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Initial stages of glass corrosion in water

Anfangsstadien der Glaskorrosion in Wasser
Authors: Richter, Thomas; Frischat, Günther Heinz; Borchardt, Günter; Scherrer, Stanislas;

Initial stages of glass corrosion in water

Abstract

Proben eines Kalk-Natronsilicatglases mit frischen Bruchflächen wurden 15, 30, 60 und 120 min lang bei 60 und 85 °C in H2O, D2O, H218O und D218O behandelt. Die ausgelaugten Schichten wurden mit NPB-SIMS, einer Methode, die Oberflächenaufladungen durch Verwendung neutraler Primärteilchen vermeidet, analysiert. Ein eindeutiger Isotopieeffekt trat weder in bezug auf die Wasserstoffisotope noch in bezug auf die Sauerstoffisotope ein. Aus diesen und Corbachs Ergebnissen wird geschlossen, daß im Anfangsstadium jedes Alkaliion gegen genau ein Hydroniumion ausgetauscht wird, während sich mit zunehmender Zeit eine wachsende Anzahl unhydratisierter Protonen am Austauschvorgang beteiligt. Die Reaktion des Calciums hängt stark von der Temperatur ab. Bei 85 °C werden Calciumionen zum Teil aus dem äußeren Bereich der hydratisierten Schicht ausgelaugt, zum anderen Teil reichern sie sich in einer bestimmten Tiefe an. Dagegen kann bei 60 °C keine Reaktion des Calciums nachgewiesen werden. Wenn das Glas irreversibler Verformung, die in der „plastischen Zone" an der Rißspitze auftritt, unterzogen wird, entsteht eine Oberflächenschicht mit veränderter Struktur. Der Einfluß dieser verformten Schicht auf die Kinetik der Auslaugung wurde durch ein einfaches mathematisches Modell berücksichtigt.

Soda-lime-silica glass samples with fresh fracture surfaces were treated in H2O, D2O, H218O, and D218O for 15, 30, 60, and 120 min at 60 and 85 °C. The leached layers were analyzed by NPB-SIMS, a technique which avoids surface charging by using neutral primary particles. A distinct isotopic effect occurred neither with respect to the hydrogen isotopes nor with respect to the oxygen isotopes. From these and Corbach's results it is concluded that in the initial stage, every alkali ion exchanges with exactly one hydronium ion, but with increasing time, a growing number of unhydrated protons may participate in the exchange process. The reaction of calcium strongly depends on temperature. At 85 °C calcium ions were found to be leached from the outer region of the hydrated layer and to be enriched in a certain depth beneath the surface. On the other hand, at 60 °C calcium does not react in a measurable degree. When the glass is subjected to irreversible deformation occurring in the "plastic zone" around the crack tip, a surface layer with a modified structure is created. The influence of this deformed layer on the leaching kinetics was taken into account by a simple mathematical model.

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selected citations
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This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
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