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  • 1
    Electronic Resource
    Electronic Resource
    [s.l.] : Nature Publishing Group
    Nature 191 (1961), S. 899-900 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] The general case has been considered by Synge2. He expressed the condition for surface wave propagation in a given plane in terms of a complex valued determinant, and deduced that surface waves are propagated only in those isolated directions for which the real and imaginary parts of this ...
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 7 (1961), S. 72-77 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The mixing efficiency of simple and pitched paddles, marine propellers, and centrifugal and disk impellers was determined by a heat transfer method in a single stage of a large pump-mix mixer-settler. The mixing devices were from 3 to 5 in. in diameter and were tested with a refined kerosene as the organic phase and water as the aqueous phase.A heat conductance was calculated from flow parameters and the efficiency and was correlated against impeller design and speed variables. For centrifugal and disk impellers UA was proportional to n1.2L3b0.3; for the paddles UA was proportional to n1.67L2.5b0.42. At normal operating speeds controlled variation of the internal recirculation of mixed phases through a centrifugal impeller did not change the efficiency.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 66 (1963), S. 196-204 
    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: 2,4-Toluoldiisocyanat kann ein Dimeres (TDID) und cin Trimeres (TDIT) bilden. Bei der Polymerisation in Substanz im Temperaturbereich von 40 bis 100°C gilt für die Anfangsgeschwindigkeiten Bei jeder Temperatur blieb die Trimerisierungsgeschwindigkeit im untersuchten Umsetzungsbereich im großen und ganzen konstant, während die Dimerisierungsgeschwindigkeit allmahlich auf Null absank. Die Gleichgewichtskonzentrationen von TDID bei 78 und 100°C waren 8,5 bzw. 7,1%. Unter den Versuchsbedingungen kamen 1. nur die sich von der Isocyanatgruppe in 4-Stellung ergebenden Oligomere bei der Di- und Trimerisation in Betracht, und 2. war die Trimerisierungs- von der Dimerisierungsreaktion unabhängig. Nimmt man für die Kinetik der Dimerisation den Vorgang an, so erhält man für Nach den Ergebnissen spielt die Di- und Trimerisierung von 2,4-TDI bei der Herstellung der Polyurethane keine groß Rolle. Indessen konnen sich bei langer Lagerung und erhohter Temperatur merkbare Mengen an TDID und TDIT bilden, so daß es wichtig ist, die Reinheit des Isocyanats unmittelbar vor Gebrauch zu bestimmen.
    Notes: 2,4 tolylene di-isocyanate can form a dimer (TDID) and a trimer (TDIT). For bulk polymerisation at temperatures in the range 40°C. to 100°C. the initial rates of these processes are given by the expressions, At each temperature the rate of trimerisation remained essentially constant over the conversion range examined, but the rate of dimerisation decreased gradually to zero. The equilibrium concentrations of TDID at 78°C. and 100°C. were 8.5 per cent and 7.1 per cent respectively.Experimental evidence indicated that under the conditions examined (i) only oligomers resulting from interaction between isocyanate groups in the 4-position were important in dimerisation and trimerisation, and (ii) the trimerisation process was independent of the dimerisation process.Assuming the kinetics of dimerisation to be represented by This investigation shows that the dimerisation and trimerisation of 2,4-TDI are not important competing processes in the cure of a polyurethane. However as appreciable amounts of TDID and TDIT can be formed as a result of prolonged storage at elevated temperatures it is important that the purity of the isocyanate is determined immediately before use.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 77 (1964), S. 185-190 
    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: Die Anfangsgeschwindigkeit der durch Eisenacetylacetonat (FeAA) katalysierten Dimerisierung und Trimerisierung von 2,4-Tolylendiisocyanat wird durch folgende Gleichungen wiedergegeben: \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\rm {d[TDID]}}} {{\rm {dt}}} = 3.8 \cdot 10^8 \rm{ }[\rm {FeAA] exp }\frac{{\rm { - 19,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\rm {d[TDIT]}}} {{\rm {dt}}} = 1.23 \cdot 10^3 \rm{ }[\rm {FeAA] exp }\frac{{\rm{ - 10,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document}Verglichen mit der durch FeAA katalysierten Urethanbildung sind die Dimerisierung und Trimerisierung unwesentliche Reaktionen. Zu dem gleichen Ergebnis waren wir bei der Untersuchung der unkatalysierten Polyurethanbildung gelangt.Es ist sehr wahrscheinlich, daß bei den verwendeten Temperaturen (25 bis 78°C) als Folge des thermischen Abbaus von FeAA der katalytische Effekt reduziert wird. Der Stabilität von FeAA kommt daher eine wichtige Rolle bei der Polyurethanbildung zu.
    Notes: The initial rates of dimerisation and trimerisation of 2,4-tolylene diisocyanate (TDI), catalysed by ferric acetyl acetonate (FeAA), are given by the expressions \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{\rm {d[TDID]}}} {{\rm {dt}}} = 3.8 \cdot 10^8 \rm{ }[\rm {FeAA] exp }\frac{{\rm { - 19,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\rm {d[TDIT]}}} {{\rm {dt}}} = 1.23 \cdot 10^3 \rm{ }[\rm {FeAA] exp }\frac{{\rm{ - 10,500}}} {{\rm {RT}}}\rm {moles ml}^{\rm { - 1}} \sec ^{ - 1} $$\end{document} Compared to the FeAA catalysed urethane reaction the processes of dimerisation and trimerisation are unimportant, a conclusion similar to that arrived at for the uncatalysed cure of a polyurethane.There is strong evidence that at the temperatures employed (25 to 78°C.), the catalytic effect is reduced as a result of thermal decomposition of FeAA. It would appear therefore that stability of FeAA is likely to be an important factor in the cure of a polyurethane.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    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: Messungen der Viskositätszahl eines thermisch im Vakuum abgebauten Polycarbonates zeigen, daß das Polymere eine statistische Kettenspaltung erleidet, im Einklang mit der Gleichung \documentclass{article}\pagestyle{empty}\begin{document}$$\log [\eta ] = - \alpha \log ({\rm t} + {\rm t}_0 ) + {\rm C}$$\end{document} Der Wert für α aus den in Methylenchlorid erhaltenen Viskositätswerten stimmt mit dem veröffentlichten, auf osmotischem Wege bestimmten Wert von 0,83 als Exponent der Kuhn-Houwink-Gleichung überein.Die Analyse der Molekulargewichtsveränderungen im Verlauf des Abbaues bei verschiedenen Temperaturen zeigt, daß der Prozeß der Kettenspaltung der ersten Ordnung gehorcht und durch die Geschwindigkeitsgleichung k = 4,8·107·e-39500/RT ausgedrückt werden kann.
    Notes: Measurements of the intrinsic viscosity of a polycarbonate degraded thermally in vacuum show that the polymer undergoes random chain scission according to the equation \documentclass{article}\pagestyle{empty}\begin{document}$$\log [\eta ] = - \alpha \log ({\rm t} + {\rm t}_0 ) + {\rm C}$$\end{document} The viscosity results obtained in methylene chloride yield a value of α, the exponent of the Kuhn-Houwink equation in agreement with the published value (0.83) obtained by osmometry.Analysis of the molecular weight changes occurring during degradation at various temperatures shows that the chain scission process obeys first order kinetics and can be expressed by the rate equation k = 4.8·107·e-39,500/RT.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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