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  • 1
    ISSN: 0933-5137
    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: Form and Mechanisms of Cracks and Fractures Caused by Simultaneous Corrosive and Dynamic Stress under Various FrequenciesDistinction of crack nucleation and crack propagation under variable frequencies and electrolytic corrosion. Relationship between crack nucleation and frequency due to differing sliding mechanisms. Crack propagation under decreasing frequencies causes transition from corrosion fatigue to cyclic stress corrosion cracking and finally stress corrosion cracking can be observed. Coordination of that transition with the increasing influence of the KISCC-value as determinant of the crack propagation.The influence of frequency on high temperature materals in hot gas atmosphere is mainly determined by creep mechanisms during top-load phase and the gas-metal-reactions. Accordingly the life time increases with growing load frequency.
    Notes: Anrißphase und Phase des Rißfortschritts bei der Betrachtung der Frequenzabhängigkeit unter elektrolytischer Korrosion. Abhängigkeit der Anrißphase von der Frequenz infolge unterschiedlicher Gleitmechanismen. Beim Rißfortschritt erfolgt mit sinkender Frequenz Übergang von Schwingungsrißkorrosion zu zyklischer Spannungsrißkorrosion und schließlich zu Spannungsrißkorrosion. Zuordnung dieses Übergangs zum zunehmenden Einfluß des KISCC-Wertes als Bestimmungsgröße für den Bruchvorgang.Frequenzabhängigkeit bei Hochtemperaturwerkstoffen in Heißgasatmosphäre im wesentlichen bestimmt durch Kriechvorgänge bei Einwirkung der Oberlast und zeitabhängige Gas-Metall-Reaktionen. Entsprechend verlängern sich die Standzeiten mit zunehmender Belastungsfrequenz.
    Additional Material: 16 Ill.
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  • 2
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; Separation of polychloro biphenyls ; Separation of organochlorine pesticides ; Splitless automated injection ; Residue level ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complicated PCB mixtures can be separated in individual compounds using glass capillary gas chromatography, (GC)2. Depending on extraction and clean-up procedure it is also possible to separate and determine organochlorine pesticides at the same time.This (GC)2 technique can be used to determine the contents of individual chlorinated biphenyls in milk products and animal feedstuffs and in the analysis of complicated extracts of soil and vegetable material.Practical aspects concerning connection of the capillary, automatic splitless injection, repeatability of the retention time, quality of the column with respect to separation and adsorption and degradation of DDT are discussed.The detection of individual chlorinated biphenyls is possible at the ppb level in fats and vegetable materials, using an extraction and clean-up procedure, based on saponification of the sample.Preliminary results for milk, obtained from several areas, are shown.
    Additional Material: 6 Ill.
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  • 3
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectra and gas chromatographic properties of 17 synthetic fluoro-, chloro- and Bromomethoxybiphenyls and 12 dichlorodimethoxybiphenyls have been examined. From this representative series it appears that the position of the methoxy group (ortho, meta and para to the biphenyl bond) in all monomethoxy compounds examined, and the positions of the two methoxy groups in most of the dimethoxy compounds, can be assigned unambiguously by their difference in fragmentation pattern. The value of this method was shown by metabolism experiments in which 4,4′-difluoro- and 4,4′-dibromobiphenyl were fed to rats and 4,4′-dichlorobiphenyl was administered to plants. All hydroxylated metabolites found were identified by gas chromatography mass spectrometry. Relationships between structure and gas chromatographic retention time of these compounds are discussed.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of 1,3-butadiene (BD) has been studied between 464 and 557°K at pressures between 49 and 450 torr. The products are 4-vinylcyclohexene (VCH) and cis, cis-cycloocta-1,5-diene (COD), and their formations are second order. The rate constant (in 1/mol · sec) for VCH is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm V} = - (24,530 \pm 120)/4.576T + (6.95 \pm 0.05) $$\end{document} and that for COD by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm C} = - (28,440 \pm 100)/4.576T + (7.65 \pm 0.04) $$\end{document}The thermal reaction of COD has also been studied. The temperature was varied from 505 to 586°K and the pressure from 15 to 51 torr. The rate constants (in sec-1) for the formations of VCH and BD are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm log}_{10} k_{{\rm VCH}} = - (51,780 \pm 120)/4.576T + (15.34 \pm 0.05) \\ {\rm log}_{10} k_{{\rm BD}} = - (56,380 \pm 100)/4.576T + (16.46 \pm 0.04) \\ \end{array} $$\end{document}A biradical mechanism seems to fit these results. The heat of formation and the entropy of COD are estimated.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 49 (1976), S. 23-48 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The progress of ultrasonic degradation of polymers in solution can be described theoretically by the aid of the model of pearlstring molecules. According to this molecular model macromolecules are built up like a pearl necklace of so-called tertiary structural units. There is correlation between molecular weight of structural units to be obtained by measuring electron micrographs and limiting molecular weight after ultrasonic degradation.Experimental results suggest that molecules resembling a string of pearls are broken at the chain between its spherical units. Two imaginable ways of degradation mechanism are discussed: fragmentary and stepless depolymerization. In the first case the chain is broken between its structural units in several steps; in the second case the pearlstring molecule is broken to all its units in one step. Mathematical consideration has provided an equation for the stepless mechanism. By the aid of this equation the complete progress of depolymerization can be calculated if the limiting molecular weight after ultrasonic degradation is known. On the other hand the limiting molecular weight may be calculated if the beginning of degradation is known. Stepless and fragmentary degradation can be distinguished by comparing the experimentally determined depolymerization with the calculated one.
