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1979 (260)
1Author    G. J. Ashwell, "., I. Diaconu, D. D. Eley, S. C. Wallwork, M. R. WillisRequires cookie*
 Title    Properties of [N,N'-di(n-propyl)-4,4'-bipyridylium] 2+ (7,7,8,8,-Tetracyanoquinodimethane) 4 2 ~  
 Abstract    The crystal structure and electrical properties of [iV,iV / -di(n-propyl)-4,4'-bipyTidylium] 2+ -(7,7,8,8-tetracyanoquinodimethane)4 2 ~, (DPrBP) 2 +(TCNQ)4 2_ , are reported. The complex is monoclinic with the space group P2\jc and lattice constants a = 13.334(1), b = 25.954(3), c = 7.877(1) A, ß = 93.66°, Z = 2. The single crystal dc resistivities at 300 K along a, b and c are 3300, 200 and 800 Q cm respectively with activation energies of 0.36, 0.22 and 0.30 eV. The existence of a hopping mechanism in addition to a frequency independent conduction process is indicated by a. c. conductivity data obtained on a compressed disc between 10 and 10 5 Hz. 
  Reference    Z. Naturforsch. 34a, 1—5 (1979); received May 3 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0001.pdf 
 Identifier    ZNA-1979-34a-0001 
 Volume    34 
2Author    Chr Bräuchle, H. Kabza, J. VoitländerRequires cookie*
 Title    Optical and ODMR Investigations of the Lowest Excited Triplet State of Dinaphtho  
 Abstract    On the basis of the phosphorescence spectrum of dinaphtho-(2'.3':1.2); (2".3":6.7)-pyrene in n-dodecane (Shpolskii matrix) at T — 1.3 K a site and vibrational analysis was performed. With the help of ODMR measurements the symmetries of the vibrational bands were determined. In this way for most of the normal modes an assignment of the type of vibration became feasible. Because of their different zero-field splittings (ZFS) five sites could be identified. The signs of the ZFS parameters as well as the kinetic rate constants of population and depopulation of the zero-field levels (ZFL) of Ti were determined. Like the ZFS the kinetic rate constants too were different for each site reflecting different interaction of the molecules with the host matrix. Radiative and radiationless processes are discussed in terms of spin-orbit coupling (SOC). 
  Reference    Z. Naturforsch. 34a, 6—12 (1979); received June 23 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0006.pdf 
 Identifier    ZNA-1979-34a-0006 
 Volume    34 
3Author    R. Brüggemann, J. VoitländerRequires cookie*
 Title    Konsequenzen einer abbildungstheoretischen Deutung von Hückel-Parametern für die Diskussion von Charge-Transfer-Effekten in Dreizentrensystemen  
 Abstract    The charge-transfer effects of systems of the general type A-B-B are investigated, A being the donor. The importance of a one-to-one correspondence between Hückel-parameters and param-eters such as effective nuclear charges and bond distances is pointed out. By using charge-transfer effects as an example it is shown that non-uniqueness leads to difficulties in interpreting charge-transfer effects. 
  Reference    Z. Naturforsch. 34a, 13 (1979); eingegangen am 20. Juli 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0013.pdf 
 Identifier    ZNA-1979-34a-0013 
 Volume    34 
4Author    K. ChristmannRequires cookie*
 Title    Adsorption of Hydrogen on a Nickel (100) Surface  
 Abstract    The adsorption of hydrogen on a clean Ni(100) single crystal surface was studied in UHV between 120 K and 500 K means of LEED, thermal desorption spectroscopy and work function measurements. H2 chemisorption occurs in two atomic states ßi and ßz with maximum desorption rates (at saturation) at 318 K and 348 K. The activation energy for desorption was determined to be 20 (± 2) kcal/mole for the /?i-state and 23 (± 1) kcal/mole for the /^-state, in excellent agreement with previous results. Saturation at 120 K corresponds to a coverage of 0.9 20%). The initial sticking probability is 0.06 (± 0.01) and the rate of adsorption follows second order kinetics. No additional LEED spots arose from the H overlayer, indicating the absence of long-range order even at 120 K. The work function results clearly show the existence of two different binding states: Whereas the /^-population gives rise to a linear increase by 100 meV (at 120 K) the ß\-state leads to a decrease of A <p to a final value of 30—40 meV. 
