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1995[X]
21Author    M. Born, C. Feike, H. W. Jäger, SpiessRequires cookie*
 Title     
 Abstract    Dedicated to Prof. W . Müller-Warmuth on the occassion of his 65th birthday Recently, 31P two-dimensional (2D) NMR has been proposed as a powerful tool for direct investigations of the connectivities between the Q" units in glasses, i.e. the medium-range order. In this paper, the principles of these experiments and applications to both polycrystalline Mg2P20 7 and a Na20 -P 2C>5 glass are demonstrated, including a theoretical description and modelling of the polarization transfer between the two inequivalent phosphorus sites in the magnesium pyrophos­ phate. 2 D 31P E x c h a n g e N M R : A new A p p r o a c h f o r a D ir e c t P r o b in g o f th e C o n n e c tiv itie s o f Q 1 U n its in G la s s e s 
  Reference    Z. Naturforsch. 50a, 169—176 (1995); received September 26 1994 
  Published    1995 
  Keywords    Exchange NMR, Connectivities, Phosphate glasses, Dipolar coupling, MAS 
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 Identifier    ZNA-1995-50a-0169 
 Volume    50 
22Author    Cengiz Akay, Aytaç YalçinerRequires cookie*
 Title     
 Abstract    N e w W e a k F ie ld D o u b le R e s o n a n c e N M R S p e c tr o m e te r * Herrn Professor W . Müller-Warmuth zum 65. Geburtstag gewidmet Weak field NMR and double resonance spectrometers are mostly homemade. In this work, some electronic units of such a spectrometer operating at 1.437 mT were designed and realized by includ­ ing new integrated circuits: an audio generator, digital sweep generator, digital additional field and delay unit, Quartz generator, NMR detector(Q-meter), AF-narrowband amplifier, phase shifter and phase sensitive detector. 
  Reference    Z. Naturforsch. 50a, 177—185 (1995); received September 26 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0177 
 Volume    50 
23Author    N.-K Kärger, W. Bär, H. Heink, G. Pfeifer, SeiffertRequires cookie*
 Title      
 Abstract    A probe system is described which allows the application of magnetic field gradient pulses with amplitudes up to 24 T/m for self-diffusion measurements by means of a PFG NMR spectrometer operating at a proton resonance frequency of 400 MHz. It is demonstrated that PFG NMR mea­ surements in the high field of a superconducting magnet necessitate precautions which are of minor relevance for measurements with iron magnets. Taking advantage of the large gradient intensity and the high sensitivity in signal detection of the described system, attenuation patterns of the NMR spin echo are observed for the first time that represent the PFG NMR analogue of the diffraction pattern of a sphere. O n th e U s e o f P u ls e d F ie ld G r a d ie n ts in a H ig h -F ie ld N M R S p e c tr o m e te r to S tu d y R e s tr ic te d D iffu s io n in Z e o lite s 
  Reference    Z. Naturforsch. 50a, 186—190 (1995); received September 26 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0186 
 Volume    50 
24Author    Clemens Ritter1, Robert Cywinski2, SueH. Kilcoyne2Requires cookie*
 Title     
 Abstract    h e N a t u r e o f th e M n M o m e n t in L a v e s P h a s e C o m p o u n d s: E v o lu tio n o f th e M a g n e tic O r d e r in H o j _ xYx M n 2 Dedicated to Prof. Dr. W . Müller-Warmuth on the Occasion of his 65th Birthday Neutron powder diffraction has been used to study the evolution of long range magnetic order in the pseudobinary CI 5 Laves phase system Hoj^Y^Mnj. Particular attention has been paid to the nature of the Mn moment. At Y-rich compositions (x > 0.9) an incommensurate antiferromag-netic structure, similar to that of YMn2 is observed. Transition to the ordered state, as in YMn2, is accompanied by a 5% expansion of the unit cell, identifying the Mn moments, of 2.7 pB, as intrinsic. The magnetic structure of compositions with x<0.7 resembles that of HoMn2 and DyMn2, with only one quarter of the chemically equivalent Mn sites possessing a moment of 0.6 pB induced by the local symmetry of the antiferromagnetically ordered Ho sublattice. Transition to the ordered state is not accompanied by a cell expansion. Between x = 0.7 and x = 0.9 there is no longe range magnetic order, nor is there an expansion of the unit cell, suggesting the total absence of either induced or intrinsic Mn moments. The results indicate that a critical Mn-Mn near neighbour distance of 2.663 Ä is necessary to sustain an intrinsic Mn moment in these compounds. 
