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  • Chemistry  (21)
  • Surface physics, nanoscale physics, low-dimensional systems
  • 2000-2004  (5)
  • 1975-1979  (12)
  • 1970-1974  (4)
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Year
  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four fractions of poly(vinyl chloride) (PVC) having appreciably different tacticity distributions were prepared by selective extractions on samples polymerised at temperatures between +60 and -50°C. They were degraded thermally at 180°C in the solid state to conversions in the range 0,2 to 0,5% and in solution at 200°C to conversions in the range 1,6 to 5%. The polyene sequence distribution was investigated by ultra violet/visible (UV/VIS) and resonance Raman spectroscopy. The results show that the type of polyene sequence distribution depends markedly on the tacticity distribution of the polymer. Cross-linking reactions occur more readily as the syndiotacticity increases. The results are discussed and interpreted with reference to previous work relating degradation processes and tacticity.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 373-378 
    ISSN: 0935-6304
    Keywords: Open tubular columns ; capillary electrochromatography ; column efficiency ; injected volume ; applied voltage ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of some instrumental parameters on column efficiency in open tubular capillary electrochromatography (OTCEC) has been evaluated. First, it was investigated whether band broadening due to the sample injection process is within a tolerable range when an open tubular column (OTC) of about 10 μm i. d. is used. As a result of the small injection profile factor (K2 = 1.3), injected volumes must be sufficiently small (less than 10 pL) to avoid a significant efficiency loss (〉5%) when hydrodynamic injection by siphoning is employed. Secondly, the kinetic performance of OTCs in a CEC system was estimated from the variation of the reduced plate height (h) with the reduced linear velocity (ν) which was controlled by the voltage applied. Reasonable agreement was obtained between the theoretical h versus ν curve and the experimental values for a group of polycyclic aromatic hydrocarbons used as test compounds. Values of 0.25 for minimum h at an optimum ν of 16 are estimated, which permit separations with around 400,000 plates per meter to be obtained in less than 5 min. Finally, the possibility of estimating the diffusion coefficients of the solutes in the mobile phase from the plot of the height of a theoretical plate versus electroosmotic flow velocity is shown.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 26 (1975), S. 703-706 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Autoclave arrangement for oxidation and corrosion tests of materials in pressurized waterThe authors describe an arrangement with an autoclave for corrosion and oxidation tests in pressurized water and steam. The autoclave has been conceived for a pressure of 250 bar at 500 °C. It is equipped with four locks enabling the specimens to be exchanged during operation without any markable influence on the working conditions. The aggressive medium can be exchanged continuously at a rate of 2,5 l/h. In addition to pressure and temperature controls the arrangement is equipped with a water quality control system.
    Notes: Es wird eine Autoklavenanlage für Korrosions-und Oxidationsuntersuchungen mit Hochdruckwasser bzw. Wasserdampf beschrieben. Die Auslegungsdaten des Autoklaven sind 250 bar bei 500 °C. Der Autoklav besitzt 4 Schleusen, über die während des Betriebes ein Probenwechsel ohne größeren Einfluß auf die Betriebsbedingungen möglich ist. Das korrodierende Medium kann kontinuierlich mit einer max. Rate von 2,5 l/h ausgetauscht werden. Neben der Druck- und Temperaturkontrolle ist eine Überwachung der Wasserqualität vorgesehen.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 28 (1977), S. 676-683 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Phase transformations of the ZrNb 3 Sn 1 alloyThe phases transformations of cold-worked Zr-Nb 3-Sn 1-alloy have been studied as a function of heat tratements between 500-600°C in vacuum. Microscopic and X-ray diffraction analyses reveal allow us to state that again of a 50% cold-worked Zr-Bb 3-Sn 1-alloy at 597°C gives rise to a maximum ß-Nb content in the ß-Zr-matrix after 4 hours annealing.
    Notes: Die Phasenumwandlungen der Zr-Nb3-Sn 1-Legierung mit verschiedenen Kaltverformungen wurden in Abhängigkeit der Wärmebehandlung bei Temperaturen zwischen 500 und 600°C im Vakuum untersucht. Durch lichtmikroskopische Beobachtung und Röntgenbeugungsanalyse konnte im Fall einer Zr-Nb 3-Sn 10-Legierung mit 50%iger Kaltverformung, die einer Wärmebehandlung bei 597°C unterworfen wurde, nachgewiesen werden. Daß die ß-Nb-Konzentration in der ß-Zr-Matrix nach etwa 4 Stunden Wärmebehandlungszeit praktisch ein Maximum erreicht hat.