  Reference    Z. Naturforsch. 34a, 22—29 (1979); received July 4 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0022.pdf 
 Identifier    ZNA-1979-34a-0022 
 Volume    34 
5Author    G. Ertl, M. Huber, N. ThieleRequires cookie*
 Title    Formation and Decomposition of Nitrides on Iron Surfaces  
 Abstract    The formation (by interaction with ammonia) and decomposition of nitrides on clean Fe surfaces was studied by means of Auger electron spectroscopy, x-ray photoelectron spectroscopy, thermal desorption spectroscopy, and scanning electron microscopy. The N atoms may exist in various forms with quite similar electronic properties, viz. as chemisorbed layer (= "surface nitride"), dissolved in a-Fe or y-Fe, as y'-nitride (= Fe4N) or as e-nitride, depending on tempera-ture as well as pressure and duration of interaction with NH3. There is no noticeable chemical shift of the ionization energies of the Fe core levels, indicating that the bond is essentially covalent. The activation energy for the decomposition of e-nitride into Fe4N + N2 is about 27 kcal/mole, that for the decomposition of Fe4N into Fe -f-N2 ranges between 51 and 57 kcal/mole, depending on the mode of preparation. The latter values are identical to those found previously for the desorption of N2 from various Fe single crystal planes and indicate that the decomposition of the chemisorbed "surface nitrides" is the rate-limiting step which prevents the spontaneous decom-position of the metastable bulk iron nitrides. 
  Reference    Z. Naturforsch. 34a, 30—39 (1979); received July 20 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0030.pdf 
 Identifier    ZNA-1979-34a-0030 
 Volume    34 
6Author    P. Gallezot, R. Weber, R. A. Dalla, Betta, M. BoudartRequires cookie*
 Title    Investigation by X-Ray Absorption Spectroscopy of Platinum Clusters Supported on Zeolites  
 Abstract    The onset of the Lm edge of the X-ray absorption spectrum of platinum in F-zeolites invol-ves an electronic transition from core to band levels producing a so-called white line. The spec-tral area of this increases and the edge position shifts to higher energies, first when the platinum particle size becomes small enough so that the clusters are in the supercages, second when the clusters are covered with oxygen, and third when multivalent cations are introduced in the zeo-lite. Both features of the absorption edge indicate that under the three above circumstances, platinum becomes more electron deficient. This conclusion had been inferred earlier from the enhanced catalytic activity of Pt clusters in Y zeolites. 
  Reference    Z. Naturforsch. 34a, 40—42 (1979); received June 26 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0040.pdf 
 Identifier    ZNA-1979-34a-0040 
 Volume    34 
7Author    Kozo Hirota, Kazuo Aizawa, Tsuneyuki NishizawaRequires cookie*
 Title    Clusius* Separation Column as a Reactor to Produce Highly Concentrated Hydrogen  
 Abstract    A Clusius' separation column of hot wall catalytic activity was applied as a reactor to produce highly concentrated hydrogen. Satisfactory results are obtained in the decomposition of hydrogen sulfide and the conversion of carbon monoxide with water. 
  Reference    Z. Naturforsch. 34a, 43—45 (1979); received December 21 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0043.pdf 
 Identifier    ZNA-1979-34a-0043 
 Volume    34 
8Author    E. Hummel, M. Domke, J. H. BlockRequires cookie*
 Title    Appearance Potentials of Field Desorbed Silver Ions  
 Abstract    The onset, eöo, in the energy distribution of field desorbed silver ions (from Ag deposit on a JF-tip) has been measured at T > 400 K. With increasing field strength (0.5 • 10 10 V/m < F < 1 • 10 10 V/m) or with decreasing temperature (800 K > T > 500 K), edo increases up to 1.5 eV. For a comparison with the eöo-values, activation energies, Q, for field desorption have been determined from Arrhenius plots (0.5 eV < Q < 2 eV). Two different kinetic regimes (desorption and diffusion) were identified. For field desorption, the sum eöo + Q is constant, irrespective of F-values. In the frame of "image hump" or "charge exchange" models, field dependent activation barriers are discussed. Temperature dependencies are related to (i) the Fermi distribution of the emitter, (ii) the distribution of F and (iii) the distribution of surface bond energies. Results are consistently explained in a three-dimensional model with directionally distinguished desorp-tion steps. 