  Reference    Z. Naturforsch. 50a, 191—198 (1995); received September 26 1994 
  Published    1995 
  Keywords    Ho1_, cY, cMn2, Magnetic structure, Neutron diffraction, Laves phase 
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 Identifier    ZNA-1995-50a-0191 
 Volume    50 
25Author    A. Seidel, B. BoddenbergRequires cookie*
 Title     
 Abstract    S tu d y o f th e D is tr ib u tio n o f S o d iu m C a tio n s in th e Z e o lite s N a X , N a Y a n d Z n N a Y U s in g C a r b o n M o n o x id e A d s o rp tio n a n d 23N a N M R T e c h n iq u e s Herrn Professor Dr. Werner Müller-Warmuth zum 65. Geburtstag gewidmet The zeolites NaX, NaY, Zn(55)NaY, and Zn(74)NaY were investigated by means of carbon monoxide adsorption and with static and magic angle spinning (MAS) 23Na NMR spectroscopy. The Na+ distribution between the sodalite (/?)-and supercages of the fully hydrated zeolites NaX and NaY were found to agree with XRD results. In the hydrated zinc-exchanged zeolites the Na + ions almost exclusively populate the /?-cages. The adsorption isotherms of CO in the dehydrated zeolites were analyzed quantitatively to yield the concentrations of Na+ residing in the supercages. The measured static and MAS 23Na NMR spectra were analyzed by comparing their widths and shapes with simulated central transition patterns and yield, inter alia, the concentrations of Na+ associated with the spectrum components. Arguments are put forward that 23Na NMR of dehydrated zeolites is well suited to distinguish Na + cations in highly symmetric environments and mobile Na+ species from others located on general positions, but further resolution is hardly feasible. 
  Reference    Z. Naturforsch. 50a, 199—210 (1995); received October 17 1994 
  Published    1995 
  Keywords    23Na NMR, Adsorption, Carbon monoxide, Zeolites, Zinc-exchange 
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 Identifier    ZNA-1995-50a-0199 
 Volume    50 
26Author    R. Ludwig, Ch Rusbüldt, PhA. Bopp, M. D. ZeidlerRequires cookie*
 Title     
 Abstract    h e A n is o tro p y o f th e M o le c u la r R e o r ie n ta tio n a l M o tio n s in L iq u id M e th a n o l Dedicated to Professor W . Müller-Warmuth on the occasion of his 65th birthday Nuclear magnetic resonance (NMR) relaxation time measurements on isotopically substituted samples yield a detailed understanding of the molecular reorientational dynamics in liquids. Reori­ entational correlation times obtained from such experiments are reported for two molecule-fixed vectors in pure liquid methanol. While the reorientational motions of single molecules are nearly isotropic at temperatures below 250 K, at 308 K the reorientational correlation time of the O-H vector becomes 2.3 times larger than that of the O-C vector. Molecular dynamics (MD) simulations give access to the complete correlation functions of the reorientational motions. Correlation times extracted from these functions fit well to the experiment in case of the O-C vector. At low temper­ atures, however, these times lie markedly above those obtained in the experiment for the O-H vector. Thus, the simulation yields reorientation times for the O-H vector that are, independent of the temperature, twice as large as those of the O-C vector. 
