o n C lu s te rs Dedicated to Prof. Dr. E. Wicke on the occasion of his 80th birthday The static electric polarizabilities a of silicon clusters with up to 60 atoms have been measured employing a mass selective molecular beam deflection method. The polarizability per atom aN = ol/N of the Sijy-clusters has been investigated for Siu and the size ranges N = 14-28, 22-34, 28-44, 34-50, 41 -58, and 42-68. The results show that the polarizability per atom decreases from N = 11 until a minimum at N « 28 is reached. The polarizability per atom increases for N > 28, passes through a maximum at N « 36 and finally converges between N « 50-70 against the value a.N = 1.9 A3. If the model of a homogeneous dielectric sphere is applied to the larger clusters one calculates that the value a.N = 1.9 Ä3 corresponds to a dielectric constant of e = 3.2. This value is significantly smaller than the dielectric constant of bulk silicon eb = 11.8. The present paper focuses on the maximum in the polarizability at N » 36. This effect is discussed with special emphasis to recent Car-Parinello calculations which have predicted cage-like silicon structures that enclose a core of several highly coordinated atoms. This structure suggests an im­ proved dielectric sphere model where the core is represented by a smaller sphere with its own dielectric constant ec. It is shown within this model that the observed maximum in polarizability is due to a significant enhancement of the core dielectric constant to a value of ec « 50. This enhance­ ment is related by means of a simple model to the effect that silicon becomes metallic under high pressure. 
  Reference    Z. Naturforsch. 50a, 445—452 (1995); received November 14 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0445 
 Volume    50 
57Author    M. Gierer, H. Bludau, H. Over, G. ErtlRequires cookie*
 Title     
 Abstract    t r u c t u r a l A n a ly s is o f a C s + O C o a d s o r p tio n P h a s e o n a R u (0 0 0 1) S u r f a c e Dedicated to Professor Dr. E. Wicke on the occasion of his 80th birthday The adsorption of oxygen onto a Ru(0001)-(2 x 2)-Cs phase with coverage 0C s = 0.25 gives rise to the formation of a Ru(0001)-(2,73 x 2 v/3)R30°-3Cs-20 coadsorption structure with three cesium and two oxygen adatoms in the unit cell. A low-energy electron-diffraction (LEED) analysis reveals that oxygen is located in threefold hollow sites on the Ru surface while the Cs atoms remain near on-top sites; this site was also found in the pure Ru(0001)-(2 x 2)-Cs phase. The oxygen-Ru bond length of (2.14 + 0.05) Ä is longer by 0.11 A than in the Ru(0001)-(2 x 2)-0 phase, indicating that the Ru-O bond is weakened in the presence of coadsorbed Cs. The Cs hard sphere radius of (1.75 ± 0.07) Ä is close to the ionic Pauling radius of 1.69 Ä. 
  Reference    Z. Naturforsch. 50a, 453—458 (1995); received September 15 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0453 
 Volume    50 
58Author    Volkmar Leute, S. Brinkmann, J. Linnenbrink, H. M. SchmidtkeRequires cookie*
 Title     
 Abstract    h e P h a s e D ia g r a m o f th e Q u a s i te r n a r y S y s te m (S n , P b) (S ,T e) The phase diagram of the quasiternary system (Snt Pb1_k)(S,Te1_,) for 900 K is determined by X-ray diffraction and by electron microprobe analysis. Moreover, the free enthalpy faces g(k, I) for the phases with cubic rocksalt structure (cub) or with the orthorhombic SnS structure (orh) are cal­ culated from the interaction parameters and from the orh ->cub transition data of the 4 quasibinary subsystems. The interaction parameters are also used to calculate the termodynamic factor for interdiffusion along quasibinary sections through the phase square and to calculate the energies of four-particle clusters. By application of the cluster model one obtains information on the local environment of the mixing particles and on the cluster processes that have effect upon interdiffusion. 
  Reference    Z. Naturforsch. 50a, 459—467 (1995); received 
  Published    1995 
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 Identifier    ZNA-1995-50a-0459 
 Volume    50 
59Author    Christian Gebauer, Olaf Klein, Ralf Schmidt, Wolfhart SeidelRequires cookie*
 Title      
 Abstract    Herrn Professor Dr. Ewald Wicke zum 80. Geburtstag gewidmet Differential cross sections have been measured by scattering He atoms from CFnCl4_" (1 < n < 4) in crossed molecular beams. The damping of the diffraction oscillations was used to extract interac­ tion potentials for these molecules which range from nearly isotropic to rather anisotropic. Macro­ scopic binary parameters, as second virial coefficients, diffusion coefficients and viscosities were calculated from these potentials. 
  Reference    Z. Naturforsch. 50a, 468—474 (1995); received August 22 1994 
  Published    1995 
  Keywords    Molecular beams Helium, Chlorofluoromethanes, Interaction potentials Binary co­ efficients 
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 Identifier    ZNA-1995-50a-0468 
 Volume    50 
60Author    TedB. Flanagan, H. NohRequires cookie*
 Title     
 Abstract    h e rm o d y n a m ic s a n d H y s te r e s is f o r H y d r o g e n S o lu tio n a n d H y d r id e F o r m a tio n in P d -N i A llo y s Pd and its fee substitutional alloys which form hydride phases exhibit hysteresis. If Pd-Ni alloys have been hydrided and then dehydrided a number of times at a moderate temperature, the hyster­ esis is reduced. The reduction of hysteresis increases with increase of XN i to 0.15 and, if the XN i = 0.15 alloy is hydrided and dehydrided (298 K) a number of times, hysteresis disappears. Hydrogen iso­ therms have been measured for annealed Pd-Ni alloys from ^,^ = 0.05 to 0.25 (273 K). These show that the width of the plateau region decreases from A TN i = 0 to «0.15 and then increases again. This trend is not apparent from previous isotherm measurements but it is consistent with the x-ray results available in the literature. Thermodynamic parameters for hydrogen absorption/desorption have been measured in the dilute phase and in the plateau region. 
  Reference    Z. Naturforsch. 50a, 475—486 (1995); received November 10 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0475 
 Volume    50 
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