  Reference    Z. Naturforsch. 34a, 46—54 (1979); received November 3 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0046.pdf 
 Identifier    ZNA-1979-34a-0046 
 Volume    34 
9Author    Emanuel Kaldis, Benno Fritzler, Winfried PetelerRequires cookie*
 Title    Hochtemperatur-Festkörperchemie von Verbindungen der seltenen Erden mit Valenzinstabilität: Nichtstöchiometrisches TmSe und Mischkristalle  
 Abstract    The phase diagram of TmSe has been measured in the composition range 0.6 x ^ 1.2 (x = mole Tm/mole Se) up to 2300 °C. Both phase diagram and lattice constants show the existence of a gross homogeneity range at 0.90 < x < 1.05. X-ray and electron diffraction at room temperature confirm the homogeneity of this phase and show no superstructures in this range but only a correlation of vacancies. A dramatic change of the lattice constant (1.7%) with nonstoichiometry shows that the latter controls the valence of Tm between 3+ and 2.71+. Density measurements indicate that both the solution of excess Tm or Se in the lattice leads to the formation of vacancies in the other sublattice. The experimental results can be explained by the existence of approx. 1% Schottky defects for all samples and nonstoichiometric vacancies increasing with deviations from stoichiometry up to 10% for the Se-rich phase boundary (each tenth lattice site vacant!). With increasing temperature the nonstoichiometric samples show two phase transitions: the first at approx. 1100°C for Tm-rich samples or approx. 1700°C for Se rich samples (the stoichiometric sample shows both transitions); the second for all samples at 2003°. At 2020 °C a eutectic appears at the composition of x = 1.00, its components melting at 2032 °C and 2028 °C. This shows that in the temperature range between the phase transitions and the eutectic temperature a decomposition of the homogeneity range must take place. This decom-position might be due to a valence segregation, the two components of the eutectic possibly being Tm 2 ' 71+ Se and Tm 3+ Se. Various measurements indicate changes of the lattice stability in TmSe as a function of stoichiometry. Thus stoichiometric samples show a minimum melting point and solution-reaction calorimetry (with 4N HCl) indicates that the composition with the highest melting point (Tm 3+ Se) has the highest stability. As it is briefly discussed the unstable states may have important implications as active states for surface phenomena and catalysis. Further change of the Tm-valence in a TmSe-containing compound exceeding the range Tm 3+ <-> Tm 2 -71+ may be achieved by mixed-crystal formation. The lattice pressure in TmSe is changed by chemical substitution leading among others to the interesting mixed crystal systems TmSei-aTea; and Tmi-^Eu^Se. The first shows two pressure-induced phase transitions accom-panied by a change of the Tm-valence from 2.25+ -> 2.52+ and 2.52+ -> 2.93+. Density measure-ments show that when the lattice collapses the number of vacancies nears 10%. 1. Einführung Ein großes Gebiet der Festkörperchemie, das hochschmelzende reaktive Chalkogenide und Pnik-tide umfaßt, bleibt für die moderne Festkörper-forschung mangels geeigneter experimenteller Me-thoden unerreichbar. Die Synthese von Ein-kristallen mit kontrollierter Stöchiometrie sowie die Bestimmung der P-T-X-Parameter, die den thermo-dynamischen Stabilitätsbereich abgrenzen und wichtige festkörperchemische und festkörperphysi-kalische Eigenschaften beeinflussen, sind nicht mit * Erste Fassung eingereicht am 27. 5. 1978. 
  Reference    Z. Naturforsch. 34a, 55 (1979); eingegangen am 2. November 1978* 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0055.pdf 
 Identifier    ZNA-1979-34a-0055 
 Volume    34 
10Author    E. Killmann, J. Eisenlauer, P. KaniutRequires cookie*
 Title    Charakterisierung von Silika (Aerosil) Hydrosolen durch Photonenkorrelationsspektroskopie  
 Abstract    The diffusion of silica(Aerosil)-hydrosols has been studied by photon correlation spectroscopy. For data analysis the method of cumulants, proposed by Koppel, was used. Effects of charge and hydratation of the silica particles and their complicated aggregated structure required an extra-polation to the solconcentration cs = 0 and the scattering angle 0 = 0. The described data analysis combined with the methodical proceeding — using Aerosil aggre-gates as a model system — shows how to evaluate the diffusion coefficient and its normalized variance. These data of characterization are important for many kinds of aggregated particles in technical applied dispersions. 
