Zachary Neale

MSE 463 Literature Research Report

Corrosion in Glass

1.0 Introduction
Glass is commonly known to be an inert material due to the fact that it can be found
almost everywhere from glass containers to window glass. The integrity of glass seems to
endure generations of natural weathering and aqueous environments. This can be observed in
the pristine appearance of glass panes of aged cathedrals and glass artwork. In the laboratory
glass is used to hold various chemicals that would corrode, dissolve, or react with containers
made from other materials. Glass beakers are the predominant receptacle for carrying out
chemical reactions in due to their inertness. Despite the evidence that supports glasss ability to
withstand chemical attack, different types of glass as well as ceramics will readily corrode in
certain environments.
In general, ceramic materials are electrical insulators and lack free charge carriers.
Therefore it is improbable for these materials to corrode through electrochemical redox
reactions. Corrosion of ceramic materials and glass is primarily caused by acid-base reactions. It
is also observed that corrosion behavior varies between non-crystalline and crystalline states of
the same composition [1].
The importance for the study of glass corrosion comes from various fields to better
understand the mechanisms that drive corrosion of glass in different environments. In past
literature, corrosion of crystalline ceramics has been of importance to geochemists in
understanding the dissolution of rocks and minerals due to weathering. The corrosion of marble
statues due to acid rain is an example of this. More recent research on glass corrosion has
investigated the stability of glass used for containing nuclear waste for nuclear waste
repositories. These materials must be designed to contain various nuclear chemicals and
survive on time scales of over thousands of years.
The remainder of this report will investigate the corrosion behavior of different glass
systems. Corrosion mechanisms will be examined and compared based on the various glasses
they apply to. A literature review will cover possible techniques to mitigating corrosion of glass.
Finally, discussion will be presented into how these corrosion mechanisms and mitigation
methods relate to topics covered in class.

2.0 Corrosion Mechanisms
There are several different mechanisms for corrosion of glass in aqueous environments.
The predominant form of corrosion depends on the composition of the glass system and the
interfacial reactions between aqueous solution and the glass surface.


2.1 Congruent dissolution by simple dissociation
Congruent dissolution of glass is the breaking up of the glass network former into
solution. It is referred to as congruent because the ratio of the compositional elements in
solution is the same as the composition of the glass in bulk. An example of this type of glass
corrosion is in the MgF
2
glass system. MgF
2
glass is transparent over the visible spectrum and is
often used in optical devices such as space telescopes. However, MgF
2
is soluble in water by the
simple dissociation reaction:

In fact the solubility of this glass is independent of pH and will reach a saturation of 0.013 g per
100 mL of water. The product is completely aqueous leaving behind no solid products on the
surface of the glass.
2.2 Congruent dissolution by chemical reaction
These reactions are pH dependent and rely on an acid-base or hydrolysis reaction at the
glass surface. An example of this type of corrosion is of MgO used as a component in refractory
materials and glasses. The MgO readily dissolves in an acidic environment through the following
reaction:

MgO is also unstable in water, resulting in another competing reaction:

()

Which also dissolves in an acid solution:
()

At more neutral pH values the formation and dissolution of magnesium hydroxide is the
dominant reaction. Similar to the other type of congruent dissolution reaction, the corrosion of
the glass surface will leave behind no solid product.
2.3 Incongruent dissolution
In glass systems consisting of multiple phases, some phases will react with the
environment while others do not. This leaves behind a network of the undissolved phase. The
remaining phase can either be in a crystalline state, such as with the dissolution of SrTiO
3
, or it
can exist as an amorphous framework called a gel-layer as seen with aluminosilicate and
borosilicate glasses. The chemical composition of the products in solution and left on the
surface are not the same as the composition in the bulk of the material. For example, in
aluminosilicate glass,

()

() ()
This type of glass corrosion can be taken advantage of for making reconstructed glass
such as Vycor glass. Vycor glass starts as a borosilicate glass that undergoes spinodal phase
separation during heat treatment. This results in separate boron oxide and silicon oxide phases.
In the presence of acid incongruent dissolution will take place in which the boron oxide
dissolves into solution. This leaves behind a porous network of silicon oxide which can be
densified through heat treatment. The resulting product is highly pure amorphous silica that
otherwise would have taken a large amount of energy if made from pure silica powder.
2.4 Ion Exchange
Ion exchange of glass is known more for its ability to strengthen glass. However,
depending on the environment, the same mechanism for strengthening glass can corrode it. Ion
exchange occurs in glass when mobile ions are leached from the more resilient glass network.
In soda-aluminosilicate glass, ion exchange is used to strength the glass when potassium ions or
lithium ions replace the sodium ions. In water, hydrogen ions which are smaller are easily
exchanged with larger sodium ions. Taking hydrogen ions out of solution increase the pH of the
solution. The breakdown of the silica structure does not occur until a high enough pH value is
reached. At around ph > 9, congruent dissolution will begin to take place. Figure 1 shows the
process of glass corrosion in soda-silicate glass starting with ion exchange and leading to
congruent dissolution [2].



