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  • Polymer and Materials Science  (47)
  • 2000-2004
  • 1970-1974  (18)
  • 1960-1964  (26)
  • 1945-1949  (3)
  • 1
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Temperature jump measurements employing optical rotation to follow transients show an upper limit of 10μsec. on the half time of the helix-random coil relaxation in poly-α, L-glutamic acid. No relaxations are observed under conditions where the polymer exists in completely helical or completely random coil form. Assuming that the helix-coil transition can be described kinetically as a pure growth process, expressions for the relaxation time are derived for three special cases. A comparison is made between the rate of the helix-coil transition and the rate of imide proton exchange.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 15 (1964), S. 201-212 
    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: Control measurements on cathodically protected pipelinesThe most important control measurement for the cathodic protection of buried pipelines is the measurement of the pipel soil potential. On the strength of experimental and theoretical investigations, it is possible to indicate safe protection potentials at which the corrosion rate becomes practically insignificant. In applying the scientific results of electro-chemistry to cathodic protection in practice, problems may be encountered if phenomena are over-simplified or if local conditions are not sufficiently taken into account.Such practical problems are not so much concerned with measuring instruments and reference electrodes; they are more associated with the measuring methods subsequently described and with the fact that influence factors difficult to ascertain must be taken into account.The cathodic polarisation at the metal surface to be protected is composed of overtensions of a penetration and a diffusion type. In addition, there occurs a resistance polarisation which may be governed, on the one hand, by the ohmic voltage drop between pipe surface and reference electrode and, on the other hand, by poorly conducting coating or insulating layers. The latter usually cause, at the same time, a change in the diffusion type overtension. Since the resistance polarisation does not partake in the reaction kinetics, this influence must be eliminated in measuring the protection potential. Since the different types of polarisation have different type curves, it is possible to ascertain the separate partial reactions in accordance with the normal methods of electro-chemistry. By means of oscillographic recordings of potential/time curves, through calculation or with the aid of suitable measuring bridges, it is possible to eliminate the resistance polarisation or to determine the ohmic voltage drop in the electrolyte.
    Notes: Die wichtigste Kontrollmessung für den kathodischen Schutz erdverlegter Rohrleitungen ist die Messung des Rohr/Boden-Potentials. An Hand experimenteller und theoretischer Untersuchungen ist es möglich, sichere Schutzpotentiale anzugeben, bei denen die Korrosionsgeschwindigkeit praktisch bedeutungslos wird. Bei der Anwendung wissenschaftlicher Ergebnisse der Elektrochemie auf den kathodischen Schutz in der Praxis können Probleme auftreten, wenn Vorgänge zu stark vereinfacht und örtliche Gegebenheiten nicht genügend berücksichtigt werden.Solche praktischen Probleme liegen weniger bei Meßgeräten und Bezugselektroden, als bei den anschließend beschriebenen Meßverfahren und der Berücksichtigung schwer erfaßbarer Einflußgrößen. Die kathodische Polarisation an der Zu schützenden Metalloberfläche Setzt sich aus einer Durchtritts- und einer Diffusionsüberspannung zusammen. Ferner tritt eine Widerstandspolarisation auf, die einerseits durch den Ohmschen Spannungsabfall zwischen Rohroberfläche und Bezugselektrode, andererseits durch schlecht leitende Deck- oder Isolierschichten gegeben sein kann. Letztere verursachen meist gleichzeitig eine Änderung der Diffusionsüberspannung. Da die Widerstandspolarisation keinen Anteil an der Reaktionskinetik besitzt, muß ihr Einfluß bei der Schutzpotentialmessung eliminiert werden. Auf Grund eines zeitlich unterschiedlichen Verhaltens der Polarisationsarten gelingt die Aufspaltung der einzelnen Teilreaktionen nach den in der Elektrochemie üblichen Verfahren. Durch oszillographische Aufnahme won Potential-Zeitkurven, durch Rechnung oder mit geeigneten Meßbrücken kann die Widerstandspolarisation ausgeschaltet bzw. der Ohmsche Spannungsabfall im Elektrolyten ermittelt werden.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 12 (1973), S. 845-856 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy estimates were made for completely charged polyglutamic acid with different assumptions concerning the placement of side chain charge. Viewed as a helix, the minimum energy structure is somewhat affected by the side-chain charge placement. The average energy of the chain viewed as a random coil is equal to or less than the average energy of the chain viewed as a helix. Unlike the polyacrylate chain, nearest-neighbor charge interaction is shown to increase the chain dimensions. Although the calculations are approximate there is little evidence to suggest that isolated polyglutamate molecules in the absence of added electrolyte should behave as rods or that there are significant amounts of locally ordered structures. Presently no experimental results exist under conditions appropriate to isolated molecular calculations.