  Reference    Z. Naturforsch. 34a, 68—75 (1979); eingegangen am 13. Juni 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0068.pdf 
 Identifier    ZNA-1979-34a-0068 
 Volume    34 
11Author    A. Knappwost, M. Raschti, Ü. AnkaraRequires cookie*
 Title    Zur Feinstruktur des Verlaufs der Adsorptionswärme mit der Belegung von Aromaten auf Silber  
 Abstract    Isosteric adsorption heats have been determined from the temperature dependences of equilibrium pressures, which in turn have been obtained from sets of very precisely measured adsorption isotherms. The dependence of the isosteric adsorption heat on the coating of the silver surface shows a remarkable structure: whenever a layer of adsorbate is filled up, inner rotations are inhibited, which results in a peak in the adsorption heat-coating curve. The adsorption isotherms of toluene, adamantane and benzotrifluoride on highly dispersed silver were measured with an ultra-sensitive adsorption balance. The nearly spherical adamantane enabled an exact determination of the specific surface area of the adsorbent. From their respective space require-ments it followed that toluene is adsorbed in ortho-and meta-positions, whereas benzotrifluoride is adsorbed with its three F-atoms on the silver surface. The energy of rotation of the CH3-and CF3-groups could also be determined. 
  Reference    Z. Naturforsch. 34a, 76—80 (1979); eingegangen am 17. Juli 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0076.pdf 
 Identifier    ZNA-1979-34a-0076 
 Volume    34 
12Author    J. Küppers, A. PlaggeRequires cookie*
 Title    The Langmuir-Hinshelwood Reaction between Oxygen and CO at Ir(l 11) Surfaces  
 Abstract    Dedicated to Prof. G. M. Schwab on the occasion of his 80th birthday The reaction of oxygen and CO to form CO2 has been investigated using an Ir (111) surface as an acting catalyst. Both instationary and stationary reaction processes have been established via separate gas exposing techniques. The instationary reaction process, achieved from coadsorbed CO and O which per se is an LH reaction is found to be controlled by an apparent activation energy of 10.7 kcal/mole. The stationary reaction with both CO and O2 continuously present in the gas phase has been simulated using a proper computer program, involving both LH and ER reaction steps. By comparison with experimental results, close agreement is found when ruling out any ER reaction step from the reaction path. 
  Reference    Z. Naturforsch. 34a, 81 (1979); received June 1 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0081.pdf 
 Identifier    ZNA-1979-34a-0081 
 Volume    34 
13Author    Volkmar Leute, Harald Böttner, Heinrich SchmidtkeRequires cookie*
 Title    Chalcogen Interdiffusion in the System Pb(S, Se)  
 Abstract    From the sulfur-and selenium-concentration profiles recorded by an electron microprobe the chalcogen interdiffusion coefficient of the system Pb(S, Se) is determined as a function of mass fraction cpbse and temperature. Undoped crystals and Pb-or chalcogen-saturated crystals are studied. The dependence of the interdiffusion coefficient on the deviation from stoichiometry shows that in the chalcogen-saturated part of the system the calcogen interdiffusion proceeds via chalcogen interstitials, whereas in the Pb-saturated part of the system the chalcogens diffuse via chalcogen vacancies. For pure PbSe it is shown that these vacancies are doubly ionized. The activation entropy of the diffusion of the chalcogens depends linearly on the ratio of activation enthalpy to solidus temperature. 
  Reference    Z. Naturforsch. 34a, 89—95 (1979); received May 30 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0089.pdf 
 Identifier    ZNA-1979-34a-0089 
 Volume    34 
14Author    H. Shindo, C. Egawa, T. Onishi, K. TamaraRequires cookie*
 Title    Mechanism of Ammonia Decomposition on Tungsten; NH 3 and ND 3 Isotope Effect  
 Abstract    Light and heavy ammonia were decomposed on a clean tungsten foil at 973—1123 K and at PNH3,ND3 ^ 0.2 Torr. The nitrogen uptake and the kinetics of the formation of nitride layers were examined during the course of the reaction. The amount of nitrogen chemisorbed (or the thickness of the nitride layers formed) at higher pressures was found to be appreciably larger from NH3 than from ND3. Addition of hydrogen had no effect on the thickness of the nitride layer nor on the rate of ammonia decomposition. These facts support the concept of a dynamic balance between two consecutive rate determining steps: supply of chemisorbed nitrogen from ammonia into the surface and consumption of the chemisorbed nitrogen through its desorption from the surface to form nitrogen molecules. 