1.
4.
O Na
Si
Si
O
O
O O Na
Si
O
O O Na
H
+

OH
-

H
+

OH
-

(water) (glass)
(Surface)
Si
O
O
O O H
Si
O
O O H
Na
+

OH
-

Na
+

OH
-

(water) (glass)
(Surface)
2.
Si
O
O
O O H
Si
O
O O H
Na
+

OH
-

(water) (glass)
(Surface)
3.
Si
O
O O H
O
O O H
(water) (glass)
(Surface)
O H
Non-
bridging
oxygen
Congruent
Dissolution
Ion Exchange
pH < 9
pH > 9
Figure 1. Two stage corrosion of soda-silicate glass.
3.0 Corrosion Mitigation
In comparison to the corrosion in metals and other materials, there are not as many
solutions to preventing corrosion in glass. The most direct way with preventing corrosion in
glass is by changing the composition of it. As see previously, the type of corrosion highly
depends on the composition of glass. Pure silicon oxide has high corrosive resistivity compared
to borosilicate and soda-lime glasses. However changing the composition will change other
properties of the glass such as refractive index, band gap, and dielectric constant.
Most cases of glass corrosion occur in stagnant aqueous environments. This is because
the pH of the solution is able to increase during stage 1 corrosion when ion exchange occurs.
However, it is unlikely glasses like window glass will be subjected to long periods of static water.
Usually water drips off the glass when it rains or it evaporates. In these cases it is unlikely for
the pH to ever get above 9.
Therefore, glass corrosion occurs most often during the storing of glass at the
manufacture. In these scenarios, large sheets of glass are often stacked on top of each other. It
is due to this small spacing between glass layers that crevice corrosion can occur. The pH of the
solution could reach 9 within several days of when it first made contact. This would then lead to
more severe corrosion such as congruent dissolution or stage 2 corrosion.
A solution to these storage problems is by using interleaving systems to separate the
glass surfaces. One method is by using interleaving paper to prevent mechanical wear during
handling and reduce pH. Inside the paper were naturally occurring organic acids that would
counteract the increase in pH if ion exchange occurred.
A similar newer solution to preventing corrosion is coating the glass surface in storage
with Poly(methyl methacrylate) (PMMA) beads. The PMMA beads by themselves increase the
separation distance between glass layers. This reduces the contact surface area produced by a
drop of water that finds its way between the glass surfaces. This can delay the increase in pH by
several weeks, however it is still not adequate for long term storage. To help counter the
increase in pH from stage 1 corrosion, a weak organic acid is mixed with the PMMA beads
during production. These methods of using interleaving systems provide corrosion protection
for over a year [3].
4.0 Discussion
The corrosion of glasses and ceramics is unique from most of the previous types of
corrosion learned in class. The most efficient way of preventing corrosion in glass is by keeping
it away from water. The same concept that Dr. Adjorlolo presented to MSE 463 that kept water
away from aluminum in airplanes could potentially be used on glass surfaces. This concept is
putting a surface additive on top of the glass surface. This surface additive acts as a physical
barrier to prevent the glass from coming in contact with water. The surface modification can be
a paint, a polymer, or it could be something that is chemically grown onto the glass. For
example, like in Vycor glass, acid can etch away the top layer of boron oxide to leave behind a
passive silicon oxide layer that would resist corrosion better.
Works Cited

[1] W. B. White, "Theory of Corrosion of Glass and Ceramics," in Corrosion of Glass, Ceramics and
Ceramic Superconductors, Noyes Publications, 1992, pp. 2-28.
[2] F. Ohuchi, MSE 473: Non-crystalline State, University of Washington, Spring 2014.
[3] P. F. Duffer, "How to Prevent Glass Corrosion," Glass Digest, 15 November 1986.