  Reference    Z. Naturforsch. 50a, 211—216 (1995); received 
  Published    1995 
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 Identifier    ZNA-1995-50a-0211 
 Volume    50 
27Author    H. J. Grabke, M. Siegers, V. K. TolpygoRequires cookie*
 Title      
 Abstract    Single crystal samples of the alloy Fe-20%Cr-5%Al with and without Y-doping were used to study the "reactive element" (RE) effect, which causes improved oxidation behaviour and formation of a protective A120 3 layer on this alloy. The oxidation was followed by AES at 10"7 mbar 0 2 up to about 1000 °C. Most observations were peculiar for this low p0 2 environment, but yttrium clearly favors the formation of Al-oxide and stabilizes it also under these conditions, probably by favoring its nucleation. The oxides formed are surface compounds of about monolayer thickness, not clearly related to bulk oxides. Furthermore, the morphologies of oxide scales were investigated by SEM, after oxidation at 1000°C for 100 h at 133 mbar 0 2. On Fe-Cr-Al the scale is strongly convoluted and tends to spalling, whereas the presence of Y leads to flat scales which are well adherent. This difference is explained by a change in growth mechanism. The tendency for separation of oxide and metal was highest for the samples with low energy metal surface, i.e. (100) and (110), the scale was better adherent on the (111) oriented surface and on the polycrystalline specimen, since in the latter cases the overall energy for scale/metal separation is higher. All observations, from the low and from the high p0 2 experiments, are discussed in relation to the approximately ten mechanisms proposed in the literature for explanation of the RE effects. 
  Reference    Z. Naturforsch. 50a, 217—227 (1995); received November 14 
  Published    1995 
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 Identifier    ZNA-1995-50a-0217 
 Volume    50 
28Author    Z. NaturforschRequires cookie*
 Title      
 Abstract    Acceleration of mass transfer in gas I liquid-reactions by sonic vibrations: fat hydrogenation as a test reaction A method for increasing the mass transfer in gas/liquid-reactions by application of sonic vibration is described. The operating frequencies have been chosen such that the surfaces of the gas bubbles vibrate in resonance. At these operating frequencies (up to 1000 Hz), the damping of sound waves by the bubbly liquid is low, which is important in large-scale applications. Hydrogenation of soybean oil in a bubble column has been carried out as a test reaction. An increase in mass transfer from dispersed bubbles to the liquid in terms of fcL aG of up to 36% has been effected by a relatively small amount of sonic power. B e s c h le u n ig u n g d e s S to f f a u s ta u s c h e s von G a s -F lü s s ig k e its -R e a k tio n e n d u rc h S c h a llw e lle n a m B e isp ie l d e r F e tth ä r tu n g 
  Reference    Z. Naturforsch. 50a, 228—234 (1995); received November 14 
  Published    1995 
  Keywords    Mass transfer, Fat hydrogenation, Gas, Liquid, Sound, Surface waves 
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 Identifier    ZNA-1995-50a-0228 
 Volume    50 
29Author    C. Meyer, D. HesseRequires cookie*
 Title      
 Abstract    , 1994 Using methods of statistical thermodynamics, adsorption isotherms for the description of differ­ ent-sized molecules are discussed by assuming the adsorbing surface to be energetically homoge­ neous and by neglecting lateral interaction forces between the adsorbed particles. In this case, besides the temperature and the partial pressures, the adsorption process is mainly influenced by a geomet­ rical interaction between the coadsorbed molecules which is modeled by a special parameter. Its value can be determined by geometrical considerations as well as by computer simulations. E in flu ß d e r M o le k ü lg rö ß e a u f A d s o rp tio n s is o th e rm e n 
  Reference    Z. Naturforsch. 50a, 235—246 (1995); received November 14 
  Published    1995 
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 Identifier    ZNA-1995-50a-0235 
 Volume    50 
30Author    G. W. Neilson, S. Ansell, J. Wilson, H. H.Requires cookie*
 Title     
 Abstract    h e S t r u c t u r a l a n d D y n a m ic P r o p e r t ie s o f so m e T ra n s itio n M e ta l A q u a C a tio n s : R e s u lts fro m N e u tr o n S c a tte r in g Dedicated to Professor Hitoshi Ohtaki on the occasion of his 60th birthday The following paper comprises a survey of the role neutron scattering methods have played to help understand the origins of the diverse properties of electrolyte solutions which contain transition metal cations. It is seen how neutron diffraction and isotopic substitution is able to resolve the local structure around contrasting ions, such as Cr3 + , Ni2+, Fe3 + , Fe2+, Cu2+, without recourse to sophisticated modelling procedures. Quasielastic neutron scattering (QNS) provides insight into the dynamics of the protons in solution. The results enable one to distinguish between cations whose water molecules are coordinated on time scales larger than 5 x 10 s, shorter than 10~10s, or intermediate between those two limits. QNS also provides information on the existence of a second relatively short-lived hydration shell distinct from the bulk water. 