    Notes: Um Aufschluß über Kinetik und Mechanismus der Ultraschall-Depolymerisation zu erhalten, wurde der Versuch unternommen, den zeitlichen Ablauf des Abbaus auf der Grundlage des Perlschnurmolekül-Modells theoretisch zu beschreiben. Nach diesem molekularen Modell sind Makromoleküle - ähnlich einer Perlschnur - aus mehreren, näherungsweise sphärischen, einheitlich und für ein gegebenes Polymeres charakteristisch großen sog. Tertiäreinheiten aufgebaut.Für den Ultraschall-Abbau von Perlschnurmolekülen werden zwei verschiedene Mechanismen diskutiert: der fragmentarische, bei dem die Perlschnurmoleküle stufenweise über Bruchstücke nach und nach zu den Tertiäreinheiten abgebaut werden und der stufenlose, bei dem die Depolymerisation der Perlschnurmoleküle unmittelbar zu den Tertiäreinheiten führt, so daß während des Abbaus nur Moleküle vom Anfangs- und Grenzmolekulargewicht, M0 und M∞, auftreten. Die mathematische Behandlung des stufenlosen Abbaus lieferte folgende Beziehung: \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {\rm M} _{\rm i} = {\rm M}_{\rm 0} \cdot {\rm M}_\infty \left[ {{\rm M}_{\rm 0} - \left( {{\rm M}_0 - {\rm M}_\infty } \right) \cdot \left( {1 - \pi } \right)^{\rm i} } \right]^{ - 1} . $\end{document} Mit Hilfe dieser Abbaugleichung lassen sich bei Kenntnis von M0, M∞ und eines einzigen Mi-Wertes, der zur Berechnung der „Zertrümmerungskonstanten“ π erforderlich ist, Abbaukurven Mi=f (Beschallungszeit i), oder umgekehrt bei Kenntnis nur des Anfangs einer experimentellen Abbaukurve Grenzmolekulargewichte berechnen. Durch Vergleich der berechneten Abbaukurve mit der experimentell bestimmten ist es möglich, zwischen stufenlosem und fragmentarischem Abbau zu unterscheiden.
    Additional Material: 13 Ill.
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  • 6
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Compounds of propylene-homopolymers with SBS-, EPM- and EPDM-rubber are principally qualified to improve impact resistance esp. at low temperatures.The relationship between the improvement of impact properties and deterioration of tensile-, flexural- and torsional strength in this case is worse than for propylene-block-copolymers. The advantage of compounds is given by the simple possibility to improve the impact resistance as wanted. It has been shown by light- and electron-optical investigations that by compoundation a new phase is formed with particle sizes of 5 μm diameter.
    Notes: Die Compoundierung von Propylen-Homopolymerisat mit SBS-, EPM- und EPDM- Kautschuk ist grundsätzlich geeignet, ein verbessertes Kälteschlagverhalten zu erreichen.Die Relation zwischen Verbesserung der Schlagzähigkeitswerte und der Verschlechterung des Spannungsverformungsverhaltens ist dabei ungünstiger als bei einem Propylen-Block-Copolymerisat. Der Vorteil der Compounds liegt in der einfachen Möglichkeit, das Schlagverhalten von Polypropylen praktisch beliebig zu gestalten.Licht- und elektronenoptische Untersuchungen zeigen, daß durch Compoundierung mit Kautschuk eine neue Phase entsteht mit Teilchendurchmessern bis zu 5 μm.
    Additional Material: 19 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1735-1745 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared spectroscopy was used for the determination of the base-pairing content of four specific tRNAs in deuterium oxide solution. Infrared spectra were obtained in the 1750-1550 cm-1 region at various temperatures ranging from about 15 to 90°C. Melting curves were constructed by plotting the molar extinction coefficient at ν = 1657 cm-1 versus temperature. These transition curves enabled us to determine the ranges of temperature which correspond to the ordered (partially double-stranded) or randomly coiled structure of the tRNA. For a set of wavenumbers the extinction coefficients at these temperatures were used for the calculation of the base-pairing content. The procedure employed here is based on a method described earlier by Thomas [(1969) Biopolymers 7, 325-334]. For the conditions selected for this investigation (Mg2+-free D2O-buffer; 0.01M tris-DCl, 0.015M NaCl, pD 7.5) the results of this determination agree within the limits of errors with the number of base pairs predicted by the cloverleaf model.
