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It is interesting that these glasses exhibited minimal corrosion from atmospheric moisture, even when exposed to 100% RH at 80°C for up to one week. Gbogi et al. [6.90] reported similar results for a ZBL glass exposed to ambient conditions for 30 days, and Robinson and Drexhage [6.91] reported no corrosion for ThF4-containing fluoride glasses up to 200°C.
The time dependency of leaching rates varied with the composition of the heavy metal fluoride additive [6.87]. Compositions containing Zr, Ba, and Th; U, Ba, and Mn; and Sc, Ba, and Y displayed a continuous decrease in corrosion rate with time. Those containing Th, Ba, Mn, and Yb or Th, Ba, Zn, and Yb displayed a minimum. Those containing Pb, K, Ga, Cd, Y, and Al displayed a plateau. Ravaine and Perera also reported a direct relationship between fluoride ion conductivity and corrosion rate. Only the Sc, Ba, and Y composition did not form the outer layer of crystalline precipitates.
Thorium-based glasses containing Zn–Ba–Y–Th, Zn– Ba– Yb–Th, or Zn–Ba–Yb–Th–Na have been reported to be 50– 100 times more resistant to dissolution than the corresponding zirconium-based glasses [6.92].
6.7 CHALCOGENIDE-HALIDE GLASSES
Lin and Ho [6.93] studied the chemical durability of As–S–I glasses exposed to neutral, acidic, and basic solutions. These glasses exhibited excellent resistance to neutral and acidic (pH 2–8) solutions; however, in basic solutions they formed thioarsenites or thioarsenates:
(6.6)
(6.7)
or:
(6.8)
As pH increased from 10 to 14, the rate of attack increased about 400 times. Higher iodine contents lowered the durability.
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For a given iodine content, increased arsenic contents also lowered durability. Plots of weight loss vs. the square root of time were linear, indicative of a diffusion-controlled process. The rate of attack on alkaline solutions increased linearly with temperature. Lin and Ho concluded that the low solubility of these glasses was consistent with the fact that the As-S bond is highly covalent in nature.
6.8 ADDITIONAL RELATED READING
Clark, D.E.; Zoitos, B.K.; Eds. Corrosion of Glass, Ceramics and Ceramic Superconductors; Noyes Publications: Park Ridge, NJ, 1992.
Paul, A. Chemistry of Glasses; Chapman and Hall: New York, 1982;
293pp.
6.9EXERCISES, QUESTIONS, AND PROBLEMS
1.Discuss how pH affects dissolution of silicate glasses including the different mechanisms at low and high pH.
2.Discuss how glass structural variations relate to dissolution and how this is related to composition.
3.What structural factor and what pH relates to the minimum dissolution rate?
4.Describe the surface area/volume ratio of the attacking fluid effects upon dissolution rate.
5.How does a surface treatment of SO2 gas diminish dissolution rates?
6.Why do A12O3 and/or ZrO2 substitutions for SiO2 increase durability?
7.How does the Si/B ratio affect dissolution in borosilicate glasses?
8.Why is the number of nonbridging oxygens important to dissolution?
9.Explain how softening points and/or thermal expansion coefficients may relate to dissolution.
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