  Reference    Z. Naturforsch. 50a, 247—256 (1995); received October 15 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0247 
 Volume    50 
31Author    H. Kanno, M. Honshoh, S. YamauchiRequires cookie*
 Title     
 Abstract    R a m a n S tu d y o f A lc o h o lic L ith iu m P e r c h l o r a t e S o lu tio n s in th e G la s s y S t a t e Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday Raman spectra of alcoholic lithium Perchlorate solutions (alcohol = methanol and ethanol) were measured as a function of LiC104 concentration. The Raman band due to nearly free hydrogen bonds shows peculiar concentration dependences: (1) its frequency shifts with LiC104 concentration in contrast to alcoholic LiX solutions (X = CI and Br), in which the Raman band due to solvated halide ions shows little frequency change with LiX concentration, and (2) the half band width shows anomalous changes with LiX concentration. Non-ionized LiC104 species in alcohol coupled with the changes of solution structure are the major cause for this peculiar behavior. 
  Reference    Z. Naturforsch. 50a, 257—262 (1995); received September 24 1994 
  Published    1995 
  Keywords    Raman spectra, Alcohol solution, Glassy state, Lithium Perchlorate, OH stretching spectrum 
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 Identifier    ZNA-1995-50a-0257 
 Volume    50 
32Author    Sergi Vizoso, BerndM. RodeRequires cookie*
 Title      
 Abstract    Monte Carlo simulations have been carried our for 5, 25, 50, and 75 weight% aqueous solutions of hydroxylamine. Changes in the microstructure of the solutions have been evaluated by means of radial and angular distribution functions, coordination number distributions and pair energy anal­ ysis. The structure of liquid hydroxylamine is strongly altered by even small amounts of water, whereas water clusters similar to the pure water are maintained up to higher NH2OH concentra­ tions. The structural entities in the mixtures are determined by hydrogen bonding and electrostatic arrangement of ligands. 