  Reference    Z. Naturforsch. 34a, 96—98 (1979); received October 23 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0096.pdf 
 Identifier    ZNA-1979-34a-0096 
 Volume    34 
15Author    F. E. WittigRequires cookie*
 Title    Solutions of Partial Differential Equations for Mean Molar Functions  
 Abstract    The well known formulas for computing the partial molar functions from a given mean molar function are treated as deferential equations for computing the mean molar function from any given partial molar function. Solutions do not depend on the number of components, but only on the choice of three indices: the index d of the dependent mole fraction xa to be eliminated prior to any computations, the index j of a pivot mole fraction xj and the index i of the partial molar function yi. An arbitrary number of additional mole fractions of the other components safe xa may be linked to the pivot mole fraction Xj. The simple solution: y = (xj — %) iy, yi = (xj — öij) 2 Xfj and Xif = d Itj/dxj holds for an arbitrary number of components, if the (c — 2) mole fractions xi safe xa and xj are transformed to new variables found from the auxiliary equa-tions. Three different cases arise if either i = d, i = j or i =(= d, i =|= j is chosen. Formulas for the three sets are provided. As an example a simple interpolation formula for ternary systems is discussed. 
  Reference    Z. Naturforsch. 34a, 99—104 (1979); received November 4 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0099.pdf 
 Identifier    ZNA-1979-34a-0099 
 Volume    34 
16Author    Ch Jung, A. Kawski, M. I. Zukowska, K. I. FluoresceneRequires cookie*
 Title    Die Schwingungsstruktur der Shpolskii-Spektren von Anthracen, 9-Methyl-und 9,10-Dimethylanthracen in n-Hexan bei 77 K. I. Fluoreszenz  
 Abstract    The 
  Reference    Z. Naturforsch. 34a, 105 (1979); eingegangen am 22. August 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0105.pdf 
 Identifier    ZNA-1979-34a-0105 
 Volume    34 
17Author    Hiroyuki Itoh, A.Barry KunzRequires cookie*
 Title    Theoretical Study of Linear NiCO and CuCO and its Implication to Adsorption  
 Abstract    Ab initio RHF-MO calculations are made for the linear NiCO and CuCO clusters. The ground states of them involve Ni 3d 9 4s 1 and Cu 3d 10 4s 1 electron configurations, respectively. The orbital energies of the CO like levels in both clusters are closely similar to each other. The CO 5<r-like level shifts toward the CO 17r-like level due to the bonding interaction of the 5 a with the metal 4s and 3dz 2 . The results are discussed in relation to the difference of the 3d-level positions and the similarity of 4s levels of Ni and Cu. For NiCO both the 4s and 3d orbitals contribute to the metal-CO binding while for CuCO only the 4 s orbital contributes to it. The present results are in agreement with the UPS experiments on adsorption. 
  Reference    Z. Naturforsch. 34a, 114—116 (1979); received October 16 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0114.pdf 
 Identifier    ZNA-1979-34a-0114 
 Volume    34 
18Author    W.C T DowellRequires cookie*
 Title    Oblique Illumination Stereoscopy in the Shadow Electron Microscope  
 Abstract    Oblique illumination, although accompanied by distor-tion, provides a simple method of obtaining stereoscopic images in a shadow electron microscope. It is not necessary to tilt the specimen. 
  Reference    Z. Naturforsch. 34a, 117—118 (1979); received October 23 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0117_n.pdf 
 Identifier    ZNA-1979-34a-0117_n 
 Volume    34 
19Author    G. H. Schleser, R. Pohling, B. MeyerRequires cookie*
 Title      
 Abstract    13 C/ 12 C variations of organic carbon have been investi-gated in an undisturbed forest soil with perched surface water. The measurements reveal a very distinct decrease of the 13 C-content with increasing depth of the soil horizons. Within 20 cm the ö 13 C-value is depleted by 1.5/°00. At present it is however not possible to verify, whether this behaviour is characteristic for undisturbed soils in general. 
  Reference    Z. Naturforsch. 34a, 119—120 (1979); received November 29 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0119_n.pdf 
 Identifier    ZNA-1979-34a-0119_n 
 Volume    34 
20Author    Siegfried HessRequires cookie*
 Title    Variational Principle for Slow Viscous Flow of Fluids with Anisotropic and Spatially Inhomogeneous Viscosity, Upper and Lower Bounds on the Frictional Force and Torque  
 Abstract    The frictional force and torque excerted by a fluid on a solid body which performs a slow translational or rotational motion is related to the rate of entropy production. Starting from the Navier-Stokes equation, a variational principle is derived for this quantity. Provided that the antisymmetric part of the viscosity tensor is smaller than its symmetric part upper and lower bounds on the force and torque are established. These bounds can be calculated with certain trial functions for the flow velocity field. 
  Reference    Z. Naturforsch. 34a, 121—125 (1979); received November 6 1978 
  Published    1979 
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 TEI-XML for    default:Reihe_A/34/ZNA-1979-34a-0121.pdf 
 Identifier    ZNA-1979-34a-0121 
 Volume    34 
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