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 12 (1973), S. 835-843 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism (CD) spectrum of poly-L-lysine and poly-L-glutamic acid has been investigated in the presence of a small percent of side-chain blocking groups. The blocking groups benzyl, methyl, and carbobenzoxy show qualitatively similar effects. Less than five mole percent of aromatic blocking groups alters the CD spectrum. Consequently, unsuspected blocking groups may account for the variation observed in CD spectra of these polymers. A weak CD band at 235-240 nm was observed for the disordered unblocked polymer even in the absence of electrolyte. Viscosity data indicate that in salt-free solutions these chains at neutral pH still behave as random coils though with reduced conformational freedom, in contrast to some polyelectrolytes which behave as rigid rods in the absence of electrolyte. The viscosity data bring into question the relevance of isolated molecule conformational calculations to experimental CD spectra.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 8 (1964), S. 953-969 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The quaternization of poly(ar-vinylbenzyl chloride) with trimethylamine is shown to be a nucleophilic displacement reaction, the kinetics of which are complicated by several factors, notably differences in the reactivities of o- and p-chloromethyl groups (position isomerism), differences in the reactivities of groups as a function of the reacted or unreacted status of immediately adjacent groups (neighboring group effect), and differences in the reactivities of groups arising from the microtacticity of the polymer segment (configurational effects). Estimates of mean rate constants, activation energies, and preexponential factors are given for high purity poly-p-vinylbenzyl chloride and for the analogous ortho polymer.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 6 (1962), S. S57 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 1 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 2025-2033 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: High molecular weight poly(vinylbenzyl chloride) fails to undergo many classical organic reactions, but may be reacted essentially quantitatively with a variety of tert-amines to yield the corresponding quaternary polymers. With dimethyl-n-alkylamines, polymers of the type are formed; these are water-soluble through R = n-decyl and methanol-soluble through R = n-hexadecyl. A number of polyridines and dialkyl sulfides react similarly to yield the corresponding polycationics. These reactions are controlled by several factors not operative in small-molecule reactions: nucleophile partitioning in the initially heterogeneous systems, swelling power of the medium for the reactant polymer, and a sharp steric limitation imposed by the configuration of the high polymer. This steric effect may be exploited by using certain hindered primary and secondary amines to prepare substituted poly-(vinylbenzylamines) which are soluble and noncrosslinked.
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  • 8
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: As of this date, tri-segmented intra-aortic balloons made from Avcothane-51 elastomer were applied in the counterpulsation treatment of about 80 cardiac patients. The combined effects induced by the implanted elastomer and the hemodynamics of pumping are analyzed by means of hematologic changes observed in a set of 28 patients who were treated at the Massachusetts General Hospital for an average period of about 4 days, and represent a widely diversified group in terms of their clinical conditions. In no case were, any significant adverse hematologic effects induced by this assist device whether the hosts had been anticoagulated or not heparinized at all. While platelet levels were somewhat affected by the assist device, the particular conditions of the patient appear to have an effect of at least, equal magnitude. In addition to platelet levels steadily decreasing with pumping time, changes in platelet levels similar to the pattern of “platelet tide” occurred with about equal frequency. Monitored in terms of erythrocyte counts and plasma hemoglobin levels, no significant degree of hemolysis could be detected. Leukocyte counts in patients having above-normal levels at the beginning of pumping returned to normal while in other cases there were no significant changes. Fibrinogen, one of the plasma proteins most sensitive to foreign surfaces, showed levels increasing from subnormal to normal as a function of pumping time. The overall in vivo performance of Avcothane-51 balloons appers to be consistent with the state of the surfaces of recovered devices, showing only the presence of occasional adherent platelets upon examination by scanning electron microscopy.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2031-2043 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Farol-Weissenberg rheogoniometer has been used to follow molecular weight changes during the degradation of certain poly-α-esters in the melt state. By observing the change in melt viscosity at low shear rates it had been shown that the decomposition of the poly(isopropylidene carboxylate) is substantially first-order with respect to the molecular weight of the residual polymer. The derived kinetic parameters are in good agreement with those previously obtained by other techniques. This provides a substantial piece of supporting evidence for the view that degradation takes place predominantly by intramolecular ester interchange involving the formation of 1,1,4,4,-tetramethylglycollide. The introduction of β-chlorine atoms into the polymer structure leads to a more complex degradation pattern. Thus the presence of a single β chlorine atom per repeat unit, as in poly(3-chloro-2-methyl-2-hydroxypropionic acid) leads to a substantially similar dependence on molecular weight with the added complication of progressive crosslinking which becomes more apparent in later stages of the reaction. This crosslinking reaction plays an increasingly important part as the extent of chlorination of the polymer is increased. In addition, the presence of chlorine leads to an increased sensitivity of the degradation reaction to the presence of oxygen.