  Reference    Z. Naturforsch. 50a, 263—273 (1995); received September 24 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0263 
 Volume    50 
33Author    G. Brolo, DonaldE. IrishRequires cookie*
 Title    Alexandre  
 Abstract    Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday Raman spectra of aqueous pyrazine have been investigated in acidic media: HCl from pH = 4 up to 11 M; HC104 from 0.1 M to 12 M; H2S04 form 0.1 M to 18 M. From observation of the shifts of the bands from neutral solutions, it has been possible to identify bands uniquely characteristic of unprotonated pyrazine and its two protonated forms. The diprotonated form was only observed for high concentrations of HC104 and H2S04. From bandfitting of the spectral contours it has been possible to construct the species distribution diagram and estimate the pK values. Raman bands of the three species have been identified and assigned. The results are used to explain an unassigned band at 1235 cm-1, reported by several authors, in SERS from pyrazine on silver and gold elec­ trodes. R a m a n S p e c tr a l S tu d ie s o f A q u e o u s A c id ic P y r a z in e S o lu tio n s 
  Reference    Z. Naturforsch. 50a, 274—282 (1995); received October 31 1994 
  Published    1995 
  Keywords    Pyrazine, Pyrazinium, SERS, Raman spectroscopy 
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 Identifier    ZNA-1995-50a-0274 
 Volume    50 
34Author    Naoki Toshima, Yumi Yamaji, Toshiharu Teranishi, Tetsu YonezawaRequires cookie*
 Title     
 Abstract    h o to s e n s itiz e d R e d u c tio n o f C a r b o n D io x id e in S o lu tio n U s in g N o b le -M e ta l C lu s te rs f o r E le c tr o n T r a n s f e r Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday Carbon dioxide was reduced to methane by visible-light irradiation of a solution composed of tris(bipyridine)ruthenium(III) as photosensitizer, ethylenediaminetetraacetic acid disodium salt as sacrificial reagent, methyl viologen as electron relay, and a colloidal dispersion of polymer-protected noble-metal clusters, prepared by alcohol-reduction, as catalyst. Among the noble-metal clusters examined, Pt clusters showed the highest activity for the formation of methane as well as hydrogen. In order to improve the activity, oxidized clusters and bimetallic clusters were also applied. For example, the CH4 yield in 3-h irradiation increased from 51 x 10"3 |xmol with unoxidized Pt clusters to 72 x 10" 3 pmol with partially oxidized ones. In the case of Pt/Ru bimetalic systems, the improve­ ment of the catalytic activity by air treatment was much greater than in case of monometallic clusters. 
  Reference    Z. Naturforsch. 50a, 283—291 (1995); received October 4 1994 
  Published    1995 
  Keywords    Carbon dioxide, Photosensitized reduction, Electron transfer, Metal cluster, Colloidal catalyst 
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 Identifier    ZNA-1995-50a-0283 
 Volume    50 
35Author    Fernando RullRequires cookie*
 Title    R a m a n  
 Abstract    S p e c tro s c o p ic S tu d y o f th e Io n A s s o c ia tio n o f L ith iu m S u lf a te A q u e o u s S o lu tio n s Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday A Raman spectroscopic study of Li2S04 aqueous solutions as function of concentration and temperature was performed. The dynamic properties of the sulfate ions were studied by a band profile analysis of their internal modes using Fourier transform methods. This analysis reveals the perturbation of the S04" vibrations due to ionic interactions. From the vt (SO;2) band profile the spectroscopic ionic association constant was calculated in the range from 5 to 80 °C. The large difference found between the values thus obtained for the association constant and the values obtained from macroscopic measurements is interpreted, assuming that Raman spectra reflect only the short-range forces acting on the ions. Using the Bjerrum equation to calculate the contribution for the long-range forces, good agreement is found between the spectroscopic and macroscopic results. 
  Reference    Z. Naturforsch. 50a, 292—300 (1995); received November 29 1994 
  Published    1995 
  Keywords    Raman spectra, Lithium sulfate, Aqueous solutions, Ionic association, Band profile 
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 Identifier    ZNA-1995-50a-0292 
 Volume    50 
36Author    Haruhiko Yokoyama, Saeko Suzuki, Masuo Goto, Kazuteru Shinozaki, Yuriko Abe, Shin-Ichi IshiguroRequires cookie*
 Title    X -R a  
 Abstract    y D if fr a c tio n S tu d y o f th e S o lv a tio n S tr u c tu r e o f th e C o b a lt (I I) I o n in N ,N -D im e th y lf o rm a m id e S o lu tio n Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday The solvation structure of Co2+ in N,N-dimethylformamide (DMF) has been studied by X-ray diffraction measurements on cobalt (II) and magnesium (II) Perchlorate solutions of the same concen­ tration, using an isostructural substitution method. The radial distribution function revealed three distinct peaks assigned to the oxygen, amido carbon (CJ, and nitrogen atoms of six planar DMF molecules in the first coordination sphere around the metal atom. The distance from the cobalt atom to each atom (O, Cx, N) is 213,299, and 423 pm, respectively. This indicates that the Co-O-Cj bond angle is 122-123° and the metal atom is close to the O-Cj-N plane of the DMF molecule. 
