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Fluid-cell Raman Spectroscopy for operando Studies of Reaction and Transport Phenomena during Silicate Glass Corrosion

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Nearly constant loss effects in borate glasses.

David M Laughman¹, Radha D Banhatti, Klaus Funke

¹Institut für Physikalische Chemie and SFB 458, Westfälische Wilhelms-Universität, Corrensstrassse 30, Münster, Germany.

Physical Chemistry Chemical Physics : PCCP

|April 17, 2009

Summary

Nearly constant loss (NCL) phenomena in borate glasses were investigated. A new model explains NCL as interacting ions with temperature-independent motion, crucial for understanding ionic conductivity.

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Area of Science:

Materials Science
Solid State Physics
Glass Science

Background:

Investigating ionic conductivity in borate glasses (xNa(2)O.(1-x)B(2)O(3)) across wide temperature (4.3 K to 573 K) and frequency (100 mHz to 1 MHz) ranges.
Understanding different nearly constant loss (NCL) phenomena is key to characterizing ionic transport in glasses.

Purpose of the Study:

To identify and characterize NCL phenomena in sodium borate glasses.
To propose a formal treatment for the NCL mechanism.
To elucidate the role of interacting ions and their motion at cryogenic temperatures.

Main Methods:

Utilizing conductivity measurements as a function of temperature and frequency.
Applying scaling properties of conductivity to isolate the NCL component.
Analyzing the frequency and temperature dependence of the NCL phenomenon.

Main Results:

Successfully isolated and characterized the NCL component in 0.3Na(2)O.0.7B(2)O(3) glass, showing it is proportional to frequency and temperature-independent.
Identified a broad-band relaxation process in amorphous boron oxide and low-sodium borate glasses, likely due to water impurities and hydrogen ion dynamics.
Proposed a formal model for NCL, attributing it to a large number of interacting ions exhibiting a 'see-saw-type' time dependence in their double-well potentials due to Coulomb interactions.

Conclusions:

The NCL phenomenon in borate glasses arises from interacting ions with temperature-independent, locally confined motion.
This ionic motion, driven by Coulomb interactions and a 'see-saw-type' potential, persists even at cryogenic temperatures.
The findings offer a new perspective on ionic conductivity mechanisms in disordered materials.