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  • 10
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Im Temperaturbereich von 60 bis 100°C wird die radikalische Polymerisation von Styrol, Methylmethacrylat und Acrylnitril von α.α′-Dicyanodibenzylen ausgelöst, die in α-und α′-Stellung mit Ester-, Nitril-, Amid- oder Phenylgruppen disubstituiert sind. Bei 100 bis 110°C ist auch das α.α.α′.α′-Tetracarboxymethyldibenzyl aktiv. Vinylacetat und Vinylchlorid werden durch diese Initiatoren kaum polymerisiert.Fur die Polymerisation des Styrols wurden die Bruttogeschwindigkeitskonstanten Kp, für viele Dibenzyle und fur Peroxide vergleichbarer Aktivitat dilatornetrisch bestirnrnt. Norrnalerweise sind die Zeit-Urnsatz-Kurven rnit den Dibenzylen und den Peroxiden vergleichbar; das Tetracyanodibenzyl allerdings bewirkt nur eine unvollstandige Polymerisation.Der große Einfiuß von Substituenten in α-Stellung oder in den Phenylringen der Dibenzyle auf die Polymerisation des Styrols wird diskutiert. Dabei ist auch die Stereochernie wichtig. Die meso-Form des Dinitrildiesters ergibt eine 2.5- bis 3.5 ma1 schnellere Polyrnerisation als das dl-Isornere.Die Dissoziationsgeschwindigkeitskonstanten kd der Initiatoren wurden NMR-spektroskopisch aus der Linienbreite bestirnmt. Die Dinitrildiester sind gute Initiatoren, wahrend die α.α′-Dicyanodibenzyle rnit weiteren Nitril- oder Phenylgruppen in α- und α′-Stellung wenig geeignet sind. SchlieBlich wurde die 1.2-Addition einiger der Dibenzyle an Styrol im Ternperaturbereich von 120 bis 150°C rnit der Methode der chernisch induzierten KernPolarisation (CIDNP) untersucht.
    Notes: The radical polymerization of styrene, methyl methacrylate and acrylonitrile is initiated by α.α′-dicyanodibenzyls α.α′-disubstituted with ester, nitrile, amide or phenyl groups in the temperature range 60 to 100°C and by α.α.α′.α′-tetracarboxymethyldibenzyl at 100 to 110°C. Vinylacetate and vinylchloride show a low reactivity.The overall polymerization rate constants Kp have been determined dilatometrically for styrene initiated by a large number of dibenzyls and comparable peroxides. The styrene polymerization curves are generally comparable with those of peroxides. A notable exception is tetracyanodibenzyl.The strong influence of α- and ring-substituents in the dibenzyls on the styrene polymerization rate is discussed. The stereochemistry is also important : the meso α.α′-dicyanodibenzyls α.α′-disubstituted with ester groups give a 2.5 to 3.5 fold faster polymerization than their dl isomers.The initiator efficiency is related to the kd values, determined from NMR line width measurements. The α.α′- dicyanodibenzyls α.α′-disubstituted with ester groups are good initiators, while those with phenyl groups and nitrile groups are inefficient.Relevant to initiation and termination, the 1.2-addition of some of the dimers to styrene at 120 to 150°C has been studied with chemically induced dynamic nuclear polarization (CIDNP).
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