Natur-, Ingenieur- Und Wirtschaftswissenschaften: Vorträge - N 416
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Langkettige line are Polymere in der Schmelze oder in konzentrierter Losung zeigen eine Reihe anomaler viskoelastischer Eigenschaften. Besonders spektakular ist das Auftreten eines Plateaus in der Zeitabhangigkeit des dynamischen Moduls, das sich mit wachsender Kettenlange immer mehr ausweitet [1]. In diesem Plateau- bereich ist die Spannung proportional zur Dehnung - es gilt das Hookesche Gesetz: Die Polymerschmelze, obwohl eine Fliissigkeit, verhaIt sich elastisch. Dieses Verhalten erinnert an die Gummielastizitat von miteinander chemisch ver- netzten Polymeren. Der dort auftretende Modul falIt allerdings nicht bei langen Zeiten auf Null ab - es gibt keinen FlieBbereich. Der Betrag des Moduls der Gummielastizitat ist proportional zur Temperatur und umgekehrt proportional zur Maschenweite des Netzwerks. Die Proportionalitat zur Temperatur wird durch entropische Krafte bewirkt, die als eine Konsequenz der Konformations- entropie der geknauelten Ketten zwischen den Netzpunkten entstehen. Diese Konformationsentropie ergibt sich aus der Anzahl der moglichen Anordnungen von Kettensequenzen im Raum. Nach dem zentralen Grenzwertsatz ist die wahr- scheinlichste Anordnung diejenige eines GauBschen Knauels, d. h., die Polymer- kette fuhrt einen Zufallsweg im Raum aus. Werden nun Kettenstiicke gestreckt, so wirkt eine entropische Kraft, die sich aus der Ableitung der freien Energie ergibt, die diese gestreckten Segmente wieder in den wahrscheinlicheren ge- knauelten Zustand zUrUckzufuhren strebt. Ausgehend von dieser Analogie zur Gummielastizitat liegt es nahe anzuneh- men, daB die Ursache des elastischen Verhaltens von Polymerschmelzen durch netzwerkartige Verschlingungen der Polymerketten untereinander bewirkt wird. Damit wird die Schmelze zu einem temporaren Netzwerk.
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