    Additional Material: 19 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 29 (1978), S. 258-265 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Influence of a mechanical treatment on the oxidation behaviour of ZrNb 3 Sn 1 alloy in oxygenIt has been found by means of gravimetric, microscopic, screen electron microscopic and x-ray diffraction investigations that the corrosion resistance of a Zr-Nb 3-Sn 1 alloy in oxygen (po2 = 3.3 × 104 Pa) between 400 and 460° C increases with increasing extent of cold rolling between 10 and 50%. Initially, the oxidation obeys a parabolic rate law with an activation energy the value of which becomes larger with increasing cold forming. After a critical thickness of the oxide layer is reached a transfer to a linear rate law occurs. The time of this transition becomes larger with increasing cold forming. Form the three processes which are responsible to the oxide layer growth mainly the diffusion of oxygen through the oxide layer via oxygen ion vacancies is the rate-determining step. In the later period of oxidation, however, a diffusion via grain boundaries must also be considered. The manner of the oxide growth is decisively determined by the cold forming regarding to a preferred orientation of the α-Zr grains in the alloy and to an epitaxial formation of oxide nucleus and of oxide crystals in the later period of oxidation.
    Notes: Mittels gravimetrischer, lichtmikroskopischer, rasterelektronenmikroskopischer und röntgendiffraktometrischer Untersuchungen wurde unmittelbar bestätigt, daß sich die Oxidationsbeständigkeit der Zr-Nb 3-Sn 1-Legierung im Sauerstoff (po2 = 3,33 × 104 Pa) bei Temperaturen zwischen 400 und 460 °C mit zunehmender Kaltverformung (zwischen 10 und 50% Kaltverformungsgrad) erhöht. Die Oxidation folgt zuerst einem parabolischen Zeitgesetz mit einer Aktivierungsenergie, deren Wert mit steigender Kaltverformung zunimmt. Nach Erreichen einer kritischen Schichtdicke wird ein Übergang zu einem linearen Zeitgesetz beobachtet. Die Übergangszeit ihrerseits nimmt mit steigender Kaltverformung zu. Obwohl während des Aufbaus des Zunders drei miteinander verknüpfte Vorgänge erfolgen, stellt die Diffusion von Sauerstoff durch die Oxidschicht über Sauerstoffionen-Leerstellen und längs von Kanten und Korngrenzen den reaktionsbestimmenden Schritt dar. Die Kaltverformung bestimmt die Art des Wachstums des Zirkonoxids, zunächst durch eine bevorzugte Orientierung der α-Zr-Körner in der Legierung und danach durch eine epitaktische Ausbildung der Oxidkeime und der Oxidkristallite im weiteren Verlauf der Oxidation.
    Additional Material: 7 Ill.
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  • 6
    ISSN: 1434-193X
    Keywords: Amino acids ; coupling ; N-Substituted amide ; Cyclizations ; Cyclic dipeptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A short synthesis of new, functionalized seven-membered ring cyclic dipeptides is described. After the coupling of N-protected β-amino acids to N-substituted α-amino tert-butyl esters, the protective groups of the terminal functions were removed and the cyclization took place diastereoselectively in the presence of the coupling agent BOP. Amide substitution was found to be effective in promoting the cyclization of linear dipeptides.
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 807-811 
    ISSN: 1434-193X
    Keywords: Proline analogues ; Asymmetric synthesis ; Schöllkopf's method ; Silicon ; Amino acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The asymmetric synthesis of a new proline surrogate, incorporating the dimethylsilyl group at position 4 of proline using Schöllkopf's bis-lactim ether method, is described.
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  • 8
    ISSN: 1434-193X
    Keywords: Thiadiazolidinones ; Spiro compounds ; Thiazoles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The design, synthesis and evaluation of a series of 1,2,4-thiadiazolidinones with potential muscarinic receptor binding properties has been performed. During the synthesis of the target compounds, we observed an interesting reductive cleavage of the thiadiazolidinone system which leads to the formation of the novel piperidine spiro triazine heterocycle. The synthesis, structural elucidation (NMR spectroscopy and X-ray diffraction) and biological evaluation of the new compounds are described. With the structures unequivocally established, a mechanism for the formation of the spiro compound is proposed.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/099462_s.pdf or from the author.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 23 (1977), S. 393-395 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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