  Reference    Z. Naturforsch. 50a, 301—306 (1995); received September 28 1995 
  Published    1995 
  Keywords    Cobalt, N,N-dimethylformamide, Solvation, X-ray, Structure 
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 Identifier    ZNA-1995-50a-0301 
 Volume    50 
37Author    Isao Okada, Toshio Nakashima, Yukio Takahagi, Junko HabasakiRequires cookie*
 Title      
 Abstract    Dedicated to Professor Hitoshi Ohtaki on the occasion of his 60th birthday Crystal growth on the (100) and (110) faces of sodium chloride from supercooled melt has been studied by molecular dynamics simulation. The growth velocity was considerably higher for the (100) plane (90-100 m/s) than for the (110) plane (transiently 40-50 m/s). Consequently, even from the (110) face, the crystal seems to grow in the [100] direction. Under the present MD conditions, ca. 2 interface layers with a considerable fraction of defects was formed, which means that the surface advances normal to itself without needing steps. 
  Reference    Z. Naturforsch. 50a, 307—315 (1995); received December 15 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0307 
 Volume    50 
38Author    Yukihiro Yoshimura, Seiji Sawamura, Yoshihiro TaniguchiRequires cookie*
 Title     
 Abstract    f fe c ts o f P r e s s u r e , T e m p e r a tu r e , a n d C o n c e n tr a tio n o n th e V is c o s ity o f A q u e o u s A m m o n iu m B ro m id e S o lu tio n Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday The viscosity of aqueous ammonium bromide solutions is measured at 0.1-1.0 mol kg-1, 278.2-323.2 K, and 0.1-375 MPa, using a high-pressure rolling-ball viscometer. The activation energy (£v) for viscous flow and Jones-Dole's B coefficient are estimated. Ev against pressure yields a concave curve with a minimum and B yields a convex one with a maximum. These phenomena are attributed to pressure, temperature, and concentration effects on the water-structure. 
  Reference    Z. Naturforsch. 50a, 316—322 (1995); received December 14 1994 
  Published    1995 
  Keywords    Viscosity, High pressure, Ammonium bromide, Activation energy, Jones-Dole's B coef­ ficient 
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 Identifier    ZNA-1995-50a-0316 
 Volume    50 
39Author    Siegfried Grossmann1, Martin HolthausRequires cookie*
 Title      
 Abstract    We consider Bose-Einstein condensation in a small cube and describe effects induced by the con­ finement. We also sketch an analogue of the Josephson effect for neutral particles, which can be realized when two almost degenerate states in a double well potential are occupied by a macroscopic number of Bosons. PACS number: 05.30.Jp 
  Reference    Z. Naturforsch. 50a, 323—326 (1995); received February 1 1995 
  Published    1995 
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 Identifier    ZNA-1995-50a-0323 
 Volume    50 
40Author    Arnold Lundén, Leif NilssonRequires cookie*
 Title     
 Abstract    f L ith iu m S u lp h a te in H e x a g o n a l S o d iu m S u lp h a te N a 2S 0 4 (I) Solid solutions of Li2S04 in the high-temperature phase Na2S04 (I) have a much higher conduc­ tivity than expected. Diffusion and electromigration experiments show that both Li+ and Na+ ions are very mobile. It is concluded that the Li+ ions go into interstitial positions of the type (1/2,0,0), while vacancies are created in the Na+ lattice. 
  Reference    Z. Naturforsch. 50a, 327—328 (1995); received November 15 1994 
  Published    1995 
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 Identifier    ZNA-1995-50a-0327 
 Volume    50 
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