    Additional Material: 7 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 1973-1986 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The backbone and side-chain conformations of the bicyclic octapeptide α-amanitin indimethylsulfoxide (DMSO) solution have ben deduced from analysis of the nmr spectrl parameters and conformational energy calculations. Several ambiguities in the nmr spectral assignments were resolved following a comparison with the recently published conformation of β-amanitin in the crystalline state. The peptide proton exchange and temperature coefficient data demonstrate strong intramolecular hyfrogen bonds for the GLY5 and Cys8 peptide protons. The vicinal proton coupling constants are consistent with the cyclic octapeptide udergoing chain reversl at the Ile6-Gly7 abd the Hyp2-Hyi3 dipeptide segments. The upfield shifts of the glycine and isoleucine protons demonstrate the folding of the indole ring of the Trp4-Cys8 brifge towards the Gly5-Ile6-Gly7 half of the Ile-amanitin molecule. The structure af α-amanitin in DMSO is defined by the (φψ) backbone rotation angles Trp4(-90, -60), Gly5 (+120, -120), Ile6(-6, +120), Gly7 (+45, +60), Cys8(-120, -60), Asn1 (+175, -175), Hyp2 (-160, -45), and Hyi3 (-90, -60). The study demonstrates that the structure of α-amanitin in solution is similar to the structure f β-amanitin in the crystalline state.
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  • 9
    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
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 48 (1975), S. 67-95 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The viscosity of solutions of polybutadiene, polymerized by n-butyllithium, with molecular weights between 22000 and 660000 in cyclohexanone, is surprisingly found dependent on the age of solutions. According to solutions in toluene and THF the dependence of concentration from ηsp/C is found in the same way for fresh solutions in cyclohexanone. With increasing age of solutions in cyclohexanone considerable decreasing of viscosity is observed. There is found at 20°C that ηsp/C is independent of concentration after 35 days and that the Staudinger index [η] does no more depend on molecular weight after 300 days. Decreasing of viscosity approaches the limiting value after about 600 days at [η] = 13 cm3/g. Viscosity and solubility in toluene of polybutadiene treated for a short period with a ketone are far extending reduced. The relationship [η] = K·Ma, investigated at solutions of polybutadiene in toluene, THF and cyclohexanone has a common point of intersection, corresponding approximately to Staudinger index and molecular weight of the ultrasonic degradation product, resp. with molecular weight of the so-called tertiary units of not degraded polymer evaluated by means of electron microscopy methods.By the aid of Einstein's relationship of viscosity and the model of pearlstring molecules, decreasing of viscosity with time may be interpreted as a consequence of alteration in the shape of macromolecules as a result of interaction with solvent environment. It can be assumed that stretched pearlstring molecules are being formed to a heap of collapsed coil containing with solvent surrounded tertiary structures. Overthat there are reasons to suppose additionally a partial degradation of solvation layer around tertiary structure.
    Notes: An Lösungen von n-BuLi-polymerisierten Polybutadienen mit Molekulargewichten zwischen 22000 und 660000 in Cyclohexanon wurde eine in der Literatur bisher nicht beschriebene Abhängigkeit der Viskosität vom Alter der Lösungen entdeckt. Während ungealterte Cyclohexanonlösungen eine mit Toluol-und THF-Lösungen übereinstimmende Konzentrationsabhängigkeit von ηspez/C aufweisen, wird mit zunehmendem Alter von Cyclohexanonlösungen ein Rückgang der Viskosität beobachtet, der  -  untersucht bei 20°C  -  nach 35 Tagen zu Konzentrationsunabhängigkeit von ηspez/C und nach 300 Tagen zu einem vom Molekulargewicht unabhängigen Staudingerindex [η] führt. Der Viskositätsrückgang endet nach ca. 600 Tagen asymptotisch bei [η] = 13 cm3/g. Kurzzeitig mit Keton behandeltes Polybutadien löst sich in Toluol nur noch extrem langsam unter gänzlich veränderten Viskositätsverhältnissen. Die für Lösungen von Polybutadien in Toluol, THF und Cyclohexanon gefundenen Beziehungen [η] = K·Ma besitzen einen gemeinsamen Schnittpunkt, dessen Koordinaten näherungsweise mit dem Staudingerindex und dem Molekulargewicht des Ultraschall-Abbauprodukts bzw. dem elektronenoptisch ermittelten Molekulargewicht der Tertiäreinheiten des unbeschallten Polymeren übereinstimmen.Auf der Grundlage von Einsteinscher Viskositätsbeziehung und Perlschnurmolekül-Modell wird der zeitabhängige Viskositätsrückgang als die Folge zweier sich überlagernder Veränderungen des solvatzustands diskutiert: Knäuelung der Perlschnurmoleküle zu einer dichten Kugelpackung der solvatisierten Tertiäreinheiten und partieller Abbau der Solvathülle der Tertiäreinheiten.
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