Untersuchungen Über Die Glasige Erstarrung Von Hochpolymeren Unter Hohen Drucken
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Untersuchungen an Polymeren im Bereich hoher Drucke wurden insbesondere im Bereich der glasigen Erstarrung bisher nur vereinzelt durchgefiihrt. Die V olumetrik ist hierbei schwierig, da sie an Stoffen durchgefiihrt werden muB, die alle Zustandsformen zwischen dem fliissigen und dem festen Zustand ein- nehmen konnen. So wurden Kompressibilitiitsmessungen im Einfrierbereich amorpher Polymerer bisher nur bis zu Drucken von 3500 at durchgefiihrt [16, 17, 19,27 und 38]. Zumeist wurde von einem linearen Anstieg der Glastemperatur mit dem Druck berichtet und es wurde versucht, das glasige Erstarren mit- dem Formalismus einer thermodynamischen Umwandlung zweiter Ordnung zu be- handeln, d. h. die Druckabhiingigkeit der Glastemperatur mit Hilfe der Glei- chungen von EHRENFEST zU beschreiben. Das Ziel der vorliegenden Arbeit war, Zustandsdiagramme von amorphem Poly- styrol im Einfrierbereich bis zu moglichst hohen Temperaturen und Drucken zu messen, um die Kenntnisse iiber das Wesen der glasigen Erstarrung zu erweitern. Polystyrol wurde als Substanz gewiihlt, weil es ein besonders groBes Temperatur- gebiet zwischen der Glastemperatur bei Normaldruck und der Temperatur der beginnenden thermischen Zersetzung aufweist. Weiterhin sind beim Polystyrol die thermodynamischen Eigenschaften bei Normaldruck bekannt. Aus den bisher bekannten Messungen kann man schlieBen, daB ein Druckbereich bis iiber 10000 at zugiinglich sein muB, um die Erscheinung der glasigen Er- starrung bei Hochpolymeren im gesamten moglichen Bereich zu verfolgen. Es wurde daher eine Apparatur entwickelt, die genaue volumetrische Messungen im Bereich bis zu 15000 at bei Temperaturen bis zU 250 C erlaubt.
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