Coupled chemical reactions in dynamic nanometric confinement: IV. Ion transmission spectrometric analysis of nanofluidic behavior and membrane formation during track etching in polymers

In recent papers, it was shown that coupled chemical-topological reactions (CCRs) with both NaOH etchant and silver salts, performed in thin swift-heavy ion-irradiated polymers under the application of a test voltage across the polymer foils, eventually gave rise to characteristic current/voltage features and Bode plots that were tentatively attributed to the formation of Ag₂O membranes within the etched tracks. The same was also found when replacing the silver ions by lithium ions, and adding fluoride ions to the NaOH etchant, to promote LiF membrane formation. Ion Transmission Spectrometry (ITS) enabled us to reconfirm the existence of these membranes beyond doubt. The membrane thickness was determined to be ∼0.2-0.4 μm in the best cases.ITS also revealed that hitherto membrane formation occurs only in ∼1% of all tracks, or even less. The reason for this poor abundance seems to be that the decisive factor for membrane formation, which is the firm anchoring of the emerging solid Ag₂O or LiF reaction products on the etched track walls, was hitherto rarely fulfilled. We attribute this tentatively to the too high test voltage applied for controlling the CCR process that might hinder the product anchoring on the walls by promoting nanofluidic electromigration. Indeed, voltage reduction seems to improve the situation.